AU744872B2 - Organic nitrile derivatives and their use as pesticides - Google Patents

Organic nitrile derivatives and their use as pesticides Download PDF

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Publication number
AU744872B2
AU744872B2 AU27181/99A AU2718199A AU744872B2 AU 744872 B2 AU744872 B2 AU 744872B2 AU 27181/99 A AU27181/99 A AU 27181/99A AU 2718199 A AU2718199 A AU 2718199A AU 744872 B2 AU744872 B2 AU 744872B2
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Australia
Prior art keywords
alkyl
halogen
alkoxy
alkenyl
phenyl
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AU27181/99A
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AU2718199A (en
Inventor
Roger Graham Hall
Ottmar Franz Huter
Miroslav Kriz
Alfons Pascual
Arthur Steiger
Stephan Trah
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Syngenta Participations AG
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Novartis AG
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Assigned to SYNGENTA PARTICIPATIONS AG reassignment SYNGENTA PARTICIPATIONS AG Alteration of Name(s) in Register under S187 Assignors: NOVARTIS AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • 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
    • A01N43/82—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 three ring hetero atoms
    • 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<
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/70—Nitro radicals
    • C07D307/71—Nitro radicals attached in position 5
    • C07D307/72—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2
    • C07D307/74—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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 with nitro or nitroso radicals directly attached to ring carbon atoms
    • C07D333/44—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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 with nitro or nitroso radicals directly attached to ring carbon atoms attached in position 5
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

I :.OPERNMKRSPECIN27181-99-OI4 dmc- IJ;O 1.2 -1I- Organic nitrile derivatives and their use as pesticides The invention relates to a compound of formula Al"'N X A2 (1)1 wherein A, and A 2 are independent of one another and in each case represent a monocyclic or bicyclic aryl radical; and A, is substituted where appropriate with substituent (R3a)ni and A 2 where appropriate with substituent (R3b)fl2; .:nj and n 2 are independently of one another 1, 2, 3 or 4, depending on the possibilities for substitution on ring system A, and A 2 and
R
3 a is halogen, Cl-C 6 alkyl, halogen- C -C 6 alkyl, C 2 -C~alkenyll, C 2 -C~alkiinyl, hallogen-0 2 -C~Alkenyl, halogen-0 2
-C
4 alkinyl, Cs-C 6 alkoxy, halogen-C 1 -Cr 6 -alkoxy, C 2
-C
6 alkenyloXy, C 2
-C
6 alkinyloxy, halogen-C 2
-C
6 alkenyloxy, halogen-C 2 -C~alkinyloxy, -OH, -SF 5 -CHO, 1
-C
6 alkyl, -C(=O)-halogen-Cj-C 6 alkyl, -C(=O)-OCI-C 6 alkyI, -C(=O)-O-halogen-C-Cralkyl,
-O-C(=O)N(R
6 2 (wherein both Rr, substituents are independent of one another), -CN,
-NO
2 -S(=O0) 2
N(R
6 2 (wherein both R 6 substituents are independent of one another), -S (=O)p-CI-C 6 alkyl, -S(=O)r-halogen-C 1
-C
6 alky, 1
-C
6 alkyl, -Q-S(=O)p-halogen-C.C 6 akyl, phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubsti1tuted or substituted in the aromatic ring independenly of one another once to five times with substituents selected from the group consisting of halogen, cyano, N0 2
CI-C
6 alkyl, halogen-
C
1
-C
6 a.ky, C 1 -C~alkoxy and halogen-C 1
-C
6 alkoxy;
-CR
5
=CR
5 Rl 4
-NR
1 1
R
12 1
-C
6 alkyl,
-CR
15 =N0R 10 or a five or six-membered heteroaryl ring, wherein the said heteroaryl ring is substituted where appropriate, depending on the substitution possibilities on P:\0PER\MKR\271I.9'9 sp.do-2811/0 A1 -2the ring, with 1 to 3 substituents selected from the group consisting of halogen,
C
1
-C
4 alkyl, Cl-C 4 haloalkyl, NO 2 and ON; R3b s halogen, CI-C 6 alkyl, halogen-C 1
-C
6 alkyl, C 2
-C
4 aikenyl, C 2
-C
4 alkinyl, halogen-C 2
-C
4 alkenyl, halogen-0 2
-C
4 alkinyl, C 1
-C
6 alkoxy, halogen-C 1
-C
6 alkoxy,
C
2
-C
6 alkenyloxy, C 2
-C
6 alkinyloxy, halogen-0 2
-C
6 alkenyloxy, halogen-C 2
-C
6 alkinyloxy, -SFs, -CHO, -C(=O)-Cl-C 6 alkyl, -C(=O)-halogen-C-C 6 alkyl, -C(=O)-0C 1
-C
6 alkyl, -C(=O)-O-halogen-Cj-C 6 alkyl, -O-C(=O)N(R 6 2 (wherein the two Re substituents are independent of one another), -ON, -NO 2 phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO 2 0 1
-C
6 alkyt, halogen-Cl-C 6 alkyI, C 1
-C
6 alkoxy and halogen-Cl-C 6 alkoxy; -S(=O)P-C 1
-C
6 alkyI in the 0. 0:4-position or -S(=O)p-halogen-Cj-Ccalky in the 4-position, with the proviso, that one of 00.. the substituents R~b is -S(=O)P-C 1
-C
6 alkyl or -S(=O)p-halogen-C 1
-C
6 alkyl; 0.
R
2 is hydrogen -C 1
-C
6 alkyl-NRjjR 12 7 a1, -COC9-C 2 oalkyl, -CH 2 O(C=O)Cl-C 6 alkyl, -Cl-C 6 alkyl-O-C 1
-C
6 alkyl-O-C 1
-C
6 alkyl, -CH 2 0(C=O)C 2
-C
6 alkenyl, 0 0 0 0-CH2O(C=O)C 2
-C
6 alkinyl, -C(=S)OC 2
-C
6 alkenyl, -C(=S)0C 2
-C
6 alkinyl,
-C(=S)SCI-C
6 alkyl, -C(=S)SC 2 -Cealkenyl, -C(=S)SC 2 -C~alkinyl, -C(=O)SC 1 -Cealkyl,
-C(=O)SC
2
-C
6 alkenyl, -C(=O)S0 2
-C
6 alkinyl, R 1
R
12 -C(=O)NRl 0 0R 1 3 0:-CH 2 0C 2
-C
6 alkenyl, -CH 2 0C 2
-C
6 alkinyl, -CH 2 0C 2
-C
6 haloalkenyl or 0
CH
2 0C 2
-C
6 haloalkinyl; Cj-C 6 alkyl, Cl-C 6 alkoxy, C 3
-C
6 cycloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 alkinyl, halogen-Cl-C 6 alkyl, halogen-0 3
-C
6 alkenyl, halogen-C 3
-C
6 alkinyl, benzyl or benzoyl, wherein the benzyl or benzoyl radical is substituted in the aromatic ring independently of one another once to three times by substituents selected from the group consisting of halogen, -ON, NO 2
C
1
-C
6 allkyl, 0 1 -C~Alkoxy, halogen-C-C 6 alkyl and halogen- 0 1 -Cealkoxy; C 1
C
6 atlkoxy-C 1
-C
6 alkyI, cyano-0 1
-C
6 alkyl, 7 a,
-OC()-R
7 a, -C(0)C()R 7 a, -OCQ-O)-Rm, -S(=O)N(R 8 2 (wherein the two Re substituents are independent of one another); cyano, -0 1 -Cealkyl- WO 99/37603 PCT/EP99/00363 -3-
N(R
5 8 -C1 -C 6 alkyl-S-C(=S)-R 8 -C1 -C 6 alkyl-S(=O)-R 9 -S(=O)p-R 9 or
-CH
2
-N(R
10 )-S0 2
-R
9 X is 0or S; p isO0,l1or 2;
R
5 is independently H or Cl-C 8 alkyl;
R
6 is independently H, CI-Cjalkyl, C 3
-C
6 cycloalkyl, phenyl or benzyl, wherein the phenyl or benzyi group is substituted in the aromatic ring where appropriate independently of one another once to three times with substituents selected from the broup consisting of halogen, -CN, N0 2 Cl-C 6 alkyl, 0 1
-C
4 alkoxy, halogen -C 1
-C
6 al kyl and halogen-
C
1
-C
6 alkoxy; or two alkyl radicals R 6 together with the nitrogen atom to which they are bonded, form a five to seven-membered ring, wherein a OH 2 group, where appropriate, is substituted by a heteroatom selected from the group consisting of 0 and S, or is substituted by NH, and wherein the five to seven-membered ring, where appropriate, is substituted once or twice with Cl-C 4 alkyl;
R
7 1 is C1 -C 6 alkoxy-C 1
-C
6 al kyl, CH 2
CH
2
CF
2 CI, 0 -C~alkylthio-C 1 -C~alkyl, acyloxy-C 1
-C
6 alkyl, halogen -C 3
-C
6 CYcloalkyl, C 3
-C
6 cycloalkyl-0 1
-C
6 alkyl, halogen-C 3 -C6-cycloalkyl-
C
1
-C
6 alkyl, aryloxy-0 1
-C
6 alkyl; or phenyl, benzyl, phenoxy or aryloxy-Cl-C 6 alkyl, which are substituted with 1 to 3 substituents selected form the group consisting of halogen, nitro, cyano, 0 1 -0 4 -alkyl, halogen-0 1
-C
4 -alkyl and halogen-0 1 -0 4 -alkoxy; R7b is H, 0 1
-C
8 alkyl, C 2
-C
8 alkenyl, halo-Cl-C 8 alkyl, halo-C 2
-C
8 alkenyl, C 1
-C
8 alkoxy, halo-Cl-C 8 alkoxy, C 3
-C
6 cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or -N(R 6 2 (in which the two R 6 are independent of one another);
R
8 is Cl-Csalkyl, Cl-Cealkoxy, halogen-Cl-O 8 alkyl, halogen -C 1
-C
8 al koxy, C 1
-O
8 alkylthio, phenyl, benzyl or -N(R 6 2 (wherein the two R 6 radicals are independent of one another); R9 is CI-C 6 alkyl, halogen-C-C 4 alkyl or aryl, which is unsubstituted or substituted once to three times, independently of one another, with subsituents selected from the group consisting Of CI-C 6 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkinyl, CI-C 4 alkoxy, halogen, cyano, halogen-Cl-C 4 alkyl, halogen-C 2
-C
4 alkenyl, halogen-0 2
-C
4 alkinyl, halogen -C 4 al koxy and nitro; Rio is H, Cl-C~alkyl, C3-C 6 cycloalkyl, phenyl oder benzyl, wherein the phenyl and benzyl radicals are unsubstituted or substituted in the aromatic ring once to three times independently of one another with substituents selected from the group consisting of -z WO 99/37603 PCT/EP99/00363 -4-
C
1
-C
4 alkyl, C 1
-C
4 alkoxy, halogen, cyano, halogen-C 1
-C
4 alkyl, halogen-Ci-C 4 alkoxy and nitro;
R
11 and R 12 are independently of one another H, C-C6 alkyl, phenyl, -COC,-C 6 alkyl, -COC1-C 6 haloalkyl, -COphenyl, or together form a five or six-member saturated or unsaturated ring, wherein if appropriate one or more, especially one, of the CH- or
CH
2 -groups is or are substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if appropriate is independently of each other substituted with 1 to 3 substituents selected from the group consisting of halogen, C-C 4 alkyl, C-C 4 haloalkyl, C 1
-C
4 haloalkoxy,
NO
2 and CN; or the two substituents
R
11 and R 12 together form a ring X
X
H
2 )q orI X
X
q is 2 or 3; and
R
13 is H, C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkinyl;
R
14 is hydrogen, CI 1
-C
6 alkyl, halogen-C 3
-C
6 alkyl, Cl-C 6 alkoxy, halogen-C-C 6 alkoxy, C2-C 6 alkenyloxy, -CHO, -C(=O)-CI-C 6 alkyl, -C(=O)-halogen-C-C 6 alkyl, -C(=O)-OC1-C 6 alkyl, -C(=O)-O-halogen-C 1
-C
6 alkyl, -CN, -NO 2 2
N(R
6 2 (wherein the two R 6 substituents are independent of one another), 6 alkyl, -S(=O),-halogen-C 1
-C
6 alkyl, 1
-C
6 alkyl, -O-S(=O),-halogen-C 1
-C
6 alkyl, phenyl, benzyl, or benzyloxy wherein each of the phenyl, benzyl, or benzyloxy substituents is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO 2
C
1
-C
6 alkyl, halogen-C 1
-C
6 alkyl, C,-C 6 alkoxy and halogen-
CI-C
6 alkoxy; and
R
15 is is hydrogen, CI-C 6 alkyl or halogen-C-C 6 alkyl; and, if appropriate, to the possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in the form of a salt, to a method for the preparation and use of these compounds, E/Z isomers and tautomers, pesticides, whose active ingredient is selected from these compounds, E/Z isomers and tautomers, and to a method for the preparation and use of these compositions, intermediate products, in free form or in the form of a salt, for the preparation of these compounds, and where appropriate their ~lr;i~iii~iT=ili~rriLT~.li~:l~-~fie*~?i^ WO 99/37603 PCT/EP99/00363 tautomers, in free form or in the form of a salt, and to a method for the preparation and use of these intermediate products and their tautomers.
In the literature, certain phenylhydrazone derivatives are proposed as active ingredients in pesticides. The biological properties of these known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further compounds with pesticidal properties, especially for the control of insects and members of the order acarina; this problem is solved according to the invention with the development of the present compounds of formula Some compounds of formula comprise asymmetrical carbon atoms, as a result of which the compounds may occur in an optically active form. Owing to the presence of the C=N double bond, the compounds may occur in E and Z isomeric forms. Atropisomers of the compounds may also occur. Formula should encompass all these possible isomeric forms and mixtures thereof, for example racemates or mixtures of E/Z isomers.
The general terms used hereinbefore and hereinafter have the following meanings, unless defined otherwise.
Groups and compounds containing carbon comprise, unless defined otherwise, in each case 1 to 8 inclusive, preferably 1 to 6 inclusive, more particularly 1 to 4 inclusive, especially 1 or 2, carbon atoms.
Alkyl as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkoxy or alkylthio is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either straight-chained, i.e.
methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl as a group per se and as a structural component of other groups and compounds, such as alkenoxy, alkenyl halide or alkenoxy halide is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either straight-chained, e.g. vinyl, 1-methylvinyl, allyl, 1-butenyl oder 2-hexenyl, or branched, such as isopropenyl.
Alkinyl as a group per se and as a structural component of other groups and compounds, such as alkinyl halide is, in each case with due consideration to the number of carbon L i-~I-~_I=I-LLI WO 99/37603 PCT/EP99/00363 -6atoms in the group or compound concerned, either straight-chained, e.g. propargyl, 2butinyl or 5-hexinyl, or branched, such as 2-ethinylpropyl or 2-propargylisopropyl.
C
3
-C
6 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Aryl is phenyl or naphthyl, especially phenyl.
Bicyclic heteroaryl is taken to mean a radical which may independently contain one or more heteroatoms only in one ring such as for example in quinolinyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl as well as in both rings such as for example in pteridinyl or purinyl.
Halogen as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkenyl halide and alkinyl halide is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, and quite particularly chlorine.
Halogen-substituted groups and compounds containing carbon, such as alkyl halide, alkenyl halide or alkinyl halide, may be partly halogenated or perhalogenated, where in the case of repeated halogenation the halogen substituents may be the same or different. Examples of alkyl halide as a group per se and as a structural component of other groups and compounds, such as alkenyl halide are methyl substituted once to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ethyl substituted once to five times by fluorine, chlorine and/or bromine, such as CH 2
CF
3
CF
2
CF
3
CF
2
CCI
3
CF
2 CHC1 2
CF
2
CHF
2
CF
2
CFCI
2
CF
2 CHBr 2
CF
2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted once to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br,
CF
2
CHFCF
3
CH
2
CF
2
CF
3 or CH(CF 3 2; and butyl or one of the isomers thereof substituted once to nine times by fluorine, chlorine and/or bromine, such as CF(CF 3
)CHFCF
3 or
CH
2
(CF
2 2
CF
3 Alkenyl halide is for example CH 2 CH=CHCI, CH 2
CH=CC
2
CH
2
CF=CF
2 or
CH
2
CH=CHCH
2 Br. Alkinyl halide is for example CH 2 C-CF, CH 2
C=CCH
2 CI or
CF
2
CF
2
C-CCH
2
F.
