EP1685111A1 - Substituted nicotinoylcarbamates as pesticides - Google Patents

Substituted nicotinoylcarbamates as pesticides

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Publication number
EP1685111A1
EP1685111A1 EP04791036A EP04791036A EP1685111A1 EP 1685111 A1 EP1685111 A1 EP 1685111A1 EP 04791036 A EP04791036 A EP 04791036A EP 04791036 A EP04791036 A EP 04791036A EP 1685111 A1 EP1685111 A1 EP 1685111A1
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EP
European Patent Office
Prior art keywords
compounds
formula
phenyl
alkyl
represents hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP04791036A
Other languages
German (de)
French (fr)
Inventor
Masahito Ito
Tetsuya Murata
Koichi Araki
Yuichi Otsu
Katsuhiko Shibuya
Norihiko Nakakura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Publication of EP1685111A1 publication Critical patent/EP1685111A1/en
Withdrawn legal-status Critical Current

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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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • 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
    • C07D213/89—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 with hetero atoms directly attached to the ring nitrogen atom
    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the invention relates to novel nicotinoylcarbamates, to their use as pesticides, preferably as insecticides and to processes for their preparation.
  • JP 321903/1994 and JP 101648/1998 describe amide type compounds or their salts and their use as agents for controlling harmful organisms.
  • the invention accordingly, provides novel nicotinoylcarbamates of the general formula (I)
  • n 0 or 1
  • W represents O or S
  • R 2 represents hydrogen, alkyl, alkenyl, aralkyl, cyanomethyl, alkoxycarbonylalkyl, aralky- loxycarbonyl, acyl, alkoxyalkyl or phenyl, and
  • R 1 represents
  • R 3 represents hydrogen or alkyl
  • R 4 represents hydrogen, alkyl, haloalkyl, phenyl or alkoxycarbonyl
  • R 5 represents hydrogen or alkyl
  • Q represents aryl that may be optionally substituted; 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted; phenyl-substituted cycloalkyl; condensed bicyclic hydro- carbon group; trimethylsilyl; al enyl or alkynyl.
  • the compounds of the formula (I), according to the present invention have strong insecticidal activities and show good compatibility to various crops.
  • the compounds of the formula (I) surprisingly show very excellent insecticidal action compared with the similar compounds to the compounds of the formula (I), described in the prior art (e.g. JP 321903/1994 and JP 101648/1998).
  • Halogen represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.
  • Alkyl represents a straight-chain or branched-chain C ⁇ -12 alkyl, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, etc. and preferably represents C 1-6 alkyl.
  • Alkenyl represents a straight-chain or branched-chain C 2- 6alkenyl, for example, vinyl, allyl, 1- propenyl, isopropenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, etc. and preferably represents C 2- alkenyl.
  • Alkynyl represents a straight-chain or branched-chain C 2-6 alkynyl, for example, ethenyl, propargyl, 1-pro ⁇ ynyl, isopropenyl, 1- (2- or 3) butynyl, 1- (2- or 3) pentenyl, 1- (2- or 3) hexenyl, etc. and preferably represents C 2-4 alky"nyl.
  • Aryl represents C 6- ⁇ o aromatic hydrocarbon cyclic group, for example, phenyl, naphthyl, etc. and preferably represents phenyl.
  • Alkyl represents, for example, benzyl, ⁇ -methylbenzyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, etc. and preferably represents benzyl.
  • Heterocyclic group represents a saturated or unsaturated 5 ⁇ 6-membered heterocyclic group containing at least one, preferably 1-3 hetero atoms selected from N, O and S and represents, for example, furyl, thienyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydrothienyl, pyrazolyl, imida- zolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyridyl, pyrimidinyl, piperidinyl, pyrazinyl, pyranyl, tetrahydropyranyl, tetrahydro
  • Condensed bicyclic hydrocarbon group represents a condensed bicyclic C9-10 hydrocarbon group, for example, indenyl, indanyl, tetrahydronaphthyl, etc. and preferably represents indanyl or tetrahydronaphthyl.
  • Cycloalkyl represents C 3-8 cycloalkyl, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably represents C5-7cycloalkyl, and particularly cyclohexyl is preferable.
  • W preferably represents O or S.
  • R 3 preferably represents hydrogen or C ]- alkyl.
  • R 4 preferably represents hydrogen, halo-C M alkyl, phenyl or C 2- alkoxycarbonyl.
  • R 5 preferably represents hydrogen or 'C h alky! .
  • p preferably represents 0 or 1.
  • q preferably represents 0 or 1.
  • Q preferably represents aryl that may be optionally substituted with at least one group selected from the group consisting of C ⁇ alkoxy, C M alkylthio, halogen, cyano, C ⁇ _ 4 alkyl, C 2-4 alkenyl, nitro, phenoxy; phenyl that may be optionally substituted; 5 ⁇ 6- membered heterocyclic group containing N, O or S, 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted with halo-C ⁇ -2 alkyl, or oxo; 4- phenylcyclohexyl; condensed bicyclic C 9- ⁇ 0 hydrocarbon group; trimethylsilyl; C 2-6 alkenyl; C 2-6 alkynyl.
  • R 2 preferably represents hydrogen, C h alky!, C 2- 6alkenyl, benzyl, cyanomethyl, or phenyl.
  • m preferably represents 0 or 1.
  • W particularly preferably represents O or S.
  • R 3 particularly preferably represents hydrogen or methyl.
  • R 4 particularly preferably represents hydrogen, methyl, trichloromefhyl, trifluoromethyl, phenyl or methoxycarbonyl.
  • R 5 particularly preferably represents hydrogen or methyl.
  • p particularly preferably represents 0 or 1.
  • q particularly preferably represents 0 or 1.
