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WO1996006086A1 - Derive de 4-cyclohexylaminopyrimidine, procede de production et produit utilise dans la lutte contre les parasites agrohorticoles - Google Patents

Derive de 4-cyclohexylaminopyrimidine, procede de production et produit utilise dans la lutte contre les parasites agrohorticoles Download PDF

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Publication number
WO1996006086A1
WO1996006086A1 PCT/JP1995/001665 JP9501665W WO9606086A1 WO 1996006086 A1 WO1996006086 A1 WO 1996006086A1 JP 9501665 W JP9501665 W JP 9501665W WO 9606086 A1 WO9606086 A1 WO 9606086A1
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Prior art keywords
group
compound
pyrimidine
chloro
formula
Prior art date
Application number
PCT/JP1995/001665
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English (en)
Japanese (ja)
Inventor
Tokio Obata
Katsutoshi Fujii
Kiyoshi Tsutsumiuchi
Yoshinori Yamanaka
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Ube Industries, Ltd.
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Application filed by Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Publication of WO1996006086A1 publication Critical patent/WO1996006086A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/18—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, directly attached to a heterocyclic or cycloaliphatic ring

Definitions

  • the present invention relates to a novel 4-cyclohexylaminopyrimidine derivative which is a pesticide for agricultural and horticultural use useful as an insecticide, acaricide, fungicide and the like.
  • the 4-cyclohexylaminopyrimidine derivative of the present invention is a novel compound, it is also known that it has a pest control activity for agricultural and horticultural use which is useful as an insecticide, acaricide, fungicide and the like. Absent.
  • An object of the present invention is to provide a novel 4-cyclohexylaminovirimidine derivative, a process for producing the same, and a pesticide for agricultural and horticultural use containing the same as an active ingredient, which are useful as insecticides, acaricides, and fungicides.
  • the present inventors have conducted studies to solve the above-mentioned problems. As a result, a novel 4-cyclohexylaminovirimidine derivative is useful as an insecticide, acaricide, fungicide, etc. The present inventors have found that they have a remarkable controlling activity as an agent, and have completed the present invention.
  • the present invention is as follows.
  • the first invention has the following formula (1):
  • R 1 represents a halogen atom, an alkoxy group having 2 to 5 carbon atoms, a hydroxyl group, an alkoxy group having 1 ⁇ 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms.
  • Q is the following equation (Qa):
  • R 2 is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a pyrimidinylamino group, an alkoxy group having 1 to 6 carbon atoms, a C00 R 3 group,
  • R 3 represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
  • R 4 represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • the second invention relates to a 4-cyclohexylaminovirimidine derivative represented by the following formula (2):
  • R 1 and * are as defined above.
  • X represents a halogen atom
  • Qac represents a substituent represented by the above formula (C) or the formula (Qc), and cyclohexylamines represented by the following formula [Compound (3-1) Wherein Q is represented by the formula (Qa) or the formula (Qc) in the above formula (1), and a method for producing the 4-cyclohexylaminopyrimidine derivative.
  • the third invention has the following formula (lc):
  • R ′, n and * are as defined above,
  • the fourth invention relates to a pesticidal composition for agricultural and horticultural use, comprising a 4-cyclohexylaminovirimidine derivative represented by the above formula (1) as an active ingredient.
  • R 1 and Q represented by the target compound, a novel 4-cyclohexylaminopyrimidine derivative [compound (1)] and its raw materials [compound (2) and compound (3-1)] are as follows: It is.
  • R 1 examples include a halogen atom, an alkoxy group having 2 to 5 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and an alkylthio group having 1 to 4 carbon atoms.
  • halogen atom examples include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a fluorine atom, a chlorine atom and a bromine atom are preferred.
  • acyloxy group examples include those having a linear or branched alkyl group; those having 2 to 4 carbon atoms are preferred; and acetyloxy groups are more preferred.
  • alkoxy group examples include linear or branched ones; those having 1 to 4 carbon atoms are preferred; and methoxy and ethoxy groups are preferred.