Some compounds of formula may, as is familiar to persons skilled in the art, occur as tautomers, especially if R 2 is H. Accordingly, any reference to compounds of formula (I) hereinbefore and hereinafter is understood to include also their corresponding tautomers, even if the latter are not specifically mentioned in each case.
-v WO 99/37603 PCTIEP99/00363 -7- Compounds of formula which show at least one basic centre may form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids substituted if appropriate by halogen, e.g. acetic acid, such as dicarboxylic acids unsaturated if appropriate, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, typically C1-C 4 alkanesulfonic or arylsulfonic acids substituted where appropriate for example by halogen, e.g. methanesulfonic or ptoluenesulfonic acid. In a broader sense, compounds of formula with at least one acid group can form salts with bases. Suitable salts with bases are for example metal salts, typically alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Corresponding internal salts where appropriate may also be formed. Compounds of formula in free form are hereinbefore and hereinafter taken to imply also their corresponding salts, and the salts where applicable are taken to mean also the free compounds of formula The same applies for tautomeric derivatives of compounds of formula and salts thereof. In each case, the free form is generally preferred.
The following forms are preferred within the scope of this invention: A compound of formula wherein A, and A 2 are independently of one another a substituent selected from the group consisting of (RDS- N )(R)n
(R
3 )n (R 3
(R
3 )m R4 WO 99/37603 PCT/EP99/00363 -8- N-N
R
N
R4 N KR /6-3
N
N
I
N-N R3 0 03 N-N
R
N
N (R 3 N^ RN
F
/4 N 1 N/j (R 3 n '3)nK :I f I NA(R N N (R3) m R4 (R3)n
N
(R
3 )m N R 3 HN SN
CH,
and especially phenyl, naphthyl, pyridyl or thiadiazolyl, very especially phenyl or pyridyl, in particular phenyl;
R
3 corresponds to R3a and R3b of formula Ra and R3b are independently of one another halogen, -CN, NO 2 halogen-C-C 2 alkyl,
C
1
-C
2 alkoxy or halogen-C1-C 2 alkoxy, halogen-C 2 -Csalkenoxy or halogen-C 2
-C
5 alkinyloxy; especially chlorine, -CN, CF 3 or OCF 3 wherein, if m n is greater than 1, the radicals R3a and R3b are independent of one another;
R
4 is H, Ci-C 4 alkyl, phenyl or benzyl; especially H and methyl; n is 0 to 5, especially 1 to 3, depending on the possibility for substitution on the ring system, and the values of n in A, are independent of the values of n in A 2 m is 0 to 4, depending on the possibility for substitution on the ring system, and the values of m in A 1 are independent of the values of m in A 2 A WO 99/37603 PCT/EP99/00363 -9the sum of m n is 0 to 5; especially 1, 2 or 3; A compound of formula wherein A 2 corresponds to substituents selected from the
SN
group consisting of furanyt, thienyl, ,an Nan
R
2 is R&a or R2b; A compound of formula wherein A, and A 2 are phenyl; A compound of formula wherein
R
2 1 is -C 1
C
6 alkyl-NR 11
R
12 0C(=X)-R 7 a, -COC 9
-C
2 oalkyl, -CI-C 6 alkyI-O-C 1
-C
6 alkyI- O-Cl -C 6 alkyl, -CH 2 O(C=O)Cl-C 6 alkyi, -CH 2 O(C=O)0 2 -0 6 alkenyl, -0H20(C=O)C 2
-C
6 alkinyl, -C(=S)00 2
-C
6 alkenyl, -C(=S)0C 2
-C
6 alkinyl, -C(=S)SC,-C 6 alkyl, -C(=S)SC 2
-C
6 alkenyl,
-C(=S)SC
2
-C
6 alkinyl, -C(=O)S0 1
-C
6 alkyl, -C(=O)SC 2
-C
6 atkenyl, -C(=O)SC 2
-C
6 alkinyl,
-C(=S)NR
11
RI
2 -C(=O)NRjo0R 13
-CH
2 0C 2
-C
6 alkenyl,
-CH
2
OC
2
-C
6 alkinyl, -CH 2 0C 2
-C
6 haloalkenyl or -CH 2 0C 2
-C
6 haloalkinyl; especially
R
2 a is -CH 2 alkyl-NR 11
R
12
-COC
9
-C
20 alkyI, -CI-C2alkyl-O-Cl-C 2 alkyI-O-Cl-C 2 alkyl -0H 2 0(C=O)C 1
-C
2 alkyl, -0H 2 0(C=O)C 2
-C
4 alkenyl, -0H 2 0(C=O)0 2
-C
4 alkinyl, -C(=S)0C 2
-C
4 alkenyl, -C(=S)0C 2
-C
4 alkinyl, -C(=S)SC,-C 2 alkyl, -C(=S)SC 2
-C
4 alkenyl,
-C(=S)SC
2
-C
4 alkinyl, -C(=O)SC 1
-C
2 alkyl, -C(=O)SC 2
-C
4 alkenyl, -C(=O)SC 2
-C
4 alkinyl, 0 1
-C
4 aikylthio-CI-C~alkyl, -C(=S)NR 11 Rl 2 -C(=O)NRjo0R 13
-CH
2
OC
2
-C
4 alkenyl,
-CH
2 0C 2
-C
4 alkinyl, -CH 2 0C 2
-C
4 haloalkenyi or -CH 2 0C 2
-C
4 haloalkinyl; in particular
R
2 is -CH 2 alkyl-NR 11
R
1 2
-COC
9
-C
20 alkyl, -0 1
-C
2 alkyl-O-C 1
-C
2 alkyl-O-Cl-C 2 alkyl,-
CH
2
O(C=O)C
1
-C
2 atkyl, -C(=O)SC 1
-C
2 alkyl, -CH 2 0C 2
-C
4 alkenyl, or -CH 2 0C 2
-C
4 alkinyl; in particular
R
2 is -CON(00H 3
)CH
3 0C(O)NHCOCH 3
-COSC
2
H
5
-COSCH
3 0CH 2 00(O)C(CH 3 3
CH
2 0C 2
H
4 0CH 3
-CH
2
OCH
2
CH=CH
2
-CH
2
OCH
2 C=-CH, -C0C 1 0
H-
2 1 A compound of formula wherein R2b is hydrogen, CI-C 4 alkyl, C 1
-C
4 alkoxy-Cj-C 4 alkyl, 7 a1, -C(=O)-Cl-C 4 alkyl,- C(=O)-halogen-C 3
-C
6 alkenyl 3
-C
6 cycloalkyl -C(=O)-O-Cl-C 2 alkyl, O-Cl-C 2 alkyl, 6 2 cyano, benzoyl or benzyl, wherein the benzoyl or benzyl radical is substituted in the aromatic ring if necessary, independently of one another, once nfl WO 99/37603 PCT/EP99/00363 to three times with a substituent selected from the group consisting of halogen, -ON, -NO 2 trifluoromethoxy and trifluoromethyl; or-C(=O)-N(R 6 2 and the two R 6 substituents are, independently of one another, H, 0 1
-C
4 alkyl, C3-C6cycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group if necessary, independently of each other, is substituted in the aromatic ring once or twice with substituents selected from the group consisting of halogen, -ON, 0 1
-C
4 alkyl, 0 1
-O
4 alkoxy, halogen-0 1
-C
2 alkyl and halogen- Cl-O 2 alkoxy; or two alkyl radicals R 6 together with the nitrogen atom to which they are attached form a five or six-membered ring, wherein a CH 2 -group if necessary is substituted by an 0 atom or by NH, and wherein the five or six-membered ring is substituted if necessary with methyl; especially R2b is hydrogen, C 1
-O
3 alkyl, CI -Calkoxy-0 1 -CAllkyl, -O 2 alkyl -O(=O)-fluoro- 0 4 -Cralkenyl -C(=O)-cyclopropyl 1
-C
2 alkyl, 1
-O
2 alkyl, 6 2 cyano, benzyl. or o-nitrobenzyl; 6 2 or 6
H
5 wherein the phenyl ring is likewise substituted once to three times with a substituent selected from the group consisting of halogen, NO 2 trifluoromethoxy and trifluoromethyl; and the two R 6 radicals are, independently of one another, H, CI-C 4 alkyl, cyclopropyl, phenyl or benzyl, wherein the phenyl or benzyl group, if necessary, independently of one another, is substituted in the aromatic ring once or twice by substituents selected from the group consisting of chlorine, -ON and O0F 3 or two R 6 alkyl radicals together with the nitrogen atom to which they are attached form a six-membered ring and wherein a OH 2 group where applicable is substituted by an 0 atom or by NCH 3 A compound of formula wherein A, is a pyridyl radical; A compound of formula wherein
(R
3 a)nil is Cl, 012, 013, -(OF 3 2 Cl-OF 3
NO
2 OCN, 01 2 -N0 2 -00F 3
-OF
3 Cl-OF 3 C1 2 0CF 3 OF2 00F 3 -C1 2 01 2 -Br, Ol-0F 3 Cl-Br-OH 3
-(CH
3 2 -Br, 01 3 -0F 3 01 2 -F-0F 3
F
2 -0F 3 -Ol, O1 2
-ON,
01 2 -0F 3 01 2
-SCF
3 C1 2
-OCF
3 C1 2 -0 2 0F 3 O1 2 -S0 2 0H 3 01 2
-OOF
2 B3r, O1 2
-OOF
2 H, 01 2 -0 2 1F 5 (N0 2 2
-CF
3 (N0 2 2 -Cl, O1 2 -S0 2
CH
3 or 01 2 -OS0 2
OF
3 especially 2-Cl, 2,3-012, 2,4-012, 2,6-012, 2,4,6-013, 3,5-(0F 3 2 2-01-4-OF 3 2-NO 2 ,2-ON, 3-ON, 4-ON, 2,6-01 2 -4-N0 2 4-00F 3 4-OF 3 3-OF 3 2-01-4-OF 3 2-01-4-NO 2 2,6-C1 2 -4-0F 3 2,6-01 2 -4-OCF 3 2,6-01 2 2,6-01 2 -4-Br, 2-Ol-4-0F 3 2-Ol-4-Br-6-0H 3 2,6-(0H 3 2 -4-Br, 2,3,6-01 3 -4-0F 3 2,6-C1 2 -3-F-4-CF 3 2,3-F 2 -4-CF 3 -6-Ol, 2,6-01 2 -4-CN, 2,4-01 2 -6-0F 3 2,6-01 2 -4-SCF 3 2,6-012-4- WO 99/37603 PCT/EP99/00363
SOOF
3 2,6-01 2 -4-S0 2 0F 3 2,6-01 2 -4-S0 2 0H 3 2,6-C1 2 -4-OCF 2 Br, 2,6-0l 2 -4-OOF 2 H, 2.6-012-4- 0 2
F
5 2,6-(N0 2 2 -4-CF 3 2,6-(N0 2 2 -4-CI, 2 ,6-01 2 -4-OSO 2
CH
3 or 2,6-C1 2 -4-0S0 2 0 F 3 very especially 2,3-012, 2,4-012, 2,6-012, 2,4,6-013, 3,5-(0F 3 2 2-01-4-OF 3 2-ON, 3-ON, 4-ON, 2,6-01 2 -4-N0 2 4-00F 3 4-C F 3 3-OF 3 2-01-4-OF 3 2-CI-4-N0 2 2,6-C1 2 -4-CF 3 2,6-01 2 -4-00F 3 2 ,6-01 2 -4-F, 2,6-Cl 2 -3-F-4-0F 3 2,3-F 2 -4-0F 3 -6-Ol, 2,6-01 2 -4-ON, 2,4-01l2-6-C F 3 2,6-01 2 -4-SCF 3 2,6-012-4-
SOOF
3 2 ,6-01 2 -4-S0 2 0F 3 2 ,6-01 2 -4-C 2
F
5 2,6-(N0 2 2 -4-0 F 3 2,6-(N0 2 2 -4-Oi, 2,6-012-4-
OSO
2
CH
3 or 2,6-01 2 -4-OSO 2
CF
3 A compound of formula wherein one (R3b)fl2 is 1
-O
6 alkyI in the 4-position or -S(=O)p-halogen- 1
-O
6 alkyI in the 4-position; especially 1
-O
3 alkyl or -S(=O)p-halogen-C 1
-O
3 alkyl; more specifically is -S(=O)p-halogen- 1
-O
3 alkyl; very especially, wherein n 2 is 1 and R3b is SOOF 3 S00 2
F
5
SOOHF
2
SOCF
2 B3r, SOOF 2 OI, SOOF 2
OF
2 Br,
SOOF
2
OF
2 CI, SOF 3 S0 2
F
5
SCHF
2
SOF
2 B3r, SOF 2 OI, SOF 2
OF
2 Br, SOF 2
OF
2 OI, S0 2 0F3, S0 2
C
2
F
5
SO
2 OH F 2
SO
2
OF
2 B3r, S0 2 0F 2 01, SO 2
OF
2
OF
2 Br, S0 2
CF
2
CF
2 Cl; A compound of formula wherein (R3b)fl2 is -ON, Cl, 012, F, F 2 Br, -NO 2
-(NO
2 2 -N0 2
-CF
3
OF
3
-(OF
3 2
-ON-OF
3 Cl-OF 3
F-
ON, -Cl-ON, -OOF 3 -Cl-NO 2 -0H 3 -N0 2
-OCH
3 -N0 2
-C
6 1- 5 -0 6
H
4 -0 6
H
4 -Ol, -0 6
H
4
-CF
3 -0 6
H
4 -0F 3 -0 6
H
4 -N0 2 -0 6
H
3 -(0F 3 2 -0 6
H
3 -01 2
-C
6
H
3 -F-ON, F-NO 2 01-NO 2 0l-NO 2 -CHO, SCF 3
SOOF
3
SO
2
CF
3 or -O(=O)0F 3 especially 4-ON, 3-ON, 4-Cl, 3,4-012, 2,3-012, 3,5-012, 2,5-012, 3,5-F 2 2,6-F 2 4-B3r, 2-F, 4-NO 2 2- N0 2 -4-CF 3 3-OF 3 4-OF 3 3,5-(0F 3 2 2-CN-4-0F 3 2-01-4-OF 3 2-F-4-ON, 3-01-4-ON, 4-00F 3 3-00F 3 4-01-3-NO 2 2-01-4-NO 2 3-0H 3 -4-N0 2 3-00H 3 -4-N0 2 4-0 6 H, 4-0 6
H
4 4-C 6
H
4 4-Cl, 4-0 6
H
4 -4-0F 3 4-0 6
H
4 -3-0F 3 4-0 6
H
4 -3-N0 2 4-0 6
H
3 -(3,5-CF 3 2 4-0 6
H
3 -2,4-01 2 4-0 6
H
3 3,4-012, 4-0 6
H
3 -3,5-01 2 4-0 6 2-F-4-ON, 2-F-4-NO 2 2-01-4-NO 2 4-01-3-NO 2 4- CHO, 4-SOF 3 4-SOOF 3 4-S0 2 0F 3 or 4-O(=O)0F 3 very especially 4-ON, 3-ON, 4-Cl, 3,4-012, 2,3-012, 3,5-012, 2,5-012, 3,5-F 2 2,6-F 2 2-F, 2-N0 2 -4-0F 3 4-
NO
2 3-OF 3 4-OF 3 3,5-(0F 3 2 2-CN-4-0F 3 2-01-4-OF 3 2-F-4-ON, 3-01-4-ON, 4-00F 3 3- 00F 3 4-01-3-NO 2 2-01-4-NO 2 3-0H 3 -4-N0 2 3-00H 3 -4-N0 2 4-C 6 1- 5 2-F-4-ON, 2-F-4-N0 2 2-01-4-NO 2 4-01-3-NO 2 4-OHO, 4-SOF 3 4-SOOF 3 4-SO 2
CF
3 or 4-O(=O)0F 3 A compound of formula wherein R2b is hydrogen; (11) A compound of formula wherein nj is 1, 2, 3or 4,preferably 2or 3; WO 99/37603 PCT/E P99/00363 -12- (12) A compound of formula wherein n 2 is 1 or 2, preferably 1; (13) A compound of formula wherein ni is 2, 3, or 4 and n 2 is 1 or 2; (14) A compound of formula wherein
R
1 1 and R 12 are independently of one another H, C 1
-C
2 alkyl, phenyl, -COC 1
-C
2 alkyl, -COphenyl, or together form a five or six-membered saturated or unsaturated ring, wherein one of the CH- or CH 2 -groups if applicable is substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if applicable is substituted with 1 or 2 substituents selected from the group consisting of C 1
-C
2 alkyl, Ci-C 2 haloalkyl, NO 2 CN; or the two substituents R 11 and R 12 together form a ring X
X
H
2 )q or
I
X X and q is 2; especially RI, and R 12 are independently of one another H, C0-C 2 alkyl, phenyl, -COC1-C 2 alkyl, COphenyl, very especially H, methyl or ethyl.
