WO2013092943A1 - Isothiazoline compounds for combating invertebrate pests - Google Patents

Isothiazoline compounds for combating invertebrate pests Download PDF

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Publication number
WO2013092943A1
WO2013092943A1 PCT/EP2012/076539 EP2012076539W WO2013092943A1 WO 2013092943 A1 WO2013092943 A1 WO 2013092943A1 EP 2012076539 W EP2012076539 W EP 2012076539W WO 2013092943 A1 WO2013092943 A1 WO 2013092943A1
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WIPO (PCT)
Prior art keywords
alkyl
compounds
ring
group
cycloalkyl
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PCT/EP2012/076539
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French (fr)
Inventor
Pascal BINDSCHÄDLER
Wolfgang Von Deyn
Karsten KÖRBER
Florian Kaiser
Michael Rack
Deborah L. Culbertson
Paul Neese
Franz-Josef Braun
Original Assignee
Basf Se
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Priority to IN4376CHN2014 priority Critical patent/IN2014CN04376A/en
Priority to ES12810287T priority patent/ES2727479T3/en
Priority to BR112014015553-4A priority patent/BR112014015553B1/en
Priority to CA2858766A priority patent/CA2858766A1/en
Priority to EP12810287.8A priority patent/EP2794601B1/en
Priority to CN201280070554.8A priority patent/CN104169278B/en
Priority to JP2014548048A priority patent/JP6415983B2/en
Application filed by Basf Se filed Critical Basf Se
Priority to KR1020147020594A priority patent/KR20140115329A/en
Priority to US14/366,161 priority patent/US9732051B2/en
Priority to MX2014006973A priority patent/MX2014006973A/en
Priority to AU2012356947A priority patent/AU2012356947A1/en
Publication of WO2013092943A1 publication Critical patent/WO2013092943A1/en
Priority to IL233312A priority patent/IL233312A0/en
Priority to ZA2014/05336A priority patent/ZA201405336B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to isothiazoline compounds which are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes, and to a method for producing them.
  • the invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.
  • Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests, in particular insects, arachnids and nematodes.
  • the object of the present invention was moreover to provide compounds which are less persistent, bioaccumulative and/or toxic than the compounds of the prior art. Especially isoxazoline insecticides show a high persistency in the soil and thus accumulate there. It has been found that these objectives can be achieved by isothiazoline compounds of the formula I below, by their steroisomers and by their salts, in particular their agriculturally or veterinarily acceptable salts.
  • the invention relates to isothiazoline compounds of formula I
  • A is a group A 1 , A 2 , A 3 or A 4 ;
  • a 2 is a group of following formula:
  • W is selected from O and S;
  • Y is selected from hydrogen, -N(R 5 )R 6 and -OR 9 ; is a group of following formula:
  • # denotes the bond to the aromatic ring of formula (I); is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroa- toms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, or is a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2, 3 or 4 heteroa- toms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substitu- ents R 11 ;
  • B 1 , B 2 and B 3 are each independently selected from the group consisting of N and CR 2 , with the proviso that at most two of B 1 , B 2 and B 3 are N;
  • G 1 , G 2 , G 3 and G 4 are each independently selected from the group consisting of N and CR 4 , with the proviso that at most two of G 1 , G 2 , G 3 and G 4 are N;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , radicals R 11 , and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromono- or heterobicyclic ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 11 ;
  • R 3a , R 3b are each independently selected from the group consisting of hydrogen, halogen, -C0 2 R 3d , hydroxyl, Ci-C 3 -alkyl, d-C 3 -haloalkyl, C 2 -C 3 -alkenyl, C 2 -C 3 - alkynyl, Ci-C 3 -alkoxy, Ci-C 3 -haloalkoxy, Ci-C 3 -alkylthio, Ci-C 3 -haloalkylthio, Ci- C 3 -alkylsulfonyl and Ci-C 3 -haloalkylsulfonyl; or
  • R 4 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF 5 , Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , Cs-Cs-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , C2- C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , radicals R 11 , and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 11 ; each R 5 is independently selected from the group consisting of hydrogen, C1-C10- alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last- mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or
  • each R 6 is independently selected from the group consisting of hydrogen, cyano, Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last- mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 8 ,
  • R 7a , R 7b are each independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 ; each R 8 is independently selected from the group consisting of cyano, azido, nitro, - SCN, -SF 5 , C3-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, where the cycloaliphatic moieties in the two last-mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 13 ;
  • phenyl optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R 16 , and
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 16 , or
  • R 8 together with the carbon atoms of an alkyl, alkenyl, alkynyl or cycloalkyi group which they are bonded to, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring, where the heterocyclic ring comprises 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, and where the carbocyclic or heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ; and
  • R 8 as a substituent on a cycloalkyi ring is additionally selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2- C6-alkynyl and C2-C6-haloalkynyl, where the aliphatic moieties in these six radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 13 ; and
  • R 9 is independently selected from the group consisting of hydrogen, cyano, Ci- Ce-alkyl, Ci-C 6 -haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-Ci-C 4 -alkyl-, C 3 -C 8 - halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cydoaliphatic moieties in the nine last-mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 3 ,
  • phenyl optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ;
  • a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ; and
  • R 9 in the groups -S(0) n R 9 and -OSO2R 9 is additionally selected from the group consisting of Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • phenyl optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ;
  • a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ;
  • R 10a and R 10b form together with the nitrogen atom they are bonded to a 3-, 4- , 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-
  • radicals R 8 1 , 2 or 3, in particular 1 , radicals R 8 ,
  • phenyl optionally substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, in particular 1 , substituents selected independently from R 16 ;
  • a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated aromatic heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or het- eroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected independently from R 16 ;
  • R 11 bound on adjacent ring atoms form together with the ring atoms to which they are bound a saturated 3-, 4-, 5-, 6-, 7-, 8- or 9-membered ring, where- in the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from
  • R 12 is independently selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6- alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-haloalkoxy-Ci- C6-alkyl, and phenyl, optionally substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, preferably 1 or 2, in particular 1 , substituents R 16 ;
  • R 13 is independently selected from the group consisting of cyano, nitro, -OH, -SH, -SCN, -SF 5 , d-Ce-alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkylthio, Ci-C 6 - haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
  • Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo; phenyl, benzyl, phenoxy, where the phenyl moiety in the three last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, in particular 1 , substituents R 16 ; and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may
  • R 13 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last- mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , substituents selected from CN, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
  • R 14 is independently selected from the group consisting of hydrogen, cyano, Ci C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C1-C6- alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from CN , Ci-C4-alkoxy, C1-C4- hal
  • Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4- cycloalkyl, C3-C4-cycloalkyl-Ci-C4-alkyl-, where the cycloalkyl moiety in the two last-mentioned radicals may be substituted by 1 or 2, in particular 1 , substituents selected from halogen and cyano; and oxo;
  • cyclic moieties in the four last- mentioned radicals may be unsubstituted and/or carry 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy,
  • Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 or 2 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 16 ;
  • R 14a and R 14b independently of each other, have one of the meanings given for R 14 ;
  • R 14a and R 14b together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substitutents selected from halogen, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • phenyl, benzyl, pyridyl and phenoxy wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3, preferably 1 or 2 in particular 1 , substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
  • R 16 is independently selected from the group consisting of halogen, nitro, cyano, -OH, -SH, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl;
  • Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
  • phenyl, benzyl, pyridyl and phenoxy wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3, in particular 1 , substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
  • two R 16 on two adjacent carbon atoms form together with the carbon atoms they are bonded to a 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, and wherein the ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; each n is independently 0, 1 or 2; and
  • each m is independently 0 or 1 ; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.
  • the present invention also provides an agricultural composition comprising at least one compound of the formula I as defined herein and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
  • the present invention also provides a veterinary composition comprising at least one compound of the formula I as defined herein and/or a veterinarily acceptable salt thereof and at least one liquid or solid carrier.
  • the present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or a salt thereof as defined herein.
  • the present invention also relates to plant propagation material, in particular seed, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof as defined herein.
  • the present invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of the formula I or a veterinarily acceptable salt thereof as defined herein. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal.
  • steroisomers encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • One center of chirality is the carbon ring atom of the isothiazoline ring carrying radical R 1 .
  • the invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantio- mers or diastereomers of the compound I or its mixtures.
  • Suitable compounds of the formula I also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
  • N-oxides relates to a form of compounds I in which at least one nitrogen atom is present in oxidized form (as NO).
  • the compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of the formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
  • Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4+ ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammo- nium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyr- ate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Suitable acid addition salts e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochloride, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hydrochloride, sulphates, phosphates, and nitrates
  • organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • invertebrate pest encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • the plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. Said young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • plants comprises any types of plants including "non-cultivated plants” and in particular "cultivated plants”.
  • non-cultivated plants refers to any wild type species or related species or related genera of a cultivated plant.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • auxin herbicides
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made re- sistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci.
  • cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ - endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • these insecticidal proteins or toxins are to be understood ex- pressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsan- to Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called " pathogenesis-related proteins" (PR proteins, see, e. g.
  • EP-A 392 225 plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications men- tioned above.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), toler- ance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • alkyl as used herein and in the alkyl moieties of alkoxy, alkylthio, alkylsulfi- nyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl and the like refers to saturated straight- chain or branched hydrocarbon radicals having 1 to 2 ("Ci-C2-alkyl"), 1 to 3 (“C1-C3- alkyl"),1 to 4 (“Ci-C 4 -alkyl”), 1 to 6 (“Ci-C 6 -alkyl”), 1 to 8 (“Ci-C 8 -alkyl”) or 1 to 10 (“Ci- Cio-alkyl”) carbon atoms.
  • Ci-C2-Alkyl is methyl or ethyl.
  • Ci-C3-Alkyl is additionally propyl and isopropyl.
  • Ci-C 4 -Alkyl is additionally butyl, 1 -methylpropyl (sec-butyl), 2- methylpropyl (isobutyl) or 1 ,1 -dimethylethyl (tert-butyl).
  • Ci-C6-Alkyl is additionally also, for example, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 - ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, or 1 - eth
  • Ci-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2- ethylhexyl and positional isomers thereof.
  • Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl and positional isomers thereof.
  • haloalkyl as used herein, which is also expressed as “alkyl which is partially or fully halogenated”, refers to straight-chain or branched alkyl groups having 1 to 2 (“Ci-C 2 -haloalkyl”), 1 to 3 (“Ci-C 3 -haloalkyl”), 1 to 4 (“Ci-C 4 -haloalkyl”), 1 to 6 (“Ci-C 6 - haloalkyl”), 1 to 8 (“Ci-C 8 -haloalkyl”) or 1 to 10 (“Ci-Cio-haloalkyl”) carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluorome- thyl, trifluoromethyl, chlorofluoromethyl,
  • Ci-C3-haloalkyl is additionally, for example, 1 -fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1 ,1 -difluoropropyl, 2,2- difluoropropyl, 1 ,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoro- propyl, 1 ,1 ,1 -trifluoroprop-2-yl, 3-chloropropyl and the like.
  • Examples for C1-C4- haloalkyl are, apart those mentioned for Ci-C3-haloalkyl, 4-chlorobutyl and the like.
  • Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like.
  • alkenyl refers to monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 3 (“C2-C3-alkenyl"), 2 to 4 (“C 2 -C4-alkenyl”), 2 to 6 (“C 2 -C 6 -alkenyl”), 2 to 8 (“C 2 -C 8 -alkenyl”) or 2 to 10 (“C 2 -Cio-alkenyl”) carbon atoms and a double bond in any position, for example C 2 -C3-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl or 1 -methylethenyl; C 2 -C4-alkenyl, such as ethenyl, 1 -propenyl,
  • haloalkenyl as used herein, which is also expressed as “alkenyl which is partially or fully halogenated”, refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 (“C 2 -C 4 -haloalkenyl"), 2 to 6 (“C 2 -C 6 -haloalkenyl”), 2 to 8 (“C2-C6-haloalkenyl”) or 2 to 10 (“C2-Cio-haloalkenyl”) carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
  • alkynyl refers to straight-chain or branched hydrocarbon groups having 2 to 3 (“C 2 -C 3 -alkynyl”), 2 to 4 (“C 2 -C 4 -alkynyl”), 2 to 6 (“C 2 -C 6 -alkynyl”), 2 to 8 (“C 2 -C8-alkynyl”), or 2 to 10 (“C 2 -Cio-alkynyl”) carbon atoms and one or two triple bonds in any position, for example C 2 -C3-alkynyl, such as ethynyl, 1 -propynyl or 2- propynyl; C 2 -C 4 -alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl and the like, C
  • cycloalkyl refers to mono- or bi- or polycyclic saturated hydrocarbon radicals having 3 to 8 (“Cs-Cs-cycloalkyl”), in particular 3 to 6 carbon atoms (“C3-C6-cycloalkyl”).
  • monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.2.1 ]heptyl, bicyclo[3.1 .1]heptyl, bicyclo[2.2.2]octyl and bicy- clo[3.2.1 ]octyl.
  • cycloalkyl denotes a monocyclic saturated hydrocarbon radical.
  • halocydoalkyl as used herein, which is also expressed as “cycloalkyl which is partially or fully halogenated”, refers to mono- or bi- or polycyclic saturated hydrocarbon groups having 3 to 8 (“Cs-Cs-halocycloalkyl” ) or preferably 3 to 6 (“C3-C6- halocycloalkyl”) carbon ring members (as mentioned above) in which some or all of the hydrogen atoms are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • cycloalkyl-Ci-C4-alkyl refers to a Cs-Cs-cycloalkyl group ("Cs-Cs-cycloalkyl- Ci-C4-alkyl”), preferably a C3-C6-cycloalkyl group ("C3-C6-cycloalkyl-Ci-C4-alkyl”), more preferably a C3-C4-cycloalkyl group (“C3-C4-cycloalkyl-Ci-C4-alkyl”) as defined above (preferably a monocyclic cycloalkyl group) which is bound to the remainder of the mol- ecule via a Ci-C4-alkyl group, as defined above.
  • Examples for C3-C4-cycloalkyl-Ci-C4- alkyl are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutyl methyl, cy- clobutylethyl and cyclobutylpropyl,
  • Examples for C3-C6-cycloalkyl-Ci-C4-alkyl, apart those mentioned for C3-C4-cycloalkyl-Ci-C4-alkyl, are cyclopentylmethyl, cyclopen- tylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.
  • C3-C8-halocycloalkyl-Ci-C4-alkyl refers to a Cs-Cs-halocycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
  • Ci-C2-alkoxy is a Ci-C2-alkyl group, as defined above, attached via an oxygen atom.
  • Ci-C3-alkoxy is a Ci-C3-alkyl group, as defined above, attached via an oxygen atom.
  • Ci-C4-alkoxy is a Ci-C4-alkyl group, as defined above, attached via an oxygen atom.
  • Ci-C6-alkoxy is a Ci-C6-alkyl group, as defined above, attached via an oxygen atom.
  • Ci-Cio-alkoxy is a Ci-Cio-alkyl group, as defined above, attached via an oxygen atom.
  • Ci-C2-Alkoxy is methoxy or ethoxy.
  • Ci-C3-Alkoxy is additionally, for example, n-propoxy and 1 -methylethoxy (iso- propoxy).
  • Ci-C4-Alkoxy is additionally, for example, butoxy, 1 -methylpropoxy (sec- butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy).
  • Ci-C6-Alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethyl propoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1-methylpropoxy or 1 -ethyl-2- methylpropoxy.
  • Ci-Cs-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof.
  • Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof.
  • Ci-C2-haloalkoxy is a Ci-C2-haloalkyl group, as defined above, attached via an oxygen atom.
  • Ci-C3-haloalkoxy is a Ci-C3-haloalkyl group, as defined above, attached via an oxygen atom.
  • Ci-C4-haloalkoxy is a Ci-C4-haloalkyl group, as defined above, attached via an oxygen atom.
  • Ci-C6-haloalkoxy is a Ci-C6-haloalkyl group, as defined above, attached via an oxygen atom.
  • Ci- Cio-haloalkoxy is a Ci-Cio-haloalkyl group, as defined above, attached via an oxygen atom.
  • Ci-C 2 -Haloalkoxy is, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCC , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2- fluoroethoxy, 2,2,2-trichloroethoxy or OC 2 F 5 .
  • Ci-C3-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy,
  • Ci-C4-Haloalkoxy is additionally, for example, 4-fluorobutoxy, 4-chlorobutoxy, 4- bromobutoxy or nonafluorobutoxy.
  • Ci-C6-Haloalkoxy is additionally, for example, 5- fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms, as defined above, where one hydrogen atom is replaced by a Ci-C4-alkoxy group, as defined above.
  • Ci-C4-alkoxy group refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms, as defined above, where one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above.
  • Examples are methoxymethyl, ethoxyme- thyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, isobu- toxymethyl, tert-butoxymethyl, 1 -methoxyethyl, 1 -ethoxyethyl, 1 -propoxyethyl, 1 - isopropoxyethyl, 1 -n-butoxyethyl, 1 -sec-butoxyethyl, 1 -isobutoxyethyl, 1 -tert- butoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-n- butoxyethyl, 2-sec-butoxyethyl, 2-isobutoxyethyl, 2-tert-butoxyethyl, 1 -methoxypropyl, 1 -ethoxypropyl, 1 -propoxyprop
  • Ci-C6-alkoxy-methyl refers to methyl in which one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above. Examples are methox- ymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec- butoxymethyl, isobutoxymethyl, tert-butoxymethyl, pentyloxymethyl, hexyloxymethyl and the like.
  • Ci-C4-Haloalkoxy-Ci-C4-alkyl is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms, wherein one of the hydrogen atoms is replaced by a Ci-C4-alkoxy group and wherein at least one, e.g. 1 , 2, 3, 4 or all of the remaining hydrogen atoms (either in the alkoxy moiety or in the alkyl moiety or in both) are replaced by halogen atoms.
  • Examples are difluoro- methoxymethyl (CHF2OCH2), trifluoromethoxymethyl, 1 -difluoromethoxyethyl , 1 - trifluoromethoxyethyl, 2-difluoromethoxyethyl, 2-trifluoromethoxyethyl, difluoro- methoxy-methyl (CH3OCF2), 1 ,1 -difluoro-2-methoxyethyl, 2,2-difluoro-2-methoxyethyl and the like.
  • Ci-C2-alkylthio is a Ci-C2-alkyl group, as defined above, attached via a sulfur atom.
  • Ci-C3-alkylthio is a Ci-C3-alkyl group, as defined above, attached via a sulfur atom.
  • Ci-C4-alkylthio is a Ci-C4-alkyl group, as defined above, attached via a sulfur atom.
  • Ci-C6-alkylthio is a Ci-C6-alkyl group, as defined above, attached via a sulfur atom.
  • Ci-Cio-alkylthio is a Ci-Cio-alkyl group, as defined above, attached via a sulfur atom.
  • Ci-C2-Alkylthio is methylthio or ethylthio.
  • Ci-C3-Alkylthio is additionally, for example, n-propylthio or 1 -methylethylthio (iso- propylthio).
  • Ci-C4-Alkylthio is additionally, for example, butylthio, 1 -methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert-butylthio).
  • Ci-C6-Alkylthio is additionally, for example, pentylthio, 1 -methylbutylthio,
  • Ci-Cs- Alkylthio is additionally, for example, heptylthio, octylthio, 2-ethylhexylthio and positional isomers thereof.
  • Ci-Cio-Alkylthio is additionally, for example, nonylthio, decylthio and positional isomers thereof.
  • Ci-C2-haloalkylthio is a Ci-C2-haloalkyl group, as defined above, attached via a sulfur atom.
  • Ci-C3-haloalkylthio is a Ci-C3-haloalkyl group, as defined above, attached via a sulfur atom.
  • Ci-C4-haloalkylthio is a Ci-C4-haloalkyl group, as defined above, attached via a sulfur atom.
  • Ci-C6-haloalkylthio is a Ci-C6-haloalkyl group, as defined above, attached via a sulfur atom.
  • Ci-C 2 -Haloalkylthio is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfur atom.
  • Ci-C 2 -Haloalkylthio is, for example, SCH 2 F, SCHF 2 , SCF 3 , SCH 2 CI, SCHC , SCCI 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2- fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-t
  • C1-C3- Haloalkylthio is additionally, for example, 2-fluoropropylthio, 3-fluoropropylthio, 2,2- difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3- dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio,
  • Ci-C4-Haloalkylthio is additionally, for example, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or nonafluorobutylthio.
  • Ci-C6-Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6- chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio.
  • C 1 -C2-a I ky Is u If i nyl is a Ci-C2-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C4-alkylsulfinyl is a Ci-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C6-alkylsulfinyl is a C1-C6- alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • C1-C10- alkylsulfinyl is a Ci-Cio-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C2-Alkylsulfinyl is methylsulfinyl or ethylsulfinyl.
  • nyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butyl- sulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfi- nyl) or 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl).
  • Ci-C6-Alkylsulfinyl is additionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3- methylbutylsulfinyl, 1 ,1 -dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl,
  • Ci-Ce-Alkylsulfinyl is additionally, for example, heptylsulfinyl, octylsulfinyl, 2- ethylhexylsulfinyl and positional isomers thereof.
  • Ci-Cio-Alkylsulfinyl is additionally, for example, nonylsulfinyl, decylsulfinyl and positional isomers thereof.
  • the term "Ci-C2-haloalkylsulfinyl” is a Ci-C2-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • the term "Ci-C4-haloalkylsulfinyl” is a Ci-C4-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • C1-C6- haloalkylsulfinyl is a Ci-C6-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-Cio-haloalkylsulfinyl is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C2-Haloalkylsulfinyl is, for example, S(0)CH 2 F, S(0)CHF 2 , S(0)CF 3 , S(0)CH 2 CI, S(0)CHCI 2 , S(0)CCI 3 , chlorofluorome- thylsulfinyl, dichlorofluoromethylsulfinyl, chlorodifluoromethylsulfinyl, 2- fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2- difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro- 2,2-difluoroethylsulfinyl, 2,2-dichloro-2-
  • Ci-C4-Haloalkylsulfinyl is additionally, for example, 2-fluoropropylsulfinyl, 3- fluoropropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl,
  • C1-C6- Haloalkylsulfinyl is additionally, for example, 5-fluoropentylsulfinyl, 5- chloropentylsulfinyl, 5-brompentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfi- nyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl.
  • Ci-C2-alkylsulfonyl is a Ci-C2-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C3-alkylsulfonyl is a Ci-C3-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C4-alkylsulfonyl is a C1-C4- alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • C1-C6- alkylsulfonyl is a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-Cio-alkylsulfonyl is a Ci-Cio-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C2-Alkylsulfonyl is methylsulfonyl or ethyl- sulfonyl.
  • Ci-C3-Alkylsulfonyl is additionally, for example, n-propylsulfonyl or 1 - methylethylsulfonyl (isopropylsulfonyl).
  • Ci-C4-Alkylsulfonyl is additionally, for example, butylsulfonyl, 1 -methylpropylsulfonyl (sec-butylsulfonyl), 2-methylpropylsulfonyl (isobu- tylsulfonyl) or 1 ,1 -dimethylethylsulfonyl (tert-butylsulfonyl).
  • Ci-C6-Alkylsulfonyl is addi- tionally, for example, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 1 ,1 -dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl,
  • d-Cs-Alkylsulfonyl is additionally, for example, heptylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl and positional isomers thereof.
  • Ci-Cio-Alkylsulfonyl is additionally, for example, nonylsulfonyl, decylsulfonyl and positional isomers thereof.
  • Ci-C2-haloalkylsulfonyl is a Ci-C2-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C3-haloalkylsulfonyl is a C1-C3- haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci- C4-haloalkylsulfonyl is a Ci-C4-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C6-haloalkylsulfonyl is a Ci-C6-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • C1-C10- haloalkylsulfonyl is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfonyl [S(0) 2 ] group.
  • Ci-C 2 -Haloalkylsulfonyl is, for example, S(0) 2 CH 2 F, S(0) 2 CHF 2 , S(0) 2 CF 3 , S(0) 2 CH 2 CI, S(0) 2 CHCI 2 , S(0) 2 CCI 3 , chlorofluoromethylsulfonyl, dichloro- fluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2- chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2- difluoroethylsulfonyl, 2,2-d
  • C1-C4- Haloalkylsulfonyl is additionally, for example, 4-fluorobutylsulfonyl, 4- chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl.
  • C1-C6- Haloalkylsulfonyl is additionally, for example, 5-fluoropentylsulfonyl, 5- chloropentylsulfonyl, 5-brompentylsulfonyl, 5-iodopentylsulfonyl, undecafluoropen- tylsulfonyl, 6-fluorohexylsulfonyl, 6-chlorohexylsulfonyl, 6-bromohexylsulfonyl, 6- iodohexylsulfonyl or dodecafluorohexylsulfonyl.
  • Examples are acetyl (methylcarbonyl), propionyl (ethylcarbonyl), propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl and the like.
  • Ci-C6-haloalkylcarbonyl a Ci-C6-haloalkylcarbonyl
  • Ci-C4-haloalkylcarbonyl Ci-C4-haloalkylcarbonyl
  • Examples are trifluoromethylcarbonyl, 2,2,2- trifluoroethylcarbonyl and the like.
  • Examples are methoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, iso- propoxycarbonyl, n-butoxycarbonyl and the like.
  • Ci-C6-haloalkoxycarbonyl a Ci-C6-haloalkoxycarbonyl
  • Ci-C4-haloalkoxycarbonyl Ci-C4-haloalkoxycarbonyl
  • Examples are trifluoromethoxycarbonyl, 2,2,2- trifluoroethoxycarbonyl and the like.
  • Ci-C6-alkylamino is a group -N(H)Ci-C6-alkyl. Examples are methylamino, ethylamino, propylamino, isopropylamino, butylamino and the like.
  • di-(Ci-C6-alkyl)amino is a group -N(Ci-C6-alkyl)2. Examples are dimethyla- mino, diethylamino, ethylmethylamino, dipropylamino, diisopropylamino, methylpropyl- amino, methylisopropylamino, ethylpropylamino, ethylisopropylamino, dibutylamino and the like.
  • the term "3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or het- eroatom groups selected from N, O, S, NO, SO and SO2, as ring members” denotes a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heteromonocyclic ring or a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members.
  • Unsaturated rings contain at least one C-C and/or C-N and/or N-N double bond(s). Maximally unsaturated rings contain as many conjugated C-C and/or C-N and/or N-N double bonds as allowed by the ring size. Maximally unsaturated 5- or 6-membered heterocyclic rings are aromatic.
  • the heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
  • Unsaturated rings contain at least one C-C and/or C-N and/or N-N double bond(s). Maximum unsaturated rings contain as many conjugated C-C and/or C-N and/or N-N double bonds as allowed by the ring size. Maximum unsaturated 5- or 6-membered heterocyclic rings are aromatic. 7- and 8-membered rings cannot be aromatic. They are homoaromatic (7-membered ring, 3 double bonds) or have 4 double bonds (8-membered ring).
  • the heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
  • Examples of a 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic ring include: Oxira- nyl, thiiranyl, aziridinyl, oxetanyl, thietanyl, azetidinyl, tetrahydrofuran-2-yl, tetrahydrofu- ran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-1 -yl, pyrrolidin-2-yl, pyrrol- idin-3-yl, pyrazolidin-1 -yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazoli- din-1 -yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl,
  • Examples of a 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic ring include: 2,3-d ihyd rofur-2-yl , 2,3-dihydrofur-3-yl, 2,4-d ihyd rofur-2-yl , 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl,
  • Examples for a 3-, 4-, 5-, 6- or 7-membered maximally unsaturated (including aromatic) heterocyclic ring are 5- or 6-membered heteroaromatic rings, such as 2-furyl, 3-furyl, 2- thienyl, 3-thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl,
  • Examples for a 8-, 9- or 10-membered saturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
  • Examples for a 8-, 9- or 10-membered partially unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
  • Examples for a 8-, 9- or 10-membered maximally unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
  • # denotes the attachment point to the remainder of the molecule.
  • the attachment point is not restricted to the ring on which is shown, but can be on either of the fused rings, and may be on a carbon or on a nitrogen ring atom. If the rings carry one or more substituents, these may be bound to carbon and/or to nitrogen ring atoms (if the latter are not part of a double bond).
  • Examples are, in addition to the saturated heteromonocy-rod rings mentioned above, carbocyclic rings, such as cyclopropyl, cyclopropanonyl, cyclobutyl, cyclobutanonyl, cyclopentyl, cyclopentanonyl, cyclohexyl, cyclohexanonyl, cyclohexadienonyl, cycloheptyl, cycloheptanonyl, cyclooctyl, cyclooctanonyl, furan-2- onyl, pyrrolidine-2-onyl, pyrrolidine-2,5-dionyl, piperidine-2-only, piperidine-2,6-dionyl and the like.
  • carbocyclic rings such as cyclopropyl, cyclopropanonyl, cyclobutyl, cyclobutanonyl, cyclopentyl, cyclopentanonyl
  • A is A 1 .
  • R 9 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8- cycloalkyl-Ci-C4-alkyl-, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6- haloalkynyl, and more preferably from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl and C3-C8-cycloalkyl-Ci-C4-alkyk
  • R 10a and R 10b are selected from the group consisting of hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
  • R 10a and R 10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl
  • R 10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl
  • R 14a , R 14b and R 16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • R 14a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl
  • R 14b is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl-, Ci-C6-alkyl substituted with a CN group, Ci-C6-alkoxyl, Ci-C6-haloalkoxy, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkyl
  • R 10a and R 10b are selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
  • R 10a and R 10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocy- die ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-al
  • R 10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl
  • R 14a , R 14b and R 16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • R 14a is preferably selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and R 14b is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkenyl, Ci-C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C4- alkyl-, Ci-C6-alkyl substituted with a CN group, phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R 16 , which are each independently preferably selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-
  • k 0, 1 , 2 or 3
  • n 0, 1 or 2
  • n 0, 1 or 2;
  • R 14a is selected from hydrogen and methyl
  • R 14b is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-methyl-, Ci- C6-alkyl substituted with a CN group, phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R 16 selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl,
  • each R 16 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
  • each R 16 is independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • R 14a is selected from hydrogen and methyl, and is specifically hydrogen
  • R 14b is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl and C3-C6-cycloalkyl- methyl-.
  • R 10a and R 10b are preferably selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl and C3-C6- halocycloalkylaminocarbonyl,
  • heterocyclic ring which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particu- lar 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio.
  • R 10a and R 10b are in this case selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C4-alkylaminocarbonyl and Ci-C4-haloalkylaminocarbonyl.
  • A is A 2 .
  • W is preferably O.
  • Y is preferably N(R 5 )R 6 ; wherein R 5 and R 6 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • R 5 and R 6 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • in A 2 Y is hydrogen.
  • R 9 has one of the above general meanings, or, in particular, is selected from hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl and Ci-C6-alkyl substituted by one radical R 13 , where R 13 has one of the above general meanings, or, in particular, one of the below preferred meanings.
  • W is O and Y is N(R 5 )R 6 ; wherein R 5 and R 6 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • W is O and Y H.
  • W is O and Y is -OR 9 , where R 9 has one of the above general meanings, or, in particular, is selected from hydrogen, C1-C6- alkyl, Ci-C6-haloalkyl and Ci-C6-alkyl substituted by one radical R 13 , where R 13 has one of the above general meanings, or, in particular, one of the below preferred meanings.
  • R 5 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl and C3-C8- halocycloalkyl, where the aforementioned aliphatic and cycloaliphatic radicals may be substituted by 1 , 2 or 3, preferably 1 , radicals R 8 ; and
  • R 6 is preferably selected from hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-C10- alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloali- phatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 8 ,
  • phenyl which may be substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, in particular 1 , substituents R 1 1 , and
  • C S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , and phen
  • R 8 , R 9 , R 10a , R 10b and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • N(R 5 )R 6 as a radical Y More preferably, in N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and -Chb-CN;
  • R 6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C10- haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the four last-mentioned aliphatic and cycloaliphatic radicals may carry 1 , 2 or 3 radicals
  • R 8 d-Ce-alkoxy, Ci-C 6 -haloalkoxy, N(R 10a )R 10b , phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R 11 , and a 3-,
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated heterocyclic ring, where the ring may further contain
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a group where R 9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl. Even more preferably, in N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and CH2-CN;
  • R 6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R 8 , C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
  • Ci-Ce-alkoxy Ci-C 6 -haloalkoxy, N(R 0a )R 0b ,
  • phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R 11 , and a 3-, 4- , 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups in- dependently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R 1 1 ; wherein R 8 and R 1 1 are as defined in claim 1 ;
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a group where R 9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
  • N(R 5 )R 6 as a radical Y is particularly preferably, in N(R 5 )R 6 as a radical Y,
  • R 5 selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and CH2-CN ;
  • R 6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R 8 , C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
  • R 10a is selected from hydrogen and Ci-C6-alkyl and R 10b is selected from a 5- or 6-membered het- eroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N , O and S as ring members, where the heteroaromatic ring may be substituted with one or more substituents R 16 ;
  • phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R 1 1 , and a 3-, 4- , 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R 1 1 ; wherein
  • R 10a is selected from the group consisting of hydrogen and Ci-C6-alkyl
  • R 10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C4- alkynyl, CH 2 -CN, Ci-C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and
  • each R 16 as a substituent on phenyl or the heterocyclic rings is independently selected from the group consisting of halogen, cyano, ni- tro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a group where R 9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
  • N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-;
  • R 8 and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
  • the 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring R 6 containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members is selected from rings D-1 to D-173 listed below in context with A 4 .
  • the ring may be sub- stituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 .
  • N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-;
  • heteromonocyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 ;
  • R 8 and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
  • N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen and Ci-C6-alkyl
  • R 6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R 8 , C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN, methyl and oxo,
  • R 8 and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a 5- or
  • the 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members is selected from rings D-1 to D-173 listed below in context with A 4 , and more preferably from rings F-1 to F-51 listed below.
  • the ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 .
  • N(R 5 )R 6 as a radical Y,
  • R 5 is selected from hydrogen and methyl, preferably hydrogen
  • R 6 is selected from Ci-C4-alkyl which carries one radical R 8 , preferably methyl which carries one radical R 8 , Ci-C4-haloalkyl, and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 het- eroatom or heteroatom group selected from S, SO and SO2, as ring member, where the heteromonocyclic ring may be substituted with one or more substitu- ents R 11 ;
  • R 8 and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring (i.e. R 5 and R 6 form together -(Chb or - (CH2)5-), wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substitu- ents independently selected from the group consisting of halogen, cyano, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • the ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substitu- ents R 11 .
  • R 9 , R 10a , R 10b and R 16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • N(R 5 )R 6 as a radical Y More preferably, in N(R 5 )R 6 as a radical Y,
  • R 9 , R 10a , R 10b and R 16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • R 10a and R 10b are preferably selected, independently of each other, from hydrogen, Ci- C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-
  • heterocyclic ring which additionally may contain 1 or 2 further heteroatoms or heteroatom groups select- ed from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio.
  • R 10a and R 10b are in this case selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C4-alkylaminocarbonyl and Ci-C4-haloalkylaminocarbonyl. Specifically, they are selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl and C3- C6-cycloalkyl. Very specifically, one of R 10a and R 10b is hydrogen and the other is C1-C4- alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl.
  • R 5 is hydrogen
  • R 6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R 8 , Cs-Ce-cycloalkyl,
  • phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R 11 , and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 heteroatom or heteroatom group selected from N, O, S, SO and SO2, as ring member or a 5- or 6- membered heteromonocyclic aromatic ring containing 1 , 2 or 3 heteroatoms selected from O, N and S as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R 11 , where the heteromonocyclic ring is preferably selected from rings of formulae F-1 to F-51 :
  • k 0, 1 , 2 or 3,
  • n 0, 1 or 2
  • R 10a is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C3- alkynyl, -CH2-CIM and Ci-C6-alkoxy-methyl;
  • R 10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, C3-C6-cycloalkyl, C3-C6-cyclohaloalkyl, phenyl which is op- tionally substituted with 1 , 2, 3, 4 or 5 substituents selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings
  • each R 16 as a substituent on phenyl or a heterocyclic ring E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
  • F-44 preference is given to F-44, F-48 and F-49.
  • W is O and Y is N(R 5 )R 6 , wherein
  • R 5 is selected from hydrogen and methyl, preferably hydrogen
  • R 6 is selected from Ci-C4-alkyl which carries one radical R 8 , preferably methyl which carries one radical R 8 ; Ci-C4-haloalkyl, and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 heteroatom or heteroatom group selected from S, SO and SO2, as ring member, where the heteromonocyclic ring may be substituted with one or more substituents R 11 ;
  • R 10a and R 10b are selected, independently of each other, from hydrogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 - alkynyl, C2-C 4 -haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C 4 -alkylcarbonyl, Ci-C 4 -haloalkylcarbonyl, Ci-C 4 -alkylaminocarbonyl, Ci-C 4 -haloalkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl and C3-C6-halocycloalkylaminocarbonyl, and preferably from hydrogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl and C3-C6-cyclo
  • each R 11 is independently selected from halogen, cyano, nitro, Ci-C 4 - alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C 4 -haloalkenyl, C2-C 4 -alkynyl and C2-C 4 -haloalkynyl; and each R 16 is independently selected from halogen, cyano, nitro, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, C3
  • R 5 and R 6 together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, C1-C4- alkyl, Ci-C 4 -haloalkyl, C2-C 4 -alkenyl, C2-C 4 -haloalkenyl, C2-C 4 -alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C 4 -alkoxy, C1-C4- haloalkoxy, Ci-C 4 -alkylthio and Ci-C 4 -haloalkylthio, and form hal
  • R 5 and R 6 form together -(CH2) 4 - or - (CH2)5-), wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • the 5- or 6-membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members is selected from rings E-1 to E-42 as defined above.
  • the ring may be substituted with one or more, preferably 1 , 2 or 3, in par- ticular 1 , substituents R 16 selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl.
  • A is A 3
  • R 7a and R 7b in the group A 3 are independently of each other selected from hydrogen, Ci-C4-alkyl and Ci-C4-haloalkyl, and more preferably one of R 7a and R 7b is hydrogen and the other is hydrogen or methyl. Specifically, both are hydrogen.
  • R 5 is preferably selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 8 ; and
  • R 6 is preferably selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 8 ,
  • heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 ;
  • R 5 is selected from hydrogen, Ci-C4-alkyl, which may be partially or fully halogenat- ed and/or may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 8 selected from cyano and Ci-C6-alkoxy; and C2-C4-alkynyl; and
  • R 8 , R 9 , R 10a , R 10b and R 11 have one of the above general meanings, or, in particular, one of the below preferred meanings.
