EP0561961A1 - Nouvelles amidines et guanidines heterocycliques utilisees comme fongicides pour plantes - Google Patents

Nouvelles amidines et guanidines heterocycliques utilisees comme fongicides pour plantes

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Publication number
EP0561961A1
EP0561961A1 EP19920901678 EP92901678A EP0561961A1 EP 0561961 A1 EP0561961 A1 EP 0561961A1 EP 19920901678 EP19920901678 EP 19920901678 EP 92901678 A EP92901678 A EP 92901678A EP 0561961 A1 EP0561961 A1 EP 0561961A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
phenyl
independently
compounds
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19920901678
Other languages
German (de)
English (en)
Inventor
Gregory Steven Basarab
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0561961A1 publication Critical patent/EP0561961A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • EP 0375414 A1 discloses as fungicides substituted guanidine and amidine compounds of the formula:
  • R 1 is H or C 1 -C 3 alkyl
  • each R 2 is independently H or C 1 -C 4 alkyl
  • R 3 is C 4 -C 20 alkyl, C 4 -C 20 alkenyl, phenyl, phenyl-C 1 -C 3 alkylene, or phenyl-C 2 -C 3 alkenylene wherein the phenyl ring can be substituted with 1-5 halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, trihalomethyl, phenyl or phenoxy;
  • R 4 is H or C 1 -C 4 alkyl
  • Y is -(CR 7 R 7 ) n -, wherein n is 2, 3 or 4, each R 7 is independently H or C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, C 2 -C 4 alkoxyalkyl; or -(CH 2 ) q -O(CO)-R 8 , wherein q is 1, 2 or 3, and R 8 is methyl or ethyl; and
  • R 4 is H or C 1 -C 3 alkyl.
  • This invention pertains to compounds of Formula I including all geometric and stereoisomers, agricultural compositions containing them and their use as fungicides.
  • W is H, C 1 -C 4 alkyl or C 3 -C 4 alkenyl
  • n 0 or 1
  • X is O, S, CR 5 R 6 or NR 7 ;
  • Y is CR 8 R 9 or CR 8 R 9 CR 10 R 11 ;
  • R 1 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 14 and R 15 are independently H or
  • R 2 is C 4 -C 20 alkyl, C 4 -C 20 alkenyl or C 4 -C 20 alkynyl each optionally
  • R 3 and R 4 are independently C 1 -C 10 alkyl; C 1 -C 10 alkoxy; NR 16 R 17 ;
  • phenyl, benzyl or phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C 1 -C 4 alkyl and C 1 -C 4 haloalkyl; or R 3 and R 4 may be taken together with the nitrogen to which they are attached to form heterocycles of the formulae:
  • R 12 and R 13 are independently H; halogen; CN; C 1 -C 6 alkyl; C 1 -C 6
  • R 12 and R 13 are independently phenyl optionally substituted with halogen, CN or C 1 -C 4 alkyl;
  • R 16 and R 17 axe independently C 1 -C 10 alkyl; or phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, CN, C 1 -C 4 alkyl and C 1 -C 4 haloalkyl;
  • R 18 and R 19 are independently H; CN; C 1 -C 4 alkyl; C 2 -C 4 alkenyl; C 1 -C 4 alkoxy; C 1 -C 4 hydroxyalkyl; or phenyl optionally substituted with 1-2 halogen;
  • R 20 and R 21 are independently H, halogen, CN, C 1 -C 4 alkyl or C 1 -C 4
  • R 22 is H, OH, halogen, CN, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
  • R 23 is H, OH, C 1 -C 3 alkyl or C 1 -C 3 alkoxy
  • R 24 is H or C 1 -C 4 alkyl
  • E is O or CH 2 ; or their agriculturally suitable salts thereof, including, but not limited to, halide, acetate, benzoate, dodecylbenzenesulfonate, methanesulfonate, sulfate and nitrate.
  • R 3 is NR 16 R 17 or C 1 -C 10 alkoxy
  • R 4 cannot be NR 16 R 17 or C 1 -C 10 alkoxy
  • R 18 and R 19 are independently CN, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 1 -C 4 alkoxy or C 1 -C 4 hydroxyalkyl.
  • Formula I contains a single double bond. However, it will be clear to one skilled in the art that the double bond is actually delocalized over the two or three nitrogen atoms of compounds of Formula I. Further, the compounds of Formula I can exist in tautomeric forms. All of these forms are understood as being within the scope of the instant invention. Compounds preferred for greatest fungicidal activity and/or ease of synthesis are:
  • W is H
  • Y is CH 2 ;
  • R 1 is H or CH 3 ;
  • R 3 and R 4 are independently C 1 -C 10 alkyl; phenyl, benzyl or
  • phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C 1 -C 4 alkyl and C 1 -C 4 haloalkyl; or R 3 and R 4 may be taken together with the nitrogen to which they are attached to form heterocycles of the formulae A-1 , A-2, A-3, A-4, A-6, A-9, A-11, A-12, A-13 or
