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WO1999052881A1 - Derives de 2-anilinopyrimidinone, intermediaires utilises dans la production de ceux-ci, procede de production correspondant et pesticides contenant ces derives comme principe actif - Google Patents

Derives de 2-anilinopyrimidinone, intermediaires utilises dans la production de ceux-ci, procede de production correspondant et pesticides contenant ces derives comme principe actif Download PDF

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Publication number
WO1999052881A1
WO1999052881A1 PCT/JP1999/001976 JP9901976W WO9952881A1 WO 1999052881 A1 WO1999052881 A1 WO 1999052881A1 JP 9901976 W JP9901976 W JP 9901976W WO 9952881 A1 WO9952881 A1 WO 9952881A1
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Prior art keywords
group
added
pyrimidinone
trifluoromethyl
amino
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PCT/JP1999/001976
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English (en)
Japanese (ja)
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WO1999052881A8 (fr
Inventor
Kenji Hirai
Takeshi Yoshizawa
Natsuko Okano
Yuriko Yoshino
Chikako Ota
Toshiki Fukuchi
Hirofumi Tomita
Shinji Kawaguchi
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Sagami Chemical Research Center
Mitsubishi Chemical Corporation
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Application filed by Sagami Chemical Research Center, Mitsubishi Chemical Corporation filed Critical Sagami Chemical Research Center
Priority to JP2000543442A priority Critical patent/JP4478854B2/ja
Priority to AU33438/99A priority patent/AU3343899A/en
Publication of WO1999052881A1 publication Critical patent/WO1999052881A1/fr
Publication of WO1999052881A8 publication Critical patent/WO1999052881A8/fr

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    • 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur 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

