WO2013026900A1 - Pyridine derivatives as microbiocides - Google Patents

Pyridine derivatives as microbiocides Download PDF

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WO2013026900A1
WO2013026900A1 PCT/EP2012/066403 EP2012066403W WO2013026900A1 WO 2013026900 A1 WO2013026900 A1 WO 2013026900A1 EP 2012066403 W EP2012066403 W EP 2012066403W WO 2013026900 A1 WO2013026900 A1 WO 2013026900A1
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alkoxy
alkyl
crc
formula
compounds
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Martin Pouliot
Laura Quaranta
Stephan Trah
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel microbiocidally active, in particular fungicidally active, 2-(pyridin-2-yl)-pyrimidines. It further relates to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
  • Fungicidally active 2-(pyridin-2-yl)-pyrimidines are described in EP270362 and EP431424.
  • the disclosed compounds are characterized by an aryl substituent in pyrimidine position 4 and non cyclic substituents at pyrimidine positions 5 and 6.
  • the present invention accordingly relates to compounds of formula (I)
  • G represents together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxy, CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, d- C 6 alkoxy-Ci-C 6 alkyl,Ci-C 6 haloalkoxy, keto, Ci-C 6 alkoximino and CrC 6 alkylendioxy; and wherein two substituents, independently selected from the group consisting of hydroxy, C C 6 alkyl, Ci-C 6 haloalkyl and CrC 6
  • R 2 is hydrogen, halogen, cyano, hydroxy, Ci-C 6 alkyl, d-C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, CrC 6 alkoxy- Ci-C 6 alkyl or d- dalkylthio;
  • R 3 is hydrogen, hydroxy, halogen, cyano, d-dalkyl, d-dalkenyl, d-dalkynyl, d-d cycloalkyl, d-dalkylthio, d-dalkoxy, d-dhaloalkyl, d-dalkoxy-d-dalkyl, d- dhaloalkoxy, mercapto, d-dalkylcarbonythio or d-dalkylcarbonyloxy;
  • R 4 is aryl or heteroaryl; or aryl or heteroaryl which is substituted, preferably when the aryl or heteroaryl is substituted they are mono-, di- or trisubstituted wherein the subtituents are preferably selected from halogen, hydroxy, cyano, nitro, formyl, d-dalkyl, C 2 -dalkenyl, C 2 - dalkynyl, d-dcycloalkyl, d-dhaloalkyl, d-dhaloalkenyl, d-dhaloalkynyl, C 3 - dhalocycloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy, d- dalkoxy-d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkylthio, d-dal
  • the invention covers all agronomically acceptable salts, stereoisomers, diastereoisomers, enantiomers, tautomers, atropisomers and N-oxides of those compounds.
  • the compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers.
  • Suitable salts of the compounds of formula (I) include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991 .
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, / ' so-propyl, n-butyl, sec-butyl, / ' so-butyl or ie f-butyl.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl group is an unsaturated straight or branched chain having at least one carbon- carbon double bond and, depending on the number of carbon atoms it contains, is, for example ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1 -methyl- 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3- methyl-3-butenyl, 1 ,1 -dimethyl-2-propeny
  • the alkynyl group is an unsaturated straight or branched chain having at least one carbon- carbon triple bond and, depending on the number of carbon atoms it contains, is, for example ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 - pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1 -butynyl, 1 -methyl-2-butynyl, 1 - methyl-3-butynyl, 2-methyl-3-butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexy
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl,
  • trifluoromethyl monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2- difluoroethyl, 2-fluoroethyl, 1 ,1 -difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, / ' so-propoxy, n-butoxy, / ' so-butoxy, sec- butoxy and ie f-butoxy, and usually methoxy or ethoxy.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, n-butylthio, /so-butyl- thio, sec-butylthio or ie f-butylthio, and usually methylthio or ethylthio.
  • Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, / ' so-butylsulphonyl, sec-butylsulphonyl or tert- butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.
  • Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, n-butylsulphinyl, / ' so-butylsulphinyl, sec-butylsulphinyl or ie f-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, / ' so-propoxymethyl or / ' so-propoxyethyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine more preferably chlorine or fluorine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or haloalkoxy.
  • Alkylamino is, for example, methylamino, ethylamino, propylamino, tert-butylamino, hexylamino as well as, for example dimethylamino, diethylamino, dipropylamino, ditert-butylamino, dihexylamino or trimethylamino, triethylamino, tripropylamino, tri tert-butylamino, trihexylamino or 2- to 3-fold substituted amines with different alkyl groups.
  • Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the aryl and heteroaryl groups are, for example, acridinyl, anthracenyl, benzimidazolyl, benzisoxazolyl, benzo[c]thiopheny, benzofuranyl, benzothiazolyl, benzothiophenyl, benzoxazolyl, cinnolinyl, furyl, imidazolyl, indazolyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, naphthalenyl, naphthyl, oxadiazolyl, oxazolyl, phenyl, preferablythesgroupsareoptionallymono-, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, qui
  • the aryl and heteroaryl groups may also be annealed to alicyclic systems or heteroalicyclic systems.
  • Alicyclic systems or heteroalicyclic systems are carbocyclic ring structure which may be saturated or unsaturated (which means having at least one endocyclic double bond or at least one triple bond) wherein in the case of the hetreoalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom, but both, the alicyclic systems and the non-aromatic heteroalicyclic systems may not be a benzenoid or other aromatic system. Examples of such polycyclic ring systems wherein the the aryl and heteroaryl groups are annealed to alicyclic systems or
  • heteroalicyclic systems are, for example 1 ,2,3,4-tetrahydro-naphthalenyl, 1 ,3-dihydro-2H-1 ,4- benzodiazepinyl, 3,4-dihydro-2H-1 ,5-benzodioxepinyl, 2,3-dihydrobenzofuranyl,1 ,3- benzodioxolyl or 2,3-dihydro-1 ,4-benzodioxinyl.
  • the alicyclic systems or heteroalicyclic systems are preferably attached through the aromatic part of the substituent to the rest of the molecule.
  • the preferred alkyl groups and the preferred alkoxy groups are methyl, ethyl, propyl, methoxy and ethoxy groups. Methyl, ethyl and methoxy groups are very particularly preferred.
  • the preferred groups for G and R-i to R 4 in any combination thereof are as set out below.
  • the present invention relates to compounds of formula (I) wherein G represents together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, preferably the 0 to 2 heteroatoms are selected from oxygen and sulfur, and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxy, CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, CrC 6 haloalkoxy, keto, Ci-C 6 alkyloximino and CrC 6 alkylendioxy; and wherein two substituents, independently
  • a further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from oxygen and sulfur.
  • a further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 oxygen.
  • a further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 sulfur.
  • a further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered non aromatic heterocyclic monocyclic or bicyclic ring system which contain 1 to 2 heteroatoms selected from oxygen and sulfur.
  • a further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic ring system.
  • the the ring system especially the 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system formed by G together with the two carbon atoms of the pyrimidine ring to which it is attached, may be a mono-, bi- or tricyclic ring system.
  • G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contains 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur are cyclopentane, tetrahydrofuran, tetrahydrothiophene, 1 ,4- dioxane, 1 ,3-dioxolane, cyclohexane, tetrahydropyrane, tetrahydrothiopyrane, 2,2,1 - bicycloheptane, 2,2,2-bicyclooctane, cycloheptane or oxepane.
  • Preferred bi- and tricyclic ring systems formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected from the group consisting of
  • R 4 has the meaning as defined for formula I above.
  • the present invention relates to compounds of formula (I) wherein the bi- and tricyclic ring systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula C o Q 26 , and in particular Q 2 , Q 3 , Q 6 ,
  • the compounds of formula (I) wherein the tricyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q 14 .
  • a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q 15 .
  • Ri represents halogen, hydroxy, Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, d-C 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, d-C 6 alkoxy- Ci-C 6 alkoxy- -Ci-C 6 alkyl, d-C 6 alkylthio, diCi-C 6 alkylamino, C 3 -C 6 cycloalkylamino, Ci-C 6 alkoxyimino, d- C 6 alkoxyimino-Ci-C 6 alkyl;
  • R 2 represents hydrogen, halogen, cyano, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, C Cealkoxy-C Cealkyl, d- C 6 alkylthio;
  • R 3 represents hydrogen, halogen, cyano, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, d-C 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, d-C 6 haloalkoxy, d- C 6 alkylthio;
  • R 4 represents aryl or heteroaryl; or aryl or heteroaryl mono-, di- or trisubstituted by halogen, hydroxy, cyano, nitro, formyl, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d- C 6 haloalkyl, d-C 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, hydroxy-Ci-C 6 alkyl, CrC 6 alkoxy-Cr
  • G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur;
  • said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxyl, d-dalkyl, d-dalkoxy, d-C 6 alkoxy-d-C 6 alkyl, keto, d-C 6 alkyloximino and d-C 6 alkylendioxy, and wherein two substituents, independently selected from the group consisting of hydroxy, d-C 6 alkyl, d-C 6 haloalkyl and d-C 6 alkoxy, may together form a saturated three- to six-membered alicyclic or non aromatic heterocyclic ring; preferably said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of
  • F is d-dalkyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy, d-C 6 alkylthio,
  • R 2 is hydrogen, halogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy,
  • R 3 is hydrogen, halogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy, d-C 6 alkylthio, d- dalkynyl,
  • R 4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C 6 alkyl, C 2 -C 6 alkynyl,d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 alkoxy-d- C 6 alkyl, Ci-C 6 alkoxy-Ci-C 6 alkoxy , Ci-C 6 alkoxy-Ci-C 6 alkoxy-Ci-C 6 alkyl, Ci-C 6 alkoxy-Cr C 6 alkylthio, CrCealkylthio-Crdalkoxy, d-C 6 alkylthio, d-C 6 haloalkoxy, d-Cealkoxyimino, C Cealkoxyimino-C Cealkyl, C 1 -C 6 alkoxy-C2-C 6 alkynyl, C 1 -C 6 alkoxyimin
  • Ci-C 4 alkyl is Ci-C 4 alkyl, C 3 -C 6 cycloalkyl, d-C 4 alkoxy,
  • R 2 is hydrogen, d-C 4 alkyl, d-C 4 alkoxy
  • R 3 is hydrogen, d-C 4 alkyl, C 3 -C 6 cycloalkyl, d-C 4 alkoxy, Ci-C 6 alkylthio, C 2 -C 6 alkynyl
  • R 4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C 6 alkyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, d-C 6 alkoxy, CrC 6 alkoxy-Cr C 6 alkyl,Ci-C 6 alkoxy-Ci-C 6 alkoxy , Ci-C 6 alkoxy-Ci-C 6 alkoxy-CrC 6 alkyl, Ci-C 6 alkoxy-Cr C 6 alkylthio, Ci-C 6 alkylthio-Ci-C 6 alkoxy, Ci-C 6 alkylthio, Ci-C 6 haloalkoxy
  • Ri represents hydrogon, halogen, cyano, hydroxy, formyl, amino, CrC 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-dhaloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-C 6 alkylthio, d-dhaloalkylthio, d-dalkylamino, did-dalkylamino, C 3 - C 6 cycloalkylamino, d-dalkylcarbonyl, d-C 6 alkoxy
  • R 2 represents hydrogen, halogen, cyano, hydroxy, d-dalkyl, d-dalkenyl, d-dalkynyl, C 3 - dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkoxy-d-dalkyl, d- dalkylthio
  • R 3 represents hydrogen, halogen, cyano, hydroxy, d-dalkyl, d-dalkenyl, d-dalkynyl, d- dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dhaloalkoxy, mercapto, d-dalkylthio;
  • R 4 represents aryl or heteroaryl; aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, nitro, formyl, d-dalkyl, d-dalkenyl, d-dalkynyl, d-dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-dalkoxy-d-dalkoxy
  • R 4 represents aryl or heteroaryl; aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, formyl, d-dalkyl, d-dalkenyl, d-dalkynyl, C 3 - dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-C 6 alkoxy-d-C 6 alkyl, d-dalkoxy-Crdalkoxy, d-C 6 alkoxy-
  • the present invention relates to compounds of formula (I) wherein
  • Ci-C 6 alkyl is Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, d-dalkoxy, d-dalkylthio,
  • R 2 is H, d-dalkyl, d-dalkoxy, CI, F;
  • R 3 is H, d-dalkyl, d-C 6 alkoxy, d-dalkylthio, C 3 -C 6 cycloalkyl, C 2 -C 6 alkynyl,
  • R 4 is phenyl which can be mono-, di- or tnsubstituted by substituents selected from the group consisting of by halogen, cyano, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d- C 6 haloalkyl, d-C 6 alkoxy, d-C 6 alkoxy-d-C 6 alkyl, Ci-C 6 alkoxy-Ci-C 6 alkoxy, d-dalkoxy-d- C 6 alkoxy-Ci-C 6 alkyl, d-C 6 alkylthio, d-C 6 alkylamino, diCi-C 6 alkylamino, d- C 6 cycloalkylamino, Ci-C 6 alkylcarbonyl, d-C 6 alkoxyimino, Ci-C 6 alkoxyimino-Ci-
  • Ri is d-dalkyl, C 3 -dcycloalkyl; preferably, d-dalkyl;
  • R 2 is H, d-dalkyl, d-dalkoxy
  • R 3 is H, d-dalkyl, d-dalkoxy
  • R 4 is phenyl which can be mono-, di- or tnsubstituted by substituents selected from the group consisting of by halogen, cyano, d-dalkyl, d-dalkenyl, C 2 -dalkynyl, C 3 -dcycloalkyl, d- dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy, d-dalkoxy-d- dalkoxy-Crdalkyl, d-dalkylthio, Crdalkylamino, diCrdalkylamino, C 3 - dcycloalkylamino, Crdalkylcarbonyl, d-dalkoxyimino, Crdalkoxyimino-Crdalkyl, d- dalkoxy-d-dalkynyl, d-
  • aryl is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen preferably CI or F, C 1 -C 4 alkyl, C 2 - C 6 alkynyl, d-dhaloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, d-dalkoxyd-dalkyl, C
  • heteroarylaryl is pyridyl or thienyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d- dalkyl, d-dalkynyl, d-dhaloalkyl, d-dalkoxy, d-dalkylthio and d-dhaloalkoxy.
  • R 4 is aryl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-dalkyl, d- dhaloalkyl, d-dalkoxy and d-dalkylthio.
  • R 4 is phenyl, pyridyl or thienyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-dalkyl, C 2 - dalkynyl, d-dhaloalkyl, d-dalkoxy, d-dalkylthio and d-dalkoxy.
  • the heteraryl groups are pyrid-2-yl or pyrid-3-yl or thienyl.
  • R 4 is phenyl, naphthyl, pyridyl, quinolinyl, pyridazinyl, cinnolinyl, pyrimidinyl, quinazolinyl, pyrazinyl, quinoxalinyl, thienyl, furyl, isoxazolyl, isothiazolyl, thiazolyl, oxazolyl, pyrazolyl, imidazolyl, pyrrolyl, oxadiazolyl, thiadiazolyl which can be mono- or disubstituted by substituents selected from halogen, d-dalkyl, d- dhaloalkyl, d-dalkylthio or d-dalkoxy;
  • R 4 is more preferably phenyl, pyridyl or thienly which can be optionally mono- or disubstituted substituted by halogen, d-dalkyl, d-dhaloalkyl, d- dalkylthio or d-dalkoxy preferably by halogen, methyl, trihaloalkyi, methylthio or methoxy.
  • R-i is hydrogen, halogen, cyano, d-C 6 alkyl, C 3 - dcycloalkyl, d-dalkoxy or d-dalkylthio; preferably halogen, d-dalkyl, cyclopropyl, d- C 6 alkoxy or CrC 6 alkylthio; more preferably CrC 4 alkyl or Ci-C 4 alkoxy and even more preferably methyl.
  • the formula T1 has the structure of formula (I) wherein the ring system formed by the pyrimidine ring together with the ring G has the structure of Q-i;
  • the formula T2 has the structure of formula (I) wherein the ring system formed by the pyrimidine ring together with the ring G has the structure of Q 2 .
  • the formula T3 to T26 are formed analogously and the substituents Ri to R 4 have the meanings as definded above.
  • embodiment E1 is represented by the compounds of formula T1
  • Embodiments E2 to E26 are defined accordingly and the substituents Ri to R 4 have the meanings as definded above.
  • the compounds of formula (l).1 wherein R-i, R 2 , R 3 , R 4 and G are as defined under formula I, can be obtained by transformation of a compound of formula (l)l, wherein R-i, R 2 , R 3 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula (l)ll, wherein R 4 is as defined under formula I and R 5 is lnCI 2 , lnCI(R 4 ), ln(R 4 ) 2 , MgCI, MgBr, Sn(R 6 ) 3 , ZnCI, ZnBr or B(OR 6 ) 2 , wherein either R 6 is independently from each other hydrogen, CrC 6 alkyl or wherein two R 6 together can form a C 3 -C 8 cycloalkyl, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dich
  • the compounds of formula (l)l wherein R-i , R 2 , R 3 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, can be obtained by transformation of a compound of formula (l)V, wherein R-i , R 2 , R 3 and G are as defined under formula I, with a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • the compounds of formula (l)V, wherein R-i , R 2 , R 3 and G are as defined under formula I can be obtained by transformation of a compound of formula V, wherein R-i , R 2 , R 3 and G are as defined under formula I, with an acid such as hydrochloric acid (e.g. Synth. Commun. 1980, 10, 241 ), benzoic acid (e.g. J. Heterocyclic Chem. 2001 , 38, 269) or dimethylammonium chloride (Chem. Pharm. Bull.
  • hydrochloric acid e.g. Synth. Commun. 1980, 10, 241
  • benzoic acid e.g. J. Heterocyclic Chem. 2001 , 38, 269
  • dimethylammonium chloride Chem. Pharm. Bull.
  • a peroxide such as hydrogen peroxide, urea- hydrogen peroxide, or sodium perborate and, optionally, a base such as sodium hydroxide, potassium hydroxide or potassium carbonate (e.g. J. Am. Chem. Soc. 1902, 24,1031 ; Synth. Commun. 1993, 23, 2833; Synth. Commun. 1997, 27, 2065).
  • the compounds of formula V, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula VII, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula VI, wherein G is as defined under formula I, a coupling agent such as ⁇ /,/V-dicyclohexylcarbodiimide, bis(2-oxo-3- oxazolidinyl)phosphinic chloride, 2-(1 /-/-benzotriazole-1 -yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or N- methylmorpholine.
  • ⁇ -cyanoeneamines of formula VI wherein G is as defined under formula I, are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula VII, wherein R-i , R 2 , and R 3 are as defined under formula I can be obtained by transformation of a compound of formula VIII wherein R-i , R 2 , and R 3 are as defined under formula I, and an oxidizing agent such as potassium permanganate, sodium dichromate or nitric acid.
  • an oxidizing agent such as potassium permanganate, sodium dichromate or nitric acid.
  • the compounds of formula V, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula (l)X, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula VI, wherein G is as defined under formula I and a base such as triethylamine, pyridine or potassium carbonate.
  • the compounds of formula (l)X can be obtained by transformation of a of formula VII, wherein R-i , R 2 , and R 3 are as defined under formula I, with a halogenating agent such as sulfonyl chloride, phosphorus oxychloride, oxalyl chloride or cyanuric chloride, and, optionally, a base such as pyridine, triethylamine or sodium carbonate.
  • a halogenating agent such as sulfonyl chloride, phosphorus oxychloride, oxalyl chloride or cyanuric chloride
  • a base such as pyridine, triethylamine or sodium carbonate.
  • the compounds of formula (l)V, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula X, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula XI, wherein G is as defined under formula I, and a base such as triethylamine, sodium methoxide or sodium ethoxide.
  • ⁇ -ketoesters of formula XI wherein G is as defined under formula I, are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula X wherein R-i , R 2 , and R 3 are as defined under formula I, can be obtained by transformation of a compound of formula XII, wherein R-i , R 2 and R 3 are as defined under formula I, with a base, such as sodium methoxide, and an ammonium salt, such as ammonium chloride.
  • a base such as sodium methoxide
  • an ammonium salt such as ammonium chloride
  • the compounds of formula XII, wherein R-i , R 2 and R 3 are as defined under formula I can be obtained by transformation of a compound of formula XIII, wherein R-i , R 2 and R 3 are as defined under formula I, with either a cyanide, such as sodium cyanide, potassium cyanide and an activating agent such as methyl iodide, dimethyl sulfate or dimethylcarbamoyl chloride, or a cyanide such as trimethylsilylcyanide and a base, such as triethylamine, ethyldiisopropylamine or pyridine.
  • a cyanide such as sodium cyanide, potassium cyanide and an activating agent such as methyl iodide, dimethyl sulfate or dimethylcarbamoyl chloride
  • a cyanide such as trimethylsilylcyanide
  • a base such as triethylamine, ethyldiisopropyl
  • the compounds of formula XIII, wherein R-i , R 2 and R 3 are as defined under formula I can be obtained by transformation of a compound of formula XIV, wherein R-i , R 2 and R 3 are as defined under formula I, with an oxidatizing agent, such as meia-chloroperbenzoic acid, hydrogen peroxide or oxone.