  • the group A 3 is selected from hydrogen, Ci-C4-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-, preferably from hydrogen and Ci-C4-alkyl; and
  • R 8 has one of the above general meanings, or, in particular, one of the below preferred meanings.
  • phenyl optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R 16 , and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroa- tom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 16 ,
  • R 9 , R 10a , R 10b , R 13 and R 16 have one of the above general meanings, or, in par- ticular, one of the below preferred meanings.
  • R 10a and R 10b together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio.
  • R 10a and R 10b in R 8 in the radicals R 5 and R 6 of the group A 3 are, inde- pendently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkyl substituted by one radical R 13 , C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and a 3- or 4-membered saturated heterocyclic ring comprising 1 heteroatom or heteroatom group selected from N, O, S, NO, SO and SO2, as ring member, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy; and are specifically, independently of each other, selected from hydrogen, Ci-C4-alkyl,
  • R 13 in R 8 in the radicals R 5 and R 6 of the group A 3 is preferably selected from CN, Ci- C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci- C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl.
  • R 16 in R 8 in the radicals R 5 and R 6 of the group A 3 is preferably selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • R 10a and R 10b are selected from hydrogen, Ci-C4-alkyl,
  • Ci-C4-haloalkyl and C3-C6-cycloalkyl are Ci-C4-haloalkyl and C3-C6-cycloalkyl
  • R 13 is selected from CN, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl and a heterocyclic ring selected from rings of formulae E-1 to
  • E-51 as defined above and preferably from Ci-C6-alkylthio, Ci-C6-haloalkylthio,
  • Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl are Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl.
  • each R 16 as a substituent on heterocyclic rings of formulae E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
  • A is A 4 .
  • a 4 is preferably selected from a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 , where R 11 has one of the above general meanings, or, in particular, one of the below preferred meanings.
  • a 4 is selected from a 3-, 4-, 5-, 6- or 7-membered saturated heteromonocyclic ring containing 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, a 5-, 6- or 7-membered partially unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, and a 5- or 6-membered aromatic heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring members, where the heteromonocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R 11 , where R 11 has one of the above general meanings, or, in particular, one of the below preferred meanings.
  • a 4 is even more preferably selected from rings of formulae D-1 to D-173
  • D-59 is in particular selected from D-59, D-65 and D-66 and is specifcally D-59.
  • each R 1 1 is independently selected from the group consisting of halogen, cyano, ni- tro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
  • radicals A 1 , A 2 , A 3 and A 4 preference is given to A 2 .
  • B 1 , B 2 and B 3 are CR 2 .
  • B 1 and B 3 are CR 2 , where R 2 is not hydrogen, and B 2 is CR 2 , where R 2 has one of the meanings given above.
  • R 2 is selected from hydrogen, halogen, cyano, azido, nitro, -SCN , SF 5 , Ci- C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , -OR 9 , -S(0) n R 9 and -N R 10a R 10b ,
  • R 8 , R 9 , R 10a and R 10b have one of the above general meanings, or, in particular, one of the below preferred meanings. More preferably, R 2 is selected from hydrogen, halogen and Ci-C2-haloalkyl, even more preferably from hydrogen, F, CI, Br and CF3, even more preferably from hydrogen, F, CI and CF3, and in particular from hydrogen and CI.
  • B 2 is CH and B 1 and B 3 have one of the general or one of the preferred meanings given above for R 2 (with the proviso that they are not hydrogen) and are preferably selected from halogen and Ci-C2-haloalkyl, even more preferably from F, CI, Br and CF3, particularly preferably from hydrogen, F, CI and CF3, and are in particular CI.
  • B 2 is CF or CCI and B 1 and B 3 have one of the general or one of the preferred meanings given above for R 2 (with the proviso that they are not hydrogen) and are preferably selected from halogen and Ci-C2-haloalkyl, such as F, CI and CF3, even more preferably from F and CI, and are in particular CI.
  • G 1 , G 3 and G 4 are CR 4 and G 2 is N or CR 4 , where R 4 has one of the meanings given above or below; or G 2 , G 3 and G 4 are CR 4 and G 1 is N or CR 4 , where R 4 has one of the meanings given above or below.
  • R 4 is selected from hydrogen, halogen, cyano, azido, nitro, Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , Cs-Cs-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , C2-C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 8 , -OR 9 , -S(0) n R 9 , and -NR 10a R 10b .
  • R 4 is selected from hydrogen, halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylsulfonyl, and even more preferably from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl,
  • G 1 , G 3 and G 4 are CH and G 2 is CR 4 , where R 4 has one of the above general or preferred meanings; or G 1 is N, G 3 and G 4 are CH and G 2 is CR 4 .
  • G 1 and G 4 are CR 4 and G 2 and G 3 are CH, where R 4 has one of the meanings given above or below.
  • G 1 , G 3 and G 4 are CH and G 2 is CR 4 , where R 4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, preferably from hydrogen, F, CI, CN, methyl, CF3, methoxy and methylthio, and specifically from hydrogen, F, CI, CN, methyl methoxy and methylthio.
  • G 1 is N
  • G 2 is CR 4 and G 3 and G 4 are CH
  • R 4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, preferably from hydrogen, F, CI, CN, methyl, CF3, methoxy and methylthio, and specifically from hydro- gen and methyl.
  • R 1 is Ci-C4-haloalkyl, specifically Ci- C2-haloalkyl and more specifically halomethyl, in particular fluoromethyl, such as fluo- romethyl, difluoromethyl and trifluoromethyl, and is very specifically trifluoromethyl.
  • R 3a and R 3b are selected, independently of each other, from hydrogen, halogen, hydroxyl, Ci-C3-alkyl, Ci-C3-alkenyl, Ci-C3-alkynyl, Ci-C3-haloalkyl, Ci-C3-alkoxy, Ci-C3-alkylthio and Ci-C3-alkylsulfonyl, more preferably from hydrogen and halogen, in particular from hydrogen and fluorine and are specifically hydrogen.
  • R 8 , R 9 , R 10a , R 10b , R 11 , R 12 , R 13 , R 14 , R 14a , R 14b , R 15 and R 16 have following preferred meanings:
  • R 8 is a substituent on a cycloalkyl group, it is even more preferably selected from the group consisting of halogen, Ci-C 4 -alkyl, Ci-C3-haloalkyl, Ci-C 4 -alkoxy and Ci-C3-haloalkoxy.
  • R 8 as a substituent on a cycloalkyl group is selected from halogen, Ci-C 4 -alkyl and Ci-C3-haloalkyl.
  • R 8 is preferably selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy-Ci- C6-alkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2- Ce-alkynyl, C 2 -C 6 -haloalkynyl, -OR 9 , -SR 9 , -N(R 10a )R 10b , phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R 16 , and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or
  • R 8 is more preferably selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs- Cs-halocycloalkyl, d-Ce-alkoxy, Ci-C 6 -haloalkoxy, -N(R 10a )R 10b , phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R 16 , and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R 16 ; where R 10a , R 10b and
  • each R 9 is independently selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Cs-Cs-cycloalkyl- Ci-C4-alkyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R 16 ; and a 3-, 4- , 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more, e.g.
  • each R 9 is independently selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R 16 ; and a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring may be substituted by one or more radicals R 16 ; where R 16 has one of the meanings given above or in particular one of the preferred meanings given below.
  • R 10a and R 10b are, independently of each other, preferably selected from hydrogen, Ci- C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6- cycloalkylaminocarbonyl, C3-C6-halocycloalkylaminocarbonyl, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or hetero
  • R 10a and R 10b together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S0 2 , as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C 2 - C4-alkenyl, C 2 -C4-haloalkenyl, C 2 -C4-alkynyl, C 2 -C4-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkyl
  • R 10a and R 10b are, independently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and a 3- or 4-membered saturated heterocyclic ring comprising 1 heteroatom or heteroatom group selected from N, O, S, NO, SO and S0 2 , as ring member, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; and are specifically, independently of each other, selected from hydrogen, Ci-C4-alkyl and Ci-C4-haloalkyl.
  • Each R 11 and each R 16 are independently of each occurrence and independently of each other preferably selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, C1-C4- haloalkylsulfinyl, Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl, and more preferably from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • Each R 12 is preferably selected from Ci-C4-alkyl and is in particular methyl.
  • R 13 is a substituent on an alkyl, alkenyl or alkynyl group, it is preferably selected from the group consisting of cyano, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, -OH, - SH, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • R 13 is a substituent on a cycloalkyl group, it is preferably selected from the group consisting of cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, -OH, -SH, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- haloalkylsulfonyl and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and
  • R 13 is a substituent on a cycloalkyl group, it is even more preferably selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C3-haloalkyl, Ci-C4-alkoxy and Ci-C3-haloalkoxy.
  • R 13 as a substituent on a cycloalkyl group is selected from halogen, Ci-C4-alkyl and Ci-C3-haloalkyl.
  • R 8 is preferably selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs- Cs-cycloalkyl, C3-Cs-halocycloalkyl, -OH, -SH, Ci-C6-alkoxy, Ci-C6-haloalkoxy and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • R 14 , R 14a and R 14b are, independently of each other, preferably selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and benzyl, where the phenyl ring in benzyl is optionally substituted 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • R 14a and R 14b together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy and Ci-C4-haloalkoxy.
  • R 14 , R 14a and R 14b are, independently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and benzyl, where the phenyl ring in benzyl is optionally substituted 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; or, R 14a and R 14b , together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents
  • Each R 15 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, phenyl, benzyl, pyridyl and phenoxy, wherein the four last-mentioned radicals may be unsubsti- tuted and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy.
  • compound I is a compound of formula IA
  • R 2 and R 4 have one of the above-given general or, in particular, one of the above-given preferred meanings
  • R 2a and R 2c independently of each other, have one of the general or, in particular, one of the preferred meanings given above for R 2 , with the proviso that they are not hydrogen, and are specifically CI or CF3 and are very specifically CI.
  • Examples of preferred compounds are compounds of the following formulae la.1 to la.31 , where the variables have one of the general or preferred meanings given above.
  • Examples of preferred compounds are the individual compounds compiled in the tables 1 to 2082 below, Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question. 70

Abstract

The present invention relates to isothiazoline compounds of formula (I) wherein the variables are as defined in the claims or the description, which are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes, and to a method for producing them. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.

Description

Isothiazoline compounds for combating invertebrate pests
The present invention relates to isothiazoline compounds which are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes, and to a method for producing them. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.
Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests, in particular insects, arachnids and nematodes.
Related insecticidal aryl azoline compounds are described in WO 201 1/092287, WO 201 1/073444, WO 2010/090344, WO 2009/1 12275 and WO 97/23212. However, these documents do not describe compounds having the characteristic substituents and substituents' arrangement as claimed in the present invention.
It is an object of the present invention to provide compounds that have a good pesticidal activity, in particular insecticidal activity, and show a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control arthropod pests and/or nematodes.
The object of the present invention was moreover to provide compounds which are less persistent, bioaccumulative and/or toxic than the compounds of the prior art. Especially isoxazoline insecticides show a high persistency in the soil and thus accumulate there. It has been found that these objectives can be achieved by isothiazoline compounds of the formula I below, by their steroisomers and by their salts, in particular their agriculturally or veterinarily acceptable salts.
Therefore, in a first aspect, the invention relates to isothiazoline compounds of formula I
Figure imgf000003_0001
wherein
A is a group A1, A2, A3 or A4;
wherein
A1 is selected from the group consisting of -C(=NR6)R8, -S(0)nR9 and
-N(R5)R6; A2 is a group of following formula:
Figure imgf000003_0002
wherein
# denotes the bond to the aromatic ring of formula (I);
W is selected from O and S;
Y is selected from hydrogen, -N(R5)R6 and -OR9; is a group of following formula:
Figure imgf000003_0003
wherein
# denotes the bond to the aromatic ring of formula (I); is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroa- toms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, or is a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2, 3 or 4 heteroa- toms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substitu- ents R11;
B1, B2 and B3 are each independently selected from the group consisting of N and CR2, with the proviso that at most two of B1, B2 and B3 are N;
G1, G2, G3 and G4 are each independently selected from the group consisting of N and CR4, with the proviso that at most two of G1, G2, G3 and G4 are N;
R1 is selected from the group consisting of Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl-, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl and -C(=0)OR15; each R2 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl, C3-C8-cycloalkyl, C2-C6-alkenyl, C2- C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR10aR10b,
phenyl which may be substituted by 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , radicals R11, and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromono- or heterobicyclic ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R11;
R3a, R3b are each independently selected from the group consisting of hydrogen, halogen, -C02R3d, hydroxyl, Ci-C3-alkyl, d-C3-haloalkyl, C2-C3-alkenyl, C2-C3- alkynyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-alkylthio, Ci-C3-haloalkylthio, Ci- C3-alkylsulfonyl and Ci-C3-haloalkylsulfonyl; or
R3a and R3b together form a group =0, =C(R3c)2, =NOH or =NOCH3; is independently selected from the group consisting of hydrogen, halogen, and CF3; is selected from the group consisting of hydrogen, Ci-C6-alkyl and C1-C3- alkyloxy-Ci-C3-alkyl-;
R4 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, Cs-Cs-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, C2- C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR10aR10b,
phenyl which may be substituted by 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , radicals R11, and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R11; each R5 is independently selected from the group consisting of hydrogen, C1-C10- alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last- mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8, and
-S(0)nR9, each R6 is independently selected from the group consisting of hydrogen, cyano, Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last- mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8,
-OR9, -NR10aR10b, -S(0)nR9, -C(=O)NR 0aN(R 0aR 0b), -Si(R12)3, -C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, in particular 1 , substituents R11, and
a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substit- uents R11; or R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroa- toms or heteroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5 substituents R11: or R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9;
R7a, R7b are each independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8; each R8 is independently selected from the group consisting of cyano, azido, nitro, - SCN, -SF5, C3-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, where the cycloaliphatic moieties in the two last-mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R13;
-Si(R12)3, -OR9, -OSO2R9, -S(0)nR9, -N(R 0a)R 0b, -C(=O)N(R 0a)R 0b,
-C(=S)N(R 0a)R 0b, -C(=0)OR9,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16, or
two R8 present on the same carbon atom of an alkyl, alkenyl, alkynyl or cycloalkyi group together form a group =0,
Figure imgf000007_0001
=S(0)mR15N(R 4a)R 4b, =NR 0a, =NOR9; or =NN(R 0a)R 0b;
or
two radicals R8, together with the carbon atoms of an alkyl, alkenyl, alkynyl or cycloalkyi group which they are bonded to, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring, where the heterocyclic ring comprises 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, and where the carbocyclic or heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16; and
R8 as a substituent on a cycloalkyi ring is additionally selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2- C6-alkynyl and C2-C6-haloalkynyl, where the aliphatic moieties in these six radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R13; and
R8 in the groups -C(=NR6)R8, -C(=0)R8 and =C(R8)2 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, where the aliphatic moieties in the six last-mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R13;
R9 is independently selected from the group consisting of hydrogen, cyano, Ci- Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl-, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cydoaliphatic moieties in the nine last-mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R 3,
-Ci-C6-alkyl-C(=0)OR15, -Ci-C6-alkyl-C(=0)N(R a)R ,
-Ci-C6-alkyl-C(=S)N(R 4a)R 4b, -Ci-C6-alkyl-C(=NR 4)N(R 4a)R 4 ,
-Si(R12)3, -S(0)nR15, -S(0)nN(R a)R , -N(R 0a)R 0 , -N=C(R13)2, -C(=0)R13, -C(=0)N(R 4a)R 4 , -C(=S)N(R 4a)R 4 , -C(=0)OR15,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16; and
R9 in the groups -S(0)nR9 and -OSO2R9 is additionally selected from the group consisting of Ci-C6-alkoxy and Ci-C6-haloalkoxy;
, R10b are selected independently from one another from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the eight last-mentioned radicals may be substituted by one or more radicals R13; Ci-C6-alkyl-C(=0)OR15, Ci-C6-alkyl- C(=0)N(R a)R , -Ci-C6-alkyl-C(=S)N(R a)R , -Ci-C6-alkyl- C(=NR )N(R a)R , d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6- haloalkylthio,
-S(0)nR15, -S(0)nN(R a)R , -C(=0)R13, -C(=0)OR15, -C(=0)N(R a)R , -C(=S)R13, -C(=S)SR15, -C(=S)N(R 4a)R 4 , -C(=NR 4)R13;
phenyl, optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R16; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16;
or
R10a and R10b form together with the nitrogen atom they are bonded to a 3-, 4- , 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 3-, 4-, 5-, 6,- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16; or R 0a and R10 together form a group =C(R13)2, =S(0)m(R15)2,
=S(0)mR15N(R 4a)R 4 , =NR14 or =NOR15; is independently selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be par- tially or fully halogenated and/or may be substituted with one or more, preferably
1 , 2 or 3, in particular 1 , radicals R8,
-OR9, -NR10aR10b, -S(0)nR9, -Si(R12)3;
phenyl, optionally substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, in particular 1 , substituents selected independently from R16; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated aromatic heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or het- eroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected independently from R16;
or two R11 present on the same ring carbon atom of an unsaturated or partially unsaturated heterocyclic ring may together form a group =0,
Figure imgf000009_0001
=S;
=S(0)m(R15)2; =S(0)mR15N(R 4a)R 4b, =NR14, =NOR15, or =NN(R 4a)R 4b;
or two R11 bound on adjacent ring atoms form together with the ring atoms to which they are bound a saturated 3-, 4-, 5-, 6-, 7-, 8- or 9-membered ring, where- in the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from
O, S, N, NR14, NO, SO and S02 and/or 1 or 2 groups selected from C=0, C=S and C=NR14 as ring members, and wherein the ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, d-Ce-alkylthio, Ci-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R16;
R12 is independently selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6- alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-haloalkoxy-Ci- C6-alkyl, and phenyl, optionally substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, preferably 1 or 2, in particular 1 , substituents R16;
R13 is independently selected from the group consisting of cyano, nitro, -OH, -SH, -SCN, -SF5, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo; phenyl, benzyl, phenoxy, where the phenyl moiety in the three last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, in particular 1 , substituents R16; and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by 1 , 2 or 3, preferably 1 or 2, in particular 1 , substituents R16;
or
two R13 present on the same carbon atom (of an alkyl, alkenyl, alkynyl or cycloal- kyl group) may together be =0, =CH(Ci-C4-alkyl), =C(Ci-C4-alkyl)Ci-C4-alkyl, =N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl);
and
R13 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last- mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , substituents selected from CN, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
and
R 3 in the groups =C(R13)2, -N=C(R13)2, -C(=0)R13, -C(=S)R13 and
-C(=NR14)R13 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last- mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from CN, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
R14 is independently selected from the group consisting of hydrogen, cyano, Ci C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C1-C6- alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from CN , Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4- cycloalkyl which may be substituted by 1 or 2, in particular 1 , substituents selected from halogen and cyano; and oxo;
Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4- cycloalkyl, C3-C4-cycloalkyl-Ci-C4-alkyl-, where the cycloalkyl moiety in the two last-mentioned radicals may be substituted by 1 or 2, in particular 1 , substituents selected from halogen and cyano; and oxo;
phenyl, benzyl, pyridyl, phenoxy, wherein the cyclic moieties in the four last- mentioned radicals may be unsubstituted and/or carry 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy,
Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl; and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 or 2 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16;
R14a and R14b, independently of each other, have one of the meanings given for R14; or
R14a and R14b, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substitutents selected from halogen, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
or
R14a and R14 or R14b and R14, together with the nitrogen atoms to which they are bound in the group -C(=N R14)N(R14a) R14b, form a 3-, 4-, 5-, 6- or 7-membered partially unsaturated or maximally unsaturated heterocyclic ring, wherein the het- erocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy; R15 is independently selected from the group consisting of hydrogen, cyano, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl and oxo; Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci- C4-alkylsulfonyl and oxo;
phenyl, benzyl, pyridyl and phenoxy, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3, preferably 1 or 2 in particular 1 , substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
R16 is independently selected from the group consisting of halogen, nitro, cyano, -OH, -SH, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl;
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
Cs-Cs-cycloalkyI which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2, in particular 1 , radicals selected from Ci-C4-alkyl, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3, in particular 1 , substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
or
two R16 present together on the same atom of an unsaturated or partially unsaturated ring may be =0, =S, =N(Ci-C6-alkyl), =NO(Ci-C6-alkyl), =CH(Ci-C4-alkyl) or =C(Ci-C4-alkyl)Ci-C4-alkyl;
or
two R16 on two adjacent carbon atoms form together with the carbon atoms they are bonded to a 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, and wherein the ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; each n is independently 0, 1 or 2; and
each m is independently 0 or 1 ; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.
The present invention also provides an agricultural composition comprising at least one compound of the formula I as defined herein and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
The present invention also provides a veterinary composition comprising at least one compound of the formula I as defined herein and/or a veterinarily acceptable salt thereof and at least one liquid or solid carrier. The present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or a salt thereof as defined herein.
The present invention also relates to plant propagation material, in particular seed, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof as defined herein.
The present invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of the formula I or a veterinarily acceptable salt thereof as defined herein. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal. The term "steroisomers" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers). Depending on the substitution pattern, the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. One center of chirality is the carbon ring atom of the isothiazoline ring carrying radical R1. The invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantio- mers or diastereomers of the compound I or its mixtures. Suitable compounds of the formula I also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
The term N-oxides relates to a form of compounds I in which at least one nitrogen atom is present in oxidized form (as NO).
The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammo- nium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyr- ate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochloride, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The term "invertebrate pest" as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. The plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. Said young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. The term "plants" comprises any types of plants including "non-cultivated plants" and in particular "cultivated plants".
The term "non-cultivated plants" refers to any wild type species or related species or related genera of a cultivated plant.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf.
http://www.bio.org/speeches/pubs/er/agri_products.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxyl- phenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made re- sistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and Lib- ertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ - endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhab- dus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood ex- pressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing Cry1 Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Her- culex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphino- thricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt- Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsan- to Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme). Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called " pathogenesis-related proteins" (PR proteins, see, e. g.
EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications men- tioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), toler- ance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany). The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group. The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term "alkyl" as used herein and in the alkyl moieties of alkoxy, alkylthio, alkylsulfi- nyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl and the like refers to saturated straight- chain or branched hydrocarbon radicals having 1 to 2 ("Ci-C2-alkyl"), 1 to 3 ("C1-C3- alkyl"),1 to 4 ("Ci-C4-alkyl"), 1 to 6 ("Ci-C6-alkyl"), 1 to 8 ("Ci-C8-alkyl") or 1 to 10 ("Ci- Cio-alkyl") carbon atoms. Ci-C2-Alkyl is methyl or ethyl. Ci-C3-Alkyl is additionally propyl and isopropyl. Ci-C4-Alkyl is additionally butyl, 1 -methylpropyl (sec-butyl), 2- methylpropyl (isobutyl) or 1 ,1 -dimethylethyl (tert-butyl). Ci-C6-Alkyl is additionally also, for example, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 - ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, or 1 - ethyl-2-methylpropyl. Ci-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2- ethylhexyl and positional isomers thereof. Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl and positional isomers thereof.
The term "haloalkyl" as used herein, which is also expressed as "alkyl which is partially or fully halogenated", refers to straight-chain or branched alkyl groups having 1 to 2 ("Ci-C2-haloalkyl"), 1 to 3 ("Ci-C3-haloalkyl"), 1 to 4 ("Ci-C4-haloalkyl"), 1 to 6 ("Ci-C6- haloalkyl"), 1 to 8 ("Ci-C8-haloalkyl") or 1 to 10 ("Ci-Cio-haloalkyl") carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluorome- thyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 - chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl. Ci-C3-haloalkyl is additionally, for example, 1 -fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1 ,1 -difluoropropyl, 2,2- difluoropropyl, 1 ,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoro- propyl, 1 ,1 ,1 -trifluoroprop-2-yl, 3-chloropropyl and the like. Examples for C1-C4- haloalkyl are, apart those mentioned for Ci-C3-haloalkyl, 4-chlorobutyl and the like.
"Halomethyl" is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like.
The term "alkenyl" as used herein refers to monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 3 ("C2-C3-alkenyl"), 2 to 4 ("C2-C4-alkenyl"), 2 to 6 ("C2-C6-alkenyl"), 2 to 8 ("C2-C8-alkenyl") or 2 to 10 ("C2-Cio-alkenyl") carbon atoms and a double bond in any position, for example C2-C3-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl or 1 -methylethenyl; C2-C4-alkenyl, such as ethenyl, 1 -propenyl,
2- propenyl, 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2- methyl-1 -propenyl, 1 -methyl-2-propenyl or 2-methyl-2-propenyl; C2-C6-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 - methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 - pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3- methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-
3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2- dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 - hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 - pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2- pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3- pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4- pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 - dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3- butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2, 3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3, 3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2- butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2- trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2-methyl-1 -propenyl, 1 -ethyl- 2-methyl-2-propenyl and the like, or C2-Cio-alkenyl, such as the radicals mentioned for C2-C6-alkenyl and additionally 1 -heptenyl, 2-heptenyl, 3-heptenyl, 1 -octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1 -nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1 -decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the positional isomers thereof. The term "haloalkenyl" as used herein, which is also expressed as "alkenyl which is partially or fully halogenated", refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C4-haloalkenyl"), 2 to 6 ("C2-C6-haloalkenyl"), 2 to 8 ("C2-C6-haloalkenyl") or 2 to 10 ("C2-Cio-haloalkenyl") carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
The term "alkynyl" as used herein refers to straight-chain or branched hydrocarbon groups having 2 to 3 ("C2-C3-alkynyl"), 2 to 4 ("C2-C4-alkynyl"), 2 to 6 ("C2-C6-alkynyl"), 2 to 8 ("C2-C8-alkynyl"), or 2 to 10 ("C2-Cio-alkynyl") carbon atoms and one or two triple bonds in any position, for example C2-C3-alkynyl, such as ethynyl, 1 -propynyl or 2- propynyl; C2-C4-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl and the like, C2-C6-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 -methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 3- methyl-1 -butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3- hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2-pentynyl, 1 -methyl-3-pentynyl, 1 -methyl-4- pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1 -pentynyl, 3-methyl-4- pentynyl, 4-methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl-2-butynyl, 1 ,1 - dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 - butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 -ethyl-1 -methyl-2- propynyl and the like; The term "haloalkynyl" as used herein, which is also expressed as "alkynyl which is partially or fully halogenated", refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C4-haloalkynyl"), 3 to 4 ("C3-C4-haloalkynyl"), 2 to 6 ("C2-C6-haloalkynyl"), 2 to 8 ("C2-C8-haloalkynyl") or 2 to 10 ("C2-Cio-haloalkynyl") carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
The term "cycloalkyl" as used herein refers to mono- or bi- or polycyclic saturated hydrocarbon radicals having 3 to 8 ("Cs-Cs-cycloalkyl"), in particular 3 to 6 carbon atoms ("C3-C6-cycloalkyl"). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.2.1 ]heptyl, bicyclo[3.1 .1]heptyl, bicyclo[2.2.2]octyl and bicy- clo[3.2.1 ]octyl. Preferably, the term cycloalkyl denotes a monocyclic saturated hydrocarbon radical.
The term "halocydoalkyl" as used herein, which is also expressed as "cycloalkyl which is partially or fully halogenated", refers to mono- or bi- or polycyclic saturated hydrocarbon groups having 3 to 8 ("Cs-Cs-halocycloalkyl" ) or preferably 3 to 6 ("C3-C6- halocycloalkyl") carbon ring members (as mentioned above) in which some or all of the hydrogen atoms are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
The term "cycloalkyl-Ci-C4-alkyl" refers to a Cs-Cs-cycloalkyl group ("Cs-Cs-cycloalkyl- Ci-C4-alkyl"), preferably a C3-C6-cycloalkyl group ("C3-C6-cycloalkyl-Ci-C4-alkyl"), more preferably a C3-C4-cycloalkyl group ("C3-C4-cycloalkyl-Ci-C4-alkyl") as defined above (preferably a monocyclic cycloalkyl group) which is bound to the remainder of the mol- ecule via a Ci-C4-alkyl group, as defined above. Examples for C3-C4-cycloalkyl-Ci-C4- alkyl are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutyl methyl, cy- clobutylethyl and cyclobutylpropyl, Examples for C3-C6-cycloalkyl-Ci-C4-alkyl, apart those mentioned for C3-C4-cycloalkyl-Ci-C4-alkyl, are cyclopentylmethyl, cyclopen- tylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl. Examples for C3-C8-cycloalkyl-Ci-C4-alkyl, apart those mentioned for C3-C6-cycloalkyl- Ci-C4-alkyl, are cycloheptylmethyl, cycloheptylethyl, cyclooctylmethyl and the like.
The term "C3-C8-halocycloalkyl-Ci-C4-alkyl" refers to a Cs-Cs-halocycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
The term "Ci-C2-alkoxy" is a Ci-C2-alkyl group, as defined above, attached via an oxygen atom. The term "Ci-C3-alkoxy" is a Ci-C3-alkyl group, as defined above, attached via an oxygen atom. The term "Ci-C4-alkoxy" is a Ci-C4-alkyl group, as defined above, attached via an oxygen atom. The term "Ci-C6-alkoxy" is a Ci-C6-alkyl group, as defined above, attached via an oxygen atom. The term "Ci-Cio-alkoxy" is a Ci-Cio-alkyl group, as defined above, attached via an oxygen atom. Ci-C2-Alkoxy is methoxy or ethoxy. Ci-C3-Alkoxy is additionally, for example, n-propoxy and 1 -methylethoxy (iso- propoxy). Ci-C4-Alkoxy is additionally, for example, butoxy, 1 -methylpropoxy (sec- butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy). Ci-C6-Alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethyl propoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1-methylpropoxy or 1 -ethyl-2- methylpropoxy. Ci-Cs-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof.
The term "Ci-C2-haloalkoxy" is a Ci-C2-haloalkyl group, as defined above, attached via an oxygen atom. The term "Ci-C3-haloalkoxy" is a Ci-C3-haloalkyl group, as defined above, attached via an oxygen atom. The term "Ci-C4-haloalkoxy" is a Ci-C4-haloalkyl group, as defined above, attached via an oxygen atom. The term "Ci-C6-haloalkoxy" is a Ci-C6-haloalkyl group, as defined above, attached via an oxygen atom. The term "Ci- Cio-haloalkoxy" is a Ci-Cio-haloalkyl group, as defined above, attached via an oxygen atom. Ci-C2-Haloalkoxy is, for example, OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCC , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2- fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. Ci-C3-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy,
3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-
C2F5, 1 -(CH2F)-2-fluoroethoxy, 1 -(CH2CI)-2-chloroethoxy or 1 -(CH2Br)-2-bromoethoxy. Ci-C4-Haloalkoxy is additionally, for example, 4-fluorobutoxy, 4-chlorobutoxy, 4- bromobutoxy or nonafluorobutoxy. Ci-C6-Haloalkoxy is additionally, for example, 5- fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.
The term "Ci-C4-alkoxy-Ci-C4-alkyl" as used herein, refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms, as defined above, where one hydrogen atom is replaced by a Ci-C4-alkoxy group, as defined above. The term "C1-C6- alkoxy-Ci-C6-alkyl" as used herein, refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms, as defined above, where one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above. Examples are methoxymethyl, ethoxyme- thyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, isobu- toxymethyl, tert-butoxymethyl, 1 -methoxyethyl, 1 -ethoxyethyl, 1 -propoxyethyl, 1 - isopropoxyethyl, 1 -n-butoxyethyl, 1 -sec-butoxyethyl, 1 -isobutoxyethyl, 1 -tert- butoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-n- butoxyethyl, 2-sec-butoxyethyl, 2-isobutoxyethyl, 2-tert-butoxyethyl, 1 -methoxypropyl, 1 -ethoxypropyl, 1 -propoxypropyl, 1 -isopropoxypropyl, 1 -n-butoxypropyl, 1 -sec- butoxypropyl, 1 -isobutoxypropyl, 1 -tert-butoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-propoxypropyl, 2-isopropoxypropyl, 2-n-butoxypropyl, 2-sec-butoxypropyl, 2- isobutoxypropyl, 2-tert-butoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3- propoxypropyl, 3-isopropoxypropyl, 3-n-butoxypropyl, 3-sec-butoxypropyl, 3- isobutoxypropyl, 3-tert-butoxypropyl and the like.
The term "Ci-C6-alkoxy-methyl" as used herein, refers to methyl in which one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above. Examples are methox- ymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec- butoxymethyl, isobutoxymethyl, tert-butoxymethyl, pentyloxymethyl, hexyloxymethyl and the like.
Ci-C6-Haloalkoxy-Ci-C6-alkyl is a straight-chain or branched alkyl group having from 1 to 6, especially 1 to 4 carbon atoms (=Ci-C6-haloalkoxy-Ci-C4-alkyl), wherein one of the hydrogen atoms is replaced by a Ci-C6-alkoxy group and wherein at least one, e.g. 1 , 2, 3, 4 or all of the remaining hydrogen atoms (either in the alkoxy moiety or in the alkyl moiety or in both) are replaced by halogen atoms. Ci-C4-Haloalkoxy-Ci-C4-alkyl is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms, wherein one of the hydrogen atoms is replaced by a Ci-C4-alkoxy group and wherein at least one, e.g. 1 , 2, 3, 4 or all of the remaining hydrogen atoms (either in the alkoxy moiety or in the alkyl moiety or in both) are replaced by halogen atoms. Examples are difluoro- methoxymethyl (CHF2OCH2), trifluoromethoxymethyl, 1 -difluoromethoxyethyl , 1 - trifluoromethoxyethyl, 2-difluoromethoxyethyl, 2-trifluoromethoxyethyl, difluoro- methoxy-methyl (CH3OCF2), 1 ,1 -difluoro-2-methoxyethyl, 2,2-difluoro-2-methoxyethyl and the like.
The term "Ci-C2-alkylthio" is a Ci-C2-alkyl group, as defined above, attached via a sulfur atom. The term "Ci-C3-alkylthio" is a Ci-C3-alkyl group, as defined above, attached via a sulfur atom. The term "Ci-C4-alkylthio" is a Ci-C4-alkyl group, as defined above, attached via a sulfur atom. The term "Ci-C6-alkylthio" is a Ci-C6-alkyl group, as defined above, attached via a sulfur atom. The term "Ci-Cio-alkylthio" is a Ci-Cio-alkyl group, as defined above, attached via a sulfur atom. Ci-C2-Alkylthio is methylthio or ethylthio. Ci-C3-Alkylthio is additionally, for example, n-propylthio or 1 -methylethylthio (iso- propylthio). Ci-C4-Alkylthio is additionally, for example, butylthio, 1 -methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert-butylthio). Ci-C6-Alkylthio is additionally, for example, pentylthio, 1 -methylbutylthio,
2-methylbutylthio, 3-methylbutylthio, 1 ,1 -dimethylpropylthio, 1 ,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1 -ethylpropylthio, hexylthio, 1 -methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2- dimethylbutylthio, 1 ,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2- trimethylpropylthio, 1 -ethyl-1 -methylpropylthio or 1-ethyl-2-methylpropylthio. Ci-Cs- Alkylthio is additionally, for example, heptylthio, octylthio, 2-ethylhexylthio and positional isomers thereof. Ci-Cio-Alkylthio is additionally, for example, nonylthio, decylthio and positional isomers thereof.
The term "Ci-C2-haloalkylthio" is a Ci-C2-haloalkyl group, as defined above, attached via a sulfur atom. The term "Ci-C3-haloalkylthio" is a Ci-C3-haloalkyl group, as defined above, attached via a sulfur atom. The term "Ci-C4-haloalkylthio" is a Ci-C4-haloalkyl group, as defined above, attached via a sulfur atom. The term "Ci-C6-haloalkylthio" is a Ci-C6-haloalkyl group, as defined above, attached via a sulfur atom. The term "C1-C10- haloalkylthio" is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfur atom. Ci-C2-Haloalkylthio is, for example, SCH2F, SCHF2, SCF3, SCH2CI, SCHC , SCCI3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2- fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio or SC2F5. C1-C3- Haloalkylthio is additionally, for example, 2-fluoropropylthio, 3-fluoropropylthio, 2,2- difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3- dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio,
3,3,3-trichloropropylthio, SCH2-C2F5, SCF2-C2F5, 1-(CH2F)-2-fluoroethylthio, 1 -(CH2CI)- 2-chloroethylthio or 1 -(CH2Br)-2-bromoethylthio. Ci-C4-Haloalkylthio is additionally, for example, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or nonafluorobutylthio. Ci-C6-Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6- chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio.
The term "C 1 -C2-a I ky Is u If i nyl" is a Ci-C2-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C4-alkylsulfinyl" is a Ci-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C6-alkylsulfinyl" is a C1-C6- alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "C1-C10- alkylsulfinyl" is a Ci-Cio-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Ci-C2-Alkylsulfinyl is methylsulfinyl or ethylsulfinyl. C 1 -C4- Al ky I s u If i nyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butyl- sulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfi- nyl) or 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl). Ci-C6-Alkylsulfinyl is additionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3- methylbutylsulfinyl, 1 ,1 -dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl,
2,2-dimethylpropylsulfinyl, 1 -ethylpropylsulfinyl, hexylsulfinyl, 1 -methylpentylsulfinyl, 2- methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1 - dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2- dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl,
1 -ethylbutylsulf inyl , 2-ethylbutylsulfinyl, 1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2- trimethylpropylsulfinyl, 1 -ethyl-1 -methylpropylsulfinyl or 1 -ethyl-2-methylpropylsulfinyl. Ci-Ce-Alkylsulfinyl is additionally, for example, heptylsulfinyl, octylsulfinyl, 2- ethylhexylsulfinyl and positional isomers thereof. Ci-Cio-Alkylsulfinyl is additionally, for example, nonylsulfinyl, decylsulfinyl and positional isomers thereof. The term "Ci-C2-haloalkylsulfinyl" is a Ci-C2-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C4-haloalkylsulfinyl" is a Ci-C4-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "C1-C6- haloalkylsulfinyl" is a Ci-C6-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-Cio-haloalkylsulfinyl" is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group. Ci-C2-Haloalkylsulfinyl is, for example, S(0)CH2F, S(0)CHF2, S(0)CF3, S(0)CH2CI, S(0)CHCI2, S(0)CCI3, chlorofluorome- thylsulfinyl, dichlorofluoromethylsulfinyl, chlorodifluoromethylsulfinyl, 2- fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2- difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro- 2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl or S(0)C2F5. Ci-C4-Haloalkylsulfinyl is additionally, for example, 2-fluoropropylsulfinyl, 3- fluoropropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl,
2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2,3-dichloropropylsulfinyl, 2- bromopropylsulfinyl, 3-bromopropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3- trichloropropylsulfinyl, S(0)CH2-C2F5, S(0)CF2-C2F5, 1 -(CH2F)-2-fluoroethylsulfinyl, 1 - (CH2CI)-2-chloroethylsulfinyl, 1 -(CH2Br)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4- chlorobutylsulfinyl, 4-bromobutylsulfinyl or nonafluorobutylsulfinyl. C1-C6- Haloalkylsulfinyl is additionally, for example, 5-fluoropentylsulfinyl, 5- chloropentylsulfinyl, 5-brompentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfi- nyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl.