  • R 12 and R 13 are independently H, halogen, CN, C 1 -C 6 alkyl, C 1 -C 6 cyanoalkyl, C 1 -C 6 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 18 and R 19 are independently H, CN, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 hydroxyalkyl;
  • R 20 and R 21 are independently H, CN or CH 3 ;
  • R 22 is H or OH.
  • X is O, CH 2 or NCH 3 ;
  • R 1 , R 8 , R 9 , R 10 , R 11 , R 14 and R 15 are H.
  • R 3 and R 4 are taken together with the nitrogen to which they are attached to form heterocycles of the formulae A-1 , A-3, A-4,
  • R 2 is C 4 -C 10 alkyl; C 3 -C 6 cycloalkyl optionally substituted with
  • R 12 and R 13 are independently H, CN, C 1 -C 6 alkyl, CF 3 or C 3 -C 4 cycloalkyl; and for salts, chloride.
  • Compounds of Formula I wherein n is 1 and W is C 1 -C 4 alkyl or C 3 -C 4 alkenyl can be prepared by the displacement of a leaving group L in 2 where W 1 is C 1 -C 4 alkyl or C 3 -C 4 alkenyl with Formula I compounds in which n is O.
  • Typical leaving groups in 2 include halides and sulfonates.
  • the reaction is run in polar solvents such as acetone or dimethylformamide (DMF), in ethereal solvents such as diethyl ether or tetrahydrofuran (THF) or in hydrocarbons such as benzene or toluene. Temperatures for the reaction range from 0 - 150°C.
  • W is H are recognized as the conjugate acids of la wherein n is 0 and are prepared by treatment of la with an acid such as HCl, acetic acid, benzoic acid or a sulfonic acid.
  • Compounds of Formula la can be prepared by displacement of a leaving group, LG, in 2 with an amine 4.
  • Typical values for LG include halides, alkoxyls, alkylthios, sulfenates and sul ⁇ nates.
  • the reaction is run with one or more equivalents of the amine with or without an added base such as potassium carbonate, triethylamine or butyllithium.
  • Appropriate solvents includes ethereal solvents such as ether or THF, hydrocarbons such as benzene or toluene or the amine itself may be used as solvent.
  • Compounds of Formula 2 in which LG is a halide can be prepared from compounds of Formula 5 by standard methods for the conversion of amides, ureas, carbamates and thiocarbamates to the corresponding iminoyl halide compounds.
  • Typical reagents for the conversion include PCI 5 , POCI 3 , PBr 5 , SOCI 2 , SOBr 2 .
  • Appropriate solvents include hydrocarbons such as benzene or toluene or
  • chlorocarbons such as methylene chloride or 1,2-dichloroethane. Temperatures for the reaction range from 25 - 150°C.
  • Compounds of Formula 3 in which LG is alkoxyl also can be prepared from 5 by treatment with an alkylating reagent such as trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate, dimethyl sulfate or methyl iodide.
  • an alkylating reagent such as trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate, dimethyl sulfate or methyl iodide.
  • the alkylation is run in hydrocarbons such as benzene or toluene or in chlorocarbons such as methylene chloride or chloroform at temperatures of 25 - 150°C.
  • Compounds of Formula 5a a subset of 5 in which X is a heteratom and Y is CR 8 R 9 , can be made from 6 and phosgene or a phosgene equivalent such as carbonyldiimidazole or diethylcarbonate in a nonprotic solvent such as THF or methylene chloride with base catalysis.
  • a nonprotic solvent such as THF or methylene chloride with base catalysis.
  • Compounds of Formula 5b, a subset of Formula 5 compounds in which X is CR 5 R 6 and Y is CR 8 R 9 are prepared from compounds of Formula 8 wherein R is lower alkyl by catalytic reduction of the nitro group to an amine followed by cyclocondensation.
  • the catalytic reduction may be carried out over a palladium or platinum catalyst on carbon in acetic acid or over Raney nickel in ethanol.
  • Hydrogen pressures of 1-50 psi and temperatures of 25-100°C may be used.
  • the cyclization is carried out in a hydrocarbon solvent such as benzene or toluene with or without heating at reflux, with or without an acid catalyst such as HCl or
  • Formula 2 to compounds of Formula 10 followed by addition of an electrophile R 9 -L wherein L is a halide or sulfonate leaving group.
  • the anion of 9 may be generated with a strong base such as potassium-t-butoxide or lithium diisopropylamide in an ethereal solvent such as THF.
  • Formula 9 compounds are generally commercially available or synthesized by procedures set out in the literature.
  • 8a (a subset of 8) may be made by reaction of nitro compound 11 with 12 where R is lower alkyl in the presence of catalytic amount of base such as Triton B ® or potassium-t-butoxide.