  • an oxidatizing agent such as meia-chloroperbenzoic acid, hydrogen peroxide or oxone.
  • the mono-, di- and trisubstituted pyridines of formula XIV are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula (l).1 wherein R-i , R 2 , R 3 , R 4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XV, wherein R-i , R 2 , R 3 and G are as defined under formula I, with a compound of formula XVI, wherein R 4 is as defined under formula I, an activating agent such as triflic anhydride and a base such as 2-chloropyridine (e.g. J. Am. Chem. Sc. 2006, 128, 14254).
  • nitriles of formula XVI are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula XV, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula VII, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula XVII, wherein G is as defined under formula I, a coupling agent such as ⁇ /,/V-dicyclohexylcarbodiimide, bis(2-oxo-3- oxazolidinyl)phosphinic chloride, 2-(1 /-/-benzotriazole-1 -yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or N- methylmorpho
  • the enamine of formula XVII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula XV, wherein R-i , R 2 , R 3 and G are as defined under formula I can be obtained by transformation of a compound of formula (l)X, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula XVII, wherein G is as defined under formula I and a base such as triethylamine, pyridine or potassium carbonate.
  • the compounds of formula (l)V, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula XVIII, wherein R-i , R 2 , and R 3 are as defined under formula I, with a compound of formula XIX, wherein G is as defined under formula I and either R 6 is independently from each other hydrogen, CrC 6 alkyl or wherein two R 6 together can form a C 3 -C 8 cycloalkyi, and ammoniac or an ammonium salt such as ammonium acetate (e.g. J. Org. Chem. 1993, 58, 414).
  • the compounds of formula XVIII, wherein R-i , R 2 and R 3 are as defined under formula I, can be obtained by transformation of a compound of formula XX, wherein R-i , R 2 and R 3 are as defined under formula I, with a carbonylating agent such as phosgene, triphosgene or oxalyl chloride (e.g. J. Med. Chem. 1991 , 34, 1630).
  • a carbonylating agent such as phosgene, triphosgene or oxalyl chloride
  • the compounds of formula (l)V, wherein R-i , R 2 , R3 and G are as defined under formula I can be obtained by transformation of a compound of formula XXI, wherein G is as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula X, wherein R-i , R 2 and R 3 are as defined under formula I, a catalyst, such as copper(l) chloride, copper(l) bromide or copper(l) iodide, a base such as potassium phosphate, sodium carbonate or cesium carbonate, and, optionally, a ligand such as dimethylethylenediamine, proline or BINOL (e.g. Synlett 2010, 17, 261 1 ).
  • a catalyst such as copper(l) chloride, copper(l) bromide or copper(l) iodide
  • a base such as potassium phosphate, sodium carbonate or cesium carbonate
  • the compounds of formula (l).1 wherein R-i , R 2 , R 3 , R 4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XXII, wherein R-i , R 2 and R 3 are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula XXIII, wherein R 4 and G are as defined under formula I and R 5 is In, MgCI, MgBr, Sn(R 6 ) 3 , ZnCI, ZnBr or B(OR 6 ) 2 , wherein either R 6 is independently from each other hydrogen, CrC 6 alkyl or wherein two R 6 together can form a C 3 -C 8 cycloalkyl, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1- bis(diphenylphosphino)
  • the mono-, di- and tri-substituted pyridines of formula XXII and the 2-metallo-substituted pyrimidines of formula XXIII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the compounds of formula (l).1 wherein R-i , R 2 , R 3 , R 4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XXIV, wherein R-i , R 2 and R 3 are as defined under formula I and R 5 is In, MgCI, MgBr, Sn(R 6 )3, ZnCI, ZnBr or B(OR 6 )2, wherein either R 6 is independently from each other hydrogen, CrC 6 alkyl or wherein two R 6 together can form a C 3 -C 8 cycloalkyl, with a compound of formula XXV, wherein R 4 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1-bis(diphenylphosphino) ferrocene
  • the metallo-substituted pyridines of formula XXIV are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • R 6 is independently from each other hydrogen, C Cealkyl or wherein two R 6 together can form a C 3 -C 8 cycloalkyl, and a catalyst, such as
  • the compounds of formula XXVI wherein G is as defined under formula I and Hal are halogens, preferably chloro, bromo or iodo, can be obtained by transformation of a compound of formula XXVII, wherein G is as defined under formula I, with a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • the pyrimidine-2,4-diones of formula XXVII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
  • the reactions to give compounds of formula (I) are advantageously carried out in aprotic inert organic solvents.
  • Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as ⁇ , ⁇ -dimethylformamide, diethylformamide or N-methylpyrrolidinone.
  • the reaction temperatures are advantageously between -20°C and +120°C.
  • the reactions are slightly exothermic and, as a rule, they can be carried out at ambient temperature.
  • the mixture may be heated briefly to the boiling point of the reaction mixture.
  • the reaction times can also be shortened by adding a few drops of base as reaction catalyst.
  • Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo- [5.4.0]undec-7-ene.
  • inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases.
  • the bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against
  • Xanthomonas spp Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus.
  • the compounds of formula (I) are also effective against Asian soybean rust (Phakopsora pachyrhizi).
  • useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • Useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticid
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors;
  • ribosome-inactivating proteins such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
  • RIP ribosome-inactivating proteins
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
  • YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab to
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1 Ab toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
  • Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • the compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
  • the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • compounds of formula (I) and inert carriers are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as acitve ingredient and an inert carrier can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • a preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant or, if desired as well, a further, other biocidally active ingredient, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means "one compound selected from the group consisting of the compounds of formulae E1.001 .C1 .1 to E26.226.C33 described in Tables 1.1 to 26.33 of the present invention": an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
  • chlorfensulphide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg.
  • TX isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomy
  • polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX,
  • development code (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX,
  • spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX,
  • tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/-pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX,
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX,
  • an insect pheromone selected from the group of substances consisting of (£)-dec-5-en-1-yl acetate with (£)-dec-5-en-1-ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1-yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,2 tetradeca-4,10-dien-1-yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (lUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en-1-yl acetate (lUPAC name) (437) + TX, (Z)-hexa
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate
  • an insecticide selected from the group of substances consisting of 1-dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo- 2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4- dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate
  • chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX,
  • methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] +
  • development code (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb
  • nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421
  • an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • azaconazole 60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole
  • the active ingredient mixture of the compounds of formula (I) selected from table P with active ingredients described above comprises a compound selected from table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or
  • mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula (I) selected from table P and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula (I) selected from table P and the active ingredients as described above is not essential for working the present invention.
  • compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing.
  • the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Example P5 Examplification of the general procedures described above Preparation of 6,6-dimethyl-2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-5H-quinazoline a) Following the general procedure described in example P3; methyl 5,5-dimethyl-2-oxo- cyclohexanecarboxylate was converted to 6,6-dimethyl-2-(6-methyl-2-pyridyl)-3,5,7,8- tetrahydroquinazolin-4-one in 41 % yield.
  • Example P6 Preparation of : 2-(6-methyl-2-pyridyl)-4-(m-tolyl)-7,8-dihvdro-6H-pyrano[3,2- dlpyrimidine a) 5-bromo-3,4-dihydro-2H-pyran was synthesized according to the procedure
  • reaction mixture was stirred for 1 h30 at 45°C before 1 ml_ of 1 M NaOH was added to neutralize trifluoromethanesulfonate salts.
  • the reaction mixture was extracted with CH 2 CI 2 .
  • the combined organic layers were dried over Na 2 S0 4 , filtered, concentrated and purified twice by Isco combiflash Rf using first 50/50 cyclohexane/AcOEt and then DCM/MeOH as eluent to give the product as a trifluoromethanesulfonate salt.
  • the resulting powder was treated with a 1 M NaOH solution and extracted with CH 2 CI 2 .
  • Example P7 Preparation of 6,6-dimethyl-2-(6-methyl-2-pyridyl)-4-(m-tolyl)-5,7- dihvdropyranor2,3-dlpyrimidine a) To a solution of malononitrile (2.00 g, 30.3 mmol) in propan-2-ol (60.6 mL) was added 3-hydroxy-2,2-dimethyl-propanal (6.18 g, 60.6 mmol). The solution was cooled to 0°C and sodium borohydride (0.687 g, 18.2 mmol) was added. The reaction mixture was stirred for 4h from 0°C to RT. The reaction was carefully quenched with water and 1 M HCI, extracted with CH 2 CI 2 .
  • reaction mixture was filtered through a pad of silica and washed with DCM.
  • the filtrate was concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give N-(5-cyano-3,3-dimethyl-2,4-dihydropyran-6-yl)-6-methyl-pyridine-2- carboxamide (3.2 g, 12 mmol, 53% Yield) as a colorless oil.
  • Example P8 Preparation of 2-(6-methyl-2-pyridyl)-4-(o-tolyl)-6,7-dihvdro-5H-pyrano[2,3- dlpyrimidine a) 6-amino-3,4-dihydro-2H-pyran-5-carbonitrile was synthesized according to the procedure described in: C emisc e Beric te, 1986 , 1 19, 1070 - 1076 b) To a solution of 6-amino-3,4-dihydro-2H-pyran-5-carbonitrile (2.30 g, 18.5 mmol) and pyridine (2.96 g, 3.01 mL, 37.4 mmol) in THF (18ml) was slowly added a solution of 6- methylpyridine-2-carbonyl chloride (3.17 g, 20.4 mmol) in THF (18ml) at 0°C.
  • Example P9 Preparation of 2-(6-methyl-2-pyridyl)-4-phenyl-5,6-dihvdrothieno[2,3- dlpyrimidine a) 5-Amino-2,3-dihydrothiophene-4-carbonitrile was synthesized according to the procedure described in: C emisc e Beric te, 1985 , 1 18, 4473 - 4485 b) To a solution of 5-amino-2,3-dihydrothiophene-4-carbonitrile (1 .00 g, 7.93 mmol) and Et 3 N (1 .60 g, 2.21 mL, 15.9 mmol) in 1 ,2-dichloroethane (15.9 mL) was added BOPCI (2.42 g, 9.51 mmol) and 6-methylpyridine-2-carboxylic acid (1 .25 g, 9.1 1 mmol).
  • Example P10 Preparation of: 2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-6H-quinazolin-5- one a) To a solution of cyclohexane-1 ,3-dione ( 0.400 g, 3.57 mmol) in ethanol (7.13 mL) was added benzaldehyde (0.416 g, 0.397 mL, 3.92 mmol) followed by sodium acetate (0.732 g, 8.92 mmol) and 6-methylpyridine-2-carboxamidine hydrochloride (0.735 g, 4.28 mmol). The reaction mixture was stirred overnight at 80°C.
  • Example P1 1 Preparation of: N-methoxy-2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-6H- quinazolin-5-imine a) To a solution of 2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihydro-6H-quinazolin-5-one (0.050 g, 0.16 mmol) in ethanol (0.63 mL) was added O-methylhydroxylamine hydrochloride (0.020 g, 0.24 mmol) followed by sodium acetate (0.026 g, 0.32 mmol). The reaction mixture was stirred for 4h at 60°C. Water was added and a precipitation occurred.
  • the line A001 signifies that R 4 is a phenyl group
  • A010 signifies that R 4 is a para-tolyl group.
  • Table 1 .1 This table discloses the 226 compounds E1.001.C1 to E1.226.C1 of formula
  • R 4 has the specific meaning given in the corresponding line, appropriately selected from the 226 lines A 001 to A 226 of Table A and R-i, R 2 and R 3 have the specific meaning as given in the embodiment C1.
  • the specific compound E1.041.C1 is the compound of the formula E1 , in which R 4 has the specific meaning given in the line A 041 of the Table A, and R-i, R 2 and R 3 have the specific meaning as given in the embodiment C1 :
  • Table 1 .2 This table discloses the 226 compounds E1 .001.C2 to E1 .226. C2 as in Table 1 .1 but Ri, R 2 and R 3 have the specific meaning as given in the embodiment C2.
  • Table 1 .3 This table discloses the 226 compounds E1 .001 .C3 to E1.226.C3 as in Table 1 .1 but Ri, R 2 and R 3 have the specific meaning as given in the embodiment C3.
  • Table 1 .4 This table discloses the 226 compounds E1 .001 .C4 to E1.226.C4 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C4.
  • Table 1 .5 This table discloses the 226 compounds E1 .001 .C5 to E1.226.C5 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C5.
  • Table 1 .6 This table discloses the 226 compounds E1 .001 .C6 to E1.226.C6 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C6.
  • Table 1 .7 This table discloses the 226 compounds E1 .001.C7 to E1.226.C7 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C7.
  • Table 1 .8 This table discloses the 226 compounds E1 .001.C8 to E1.226.C8 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C8.
  • Table 1 .9 This table discloses the 226 compounds E1 .001.C9 to E1.226.C9 as in Table 1 .1 but R-i , R 2 and R 3 have the specific meaning as given in the embodiment C9.
  • Table 1.10 This table discloses the 226 compounds E1 .001 .C10 to E1.226.C10 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C10.
  • Table 1.1 1 This table discloses the 226 compounds E1 .001 .C1 1 to E1.226.C1 1 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C1 1.
  • Table 1.12 This table discloses the 226 compounds E1 .001 .C12 to E1.226.C12 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C12.
  • Table 1.13 This table discloses the 226 compounds E1 .001 .C13 to E1.226.C13 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C13.
  • Table 1.14 This table discloses the 226 compounds E1 .001 .C14 to E1.226.C14 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C14.
  • Table 1.15 This table discloses the 226 compounds E1 .001 .C15 to E1.226.C15 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C15.
  • Table 1.16 This table discloses the 226 compounds E1 .001 .C16 to E1.226.C16 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C16.
  • Table 1.17 This table discloses the 226 compounds E1 .001 .C17 to E1.226.C17 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C17.
  • Table 1.18 This table discloses the 226 compounds E1 .001 .C18 to E1.226.C18 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C18.
  • Table 1.19 This table discloses the 226 compounds E1 .001 .C19 to E1.226.C19 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C19.
  • Table 1.20 This table discloses the 226 compounds E1 .001 .C20 to E1.226.C20 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C20.
  • Table 1.21 This table discloses the 226 compounds E1 .001 .C21 to E1.226.C21 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C22.
  • Table 1.23 This table discloses the 226 compounds E1 .001 .C23 to E1.226.C23 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C23.
  • Table 1.24 This table discloses the 226 compounds E1 .001 .C24 to E1.226.C24 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C24.
  • Table 1.25 This table discloses the 226 compounds E1 .001 .C25 to E1.226.C25 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C25.
  • Table 1.26 This table discloses the 226 compounds E1 .001 .C26 to E1.226.C26 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C26.
  • Table 1.27 This table discloses the 226 compounds E1 .001 .C27 to E1.226.C27 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C27.
  • Table 1.28 This table discloses the 226 compounds E1 .001.C28 to E1.226.C28 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C28.
  • Table 1.29 This table discloses the 226 compounds E1 .001 .C29 to E1.226.C29 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C29.
  • Table 1.30 This table discloses the 226 compounds E1 .001 .C30 to E1.226.C30 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C30.
  • Table 1.31 This table discloses the 226 compounds E1 .001 .C31 to E1.226.C31 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C31.
  • Table 1.32 This table discloses the 226 compounds E1 .001 .C32 to E1.226.C32 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C32.
  • Table 1.33 This table discloses the 226 compounds E1 .001 .C33 to E1.226.C33 as in Table
  • R-i , R 2 and R 3 have the specific meaning as given in the embodiment C33.
  • Table 2.1 This table discloses the 226 compounds E2.001 .C1 to E2.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A Tables 2.2 to 2.33: each of these 32 tables specifically discloses 226 compounds E2.001.CX to E2.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1 .33.
  • the compound E2.086.C20 has the following formula:
  • Table 3.1 This table discloses the 226 compounds E3.001.C1 to E3.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 3.2 to 3.33 each of these 32 tables specifically discloses 226 compounds E3.001.CX to E3.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 4.1 This table discloses the 226 compounds E4.001 .C1 to E4. 226. C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 4.2 to 4.33 each of these 32 tables specifically discloses 226 compounds E4.001.CX to E4.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 5.1 This table discloses the 226 compounds E5.001 .C1 to E5. 226. C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 5.2 to 5.33 each of these 32 tables specifically discloses 226 compounds E5.001 .CX to E5.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 6.1 This table discloses the 226 compounds E6.001.C1 to E6.226.C1 of the formula in which, for each of these 226 specific compounds, each of the variables R-i , R 2 , R 3 , have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 6.2 to 6.33 each of these 32 tables specifically discloses 226 compounds E6.001.CX to E6.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 7.1 This table discloses the 226 compounds E7.001.C1 to E7.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 7.2 to 7.33 each of these 32 tables specifically discloses 226 compounds E7.001.CX to E7.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 8.1 This table discloses the 226 compounds E8.001.C1 to E8.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 8.2 to 8.33 each of these 32 tables specifically discloses 226 compounds E8.001.CX to E8.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • Table 9.1 This table discloses the 226 compounds E9.001.C1 to E9.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 9.2 to 9.33 each of these 32 tables specifically discloses 226 compounds E9.001.CX to E9.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
  • This table discloses the 226 compounds E10.001 .C1 to E10.226.
  • Table 1 1 .1 This table discloses the 226 compounds E1 1.001 .C1 to E1 1.226. C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 12.1 This table discloses the 226 compounds E12.001 .C1 to E12.226.
  • Tables 12.2 to 12.33 each of these 32 tables specifically discloses 226 compounds E12.001 .CX to E12.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1.33.
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Tables 14.2 to 14.33 each of these 32 tables specifically discloses 226 compounds E14.001 .CX to E14.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
  • Table 15.1 This table discloses the 226 compounds E15.001 .C1 to E15.226. C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 16.1 This table discloses the 226 compounds E16.001 .C1 to E16.001.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 18.1 This table discloses the 226 compounds E18.001 .C1 to E18.226. C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • This table discloses the 226 compounds E20.001 .C1 to E20.226.C1 of the
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 21 .1 This table discloses the 226 compounds E21 .001.C1 to E21.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 22.1 This table discloses the 226 compounds E22.001 .C1 to E22.226.C1 of the formula
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • This table discloses the 226 compounds E23.001 .C1 to E23.226.C1 of the
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • This table discloses the 226 compounds E24.001 .C1 to E24.226.C1 of the
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • This table discloses the 226 compounds E25.001 .C1 to E25.226.C1 of the
  • each of the variables R-i , R 2 , R 3 have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 26.1 discloses the 226 compounds E26.001 .C1 to E26.226.C1 of the formula in which, for each of these 226 specific compounds, each of the variables R-i , R 2 , R 3 , have the specific meaning given in the embodiment C1 and R 4 is selected from one of the lines 001 to 226 in Table A
  • Table 27 shows selected m.p. and/or LCMS data and retention times/MW for compounds of Tables 1 .1 to 26.33.
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.
  • Instrument Parameter lonisation method: Electrospray ; Polarity: positive (negative) ions Capillary (kV) 3.00, Cone (V) 30.00 , Extractor (V) 2.00, Source Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400
  • Instrument Parameter lonisation method: Electrospray ; Polarity: positive (negative) ions Capillary (kV) 3.80, Cone (V), Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) OFF, Desolvation Gas Flow (L/Hr) 600
  • Table 27 Meltinq point data and/or retention times for compounds of Table 1 to 26:
  • Example F-1.1 to F-1.2 Emulsifiable concentrates
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • Example F-2 Emulsifiable concentrate
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • the novel compound is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is then removed by distillation under vacuum.
  • Example F7 Flowable concentrate for seed treatment
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Biological example 1 fungicidal activity against Alternaria solani I tomato / leaf disc (early blight)
  • Tomato leaf disks cv. Baby were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf disks were incubated at 23 °C / 21 °C (day/night) and 80% relative humidity (rh) under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
  • Biological example 2 fungicidal activity against Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat)
  • Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks were incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
  • Biological example 3 fungicidal activity against Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)
  • Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.
  • DMSO fetal sulfate
  • Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was measured photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Biological example 6 fungicidal activity against Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)
  • Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Biological example 7 fungicidal activity against Mvcosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
  • DMSO DMSO
  • Biological example 8 fungicidal activity against Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)
  • Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Biological example 9 fungicidal activity against Phaeosphaeria nodorum (Septoria nodorum) /wheat / leaf disc preventative (Glume blotch)
  • Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated test leaf disks were incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • Biological example 10 fungicidal activity against Phytophthora infestans I tomato / leaf disc preventative (late blight)
  • Tomato leaf disks were placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks were incubated at 16°C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • Biological example 1 1 fungicidal activity against Plasmopara viticola I grape / leaf disc preventative (late blight)
  • Grape vine leaf disks were placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks were incubated at 19°C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).
  • Biological example 12 fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
  • Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf segments were incubated at 19°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application).
