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WO1996008475A1 - Pesticidal pyridine derivatives - Google Patents

Pesticidal pyridine derivatives Download PDF

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Publication number
WO1996008475A1
WO1996008475A1 PCT/EP1995/003464 EP9503464W WO9608475A1 WO 1996008475 A1 WO1996008475 A1 WO 1996008475A1 EP 9503464 W EP9503464 W EP 9503464W WO 9608475 A1 WO9608475 A1 WO 9608475A1
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Prior art keywords
alkyl
halogen
halo
formula
halogen atoms
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Application number
PCT/EP1995/003464
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French (fr)
Inventor
Harald Walter
Original Assignee
Novartis Ag
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Filing date
Publication date
Application filed by Novartis Ag filed Critical Novartis Ag
Priority to AU35210/95A priority Critical patent/AU3521095A/en
Priority to EP95931980A priority patent/EP0781275A1/en
Priority to JP8509866A priority patent/JPH10505824A/en
Publication of WO1996008475A1 publication Critical patent/WO1996008475A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
    • A01N45/02—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring having three carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • 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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D413/12—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 linked by a chain containing hetero atoms as chain links

Definitions

  • R 1 and R 2 are each independently of the other C 1 -C 6 alkyl, halo- C 1 -C 6 alkyl containing 1 to
  • R 1 and R 2 taken together, form a saturated or unsaturated 5- to 7-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
  • R 3 and R 4 are each independently of the other hydrogen, C 1 -C 6 alkyl or halogen;
  • R 5 is hydrogen, C 1 -C 6 alkyl which is unsubstituted or substituted by cyano, nitro, halogen, carboxyl, C 1 -C 2 alkoxycarbonyl, C 1 -C 2 alkanoyl, C 1 -C 2 alka ⁇ esulfonyl or phenylsulfonyl,
  • X is a C 1 -C 5 chain which may contain one or two double bonds, one or two triple bonds as well as one or two hetero atoms selected from O, S and N, and which are unsubstituted or substituted by C 1 -C 4 alkyl, halo- C 1 -C 4 alkyl containing 1 to 5 halogen atoms,
  • Y is a group of formulae (a) to (x); R 6 and R 7 are each independently of the other hydrogen, halogen, C 1 -C 6 alkyl,
  • halo-C 1 -C 6 alkyl containing 1 to 5 halogen atoms C 1 -C 2 alkoxy- C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy containing 1 to 5 halogen atoms, C 1 -C 6 alkylthio, C 1 -C 6 alkanesulfinyl, C 1 -C 6 alkanesulfonyl, phenyl, benzyl, phenoxy, phenylthio, hydroxy, mercapto, nitro, cyano, C 1 -C 4 alkanoyl, halo- C 1 -C 4 alkanoyl or C 1 -C 4 alkoxycarbonyl;
  • the invention further relates to the preparation of these compounds, to agrochemical compositions comprising at least one of said compounds as active ingredient, and to the use of said compounds or compositions for pest control, preferably as microbicides, insecticides and acaricides in agriculture and horticulture.
  • the compounds of formula I and their possible tautomers may be obtained in salt form.
  • the compounds of formula I contain at least at least one basic centre, they may typically form acid addition salts.
  • These salts may conveniently be formed with a mineral acid such as sulfuric acid, a phosphoric acid or a hydrohalic acid, with an organic carboxylic acid such as acetic acid, oxalic acid, malonic acid, fumaric acid or phthalic acid, with a hydroxy carboxy lie acid such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with an organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid.
  • Suitable salts with bases are typically metal salts such as alkali metal salts or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
  • metal salts such as alkali metal salts or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine typically ethylamine, diethylamine, triethylamine or dimethylpropylamine,
  • Corresponding inner salts may also be formed.
  • Agrochemically acceptable salts are preferred within the scope of this invention.
  • the compounds of formula I contain asymmetrical carbon atoms, then the compounds are obtained in optically active form. Owing to the presence of double bonds the compounds may be obtained in the [E] or [Z] form. Atropisomerism can also occur.
  • the invention relates not only to the pure is ⁇ mers, e.g. enantiomers and diastereoisomers, but also to all possible mixtures of isomers, e.g. mixtures of diastereoisomers, racemates or mixtures of racemates. Unless otherwise indicated, the general terms used throughout this specification have the following meanings:
  • Alkyl groups are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl or 3-hexyl.
  • Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl or but-2-en-1-yl.
  • Preferred alkenyl radials contain 3 to 4 carbon atoms in the chain.
  • Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl or but-1-yn-3-yI. The preferred meaning is propargyl.
  • Halogen and halo substituents will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings.
  • Haloalkyl can contain identical or different halogen atoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
  • halogen atoms typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
  • Alkoxy is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Methoxy and ethoxy are preferred.
  • Haloalkoxy is typically difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
  • Cycloalkyl depending on the size of the ring, is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
  • alkanoyl is straight-chain or branched and is typically formyl, acetyl, propionyl, butyryl or pivaloyl.
  • preferred compounds are:
  • R 1 and R 2 are each independently of the other C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl containing 1 to
  • R 1 and R 2 taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
  • R 3 and R 4 are each independently of the other hydrogen, C 1 -C 4 alkyl or halogen;
  • R 5 is hydrogen, C 1 -C 4 alkyl or methyl which is substituted by cyano, nitro, halogen, carboxyl, methoxycarbonyl or phenylsulfonyl;
  • R 6 and R 7 are each independently of the other hydrogen, halogen, C 1 -C 4 alkyl, halo- C 1 -C 4 - alkyl containing 1 to 5 halogen atoms, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy containing 1 to 5 halogen atoms, hydroxy or C 1 -C 4 aIkanoyl; and wherein
  • R 5 is hydrogen, C 1 -C 6 alkyl or benzyl.
  • R 1 and R 2 are each independently of the other C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl containing 1 to 5 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl,
  • C 1 -C 2 alkanoyl-C 1 -C 4 alkyl C 1 -C 2 alkoxycarbonyl-C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfinyl-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, halo- C 2 -C 4 alkenyl containing 1, 2 or 3 halogen atoms, C 2 -C 4 alkynyl, halo-C 2 -C 4 alkynyl containing 1, 2 or 3 halogen atoms, C 3 -C 7 cycloalkyl or halogen; or
  • R 1 and R 2 taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
  • R 3 and R 4 are each independently of the other hydrogen, C 1 -C 4 alkyl or halogen;
  • R 5 is hydrogen or C 1 -C 4 alkyl
  • R 6 and R 7 are each independently of the other hydrogen, halogen, C 1 -C 4 alkyl, haIo- C 1 -C 4 - alkyl containing 1 to 5 halogen atoms, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy containing 1 to 5 halogen atoms, hydroxy or C 1 -C 4 alkanoyl; and wherein X and Y have the given meanings.
  • R 1 is C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl containing 1 to 5 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 4 alkyl or C 3 -C 7 cycloalkyl;
  • R 2 is halogen
  • R 3 and R 4 are hydrogen
  • R 5 is hydrogen or C 1 -C 4 alkyl
  • X is a C 1 -C 3 chain which may contain a double bond or a triple bond and which is unsubstituted or substituted by C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, hydroxy or halogen.