  • alkylthio group examples include those having a linear or branched alkyl group; a methylthio group and an ethylthio group are preferred.
  • Q examples include a substituent represented by the above formula (Qa), (Qb), or (Qc).
  • the compound (1) in which the substituent Q is represented by the formula (Cia), (Qb), or (CLc) is referred to as a compound (la), a compound (lb), or a compound (lc), respectively.
  • R 2 in formula (C) a 1-8C alkyl group having a carbon Fuweniru group, pyrimidinyl ⁇ amino group, alkoxy groups having 1-6 carbon atoms, C 00 R 3 groups, Amino group, NHC 0 group And the like.
  • alkyl group examples include straight-chain or branched ones; those having 1 to 5 carbon atoms are preferable; and methyl, ethyl, t-butyl and n-alkyl groups. Pentyl groups are preferred.
  • the phenyl group examples include unsubstituted or substituted ones.
  • the pyrimidinylamino group preferably has the following formula (Qa-1):
  • R 1 and * are as defined above,
  • R 1 in the substituent (Qa-1) is preferably a halogen atom, an acyloxy group having 2 to 5 carbon atoms, a hydroxyl group, or the like; More preferable substituent (Qa-l) is described in Table 2 below. And the substituents R 2 corresponding to the compounds (la-42) to (la-48) described in (1).
  • alkoxy group examples include straight-chain or branched ones; those having 1 to 4 carbon atoms are preferred; and methoxy, ethoxy and n-butoxy groups are preferred.
  • R 3 is the C00 R 3 groups, linear or branched having 1-4 ⁇ alkyl group carbon and hydrogen atoms can be mentioned; as the alkyl group, Echiru group, is t one-butyl group preferable.
  • R 4 in the NH COR 4 group examples include a linear or branched alkyl group having 1 to 8 carbon atoms, and a linear or branched alkoxy group having 1 to 8 carbon atoms.
  • a linear or branched alkyl group having 1 to 8 carbon atoms examples include a linear or branched alkyl group having 1 to 8 carbon atoms, and a linear or branched alkoxy group having 1 to 8 carbon atoms.
  • a methyl group and a t-butyl group are preferable; and as an alkoxy group, a t-butoxy group is preferable.
  • n 2 or 3.
  • Examples of the compound (1) include compounds obtained by combining the above-mentioned various substituents.
  • Preferred compounds from the viewpoint of drug efficacy are as follows.
  • these compounds (1) include compounds ((la-1). (La-7), (la-8), (la-11), and (la-13) described in Table 2 below. ) To (la-19), (la-21), (la-22), (la-25), (la-26), (la-29), (la-30), (la-40), (la-41), (la-47), (la-48) ⁇ , compound (lb-4), compound (lc-4) and the like.
  • compound (1) of the present invention has an amino group
  • acid addition salts derived therefrom are also included in the present invention.
  • Examples of the acid that forms an acid addition salt include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, and phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, maleic acid, and aconic acid.
  • Carboxylic acids such as (1); organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and P-toluenesulfonic acid;
  • the carbon atom marked with * is an asymmetric carbon atom, and any optical isomer, racemate, diastereomer compound or a mixture thereof is included in the present invention. .
  • Preferred embodiments for producing the 4-cyclohexylaminovirimidine derivative represented by the above formula (1) include the synthesis methods 1 and 2 described as the second and third inventions. In addition, the following five production methods (synthesis methods 3 to 7) can be mentioned.
  • R 6 represents a halogen atom, and a 4-cyclohexylaminopyrimidine derivative represented by
  • R 7 represents an acyloxy group having 2 to 5 carbon atoms
  • R 1 is a 4-cyclohexylamino pyrimidine derivative [compound (1-2) Name. ] Manufacturing method.
  • R 5 represents a lower alkyl group
  • Y represents an oxygen atom or a sulfur atom, and is reacted with an alcohol (or a mercaptan) represented by the following formula (1):
  • R 1 is a lower alkoxy group (or a lower alkyl group)
  • a 4-cyclohexylaminovirimidine derivative [referred to as compound (1-4)].