  • Biological example 13 fungicidal activity against Pyrenophora teres I barley / leaf disc preventative (Net blotch)
  • Barley leaf segments cv. Hasso were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segmens were inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments were incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
  • Biological example 14 fungicidal activity against Thanatephorus cucumeris (Rhizoctonia solani) I liquid culture (foot rot, damping-off)
  • Mycelia fragments of a newly grown liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • 129, 131 , 132, 133, 134, 135, 136, 142, and 147 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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Abstract

Compounds of formula (I) wherein the other substituents R1, R2, R3, and G are as defined in claim 1, and their use as microbiocides.

Description

PYRIDINE DERIVATIVES AS MICROBIOCIDES
The present invention relates to novel microbiocidally active, in particular fungicidally active, 2-(pyridin-2-yl)-pyrimidines. It further relates to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
Fungicidally active 2-(pyridin-2-yl)-pyrimidines are described in EP270362 and EP431424. The disclosed compounds are characterized by an aryl substituent in pyrimidine position 4 and non cyclic substituents at pyrimidine positions 5 and 6.
It has been found now that novel 2-(pyridin-2-yl)-pyrimidines with an aryl or heteroaryl group at the position 4 of the pyrimidine ring and a fused 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system at the position 5 and 6, show improved properties.
The present invention accordingly relates to compounds of formula (I)
Figure imgf000002_0001
wherein
G represents together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxy, CrC6alkyl, CrC6haloalkyl, CrC6alkoxy, d- C6alkoxy-Ci-C6alkyl,Ci-C6haloalkoxy, keto, Ci-C6alkoximino and CrC6alkylendioxy; and wherein two substituents, independently selected from the group consisting of hydroxy, C C6alkyl, Ci-C6haloalkyl and CrC6alkoxy, may together form a saturated three- to six- membered alicyclic or heterocyclic ring. represents halogen, cyano, hydroxy, formyl, amino, d-C8alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, d-dhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-
C6halocycloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-dalkylthio, d-dhaloalkylthio, Ci-C6alkylsulfinyl, d-C6alkylsulfonyl, d- dalkylsulfonyl-d-dalkyl, d-dalkylsulfoximino-d-dalkyl,d-dalkylamino, diC
dalkylamino, d-dcycloalkylamino, d-dalkylcarbonyl, d-dalkoxycarbonyl, d- dalkylaminocarbonyl, did-dalkylaminocarbonyl, d-dalkoxyimino or d-C6alkoxyimino-d- C6alkyl;
R2 is hydrogen, halogen, cyano, hydroxy, Ci-C6alkyl, d-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, CrC6alkoxy- Ci-C6alkyl or d- dalkylthio;
R3 is hydrogen, hydroxy, halogen, cyano, d-dalkyl, d-dalkenyl, d-dalkynyl, d-d cycloalkyl, d-dalkylthio, d-dalkoxy, d-dhaloalkyl, d-dalkoxy-d-dalkyl, d- dhaloalkoxy, mercapto, d-dalkylcarbonythio or d-dalkylcarbonyloxy;
R4 is aryl or heteroaryl; or aryl or heteroaryl which is substituted, preferably when the aryl or heteroaryl is substituted they are mono-, di- or trisubstituted wherein the subtituents are preferably selected from halogen, hydroxy, cyano, nitro, formyl, d-dalkyl, C2-dalkenyl, C2- dalkynyl, d-dcycloalkyl, d-dhaloalkyl, d-dhaloalkenyl, d-dhaloalkynyl, C3- dhalocycloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy, d- dalkoxy-d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkylthio, d-dalkylthio-d-dalkoxy, d- dhaloalkoxy, d-dalkylthio, d-dhaloalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d- dalkylamino, did-dalkylamino, C3-dcycloalkylamino, (d-dalkyl)(d-dcycloalkyl)amino, did-dcycloalkylamino, d-dalkylcarbonyl, d-dalkoxycarbonyl, d-dalkylaminocarbonyl, did-dalkylaminocarbonyl, d-dalkoxycarbonyloxy, d-dalkylaminocarbonyloxy, diCr dalkylaminocarbonyloxy, d-dalkylcarbonyloxy, d-dalkylcarbonylamino, d- dalkylcarbonyl-Crdalkylamino, Crdalkoxyimino, Crdalkoxyimino-Crdalkyl, trid. 6alkylsilyl, Crdalkoxy-C^dalkynyl, d-dalkoxyimino-d-dalkynyl, d-dalkylthio-d- dalkynyl, hydroxy-d-dalkynyl, d-dalkylthio-Crdalkyl or hydroxy-d-dalkyl;
and agronomically acceptable salts, stereoisomers, diastereoisomers, enantiomers, tautomers, atriopisomers and N-oxides of those compounds. The invention covers all agronomically acceptable salts, stereoisomers, diastereoisomers, enantiomers, tautomers, atropisomers and N-oxides of those compounds. The compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C or C=N bonds, in which case compounds of formula (I) may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Also atropisomerism may occur as a result of a restricted rotation about a single bond.
Suitable salts of the compounds of formula (I) include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid.
N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991 .
The alkyl groups occurring in the definitions of the substituents (including the alkyl moiety of alkoxy, alkylthio, etc.) can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, /'so-propyl, n-butyl, sec-butyl, /'so-butyl or ie f-butyl.
Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
The alkenyl group is an unsaturated straight or branched chain having at least one carbon- carbon double bond and, depending on the number of carbon atoms it contains, is, for example ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1 -methyl- 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3- methyl-3-butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 - pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4- pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1 -dimethyl-2- butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl- 3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, and usually 2-propenyl, 1 -methyl-2-propenyl, 2-butenyl, 2-methyl-2-propenyl.
The alkynyl group is an unsaturated straight or branched chain having at least one carbon- carbon triple bond and, depending on the number of carbon atoms it contains, is, for example ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 - pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1 -butynyl, 1 -methyl-2-butynyl, 1 - methyl-3-butynyl, 2-methyl-3-butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1 -pentynyl, 4-methyl-1-pentynyl, 1- methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1 -methyl- 4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 3,3,-dimethyl-1-butynyl, 1-ethyl-2- butynyl, 1 ,1-dimethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 ,1-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl.
Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl,
trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2- difluoroethyl, 2-fluoroethyl, 1 ,1 -difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl. Alkoxy is, for example, methoxy, ethoxy, propoxy, /'so-propoxy, n-butoxy, /'so-butoxy, sec- butoxy and ie f-butoxy, and usually methoxy or ethoxy.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, n-butylthio, /so-butyl- thio, sec-butylthio or ie f-butylthio, and usually methylthio or ethylthio.
Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, /'so-butylsulphonyl, sec-butylsulphonyl or tert- butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl. Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, n-butylsulphinyl, /'so-butylsulphinyl, sec-butylsulphinyl or ie f-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl.
Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, /'so-propoxymethyl or /'so-propoxyethyl.
Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine more preferably chlorine or fluorine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or haloalkoxy. Alkylamino is, for example, methylamino, ethylamino, propylamino, tert-butylamino, hexylamino as well as, for example dimethylamino, diethylamino, dipropylamino, ditert-butylamino, dihexylamino or trimethylamino, triethylamino, tripropylamino, tri tert-butylamino, trihexylamino or 2- to 3-fold substituted amines with different alkyl groups.
Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The aryl and heteroaryl groups are, for example, acridinyl, anthracenyl, benzimidazolyl, benzisoxazolyl, benzo[c]thiopheny, benzofuranyl, benzothiazolyl, benzothiophenyl, benzoxazolyl, cinnolinyl, furyl, imidazolyl, indazolyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, naphthalenyl, naphthyl, oxadiazolyl, oxazolyl, phenyl, preferablythesgroupsareoptionallymono-, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, thiadiazolyl, thiazoyl, thienyl, which can be optionally substituted, preferably these groups are optionally mono-, di- or trisubstituted. Further to this, the aryl and heteroaryl groups may also be annealed to alicyclic systems or heteroalicyclic systems. Alicyclic systems or heteroalicyclic systems are carbocyclic ring structure which may be saturated or unsaturated (which means having at least one endocyclic double bond or at least one triple bond) wherein in the case of the hetreoalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom, but both, the alicyclic systems and the non-aromatic heteroalicyclic systems may not be a benzenoid or other aromatic system. Examples of such polycyclic ring systems wherein the the aryl and heteroaryl groups are annealed to alicyclic systems or
heteroalicyclic systems are, for example 1 ,2,3,4-tetrahydro-naphthalenyl, 1 ,3-dihydro-2H-1 ,4- benzodiazepinyl, 3,4-dihydro-2H-1 ,5-benzodioxepinyl, 2,3-dihydrobenzofuranyl,1 ,3- benzodioxolyl or 2,3-dihydro-1 ,4-benzodioxinyl. The alicyclic systems or heteroalicyclic systems are preferably attached through the aromatic part of the substituent to the rest of the molecule. ln the preferred compounds of the formula (I) the preferred alkyl groups and the preferred alkoxy groups are methyl, ethyl, propyl, methoxy and ethoxy groups. Methyl, ethyl and methoxy groups are very particularly preferred.
In particularly preferred embodiments of the invention, the preferred groups for G and R-i to R4 in any combination thereof, are as set out below.
Preferably the present invention relates to compounds of formula (I) wherein G represents together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, preferably the 0 to 2 heteroatoms are selected from oxygen and sulfur, and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxy, CrC6alkyl, CrC6haloalkyl, CrC6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, CrC6haloalkoxy, keto, Ci-C6alkyloximino and CrC6alkylendioxy; and wherein two substituents, independently selected from the group consisting of hydroxy, Ci-C6alkyl, C Cehaloalkyl and C Cealkoxy, may together form a saturated three- to six-membered alicyclic or non aromatic heterocyclic ring.
A further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from oxygen and sulfur.
A further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 oxygen.
A further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 sulfur.
A further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered non aromatic heterocyclic monocyclic or bicyclic ring system which contain 1 to 2 heteroatoms selected from oxygen and sulfur.
A further preferred embodiment are the compounds of formula (I) wherein G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8- membered alicyclic ring system.
In the 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system only atoms which are ring members are counted together with those that are exclusively part of the pyrimidine ring e.g in Q-i G is a 5-membered monocyclic ring system; in Q14 G is a 6-membered monocyclic ring system. In Q12 G is a 5-membered bicyclic ring system and in Q13 G is a 6-membered bicyclic ring system The substituents of the 5- to 8- membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system are not counted;
The the ring system, especially the 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system formed by G together with the two carbon atoms of the pyrimidine ring to which it is attached, may be a mono-, bi- or tricyclic ring system. Examples for which G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contains 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur are cyclopentane, tetrahydrofuran, tetrahydrothiophene, 1 ,4- dioxane, 1 ,3-dioxolane, cyclohexane, tetrahydropyrane, tetrahydrothiopyrane, 2,2,1 - bicycloheptane, 2,2,2-bicyclooctane, cycloheptane or oxepane.
Preferred bi- and tricyclic ring systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected from the group consisting of
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000010_0002
wherein R4 has the meaning as defined for formula I above.
Most preferably the present invention relates to compounds of formula (I) wherein the bi- and tricyclic ring systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula C o Q26, and in particular Q2, Q3, Q6,
Figure imgf000010_0003
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Qi .
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q2.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q3. ln a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q4.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q5.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q6.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q7.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q8.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q9.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Qi0.
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Qn .
In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Qi2.
In a preferred embodiment are the compounds of formula (I) wherein the tricyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q13.
In a preferred embodiment are the compounds of formula (I) wherein the tricyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q14. ln a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q15.
In a preferred embodiment are the compounds of orrmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q16.
In a preferred embodiment are the compounds of orrmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q17.
In a preferred embodiment are the compounds of orrmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Qi8.
In a preferred embodiment are the compounds of rmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q19.
In a preferred embodiment are the compounds of rmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q20.
In a preferred embodiment are the compounds of rmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q2i .
In a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q22.
In a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen s, for the compounds of formula (I are selected of formula Q23.
In a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen :s, for the compounds of formula (I are selected of formula Q24.
In a preferred embodiment are the compounds of brmula (I) wherein the bicyclic sys ems, formed by the the pyrimidine, G and its substituen :s, for the compounds of formula (I are selected of formula Q25. In a preferred embodiment are the compounds of formula (I) wherein the bicyclic systems, formed by the the pyrimidine, G and its substituents, for the compounds of formula (I) are selected of formula Q26.
In a preferred embodiment
represents halogen, hydroxy, formyl, amino, d-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci- Cealkoxy, CrCealkoxy-Crdalkyl, d-Cealkoxy-CrCealkoxy-d-Cealkyl, d-C6haloalkoxy, d- C6alkylthio, d-C6haloalkylthio, d-Cealkylamino, did-Cealkylamino, C3-C6cycloalkylamino, Ci-C6alkylcarbonyl, d-C6alkoxycarbonyl, d-C6alkylaminocarbonyl, did- C6alkylaminocarbonyl, d-C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl;
more preferred Ri represents halogen, hydroxy, Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, d-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, d-C6alkoxy- Ci-C6alkoxy- -Ci-C6alkyl, d-C6alkylthio, diCi-C6alkylamino, C3-C6cycloalkylamino, Ci-C6alkoxyimino, d- C6alkoxyimino-Ci-C6alkyl;
R2 represents hydrogen, halogen, cyano, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, d-C6 alkoxy, d-C6haloalkoxy, C Cealkoxy-C Cealkyl, d- C6alkylthio;
R3 represents hydrogen, halogen, cyano, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, d-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, d-C6haloalkoxy, d- C6alkylthio;
R4 represents aryl or heteroaryl; or aryl or heteroaryl mono-, di- or trisubstituted by halogen, hydroxy, cyano, nitro, formyl, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d- C6haloalkyl, d-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, hydroxy-Ci-C6alkyl, CrC6alkoxy-Cr
C6alkoxy, Ci-C6alkoxy-Ci-C6alkoxy-CrC6alkyl, Ci-C6alkoxy-Ci-C6alkylthio, Ci-C6alkylthio-Cr C6alkoxy, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-C6haloalkylthio, Ci-C4alkylsulfinyl, d- dalkylsulfonyl, CrC6alkylamino, diCrC6alkylamino, C3-C6cycloalkylamino, d- C6alkylcarbonyl, d-C6alkoxycarbonyl, CrC6alkylaminocarbonyl, diCrC6alkylaminocarbonyl, d-C6alkoxycarbonyloxy, CrC6alkylaminocarbonyloxy, diCrC6alkylaminocarbonyloxy, C2- C6alkylcarbonyloxy, CrC6alkylcarbonylamino, CrC6alkylcarbonyl-CrC6alkylamino, Cr C6alkoxyimino, CrC6alkoxyimino-CrC6alkyl, CrC6alkoxy-C2-C6alkynyl, d-C6alkoxyimino- C2-C6alkynyl, CrC6alkylthio-C2-C6alkynyl, hydroxy-C2-C6alkynyl or Crdalkylthio-CrCealkyl; More preferred R4 represents aryl or heteroaryl; or aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, formyl, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-dhaloalkyl, d-dalkoxy, d-C6alkoxy-d-C6alkyl, hydroxy-Ci-C6alkyl, d- dalkoxy-Crdalkoxy, d-dalkoxy-d-dalkoxy-d-dalkyl , d-dalkoxy-d-dalkylthio, d- dalkylthio-Crdalkoxy, d-C6alkylthio, d-dalkylamino, did-dalkylamino, C3- dcycloalkylamino, d-C6alkylcarbonyl, d-dalkoxyimino, d-dalkoxyimino-d-dalkyl, d- dalkoxy-d-dalkynyl, d-dalkoxyimino-d-dalkynyl, d-dalkylthio-d-dalkynyl, hydroxy- C2-C6alkynyl or d-C6alkylthio-d-C6alkyl;
Further preferred, the present invention relates to compounds of formula (I) wherein
G represents, together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur;
and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxyl, d-dalkyl, d-dalkoxy, d-C6alkoxy-d-C6alkyl, keto, d-C6alkyloximino and d-C6alkylendioxy, and wherein two substituents, independently selected from the group consisting of hydroxy, d-C6alkyl, d-C6haloalkyl and d-C6alkoxy, may together form a saturated three- to six-membered alicyclic or non aromatic heterocyclic ring; preferably said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-dalkyl, d-dalkoxy, d-C6alkoxy-d-C6alkyl, and wherein two substituents, independently selected from the group consisting of d-C6alkyl and d- dalkoxy, may together form a saturated three- to six-membered alicyclic or non aromatic heterocyclic ring;
In a further embodiment
F is d-dalkyl, C3-C6cycloalkyl, d-C6alkoxy, d-C6alkylthio,
R2 is hydrogen, halogen, d-C6alkyl, C3-C6cycloalkyl, d-C6alkoxy,
R3 is hydrogen, halogen, d-C6alkyl, C3-C6cycloalkyl, d-C6alkoxy, d-C6alkylthio, d- dalkynyl,
R4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C6alkyl, C2-C6alkynyl,d-C6haloalkyl, d-C6alkoxy, d-C6alkoxy-d- C6alkyl, Ci-C6alkoxy-Ci-C6alkoxy , Ci-C6alkoxy-Ci-C6alkoxy-Ci-C6alkyl, Ci-C6alkoxy-Cr C6alkylthio, CrCealkylthio-Crdalkoxy, d-C6alkylthio, d-C6haloalkoxy, d-Cealkoxyimino, C Cealkoxyimino-C Cealkyl, C1-C6alkoxy-C2-C6alkynyl, C1-C6alkoxyimino-C2-C6alkynyl, C2- C6alkynyl or CrCealkylthio-Crdalkyl; or pyridyl, thienyl, thiazolyl, furanyl, quinolinyl, dihydro- benzofuran, benzo[1 ,3]dioxole, 3,4-Dihydro-2H-benzo[b][1 ,4]dioxepine which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, Ci-C6alkyl, C2-C6alkynyl,C1-C6haloalkyl, d-C6alkoxy, d-Cealkoxy-CrCealkyl.d-Cealkoxy-CrCealkoxy, C Cealkoxy-C Cealkoxy-C Cealkyl, Crdalkoxy-CrCealkylthio, C Cealkylthio-C Cealkoxy, CrC6alkylthio, CrC6alkoxyimino, CrC6alkoxyimino-CrC6alkyl, CrC6alkoxy-C2-C6alkynyl, d- C6alkoxyimino-C2-C6alkynyl, C2-C6alkynyl or CrC6alkylthio-CrC6alkyl; preferably R4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, CrC6alkyl, C2-C6alkynyl,CrC6haloalkyl, CrC6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, d- C6alkoxy-Ci-C6alkoxy, Ci-C6alkoxy-Ci-C6alkoxy-CrC6alkyl, Ci-C6alkoxy-Ci-C6alkylthio, d- C6alkylthio-Ci-C6alkoxy, Ci-C6alkylthio, Ci-C6haloalkoxy, CrC6alkoxyimino, d- C6alkoxyimino-Ci-C6alkyl, Ci-C6alkoxy-C2-C6alkynyl, Ci-C6alkoxyimino-C2-C6alkynyl, C2- C6alkynyl or Ci-C6alkylthio-Ci-C6alkyl;
In a further embodiment
is Ci-C4 alkyl, C3-C6 cycloalkyl, d-C4 alkoxy,
R2 is hydrogen, d-C4alkyl, d-C4alkoxy
R3 is hydrogen, d-C4alkyl, C3-C6 cycloalkyl, d-C4alkoxy, Ci-C6alkylthio, C2-C6alkynyl, R4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C6alkyl, C2-C6alkynyl, d-C6haloalkyl, d-C6alkoxy, CrC6alkoxy-Cr C6alkyl,Ci-C6alkoxy-Ci-C6alkoxy , Ci-C6alkoxy-Ci-C6alkoxy-CrC6alkyl, Ci-C6alkoxy-Cr C6alkylthio, Ci-C6alkylthio-Ci-C6alkoxy, Ci-C6alkylthio, Ci-C6haloalkoxy, CrC6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, d-dalkoxy-d-Cealkynyl, Ci-C6alkoxyimino-C2-C6alkynyl, C2- C6alkynyl or Ci-C6alkylthio-Ci-C6alkyl; or pyridyl, thienyl, thiazolyl, furanyl, which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d- C6alkyl, C2-C6alkynyl, d-C6haloalkyl, d-C6alkoxy, CrCealkoxy-CrCealkyl.d-Cealkoxy-Cr C6alkoxy , Crdalkoxy-CrCealkoxy-CrCealkyl, CrC6alkoxy-CrC6alkylthio, CrC6alkylthio - CrC6alkoxy,CrC6alkylthio, CrC6alkoxyimino, CrC6alkoxyimino-CrC6alkyl, CrC6alkoxy-C2- C6alkynyl, CrC6alkoxyimino-C2-C6alkynyl, C2-C6alkynyl or CrC6alkylthio-CrC6alkyl.