  • R 1 is C 1 -C 4 alkyl, or C 3 -C 7 Cycloalkyl
  • R 2 is chloro or bromo
  • R 3 and R 4 is hydrogen
  • R 5 is hydrogen
  • X is a group of formula -CH 2 -, -CH(CH 3 )-, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )-,
  • Y is an isocyclic group of formulae (a), (b), (n), (o), (t), (u);
  • R 6 and R 7 are each independently of the other hydrogen, chloro, bromo, C 1 -C 2 alkyl, halomethyl containing 1 to 3 halogen atoms, C 1 -C 2 alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C 1 -C 2 alkanoyl.
  • Y is a heterocyclic group of formulae (c), (d), (f), (g), (h), (i), (j), (k), (l), (m), (p), (q), (r), (s), (v), (w), (x);
  • R 6 and R 7 are each independently of the other hydrogen, chloro, bromo, C 1 -C 2 alkyl, halomethyl containing 1 to 3 halogen atoms, C 1 -C 2 alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C 1 -C 2 alkanoyl.
  • Y is a group of formulae (a), (b), (c), (j) or (n);
  • R 6 and R 7 are each independently of the other hydrogen, halogen or C 1 -C 4 alkyl.
  • R 6 and R 7 are each independently of the other hydrogen, halogen or C 1 -C 4 alkyl.
  • R 1 is methyl or ethyl
  • X s a group of formula -CH 2 -.
  • R 10 and R 11 are each independently of the other hydrogen, or halogen
  • Y is a group of formulae (a) to (x); and, among these compounds, in particular those wherein
  • R 10 is hydrogen or chloro and R 11 is hydrogen, fluoro or chloro.
  • Suitable condensing agents are N,N-dicyclohexylcarbodiimide, phosphorus pentachloride, phosgene and thionyl chloride.
  • R 5 -L IV wherein R 5 is as defined for formula I, and L is a leaving group, e.g. a halogen, tosylate, mesylate or triflate, in a solvent, conveniently in DMF, THF, dioxane, dimethyl acetamide, dimethyl sulfoxide, tert-butylmethyl ether, in the presence of a base, e.g.
  • a compound of formula Y-CO-CH 3 (Na) is reacted with Tl 3+ in the presence of HClO 4 or with TI( ⁇ O 3 ) 3 on montmorillonite K-10 (TTN-K-10 reagent) in a suitable solvent, e.g. in an alcohol such as methanol, and subsequently hydrolysed (J. Med. Chem., Vol. 22, S. 1068 (1979); Synthesis, 1979, p. 481).
  • a compound of formula Y-CHO (Vb) is reacted with (CH 3 ) 2 N-CH[PO(OC 2 H5) 2 ] 2 and subsequently hydrolysed (Synth. Comm., Vol. 12, p. 415 (1982).
  • a compound of formula Y-CH 2 -Hal (Vc) is reacted with CN- and subsequently hydrolysed.
  • a compound of formula Y-NH 2 (Vd) is diazotised with an organic or inorganic nitrite, the diazo compound is reacted with an acrylate in the presence of CuCl, and the resultant compound is subsequently hydrolysed (Meerwein arylation).
  • the above described reactions are carried out in per se known manner, conveniently in the absence or in the presence of a suitable solvent or diluent or of a mixture thereof, and, as required, with cooling, at room temperature or with heating, suitably in the temperature range from c. -20°C to the boiling temperature of the reaction medium, preferably from c. -20°C to c. +150°C, and, if necessary, in a closed reactor under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers such as diethyl ether, tert-butylmethyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters such as ethyl acetate, or butyl acetate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide,
  • hexamethylphosphoric triamide nitriles such as acetonitrile
  • sulfoxides such as dimethyl sulfoxide.
  • Bases used in excess for example triethylamine, pyridine,
  • N-methylmorpholine or N,N-diethylaniline may also be used as solvents or diluents.
  • suitable bases are hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or alkaline earth metals, alkylamines, alkylenediamines, cycloalkylamines or N-alkylated and unsaturated or saturated cycloalkylamines, unsaturated or saturated basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Typical examples of such bases are sodium
  • hydroxide sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate and potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine,
  • cyclohexylamine N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyl trimethylammonium hydroxide as well as 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
  • DBU 1,8-diazabicyclo[5.4.0]undec-5-ene
  • reaction can be carried out under phase transfer catalysis in an organic solvent, e.g. methylene chloride or toluene, in the presence of an aqueous basic solution, e.g. sodium hydroxide solution, and of a phase transfer catalyst, e.g. tetrabutylammonium hydrogen sulfate.
  • organic solvent e.g. methylene chloride or toluene
  • a phase transfer catalyst e.g. tetrabutylammonium hydrogen sulfate.
  • N-(4-pyridyl)carboxamides as pesticides, inter alia from patent application WO 93/04580.
  • the compounds of formula I of this invention differ structurally from these compounds in characteristic manner.
  • the compounds of formula I can be used in agriculture and related fields as pest control agents for controlling plant pests. They are distinguished by their excellent activity at low concentrations, they are well tolerated by plants and are environmentally safe. They have very useful curative, preventive and, in particular, systemic properties, and can be used for protecting numerous cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests which occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which also grow later are protected from infestation, for example by phytopathogenic microorganisms.
  • the compounds of formula I can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungal infections as well as against phytopathogenic fungi which occur in the soil.
  • the compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); and Basidiomycetes (e.g. Rhizocotonia, Hemileia, Puccinia). They are also effective against the class of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia and Uncinula), and especially against that of the Oomycetes (e.g. Phytophthora, Pythium and Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria
  • Basidiomycetes e.g. Rhizocotonia, Hemileia, Puccinia
  • They are also effective against
  • the compounds of formula I are also useful pest control agents for controlling insects and/or acarina in crop plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry and in the storage and material protection sectors as well as in the hygiene sector, and for controlling pests of animals, especially on domestic animals and productive livestock.
  • the activity of the compounds of formula I may be observed in an immediate kill of the pests or sometime later, for example in moulting or in diminished oviposition and/or hatching rate.
  • the animal pests typically include those of the order Lepidoptera, Coleoptera, Orthoptera, Isoptera, Acarina (e.g. Boophilus spp.).
  • Target crops suitable for the plant protective utility disclosed herein typically comprise within the scope of the present invention the following species of plants:
  • cereals wheat, barley, rye, oats, rice, maize, sorghum and related species
  • beet sucgar beet and fodder beet
  • pomes drupes and soft fruit
  • leguminous plants beans, lentils, peas, soybeans
  • oil plants rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts
  • cucurbits cucumbers, marrows, melons
  • fibre plants cotton, flax, hemp, jute
  • citrus fruit oranges, lemons, grapefruit, mandarins
  • vegetables spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, sweet peppers
  • lauraceae avocados, cinnamon, camphor
  • plants such as tobacco, nuts, coffee, egg-plants, sugar cane, tea, pepper, vine
  • the compounds of formula I are usually applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
  • These further compounds can be fertilisers or micronutrient donors as well as other preparations that influence plant growth. It is also possible in this connection to use selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, together with optional carriers, surfactants or application-promoting adjuvants commonly employed in the art of formulation.
  • Suitable carriers and adjuvants may be solid or liquid and correspond to the appropriate substances ordinarily employed in formulation technology, including natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
  • a prefe ⁇ ed method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compound 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 granular formulations can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they 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 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.
  • Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare, preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha.
  • advantageous rates of application are from 10 mg to 1 g of active ingredient per kg of seeds.