  • Q particularly preferably represents phenyl which is optionally substituted with one or more groups selected from the group consisting of methoxy, methylthio, fluoro, chloro, bromo, iodo, cyano, methyl, vinyl, nitro, trifluoromethyl, phenoxy, phenyl, chloro-substituted phenyl, tolyl and
  • thienyl furyl, thienyl, trifluoromethylpyrazolyl, pyridyl, trifluoromethylpyridyl, tetrahy- dropyranyl, tetrahydrothiopyranyl, piperidinyl, l-(tert-butoxycarbonyl)-4-piperidinyl, pyr- rolidinyltetrahydrofuryl, 1,1-dioxo-tetrahydrothiopyranyl, 4-phenylcyclohexyl, indanyl, tetrahydronaphthyl, trimethylsilyl, C 2 . alkenyl ⁇ alkynyl.
  • R 2 particularly preferably represents hydrogen, C ⁇ alkyl, C 2-4 alkenyl, benzyl, cyanomethyl, C ⁇ -2 alkoxy-carbonylmethyl, benzyloxycarbonyl, acetyl, C ⁇ -2 alkoxymethyl or phenyl.
  • n particularly preferably represents 0.
  • W very particularly preferably represents O.
  • R 2 very particularly preferably represents hydrogen.
  • R 3 very particularly preferably represents hydrogen.
  • R 4 very particularly preferably represents hydrogen.
  • the abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and also, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.
  • the compounds of the formula (I) can be obtained by any of the following preparation processes a), b), c), d) or e). Particularly the compounds of the formula (I), in which R2 represents hydrogen and m represents 0, can be synthesized by the preparation processes a), b) or c), and the com- pounds of the formula (I), in which R2 represents another group than hydrogen and m represents 0, can be synthesized by the preparation process d), and further the compounds of the formula (I), in which m represents 1, can be synthesized by the preparation process e).
  • R 1 has the same definition as aforementioned, in the presence of inert solvents.
  • R 1 has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
  • R 1 has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
  • R 2 is as defined above, except hydrogen and Hal represents halogen, in the presence of inert solvents, and if appropriate, in the presence of a base.
  • W, R 1 and R 2 have the same definition as aforementioned, are oxidized in the presence of inert solvents.
  • the preparation process a) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinoyl isocyanate and ben- zyl alcohol are used as starting materials.
  • the preparation process b) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinamide and benzyl chloroformate are used as starting materials.
  • the preparation process c) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinoyl chloride and benzyl carbamate are used as starting materials.
  • the preparation process d) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that benzyl N-(4-trifluoromethyl-3- pyridylcarbonyl)carbamate and methyl chloride are used as starting materials.
  • the preparation process e) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that benzyl N-(4-trifluoromefhyl-3- pyridylcarbonyl)carbamate is used as starting material and m-chloroperbenzoic acid, as oxidizing agent.
  • the compounds of the formula (H) in the preparation process a) can be easily obtained according to the process described in, for example, J. Med. Chem., p.1630 (1991), J. Chem. Soc, p.153 (1958).
  • the alcohols of formula (ITf) are well known in the field of organic chemistry; as their representa- five examples the following compounds may be mentioned: benzyl alcohol, ⁇ -mefhylbenzyl alcohol, phenol, 2-phenyl-isopropanol, trimethylsilylmethanol, 2-(trimethylsilyl)ethanol, 3- furylmethanol, 2-furylmethanol, 2-thienylmethanol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 4-vinylbenzyl alcohol, 4-methylthiobenzyl alcohol, 2- chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-pyridylmethyl alcohol, 3- pyridylmefhyl alcohol, 4-pyridylmethyl alcohol, 3-cyanobenzyl alcohol, trimethylsilylmethanol, 4- methylbenzyl alcohol, 2,4-dichlorobenzyl alcohol, 2,6-dichlorobenz
  • 4-tetrahydrothiopyranyl alcohol, 2-(l,2,3,4- tetrahydronaphthyl) alcohol, 4-phenoxybenzyl alcohol can be easily obtained, for example, by reducing their corresponding known ketones using sodium borohydride.
  • 4-Trifluoronicotinamide is a known compound, (c.f. JP 321903/1994.)
  • chloroformic acid esters of formula (TV) are well known in the field of organic chemistry and can be easily obtained generally by reacting phosgene with the corresponding alcohols in the presence of a tertiary amine.
  • 4-Trifluoromethylnicotinoyl chloride can be easily obtained, for example, by a reaction of known 4-trifluoromethylnicotinic acid and thionyl chloride.
  • the carbamic acid esters of formula (V) are well known in the field of organic chemistry and can be obtained by known processes.
  • halides of formula (VT) are well known in the field of organic chemistry; as their representative examples there can be mentioned the following: chloromethyl ethyl ether, acetyl chloride, benzyl chloroformate, ethyl bromoacetate, benzyl bromide, allyl bromide, ethyl iodide, etc.
  • oxidizing agent used for oxidation there can be mentioned m- chloroperbenzoic acid.
  • the aforementioned preparation process a) can be conducted, for example, according to the proc- ess described in J. Chem. Soc, p.1091 (1957) and ibid. p. 4458 (1956).
  • the reaction of the preparation process a) can be conducted using an adequate diluent singly or mixed.
  • aliphatic, alicyclic and aromatic hydrocarbons may be optionally chlorinated
  • pentane, hexane, cyclohex- ane petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroefhane, chlorobenzene, dichlorobenzene, etc.
  • ethers for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahy- drofuran (THF), diethylene glycol dimethyl ether (DGM), etc.
  • nitriles for example, ethyl ether, methyl ethyl
  • the reaction of the preparation process a) can be conducted in a substantially wide range of temperature. However, it can be conducted in a range of generally about 0 — about 100°C, preferably about 0 - about 50°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (JJf) to 1 mole of compounds of the formula (IT) in a diluent, for example, 1,2-dichloroethane.
  • the aforementioned preparation processes b), c), d) and e) can be conducted under the similar reaction conditions by using a diluent mentioned in the above-mentioned preparation process a) except dimethylformamide.