In a further embodiment Ri represents hydrogon, halogen, cyano, hydroxy, formyl, amino, CrC8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-dhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-C6alkylthio, d-dhaloalkylthio, d-dalkylamino, did-dalkylamino, C3- C6cycloalkylamino, d-dalkylcarbonyl, d-C6alkoxycarbonyl, d-C6alkylaminocarbonyl, did- dalkylaminocarbonyl, d-dalkoxyimino, d-dalkoxyimino-d-dalkyl; more preferred R-i represents hydrogen, halogen, hydroxy, fornyl, d-C8alkyl, d-dalkenyl, d-dalkynyl, C3- dcycloalkyl, d-dhaloalkyl, C3-dhalocycloalkyl, d-dalkoxy, d-C6alkoxy-d-C6alkyl, d- dalkoxy-d-dalkoxy-d-dalkyl, d-dalkylthio, d-dalkylamino, did-dalkylamino, C3- dcycloalkylamino, d-dalkoxyimino, Crdalkoxyimino-Crdalkyl;
R2 represents hydrogen, halogen, cyano, hydroxy, d-dalkyl, d-dalkenyl, d-dalkynyl, C3- dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkoxy-d-dalkyl, d- dalkylthio
R3 represents hydrogen, halogen, cyano, hydroxy, d-dalkyl, d-dalkenyl, d-dalkynyl, d- dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dhaloalkoxy, mercapto, d-dalkylthio; R4 represents aryl or heteroaryl; aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, nitro, formyl, d-dalkyl, d-dalkenyl, d-dalkynyl, d-dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-dalkoxy-d-dalkoxy , d- dalkoxy-d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkylthio, d-dalkylthio-d-dalkoxy, d- dalkylthio, d-dhaloalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dalkylamino, diCr dalkylamino, d-dcycloalkylamino, d-dalkylcarbonyl, d-dalkoxycarbonyl, d- dalkylaminocarbonyl, did-dalkylaminocarbonyl, d-dalkoxycarbonyloxy, d- dalkylaminocarbonyloxy, did-dalkylaminocarbonyloxy, d-dalkylcarbonyloxy, d- dalkylcarbonylamino, d-dalkylcarbonyl-d-dalkylamino, d-dalkoxyimino, C
dalkoxyimino-Crdalkyl, d-dalkoxy-d-dalkynyl, d-dalkoxyimino-d-dalkynyl, d- dalkylthio-d-dalkynyl, hydroxy-d-dalkynyl, d-dalkylthio-Crdalkyl, hydroxy- C dalkyl; more preferred R4 represents aryl or heteroaryl; aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, formyl, d-dalkyl, d-dalkenyl, d-dalkynyl, C3- dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-C6alkoxy-d-C6alkyl, d-dalkoxy-Crdalkoxy, d-C6alkoxy-d-C6alkoxy-d-C6alkyl , d-dalkoxy-Crdalkylthio, Crdalkylthio-Crdalkoxy, CrC6alkylthio, Ci-C6alkylamino, diCi-C6alkylamino, C3-C6cycloalkylamino, C C6alkylcarbonyl, d-dalkoxyimino, d-dalkoxyimino-d-dalkyl, C1-C6alkoxy-C2-C6alkynyl, C1-C6alkoxyimino-C2-C6alkynyl, C1-C6alkylthio-C2-C6alkynyl, hydroxy-C2-C6alkynyl, C dalkylthio-d-dalkyl or hydroxy- d-dalkyl;
Preferably the present invention relates to compounds of formula (I) wherein
is Ci-C6alkyl, C3-C6cycloalkyl, d-dalkoxy, d-dalkylthio,
R2 is H, d-dalkyl, d-dalkoxy, CI, F;
R3 is H, d-dalkyl, d-C6alkoxy, d-dalkylthio, C3-C6cycloalkyl, C2-C6alkynyl,
R4 is phenyl which can be mono-, di- or tnsubstituted by substituents selected from the group consisting of by halogen, cyano, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d- C6haloalkyl, d-C6alkoxy, d-C6alkoxy-d-C6alkyl, Ci-C6alkoxy-Ci-C6alkoxy, d-dalkoxy-d- C6alkoxy-Ci-C6alkyl, d-C6alkylthio, d-C6alkylamino, diCi-C6alkylamino, d- C6cycloalkylamino, Ci-C6alkylcarbonyl, d-C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, d- dalkoxy-d-dalkynyl, d-dalkoxyimino-d-dalkynyl, d-dalkylthio-d-dalkynyl, hydroxy- d-dalkynyl, d-dalkylthio-d-dalkyl or hydroxy- d-dalkyl; or pyridyl, thienyl, dihydro- benzofuran, benzo[1 ,3]dioxole, 3,4-Dihydro-2H-benzo[b][1 ,4]dioxepine which can be mono-, di- or tnsubstituted by substituents selected from the group consisting of halogen, d-C6alkyl, C2-C6alkynyl,d-C6haloalkyl, d-C6alkoxy, d-dalkoxy-d-dalkoxy, d-dalkoxy-d- dalkoxy-d-dalkyl, d-dalkylthio and d-dhaloalkoxy;
More preferably the present invention relates to compounds of formula (I) wherein
Ri is d-dalkyl, C3-dcycloalkyl; preferably, d-dalkyl;
R2 is H, d-dalkyl, d-dalkoxy;
R3 is H, d-dalkyl, d-dalkoxy;
R4 is phenyl which can be mono-, di- or tnsubstituted by substituents selected from the group consisting of by halogen, cyano, d-dalkyl, d-dalkenyl, C2-dalkynyl, C3-dcycloalkyl, d- dhaloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy, d-dalkoxy-d- dalkoxy-Crdalkyl, d-dalkylthio, Crdalkylamino, diCrdalkylamino, C3- dcycloalkylamino, Crdalkylcarbonyl, d-dalkoxyimino, Crdalkoxyimino-Crdalkyl, d- dalkoxy-d-dalkynyl, d-dalkoxyimino-d-dalkynyl, d-dalkylthio-d-C6alkynyl, hydroxy- d-dalkynyl, d-C6alkylthio-d-C6alkyl or hydroxy- Crdalkyl; or pyridyl, thienyl, dihydro- benzofuran, benzo[1 ,3]dioxole, 3,4-Dihydro-2H-benzo[b][1 ,4]dioxepine which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, CrC6alkyl, C2-C6alkynyl, d-dhaloalkyl, d-dalkoxy, d-dalkylthio and d-dhaloalkoxy;
In a further preferred embodiment aryl is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen preferably CI or F, C1-C4alkyl, C2- C6alkynyl, d-dhaloalkyl, C1-C4alkoxy, C1-C4alkylthio, d-dalkoxyd-dalkyl, C
C6alkoxyC3-C6alkoxy, d-dalkoxyd-dalkoxyd-dalkyl, and d-dhaloalkoxy.
In a further preferred embodiment preferably heteroarylaryl is pyridyl or thienyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d- dalkyl, d-dalkynyl, d-dhaloalkyl, d-dalkoxy, d-dalkylthio and d-dhaloalkoxy.
In a further preferred embodiment of the invention, R4 is aryl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-dalkyl, d- dhaloalkyl, d-dalkoxy and d-dalkylthio.
In a further preferred embodiment R4 is phenyl, pyridyl or thienyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-dalkyl, C2- dalkynyl, d-dhaloalkyl, d-dalkoxy, d-dalkylthio and d-dalkoxy.
Preferably the heteraryl groups are pyrid-2-yl or pyrid-3-yl or thienyl.
In a further preferred embodiment R4 is phenyl, naphthyl, pyridyl, quinolinyl, pyridazinyl, cinnolinyl, pyrimidinyl, quinazolinyl, pyrazinyl, quinoxalinyl, thienyl, furyl, isoxazolyl, isothiazolyl, thiazolyl, oxazolyl, pyrazolyl, imidazolyl, pyrrolyl, oxadiazolyl, thiadiazolyl which can be mono- or disubstituted by substituents selected from halogen, d-dalkyl, d- dhaloalkyl, d-dalkylthio or d-dalkoxy;
In a further preferred embodiment R4 is more preferably phenyl, pyridyl or thienly which can be optionally mono- or disubstituted substituted by halogen, d-dalkyl, d-dhaloalkyl, d- dalkylthio or d-dalkoxy preferably by halogen, methyl, trihaloalkyi, methylthio or methoxy.
In a further preferred embodiment R-i is hydrogen, halogen, cyano, d-C6alkyl, C3- dcycloalkyl, d-dalkoxy or d-dalkylthio; preferably halogen, d-dalkyl, cyclopropyl, d- C6alkoxy or CrC6alkylthio; more preferably CrC4alkyl or Ci-C4alkoxy and even more preferably methyl.
Further preferred embodiments of the present invention are the embodiments E1 to E26, which are defined as compounds of formula (I) which are represented by one formula selected from the group consisting of the formulae T1 to T26 as described below, wherein in formulae T1 to T26 the substituents R-i, R2, R3 and R4 have the meanings as described above. The formula T1 has the structure of formula (I) wherein the ring system formed by the pyrimidine ring together with the ring G has the structure of Q-i; The formula T2 has the structure of formula (I) wherein the ring system formed by the pyrimidine ring together with the ring G has the structure of Q2. The formula T3 to T26 are formed analogously and the substituents Ri to R4 have the meanings as definded above.
For example, embodiment E1 is represented by the compounds of formula T1
Figure imgf000019_0001
and the substituents Ri to R4 have the meanings as definded above.
Embodiments E2 to E26 are defined accordingly and the substituents Ri to R4 have the meanings as definded above.
Compounds of formula (I) may be prepared as shown in the following schemes.
The compounds of formula (l).1 , wherein R-i, R2, R3, R4 and G are as defined under formula I, can be obtained by transformation of a compound of formula (l)l, wherein R-i, R2, R3 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula (l)ll, wherein R4 is as defined under formula I and R5 is lnCI2, lnCI(R4), ln(R4)2, MgCI, MgBr, Sn(R6)3, ZnCI, ZnBr or B(OR6)2, wherein either R6 is independently from each other hydrogen, CrC6 alkyl or wherein two R6 together can form a C3-C8 cycloalkyl, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1 - bis(diphenylphosphino)ferrocene]dichloropalladium(ll), palladium acetate or
bis(diphenylphosphine)palladium(ll) chloride.
Figure imgf000020_0001
The compounds of formula (l)l, wherein R-i , R2, R3 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, can be obtained by transformation of a compound of formula (l)V, wherein R-i , R2, R3 and G are as defined under formula I, with a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
Figure imgf000020_0002
The compounds of formula (l)V, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula V, wherein R-i , R2, R3 and G are as defined under formula I, with an acid such as hydrochloric acid (e.g. Synth. Commun. 1980, 10, 241 ), benzoic acid (e.g. J. Heterocyclic Chem. 2001 , 38, 269) or dimethylammonium chloride (Chem. Pharm. Bull. 1983, 31, 401 ), or a peroxide such as hydrogen peroxide, urea- hydrogen peroxide, or sodium perborate and, optionally, a base such as sodium hydroxide, potassium hydroxide or potassium carbonate (e.g. J. Am. Chem. Soc. 1902, 24,1031 ; Synth. Commun. 1993, 23, 2833; Synth. Commun. 1997, 27, 2065).
Figure imgf000021_0001
The compounds of formula V, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula VII, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula VI, wherein G is as defined under formula I, a coupling agent such as Λ/,/V-dicyclohexylcarbodiimide, bis(2-oxo-3- oxazolidinyl)phosphinic chloride, 2-(1 /-/-benzotriazole-1 -yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or N- methylmorpholine.
Figure imgf000021_0002
The β-cyanoeneamines of formula VI, wherein G is as defined under formula I, are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
The compounds of formula VII, wherein R-i , R2, and R3 are as defined under formula I, can be obtained by transformation of a compound of formula VIII wherein R-i , R2, and R3 are as defined under formula I, and an oxidizing agent such as potassium permanganate, sodium dichromate or nitric acid.
Figure imgf000022_0001
(VIII) (VII) 0 H
The mono-, di- and trisubstituted 2-methylpyridines of formula VIII, wherein R-i , R2, and R3 are as defined under formula I, are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
Alternatively, the compounds of formula V, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula (l)X, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula VI, wherein G is as defined under formula I and a base such as triethylamine, pyridine or potassium carbonate.
Figure imgf000022_0002
The compounds of formula (l)X, wherein R-i , R2, and R3 are as defined under formula I, can be obtained by transformation of a of formula VII, wherein R-i , R2, and R3 are as defined under formula I, with a halogenating agent such as sulfonyl chloride, phosphorus oxychloride, oxalyl chloride or cyanuric chloride, and, optionally, a base such as pyridine, triethylamine or sodium carbonate.
Figure imgf000023_0001
Alternatively, the compounds of formula (l)V, wherein R-i , R2, R3 and G are as defined under formula I, can be obtained by transformation of a compound of formula X, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula XI, wherein G is as defined under formula I, and a base such as triethylamine, sodium methoxide or sodium ethoxide.
Figure imgf000023_0002
The β-ketoesters of formula XI, wherein G is as defined under formula I, are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
The compounds of formula X, wherein R-i , R2, and R3 are as defined under formula I, can be obtained by transformation of a compound of formula XII, wherein R-i , R2 and R3 are as defined under formula I, with a base, such as sodium methoxide, and an ammonium salt, such as ammonium chloride.
Figure imgf000024_0001
The compounds of formula XII, wherein R-i , R2 and R3 are as defined under formula I, can be obtained by transformation of a compound of formula XIII, wherein R-i , R2 and R3 are as defined under formula I, with either a cyanide, such as sodium cyanide, potassium cyanide and an activating agent such as methyl iodide, dimethyl sulfate or dimethylcarbamoyl chloride, or a cyanide such as trimethylsilylcyanide and a base, such as triethylamine, ethyldiisopropylamine or pyridine.
Figure imgf000024_0002
The compounds of formula XIII, wherein R-i , R2 and R3 are as defined under formula I, can be obtained by transformation of a compound of formula XIV, wherein R-i , R2 and R3 are as defined under formula I, with an oxidatizing agent, such as meia-chloroperbenzoic acid, hydrogen peroxide or oxone.
Figure imgf000024_0003
The mono-, di- and trisubstituted pyridines of formula XIV are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar. Alternatively, the compounds of formula (l).1 , wherein R-i , R2, R3, R4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XV, wherein R-i , R2, R3 and G are as defined under formula I, with a compound of formula XVI, wherein R4 is as defined under formula I, an activating agent such as triflic anhydride and a base such as 2-chloropyridine (e.g. J. Am. Chem. Sc. 2006, 128, 14254).
Figure imgf000025_0001
The nitriles of formula XVI are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
The compounds of formula XV, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula VII, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula XVII, wherein G is as defined under formula I, a coupling agent such as Λ/,/V-dicyclohexylcarbodiimide, bis(2-oxo-3- oxazolidinyl)phosphinic chloride, 2-(1 /-/-benzotriazole-1 -yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or N- methylmorpholine.
Figure imgf000025_0002
The enamine of formula XVII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar. Alternatively, the compounds of formula XV, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula (l)X, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula XVII, wherein G is as defined under formula I and a base such as triethylamine, pyridine or potassium carbonate.
Figure imgf000026_0001
Alternatively, the compounds of formula (l)V, wherein R-i , R2, R3 and G are as defined under formula I can be obtained by transformation of a compound of formula XVIII, wherein R-i , R2, and R3 are as defined under formula I, with a compound of formula XIX, wherein G is as defined under formula I and either R6 is independently from each other hydrogen, CrC6 alkyl or wherein two R6 together can form a C3-C8 cycloalkyi, and ammoniac or an ammonium salt such as ammonium acetate (e.g. J. Org. Chem. 1993, 58, 414).
Figure imgf000026_0002
The compounds of formula XVIII, wherein R-i , R2 and R3 are as defined under formula I, can be obtained by transformation of a compound of formula XX, wherein R-i , R2 and R3 are as defined under formula I, with a carbonylating agent such as phosgene, triphosgene or oxalyl chloride (e.g. J. Med. Chem. 1991 , 34, 1630).
Figure imgf000027_0001
Alternatively, the compounds of formula (l)V, wherein R-i , R2, R3 and G are as defined under formula I, can be obtained by transformation of a compound of formula XXI, wherein G is as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula X, wherein R-i , R2 and R3 are as defined under formula I, a catalyst, such as copper(l) chloride, copper(l) bromide or copper(l) iodide, a base such as potassium phosphate, sodium carbonate or cesium carbonate, and, optionally, a ligand such as dimethylethylenediamine, proline or BINOL (e.g. Synlett 2010, 17, 261 1 ).
Figure imgf000027_0002
Alternatively, the compounds of formula (l).1 , wherein R-i , R2, R3, R4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XXII, wherein R-i , R2 and R3 are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, with a compound of formula XXIII, wherein R4 and G are as defined under formula I and R5 is In, MgCI, MgBr, Sn(R6)3, ZnCI, ZnBr or B(OR6)2, wherein either R6 is independently from each other hydrogen, CrC6 alkyl or wherein two R6 together can form a C3-C8cycloalkyl, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1- bis(diphenylphosphino) ferrocene]dichloropalladium(ll), palladium acetate or
bis(diphenylphosphine)palladium(ll) chloride.
Figure imgf000028_0001
The mono-, di- and tri-substituted pyridines of formula XXII and the 2-metallo-substituted pyrimidines of formula XXIII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar.
Alternatively, the compounds of formula (l).1 , wherein R-i , R2, R3, R4 and G are as defined under formula I, can be obtained by transformation of a compound of formula XXIV, wherein R-i , R2 and R3 are as defined under formula I and R5 is In, MgCI, MgBr, Sn(R6)3, ZnCI, ZnBr or B(OR6)2, wherein either R6 is independently from each other hydrogen, CrC6 alkyl or wherein two R6 together can form a C3-C8cycloalkyl, with a compound of formula XXV, wherein R4 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, and a catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1-bis(diphenylphosphino) ferrocene]dichloropalladium(ll), palladium acetate or bis(diphenylphosphine)palladium(ll) chloride.
Figure imgf000028_0002
The metallo-substituted pyridines of formula XXIV are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar. The compounds of formula XXV, wherein R4 and G are as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo,can be obtained by transformation of a compound of formula XXVI, wherein G is as defined under formula I and Hal are halogens, preferably chloro, bromo or iodo, with a compound of formula (1)11, wherein R4 is as defined under formula I and R5 is lnCI2, lnCI(R4), ln(R4)2, MgCI, MgBr, Sn(R6)3, ZnCI, ZnBr or
B(OR6)2, wherein either R6 is independently from each other hydrogen, C Cealkyl or wherein two R6 together can form a C3-C8cycloalkyl, and a catalyst, such as
tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1 -bis(diphenylphosphino) ferrocene]dichloropalladium(ll), palladium acetate or bis(diphenylphosphine)palladium(ll) chloride.
Figure imgf000029_0001
XXVI XXVII
The compounds of formula XXVI, wherein G is as defined under formula I and Hal are halogens, preferably chloro, bromo or iodo, can be obtained by transformation of a compound of formula XXVII, wherein G is as defined under formula I, with a halogenating agent such as phosphorus oxyhalides or thionyl halides e.g. phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
Figure imgf000029_0002
(XXVII) λλν ι
The pyrimidine-2,4-diones of formula XXVII are known compounds or may be obtained readily from known compounds using processes that are routine in the art and with which the skilled man will be familiar. The reactions to give compounds of formula (I) are advantageously carried out in aprotic inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as Ν,Ν-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are advantageously between -20°C and +120°C. In general, the reactions are slightly exothermic and, as a rule, they can be carried out at ambient temperature. To shorten the reaction time, or else to start the reaction, the mixture may be heated briefly to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as reaction catalyst. Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo- [5.4.0]undec-7-ene. However, inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases. The bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
The compounds of formula (I) and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisams, such as fungi, bacteria or viruses.
The invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof. The compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants. The compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
Furthermore, the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against
Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus). The compounds of formula (I) are also effective against Asian soybean rust (Phakopsora pachyrhizi). Within the scope of the invention, useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®. The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors;
ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by δ-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1 Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); Nature- Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1 Ab toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150
Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
The compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof. To this end compounds of formula (I) and inert carriers are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants (auxiliaries) can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
The compounds of formula (I) or compositions, comprising a compound of formula (I) as acitve ingredient and an inert carrier, can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. A preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant or, if desired as well, a further, other biocidally active ingredient, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active
compounds (surfactants).