  • the compound (2) and the compound (3-1) are reacted in a solvent or without a solvent to obtain a compound (la) or a compound (lc) [Q in the compound (1) Or a compound represented by Qc), wherein the reaction can be promoted by reacting in the presence of a base.
  • R 1 , X, * and Qac are as defined above.
  • the type of the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • the solvent can be used in such an amount that the compound (2) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • the type of the base is not particularly limited.
  • organic bases such as triethylamine, pyridin, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-indene (DBU)
  • Alkali metal alkoxides such as bases, sodium methoxide, sodium ethoxide, inorganic hydrides such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate Bases may be mentioned; organic bases are preferred.
  • the amount of the base to be used is 0.001 to 5 moles, preferably 0.8 to 2 moles, relative to compound (2).
  • the reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used or less; C is preferred.
  • the reaction time varies depending on the above concentration and temperature; it is usually 0.3 to 4 hours.
  • the amount of the starting compound used is 0.5 to 2 times mol of compound (3-1) relative to compound (2); preferably 1.0 to 1.2 times mol.
  • the raw material compound (2) in which R 1 is represented by X is usually prepared by compound (7-1) and compound (7-1) as shown below, as in the method described in JP-A-5-94417. (8-1) with a solvent in a solvent.
  • the solvent examples include the above-mentioned solvents; the amount of the solvent can be used such that the amount of the compound (7-1) is 5 to 80% by weight.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower.
  • the reaction time varies depending on the above concentration and temperature; it is usually 2 to 10 hours.
  • the amount of the starting compound to be used is 0.5 to 3 times mol of compound (8-1) relative to compound (7-1); preferably 0.9 to 1.2 times mol.
  • the starting compound (2) when R 1 is other than X can be produced by the method described in JP-A-5-320141.
  • Compound (7-1) can be produced, for example, according to the method described in Journal of Chemical ⁇ Society (JC S) 3478-3481 (1955) as shown in the following formula. Can be.
  • the compound (2) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, appropriately by known means such as recrystallization and various types of chromatography. It can be purified.
  • Examples of the compound (2) include the compounds (2-1) to (2-7) shown in Table 1 below.
  • Compound (3-1) used in the present invention can be produced by carrying out a reaction as shown in the following formula. ⁇ "NH2_rei ⁇ ⁇ . ⁇ "
  • R 2 in the formula represented by compound (3-1) is a t-butyl group.
  • the target compound (1) synthesized as described above includes the compounds (la-l) to (la-149) and the compounds (lc-l) to (lc-4) shown in Table 2 below.
  • R 1 in the formula represented by the compound (la) is a chlorine atom
  • R 2 is a t-butyl group.
  • the compound (lc) is hydrolyzed under acidic conditions to obtain the compound (lb) [Q in the compound (1) is a compound represented by Qb]. .
  • Examples of the acid used for the hydrolysis include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid, carboxylic acids such as acetic acid, oxalic acid, and tartaric acid, methanesulfonic acid, benzenesulfonic acid, and ⁇ -toluene.
  • examples thereof include organic sulfonic acids such as sulfonic acid; hydrochloric acid and acetic acid are preferred.
  • the amount of the acid to be used is 0.1 to 5 moles to compound (lc); preferably 0.1 to 2 moles.
  • Examples of the type of the solvent include ketones, amides, and ethers described in Synthesis Method 1, alcohols (such as methanol, ethanol, propanol, and butanol), water, and a mixture of the above solvents. But preferably a mixture of alcohols and water.
  • the solvent can be used in such an amount that the compound (lc) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; room temperature to 5 O'C is preferred.
  • reaction time varies depending on the concentration and the temperature described above; After completion of the reaction, the compound (lb) produced as described above is subjected to ordinary post-treatments such as extraction, shrinkage, and thigh, and if necessary, appropriately by known means such as recrystallization and various types of chromatography. It can be purified.
  • Examples of compound Ub) include compounds Ub-l) to (lb-4) shown in Table 2 below.