  • the preparation process b) can be conducted, for example, according to the process described in J. Med. Chem., p. 2504 (1991).
  • the preparation process c) can be conducted, for example, according to the process described in J. Chem. Soc, p. 451 (1964).
  • the preparation process d) can be conducted, for example, according to the process described in Heterocycles, p. 373 (1987).
  • the prepa- ration process e) can be conducted, for example, according to the process described in J. Med. Chem., p. 2925 (1995).
  • the preparation processes b), c) and d) can be conducted also in the presence of a base.
  • a suitable base may be mentioned: carbonates of alkali metals, for example, potassium carbonate; tertiary amines, N,N-dialkylanilines and pyridines, for example, triethylamine, 1,1,4,4- tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), 1,8- diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
  • TMEDA 1,1,4,4- tetramethylethylenediamine
  • DMAP 4- dimethylaminopyridine
  • DABCO 1,8- diazabicyclo[5,4,0]undec-7-ene
  • DBU
  • the compounds of the formula (I) show strong insecticidal action.
  • the compounds of the present invention can, therefore, be used as insecticidal agents.
  • the active compounds of the present invention exhibit exact controlling effect against harmful insects without phytotoxicity against cultured plants.
  • the compounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests, etc. and applied for their extermination.
  • coleoptera pests for example, Callosobruchus Chinensis, Sito- philus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Manochamus alternatus, Lissor- hoptrus oryzophilus, Lyctus bruneus;
  • Lepidoptera pests for example,
  • Lymantria dispar Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrel- la;
  • Hemiptera pests for example,
  • Nephotettix cincticeps Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum, Psylla spp.Bemisia argentifolii;
  • Orthoptera pests for example,
  • Homoptera pests for example,
  • Diptera pests for example,
  • Musca domestica Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tri- taeniorhynchus, etc.
  • Thysanoptera pests for example, Thrips palmi Karny, Frankliniella occidentalis.
  • the compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes.
  • animal-parasitic pests there can be mentioned the following pests:
  • insects there can be mentioned, for example,
  • Gastrophilus spp. Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, etc.
  • insects substances having insecticidal action against pests, which include all of them, are in some cases called as insecticides
  • the active compounds of the formula (I) can be made into customary formulation forms, when they are used as insecticides.
  • formulation forms there can be mentioned, for example, solutions, emulsifiable concentrates, wettable powders, water dispersible granules, suspensions, powders, foaming agents, pastes, tablets, granules, aerosols, active compound-impregnated natural and synthetic substances, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc.
  • formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
  • extenders namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
  • organic solvents can also be used as auxiliary solvents.
  • liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc.
  • aromatic hydrocarbons for example, xylene, toluene, alkylnaphthalene, etc.
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.
  • aliphatic hydrocarbons for example, cyclohexane etc.
  • paraffins for example, mineral oil fractions etc.
  • alcohols for example, butanol, glycols and their ethers, esters, etc.
  • ketones for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • strongly polar solvents for example, dimethylformamide, dimethyl sulfoxide, etc.
  • Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons.
  • ground natural minerals for example, kao- lin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.
  • ground synthetic minerals for example, highly dispersed silicic acid, alumina, silicates, etc.
  • crushed and fractionated rocks for example, calcite, marble, pumice, sepiolite, dolomite, etc.
  • synthetic granules of inorganic and organic meals for example, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.
  • nonionic and anionic emulsifiers for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates, arylsul- fonates, etc.], albumin hydrolysis products, etc.
  • Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose, etc.
  • Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates).
  • tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.) etc.
  • Colorants can also be used.
  • inorganic pigments for example, iron oxide, titanium oxide, Prussian Blue, etc.
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phfhalocyanine dyestuffs
  • nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Said formulations can contain the aforementioned active components of the amount in the range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight.
  • the active compounds of the formula (I) of the present invention can exist also as a mixed agent with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides, etc. in the form of their commercially useful formulations and in the application forms prepared from such formulations.
  • insecticides for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microbes, etc.
  • the active compounds of the formula (I) can exist also as a mixed agent with a synergist and as such formulations and application forms commercially useful ones can be mentioned. Said synergist itself must not be active, but is a compound that enhances the action of the active compound.
  • the content of the active compounds of the formula (I) in a commercially useful application form can be varied in a wide range.
  • the concentration of the active compounds of the formula (I) at the time of application can be, for example, in the range of 0.0000001-100 % by weight, preferably in the range of 0.00001-1 % by weight.
  • the compounds of the formula (I) can be used by usual methods suitable to the application forms.
  • the active compounds of the present invention have a good stability against alkali on calcific substances and further show an excellent residual effectiveness in wood and soil.
  • Ph represents phenyl
  • Me represents methyl
  • Et represents ethyl
  • tert-Bu represents tert-butyl
  • Fu represents furyl
  • Th represents thienyl
  • Py represents pyridyl
  • Nap represents naphthyl
  • Pyz represents pyrazolyl
  • Pip represents piperidinyl
  • Pyrr represents pyrrolidinyl
  • c- Hex represents cyclohexyl.
  • test solution Solvent: Dimethylformamide 7 parts by weight; Emulsifier: Poly- oxyethylene alkyl phenyl ether 3 part by weight
  • Test method About 30 bred Myzus persicae* resistant to organophosphorous agents and carbamates were inoculated per 1 seedling of eggplant planted in a vinyl pot of 6cm diameter. One day after the inoculation, a sufficient amount of a diluted aqueous solution of a prescribed concentration of an active compound prepared as mentioned above, was sprayed by using a spray gun. After spraying it was placed in a green house of 28°C and the rate of death was calculated 7 days after the spraying. Test was repeated twice.
  • Formulation Example 1 (Granule) To a mixture of 10 parts of the compound of the present invention (No. 1), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water are added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.