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
The following mixtures of the compounds of formula (I) with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds of formulae E1.001 .C1 .1 to E26.226.C33 described in Tables 1.1 to 26.33 of the present invention"): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
(lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-/V-methyl-/V-1-naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881 ) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (lUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71 ) + TX, benzyl benzoate (lUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bromopropylate (94) + TX, buprofezin (99) + TX,
butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX,
chlorfensulphide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201 ) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071 ) + TX, dimefox (1081 ) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1 102) + TX, diphenyl sulfone (lUPAC name) (1 103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1 134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fen- pyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1 161 ) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1 174) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (lUPAC name) (542) + TX, isocarbophos
(alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils
(alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX,
polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492
(development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX,
spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX,
tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/-pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (lUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1 ) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX,
Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis
(alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide
(scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51 ) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151 ) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191 ) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431 ) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491 ) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX,
diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,
an insect pheromone selected from the group of substances consisting of (£)-dec-5-en-1-yl acetate with (£)-dec-5-en-1-ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1-yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,2 tetradeca-4,10-dien-1-yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (lUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en-1-yl acetate (lUPAC name) (437) + TX, (Z)-hexadec-13-en-1 1 -yn-1-yl acetate (lUPAC name) (438) + TX, (Z)-icos-13-en-10-one (lUPAC name) (448) + TX, (Z)-tetradec- 7-en-1 -al (lUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (lUPAC name) (783) + TX, (Z)- tetradec-9-en-1-yl acetate (lUPAC name) (784) + TX, (7£,9Z)-dodeca-7,9-dien-1 -yl acetate (lUPAC name) (283) + TX, (9Z,1 1 £)-tetradeca-9,1 1-dien-1-yl acetate (lUPAC name) (780) + TX, (9Z, 12£)-tetradeca-9,12-dien-1-yl acetate (lUPAC name) (781 ) + TX, 14- methyloctadec-1-ene (lUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5- one (lUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1 -yl acetate (lUPAC name) (286) + TX, dodec-9-en-1 -yl acetate (lUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (lUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (lUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421 ) + TX, grandlure I (alternative name) (421 ) + TX, grandlure II (alternative name) (421 ) + TX, grandlure III (alternative name) (421 ) + TX, grandlure IV (alternative name) (421 ) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481 ) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1-yl acetate (lUPAC name) (588) + TX, octadeca-3,13-dien-1 -yl acetate (lUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-1 1 -en-1-yl acetate (lUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B-i (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate
[CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1-dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo- 2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4- dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (lUPAC name) (1066) + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate (lUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate (lUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (lUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (lUPAC name) (984) + TX, 2-imidazolidone (lUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (lUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (lUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (lUPAC name) (917) + TX, 3-methyl-1- phenylpyrazol-5-yl dimethylcarbamate (lUPAC name) (1283) + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate (lUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate (lUPAC name) (1085) + TX, abamectin (1 ) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (lUPAC name) (861 ) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41 ) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium
hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (lUPAC/Chemical
Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (lUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX,
bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (lUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (1 19) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX,
chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (101 1 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031 ) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051 ) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl
(alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (lUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081 ) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex- diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1 100) + TX, dioxacarb (1 101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX, dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1 1 15) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1 1 18) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1 120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, endrin (1 122) + TX, EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1 124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (I UPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1 136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1 143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1 147) + TX, fenchlorphos (1 148) + TX, fenethacarb (1 149) + TX, fenfluthrin (1 150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1 153) + TX, fenoxycarb (340) + TX, fenpirithrin (1 155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451 -65-7) + TX, flucofuron (1 168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171 ) + TX, flumethrin (372) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, fonofos (1 191 ) + TX, formetanate
(405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, fosmethilan (1 194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma- cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (121 1 ) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (lUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O- (methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251 ) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (lUPAC name) (1014) + TX, magnesium phosphide (lUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX,
methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene
(lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1 ) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl
ethylphosphonothioate (lUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (lUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (lUPAC name) (1075) + TX, Ο,Ο, Ο',Ο'-tetrapropyl dithiopyrophosphate (lUPAC name) (1424) + TX, oleic acid (lUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (lUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651 ) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (71 1 ) + TX, quinalphos- methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381 ) + TX, R-1492
(development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron- sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791 ) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431 ) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441 ) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121 -52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon
[337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313- 25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin
[915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX,
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb
(1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, pyriprole [394730-71 -3] + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1 ,1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5- thiadiazinan-3-ylacetic acid (lUPAC name) (1286) + TX, 6-isopentenylaminopurine
(alternative name) (210) + TX, abamectin (1 ) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (1 18) + TX, carbon disulfide (945) + TX, carbosulfan (1 19) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051 ) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (lUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231 ) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin
(1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone
[318290-98-1] + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol
(alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301 ) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1 183) + TX, flupropadine hydrochloride (1 183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (lUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (lUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (lUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341 ) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoro- acetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421
(development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
and biologically active compounds selected from the group consisting of azaconazole (60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole
[83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674- 21 -0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [1251 16-23-6] + TX, myclobutanil [88671 -89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88- 6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41 -4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [1 12281-77-3] + TX, triadimefon [43121 - 43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771 -68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71 -9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221 -53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91 -4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph
[81412-43-3] + TX, cyprodinil [121552-61 -2] + TX, mepanipyrim [1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-1 1 -4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21 -7] + TX, debacarb [62732-91 -6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332- 86-5] + TX, dichlozoline [24201 -58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471 -44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691 -80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41 -0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90- 6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961 -52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21 -7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [1 17428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01 -7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071 -83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425- 06-1 ] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205- 21 -4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731-27-1] + TX, bordeaux mixture [801 1 - 63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1 ] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131 -72-6] + TX, nitrothal-isopropyl [10552- 74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX,
isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18- 6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101 -05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01 -2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897- 45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam
[162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [2391 10-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfo- carb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [1 1 1 13-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41 -1 ] + TX, proquinazid [189278-12-4] + TX, pyroquilon
[57369-32-1 ] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51 -6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281 ) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685- 58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-l ,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid [2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-amide (disclosed in WO
2008/148570) + TX, 1 -[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-1 ,2-oxazol-3-yl]-1 ,3- thiazol-2-yl]piperidin-1 -yl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1-yl]ethanone + TX, 1 -[4- [4-[5-(2,6-difluorophenyl)-4,5-dihydro-1 ,2-oxazol-3-yl]-1 ,3-thiazol-2-yl]piperidin-1-yl]-2-[5- methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone [1003318-67-9], both disclosed in WO 2010/123791 , WO 2008/013925, WO 2008/013622 and WO 201 1/051243 page 20) +TX, (S)-[3-(4-Chloro-2-fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl-methanol + TX, 3-(4-Chloro-2-fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl- methanol + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, 3-(difluoromethyl)-N-methoxy-1- methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]-1 H-pyrazole-4-carboxamide + TX, 4-[(5S)- 5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3- yl)benzamide (WO201 1/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-(thietan-3-yl)benzamide (WO201 1/104089) + TX, 4-[(5S)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(cis-1-oxo-thietan-3- yl)benzamide (WO201 1/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-(cis-1-oxo-thietan-3-yl)benzamide (WO201 1/104089) + TX, 4-[(5S)- 5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(trans-1-oxo-thietan-3- yl)benzamide (WO201 1/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-(trans-1-oxo-thietan-3-yl)benzamide (WO201 1/104089) + TX, 4- [(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(1 ,1-dioxothietan-3-yl)-2- methyl-benzamide (WO201 1/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-N-(1 , 1 -dioxothietan-3-yl)-2-methyl-benzamide
(WO201 1/104089) + TX, 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]- 2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (WO201 1/104089) + TX, 4- [(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]benzamide (WO201 1/104089) + TX, Penflufen [494793-67-8] and TX, 5-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-(1 ,2,4-triazol-1 - yl)benzonitrile (WO2007/075459) + TX, 5-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-(1 ,2,4-triazol-1-yl)benzonitrile (WO2007/075459) + TX. The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known.
Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop
Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number.
The active ingredient mixture of the compounds of formula (I) selected from table P with active ingredients described above comprises a compound selected from table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios. The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound of formula (I) selected from table P and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) selected from table P and the active ingredients as described above is not essential for working the present invention. The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
The following non-limiting examples illustrate the above-described invention in greater detail without limiting it.
Example P1 :
Preparation of : 2-(6-methyl-2-pyridyl)-4-(m-tolyl)-6,7-dihvdro-5/-/-pyranor2,3-dlpyrimidine a) To a solution of iBuOK (5.35 g, 47.7 mmol) in iBuOH (24 mL) was added portion wise malononitrile (3.00 g, 45.4 mmol) followed by 3-bromopropanol (6.63 g, 4.14 mL, 47.7 mmol). The reaction mixture was stirred overnight at 50°C. The precipitate was filtered and washed with iBuOH. The filtrate was concentrated under reduced pressure and ice was added to the resulting oil. The white precipitate that formed was filtered and washed with water to give 6-amino-3,4-dihydro-2/-/-pyran-5-carbonitrile (0.87 g, 15% Yield). The product was used in the next step without any further purification.
1H NMR (400 MHz, CDCI3) δ 1.86 (br s, 2H), 2.25 (br s, 2H), 4.13 (br d, J=4.4 Hz, 2H), 4.25 (br s, 2H) b) To a solution of 6-methylpyridine-2-carboxylic acid (1 .20 g, 8.75 mmol) in
dichloromethane (12 mL) was added thionyl chloride (19.7 g, 12.0 ml_, 165 mmol). The reaction mixture was stirred for 2h at 65°C at which time all the solids were soluble in dichloromethane. All the volatiles were removed in vacuo to afford 6- methylpyridine-2-carbonyl chloride (1 .36 g, 8.75 mmol, 100% Yield) as a black oily solid. The product was used in the next step without any further purification. c) To a solution of 6-amino-3,4-dihydro-2/-/-pyran-5-carbonitrile (0.950 g, 7.65 mmol) and pyridine (1 .22 g, 1.24 mL, 15.5 mmol) in THF (7.5 mL) was slowly added a solution of 6-methylpyridine-2-carbonyl chloride (1 .31 g, 8.42 mmol) in THF (7.5 mL) at 0 °C. The reaction mixture was stirred overnight at rt and the resulting mixture was filtered through a pad of silica and washed with dichloromethane. The filtrate was concentrated and purified by flash chromatography to afford /V-(5-cyano-3,4-dihydro- 2H-pyran-6-yl)-6-methyl-pyridine-2-carboxamide (1 .30 g, 5.30 mmol, 70% Yield) as a colorless oil.
LCMS : 0.74 min; method U; [M+H]+ = 244
1H NMR (400 MHz, CDCI3) δ 1.91 - 2.03 (m, 2H), 2.44 (t, J=6.6 Hz, 2H), 2.60 (s, 3H), 4.23 - 4.35 (m, 2H), 7.35 (d, J=7.7 Hz, 1 H), 7.77 (t, J=7.7 Hz, 1 H), 8.06 (d, J=7.7 Hz, 1 H), 10.09 (br s, 1 H) d) To a solution of /V-(5-cyano-3,4-dihydro-2/-/-pyran-6-yl)-6-methyl-pyridine-2- carboxamide (0.100 g, 0.41 1 mmol) in dry toluene (1.1 mL) was added SnCI4 (0.139 g, 0.063 mL, 0.53 mmol). The reaction mixture was stirred at 1 10°C for 1 day and then carefully quenched with NaHC03. The aqueous phase was extracted with dichloromethane and the combined organic layers were washed with brine, dried over
Na2S04, and concentrated under reduced pressure. The residue was purified by flash chromatography to afford 2-(6-methyl-2-pyridyl)-3,5,6,7-tetrahydropyrano[2,3- d]pyrimidin-4-one (0.045 g, 0.18 mmol, 45% Yield) as a yellow solid. LCMS: 1.31 min; method A; [M+H]+ = 244
1H NMR (400 MHz, CDCI3) δ 1.98 - 2.08 (m, 2H), 2.61 (s, 3H), 2.62 - 2.68 (m, 2H), 4.34 - 4.42 (m, 2H), 7.32 (d, J=7.7 Hz, 1 H), 7.76 (t, J=7.7 Hz, 1 H), 8.21 (d, J=7.7 Hz, 1 H), 10.76 - 1 1 .1 1 (br s, 1 H)
) To a flask containing 2-(6-methyl-2-pyridyl)-3,5,6,7-tetrahydropyrano[2,3-d]pyrimidin- 4-one (0.040 g, 0.16 mmol) was added POCI3 (0.10 g, 0.060 ml_, 0.66 mmol). The mixture was heated at 100°C under microwave irradiation for 5 min. The residue was dissolved in dichloromethane and slowly quenched at 0°C with a sat. NaHC03. The aqueous phase was then extracted with dichloromethane and the combined organic layers were washed with brine, dried over Na2S04 and concentrated under reduced pressure to give 4-chloro-2-(6-methyl-2-pyridyl)-6,7-dihydro-5/-/-pyrano[2,3- d]pyrimidine as a yellow oil which was used in the following step without further purification.
LCMS: 1.21 min; method A; [M+H]+ = 262
To a solution of 4-chloro-2-(6-methyl-2-pyridyl)-6,7-dihydro-5/-/-pyrano[2,3- d]pyrimidine (0.050 g, 0.19 mmol) in DME (0.55 mL) was added the m-tolylboronic acid (0.031 g, 0.23 mmol) and the Na2C03 (2 mol/L, 0.29 mL, 0.58 mmol). The reaction mixture was then degased with nitrogen and PdCI2(dppf).CH2Cl2 (0.016 g, 0.019 mmol) was added. The mixture was stirred for 1 h at 90 °C, cooled and then quenched with water. The aqueous phase was extracted with ethyl acetate and the combined organic layers were dried over Na2S04 and concentrated under reduced pressure. The residue was purified by flash chromatograph to afford 2-(6-methyl-2- pyridyl)-4-(m-tolyl)-6,7-dihydro-5H-pyrano[2,3-d]pyrimidine (0.043 g, 0.14 mmol, 71 % Yield) as a white solid.
LCMS: 1.35 min; method A; [M+H]+ = 318
mp: 146-149 °C
1H NMR (400 MHz, CDCI3) δ 1.94 - 2.07 (m, 2H), 2.44 (s, 3H), 2.69 (s, 3H), 2.87 (t, J=6.2 Hz, 2H), 4.42 - 4.53 (m, 2H), 7.22 (d, J=7.7 Hz, 1 H), 7.28 (br s, 1 H), 7.36 (t, J=7.5 Hz, 1 H), 7.46 (d, J=7.7 Hz, 1 H), 7.54 (br s,1 H), 7.68 (t, J=7.7 Hz, 1 H), 8.27 (d, J=7.7 Hz, 1 H) Example P2:
Preparation of : 2-(6-methyl-2-pyridyl)-4-phenyl-5,6,7,8-tetrahydroquinazoline a) To a solution of ethyl 2-oxocyclohexanecarboxylate (18.9 mL, 1 18 mmol) in methanol (120 mL) was added the ammonium carbamate (9.20 g, 1 18 mmol). The resulting mixture was stirred at rt for 1 h after which time the ammonium carbamate had completely dissolved. The reaction mixture was stirred for an additional 1 h before the volatiles were removed under reduced pressure to afford ethyl 2-aminocyclohexene- 1-carboxylate as a white-yellowish solid (19.9 g, quantitative yield).
1H NMR (400 MHz, CDCI3) δ 1.28 (t, J=7.2 Hz, 3H), 1.57 - 1.71 (m, 4H), 2.21 (t, J=6.1
Hz, 2H), 2.26 (t, J=6.1 Hz, 2H), 4.15 (q, J=7.2 Hz, 2H), 6.06 (br s, 2H) b) To a solution of ethyl 2-aminocyclohexene-1 -carboxylate (0.300 g, 1 .77 mmol) in THF (5 mL) and pyridine (0.28 mL, 3.58 mmol) at 0 °C was added dropwise a solution of 6-methylpyridine-2-carbonyl chloride (0.300 g; 1 .95 mmol) in THF (1 mL). The resulting mixture was stirred at rt overnight, diluted with ethyl acetate, washed with sat. NaHC03, sat. NH4CI and brine. The organic layer was dried over Na2S04 and concentrated under reduced pressure. The residue was purified by flash
chromatography to afford ethyl 2-[(6-methylpyridine-2-carbonyl)amino]cyclohexene-1- carboxylate as a yellow solid (0.520 g, quantitative yield).
LCMS: 1.98 min; method A; [M+H]+ = 289
1H NMR (400 MHz, CDCI3) δ 1.33 (t, J=7.2 Hz, 3H), 1.60 - 1.76 (m, 4H), 2.37 - 2.43 (m, 2H), 3.12 - 3.18 (m, 2H), 4.29 (d, J=7.0 Hz, 2H), 7.31 (d, J=7.7 Hz, 1 H), 7.74 (t, J=7.7 Hz, 1 H), 8.00 (d, J=7.7 Hz, 1 H), 13.19 (br s, 1 H) c) To a solution of ethyl 2-[(6-methylpyridine-2-carbonyl)amino]cyclohexene-1 - carboxylate (1 .00 g, 3.47 mmol) in ethanol (5 mL) was added NaOH (5N, 2.78 mL, 13.9 mmol). The solution was heated to 60 °C for 20 min and then cooled to rt before it was slowly poored in a cold HCI 3N solution. The precipitate that formed was filtered and dried in vacuo to afford 2-[(6-methylpyridine-2- carbonyl)amino]cyclohexene-1 -carboxylic acid as a white powder (0.460 mg, 51 %). LCMS: 1 .62 min ZDQ; [M+H]+ = 261 1H NMR (400 MHz, CDCI3) δ 1.60 - 1 .81 (m, 4H), 2.46 (t, J=6.0 Hz, 2H), 2.62 (s, 3H), 3.21 (t, J=6.0 Hz, 2H), 7.31 (d, J=7.7 Hz, 1 H), 7.75 (t, J=7.7 Hz, 1 H), 7.99 (d, J=7.7 Hz, 1 H), 12.04 (br s, 1 H), 13.50 (s, 1 H) d) To a solution of 2-[(6-methylpyridine-2-carbonyl)amino]cyclohexene-1-carboxylic acid (0.100 g, 0.390 mmol) in DMF ( 1 mL) was successively EDC (0.070 g, 0.44 mmol), HOBt (0.060 g, 0.44 mmol) and triethylamine (0.10 mL, 0.77 mmol). The reaction mixture was stirred at rt overnight and LCMS (1.53 min; method A; [M+H]+ = 243) showed complete conversion to 2-(6-methyl-2-pyridyl)-5,6,7,8-tetrahydro-3,1 - benzoxazin-4-one. Ammonium hydroxide (7N, 0.060 mL, 0.43 mmol) was added and the reaction mixture was stirred for 1 h at rt. The solution was then diluted with dichloromethane, washed with brine, dried over Na2S04 and concentrated under reduced pressure. The residue was purified by flash chromatography to afford 2-(6- methyl-2-pyridyl)-5,6,7,8-tetrahydro-3H-quinazolin-4-one as a white solid (0.050 mg, 53% yield over two steps).
LCMS: 1.58 min; method A; [M+H]+ = 242
1H NMR (400 MHz, CDCI3) δ 1.73 - 1.91 (m, 4H), 2.60 (s, 1 H), 2.72 (t, J=6.2 Hz, 2H), 7.29 (d, J=7.7 Hz, 1 H), 7.75 (t, J=7.9 Hz, 1 H), 8.21 (d, J=7.7 Hz, 1 H), 10.99 (br s, 1 H) e) A mixture of 2-(6-methyl-2-pyridyl)-5,6,7,8-tetrahydro-3H-quinazolin-4-one (0.330 g, 1.37 mmol) and phosphorus oxychloride (1 mL) was heated at 120 °C for 20 min. The excess POCI3 was removed under reduced pressure. The residue was dissolved in dichloromethane and then sat. NaHC03 was slowly added until basic pH was observed. The solutions were stirred for 30 min and then the aqueous phase was extracted with dichloromethane. The combined organic layers were washed with brine, dried over Na2S04 and concentrated under reduced pressure to afford 4- chloro-2-(6-methyl-2-pyridyl)-5,6,7,8-tetrahydroquinazoline. The product was used in the next step without any further purification.
LCMS: 1.49 min; method A; [M+H]+ = 260/262 f) To a solution of the crude 4-chloro-2-(6-methyl-2-pyridyl)-5, 6,7,8- tetrahydroquinazoline in DME (4 mL) was added sodium carbonate (2N, 3.0 mL), phenylboronic acid (0.26 g, 2.1 mmol) and PdCI2(dppf).CH2CI2 (0.16 g, 0.19 mmol). The reaction mixture was heated at 1 10 °C overnight, cooled to rt and diluted with dichloromethane. The organic phase was washed with sat. NaHC03, dried over Na2S04 and concentrated under reduced pressure. The residue was purified by flash chromatography to afford 2-(6-methyl-2-pyridyl)-4-phenyl-5, 6,7,8- tetrahydroquinazoline as a light pink solid (0.340 mg; 82% yield over two steps), mp: 139-141 °C
1H NMR (400 MHz, CDCI3) δ 1.73 - 1 .86 (m, 2 H), 1.91 - 2.03 (m, 2 H), 2.72 (s, 3 H), 2.81 (t, J=6.24 Hz, 2 H), 3.16 (t, J=6.60 Hz, 2 H), 7.15 - 7.27 (m, 3 H), 7.42 - 7.53 (m, 2 H), 7.62 - 7.74 (m, 2 H), 8.26 (d, J=8.07 Hz, 1 H).