  • the compound (1-1) and the compound (4) are reacted in a solvent or without a solvent to give the compound (II) [R ′ in the compound (1) is a lower acyloxy group.
  • a certain compound] can be obtained by reacting in the presence of a base.
  • Examples of the type of the solvent include aliphatic carboxylic acids such as acetic acid and propionic acid, and mixtures thereof in addition to the solvents described in Synthetic Method 1. N, N-dimethylformamide and the introduced The same aliphatic carboxylic acid as the acyloxy group is preferred.
  • the amount of the solvent used can be such that the compound (1-1) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • Examples of the type of the base include the bases described in Synthesis method 1; an inorganic base is preferred.
  • the amount of the base to be used is 1 to 5 moles relative to compound (1-1); preferably 2 to 5 moles.
  • the reaction temperature is not particularly limited, be at a temperature within range of the boiling point of the solvent used at room temperature; 60 ⁇ ; 120 e C is preferred.
  • the reaction time varies depending on the above concentration and temperature; it is usually 2 to 10 hours.
  • the target compound (1-2) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration and the like, and, if necessary, recrystallization and various chromatographies. It can be appropriately purified by a known means such as one.
  • the compound (1-2) and the compound (5) are reacted in a solvent to form the compound (1-3) ⁇ the compound in which R 1 in the compound (1) is a hydroxyl group].
  • This is a method of obtaining a compound, and the reaction can be promoted by reacting in the presence of a base.
  • R 7 , * and M are as defined above.
  • Examples of the solvent include, in addition to the ethers, ketones, and amides described in Synthesis Method 1, alcohols (such as methanol, ethanol, propanol, and butanol), water, and a mixture of the above solvents. But a mixture of alcohols and water is preferred.
  • the solvent can be used in such an amount that the compound (1-2) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • Examples of the type of the base include the inorganic bases described in Synthesis Method 1; sodium hydroxide and potassium hydroxide are preferred.
  • the amount of the base to be used is 1 to 5 moles relative to compound (1-2); preferably 2 to 5 moles.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower; preferably room temperature to 5 CTC.
  • the reaction time varies depending on the concentration and the temperature as described above; is there.
  • the target compound (1-3) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, rupturing, etc., and, if necessary, recrystallization and various chromatographic methods. It can be appropriately purified by known means such as.
  • the compounds shown in Table 2 below ((la-5), (la-6), (la-15), (la-16), (la-39), ( (la-45), (la-46), (la-53), (la-54), (la-61), (la-62), (la-71)-(la-73), (la- 83)-(la-85), (la-89)-(la-91), (la-107)-(la-109), (la-119)-(la-121), (la-131) ⁇ (La-133), (la-143) ⁇ a-145) ⁇ , compound (lb-3), compound (lc-3) and the like.
  • the compound (1-1) and the compound (6) are reacted in a solvent or without a solvent as follows to obtain a compound (1-4) [R 1 in the compound (1) has 1 carbon atom. Or a compound having 4 to 4 alkoxy groups or an alkylthio group having 1 to 4 carbon atoms].
  • the reaction can be promoted by reacting in the presence of a base.
  • Examples of the type of the solvent include ethers, ketones, amides and a mixture of the above-mentioned solvents described in Synthesis Method 1. Ketones and amides are preferred.
  • the amount of the solvent used should be such that the compound (1-1) accounts for 5 to 80% by weight. But preferably 10-70% by weight.
  • Examples of the type of the base include the bases described in Synthesis method 1; an inorganic base is preferred.
  • the amount of the base used is 1 to 5 moles per 1 mole of the compound; 1 to 3 moles is preferable.
  • the reaction temperature is not particularly limited, but is in the temperature range from room temperature to the boiling point of the solvent used or less; room temperature to 6O'C is preferred.
  • the reaction time varies depending on the above concentration and temperature, but is usually 0.3 to 2 hours.
  • the target compound (1-4) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization and various chromatographic methods. It can be appropriately purified by known means such as.