  • compositions, preparations or mixtures containing the compound of formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, conveniently by homogeneously mixing and/or grinding the active ingredient with extenders, as with a solvent (mixture), a solid carrier and, in some cases,
  • surfactants are surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, the fractions containing 8 to 12 carbon atoms, typically xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins; also alcohols and glycols and their ethers and esters, such as ethanol, diethylene glycol,
  • 2-methoxyethanol or 2-ethoxyethanol ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyr ⁇ olidone, dimethyl sulfoxide or dimethyl formamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
  • the solid carriers typically used for dusts and dispersible powders are usually natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • highly dispersed silica or highly dispersed absorbent polymers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand.
  • a great number or pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood as comprising mixtures of surfactants.
  • Suitable anionic surfactants can be water-soluble soaps as well as water-soluble synthetic surface-active compounds.
  • nonionic surfactants are nonylphenolpolyethoxyethanols
  • polyethoxylated castor oil polyadducts of polypropylene and polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and
  • Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituents, at least one C 8 -C 22 alkyl radical and, as further substituents, optionally halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the agrochemical compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 % to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
  • compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other chemical agents to obtain special effects.
  • benzo[b]thiophen-2-ylacetic acid and 0.97 g (0.0046M) of N,N-dicyclohexylcarbodiimide (DCC) are stirred in 30 ml of absolute methylene chloride at 20-25° for 18 h under anhydrous conditions.
  • the reaction mixture is filtered and the methylene chloride is stripped off in a water-jet vacuum.
  • Wheat plants are sprayed to drip point 6 days after sowing with an aqueous spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound and infected 24 hours later with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95-100 % relative humidity at 20°C), the plants are stood at 22°C in a greenhouse. Evaluation of fungal infestation is made 12 days after infection. b) Systemic action
  • Wheat plants are drenched 5 days after sowing with an aqueous spray mixture (0.006 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of plants. After 48 hours, the plants are infected with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95-100 % relative humidity at 20°C), the plants are stood at 22°C in a greenhouse. Evaluation of fungal infestation is made 12 days after infection
  • Example B-2 Action against Phytophthora infestans on tomatoes
  • tomato plants are sprayed to drip point with a spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound.
  • the tomato plants are treated 24 hours later with a conidia suspension of the fungus. Evaluation of fungal infestation is made after the plants have been incubated for 5 days at 20°C and 90-100°C relative humidity.
  • tomato plants are drenched with an aqueous spray mixture (0.006 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of plants. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Evaluation of fungal infestation is made after the plants have been incubated for 5 days at 20°C and 90-100°C relative humidity.
  • Example B-3 Residual-protective action against Cercospora arachidicola on groundnut plants
  • Groundnut plants 10-15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 48 hours later with a conidia suspension of the fungus.
  • the infected plants are incubated for 72 hours at c. 21°C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.
  • Example B-4 Action against Plasmopara viticola on vines
  • Vine seedlings in the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 24 hours later with a sporangia suspension of the fungus.
  • aqueous spray mixture (0.02 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 24 hours later with a sporangia suspension of the fungus.
  • Example B-5 Action against Colletotrichum lagenarium on cucumbers
  • Cucumber plants are sprayed with an aqueous spray mixture (0.002 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 2 days later with a spore suspension (1.5x10 5 spores/ml) of the fungus and incubated for 36 hours at 23°C and high humidity Incubation is then continued at normal humidity and c. 22°C. Evaluation of fungal infestation is made 8 days after infection.
  • Example B-6 Residual protective action against Nenturia inaequalis on apple shoots
  • Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with a spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound.
  • the plants are infected 24 hours later with a conidia suspension of the fungus.
  • the plants are then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20-24°C. Scab infestation is evaluated 12 days after infection.
  • Barley plants about 8 cm in height are sprayed to drip point with a spray mixture
  • Barley plants about 8 cm in height are drenched with an aqueous spray mixture (0.002 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of the plants.
  • the treated plants are dusted 48 hours later with conidia of the fungus.
  • the infected plants are then stood in a greenhouse at c. 22°C and evaluation of infestation is made 12 days after infection.
  • Example B8 Action against Podosphaera leucotricha on apple shoots
  • Apple cuttings with c. 15 cm fresh shoots are sprayed with a spray mixture (0.06 % a.i.) of the test compound.
  • the plants are infected 24 hours later with a conidia suspension of the fungus and then stood in a humidity chamber at 70 % relative humidity at 20°C. Fungus infestation is evaluated 12 days after infection.
  • Example B-9 Action against Nilaparvata lugens
  • Rice plants are treated with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm. When the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stage. Evaluation is made 21 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.
  • Example B-10 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm.
  • the cabbage plants are populated with 10 caterpillars of Plutella xylostella in the 3rd stage and placed in a plastic container. Evaluation is made 3 days later. The percentage reduction of the population and of feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.
  • Example B-11 Action against Musca domestica
  • a sugar lump is moistened with a solution of the test compound such that, after drying overnight, the concentration of test compound in the sugar is 250 ppm.
  • the treated sugar lump is placed in an aluminium dish together with a most cotton wool swab and 10 adult
  • Musca domestica of an OP-resistent strain The dish is then covered with a glass beaker and incubated at 25°C. The mortality rate is determined 24 hours later.
  • Example B-12 Action against Tetranychus urticae
  • Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed 1 day later with an aqueous emulsion spray formulation containing 400 ppm of test compound. The plants are then incubated for 6 days at 25°C and afterwards evaluated.
  • the percentage reduction in the population is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.
  • Example B-13 Action against a mixed population of Tetranychus cinnabarinus
  • Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs,
  • test compounds are sprayed on to the plants 24 hours after infection at rates of 200, 100, 50 mg a.i./litre in an automatic spray cabinet.
  • the test compounds are formulated and diluted with water to the appropriate concentrations. The test is evaluated for the percentage kill of eggs, larvae/nymphs and adults 2 and 7 days after application.
  • Replete adult female ticks are fixed with adhesive tape to a PVC sheet and covered with a cotton wool swab.
  • the test organisms are then treated by impregnating the cotton wool swab with 10 ml of an aqueous solution containing the test compound in a concentration of 125 ppm.
  • the cotton wool swab is then removed and the ticks are incubated for

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Abstract

The invention relates to compounds of formula (I) wherein: R1 and R2 are each independently of the other C1-C¿6alkyl, halo-C¿1?-C6alkyl containing 1-5 halogen atoms, C1-C¿2alkoxy-C¿1?-C6alkyl, nitro-C1-C6alkyl, cyano-C1-C6alkyl, C1-C2alkanoyl-C1-C6alkyl, C1-C2alkoxycarbonyl-C1-C6alkyl, C1-C2alkylthio-C1-C6alkyl,C1-C2alkanesulfinyl-C1-C6alkyl, C1-C2alkanesulfonyl-C1-C6alkyl, C2-C6alkenyl, halo-C2-C6alkenyl containing 1-5 halogen atoms, C2-C6alkynyl, halo-C2-C6alkynyl containing 1-5 halogen atoms, C3-C7cycloalkyl or halogen; or R1 and R2, taken together, form a saturated or unsaturated 5- to 7-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S; R3 and R4 are each independently of the other hydrogen, C1-C6alkyl or halogen; R5 is hydrogen, C1-C6alkyl which is unsubstituted or substituted by cyano, nitro, halogen, carboxyl, C1-C2alkoxycarbonyl, C1-C2alkanoyl, C1-C2alkanesulfonyl or phenylsulfonyl, C2-C6alkenyl, C2-C6alkynyl or benzyl; X is a C1-C5chain which may contain one or two double bonds, one or two triple bonds as well as one or two hetero atoms selected from O, S and N, and which are unsubstituted or substituted by C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms, C2-C4alkenyl, halo-C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl, hydroxy or halogen; Y is a group of formulae (a) to (x); R6 and R7 are each independently of the other hydrogen, halogen, C1-C6alkyl, halogen-C1-C6alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy-C1-C6alkyl, C1-C6alkoxy, halo-C1-C6alkoxy containing 1 to 5 halogen atoms, C1-C6alkylthio, C1-C6alkanesulfinyl, C1-C6alkanesulfonyl, phenyl, benzyl, phenoxy, phenylthio, hydroxy, mercapto, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl. The compounds are agrochemical control agents and are suitable for pest control.