LCMS: 1.43 min; method A; [M+H]+ = 302
Example P3:
General procedure for the synthesis of 2-(6-methyl-2-pyridyl)-1 H-pyrimidin-6-ones To a mixture of a methyl 2-oxocycloalkanecarboxylate (1 equiv.) and 6-methylpyridine-2- carboxamidine (1 equiv.) in ethanol was added triethylamine (1 .5 equiv.). The resulting mixture was heated under reflux for 5h, cooled down to RT and then filtered. The filtrate was concentrated and purified by flash column chromatography. Example P4:
General procedure for the synthesis of 2-(6-methyl-2-pyridyl)-4-aryl( or heteroarvD-Pyrimidine
A mixture of 2-(6-methyl-2-pyridyl)-1 H-pyrimidin-6-ones (1 equiv.) and phosphorus oxychloride (4 equiv.) was heated for 20 min at 120 °C. The reaction mixture was cooled to RT, and the excess phosphorus oxychloride removed under reduced pressure. The resulting crude 4-chloro-2-(6-methyl-2-pyridyl)pyrimidine was dissolved in DME and sodium carbonate (2N, 6 equiv.), phenylboronic acid (1 .1 equiv.) and PdCI2(dppf) (0.1 equiv.) where then added successively. The resulting mixture was heated under reflux for 5h. The mixture was cooled to RT, diluted with water and then extracted with ethyl acetate. The combined organic layers were dried with sodium sulfate, concentrated under reduced pressure and purified by flash column chromatography.
Example P5: Examplification of the general procedures described above Preparation of 6,6-dimethyl-2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-5H-quinazoline a) Following the general procedure described in example P3; methyl 5,5-dimethyl-2-oxo- cyclohexanecarboxylate was converted to 6,6-dimethyl-2-(6-methyl-2-pyridyl)-3,5,7,8- tetrahydroquinazolin-4-one in 41 % yield.
1 H NMR (400 MHz, CDCI3) δ 1.03 (s, 6 H), 1 .57 (s, 2 H), 1.62 (t, J=6.6 Hz, 2 H), 2.42 (s, 2 H), 2.60 (s, 3 H), 2.75 (t, J=6.6 Hz, 2 H), 7.29 (d, J=7.7 Hz, 1 H), 7.74 (t, J=7.7 Hz, 1 H), 8.21 (d, J=7.7 Hz, 1 H), 1 1.01 (bs, 1 H).
b) Following the general procedure described in example P4; 6,6-dimethyl-2-(6-methyl- 2-pyridyl)-3,5,7,8-tetrahydroquinazolin-4-one (200 mg, 0.743 mmol) and phosphorus oxychloride (4 equiv., 0.27 mL) were heated for 20 min at 120 °C. The reaction mixture was cooled down to RT, and the excess phosphorus oxychloride removed under reduced pressure. The resulting crude 4-chloro-6,6-dimethyl-2-(6-methyl-2- pyridyl)-7,8-dihydro-5H-quinazoline was dissolved in 3 mL DME and subjected to the described Suzuki cross coupling reaction conditions to afford, after flash column chromatography (0 to 10% ethyl acetate in dichloromethane), 6,6-dimethyl-2-(6- methyl-2-pyridyl)-4-phenyl-7,8-dihydro-5H-quinazoline (1 1 1 mg, 46% yield for 2 steps) as a pink solid.
1H NMR (400 MHz, CDCI3) δ 0.97 (s, 6 H), 1 .75 (t, J=6.6 Hz, 2 H), 2.58 - 2.64 (m, 2 H), 2.74 (s, 3 H), 3.20 (t, J=7.0 Hz, 2 H), 7.24 (s, 1 H), 7.46 - 7.54 (m, 3 H), 7.65 (d,
J=6.2 Hz, 2 H), 7.72 (t, J=7.7 Hz, 1 H), 8.28 (d, J=7.7 Hz, 1 H).
Example P6: Preparation of : 2-(6-methyl-2-pyridyl)-4-(m-tolyl)-7,8-dihvdro-6H-pyrano[3,2- dlpyrimidine a) 5-bromo-3,4-dihydro-2H-pyran was synthesized according to the procedure
described in: Tetrahedron, 1992 , 48, 2681 - 2690. b) To a flask containing 6-methylpyridine-2-carboxamide (1 .00 g, 7.36 mmol) in toluene (7.35 mL) was added 5-bromo-3,4-dihydro-2H-pyran (1 .00 g, 6.13 mmol), Cul (0.140 g, 0.736 mmol), N,N'-dimethylethylenediamine (0.130 g, 0.158 mL, 1.47 mmol) and potassium carbonate (1 .70 g, 12.3 mmol). The reaction mixture was stirred overnight at 1 10°C. The crude mixture was diluted with EtOAc and filtered through a pad of celite. The filtrate was concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give N-(3,4-dihydro-2H- pyran-5-yl)-6-methyl-pyridine-2-carboxamide (1 .02 g, 4.67 mmol, 76% Yield) as a white solid.
LCMS: 1.45min; method A; [M+H]+ = 219
1H NMR (400 MHz, CDCI3) δ 2.00 (quint, J=4.0 Hz, 2H), 2.40 (t, J=4.0 Hz, 3H), 2.58 (s, 3H), 3.99 (t, J=4.0 Hz, 2H), 7.27 (d, J=7.7 Hz, 1 H), 7.31 (s, 1 H), 7.73 (t, J=7.7 Hz, 1 H), 8.00 (d, J=7.7 Hz, 1 H), 8.96 (s, 1 H)
To a flask containing a stirring mixture of N-(3,4-dihydro-2H-pyran-5-yl)-6-methyl- pyridine-2-carboxamide (0.150 g, 0.687 mmol), 2-chloropyridine (0.0936 g, 0.078 ml_, 0.825 mmol) and 3-methylbenzonitrile (0.097 g, 0.098 ml_, 0.83 mmol) in DCM (2.3 mL) was added dropwise triflic anhydride (0.213 g, 0.125 ml_, 0.756 mmol) at -78°C. After 5 min, the mixture was placed in an ice-water bath for 10 min and warmed to 0°C. Then the reaction mixture was stirred for 1 h30 at 45°C before 1 ml_ of 1 M NaOH was added to neutralize trifluoromethanesulfonate salts. The reaction mixture was extracted with CH2CI2. The combined organic layers were dried over Na2S04, filtered, concentrated and purified twice by Isco combiflash Rf using first 50/50 cyclohexane/AcOEt and then DCM/MeOH as eluent to give the product as a trifluoromethanesulfonate salt. The resulting powder was treated with a 1 M NaOH solution and extracted with CH2CI2. The combined organic layers were washed with water, dried over Na2S04, filtered and concentrated to give 2-(6-methyl-2-pyridyl)-4-(m-tolyl)-7,8-dihydro-6H-pyrano[3,2- d]pyrimidine (0.030 g, 0.095 mmol, 14% Yield) as a yellow oil.
LCMS: 1 .39min; method A; [M+H]+ = 318
1H NMR (400 MHz, CDCI3) δ 2.16 - 2.26 (m, 2H), 2.46 (s, 3H), 2.72 (s, 3H), 3.19 (t, J=6.6 Hz, 2H), 4.35 (t, J=6.6 Hz, 2H), 7.21 (d, J=7.3 Hz, 1 H), 7.28 (d, J=7.7 Hz, 1 H), 7.37 (m, 1 H), 7.71 (t, J=7.7 Hz, 3H), 7.96 - 8.03 (m, 2H), 8.30 (d, J=7.7 Hz, 1 H)
Example P7: Preparation of 6,6-dimethyl-2-(6-methyl-2-pyridyl)-4-(m-tolyl)-5,7- dihvdropyranor2,3-dlpyrimidine a) To a solution of malononitrile (2.00 g, 30.3 mmol) in propan-2-ol (60.6 mL) was added 3-hydroxy-2,2-dimethyl-propanal (6.18 g, 60.6 mmol). The solution was cooled to 0°C and sodium borohydride (0.687 g, 18.2 mmol) was added. The reaction mixture was stirred for 4h from 0°C to RT. The reaction was carefully quenched with water and 1 M HCI, extracted with CH2CI2. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 6-amino-3,3-dimethyl- 2,4-dihydropyran-5-carbonitrile (3.4 g, 22 mmol, 74% Yield) as white crystals. LCMS: 1.26min; method A; [M+H]+ = 153
1H NMR (400 MHz, CDCI3) δ ppm 0.99 (s, 6H), 2.00 (s, 2H), 3.68 (s, 2H), 4.28 (br s, 2H) b) To a solution of 6-amino-3,3-dimethyl-2,4-dihydropyran-5-carbonitrile (3.4 g, 22 mmol) and pyridine (3.9 g, 4.0 mL, 49 mmol) in THF (22ml) was slowly added a solution of 6-methylpyridine-2-carbonyl chloride (3.8 g, 25 mmol) in THF (18ml) at RT. The reaction mixture was then stirred overnight at RT. The reaction mixture was filtered through a pad of silica and washed with DCM. The filtrate was concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give N-(5-cyano-3,3-dimethyl-2,4-dihydropyran-6-yl)-6-methyl-pyridine-2- carboxamide (3.2 g, 12 mmol, 53% Yield) as a colorless oil.
LCMS: 1.61 min; method A; [M+H]+ = 272
1H NMR (400 MHz, CDCI3) δ ppm 1.07 (s, 6H), 2.19 (s, 2H), 2.61 (s, 3H), 3.87 (s, 2H), 7.35 (d, J=7.7 Hz, 1 H), 7.77 (t, J=7.7 Hz, 1 H), 8.05 (d, J=7.7 Hz, 1 H), 7.37 (m, 1 H), 10.1 1 (br s, 1 H) c) To a solution of N-(5-cyano-3,3-dimethyl-2,4-dihydropyran-6-yl)-6-methyl-pyridine- 2-carboxamide (2.60 g, 9.58 mmol) in pyridine (18.7 g, 19.2 mL, 9.58 mmol) was added dimethylamine hydrochloride (1 .56 g, 19.2 mmol). The reaction mixture was stirred overnight at 1 15°C. The pyridine was removed under reduced pressure and the residue was poured into ice water. The precipitate was filtered, washed with water and dried under reduced pressure to give 6,6-dimethyl-2-(6- methyl-2-pyridyl)-5,7-dihydro-3H-pyrano[2,3-d]pyrimidin-4-one (1 .95 g, 7.19 mmol,
75% Yield) as a beige solid.
LCMS: 1.51 min; method A; [M+H]+ = 272
1H NMR (400 MHz, CDCI3) δ ppm 1.08 (s, 6H), 2.42 (s, 2H), 2.60 (s, 3H), 3.94 (s, 2H), 7.32 (d, J=7.70 Hz, 1 H), 7.76 (t, J=7.7 Hz, 1 H), 8.21 (d, J=7.70 Hz, 1 H),
10.97 (br s, 1 H) d) To a vial containing 6,6-dimethyl-2-(6-methyl-2-pyridyl)-5,7-dihydro-3H- pyrano[2,3-d]pyrimidin-4-one (0.330 g, 1.22 mmol) was added POCI3 (0.746 g, 0.447 ml_, 4.87 mmol). The reaction mixture was heated at 100°C under microwave irradiation for 5 min. The residue was dissolved in CH2CI2 and slowly quenched with a sat. solution of NaHC03 at 0°C. The aqueous phase was then extracted with dichloromethane and the combined organic layers were washed with brine, dried over Na2S04 and concentrated under reduced pressure to give 4- chloro-6,6-dimethyl-2-(6-methyl-2-pyridyl)-5,7-dihydropyrano[2,3-d]pyrimidine (0.365 g, 1.26 mmol) as a yellow oil. The product was used in the next step without further purification.
LCMS: 1.51 min; method A; [M+H]+ = 290
e) To a solution of 4-chloro-6,6-dimethyl-2-(6-methyl-2-pyridyl)-5,7- dihydropyrano[2,3-d]pyrimidine (0.1 15 g, 0.397 mmol) in DME (1.1 mL) was added m-tolylboronic acid (0.065 g, 0.48 mmol) and Na2C03 (0.595 mL, 1.19 mmol). Then the reaction mixture was degased under nitrogen atmosphere and ultrasonic bath during 10 min. PdCI2(dppf) CH2CI2 (0.0324 g, 0.0397 mmol) was added and the reaction mixture was stirred for 1 h30 at 95°C. Water was added and the solution was extracted with AcOEt. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 6,6-dimethyl-2-(6- methyl-2-pyridyl)-4-(m-tolyl)-5,7-dihydropyrano[2,3-d]pyrimidine (0.1 10 g, 0.318 mmol, 80% Yield) as a beige powder,
mp: 155-158°C
LCMS: 1.52min; method A; [M+H]+ = 346 1H NMR (400 MHz, CDCI3) δ ppm 1.02 (s, 6H), 2.45 (s, 3H), 2.65 (s, 2H), 2.70 (s, 3H), 4.07 (s, 2H), 7.22 (d, J=7.3 Hz, 1 H), 7.28 (d, J=7.7 Hz, 1 H), 7.37 (t, J=7.5 Hz, 1 H), 7.42 - 7.46 (m, 1 H), 7.54 (s, 1 H), 7.69 (t, J=7.7 Hz, 1 H), 8.28 (d, J=7.7 Hz, 1 H)
Example P8: Preparation of 2-(6-methyl-2-pyridyl)-4-(o-tolyl)-6,7-dihvdro-5H-pyrano[2,3- dlpyrimidine a) 6-amino-3,4-dihydro-2H-pyran-5-carbonitrile was synthesized according to the procedure described in: C emisc e Beric te, 1986 , 1 19, 1070 - 1076 b) To a solution of 6-amino-3,4-dihydro-2H-pyran-5-carbonitrile (2.30 g, 18.5 mmol) and pyridine (2.96 g, 3.01 mL, 37.4 mmol) in THF (18ml) was slowly added a solution of 6- methylpyridine-2-carbonyl chloride (3.17 g, 20.4 mmol) in THF (18ml) at 0°C. The reaction mixture was then stirred overnight at RT. The reaction mixture was filtered through a pad of silica and washed with DCM. The filtrate was concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give N-(5-cyano- 3,4-dihydro-2H-pyran-6-yl)-6-methyl-pyridine-2-carboxamide (3.155 g, 9.78 mmol, 70% Yield) as a colorless oil.
LCMS: 1 .41 min; method A; [M+H]+ = 244
1H NMR (400 MHz, CDCI3) δ ppm 1 .94 - 2.02 (m, 2H), 2.44 (t, J=6.6 Hz, 2H), 2.60 (s, 3H), 4.28 - 4.33 (m, 2H), 7.35 (d, J=7.7 Hz, 1 H), 7.77 (t, J=7.7 Hz, 1 H), 8.06 (d, J=7.7 Hz, 1 H), 10.09 (br s, 1 H) c) To a solution of N-(5-cyano-3,4-dihydro-2H-pyran-6-yl)-6-methyl-pyridine-2- carboxamide (1 .34 g, 5.51 mmol) in pyridine (1 1.0 mL) was added dimethylamine hydrochloride (0.898 g, 1 1.0 mmol). The reaction mixture was stirred overnight at 120°C. The pyridine was then removed under reduced pressure and the residue was poured into ice water. The precipitate was filtered, washed with water and dried under reduced pressure to give 2-(6-methyl-2-pyridyl)-3,5,6,7-tetrahydropyrano[2,3- d]pyrimidin-4-one (0.900 g, 3.70 mmol, 67% yield) as a beige solid.
LCMS: 1.31 min; method A; [M+H]+ = 244 1H NMR (400 MHz, CDCI3) δ ppm 1 .99 - 2.09 (m, 2H), 2.60 (s, 3H), 2.64 (t, J=6.4 Hz, 2H), 4.34 - 4.41 (m, 2H), 7.31 (d, J=7.7 Hz, 1 H), 7.75 (t, J=7.7 Hz, 1 H), 8.20 (d, J=7.7 Hz, 1 H), 10.94 (br s, 1 H) d) To a vial containing 2-(6-methyl-2-pyridyl)-3,5,6,7-tetrahydropyrano[2,3-d]pyrimidin-4- one (0.350 g, 1.44 mmol) was added POCI3 (0.882 g, 0.528 mL, 5.75 mmol). The reaction mixture was heated at 100°C under microwave irradiation for 7 min. POCI3 was removed under reduced pressure to give 4-chloro-2-(6-methyl-2-pyridyl)-6,7- dihydro-5H-pyrano[2,3-d]pyrimidine (0.376 g, 1 .44 mmol, 100% yield) as a yellow oil. The product was used in the following step without further purification.
LCMS: 1.20min; method A; [M+H]+ = 262 e) To a solution of 4-chloro-2-(6-methyl-2-pyridyl)-6,7-dihydro-5H-pyrano[2,3- d]pyrimidine (0.120 g, 0.459 mmol) in DME (1 .3 mL) was added o-tolylboronic acid (0.075 g, 0.55 mmol) and Na2C03 2M (0.92 mL, 1.8 mmol). Then the reaction mixture was degased under nitrogen atmosphere and ultrasonic bath during 10 min. PdCI2(dppf) CH2CI2 (0.037 g, 0.046 mmol) was added and the mixture was stirred for 8h at 95°C. Water was added and the mixture was extracted with CH2CI2. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 2-(6-methyl-2-pyridyl)-4-(o-tolyl)-6,7-dihydro-5H-pyrano[2,3-d]pyrimidine ( 0.129 g, 0.406 mmol, 89% Yield) as a beige powder,
mp: 104-109°C
LCMS: 1 .32min; method A; [M+H]+ = 318
1H NMR (400 MHz, CDCI3) δ ppm 2.00 (quin, J=5.7 Hz, 2H), 2.21 (s, 3H), 2.49 - 2.56 (m, 2H), 2.68 (s, 3H), 4.45 (t, J=5.0 Hz, 2H), 7.20 (d, J=7.3 Hz, 1 H), 7.24 - 7.37 (m, 4H), 7.65 (t, J=7.7 Hz, 1 H), 8.18 (d, J=7.7 Hz, 1 H)
Example P9: Preparation of 2-(6-methyl-2-pyridyl)-4-phenyl-5,6-dihvdrothieno[2,3- dlpyrimidine a) 5-Amino-2,3-dihydrothiophene-4-carbonitrile was synthesized according to the procedure described in: C emisc e Beric te, 1985 , 1 18, 4473 - 4485 b) To a solution of 5-amino-2,3-dihydrothiophene-4-carbonitrile (1 .00 g, 7.93 mmol) and Et3N (1 .60 g, 2.21 mL, 15.9 mmol) in 1 ,2-dichloroethane (15.9 mL) was added BOPCI (2.42 g, 9.51 mmol) and 6-methylpyridine-2-carboxylic acid (1 .25 g, 9.1 1 mmol). The reaction mixture was stirred for 1 h30 under reflux. The 1 ,2-dichloroethane was partially evaporated and sat NaHC03 was added. The aqueous phase was extracted with CH2CI2. The combined organic layers were washed with water, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give N-(4-cyano-2,3-dihydrothiophen-5-yl)-6-methyl- pyridine-2-carboxamide (0.900 g, 3.67 mmol, 46% Yield) as a yellow solid.
LCMS: 1 .62min; method A; [M-H]" = 244
1H NMR (400 MHz, CDCI3) δ ppm 2.64 (s, 3H), 2.95 (t, J=8.6 Hz, 2H), 3.34 (t, J=8.6 Hz, 2H), 7.39 (d, J=7.7 Hz, 1 H), 7.79 (t, J=7.9 Hz, 1 H), 8.02 (d, J=7.7 Hz, 1 H), 10.89 (br s, 1 H) c) To a solution of N-(4-cyano-2,3-dihydrothiophen-5-yl)-6-methyl-pyridine-2- carboxamide (0.820 g, 3.34 mmol) in pyridine (6.69 mL) was added dimethylamine hydrochloride (0.818 g, 10.0 mmol). The reaction mixture was stirred for 3 days at 1 15°C. The pyridine was removed under reduced pressure and the residue was poured into ice water. The aqueous layer was extracted with CH2CI2. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using CH2CI2/AcOEt as eluent to give 2-(6-methyl-2-pyridyl)-5,6- dihydro-3H-thieno[2,3-d]pyrimidin-4-one (0.670 g, 2.73 mmol, 82% Yield) as an orange solid.