  • Compounds of Formula 5c a subset of 5 wherein X is a heteroatom and Y is CR 8 R 9 CR 10 R 11 , can be made from 12 and phosgene or a phosgene equivalent as in the preparation of 5a (vide supra).
  • Compounds of Formula 13 can be prepared by a variety of methods. For example, treatment of 14 with 15 in the presence of a base such as potassium-t- butoxide or Triton B ® affords 16 which may be reduced with lithium aluminum hydride, palladium on charcoal in acetic acid or Raney nickel in ethanol to form 13.
  • a base such as potassium-t- butoxide or Triton B ®
  • Formula 14 compounds may be prepared by standard literature procedures for the
  • Compounds of Formula 5d may be prepared by reaction of a compound of Formula 12, wherein R is lower alkyl and L is a leaving group such as a halide in a hydrocarbon solvent such as benzene at elevated pressures and temperature (25 - 150°C).
  • Compounds of Formula 12 are in turn obtained by treatment of compounds of Formula 18 with HBr or HCl in a lower alcohol solvent.
  • R in 20, 21 and 22 is lower alkyl and L is a leaving group such as a halide or p-toluenesulfonate.
  • the conversion of 22 to 19 is carried out by standard literature methods of ester hydrolysis followed by cyclization to the anhydride.
  • Amines 4 are generally available commercially or else are known in the literature. The synthesis of amines 4 in which R 3 and R 4 are taken together with the nitrogen to form the heterocycle of A-9 has been described (Rahier, A. et al.,
  • Amines 4 in which R 3 and R 4 taken together with the nitrogen to form the heterocycle of A-11 or A-12 may be synthesized from amines such as 22 (Rahier, A., et al., Phytochemistry. vol. 24, No. 6, pp 1223-1232, 1985) by methods known to those skilled in the art.
  • reaction of 22 with a base such as potassium t-butoxide and an alkylating reagent or an acid affords 25 which may in turn be converted to heterocycles of Formula A-11a (a subset of A 11) as described for the conversion of 22 to A-12a.
  • Formula 1 compounds can contain two or more asymmetric carbon atoms.
  • the stereoisomers that result can be separated using standard methods known in the art if desired.
  • Triethylphosphonoacetate 29.4 mL, 0.148 mol was added dropwise. The solution was warmed to room temperature and stirred until gas evaluation ceased. 4-t-Butylbenzaldehyde (20.0 g, 0.124 mol) was added dropwise and the reaction mixture was heated at 65°C for 1 h and stirred at room temperature overnight. After quenching with aqueous NH 4 CI, solvent was removed and the aqueous residue was taken up in ether. The ether was washed twice with water and once with brine. Drying
  • reaction mixture was acidified with aqueous HCl, and extracted with methylene chloride.
  • organic layer was washed with water and brine, dried (MgSO 4 ) and solvent was removed to afford 24.4 g of ethyl-3-(4-t-butylphenyl)-4-nitrobutyrate as an oil.
  • t-Bu is tertiary butyl
  • Hex is hexyl
  • Ph is phenyl
  • n-BU is normal butyl
  • Bnz is benzyl
  • Me-O is methoxy
  • CN is cyano
  • TMS is trimethylsilyl
  • t-Am is tertiary amyl.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • Active ingredients plus at least one of a surfactant or a diluent equals 100 weight percent.
  • Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E.Browning, "Agglomeration",
  • the ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter.
  • the product is reblended before packaging.
  • Example C An oily active ingredient is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
  • Example C An oily active ingredient is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
  • Example D The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns.
  • the resulting thick suspensions may be applied directly, but preferably after being extended with oils or emulsified in water.
  • the ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
  • the active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period. The product is then gently dried to remove solvent and the granules are packaged.
  • polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol 5.0% ether
  • the ingredients are blended and milled together in a homogenizer to produce particles essentially all under 5 microns in size.
  • the salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
  • Example I The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
  • Example I The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
  • Example J The ingredients are combined and stirred together to produce a solution.