The term "Ci-C2-alkylsulfonyl" is a Ci-C2-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C3-alkylsulfonyl" is a Ci-C3-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C4-alkylsulfonyl" is a C1-C4- alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "C1-C6- alkylsulfonyl" is a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-Cio-alkylsulfonyl" is a Ci-Cio-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Ci-C2-Alkylsulfonyl is methylsulfonyl or ethyl- sulfonyl. Ci-C3-Alkylsulfonyl is additionally, for example, n-propylsulfonyl or 1 - methylethylsulfonyl (isopropylsulfonyl). Ci-C4-Alkylsulfonyl is additionally, for example, butylsulfonyl, 1 -methylpropylsulfonyl (sec-butylsulfonyl), 2-methylpropylsulfonyl (isobu- tylsulfonyl) or 1 ,1 -dimethylethylsulfonyl (tert-butylsulfonyl). Ci-C6-Alkylsulfonyl is addi- tionally, for example, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 1 ,1 -dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl,
2,2-dimethylpropylsulfonyl, 1 -ethylpropylsulfonyl, hexylsulfonyl, 1 -methylpentylsulfonyl,
2- methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 ,1 - dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2- dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl,
1 - ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2-trimethylpropylsulfonyl, 1 ,2,2- trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl or 1 -ethyl-2- methylpropylsulfonyl. d-Cs-Alkylsulfonyl is additionally, for example, heptylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl and positional isomers thereof. Ci-Cio-Alkylsulfonyl is additionally, for example, nonylsulfonyl, decylsulfonyl and positional isomers thereof.
The term "Ci-C2-haloalkylsulfonyl" is a Ci-C2-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C3-haloalkylsulfonyl" is a C1-C3- haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci- C4-haloalkylsulfonyl" is a Ci-C4-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C6-haloalkylsulfonyl" is a Ci-C6-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "C1-C10- haloalkylsulfonyl" is a Ci-Cio-haloalkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Ci-C2-Haloalkylsulfonyl is, for example, S(0)2CH2F, S(0)2CHF2, S(0)2CF3, S(0)2CH2CI, S(0)2CHCI2, S(0)2CCI3, chlorofluoromethylsulfonyl, dichloro- fluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2- chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2- difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl or S(0)2C2F5. Ci-C3-Haloalkylsulfonyl is additionally, for example, 2-fluoropropylsulfonyl,
3- fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl,
2- chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2- bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3- trichloropropylsulfonyl, S(0)2CH2-C2F5, S(0)2CF2-C2F5, 1 -(CH2F)-2-fluoroethylsulfonyl, 1 -(CH2CI)-2-chloroethylsulfonylor 1 -(CH2Br)-2-bromoethylsulfonyl. C1-C4- Haloalkylsulfonyl is additionally, for example, 4-fluorobutylsulfonyl, 4- chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl. C1-C6- Haloalkylsulfonyl is additionally, for example, 5-fluoropentylsulfonyl, 5- chloropentylsulfonyl, 5-brompentylsulfonyl, 5-iodopentylsulfonyl, undecafluoropen- tylsulfonyl, 6-fluorohexylsulfonyl, 6-chlorohexylsulfonyl, 6-bromohexylsulfonyl, 6- iodohexylsulfonyl or dodecafluorohexylsulfonyl.
The substituent "oxo" replaces a Chb group by a C(=0) group.
The term "alkylcarbonyl" is a Ci-C6-alkyl ("Ci-C6-alkylcarbonyl"), preferably a C1-C4- alkyl ("Ci-C4-alkylcarbonyl") group, as defined above, attached via a carbonyl [C(=0)] group. Examples are acetyl (methylcarbonyl), propionyl (ethylcarbonyl), propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl and the like.
The term "haloalkylcarbonyl" is a Ci-C6-haloalkyl ("Ci-C6-haloalkylcarbonyl"), preferably a Ci-C4-haloalkyl ("Ci-C4-haloalkylcarbonyl") group, as defined above, attached via a carbonyl [C(=0)] group. Examples are trifluoromethylcarbonyl, 2,2,2- trifluoroethylcarbonyl and the like.
The term "alkoxycarbonyl" is a Ci-C6-alkoxy ("Ci-C6-alkoxycarbonyl"), preferably a Ci- C4-alkoxy ("Ci-C4-alkoxycarbonyl") group, as defined above, attached via a carbonyl [C(=0)] group. Examples are methoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, iso- propoxycarbonyl, n-butoxycarbonyl and the like.
The term "haloalkoxycarbonyl" is a Ci-C6-haloalkoxy ("Ci-C6-haloalkoxycarbonyl"), preferably a Ci-C4-haloalkoxy ("Ci-C4-haloalkoxycarbonyl") group, as defined above, attached via a carbonyl [C(=0)] group. Examples are trifluoromethoxycarbonyl, 2,2,2- trifluoroethoxycarbonyl and the like.
The term "Ci-C6-alkylamino" is a group -N(H)Ci-C6-alkyl. Examples are methylamino, ethylamino, propylamino, isopropylamino, butylamino and the like.
The term "di-(Ci-C6-alkyl)amino" is a group -N(Ci-C6-alkyl)2. Examples are dimethyla- mino, diethylamino, ethylmethylamino, dipropylamino, diisopropylamino, methylpropyl- amino, methylisopropylamino, ethylpropylamino, ethylisopropylamino, dibutylamino and the like.
The term "3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or het- eroatom groups selected from N, O, S, NO, SO and SO2, as ring members" denotes a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heteromonocyclic ring or a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members.
Unsaturated rings contain at least one C-C and/or C-N and/or N-N double bond(s). Maximally unsaturated rings contain as many conjugated C-C and/or C-N and/or N-N double bonds as allowed by the ring size. Maximally unsaturated 5- or 6-membered heterocyclic rings are aromatic. The heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
The term "3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members" [wherein "maximum unsaturated" includes also "aromatic"] as used herein denotes monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or maximum unsaturated (including aromatic). The term "3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members" [wherein "maximum unsaturated" includes also "aromatic"] as used herein further also encompasses 8-membered heteromonocyclic radicals containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, the monocyclic radicals being saturated, partially unsaturated or maximum unsaturated (including aromatic). Unsaturated rings contain at least one C-C and/or C-N and/or N-N double bond(s). Maximum unsaturated rings contain as many conjugated C-C and/or C-N and/or N-N double bonds as allowed by the ring size. Maximum unsaturated 5- or 6-membered heterocyclic rings are aromatic. 7- and 8-membered rings cannot be aromatic. They are homoaromatic (7-membered ring, 3 double bonds) or have 4 double bonds (8-membered ring). The heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
Examples of a 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic ring include: Oxira- nyl, thiiranyl, aziridinyl, oxetanyl, thietanyl, azetidinyl, tetrahydrofuran-2-yl, tetrahydrofu- ran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-1 -yl, pyrrolidin-2-yl, pyrrol- idin-3-yl, pyrazolidin-1 -yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazoli- din-1 -yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin- 4-yl, oxazolidin-5-yl, isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5- yl, thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4- oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3- yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-1 -yl, 1 ,3,4- triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2- yl, piperidin-1 -yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahy- dropyrimidin-5-yl, piperazin-1 -yl, piperazin-2-yl, 1 ,3,5-hexahydrotriazin-1 -yl,
1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl, morpholin-2-yl, morpholin- 3-yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1 - oxothiomorpholin-2-yl, 1 -oxothiomorpholin-3-yl, 1 -oxothiomorpholin-4-yl, 1 ,1 - dioxothiomorpholin-2-yl, 1 ,1 -dioxothiomorpholin-3-yl, 1 ,1 -dioxothiomorpholin-4-yl, aze- pan-1 -, -2-, -3- or -4-yl, oxepan-2-, -3-, -4- or -5-yl, hexahydro-1 ,3-diazepinyl, hexahy- dro-1 ,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro- 1 ,3-dioxepinyl, hexahydro-1 ,4-dioxepinyl and the like.
Examples of a 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic ring include: 2,3-d ihyd rofur-2-yl , 2,3-dihydrofur-3-yl, 2,4-d ihyd rofur-2-yl , 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl,
3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,
2- isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-
3- yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,
2- isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,
2.3- dihydropyrazol-5-yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl,
3.4- dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1 -yl,
4.5- dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,
2.3- d i hyd rooxazol-2-yl , 2 , 3-d i hyd rooxazol-3-yl , 2 , 3-d i hyd rooxazol-4-yl ,
2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,
3.4- dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,
3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridi- nyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropy- rimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydro- pyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3-yl, 2,3,4,5- tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -
3- , -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7- tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -
4- , -5-, -6- or -7-yl, tetrahydro-1 ,3-diazepinyl, tetrahydro-1 ,4-diazepinyl, tetrahydro-1 ,3- oxazepinyl, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3-dioxepinyl and tetrahydro-1 ,4- dioxepinyl.
Examples for a 3-, 4-, 5-, 6- or 7-membered maximally unsaturated (including aromatic) heterocyclic ring are 5- or 6-membered heteroaromatic rings, such as 2-furyl, 3-furyl, 2- thienyl, 3-thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl,
5- pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1 - imidazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4-triazol-1 -yl, 1 ,3,4-triazol-2-yl, 2-pyridinyl, 3- pyridinyl, 4-pyridinyl, 1 -oxopyridin-2-yl, 1 -oxopyridin-3-yl, 1 -oxopyridin-4-yl,3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl, and also homoaromatic radicals, such as 1 H-azepine, 1 H-[1 ,3]-diazepine and 1 H-[1 ,4]- diazepine.
Examples for a 8-, 9- or 10-membered saturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
Figure imgf000031_0001
Figure imgf000032_0001
Examples for a 8-, 9- or 10-membered partially unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
Figure imgf000032_0002
Figure imgf000033_0001
Figure imgf000033_0002
Examples for a 8-, 9- or 10-membered maximally unsaturated heterobicyclic ring containing 1 , 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members are:
Figure imgf000033_0003
Figure imgf000034_0001
In the above structures # denotes the attachment point to the remainder of the molecule. The attachment point is not restricted to the ring on which is shown, but can be on either of the fused rings, and may be on a carbon or on a nitrogen ring atom. If the rings carry one or more substituents, these may be bound to carbon and/or to nitrogen ring atoms (if the latter are not part of a double bond).
A saturated 3-, 4-, 5-, 6-, 7-, 8- or 9-membered ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from O, S, N, NR14, NO, SO and SO2 and/or 1 or 2 groups selected from C=0, C=S and C=NR14 as ring members is either carbocyclic or heterocyclic. Examples are, in addition to the saturated heteromonocy- clic rings mentioned above, carbocyclic rings, such as cyclopropyl, cyclopropanonyl, cyclobutyl, cyclobutanonyl, cyclopentyl, cyclopentanonyl, cyclohexyl, cyclohexanonyl, cyclohexadienonyl, cycloheptyl, cycloheptanonyl, cyclooctyl, cyclooctanonyl, furan-2- onyl, pyrrolidine-2-onyl, pyrrolidine-2,5-dionyl, piperidine-2-only, piperidine-2,6-dionyl and the like.
The remarks made below concerning preferred embodiments of the variables of the compounds of formula I, especially with respect to their substituents A, A1, A2, A3, A4, B , B2, B3, G1, G2, G3, G4, R1, R2, R3a, R3b, R3c, R4, R5, R6, R7, R8, R9, R10a, R10b, R11, R12, R13, R14, R14a, R14b, R15, R16, m and n, the features of the use and method according to the invention and of the composition of the invention are valid both on their own and, in particular, in every possible combination with each other.
In one embodiment of the invention, A is A1.
In one preferred embodiment, A1 is selected from -C(=NR6)R8 and -N(R5)R6 and is more preferably -C(=NR6)R8; wherein R5, R6 and R8 have one of the above general meanings, or, in particular, one of the below preferred meanings.
R6 as a radical in the group -C(=NR6)R8 is preferably selected from hydrogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last- mentioned aliphatic and cycloaliphatic radicals each independently may be partially or fully halogenated and/or may be substituted with 1 , 2, 3, 4, 5 or 6, preferably 1 , 2 or 3, in particular 1 , substituents R8; OR9 and NR10aR10b; wherein R8, R9, R10a and R10b have one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, R6 in -C(=NR6)R8 is selected from hydrogen, Ci-Cio-alkyl, C3-C8- cycloalkyl, wherein the two last-mentioned aliphatic and cycloaliphatic radicals each independently may be partially or fully halogenated and/or may be substituted with 1 , 2 or 3, preferably 1 or 2, in particular 1 , substituents R8; OR9 and NR10aR10b; wherein R8, R9, R10a and R10b have one of the above general meanings, or, in particular, one of the below preferred meanings.
Even more preferably, R6 in -C(=NR6)R8 is selected from OR9 and NR10aR10b; wherein R8, R9, R10a and R10b have one of the above general meanings, or, in particular, one of the below preferred meanings. In OR9 as a preferred meaning of R6 in -C(=NR6)R8, R9 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8- cycloalkyl-Ci-C4-alkyl-, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6- haloalkynyl, and more preferably from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl and C3-C8-cycloalkyl-Ci-C4-alkyk
In NR10aR10b as a preferred meaning of R6 in -C(=NR6)R8, R10a and R10b, independently of each other, are selected from the group consisting of hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
-C(=0)OR15, -C(=0)N(R 4a)R 4 , -C(=S)N(R 4a)R 4 , phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more sub- stituents R16;
or R10a and R10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; wherein R14a, R14b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably,
R10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R10b is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, d-Ce-alkylcarbonyl, Ci-C6- haloalkylcarbonyl, -C(=0)OR15, -C(=0)N(R 4a)R 4b, -C(=S)N(R 4a)R 4b, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 5- or 6- membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more substituents R16;
wherein R14a, R14b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
In the above radicals R10a and R10b,
R14a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R14b is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl-, Ci-C6-alkyl substituted with a CN group, Ci-C6-alkoxyl, Ci-C6-haloalkoxy, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51 defined below.
In an alternatively preferred embodiment, R10a and R10b, independently of each other, are selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
-C(=0)N(R14a)R14 , -C(=S)N(R14a)R14 , phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16;
or R10a and R10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocy- die ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; wherein R14a, R14b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
In an alternatively more preferred embodiment,,
R10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R10b is selected from -C(=0)N(R14a)R14b, -C(=S)N(R14a) R14b, phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 5- or 6-membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N , O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16;
wherein R14a, R14b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
In the above radicals R10a and R10b of the above alternatively preferred and more preferred embodiments,
R14a is preferably selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and R14b is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkenyl, Ci-C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C4- alkyl-, Ci-C6-alkyl substituted with a CN group, phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R16, which are each independently preferably selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of following formulae E-1 to E-51 :
Figure imgf000037_0001
E-1 E-2 E-3 E-4 E-5
Figure imgf000038_0001
E-6 E-7 E-9
Figure imgf000038_0002
E-10 E-11 E-12 E-13 E-14
Figure imgf000038_0003
E-51 wherein
k is 0, 1 , 2 or 3, n is 0, 1 or 2,
n is 0, 1 or 2; and
each R16 is independently selected from the group consisting of halogen, cy- ano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or two R16 present on the same carbon atom of a saturated ring may form to- gether a group =0 or =S.
More preferably, in the above radicals R10a and R10b,
R14a is selected from hydrogen and methyl; and
R14b is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-methyl-, Ci- C6-alkyl substituted with a CN group, phenyl which is optionally substituted with 1 , 2, 3 or 4, preferably 1 , 2 or 3, in particular 1 , substituents R16 selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl; and a 4-membered saturated heterocyclic ring comprising one heteroatom or heteroatom group selected from S, SO and SO2 as ring member (ring E-44), where the heterocyclic ring is optionally substituted with one or more, preferably 1 or 2, in particular 1 , substituents R16;
wherein each R16 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom may form together a group =0 or =S..
Preferably, in the above radicals, each R16 is independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
Specifically, in the above radicals R10a and R10b,
R14a is selected from hydrogen and methyl, and is specifically hydrogen; and
R14b is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl and C3-C6-cycloalkyl- methyl-. R8 as a radical in the group -C(=NR6)R8 is preferably selected from hydrogen, C1-C4- alkyl, Ci-C4-haloalkyl and NR10aR10b, and more preferably from hydrogen and
NR10aR10b, and is specifically hydrogen. In this case (i.e. in NR10aR10b as a meaning of R8), R10a and R10b are preferably selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl and C3-C6- halocycloalkylaminocarbonyl,
or, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particu- lar 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio.
More preferably, R10a and R10b are in this case selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C4-alkylaminocarbonyl and Ci-C4-haloalkylaminocarbonyl.
In an alternative embodiment of the invention, A is A2. In A2, W is preferably O.
In A2, Y is preferably N(R5)R6; wherein R5 and R6 have one of the above general meanings, or, in particular, one of the below preferred meanings. In an alternatively preferred embodiment, in A2 Y is hydrogen.
In an alternatively preferred embodiment, in A2 Y is -OR9. R9 has one of the above general meanings, or, in particular, is selected from hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl and Ci-C6-alkyl substituted by one radical R13, where R13 has one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, in A2, W is O and Y is N(R5)R6; wherein R5 and R6 have one of the above general meanings, or, in particular, one of the below preferred meanings. In alternatively more preferred embodiment, in A2, W is O and Y H.
In alternatively more preferred embodiment, in A2, W is O and Y is -OR9, where R9 has one of the above general meanings, or, in particular, is selected from hydrogen, C1-C6- alkyl, Ci-C6-haloalkyl and Ci-C6-alkyl substituted by one radical R13, where R13 has one of the above general meanings, or, in particular, one of the below preferred meanings.
In N (R5)R6 as a radical Y,
R5 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl and C3-C8- halocycloalkyl, where the aforementioned aliphatic and cycloaliphatic radicals may be substituted by 1 , 2 or 3, preferably 1 , radicals R8; and
R6 is preferably selected from hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-C10- alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloali- phatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8,
OR9, N R10aR10b, S(0)nR9, C(=O)N R 0aN(R 0aR 0b), C(=0)R8,
phenyl which may be substituted with 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3, in particular 1 , substituents R1 1 , and
a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substit- uents R1 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, N , N H , C=0 and
C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R11 ; or
R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9;
wherein R8, R9, R10a, R10b and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and -Chb-CN; and
R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C10- haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the four last-mentioned aliphatic and cycloaliphatic radicals may carry 1 , 2 or 3 radicals
R8; d-Ce-alkoxy, Ci-C6-haloalkoxy, N(R10a)R10b, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-,
4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11; wherein R8 and R11 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated heterocyclic ring, where the ring may further contain
1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a group where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl. Even more preferably, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and CH2-CN; and
R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
Ci-Ce-alkoxy, Ci-C6-haloalkoxy, N(R 0a)R 0b,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4- , 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups in- dependently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R1 1 ; wherein R8 and R1 1 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, N H and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a group where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
Particularly preferably, in N(R5)R6 as a radical Y,
R5 selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and CH2-CN ; and
R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
d-Ce-alkoxy, Ci-C6-haloalkoxy, N(R10a)R10b, wherein R10a is selected from hydrogen and Ci-C6-alkyl and R10b is selected from a 5- or 6-membered het- eroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N , O and S as ring members, where the heteroaromatic ring may be substituted with one or more substituents R16;
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R1 1 , and a 3-, 4- , 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R1 1 ; wherein
each R1 1 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or two R1 1 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
R8 is selected from OH , CN , Cs-Cs-cycloalkyl which optionally carries a CN substituent, Cs-Cs-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, - C(=O)N(R10a)R10b, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substitu- ents R16, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroa- toms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R16;
wherein
R10a is selected from the group consisting of hydrogen and Ci-C6-alkyl;
R10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C4- alkynyl, CH2-CN, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and
each R16 as a substituent on phenyl or the heterocyclic rings is independently selected from the group consisting of halogen, cyano, ni- tro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6- membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; or
R5 and R6, together with the nitrogen atom to which they are bound, form a group where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
Alternatively, more preferably, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-; and
R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, where the four last-mentioned aliphatic and cycloaliphatic radicals may carry 1 , 2 or 3, preferably 1 , radicals R8; C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heteromon- ocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11;
wherein R8 and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0, preferably from O, NH and C=0, as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Preferably, the 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring R6 containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members is selected from rings D-1 to D-173 listed below in context with A4. The ring may be sub- stituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11.
Alternatively, particularly preferably, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-; and
R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN, methyl and oxo; Ci-C4-alkyl which carries one radical R8; C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring con- taining 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from
N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11;
wherein R8 and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0, preferably from O, NH and C=0, as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
Alternatively, even more preferably, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen and Ci-C6-alkyl; and
R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN, methyl and oxo,
C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11;
wherein R8 and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or
6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0, preferably from O, NH and C=0, as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
Preferably the 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members is selected from rings D-1 to D-173 listed below in context with A4, and more preferably from rings F-1 to F-51 listed below. The ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11. In particular, in N(R5)R6 as a radical Y,
R5 is selected from hydrogen and methyl, preferably hydrogen; and
R6 is selected from Ci-C4-alkyl which carries one radical R8, preferably methyl which carries one radical R8, Ci-C4-haloalkyl, and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 het- eroatom or heteroatom group selected from S, SO and SO2, as ring member, where the heteromonocyclic ring may be substituted with one or more substitu- ents R11;
wherein R8 and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring (i.e. R5 and R6 form together -(Chb or - (CH2)5-), wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substitu- ents independently selected from the group consisting of halogen, cyano, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Preferably the 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 het- eroatom or heteroatom group selected from S, SO and SO2, as ring member is selected from rings D-72, D-77, D-78 and D-100 to D-102 listed below in context with A4. The ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substitu- ents R11. More preference is given to ring D-72 with n = 0 (thietan-3-yl) and its oxidized analogs with n = 1 and n = 2 (1 -oxo-thietan-3-yl and 1 ,1 -dioxo-thietan-3-yl)
In N(R5)R6 as a radical Y,
R8 as a substituent on an aliphatic or cycloaliphatic group is preferably selected from cyano, Cs-Cs-cycloalkyl which may be substituted by 1 or 2 substituents selected from CN, methyl and oxo, C3-C8-halocycloalkyl, OR9, S(0)nR9, N(R 0a)R 0b, C(=O)N(R 0a)R 0b, C(=0)OR9, phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16; and
R8 in the group C(=0)R8 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, OR9 and N(R 0a)R 0b;
wherein R9, R10a, R10b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, in N(R5)R6 as a radical Y,
R8 as a substituent on an aliphatic or cycloaliphatic group is selected from Cs-Cs- cycloalkyl, Cs-Cs-halocycloalkyl, -C(=O)N(R 0a)R 0 , -C(=S)N(R 0a)R 0 , -C(=0)OR9, phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16;
or
two R8 present on the same carbon atom together form a group =0,
Figure imgf000048_0001
=S; =S(0)m(R15)2, =S(0)mR15N(R 4a)R 4b, =NR 0a, =NOR9; or =NNR10aR10b;
and
R8 in the group C(=0)R8 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, OR9 and N(R 0a)R 0b;
wherein R9, R10a, R10b and R16 have one of the above general meanings, or, in particular, one of the below preferred meanings.
Even more preferably, in N(R5)R6 as a radical Y, R8 as a substituent on an aliphatic or cycloaliphatic group is selected from -C(=O)N(R10a)R10b, phenyl and a 5- or 6- membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16.
In this case,
R10a and R10b are preferably selected, independently of each other, from hydrogen, Ci- C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-
C6-cycloalkylaminocarbonyl and C3-C6-halocycloalkylaminocarbonyl,
or, together with the nitrogen atom to which they are bound, form a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups select- ed from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio.
More preferably, R10a and R10b are in this case selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C4-alkylaminocarbonyl and Ci-C4-haloalkylaminocarbonyl. Specifically, they are selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl and C3- C6-cycloalkyl. Very specifically, one of R10a and R10b is hydrogen and the other is C1-C4- alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl.
In an alternative particular embodiment, in N(R5)R6 as Y,
R5 is hydrogen;
R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, Cs-Ce-cycloalkyl,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 heteroatom or heteroatom group selected from N, O, S, SO and SO2, as ring member or a 5- or 6- membered heteromonocyclic aromatic ring containing 1 , 2 or 3 heteroatoms selected from O, N and S as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11, where the heteromonocyclic ring is preferably selected from rings of formulae F-1 to F-51 :
Figure imgf000049_0001
F-1 F-2 F-3 F-4 F-5
Figure imgf000049_0002
F-6 F-8 F-9
Figure imgf000049_0003
F-10 F-11 F F-13 F-14
Figure imgf000049_0004
F-25 F-26 F-27 F-28 F-29
Figure imgf000050_0001
F-50 F-51 wherein
k is 0, 1 , 2 or 3,
n is 0, 1 or 2, and
each R11 is independently selected from the group consisting of halogen, cy- ano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or two R11 present on the same carbon atom of a saturated ring may form to- gether =0 or =S;
R8 is selected from Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C6-alkylthio, Ci- Ce-haloalkylthio, -C(=O)N(R10a)R10b, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined above;
wherein
R10a is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C3- alkynyl, -CH2-CIM and Ci-C6-alkoxy-methyl;
R10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, C3-C6-cycloalkyl, C3-C6-cyclohaloalkyl, phenyl which is op- tionally substituted with 1 , 2, 3, 4 or 5 substituents selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined above; and
each R16 as a substituent on phenyl or a heterocyclic ring E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and preferably form a 5- or 6-membered saturated heterocyclic ring, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy.
Among the above rings, preference is given to F-44, F-48 and F-49. Particular preference is given to ring F-44 with n = 0 (thietan-3-yl) and its oxidized analogs with n = 1 and n = 2 (1 -oxo-thietan-3-yl and 1 ,1 -dioxo-thietan-3-yl).
Specifically, in A2, W is O and Y is N(R5)R6, wherein
R5 is selected from hydrogen and methyl, preferably hydrogen; and
R6 is selected from Ci-C4-alkyl which carries one radical R8, preferably methyl which carries one radical R8; Ci-C4-haloalkyl, and a 4-, 5- or 6-membered saturated heteromonocyclic ring containing 1 heteroatom or heteroatom group selected from S, SO and SO2, as ring member, where the heteromonocyclic ring may be substituted with one or more substituents R11;
wherein R8 is selected from -C(=O)N(R10a)R10b, phenyl and a 5- or 6-membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16, wherein
R10a and R10b are selected, independently of each other, from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci- C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl and C3-C6-halocycloalkylaminocarbonyl, and preferably from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl and C3-C6-cycloalkyl, where it is preferred that one of R10a and R10b is hydrogen and the other is Ci-C4-alkyl, Ci- C4-haloalkyl or C3-C6-cycloalkyl;
each R11 is independently selected from halogen, cyano, nitro, Ci-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and each R16 is independently selected from halogen, cyano, nitro, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, and form preferably a 5- or 6- membered saturated heterocyclic ring (i.e. R5 and R6 form together -(CH2)4- or - (CH2)5-), wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Preferably the 4-, 5- or 6-membered saturated heteromonocyclic ring R6 containing 1 heteroatom or heteroatom group selected from S, SO and SO2, as ring member is selected from rings D-72 (= F-44), D-77 (= F-48), D-78 (= F-49) and D-100 to D-102 listed below in context with A4. The ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11 as defined above. More preference is given to rings D-72 (= F-44), D-77 (= F-48) and D-78 (= F-49). Particular preference is given to ring D-72 (= F-44) with n = 0 (thietan-3-yl) and its oxidized analogs with n = 1 and n = 2 (1 -oxo-thietan-3-yl and 1 ,1 -dioxo-thietan-3-yl).
Preferably the 5- or 6-membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members is selected from rings E-1 to E-42 as defined above. The ring may be substituted with one or more, preferably 1 , 2 or 3, in par- ticular 1 , substituents R16 selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl. In an alternative embodiment of the invention, A is A3.
Preferably, R7a and R7b in the group A3 are independently of each other selected from hydrogen, Ci-C4-alkyl and Ci-C4-haloalkyl, and more preferably one of R7a and R7b is hydrogen and the other is hydrogen or methyl. Specifically, both are hydrogen.
In the group A3,
R5 is preferably selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8; and
R6 is preferably selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8,
-OR9, -NR10aR10b, -S(0)nR9, -C(=O)NR 0aN(R 0aR 0b), -C(=0)R8,
and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated het- erocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or het- eroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R11;
or
R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9 wherein R8, R9, R10a, R10b and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, in the group A3,
R5 is selected from hydrogen, Ci-C4-alkyl, which may be partially or fully halogenat- ed and/or may be substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R8 selected from cyano and Ci-C6-alkoxy; and C2-C4-alkynyl; and
R6 is selected from -S(0)nR9 and -C(=0)R8,
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated het- erocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or het- eroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl,
C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R11;
wherein R8, R9, R10a, R10b and R11 have one of the above general meanings, or, in particular, one of the below preferred meanings.
Even more preferably, in the group A3, is selected from hydrogen, Ci-C4-alkyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-, preferably from hydrogen and Ci-C4-alkyl; and
is -C(=0)R8;
wherein R8 has one of the above general meanings, or, in particular, one of the below preferred meanings.
R8 in -C(=0)R8 as a meaning of the radicals R5 and R6 of the group A3 is preferably selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C0-cycloalkyl, C3- Co-halocycloalkyl, where the aliphatic and cycloaliphatic moieties in the four last- mentioned radicals may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R13;
-OR9, -S(0)nR9, -N(R 0a)R 0b,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, in particular 1 , substituents R16, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroa- tom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R16,
wherein R9, R10a, R10b, R13 and R16 have one of the above general meanings, or, in par- ticular, one of the below preferred meanings.
More preferably, R8 in -C(=0)R8 as a meaning of the radicals R5 and R6 of the group A3 is selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl substituted by one radical R13, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, -N(R10a)R10b, phenyl which is optionally substituted with 1 , 2, 3, 4 or 5 substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3- C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined above.
R9 in -OR9 as a meaning of R8 in the group -C(=0)R8 as a meaning of the radicals R5 and R6 of the group A3 is preferably selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C0- halocycloalkyl and C3-C8-cycloalkyl-Ci-C4-alkyl-, and more preferably from Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl and C3-C0-cycloalkyl-Ci-C4- alkyk R10a and R10b in -N(R10a)R10b as a meaning of R8 in the group -C(=0)R8 as a meaning of the radicals R5 and R6 of the group A3 are, independently of each other, preferably selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkyl substituted by one radical R13, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C1-C4- alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, C3- C6-halocycloalkylaminocarbonyl, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroa- toms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio;
or, R10a and R10b, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio.
More preferably, R10a and R10b in R8 in the radicals R5 and R6 of the group A3 are, inde- pendently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkyl substituted by one radical R13, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and a 3- or 4-membered saturated heterocyclic ring comprising 1 heteroatom or heteroatom group selected from N, O, S, NO, SO and SO2, as ring member, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy; and are specifically, independently of each other, selected from hydrogen, Ci-C4-alkyl and Ci-C4-haloalkyl.
R13 in R8 in the radicals R5 and R6 of the group A3 is preferably selected from CN, Ci- C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci- C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl.
R16 in R8 in the radicals R5 and R6 of the group A3 is preferably selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy. Specifically, R8 in the group -C(=0)R8 in the radicals R5 and R6 of the group A3 is selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl substituted by one radical R13, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, -N(R10a)R10b, phenyl which is optionally substituted with 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 and in particular 1 , substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci- C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl, and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined above, wherein
R10a and R10b, independently of each other, are selected from hydrogen, Ci-C4-alkyl,
Ci-C4-haloalkyl and C3-C6-cycloalkyl;
R13 is selected from CN, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylsulfonyl and a heterocyclic ring selected from rings of formulae E-1 to
E-51 as defined above and preferably from Ci-C6-alkylthio, Ci-C6-haloalkylthio,
Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl; and
each R16 as a substituent on heterocyclic rings of formulae E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S.
More specifically, R8 in the group -C(=0)R8 in the radicals R5 and R6 of the group A3 is selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl substituted by one radical R13, Cs-Cs-cycloalkyl and Cs-Cs-halocycloalkyl, where R13 is selected from CN, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, preferably from Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfonyl and C1-C6- haloalkylsulfonyl and in particular from Ci-C6-alkylthio, Ci-C6-haloalkylthio, C1-C6- alkylsulfonyl and Ci-C6-haloalkylsulfonyl. Alternatively, in the group A3, R5 and R6 are in particular hydrogen.
In an alternative embodiment of the invention, A is A4. A4 is preferably selected from a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11, where R11 has one of the above general meanings, or, in particular, one of the below preferred meanings.
More preferably, A4 is selected from a 3-, 4-, 5-, 6- or 7-membered saturated heteromonocyclic ring containing 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, a 5-, 6- or 7-membered partially unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, and a 5- or 6-membered aromatic heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring members, where the heteromonocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents R11, where R11 has one of the above general meanings, or, in particular, one of the below preferred meanings.
A4 is even more preferably selected from rings of formulae D-1 to D-173
Figure imgf000058_0001
D-1 D-2 D-3 D-4 D-5
Figure imgf000058_0002
D-6 D-7 D-8 D-9 D-10
Figure imgf000058_0003
D-1 1 D-12 D-13 D-14
Figure imgf000058_0004
D-15 D-16 D-17 D-18 D-19
Figure imgf000059_0001
Figure imgf000060_0001
D-55 D-56 D-57 D-58 D-59
Figure imgf000060_0002
D-60 D-61 D-62 D-63 D-64
Figure imgf000060_0003
D-65 D-66 D-67 D-68 D-69
Figure imgf000060_0004
D-70 D-71 D-72 D-73 D-74
Figure imgf000060_0005
D-75 D-76 D-77 D-78 D-79
Figure imgf000060_0006
D-80 D-81 D-82 D-83 D-84
Figure imgf000060_0007
D-85 D-87 D-88 D-89
Figure imgf000061_0001
D-90 D-91 D-92 D-93 D-94
Figure imgf000061_0002
D-95 D-96 D-97 D-98 D-99
Figure imgf000061_0003
D-100 D-101 D-102 D-103 D-104
Figure imgf000061_0004
D-105 D-106 D-107 D-108 -109
D-120 D-121 D-122 D-123 D-124
Figure imgf000061_0006
D-125 D-126 D-127 D-128 D-129
Figure imgf000062_0001
D-130 D-131 D-132 D-133 D-134
Figure imgf000062_0002
D-135 D-136 D-137 D-138 D-139
Figure imgf000062_0003
D-155 D-156 D-157 D-158 D-159
Figure imgf000062_0004
D-160 D-161 D-162 D-163 D-164 11)
Figure imgf000063_0001
D-170 D-171 D-172 D-173 wherein k is 0, 1 , 2 or 3, n is 0, 1 or 2 and R1 1 has one of the above general meanings, or, in particular, one of the below preferred meanings;
and is in particular selected from D-59, D-65 and D-66 and is specifcally D-59.
Preferably, in the above rings D-1 to D-173,
each R1 1 is independently selected from the group consisting of halogen, cyano, ni- tro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R1 1 present on the same carbon atom of a saturated or partially unsaturated ring may form together =0 or =S.
Among the radicals A1, A2, A3 and A4, preference is given to A2.
Preferably, B1, B2 and B3 are CR2.
More preferably, B1 and B3 are CR2, where R2 is not hydrogen, and B2 is CR2, where R2 has one of the meanings given above.
Preferably, R2 is selected from hydrogen, halogen, cyano, azido, nitro, -SCN , SF5, Ci- C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, -OR9, -S(0)nR9 and -N R10aR10b,
wherein R8, R9, R10a and R10b have one of the above general meanings, or, in particular, one of the below preferred meanings. More preferably, R2 is selected from hydrogen, halogen and Ci-C2-haloalkyl, even more preferably from hydrogen, F, CI, Br and CF3, even more preferably from hydrogen, F, CI and CF3, and in particular from hydrogen and CI. Specifically, B2 is CH and B1 and B3 have one of the general or one of the preferred meanings given above for R2 (with the proviso that they are not hydrogen) and are preferably selected from halogen and Ci-C2-haloalkyl, even more preferably from F, CI, Br and CF3, particularly preferably from hydrogen, F, CI and CF3, and are in particular CI.
Alternatively, B2 is CF or CCI and B1 and B3 have one of the general or one of the preferred meanings given above for R2 (with the proviso that they are not hydrogen) and are preferably selected from halogen and Ci-C2-haloalkyl, such as F, CI and CF3, even more preferably from F and CI, and are in particular CI.
Preferably, G1 , G3 and G4 are CR4 and G2 is N or CR4, where R4 has one of the meanings given above or below; or G2, G3 and G4 are CR4 and G1 is N or CR4, where R4 has one of the meanings given above or below. Preferably, R4 is selected from hydrogen, halogen, cyano, azido, nitro, Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, Cs-Cs-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, C2-C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more, preferably 1 , 2 or 3, in particular 1 , radicals R8, -OR9, -S(0)nR9, and -NR10aR10b. More preferably, R4 is selected from hydrogen, halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylsulfonyl, and even more preferably from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, and specifically from hydrogen, methyl and CF3.
More preferably, G1 , G3 and G4 are CH and G2 is CR4, where R4 has one of the above general or preferred meanings; or G1 is N, G3 and G4 are CH and G2 is CR4. In another embodiment, G1 and G4 are CR4 and G2 and G3 are CH, where R4 has one of the meanings given above or below. Even more preferably, G1, G3 and G4 are CH and G2 is CR4, where R4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, preferably from hydrogen, F, CI, CN, methyl, CF3, methoxy and methylthio, and specifically from hydrogen, F, CI, CN, methyl methoxy and methylthio.
Alternatively, even more preferably, G1 is N, G2 is CR4 and G3 and G4 are CH, where R4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, preferably from hydrogen, F, CI, CN, methyl, CF3, methoxy and methylthio, and specifically from hydro- gen and methyl.