LCMS: 1 .45min; method A; [M+H]+ = 246
1H NMR (400 MHz, CDCI3) δ ppm 2.60 (s, 3H), 3.29 - 3.37 (m, 2H), 3.43 - 3.51 (m, 2H), 7.32 (d, J=7.7 Hz, 1 H), 7.76 (t, J=7.9 Hz, 1 H), 8.21 (d, J=7.7 Hz, 1 H), 10.96 (br s, 1 H) d) To a flask containing 2-(6-methyl-2-pyridyl)-5,6-dihydro-3H-thieno[2,3-d]pyrimidin-4- one (0.070 g, 0.29 mmol) was added POCI3 (0.18 g, 0.10 mL, 1 .1 mmol). The mixture was heated at 100°C under microwave irradiation for 5 min. POCI3 was removed under reduced pressure to give 4-chloro-2-(6-methyl-2-pyridyl)-5,6-dihydrothieno[2,3- d]pyrimidine as a brown oil. The crude product was used in the next step without further purification. e) To a solution of 4-chloro-2-(6-methyl-2-pyridyl)-5,6-dihydrothieno[2,3-d]pyrimidine (0.075 g, 0.28 mmol) in DME (0.81 mL) was added phenylboronic acid (0.042 g, 0.34 mmol) and Na2C03 (0.71 mL, 1 .4 mmol). Then the reaction mixture was degased under nitrogen atmosphere and ultrasonic bath during 10 min. PdCI2(dppf) CH2CI2 (0.023 g, 0.028 mmol) was added and the reaction mixture was stirred overnight at 95°C. Water was added and the aqueous layer was extracted with CH2CI2. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 2-(6-methyl-2-pyridyl)-4-phenyl-5,6-dihydrothieno[2,3-d]pyrimidine (0.063 g, 0.21 mmol, 73% Yield) as a light yellow powder,
mp: 129-134°C
1H NMR (400 MHz, CDCI3) δ ppm 2.73 (s, 3H), 3.38 - 3.46 (m, 2H), 3.55 - 3.64 (m,
2H), 7.25 (d, J=7.7 Hz, 1 H), 7.46 - 7.56 (m, 3H), 7.72 (t, J=7.7 Hz, 1 H), 7.87 (dd, J=7.9, 1 .65 Hz, 2H), 8.34 (d, J=7.7 Hz, 1 H)
Example P10: Preparation of: 2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-6H-quinazolin-5- one a) To a solution of cyclohexane-1 ,3-dione ( 0.400 g, 3.57 mmol) in ethanol (7.13 mL) was added benzaldehyde (0.416 g, 0.397 mL, 3.92 mmol) followed by sodium acetate (0.732 g, 8.92 mmol) and 6-methylpyridine-2-carboxamidine hydrochloride (0.735 g, 4.28 mmol). The reaction mixture was stirred overnight at 80°C. The ethanol was evaporated, water was added and the solution was extracted with CH2CI2. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 2-(6-methyl-2- pyridyl)-4-phenyl-4,6,7,8-tetrahydro-3H-quinazolin-5-one (0.680 g, 2.14 mmol, 60% Yield, 1 .7/1 mixture of tetrahydroquinazolinone isomers) as a yellow gum..
LCMS: 0.64min; method A; [M+H]+ = 318
1H NMR of the major compound (400 MHz, CDCI3) δ ppm 1 .93 - 2.15 (m, 2H), 2.32 - 2.47 (m, 2H), 2.48 - 2.77 (m, 2H), 2.53 (s, 3H), 5.79 (s, 1 H), 7.15 - 7.34 (m, 4H), 7.37 - 7.45 (m, 2H), 7.65 - 7.73 (m, 1 H), 8.23 (d, 1 H), 8.39 (br s, 1 H) ; minor compound δ ppm 1.93 - 2.15 (m, 2H), 2.32 - 2.47 (m, 2H), 2.48 - 2.77 (m, 2H), 2.60 (s, 3H), 5.97 (s, 1 H), 7.15 - 7.34 (m, 4H), 7.37 - 7.45 (m, 3H), 7.65 - 7.73 (m, 1 H), 8.09 (d, 1 H), 8.83 (br s, 1 H) b) To a solution of 2-(6-methyl-2-pyridyl)-4-phenyl-4,6,7,8-tetrahydro-3H-quinazolin-5- one (0.670 g, 2.1 1 mmol) in toluene (21 mL) was added DDQ (0.719 g, 3.17 mmol). The reaction mixture was stirred for 30min at RT. 10ml of NaOH 1 M was then added followed by water, and the aqueous phase was extracted with AcOEt. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give 2-(6-methyl-2-pyridyl)-4- phenyl-7,8-dihydro-6H-quinazolin-5-one (0.460 g, 1.46 mmol, 69% Yield) as a white solid.
mp: 154-161 °C
1H NMR (400 MHz, CDCI3) δ ppm 2.27 (quin, J=6.4 Hz, 2H), 2.75 (s, 3H), 2.76 - 2.82
(m, 2H), 3.36 (t, J=6.2 Hz, 2H), 7.31 (d, J=7.7 Hz, 1 H), 7.42 - 7.52 (m, 3H), 7.59 - 7.66 (m, 2H), 7.76 (t, J=7.9 Hz, 1 H), 8.42 (d, J=8.1 Hz, 1 H)
Example P1 1 : Preparation of: N-methoxy-2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihvdro-6H- quinazolin-5-imine a) To a solution of 2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihydro-6H-quinazolin-5-one (0.050 g, 0.16 mmol) in ethanol (0.63 mL) was added O-methylhydroxylamine hydrochloride (0.020 g, 0.24 mmol) followed by sodium acetate (0.026 g, 0.32 mmol). The reaction mixture was stirred for 4h at 60°C. Water was added and a precipitation occurred. The precipitate was filtered, washed with water and dried under reduced pressure to give N-methoxy-2-(6-methyl-2-pyridyl)-4-phenyl-7,8-dihydro-6H- quinazolin-5-imine (0.046 g, 0.13 mmol, 84% Yield) as a white solid,
mp: 107-109 °C
1H NMR (400 MHz, CDCI3) δ ppm 1.98 (quin, J=6.42 Hz, 2H), 2.73 (s, 3H), 2.82 (t,
J=7.0 Hz, 2H), 3.06 - 3.1 1 (m, 2H), 7.26 (d, J=7.7 Hz, 1 H), 7.38 - 7.43 (m, 3H), 7.64 - 7.68 (m, 2H), 7.72 (t, J=7.7 Hz, 1 H), 8.37 (d, J=7.7 Hz, 1 H) Table A below in combination with preferred embodiments C1 to C33 defines chemical designations for the substituents R-i, R2, R3 and R4 for the compounds of formula (I). Table 1 .1 to Table 26.33 define chemical designations for the substituents R-i, R2, R3, R4 and G for the compounds of formula (I).
Figure imgf000073_0001
Table A: chemical designations for substituent R4 of the compound of formula (I):
For example, the line A001 signifies that R4 is a phenyl group, or A010 signifies that R4 is a para-tolyl group.
Figure imgf000073_0002
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
The preferred embodiment C1 consists of 1 he combination of Ri = SCH3, R2 - H and R3 = H.
The preferred embodiment C2 consists of 1 he combination of R-i = CH3, R2 = H and R3 = H.
The preferred embodiment C3 consists of 1 he combination of R-i = CI, R2 = H and R3 = H.
The preferred embodiment C4 consists of 1 he combination of R-i = OCH3, R2 = H and R3 = H.
The preferred embodiment C5 consists of 1 he combination of R-i = CH(CH2)2, R2 = H and R3 = H.
The preferred embodiment C6 consists of 1 he combination of R-i = SCH3, R2 = CH3 and R3 = H.
The preferred embodiment C7 consists of 1 he combination of R-i = SCH3, R2 = OCH3 and R3 = H.
The preferred embodiment C8 consists of 1 he combination of R-i = OCH3 , R2 = = CH3 and R3 = H.
The preferred embodiment C9 consists of 1 he combination of R-i = CH3, R2 = CH3 and R3 = H.
The preferred embodiment C10 consists ol " the combination of R-i - CH3, R2 - OCH3 and R3 = H.
The preferred embodiment C1 1 consists o " the combination of Ri = CH3, R2 = F and R3 = H.
The preferred embodiment C12 consists o " the combination of Ri = CH(CH2)2 R2 = CH3 and R3 = H
The preferred embodiment C13 consists ol " the combination of Ri = CH(CH2)2 R2 = OCH3 and R3 = u n .
The preferred embodiment C14 consists o " the combination of Ri = CH(CH2)2 R2 = F and R3 = H.
The preferred embodiment C15 consists ol " the combination of Ri = OCH3, R2 = H and R3 = CH3.
The preferred embodiment C16 consists ol " the combination of Ri = OCH3, R2 = H and R3 = CI.
The preferred embodiment C17 consists o " the combination of Ri = OCH3, R2 = H and R3 = OCH3.
The preferred embodiment C18 consists ol " the combination of Ri = OCH3, R2 = H and R3 = SCH3.
The preferred embodiment C19 consists ol " the combination of R-i = OCH3, R2 = H and R3 =
CH(CH2)2.
The preferred embodiment C20 consists ol " the combination of R-i = CH3, R2 = H and R3 = CCH.
The preferred embodiment C21 consists o " the combination of R-i = CH3, R2 = H and R3 = CI.
The preferred embodiment C22 consists o " the combination of R-i = CH3, R2 = H and R3 = OCH3.
The preferred embodiment C23 consists ol " the combination of R-i = CH3, R2 = H and R3 = SCH3.
The preferred embodiment C24 consists o " the combination of R-i = CH3, R2 = H and R3 = CH(CH2)2
The preferred embodiment C25 consists ol " the combination of R-i = SCH3, R2 = H and R3 = CH3.
The preferred embodiment C26 consists ol " the combination of R-i = SCH3, R2 = H and R3 = OCH3.
The preferred embodiment C27 consists o " the combination of Ri = SCH3, R2 = H and R3 = CCH.
The preferred embodiment C28 consists ol " the combination of Ri = SCH3,R2 : = H and R3 = SCH3.
The preferred embodiment C29 consists ol " the combination of Ri = SCH3,, R2 = H and R3 = CI.
The preferred embodiment C30 consists ol " the combination of Ri = OCH3, R2 = H and R3 = CCH.
The preferred embodiment C31 consists ol " the combination of Ri = CH(CH2)2 R2 = H and R3 = CH3
The preferred embodiment C32 consists ol " the combination of Ri = CH(CH2)2 R2 = H, 3 and R3 =
OCH3. The preferred embodiment C33 consists of the combination of Ri = CH(CH2)2, R2 = H, 3 and SCH3.
Table 1 .1 : This table discloses the 226 compounds E1.001.C1 to E1.226.C1 of formula
Figure imgf000092_0001
in which, for each of these 226 specific compounds, R4 has the specific meaning given in the corresponding line, appropriately selected from the 226 lines A 001 to A 226 of Table A and R-i, R2 and R3 have the specific meaning as given in the embodiment C1. For example, the specific compound E1.041.C1 is the compound of the formula E1 , in which R4 has the specific meaning given in the line A 041 of the Table A, and R-i, R2 and R3 have the specific meaning as given in the embodiment C1 :
Figure imgf000092_0002
According to the same system, also all of the other 226 specific compounds disclosed in each of the Tables 1.2 to 1 .33 as well as all of the specific compounds disclosed in the Tables 2.1 to 26.33 are specified analogously. Thus all of the other matrixes of 226 specific compounds disclosed in the Tables 1 as well as all of those disclosed in the Tables 2 to 26 are specified according to the same system
Table 1 .2: This table discloses the 226 compounds E1 .001.C2 to E1 .226. C2 as in Table 1 .1 but Ri, R2 and R3 have the specific meaning as given in the embodiment C2.
Table 1 .3: This table discloses the 226 compounds E1 .001 .C3 to E1.226.C3 as in Table 1 .1 but Ri, R2 and R3 have the specific meaning as given in the embodiment C3. Table 1 .4: This table discloses the 226 compounds E1 .001 .C4 to E1.226.C4 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C4.
Table 1 .5: This table discloses the 226 compounds E1 .001 .C5 to E1.226.C5 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C5.
Table 1 .6: This table discloses the 226 compounds E1 .001 .C6 to E1.226.C6 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C6.
Table 1 .7: This table discloses the 226 compounds E1 .001.C7 to E1.226.C7 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C7.
Table 1 .8: This table discloses the 226 compounds E1 .001.C8 to E1.226.C8 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C8.
Table 1 .9: This table discloses the 226 compounds E1 .001.C9 to E1.226.C9 as in Table 1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C9.
Table 1.10: This table discloses the 226 compounds E1 .001 .C10 to E1.226.C10 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C10.
Table 1.1 1 : This table discloses the 226 compounds E1 .001 .C1 1 to E1.226.C1 1 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C1 1.
Table 1.12: This table discloses the 226 compounds E1 .001 .C12 to E1.226.C12 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C12.
Table 1.13: This table discloses the 226 compounds E1 .001 .C13 to E1.226.C13 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C13.
Table 1.14: This table discloses the 226 compounds E1 .001 .C14 to E1.226.C14 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C14.
Table 1.15: This table discloses the 226 compounds E1 .001 .C15 to E1.226.C15 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C15.
Table 1.16: This table discloses the 226 compounds E1 .001 .C16 to E1.226.C16 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C16.
Table 1.17: This table discloses the 226 compounds E1 .001 .C17 to E1.226.C17 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C17.
Table 1.18: This table discloses the 226 compounds E1 .001 .C18 to E1.226.C18 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C18.
Table 1.19: This table discloses the 226 compounds E1 .001 .C19 to E1.226.C19 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C19.
Table 1.20: This table discloses the 226 compounds E1 .001 .C20 to E1.226.C20 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C20.
Table 1.21 : This table discloses the 226 compounds E1 .001 .C21 to E1.226.C21 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C21. Table 1.22: This table discloses the 226 compounds E1 .001.C22 to E1.226.C22 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C22.
Table 1.23: This table discloses the 226 compounds E1 .001 .C23 to E1.226.C23 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C23.
Table 1.24: This table discloses the 226 compounds E1 .001 .C24 to E1.226.C24 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C24.
Table 1.25: This table discloses the 226 compounds E1 .001 .C25 to E1.226.C25 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C25.
Table 1.26: This table discloses the 226 compounds E1 .001 .C26 to E1.226.C26 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C26.
Table 1.27: This table discloses the 226 compounds E1 .001 .C27 to E1.226.C27 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C27.
Table 1.28: This table discloses the 226 compounds E1 .001.C28 to E1.226.C28 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C28.
Table 1.29: This table discloses the 226 compounds E1 .001 .C29 to E1.226.C29 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C29.
Table 1.30: This table discloses the 226 compounds E1 .001 .C30 to E1.226.C30 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C30.
Table 1.31 : This table discloses the 226 compounds E1 .001 .C31 to E1.226.C31 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C31.
Table 1.32: This table discloses the 226 compounds E1 .001 .C32 to E1.226.C32 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C32.
Table 1.33: This table discloses the 226 compounds E1 .001 .C33 to E1.226.C33 as in Table
1 .1 but R-i , R2 and R3 have the specific meaning as given in the embodiment C33.
Table 2.1 : This table discloses the 226 compounds E2.001 .C1 to E2.226.C1 of the formula
Figure imgf000094_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A Tables 2.2 to 2.33: each of these 32 tables specifically discloses 226 compounds E2.001.CX to E2.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1 .33. As an example the compound E2.086.C20 has the following formula:
Figure imgf000095_0001
Table 3.1 : This table discloses the 226 compounds E3.001.C1 to E3.226.C1 of the formula
Figure imgf000095_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 3.2 to 3.33: each of these 32 tables specifically discloses 226 compounds E3.001.CX to E3.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 4.1 : This table discloses the 226 compounds E4.001 .C1 to E4. 226. C1 of the formula
Figure imgf000096_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 4.2 to 4.33: each of these 32 tables specifically discloses 226 compounds E4.001.CX to E4.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 5.1 : This table discloses the 226 compounds E5.001 .C1 to E5. 226. C1 of the formula
Figure imgf000096_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 5.2 to 5.33: each of these 32 tables specifically discloses 226 compounds E5.001 .CX to E5.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 6.1 : This table discloses the 226 compounds E6.001.C1 to E6.226.C1 of the formula
Figure imgf000097_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 6.2 to 6.33: each of these 32 tables specifically discloses 226 compounds E6.001.CX to E6.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 7.1 : This table discloses the 226 compounds E7.001.C1 to E7.226.C1 of the formula
Figure imgf000097_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 7.2 to 7.33: each of these 32 tables specifically discloses 226 compounds E7.001.CX to E7.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 8.1 : This table discloses the 226 compounds E8.001.C1 to E8.226.C1 of the formula
Figure imgf000098_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 8.2 to 8.33: each of these 32 tables specifically discloses 226 compounds E8.001.CX to E8.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
Table 9.1 : This table discloses the 226 compounds E9.001.C1 to E9.226.C1 of the formula
Figure imgf000098_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 9.2 to 9.33: each of these 32 tables specifically discloses 226 compounds E9.001.CX to E9.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1 .2 to 1.33.
This table discloses the 226 compounds E10.001 .C1 to E10.226. C1 of the
Figure imgf000099_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 10.2 to 10.33: each of these 32 tables specifically discloses 226 compounds
E10.001 .CX to E10.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1.33.
Table 1 1 .1 : This table discloses the 226 compounds E1 1.001 .C1 to E1 1.226. C1 of the formula
Figure imgf000099_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 1 1.2 to 1 1.33: each of these 32 tables specifically discloses 226 compounds
E1 1.001.CX to E1 1.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1.33.
Table 12.1 : This table discloses the 226 compounds E12.001 .C1 to E12.226. C1 of the formula
Figure imgf000100_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 12.2 to 12.33: each of these 32 tables specifically discloses 226 compounds E12.001 .CX to E12.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1.33.
This table discloses the 226 compounds E13.001 .C1 to E13.226. C1 of the
Figure imgf000100_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 13.2 to 13.33: each of these 32 tables specifically discloses 226 compounds
E13.001 .CX to E13.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1.33.
This table discloses the 226 compounds E14.001 .C1 to E14.226.C1 of the (E14),
R4 H3C CH3 in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 14.2 to 14.33: each of these 32 tables specifically discloses 226 compounds E14.001 .CX to E14.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 15.1 : This table discloses the 226 compounds E15.001 .C1 to E15.226. C1 of the formula
Figure imgf000101_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 15.2 to 15.33: each of these 32 tables specifically discloses 226 compounds
E15.001 . CX to E15.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 16.1 : This table discloses the 226 compounds E16.001 .C1 to E16.001.C1 of the formula
Figure imgf000102_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 16.2 to 16.33: each of these 32 tables specifically discloses 226 compounds
E16.001 .CX to E16.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E17.001 .C1 to E17.226. C1 of the
Figure imgf000102_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 17.2 to 17.33: each of these 32 tables specifically discloses 226 compounds
E17.001 .CX to E17.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 18.1 : This table discloses the 226 compounds E18.001 .C1 to E18.226. C1 of the formula
Figure imgf000103_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 18.2 to 18.33: each of these 32 tables specifically discloses 226 compounds
E18.001 .CX to E18.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E19.001 .C1 to E19.226. C1 of the
Figure imgf000103_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 19.2 to 19.33: each of these 32 tables specifically discloses 226 compounds
E19.001 .CX to E19.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E20.001 .C1 to E20.226.C1 of the
Figure imgf000104_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 20.2 to 20.33: each of these 32 tables specifically discloses 226 compounds
E20.001 .CX to E20.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 21 .1 : This table discloses the 226 compounds E21 .001.C1 to E21.226.C1 of the formula
Figure imgf000104_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 21.2 to 21.33: each of these 32 tables specifically discloses 226 compounds
E21 .001 .CX to E21.226. CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 22.1 : This table discloses the 226 compounds E22.001 .C1 to E22.226.C1 of the formula
Figure imgf000105_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 22.2 to 22.33: each of these 32 tables specifically discloses 226 compounds
E22.001 .CX to E22.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E23.001 .C1 to E23.226.C1 of the
Figure imgf000105_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 23.2 to 23.33: each of these 32 tables specifically discloses 226 compounds
E23.001 .CX to E23.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E24.001 .C1 to E24.226.C1 of the
Figure imgf000106_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 24.2 to 24.33: each of these 32 tables specifically discloses 226 compounds
E24.001 .CX to E24.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
This table discloses the 226 compounds E25.001 .C1 to E25.226.C1 of the
Figure imgf000106_0002
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 25.2 to 25.33: each of these 32 tables specifically discloses 226 compounds
E25.001 .CX to E25.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 26.1 : This table discloses the 226 compounds E26.001 .C1 to E26.226.C1 of the formula
Figure imgf000107_0001
in which, for each of these 226 specific compounds, each of the variables R-i , R2, R3, have the specific meaning given in the embodiment C1 and R4 is selected from one of the lines 001 to 226 in Table A
Tables 26.2 to 26.33: each of these 32 tables specifically discloses 226 compounds
E26.001 .CX to E26.226.CX, where CX corresponds to each of the embodiments C2 to C33, in analogy with tables 1.2 to 1 .33
Table 27 shows selected m.p. and/or LCMS data and retention times/MW for compounds of Tables 1 .1 to 26.33.
Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point.
The analytical methods used are described here below: Method U :
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) lonisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da
DAD Wavelength range (nm): 210 to 400
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water/Methanol 9:1 ,0.1 % formic acid and Solvent B: Acetonitrile,0.1 % formic acid )
Time (minutes) A (%) B (%) Flow rate (ml/min)
0 100 0 0.75 2.5 0 100 0.75
2.8 0 100 0.75
3.0 100 0 0.75
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.