Description

PESTICIDAL PYRIDINE DERIVATIVES The present invention relates to novel pesticidal compounds of formula I
Figure imgf000003_0001
wherein:
R1 and R2 are each independently of the other C1-C6alkyl, halo- C1-C6alkyl containing 1 to
5 halogen atoms, C1-C2alkoxy- C1-C6alkyl, nitro- C1-C6alkyl, cyano-C1-C6alkyl,
C1-C2alkanoyl-C1-C6alkyl, C1-C2alkoxycarbonyl-C1-C6alkyl, C1-C2alkylthio-C1-C6alkyl,
C1-C2alkanesulfinyl-C1-C6alkyl, C1-C2alkanesulfonyl- C1-C6alkyl, C2-C6alkenyl, halo-
C2-C6alkenyl containing 1-5 halogen atoms, C2-C6alkynyl, halo-C2-C6alkynyl containing
1-5 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 5- to 7-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
R3 and R4 are each independently of the other hydrogen, C1-C6alkyl or halogen;
R5 is hydrogen, C1-C6alkyl which is unsubstituted or substituted by cyano, nitro, halogen, carboxyl, C1-C2alkoxycarbonyl, C1-C2alkanoyl, C1-C2alkaπesulfonyl or phenylsulfonyl,
C2-C6alkenyl, C2-C6alkynyl or benzyl;
X is a C1-C5chain which may contain one or two double bonds, one or two triple bonds as well as one or two hetero atoms selected from O, S and N, and which are unsubstituted or substituted by C1-C4alkyl, halo- C1-C4alkyl containing 1 to 5 halogen atoms,
C2-C4alkenyl, halo-C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl,
C3-C7cycloalkyl, hydroxy or halogen;
Y is a group of formulae (a) to (x);
Figure imgf000004_0001
R6 and R7 are each independently of the other hydrogen, halogen, C1-C6alkyl,
halo-C1-C6alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy- C1-C6alkyl, C1-C6alkoxy, halo-C1-C6alkoxy containing 1 to 5 halogen atoms, C1-C6alkylthio, C1-C6alkanesulfinyl, C1-C6alkanesulfonyl, phenyl, benzyl, phenoxy, phenylthio, hydroxy, mercapto, nitro, cyano, C1-C4alkanoyl, halo- C1-C4alkanoyl or C1-C4alkoxycarbonyl;
or, whenever obtained, a tautomer thereof in the free form or in salt form.
The invention further relates to the preparation of these compounds, to agrochemical compositions comprising at least one of said compounds as active ingredient, and to the use of said compounds or compositions for pest control, preferably as microbicides, insecticides and acaricides in agriculture and horticulture.
The compounds of formula I and their possible tautomers may be obtained in salt form. As the compounds of formula I contain at least at least one basic centre, they may typically form acid addition salts. These salts may conveniently be formed with a mineral acid such as sulfuric acid, a phosphoric acid or a hydrohalic acid, with an organic carboxylic acid such as acetic acid, oxalic acid, malonic acid, fumaric acid or phthalic acid, with a hydroxy carboxy lie acid such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with an organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid.
Compounds of formula I having at least one acidic group can also form salts with bases. Suitable salts with bases are typically metal salts such as alkali metal salts or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
Corresponding inner salts may also be formed. Agrochemically acceptable salts are preferred within the scope of this invention.
If the compounds of formula I contain asymmetrical carbon atoms, then the compounds are obtained in optically active form. Owing to the presence of double bonds the compounds may be obtained in the [E] or [Z] form. Atropisomerism can also occur. The invention relates not only to the pure isσmers, e.g. enantiomers and diastereoisomers, but also to all possible mixtures of isomers, e.g. mixtures of diastereoisomers, racemates or mixtures of racemates. Unless otherwise indicated, the general terms used throughout this specification have the following meanings:
Alkyl groups are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl or 3-hexyl.
Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Preferred alkenyl radials contain 3 to 4 carbon atoms in the chain.
Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl or but-1-yn-3-yI. The preferred meaning is propargyl.
Halogen and halo substituents will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings.
Haloalkyl can contain identical or different halogen atoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
Alkoxy is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Methoxy and ethoxy are preferred.
Haloalkoxy is typically difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
Cycloalkyl, depending on the size of the ring, is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
Depending on the number of carbon atoms comprised in the particular case, alkanoyl is straight-chain or branched and is typically formyl, acetyl, propionyl, butyryl or pivaloyl. Within the scope of this invention, preferred compounds are:
(1) Compounds of formula I, wherein
R1 and R2 are each independently of the other C1-C4alkyl, halo-C1-C4alkyl containing 1 to
5 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl,
C1-C2alkanoyl-C1-C4alkyl, C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl,
C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo-
C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl, halo-C2-C4alkynyl containing 1, 2 or 3 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or halogen;
R5 is hydrogen, C1-C4alkyl or methyl which is substituted by cyano, nitro, halogen, carboxyl, methoxycarbonyl or phenylsulfonyl;
R6 and R7 are each independently of the other hydrogen, halogen, C1-C4alkyl, halo- C1-C4- alkyl containing 1 to 5 halogen atoms, C1-C4alkoxy, halo-C1-C4alkoxy containing 1 to 5 halogen atoms, hydroxy or C1-C4aIkanoyl; and wherein
X and Y have the given meanings.
(2) Among the compounds described in (1), those compounds wherein:
R5 is hydrogen, C1-C6alkyl or benzyl.
(3) Compounds of formula I, wherein;
R1 and R2 are each independently of the other C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy- C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl,
C1-C2alkanoyl-C1-C4alkyl, C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl, halo-C2-C4alkynyl containing 1, 2 or 3 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S; R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or halogen;
R5 is hydrogen or C1-C4alkyl;
R6 and R7 are each independently of the other hydrogen, halogen, C1-C4alkyl, haIo- C1-C4- alkyl containing 1 to 5 halogen atoms, C1-C4alkoxy, halo-C1-C4alkoxy containing 1 to 5 halogen atoms, hydroxy or C1-C4alkanoyl; and wherein X and Y have the given meanings.
(4) Among the compounds of formula I described in (3), those compounds wherein:
R1 is C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy- C1-C4alkyl or C3-C7cycloalkyl;
R2 is halogen;
R3 and R4 are hydrogen;
R5 is hydrogen or C1-C4alkyl;
X is a C1-C3chain which may contain a double bond or a triple bond and which is unsubstituted or substituted by C1-C4alkyl, C3-C7cycloalkyl, hydroxy or halogen.