Preferably, R1 is selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl C3-C6-halocycloalkyl or C(=0)OR13; more preferably, from Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl and C(=0)OR15, even more preferably from Ci-C4-alkyl, Ci-C4-haloalkyl and -C(=0)OR15, and particularly preferably from Ci-C4-haloalkyl and -C(=0)OR15, wherein R15 is preferably Ci-C4-alkyl. In particular, R1 is Ci-C4-haloalkyl, specifically Ci- C2-haloalkyl and more specifically halomethyl, in particular fluoromethyl, such as fluo- romethyl, difluoromethyl and trifluoromethyl, and is very specifically trifluoromethyl.
Preferably, R3a and R3b are selected, independently of each other, from hydrogen, halogen, hydroxyl, Ci-C3-alkyl, Ci-C3-alkenyl, Ci-C3-alkynyl, Ci-C3-haloalkyl, Ci-C3-alkoxy, Ci-C3-alkylthio and Ci-C3-alkylsulfonyl, more preferably from hydrogen and halogen, in particular from hydrogen and fluorine and are specifically hydrogen.
If not specified otherwise above, R8, R9, R10a, R10b, R11, R12, R13, R14, R14a, R14b, R15 and R16 have following preferred meanings:
In case R8 is a substituent on an alkyl, alkenyl or alkynyl group, it is preferably selected from the group consisting of cyano, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, -OR9, -SR9, -C(=O)N(R 0a)R 0b, -C(=S)N(R 0a)R 0 , -C(=0)OR9, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocy- die ring may be substituted by one or more radicals R16; where R9, R10a, R10b and R16 have one of the meanings given above or in particular one of the preferred meanings given below. In case R8 is a substituent on an alkyl, alkenyl or alkynyl group, it is even more preferably selected from the group consisting of cyano, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, -C(=O)N(R10a)R10b, -C(=S)N(R10a)R10b, -C(=0)OR9, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R16; where R9, R10a, R10b and R16 have one of the meanings given above or in particular one of the preferred meanings given below. In particular it is selected from the group consisting of cyano, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, -C(=O)N(R 0a)R 0 , -C(=S)N(R 0a)R 0 , -C(=0)OR9, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R16; where R9, R10a, R10b and R16 have one of the meanings given above or in particular one of the preferred meanings given below.
In case R8 is a substituent on a cycloalkyl group, it is preferably selected from the group consisting of cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, -OR9, -OSO2R9, -SR9, -N(R 0a)R 0 , -C(=O)N(R 0a)R 0 , -C(=S)N(R 0a)R 0 , -C(=0)OR9 , phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R16; where R9, R10a, R10b and R16 have one of the meanings given above or in particular one of the preferred meanings given below.
In case R8 is a substituent on a cycloalkyl group, it is even more preferably selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C3-haloalkyl, Ci-C4-alkoxy and Ci-C3-haloalkoxy. In particular, R8 as a substituent on a cycloalkyl group is selected from halogen, Ci-C4-alkyl and Ci-C3-haloalkyl.
In case of R8 in a group -C(=0)R8, =C(R8)2 or -C(=NR6)R8, R8 is preferably selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy-Ci- C6-alkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2- Ce-alkynyl, C2-C6-haloalkynyl, -OR9, -SR9, -N(R10a)R10b, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroa- torn groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R16; where R9, R10a, R10b and R16 have one of the meanings given above or in particular one of the preferred meanings given below. In case of R8 in a group -C(=0)R8, =C(R8)2 or -C(=NR6)R8, R8 is more preferably selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs- Cs-halocycloalkyl, d-Ce-alkoxy, Ci-C6-haloalkoxy, -N(R10a)R10b, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R16; where R10a, R10b and R16 have has one of the meanings given above or in particular one of the preferred meanings given below. Preferably, each R9 is independently selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Cs-Cs-cycloalkyl- Ci-C4-alkyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16; and a 3-, 4- , 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more, e.g. 1 , 2, 3 or 4, preferably 1 or 2, more preferably 1 , radicals R16, where R16 has one of the meanings given above or in particular one of the preferred meanings given below. More preferably, each R9 is independently selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16; and a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring may be substituted by one or more radicals R16; where R16 has one of the meanings given above or in particular one of the preferred meanings given below.
R10a and R10b are, independently of each other, preferably selected from hydrogen, Ci- C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkylaminocarbonyl, Ci-C4-haloalkylaminocarbonyl, C3-C6- cycloalkylaminocarbonyl, C3-C6-halocycloalkylaminocarbonyl, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2- C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio;
or, R10a and R10b, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S02, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio.
More preferably, R10a and R10b are, independently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and a 3- or 4-membered saturated heterocyclic ring comprising 1 heteroatom or heteroatom group selected from N, O, S, NO, SO and S02, as ring member, where the heterocyclic ring is optionally substituted with one or more, preferably 1 , 2 or 3, in particular 1 , substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; and are specifically, independently of each other, selected from hydrogen, Ci-C4-alkyl and Ci-C4-haloalkyl.
Each R11 and each R16 are independently of each occurrence and independently of each other preferably selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, C1-C4- haloalkylsulfinyl, Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl, and more preferably from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
Each R12 is preferably selected from Ci-C4-alkyl and is in particular methyl.
In case R13 is a substituent on an alkyl, alkenyl or alkynyl group, it is preferably selected from the group consisting of cyano, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, -OH, - SH, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
In case R13 is a substituent on a cycloalkyl group, it is preferably selected from the group consisting of cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, -OH, -SH, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- haloalkylsulfonyl and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
In case R13 is a substituent on a cycloalkyl group, it is even more preferably selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C3-haloalkyl, Ci-C4-alkoxy and Ci-C3-haloalkoxy. In particular, R13 as a substituent on a cycloalkyl group is selected from halogen, Ci-C4-alkyl and Ci-C3-haloalkyl.
In case of R13 in a group -C(=0)R13, -C(=S)R13, =C(R13)2 or -C(=NR 4)R13, R8 is preferably selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs- Cs-cycloalkyl, C3-Cs-halocycloalkyl, -OH, -SH, Ci-C6-alkoxy, Ci-C6-haloalkoxy and phenyl which may be substituted by 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
R14, R14a and R14b are, independently of each other, preferably selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and benzyl, where the phenyl ring in benzyl is optionally substituted 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
or, R14a and R14b, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy and Ci-C4-haloalkoxy.
More preferably, R14, R14a and R14b are, independently of each other, selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and benzyl, where the phenyl ring in benzyl is optionally substituted 1 , 2 or 3, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; or, R14a and R14b, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, which additionally may contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may carry 1 or 2, in particular 1 , substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy and Ci-C4-haloalkoxy.
Each R15 is preferably selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, phenyl, benzyl, pyridyl and phenoxy, wherein the four last-mentioned radicals may be unsubsti- tuted and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy.
In a particular embodiment of the invention, compound I is a compound of formula IA
Figure imgf000070_0001
where A, R2 and R4 have one of the above-given general or, in particular, one of the above-given preferred meanings, and R2a and R2c, independently of each other, have one of the general or, in particular, one of the preferred meanings given above for R2, with the proviso that they are not hydrogen, and are specifically CI or CF3 and are very specifically CI.
Examples of preferred compounds are compounds of the following formulae la.1 to la.31 , where the variables have one of the general or preferred meanings given above. Examples of preferred compounds are the individual compounds compiled in the tables 1 to 2082 below, Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question. 70
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Table 1
Compounds of the formula la.1 in which R14b is hydrogen, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2
Compounds of the formula la.1 in which R14b is methyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 3
Compounds of the formula la.1 in which R14b is ethyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 4
Compounds of the formula la.1 in which R14b is propyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 5
Compounds of the formula la.1 in which R14b is isopropyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 6
Compounds of the formula la.1 in which R14b is n-butyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 7
Compounds of the formula la.1 in which R14b is sec-butyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 8
Compounds of the formula la.1 in which R14b is isobutyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 9
Compounds of the formula la.1 in which R14b is tert-butyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 10
Compounds of the formula la.1 in which R14b is isopropenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1 1
Compounds of the formula la.1 in which R14b is cyclopropyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 12
Compounds of the formula la.1 in which R14b is 2,2-difluoroethyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 13
Compounds of the formula la.1 in which R14b is 2,2,2-trifluoroethyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 14
Compounds of the formula la.1 in which R14b is 3,3,3-trifluoropropyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 15
Compounds of the formula la.1 in which R14b is Chb-CN, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 16
Compounds of the formula la.1 in which R14b is Chb-isopropenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 17
Compounds of the formula la.1 in which R14b is Chb-cyclopropyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 18
Compounds of the formula la.1 in which R14b is thietan-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 19
Compounds of the formula la.1 in which R14b is 1 -oxo-thietan-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 20
Compounds of the formula la.1 in which R14b is 1 ,1 -dioxo-thietan-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 21
Compounds of the formula la.1 in which R14b is allyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 22
Compounds of the formula la.1 in which R14b is propargyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 23
Compounds of the formula la.1 in which R14b is methoxy, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 24
Compounds of the formula la.1 in which R14b is ethoxy, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 25
Compounds of the formula la.1 in which R14b is isopropoxy, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Tables 26 to 50
Compounds of the formula la.2 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 51 to 75
Compounds of the formula la.3 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 76 to 100
Compounds of the formula la.4 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 101 to 125
Compounds of the formula la.5 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 126 to 150
Compounds of the formula la.6 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 151 to 175
Compounds of the formula la.7 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 176 to 200
Compounds of the formula la.8 in which R14b is as defined in any of tables 1 to 25 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 201 Compounds of the formula la.9 in which R10b is phenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 202
Compounds of the formula la.9 in which R10b is 2-fluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 203
Compounds of the formula la.9 in which R10b is 3-fluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 204
Compounds of the formula la.9 in which R10b is 4-fluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 205
Compounds of the formula la.9 in which R10b is 2-chlorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 206
Compounds of the formula la.9 in which R10b is 3-chlorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 207
Compounds of the formula la.9 in which R10b is 4-chlorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 208
Compounds of the formula la.9 in which R10b is 2,3-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 209
Compounds of the formula la.9 in which R10b is 2,4-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 210
Compounds of the formula la.9 in which R10b is 2,5-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 21 1
Compounds of the formula la.9 in which R10b is 2,6-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 212
Compounds of the formula la.9 in which R10b is 3,4-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 213
Compounds of the formula la.9 in which R10b is 3,5-difluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 214 Compounds of the formula la.9 in which R10b is 3,4,5-trifluorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 215
Compounds of the formula la.9 in which R10b is 2,4-dichlorophenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 216
Compounds of the formula la.9 in which R10b is 3,5-dichlorophenyl, and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 217
Compounds of the formula la.9 in which R10b is 2-methylphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 218
Compounds of the formula la.9 in which R10b is 3-methylphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 219
Compounds of the formula la.9 in which R10b is 4-methylphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 220
Compounds of the formula la.9 in which R10b is 2-methoxyphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 221
Compounds of the formula la.9 in which R10b is 3-methoxyphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 222
Compounds of the formula la.9 in which R10b is 4-methoxyphenyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 223
Compounds of the formula la.9 in which R10b is pyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 224
Compounds of the formula la.9 in which R10b is 3-chloropyridin-2-yl, and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 225 Compounds of the formula la.9 in which R10b is 4-chloropyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 226
Compounds of the formula la.9 in which R10b is 5-chloropyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 227
Compounds of the formula la.9 in which R10b is 6-chloropyridin-2-yl, and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 228
Compounds of the formula la.9 in which R10b is 3-methoxypyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 229
Compounds of the formula la.9 in which R10b is 4-methoxypyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 230
Compounds of the formula la.9 in which R10b is 5-methoxypyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 231
Compounds of the formula la.9 in which R10b is 6-methoxypyridin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 232
Compounds of the formula la.9 in which R10b is pyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 233
Compounds of the formula la.9 in which R10b is 2-chloropyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 234
Compounds of the formula la.9 in which R10b is 4-chloropyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 235 Compounds of the formula la.9 in which R10b is 5-chloropyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 236
Compounds of the formula la.9 in which R10b is 6-chloropyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 237
Compounds of the formula la.9 in which R10b is 2-methoxypyridin-3-yl, and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 238
Compounds of the formula la.9 in which R10b is 4-methoxypyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 239
Compounds of the formula la.9 in which R10b is 5-methoxypyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 240
Compounds of the formula la.9 in which R10b is 6-methoxypyridin-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 241
Compounds of the formula la.9 in which R10b is pyridin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 242
Compounds of the formula la.9 in which R10b is 2-chloropyridin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 243
Compounds of the formula la.9 in which R10b is 3-chloropyridin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 244
Compounds of the formula la.9 in which R10b is 2-methoxypyridin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 245 Compounds of the formula la.9 in which R10b is 3-methoxypyridin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 246
Compounds of the formula la.9 in which R10b is pyrimidin-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 247
Compounds of the formula la.9 in which R10b is pyrimidin-4-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 248
Compounds of the formula la.9 in which R10b is pyrimidin-5-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 249
Compounds of the formula la.9 in which R10b is pyrrol-2-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 250
Compounds of the formula la.9 in which R10b is pyrrol-3-yl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 251
Compounds of the formula la.9 in which R10b is hydrogen, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 252
Compounds of the formula la.9 in which R10b is methyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 253
Compounds of the formula la.9 in which R10b is ethyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 254
Compounds of the formula la.9 in which R10b is isopropyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 255
Compounds of the formula la.9 in which R10b is methylcarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 256
Compounds of the formula la.9 in which R10b is ethylcarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 257
Compounds of the formula la.9 in which R10b is isopropylcarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 258
Compounds of the formula la.9 in which R10b is methoxycarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 259
Compounds of the formula la.9 in which R10b is ethoxycarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 260
Compounds of the formula la.9 in which R10b is isopropoxycarbonyl, and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 261 to 320
Compounds of the formula la.10 in which R10b is as defined in any of tables 201 to 260 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 321 to 380
Compounds of the formula la.1 1 in which R10b is as defined in any of tables 201 to 260 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 381 to 440
Compounds of the formula la.12 in which R10b is as defined in any of tables 201 to 260 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 441
Compounds of the formula la.13 in which R6 is hydrogen and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 442
Compounds of the formula la.13 in which R6 is methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 443
Compounds of the formula la.13 in which R6 is ethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 444
Compounds of the formula la.13 in which R6 is propyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 445
Compounds of the formula la.13 in which R6 is isopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 446 Compounds of the formula la.13 in which R6 is n-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 447
Compounds of the formula la.13 in which R6 is sec-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 448
Compounds of the formula la.13 in which R6 is isobutyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 449
Compounds of the formula la.13 in which R6 is tert-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 450
Compounds of the formula la.13 in which R6 is CH2-C(CH3)3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 451
Compounds of the formula la.13 in which R6 is -CH2CIM and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 452
Compounds of the formula la.13 in which R6 is -CH2-CH=CH2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 453
Compounds of the formula la.13 in which R6 is -CH2C≡CH and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 454
Compounds of the formula la.13 in which R6 is CH2CH2OH and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 455
Compounds of the formula la.13 in which R6 is -CH2CH2OCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 456
Compounds of the formula la.13 in which R6 is -CH2CH2OCH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 457
Compounds of the formula la.13 in which R6 is -CH2CH2OCF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 458
Compounds of the formula la.13 in which R6 is -CH2CH2OCH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 459 Compounds of the formula la.13 in which R6 is -CH(CH3)CH20CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 460
Compounds of the formula la.13 in which R6 is -CH(CH3)CH20CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 461
Compounds of the formula la.13 in which R6 is -CH2CH2SCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 462
Compounds of the formula la.13 in which R6 is -CH2CH2S(0)CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 463
Compounds of the formula la.13 in which R6 is -CH2CH2S(0)2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 464
Compounds of the formula la.13 in which R6 is -CH2CH2SCH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 465
Compounds of the formula la.13 in which R6 is -CH2CH2S(0)CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 466
Compounds of the formula la.13 in which R6 is -ChbChbS D^CI-bCHs and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 467
Compounds of the formula la.13 in which R6 is -CH(CH3)CH2SCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 468
Compounds of the formula la.13 in which R6 is -CH(CH3)CH2S(0)CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 469
Compounds of the formula la.13 in which R6 is -CH(CH3)CH2S(0)2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 470 Compounds of the formula la.13 in which R6 is -C(CH3)2CH2SCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 471
Compounds of the formula la.13 in which R6 is -C(CH3)2CH2S(0)CH3 and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 472
Compounds of the formula la.13 in which R6 is -C(CH3)2CH2S(0)2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 473
Compounds of the formula la.13 in which R6 is -CH2CH2SCF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 474
Compounds of the formula la.13 in which R6 is CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 475
Compounds of the formula la.13 in which R6 is CH2CHF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 476
Compounds of the formula la.13 in which R6 is CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 477
Compounds of the formula la.13 in which R6 is CH2CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 478
Compounds of the formula la.13 in which R6 is CH(CH3)CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 479
Compounds of the formula la.13 in which R6 is CH(CF3)2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 480
Compounds of the formula la.13 in which R6 is CH2CH2CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 481
Compounds of the formula la.13 in which R6 is CH2CH2CH=CF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 482 Compounds of the formula la.13 in which R6 is CH2CH2CF=CF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 483
Compounds of the formula la.13 in which R6 is cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 484
Compounds of the formula la.13 in which R6 is 1 -cyano-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 485
Compounds of the formula la.13 in which R6 is 1 -(pyridin-2-yl)-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 486
Compounds of the formula la.13 in which R6 is cyclobutyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 487
Compounds of the formula la.13 in which R6 is cyclopentyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 488
Compounds of the formula la.13 in which R6 is cyclohexyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 489
Compounds of the formula la.13 in which R6 is -Chb-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 490
Compounds of the formula la.13 in which R6 is -CH2-(1 -cyano-cyclopropyl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 491
Compounds of the formula la.13 in which R6 is -CH2-(2,2-difluorocyclopropyl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 492
Compounds of the formula la.13 in which R6 is -CH2-(2,2-dichlorocyclopropyl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 493 Compounds of the formula la.13 in which R6 is -Chb-cyclobutyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 494
Compounds of the formula la.13 in which R6 is -CH2-(2,2-difluorocyclobutyl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 495
Compounds of the formula la.13 in which R6 is -Chb-cyclopentyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 496
Compounds of the formula la.13 in which R6 is -Chb-cyclohexyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 497
Compounds of the formula la.13 in which R6 is 1 ,1-difluorocyclobut-3-yl and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 498
Compounds of the formula la.13 in which R6 is -CH2-1 ,1 -difluorocyclobut-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 499
Compounds of the formula la.13 in which R6 is thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 500
Compounds of the formula la.13 in which R6 is 1 -oxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 501
Compounds of the formula la.13 in which R6 is 1 ,1-dioxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 502
Compounds of the formula la.13 in which R6 is 3-methyl-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 503
Compounds of the formula la.13 in which R6 is 3-methyl-1 -oxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 504 Compounds of the formula la.13 in which R6 is 3-methyl-1 ,1 -dioxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 505
Compounds of the formula la.13 in which R6 is -CH2-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 506
Compounds of the formula la.13 in which R6 is -CH2-(1 -oxo-thietan-3-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 507
Compounds of the formula la.13 in which R6 is -CH2-(1 ,1 -dioxo-thietan-3-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 508
Compounds of the formula la.13 in which R6 is tetrahydrothiophen-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 509
Compounds of the formula la.13 in which R6 is 1 -oxo-tetrahydrothiophen-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 510
Compounds of the formula la.13 in which R6 is 1 ,1-dioxo-tetrahydrothiophen-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 51 1
Compounds of the formula la.13 in which R6 is phenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 512
Compounds of the formula la.13 in which R6 is 2-nitrophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 513
Compounds of the formula la.13 in which R6 is pyridin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 514
Compounds of the formula la.13 in which R6 is pyridin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 515 Compounds of the formula la.13 in which R6 is pyridin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 516
Compounds of the formula la.13 in which R6 is pyrimidin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 517
Compounds of the formula la.13 in which R6 is pyrimidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 518
Compounds of the formula la.13 in which R6 is pyrimidin-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 519
Compounds of the formula la.13 in which R6 is thiazol-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 520
Compounds of the formula la.13 in which R6 is 4-trifluoromethylthiazol-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 521
Compounds of the formula la.13 in which R6 is oxetan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 522
Compounds of the formula la.13 in which R6 is tetrahydrofuran-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 523
Compounds of the formula la.13 in which R6 is tetrahydrofuran-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 524
Compounds of the formula la.13 in which R6 is 2-oxotetrahydrofuran-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 525
Compounds of the formula la.13 in which R6 is 2-oxopyrrolidin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 526 Compounds of the formula la.13 in which R6 is 1 -methyl-2-oxopyrrolidin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 527
Compounds of the formula la.13 in which R6 is 2-oxo-1 -(2,2,2-trifluoroethyl)-pyrrolidin- 3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 528
Compounds of the formula la.13 in which R6 is azetidin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 529
Compounds of the formula la.13 in which R6 is 1 -acetyl-azetidin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 530
Compounds of the formula la.13 in which R6 is -NH-phenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 531
Compounds of the formula la.13 in which R6 is -NH-pyridin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 532
Compounds of the formula la.13 in which R6 is -NH-pyridin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 533
Compounds of the formula la.13 in which R6 is -NH-pyridin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 534
Compounds of the formula la.13 in which R6 is -N(CH3)-pyridin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 535
Compounds of the formula la.13 in which R6 is -NH-pyrimidin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 536
Compounds of the formula la.13 in which R6 is -NH-pyrimidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 537
Compounds of the formula la.13 in which R6 is -NH-pyrimidin-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 538
Compounds of the formula la.13 in which R6 is -CH2-COOCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 539
Compounds of the formula la.13 in which R6 is -CH2-COO-CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 540
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 541
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 542
Compounds of the formula la.13 in which R6 is -CH2-CONH-CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 543
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH2CF3 and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 544
Compounds of the formula la.13 in which R6 is -Chb-CONH-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 545
Compounds of the formula la.13 in which R6 is -Chb-CONH-isopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 546
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH(CF3)CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 547
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH(CF3)2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 548 Compounds of the formula la.13 in which R6 is -CH2-CONH-CH2CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 549
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH2CN and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 550
Compounds of the formula la.13 in which R6 is -CH2-CONH-CH2C≡CH and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 551
Compounds of the formula la.13 in which R6 is -CH2-CON(CH3)-CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 552
Compounds of the formula la.13 in which R6 is -CH(CH3)-CONH-CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 553
Compounds of the formula la.13 in which R6 is -Chb-CONH-Chb-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 554
Compounds of the formula la.13 in which R6 is -CH2-CONH-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 555
Compounds of the formula la.13 in which R6 is -CH2-CONH-1 -oxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 556
Compounds of the formula la.13 in which R6 is -CH2-CONH-1 ,1 -dioxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 557
Compounds of the formula la.13 in which R6 is benzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 558 Compounds of the formula la.13 in which R6 is 2-fluorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 559
Compounds of the formula la.13 in which R6 is 3-fluorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 560
Compounds of the formula la.13 in which R6 is 4-fluorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 561
Compounds of the formula la.13 in which R6 is 2-chlorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 562
Compounds of the formula la.13 in which R6 is 3-chlorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 563
Compounds of the formula la.13 in which R6 is 4-chlorobenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 564
Compounds of the formula la.13 in which R6 is 2-methoxybenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 565
Compounds of the formula la.13 in which R6 is 3-methoxybenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 566
Compounds of the formula la.13 in which R6 is 4-methoxybenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 567
Compounds of the formula la.13 in which R6 is 2-methylsulfanylbenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 568
Compounds of the formula la.13 in which R6 is 3-methylsulfanylbenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 569
Compounds of the formula la.13 in which R6 is 4-methylsulfanylbenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 570 Compounds of the formula la.13 in which R6 is 2-methylsulfonylbenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 571
Compounds of the formula la.13 in which R6 is 3-methylsulfonylbenzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 572
Compounds of the formula la.13 in which R6 is 4-methylsulfonylbenzyl and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 573
Compounds of the formula la.13 in which R6 is pyridin-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 574
Compounds of the formula la.13 in which R6 is pyridin-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 575
Compounds of the formula la.13 in which R6 is 6-chloro-pyridin-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 576
Compounds of the formula la.13 in which R6 is pyridin-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 577
Compounds of the formula la.13 in which R6 is 5-chloro-pyridin-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 578
Compounds of the formula la.13 in which R6 is 6-(trifluoromethyl)-pyridin-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 579
Compounds of the formula la.13 in which R6 is 6-(trifluoromethyl)-pyridin-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 580 Compounds of the formula la.13 in which R6 is pyrimidin-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 581
Compounds of the formula la.13 in which R6 is pyrimidin-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 582
Compounds of the formula la.13 in which R6 is pyrimidin-5-yl-methyl and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 583
Compounds of the formula la.13 in which R6 is pyridazin-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 584
Compounds of the formula la.13 in which R6 is pyrazin-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 585
Compounds of the formula la.13 in which R6 is thien-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 586
Compounds of the formula la.13 in which R6 is thien-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 587
Compounds of the formula la.13 in which R6 is thiazol-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 588
Compounds of the formula la.13 in which R6 is thiazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 589
Compounds of the formula la.13 in which R6 is thiazol-5-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 590
Compounds of the formula la.13 in which R6 is 2-chloro-thiazol-5-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 591 Compounds of the formula la.13 in which R6 is isothiazol-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 592
Compounds of the formula la.13 in which R6 is isothiazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 593
Compounds of the formula la.13 in which R6 is isothiazol-5-yl-methyl and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 594
Compounds of the formula la.13 in which R6 is oxazol-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 595
Compounds of the formula la.13 in which R6 is oxazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 596
Compounds of the formula la.13 in which R6 is oxazol-5-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 597
Compounds of the formula la.13 in which R6 is isoxazol-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 598
Compounds of the formula la.13 in which R6 is isoxazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 599
Compounds of the formula la.13 in which R6 is isoxazol-5-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 600
Compounds of the formula la.13 in which R6 is [1 ,2,3]-thiadiazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 601 Compounds of the formula la.13 in which R6 is [1 ,3,4]-thiadiazol-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 602
Compounds of the formula la.13 in which R6 is 1 -methyl-imidazol-2-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 603
Compounds of the formula la.13 in which R6 is 1 -methyl-imidazol-4-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 604
Compounds of the formula la.13 in which R6 is 1 -methyl-imidazol-5-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 605
Compounds of the formula la.13 in which R6 is 1 -methyl-pyrazol-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 606
Compounds of the formula la.13 in which R6 is 2-methyl-pyrazol-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 607
Compounds of the formula la.13 in which R6 is tetrahydrofuran-3-yl-methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 608
Compounds of the formula la.13 in which R6 is 1 ,3-dioxolan-2-yl-methyl and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 609
Compounds of the formula la.13 in which R6 is 2-pyridyl-eth-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 610
Compounds of the formula la.13 in which R6 is (1 R)-2-pyridyl-eth-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 61 1 Compounds of the formula la.13 in which R6 is (1 S)-2-pyridyl-eth-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 612
Compounds of the formula la.13 in which R6 is -CONH2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 613
Compounds of the formula la.13 in which R6 is -CONH-CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 614
Compounds of the formula la.13 in which R6 is -CONH-CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 615
Compounds of the formula la.13 in which R6 is -CONH-CH2CH2CH3 and the combina- tion of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 616
Compounds of the formula la.13 in which R6 is -CONH-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 617
Compounds of the formula la.13 in which R6 is -CONH-Chb-cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 618
Compounds of the formula la.13 in which R6 is -CONH-phenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 619
Compounds of the formula la.13 in which R6 is -CONH-benzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 620
Compounds of the formula la.13 in which R6 is -NHCO-NH-CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 621
Compounds of the formula la.13 in which R6 is -NHCO-NH-CH2CHF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 622 Compounds of the formula la.13 in which R6 is -CH=NOCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 623
Compounds of the formula la.13 in which R6 is -CH=NOCH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 624
Compounds of the formula la.13 in which R6 is 3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 625
Compounds of the formula la.13 in which R6 is 2-methyl-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 626
Compounds of the formula la.13 in which R6 is 2-ethyl-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 627
Compounds of the formula la.13 in which R6 is 2-propyl-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 628
Compounds of the formula la.13 in which R6 is 2-butyl-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 629
Compounds of the formula la.13 in which R6 is 2-(but-2-yl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 630
Compounds of the formula la.13 in which R6 is 2-(3-bromopropyl)-3-oxo-isoxazolidin-4- yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 631
Compounds of the formula la.13 in which R6 is 2-(2-fluoroethyl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 632 Compounds of the formula la.13 in which R6 is 2-(2,2-difluoroethyl)-3-oxo-isoxazolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 633
Compounds of the formula la.13 in which R6 is 2-(2,2,2-trifluoroethyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 634
Compounds of the formula la.13 in which R6 is 2-(3,3,3-trifluoropropyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 635
Compounds of the formula la.13 in which R6 is 2-(2-methoxyethyl)-3-oxo-isoxazolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 636
Compounds of the formula la.13 in which R6 is 2-(1 -methoxy-prop-2-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 637
Compounds of the formula la.13 in which R6 is 2-cyclobutyl-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 638
Compounds of the formula la.13 in which R6 is 2-(2-methylcyclohex-1 -yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 639
Compounds of the formula la.13 in which R6 is 2-(phenylmethyl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 640
Compounds of the formula la.13 in which R6 is 2-(1 -phenyl-eth-1 -yl)-3-oxo-isoxaolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 641
Compounds of the formula la.13 in which R6 is 2-(2-phenyl-eth-1 -yl)-3-oxo-isoxazolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 642
Compounds of the formula la.13 in which R6 is 2-[(3-chlorophenyl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 643
Compounds of the formula la.13 in which R6 is 2-[(2-fluorophenyl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 644
Compounds of the formula la.13 in which R6 is 2-[(4-methoxyphenyl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 645
Compounds of the formula la.13 in which R6 is 2-[(2-trifluoromethylphenyl)-methyl]-3- oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 646
Compounds of the formula la.13 in which R6 is 2-[(2-trifluoromethoxyphenyl)-methyl]-3- oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound cor- responds in each case to one row of Table A
Table 647
Compounds of the formula la.13 in which R6 is 2-(pyridin-2-yl-methyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 648
Compounds of the formula la.13 in which R6 is 2-(pyridin-3-yl-methyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 649
Compounds of the formula la.13 in which R6 is 2-[(2-chloropyridin-5-yl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 650
Compounds of the formula la.13 in which R6 is 2-[(1 -methyl-1 H-imidazol-4-yl)-methyl]- 3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 651 Compounds of the formula la.13 in which R6 is 2-[(furan-2-yl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 652
Compounds of the formula la.13 in which R6 is 2-[(2-thiophen-2'-yl)-eth-1 -yl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 653
Compounds of the formula la.13 in which R6 is 2-[2-(indol-3'-yl)-eth-1 -yl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 654
Compounds of the formula la.13 in which R6 is 2-[(1 H-benzimidazol-2-yl)-methyl]-3- oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound cor- responds in each case to one row of Table A
Table 655
Compounds of the formula la.13 in which R6 is 2-[(oxetan-2-yl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 656