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Abstract

Novel nicotinoylcarbamates represented by the general formula (I) wherein W, R1, R2, W and m are as defined in the specification, their use as pesticides, and processes for their preparation are described.

Description

SUBSTITUTED NICOTINOYLCARBAMATES AS PESTICIDES
The invention relates to novel nicotinoylcarbamates, to their use as pesticides, preferably as insecticides and to processes for their preparation.
JP 321903/1994 and JP 101648/1998 describe amide type compounds or their salts and their use as agents for controlling harmful organisms.
The invention, accordingly, provides novel nicotinoylcarbamates of the general formula (I)
in which
m represents 0 or 1,
W represents O or S,
R2 represents hydrogen, alkyl, alkenyl, aralkyl, cyanomethyl, alkoxycarbonylalkyl, aralky- loxycarbonyl, acyl, alkoxyalkyl or phenyl, and
R1 represents
wherein
R3 represents hydrogen or alkyl,
R4 represents hydrogen, alkyl, haloalkyl, phenyl or alkoxycarbonyl,
R5 represents hydrogen or alkyl,
p represents 0 or 1, q represents 0 or 1, and
Q represents aryl that may be optionally substituted; 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted; phenyl-substituted cycloalkyl; condensed bicyclic hydro- carbon group; trimethylsilyl; al enyl or alkynyl.
The compounds of the formula (I), according to the present invention, have strong insecticidal activities and show good compatibility to various crops.
According to the present invention the compounds of the formula (I) surprisingly show very excellent insecticidal action compared with the similar compounds to the compounds of the formula (I), described in the prior art (e.g. JP 321903/1994 and JP 101648/1998).
In the present specification, the following definitions shall apply if no specific other definition is given:
"Halogen" represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.
"Alkyl" represents a straight-chain or branched-chain Cι-12alkyl, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, etc. and preferably represents C1-6alkyl.
Each alkyl part of "haloalkyl", "alkoxycarbonyl", "alkoxycarbonylalkyl" and "alkoxyalkyl" there can be mentioned the same as described in the above-mentioned "alkyl".
"Alkenyl" represents a straight-chain or branched-chain C2-6alkenyl, for example, vinyl, allyl, 1- propenyl, isopropenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, etc. and preferably represents C2- alkenyl.
"Alkynyl" represents a straight-chain or branched-chain C2-6alkynyl, for example, ethenyl, propargyl, 1-proρynyl, isopropenyl, 1- (2- or 3) butynyl, 1- (2- or 3) pentenyl, 1- (2- or 3) hexenyl, etc. and preferably represents C2-4alky"nyl.
"Aryl" represents C6-ιo aromatic hydrocarbon cyclic group, for example, phenyl, naphthyl, etc. and preferably represents phenyl.
"Aralkyl" represents, for example, benzyl, α-methylbenzyl, 2-phenylethyl, α,α-dimethylbenzyl, etc. and preferably represents benzyl. "Heterocyclic group" represents a saturated or unsaturated 5~6-membered heterocyclic group containing at least one, preferably 1-3 hetero atoms selected from N, O and S and represents, for example, furyl, thienyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydrothienyl, pyrazolyl, imida- zolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyridyl, pyrimidinyl, piperidinyl, pyrazinyl, pyranyl, tetrahydropyranyl, tetrahydrothiopyranyl, thiopyranyl, etc.
"Condensed bicyclic hydrocarbon group" represents a condensed bicyclic C9-10 hydrocarbon group, for example, indenyl, indanyl, tetrahydronaphthyl, etc. and preferably represents indanyl or tetrahydronaphthyl.
"Aralkyl" part of "aralkyloxycarbonyl" represents the same group as described in the above- mentioned definition of "aralkyl".
"Cycloalkyl" represents C3-8cycloalkyl, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably represents C5-7cycloalkyl, and particularly cyclohexyl is preferable.
Preferred substituents or preferred ranges of the radicals present in the formulae (I) and the corre- sponding intermediate compounds are defined below.
W preferably represents O or S.
R3 preferably represents hydrogen or C]- alkyl.
R4 preferably represents hydrogen, halo-CMalkyl, phenyl or C2- alkoxycarbonyl.
R5 preferably represents hydrogen or 'Chalky! .
p preferably represents 0 or 1. <
q preferably represents 0 or 1.
Q preferably represents aryl that may be optionally substituted with at least one group selected from the group consisting of C^alkoxy, CMalkylthio, halogen, cyano, Cι_4alkyl, C2-4 alkenyl, nitro, phenoxy; phenyl that may be optionally substituted; 5~6- membered heterocyclic group containing N, O or S, 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted with halo-Cι-2alkyl, or oxo; 4- phenylcyclohexyl; condensed bicyclic C9-ι0 hydrocarbon group; trimethylsilyl; C2-6 alkenyl; C2-6 alkynyl. R2 preferably represents hydrogen, Chalky!, C2-6alkenyl, benzyl, cyanomethyl, or phenyl.
m preferably represents 0 or 1.
W particularly preferably represents O or S.
R3 particularly preferably represents hydrogen or methyl.
R4 particularly preferably represents hydrogen, methyl, trichloromefhyl, trifluoromethyl, phenyl or methoxycarbonyl.
R5 particularly preferably represents hydrogen or methyl.
p particularly preferably represents 0 or 1.
q particularly preferably represents 0 or 1.
Q particularly preferably represents phenyl which is optionally substituted with one or more groups selected from the group consisting of methoxy, methylthio, fluoro, chloro, bromo, iodo, cyano, methyl, vinyl, nitro, trifluoromethyl, phenoxy, phenyl, chloro-substituted phenyl, tolyl and
thienyl, furyl, thienyl, trifluoromethylpyrazolyl, pyridyl, trifluoromethylpyridyl, tetrahy- dropyranyl, tetrahydrothiopyranyl, piperidinyl, l-(tert-butoxycarbonyl)-4-piperidinyl, pyr- rolidinyltetrahydrofuryl, 1,1-dioxo-tetrahydrothiopyranyl, 4-phenylcyclohexyl, indanyl, tetrahydronaphthyl, trimethylsilyl, C2. alkenyl ^ alkynyl.