A compound of formula wherein at least one R3a and/or R3b is/are -CR 5
=CR
5
R
4 and
R
1 4 is hydrogen, C1-C 6 alkyl, halogen-C-Cealkyl, -CHO, 6 alkyl, halogen-C 1
-C
6 alkyl, 6 alkyl, -C(=O)-O-halogen-C-C 6 alkyl, -CN, -NO 2 S(=0) 2
N(R
6 2 (wherein the two Re substituents are independent of one another),
C
1
-C
6 alkyl, phenyl, benzyl or benzyloxy; and Rs is hydrogen or C1-C 2 alkyl; especially an Raa or R3b is -CR 5 =CRsR 4
R
1 4 is hydrogen, C,-C 2 alkyl, halogen-C-C 2 alkyl, phenyl or benzyl; and
R
15 is methyl or CF 3 (16) A compound of formula wherein Rs is independently H or CC2alkyl; (17) A compound of formula wherein 'WO 99/37603 PCT/EP99/00363 -13n 2 is1 and (R3b)fl2 is SCH 3
SCF
3
SC
2
H-
5
SC
2
F
5
SOCH
3 S00 2 H, SOC 2
F
5
SO
2
N(CH
3 2
SO
2
N(C
2
H
5 2
SO
2
CH
3
SO
2
CF
3 S0 2
C
2
H-
5 S0 2
C
2
F
5
SOCF
3
SOCHF
2
SOCF
2 B3r, SOCF 2 CI, SOCF 2
CF
2 Br,
SOCF
2
CF
2 CI, SCHF 2
SCF
2 B3r, SCF 2 CI, SGF 2
CF
2 Br, SCF 2
CF
2 CI, SO 2
CHF
2
SO
2
CF
2 Br,
SO
2
CF
2 CI, SO 2
CF
2
CF
2 Br or SO 2
CF
2
CF
2 CI; in particular
SCF
3
SC
2
F
5
SOCF
3
SQC
2
F
5
SO
2
CF
3 or S0 2
C
2
F
5 and
R
2 is R 2 or R2b, especially H, -CH 2 0C 2
H
5
-COCH
3
-CH
3 -CN, -CH 2 C=CH, -C 2 1- 5
-COOCH
3 or -CON(0H 3
)OCH
3 Especially preferred within the scope of this invention are the compounds of formula (I) listed in Tables 3 to 27 and, where applicable, the E/Z isomers and E/Z isomeric mixtures thereof.
A further object of the invention is the method for preparing the compounds of formula (1) and where appropriate their E/Z isomers, E/Z isomeric mixtures, and/or tautomers thereof in each case in free form or in the form of a salt, comprising either a) for the preparation of a compound of formula wherein the substituents A, and A 2 are as defined hereinbefore, and R. is hydrogen, aa) the diazotization of a compound of formula
A
1
-NH
2 (11l), wherein A, is as defined hereinbefore under formula and ab) reaction of the diazoniumn salt with a compound of formula
CN
W
A
2 wherein A 2 is as defined hereinbef ore under formula 1I) and W is hydrogen or a removable group; or b) for the preparation of a compound of formula
R
2
CN
I (1a), Al 1-1 N A 2 A WO 99/37603 PCT/EP99/00363 -14wherein A 2 and R 2 are as defined hereinbefore for R2a and R2b in the compounds of formula the reaction of a compound of formula
R
2 Hal Ns J. (II), A, N A, wherein A 2 and R 2 are as defined hereinbefore for R2a and R2b in the compounds of formula and Hal is a halogen atom, preferably chlorine or bromine, especially chlorine, with a metal cyanide, preferably an alkaline metal cyanide, especially with sodium cyanide; or c) for the preparation of a compound of formula wherein R 2 is different from H, the reaction of a compound of formula wherein R 2 is hydrogen, with a compound of formula
R
2 -Q wherein R 2 is as defined hereinbefore for R2a and R2b in formula and Q is a leaving group, preferably chlorine, bromine or iodine, especially iodine, preferably in the presence of a base; or and in each case, if so desired, the conversion of a compound of formula or an E/Z isomer or tautomer thereof in free form or in the form of a salt and obtainable by means of the method or by other means to another compound of formula or an E/Z isomer or tautomer thereof in free form or in the form of a salt, the separation of a mixture of E/Z isomers obtainable by means of the method or by other means, and the isolation of the desired isomer, and/or the conversion of a free compound of formula or an E/Z isomer or tautomer thereof, obtainable by means of the method or by other means, to a salt, or the conversion of a salt, obtainable by means of the method or by other means, of a compound of formula or of an E/Z isomer or tautomer thereof to the free compound of formula or an E/Z isomer or tautomer thereof, or to another salt.
A further object of the invention is a method for the preparation of a compound d) of formula WO 99/37603 PCT/EP99/00363 R2 Hal A/ N A (lla), A1 A2 wherein A 2 and R 2 are as defined hereinbefore for R2a and R2b in the compounds of formula and Hal is a halogen atom, and where applicable the E/Z isomers and tautomers thereof, in free form or in the form of a salt, comprising the reaction of a compound of formula R2
O
A N A (VIII),
H
wherein the radicals A, and A, and R, have the same meaning as defined hereinbefore under formula (lla) for R2a and R2b, with a halogenation agent, or e) of formula
R
2 Hal A/ N A (lib), wherein R, and the two radicals A, and A, have the same meaning as defined hereinbefore for A 2 R2a and R2b under formula and Hal is a halogen atom, preferably chlorine, comprising the reaction of a compound of formula
R
2
H
/N NA
(IX),
Al N A2 wherein R, and the two radicals A, and A 2 have the same meaning as defined hereinbefore under formula (Ilb), with N-bromosuccinimide or N-chlorosuccinimide in the presence of a thio ether, and in each case, if so desired, the conversion of a compound of formula (II) or an E/Z isomer or tautomer thereof in free form or in the form of a salt and obtainable by means of the method or by other means to another compound of formula (II) or an E/Z isomer or tautomer thereof in free form or in the form of a salt, the separation of a mixture of E/Z WO 99/37603 PCT/EP99/00363 -16isomers obtainable by means of the method or by other means, and the isolation of the desired isomer, and/or the conversion of a free compound of formula (11) or an E/Z isomer or tautomer thereof, obtainable by means of the method or by other means, to a salt, or the conversion of a salt, obtainable by means of the method or by other means, of a compound of formula (11) or of an E/Z isomer or tautomer thereof to the free compound of formula (11) or an E/Z isomer or tautomer thereof, or to another salt.
The reactions described hereinbeore and hereinafter are carried out in known manner, wherein the work may be performed, depending on requirements, with cooling, at room temperature, or with heating, e.g. in a temperature range from about 0°C to the boiling temperature of the reaction medium, preferably from about 20 0 C to about +120 0
C,
especially at 600C to 800C and, if necessary, in a closed container, under pressure and in an inert gas atmosphere, e.g. under nitrogen or argon, and/or under anhydrous conditions.
Preferred are reactions carried out at normal pressure under nitrogen. The reaction partners can be reacted with one another as they are, i.e. without the addition of a solvent or diluent, e.g. in the melt. In most cases, however, the addition of an inert solvent or diluent, or a mixture thereof, is of advantage. Especially advantageous reaction conditions are described in the Examples.
The isolation of the products takes place according to usual methods, e.g. by filtration, crystallization, distillation or chromatography or any suitable combination of these methods.
Variant a): aa) Diazotization takes place under conditions familiar to persons skilled in the art, i.e. in the presence of strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide, usually in the presence of water, but also in pure sulfuric acid.
Depending on the basicity of the aromatic amine, the reaction takes place in a temperature range from about -10°C to about +200C, or if necessary even at a higher temperature, for example at 600C to 800C.
The reaction time is preferably about 1 to about 2 hours.
The product is usually not isolated, but processed further in the next reaction step.
Especially preferred conditions for the reaction are described in Example H6/a.
1 -i i~j +li5~o ru~r~ I L~i ~iil~il~,-~,~riar~,~~,iaii, WO 99/37603 .PCT/EP99/00363 -17ab) The reaction usually takes place in the presence of water and preferably in the presence of an organic carboxylic acid, such as formic acid, chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, oxalic, malonic, succinic, maleic, fumaric or phthalic acid; especially preferred is the addition of acetic acid.
A removable group W is taken to mean an electrophilic group which is readily removable under the prevailing reaction conditions. Especially suitable for this are or OC(=O)R, wherein R is H, Ci-C 4 alkyl, halogen-C 1
-C
4 alkyl, C 1
-C
4 alkoxy, halogen-
C
1
-C
4 alkoxy, -CN, or organic sulfonates, such as C 1
-C
4 alkane or arylsulfonates substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonate.
The reaction is advantageously carried out within a temperature range of about -10°C to about +30 0 C, preferably from about 0°C to about The reaction time of about 0.5 to about 8 hours is preferred, especially about 2 to about 4 hours.
Variant b): Suitable for the reaction are transition metal cyanides, such as CuCN or Ni(CN) as well as alkaline earth and alkaline metal cyanides; especially KCN and NaCN.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxan; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N diethylformamide, N,N dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide, or water. Preferred are alcohols and water or alcohol water mixtures.
The reaction is advantageously carried out within a temperature range from about 0°C to about 80°C, preferably from about 20°C to about 30°C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
1 ~a- WO 99/37603 PCT/EP99/00363 -18- The reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about hours.
In a preferred form of variant a compound of formula (II) is reacted in an ethanol water mixture with sodium cyanide at room temperature.
Variant c): Suitable leaving groups Q in compounds of formula are for example hydroxy, C1-Csalkoxy, halogen-C-C 8 alkoxy, C-C 8 alkanoyloxy, mercapto, C 1
-C
8 alkylthio, halogen-
C
1
-C
8 alkylthio, C -C 8 alkanesulfonyloxy, halogen-C 1 -C8alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy or halogen, especially halogen, in particular bromine or chlorine.
Suitable bases for facilitating the reaction are e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, cycloalkylamines (N-alkylated where appropriate and unsaturated where appropriate), basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples are: sodium hydroxide, hydride, amide, methanolate, acetate, and carbonate, potassium tert-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,Ndimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, Nmethylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5ene (DBU). Preferred are alkaline metal and earth alkaline metal carbonates, alkylamines and alkaline metal or earth alkaline metal alkanolates.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons, typically benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethylether, dimethoxydiethylether, tetrahydrofuran or dioxan; esters, such as ethyl acetate and methyl acetate; and sulfoxides, such as dimethyl sulfoxide. Preferred are ethers, such as tert-butyl methyl ether, tetrahydrofuran or dioxan, and esters, such as ethyl acetate.
±SV~~i~-.~flfl4 WO 99/37603 PCT/EP99/00363 -19- The reaction is advantageously carried out within a temperature range from about 00C to about +1200C, preferably from about 00C to about +800C.
The reaction time of about 0.1 to about 24 hours is preferred, especially about 0.5 to about 2 hours.
Variant d): The reaction preferably takes place in the presence of an acid catalyst, for example in the presence of a carboxylic acid, such as formic acid, acetic acid, malonic acid or oxalic acid, or also a sulfonic acid, such as C,-C 4 alkane or arylsulfonic acid substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonic acid.
Especially suitable are solvents which are suited to azeotropic removal of water. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, dimethoxydiethyl ether; ketones, such as methyl isobutyl ketone; alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol.
The reaction is advantageously carried out within a temperature range of about 60°C to about 180 0 C, preferably 80°C to about 130°C, in many cases at the reflux temperature of the reaction medium.
The preferred reaction time is about 6 to about 72 hours, especially about 12 to about 48 hours.
In a preferred form of variant the reaction is carried out at 800 C to 140°C in an alcohol or an aromatic hydrocarbon in the presence of C1-C 4 carboxylic acid.
Variant e): Preferred halogenation agents are Cl2, Br 2 SOCI,, S0 2 CI,, POCI,, PCI,, PCI, and COCI,.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or WO 99/37603 PCT/EP99/00363 tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxan; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide,
N,N
diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile.
The reaction is advantageously carried out within a temperature range from about 0°C to about 180°C, preferably from about 50°C to about 1000C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about 6 hours.
The compounds of formulae (Ila), (lib) und (VIII) may be present in the form of one of the possible isomers or as a mixture thereof, depending for example on the number and the absolute and relative configuration of the asymmetric carbon atoms as pure isomers, such as enantiomers and/or diastereomers or isomer mixtures, such as mixtures of enantiomers, for example racemates; the invention relates both to the pure isomers and to all possible isomeric mixtures, and is hereinbefore and hereinafter understood as doing so, even if stereochemical details are not specifically mentioned in every case.
Diastereomer mixtures and racemate mixtures of compounds of formulae (lla), (lib) and (VIII), obtainable as described in the method depending on the starting materials and working procedures selected- or by other means, can, owing to the physicochemical differences of the constituents, be separated in known manner into the pure diastereomers or racemates, for example by fractionated crystallization, distillation and/or chromatography.
The resolution of correspondingly obtainable mixtures of enantiomers, such as racemates, can be achieved by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, e.g. high-pressure liquid chromatography (HPLC) on acetyl cellulose, by the use of suitable microorganisms, by cleavage with specific immobilized enzymes, through the formation of inclusion compounds, e.g. using chiral crown ether, wherein only one enantiomer is complexed.
According to the invention, apart from isolation of corresponding isomer mixtures, generally known methods of diastereoselective or enantioselective synthesis can also be applied to ~clli~lr^L~L1~ WO 99/37603 PCT/EP99/00363 -21obtain pure diastereomers or enantiomers, e.g. by carrying out the method of the invention using educts with correspondingly suitable stereochemistry.
It is of advantage to isolate or synthesize the biologically more active isomer in each case, e.g. enantiomer or mixture of isomers, e.g. enantiomer mixture, if the individual components show differences in biological efficacy.
Compounds of formula (Ila), (lib) und (VIII) can also be obtained in the form of their hydrates and/or also can include other solvents used for example where necessary for the crystallization of compounds present in solid form.
The invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or especially under the reaction conditions produces a starting material in the form of a derivative or a salt and/or its racemate or enantiomer.
In the method of the present invention, the starting materials and intermediates used are preferably those that lead to the compounds of formula described at the beginning as being especially useful.
The invention relates in particular to the manufacturing processes described in Examples H1, H2, H4 and Starting materials and intermediate products used according to the invention for the preparation of compounds of formula and in particular the compounds of formulae (11), (111), (IV) and (VIII), which are new, and their use and methods for their preparation likewise form an object of the invention.
Compounds of formulae (Ila), (lib) and (VIII) as well as the use thereof for the preparation of compounds of formula represent a further object of the invention.
The compounds of formulae (111) to (VI) and (IX) are known or can be prepared according to known methods.
A further object of the invention is a method for controlling pests using a compound of formula wherein A 1
A
2 and R 2 have the same meaning as defined hereinbefore for formula The compounds of formula according to the invention are active substances of preventive and/or curative merit for use in pest control and offer a very favourable spectrum .4 WO 99/37603 PCT/EP99/00363 -22of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants even at low concentrations. The compositions according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, and also of those showing resistance, for example insects or members of the order acarina. The insecticidal, ovicidal, and/or acaricidal effect of the compositions of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or the eggs thereof, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a destruction rate (mortality) of at least 50 to The animal pests include for example: Members of the orders lepidoptera, coleoptera, orthoptera, isoptera, psocoptera, anoplura, mallophaga, thysanoptera, heteroptera, homoptera, hymenoptera, diptera, siphonaptera, thysanura and acarina; especially preferred is the control of pests of the genera and species which are described in EP-A-736'252, and which are included here by reference.
Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.
Target crops within the scope of this application include especially cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g.
pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as pumpkins, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.
The active ingredients of the invention are especially suitable for the control of insects and members of the order acarina, in particular crop-eating and damaging insects, such as i -I WO 99/37603 PCT/EP99/00363 -23 Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cultivated plants of cotton, fruit, maize, soya, rape and vegetables.
Other indication areas for the active ingredients of the invention are the protection of stored products and stores and of material and, in the hygiene sector, in particular the protection of domestic animals and livestock against pests of said type.
The invention therefore relates also to pesticides which comprise a compound of formula wherein A 1
A
2 and R 2 have the same meaning as defined hereinbefore for formula with the exception of 1-phenylhydrazono-2-nitriloethylbenzene, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances (chosen in accordance with the intended objectives and prevailing circumstances), comprising at least one active ingredient of the invention.
In these compositions, the active ingredient is employed in pure form, the solid active ingredients in a specific particle size, or preferably together with at least one of the adjuvants conventionally used in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, and anionic surfactants in the compositions used according to the invention, are the same as those which are described in EP-A-736'252 (CASE 20400) and which are included in the present object of the invention by reference.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, wherein 0 to 25%, especially 0.1 to 20%, of the composition may as a rule be surfactant in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are thus S composed in particular as described in EP-A-736'252.
The activity of the compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal, acaricidal, and/or WO 99/37603 PCT/EP99/00363 -24fungicidal substances. Additional active ingredients are, for example, substances from the following classes: organophosphorus compounds, nitrophenols and derivatives, formamidine, urea, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions of the invention can also comprise other solid or liquid adjuvants, such as stabilizers, e.g. vegetable oils, epoxidized where appropriate epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, and also fertilizers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, nematocides, molluscicides or selective herbicides.
The compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding and/or sieving a solid active ingredient or active ingredient mixture, e.g. to a specific particle size, and in the presence of at least one adjuvant, for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s). These methods for preparing compositions of the invention and the use of compounds of formula for preparing these compositions likewise form an object of the invention.
The methods of application for the compositions, i.e. the methods of controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention.
Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rates of application are generally 1 to 2000 g of active ingredient per hectare (ha approximately 2.471 acres), especially 10 to 1000 g a.i./ha, and preferably 20 to 600 g a.i./ha.
A preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question. However, the active ingredients can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field.
WO 99/37603 PCT/EP99/00363 The compositions of the invention are also suitable for protecting plant propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from fungal infections and animal pests. The propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition. The composition can also be given when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.
The invention is illustrated by the following examples. They do not impose any limitation on the invention. Temperatures are given in degrees celsius.
Preparative examples Example H1: Preparation of 4-nitrobenzoic acid-N'-(2,6-dichloro-4-trifluoromethylphenyl)hydrazide of formula CI H O
I
F N. H ClH N F 0 A solution of 35.85 g 4-nitrobenzoyl chloride in 150 ml dichloromethane is added dropwise over a period of about 60 minutes to 45.1 g 2 6 -dichloro-4-trifluoromethylphenylhydrazine in 1000 ml dichloromethane while stirring at 0 to 50C, and the stirring is then continued for a further 60 minutes at room temperature. For 20 minutes the mixture is vigorously stirred while 20.4 g triethylamine is fed in. Stirring is then continued for 3 hours at room temperature. The organic phase is washed three times with 500 ml of water each time, dried on sodium sulfate and the solvents removed in the rotary evaporator. After recrystallization of the residue from toluene, the title product is obtained at a melting point of 188-190 °C.
Example H2: Preparation of 2 6 -dichloro-4-trifluoromethylphenyl)hydrazono]chloromethyl}-nitrobenzene of formula r y- WO 99/37603 PCT/EP99/00363 -26 CI H CI
N
Cl N
F
F 0 To a solution of 69.3 g 4-nitrobenzoic acid-N'-(2,6-dichloro-4-trifluoromethylphenyl)hydrazide in 600 ml toluene, 33.9 g thionyl chloride is added dropwise while stirring at room temperature. The mixture is then heated to 1050C and stirred for 6 hours. After cooling, the mixture is concentrated to dryness by evaporation on the rotary evaporator and the residue crystallized out from toluene. The title compound is obtained at a melting point of 117- 118 0 C (compound 1.20).
Example H3: The other compounds listed in Table 1 can be prepared in a manner analogous to that described under Example H2.
Table 1: Compounds of formula H CI
SN
(R
3 (R 3 b)n 2 1.1 1.2 1.3 1.4 1.6 1.7 1.8 1.9 1.10 1.11 1.12 1.13 1.14
(R
3 a)nl 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,6-CI 2 -4-CF 3 2,6-CI 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,4-C1 2 -6-CF 3 2-CI-4-CF 3 -6-F 2,6-C1 2 -3-F-4-CF 3 2,3,6-C1 3 -4-CF 3 2,4,6-CI3 2,4,6-C13 2,4,6-Cl3 2,6-C1 2 -4-CF 3 (R3b)n2 4-Br 4-COCF 3 3-NO 2 -4-CI 2-F-4-N0 2 4-SCF 3 4-SCH 3 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-SO 2
CH
3 4-SCH 3 4-SCF 3 4-F mp °C 124-125 107-108 141-143 88-90 137-138 89-90 128-129 135-137 143-144 121-123 Amorphous 78-79 92-94 97-98 WO 99/37603 WO 9937603PCT/EP99/00363 27
(R
3 .)ni (RAQfl mp 0
C
1.15 1.16 1.17 1.18 1.19 1.20 2,6-C1 2 -4-CF 3 2,4,6-CI3 2,6-(N0 2 2 -4-CF 3 2-C!-4-OCF 3 -6-N0 2 2-CI-4-CF 3 2,6-C1 2 -4-CF 3 4-SO 2
N(CH
3 2 4-CHO 4-NO 2 4-NO 2 3-NO 2 -4-CI 4-NO 2 163-164 152-154 189-19 1 147-148 188-1 117-118 Example H-4: Preparation of 4 -f{l-I(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-2nitriloethyllnitrobenzene of formula C1 H
NI
F I F 0 To 10.7 g sodium cyanide in 240 ml water and 160 ml ethanol, 51.5 g solid 4-f 1 d ichloro- 4 -triflIuo romethylph enyl) hyd razonolch lo rom ethyl In itrobe nze ne is added in portions over a period of about one hour. The reaction mixture is stirred for 18 hours at room temperature and then poured onto 6 1 of ice water. The precipitate is filtered, washed three times with water, dissolved in ethyl acetate and washed with 15% NaCI solution. The organic phase is dried, filtered over sodium sulfate, and concentrated to dryness by evaporation on the rotary evaporator. The residue is crystallized out from toluene. This yields the title compound with a melting point of 160-161 OC.
Example H-5: Preparation of 4-f 1 -I(2,6-dichloro-4-trif luoromethylphenyy.-N.methyl-N methoxycarbamoylhydrazono]-2-nitriloethyl }nitrobenzene of formula WO 99/37603 PCT/EP99/00363 -28- O-N N N
NF
CI N
F
F 0 To 1.2 g 2 ,6-dichloro-4-trifluoromethylphenyl)hydrazono]-2-nitriloethyl}nitrobenzene in 50 ml tetrahydrofuran, 0.44 g of finely pulverized potassium tert-butylate is added at room temperature. The mixture is stirred for 10 minutes, resulting in a deep red solution. 0.48 g methylmethoxycarbamoyl chloride is added and the mixture stirred for three hours. The solvent is removed in the rotary evaporator and the residue dissolved in ethyl acetate. The ethyl acetate phase is washed with water and NaCI solution, dried over sodium sulfate, and concentrated to dryness by evaporation under a vacuum. The residue is chromatographed over a silica gel column with hexane tetrahydrofuran in the ratio 5:1. Concentration by evaporation of the fractions 6-14 yields the title compound with a melting point of 96-97°C (compound 2.1).
Example 6: The other compounds listed in Tables 2 and 3 can also be prepared in a manner analogous to that described under Example Table 2: Compounds of formula
N
R2 NII
(R
3 (R3b)n 2
C
3
H
3
F
2 cyc is 2,2-difluoro-cycloprop-1-yl 4-C(NOMe)CF 3 stands for the substituent 4-C(=NOCH 3
)CF
3 No. (R 3 a)ni (R3b)n2 R2 mp (oC) 2.1 2,6-CI 2 -4-CF 3 4-NO 2
-CON(OCH
3
)CH
3 96-97 2.2 2,6-C12-4-CF 3 4-NO 2
-COSC
2 Hs 198-199 2.3 2,6-CI 2 -4-CF 3 4-NO 2
-COSCH
3 198-200 2.4 2,6-C 2 -4-CF 3 4-NO 2
-CH
2 0C(O)C(CH 3 3 87-90 WO 99/37603 WO 9937603PCT/EP99/00363 29 No. (R 3 0111 2,6-C1 2 -4-CF 3 2.6 2,6-C1 2 -4-CF 3 2.7 2,6-C1 2 -4-CF 3 2.8 2,6-C1 2 -4-CF 3 2.9 2,6-Cl 2 -,4-CF 3 2.10 2,6-C1 2 -4-CF 3 2.11 2,6-C1 2 -4-CF 3 2.12 2,6-Cl 2 -4-CF 3 2.13 2,6-01 2 -4-CF 3 2.14 2,6-C1 2 -4-CF 3 2.15 2,6-C1 2 -4-CF 3 2.16 2,6-C1 2 -4-CF 3 2.17 2,6-C1 2 -4-CF 3 2.18 2,6-C1 2 -4-CF 3 2.19 2,4,6-C 3 2.20 2,4,6-C 3 2.21 2,4,6-C 3 2.22 2,4,6-Cl 3 2.23 2,4,6-C 3 2.24 2,4,6-C 3 2.25 2,4,6-C 3 2.26 2,4,6-C 3 2.27 2,4,6-C 3 2.28 2,4,6-Cl 3 (R3b)fl2 4-NO 2 4-NO 2 4-NO 2 4-SOCF 3 4-SO 2
CF
3 4-SCF 3 4-SOCF 3 4-SO 2
CF
3 4-SCH 3 4-SO 2 N(CH3) 2 4-SO 2 N(CH3) 2 4-SCH 3 4-F 4-F 4-SCF 3 4-SOCF 3 4-SO 2
CF
3 4-SCH 3 4-SO 2
CH
3 4-SOCH 3 4-SOCF 3 4-SO 2
CF
3 4-SO 2
CH
3 4-SOCH 3 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NH2 4-NO 2 4-NO 2 4-NO 2
-CH
2 0C 2
H
4 0CH 3
-CH
2 0CH 2
CH=CH
2
-CH
2
OCH
2
C=-CH
-H
-H
-H
-CH
2 0C 2
H
5
-CH
2 0C 2
H
5
-H
-H
-CH
2 0C 2
H
5
-CH
2 0C 2
H
5
-H
-CH
2 0C 2 Hs
-H
-H
-H
-H
-H
-H
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2 0C 2
H
5
-CH
2 0C 2
H
5
-H
-CH
3
-CH
2
OC
2 Hr, -C0 2
C
2
H
5
-CH
2
OC
2
H
5
-COC
4
H
9 n
-COCH(CH
3 2
-COCH
2
C(CH)
3 mp (00) 63-65 73-74 99-1 00 157-1 58 108-1 09 156 Oil Oil 147-1 49 201-202 136 80-81 126-1 28 Oil 126-1 27 133-1 146-148 113 205-206 21 6-217 Oil 86-88 104-1 Oil 175-1 76 125-1 26 94-95 Resin 142-1 43 149-1 138-1 39 135-1 36 2.29 2.30 2.31 2.32 2.33 2.34 2.35 2.36 2-CI-4-OCF 3 -6-N0 2 2-CI-4-00
F