Compounds of the formula la.13 in which R6 is 2-[(tetrahydrofuran-2-yl)-methyl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 657
Compounds of the formula la.13 in which R6 is 2-[(2-[1 ',3']dioxolan-2'-yl)-eth-1 -yl]-3- oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 658
Compounds of the formula la.13 in which R6 is 2-[(2-morpholin-4'-yl)-eth-1 yl]-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 659
Compounds of the formula la.13 in which R6 is 2-[(2-benzo[1 ',3']dioxol-5'-yl)-eth-1 -yl]-3- oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound cor- responds in each case to one row of Table A
Table 660
Compounds of the formula la.13 in which R6 is 2-[(2,3-dihydro-benzo[1 ,4]dioxin-6-yl)- methyl]-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 661
Compounds of the formula la.13 in which R6 is 2-(2-chlorophenyl)-3-oxo-isoxazolidin-4- yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 662
Compounds of the formula la.13 in which R6 is 2-(3-fluorophenyl)-3-oxo-isoxazolidin-4- yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 663
Compounds of the formula la.13 in which R6 is 2-(2-methylphenyl)-3-oxo-isoxazolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 664
Compounds of the formula la.13 in which R6 is 2-(2-chloro-6-methylphenyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 665
Compounds of the formula la.13 in which R6 is 2-(2-trifluoromethylphenyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corre- sponds in each case to one row of Table A
Table 666
Compounds of the formula la.13 in which R6 is 2-(2,4-dimethoxyphenyl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 667
Compounds of the formula la.13 in which R6 is 2-(3-methylpyrid-2-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 668
Compounds of the formula la.13 in which R6 is 2-(1 ,3-dimethyl-1 H-pyrazol-5-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 669
Compounds of the formula la.13 in which R6 is 2-(4-methylthiazol-2-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 670 Compounds of the formula la.13 in which R6 is 2-(5-methylthiadiazol-2-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 671
Compounds of the formula la.13 in which R6 is 2-(quinolin-2-yl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 672
Compounds of the formula la.13 in which R6 is 2-(quinolin-5-yl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 673
Compounds of the formula la.13 in which R6 is 2-(benzothiazol-6-yl)-3-oxo-isoxazolidin- 4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 674
Compounds of the formula la.13 in which R6 is 2-(4-methylbenzothiazol-2-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 675
Compounds of the formula la.13 in which R6 is 2-(thietan-3-yl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 676
Compounds of the formula la.13 in which R6 is 2-(1 -oxo-thietan-3-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 677
Compounds of the formula la.13 in which R6 is 2-(1 ,1 -dioxo-thietan-3-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 678
Compounds of the formula la.13 in which R6 is 2-(3-methylthietan-3-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corre- sponds in each case to one row of Table A
Table 679
Compounds of the formula la.13 in which R6 is 2-(oxetan-3-yl)-3-oxo-isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 680
Compounds of the formula la.13 in which R6 is 2-(tetrahydropyran-4-yl)-3-oxo- isoxazolidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 681 to 920
Compounds of the formula la.14 in which R6 is as defined in any of tables 441 to 680 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 921 to 1 160
Compounds of the formula la.15 in which R6 is as defined in any of tables 441 to 680 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1 161 to 1400
Compounds of the formula la.16 in which R6 is as defined in any of tables 441 to 680 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1401
Compounds of the formula la.17 in which R8 is methyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1402
Compounds of the formula la.17 in which R8 is ethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1403
Compounds of the formula la.17 in which R8 is propyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1404
Compounds of the formula la.17 in which R8 is isopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1405
Compounds of the formula la.17 in which R8 is n-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1406
Compounds of the formula la.17 in which R8 is sec-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1407
Compounds of the formula la.17 in which R8 is isobutyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1408 Compounds of the formula la.17 in which R8 is tert-butyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1409
Compounds of the formula la.17 in which R8 is CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1410
Compounds of the formula la.17 in which R8 is CH2CHF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 141 1
Compounds of the formula la.17 in which R8 is CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1412
Compounds of the formula la.17 in which R8 is CH2CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1413
Compounds of the formula la.17 in which R8 is cyclopropyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1414
Compounds of the formula la.17 in which R8 is methylthiomethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1415
Compounds of the formula la.17 in which R8 is ethylthiomethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1416
Compounds of the formula la.17 in which R8 is methylsulfinylmethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1417
Compounds of the formula la.17 in which R8 is ethylsulfinylmethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1418
Compounds of the formula la.17 in which R8 is methylsulfonylmethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1419
Compounds of the formula la.17 in which R8 is ethylsulfonylmethyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1420 Compounds of the formula la.17 in which R8 is phenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1421
Compounds of the formula la.17 in which R8 is 2-fluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1422
Compounds of the formula la.17 in which R8 is 3-fluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1423
Compounds of the formula la.17 in which R8 is 4-fluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1424
Compounds of the formula la.17 in which R8 is 2,3-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1425
Compounds of the formula la.17 in which R8 is 2,4-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1426
Compounds of the formula la.17 in which R8 is 2,5-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1427
Compounds of the formula la.17 in which R8 is 2,6-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1428
Compounds of the formula la.17 in which R8 is 3,4-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1429
Compounds of the formula la.17 in which R8 is 3,5-difluorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1430
Compounds of the formula la.17 in which R8 is 2-chlorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1431
Compounds of the formula la.17 in which R8 is 3-chlorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1432
Compounds of the formula la.17 in which R8 is 4-chlorophenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1433 Compounds of the formula la.17 in which R8 is 2-methoxyphenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1434
Compounds of the formula la.17 in which R8 is 3-methoxyphenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1435
Compounds of the formula la.17 in which R8 is 4-methoxyphenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1436
Compounds of the formula la.17 in which R8 is thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1437
Compounds of the formula la.17 in which R8 is 1 -oxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1438
Compounds of the formula la.17 in which R8 is 1 ,1-dioxo-thietan-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 1439
Compounds of the formula la.17 in which R8 is pyridin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1440
Compounds of the formula la.17 in which R8 is pyridin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1441
Compounds of the formula la.17 in which R8 is pyridin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1442
Compounds of the formula la.17 in which R8 is 4-chloropyridin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1443
Compounds of the formula la.17 in which R8 is -NH-CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1444
Compounds of the formula la.17 in which R8 is -NH-CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1445
Compounds of the formula la.17 in which R8 is -NH-CH2CH2CH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1446
Compounds of the formula la.17 in which R8 is -NH-CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1447
Compounds of the formula la.17 in which R8 is -NH-CH2CHF2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1448
Compounds of the formula la.17 in which R8 is -NH-CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1449
Compounds of the formula la.17 in which R8 is -NH-phenyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 1450
Compounds of the formula la.17 in which R8 is -NH-benzyl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Tables 1451 to 1500
Compounds of the formula la.18 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1501 to 1550
Compounds of the formula la.19 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1551 to 1600
Compounds of the formula la.20 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1601 to 1650
Compounds of the formula la.21 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1651 to 1700
Compounds of the formula la.22 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1701 to 1750
Compounds of the formula la.23 in which R8 is as defined in any of tables1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Tables 1751 to 1800
Compounds of the formula la.24 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1801 to 1850
Compounds of the formula la.25 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1851 to 1900
Compounds of the formula la.26 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1901 to 1950
Compounds of the formula la.27 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Tables 1951 to 2000
Compounds of the formula la.28 in which R8 is as defined in any of tables 1401 to 1450 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2001
Compounds of the formula la.29 in which A4 is 1 H-pyrrol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2002
Compounds of the formula la.29 in which A4 is 1 H-3-chloro-pyrrol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2003
Compounds of the formula la.29 in which A4 is 1 H-3-cyano-pyrrol-1 -yl and the combi- nation of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2004
Compounds of the formula la.29 in which A4 is 1 H-pyrazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2005
Compounds of the formula la.29 in which A4 is 1 H-4-cloro-pyrazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2006 Compounds of the formula la.29 in which A4 is 1 H-4-cyano-pyrazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2007
Compounds of the formula la.29 in which A4 is 1 H-imidazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2008
Compounds of the formula la.29 in which A4 is 1 H-4-chloro-imidazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2009
Compounds of the formula la.29 in which A4 is 1 H-4-cyano-imidazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2010
Compounds of the formula la.29 in which A4 is 1 H-[1 ,2,4]-triazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 201 1
Compounds of the formula la.29 in which A4 is 1 H-[1 ,2,4]-3-chloro-triazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2012
Compounds of the formula la.29 in which A4 is 1 H-[1 ,2,4]-3-cyano-triazol-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2013
Compounds of the formula la.29 in which A4 is 1 H-1 -methyl-pyrrol-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2014
Compounds of the formula la.29 in which A4 is 1 H-1 -methyl-pyrrol-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2015
Compounds of the formula la.29 in which A4 is 1 H-1 -methyl-pyrazol-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2016 Compounds of the formula la.29 in which A4 is 1 H-1 -methyl-pyrazol-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2017
Compounds of the formula la.29 in which A4 is 1 H-1 ,3-dimethyl-pyrazol-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2018
Compounds of the formula la.29 in which A4 is 1 H-1 -methyl-3-trifluoromethyl-pyrazol-5- yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2019
Compounds of the formula la.29 in which A4 is 1 H-1 -[1 ,2,3]-triazol-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2020
Compounds of the formula la.29 in which A4 is pyridin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2021
Compounds of the formula la.29 in which A4 is pyridin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2022
Compounds of the formula la.29 in which A4 is pyridin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2023
Compounds of the formula la.29 in which A4 is pyrimidin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2024
Compounds of the formula la.29 in which A4 is pyrimidin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2025
Compounds of the formula la.29 in which A4 is pyrimidin-5-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2026
Compounds of the formula la.29 in which A4 is pyrazin-2-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Tables 2027 to 2052 Compounds of the formula la.30 in which A4 is as defined in any of tables 2001 to 2026 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2053
Compounds of the formula la.31 in which Y is H and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2054
Compounds of the formula la.31 in which Y is OH and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2055
Compounds of the formula la.31 in which Y is OCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2056
Compounds of the formula la.31 in which Y is OC2H5 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2057
Compounds of the formula la.31 in which Y is OC(CH3)3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2058
Compounds of the formula la.31 in which Y is OCH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2059
Compounds of the formula la.31 in which Y is OCH2CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2060
Compounds of the formula la.31 in which Y is OCH2-(pyridine-2-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2061
Compounds of the formula la.31 in which Y is aziridin-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2062
Compounds of the formula la.31 in which Y is azetidin-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2063
Compounds of the formula la.31 in which Y is pyrrolidin-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2064 Compounds of the formula la.31 in which Y is piperidin-1 -yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2065
Compounds of the formula la.31 in which Y is morpholin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2066
Compounds of the formula la.31 in which Y is thiomorpholin-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2067
Compounds of the formula la.31 in which Y is thiazinan-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2068
Compounds of the formula la.31 in which Y is 1 -oxo-thiazinan-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2069
Compounds of the formula la.31 in which Y is 1 ,1 -dioxo-thiazinan-4-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2070
Compounds of the formula la.31 in which Y is thiazolidin-3-yl and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2071
Compounds of the formula la.31 in which Y is -N=S(CH3)2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2072
Compounds of the formula la.31 in which Y is -N=S(C2H5)2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2073
Compounds of the formula la.31 in which Y is -N=S[CH(CH3)2]2 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A Table 2074
Compounds of the formula la.31 in which Y is -N(CH3)-CH2-(thiazol-4-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2075
Compounds of the formula la.31 in which Y is -N(C2H5)-CH2-(thiazol-4-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2076 Compounds of the formula la.31 in which Y is -N(CH3)-CH2-(pyridin-2-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2077
Compounds of the formula la.31 in which Y is -N(C2H5)-CH2-(pyridin-2-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2078
Compounds of the formula la.31 in which Y is -N(CH2CN)-CH2-(pyridin-2-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2079
Compounds of the formula la.31 in which Y is -N(CH2-C≡CH)-CH2-(pyridin-2-yl) and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2080
Compounds of the formula la.31 in which Y is -N(CH3)-CH2-CONH-CH2CF3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2081
Compounds of the formula la.31 in which Y is -N^Hsj-Ch -CONH-CI-bCFs and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table 2082
Compounds of the formula la.31 in which Y is -N(CH3)-OCH3 and the combination of R2a, R2b, R2c and R4 for a compound corresponds in each case to one row of Table A
Table A
No. R2a R2b R2c R4
A-1 F H F H
A-2 F F F H
A-3 F CI F H
A-4 F Br F H
A-5 F H CI H
A-6 F H Br H
A-7 CI H CI H
A-8 CI CI CI H
A-9 CI F CI H R2a R2b R2c R4
A-10 CI Br CI H
A-1 1 CI H Br H
A-12 Br H Br H
A-13 Br F Br H
A-14 Br CI Br H
A-15 CFs H F H
A-16 CFs H CI H
A-17 CFs H Br H
A-18 CFs H CFs H
A-19 CFs F F H
A-20 CFs CI CI H
A-21 CFs Br Br H
A-22 SF5 H F H
A-23 SF5 H CI H
A-24 SF5 H Br H
A-25 SF5 H CFs H
A-26 F H F CHs
A-27 F F F CHs
A-28 F CI F CHs
A-29 F Br F CHs
A-30 F H CI CHs
A-31 F H Br CHs
A-32 CI H CI CHs
A-33 CI CI CI CHs
A-34 CI F CI CHs
A-35 CI Br CI CHs
A-36 CI H Br CHs
A-37 Br H Br CHs
A-38 Br F Br CHs
A-39 Br CI Br CHs
A-40 CFs H F CHs
A-41 CFs H CI CHs
A-42 CFs H Br CHs
A-43 CFs H CFs CHs
A-44 CFs F F CHs
A-45 CFs CI CI CHs
A-46 CFs Br Br CHs
Figure imgf000117_0001
R2a R2b R2c R4
A-84 CI F CI CH(CHs)2
A-85 CI Br CI CH(CHs)2
A-86 CI H Br CH(CHs)2
A-87 Br H Br CH(CHs)2
A-88 Br F Br CH(CHs)2
A-89 Br CI Br CH(CHs)2
A-90 CFs H F CH(CHs)2
A-91 CFs H CI CH(CHs)2
A-92 CFs H Br CH(CHs)2
A-93 CFs H CFs CH(CHs)2
A-94 CFs F F CH(CHs)2
A-95 CFs CI CI CH(CHs)2
A-96 CFs Br Br CH(CHs)2
A-97 SF5 H F CH(CHs)2
A-98 SF5 H CI CH(CHs)2
A-99 SF5 H Br CH(CHs)2
A-100 SF5 H CFs CH(CHs)2
A-101 F H F CHF2
A-102 F F F CHF2
A-103 F CI F CHF2
A-104 F Br F CHF2
A-105 F H CI CHF2
A-106 F H Br CHF2
A-107 CI H CI CHF2
A-108 CI CI CI CHF2
A-109 CI F CI CHF2
A-1 10 CI Br CI CHF2
A-1 1 1 CI H Br CHF2
A-1 12 Br H Br CHF2
A-1 13 Br F Br CHF2
A-1 14 Br CI Br CHF2
A-1 15 CFs H F CHF2
A-1 16 CFs H CI CHF2
A-1 17 CFs H Br CHF2
A-1 18 CFs H CFs CHF2
A-1 19 CFs F F CHF2
A-120 CFs CI CI CHF2 R2a R2b R2c R4
A-121 CFs Br Br CHF2
A-122 SF5 H F CHF2
A-123 SF5 H CI CHF2
A-124 SF5 H Br CHF2
A-125 SF5 H CFs CHF2
A-126 F H F CFs
A-127 F F F CFs
A-128 F CI F CFs
A-129 F Br F CFs
A-130 F H CI CFs
A-131 F H Br CFs
A-132 CI H CI CFs
A-133 CI CI CI CFs
A-134 CI F CI CFs
A-135 CI Br CI CFs
A-136 CI H Br CFs
A-137 Br H Br CFs
A-138 Br F Br CFs
A-139 Br CI Br CFs
A-140 CFs H F CFs
A-141 CFs H CI CFs
A-142 CFs H Br CFs
A-143 CFs H CFs CFs
A-144 CFs F F CFs
A-145 CFs CI CI CFs
A-146 CFs Br Br CFs
A-147 SF5 H F CFs
A-148 SF5 H CI CFs
A-149 SF5 H Br CFs
A-150 SFs H CFs CFs
A-151 F H F CH2-CH=CH2
A-152 F F F CH2-CH=CH2
A-153 F CI F CH2-CH=CH2
A-154 F Br F CH2-CH=CH2
A-155 F H CI CH2-CH=CH2
A-156 F H Br CH2-CH=CH2
A-157 CI H CI CH2-CH=CH2
Figure imgf000120_0001
611
6££9/.0/ZlOZd3/I3d £t6Z60/£ioz OAV R2a R2b R2c R4
A-195 CFs CI CI CH=CH2
A-196 CFs Br Br CH=CH2
A-197 SF5 H F CH=CH2
A-198 SF5 H CI CH=CH2
A-199 SF5 H Br CH=CH2
A-200 SF5 H CFs CH=CH2
A-201 F H F C≡CH
A-202 F F F C≡CH
A-203 F CI F C≡CH
A-204 F Br F C≡CH
A-205 F H CI C≡CH
A-206 F H Br C≡CH
A-207 CI H CI C≡CH
A-208 CI CI CI C≡CH
A-209 CI F CI C≡CH
A-210 CI Br CI C≡CH
A-21 1 CI H Br C≡CH
A-212 Br H Br C≡CH
A-213 Br F Br C≡CH
A-214 Br CI Br C≡CH
A-215 CFs H F C≡CH
A-216 CFs H CI C≡CH
A-217 CFs H Br C≡CH
A-218 CFs H CFs C≡CH
A-219 CFs F F C≡CH
A-220 CFs CI CI C≡CH
A-221 CFs Br Br C≡CH
A-222 SF5 H F C≡CH
A-223 SF5 H CI C≡CH
A-224 SF5 H Br C≡CH
A-225 SF5 H CFs C≡CH
A-226 F H F cCsH5 *
A-227 F F F cCsH5 *
A-228 F CI F cCsH5 *
A-229 F Br F cCsH5 *
A-230 F H CI cCsH5 *
A-231 F H Br cCsH5 * R2a R2b R2c R4
A-232 CI H CI cCsH5 *
A-233 CI CI CI cCsH5 *
A-234 CI F CI cCsH5 *
A-235 CI Br CI cCsH5 *
A-236 CI H Br cCsH5 *
A-237 Br H Br cCsH5 *
A-238 Br F Br cCsH5 *
A-239 Br CI Br cCsH5 *
A-240 CFs H F cCsH5 *
A-241 CFs H CI cCsH5 *
A-242 CFs H Br cCsH5 *
A-243 CFs H CFs cCsH5 *
A-244 CFs F F cCsH5 *
A-245 CFs CI CI cCsH5 *
A-246 CFs Br Br cCsH5 *
A-247 SF5 H F cCsH5 *
A-248 SF5 H CI cCsH5 *
A-249 SF5 H Br cCsH5 *
A-250 SF5 H CFs cCsH5 *
A-251 F H F F
A-252 F F F F
A-253 F CI F F
A-254 F Br F F
A-255 F H CI F
A-256 F H Br F
A-257 CI H CI F
A-258 CI CI CI F
A-259 CI F CI F
A-260 CI Br CI F
A-261 CI H Br F
A-262 Br H Br F
A-263 Br F Br F
A-264 Br CI Br F
A-265 CFs H F F
A-266 CFs H CI F
A-267 CFs H Br F
A-268 CFs H CFs F R2a R2b R2c R4
A-269 CFs F F F
A-270 CFs CI CI F
A-271 CFs Br Br F
A-272 SF5 H F F
A-273 SF5 H CI F
A-274 SF5 H Br F
A-275 SF5 H CFs F
A-276 F H F CI
A-277 F F F CI
A-278 F CI F CI
A-279 F Br F CI
A-280 F H CI CI
A-281 F H Br CI
A-282 CI H CI CI
A-283 CI CI CI CI
A-284 CI F CI CI
A-285 CI Br CI CI
A-286 CI H Br CI
A-287 Br H Br CI
A-288 Br F Br CI
A-289 Br CI Br CI
A-290 CFs H F CI
A-291 CFs H CI CI
A-292 CFs H Br CI
A-293 CFs H CFs CI
A-294 CFs F F CI
A-295 CFs CI CI CI
A-296 CFs Br Br CI
A-297 SF5 H F CI
A-298 SF5 H CI CI
A-299 SF5 H Br CI
A-300 SF5 H CFs CI
A-301 F H F Br
A-302 F F F Br
A-303 F CI F Br
A-304 F Br F Br
A-305 F H CI Br R2a R2b R2c R4
A-306 F H Br Br
A-307 CI H CI Br
A-308 CI CI CI Br
A-309 CI F CI Br
A-310 CI Br CI Br
A-31 1 CI H Br Br
A-312 Br H Br Br
A-313 Br F Br Br
A-314 Br CI Br Br
A-315 CFs H F Br
A-316 CFs H CI Br
A-317 CFs H Br Br
A-318 CFs H CFs Br
A-319 CFs F F Br
A-320 CFs CI CI Br
A-321 CFs Br Br Br
A-322 SF5 H F Br
A-323 SF5 H CI Br
A-324 SF5 H Br Br
A-325 SF5 H CFs Br
A-326 F H F CN
A-327 F F F CN
A-328 F CI F CN
A-329 F Br F CN
A-330 F H CI CN
A-331 F H Br CN
A-332 CI H CI CN
A-333 CI CI CI CN
A-334 CI F CI CN
A-335 CI Br CI CN
A-336 CI H Br CN
A-337 Br H Br CN
A-338 Br F Br CN
A-339 Br CI Br CN
A-340 CFs H F CN
A-341 CFs H CI CN
A-342 CFs H Br CN
Figure imgf000125_0001
Figure imgf000126_0001
R2a R2b R2c R4
A-417 CFs H Br OCH(CHs)2
A-418 CFs H CFs OCH(CHs)2
A-419 CFs F F OCH(CHs)2
A-420 CFs CI CI OCH(CHs)2
A-421 CFs Br Br OCH(CHs)2
A-422 SF5 H F OCH(CHs)2
A-423 SF5 H CI OCH(CHs)2
A-424 SF5 H Br OCH(CHs)2
A-425 SF5 H CFs OCH(CHs)2
A-426 F H F OCH2CH=CH2
A-427 F F F OCH2CH=CH2
A-428 F CI F OCH2CH=CH2
A-429 F Br F OCH2CH=CH2
A-430 F H CI OCH2CH=CH2
A-431 F H Br OCH2CH=CH2
A-432 CI H CI OCH2CH=CH2
A-433 CI CI CI OCH2CH=CH2
A-434 CI F CI OCH2CH=CH2
A-435 CI Br CI OCH2CH=CH2
A-436 CI H Br OCH2CH=CH2
A-437 Br H Br OCH2CH=CH2
A-438 Br F Br OCH2CH=CH2
A-439 Br CI Br OCH2CH=CH2
A-440 CFs H F OCH2CH=CH2
A-441 CFs H CI OCH2CH=CH2
A-442 CFs H Br OCH2CH=CH2
A-443 CFs H CFs OCH2CH=CH2
A-444 CFs F F OCH2CH=CH2
A-445 CFs CI CI OCH2CH=CH2
A-446 CFs Br Br OCH2CH=CH2
A-447 SF5 H F OCH2CH=CH2
A-448 SF5 H CI OCH2CH=CH2
A-449 SF5 H Br OCH2CH=CH2
A-450 SF5 H CFs OCH2CH=CH2
A-451 F H F 0-cCsH5 *
A-452 F F F 0-cCsH5 *
A-453 F CI F 0-cCsH5 *
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
R2a R2b R2c R4
A-602 F F F SCH(CHs)2
A-603 F CI F SCH(CHs)2
A-604 F Br F SCH(CHs)2
A-605 F H CI SCH(CHs)2
A-606 F H Br SCH(CHs)2
A-607 CI H CI SCH(CHs)2
A-608 CI CI CI SCH(CHs)2
A-609 CI F CI SCH(CHs)2
A-610 CI Br CI SCH(CHs)2
A-61 1 CI H Br SCH(CHs)2
A-612 Br H Br SCH(CHs)2
A-613 Br F Br SCH(CHs)2
A-614 Br CI Br SCH(CHs)2
A-615 CFs H F SCH(CHs)2
A-616 CFs H CI SCH(CHs)2
A-617 CFs H Br SCH(CHs)2
A-618 CFs H CFs SCH(CHs)2
A-619 CFs F F SCH(CHs)2
A-620 CFs CI CI SCH(CHs)2
A-621 CFs Br Br SCH(CHs)2
A-622 SF5 H F SCH(CHs)2
A-623 SF5 H CI SCH(CHs)2
A-624 SF5 H Br SCH(CHs)2
A-625 SF5 H CFs SCH(CHs)2
A-626 F H F SCH2CH=CH2
A-627 F F F SCH2CH=CH2
A-628 F CI F SCH2CH=CH2
A-629 F Br F SCH2CH=CH2
A-630 F H CI SCH2CH=CH2
A-631 F H Br SCH2CH=CH2
A-632 CI H CI SCH2CH=CH2
A-633 CI CI CI SCH2CH=CH2
A-634 CI F CI SCH2CH=CH2
A-635 CI Br CI SCH2CH=CH2
A-636 CI H Br SCH2CH=CH2
A-637 Br H Br SCH2CH=CH2
A-638 Br F Br SCH2CH=CH2 R2a R2b R2c R4
A-639 Br CI Br SCH2CH=CH2
A-640 CFs H F SCH2CH=CH2
A-641 CFs H CI SCH2CH=CH2
A-642 CFs H Br SCH2CH=CH2
A-643 CFs H CFs SCH2CH=CH2
A-644 CFs F F SCH2CH=CH2
A-645 CFs CI CI SCH2CH=CH2
A-646 CFs Br Br SCH2CH=CH2
A-647 SF5 H F SCH2CH=CH2
A-648 SF5 H CI SCH2CH=CH2
A-649 SF5 H Br SCH2CH=CH2
A-650 SF5 H CFs SCH2CH=CH2
A-651 F H F S-cCsH5 *
A-652 F F F S-cCsH5 *
A-653 F CI F S-cCsH5 *
A-654 F Br F S-cCsH5 *
A-655 F H CI S-cCsH5 *
A-656 F H Br S-cCsH5 *
A-657 CI H CI S-cCsH5 *
A-658 CI CI CI S-cCsH5 *
A-659 CI F CI S-cCsH5 *
A-660 CI Br CI S-cCsH5 *
A-661 CI H Br S-cCsH5 *
A-662 Br H Br S-cCsH5 *
A-663 Br F Br S-cCsH5 *
A-664 Br CI Br S-cCsH5 *
A-665 CFs H F S-cCsH5 *
A-666 CFs H CI S-cCsH5 *
A-667 CFs H Br S-cCsH5 *
A-668 CFs H CFs S-cCsH5 *
A-669 CFs F F S-cCsH5 *
A-670 CFs CI CI S-cCsH5 *
A-671 CFs Br Br S-cCsH5 *
A-672 SF5 H F S-cCsH5 *
A-673 SF5 H CI S-cCsH5 *
A-674 SF5 H Br S-cCsH5 *
A-675 SF5 H CFs S-cCsH5 *
Figure imgf000134_0001
Figure imgf000135_0001
* CC3H5 = cyclopropyl
Among the above compounds, preference is given to compounds la.1 , la.13, la.17, la.19 and la.20 and especially to la.13.
The compounds of the formula (I) can be prepared by novel methods as described below or and in the synthesis descriptions of the working examples, or by standard methods of organic chemistry, e.g. by the methods described hereinafter or in the synthesis descriptions of the working examples. The substituents, variables and indices are as defined above for formula (I), if not otherwise specified.
The invention relates to a method for preparing compounds of formula I as defined in any of the preceding claims, where however R3b is hydrogen, which method comprises dehydrating a compound of formula II
Figure imgf000135_0002
wherein B1, B2, B3, G1, G2, G3, G4, R1, R3a and R3b are as defined above and A is A or a precursor of A;
to give a compound Γ
Figure imgf000136_0001
and, if necessary (i.e. if A' is a precursor of A), converting the group A into a group A.
A' as a precursor of A is typically a halogen atom, CN, carboxy, tert-butoxycarbonyl, an acetale group, a protected aldehyde group or -OS02-Rz1, where Rz1 is Ci-C4-alkyl, Ci- C4-haloalkyl or phenyl which may be substituted by 1 , 2 or 3 radicals selected from Ci- C4-alkyl, Ci-C4-haloalkyl Ci-C4-alkoxy or Ci-C4-haloalkoxy. A' as a precursor of A is preferably a halogen atom or -OS02-Rz1, where Rz1 is as defined above, and is more preferably a halogen atom or Otriflate.
Dehydration either occurs spontaneously or with the help of dehydrating agents, such as molecular sieves, acid-washed molecular sieves, magnesium sulfate, sodium sulfate, silica gel, SOC , POC , Burgess reagent, trifluoroacetic anhydride, p-toluene sulfonic acid, anhydrous HCI or sulfuric acid. Preferably, p-toluene sulfonic acid or acid- washed molecular sieves are used. The water formed may alternatively be removed, e.g. by azeotropic distillation, e.g. with benzene/toluene as entrainer, e.g. using a Dean Stark trap.
The compound of formula II, in which R3b is hydrogen, is preferably obtained by reacting a compound of formula IV
Figure imgf000136_0002
with an amination agent to give a compound of formula III
Figure imgf000137_0001
which reacts spontaneously to the compound II;
wherein B1, B2, B3, G1, G2, G3, G4, R1 and R3a are as defined above and A' is A or a precursor of A.
Depending on the amination agents used, amination can the carried out in a one step reaction, wherein compound IV reacts directly to compound III, or as a two step reaction, wherein the SH group of compound IV is first oxidized to a S-CI group, which then further reacts to a S-Nhb group, thus giving compound III.
Suitable amination agents for the one step reaction are for example HOSA (hydroxyla- mine-O-sulfonic acid), which is generally used in the presence of a base (suitable bases being for example sodium hydrogen phosphate, potassium hydrogen phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methanolate, triethylamine and the like), 0-(diphenylphosphoryl)hydroxyl amine, , which is generally also used in the presence of a base (suitable bases being for example sodium hydrogen phosphate, potassium hydrogen phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methanolate, triethylamine and the like), 2,4-dinitrophenylhydroxyl amine, O- mesitylensulfonylhydroxylamine and 2-oxa-1 -azaspiro[2.5]octane, among which HOSA and 0-(diphenylphosphoryl)hydroxyl amine are preferred.
The amination is preferably carried out in a solvent, suitable solvents being for example chlorinated alkanes, such as methylene chloride or chloroform, aromatic solvents, such as benzene, toluene, the xylenes, chlorobenzene or dichlorobenzene, and ethers, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylene- gylcol dimethylether, tetrahydrofuran (THF) or dioxane and the like.
The reaction is suitably carried out low temperature, e.g. at from -100 to 0°C or -78 to 0°C. Generally, the compound IV is dispersed in a solvent and cooled to the desired temperature and the base is added followed by the amination agent, or the amination agent is added followed by the base, or base and amination agent are added simultaneously.
In a preferred embodiment, HOSA is used in combination with an amine base, such as triethylamine. In this case, it is preferred to cool compound IV to -30 to 0°C, preferably - 20 to -10°C, to add the amine base at this temperature and then HOSA and keep the reaction at approximately -10 to 0°C.
In an alternatively preferred embodiment, 0-(diphenylphosphoryl)hydroxyl amine is used in combination with a base, preferably with an inorganic base, such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate and specifically sodium hydrogen phosphate. In this case, it is preferred to cool compound IV to -80 to -30°C, preferably - 80 to -70°C, to add the base at this temperature and then O- (diphenylphosphoryl)hydroxyl amine and keep the reaction at approximately 0°C to room temperature. In the two step reaction, the compound IV is first reacted with a chlorination agent which converts the SH group into an S-CI group. Suitable chlorination agents are for example sulfurylchloride, N-chloro succinimide (NCS), sodium hypochlorite, monochlo- roamine (NH2CI) or chlorine, which is preferably used in the presence of FeC . The chlorination can be carried out in analogy to the method described in Synthesis 1987, 1987, 683-688, Tetrahedron 66(36), 2010, 7279-7287, J. Org. Chem. 59(4), 1994, 914- 921 , J. Org. Chem. 63, 1998, 4878-4888 or J. Chem Soc. 1938, 21 14-21 17.
The chlorination is generally carried out in a solvent. Suitable solvents are for example ethers, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylenegylcol dimethylether, tetrahydrofuran or dioxane.
The reaction temperature can vary over wide ranges and is generally from 0°C to the boiling point of the reaction mixture (if a solvent is used). The chlorinated compound is then reacted without isolation with ammonia or ammonium hydroxide. If anhydrous ammonia is used, the reaction is generally carried out at from -78 to - 33°C. If aqueous ammonia or ammonium hydroxide is used, the reaction can also be carried out at higher temperatures, such as 0 to 25°C. The reaction is generally carried out in a solvent. Suitable solvents are for example the above-listed ethers, among which the water-miscible ethers, such as THF and dioxane, are preferred. In general, the chlorinated compound is dissolved in a solvent to which ammonia or ammonium hydroxide is added. The reaction can be carried out as described, for example, in Synthesis, 1987, 8, 683-688.
The chlorination/amination can also be carried as a one pot reaction. For example, the thiol IV is reacted simultaneously with a chlorinating agent (such as NCS or aqueous sodium hypochlorite) and anhydrous or aqueous ammonia in ethereal solvents (such as THF or Et20) or water. Preferred is the reaction with NCS in a mixture of THF and anhydrous liquid ammonia at -33°C. For instance, a solution of the thiol IV in THF is added to a solution of NCS (N-chlorosuccinimide) in THF/liquid ammonia at -78°C. The solution is warmed to -30°C and stirred until the ammonia has evaporated. Alternatively, at 0°C, a solution of the sodium thiolate (NaSR) in water is added to a mixture of aqueous ammonia (25%) and aqueous sodium hypochlorite (1 N). The one pot chlorin- ation/amination reaction can be carried out as described, for example, in Tetrahedron 2010, 66, 7279-7287 or in J. Org. Chem. 1994, 59, 914-921.
Compound III can virtually not be isolated as it generally reacts spontaneously in a ring-closing reaction to compound II.
The compound of formula IV is preferably prepared by reacting a compound of formula
V
Figure imgf000139_0001
wherein B1, B2, B3, G1, G2, G3, G4, R1 and R3a are as defined in any of claims 1 to 32 and A' is A or a precursor of A; with a sulfur source.
Suitable sulfur sources are for example H2S, metal hydrogen sulfides, such as NaSH or KSH, metal sulfides, such as Na2S, K2S Li2S, Cu2S, MgS, CaS, CuS, FeS and the like, ammonium sulfide [(NH4)2S], tetraalkylammonium sulfides (R4NSH), such as tetrame- thylammonium sulfide, tetraethylammonium sulfide, tetrapropylammonium sulfide and the like, or bistrimethylsilyl sulfide.
H2S as a sulfur source is generally used in the presence of a base, such as Na2C03, K2C03, Cs2C03, sodium acetate, potassium acetate, cesium acetate, amines, such as diethylamine, dipropylamine, triethylamine, diisopropylethylamine and the like, or basic nitrogen-containing heterocycles, such as pyrrolidine, piperidine, piperazine, pyridine, lutidine and the like. Alternatively, H2S as a sulfur source can be used in the presence of a Lewis acid, such as AICIs or FeCI3.
The reaction of compound V with a sulfur source is generally carried out in a solvent, suitable solvents being for example chlorinated alkanes, such as methylene chloride or chloroform, and aromatic solvents, such as benzene, toluene, the xylenes, chloroben- zene or dichlorobenzene.
The reaction temperature can vary over a wide range, such as -78°C to room temperature.
In general, compound V is dissolved in a solvent, optionally cooled, then the base (if used) and subsequently the sulfur source is added
The compound V can alternatively be reacted with a sulfur source which provides a compound IV which is protected at the thiol group SH by a protective group (S-PG). This is advantageous if compound IV is for example subjected to harsher purification conditions or is derivatized, e.g. for converting the precursor group A' into a group A or for modifying group A at this stage. Moreover, purification of the protected product is easier.
Suitable sulfuration reagents which give such protected thiols are for example thiourea (NH2-C(=S)-NH2), optionally substituted benzyl thiols, such as benzylthiol, o- or p- methoxy-benzylthiol, o- or p-hydroxybenzylthiol, o- or p-acetoxybenzylthiol, o- or p- nitrobenzylthiol or 2,4,6-trimethylbenzylthiol, pyridin-4-yl-methylthiol, quinolin-2-yl- methylthiol, benzyl metal sulfides, such as sodium benzylsulfide, phenylthiol, 2,4- dinitrophenylthiol, tritylthiol, tert-butylthiol, compounds of formula R-C(=0)-NH-CH3-SH, wherein R is methyl, tert-butyl, allyl, phenyl or benzyl, 2-trimethylsilanyl-ethanethiol, 2- (2,4-dinitrophenyl)-ethanethiol, 2-phenylsulfonyl-ethanethiol, acylated thiols, such as methylcarbonylthiol or phenylcarbonylthiol, and thiocarbamates R-NH-C(=0)-SH, wherein R is e.g. methyl or ethyl.
The benzyl and alkyl thiols are generally used in the presence of a base, such as sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium hydrogenphosphate, potassium hydrogenphosphate, sodium carbonate, potassium carbonate, caesium carbonate, sodium hydride, potassium hydride, lithium diisopropyl amide (LDA), sodium methanolate, sodium ethanolate, potassium tert-butoxide, aqueous sodium tetraborate, n-butyllithium, tert-butylithium, tetrabutylammoniumfluoride (TBAF), NaHMDS and the like, or in the presence of a Lewis or Bronsted acid, such as FeCIs, Zn(CI04)2, Cu(BF4)2, HBF4 or HCI04.
The reaction is preferably carried out in a solvent, suitable solvents being for example chlorinated alkanes, such as methylene chloride or chloroform, and ethers, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylenegylcol dimethylether, tetrahydrofuran (THF) or dioxane and the like.
The reaction temperature can vary over a wide range, such as from -25°C to the boiling point of the reaction mixture.
The acylated thiols can be reacted neat or in a solvent, suitable solvents being for ex- ample chlorinated alkanes, such as methylene chloride or chloroform, and ethers, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylenegylcol dimethylether, tetrahydrofuran (THF) or dioxane and the like. They can be used with or without a base. The S-protected compound IV can then be deprotected to the free thiol IV under conditions generally known for the respective protective group, such as described, for example, in Peter G. M. Wuts, Theodora Greene, Protective Groups in Organic Synthesis, 4th edition, John Wiley & Sons, Inc., 2007, Chapter 6. Among the above sulfur sources, preference is given to H2S, especially used in the presence of a base, such as Na2C03, K2CO3, CS2CO3, sodium acetate, potassium acetate, cesium acetate, amines, such as diethylamine, dipropylamine, triethylamine, diisopropylethylamine and the like, or basic nitrogen-containing heterocycles, such as pyrrolidine, piperidine, piperazine, pyridine, lutidine and the like, and preferably in the presence of an amine, such as triethylamine.
In a preferred embodiment of the method of the invention, the reaction of compound IV to compound Γ via compounds III and II is carried out as a one-pot reaction.
In an alternatively preferred embodiment of the method of the invention, the reaction of compound V to compound Γ via compounds IV, III and II is carried out as a one-pot reaction.
Compound V can be prepared in analogy to the method described in EP-A-2172462.
Compounds II (in which R3b is not necessarily hydrogen) can be prepared alternatively by reacting a compound of formula VII
Figure imgf000142_0001
with an amination agent to give a compound of formula VI
Figure imgf000142_0002
which reacts spontaneously to the compound II;
wherein B1, B2, B3, G1, G2, G3, G4, R1, R3a and R3b are as defined above and A' is A or a precursor of A.
The reaction can be carried out in analogy to that of compounds IV and III The compound of formula VII is preferably obtained by reacting a compound of formula VIII with a compound of formula IX
Figure imgf000143_0001
The reaction is preferably carried out as a Mukaiyama aldol reaction. To this purpose, the trialklysilyl-enolate derivative of IX is reacted with VIII in the presence of a Lewis acid, such as TiCU or BF3[0(C2H5)2]. Alternatively, the reaction can be carried out in the presence of a strong base, such as lithium diisopropylamide (LDA), sodium bistrime- thylsilylamide (sodium hexamethyldisilazide; NaHMDS) and amines, such as triethyla- mine, tripropylamine or diisopropylethylamine.
The reaction is generally carried out in a solvent.
If a lithium or sodium base is used, the solvent is suitably an ether, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylenegylcol di- methylether, tetrahydrofuran (THF) or dioxane and the like. Suitable reaction temperatures range from -78 to 25°C.
If an amine base is used, the solvent is suitably an ether, such as diethylether, dipropylether, methyl tert-butylether, methyl isobutylether, ethylenegylcol dimethylether, tetrahydrofuran (THF) or dioxane, or an alkane, such as pentane, hexane or heptane. Suitable reaction temperatures range from 25 to 100°C.
The compound of formula VIII can be obtained by reacting a compound of formula X with a sulfuration agent, such as Lawesson's reagent or P2S5
Figure imgf000143_0002
The reaction is generally carried out in a solvent, suitable solvents being for example aromatic solvents, such as benzene, toluene, the xylenes, chlorobenzene or dichloro- benzene, ethers, such as diethylether, dipropylether, methyl tert-butylether, methyl iso- butylether, ethylenegylcol dimethylether, tetrahydrofuran (THF) or dioxane, and hexa- methyl phosphoric acid triamide (HMPA).
The reaction is generally carried out at a temperature of from 25°C to the boiling point of the reaction mixture.
The invention further relates to a method for preparing compounds of formula I as defined above, wherein R1 is CF3, which method comprises reacting a compound of for- mula XI
Figure imgf000144_0001
wherein B1, B2, B3, G1, G2, G3, G4, R3a and R3b are as defined above and A' is A or a precursor of A;
with a fluorinating agent
to give a compound I"
Figure imgf000144_0002
and, if necessary (i.e. if A is a precursor of A), converting the group A into a group A.
Suitable fluorinating agents are, for example, SF4, preferably in combination with HF or BF3[0(C2H5)2], phenylsulfur trifluoride (Ph-SFs), preferably in combination with HF and pyridine, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride ("Fluoled"), and bis(2- methoxyethyl)aminosulfur trifluoride [(CHsOChbCI-b^NSFs]. Among these, preference is given to SF4 in combination with HF.
If SF4 in combination with HF is used, the reaction is carried out neat, i.e. without any further solvent. The reaction is generally carried out under elevated pressure stemming from the reactants, e.g. at a pressure of from 2 to 10 bar, preferably from 5 to 8 bar. The reaction temperature can vary over wide ranges, such as from 25 to 120°C, preferably from 60 to 100°C. Alternatively, fluorination can be carried out by a two step method, in which the carbox- yl group on the isothiazoline ring is first converted into a CC group, and this is subsequently fluorinated to the CF3 group.
The conversion of the COOH group to the CCI3 group is preferably carried out by reacting the compound VI with PCI5 and phenyl-phosphoroxy dichloride (Ph-P(=0)Cl2).
The reaction can be carried out neat, i.e. without any further solvent. Suitably, the reac- tion is carried out at elevated temperatures, for example at from 50° to reflux and preferably at reflux.
Fluorination agents for converting the CCI3 group into a CF3 group are those mentioned above, and further HF and HF in combination with SbCIs and HF in combination with Cl2 and SbF3.
The reaction can be carried out neat, i.e. without any further solvent. The reaction temperature can vary over wide ranges, for examples from 25 to 300°C, preferably from 50 to 200°C and in particular from 80 to 120°C. If the fluorination agent is HF or HF in combination with a further agent, the reaction generally takes place at the pressure stemming from HF and ranging generally from 2 to 10 bar, preferably from 5 to 8 bar.
The compound of formula XI is preferably obtained by hydrolyzing a compound of formula XII
Figure imgf000145_0001
wherein B1, B2, B3, G1, G2, G3, G4, R3a and R3b are as defined above, A is A or a precursor of A and R is Ci-C4-alkyl.
Hydrolysis can be carried out by any suitable means known for hydrolyzing ester groups, such as acidic conditions, e.g. using hydrochloric acid, hydrobromic acid, sulfuric acid, trifluoroacetic acid, etc., or by basic conditions, e.g. using an alkali metal hydroxide, such as LiOH, NaOH or KOH, or an alkali metal carbonate, such as sodium or potassium carbonate. The compound of formula XII is in turn preferably obtained by reacting a compound XIII with a compoun
Figure imgf000146_0001
wherein B1, B2, B3, G1, G2, G3, G4, R1, R3a and R3b are as defined above, A' is A or a precursor of A and R is Ci-C4-alkyl.
The reaction is carried out at elevated temperature, e.g. at from 90 to 200°C, preferably from 100 to 180°C and in particular from 120 to 160°C, e.g. at about 140°C. The compound of formula XIII can in turn be obtained by reacting a compound XVI with a compound XVII
Figure imgf000146_0002
(XVI) (XVII) The reaction is generally carried out in a solvent, suitable solvents being for example aromatic solvents, such as benzene, toluene, the xylenes, chlorobenzene and dichlo- robenzene. The reaction temoerature is preferably from 80 to 140°C, more preferably from 100 to 120°C. The invention further relates to a method for preparing compounds of formula I as defined above, wherein however R1 is CF3, which method comprises reacting a compound of formula XIII as define mula XV
Figure imgf000146_0003
wherein B1, B2, B3, R3a and R3b are as defined above,
to give a compound I"
Figure imgf000147_0001
and, if necessary, converting the group A' into a group A.
The reaction is carried out at elevated temperature, e.g. at from 90 to 200°C, preferably from 100 to 180°C and in particular from 120 to 160°C, e.g. at about 140°C.