Method U-2 :
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) lonisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da
DAD Wavelength range (nm): 210 to 400
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water/Methanol 9:1 ,0.1 % formic acid and Solvent B: Acetonitrile,0.1 % formic acid )
Figure imgf000108_0001
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.
Method A
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter: lonisation method: Electrospray ; Polarity: positive (negative) ions Capillary (kV) 3.00, Cone (V) 30.00 , Extractor (V) 2.00, Source Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400
Mass range: 100 to 900 Da (LC8 apolar: 150 - 1000 Da)
HP 1 100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ) / binary pump
(ZDQ), heated column compartment and diode-array detector.
Column: Phenomenex Gemini C18, 3 μηη particle size, 1 10 Angstrom, 30 x 3 mm,
Temp: 60 °C
DAD Wavelength range (nm): 200 to 500
Solvent Gradient:
A = water + 0.05 % HCOOH
B= Acetonitril/Methanol (4:1 , v:v) + 0.04 % HCOOH
Figure imgf000109_0002
Method B
ZMD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter: lonisation method: Electrospray ; Polarity: positive (negative) ions Capillary (kV) 3.80, Cone (V), Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) OFF, Desolvation Gas Flow (L/Hr) 600
Mass range: 100 to 900 Da
HP 1 100 HPLC from Agilent: solvent degasser, binary pump, heated column compartment and diode-array detector.
Column: Phenomenex Gemini C18, 3 μηη particle size, 1 10 Angstrom, 30 x 3 mm,
Temp: 60 °C
DAD Wavelength range (nm): 200 to 500
Solvent Gradient:
A = water + 0.05 % HCOOH
B= Acetonitril/Methanol (4:1 , v:v) + 0.04 % HCOOH
Figure imgf000109_0001
2.00 0.0 100.0 1.700
2.80 0.0 100.0 1.700
2.90 95.0 5.0 1.700
3.00 95.0 5.0 1.700
Table 27: Meltinq point data and/or retention times for compounds of Table 1 to 26:
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
1 .57 316 A
131
106-108 °C
132
86-90 °C
133
135-138 °C
134
120-123 °C
135
83-88 °C
136
137 void 158-161 °C
138
131-134 °C
139
122-126 °C
140
1 .55 324 A
141 CI
129-134 °C
142
137-142 °C
143
Figure imgf000134_0001
Figure imgf000135_0001
Formulation examples for compounds of formula (I):
Example F-1.1 to F-1.2: Emulsifiable concentrates
Figure imgf000135_0002
Emulsions of any desired concentration can be prepared by diluting such concentrates with water. Example F-2: Emulsifiable concentrate
Figure imgf000136_0001
Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
Examples F-3.1 to F-3.4: Solutions
Figure imgf000136_0002
Examples F-4.1 to F-4.4: Granulates
Figure imgf000136_0003
The novel compound is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is then removed by distillation under vacuum.
Examples F-5.1 and F-5.2: Dusts Components F-5.1 F-5.2
compound of Tables 1 -27 2% 5%
highly dispersed silicic acid 1 % 5%
Talcum 97% -
Kaolin - 90%
Ready for use dusts are obtained by intimately mixing all components.
Examples F-6.1 to F-6.3: Wettable powders
Figure imgf000137_0001
All components are mixed and the mixture is thoroughly ground in a suitable mill to give wettable powders which can be diluted with water to suspensions of any desired concentration.
Example F7: Flowable concentrate for seed treatment
Components F-7
compound of Tables 1 -27 40 %
propylene glycol 5 %
copolymer butanol PO/EO 2 %
tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one 0.5 %
(in the form of a 20% solution in water)
monoazo-pigment calcium salt 5 %
Silicone oil 0.2 %
(in the form of a 75 % emulsion in water)
Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Biological examples:
Biological example 1 : fungicidal activity against Alternaria solani I tomato / leaf disc (early blight)
Tomato leaf disks cv. Baby were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks were incubated at 23 °C / 21 °C (day/night) and 80% relative humidity (rh) under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application). Compounds (from table 27) 14, 16, 23, 24, 33, 34, 37, 41 , 49, 50, 54, 57, 59, 65, 67, 68, 70, 81 , 82, 83, 89, 94, 100, 120, 134, 135, 143, 145 and 146 at 200 ppm give at least 70% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 2: fungicidal activity against Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat)
Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
Compounds (from table 27) 1 , 2, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 20, 23, 24, 25, 26, 28, 31 , 32, 33, 34, 35, 36, 37, 38, 40, 41 , 42, 43, 44, 45, 53, 57, 58, 59, 64, 65, 66, 67, 68, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 85, 86, 89, 91 , 92, 93, 94, 95, 96, 97, 99, 104, 105, 106, 108, 109, 1 10, 1 1 1 , 1 12, 1 13, 1 15, 1 16, 1 17, 1 18, 1 19, 120, 121 , 122, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 134, 135, 139, 140, 142, 146, 148, 149, 151 and 152 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 3: fungicidal activity against Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.
Compounds (from table 27) 1, 2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 20, 23, 24, 25, 26, 27, 28, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 138, 139, 140, 141, 142, 143, 144, 145, 146, 149, 151 and 152 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 4: fungicidal activity against Gaeumannomyces graminis I liquid culture (Take-all of cereals)
Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application.
Compounds (from table 27) 1,2,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20,21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 63, 64, 65, 66, 68, 69, 71, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 115, 116, 117, 119, 120, 121, 122, 123, 124, 125, 126, 128, 129, 131, 132, 133, 134, 135, 136, 139, 140, 141, 143, 146, 151 and 152 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Bioloqical example 5: fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) I liquid culture (Anthracnose)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was measured photometrically 3-4 days after application.
Compounds (from table 27) 1 , 2, 6, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 20, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 105, 106, 107, 108, 1 10, 1 1 1 , 1 12, 1 13, 1 15, 1 16, 1 17, 1 18, 1 19, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 134, 135, 136, 140, 142, 143, 144, 145, 146, 147, 151 and 152 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 6: fungicidal activity against Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
Compounds (from table 27) 8, 9, 10, 1 1 , 13, 17, 19, 23, 25, 26, 28, 29, 31 , 33, 37, 38, 39, 42, 43, 44, 45, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 63, 64, 65, 66, 67, 69, 70, 71 , 73, 74, 77, 81 , 82, 83, 84, 85, 86, 87, 89, 91 , 92, 93, 96, 99, 100, 101 , 102, 103, 106, 107, 108, 1 10, 1 1 1 , 1 18, 120, 121 , 122, 123, 125, 126, 127, 128, 129, 131 , 132, 133, 134, 135, 136, 140, 142, 143, 144, 145, 146, 147, 151 and 152 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 7: fungicidal activity against Mvcosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
Compounds (from table 27) 1 , 6, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 19, 20, 22, 23, 24, 25,
26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 104, 105, 106, 108, 109, 1 10, 1 1 1 , 1 12, 1 13, 1 15, 1 16, 1 17, 1 18, 1 19, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 134, 135, 136, 138, 139, 140, 142,143, 144, 145, 146, 147, 151 and 152y at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 8: fungicidal activity against Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4- 5 days after application.
Compounds (from table 27) 1 , 2, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 19, 20, 21 , 24, 26,
27, 28, 29, 30, 31 , 33, 36, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 104, 105, 106, 108, 109, 1 10, 1 1 1 , 1 12, 1 13, 1 15, 1 18, 120, 121 , 122, 123, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 134, 135, 136, 141 , 142, 143, 144, 145, 146, 147 and 151 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 9: fungicidal activity against Phaeosphaeria nodorum (Septoria nodorum) /wheat / leaf disc preventative (Glume blotch)
Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks were incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
Compounds (from table 26) 1 , 2, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 20, 23, 24, 25, 26, 28, 29, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 77, 78, 80, 81 , 82, 83, 84, 85, 86, 87, 90, 91 , 92, 93, 94, 95, 96, 99, 100, 101 , 105, 106, 108, 109, 1 10, 1 1 1 , 1 12, 1 13, 1 18, 120, 121 , 122, 123, 125, 126, 127, 128, 130, 131 , 132, 133, 134, 135, 136, 139, 141 , 142, 143, 144, 145, 146, 147, 148, 149, 150, 151 and 152 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 10: fungicidal activity against Phytophthora infestans I tomato / leaf disc preventative (late blight)
Tomato leaf disks were placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks were incubated at 16°C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
Compounds (from table 27) 1 1 , 24, 48, 50, 53, 54, 56, 58, 142, 143 and 147 at 200 ppm give at least 70% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 1 1 : fungicidal activity against Plasmopara viticola I grape / leaf disc preventative (late blight)
Grape vine leaf disks were placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks were incubated at 19°C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application). Compounds (from table 27) 1 , 2, 8, 14, 16, 25, 26, 31 , 43, 50, 53, 58, 60, 77, 83, 87, 142, 143, 145, 146 and 147 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 12: fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application).
Compounds (from table 27) 1 , 2, 6, 7, 8, 9, 10, 13, 15, 16, 20, 23, 24, 25, 26, 28, 31 , 32, 33, 35, 36, 37, 38, 39, 42, 43, 44, 45, 47, 48, 49, 50, 52, 53, 58, 59, 63, 64, 65, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 80, 81 , 82, 83, 85, 86, 90, 91 , 92, 93, 94, 95, 96, 99, 102, 103, 104, 106, 107, 108, 1 10, 1 1 1 , 1 12, 1 15, 1 18, 120, 121 , 122, 124, 125, 127, 128, 130, 131 , 132, 134, 135, 142, 145, 146, 147, 151 and 152 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 13: fungicidal activity against Pyrenophora teres I barley / leaf disc preventative (Net blotch)
Barley leaf segments cv. Hasso were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments were incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
Compounds (from table 27) 1 , 2, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 20, 23, 24, 28, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 104, 105, 106, 108, 109, 1 10, 1 1 1 , 1 12, 1 13, 1 15, 1 16, 1 17, 1 18, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 134, 135, 136, 138, 139, 140, 141 , 142, 143, 144, 145, 146, 147, 148, 151 and 152 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Biological example 14: fungicidal activity against Thanatephorus cucumeris (Rhizoctonia solani) I liquid culture (foot rot, damping-off)
Mycelia fragments of a newly grown liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.
Compounds (from table 27) 8, 9, 10, 1 1 , 13, 33, 37, 38, 39, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 99, 100, 102, 103, 104, 106, 107, 108, 1 10, 1 1 1 , 1 12, 1 13, 120, 121 , 122, 123, 125, 126, 127, 128,
129, 131 , 132, 133, 134, 135, 136, 142, and 147 at 20 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Claims

Claims:
1. Compounds of formula (I)
Figure imgf000145_0001
wherein
G represents together with the two carbon atoms of the pyrimidine ring to which it is attached, a 5- to 8-membered aliphatic carbocyclic or non aromatic heterocyclic monocyclic or bicyclic ring system which contain 0 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; and wherein said 5- to 8-membered alicyclic or non aromatic heterocyclic monocyclic or bicyclic ring system can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, hydroxy, Ci-C6alkyl, d- C6haloalkyl, d-dalkoxy, d-dalkoxy-d-dalkyl,d-dhaloalkoxy, keto, d-dalkoximino and C-i-C6alkylendioxy; and wherein two substituents, independently selected from the group consisting of hydroxy, C-|-C6alkyl, C-|-C6haloalkyl and C-|-C6alkoxy, may together form a saturated three- to six-membered alicyclic or heterocyclic ring.
Ri represents halogen, cyano, hydroxy, formyl, amino, Ci-C8alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, d-dhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- dhalocycloalkyl, d-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, d-dhaloalkoxy, d-dalkylthio, d-dhaloalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d- dalkylsulfonyl-d-dalkyl, d-dalkylsulfoximino-d-dalkyl,d-dalkylamino, diCr dalkylamino, C3-dcycloalkylamino, d-dalkylcarbonyl, d-dalkoxycarbonyl, d- dalkylaminocarbonyl, diCrdalkylaminocarbonyl, d-dalkoxyimino or d-dalkoxyimino-Cr dalkyl;
R2 is hydrogen, halogen, cyano, hydroxy, d-dalkyl, d-dalkenyl, d-dalkynyl, C3- dcycloalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkoxy- d-dalkyl or d- dalkylthio; R3 is hydrogen, hydroxy, halogen, cyano, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6 cycloalkyl, CrC6alkylthio, CrC6alkoxy, CrC6haloalkyl, Ci-C6alkoxy-Ci-C6alkyl, d- C4haloalkoxy, SH, C1-C4alkylcarbonythio or C1-C4alkylcarbonyloxy;
R4 is aryl or heteroaryl; or aryl or heteroaryl which is substituted, preferably when the aryl or heteroaryl is substituted they are mono-, di- or trisubstituted wherein the subtituents are preferably selected from halogen, cyano, nitro, formyl, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-dhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, hydroxy, d-dalkoxy, d-dalkoxy-d-dalkyl, d-dalkoxy-d-dalkoxy, d-dalkoxy-d- dalkoxy-d-dalkyl , d-dalkoxy-d-dalkylthio, d-dalkylthio - d-C6alkoxy, d- dhaloalkoxy, d-dalkylthio, d-dhaloalkylthio, d-C6alkylsulfinyl, d-dalkylsulfonyl, d- dalkylamino, did-dalkylamino, C3-dcycloalkylamino, (d-dalkyl)(C3-dcycloalkyl)amino, did-dcycloalkylamino, d-dalkylcarbonyl, d-dalkoxycarbonyl, d-dalkylaminocarbonyl, did-dalkylaminocarbonyl, d-dalkoxycarbonyloxy, d-dalkylaminocarbonyloxy, diCr dalkylaminocarbonyloxy, d-dalkylcarbonyloxy, d-dalkylcarbonylamino, d- dalkylcarbonyl-d-dalkylamino, d-C6alkoxyimino, d-dalkoxyimino-Crdalkyl, triCi- 6alkylsilyl, d-dalkoxy-C2-dalkynyl, d-dalkoxyimino-d-dalkynyl, d-dalkylthio-d- dalkynyl, hydroxy-d-dalkynyl, d-dalkylthio-Ci-dalkyl or hydroxy-d-dalkyl; and agronomically acceptable salts, stereoisomers, diastereoisomers, enantiomers, tautomers atropisomers and N-oxides of those compounds;
2. Compounds of formula (I) according to claim 1 characterized in that the ring systems formed by the pyrimidine ring together with the substituent G are selected from the group consisting of
Figure imgf000146_0001
Figure imgf000147_0001
šnd
Figure imgf000148_0001
wherein R4 has the meaning as defined for formula I above.
3. Compounds of formula (I) according to claim 1 characterized in that
Ri represents halogen, hydroxy, formyl, CrC8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrC6haloalkyl, C3-C6halocycloalkyl, CrC6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, d- Cealkoxy-CrCealkoxy-d-Cealkyl, CrC6alkylthio, d-Cealkylamino, did-Cealkylamino, C3- C6cycloalkylamino, d-Cealkoxyimino, d-Cealkoxyimino-CrCealkyl;
R2 represents hydrogen, halogen, cyano, d-C6alkyl, C3-C6cycloalkyl, d-C6haloalkyl, d- C6alkoxy, d-C6haloalkoxy, CrC6alkoxy-CrC6alkyl, d-C6alkylthio;
R3 represents hydrogen, halogen, cyano, d-C6alkyl, C3-C6cycloalkyl, d-C6haloalkyl, d- C6alkoxy, C Cealkoxy-C Cealkyl, CrC6haloalkoxy, C2-C6alkynyl, d-C6alkylthio;
R4 represents aryl or heteroaryl; or aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, nitro, formyl, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-C6haloalkyl, CrC6alkoxy, CrC6alkoxy-CrC6alkyl, hydroxy- CrCealkyl.d-Cealkoxy-d-Cealkoxy _ Q C6alkoxy-Ci-C6alkoxy-Ci-C6alkyl , Ci-C6alkoxy-Ci-C6alkylthio, Ci-C6alkylthio-Ci-C6alkoxy, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-C6haloalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, d- C6alkylamino, diCrC6alkylamino, C3-C6cycloalkylamino, Ci-C6alkylcarbonyl, d- C6alkoxycarbonyl, CrC6alkylaminocarbonyl, diCrC6alkylaminocarbonyl, d- C6alkoxycarbonyloxy, Ci-C6alkylaminocarbonyloxy, diCi-C6alkylaminocarbonyloxy, C2- C6alkylcarbonyloxy, CrC6alkylcarbonylamino, Ci-C6alkylcarbonyl-Ci-C6alkylamino, d- C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, CrC6alkoxy-C2-C6alkynyl, Ci-C6alkoxyimino- C2-C6alkynyl, CrC6alkylthio-C2-C6alkynyl and hydroxy-C2-C6alkynyl or CrC6alkylthio-Cr C6alkyl;
4. Compounds of formula (I) according to claim 1 characterized in that
R4 represents aryl or heteroaryl; or aryl or heteroaryl mono-, di- or trisubstituted by halogen, cyano, formyl, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-C6haloalkyl, d- C6alkoxy, CrC6alkoxy-CrC6alkyl, hydroxy-CrC6alkyl, CrC6alkoxy-CrC6alkoxy, CrC6alkoxy- CrC6alkoxy-CrC6alkyl , CrC6alkoxy-CrC6alkylthio, CrC6alkylthio-CrC6alkoxy, Cr C6alkylthio, Ci-C6alkylamino, diCi-C6alkylamino, C3-C6cycloalkylamino, CrC6alkylcarbonyl, Ci-C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, Ci-C6alkoxy-C2-C6alkynyl, CrC6alkoxyimino- C2-C6alkynyl, C1-C6alkylthio-C2-C6alkynyl and hydroxy-C2-C6alkynyl or Ci-C6alkylthio-Ci- C6alkyl;
5. Compounds of formula (I) according to claim 1 characterized in that
is Ci-C6alkyl, C3-C6cycloalkyl, d-C6alkoxy, d-C6alkylthio
R2 is H, C C6alkyl, C C6alkoxy, CI, F
R3 is H, Ci-C6alkyl, d-C6alkoxy, C Cealkylthio, C3-C6cycloalkyl, C2-C6alkynyl
R4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of by halogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d- C6haloalkyl, CrC6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, Ci-C6alkoxy-Ci-C6alkoxy, Ci-C6alkoxy-Cr C6alkoxy-Ci-C6alkyl, CrC6alkylthio, Ci-C6alkylamino, diCi-C6alkylamino, C3- C6cycloalkylamino, CrC6alkylcarbonyl, Ci-C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, d- C6alkoxy-C2-C6alkynyl, Ci-C6alkoxyimino-C2-C6alkynyl, Ci-C6alkylthio-C2-C6alkynyl, hydroxy- C2-C6alkynyl, Ci-C6alkylthio-Ci-C6alkyl or hydroxy- Ci-C6alkyl; or pyridyl, thienyl, dihydro- benzofuran, benzo[1 ,3]dioxole, 3,4-Dihydro-2H-benzo[b][1 ,4]dioxepine which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C6alkyl, C2-C6alkynyl d-C6haloalkyl, d-C6alkoxy, Ci-C6alkoxy-Ci-C6alkoxy, d-C6alkoxy-Ci- C6alkoxy-d-C6alkyl, d-C6alkylthio and d-C6haloalkoxy;
6. Compounds of formula (I) according to claim 1 characterized in that
is d-C3alkyl, C3-C6cycloalkyl; preferably, d-C3alkyl
R2 is H, C C3alkyl, C C3alkoxy;
R3 is H, C C3alkyl, C C3alkoxy
R4 is phenyl which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-C6haloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, Ci-C6alkoxy-Ci-C6alkoxy, Ci-C6alkylthio, d- C6alkylamino, diCi-C6alkylamino, C3-C6cycloalkylamino, Ci-C6alkylcarbonyl, d- C6alkoxyimino, Ci-C6alkoxyimino-Ci-C6alkyl, Ci-C6alkoxy-C2-C6alkynyl, d-C6alkoxyimino- C2-C6alkynyl, Ci-C6alkylthio-C2-C6alkynyl, hydroxy-C2-C6alkynyl, Ci-C6alkylthio-Ci-C6alkyl or hydroxy- Ci-C6alkyl;or pyridyl, thienyl, dihydro-benzofuran, benzo[1 ,3]dioxole, 3,4-Dihydro- 2H-benzo[b][1 ,4]dioxepine which can be mono-, di- or trisubstituted by substituents selected from the group consisting of halogen, CrC6alkyl, C2-C6alkynyl, CrC6haloalkyl, CrC6alkoxy, CrC6alkylthio and CrC6haloalkoxy;
7. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) as defined in claim 1 or a composition, a compound of formula (I) as defined in claim 1 as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
8. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) as defined in claim 1 and at least one auxiliary.
9. A method of controlling phytopathogenic diseases on useful plants or plant propagation material thereof, which comprises applying to said plant propagation material a fungicidally effective amount of a plant propagation material protecting composition comprising a compound of formula (I) as defined in claim 1 , together with a suitable carrier therefor.
10. A composition comprising a fungicidally effective amount of a compound of formula (I) as defined in claim 1 , optionally comprising at least one additional active ingredient.
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