3 -6-N0 2 2-CI-4-OCF 3 -6-N0 2 2-CI-4-OCF 3 -6-N0 2 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 WO 99/37603 W099/7603PCT/E P99/00363 30 No. (R 3 a)ni (R3b)fl2 2.37 2,6-C1 2 -4-CF 3 2.38 2,6-C1 2 -4-0F 3 2.39 2,6-C1 2 -4-0F 3 2.40 2,6-C1 2 -4-0F 3 2.41 2,6-01 2 -4-0F 3 2.42 2,6-01 2 -4-0F 3 2.43 2-CI-4-00F 3 -6-N0 2 2.44 2-CI-4-OCF 3 -6-N0 2 2.45 2-OI-4-OCF 3 -6-NH 2 2.46 2,6-C1 2 -4-CF 3 2.47 2,6-C1 2 -4-CF 3 2.48 2,6-C1 2 -4-0F 3 2.49 2,6-C1 2 -4-0F 3 2.50 2,6-C1 2 -4-CF 3 2.51 2-01-4-OC F 3 -6-
NHCOCH
3 2.52 2-OI-4-OCF 3 -6-
NHCOCH
3 2.53 2,6-C1 2 -4-CF 3 2.54 2,6-C1 2 -4-0F 3 2.55 2,6-C1 2 -4-CF 3 2.56 2,6-C1 2 -4-0F 3 2.57 2,6-C1 2 -4-0F 3 2.58 2,6-01 2 -4-CF 3 2.59 2,6-C1 2 -4-CF 3 2.60 2,6-C1 2 -4-CF 3 2.61 2,6-C1 2 -4-0F 3 2.62 2,6-01 2 -4-0F 3 2.63 2,6-01 2 -4-CF 3 2.64 2,6-C1 2 -4-CF 3 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-CN 4-ON 4-CN 4-NO 2 4-NO 2 4-NHOOCH 3 4-NHCOCF 3 4-N-Pyrrol 4-ON 4-ON 4-S0 2 F7 5 4-SOC 2
F
5 4-S0 2
C
2
F
5 4-SOC 2
F
5 4-SOC 2
F
5 4-SOC 2 Fs 4-S00 2
F
5 4-S0 2
C
2
F
5 4-S0 2
C
2
F
5 4-S0 2 0 2
F
5 4-SOCF 3 4-SOC F 3 4-SOOF 3 4-SOCF 3
R
2 mp (00) -C00H 2 0 6
H
5 129-131
-COC
3
H
7 n 142-1 43
-COCH
2
CH
2 OI 140-1 42 -C0CsH 11 n 144-145 -C00 10
H
21 Oil -C0C 7
H-
15 n 85-86 -H 191-193
-CH
2 0C 2
H
5 60-61
-CH
2 00 2
H
5 Resin -C00H 2 00H 3 152-153
-COCH
2
O
3
H
3
F
2 CYC 154-155
-CH
2 0C 2
H
5 129-130
-CH
2 0C 2
H
5 155-156
-CH
2 0C 2
H
5 104-1
-CH
2 0C 2
H
5 136-137
-CH
2 0C 2
H
5
-H
-H
-H
-CH
2 0C 2
H
5 -C00H 3
-OH
3
-CH
2 0C 2
H
5
-COCH
3
-OH
3
-ON
-CH
2
C-=CH
-0000H 3 86-87 134-1 142-1 43 153-1 58 Resin Resin Resin Resin Amorphous Amorphous Solid Resin Resin Resin Resin 2.65 2.66 2, 6-C12-4-C
F
3 2,6-C1 2 -4-CF 3 WO 99/37603 WO 9937603PCT/EP99/00363 No. (R 3 a)nI 2.67 2,6-C1 2 -4-CF 3 2.68 2,6-Cl 2 -4-CF 3 2.69 2,6-C1 2 -4-CF 3 2.70 2,6-C1 2 -4-CF 3 2.71 2,6-C1 2 -4-CF 3 2.72 2,6-Cl 2 -4-CF 3 2.73 2,6-C1 2 -4-CF 3 2.74 2,6-C1 2 -4-CF 3 2.75 2,6-C1 2 -4-CF 3 2.76 2,6-Cl 2 -4-CF 3 2.77 2,6-Cl 2 -4-CF 3 2.78 2,4,6-013 2.79 2,6-C1 2 -4-0F 3 2.80 2,6-C1 2 -4-CF 3 2.81 2,6-C1 2 -4-CF 3 2.82 2,4,6-C 3 2.83 2,4,6-013 2.84 2,4,6-C13 2.85 2,6-C1 2 -4-CF 3 2.86 2,6-C1 2 -4-CF 3 2.87 2,6-C1 2 -4-CF 3 2.88 2-CI-4-CF 3 -6-F 2.89 2,6-C1 2 -3-F-4-CF 3 2.90 2,4-C1 2 -6-0F 3 2.91 2,4,6-013 2.92 2,4,6-C13 2.93 2,6-C1 2 -4-CF 3 2.94 2,6-C1 2 -4-CF 3 2.95 2,6-Ci 2 -4-CF 3 2.96 2,4,6-013 2.97 2,4,6-013 2.98 2,4,6-013 (R3b)l2 4-SOCF 3 4-SOCF 3 4-SOCF 3 4-SO 2
CF
3 4-SO 2
CF
3 4-S0 2 0F 3 4-S0 2 0F 3 4-SO 2
CF
3 4-SO 2
CF
3 4-SOCF 3 4-SO 2
CF
3 4-SO 2
CF
3 4-NO 2 4-NO 2 4-NO 2 4-SCF 3 4-SOC F 3 4-S 020F 3 4 -S CF 3 4-SOCF 3 4-S0 2
CF
3 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-ON 3-CH 3 -4-N0 2 4-C(NOMe)CF 3 4-C(NOMe)CF 3 4-C(NOMe)CF 3 4-C(NOMe)CF 3 4-CH=NOH R2 mp
-COCH
3 Amorphous
-CON(CH
3
)OCH
3 Resin
-OH
3 Amorphous
-CON(CH
3
)OCH
3 106-1 07
-COOCH
3 Amorphous
-CH
2 C=-CH Resin
-COCH
3 AmorDhous
-C
2
H
5
-OH
3
-CH
2
CH
2
N(C
2
H
5 2
-CH
2
CH
2
N(C
2
H
5 2
-CH
2
CH
2
N(C
2
H
5 2
-COCH
2 0C(O)CH 3
-COCH
2
SCH
3
-CO(CH
3 2 00(O)CH 3
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2 C3H 3
F
2
CYC
-CH
2 0 2
H
5
-H
-CH
2 0C 2
H
5
-H
-CH
2 0C 2
H
5 Resin Resin amorph Qel Qel 175-177 Harz 149-1 97-98 91-93 153-154 75-77 114-115 154-1 113-114 103-1 04 174-1 153-1 54 134-1 138-1 39 Harz 145-146 92-93 134-1 Oil 'WO 99/37603 WO 9937603PCT/EP99/00363 No. (R3a)ni (R3b)fl 2
C-
2.99 2,6-C1 2 -4-CF 3 2.100 2,6-C1 2 -4-CF 3 2.101 2,6-C1 2 -4-CF 3 2.102 2,6-C1 2 -4-CF 3 2.103 2,6-C1 2 -4-CF 3 2.104 2,6-C1 2 -4-CF 3 2.105 2,6-C1 2 -4-CF 3 2.106 2,6-C1 2 -4-CF 3 2.107 2,6-C1 2 -4-CF 3 2.108 2,6-C1 2 -4-CF 3 2.109 2,6-C1 2 -4-CF 3 2.110 2,6-C1 2 -4-CF 3 2.111 2,6-C1 2 -4-CF 3 2.112 2,6-C1 2 -4-CF 3 2.113 2,6-C1 2 -4-CF 3 2.114 2,6-Ci 2 -4-CF 3 2.115 2,6-C1 2 -4-CF 3 2.116 2,6-C1 2 -4-CF 3 2.117 2,6-C1 2 -4-CF 3 2.118 2,6-C1 2 -4-CF 3 2.119 2,6-C1 2 -4-CF 3 2.120 2,6-C1 2 -4-CF 3 2.121 2,6-C1 2 -4-CF 3 2.122 2,6-C1 2 -4-CF 3 2.123 2,6-C1 2 -4-CF 3 2.124 2,6-C1 2 -4-CF 3 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-SON(CH3) 2 4- SOC F 3 4-S0 2
CF
3 4-SOCF 3 4-S0 2
CF
3 4-SOCF 3 4-SO 2
CF
3 4- SCF 2
H
4-SC F 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
4-SC F 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
4-SOCF 3 4-SO 2
CF
3 4-SOCF 3 4-S 0 2
CF
3 4-SOC
F
3
-COCH
2
OC
6
H
5
-COCH
2
OC
6
H
4 -4-N0 2
-COCH
2
OC
6
H
4 -4-F
-COCH
2
OC
6
H
4 -4-Br
-COCH
2
OC
6
H
4 -4-CF 3
-COCH
2
OC
6
H
4 -3-CF 3
-COCH
2
OC
6
H
4 -2-F
-COCH
2
OC
6
H
4 -3-N0 2
-COCH
2
OC
6
H
4 -3-Br
-COCH
2
OC
6
H
4 -3-F
-COOH
2
OC
6
H
4 -4-CI
-COCH
2
OC
6
H
4 -3-CH 3 -4
-COCH
2
OC
6
H
4 -3-CI,4-F
-H
-CH
2 0CH 3
-CH
2 0CH 3
-CH(CH
3 2
-CH(CH
3 2
-CH
2 00H(CH 3 2
-CH
2
OCH(CH
3 2
H
-COCH
3
-COCH
3
-COCH
3
-CH
2 0C 2
H
5
-CH
2
OC
2
H
5
-CH
2 0C 2
H
5
-COCH
3
-COCH
3
-COOCH
3
-COOCH
3
-C
2 Hs mp (OC) a morph 189-1 92 a morph 146-1 48 155-158 111-114 harz 140-1 43 125-1 28 112-114 143-1 47 -Cl 163-167 150-1 53 Harz Harz Harz 91-92 Harz amorph amorph 152-1 53 110-112 amorph 174-1 76 91-92 94-96 182-1 84 amorph 152-1 54 181-1 83 170-1 72 83-87 2.125 2.126 2.127 2.128 2.129 2.130 2,6-C 2 -4-CF 3 2,4,6-C 3 2,4,6-C 3 2,4,6-C 3 2,4,6-C 3 2,4,6-C 3 WO 99/37603 WO 9937603PCTIEP99/00363 33 No. (R 3 a)nIl (R 3 b)fl 2 mp (00) 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 2.156 2.157 2.158 2.159 2.160 2.161 2.162 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-C 3 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-013 2,4,6-C13 2,4,6-013 2,4,6-013 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,4,6-013 2,6-01 2 -4-0F 3 2,4,6-013 2,4-01 2 -6-0F 3 2-CI-4-CF 3 -6-F 2,6-01 2 -3-F-4-0F 3 2, 6-C12-4-C F 3 2,6-01 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,3,6-01 3 -4-0F 3 2,4,6-013 2,4,6-C13 2,4,6-013 2,4,6-013 2-0I-4-CF 3 -6-F 4-S0 2 0F 3 4-SOCF 3 4-S0 2 0F 3 4-SOCF 3 4-SOCF 3 4-SCF 3 4-SOH F 2 4-SOCHF 2 4-S0 2 0H F 2 4-SC HF 2 4-SOCH F 2 4-S0 2 0HF 2 4-SOCHF 2 4-5 020H F 2 4-SCHF 2 4-SC 2
F
5 4-NO 2 4-ON 3-0H 3 -4-N0 2 4-NO 2 4-NO 2 4-NO 2 4-NO 2 4-SCF 3 4-SOC F 3 4-S0 2 0F 3 4-NO 2 4-SOF 3 4-SOC
F
3 4-S0 2
CF
3 4-S0 2
F
5 4-S0 2
F
5
-OH
3
-OH
3
-OH
2 OCH(0H 3 2
-CH(CH
3 2
-CH
2 0 2
H
5
H
H
H
-CH
2 0 2
H
5
-CH
2 0C 2
H
5
-CH
2
OC
2
H
5
-COCH
3
-COCH
3 -000IH 3
-OH
3 -000H 2
H
2
CF
2 C1
-COCH
2
CH
2
CF
2
CI
-COO H 2 0H 2 0F 2 01 -000H 2
H
2 0F 2 01 -COO H 2 0 H 2 0F 2 Cl
-COCH
2
OH
2
CF
2
CI
-000H 2
H
2 0F 2 01
-COCH
2
CH
2
CF
2
CI
-000H 2
H
2 0F 2
CI
-COCH
2
CH
2
OF
2
CI
-000H 2
H
2 0F 2 01
-COCH
2
CH
2
CF
2
CI
-C00H 2 0H 2 0F 2 01 -000H 2
H
2 0F 2 01
-H
-H
72-74 80-84 120-1 24 Ha rz 103-1 08 84-86 113-114 160-16 1 194-1 Harz 111-113 168-1 69 146-148 187-1 89 97-99 OeI 189-1 167-1 68 108-1 09 157-1 58 143-1 44 152-1 53 126-1 27 121 -122 129-1 165-1 66 128-1 29 88-89 63-65 143-1 44 103-1 04 100-1 01 WO 99/37603 WO 9937603PCT/EP99/00363 34 No. (R 3 (Rab)fl2 mp (OC) 2.163 2.164 2.165 2.166 2.167 2.168 2.169 2.170 2.171 2.172 2. 173 2.174 2.175 2.176 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 2,3 ,6-01 3 -4-CF 3 2,6-0l 2 -3-F-4-CF 3 2,6-01 2 -4-NO 2 2,4-01 2 -6-0F 3 2,4,6-C 3 2,4,6-013 2,4,6-013 2,4,6-013 2-CI-4-0F 3 -6-F 2-CI-4-0F 3 -6-F 2-CI-4-CF 3 -6-F 2-CI-4-CF 3 -6-F 2,3,6-01 3 -4-CF 3 2,3,6-C 3 -4-CF 3 2,3,6-C 3 -4-CF 3 2,3,6-C1 3 -4-0F 3 2,6-C1 2 -3-F-4-0F 3 2,6-01 2 -3-F-4-0F 3 2 ,6-C1 2 -3-F-4-C F 3 2 ,6-01 2 -3-F-4-0F 3 2, 6-C1 2 -4-N0 2 2,6-01 2 -4-N0 2 2,6-C1 2 -4-N0 2 2,6-01 2 -4-N0 2 2,4,6-CI3 2,4,6-013 2,4-C1 2 -6-0F 3 2 ,4-01 2 -6-CF 3 2,4-C1 2 -6-0F 3 2,4-01 2 -6-CF 3 2-CI-4-CF 3 -6-F 2-CI-4-CF 3 -6-F 4-S0 2
F
5 4-SC 2 Fs 4-SC 2
F
5 4-SC 2 Fs 4-SC 2
F
5 4-SC 2
F
5 4-S0 2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-S0 2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-S0 2 Fs 4-SC 2
F
5 4-SC 2
F
5 4-SC 2 Fs 4-SC 2
F
5 4-SC 2 Fs 4-SC 2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-S0 2
F
5 4-SOC 2
F
5 4-S0 2
C
2
F
5 4-SC 2
F
5 4-SC 2
F
5 4-S0 2
F
5 4-SC 2
F
5 4-S00 2
F
5 4-S0 2
C
2
F
5
-H
-H
-H
-H
-CH
2 0 2
H
5
-COOCH
3
-COCH
3
-CH
3
-CH
2 0 2 Hs
-COOCH
3 -COGH1 3
-OH
3
-CH
2 0 2
H
5
-COOCH
3
-COCH
3
-OH
3
-CH
2 0 2
H
5
-COOCH
3
-COCH
3
-OH
3
-CH
2 0 2
H
5
-COOCH
3
-COGH
3
-CH
3
-CH
2 0 2
H
5
-CH
2 0 2
H
5
-CH
2 0 2
H
5
-COOCH
3
-COCH
3
-OH
3
-CH
2 0 2
H
5
-CH
2 0 2
H
5 119-1 101 -102 139-1 93-94 Harz 104-1 102-1 03 Harz Harz 80-81 86-87 Harz Harz Harz Harz Harz Harz Harz Harz Harz Harz Harz 92-94 Harz Harz 103-1 04 Harz Harz Harz Harz Harz Harz WO 99/37603 WO 9937603PCT/EP99/00363 No. (Raa)ni 2.195 2 ,3,6-0j 3 -4-0F 3 2.196 2,3,6-C1 3 -4-CF 3 2.197 2,6-01 2 -3-F-4-CF 3 2.198 2,6-C1 2 -3-F-4-0F 3 2.199 2,6-01 2 -4-N0 2 2.200 2,6-C1 2 -4-N0 2 2.201 2,4-C1 2 -6-CF 3 2.202 2,4-C1 2 -6-0F 3 2.203 2,4,6-013 2.204 2,4,6-0I3 (R3b)l2
R
2.205 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 2-0I-4-0F 3 -6-F 2-CI-4-0F 3 -6-F 2,3,6-C1 3 -4-CF 3 2,3,6-01 3 -4-CF 3 2,6-C1 2 -3-F-4-0F 3 2,6-C1 2 -3-F-4-CF 3 2,6-01 2 -4-N0 2 2,6-01 2 -4-N0 2 2,3,6-01 3 -4-CF 3 2,3,6-C1 3 -4-CF 3 2,4,6-013 2,4,6-CI3 2,4,6-013 2,4,6-CI3 4-SOC 2
F
5 4-S0 2
C
2
F
5 4-S00 2
F
5 4-S0 2 0 2 Fs 4-SOC 2
F
5 4-S0 2 0 2
F
5 4-S00 2
F
5 4-S0 2 2
F
5 4-S00 2
F
5 4-S0 2 0 2
F
5 4-S00 2
F
5 4-S0 2 0 2
F
5 4-S00 2
F
5 4-S0 2 2
F
5 4-SOC 2
F
5 4-S0 2 2
F
5 4-S00 2
F
5 4-S0 2 0 2
F
5 4-SOC 2
F
5 4-S0 2
C
2
F
5 4-S00 2
F
5 4-S0 2 2
F
5 4-SOF 2
OHFCF
3 4-
SOOF
2
CHFCF
3 4-
SO
2
CF
2
CHFOF
3 4-SCF 2
OHFCF
3 4-
SOOF
2
CHFCF
3 4-
SO
2
CF
2
CHFCF
3
-CH
2 0C 2
H
5
-CH
2 0C 2
H
5
-CH
2 0C 2
H
5
-CH
2 0 2
H
5
-CH
2 0 2
H
-CH
2 0 2
H
-CH
2 0 2
H
5
-CH
2 0 2
H
5 -0000H 3 -0000H 3 -0000H 3 -0000H 3
-COOOH
3 -0000H 3 -0000 H 3 -0000H 3 -C000H 3 -0000H 3
-COOCH
3 -0000H 3 -OOCH1 3 -OOCH1 3
-H
-H
mp (00) Ha rz Ha rz H arz H arz Harz 108-110 Harz 131-1 33 Ha rz Harz Ha rz Ha rz 2.219 2,4,6-C13 2.220 2.22 1 2,6-01 2 -4-CF 3 2,6-01 2 -4-CF 3 2.222 2,6-01 2 -4-CF 3 WO 99/37603 WO 9937603PCT/EP99/00363 36 No. (R 3 a)ni (R3b)fl2 mp (00) 180-18 1 2.223 2,6-(N0 2 2 -4-CF 3 2.224 2,6-(N0 2 2 4-CF 3 2.225 2,6-(NO 2 2 2.226 2,6-(N0 2 2 -4-CF 3 2.227 2,6-(N0 2 2 4-CF 3 2.228 2,6-(N0 2 2 2.229 2,6-(N0 2 2 -4-CF 3 2.230 2,6-(N0 2 2 4-CF 3 2.231 2,6-(NO 2 2 2.232 2,6-(NO 2 2 -4-CF 3 2.233 2,6-(N0 2 2 4-C F 3 2.234 2,6-(N0 2 2 2.235 2,6-(N0 2 2 -4-0F 3 2.236 2,6-(N0 2 2 4-CF 3 2.237 2,6-(N0 2 2 2.238 2,6-(NO 2 2 -4-CF 3 2.239 2,6-(N0 2 2 -4-
CF
3 2.240 2,6-(N0 2 2 2.241 2,6-(N0 2 2 -4-0F 3 2.242 2,6-(N0 2 2 4-CF 3 2.243 2,6-(N0 2 2 4-NO 2 4-NO 2 4-NO 2 4-SC F 3 4-SO00F 3 4-SON(CH3) 2 4-S0 2 N(CH3) 2 4-SCH 3 4-F 4-Br 4-SOC F 3 4-F 4-Br 4- SOC F 3 4-F 4-Br 4-SOC F 3 4-SOCF 3
-CH
3
-COOCH
3
-CH
2 0 2
H
-OH
3
-COOCH
3
-CH
2 0 2
H
-CH
2 00H(CH 3 2
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2 00 6
H
4 -4-F
-OH
3
-COOCH
3
-CH
2 0 2
H
-OH
3
-COOCH
3
-CH
2 0 2
H
-CH
2 00H(CH 3 2
-COCH
2
C
3
H
3
F
2
CYC
-COCH
2 00 6
H
4 -4-F WO 99/37603 WO 9937603PCT/EP99/00363 37- Table 3: Compounds of formula No.