Compounds Γ or I", in which A is a precursor of A can be converted as shown below into the different groups A1 to A4. Compounds Γ or I", in which A is CI, Br, I or -OS02-Rz1, where Rz1 is as defined above, can be converted to compounds I wherein A is a group A1, wherein A1 is an imino group -C(=NR6)R8, by reaction with carbon monoxide and a hydride source, such as triethylsilane, in the presence of a transition metal complex catalyst, preferably a palladium catalyst, to a carbonyl compound XVIII. This reaction converts the starting group A into a carbonyl grou
Figure imgf000147_0002
The aldehyde XVIII can also be obtained by reducing the methyl ester XXI (see below; R = methyl) with diisobutylaluminium hydride (DIBAL-H) either directly to the aldehyde XVIII or via the corresponding alcohol, which is then oxidized to the aldehyde.
For obtaining compounds in which R8 in the imino group is H, such carbonyl compounds XVIII are then reacted with an amine (derivative) NH2R6. Alternatively, the compound Γ or I", in which A is CI, Br, I or -OS02-Rz1, where Rz1 is as defined above, can be reacted in a one pot reaction with carbon monoxide and hydrogen in the presence of a transition metal complex catalyst and the amine NH2R6. For obtaining compounds in which R8 in the imino group is not H, the carbonyl compounds are reacted with a Grignard reagent R8-MgHal, where Hal is CI, Br or I, or an organolithium compound R8-Li to obtain an alcohol of formula XIX
Figure imgf000148_0001
which is then oxidized to a carbonyl compound of the formula XX
Figure imgf000148_0002
This is then reacted with an amine NH2R6 to the respective imine compound.
These reactions can be carried out in analogy to the methods described in PCT/EP 201 1/060388 or in WO 2010/072781 and the references cited therein, especially WO 2006135763, Fattorusso et al, J. Med. Chem. 2008, 51 , 1333-1343 and WO
2008/122375.
Compounds I wherein A is a group A1, wherein A1 is -S(0)nR9 or -N(R5)R6, can for ex- ample be prepared by reacting a compound Γ or I" wherein A' is CI, Br or I in a
Ullmann-type reaction with an amine NHR5R6 or a thiol SHR9 in the presence of a Cu(l) catalyst. To obtain a compound wherein A1 is -S(0)nR9 wherein n is not 0 the thiol can then be oxidized, e.g. with hydrogen peroxide. Amine and thiol groups can further be introduced in a Buchwald-Hartwig reaction by reacting a compound Γ or I" wherein A' is CI, Br or I with an amine NHR5R6 or a thiol HSR9 in the presence of a palladium catalyst, such as PdC (dppf) in the presence of a base, such as cesium carbonate or N,N- diisopropylethyl amine, and optionally in the presence of a phosphine ligand, such as Xantphos ("4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene").
Thioethers (A1 = -SR9) can further be introduced by reacting a compound Γ or I" wherein A' is F in an SNAr reaction (nucleophilic aromatic substitution reaction) with a thiol HSR9 in the presence of a base, such as potassium carbonate (K2CO3), or with a thio- late (e.g. NaSR9).
Compounds I wherein A is a group A2, wherein W is O and Y is OR9 can be prepared by reacting a compound Γ or I" wherein A' is CI, Br, I or Otriflate with carbon monoxide in the presence of a palladium catalyst and an alcohol R9OH. Compounds I wherein A is a group A2, wherein W is O and Y is NR5R6 can be prepared by reacting a compound Γ or I" wherein A' is CI, Br, I or Otriflate with carbon monoxide in the presence of a palladium catalyst and an alcohol ROH, wherein R is Ci-C4-alkyl, to a compound of formu- la XXI. Suitable palladium catalysts are for example those described in PCT/EP 201 1/060388.
Figure imgf000149_0001
This ester is then hydrolyzed to the respective carboxylic acid, which is the reacted under standard amidation conditions with an amine NHR5R6. Hydrolyzation can be car- ried out under standard conditions, e.g. under acidic conditions using for example hydrochloric acid, sulfuric acid or trifluoroacetic acid, or under basic conditions using for example an alkali metal hydroxide, such as LiOH, NaOH or KOH. Amidation is preferably carried out by activation of the carboxylic acids with oxalylchloride [(COCI)2] or thio- nylchloride (SOC ) to the respective acid chlorides, followed by reaction with an amine NHR5R6. Alternatively, amidation is carried out in in the presence of a coupling reagent. Suitable coupling reagent (activators) are well known and are for instance selected from carbodiimides, such as DCC (dicyclohexylcarbodiimide) and DCI (diisopropylcar- bodiimide), benzotriazol derivatives, such as HATU (0-(7-azabenzotriazol-1 -yl)- Ν,Ν,Ν',Ν'-tetramethyluronium hexafluorophosphate), HBTU ((O-benzotriazol-1 -yl)- Ν,Ν,Ν',Ν'-tetramethyluronium hexafluorophosphate) and HCTU (1 H-benzotriazolium-1 - [bis(dimethylamino)methylene]-5-chloro tetrafluoroborate) and phosphonium-derived activators, such as BOP ((benzotriazol-1 -yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate), Py-BOP ((benzotriazol-l -yloxy)-tripyrrolidinphosphonium hexafluorophosphate) and Py-BrOP (bromotripyrrolidinphosphonium hexafluorophosphate). Generally, the activator is used in excess. The benzotriazol and phosphonium coupling reagents are generally used in a basic medium. Compounds I wherein A is a group A2, wherein W is S and Y is NR5R6 or OR9, can be prepared by reacting the corresponding oxo-compound (W is O) with Lawesson's reagent (CAS 19172-47-5), see for example Jesberger et al., Synthesis, 2003, 1929-1958 and references therein. For compounds wherein Y is NR5R6, solvents such as HMPA or THF at an elevated temperature such as 60°C to 100°C can be used. Preferred reaction conditions are THF at 65°C. For compounds wherein Y is OR9, solvent free conditions or solvents such as toluene at temperatures such as 100°C to 200°C, preferably 140°C, are suitable reaction conditions. Compounds I wherein A is a group A3, wherein R7a and R7b are hydrogen, can be prepared by reducing a compound XXI or XVIII for example with LAH (lithium aluminium hydride) or DIBAL-H (diisobutyl aluminium hydride) to a compound XXII.
Figure imgf000150_0001
This is then reacted in an SN reaction with an amine NHR5R6. For this purpose, the OH group can first be converted into a better leaving group, e.g. into a sulfonate (for example mesylate, tosylate or a triflate group). If R6 is a group -C(0)R8, it is alternatively possible to react compound XXII with an amine N H2R5 and react then the resulting benzylic amine with an acid R8-COOH or a derivative thereof, such as its acid chloride R8-COCI, in an amidation reaction.
Compounds I wherein A is a group A3, wherein R7a is optionally substituted alkyl or optionally substituted cycloalkyl and R7b is hydrogen, can be prepared by subjecting a ketone XX, in which R8 corresponds to R7a which is optionally substituted Ci-C6-alkyl c optionally substituted Cs-Cs-cycloalkyl, to a reductive amination to furnish compounds XXIII. Typical conditions for the reductive amination are: Reacting ketone XX with an amine H2N R5 to yield the corresponding imine which is reduced to amine XIII with a reducing agent reagent such as Na(CN)BH3. The reaction from ketone XX to amine XXIII may also be carried out as a one pot procedure. (XXIII)
For obtaining compounds in which R7a and R7b are optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl or optionally substituted alkynyl, carbonyl compounds such as XX, in which R8 corresponds to R7a which is optionally substituted Ci-C6-alkyl, optionally substituted Cs-Cs-cycloalkyl, optionally substituted C2-C6-alkenyl or optionally substituted C2-C6-alkynyl, is reacted with a Grignard reagent R7b-MgHal, where Hal is CI, Br or I, or an organolithium compound R7b-Li, where R7b is optionally substituted Ci-C6-alkyl, optionally substituted Cs-Cs-cycloalkyl, optionally substituted C2-C6-alkenyl or optionally substituted C2-C6-alkynyl, to obtain an alcohol of formula XXIV.
Figure imgf000151_0001
Alcohol XXIV can then be converted into amine XXV via the corresponding azide, as described, for example 48.
Figure imgf000151_0002
If desired, this can be converted into compounds I wherein R5 and R6 are different from hydrogen, for example by standard alkylation reactions.
Compounds I wherein A is a group A3, wherein R7a is optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or CN and R7b is hydrogen, can be prepared by converting an aldehyde XVIII into an imine XXVI by reaction with an amine derivative NH2R6, wherein R6 is tert-butyl sulfinyl, or, for preparing a compound with R7a = CN, tosylate.
Figure imgf000152_0001
This imine is then reacted with a compound H-R7a in an addition reaction under condi- tions as described for example in J. Am. Chem. Soc. 2009, 3850-3851 and the references cited therein, or, for introducing CN as a group R7a, Chemistry - A European Journal 2009, 15, 1 1642-1 1659.
Compounds I wherein A is a group A3, wherein both R7a and R7b are optionally substi- tuted alkyl, alkenyl, alkynyl, cycloalkyl or CN, can be prepared analogously by converting a ketone XX, wherein R8 is has the meaning desired for R7b and is optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or CN, into an imine by reaction with an amine derivative NH2R6, wherein R6 is tert-butyl sulfinyl, or, for preparing a compound with R7a = CN, tosylate.
Figure imgf000152_0002
This imine is then reacted with a compound H-R7a in an addition reaction under condi- tions as described for example in J. Org. Chem 2002, 67, 7819-7832 and the references cited therein, or, for introducing CN as a group R7a, Chemistry - A European Journal 2009, 15, 1 1642-1 1659.
If desired, R6 can then be removed to yield an amino group NH2.
Compounds I wherein A is A4 can be prepared by standard ring coupling reactions. For example, compounds, wherein A4 is an N-bound heterocyclic ring can be prepared by reacting a compound Γ or I" wherein A' is CI, Br or I with the respective ring A4-H (H being on the nitrogen ring atom to be coupled) under Ullmann coupling conditions, such as described, for example, in WO 2007/075459. Typically, copper(l) iodide or copper(l) oxide and a ligand such as 1 ,2-cyclohexyldiamine is used, see for example Kanemasa et al., European Journal of Organic Chemistry, 2004, 695-709. If A' is F, the reaction is typically run in a polar aprotic solvent such as Ν,Ν-dimethylformamide, N,N- dimethylacetamide or N-methylpyrrolidone, and in the presence of an inorganic base such as sodium, potassium or cesium carbonate.
Compounds, wherein A4 is a C-bound heterocyclic ring can be prepared by reacting a compound Γ or I" wherein A is Br or I with the boronic acid of the respective ring A4- B(OH)2 or the boronate ester of the respective ring A4-B(OR2) under Suzuki reaction conditions via Pd-catalyzed cross coupling, such as described, for example, in WO 2007/075459. A typical catalyst is tetrakis(triphenylphosphine)palladium(0). Solvents such as tetrahydrofuran, acetonitrile, diethyl ether and dioxane are suitable. The boronic acids A4-B(OH)2 are either commercially available or can be prepared by known methods. Other methods for introduction of the heterocyclic groups A4 are the Heck, Stille, Kumada and Buchwald-Hartwig coupling procedures; see for example Tetrahedron, 2004, 60, 8991 -9016.
As a rule, the compounds of formula (I) including their stereoisomers, salts, and N- oxides, and their precursors in the synthesis process, can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula (I) can advantageously be pre- pared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.
Due to their excellent activity, the compounds of the present invention may be used for controlling invertebrate pests. Accordingly, the present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the present invention or a composition as defined above.
Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from invertebrate pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "sub- strate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated. In the sense of the present invention, "invertebrate pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes. In the sense of the present invention, "invertebrate pests" are most preferably insects. The invention further provides an agricultural composition for combating invertebrate pests, which comprises such an amount of at least one compound according to the invention and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may comprise a single active compound of the present invention or a mixture of several active compounds of the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers or a salt as well as individual tautomers or mixtures of tautomers.
The compounds of the present invention, including their salts, stereoisomers and tau- tomers, are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes. They are especially suitable for efficiently combating or controlling the following pests: Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chei- matobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosel- la, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliar- ia, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fis- cellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blan- cardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Pieris rapae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacio- nia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis; beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscur- us, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus po- morum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastopha- gus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus len- tis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthor- rhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vesperti- nus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunc- tata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brun- neipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptino- tarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobi- us pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus grana- ria; flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles mini- mus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrys- ops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phor- bia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Taba- nus similis, Tipula oleracea, and Tipula paludosa; thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g.
Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solu- bea insularis, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycau- dus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmanni- anae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lac- tucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalo- nicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi,
Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera au- rantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma spp., and Arilus critatus; ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Mon- omorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, So- lenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole meg- acephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula macula- ta, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile; crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina; arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hy- alomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holo- cyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis;
Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai,
Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ul- mi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa; fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata, millipedes (Diplopoda), e.g. Narceus spp.,
Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo- vicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. Collembola (springtails), e.g. Onychiurus ssp..
The compounds of the present invention, including their salts, stereoisomers and tau- tomers, are also suitable for controlling nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javani- ca, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, An- guina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bur- saphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Crico- nema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Helio- cotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Ro- tylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
The compounds of the present invention, including their salts, stereoisomers and tau- tomers, are particularly useful for controlling insects, preferably sucking or piercing and chewing and biting insects such as insects from the genera Lepidoptera, Coleoptera and Hemiptera, in particular Lepidoptera, Coleoptera and true bugs.
The compounds of the present invention, including their salts, stereoisomers and tau- tomers, are moreover useful for controlling insects of the orders Thysanoptera, Diptera (especially flies, mosquitos), Hymenoptera (especially ants) and Isoptera (especially termites.
The compounds of the present invention, including their salts, stereoisomers and tau- tomers, are particularly useful for controlling insects of the orders Lepidoptera and Coleoptera.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a pesticidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the species to be controlled, the treated cultivated plant or material, the climat- ic conditions and the specific compound I used.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emul- sions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F In- forma, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dis- persants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetra- hydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phospho- nates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kao- lins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in
McCutcheon' s, Vol.1 : Emulsifiers & Detergents, McCutcheon' s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sul- fonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccin- ates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinyl- alcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, poly- ethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or pol- ybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothia- zolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad
100 wt%. Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water- insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I according to the invention are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt%and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
iv) Microemulsion (ME)
5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable micro- emulsion.
iv) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dis- persed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of
poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4' - diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
ix) Dustable powders (DP, DS)
1 -10 wt% of a compound I according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%. x) Granules (GR, FG)
0.5-30 wt% of a compound I according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xi) Ultra-low volume liquids (UL)
1 -50 wt% of a compound I according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active sub- stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treamtent (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, prefera- bly 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate. In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances from the groups M) or F) (see below), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances from the groups M) or F) (see below), can be applied jointly (e.g. after tank mix) or consecutively. The following categorized list M of pesticides represents insecticidal mixture partners, which are, whenever possible, classified according to the Insecticide Resistance Action Committee (IRAC), and together with which the compounds according to the present invention may be used. The combined use of the compounds of the present invention with the following pesticides may result in potential synergistic effects. The following examples of insecticidal mixing partners are provided with the intention to illustrate the possible combinations, but not to impose any limitation to the obtainable mixtures:
M.1 Acetylcholine esterase (AChE) inhibitors from the class of
M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pi- rimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethopro- phos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, mala- thion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, prope- tamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vami- dothion;
M.2. GABA-gated chloride channel antagonists such as:
M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or
M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyra- fluprole and pyriprole;
M.3 Sodium channel modulators from the class of
M.3A pyrethroids, for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans alle- thrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imipro- thrin, meperfluthrin,metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyre- thrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or
M.3B sodium channel modulators such as DDT or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of
M.4A neonicotinoids, for example acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or
M.4B nicotine.
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or spinetoram; M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
M.7 Juvenile hormone mimics, such as
M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as
M.7B fenoxycarb, or
M.7C pyriproxyfen; M.8 miscellaneous non-specific (multi-site) inhibitors, for example
M.8A alkyl halides as methyl bromide and other alkyl halides, or
M.8B chloropicrin, or
M.8C sulfuryl fluoride, or
M.8D borax, or
M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, for example
M.9B pymetrozine, or
M.9C flonicamid;
M.10 Mite growth inhibitors, for example
M.10A clofentezine, hexythiazox and diflovidazin, or
M.10B etoxazole; M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebri- onis, or the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase, for example
M.12A diafenthiuron, or
M.12B organotin miticides such as azocydotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or
M.12D tetradifon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, for example chlorfenapyr, DNOC or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereis- toxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium; M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin;
M.17 Moulting disruptors, Dipteran, as for example cyromazine; M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfeno- zide, tebufenozide, halofenozide, fufenozide or chromafenozide;
M.19 Octopamin receptor agonists, as for example amitraz; M.20 Mitochondrial complex III electron transport inhibitors, for example
M.20A hydramethylnon, or
M.20B acequinocyl, or
M.20C fluacrypyrim; M.21 Mitochondrial complex I electron transport inhibitors, for example
M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad or tolfenpyrad, or
M.21 B rotenone; M.22 Voltage-dependent sodium channel blockers, for example
M.22A indoxacarb, or
M.22B metaflumizone;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, for example
M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or
M.24B cyanide.
M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen; M.28 Ryanodine receptor-modulators from the class of diamides, as
for example flubendiamide, chloranthraniliprole (rynaxypyr®), cyanthraniliprole (cyazypyr®), or the phthalamide compounds
M.28.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2-tetrafluor-1 -(trifluormethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and
M.28.2: (S)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2-tetrafluor-1 -(trifluormethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, or the compound
M.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3- chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide, or the compound
M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate;
M.X insecticidal active compounds of unknown or uncertain mode of action, as for example azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinome- thionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, or the compound
M.X.1 : 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl- N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-benzamide, or the compound
M.X.2: cyclopropaneacetic acid, l .l'- S^R^aR.eS.eaS.^R.^aS.^bSH-I^- cyclopropylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy- 4,6a, 12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)-2H , 1 1 H-naphtho[2, 1 -b]pyrano[3,4-e]pyran- 3,6-diyl] ester, or the compound
M.X.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]- tetradec-1 1 -en-10-one, or the compound
M.X.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en- 2-one, or the compound
M.X.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)- 1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582).
The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.
The phthalamides M.28.1 and M.28.2 are both known from WO 2007/101540. The an- thranilamide M.28.3 has been described in WO2005/077943. The hydrazide compound M.28.4 has been described in WO 2007/043677.-The quinoline derivative flometoquin is shown in WO2006/013896. The aminofuranone compounds flupyradifurone is known from WO 2007/1 15644. The sulfoximine compound sulfoxaflor is known from
WO2007/149134. The isoxazoline compound M.X.1 has been described in
WO2005/085216. The pyripyropene derivative M.X.2 has been described in WO 2006/129714. The spiroketal-substituted cyclic ketoenol derivative M.X.3 is known from WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.X.4 from WO2008/06791 1. Finally triazoylphenylsulfide like M.X.5 have been described in WO2006/043635 and biological control agents on basis of bacillus firmus in
WO2009/124707. The following list F of active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
F.I) Respiration Inhibitors
F.1-1 ) Inhibitors of complex III at Qo site (e.g. strobilurins)
strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chlorodin- carb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N methyl-acetamide;
oxazolidinediones and imidazolinones: famoxadone, fenamidone;
F.I-2) Inhibitors of complex II (e.g. carboxamides):
carboxanilides: benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopy- ram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5- carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyra- zole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H- pyrazole-4 carboxamide;
F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom;
F.I-4) Other respiration inhibitors (complex I, uncouplers)
diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam;
nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
F.ll) Sterol biosynthesis inhibitors (SBI fungicides)
F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;
imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
F.II-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines)
morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine;
F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;
F.lll) Nucleic acid synthesis inhibitors
F.III-1 ) RNA, DNA synthesis
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
isoxazoles and iosothiazolones: hymexazole, octhilinone;
F.III-2) DNA topisomerase inhibitors: oxolinic acid;
F.III-3) Nucleotide metabolism (e.g. adenosin-deaminase)
hydroxy (2-amino)-pyrimidines: bupirimate;
F.IV) Inhibitors of cell division and or cytoskeleton
F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine
F.IV-2) Other cell division inhibitors
benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopico- lide, zoxamide;
F.IV-3) Actin inhibitors: benzophenones: metrafenone;
F.V) Inhibitors of amino acid and protein synthesis
F.V-1 ) Mmethionine synthesis inhibitors (anilino-pyrimidines)
anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
F.V-2) Protein synthesis inhibitors (anilino-pyrimidines)
antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomy- cin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors
F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines)
dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
phenylpyrroles: fenpiclonil, fludioxonil;
F.VI-2) G protein inhibitors: quinolines: quinoxyfen;
F.VI I) Lipid and membrane synthesis inhibitors
F.VI 1-1 ) Phospholipid biosynthesis inhibitors
organophosphorus compounds: edifenphos, iprobenfos, pyrazophos;
dithiolanes: isoprothiolane;
F.VII-2) Lipid peroxidation
aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
F.VII-3) Carboxyl acid amides (CAA fungicides)
cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N- (1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; F.VII-4) Compounds affecting cell membrane permeability and fatty acides
carbamates: propamocarb, propamocarb-hydrochlorid
F.VIII) Inhibitors with Multi Site Action
F.VIII-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,
methasulphocarb, metiram, propineb, thiram, zineb, ziram;
F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N- (4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
F.VIII-4) Guanidines: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
F.VIII-5) Ahtraquinones: dithianon;
F.IX) Cell wall synthesis inhibitors
F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B;
F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil;
F.X) Plant defence inducers
F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl;
F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium;
phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusulfamide, flutianil, methasulfocarb, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-but- oxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy- 2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4-fluoro-3-trifluoro- methyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'- (5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}- thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)-amide, 2-{1 -[2- (5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, methoxy-acetic acid 6-tert- butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-Methyl-2-{1 -[(5-methyl-3-trifluoro- methyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 - yl]-4-thiazolecarboxamide, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyri- dine, pyrisoxazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1 car- bothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid am- ide, 5-chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chlo- ro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; F.XI) Growth regulators:
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegu- lac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri iodobenzoic acid, trinexapac-ethyl and uniconazole;
F.XI I) Biological control agents
antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest, Inc., USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. SONATA® and BALLAD® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product BOTRY- ZEN from BotriZen Ltd., New Zealand), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand).
The invertebrate pest (also referred to as "animal pest"), i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing or may grow can be contacted with the compounds of the present invention or composition(s) comprising them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the invertebrate pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (apply- ing the compounds/compositions to the locus of the invertebrate pest or plant).
The compounds of the present invention or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of the present invention. The term "crop" refers both to growing and harvested crops.
The compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sug- ar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insec- ticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
Moreover, invertebrate pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of the present invention. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
The compounds of the present invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of the present invention may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of the present invention. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of applica- tion, and the like.
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2. Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 5 g to 500 g per hectare, more desirably from 5 g to 200 g per hectare.
The compounds of the present invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
The compounds of the present invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of the present invention are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics. The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cock- roaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active ingredient.
Formulations of compounds of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are prefer- ably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethox- ylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzo- ate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, pro- pellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
The compounds of the present invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of the present invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tset- se-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knit- goods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-Diethyl-meta-toluamide (DEET), N,N- diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1 -yl-carbonyl)-2-methylpiperine, (2- hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methyl- neodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl- 2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl ver- satate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2- ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets. The compounds of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of the present invention are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like. The compounds of the present invention are also suitable for the treatment of plant propagation material, especially seeds, in order to protect them from insect pest, in particular from soil-living insect pests and the resulting plant' s roots and shoots against soil pests and foliar insects.
The compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant' s roots and shoots against soil pests and foliar insects. The protection of the resulting plant' s roots and shoots is preferred. More preferred is the protection of resulting plant' s shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the present invention, including a salt thereof. Particularly preferred is a method, wherein the plant' s roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.
The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The present invention also comprises seeds coated with or containing the active com- pound.
The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the active compound may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the active compound can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imid- azolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A 242 236, EP-A 242 246) (WO 92/00377) (EP-A 257 993, U.S. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A 142 924, EP-A 193 259),
Furthermore, the active compound can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO
91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
The seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants. Compositions which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Gel-Formulations (GF)
I Dustable powders (DP, DS) Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
Seed Treatment formulations may additionally also comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrol- idones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers. Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®)
In the treatment of seed, the application rates of the compounds of the present invention are generally from 0.01 g to 10 kg per 100 kg of seed, preferably from 0.05 g to 5 kg per 100 kg of seed, more preferably from 0.1 g to 1000 g per 100 kg of seed and in particular from 0.1 g to 200 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the present invention, including an agriculturally useful salt of it, as defined herein. The amount of the compound of the present invention, including an agriculturally useful salt thereof will in general vary from 0.01 g to 10 kg per 100 kg of seed, preferably from 0.05 g to 5 kg per 100 kg of seed, in particular from 0.1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
Methods which can be employed for treating the seed are, in principle, all suitable seed treatment and especially seed dressing techniques known in the art, such as seed coating (e.g. seed pelleting), seed dusting and seed imbibition (e.g. seed soaking). Here, "seed treatment" refers to all methods that bring seeds and the compounds of the present invention into contact with each other, and "seed dressing" to methods of seed treatment which provide the seeds with an amount of the compounds of the present invention, i.e. which generate a seed comprising a compound of the present invention. In principle, the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed. The seed can be treated immediately be- fore, or during, the planting of the seed, for example using the "planter's box" method. However, the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed. Expediently, the treatment is applied to unsown seed. As used herein, the term "unsown seed" is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant. Specifically, a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If ap- propriate, this is followed by a drying step.
The compounds of the present invention, including their stereoisomers, veterinarily acceptable salts or N-oxides, are in particular also suitable for being used for combating parasites in and on animals.
An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual con- trol of the parasites.
The invention also relates to compositions comprising a parasiticidally effective amount of compounds of the present invention, including their stereoisomers, veterinarily acceptable salts or N-oxides, and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of the present invention, including its stereoisomers, veterinarily acceptable salts or N-oxides, or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of the present invention, including its stereoisomers, veterinarily acceptable salts or N-oxides, or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly it has now been found that compounds of formula (I) and their stereoiso- mers, veterinarily acceptable salts, tautomers and N-oxides, are suitable for combating endo- and ectoparasites in and on animals.
The compounds of the present invention, especially compounds of formula (I) and their stereoisomers, veterinarily acceptable salts, tautomers and N-oxides, and compositions comprising them are preferably used for controlling and preventing infestations of and infections in animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur- bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Compounds of the present invention, including their stereoisomers, veterinarily acceptable salts or N-oxides, and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of the present invention, including their stereoisomers, veterinarily acceptable salts or N-oxides, and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intes- tinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Lep- toconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar- gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcoph- aga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Taba- nus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo- vicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni,
Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodo- rus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonys- sus bacoti and Dermanyssus gallinae,
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp, Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Tricho- dectes spp., and Felicola spp,
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Tri- churidae) Trichuris spp., Capillaria spp,
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habro- nema spp., Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp.,
Macracanthorhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
The present invention relates to the therapeutic and the non-therapeutic use of compounds of the present invention and compositions comprising them for controlling and/or combating parasites in and/or on animals. The compounds of the present inven- tion and compositions comprising them may be used to protect the animals from attack or infestation by parasites by contacting them with a parasiticidally effective amount of compounds of the present invention and compositions containing them.
The compounds of the present invention and compositions comprising them can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). As such, "contacting" includes both direct contact (applying the pesticidal mixtures/compositions containing the compounds of the present invention directly on the parasite, which may include an indirect contact at its locus-P, and optionally also administrating the pesticidal mixtures/composition directly on the animal to be protected) and indirect contact (applying the compounds/compositions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of the present invention. "Locus-P" as used above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions of the present invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing condi- tions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compounds of the present invention can also be applied preventively to places at which occurrence of the pests or parasites are expected.
Administration can be carried out both prophylactically and therapeutically. Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
The compounds of the invention have a distinctly shorter half live in the soil and thus are significantly less persistent than isoxazoline compounds of similar structure and insecticidal activity.
Examples The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.
Preparation Examples
Compounds can be characterized e.g. by coupled High Performance Liquid Chroma- tography / mass spectrometry (HPLC/MS), by 1H-NMR and/or by their melting points. Analytical HPLC column:
Method A: Analytical UPLC column: RP-18 column Chromolith Speed ROD, 50 x 4.6 mm, from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C. Flow: 1.8 mL/min. MS-method: ESI positive.
Method B: Analytical UPLC column: Phenomenex Kinetex 1 ,7 μηι XB-C18 100A; 50 x 2.1 mm from Phenomenex, Germany. Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio from 5:95 to 100:0 in 1 .5 min at 60 °C. Flow: 0.8 mL/min to 1 mL/min in 1.5 min. MS-method: ESI positive.
1H-NMR, respectively 13C-NMR: The signals are characterized by chemical shift (ppm, δ [delta]) vs. tetramethylsilane, respectively CDC for 13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.
Abbreviations used are: h for hour(s), min for minute(s), r.t./room temperature for 20- 25°C, THF for tetrahydrofuran, OAc for acetate.
C.1 Compound examples 1
Compound examples 1 -1 to 1 -20 correspond to compounds of formula C.1 :
Figure imgf000186_0001
wherein R2a, R2b, R2c, R4, and R6 of each synthesized compound is defined of table C.1 below.
The compounds were synthesized in analogy to Synthesis Example S.1 .
Table d
Figure imgf000186_0002
Figure imgf000187_0001
C.2 Compound examples 2 Compound examples 2-1 to 2-233 correspond to compounds of formula C.2:
Figure imgf000187_0002
wherein R2a, R2b, R2c, R4, and Y of each synthesized compound is defined in one row of table C.2 below.
The compounds were synthesized in analogy to Synthesis Example S.2.
Table C.2
Ex. R2a, R2b, R2c R4 Y HPLC-MS:
Method, Rt (min) & [M+H]+ or
1 H-NMR
2-1 CI, H, CI CH3 NHCH2C(=0)-NHCH2CF3 A 4.242 572.0
NHCH2C(=0)-
2-2 CI, H, CI CH3 B 1.348 530.1
NHCH2(cyclopropyl)
Figure imgf000188_0001
Ex. R2< R2b, R2c R4 Y HPLC-MS:
Method, Rt (min) & [M+H]+
1 H-NMR
(s, 2H), 4.2 (d, 1 H), 3.9 (d, 1 H)
2-37 CI, H, CI CI NHCH2-(4-pyridyl) B 1.150 544.2
2-38 CI, H, CI CI NH-CeHs B 1.508 530.9
2-39 CI, H, CI CI NHCH2-(6-CI-pyrid-3-yl) B 1.447 580.0
NH-(1 , 1-dioxo-thiethan-3-
2-40 CI, H, CI CI B 1.196 557.0
yi)
2-41 CI, H, CI F NHCH2-(4-thiazolyl) B 1.396 534.0
2-42 CI, H, CI CI NH-(3-pyridyl) B 1.202 531.9
NHCH2-(3,3-difluoro-
2-43 CI, H, CI CH3 cyclobut-1-yl) B 1.466 537.3
2-44 CI, H, CI CI NH-(2-pyridyl) B 1.429 531 .8
2-45 CI, H, CI CI NH-(4-pyridyl) B 1.170 532.0
2-46 CI, H, CI CH3 NH-CH2-(2-nitrophenyl) B 1.485 568.3
2-47 CI, H, CI CI N(CH3)-CH2-(2-pyridyl) B 1.314 560.0
2-48 CI, H, CI CI NHCH2-(4-pyrimidyl) B 1.343 546.8
N(CH2CH3)-CH2-(2-
2-49 CI, H, CI CI B 1.338 573.8
pyridyl)
2-50 CI, H, CI CI NHCH2-(2-pyrimidyl) B 1.374 547.4
2-51 CI, H, CI CH3 NHCH2-(cyclobutyl) B 1.51 1 501 .1
2-52 CI, H, CI CH3 NHCH2-(cyclopentyl) B 1.546 516.8
2-53 CI, H, CI CH3 NHCH2-(2-pyrazinyl) B 1.353 525.0
2-54 CI, H, CI CH3 NHCH2-(3-pyridyl) B 1.128 524.3
2-55 CI, H, CI CH3 NHCH2-(4-pyridyl) B 1.130 524.2
2-56 CI, H, CI CH3 NH-(2-pyridyl) B 1.351 510.3
2-57 CI, H, CI CH3 NH-(3-pyridyl) B 1.183 510.3
2-58 CI, H, CI CH3 NH-(4-pyridyl) B 1.174 510.3
2-59 CI, H, CI CH3 NHCH2-(2-pyrimidyl) B 1.355 525.3
2-60 CI, H, CI CH3 NHCH2-(4-pyrimidyl) B 1.331 525.3
2-61 CI, H, CI CH3 NH-CeHs B 1.514 509.3
2-62 CI, H, CI CH3 N(CH3)-CH2-(2-pyridyl) B 1.274 538.3
N(CH2CH3)-CH2-(2-
2-63 CI, H, CI CH3 B 1.305 552.3
pyridyl)
N(CH2CCH)-CH2-(2-
2-64 CI, H, CI CH3 B 1.331 562.3
pyridyl)
2-65 CI, H, CI CH3 N(CH3)-CH2-(4-thiazolyl) B 1.438 544.3
2-66 CI, H, CI CH3 N(CH3)-OCH3 B 1.448 477.0
2-67 CI, H, CI CH3 NH-CH2-(2-oxazolyl) B 1.363 514.1
2-68 CI, H, CI CH3 NH-(3-oxetanyl) B 1.223 489.1
2-69 CI, H, CI CH3 pyrrol id in-1-yl B 1.463 487.3
2-70 CI, H, CI CH3 azetidin-1-yl B 1.422 474.8
2-71 CI, H, CI CH3 NH-cyclobutyl B 1.467 487.0
Figure imgf000190_0001
Figure imgf000191_0001
Ex. R2 R2b, R2c R4 Y HPLC-MS:
Method, Rt (min) & [M+H]+
1 H-NMR
yi)
2-140 CI, CI, CI SCH3 NHCH2C(=0)-NHCH2CF3 B 1.434 640.0
2-141 CI, CI, CI SCH3 NHCH2-(4-thiazolyl) B 1.442 598.0
2-142 CI, CI, CI SCH3 NHCH2-(2-thiazolyl) B 1.444 598.0
2-143 CI, CI, CI CH3 NHCH2-(2-thiazolyl) B 1.449 566.1
NHCH(CH3)C(=0)-
2-144 CI, H, CI CH3 B 1.402 586.2
NHCH2CF3
2-145 CI, H, CI CH3 NHCH2C(=0)-NHCH2CH3 B 1.326 518.2
NHCH2C(=0)-
2-146 CI, H, CI CH3 B 1.362 532.2
NHCH(CH3)2
2-147 CI, H, CI CH3 NHCH2C(=0)-NHCH3 B 1.281 504.2
NHCH2C(=0)-
2-148 CI, H, CI CH3 B 1.355 532.3
NHCH2CH2CH3
NHCH2-(1 ,3-dioxolan-2-
2-149 CI, H, CI CH3 B 1.368 519.2
yi)
2-150 CI, CI, CI CI NHCH2-(2-pyridyl) B 1.245 580.1
2-151 CI, CI, CI CI NHCH2-(2-pyrimidyl) B 1.433 581 .1
2-152 CI, CI, CI CI NHCH2-(2-thiazolyl) B 1.450 586.1
2-153 CI, CI, CI CI NHCH2C(=0)-NHCH2CF3 B 1.440 628.1
2-154 CI, CI, CI CI NHCH2CF3 B 1.508 571 .1
1 H NMR (400 MHz,CDCI3): δ 7.8 (s, 1 H), 7.8-7.6 (m, 2H), 7.4
2-155 CI, CI, CI CI NH-(1 , 1-dioxo-thiethan-3- (s, 2H), 7.1 (d, 1 H), 5.0-4.8 (m,
1 H), 4.7-4.6 (m, 2H), 4.2 (d, yi) 1 H), 4.2-4.0 (m, 2H), 3.9 (d, 1 H)
2-156 CI, H, CI CH3 OH B 1.419 434.1
2-157 CI, CI, CI CH3 OH B 1.472 470.1
2-158 CI, CI, CI SCH3 OH B 1.466 500.1
2-159 CI, CI, CI CI OH B 1.477 490.0
2-160 CI, F, CI CH3 OC(CH3)3 B 1.678 508.2
2-161 CI, F, CI CH3 OH B 1.417 454.0
2-162 CI, F, CI CH3 NHCH2C(=0)-NHCH2CF3 B 1.373 590.2
NH-(1 , 1-dioxo-thiethan-3-
2-163 CI, F, CI CH3 B 1.344 555.2
yi)
2-164 CI, F, CI CH3 NHCH2-(2-pyridyl) B 1.190 542.3
2-165 CI, F, CI CH3 NHCH2CF3 B 1.451 533.3
2-166 CI, F, CI CH3 NHCH2-(2-thiazolyl) B 1.391 548.1
2-167 CI, CI, CI OCH3 OC(CH3)3 B 1.651 542.2
2-168 CI, CI, CI OCH3 OH B 1.424 484.2
2-169 CI, CI, CI OCH3 NHCH2C(=0)-NHCH2CF3 B 1.434 624.1
NH-(1 , 1-dioxo-thiethan-3-
2-170 CI, CI, CI OCH3 B 1.410 589.1
yi)
2-171 CI, CI, CI OCH3 NHCH2-(2-pyridyl) B 1.245 574.1 Ex. R2a, R2b, R2c R4 Y HPLC-MS:
Method, Rt (min) & [M+H]+
1 H-NMR
2-172 CI, CI, CI OCH3 NHCH2-(2-thiazolyl) B 1.469 580.1
2-173 CI, CI, CI OCH3 NHCH2CH2CF3 B 1.537 579.1
2-174 CI, H, CF3 CH3 OC(CH3)3 B 1.657 524.3
2-175 CI, CI, CI H OC(CH3)3 B 1.687 512.1
2-176 CI, H, CF3 CH3 OH B 1.413 468.2
2-177 CI, CI, CI H OH B 1.435 456.1
2-178 CI, H, CI CH3 NHNH-(2-pyridyl) B 1.153 525.2
2-179 CI, H, CI CH3 NHN(CH3)-(2-pyridyl) B 1.201 539.2
2-180 CI, H, CI CH3 NHCH2CH2CH2CH3 B 1.480 489.2
2-181 CI, H, CF3 CH3 NHCH2C(=0)-NHCH2CF3 B 1.358 606.3
2-182 CI, H, CF3 CH3 NHCH2-(2-pyridyl) B 1.185 558.4
NH-(1 , 1-dioxo-thiethan-3-
2-183 CI, H, CF3 CH3 B 1.343 571 .2
yi)
2-184 CI, H, CF3 CH3 NHCH2-(2-thiazolyl) B 1.384 564.2
2-185 CI, H, CF3 CH3 NHCH2CH2CF3 B 1.450 563.2
2-186 CI, CI, CI H NHCH2C(=0)-NHCH2CF3 B 1.393 594.2
1 H NMR (400 MHz,CDCI3): δ
8.1- 7.7 (m, 4H), 7.4 (s, 2H), 6.9-
2-187 CI, CI, CI H NH-(1 , 1-dioxo-thiethan-3- 6.8 (m, 1 H), 5.0-4.8 (m, 1 H),
4.8-4.6 (m, 2H), 4.2 (d, 1 H), yi) 4.2- 4.0 (m, 2H), 3.9 (d, 1 H)
2-188 CI, CI, CI H NHCH2-(2-pyridyl) B 1.21 1 544.1
2-189 CI, CI, CI H NHCH2-(2-thiazolyl) B 1.409 552.1
2-190 CI, CI, CI H NHCH2CH2CF3 B 1.470 550.3
2-191 CI, H, CI CH3 NHCH2-(6-CF3-pyrid-2-yl) B 1.310 592.3
2-192 CI, H, CI CH3 NHNHC(=0)-NHCH2CF3 B 1.317 573.3
NH-(2-
2-193 CI, H, CI CH3 B 1.335 517.2
oxotetra hyd rof u ran-3-yl)
2-194 CI, H, CI CH3 OCH2-(2-pyridyl) B 1.420 525.3
NH-[2-oxo-1 -(2,2,2-
2-195 CI, H, CI CH3 trifluoroethyl)pyrrolidin-3- B 1.388 598.2
yi]
2-196 CI, H, CI CH3 OCH2CH2CF3 B 1.593 530.2
2-197 CI, H, CI CH3 NH-(2-pyrazinyl) B 1.421 51 1 .2
2-198 CI, H, CI CH3 NH2 B 1.310 433.2
2-199 CI, H, CI CH3 NHCH=NOCH3 B 1.459 490.3
2-200 CI, H, CI CH3 NH-(1-acetylazetidin-3-yl) B 1.284 530.3
NH-(1-methyl-2-oxo-
2-201 CI, H, CI CH3 B 1.296 530.3
pyrrolidin-3-yl)
2-202 CI, H, CI CH3 NHCH2CH2OH A 3.705 477.0
2-203 CI, H, CI CH3 NHCH2CH2OCH2CH3 A 4.141 505.0
2-204 CI, H, CI CH3 NHCH2CH2OCH2CF3 A 4.277 559.0
2-205 CI, H, CI CH3 NH2 B 1.398 434.2
2-206 CI, H, CI CH3 NHCH2CH2OCH3 B 1.353 491 .4
2-207 CI, H, CI CH3 NHCH(CH3)CH2OCH3 B 1.393 505.3 Ex. R2a, R2b, R2c R4 Y HPLC-MS:
Method, Rt (min) & [M+H]+ or
1 H-NMR
2-208 CI, H, CI CH3 NHCH2CH2CH2CF3 B 1.459 543.0
2-209 CI, H, CI CH3 NHCH2CF2CF3 B 1.494 565.2
2-210 CI, H, CI CH3 NHCH2CH2SCF3 B 1.487 561 .4
2-21 1 CI, H, CI CH3 NHCH2CH2OCF3 B 1.447 545.3
N(CH3)-CH2C(=0)-
2-212 CI, H, CI CH3 B 1.377 586.4
NHCH2CF3
2-213 CI, H, CI SCH3 NHCH2CF3 B 1.444 547.1
2-214 CI, H, CI SCH3 pyrrol id in-1-yl B 1.463 519.2
2-215 CI, H, CI SCH3 NHCH2-(2-pyridyl) B 1.200 556.2
2-216 CI, H, CI SCH3 NHCH2C(=0)-NHCH2CF3 B 1.369 604.2
2-217 CI, H, CI SCH3 NHCH2-(2-pyrimidyl) B 1.346 557.2
2-218 CI, H, CI SCH3 NHCH2-(2-thiazolyl) B 1.371 564.0
NH-(1 , 1-dioxo-thiethan-3-
2-219 CI, H, CI SCH3 B 1.331 569.2 yi)
2-220 CI, H, CI SCH3 NH-(3-thiethanyl) B 1.425 538.9
NHCH2C(=0)-
2-221 CI, H, CI CH3 B 1.319 528.4
NHCH2CCH
NHCH2C(=0)-N(CH3)-
2-222 CI, H, CI CH3 B 1.402 586.4
CH2CF3
2-223 CI, H, CI CH3 NH-(4-CF3-thiazol-2-yl) B 1.407 584.4
2-224 CI, CI, CI CH3 NHCH2-(2-pyrimidyl) B 1.397 561 .1
2-225 CI, F, CI CH3 NHCH2-(2-pyrimidyl) B 1.340 543.2
2-226 CI, H, CI CH3 NHCH2-(5-CI-pyrid-2-yl) B 1.400 560.1
2-227 CI, H, CF3 CH3 NHCH2-(2-pyrimidyl) B 1.382 559.2
2-228 CI, H, CI CH3 NHNH-(2-pyrimidyl) B 1.341 526.2
2-229 CI, H, CI CH3 NH-(5-pyrimidyl) B 1.382 51 1 .0
2-230 CI, H, CI CH3 NH-(2-pyrimidyl) B 1.349 51 1.0
2-231 CI, H, CI CH3 NHCH=NOCH2CF3 B 1.527 557.9
NHNHC(=0)-
2-232 CI, H, CI CH3 B 1.318 555.4
NHCH2CHF2
2-233 CI, H, CI CH3 NHCH2C(=0)-NHCH2CN B 1.300 529.3
NH-(3-oxo-isoxazolidin-4-
2-234 CI, H, CI CH3 B 1.282 519.9 yi)
C.3 Compound examples 3 Compound examples 3-1 to 3-28 correspond to compounds of formula C.3:
Figure imgf000195_0001
wherein R2a, R2b, R2c, R4, R5 and R6 of each synthesized compound is defined row of table C.3 below.