  • the product can be extended with oils, or emulsified in water.
  • the active ingredient is blended with attapulgite and pyrophyllite and then passed thorugh a hammer-mill to produce particles substantially all below 200 microns.
  • the ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
  • the compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include, Venturia inaequalis, Cercosporidium personatum, Cercospora arachidicola, Cercospora beticola, Pseudocercosporella herpotrichoides. Erysiphe graminis.
  • Puccinia strüformis Puccinia arachidis. Pyricularia oryzae, Phytophthora infestans. Plasmopara viticola. Peronospora tabacina,
  • Pseudoperonospora cubensis Pythium aphanidermatum. Botrytis cinerea. Monilinia fructicola, Altemaria brassicae. Septoria nodorum. and other species closely related to these pathogens. They also control seed pathogens.
  • the compounds of this invention can be mixed with various fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material.
  • Suitable agents of this type are well-known to those skilled in the art. Some of these agents are listed below:
  • N-isopropylphosphoramidic acid O-ethyl-O'-[4-(methylthio)-m-tolyl]- diester (fenamiphos)
  • Disease control is ordinarily accomplished by applying an effective amount of the compounds of the invention either pre-infection or post-infection to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compound also may be applied to the seed, to protect the seed and seedling.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to
  • test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on wheat seedlings. The following day the seedlings are inoculated with a spore dust of Erysiphe graminis f. sp.tritici. (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings are made. Test B
  • test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on wheat seedlings. The following day the seedlings are inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings are made.
  • Puccinia recondita the causal agent of wheat leaf rust
  • test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on tomato seedlings. The following day the seedlings are inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings are made.
  • Phytophthora infestans the causal agent of potato and tomato late blight
  • test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspendend at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters).
  • This suspension is sprayed to the point of run-off on potato plants.
  • the plants are inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20° C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings are made.
  • test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on grape seedlings. The following day the seedlings are inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings are made.
  • Plasmopara viticola the causal agent of grape downy mildew
  • Results for Tests A to E are given in Table 1.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls).
  • NT indicates that no test was performed.
  • the number compounds in Table 1 are identified in Index Table A.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Composés de la formule (I) comprenant tous des stéréoisomères géométriques, compositions agricoles les contenant et leur emploi comme fongicides.
EP19920901678 1990-12-13 1991-12-10 Nouvelles amidines et guanidines heterocycliques utilisees comme fongicides pour plantes Withdrawn EP0561961A1 (fr)

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US62688790A 1990-12-13 1990-12-13
US626887 2003-07-24

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WO1996015104A2 (fr) * 1994-11-14 1996-05-23 Nzym, Inc. Methodes et compositions pour le traitement de mycoses phytopathogenes
EP2585453A4 (fr) * 2010-06-28 2014-10-22 Harvard College Composés pour inhiber la prolifération cellulaire

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DE1770158A1 (de) * 1962-07-10 1971-09-23 Geigy Ag J R Neue heterocyclische Amine
FR1516776A (fr) * 1966-07-21 1968-03-15 Rhone Poulenc Sa Nouveaux dérivés du pyrrole et leur préparation
FR2186236B1 (fr) * 1972-05-03 1975-08-01 Logeais Labor Jacques
US4064348A (en) * 1975-10-21 1977-12-20 The Dow Chemical Company 2-Cycloalkyl-amino-2-oxazolines
GB8829935D0 (en) * 1988-12-22 1989-02-15 Dow Chemical Co Fungicidal compounds,their production and use

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Title
See references of WO9210475A1 *

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