(5) Among the compounds of formula I described in (4), those compounds wherein:
R1 is C1-C4alkyl, or C3-C7Cycloalkyl
R2 is chloro or bromo;
R3 and R4 is hydrogen;
R5 is hydrogen;
X is a group of formula -CH2-, -CH(CH3)-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-,
-CH(CH3)CH2-, -CH=CH-, CH=CH-CH2 or CH2-CH=CH-.
(6) Compounds of formula I, wherein:
Y is an isocyclic group of formulae (a), (b), (n), (o), (t), (u);
R6 and R7 are each independently of the other hydrogen, chloro, bromo, C1-C2alkyl, halomethyl containing 1 to 3 halogen atoms, C1-C2alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C1-C2alkanoyl.
(7) Compounds of formula I, wherein:
Y is a heterocyclic group of formulae (c), (d), (f), (g), (h), (i), (j), (k), (l), (m), (p), (q), (r), (s), (v), (w), (x);
R6 and R7 are each independently of the other hydrogen, chloro, bromo, C1-C2alkyl, halomethyl containing 1 to 3 halogen atoms, C1-C2alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C1-C2alkanoyl.
(8) Among the compounds of formula I described in (1), those compounds wherein:
Y is a group of formulae (a), (b), (c), (j) or (n);
R6 and R7 are each independently of the other hydrogen, halogen or C1-C4alkyl. (9) Among the compounds of formula I described in (3), those compounds wherein: X is a group of formula -CH2-, -CH2CH2-, -CH2CH2CH2- or -CH=CH- ;
R6 and R7 are each independently of the other hydrogen, halogen or C1-C4alkyl.
(10) Among the compounds of formula I described in (9), those compounds wherein:
R1 is methyl or ethyl;
X s a group of formula -CH2-.
(11) Compounds of formula 1.5
Figure imgf000009_0001
wherein:
R10 and R11 are each independently of the other hydrogen, or halogen;
Y is a group of formulae (a) to (x); and, among these compounds, in particular those wherein
R10 is hydrogen or chloro and R11 is hydrogen, fluoro or chloro.
The compounds of formula I can be prepared as follows:
A compound of formula II
Y-X-COOH II or the acid halide thereof, wherein X and Y are as defined for formula I, is reacted with a compound of formula III
Figure imgf000010_0001
wherein R1 to R5 have the meanings given for formula I, in the absence or in the presence of a suitable condensing agent and/or of a base, to give a compound of formula I.
Illustrative examples of suitable condensing agents are N,N-dicyclohexylcarbodiimide, phosphorus pentachloride, phosgene and thionyl chloride.
It is also posssible to prepare compounds of formula I, wherein R5 has the given meanings, but is not hydrogen, by reacting a compound of formula la
Figure imgf000010_0002
wherein R1 to R4, X and Y have the meanings given for formula I, with a compound of formula IV
R5-L IV, wherein R5 is as defined for formula I, and L is a leaving group, e.g. a halogen, tosylate, mesylate or triflate, in a solvent, conveniently in DMF, THF, dioxane, dimethyl acetamide, dimethyl sulfoxide, tert-butylmethyl ether, in the presence of a base, e.g.
sodium hydride, potassium hydride, potassium tert-butylate, sodium methylate, triethylamine, pyridine, potassium carbonate.
Depending on the significance of X, compounds of formula II can be prepared as follows:
(1) Compounds of formula Y-CH2-COOH (II.1), wherein Y has the meanings given for formula I: a) A compound of formula Y-CO-CH3 (Na) is reacted with S/morpholine or with ammonium polysulfide solution and subsequently hydrolised. (Willgerodt or
Willgerodt-Kindler reaction). b) A compound of formula Y-CO-CH3 (Na) is reacted with Tl3+ in the presence of HClO4 or with TI(ΝO3)3 on montmorillonite K-10 (TTN-K-10 reagent) in a suitable solvent, e.g. in an alcohol such as methanol, and subsequently hydrolysed (J. Med. Chem., Vol. 22, S. 1068 (1979); Synthesis, 1979, p. 481). c) A compound of formula Y-CHO (Vb) is reacted with (CH3)2N-CH[PO(OC2H5)2]2 and subsequently hydrolysed (Synth. Comm., Vol. 12, p. 415 (1982). d) A compound of formula Y-CH2-Hal (Vc) is reacted with CN- and subsequently hydrolysed.
(2) Compounds of formula Y-CH=CH-COOH (II.2), wherein Y has the meanings given for formula I are prepared as follows:
A compound of formula Y-NH2 (Vd) is diazotised with an organic or inorganic nitrite, the diazo compound is reacted with an acrylate in the presence of CuCl, and the resultant compound is subsequently hydrolysed (Meerwein arylation).
(3) Compounds of formula Y-CH2-CH2-COOH (II.3), wherein Y has the meanings given for formula I:
by catalytic hydrogenation of a compound of formula Y-CH=CH-COOH (II.2).
[Arzneimittel Forsch. Vol.30, p. 454 (1980)].
(4) Compounds of formula Y-CH2CH2CH2-COOH (II.4), wherein Y has the meanings given for formula I: a compound of formula Y-H (Ve) is acylated with succinic anhydride in the presence of AlCl3 to give a compound of formula Y-CO-CH2CH2-COOH (II.5 ) and subsequently reduced with hydrazine hydrate (Arzneimittel Forsch. Vol.30, p. 454 (1980).
Compounds of formula III are known, e.g. from J. Med. Chem. 1989, 32, 1970-77, and can be prepared by the methods described therein.
The above described reactions are carried out in per se known manner, conveniently in the absence or in the presence of a suitable solvent or diluent or of a mixture thereof, and, as required, with cooling, at room temperature or with heating, suitably in the temperature range from c. -20°C to the boiling temperature of the reaction medium, preferably from c. -20°C to c. +150°C, and, if necessary, in a closed reactor under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Illustrative examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers such as diethyl ether, tert-butylmethyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters such as ethyl acetate, or butyl acetate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or
hexamethylphosphoric triamide; nitriles such as acetonitrile; and sulfoxides such as dimethyl sulfoxide. Bases used in excess, for example triethylamine, pyridine,
N-methylmorpholine or N,N-diethylaniline, may also be used as solvents or diluents. Illustrative examples of suitable bases are hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or alkaline earth metals, alkylamines, alkylenediamines, cycloalkylamines or N-alkylated and unsaturated or saturated cycloalkylamines, unsaturated or saturated basic heterocycles, ammonium hydroxides and carbocyclic amines. Typical examples of such bases are sodium
hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate and potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine,
cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyl trimethylammonium hydroxide as well as 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
Alternatively, the reaction can be carried out under phase transfer catalysis in an organic solvent, e.g. methylene chloride or toluene, in the presence of an aqueous basic solution, e.g. sodium hydroxide solution, and of a phase transfer catalyst, e.g. tetrabutylammonium hydrogen sulfate.
It is already known to use N-(4-pyridyl)carboxamides as pesticides, inter alia from patent application WO 93/04580. The compounds of formula I of this invention differ structurally from these compounds in characteristic manner. The compounds of formula I can be used in agriculture and related fields as pest control agents for controlling plant pests. They are distinguished by their excellent activity at low concentrations, they are well tolerated by plants and are environmentally safe. They have very useful curative, preventive and, in particular, systemic properties, and can be used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests which occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which also grow later are protected from infestation, for example by phytopathogenic microorganisms.
The compounds of formula I can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungal infections as well as against phytopathogenic fungi which occur in the soil.