The compounds were synthesized in analogy to Synthesis Example S.3.
Table C.3
Figure imgf000195_0002
C.4 Compound examples 4 Compound example 4-1 corresponds to compounds of formula C.4:
Figure imgf000196_0001
wherein R2a, R2b, R2c, R4, and A4 of each synthesized compound is defined in one row of table C.4 below.
Compound 4-1 was synthesized in analogy to Synthesis Example S.2. The starting material (2-(1 ,2,4-triazoM -yl)-5-[(Z)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-2- enoyl]benzonitrile) was prepared in analogy to the method described in EP-A-2172462.
Table C.4
Figure imgf000196_0002
C.5 Compound examples 5
Compound examples 5-1 to 5-15 correspond to compounds of formula C.5:
Figure imgf000197_0001
wherein R2a, R2b, R2c, R3a, G1, R4a, R4b, and Y of each synthesized compound is defined in one row of table C.5 below.
Compounds 5-1 to 5-3 were synthesized in analogy to Synthesis Example S.4.
Compounds 5-4 to 5-15 were synthesized in analogy to Synthesis Example S.2.
Table C.5
Figure imgf000198_0001
C.6 Compound examples 6 (Intermediates)
Intermediates 6-1 to 6-7 correspond to compounds of formula C.6:
Figure imgf000199_0001
wherein R2a, R2b, R2c, R4, and YY of each synthesized compound is defined in one row of table C.6 below.
Figure imgf000199_0002
Synthesis Example S.1
1 -[(E)-[4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methyleneamino]-3-ethyl-urea
(Compound example 1 -5; compound of formula IA, wherein R2a and R2c are CI, R2 is H, R4 is methyl and A is A1 = -CH(=N-NH-C(=0)-NH-CH2CH3). Step 1 : 1 -(4-Bromo-3-methyl-phenyl)-3-(3,5-dichlorophenyl)-3-sulfanyl-butan-1 -one
1 -(4-Bromo-3-methyl-phenyl)-3-(3,5-dichlorophenyl)but-2-en-1 -one (21 .5 g, 4:1 -mixture of E/Z-isomers) in CH2CI2 (400 mL) was treated with triethylamine (68 mL). At 0°C, gaseous hydrogen sulfide (H2S) was bubbled through the solution for 10 min. The mixture was stirred for another 20 min at 0°C, and then diluted with CH2CI2 (300 mL). The organic layer was washed with 6% aqueous hydrochloric acid (300 mL), dried (MgS04), filtered, and concentrated.
The product was obtained as a yellowish oil (23.1 g, 99.7%).
HPLC-MS (method B): 1 .557 min, M = 472.90.
Step 2: 3-(4-Bromo-3-methyl-phenyl)-5-(3,5-dichlorophenyl)-5-methyl-4H-isothiazole
At -15°C, the product of step 1 (23 g) in CH2CI2 (400 mL) was treated with triethylamine (27.1 mL) and with a solution of hydroxylamine-O-sulfonic acid ("HOSA", 6.23 g) in water (10 mL). The reaction was warmed to 0°C and stirred at 0°C for 45 min, and then diluted with CH2CI2 (400 mL). The organic layer was washed with saturated aqueous NH4CI solution (3x), dried (MgS04), and filtered. To the obtained solution, acid washed molecular sieves (AW 300, 150 g) were added and the mixture was stirred vigorously for 90 min at room temperature. Then, the molecular sieves were filtered off, and the filtrate concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The obtained pale yellow solid (19.5 g) was ti- turated with hexanes (3x) to afford the product as a white solid (15.6g, 68%).
HPLC-MS (method B): 1 .697 min, M = 469.90.
Step 3: Methyl 4-[5-(3,5-dichlorophenyl)-5-methyl-4H-isothiazol-3-yl]-2-methyl- benzoate
The product of step 2 (14.6 g) in methanol/THF (63 mL/6 mL) was treated with [1 ,1 - bis(diphenylphosphino)ferrocene]dichloropalladium(ll) ("Pd(dppf)Cl2", 5.08 g),
Pd(OAc)2 (0.42 g), NaOAc (3.7 g). The reaction was subsequently pressurized twice with N2 (3.5 bar) and three times with carbon monoxide (5 bar). Then, the mixture was pressurized with carbon monoxide (7.5 bar) and heated at 80°C (internal temperature) for 13 h. Thereby, the carbon monoxide pressure was adjusted several times back to 7.5 bar. Then, the reaction was cooled to room temperature, filtered over celite (CH2CI2) and subsequently filtered over a plug of silica gel. The product was obtained as a pale yellow foam (13.1 g, 89%).
HPLC-MS (method A): 3.974 min, M = 566.00.
Step 4: [4-[5-(3,5-Dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methanol
To a solution of the product of step 3 (4.9 g) in CH2CI2 (100 ml.) at 0 °C was added a solution of DIBAL-H in toluene (1 .5 M, 16 ml_). The resulting solution was stirred at 0 °C for 90 min and quenched by adding MeOH (10 ml_). A saturated solution of Ro- chelle's salt (potassium sodium tartrate, CAS 304-59-6) (100 ml.) was added, followed by vigorous stirring at r.t. for 2 h. Then, CH2CI2 (300 ml.) was added, and the organic layer was washed with water, dried (Na2S04), filtered, and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/hexanes). The product was obtained as pale yellow solid (3.45 g, 75%).
HPLC-MS (methode A): 4.390 min, M = 419.95. Step 5: 4-[5-(3,5-Dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- benzaldehyde
To a solution of the product of step 1 (1 g) in CH2CI2 (40 ml.) at r.t. was added Dess- Martin-Periodane (CAS 87413-09-0) (1.1 1 g). The reaction was stirred overnight, fil- tered and concentrated. The residue was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as a viscous oil (0.81 g, 81 %).
HPLC-MS (method A): 4.036 min, M = 417.90. Step 6: 1 -[(E)-[4-[5-(3,5-Dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methyleneamino]-3-ethyl-urea
A solution of the product of step 2 (0.15 g) and 1 -ammonium-3-ethyl urea hydrochloride (60 mg) in EtOH (4 mL) and acetic acid (0.14 mL) was stirred at 70 °C overnight, and concentrated. The residue was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as a pale yellow foam (0.10 g, 55%).
HPLC-MS (method B): 1.484 min, M = 505.0. Synthesis Example S.2
4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4H-isothiazol-3-yl]-2-methyl-N-[2-oxo-2- (2,2,2-trifluoroethylamino)ethyl]benzamide
(Compound example 2-1 ; compound of formula IA, wherein R2a and R2c are CI, R2 is H, R4 is methyl and A is A2 = -C(=0)-NH-CH2-C(=0)-NH-CH2CF3)
Step 1 : 4-[5-(3,5-dichlorophenyl)-5-methyl-4H-isothiazol-3-yl]-2-methyl-benzoic acid To a solution of methyl 4-[5-(3,5-dichlorophenyl)-5-methyl-4H-isothiazol-3-yl]-2-methyl- benzoate (= the product of step 3 of example 1 ) (2.4 g) in THF (50 mL) was added a solution of LiOH (0.51 g) in water (50 mL). The reaction was stirred for 16 h at room temperature, then diluted with water (300 mL) and washed with CH2CI2 (3x). The aqueous phase was acidified with aqueous 1 M HCI to pH 1 -2 and extracted with CH2CI2 (3x). The combined organic layers were washed with water, dried (Na2S04), filtered, and concentrated. The product was obtained as a pale yellow solid (2.24 g, 96%).
HPLC-MS (method A): 4.458 min, M = 433.95. Step 2: 4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4H-isothiazol-3-yl]-2-methyl-N-[2- oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide
To a solution of the product of step 1 (2.2 g), [2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]ammonium chloride (1.22 g) and bromotripyrrolidinophospho- nium hexafluorophosphate ("PyBroP", 2.95 g) in CH2CI2 (100 mL) at room temperature was added A/,A/-diisopropylethylamine (3.53 mL). The reaction was stirred at room temperature for 16 h, then concentrated and redissolved in ethyl acetate (200 mL). The organic layer was washed with 5% aqueous HCI (2x) and 5% aqueous K2CO3 (2x), dried (Na2S04), filtered, and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as amorphous white foam (2.45 g, 84%).
HPLC-MS (method A): 4.045 min, M = 572.00. Synthesis Example S.3
N-[[4-[5-(3,5-Dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methyl]-N-ethyl-2-ethylsulfanyl-acetamide
(Compound example 3-3; compound of formula IA, wherein R2a and R2c are CI, R2 is H, R4 is methyl and A is A3 = -CH2-N(CH2CH3)-C(=0)-CH2SCH2CH3). Step 1 : N-[[4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methyl]ethanamine To a solution of [4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2- methyl-phenyl]methanol (i.e. the product of example 1 , step 4) (1 .5 g) in CH2CI2 (50 mL) was added triethylamine (0.75 mL) and methansulfonylchloride (0.63 g) at r.t.. The reaction was stirred at r.t. overnight, then diluted with ethyl acetate (200 mL), and washed with water (3x), dried (Na2S04), filtered, and concentrated to afford the crude mesylate (1.19 g) that was re-dissolved in acetonitrile (30 mL) and treated with a solution of ethylamine in THF (2 M, 8.8 mL). The reaction was stirred overnight at r.t.. The residue was taken up in ethyl acetate and washed with 5% aqueous potassium carbonate solution (3x), dried (Na2S04), filtered, and concentrated to afford the product as a solid (0.98 g, 59%).
HPLC-MS (method B): 1.139 min, M = 447.3.
Step 2: N-[[4-[5-(3,5-Dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl- phenyl]methyl]-N-ethyl-2-ethylsulfanyl-acetamide
To a solution of the product of step 1 (0.30 g), (ethylthio)acetic acid (0.10 g) and bro- motripyrrolidinophosphonium hexafluorophosphate ("PyBroP", 0.39 g) in CH2CI2 (20 mL) at r.t. was added A/,A/-diisopropylethylamine (0.47 mL). The reaction was stirred at r.t. for 16 h, then concentrated to afford a residue that was purified by flash chromatog- raphy on silica gel (ethyl acetate/cyclohexane). The product was obtained as amorphous foam (330 mg, 90%).
HPLC-MS (method A): 4.639 min, M = 549.00. Synthesis Example S.4
4-[5-(3,5-dichlorophenyl)-4-fluoro-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl-N-[2- oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide
(Compound example 5-1 ; compound of formula C.5, wherein R2a and R2c are CI, R2b is H, R3a is F, G is CH, R4a is H, R4b is methyl and Y is -NHCH2-C(=0)-NHCH2CF3).
Step 1 : tert-butyl 4-[5-(3,5-dichlorophenyl)-4-fluoro-5-(trifluoromethyl)-4H-isothiazol-3- yl]-2-methyl-benzoate To a solution of [tert-butyl 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3- yl]-2-methyl-benzoate (prepared from "tert-butyl 4-[(Z)-3-(3,5-dichlorophenyl)-4,4,4- trifluoro-but-2-enoyl]-2-methyl-benzoate" in analogy to Synthesis Example S.1 , step 1 and step 2) (2.55 g) in THF (40 mL) under nitrogen at -78°C was added LiHMDS (5.7 mL, 1 M solution in THF) and the mixture was stirred for 1 .5 h at -78°C. Then,
/V-fluorobenzenesulfonimide ("NFSI", 2.1 g) was added at -78°C in one portion and the mixture was stirred at -78°C for another 2 h. Then, the reaction was quenched with saturated aqueous NH4CI solution. EtOAc was added and the organic layer was washed with water (3x), dried (Na2S04), filtered, and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as yellow oil (1 .65 g, 62%).
1 H NMR (400 MHz,CDCI3, signals of major diastereomer): δ 7.9 (d, 1 H), 7.7-7.6 (m, 2H), 7.5 (s, 1 H), 7.4 (s, 2H), 6.4 (d, 1 H, CHF), 2.6 (s, 3H), 1 .6 (s, 9H).
Step 2: 4-[5-(3,5-dichlorophenyl)-4-fluoro-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2- methyl-benzoic acid
To a solution of the product of step 1 (0.36 g) in CH2CI2 (20 mL) at 0°C was added tri- fluoroacetic acid ("TFA", 10 mL), and the mixture was stirred at r.t. overnight. Then, the reaction was concentrated, azeotroped with CH2CI2 (5x) and triturated with petroleum ether / EtOAc (40:1 ) to obtain the product as a pale yellow solid (0.28 g, 87%).
1 H NMR (400 MHz, d6-DMSO, signals of major diastereomer): δ 8.0-7.8 (m, 4H), 7.7 (s, 2H), 7.5 (d, 1 H, CHF), 2.6 (s, 3H).
Step 3: 4-[5-(3,5-dichlorophenyl)-4-fluoro-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2- methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide To a solution of the product of step 2 (0.25 g) in toluene/CH2Cl2 (1 :1 , 20 mL) was added A/,A/-dimethylformamide ("DMF", 1 drop) and oxalyl chloride (0.14 mL). The reaction was stirred overnight, concentrated, and azeotroped with CH2CI2 (5x). The obtained residue (0.26 g) was dissolved in THF (30 mL) and added to a solution of 2-amino-/V- (2,2,2-trifluoroethyl)acetamide hydrochloride and triethylamine (0.22 g) in THF (30 mL). The reaction was stirred overnight, filtered and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as amorphous foam (0.13 g, 40%). HPLC-MS (method B): 1.364 min, M = 590.2.
II. Evaluation of pesticidal activity:
The activity of the compounds of formula I of the present invention can be
demonstrated and evaluated by the following biological test. B.1 Cotton aphid (Aphis gossypii)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, the compounds 2-4, 2-10, 2-12, 2-15, 2-19, 2-26, 2-27, 2-28, 2-29, 2-31 , 2- 32, 2-35, 2-37, 2-38, 2-42, 2-43, 2-47, 2-48, 2-49, 2-50, 2-53, 2-57, 2-59, 2-62, 2-63, 2- 65, 2-68, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-82, 2-83, 2-86, 2-88, 2-93, 2-99, 2-109, 2-1 18, 2-137, 2-138, 2-142, 2-143, 2-145, 2-149, 2-150, 2-151 , 2-152, 2-153, 2-162, 2-163, 2- 164, 2-166, 2-171 , 2-178, 2-182, 2-183, 2-185, 2-195, 2-199, 3-1 1 , and 3-12 at 100 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.2 Cowpea aphid (Aphis craccivora)
Potted cowpea plants colonized with approximately 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours. In this test, the compounds 1 -13, 2-1 , 2-2, 2-4, 2-8, 2-9, 2-10,2-11,2-12, 2-15, 2-19, 2- 26, 2-28, 2-32, 2-33, 2-34, 2-35, 2-36, 2-38, 2-47, 2-51, 2-54, 2-55, 2-59, 2-69, 2-137, 2-142, 2-150, 2-151, 2-152, 2-162, 2-164, 2-165, 2-166, 2-178, 2-180, 2-181, 2-182, 2-
184, 2-185, 2-197, 2-199, 2-200, 2-215, 2-217, 2-218, 2-220, 2-223, 2-224, 2-225, 2- 227, 3-1,3-2, 3-8, 3-9, 3-11, 3-12, 3-21, 3-23, 4-1, and 5-2 at 500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.3 Diamond back moth (Plutella xylostella) Leaves of Chinese cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dished lined with moist filter paper. Mortality was recorded 24, 72, and 120 hours after treatment.
In this test, the compounds 1-1, 1-2, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-15, 2-1 , 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11,2-12,2-13, 2-15, 2-18, 2-19, 2-20, 2-21, 2-22, 2-23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31, 2-32, 2-33, 2-34, 2-35, 2-36, 2-37, 2-38, 2-39, 2-40, 2-41, 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-50, 2-51, 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-76, 2-77, 2-78, 2-80, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101, 2-102, 2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109, 2- 111, 2-112, 2-114, 2-115, 2-116, 2-117, 2-118, 2-119, 2-120, 2-121, 2-123, 2-124, 2- 125, 2-126, 2-127, 2-128, 2-129, 2-130, 2-131, 2-132, 2-133, 2-134, 2-135, 2-136, 2- 137, 2-138, 2-139, 2-140, 2-141, 2-142, 2-143, 2-144, 2-145, 2-146, 2-147, 2-148, 2- 149, 2-150, 2-151, 2-152, 2-153, 2-154, 2-155, 2-162, 2-163, 2-164, 2-165, 2-166, 2- 169, 2-170, 2-171, 2-172, 2-173, 2-178, 2-179, 2-180, 2-181, 2-182, 2-183, 2-184, 2-
185, 2-186, 2-188, 2-189, 2-190, 2-191, 2-192, 2-193, 2-194, 2-195, 2-197, 2-198, 2- 199, 2-200, 2-201, 2-202, 2-203, 2-204, 2-206, 2-207, 2-208, 2-209, 2-210, 2-211, 2- 212, 2-213, 2-214, 2-215, 2-216, 2-217, 2-218, 2-219, 2-220, 2-221, 2-222, 2-223, 2- 224, 2-225, 2-226, 2-227, 3-1 , 3-2, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11 , 3-12, 3- 13, 3-14, 3-16, 3-17, 3-18, 3-19, 3-20, 3-21, 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 4-1,5-1, 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls. B.4 Green Peach Aphid (Myzus persicae)
For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5- 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1°C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-7, 1-8, 1-9, 1-10, 1-12, 1-13, 1-14, 1 -15, 2-1 , 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11,2-12,2-13, 2-15, 2-18, 2-19, 2-20, 2-21, 2-23, 2-24, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31, 2-32, 2-33, 2-35, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-51 , 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-76, 2-77, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87,
2- 88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101 , 2- 102, 2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-110, 2-111, 2-112, 2-113, 2- 114, 2-115, 2-116, 2-117, 2-118, 2-119, 2-120, 2-121, 2-123, 2-124, 2-125, 2-126, 2- 127, 2-128, 2-129, 2-130, 2-131, 2-132, 2-133, 2-134, 2-135, 2-136, 2-137, 2-138, 2- 139, 2-140, 2-141, 2-142, 2-143, 2-145, 2-146, 2-147, 2-148, 2-149, 2-150, 2-151, 2- 152, 2-153, 2-154, 2-155, 2-159, 2-160, 2-162, 2-163, 2-164, 2-165, 2-166, 2-167, 2- 168, 2-169, 2-170, 2-171, 2-172, 2-173, 2-177, 2-178, 2-179, 2-180, 2-181, 2-182, 2- 183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2-190, 2-191, 2-192, 2-193, 2-194, 2- 195, 2-196, 2-197, 2-199, 2-200, 2-201, 2-202, 2-203, 2-204, 2-206, 2-207, 2-208, 2- 209, 2-210, 2-211, 2-215, 2-216, 2-217, 2-218, 2-219, 2-220, 2-221, 2-222, 2-223, 2- 224, 2-225, 2-226, 2-227, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11,3-12, 3-13, 3-14,
3- 16, 3-17, 3-18, 3-19, 3-20, 3-21, 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 3-28, 4-1, 5-1, 5- 2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.5 Mediterranean fruitfly (Ceratitis capitata)
For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consist- ed of microtiter plates containing an insect diet and 50-80 C. capitata eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 ± 1°C and about 80 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12,
1- 13, 1-14, 2-1,2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-15, 2-18,
2- 19, 2-20, 2-21, 2-23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31, 2-32, 2-33, 2-34, 2-35, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-51 , 2-52, 2-53,
2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-76, 2-77, 2-78, 2-80, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101 , 2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-1 1 1 , 2-1 12, 2-1 14, 2- 1 15, 2-1 16, 2-1 17, 2-1 18, 2-1 19, 2-120, 2-121 , 2-123, 2-124, 2-125, 2-126, 2-127, 2- 128, 2-129, 2-130, 2-131 , 2-132, 2-133, 2-135, 2-138, 2-140, 2-141 , 2-142, 2-143, 2- 146, 2-147, 2-148, 2-149, 2-150, 2-151 , 2-152, 2-153, 2-154, 2-155, 2-162, 2-163, 2- 164, 2-165, 2-166, 2-169, 2-170, 2-171 , 2-172, 2-178, 2-179, 2-180, 2-181 , 2-182, 2- 183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2-190, 2-191 , 2-192, 2-194, 2-195, 2- 197, 2-198, 2-199, 2-200, 2-201 , 2-202, 2-203, 2-206, 2-207, 2-209, 2-212, 2-215, 2- 216, 2-217, 2-218, 2-220, 2-221 , 2-222, 2-223, 2-224, 2-225, 2-226, 2-227, 3-3, 3-4, 3- 5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-1 1 , 3-12, 3-13, 3-14, 3-16, 3-17, 3-18, 3-19, 3-20, 3-21 , 3- 22, 3-23, 3-24, 3-25, 3-26, 3-27, 3-28, 4-1 , 5-1 , 5-2, 5-3, 5-4, and 5-7 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.6 Orchid thrips (dichro moth rips corbetti)
Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound was diluted to a concentration of 500 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone:water (vohvol), plus 0.01 % vol/vol Kinetic® surfactant.
Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The level of thrips mortality was extrapolated from pre-treatment thrips numbers. In this test, the compounds 1 -1 , 1 -2, 1 -5, 1 -7, 1 -8, 1 -9, 1 -10, 1 -13 2-1 , 2-2, 2-3, 2-4, 2- 5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-1 1 , 2-12, 2-13, 2-15, 2-18, 2-19, 2-20, 2-21 , 2-22, 2-23, 2- 26, 2-27, 2-28, 2-29, 2-30, 2-31 , 2-33, 2-34, 2-35, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2- 43, 2-45, 2-46, 2-47, 2-48, 2-49, 2-50, 2-51 , 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2- 59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2- 74, 2-75, 2-76, 2-77, 2-78, 2-80, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2- 90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101 , 2-102, 2-103, 2- 104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-1 1 1 , 2-1 12, 2-1 13, 2-1 14, 2-1 15, 2-1 16, 2- 1 17, 2-1 18, 2-1 19, 2-120, 2-121 , 2-123, 2-124, 2-125, 2-126, 2-127, 2-128, 2-129, 2- 130, 2-131 , 2-132, 2-133, 2-134, 2-135, 2-136, 2-137, 2-138, 2-139, 2-140, 2-141 , 2- 142, 2-143, 2-144, 2-145, 2-146, 2-147, 2-148, 2-149, 2-150, 2-151 , 2-152, 2-153, 2- 154, 2-155, 2-162, 2-163, 2-164, 2-165, 2-166, 2-169, 2-170, 2-171 , 2-172, 2-173, 2- 178, 2-179, 2-180, 2-181 , 2-182, 2-183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2- 190, 2-192, 2-193, 2-195, 2-197, 2-198, 2-199, 2-200, 2-201 , 2-202, 2-203, 2-204, 2- 206, 2-207, 2-208, 2-209, 2-210, 2-21 1 , 2-212, 2-213, 2-214, 2-215, 2-216, 2-217, 2- 218, 2-219, 2-220, 2-221 , 2-222, 2-223, 2-224, 2-225, 2-226, 2-227, 3-1 , 3-2, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-1 1 , 3-12, 3-13, 3-14, 3-15, 3-16, 3-17, 3-18, 3-19, 3-20, 3-21 , 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 4-1 , 5-1 , 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.7 Rice green leafhopper (Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water (vohvol), and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compounds 1 -7, 2-1 , 2-2, 2-4, 2-5, 2-6, 2-9, 2-10, 2-1 1 , 2-13, 2-15, 2- 19, 2-23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31 , 2-32, 2-33, 2-35, 2-37, 2-38, 2-40, 2-41 , 2- 42, 2-43, 2-45, 2-47, 2-48, 2-49, 2-50, 2-51 , 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2- 59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-81 , 2- 82, 2-83, 2-84, 2-85, 2-86, 2-88, 2-89, 2-91 , 2-93, 2-94, 2-95, 2-97, 2-99, 2-100, 2-101 , 2-102, 2-104, 2-107, 2-108, 2-109, 2-1 12, 2-1 14, 2-1 15, 2-1 16, 2-1 18, 2-1 19, 2-120, 2- 121 , 2-124, 2-126, 2-127, 2-128, 2-129, 2-131 , 2-132, 2-133, 2-134, 2-135, 2-136, 2- 137, 2-138, 2-139, 2-140, 2-141 , 2-142, 2-143, 2-145, 2-146, 2-147, 2-148, 2-149, 2- 150, 2-151 , 2-152, 2-153, 2-154, 2-155, 2-162, 2-163, 2-164, 2-165, 2-166, 2-170, 2- 178, 2-179, 2-180, 2-181 , 2-182, 2-183, 2-184, 2-185, 2-193, 2-195, 2-197, 2-199, 2- 200, 2-201 , 2-203, 2-204, 2-206, 2-207, 2-208, 2-209, 2-210, 2-21 1 , 2-212, 2-213, 2- 214, 2-215, 2-216, 2-217, 2-218, 2-219, 2-220, 2-222, 2-224, 2-225, 2-226, 2-227, 3-3, 3-4, 3-6, 3-7, 3-8, 3-10, 3-1 1 , 3-12, 3-17, 3-18, 3-19, 3-21 , 3-23, 3-24, 3-25, 3-26, 4-1 , 5-2, and 5-3 at 500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.8 Silverleaf whitefly (bemisia argentifolii)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and about 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and a nontoxic Tygon® tubing connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid. Test plants were maintained in a growth room at about 25°C and about 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
In this test, the compounds 1 -7, 1 -9, 1 -10, 2-2, 2-3, 2-4, 2-5, 2-10, 2-1 1 , 2-12, 2-13, 2- 15, 2-23, 2-26, 2-28, 2-29, 2-31 , 2-33, 2-35, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2-43, 2- 47, 2-48, 2-49, 2-50, 2-53, 2-57, 2-58, 2-59, 2-62, 2-63, 2-65, 2-66, 2-67, 2-68, 2-71 , 2- 72, 2-73, 2-74, 2-75, 2-77, 2-81 , 2-82, 2-83, 2-84, 2-86, 2-87, 2-88, 2-90, 2-91 , 2-92, 2- 93, 2-95, 2-96, 2-99, 2-100, 2-109, 2-1 10, 2-1 14, 2-1 15, 2-121 , 2-123, 2-128, 2-130, 2- 134, 2-136, 2-137, 2-138, 2-139, 2-140, 2-142, 2-143, 2-145, 2-146, 2-148, 2-149, 2- 150, 2-151 , 2-152, 2-153, 2-154, 2-155, 2-162, 2-163, 2-164, 2-165, 2-166, 2-169, 2- 171 , 2-172, 2-173, 2-178, 2-179, 2-181 , 2-182, 2-183, 2-185, 2-186, 2-188, 2-189, 2- 190, 2-195, 2-199, 3-1 , 3-4, 3-6, 3-7, 3-9, 3-10, 3-1 1 , 3-12, and 3-19 at 100 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls. B.9 Southern armyworm (Spodoptera eridania)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1 st true leaf stage. Test solutions were sprayed onto the foliage by an au- tomated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 1 1 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25°C and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to pre- vent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.
In this test, the compounds 1-1, 1-2, 1-5, 1-7, 1-8, 1-9, 1-10, 1-11, 1-13, 1-14,2-1,2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11,2-12,2-13, 2-15, 2-18, 2-19, 2-20, 2-21 , 2- 23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31 , 2-32, 2-33, 2-35, 2-37, 2-38, 2-39, 2-40, 2-41 , 2- 42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-50, 2-51, 2-52, 2-53, 2-54, 2-55, 2-56, 2- 57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71, 2- 72, 2-73, 2-74, 2-75, 2-76, 2-77, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2- 90, 2-91, 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101, 2-102, 2-103, 2- 104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-110, 2-112, 2-114, 2-115, 2-116, 2-117, 2- 118, 2-119, 2-120, 2-121, 2-123, 2-124, 2-125, 2-126, 2-127, 2-128, 2-129, 2-130, 2- 131, 2-132, 2-133, 2-134, 2-135, 2-136, 2-137, 2-138, 2-139, 2-140, 2-141, 2-142, 2- 143, 2-144, 2-145, 2-146, 2-147, 2-148, 2-149, 2-150, 2-151, 2-152, 2-153, 2-154, 2- 155, 2-162, 2-163, 2-164, 2-165, 2-166, 2-169, 2-170, 2-171 , 2-172, 2-173, 2-178, 2- 179, 2-180, 2-181, 2-182, 2-183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2-190, 2- 191, 2-192, 2-193, 2-195, 2-197, 2-198, 2-199, 2-200, 2-202, 2-203, 2-204, 2-206, 2- 207, 2-208, 2-209, 2-210, 2-212, 2-214, 2-216, 2-221, 2-222, 2-224, 2-225, 2-226, 2- 227, 3-1,3-2, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-17, 3-18, 3-19, 3-20, 3-21 , 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 4-1 , 5-2, 5-3, 5-6 and 5-7 at 1 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.10 Vetch aphid (Megoura viciae) For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μΙ, using a custom built micro atomizer, at two replications.
After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 ± 1°C and about 50 ± 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-7, 1-8, 1-9, 1-10, 1-12, 1-13, 1-15, 2-1,2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11,2-12, 2-13, 2-15, 2-19, 2-20, 2-21, 2-23, 2-24, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31 , 2-32, 2-33, 2-35, 2-36, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-51 , 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71, 2-72, 2-73, 2-74, 2-75, 2-77, 2-79, 2-81, 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101 , 2-102, 2- 104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-110, 2-111, 2-112, 2-114, 2-115, 2-116, 2- 117, 2-118, 2-119, 2-120, 2-121, 2-123, 2-124, 2-125, 2-126, 2-127, 2-128, 2-129, 2- 130, 2-131, 2-132, 2-133, 2-134, 2-135, 2-136, 2-137, 2-138, 2-139, 2-140, 2-141, 2- 142, 2-143, 2-145, 2-146, 2-147, 2-148, 2-149, 2-150, 2-151, 2-152, 2-153, 2-154, 2- 155, 2-159, 2-162, 2-163, 2-164, 2-165, 2-166, 2-170, 2-171, 2-172, 2-173, 2-178, 2- 179, 2-180, 2-181, 2-182, 2-183, 2-184, 2-185, 2-186, 2-188, 2-189, 2-190, 2-191, 2- 192, 2-193, 2-194, 2-195, 2-197, 2-198, 2-199, 2-200, 2-201, 2-202, 2-203, 2-204, 2- 206, 2-207, 2-208, 2-209, 2-210, 2-211, 2-213, 2-214, 2-215, 2-216, 2-217, 2-218, 2- 219, 2-220, 2-221, 2-222, 2-223, 2-224, 2-225, 2-226, 2-227, 3-6, 3-7, 3-8, 3-9, 3-10, 3-
II, 3-12, 3-13, 3-14, 3-16, 3-17, 3-18, 3-19, 3-20, 3-21, 3-22, 3-23, 3-24, 3-25, 3-26, 3- 27, 3-28, 4-1, 5-1,5-2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls. B.11 Tobacco budworm (Heliothis virescens) I
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 ± 1°C and about 80 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed. In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13,
1- 14, 1-15, 2-1,2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-15, 2-17,
2- 18, 2-19, 2-20, 2-21, 2-22, 2-23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31, 2-32, 2-33, 2-34, 2-35, 2-36, 2-37, 2-38, 2-39, 2-40, 2-41, 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-51, 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-77, 2-78, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98,
2- 99, 2-100, 2-101, 2-102, 2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-110, 2-
III, 2-112, 2-114, 2-115, 2-116, 2-117, 2-118, 2-119, 2-120, 2-121, 2-122, 2-123, 2- 124, 2-125, 2-126, 2-127, 2-128, 2-129, 2-130, 2-131, 2-132, 2-133, 2-134, 2-135, 2- 136, 2-137, 2-138, 2-139, 2-140, 2-141, 2-142, 2-143, 2-147, 2-148, 2-149, 2-150, 2- 151, 2-152, 2-153, 2-154, 2-155, 2-156, 2-157, 2-158, 2-160, 2-161, 2-162, 2-163, 2- 164, 2-165, 2-166, 2-167, 2-169, 2-170, 2-171, 2-172, 2-173, 2-174, 2-175, 2-177, 2- 178, 2-179, 2-180, 2-181, 2-182, 2-183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2- 190, 2-191, 2-192, 2-193, 2-194, 2-195, 2-196, 2-197, 2-198, 2-199, 2-200, 2-201, 2- 202, 2-203, 2-204, 2-206, 2-207, 2-208, 2-209, 2-210,2-211, 2-212, 2-213, 2-215, 2- 216, 2-217, 2-218, 2-219, 2-220, 2-221, 2-222, 2-223, 2-224, 2-225, 2-226, 2-227, 3-3,
3- 4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-14, 3-15, 3-16, 3-17, 3-18, 3-19, 3- 20, 3-21 , 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 3-28, 4-1 , 5-1 , 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls. B.12 Boll weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24- well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 20 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 23 ± 1 °C and about 50 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed. In this test, the compounds 1 -1 , 1 -2, 1 -3, 1 -4, 1 -5, 1 -7, 1 -8, 1 -9, 1 -10, 1 -1 1 , 1 -12, 1 -13,
1 - 14, 1 -15, 2-1 , 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-1 1 , 2-12, 2-13, 2-15, 2-18,
2- 19, 2-20, 2-21 , 2-22, 2-23, 2-26, 2-27, 2-28, 2-29, 2-30, 2-31 , 2-32, 2-33, 2-34, 2-35, 2-36, 2-37, 2-38, 2-39, 2-40, 2-41 , 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 2-51 , 2-52, 2-53, 2-54, 2-55, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61 , 2-62, 2-63, 2-64, 2-65, 2-66, 2-67, 2-68, 2-69, 2-70, 2-71 , 2-72, 2-73, 2-74, 2-75, 2-76, 2-77, 2-78, 2-79, 2-80, 2-81 , 2-82, 2-83, 2-84, 2-85, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91 , 2-92, 2-93, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101 , 2-102, 2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109,
2- 1 10, 2-1 1 1 , 2-1 12, 2-1 13, 2-1 14, 2-1 15, 2-1 16, 2-1 17, 2-1 18, 2-1 19, 2-120, 2-121 , 2- 123, 2-124, 2-125, 2-126, 2-127, 2-128, 2-129, 2-130, 2-131 , 2-132, 2-133, 2-134, 2- 135, 2-136, 2-137, 2-138, 2-139, 2-140, 2-141 , 2-142, 2-143, 2-145, 2-146, 2-147, 2- 148, 2-149, 2-150, 2-151 , 2-152, 2-153, 2-154, 2-155, 2-157, 2-158, 2-160, 2-162, 2- 163, 2-164, 2-165, 2-166, 2-167, 2-168, 2-169, 2-170, 2-171 , 2-172, 2-173, 2-178, 2- 179, 2-180, 2-181 , 2-182, 2-183, 2-184, 2-185, 2-186, 2-187, 2-188, 2-189, 2-190, 2- 191 , 2-192, 2-193, 2-194, 2-195, 2-196, 2-197, 2-198, 2-199, 2-200, 2-201 , 2-202, 2- 203, 2-204, 2-206, 2-207, 2-208, 2-209, 2-210, 2-21 1 , 2-212, 2-213, 2-214, 2-215, 2- 216, 2-217, 2-218, 2-219, 2-220, 2-221 , 2-222, 2-223, 2-224, 2-225, 2-226, 2-227, 3-3,
3- 4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-1 1 , 3-12, 3-13, 3-14, 3-15, 3-16, 3-17, 3-18, 3-19, 3- 20, 3-21 , 3-22, 3-23, 3-24, 3-25, 3-26, 3-27, 3-28, 4-1 , 5-1 , 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, and 5-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.13 Colorado potato beetle (Leptinotarsa decemlineata)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Eggplants were grown 2 plants to a pot and were selected for treatment at the 1st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. The treated foliage was then cut and removed from the pot and placed in a 5-inch Petri dish lined with moistened filter paper. Five beetle larvae were introduced into each Petri dish and the dish was covered by a Petri dish lid. Petri dishes were maintained in a growth room at 25°C and 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the dishes. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.