  • the compound (1-1) and the compound (7) are reacted in a solvent to obtain the compound (1-5) ⁇ the compound in which R 1 in the compound (1) is a fluorine atom]
  • the reaction can be promoted by heating and reacting.
  • Examples of the type of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 1.3-dimethyl-2-imidazolidone; dimethyl sulfoxide; sulfolane; Can be mentioned.
  • the solvent can be used in such an amount that the compound (1-1) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • Examples of the compound (7) include an alkali metal fluorine compound; preferred are cesium fluoride and potassium fluoride.
  • the ratio of the solvent to be used is 1 to 5 moles relative to compound (1-1); preferably, it is 1.2 to 3 moles.
  • the reaction temperature is not particularly limited, be at a temperature within range of the boiling point of the solvent used at room temperature; 1 0 0 ⁇ 1 4 0 e C is preferred.
  • the reaction time varies depending on the concentration and temperature as described above; it can be usually carried out for 1 to 8 hours.
  • Compound U-5) can be synthesized by reacting compound (1-3) with a fluorinating agent in a solvent, in addition to synthesis method 6, as follows.
  • Synthesis method 7 is a method of reacting compound (1-3) with a fluorinating agent in a solvent to obtain compound U-5).
  • solvent examples include chlorinated or non-chlorinated aromatic, aliphatic, and alicyclic hydrocarbons described in Synthesis Method 1; ethers such as getyl ether, tetrahydrofuran, and dioxane; And the like.
  • the amount of the solvent to be used may be such that the compound (1-3) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • the fluorinating agent is not particularly limited,
  • DAST Getyl aminosulfur trifluorofluoride
  • the amount to be used is 1 to 5 moles relative to compound (1-3); preferably 1 to 2 moles relative to compound (1-1).
  • the reaction temperature is not particularly limited, but is in a range of from the ice-cooling temperature to the boiling point of the solvent used or lower; preferably from the ice-cooling temperature to room temperature.
  • the reaction time varies depending on the concentration and temperature, but is usually 0.3 to 2 hours.
  • the target compound (1-5) produced by Synthetic Methods 6 and 7 is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means.
  • Compound U-5) includes the compounds ((la-7), (la-8), (la-17), (la-18), (la-25), (la -26), (la-29), (la-30), (la-40), (la-41), (la-47), (la-48), (la-55), (la-56 ), (la-63), (la-64), (la-74) to (la-76), (la-86 to (la-88), (la-92) to (la-97), ( (la-110)-(la-112), (la-122)-(la-124), (la-134)-(la-136), (la-147) ⁇ , compound (lb-4), compound (Lc-4) and the like.
  • Examples of pests in agricultural and horticultural activities in which the compound (1) of the present invention has a controlling effect include agricultural and horticultural pests [for example, Hemiptera (Pteromorpha, Lepidoptera, Aphids, Whitefly) and the like.
  • Eyes (Lepidoptera, Convolvulus, Coleoptera, Mephides, Beetles, cabbage beetles, etc.); , Flies, powers, cockroaches, etc.), storage pests (such as terrestrial mushrooms, beetles, etc.), mosquitoes in the soil, pine woods, ticks, etc., and agricultural and horticultural pathogens (eg, Wheat rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato blight, etc.).
  • the pesticidal composition for agricultural and horticultural use of the present invention has a remarkable insecticidal, acaricidal and bactericidal effect, and contains at least one compound (1) as an active ingredient.
  • the compound (1) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powders, emulsions, fine granules, granules IJ, It is preferably used as a composition such as a wettable powder, an oily suspension, or an aerosol).
  • a carrier for example, a surfactant, a dispersant, an auxiliary agent and the like (for example, powders, emulsions, fine granules, granules IJ, It is preferably used as a composition such as a wettable powder, an oily suspension, or an aerosol).
  • Carriers include, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, cake sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (Benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone) ), Esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), Liquid carrier such as
  • surfactants and dispersants that can be used to improve the performance of this agent, such as adhesion to animals and plants, improved absorption, and dispersion, emulsification, and spreading of drugs, include alcohol sulfates and alkyl sulfones. Acid salts, lignin sulfonates, polyoxyethylene glycol ethers, and the like. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol Cole, gum arabic and the like can be used as adjuvants.