R2 particularly preferably represents hydrogen, C^alkyl, C2-4alkenyl, benzyl, cyanomethyl, Cι-2alkoxy-carbonylmethyl, benzyloxycarbonyl, acetyl, Cι-2alkoxymethyl or phenyl.
m particularly preferably represents 0.
W very particularly preferably represents O.
R2 very particularly preferably represents hydrogen.
R3 very particularly preferably represents hydrogen.
R4 very particularly preferably represents hydrogen. The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and also, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.
Preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings mentioned above as being preferred.
Particular preference according to the invention is given to compounds of the formula (1) which contain a combination of the meanings listed above as being particularly preferred.
Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
The compounds of the formula (I) can be obtained by any of the following preparation processes a), b), c), d) or e). Particularly the compounds of the formula (I), in which R2 represents hydrogen and m represents 0, can be synthesized by the preparation processes a), b) or c), and the com- pounds of the formula (I), in which R2 represents another group than hydrogen and m represents 0, can be synthesized by the preparation process d), and further the compounds of the formula (I), in which m represents 1, can be synthesized by the preparation process e).
Preparation process (a): in case R2 = hydrogen, m = 0:
Compounds of the formula
wherein W has the same definition as aforementioned, are reacted with compounds of the formula
R' - OH (m)
wherein R1 has the same definition as aforementioned, in the presence of inert solvents.
Preparation process (b): in case W = 0, R2 = hydrogen, m = 0:
4-trifluoromethylnicotinamide is reacted with compounds of the formula O CI— C-OR1 (IV)
wherein R1 has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
Preparation process (c): in case W = 0, R2 = hydrogen, m = 0:
4-trifluoromethylnicotinoyl chloride is reacted with compounds of the formula
O
II
H2N— C-OR (V)
wherein R1 has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
Preparation process (d): in case R2 = as defined above, except hydrogen, m = 0:
Compounds of the formula
wherein W and R1 have the same definition as aforementioned, are reacted with compounds of the formula
R2' -Hal (VI)
wherein R2 is as defined above, except hydrogen and Hal represents halogen, in the presence of inert solvents, and if appropriate, in the presence of a base.
Preparation process (e): in case m = 1 :
Compounds of the formula
wherein W, R1 and R2 have the same definition as aforementioned, are oxidized in the presence of inert solvents.
The preparation process a) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinoyl isocyanate and ben- zyl alcohol are used as starting materials.
The preparation process b) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinamide and benzyl chloroformate are used as starting materials.
The preparation process c) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that 4-trifluoromethylnicotinoyl chloride and benzyl carbamate are used as starting materials.
The preparation process d) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that benzyl N-(4-trifluoromethyl-3- pyridylcarbonyl)carbamate and methyl chloride are used as starting materials.
The preparation process e) to prepare compounds of the formula (I) can be illustrated by the following reaction scheme in case, for example, that benzyl N-(4-trifluoromefhyl-3- pyridylcarbonyl)carbamate is used as starting material and m-chloroperbenzoic acid, as oxidizing agent.
The compounds of the formula (H) in the preparation process a) can be easily obtained according to the process described in, for example, J. Med. Chem., p.1630 (1991), J. Chem. Soc, p.153 (1958).
The alcohols of formula (ITf) are well known in the field of organic chemistry; as their representa- five examples the following compounds may be mentioned: benzyl alcohol, α-mefhylbenzyl alcohol, phenol, 2-phenyl-isopropanol, trimethylsilylmethanol, 2-(trimethylsilyl)ethanol, 3- furylmethanol, 2-furylmethanol, 2-thienylmethanol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 4-vinylbenzyl alcohol, 4-methylthiobenzyl alcohol, 2- chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-pyridylmethyl alcohol, 3- pyridylmefhyl alcohol, 4-pyridylmethyl alcohol, 3-cyanobenzyl alcohol, trimethylsilylmethanol, 4- methylbenzyl alcohol, 2,4-dichlorobenzyl alcohol, 2,6-dichlorobenzyl alcohol, 2-bromobenzyl alcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, l-phenyl-2,2,2-trifluoroethanol, diphenylmethanol, 2-trifluoromethylbenzyl alcohol, 3- trifluoromethylbenzyl alcohol, 4-trifluoromethylbenzyl alcohol, 2-fluorobenzyl alcohol, 3- fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 4-nitrobenzyl alcohol, α-methoxycarbonylbenzyl alcohol, 3-iodobenzyl alcohol, 5-trifluoromethyl-2-pyridylmethanol, 3-phenoxybenzyl alcohol, 4- phenoxybenzyl alcohol, 2-methylbenzyl alcohol, 3-mefhylbenzyl alcohol, 2,4-dimethylbenzyl alcohol, 4-biphenylylmethanol, 1-naρhthylmethanol, 2-naphthylmefhanol, 2,2-dimethyl-3- phenylpropanol, l-phenyl-2,2,2-trichloroethanol, 2-phenethyl alcohol, 2-phenylpropanol, 1 -indanyl alcohol, 2-indanyl alcohol, l-(l,2,3,4-tetrahydronaphthyl) alcohol, 2-(l,2,3,4-tetrahydronaphthyl) alcohol, 4-tetrahydropyranyl alcohol, 4-tetrahydrothiopyranyl alcohol, 4-piperidinyl alcohol, 2- pyrrolidinyl alcohol, 3-pyrrolidinyl alcohol, 2-tetrahydrofurfuryl alcohol, 4-phenyl-cyclohexyl alcohol, 4-(2-thienyl)benzyl alcohol, 4-(4-chlorophenyl)benzyl alcohol, etc.