The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); and Basidiomycetes (e.g. Rhizocotonia, Hemileia, Puccinia). They are also effective against the class of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia and Uncinula), and especially against that of the Oomycetes (e.g. Phytophthora, Pythium and Plasmopara).
The compounds of formula I are also useful pest control agents for controlling insects and/or acarina in crop plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry and in the storage and material protection sectors as well as in the hygiene sector, and for controlling pests of animals, especially on domestic animals and productive livestock. The activity of the compounds of formula I may be observed in an immediate kill of the pests or sometime later, for example in moulting or in diminished oviposition and/or hatching rate.
The animal pests typically include those of the order Lepidoptera, Coleoptera, Orthoptera, Isoptera, Acarina (e.g. Boophilus spp.).
Target crops suitable for the plant protective utility disclosed herein typically comprise within the scope of the present invention the following species of plants:
cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species), beet (sugar beet and fodder beet), pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, gooseberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucurbits (cucumbers, marrows, melons), fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, sweet peppers), lauraceae (avocados, cinnamon, camphor), and plants such as tobacco, nuts, coffee, egg-plants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds of formula I are usually applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These further compounds can be fertilisers or micronutrient donors as well as other preparations that influence plant growth. It is also possible in this connection to use selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, together with optional carriers, surfactants or application-promoting adjuvants commonly employed in the art of formulation.
Suitable carriers and adjuvants may be solid or liquid and correspond to the appropriate substances ordinarily employed in formulation technology, including natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
A prefeπed method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, 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 compound 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 granular formulations can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation of the fungicide or coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they 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 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.
Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare, preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. For use as seed dressing agents, advantageous rates of application are from 10 mg to 1 g of active ingredient per kg of seeds.
The formulations, i.e. the compositions, preparations or mixtures containing the compound of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, conveniently by homogeneously mixing and/or grinding the active ingredient with extenders, as with a solvent (mixture), a solid carrier and, in some cases,
surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, the fractions containing 8 to 12 carbon atoms, typically xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins; also alcohols and glycols and their ethers and esters, such as ethanol, diethylene glycol,
2-methoxyethanol or 2-ethoxyethanol, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrτolidone, dimethyl sulfoxide or dimethyl formamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers typically used for dusts and dispersible powders are usually natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly dispersed silica or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number or pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be water-soluble soaps as well as water-soluble synthetic surface-active compounds.
Typical examples of nonionic surfactants are nonylphenolpolyethoxyethanols,
polyethoxylated castor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and
octylphenoxypolyethoxyethanol.
Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituents, at least one C8-C22alkyl radical and, as further substituents, optionally halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
Further surfactants customarily employed in formulation technology are familiar to those skilled in the art or may be found in the relevant literature.
The agrochemical compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 % to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally use dilute formulations.
The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other chemical agents to obtain special effects.
The invention is illustrated in more detail by the following non-limitative Examples. The following abbreviations are used: Ac = acetyl; Et = ethyl; i-Pr = isopropyl; Me = methyl; Ph = phenyl; Pr = n-propyl; Bu = n-butyl; m.p. = melting point. DS = diastereoisomer; Reg = regioisomer. "NMR" stands for "nuclear magnetic resonance spectrum". MS = mass spectrum. "%" stands for "percent by weight", unless another concentration in another unit is indicated.
Preparation of the compounds of the invention
Example P-1 (compound 1.9)
2-(Benzo[b]thiophen-2-yl)-N-(3-chloro-2-methylpyridin-4-yl)acetamide
Figure imgf000017_0001
0.71 g (0.005M) of 4-amino-3-chloro-2-methylpyridine, 0.96 g (0.005M) of
benzo[b]thiophen-2-ylacetic acid and 0.97 g (0.0046M) of N,N-dicyclohexylcarbodiimide (DCC) are stirred in 30 ml of absolute methylene chloride at 20-25° for 18 h under anhydrous conditions. The reaction mixture is filtered and the methylene chloride is stripped off in a water-jet vacuum. The residue is purified by column chromatography over silica gel (eluant: ethyl acetate/toexane 1:1), affording 1.1 g of 2-(benzo[b]thiophen- 2-yl)-N-(3-chloro-2-methylpyridin-4-yl)acetamide as a yellow powder with a melting point of 150-152°C.
The compounds listed in the following Table can be prepared in analogous manner.
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Biological Examples: A Microbicidal activity
B-1: Action against Puccinia graminis in wheat
a) Residual protective action
Wheat plants are sprayed to drip point 6 days after sowing with an aqueous spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound and infected 24 hours later with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95-100 % relative humidity at 20°C), the plants are stood at 22°C in a greenhouse. Evaluation of fungal infestation is made 12 days after infection. b) Systemic action
Wheat plants are drenched 5 days after sowing with an aqueous spray mixture (0.006 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of plants. After 48 hours, the plants are infected with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95-100 % relative humidity at 20°C), the plants are stood at 22°C in a greenhouse. Evaluation of fungal infestation is made 12 days after infection
Example B-2: Action against Phytophthora infestans on tomatoes
a) Residual-protective action
After a growth period of 3 weeks, tomato plants are sprayed to drip point with a spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound. The tomato plants are treated 24 hours later with a conidia suspension of the fungus. Evaluation of fungal infestation is made after the plants have been incubated for 5 days at 20°C and 90-100°C relative humidity.
b) Systemic action
After a growth period of 3 weeks, tomato plants are drenched with an aqueous spray mixture (0.006 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of plants. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Evaluation of fungal infestation is made after the plants have been incubated for 5 days at 20°C and 90-100°C relative humidity.
Compounds of the Tables, in particular compounds 1.1, 1.5, 1.6, 1.9, 1.23,1.50, 1.53, 5.2, 5.45.10, 5.11, 5.14, 5.15, 5.21 show good activity. Example B-3: Residual-protective action against Cercospora arachidicola on groundnut plants
Groundnut plants 10-15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at c. 21°C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.
Compounds of the tables show good activity.
Example B-4: Action against Plasmopara viticola on vines
Vine seedlings in the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 24 hours later with a sporangia suspension of the fungus.
Evaluation of fungal infestation is made after the plants have been incubated for 6 days at
20°C and 95-100°C relative humidity.
Compounds of the tables, in particular compounds 1.1, 1.20, 1.23, 1.26, 1.50, 1.53, 1.53,
5.10, 5.11, 5.12, 5.22, 5.23 show good activity.
Example B-5: Action against Colletotrichum lagenarium on cucumbers
Cucumber plants are sprayed with an aqueous spray mixture (0.002 ppm a.i.) prepared from a wettable powder formulation of the test compound and infected 2 days later with a spore suspension (1.5x105 spores/ml) of the fungus and incubated for 36 hours at 23°C and high humidity Incubation is then continued at normal humidity and c. 22°C. Evaluation of fungal infestation is made 8 days after infection.
Compounds of the tables show good activity.
Example B-6: Residual protective action against Nenturia inaequalis on apple shoots
Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with a spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20-24°C. Scab infestation is evaluated 12 days after infection.