  • the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination, respectively, depending on the purpose of each.
  • the concentration of the active ingredient is usually from 1 to
  • Nitrogen gas was blown into the reaction solution to remove excess dissolved chlorine gas. Then, the solvent was distilled off under reduced pressure, and the obtained residue was distilled under reduced pressure to obtain 240 g of the target substance as a pale yellow liquid.
  • the target compound (1) was synthesized.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluted with toluene) to obtain 1.3 g of a colorless oily compound (la-1) (cis form) from the second fraction. From the first fraction, 0.9 g of a colorless crystalline compound (la-2) (trans form) was obtained.
  • the solvent was distilled off under reduced pressure, water was added to the obtained residue, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the solvent was distilled off under reduced pressure, water was added to the obtained residue, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • cis-isomer was obtained in an amount of 0.05 g, and the first fraction was obtained as a colorless oil (0.13 g) as a target compound (la-30) (trans-isomer).
  • the solvent was distilled off under reduced pressure, water was added to the obtained residue, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the solvent was distilled off under reduced pressure, water was added to the obtained residue, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the compound (la-38) (2.5 g) was dissolved in ethanol (100 ml), a 1 N aqueous solution of sodium hydroxide (50 ml) was added, and the mixture was stirred at room temperature for 2 hours.
  • the obtained colorless crystals were washed with hexane to obtain 0.22 g of the target compound as colorless crystals.
  • 1,4-Six-hexandiamine (10 g) was dissolved in a mixture of toluene (100 ml) and triethylamine (10 ml) to give 4,5-dichloro-6- (1-chloroethyl) pyrimidine (10-ml). 10 g) and stirred at room temperature for 4 hours.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluting with ethyl acetate) to give 8.0 g of the target compound as a colorless viscous liquid.
  • the resulting residue was purified by a silica gel column ( ⁇ -gel C-200, eluting with ethyl acetate) to obtain 0.06 g of the target compound (la-43) as a colorless viscous liquid from the first fraction. From the second fraction, 0.08 g of the target compound (la-44) as a colorless liquid was obtained.
  • the resulting residue was purified by a silica gel column (Peco-gel C-200, eluting with ethyl acetate) to obtain 0.06 g of the target compound as a glassy solid.
  • the obtained residue was purified by a silica gel column ( ⁇ -gel C-200, eluting with ethyl acetate) to obtain 0.08 g of the objective compound as a glassy solid.
  • the compound (la-45) (0.06 g) was dissolved in chloroform (1 Om 1), and DAST (0.1 g) was added dropwise with stirring under ice-cooling, followed by stirring at room temperature for 5 hours. After completion of the reaction, water was slowly added to the reaction mixture under ice-cooling and stirring, and the chloroform layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the compound (la-80) (1.2 g ) was dissolved in ethanol (50 ml ), an IN-sodium hydroxide aqueous solution (50 ml) was added, and the mixture was stirred at room temperature for 2 hours.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluting with ethyl acetate) to obtain 1.2 g of the target compound as a colorless oily liquid.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluted with ethyl acetate) to give 0.8 g of the target compound as a colorless oily liquid.
  • 1,4-Cyclohexanediamine (10 g) is dissolved in acetonitrile (100 ml), and ice-cooled solution of 4,5-dichloro-6- (1-chloroethyl) pyrimidine (3.7 g) in acetonitrile (50 ml) was added dropwise, and the mixture was stirred at room temperature for 5 hours.
  • the solvent was distilled off under reduced pressure, and water was added to the obtained residue.
  • the target compound was extracted with ter and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluted with ethyl acetate) to give 5.0 g of the target compound as a colorless oily liquid.
  • the resulting residue was purified by a silica gel column (Pecogel C-200, eluted with ethyl acetate) to give 1.5 g of the target compound as colorless crystals.