Among the above-mentioned alcohols, for example, 4-tetrahydrothiopyranyl alcohol, 2-(l,2,3,4- tetrahydronaphthyl) alcohol, 4-phenoxybenzyl alcohol can be easily obtained, for example, by reducing their corresponding known ketones using sodium borohydride. 4-Trifluoronicotinamide is a known compound, (c.f. JP 321903/1994.)
The chloroformic acid esters of formula (TV) are well known in the field of organic chemistry and can be easily obtained generally by reacting phosgene with the corresponding alcohols in the presence of a tertiary amine.
4-Trifluoromethylnicotinoyl chloride can be easily obtained, for example, by a reaction of known 4-trifluoromethylnicotinic acid and thionyl chloride.
The carbamic acid esters of formula (V) are well known in the field of organic chemistry and can be obtained by known processes.
The compounds of the formula (la) in the preparation process d) are the compounds of the formula (1) of the present invention, in case that R2 represents hydrogen, obtained by the preparation processes a), b) (in case W = 0) or c) (in case W = 0).
The halides of formula (VT) are well known in the field of organic chemistry; as their representative examples there can be mentioned the following: chloromethyl ethyl ether, acetyl chloride, benzyl chloroformate, ethyl bromoacetate, benzyl bromide, allyl bromide, ethyl iodide, etc.
The compounds of the formula (le) in the preparation process e) are the compounds of the formula (I) of the present invention, in case that m = 0.
As a representative example of the oxidizing agent used for oxidation there can be mentioned m- chloroperbenzoic acid.
The aforementioned preparation process a) can be conducted, for example, according to the proc- ess described in J. Chem. Soc, p.1091 (1957) and ibid. p. 4458 (1956).
The reaction of the preparation process a) can be conducted using an adequate diluent singly or mixed. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohex- ane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroefhane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahy- drofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; acid amides, for example, dimethylformamide (DMF), dimethy- lacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA), etc. The reaction of the preparation process a) can be conducted in a substantially wide range of temperature. However, it can be conducted in a range of generally about 0 — about 100°C, preferably about 0 - about 50°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.
In conducting the preparation process a), the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (JJf) to 1 mole of compounds of the formula (IT) in a diluent, for example, 1,2-dichloroethane.
The aforementioned preparation processes b), c), d) and e) can be conducted under the similar reaction conditions by using a diluent mentioned in the above-mentioned preparation process a) except dimethylformamide.
The preparation process b) can be conducted, for example, according to the process described in J. Med. Chem., p. 2504 (1991). The preparation process c) can be conducted, for example, according to the process described in J. Chem. Soc, p. 451 (1964). The preparation process d) can be conducted, for example, according to the process described in Heterocycles, p. 373 (1987). The prepa- ration process e) can be conducted, for example, according to the process described in J. Med. Chem., p. 2925 (1995).
The preparation processes b), c) and d) can be conducted also in the presence of a base. As a suitable base may be mentioned: carbonates of alkali metals, for example, potassium carbonate; tertiary amines, N,N-dialkylanilines and pyridines, for example, triethylamine, 1,1,4,4- tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), 1,8- diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
The compounds of the formula (I) show strong insecticidal action. The compounds of the present invention can, therefore, be used as insecticidal agents. And the active compounds of the present invention exhibit exact controlling effect against harmful insects without phytotoxicity against cultured plants. The compounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests, etc. and applied for their extermination.
As examples of such pests there can be mentioned the following pests:
As insects, there can be mentioned coleoptera pests, for example, Callosobruchus Chinensis, Sito- philus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Manochamus alternatus, Lissor- hoptrus oryzophilus, Lyctus bruneus;
Lepidoptera pests, for example,
Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrel- la;
Hemiptera pests, for example,
Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum, Psylla spp.Bemisia argentifolii;
Orthoptera pests, for example,
Blatella germanica, Periplaneta americana, Gryllotalpa africana, Locusta migratoria migratoriodes;
Homoptera pests, for example,
Reticulitermes speratus, Coptotermes formosanus;
Diptera pests, for example,
Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tri- taeniorhynchus, etc.
Thysanoptera pests, for example, Thrips palmi Karny, Frankliniella occidentalis.
Moreover, in the field of veterinary medicine, the compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes. As examples of such animal-parasitic pests there can be mentioned the following pests:
As insects there can be mentioned, for example,
Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, etc.
In the present invention substances having insecticidal action against pests, which include all of them, are in some cases called as insecticides The active compounds of the formula (I) can be made into customary formulation forms, when they are used as insecticides. As formulation forms there can be mentioned, for example, solutions, emulsifiable concentrates, wettable powders, water dispersible granules, suspensions, powders, foaming agents, pastes, tablets, granules, aerosols, active compound-impregnated natural and synthetic substances, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc.
These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
In case that water is used as extender, for example, organic solvents can also be used as auxiliary solvents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols and their ethers, esters, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), and water.
Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons.
As solid diluents there can be mentioned, for example, ground natural minerals (for example, kao- lin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.), etc.
As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.
As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates, arylsul- fonates, etc.], albumin hydrolysis products, etc.
Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose, etc.
Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.) etc.
Colorants can also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phfhalocyanine dyestuffs, and further traces nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Said formulations can contain the aforementioned active components of the amount in the range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight.
The active compounds of the formula (I) of the present invention can exist also as a mixed agent with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides, etc. in the form of their commercially useful formulations and in the application forms prepared from such formulations. Here, as the above-mentioned insecticides, there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microbes, etc.
Further, the active compounds of the formula (I) can exist also as a mixed agent with a synergist and as such formulations and application forms commercially useful ones can be mentioned. Said synergist itself must not be active, but is a compound that enhances the action of the active compound.
The content of the active compounds of the formula (I) in a commercially useful application form can be varied in a wide range.
The concentration of the active compounds of the formula (I) at the time of application can be, for example, in the range of 0.0000001-100 % by weight, preferably in the range of 0.00001-1 % by weight.