3.1 3.2 3.3 3.4 3.6 3.7 3.8 3.9 3.10 3.11 (R3a), 1 2,6-01 2 -4-CF 3 2 ,6-C1 2 -4-0F 3 2,6-01 2 -4-CF 3 2 ,6-C 12-4-C F 3 2,4,6-Cl 3 2,4,6-013 2-C1-4-CF 3 216-C1 2 -4-CF 3 2,6-C1 2 -4-CF 3 2,6-C1 2 -4-C F 3 2,6-C1 2 -4-CF 3 (R 3 a N A
A
2 R I
-H
-N
-CH
2
OC
N
-H
-C
H
2 0C N o
-H
-CH 2
OC
0 N*
-H
0
-H
0 S N'
-H
0
S
-H
-H
N
0
-COCH
3
N-
0 2
H
2
H
mp (00) 188 169-1 128-1 32 152-1 53 192 3.12 2,6-C1 2 -4-CF 3 WO 99/37603 WO 9937603PCT/EP99/00363 38 No. (R3a), 1 mp (OC) 3.13 2,6-01 2 -4-CF 3 3.14 2,6-C1 2 -4-CF 3 3.15 2,6-C1 2 -4-0F 3 3.16 2,6-(N0 2 2 -4-CF 3 3.17 2,6-(N0 2 2 -4-0F 3 -5-OI 3.18 2,6-(N0 2 2 3.19 2,6-(N0 2 2 -4-0F 3 3.20 2,6-(N0 2 2 -4-CF 3 -5-CI 3.21 2,6-(N0 2 2 3.22 2,6-(N0 2 2 -4-0F 3 3.23 2,6-(N0 2 2 -4-0F 3 -5-CI 3.24 2,6-(N0 2 2 3.25 2,6-(N0 2 2 -4-CF 3 3.26 2,6-(N0 2 2 -4-CF 3 -5-OI 3.27 2,6-(N0 2 2 3.28 2,6-(N0 2 2 -4-0F 3
N
N-
0
N
N-
0
N
N -o
N
0
N
0 0 0 0I 0 0 0N
-N
s
N
s
'-N
-OH
3
-H
-CH
2 0 2
H
108 172-1 73
-H
-H
-H
-OH
3
-OH
3
-H
-CH
3 -000H 3
-COCH
2
C
3
H
3
F
2
CYC
H
-OH
3
-COCH
3
-COCH
2
C
3
H
3
F
2
CYC
V WO 99/37603 WO 9937603PCTIEP99/00363 39 Table A R2 (R3b)fl 2 A.1) A.2) A.3) A.4) A.6) A.7) A.8) A.9) A.1 1) A.12) A.13) A.14) A.16) A.17) A.18) A.19) A.21) A.22) A.23) A.24) A.26) A.27) A.28) A.29) -CON(00H 3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3 )0H 3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3 -CON(O0H 3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3 -CON(O0H 3 )0H 3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3
)CH
3
-CON(OCH
3 )0H 3
-CON(OCH
3
)CH
3 -C(0)NHOCH 3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3 4-ON 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-OH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-N0 2 4-SC F 3 4-SO00F 3 4-S0 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COCF 3 4-CHO 4-C1-3-NO 2 4-NH 2 3-CI-4-CN 3-OCH 3 -4-N0 2 3-01-4-NO 2 3-F-4-N0 2 4-C 6
H
4 -4-CN 4-C 6
H
4 -2-CN 4-ON 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-OH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 Mimi WO 99/37603 WO 9937603PCT/E P99/00363 40
H
2 (R3b)l2 A.31) A.32) A.33) A.34) A.36) A-37) A.38) A.39) A.41) A.42) A.43) A.44) A.46) A.47) A.48) A.49) A.51) A.52) A.53) A.54) A.56) A.57) A.58) A.59) A.61) A.62)
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-C(O)NHOCH
3
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5
-COSC
2
H
5 4-C 6
H
4 -2-N0 2 4-SC F 3 4-SOCF 3 4-SO 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COCF 3 4-CHO 4-Cl- 3-NO 2 4-NH 2 3-CI-4-CN 3-OCH 3 -4-N0 2 3-CI-4-NO 2 3-F-4-N0 2 4-C 6
H
4 -4-CN 4-C 6
H
4 -2-CN 4-CN 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-CH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-NO 2 4-C 6
H
4 -2-N0 2 4-SCF 3 4-SOCF 3 4-SO 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COCF 3 4-CHO 4-CI-3-N0 2 WO 99/37603 WO 9937603PCTIEP99/00363 -41
H
2 (R3b)fl2 A.63) A.64) A.66) A.67) A.68) A.69) A.71) A.72) A.73) A.74) A.76) A.77) A.78) A.79) A.81) A.82) A.83) A.84) A.86) A.87) A.88) A.89) A.91) A.92) A.93) A.94)
-COSO
2
H
5
-COSO
2
H
5 -00S0 2
H
5
-COSC
2
H
5
-OOSC
2
H
5
-COSC
2
H
5
-OOSC
2
H
5
-COSOH
3
-OOSOH
3
-COSCH
3
-COSOH
3
-OOSCH
3
-COSCH
3
-COSOH
3
-COSCH
3
-COSCH
3
-COSCH
3
-OOSCH
3
-COSCH
3
-OOSOH
3
-COSCH
3
-COSOH
3
-COSOH
3
-COSCH
3
-COSCH
3
-COSCH
3
-COSOH
3
-OOSCH
3
-OOSCH
3
-OOSCH
3
-CH
2 0C(O)C(0H 3 3
-OH
2 0C(O)C(CH 3 3 4-NH 2 3-CI-4-CN 3-00H 3 -4-N0 2 3-01-4-NO 2 3-F-4-N0 2 4-C 6
H
4 -4-ON 4-0 6
H
4 -2-CN 4-ON 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-OH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-NO 2 4-SC F 3 4-SOOF 3 4-S 020F 3 2-F-4-ON 2-F- 4-NO 2 4-COO F 3 4-CHO 4-01- 3-NO 2 4-NH 2 3-01-4-CN 3-OCH 3 -4-N0 2 3-01-4-NO 2 3-F-4-N0 2 4-C 6
H
4 -4-ON 4-0 6
H
4 -2-ON 4-ON 4-NO 2 WO 99/37603 WO 9937603PCT/EP99/00363 42
H
2 (R3b)fl2 A.96) A.97) A.98) A.99) A. 100) A.101) A. 102) A.103) A. 104) A. 105) A.106) A. 107) A. 108) A.109) A.110) A.1 11) A. 112) A.1 13) A. 114) A. 115) A. 116) A. 117) A.118) A.1 19) A.120) A.121) A.122) A.123) A.124) A.125) A.126)
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 00(O)C(CH 3 3
-CH
2
OC(O)C(CH
3 3
-CH
2
OC(O)C(CH
3 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2 00 2
H
4 0CH 3
-CH
2
OC
2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3 4-CF 3 2-Cl 4-NO 2 3-CH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-N0 2 4-SC F 3 4- SOC F 3 4-SO 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COCF 3 4-CHO 4-CI-3-N0 2 4-NH 2 3-CI-4-CN 3-O0H 3 -4-N0 2 3-CI-4-N0 2 3-F-4-N0 2 4-0 6
H
4 -4-CN 4-0 6
H
4 -2-CN 4-CN 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-OH 3 4-NO 2 4-Cl 4-0 6
H
4 -4-N0 2 4-0 6
H
4 -2-N0 2 4-SC F 3 4-SOCF 3 4-S0 2
CF
3 WO 99/37603 WO 9937603PCT/EP99/00363 43
R
2 (R3b)fl2 A. 127) A. 128) A. 129) A. 130) A.131) A. 132) A. 133) A. 134) A. 135) A. 136) A. 137) A. 138) A. 139) A. 140) A.141) A. 142) A. 143) A. 144) A. 145) A. 146) A. 147) A. 148) A. 149) A. 150) A.151) A. 152) A.153) A. 154) A.155) A. 156) A.157) A.1 58)
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-CH
2 0C 2
H
4 0CH 3
-OH
2 00H 2 CH=0H 2
-OH
2 00H 2 CH=0H 2
-CH
2 0CH 2
CH=CH
2
-CH
2
OCH
2
CH=CH
2
-CH
2 00H 2
CH=CH
2
-CH
2 00H 2
CH=CH
2
-CH
2 00H 2
OH=CH
2
-OH
2
OCH
2 OH=0H 2
-CH
2 0CH 2
CH=CH
2
-OH
2
OCH
2 CH=0H 2
-CH
2 0CH 2 CH=0H 2
-CH
2
OCH
2
CH=CH
2
-OH
2 0CH 2
CH=CH
2
-CH
2 0CH 2 CH=0H 2
-CH
2 00H 2
CH=CH
2
-CH
2
OCH
2
CH=CH
2
-CH
2 0CH 2
CH=CH
2
-CH
2
OCH
2
CH=CH
2
-CH
2
OCH
2
CH=CH
2
-CH
2
OCH
2
CH=CH
2 2-F-4-CN 2-F- 4-NO 2 4-OF 3 4-CHO 4-Cl- 3-NO 2 4-NH 2 3-CI-4-CN 3-00H 3 -4-N0 2 3-01-4-NO 2 3-F-4-N0 2 4-0 6
H
4 -4-CN 4-C 6
H
4 -2-ON 4-CN 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-OH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-N0 2 4-SC F 3 4-SOCF 3 4-S 020F 3 2-F-4-CN 2-F- 4-NO 2 4-000 F 3 4-CHO 4-01-3-NO 2 4-NH 2 3-0I-4-ON 3-00H 3 -4-N0 2 3-01-4-NO 2 WO 99/37603 WO 9937603PCT[EP99/00363 44
H
2 (R3b)n2 A. 159) A. 160) A.161) A. 162) A. 163) A. 164) A. 165) A. 166) A. 167) A. 168) A. 169) A. 170) A.171) A. 172) A. 173) A. 174) A. 175) A. 176) A. 177) A. 178) A.179) A. 180) A.1 81) A. 182) A. 183) A. 184) A. 185) A. 186) A. 187) A. 188)
-CH
2 00H 2
CH=CH
2
-CH
2 00H 2
CH=CH
2
-CH
2 0CH 2
CH=CH
2
-CH
2 00H 2
C=ECH
-CH
2 0CH 2
CE=CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2 00H 2 C=2CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2 00H 2
C=ECH
-CH
2 0CH 2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-CH
2
OCH
2
C=-CH
-C0C 0
H
21 -C00 10
H
21 -C00 10
H
21 -COG 10
H
21 3-F-4-N0 2 4-C 6
H
4 -4-CN 4-C 6
H
4 -2-CN 4-CN 4-NO 2 4-CF 3 2-Cl 4-NO 2 3-CH 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-N0 2 4-SCF 3 4-SOCF 3 4-SO 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COCF 3 4-CHO 4-Cl- 3-NO 2 4-NH 2 3-CI-4-CN 3-OCH 3 -4-N0 2 3-01-4-NO 2 3-F-4-N0 2 4-C 6
H
4 -4-CN 4-0 6
H
4 -2-CN 4-CN 4-NO 2 4-CF 3 2-Cl 4-NO 2 WO 99/37603 WO 9937603PCT/E P99/00363 45
R
2 (R3b)fl2 A. 189) A. 190) A.191) A. 192) A. 193) A. 194) A. 195) A.196) A. 197) A. 198) A. 199) A.200) A.201) A.202) A.203) A.204) A.205) A.206) A.207) A.208) A.209) A.21 0) A.21 1) A.212) A.21 3) A.214) A.215) A-216) A.217) A.218) A.219) A.220) -C0CioH 21 -C0C 0
H
2 -C0C 0
H
21 -C0C 0
H
21 -C0C 0
H
21 -C0C 0
H
21
-COC
0
H
21 -C0C 0
H
21 -C0C 0
H
21 -000 10
H
21 -C0C 0
H
21 -C0C 0
H
21 -C0C 0
H
21 -C0C 0
H
21 -C00 10
H
21 -C0C 0
H
21 -C00 10
H
21 -C0C 0
H
21 -C0C 0
H
21
-H
-H
-H
-H
-H
-H
-H
-H
-H
-H
-H
-H
-H
3-C H 3 4-NO 2 4-Cl 4-C 6
H
4 -4-N0 2 4-C 6
H
4 -2-N0 2 4-SCF 3 4-SOCF 3 4-SO 2
CF
3 2-F-4-CN 2-F- 4-NO 2 4-COO F 3 4-CHO 4-01-3-NO 2 4-NH 2 3-CI-4-CN 3-OCH 3 -4-N0 2 3-CI-4-N0 2 3-F-4-N0 2 4-C 6
H
4 -4-CN 4-C 6
H
4 -2-CN 4-SC F 3 4-SO00F 3 4-S0 2
CF
3 4-S0 2
F
4-SOC 2
F
4-S0 2
C
2
F
4-SC F 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
4-SCF 2
CI
4-SOC F 2 C I 4-SO 2
CF
2
CI
4-SFs WO 99/37603 PCT/EP99/00363 46 R2 (R3b)fl2 A.221) -H
SCF
2 Br A.222) -H
SOOF
2 Br A.223) -H
SO
2
CF
2 Br A.224) -H
SCF
2
CF
2 Br A.225) -H
SOCF
2
CF
2 Br A.226) -H
SO
2
OF
2
OF
2 Br A.227) -OH 3 4-SCF 3 A.228) -OH 3 4-SOOF 3 A.229) -CH 3 4-S0 2
CF
3 A.230) -OH 3 4-SC 2
F
A.231) -OH 3 4-S00 2
F
A.232) -OH 3 4-S0 2 0 2
F
A.233) -OH 3 4-SOF 2
H
A.234) -OH 3 4-SOCF 2
H
A.235) -OH 3 4-SO 2
OF
2
H
A.236) -OH 3 4-SCF 2
CI
A.237) -OH 3 4-SOCF 2
CI
A.238) -OH 3 4-S0 2
CF
2
CI
A.239) -OH 3 4-SFs A.240) -OH 3 SCF 2 Br A.241) -OH 3 SOCF 2 Br A.242) -OH 3 SO 2
CF
2 Br A.243) -OH 3 SCF 2
OF
2 Br A.244) -OH 3 SOCF 2
OF
2 Br A.245) -OH 3 SO 2
CF
2
CF
2 Br A.246) -C 2
H
5 4-SCF 3 A.247) -C 2
H
5 4-SOOF 3 A.248) -C 2
H
5 4-S0 2 0F 3 A.249) -C 2
H
5 4-SC 2
F
A.250) -C 2
H
5 4-S00 2
F
A.251) -C 2
H
5 4-S0 2
C
2 Fs A.252) -C 2
H
5 4-SCF 2
H
WO 99/37603 PCT/EP99/00363 47 R2 (R3b)l2 A.253) -0 2
H
5 4-SOCF 2
H
A.254) -C 2
H
5 4-SO 2
CF
2
H
A.255) -254-SCF 2
CI
A.256) -0 2
H
5 4-SOCF 2
CI
A.257) -254-SO 2
CF
2
CI
A.258) -C 2
H
5 4-SF A.259) -0 2
H
5 SCF 2 Br A.260) -C 2
H
5 SOCF 2 Br A.261) -C 2
H
5 SO 2
CF
2 Br A.262) -0 2
H
5 SCF 2
CF
2 Br A.263) -0 2
H
5 SOCF 2
CF
2 Br A.264) -C 2
H
5 SO 2
CF
2
CF
2 Br A.265)
-CH(CH
3 2 4-SCF 3 A.266) -CH(CH 3 2 4-SOCF 3 A.267) -CH(0H 3 2 4-SO 2
CF
3 A.268) -CH(CH 3 2 4-SC 2
F
A.269) -CH(CH 3 2 4-SOC 2 Fs A.270)
-CH(CH
3 2 4-S0 2
C
2
F
A.271) -CH(0H 3 2 4-SCF 2
H
A.272) -CH(CH 3 2 4-SOCF 2
H
A.273) -CH(CH 3 2 4-SO 2
CF
2
H
A.274)
-CH(CH
3 2 4-SCF 2
CI
A.275) -CH(CH 3 2 4-SOCF 2
CI
A.276) -CH(CH 3 2 4-SO 2
CF
2
CI
A.277) -CH(CH 3 2 4-SF A.278) -CH(CH 3 2 SCF 2 Br A.279) -CH(CH 3 2 SOCF 2 Br A.280) -CH(CH 3 2 SO 2
CF
2 Br A.281) -CH(CH 3 2 SCF 2
CF
2 Br A.282) -CH(CH 3 2 SOCF 2