Compounds of the tables, in particular compounds 1.1, 1.5, 1.6, 1.9, 1.23,1.50, 1.53, 5.2, 5.45.10, 5.11, 5.14, 5.15, 5.21 show good activity. Example B7: Action against Erysiphe graminis on barley
a) Residual protective action
Barley plants about 8 cm in height are sprayed to drip point with a spray mixture
(0.02 % a.i.) prepared from a wettable powder formulation of the test compound and the treated plants are dusted with conidia of the fungus 3 to 4 hours later. The infected plants are stood in a greenhouse at c. 22°C and fungus infestation is evaluated 10 days after infection. Compounds of the tables, in particular compounds 1.1, 1.5, 1.6, 1.9, 1.23,1.50, 1.53, 5.2, 5.45.10, 5.11, 5.14, 5.15, 5.21 show good activity. b) Systemic action
Barley plants about 8 cm in height are drenched with an aqueous spray mixture (0.002 % a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come in contact with the growing parts of the plants. The treated plants are dusted 48 hours later with conidia of the fungus. The infected plants are then stood in a greenhouse at c. 22°C and evaluation of infestation is made 12 days after infection.
Compounds of the tables show good activity.
Example B8: Action against Podosphaera leucotricha on apple shoots
Apple cuttings with c. 15 cm fresh shoots are sprayed with a spray mixture (0.06 % a.i.) of the test compound. The plants are infected 24 hours later with a conidia suspension of the fungus and then stood in a humidity chamber at 70 % relative humidity at 20°C. Fungus infestation is evaluated 12 days after infection.
Compounds of the tables show good activity.
Biological Examples: B Insecticidal activity
Example B-9: Action against Nilaparvata lugens
Rice plants are treated with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm. When the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stage. Evaluation is made 21 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.
The compounds of the tables effect a more than 90 % kill. Example B-10: Action against Plutella xylostella caterpillars
Young cabbage plants are sprayed with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm. When the spray coating has dried, the cabbage plants are populated with 10 caterpillars of Plutella xylostella in the 3rd stage and placed in a plastic container. Evaluation is made 3 days later. The percentage reduction of the population and of feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.
Compounds of the tables show good activity.
Example B-11: Action against Musca domestica
A sugar lump is moistened with a solution of the test compound such that, after drying overnight, the concentration of test compound in the sugar is 250 ppm. The treated sugar lump is placed in an aluminium dish together with a most cotton wool swab and 10 adult
Musca domestica of an OP-resistent strain. The dish is then covered with a glass beaker and incubated at 25°C. The mortality rate is determined 24 hours later.
Compounds of the tables, in particular compounds 1.1, 1.5, 1.6, 1.9, 1.23,1.50, 1.53, 5.2,
5.45.10, 5.11, 5.14, 5.15, 5.21 show good activity.
Biological Examples C: Acaracidal activity
Example B-12: Action against Tetranychus urticae
Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed 1 day later with an aqueous emulsion spray formulation containing 400 ppm of test compound. The plants are then incubated for 6 days at 25°C and afterwards evaluated.
The percentage reduction in the population (percentage kill) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.
Compounds of the tables show good activity.
Example B-13: Action against a mixed population of Tetranychus cinnabarinus
Dilution series
Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs,
larvae/nymphs, adults) of an OP-tolerant strain of Tetranychus cinnabarinus. The test compounds are sprayed on to the plants 24 hours after infection at rates of 200, 100, 50 mg a.i./litre in an automatic spray cabinet. The test compounds are formulated and diluted with water to the appropriate concentrations. The test is evaluated for the percentage kill of eggs, larvae/nymphs and adults 2 and 7 days after application.
Compounds of the tables effect over 70 % kill in dilutions up to 50 mg a.L/litre.
Example B-14: Action against Boophilus microplus
Replete adult female ticks are fixed with adhesive tape to a PVC sheet and covered with a cotton wool swab. The test organisms are then treated by impregnating the cotton wool swab with 10 ml of an aqueous solution containing the test compound in a concentration of 125 ppm. The cotton wool swab is then removed and the ticks are incubated for
4 weeks for oviposition. The action is observed as kill or sterility of the females or takes the form of ovicidal action against the eggs.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000051_0001
wherein:
R1 and R2 are each independently of the other C1-C6alkyl, halo-C1-C6alkyl containing 1 to
5 halogen atoms, C1-C2alkoxy-C1-C6alkyl, nitro-C1-C6alkyl, cyano-C1-C6alkyl,
C1-C2alkanoyl-C1-C6alkyl, C1-C2alkoxycarbonyl-C1-C6alkyl, C1-C2alkylthio-C1-C6alkyl, C1-C2alkanesulfinyl-C1-C6alkyl, C1-C2alkanesulfonyl-C1-C6alkyl, C2-C6alkenyl, halo-
C2-C6alkenyl containing 1-5 halogen atoms, C2-C6alkynyl, halo-C2-C6alkynyl containing
1-5 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 5- to 7-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
R3 and R4 are each independently of the other hydrogen, C1-C6alkyl or halogen;
R5 is hydrogen, C1-C6alkyl which is unsubstituted or substituted by cyano, nitro, halogen, carboxyl, C1-C2alkoxycarbonyl, C1-C2alkanoyl, C1-C2alkanesulfonyl or phenylsulfonyl,
C2-C6alkenyl, C2-C6alkynyl or benzyl;
X is a C1-C5chain which may contain one or two double bonds, one or two triple bonds as well as one or two hetero atoms selected from O, S and N, and which is unsubstituted or substituted by C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms,
C2-C4alkenyl, halo-C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl,
C3-C7cycloalkyl, hydroxy or halogen;
Y is a group of formulae (a) to (x);
Figure imgf000052_0001
R6 and R7 are each independently of the other hydrogen, halogen, C1-C6alkyl,
halo-C1-C6alkyI containing 1 to 5 halogen atoms, C1-C2alkoxy-C1-C6alkyl, C1-C6alkoxy, halo-C1-C6alkoxy containing 1 to 5 halogen atoms, C1-C6alkylthio, C1-C6alkanesulfinyl, C1-C6alkanesulfonyl, phenyl, benzyl, phenoxy, phenylthio, hydroxy, mercapto, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl;
or, whenever obtained, a tautomer thereof in the free form or in salt form.
2. A compound according to claim 1, wherein
R1 and R2 are each independently of the other C1-C4alkyl, halo-C1-C4alkyl containing 1 to
5 halogen atoms, C1-C2alkoxy- C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl,
C1-C2alkanoyl- C1-C4alkyl, C1-C2alkoxycarbonyl- C1-C4alkyl, C1-C2alkylthio- C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4 alkenyl, halo-
C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl, halo-C2-C4alkynyl containing 1, 2 or 3 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S;
R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or halogen;
R5 is hydrogen, C1-C4alkyl or methyl which is substituted by cyano, nitro, halogen, carboxyl, methoxycarbonyl or phenylsulfonyl;
R6 and R7 are each independently of the other hydrogen, halogen, C1-C4alkyl, halo-C1-C4- alkyl containing 1 to 5 halogen atoms, C1-C4alkoxy, halo-C1-C4alkoxy containing 1 to 5 halogen atoms, hydroxy or C1-C4alkanoyl; and wherein
X and Y have the given meanings.
3. A compound according to claim 1, wherein:
R5 is hydrogen, C1-C6alkyl or benzyl.