The compounds of the formula (I) can be used by usual methods suitable to the application forms. In case of application against hygienic pests and stored grain pests the active compounds of the present invention have a good stability against alkali on calcific substances and further show an excellent residual effectiveness in wood and soil.
Then the present invention will be described more specifically by examples. The present inven- tion, however, should not be restricted only to them in any way.
Synthesis Example 1
After oxalyl chloride (0.14 ml) was added to a suspension of 4-trifluoromethyl-mcotinamide (0.2 g) in 1,2-dichloroethane (10 ml) at room temperature, the mixture was refluxed for 2 hours. The solvent was distilled off under reduced pressure and the residue was dissolved in methylene chloride. Benzyl alcohol (0.11 g) was added to the solution and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure and the residue was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 3:1) to obtain benzyl N-(4-trifluoromefhyl-3-pyridylcarbonyl)carbamate (0.24 g).
1H-NMR: 8.85 (1H, d), 8.72 (1H, s), 7.94 (lH,brs), 7.56 (1H, d), 7.4-7.2 (5H, m), 5.11 (2H, s)
Synthesis Example 2
To a methylene chloride solution of 4-trifluoromethyl-nicotimc acid (lg) and catalytic amount of N,N-dimethylformamide, oxalyl chloride (0.5 ml) was added and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure and the residue was dissolved in toluene. Potassium carbonate (0.5 g) and tetrabutylammonium thiocyanate (1.89 g) were added to the solution and the mixture was stirred for 30 minutes. Then trimethylsilylmetha- nol (0.66 g) was added thereto and the mixture was stirred at room temperature for 1 hour. After diluting the reaction mixture with ethyl acetate, it was washed with water, IN hydrochloric acid and saturated aqueous solution of sodium chloride and the organic layer was dried with magne- sium sulfate. The solvent was distilled off under reduced pressure and the residue was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 5:1) to obtain trimetyl- silanylmethyl N-(4-trifluoromethyl-3-ρyridylcarbonyl)thiocarbamate (0.77 g). mp: 105-107°C
Synthesis Example 3
60 % Sodium hydride (36 mg) was suspended in N,N-dimethylformamide and N,N- dimethylformamide solution of benzyl N-(4-trifluoromethyl-3-pyridylcarbonyl)carbamate (0.4 g) was slowly added thereto. After stirring the mixture at room temperature for 30 minutes, methyl iodide (0.35 g) was added thereto and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate, washed with saturated aqueous solution of sodium chloride and the organic layer was dried with magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 6:1) to obtain benzyl N-methyl-N-(4-trifluoromethyl-3-pyridyl- carbonyl)carbamate (0.33 g). nD 20: 1.5185
Synthesis Example 4
m-Chloroperbenzoic acid (0.27 g) was slowly added to a methylene chloride solution of benzyl N- (4-trifluoromethyl-3-pyridylcarbonyl)carbamate (0.3 g). After stirring at room temperature for 12 hours, the reaction solution was washed with saturated aqueous solution of sodium hydrogen carbonate and saturated aqueous solution of sodium chloride, and the organic layer was dried with magnesium sulfate. The solvent was distilled off under reduced pressure and the obtained crystals were recrystallized from toluene to obtain benzyl (l-oxy-4-trifluoromethyl-3-pyridylcarbonyl)- carbamate (0.18 g). mp: 204-205°C The compounds of the formula (I) of the present invention obtained by the similar processes to the above-mentioned Synthesis Examples are shown in the following Table 1, together with the compounds shown in the above-mentioned Synthesis Examples.
In the Table, Ph represents phenyl, Me represents methyl, Et represents ethyl, tert-Bu represents tert-butyl, Fu represents furyl, Th represents thienyl, Py represents pyridyl, Nap represents naphthyl, Pyz represents pyrazolyl, Pip represents piperidinyl, Pyrr represents pyrrolidinyl and c- Hex represents cyclohexyl.
Table 1
Fu = Furanyl, Th = Thienyl, PH = Phenyl, Py = Pyrridyl, Pyrr = Pyrrolyl
'H-NMR values mentioned as a-1 in the above-mentioned Table 1 are as follows (chemical shift δ in ppm):
Biological Test Example 1:
Test against Myzus persicae* resistant to organophosphorous agents and carbamates
Preparation of test solution: Solvent: Dimethylformamide 7 parts by weight; Emulsifier: Poly- oxyethylene alkyl phenyl ether 3 part by weight
In order to make an appropriate formulation of an active compound 1 part by weight of the active compound was dissolved in the above-mentioned amount of solvent containing the above- mentioned amount of emulsifier and the solution was diluted with water to a prescribed concentration.
Test method: About 30 bred Myzus persicae* resistant to organophosphorous agents and carbamates were inoculated per 1 seedling of eggplant planted in a vinyl pot of 6cm diameter. One day after the inoculation, a sufficient amount of a diluted aqueous solution of a prescribed concentration of an active compound prepared as mentioned above, was sprayed by using a spray gun. After spraying it was placed in a green house of 28°C and the rate of death was calculated 7 days after the spraying. Test was repeated twice.
Results: The compounds No. 1, 3, 5, 6, 8, 9, 14, 18, 23, 29, 33, 35, 38, 40, 44, 54, 55, 59, 62, 70, 73, 84 offered to the test as specific examples showed 100% of rate of death at lOOppm concentration of the effective component.
Formulation Example 1 (Granule) To a mixture of 10 parts of the compound of the present invention (No. 1), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water are added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.
Formulation Example 2 (Granules)
95 Parts of clay mineral particles having particle diameter distribution in the range of 0.2-2mm are put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention (No. 1) are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.
Formulation Example 3 (Emulsifiable concentrate)
30 Parts of the compound of the present invention (No. 1), 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsifiable concentrate.