CF
2 Br A.283) -CH(CH 3 2 SO 2
CF
2
CF
2 Br A.284) -COCH 3 4-SCF 3 WO 99/37603 PCT/EP99/00363 48
R
2 (R3b)fl2 A.285) -COCH 3 4-SOCF 3 A.286) -COCH 3 4-SO 2
CF
3 A.287) -COGH 3 4-SC 2
F
A.288) -GOGH 3 4-SOC 2
F
A.289) -GOGH 3 4-S0 2
C
2
F
A.290) -GOGH 3 4-SCF 2
H
A.291) -COCH 3 4-SOCF 2
H
A.292) -GOGH 3 4-SO 2
CF
2
H
A.293) -COGH 3 4-SCF 2
GI
A.294) -COCH 3 4-SOCF 2
CI
A.295) -COGH 3 4-SO 2
CF
2
CI
A.296) -COCH 3 4-SF A.297) -GOCH 3 SCF 2 Br A.298) -GOGH 3 SOCF 2 Br A.299) -GOGH 3 SO 2
CF
2 Br A.300) -GOGH 3 SCF 2
CF
2 Br A.301) -GOGH 3 SOCF 2
CF
2 Br A.302) -GOGH 3 SO 2
CF
2
CF
2 Br A.303) -COC 2
H
5 4-SGF 3 A.304) -COC 2
H
5 4-SOCF 3 A.305) -COC 2
H
5 4-SO 2
CF
3 A.306) -COC 2
H
5 4-SC 2
F
A.307) -COC 2
H
5 4-SOC 2
F
A.308) -COC 2
H
5 4-S0 2
C
2 Fs A.309) -000 2
H
5 4-SCF 2
H
A.31 0) -GOC 2
H
5 4-SOCF 2
H
A.31 1) -COC 2
H
5 4-SO 2
CF
2
H
A.312) -COC 2
H
5 4-SCF 2
CI
A.31 3) -COC 2
H
5 4-SOCF 2
CI
A.31 4) -COC 2
H
5 4-SO 2
GF
2
CI
A.315) -COC 2
H
5 4-SF A.31 6) -CO 2
CH
3 4-SCF 3
S
WO 99/37603 PCTIEP99/00363 49 R2 (R3b)fl2 A.317) -C00 2
H
5 SCF 2 Br A.318) -COC 2
H
5 SOCF 2 Br A.319) -COC 2
H
5 SO 2
CF
2 Br *A.320) -COC 2
H
5 SCF 2
CF
2 Br A.321) -C00 2
H
5 SOCF 2
CF
2 Br A.322) -CO 2
CH
3 SO 2
CF
2
CF
2 Br A.323)
-CO
2
CH
3 4-SOCF 3 A.324) -CO 2
CH
3 4-S020 F 3 A.325) -C0 2
CH
3 4-SC 2
F
A.326) -C0 2
CH
3 4-S00 2
F
A.327) -CO 2
CH
3 4-S0 2 0 2
F
A.328) -C0 2
CH
3 4-SCF 2
H
A.329) -C0 2
CH
3 4-SOCF 2
H
A.330) -CO 2
CH
3 4-SO 2
CF
2
H
A.331) -C0 2
CH
3 4-SCF 2
CI
A.332) -C0 2
CH
3 4-SOCF 2
CI
A.333) -CO 2
CH
3 4-SO 2
CF
2
CI
A.334) -C0 2
CH
3 4-SF A.335) -C0 2
CH
3 SCF 2 Br A.336) -CO 2
CH
3 SOCF 2 Br A.337) -C0 2
CH
3 S0 2
CF
2 Br A.338) -CO 2
CH
3 SCF 2
CF
2 Br A.339) -C0 2
CH
3 SOCF 2
CF
2 Br A.340) -C0 2
CH
3 S0 2
CF
2
CF
2 Br A.341) -C0 2
C
2
H
5 4-SCF 3 A.342) -C0 2
C
2
H
5 4-SOCF 3 A.343) -C0 2
C
2
H
5 4-SO 2
CF
3 A.344) -C0 2
C
2
H
5 4-SC 2
F
A.345) -C0 2 2
H
5 4-SOC 2
F
A.346) -C0 2
C
2
H
5 4-S0 2
C
2
F
A.347) -C0 2
C
2
H
5 4-SCF 2
H
A.348) -C0 2
C
2 Hs 4-SOCF 2
H
WO 99/37603 WO 9937603PCT/EP99/00363 50 R2 (R3b)fl2 A.349) A .350) A.351) A.352) A.353) A.354) A.355) A.356) A.357) A.358) A.359) A.360) A.361) A.362) A.363) A.364) A.365) A.366) A.367) A.368) A.369) A.370) A.371) A.372) A.373) A.374) A.375) A.376) A.377) A.378) A.379) A.380) -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5 -C0 2
C
2
H
5
-CH
2 00 2
H
5
-CH
2 00 2
H
5
-CH
2 00 2
H
5
-CH
2 00 2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2 00 2
H
5
-CH
2 00 2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2
OC
2
H
5
-CH
2 0C 2
H
5
-CH
2
OC
2
H
5
-CH
2
OCH
3
-CH
2 0CH 3 4-SO 2
CF
2
H
4-SCF 2
CI
4-SOC F 2 C I 4-SO 2
CF
2
CI
4-SF
SCF
2 Br SOC F 2 Br
SO
2
CF
2 Br
SCF
2
CF
2 Br
SOCF
2
CF
2 Br
SO
2
CF
2
CF
2 Br 4-SC F 3 4-S OCF 3 4-S0 2
CF
3 4-SC 2
F
4-S0C 2
F
4-S0 2
C
2
F
4 -S CF 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
4-S CF 2
CI
4-SOCF 2
CI
4-SO 2
CF
2
CI
4-SF
SCF
2 Br SOC F 2 B r
SO
2
CF
2 Br
SCF
2
CF
2 Br
SOCF
2
CF
2 Br
SO
2
CF
2
CF
2 Br 4-SCF 3 4 -SOC F 3 WO 99/37603 WO 9937603PCT/EP99/00363 51 r12 (R3b)fl2 A.381) A.382) A.383) A.384) A.385) A.386) A.387) A.388) A.389) A.390) A.391) A.392) A.393) A.394) A.395) A.396) A.397) A.398) A.399) A.400) A.401) A.402) A.403) A.404) A.405) A.406) A.407) A.408) A.409) A.41 0) A.41 1) A.412)
-CH
2 00H 3
-CH
2
OCH
3
-CH
2 00H 3
-CH
2 00H 3
-CH
2 00H 3
-CH
2 00H 3
-CH
2
OCH
3
-CH
2
OCH
3
-CH
2 0CH 3
-CH
2
OCH
3
-CH
2
OCH
3
-CH
2 00H 3
-CH
2 00H 3
-CH
2 00H 3
-CH
2 00H 3
-CH
2
OCH
3
-CH
2 00H 3
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-.C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7 4-SO 2
CF
3 4-SC 2
F
4-S00 2
F
4-S0 2
C
2
F
4-SC F 2
H
4-SOC F 2
H
4-SO 2 C F 2
H
4-SC F 2 C I 4-SOCF 2
CI
4-SO 2
CF
2
CI
4-SF
SCF
2 Br SOC F 2 Br S 0 2 C F 2 B r
SCF
2
CF
2 Br
SOCF
2
CF
2 Br
SO
2
CF
2
CF
2 Br 4-SC F 3 4-SOC F 3 4-S0 2
CF
3 4-SC 2
F
4-S0C 2
F
4-S 0 2
C
2
F
4-SC F 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
4-SCF 2
CI
4-SOCF 2
CI
4-SO 2
CF
2
CI
4-SF SC F 2 B r SOC F 2 B r WO 99/37603 WO 9937603PCT/EP99/00363 52 H2 (R3b)fl2 A.413) A.414) A.415) A.416) A.417) A.418) A.419) A.420) A.421) A.422) A.423) A.424) A.425) A.426) A.427) A.428) A.429) A.430) A.431) A.432) A.433) A.434) A.435) A.436) A.437) A.438) A.439) A.440) A.441) A.442) A.443) A.444)
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2 O-n-C 3
H
7
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2 N(0H 3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3 )C0 2 0H 3
-CH
2
N(CH
3
)CO
2
CH
3
-CH
2
N(CH
3 )C0 2 0H 3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3 )S0 2
CH
3 S0 2
CF
2 Br
SCF
2
CF
2 Br
SOCF
2
CF
2 Br
SO
2
CF
2
CF
2 Br 4-SC F 3 4-SO00F 3 4-S0 2
CF
3 4-SC 2
F
4-S00 2
F
4-S0 2
C
2
F
4-SC F 2
H
4-SO00F 2
H
4-5 020F 2
H
4-SCF 2
CI
4-SOC F 2
CI
4-SO 2
CF
2
CI
4-SF SC F 2
B
SOCF
2 Br
SO
2
CF
2 Br SC F 2 C F 2 B r
SOCF
2
CF
2 Br S0 2
CF
2
CF
2 Br 4-SCF 3 4-SOC F 3 4-SO 2
CF
3 4-SC 2
F
4-S00 2
F
4-S0 2
C
2
F
4-SC F 2
H
4-SOCF 2
H
4-SO 2
CF
2
H
WO 99/37603 WO 9937603PCTIEP99/00363 53 A.445) A .446) A.447) A .44 8) A.449) A.450) A.451) A.452) A.453) A.454)
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3
-CH
2
N(CH
3
)SO
2
CH
3 (RAb112 4-SC F 2
CI
4-SOCF 2
CI
4-SO 2
CF
2
CI
4-SF
SCF
2 Br
SOCF
2 Br
SO
2
CF
2 B3r
SCF
2
CF
2 Br
SOCF
2
CF
2 Br
SO
2
CF
2
CF
2 Br Table 4: Compounds of general formula
RCN
(R
3 a)1 I-)n b), wherein (R31)n1 is 2,6-C1 2 -4-CF 3 and R 2 and (R3b)fl2 each correspond to a line of Table A.
Table Compounds of general formula wherein (R3a)nl is 2,4,6-013 and R 2 and (RAbf2 each correspond to one line of Table A.
Table 6: Compounds of general formula wherein (R 3 a)nl is 2-CI-4-CF 3 and R 2 and (R3b)nleach correspond to one line of Table A.
Table 7: Compounds of general formula wherein (R3a)nl is 2,6-C1 2 -4-N0 2 and R 2 and (R3b)l2 each correspond to one line of Table A.
Table 8: Compounds of general formula wherein (R 3 a,)nl is 2,6-C1 2 -4-OCF 3 and R 2 and (R3b)l2 each correspond to one line of Table A.
17" S- WO 99/37603 PCT/E P99/00363 -54- Table 9: Compounds of general formula wherein (R3a)n, is 2,6-C1 2 -4-F and R 2 and (R3b)n2 each correspond to one line of Table A.
Table Compounds of general formula wherein (R3a)nl is 2,6-CI 2 -4-Br and R 2 and (R3b)n2 each correspond to one line of Table A.
Table 11: Compounds of general formula wherein (R 3 a)ni is 2-CI-4-CF 3 -6-F and R 2 and (R3b)n2 each correspond to one line of Table A.
Table 12: Compounds of general formula wherein (R 3 a)ni is 2,3,6-C 3 -4-CF 3 and R2 and (R3b)n each correspond to one line of Table A.
Table 13: Compounds of general formula wherein (R 3 a)n is 2,6-C1 2 -3-F-4-CF 3 and R 2 and (R3b)n each correspond to one line of Table A.
Table 14: Compounds of general formula wherein (R 3 a)ni is 2,3-F 2 -4-CF 3 -6-CI and R 2 and (R3b)n each correspond to one line of Table A.
Table Compounds of general formula wherein (R 3 a)nl is 2,6-CI-4-CN and R 2 and (R3b)n each correspond to one line of Table A.
Table 16: Compounds of general formula wherein (R3a),l is 2,4-CI 2 -6-CF 3 and R2 and (R3b)n2 each correspond to one line of Table A.
Table 17: Compounds of general formula wherein (R 3 a)ni is 2,6-C1 2 -4-SCF 3 and R2 and (R3b)n 2 each correspond to a line of Table A.
Table 18: Compounds of general formula wherein (R 3 a)n, is 2,6-C1 2 -4-SOCF 3 and R 2 and (R3b)n2 each correspond to a line of Table A.
Table 19: Compounds of general formula wherein (R 3 a)ni is 2,6-C1 2 -4-SO 2
CF
3 and R 2 and (R3b)n2 each correspond to a line of Table A.
4 1i WO 99/37603 PCT/EP99/00363 Table Compounds of general formula wherein (R 3 a)nl is 2,6-C1 2 -4-SO 2
CH
3 and R2 and (R3b)n2 each correspond to a line of Table A.
Table 21: Compounds of general formula wherein (R 3 a)ni is 2,6-C1 2 -4-OCF 2 Br and R 2 and (R3b)n2 each correspond to one line of Table A.
Table 22: Compounds of general formula wherein (R 3 a)ni is 2,6-CI 2 -4-OCF 2 H and R2 and (R3b)n2 each correspond to one line of Table A.
Table 23: Compounds of general formula wherein (R3a)nl is 2,6-C1 2 -4-C 2 Fs and R 2 and (R3b)n2 each correspond to one line of Table A.
Table 24: Compounds of general formula wherein (R 3 a)ni is 2,6-(N0 2 2 -4-CF 3 and R 2 and (R3b)n2 each correspond to one line of Table A.
Table Compounds of general formula wherein (R 3 a)n, is 2,6-(N0 2 2 -4-CI and R 2 and (R3b)n2 each correspond to one line of Table A.
Table 26: Compounds of general formula wherein (R3a)ni is 2,6-CI 2 -4-OSO 2
CH
3 and R 2 and (R3b)n2 each correspond to a line of Table A.
Table 27: Compounds of general formula wherein (R3a)ni is 2,6-CI 2 -4-OSO 2
CF
3 and R 2 and (R3b)n2 each correspond to a line of Table A.
Table 28: Compounds of general formula wherein (R3a) is 2,6-CI 2 -4-SF 5 and R 2 and (R3b)n2 each correspond to a line of Table A.
Examples of formulations of compounds of the invention, i.e. solutions, granulates, dusts, wettable powders, emulsifiable concentrates, coated granules, and suspension concentrates are of the types listed for instance in EP-A-580'553(Case 19164), Examples F1 to i7- ~i l iifilijbii~j~i- WO 99/37603 PCT/EP99/00363 -56- Biological Examples Example B1: Ovicidal effect on Heliothis virescens Eggs of Heliothis virescens deposited on filter paper are immersed briefly in a test solution comprising 400 ppm of the mixture of active ingredients to be tested in acetone/water. After the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching rate of the eggs is compared with that for untreated controls reduction in hatching rate).