In this test, the compounds 1 -2, 2-1 , 2-4, 2-5, 2-6, 2-10, 2-1 1 , 2-12, 2-13, 2-19, 2-20, 2- 26, 2-27, 2-28, 2-31 , 2-32, 2-33, 2-35, 2-37, 2-38, 2-40, 2-43, 2-49, 2-50, 2-53, 2-57, 2- 58, 2-59, 2-61 , 2-67, 2-68, 2-71 , 2-72, 2-73, 2-74, 2-82, 2-83, 2-88, 2-89, 2-93, 2-108, 2-1 12, 2-1 16, 2-1 18, 2-1 19, 2-120, 2-124, 2-126, 2-127, 2-128, 2-129, 2-131 , 2-132, 2- 133, 2-135, 2-137, 2-138, 2-141 , 2-143, 2-147, 2-148, 2-149, 2-150, 2-151 , 2-153, 2- 154, 2-155, 2-162, 2-163, 2-165, 2-170, 2-178, 2-179, 2-180, 2-181 , 2-182, 2-185, 2- 186, 2-187, 2-193, 2-197, 2-199, 2-200, 3-4, 3-5, 3-7, 3-8, 3-9, 3-17, and 3-18 at 1 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.
B.14 Red spider Mite (Tetranychus kanzawai)
The active compound was dissolved at the desired concentration in a mixture of 1 :1 (v/v) distilled water : acetone. A surfactant (Alkamuls® EL 620) was added at the rate of 0.1 % (v/v).
Potted cowpea beans of 7-10 days of age were cleaned with tap water and sprayed with 5 ml of the test solution using air driven hand atomizer. The treated plants were allowed to air dry and afterwards inculated with 20 or more mites by clipping a cassava leaf section with known mite population. Treated plants were placed inside a holding room at about 25-27°C and about 50-60% relatice humidity.
Mortality was detremined by counting the live mites 72 HAT. Percent mortality was assessed after 72 h. In this test, the compounds 2-1 , 2-2, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-12, 2-13, 2-15, 2-26, 2-27, 2-28, 2-29, 2-30, 2-32, 2-37, 2-40, 2-43, 2-48, 2-51 , 2-54, 2-55, 2-59, 2-60, 2-68, 2-70, 2-71 , 2-72, 2-73, 2-75, 2-77, 2-82, 2-86, 2-97, 2-98, 2-99, 2-100, 2-108, 2- 1 16, 2-1 18, 2-1 19, 2-120, 2-124, 2-126, 2-127, 2-128, 2-129, 2-131 , 2-132, 2-133, 2- 134, 2-135, 2-136, 2-137, 2-138, 2-139, 2-140, 2-141 , 2-142, 2-143, 2-145, 2-146, 2- 147, 2-148, 2-149, 2-151 , 2-153, 2-162, 2-165, 2-166, 2-178, 2-179, 2-180, 2-181 , 2- 182, 2-183, 2-184, 2-185, 2-186, 2-193, 2-195, 2-199, 2-200, 2-201 , 2-202, 2-203, 2- 204, 2-206, 2-207, 2-208, 2-209, 2-210, 2-21 1 , 2-213, 2-214, 2-215, 2-216, 2-217, 2- 218, 2-219, 2-220, 2-221 , 2-222, 2-224, 2-225, 2-226, 3-1 , 3-7, 3-8, 3-10, 3-1 1 , 3-12, 3- 21 , 3-22, 3-23, 3-24, 5-1 , 5-2, and 5-3 at 500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

Claims

We claim:
1 . Isothiazoline compounds of the formula I
Figure imgf000216_0001
wherein
A is a group A1, A2, A3 or A4;
wherein
A1 is selected from the group consisting of -C(=NR6)R8, -S(0)nR9 and -N(R5)R6;
A2 is a group of following formula:
Figure imgf000216_0002
wherein
# denotes the bond to the aromatic ring of formula (I);
W is selected from O and S;
Y is selected from hydrogen, -N(R5)R6 and -OR9; is a group of following formula:
Figure imgf000216_0003
wherein
# denotes the bond to the aromatic ring of formula (I); A4 is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, or is a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring is optionally substituted with one or more substituents R11;
B1, B2 and B3 are each independently selected from the group consisting of N and CR2, with the proviso that at most two of B1, B2 and B3 are N;
G1, G2, G3 and G4 are each independently selected from the group consisting of N and CR4, with the proviso that at most two of G1, G2, G3 and G4 are N;
R1 is selected from the group consisting of Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl-, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl and -C(=0)OR15; each R2 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, wherein the four last mentioned aliphatic and cyclo- aliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR10aR10b,
phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R11, and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromono- or heterobicyclic ring may be substituted by one or more radicals R11;
R3a, R3b are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, -C02R3d, Ci-C3-alkyl, Ci-C3-haloalkyl, C2-C3- alkenyl, C2-C3-alkynyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-alkylthio, Ci- C3-haloalkylthio, Ci-C3-alkylsulfonyl and Ci-C3-haloalkylsulfonyl; or
R3a and R3b together form a group =0, =C(R3c)2, =NOH or =NOCH3; each R3c is independently selected from the group consisting of hydrogen, halogen, CH3 and CF3;
R3d is selected from the group consisting of hydrogen, Ci-C6-alkyl and C1-C3- alkyloxy-Ci-C3-alkyl-; each R4 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C3- Ce-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C2-C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR10aR10b,
phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R11, and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted by one or more radicals R11; each R5 is independently selected from the group consisting of hydrogen, Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more substituents R8, and
-S(0)nR9, each R6 is independently selected from the group consisting of hydrogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more substituents
R8,
-OR9, -NR10aR10b, -S(0)nR9, -C(=O)NR 0aN(R 0aR 0b), -Si(R12)3, -C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more substituents R11; or R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl,
Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last-mentioned radicals may be substituted by one or more radi- cals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5 substituents R11; or R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9; R7a, R7b are each independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl and C2- C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R8; each R8 is independently selected from the group consisting of cyano, azido, nitro, -SCN, -SF5, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, where the cycloaliphatic moieties in the two last-mentioned radicals may be substituted by one or more radicals R13;
-Si(R12)3, -OR9, -OSO2R9, -S(0)nR9, -N(R 0a)R 0 , -C(=O)N(R 0a)R 0 ,
-C(=S)N(R 0a)R 0b, -C(=0)OR9,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroa- torn groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16,
or
two R8 present on the same carbon atom of an alkyl, alkenyl, alkynyl or cy- cloalkyl group together form a group =0,
Figure imgf000219_0001
=S(0)mR15N(R 4a)R 4 , =NR 0a, =NOR9; or =NN(R 0a)R 0 ; or
two radicals R8, together with the carbon atoms of an alkyl, alkenyl, alkynyl or cycloalkyl group which they are bonded to, form a 3-, 4-, 5-, 6-, 7- or 8- membered saturated or partially unsaturated carbocyclic or heterocyclic ring, where the heterocyclic ring comprises 1 , 2, 3 or 4 heteroatoms or het- eroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, and where the carbocyclic or heterocyclic ring is optionally substituted with one or more substituents R16; and
R8 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, where the aliphatic moieties in these six radicals may be substituted by one or more radicals R13; and
R8 in the groups -C(=NR6)R8, -C(=0)R8 and =C(R8)2 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6- haloalkynyl, where the aliphatic moieties in the six last-mentioned radicals may be substituted by one or more radicals R13; each R9 is independently selected from the group consisting of hydrogen, cy- ano, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl-, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the nine last-mentioned radicals may be substituted by one or more radicals R 3,
-Ci-C6-alkyl-C(=0)OR15, -Ci-C6-alkyl-C(=0)N(R a)R ,
-Ci-C6-alkyl-C(=S)N(R 4a)R 4b, -Ci-C6-alkyl-C(=NR 4)N(R 4a)R 4b,
-Si(R12)3, -S(0)nR15, -S(0)nN(R a)R , -N(R 0a)R 0 , -N=C(R13)2, -C(=0)R13, -C(=0)N(R 4a)R 4 , -C(=S)N(R 4a)R 4 , -C(=0)OR15,
phenyl, optionally substituted with one or more substituents R16; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroa- tom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16; and
R9 in the groups -S(0)nR9 and -OSO2R9 is additionally selected from the group consisting of Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R10a, R10b are selected independently from one another from the group consist- ing of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, where the aliphatic and cycloaliphatic moieties in the eight last- mentioned radicals may be substituted by one or more radicals R13;
-Ci-C6-alkyl-C(=0)OR15, -Ci-C6-alkyl-C(=0)N (R a)R , -Ci-C6-alkyl- C(=S)N(R a)R , -Ci-C6-alkyl-C(=N R )N(R a)R , Ci-C6-alkoxy, Ci-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio,
-S(0)nR15, -S(0)nN(R a)R , -C(=0)R13, -C(=0)OR15, -C(=0)N(R a)R , -C(=S)R13, -C(=S)SR15, -C(=S)N(R 4a) R 4 , -C(=N R 4)R13;
phenyl, optionally substituted with 1 , 2, 3 or 4, substituents R16; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or het- eroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16;
or
R10a and R10b form together with the nitrogen atom they are bonded to a
3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-
C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a 3-, 4-, 5-, 6,- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents R16;
or R 0a and R10 together form a group =C(R13)2, =S(0)m(R15)2,
=S(0)mR15N(R 4a)R 4 , =N R14 or =NOR15; is independently selected from the group consisting of halogen, cyano, az- ido, nitro, -SCN, -SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more radicals R8,
-OR9, -NR10aR10b, -S(0)nR9, -Si(R12)3;
phenyl, optionally substituted with 1 , 2, 3, 4, or 5 substituents selected independently from R16; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated aromatic heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents selected independently from R16;
or two R11 present on the same ring carbon atom of an unsaturated or par- tially unsaturated heterocyclic ring may together form a group =0,
Figure imgf000222_0001
=S; =S(0)m(R15)2; =S(0)mR15N(R 4a)R 4b, =NR14, =NOR15, or =NN(R 4a)R 4b; or two R11 bound on adjacent ring atoms form together with the ring atoms to which they are bound a saturated 3-, 4-, 5-, 6-, 7-, 8- or 9-membered ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from O, S, N, NR14, NO, SO and SO2 and/or 1 or 2 groups selected from C=0, C=S and C=NR14 as ring members, and wherein the ring may be substituted by one or more radicals selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring mem- bers, where the heterocyclic ring may be substituted by one or more radicals R16; each R12 is independently selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, C1-C6- haloalkoxy-Ci-C6-alkyl, and
phenyl, optionally substituted with 1 , 2, 3, 4, or 5 substituents R16; each R13 is independently selected from the group consisting of cyano, nitro,
-OH, -SH, -SCN, -SF5, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci- C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, tert- butyldimethylsilyl,
Cs-Cs-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo; phenyl, benzyl, phenoxy, where the phenyl moiety in the three last-mentioned radicals may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents R16; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by 1 , 2 or 3 substituents R16;
or
two R13 present on the same carbon atom of an alkyl, alkenyl, alkynyl or cycloalkyl group may together be =0, =CH(Ci-C4-alkyl), =C(Ci-C4-alkyl)Ci-
C4-alkyl, =N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl);
and
R13 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from CN, C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
and
R13 in the groups =C(R13)2, -N=C(R13)2, -C(=0)R13, -C(=S)R13 and
-C(=NR14)R13 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from CN, C3-C4- cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo; each R14 is independently selected from the group consisting of hydrogen, cy- ano, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from CN, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4- cycloalkyl which may be substituted by 1 or 2 substituents selected from halogen and cyano; and oxo;
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4-cycloalkyl, C3-C4-cycloalkyl-Ci-C4-alkyl-, where the cycloalkyl moiety in the two last-mentioned radicals may be substituted by 1 or 2 substituents selected from halogen and cyano; and oxo;
phenyl, benzyl, pyridyl, phenoxy, wherein the cyclic moieties in the four last- mentioned radicals may be unsubstituted and/or carry 1 , 2 or 3 substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy and (Ci-C6-alkoxy)carbonyl; and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16;
R14a and R14b, independently of each other, have one of the meanings given for R14; or
R14a and R14b, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring op- tionally carries one or more substituents selected from halogen, Ci-C4-alkyl,
Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
or
R14a and R14 or R14b and R14, together with the nitrogen atoms to which they are bound in the group -C(=NR14)N(R14a)R14b, form a 3-, 4-, 5-, 6- or 7- membered partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; each R15 is independently selected from the group consisting of hydrogen, cy- ano, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-
C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl and oxo;
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, C1-C4- alkylsulfonyl and oxo;
phenyl, benzyl, pyridyl and phenoxy, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl; each R16 is independently selected from the group consisting of halogen, nitro, cyano, -OH, -SH, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, feri-butyldimethylsilyl; Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-
C4-haloalkoxy and oxo;
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and oxo;
phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
or
two R16 present together on the same atom of an unsaturated or partially unsaturated ring may be =0, =S, =N(Ci-C6-alkyl), =NO(Ci-C6-alkyl), =CH(Ci-C4-alkyl) or =C(Ci-C4-alkyl)Ci-C4-alkyl;
or
two R16 on two adjacent carbon atoms form together with the carbon atoms they are bonded to a 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, and wherein the ring optionally carries one or more substituents selected from halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy; each n is independently 0, 1 or 2; and
each m is independently 0 or 1 ; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.
2. The compounds as claimed in claim 1 , where A is A1 and A1 is selected from
-C(=NR6)R8 and -N(R5)R6 and is preferably -C(=NR6)R8; wherein R5, R6 and R8 are as defined in claim 1.
The compounds as claimed in claim 2, where R6 in -C(=NR6)R8 is selected from hydrogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals each independently may be partially or fully halogenated and/or may be substituted with 1 , 2, 3, 4, 5 or 6 substituents R8; -OR9 and -NR10aR10b; wherein R8, R9, R10a and R10b are as defined in claim 1.
The compounds as claimed in claim 3, where R6 in -C(=NR6)R8 is selected from -OR9 and -NR10aR10b; wherein R9, R10a and R10b are as defined in claim 1 .
The compounds as claimed in any of claims 2 to 4, where R9 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3 C8-cycloalkyl-Ci-C4-alkyl-, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, and preferably from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3 Cs-cycloalkyl, Cs-Cs-halocycloalkyl and C3-Cs-cycloalkyl-Ci-C4-alkyl-.
The compounds as claimed in any of claims 2 to 4, where R6 in -C(=NR6)R8 is -NR10aR10b, where
R10a and R10b, independently of each other, are selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
-C(=0)OR15, -C(=0)N(R 4a)R 4 , -C(=S)N(R 4a)R 4 , phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heter ocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16;
or R10a and R10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximal ly unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci- C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; wherein R14a, R14b and R16 are as defined in claim 1.
The compounds as claimed in claim 6, where
R10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R10b is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, d-Ce-alkylcarbonyl, Ci-C6- haloalkylcarbonyl, -C(=0)OR15, -C(=0)N(R 4a)R 4b, -C(=S)N(R 4a)R 4b, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 5- or 6-membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more substituents R16;
wherein R14a, R14b and R16 are as defined in claim 1 .
The compounds as claimed in any of claims 6 and 7, where
R14a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R14b is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2- C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl-, Ci-C6-alkyl substituted with a CN group, Ci-C6-alkoxyl, Ci-C6-haloalkoxy, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51
Figure imgf000227_0001
E-1 E-2 E-3 E-4 E-5
Figure imgf000227_0002
E-6 E-7 E-8 E-9
Figure imgf000227_0003
E-10 E-11 E-12 E-13 E-14
Figure imgf000228_0001
wherein
k is 0, 1 , 2 or 3,
n is 0, 1 or 2; and
each R16 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated ring may form together =0 or =S.
The compounds as claimed in claim 6, where R6 in -C(=N R6)R8 is
-N R10aR10b, where
R10a and R10b, independently of each other, are selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkylcarbonyl, Ci-C6-haloalkylcarbonyl,
-C(=0)N(R14a)R14b, -C(=S)N(R14a)R14b, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16;
or R10a and R10b form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci- C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl;
wherein R14a. R14b and R16 are as defined in claim 1 .
The compounds as claimed in claim 9, where
R10a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R10 is selected from -C(=0)N(R14a)R14 , -C(=S)N(R14a) R14 , phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents R16, and a 5- or 6- membered heteroaromatic ring comprising 1 , 2 or 3 heteroatoms selected from N, O and S, as ring members, where the heteroaromatic ring is optionally substituted with one or more substituents R16;
wherein R14a, R14b and R16 are as defined in claim 1 .
The compounds as claimed in any of claims 9 and 10, where
R14a is selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl; and
R14b is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2- C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci- C4-alkyl-, Ci-C6-alkyl substituted with a CN group, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51
Figure imgf000230_0001
E-1 E-2 E-3 E-4 E-5
Figure imgf000230_0002
E-6 E-7
Figure imgf000230_0003
E-10 E-11 E-12 E-13
Figure imgf000230_0004
E-15 E-16 E-17 E-18 E-19
Figure imgf000231_0001
E-20 E-21 E-22 E-23 E-24
Figure imgf000231_0002
E-25 E-26 E-27 E-28 E-29
Figure imgf000231_0003
E-30 E-31 E-32 E-33 E-34
Figure imgf000231_0004
E-40 E-41 E-42 E-43 E-44
Figure imgf000231_0005
E-45 E-46 E-47 E-48 E-49
Figure imgf000231_0006
E-51 wherein
k is 0, 1 , 2 or 3,
n is 0, 1 or 2; and
each R16 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated ring may form together =0 or =S.
The compounds as claimed in any of claims 2 to 1 1 , where R8 in -C(=NR6)R8 as a meaning for A1 is selected from hydrogen and NR10aR10b and is preferably hydrogen.
The compounds as claimed in claim 1 , where A is A2 and in A2 W is O.
The compounds as claimed in any of claims 1 and 13, where in A2 Y is H or -OR9, wherein R9 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl and C1-C6- alkyl substituted by one radical R13, where R13 is preferably selected from CN , Ci- C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C1-C6- alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined in claim 1 1 .
The compounds as claimed in any of claims 1 and 13, where in A2 Y is -N(R5)R6; wherein R5 and R6 are as defined in claim 1 .
The compounds as claimed in claim 15, where
R5 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2- C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl and C3- Cs-halocycloalkyl, where the aforementioned aliphatic and cycloaliphatic radicals may be substituted by 1 , 2 or 3 radicals R8; and
R6 is selected from hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R8,
-OR9, -N R10aR10b, -S(0)nR9, -C(=O) N R 0aN(R 0aR 0b), -C(=0)R8,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R1 1 , and a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted with one or more substituents R1 1 ; or R5 and R6, together with the nitrogen atom to which they are bound, form a
3- , 4-, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, N , N H , C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last-mentioned radicals may be substituted by one or more radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5 substituents R1 1 ;
or
R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =N R10a or =NOR9; wherein R8, R9, R10a, R10b and R1 1 are as defined in claim 1 .
The compounds as claimed in claim 16, where
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and -CH2-CN ; and R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2- Cio-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the four last-mentioned aliphatic and cycloaliphatic radicals may carry 1 , 2 or 3 radicals R8; Ci-C6-alkoxy, Ci-C6-haloalkoxy, N(R10a)R10b, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R1 1 , and a 3-,
4- , 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or het- eroatom groups independently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R1 1 ;
wherein R8 and R1 1 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, N H and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
or R5 and R6, together with the nitrogen atom to which they are bound, form a group
Figure imgf000234_0001
where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
The compounds as claimed in claim 17, where
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and Chb-CN; and R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6- cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
d-Ce-alkoxy, Ci-C6-haloalkoxy, N(R 0a)R 0b,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R1 1 , and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or het- eroatom groups independently selected from N , O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R1 1 ;
wherein R8 and R1 1 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, N H and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a group
Figure imgf000234_0002
where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
The compounds as claimed in claim 18, where
R5 selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl and CH2-CN ; and R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C2-C6-alkenyl, C2-Cio-haloalkenyl, C2-C6-alkynyl, C3-C6- cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN and pyridyl;
d-Ce-alkoxy, Ci-C6-haloalkoxy, N(R10a)R10b, wherein R10a is selected from hydrogen and Ci-C6-alkyl and R10b is selected from a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N , O and S as ring members, where the heteroaromatic ring may be substituted with one or more substituents R16;
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or het- eroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11;
wherein
each R11 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R11 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
R8 is selected from OH, CN, Cs-Cs-cycloalkyl which optionally carries a CN substituent, Cs-Cs-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, d-Ce-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfonyl, Ci-C6- haloalkylsulfonyl, -C(=O)N(R10a)R10b, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R16;
wherein
R10a is selected from the group consisting of hydrogen and C1-C6- alkyl;
R10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C4-alkynyl, CH2-CN, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and each R16 as a substituent on phenyl or the heterocyclic rings is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a group
Figure imgf000236_0001
where R9 is selected from Ci-C6-alkyl and Ci-C6-haloalkyl.
The compounds as claimed in claim 16, where
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, -CH2-CN and C1-C6- alkoxy-methyl-; and
R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the four last-mentioned aliphatic and cycloali- phatic radicals may carry 1 , 2 or 3 radicals R8; -C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11 , and a 3-,
4- , 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or het- eroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11 ;
wherein R8 and R11 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a
5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy. The compounds as claimed in claim 20, where
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, CH2-CN and C1-C6- alkoxy-methyl-; and is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C3-C6-cycloalkyl which may be substituted by 1 or 2 substituents selected from F, CN, methyl and oxo,
-C(=0)R8, phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic ring may be substituted with one or more substituents R11;
wherein R8 and R11 are as defined in claim 1 ;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
The compounds as claimed in any of claims 16 to 18, 20 and 21 , where
R8 as a substituent on an aliphatic or cycloaliphatic group is selected from cyano, Cs-Ce-cycloalkyI which may be substituted by 1 or 2 substituents selected from CN, methyl and oxo, C3-Ce-halocycloalkyl, -OR9, -S(0)nR9, - N(R 0a)R 0b, -C(=O)N(R 0a)R 0b, -C(=0)OR9, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16; and
R8 in the group -C(=0)R8 is selected from hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, -OR9 and -N(R 0a)R 0b;
wherein R9, R10a, R10b and R16 are as defined in claim 1 .
The compounds as claimed in claim 22, where
R5 is hydrogen;
R6 is selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C3-C6-cycloalkyl,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R11, and a heteromonocyclic ring selected from rings of formulae F-1 to F-51
Figure imgf000238_0001
F-1 F-2 F-3 F-4
Figure imgf000238_0002
F-6 F-8 F-9
Figure imgf000238_0003
F-10 F-11 F-12 F-13 F-14
Figure imgf000238_0004
F-15 F-16 F-17 F-18 F-19
Figure imgf000238_0005
F-20 F-21 F-22 F-23 F-24
Figure imgf000238_0006
F-25 F-26 F-27 F-28 F-29
Figure imgf000238_0007
F-30 F-31 F-32 F-33 F-34
Figure imgf000238_0008
Figure imgf000239_0001
F-40 F-41 F-42 F-43 F-44
Figure imgf000239_0002
F-45 F-46 F-47 F-48 F-49
Figure imgf000239_0003
F-51 wherein
k is 0, 1 , 2 or 3,
n is 0, 1 or 2, and
each R11 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R11 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
R8 is selected from Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C1-C6- alkylthio, Ci-C6-haloalkylthio, -C(=O)N(R10a)R10b, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined in claim 1 1 ;
wherein
R10a is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C3-alkynyl, -CH2-CN and Ci-C6-alkoxy-methyl;
R 10b is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-cyclohaloalkyl, phenyl which is optionally substituted with 1 , 2, 3, 4 or 5 substituents selected from the group consisting of halogen, cyano, nitro, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined in claim 1 1 ; and each R16 as a substituent on phenyl or heterocyclic rings of formulae E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
or
R5 and R6, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring, where the ring may further contain 1 or 2 heteroatoms or heteroatom-containing groups selected from O, S, SO, SO2, NH and C=0 as ring members, wherein the heterocyclic ring may be substituted with 1 , 2 or 3 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
The compounds as claimed in claim 1 , where A is A3 and in A3 R7a and R7b are independently of each other selected from hydrogen, Ci-C4-alkyl and C1-C4- haloalkyl, and where preferably one of R7a and R7b is hydrogen and the other is hydrogen or methyl.
25. The compounds as claimed in any of claims 1 and 24, where in A3
R5 is selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more substituents R8; and
R6 is selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R8,
-OR9, -NR10aR10b, -S(0)nR9, -C(=O)NR 0aN(R 0aR 0b), -C(=0)R8, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or het- erobicyclic ring may be substituted with one or more substituents R11; or
R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last-mentioned radicals may be substituted by one or more radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5 substituents R11;
or
R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9 wherein R8, R9, R10a, R10b and R11 are as defined in claim 1 .
The compounds as claimed in claim 25, where
R5 is selected from hydrogen, Ci-C4-alkyl, C2-C3-alkynyl, -CH2-CN and C1-C6- alkoxy-methyl- and preferably from hydrogen and Ci-C4-alkyl; and
R6 is -C(=0)R8;
wherein R8 is as defined in claim 1.
27. The compounds as claimed in claim 25 or 26, where R8 is selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, where the aliphatic and cycloaliphatic moieties in the four last- mentioned radicals may be substituted by one or more radicals R13;
-OR9, -S(0)nR9, -N(R 0a)R 0b,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R16, and a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R16,
wherein R9, R10a, R10b, R13 and R16 are as defined in claim 1 .
28. The compounds as claimed in claim 27, where R8 is selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl substituted by one radical R13, Cs-Cs-cycloalkyl, C3-Ce-halocycloalkyl, -N(R10a)R10b, phenyl which is optionally substituted with 1 , 2, 3, 4 or 5 substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3- C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl and C2-C4-haloalkynyl; and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined in claim 1 1 ,
wherein
R10a and R10b, independently of each other, are selected from hydrogen, C1-C4- alkyl, Ci-C4-haloalkyl and C3-C6-cycloalkyl; and
R13 is selected from CN, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl and a heterocyclic ring selected from rings of formulae E-1 to E-51 as defined in claim 1 1 and preferably from Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfonyl and Ci-C6-haloalkylsulfonyl; and each R16 as a substituent on heterocyclic rings of formulae E-1 to E-51 is independently selected from the group consisting of halogen, cyano, nitro, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or
two R16 present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S.
29. The compounds as claimed in claim 25, where R5 and R6 are hydrogen.
The compounds as claimed in claim 1 , where A is A4 and A4 is selected from rings of formulae D-1 to D-173
Figure imgf000242_0001
D-8 D-9 D-10
Figure imgf000243_0001
Figure imgf000244_0001
D-45 D-46 D-47 D-48 D-49
Figure imgf000244_0002
D-50 D-51 D-52 D-53 D-54
Figure imgf000244_0003
D-55 D-56 D-57 D-58 D-59
Figure imgf000244_0004
D-60 D-61 D-62 D-63 D-64
Figure imgf000244_0005
D-65 D-66 D-67 D-68 D-69
Figure imgf000244_0006
D-70 D-71 D-72 D-73 D-74
Figure imgf000244_0007
D-75 D-76 D-77 D-78 D-79
Figure imgf000245_0001
D-80 D-81 D-82 D-83 D-84
Figure imgf000245_0002
D-90 D-91 D-92 D-93 D-94
Figure imgf000245_0003
D-95 D-96 D-97 D-98 D-99
(
Figure imgf000245_0004
D-100 D-101 D-102 D-103 D-104
Figure imgf000245_0005
D-105 D-106 D-107 D-108 D-109
Figure imgf000245_0006
D-110 D-111 D-112 D-113 D-114
Figure imgf000246_0001
D-115 D-116 D-117 D-118 D-119
Figure imgf000246_0002
D-120 D-121 D-123 D-124
(R11) K (R11) K (R11) K (R11) K
Figure imgf000246_0003
D-125 D-126 D-127 D-128 D-129
Figure imgf000246_0004
D-130 D-131 D-132 D-133 D-134
Figure imgf000246_0005
D-145 D-146 D-147 D-148 D-149
Figure imgf000247_0001
Figure imgf000247_0002
1
Figure imgf000247_0003
D-160 D-161 D-162 D-163 D-164
Figure imgf000247_0004
D-170 D-171 D-172 D-173 wherein
k is 0, 1 , 2 or 3;
n is 0, 1 or 2; and
R11 is as defined in claim 1 ;
and is preferably selected from D-59, D-65 and D-66 and is in particular D-59. 1 . The compounds as claimed in claim 30, wherein
each R11 is independently selected from the group consisting of halogen, cy- ano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2- C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; or two R11 present on the same carbon atom of a saturated or partially unsaturated ring may form together =0 or =S.
The compounds as claimed in any of the preceding claims, where B1, B2 and B3 are CR2.
The compounds as claimed in claim 32, where B1 and B3 are CR2, where R2 is not hydrogen, and B2 is CR2, where R2 has one of the meanings given in claim 1.
The compounds as claimed in any of the preceding claims, where R2 is selected from hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl, C3-C8- cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R8, -OR9, -S(0)nR9 and -NR10aR10b, wherein R8, R9, R10a and R10b are as defined in claim 1.
35. The compounds as claimed in claim 34, where R2 is selected from hydrogen, halogen and Ci-C2-haloalkyl, preferably from hydrogen, F, CI, Br and CF3 and in particular from hydrogen and CI.
36. The compounds as claimed in any of the preceding claims, where G1, G2, G3 and G4 are CR4; or G1, G3 and G4 are CR4 and G2 is N; or G2, G3 and G4 are CR4 and G1 is N , where R4 has one of the meanings given in claim 1. 37. The compounds as claimed in claim 36, where G1, G3 and G4 are CH and G2 is CR4, where R4 has one of the meanings given in claim 1.
38. The compounds as claimed in claim 36, where G1 is N or CH, G3 and G4 are CH and G2 is CR4, where R4 has one of the meanings given in claim 1 .
39. The compounds as claimed in any of the preceding claims, where R4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C3- C5-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio.
40. The compounds as claimed in any of the preceding claims, where R1 is selected from Ci-C4-haloalkyl and -C(=0)OR15, wherein R15 is Ci-C4-alkyl, and where R1 is preferably CF3.
41 . The compounds as claimed in any of the preceding claims, where R3a and R3b are selected, independently of each other, from hydrogen and halogen, preferably hydrogen and fluorine and are in particular hydrogen.
42. A method for preparing compounds of formula I as defined in any of the preceding claims, which method comprises dehydrating a compound of formula II
Figure imgf000249_0001
wherein B1, B2, B3, G1, G2, G3, G4, R1, R3a and R3b are as defined in any of the preceding claims and A' is A or a precursor of A;
to give a compound Γ
Figure imgf000249_0002
and, if necessary, converting the group A' into a group A.
43. The method as claimed in claim 42, where the compound of formula II, in which R3b is hydrogen, is obtained by reacting a compound of formula IV
(IV)
Figure imgf000249_0003
with an amination agent to give a compound of formula III
Figure imgf000250_0001
which reacts spontaneously to the compound II;
wherein B1, B2, B3, G1, G2, G3, G4, R1 and R3a are as defined in any of claims 1 to 41 and A' is A or a precursor of A.
The method as claimed in claim 43, where the compound of formula IV is pre pared by reacting a compound of formula V
Figure imgf000250_0002
wherein B1, B2, B3, G1, G2, G3, G4, R1 and R3a are as defined in any of claims 1 to 41 and A is A or a precursor of A;
with a sulfur source.
The method as claimed in any of claims 42 to 44, where the reaction of compound IV to compound Γ via compounds III and II is carried out as a one-pot reaction, or wherein the reaction of compound V to compound Γ via compounds IV, III and II is carried out as a one-pot reaction.
The method as claimed in claim 42, where the compound of formula II is obtained by reacting a compound of formula VII
Figure imgf000251_0001
with an amination agent to give a compound of formula VI
Figure imgf000251_0002
which reacts spontaneously to the compound II;
wherein B1, B2, B3, G1, G2, G3, G4, R1, R3a and R3b are as defined in any of claims 1 to 41 and A' is A or a precursor of A.
The method as claimed in claim 46, where the compound of formula VII is obtained by reacting a compound of formula VIII with a compound of formula IX
Figure imgf000251_0003
A method for preparing compounds of formula I as defined in any of claims 1 to 41 , wherein however R1 is CF3, which method comprises reacting a compound of formula XI
Figure imgf000252_0001
wherein B1, B2, B3, G1, G2, G3, G4, R3a and R3b are as defined in any of claims 1 to 41 and A' is A or a precursor of A;
with a fluorinating agent
to give a compound I"
Figure imgf000252_0002
and, if necessary, converting the group A into a group A.
The method as claimed in claim 48, where the fluorination agent is SF4 in combi nation with HF.
The method as claimed in any of claims 48 and 49, where the compound of formula XI is obtained by hydrolyzing a compound of formula XII
Figure imgf000252_0003
wherein B1, B2, B3, G1, G2, G3, G4, R3a and R3b are as defined in claims 1 to 41 , A is A or a precursor of A and R is Ci-C4-alkyl. The method as claimed in claim 50, where the compound of formula XII is obtained by reacting a compound XIII with a compound XIV
Figure imgf000253_0001
wherein B1 , B2, B3, G1 , G2, G3, G4, R1 and R3a are as defined in any of claims 1 to 41 , A' is A or a precursor of A and R is Ci-C4-alkyl.
A method for preparing compounds of formula I as defined in any of claims 1 to 41 , wherein R1 is CF3, which method comprises reacting a compound of formula XI I I as defined in claim 51 with a compound of formula XV
Figure imgf000253_0002
wherein B1 , B2, B3, R3a and R3b are as defined in any of claims 1 to 41 , to give a compound I"
Figure imgf000253_0003
and, if necessary, converting the group A' into a group A.
An agricultural composition comprising at least one compound of the formula I , as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one agriculturally acceptable salt thereof, and at least one inert liquid and/or solid agriculturally acceptable carrier.
A veterinary composition comprising at least one compound of the formula I , as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one veter- inarily acceptable salt thereof, and at least one inert liquid and/or solid veterinarily acceptable carrier. 55. The use of a compound as defined in any of claims 1 to 41 , of a stereoisomer and/or of an agriculturally or veterinarily acceptable salt thereof for combating in- vertebrate pests.
56. The use of a compound as defined in any of claims 1 to 41 , of a stereoisomer and/or of a veterinarily acceptable salt thereof, for treating or protecting an animal from infestation or infection by invertebrate pests.
57. A method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, plant propagation material, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, plant propagation material, soils, surfaces or spaces to be protected from invertebrate pest attack or infestation with a pesticidally effective amount of at least one imine compound of the formula I as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one agriculturally acceptable salt thereof.
58. The method as claimed in claim 57, for protecting plants from attack or infestation by invertebrate pests, which method comprises treating the plants with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one agriculturally ac- ceptable salt thereof.
59. The method as claimed in claim 58, for protecting plant propagation material and/or the plants which grow therefrom from attack or infestation by invertebrate pests, which method comprises treating the plant propagation material with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one agriculturally acceptable salt thereof.
60. Plant propagation material, comprising at least one compound of the formula I as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one agriculturally acceptable salt thereof.
61 . A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidal- ly effective amount of at least one compound of the formula I as defined in any of claims 1 to 41 , a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.
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