  • the compound (la-98) (1.0 g) was dissolved in a solution consisting of 1,4-dioxane (20 ml) and water (20 ml), and anhydrous sodium carbonate (0.5 g) and di-tert. —Butyl dicarbonate (lg) was added, and the mixture was stirred at room temperature for 3 hours.
  • the compound (la-128) (0.4 g) was dissolved in ethanol (30 ml), a 1 N aqueous solution of sodium hydroxide (30 ml) was added, and the mixture was stirred at room temperature for 2 hours.
  • the obtained residue was purified by a silica gel column (Pecogel C-200, eluted with ethyl acetate) to give 0.3 g of the target compound as colorless crystals.
  • the compound (la-131) (0.3 g) was dissolved in dichloromethane (20 ml), and DAST (0.4 g) was added dropwise with stirring under ice-cooling, followed by stirring at room temperature for 4 hours.
  • n-Pentylcyclohexylamine (1.1 g) is dissolved in a mixture of N, N-dimethylformamide (20 ml) and triethylamine (10 ml), and 4,5-dichloro-6 - a (1 one Kuroroechiru) pyrimidine (1. 7 g) was added and stirred for 4 hours at about 60 e C.
  • the obtained residue was purified by silica gel column (Ecogel C-200, eluted with toluene) to give 1.6 g of the target compound as a colorless liquid.
  • the compound (la-140) (1.5 g) was dissolved in ethanol (2 Om 1), 1N—water / aqueous sodium hydroxide solution (20 ml) was added, and the mixture was stirred at room temperature for 2 hours.
  • the solvent is distilled off under reduced pressure
  • the target compound is extracted from the residue with ethyl acetate, washed with a saturated aqueous solution of sodium carbonate, washed with water, dried over anhydrous sodium sulfate, and then the solvent is distilled off under reduced pressure did.
  • 1,4-Dioxaspiro (4,5) decane-1-ylamine (8.5 g) is dissolved in triethylamine (20 ml), and 4,5-dichloro-6- (1-chloroethyl) pyrimidine (14 g) is added. In addition, the mixture was stirred at about 60 ° C for 4 hours.
  • Table 2 shows the compounds synthesized as described above.
  • Toxane (trade name; manufactured by Sanyo Chemical Industries, Ltd.) (10 parts by weight) was added to compound (la-1) (20 parts by weight and xylene (70 parts by weight)), mixed uniformly, and dissolved to obtain an emulsion.
  • Each wettable powder of the compound (1) shown in Table 2 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%).
  • the soybean leaves were immersed for 30 seconds, placed one by one into each plastic cup, and air-dried. In each of these cups, release 10 moss montouts (2nd instar larvae), cover them, and leave them in a constant temperature room at 25 ° C. After 2 days, count the number of live and dead insects in each cup to obtain the kill rate.
  • a surfactant 0.01%
  • Each wettable powder of the compound (1) shown in Table 2 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and the cabbage was added to each of these chemical solutions.
  • Leaf pieces (5 x 5 cm) were soaked for 30 seconds, placed one at a time in each plastic cup, and air-dried.
  • Each wettable powder of the compound (1) shown in Table 2 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%). Rice seedlings were immersed for 30 seconds, air-dried, and inserted into each glass cylinder. Next, release 10 mosquitoes (4th instar larvae) into each cylinder, plug them with a porous plug, leave them in a constant temperature room at 25'C, and count the number of live and dead insects 4 days later to calculate the insecticidal rate. .
  • Each wettable powder of the compound (1) shown in Table 2 prepared according to Example 2 was diluted with water containing a surfactant (0.01%) to 3 ⁇ 0 ppm, and each of these chemical solutions was diluted.
  • the rice seedlings were immersed in them for 30 seconds, air-dried, and inserted into each glass cylinder.
  • Each wettable powder of the compound (1) shown in Table 2 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and 1
  • Each bean leaf piece (2 Omm in diameter) in which 0 female female adults were infested was immersed for 15 seconds.
  • each leaf piece was left in a constant temperature room at 25 eC , and three days later, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate.