Compounds listed in Tables 3 to 5 show good activity against Heliothis virescens. In particular, compounds 2.1 to 2.5, 2.8 to 2.13 and 3.7 show a response of more than Example B2: Effect on Spodoptera littoralis caterpillars Young soya plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposit has dried, the soya plants are populated with 10 thirdinstar larvae of Spodoptera littoralis and placed in a plastic container. Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage response) is determined by comparing the number of dead larvae and the extent of feeding damage on the treated plants with those on the untreated plants.
The compounds of table 1 show good efficacy against Spodoptera littoralis in this test. In particular, compounds 2.1 to 2.5, 2.7 to 2.18 and 3.7 to 3.9 show a response of more than Example B3: Effect on Diabrotica balteata larvae Corn seedlings are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After drying of the spray deposit, the corn seedlings are inoculated with second-instar larvae of Diabrotica balteata and placed in a plastic container. Six days later they are evaluated. The percentage reduction of the population response) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Diabrotica balteata in this test.
In particular, compounds 2.1 to 2.4, 2.6, 2.7, 2.11, 2.25 to 2.28 and 3.9 show a response of more than T WO 99/37603 PCT/E P99/00363 -57- Example B4: Effect on Plutella xvlostella caterpillars Young cabbage plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposit has dried, the cabbage plants are populated with third-instar larvae of Plutella xylostella and placed in a plastic container. Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage response) is determined by comparing the number of dead larvae and the extent of feeding damage on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Plutella xylostella in this test.
Example B5: Effect on Tetranychus urticae Young bean plants are inoculated with a mixed population of Tetranychus urticae and, one day later, are sprayed with an aqueous emulsion containing 400 ppm of active ingredient.
The plants are incubated for 6 days at 25°C and then evaluated. The percentage reduction of the population response) is determined by comparing the number of dead eggs, larvae, and adults on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Tetranychus urticae in this test.
Example B6: Effect on Aphis craccivora Pea seedlings are infected with Aphis craccivora, then sprayed with an emulsion containing 400 ppm of active ingredient and incubated at 20°C. Three and six days later they are evaluated. The percentage reduction of the population response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Aphis craccivora in this test.
In particular, compounds 2.7, 2.22 and 3.8 show a good response of more than Example B7: Effect on Myzus persicae Pea seedlings are infected with Myzus persicae, then sprayed with an emulsion containing 400 ppm of active ingredient and incubated at 20 0 C. Three and six days later they are evaluated. The percentage reduction of the population response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
icj P,\OPERWMKR27I 8l-99 spcdo-2VL12A)l -58- The compounds of Tables 3 to 5 show good efficacy against Myzus persicae in this test. In particular, compounds 3.7 and 3.13 show a good response of more then Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
*F *o o.
o• o

Claims (3)

1. Compound of formula N IN X A(A2 wherein A, and A 2 are independent of one another and in each case represent a monocyclic or 10 bicyclic aryl radical; and A, is substituted where appropriate with substituent (R 3 a)ni and A 2 where appropriate 00..with substituent (R3b)fl2; 0 nj and n 2 are independently of one another 1, 2, 3 or 4, depending on the possibilities for substitution on ring system A, and A 2 and 0* 0: 15 R 3 a is halogen, Cl-C 6 alkyl, halogen- Cj -C&Ikyll O-C 4 alkenyl, C 2 -C 4 alkinyl, halogen-C 2 -C 4 alkenyf, halogen-C 2 -C 4 alkinyl, 0*00:Cl -O 6 alkoxy, halogen-Cl-Cs-alkoxy, 0 2 -Cralkenyloxy, C 2 -C 6 alkinyloxy, halogen-C2-Calkenyloxy, halogen-C 2 -Csalkinyloxy, -OH, -SFr,, -CHO, -C(=O)-Cj-C 6 alkytl, -C(=-O)-halogen-Ct-CraIkyt, -O(=O)-0C 1 -C 6 aIky, -C(=_O)-O-hafogen-C 1 -C 6 aIkyI, 0000N R wh r i o h R ub tt e t r i d p n e t o ne a o h r, N 0: -O 2 6 2 (wherein both 6 substituents are independent of one another), N, -S(=O)-Cj-Coaky1, -S(=O)p-halogen-C 1 -C 6 akyl, -O-S(=O)p-O 1 -C 6 aIkyI, -0-S(=O)p-halogen-C-Ceaky1, phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenioxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of ha logen, cyano, NO 2 Ci-C 6 alkyI, halogen- C 1 -C 6 allkyI, C 1 -OCalloxy and halogen-0 1 -C 6 alkoxy.; -CR 5 =CR 5 R 14 -NRjjR 12 1 -C 6 aIkyI, -CR 15 =N0R 10 or a five or six-membered heteroaryl ring, wherein the said heteroaryl- ring is substituted where appropriate, depending on the substitution possibilities on PAOPERMFKi1.271I,)19 W o-281121 60 the ring, with 1 to 3 substituents selected from the group consisting of halogen, C 1 -C 4 aIlkYl, Cl-C 4 haloalkyl, NO 2 and ON; R3b is halogen, Cl -Cralkyl, halogen-C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkinyl, halogen-C 2 -C 4 alkenyl, halogen-C 2 -C 4 alkinyl, C, -C 6 alkoxy, halogen -CI -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkinyloxy, halogen-C 2 -C~alkenyloxy, halogen-0 2 -C~alkinyloxy, -Ss -CHO, 1 -C 6 alkyl, -C(=O)-halogen-0 1 -C 6 alkyl, -C(=O)-OCJ -C 6 alkyl, -C(=O)-O-halogen-0 1 -C 6 alkyl,. -O-C(=O)N(R 6 2 (wherein the two R 6 substituents are independent of one another), -ON, -NO 2 phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO 2 Cl-C 6 alkyl, halgen-C 6 alkyl, C, -Cralkoxy and halogen-C-C 6 alkoxy; -C 6 alky in the
4-position or -S(=O)p-halogen-Cj-C 6 alkyl in the 4-position, with the proviso, that one of the substituents R 3 b, is -S(=O)p-C 1 -Cealky I or -S(=O)p-halogen-Cj-C 6 alkyl; R 2 is hydrogen -C 1 -C 6 alkyl-NR 1 RI 2 7 -COC 9 -C 20 alkyl, -CH 2 0(C=O)CI-C 6 alkyl, -Cealkyl-O-Ci-C 6 alkyl-O-C 1 -C 6 alkyl, -0H 2 0(C=O)C 2 -0 6 alkenyl, -0H20(C=O)C 2 -Cralkinyl, -C(=S)00 2 -Cralkenyl, -O(=S)00 2 -Oealkinyl, -C(=S)SCI-Cealkyl, -C(=S)S0 2 -Cralkenyl, -C(=S)S0 2 -C 6 alkinyl, -C(=O)SC 1 -Cealkyl, -C(=O)SC 2 -C 6 alkenyl, -O(=O)SC 2 -Cealkinyl, -C(=S)NR 11 R 1 2 -C(=O)NR 10 0OR 13 -CH 2 0C 2 -C 6 alkenyl, -CH 2 0C 2 -C 6 alkinyl, -CH 2 0 2 -C 6 haloalkenyl or -CH 2 0 2 -Cehaloalkinyl; -OH, Cj-C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 6 CYcloalkyl, C 3 -C 6 alkenyl, C 3 -C~alkinyl, halogen-CI-C 6 alkyl, halogen-C 3 -Coalkenyl, halogen-C 3 -C 6 alknyl, benzyl or benzoyl, wherein the benzyl or benzoyl radical is substituted. in the aromatic ring independently of one another once to three times by substituents selected from the group consisting of halogen, -CN, NO 2 C 1 -C 6 alkyl, C 1 -Cfalkoxy, halogeh-C,-C 6 alkyl and halogen- 0 1 -C 6 alkoxy; C,-Coalkoxy-Cl-O 6 alkyl, cyano-Cl-O 6 alkyl, 7 a, Rmb, -OC(O=)-R 7 a, C(=O)C(O)-R 7 a, 2 (wherein the two R 6 substituents are independent of one another); cyano, -C,-Coalkyll- WO 99/37603 PCT/EP99/00363
61- N(R 5 -01 -C 6 alkyl-S-C(=S)-R 8 -01 -C,,alkyl-S(=O)p-R 9 -S(=O)p-R 9 or -OH 2 N(R 10 )-S0 2 -R 9 X is 0or S; p isO0, 1or 2; R 5 is independently H or Cl-C~alkyl; R 6 is independently H, Cl-C 8 alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group is substituted in the aromatic ring where appropriate independently of one another once to three times with substituents selected from the group consisting of halogen, -CN, N0 2 Cl-C 6 alkyl, Cl-C 4 alkoxy, halogen-Cl-C 6 alkyl and halogen- C 1 -C 6 alkoxy; or two alkyl radicals R 6 together with the nitrogen atom to which they are bonded, form a five to seven-membered ring, wherein a OH 2 group, where appropriate, is substituted by a heteroatom selected from the group consisting of 0 and S, or is substituted by NH, and wherein the five to seven-membered ring, where appropriate, is substituted once or twice with CI-C 4 alkyl; R 7 a is Cl-C~akoxy-C 1 -C~alkyI, CH 2 CH 2 CF 2 Cl, Ci -C 6 alkylthiO-Cl-C 6 alkyl, acyloxy-C 1 -C 6 alkyl, halogen-C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 6 alkyl, halogen-C3-0 6 -cycloalkyl- Cl-C 6 alkyl, aryloxy-Cl-C 6 alkyl; or phenyl, benzyl, phenoxy or arylOXY-Cl-C 6 alkyl, which are substituted with 1 to 3 substituents selected form the group consisting of halogen, nitro, cyano, CI-C 4 -alkyl, halogen-Cl-C 4 -alkyl and halogen-C-C 4 -alkoxy; R7b is H, C 1 -C 8 alkyI, C 2 -C 8 alkenyl, halo-C 1 -C~alkyl, halo-0 2 -C 8 alkenyl, Cl-C 8 alkoxy, halo-C 1 -C 8 alkoxy, C 3 -C 6 cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or -N(R 6 2 (in which the two R6 are independent of one another); R 8 is C 1 -C~alkyl, CI-C~alkoxy, halogen -C 1 -Caalkyl, halogen-0 1 -C 8 alkoxy, Cl-C~alkylthio, phenyl, benzyl or -N(R 6 2 (wherein the two R6 radicals are independent of one another); R 9 is 0 1 -C 6 alkyl, halogen-C-C 4 alkyl or aryl, which is unsubstituted or substituted once to three times, independently of one another, with subsituents selected from the group consisting Of Cl-C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkinyl, Cl-C 4 alkoxy, halogen, cyano, halogen-Cl-C 4 alkyl, halogen-0 2 -C 4 alkenyl, haloge n-C 2 -C 4 al kin yl, halogen-Cl-C 4 alkoxy and nitro; Rio is H, Cl-C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl oder benzyl, wherein the phenyl and benzyl radicals are unsubstituted or substituted in the aromatic ring once to three times independently of one another with substituents selected from the group consisting of WO 99/37603 PCT/EP99/00363 -62- C 1 -C 4 alkyl, C,-C 4 alkoxy, halogen, cyano, halogen-C 1 -C 4 alkyl, halogen-CI-Calkoxy and nitro; R 11 i and R 12 are independently of one another H, C 1 -C alkyl, phenyl, -COCI-C 6 alkyl, -COC 1 -C 6 haloalkyl, -COphenyl, or together form a five or six-member saturated or unsaturated ring, wherein if appropriate one or more, especially one, of the CH- or CH 2 -groups is or are substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if appropriate is indepen- dently of each other substituted with 1 to 3 substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, NO 2 and CN; or the two substituents R 11 and R 12 together form a ring X X H 2 )q or X X q is 2 or 3; and R 1 3 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkinyl; R 14 is hydrogen, C 1 -C 6 alkyl, halogen-C 3 -C 6 alkyl, Cl-C 6 alkoxy, halogen-C-C 6 alkoxy, C 2 -C 6 alkenyloxy, -CHO, -C(=0)-Cl-C 6 alkyl, -C(=O)-halogen-C -C 6 alkyl, -C(=0)-OC 1 -C 6 alkyl, -C(=0)-O-halogen-C 1 -C 6 alkyl, -CN, -NO 2 2 N(R 6 2 (wherein the two R 6 substituents are independent of one another), 6 alkyl, -S(=O),-halogen-Cj-C 6 alkyl, 1 -C 6 alkyl, -O-S(=O),-halogen-C-C 6 alkyl, phenyl, benzyl, or benzyloxy wherein each of the phenyl, benzyl, or benzyloxy substituents is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO 2 C 1 -C 6 alkyl, halogen-C 1 -C 6 alkyl, C 1 -C 6 alkoxy and halogen- C 1 -C 6 alkoxy; and R 1 5 is hydrogen, C 1 -C 6 alkyl or halogen-C 1 -C 6 alkyl; and, if appropriate, to the possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in the form of a salt, to a method for the preparation and use of these compounds, E/Z isomers and tautomers, pesticides, whose active ingredient is selected from these compounds, E/Z isomers and tautomers, and to a method for the preparation and use of these compositions, intermediate products, in free form or in the form of a salt, for the preparation of these compounds, and where appropriate their 1 r -63- tautomers, in free form or in the form of a salt, and to a method for the preparation and use of these intermediate products and their tautomers. 2. A compound of formula according to claim 1 in free form. 3. A compound of formula according to claim 1, wherein A 1 and A 2 are phenyl. 4. A compound of formula according to claims 1 to 3 wherein R 2 is -C 1 -C 6 alkyl-NR 11 R 1 2 -COC 9 -C 20 alkyl, -C -C 6 alkyl-O-Cl-C 6 alkyl-O-Cl-C 6 alkyl, -CH 2 0(C=O)Ci-C 6 alkyl, -CH 2 0(C=O)C 2 -C 6 alkenyl, -CH 2 0(C=O)C2-C 6 alkinyl, -C(=S)OC 2 -C 6 alkenyl, -C(=S)OC 2 -C 6 alkinyl, -C(=S)SCi-C 6 alkyl, -C(=S)SC 2 -C6alkenyl, -C(=S)SC 2 -C 6 alkinyl, -C(=O)SCI-C 6 alkyl, -C(=O)SC 2 -C 6 alkenyl, -C(=O)SC2-C 6 alkinyl, -C(=S)NR 11 R 12 -C(=O)NR 10 OR 1 3 -CH 2 0C 2 -C 6 alkenyl, -CH 2 0C2-C 6 alkinyl, -CH 2 OC 2 -C 6 haloalkenyl or -CH 2 0C 2 -C 6 haloalkinyl. 5. A compound of formula according to claims 1 to 4, wherein ni is 2, 3, or 4 and n2 is 1 or 2. .4 6. A pesticidal composition comprising at least one compound of formula according to claim 1 as active ingredient, either in free form or in the form of an agrochemically acceptable salt, and at least one adjuvant. 7. A method for the control of pests comprising applying a composition of claim 6 to pests or 1* their habitat. 8. A method according to claim 7 for the control of insects and members of the order acarina. S 9. A method for preparing a composition of claim 6 which contains at least one adjuvant and comprises the intimate mixing and/or grinding of.the active ingredient.with the adjuvant(s). The use of a compound of formula according to claim 1, either in free form or in the form of an agrochemically acceptable salt, for preparing a composition of claim 6. 11. The use of a composition of claim 6 for the control of pests. 12. The use of claim 11 for the protection of plant propagation material. 13. A method for the control of pests in relation to plant propagation material which comprises treatment of said propagation material or of the locus for cultivation of said propagation material with a composition of claim 6. ^SLE^ l l v v-a^ -"esm. p& P:\OPERWMKRU27ISI.99 wp.doc-29II2/01 64 14. Plant propagation material which is treated according to the method described in claim 13. A compound according to claim 1, substantially as hereinbefore described with reference to the examples. DATED this 28th day of December, 2001 Novartis AG By DAVIES COLLISON CAVE Patent Attorneys for the Applicant B B B. ~cRA~ Vr S~
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