4. A compound according to claim 1, wherein;
R1 and R2 are each independently of the other C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl,
C1-C2alkanoyl-C1-C4alkyl, C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl containing 1, 2 or 3 halogen atoms, C2-C4alkynyl, halo-C2-C4alkynyl containing 1, 2 or 3 halogen atoms, C3-C7cycloalkyl or halogen; or
R1 and R2, taken together, form a saturated or unsaturated 6-membered carbocyclic or heterocyclic ring which may contain one or two hetero atoms selected from O and S; R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or halogen;
R5 is hydrogen or C1-C4alkyl;
R6 and R7 are each independently of the other hydrogen, halogen, C1-C4alkyl, halo-C1-C4- alkyl containing 1 to 5 halogen atoms, C1-C4alkoxy, halo-C1-C4alkoxy containing 1 to 5 halogen atoms, hydroxy or C1-C4alkanoyl; and wherein
X and Y have the given meanings.
5. A compound according to claim 4, wherein:
R1 is C1-C4alkyl, halo-C1-C4alkyl containing 1 to 5 halogen atoms, C1-C2alkoxy- C1-C4alkyl or C3-C7cycloalkyl;
R2 is halogen;
R3 and R4 are hydrogen;
R5 is hydrogen or C1-C4alkyl;
X is a C1-C3chain which may contain a double bond or a triple bond and which is unsubstituted or substituted by C1-C4alkyl, C3-C7cycloalkyl, hydroxy or halogen.
6. A compound according to claim 5, wherein:
R1 is C1-C4alkyl, or C3-C7cycloalkyl
R2 is chloro or bromo;
R3 and R4 is hydrogen;
R5 is hydrogen;
X is a group of formula -CH2-, -CH(CH3)-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-,
-CH(CH3)CH2-, -CH=CH-, CH=CH-CH2 or CH2-CH=CH-.
7. A compound according to claim 1, wherein:
Y is an isocyclic group of formula (a), (b), (n), (o), (t) or (u);
R6 and R7 are each independently of the other hydrogen, chloro, bromo, C1-C2alkyl, halomethyl containing 1 to 3 halogen atoms, C1-C2alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C1-C2alkanoyl.
8. A compound according to claim 1, wherein:
Y is a heterocyclic group of formula (c), (d), (f), (g), (h), (i), (j), (k), (l), (m), (p), (q), (r), (s), (v), (w) or (x);
R6 and R7 are each independently of the other hydrogen, chloro, bromo, C1-C2alkyl, halomethyl containing 1 to 3 halogen atoms, C1-C2alkoxy, halomethoxy containing 1 to 3 halogen atoms, haloethoxy containing 1 to 4 halogen atoms, or C1-C2alkanoyl.
9. A compound according to claim 4, wherein:
Y is a group of formula (a), (b), (c), (j) or (n);
R6 and R7 are each independently of the other hydrogen, halogen or C1-C4alkyl.
10. A compound according to claim 6, wherein:
X is a group of formula -CH2-, -CH2CH2-, -CH2CH2CH2- or -CH=CH- ;
R6 and R7 are each independently of the other hydrogen, halogen or C1-C4alkyl.
11. A compound according to claim 10, wherein:
R1 is methyl or ethyl;
X is a group of formula -CH2-.
12. A compound according to claim 1 of formula la
a
Figure imgf000055_0001
wherein:
R10 and R11 are each independently of the other hydrogen, or halogen;
Y is a group of formulae (a) to (x).
13. A process for the preparation of a compound of formula I as claimed in claim 1, which comprises reacting a compound of formula II
Y-X-COOH II or the acid halide thereof, wherein X and Y are as defined for formula I, with a compound of formula III
Figure imgf000056_0001
wherein R1 to R5 have the meanings given for formula I, in the absence or in the presence of a suitable condensing agent and/or of a base, to give a compound of formula I.
14. A process for the preparation of a compound of formula I, wherein R5 is as defined in claim 1, but is not hydrogen, which comprises reacting a compound of formula la a
Figure imgf000056_0002
wherein R1 to R4, X and Y have the meanings given for formula I, with a compound of formula IV
R5-L IV wherein R5 is as defined for formula I, and L is a leaving group, in the presence of a base.
15. A composition for controlling pests, which comprises as active ingredient at least one compound as claimed in claim 1 in the free form or in the form of an agrochemically acceptable salt, together with a suitable carrier therefor.
16. A composition according to claim 15, wherein the pests to be controlled are phythopathogenic microorganisms.
17. A composition according to claim 15, wherein the pests to be controlled are insects or acarina.
18. A method of controlling pests, which comprises applying a pesticidally effective amount of a compound as claimed in claim 1 to said pests or to the locus thereof.
19. A method according to claim 18, wherein the pests to be controlled are phythopathogenic microorganisms.
20. A method according to claim 18, wherein the pests to be controlled are insects or acarina.
21. A method according to claim 18, wherein seeds are treated.
22. Seeds treated by the method as claimed in claim 21.
PCT/EP1995/003464 1994-09-13 1995-09-02 Pesticidal pyridine derivatives WO1996008475A1 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0784615A1 (en) * 1994-09-28 1997-07-23 Hoechst Schering AgrEvo GmbH Use of substituted pyridines as pest-control agents and fungicides
WO1999000375A1 (en) * 1997-06-26 1999-01-07 Bayer Aktiengesellschaft Substituted aminoheterocyclylamides
WO1999025694A1 (en) * 1997-11-14 1999-05-27 Bayer Aktiengesellschaft Condensed pyridine derivatives
WO2001055145A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2001055141A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2001055137A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
US6335325B1 (en) 1997-11-14 2002-01-01 Bayer Aktiengesellschaft Acylated 4-aminopyridine derivatives as pesticides and fungicides
WO2003059903A3 (en) * 2002-01-18 2003-12-11 Bayer Cropscience Ag Substituted 4-aminopyridine derivatives used as pest control agents
US8034940B2 (en) 2006-08-09 2011-10-11 Bristol-Myers Squibb Company Modulators of glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326331A2 (en) * 1988-01-29 1989-08-02 DowElanco Substituted quinolines and cinnolines
WO1993004580A1 (en) * 1991-09-03 1993-03-18 Dowelanco N-(4-pyridyl or 4-quinolinyl) arylacetamide pesticides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326331A2 (en) * 1988-01-29 1989-08-02 DowElanco Substituted quinolines and cinnolines
WO1993004580A1 (en) * 1991-09-03 1993-03-18 Dowelanco N-(4-pyridyl or 4-quinolinyl) arylacetamide pesticides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0784615A1 (en) * 1994-09-28 1997-07-23 Hoechst Schering AgrEvo GmbH Use of substituted pyridines as pest-control agents and fungicides
WO1999000375A1 (en) * 1997-06-26 1999-01-07 Bayer Aktiengesellschaft Substituted aminoheterocyclylamides
WO1999025694A1 (en) * 1997-11-14 1999-05-27 Bayer Aktiengesellschaft Condensed pyridine derivatives
US6335325B1 (en) 1997-11-14 2002-01-01 Bayer Aktiengesellschaft Acylated 4-aminopyridine derivatives as pesticides and fungicides
WO2001055145A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2001055141A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2001055137A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2001055135A1 (en) * 2000-01-28 2001-08-02 Syngenta Limited Azine derivatives as pesticides
WO2003059903A3 (en) * 2002-01-18 2003-12-11 Bayer Cropscience Ag Substituted 4-aminopyridine derivatives used as pest control agents
US8034940B2 (en) 2006-08-09 2011-10-11 Bristol-Myers Squibb Company Modulators of glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof

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TW306916B (en) 1997-06-01
ZA957631B (en) 1996-04-10
EP0781275A1 (en) 1997-07-02
JPH10505824A (en) 1998-06-09
IL115234A0 (en) 1995-12-31
AU3521095A (en) 1996-03-29

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