  • the evaluation of the acaricidal effect was shown in four stages (A: 100%, B: less than 100 to 80%, C: less than 80 to 60%, D: less than 60%) according to the range of the acaricidal rate.
  • Table 7 shows the results of the evaluation of the acaricidal effect. Table 7 Efficacy test for two female adults
  • the plants were cultivated in a glass greenhouse for 2 days, and then a conidia spore suspension of the rice blast fungus prepared from the diseased leaves was spray-inoculated uniformly on the plant leaves.
  • the evaluation of the bactericidal effect was performed in 6 stages (0: whole disease, 1: lesion area about 60%, 2 : lesion area about 40%, 3 : Lesion area is about 2 °%, 4: Lesion area is 10% or less, 5: No lesion).
  • Table 8 shows the results. Table 8 Efficacy test for rice blast
  • Wheat (cultivar: Kobushi wheat) was grown in plastic flower pots with a diameter of 6 cm per pot, and seedlings of 1.5-leaf stage were prepared according to Example 2 and shown in Table 2.
  • the wettable powder of the compound (1) was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed at 2 Om 1 per pot.
  • novel 4-cyclohexylaminovirimidine derivative of the present invention has excellent effects such as insecticide, killing, and sterilization, and is useful as a pesticide for agricultural and horticultural use.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Dérivé de 4-cyclohexylaminopyrimidine représenté par la formule générale (1), dans laquelle R1 représente halogène, C¿2?-C5 acyloxy, hydroxy, C1-C4 alcoxy ou C1-C4 alkylthio; Q représente un substituant représenté par la formule générale (Qa), etc. (dans laquelle R?2¿ représente C¿1?-C8 alkyle, phényle, pyrimidinylamino, C1-C6 alcoxy, COOR?3¿, amino ou NHCOR4); et l'atome de carbone marqué d'un astérisque représente un atome de carbone asymétrique.
PCT/JP1995/001665 1994-08-23 1995-08-23 Derive de 4-cyclohexylaminopyrimidine, procede de production et produit utilise dans la lutte contre les parasites agrohorticoles WO1996006086A1 (fr)

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JP19826294 1994-08-23
JP6/198262 1994-08-23

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WO1996006086A1 true WO1996006086A1 (fr) 1996-02-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852023A (en) * 1995-03-29 1998-12-22 Hoechst Schering Agrevo Gmbh Cyclohexylamino and cycloalkoxy nitrogen heterocycles, processes for their preparation, and their use as pesticides and fungicides
WO1999031072A1 (fr) * 1997-12-18 1999-06-24 E.I. Du Pont De Nemours And Company Arthropodicides et fongicides de cyclohexylamine
WO2005095357A3 (fr) * 2004-03-30 2006-01-19 Taisho Pharmaceutical Co Ltd Derives de pyrimidine et procedes de traitement lies a l'utilisation de ceux-ci

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06247939A (ja) * 1993-02-26 1994-09-06 Ube Ind Ltd アミノピリミジン誘導体、その製法及び有害生物防除剤

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06247939A (ja) * 1993-02-26 1994-09-06 Ube Ind Ltd アミノピリミジン誘導体、その製法及び有害生物防除剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852023A (en) * 1995-03-29 1998-12-22 Hoechst Schering Agrevo Gmbh Cyclohexylamino and cycloalkoxy nitrogen heterocycles, processes for their preparation, and their use as pesticides and fungicides
WO1999031072A1 (fr) * 1997-12-18 1999-06-24 E.I. Du Pont De Nemours And Company Arthropodicides et fongicides de cyclohexylamine
WO2005095357A3 (fr) * 2004-03-30 2006-01-19 Taisho Pharmaceutical Co Ltd Derives de pyrimidine et procedes de traitement lies a l'utilisation de ceux-ci
RU2373197C2 (ru) * 2004-03-30 2009-11-20 Тайсо Фармасьютикал Ко., Лтд. Пиримидиновые производные, обладающие активностью в отношении мсн

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