Formulation Example 4 (Wettable powder)
15 Parts of the compound of the present invention (No. 1), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powder) and powder clay (1:5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formalin-condensate are crushed and mixed to make a wettable powder.
Formulation Example 5 (Water dispersible granule)
20 Parts of the compound of the present invention (No. 1), 30 parts of sodium ligninsulfonate, 15 parts of bentonite and 35 parts of calcined diatomaceous earth powder are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

Claims

1. Compounds of formula (I)
in which m represents 0 or 1,
W represents O or S,
R2 represents hydrogen, alkyl, alkenyl, aralkyl, cyanomethyl, alkoxycarbonylalkyl, aralky- loxycarbonyl, acyl, alkoxyalkyl or phenyl, and
R represents
wherein
R3 represents hydrogen or alkyl,
R4 represents hydrogen, alkyl, haloalkyl, phenyl or alkoxycarbonyl,
R5 represents hydrogen or alkyl, p represents 0 or 1, q represents 0 or 1, and
Q represents aryl that may be optionally substituted; 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted; phenyl-substituted cycloalkyl; condensed bicyclic hydro- carbon group; trimethylsilyl; alkenyl or alkynyl.
2. Compounds of formula (I) as defined in Claim 1 wherein W represents O or S,
R3 represents hydrogen or
R4 represents hydrogen, CMalkyl, phenyl or C2- alkoxycarbonyl,
R5 represents hydrogen or p represents 0 or 1, q represents 0 or 1,
Q represents aryl which is optionally substituted with one or more groups selected from the group consisting of halogen, cyano, Cι-4alkyl, C2-4 alkenyl, nitro, halo-C]-4alkyl; phenoxy; phenyl that may be optionally substituted; 5~6-membered hetero- cyclic group containing N, O or S, 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and may be optionally substituted with halo-Cι-2alkyl, C^alkoxy-carbonyl or oxo; 4-phenylcyclohexyl; condensed bicyclic C9-ι0 hydrocarbon group; trimethylsilyl; C2-6 alkenyl; C2-6 alkynyl,
R2 represents hydrogen, Cι-6alkyl, C2-6alkenyl, benzyl, cyanomethyl, 4alkyl, benzyloxycarbonyl, or phenyl., m represents 0 or 1.
3. Compounds as defined in Claims 1 or 2 wherein
W represents O or S, R3 represents hydrogen or methyl,
R4 represents hydrogen, methyl, trichloromefhyl, trifluoromethyl, phenyl or methoxycarbonyl,
R5 represents hydrogen or methyl, p represents 0 or 1, q represents 0 or 1, Q represents phenyl which is optionally substituted with one or more groups selected from the group consisting of methoxy, mefhylthio, fluoro, chloro, bromo, iodo, cyano, methyl, vinyl, nitro, trifluoromethyl, phenoxy, phenyl, chloro-substituted phenyl, tolyl or thienyl, furyl, thienyl, trifluoromethylpyrazolyl, pyridyl, trifluoromethylpyridyl, tetrahy- dropyranyl, tetrahydrothiopyranyl, piperidinyl, l-(tert-butoxycarbonyl)-4-piperidinyl, pyr- rolidinyltefrahydrofuryl, 1,1-dioxo-tetrahydrothiopyranyl, 4-phenylcyclohexyl, indanyl, tetrahydronaphthyl, trimethylsilyl, C2-4 alkenyl C2-4 alkynyl, R2 represents hydrogen, C2-4alkenyl, benzyl, cyanomethyl, C]-2alkoxy-carbonyl- methyl, benzyloxycarbonyl, acetyl, C1-2alkoxymethyl or phenyl, m particularly preferably represents 0.
Process for the preparation of the compounds of the formula (I) set forth in claim 1, characterized in that a) in case R2 represents hydrogen and m represents 0: Compounds of the formula
wherein W has the same definition as aforementioned, are reacted with compounds of the formula
RJ - OH (III) wherein R1 has the same definition as aforementioned, in the presence of one or more inert solvents, or, b) in case W represents oxygen 0 and R2 represents hydrogen and m = 0 (zero)
4-trifluoromethylnicotinamide is reacted with compounds of the formula
O
11 1
CI— C-OR1 (IV)
wherein R1 has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base, or, c) in case W represents oxygen 0 and R2 represents hydrogen and m = 0 (zero)
4-trifluoromethylnicotinoyl chloride is reacted with compounds of the formula
O
I1I1
H2N- -C-OR ,1' (V)
wherein Rl has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base, or, d) in case R2 represents defined above except hydrogen and m represents 0 (zero) Compounds of the formula
wherein W and R1 have the same definition as aforementioned, are reacted with compounds of the formula R2' -Hal CVΪ) wherein R2' represents a group defined to the aforementioned R2 other than hydrogen and Hal represents halogen, in the presence of inert solvents, and if appropriate, in the presence of a base, or, e) in case m represents 1 Compounds of the formula
wherein W, R1 and R2 have the same definition as aforementioned, are oxidized in the presence of inert solvents.
5. Insecticidal compositions characterized in that they contain at least one compound of the formula (I) according to any of claims 1, 2 or 3.
6. A method of controlling pests characterized in that compounds of formula (I) according to any of claims 1. 2 or 3 are allowed to act on pests and / or their habitat.
Use of compounds of formula (I) according to any of claims 1. 2 or for controlling pests.
8. A process for the preparation of pesticidal compositions characterized in that compounds of the formula (I) are mixed with extenders and / or surface active agents.
EP04791036A 2003-11-13 2004-10-29 Substituted nicotinoylcarbamates as pesticides Withdrawn EP1685111A1 (en)

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US10104903B2 (en) 2009-07-31 2018-10-23 Mars, Incorporated Animal food and its appearance
US9210945B2 (en) 2009-07-31 2015-12-15 The Iams Company Animal food having low water activity
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US9173423B2 (en) 2009-07-31 2015-11-03 The Iams Company Animal food kibble with electrostatically adhered dusting
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