Definitions

  • the present invention relates to 2-anilinopyrimidinone derivatives, production intermediates, methods for producing them, and pesticides containing them as active ingredients.
  • the present invention relates to a pesticide containing a 2-anilinobilimidinone derivative as an active ingredient.
  • a pesticide containing a 2-anilinobilimidinone derivative as an active ingredient.
  • insecticides, pesticides, fungicides, and herbicides that are effective in controlling agricultural and horticultural pests.
  • pests that have acquired resistance to pesticides that have been widely used in the past.
  • various pesticides such as triazoles (triadimefon), benzimidazoles (benomimil) in disease situations. , Thiophanemethyl, etc.), dicarboxyimides (procymidone, iprodione, etc.), phenylamides (metalaxyl, oxadixyl, etc.), and various diseases that have acquired resistance to pesticides have emerged in various places.
  • organophosphorus compounds dinitrothion, malathion, protiphos, DDVP, etc.
  • pyrethroids permethrin, cypermeline, fenvalerate, cyhalothrin, etc.
  • benzoylpereas It is becoming increasingly difficult to control pests that have acquired resistance to pesticides such as difluvenzuron, tefluvenzuron, chlorfluazuron) and neristoxin (cartap, bensultap).
  • pesticides for which pests have not yet acquired resistance for example, dithiocarbamate-phthalimid-based pesticides.
  • a new insecticide that shows a sufficient control effect even at low doses against various pests that have acquired resistance to conventional general-purpose agricultural and horticultural fungicides, insecticides, and acaricides, and that has little adverse effect on the environment.
  • agents There is a strong need for the development of agents.
  • acaricides the development of highly safe acaricides is also expected, as they show an excellent control effect even against mites that are resistant to conventional acaricides.
  • W093 / 21162 discloses a 2-arylaminopyrimidinone derivative having a structure similar to the compound of the present invention, There is no description of a compound having an aralkyl group on the nitrogen atom at the 3-position of the pyrimidinone ring.
  • the above publication does not disclose any physiological activity other than the herbicidal activity and the activity as a plant growth regulator of these compounds, such as bactericidal activity, insecticidal activity and acaricidal activity. Disclosure of the invention
  • An object of the present invention is to provide a high control effect against various pests that are resistant to conventional agricultural and horticultural fungicides, insecticides, and acaricides, as well as high safety against crops and excellent killing against weeds. It is to provide a new pesticide having herbal activity.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, as shown in the following general formula (1), a 21-anilininopyrimidinone derivative having an aralkyl group on the 3-position nitrogen atom has the above-mentioned characteristics.
  • the present invention has been found to be a compound having the same.
  • the present invention provides a compound represented by the general formula (1)
  • R 1 represents a halogen atom; ( ⁇ to (: 4 alkyl group or ⁇ to haloalkyl group; represents a hydrogen atom; to alkyl group; to (: 4 haloalkyl group)
  • C 4 alkyl group (( ⁇ - alkoxy ( ⁇ ⁇ (: 4 alkoxy) - alkyl group; ( ⁇ C 4 alkylthio) - (- 4 alkyl group; (( ⁇ - (5 Ashiruokishi) d -C 4 alkyl group; Chioshiana Bok (( ⁇ - (- 4 alkyl) group; ⁇ c 4 alkenyl group; c 3 to c 4 alkynyl; c t to c 5 Ashiru group; ( ⁇ alkoxy) carboxamide sulfonyl group; aminocarbonyl group; (( ⁇ - (alkyl) aminocarbonyl group; di-alkyl) ⁇ amino carbonyl group; ( ⁇ ⁇ (: 4 alkyl).
  • sulfo two Le radical a represents a methylene group optionally substituted
  • p is 1
  • X is a hydrogen atom; a halogen atom; an alkyl group; alkoxy) ⁇ C 4 alkyl group; ⁇ ⁇ shea Le group; a carboxy group; ( ⁇ alkoxy) Carbonyl group; cyano group; hydroxyl Group; C ; -alkoxy group;-halo alkoxy group; (C! ⁇ Alkoxy
  • R 1 R ⁇ AX m and p represent the same meaning as described above; R 3 represents a C 4 alkyl group; q represents 0 or 2); and a pyrimidinone derivative represented by the formula: General formula (3)
  • the present invention relates to a method for producing a 2-anilinobilimidinone derivative represented by the formula:
  • the present invention provides a compound represented by the general formula (lb):
  • R 2 ′ is ⁇ ⁇ (: 4 alkyl group; ⁇ (: 4 haloalkyl group; (( ⁇ ⁇ (: 4 alkoxy)) ( ⁇ ⁇ alkyl group; ( ⁇ (: 4 haloalkoxy) ⁇ (: 4 alkyl group; (( ⁇ - alkoxy - (- 4 alkoxy) - (4 alkyl group; (CL ⁇ C 4 ⁇ alkylthio) -C 4 alkyl group; (C i ⁇ C 5 Ashiruokishi) -C 4 alkyl group: thiocyanato (( ⁇ To (: 4 alkyl) group; to C 4 alkenyl group; to C 4 alkynyl group; to (: 5 acyl group; (C i to C 4 alkoxy) carbonyl group; amino carbonyl group; (to C 4 alkyl) ⁇ amino carbonyl group; di ( ⁇ (4 ⁇ alkyl) aminocarbonyl group; (( ⁇ - (
  • the present invention also provides a compound of the present invention represented by the general formula (2a) which is a raw material for producing a 2-anilinobilimidine derivative represented by the general formula (1): Ff'SOq
  • the present invention relates to a method for producing a pyrimidinone derivative represented by the formula:
  • R 1 examples include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a methyl group, an ethyl group, a propyl group; Alkyl groups such as isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group; fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trifluoromethyl group, 1-chloroethyl group And haloalkyl groups such as 2-chloroethyl group and 3-chloromethylpropyl group, and are preferably a halogen atom, especially a chlorine atom, a haloalkyl group, especially a trifluoromethyl group and a trichloromethyl group.
  • a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom
  • R 2 and R 2 ′ each represent a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group; a chloromethyl group, a trifluoromethyl group, a 2-chloroethyl group; Haloalkyl groups such as 3-fluoropropyl group; methoxymethyl group, ethoxymethyl group, propyloxime Alkoxyalkyl groups such as tyl group, butoxymethyl group, 1-methoxyl group and 2-methoxyethyl group; haloalkoxyalkyl groups such as trichloromethoxymethyl group and trifluoromethoxymethyl group; 2-methoxyl group Alkoxyalkoxyalkyl groups such as ethoxymethyl group and 2-ethoxyethoxymethyl group; alkylthioalkyl groups such as methylthiomethyl group, ethyl
  • Substituents on the methylene group represented by A include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group; methoxy group, ethoxy group, propoxy group, butoxy group, etc.
  • Lower alkoxy groups such as methoxycarbonyl and ethoxycarbonyl groups A lower alkoxycarbonyl group; a cyano group;
  • X include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a sec-butyl group.
  • Haloalkyl group such as methoxymethyl group, 2-methoxylethyl group, ethoxymethyl group, 2-ethoxylethyl group; and acyl group such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, and bivaloyl group.
  • Y represents a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group.
  • Haloalkyl groups such as 2-chloroethyl group and 3-chloropropyl group; alkoxyalkyl groups such as methoxymethyl group, 2-methoxyethyl group, ethoxymethyl group and 2-ethoxyethyl group; 2-propenyl group Alkenyl groups such as, 2-methyl-2-propenyl group, 2-butenyl group, 3-methyl-2-butenyl group, 1-buten-3-yl group; propargyl group, 2-butynyl group, Alkynyl groups such as 1-butyne-3-yl group; formyl group, acetyl group, propionyl group, butyryl group, valeryl group, bivaloyl group, etc .; carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbo Alkoxy carboxy such as benzyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-
  • Haloalkoxy groups such as 3-chloropropoxy, 2-chloro-1-methylethoxy and 2,2,2-trifluoroethoxy; methoxymethoxy, ethoxymethoxy, isopropoxymethoxy, 2- Alkoxyalkoxy groups such as methoxychetoxy group; carboxyalkoxy groups such as carboxymethoxy group and 1- (carboxy) ethoxyquin group; methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, 1- (methoxycarbonyl) E Alkoxycarbonylalkoxy groups such as toxic groups; 2-propenyloxy group, 2-methyl-2-propenyloxy group, 2-butenyloxy group, 3-methyl-2-butenyloxy group, 1-butene-3-yloxy Alkenyloxy groups such as 2-alkynoxy group, 1-methyl-2-propynyloxy group, 2-alkynyloxy group such as 2-butynyloxy group; phenyloxy group
  • Haloalkylthio groups such as chloromethylthio, difluoromethylthio, trifluoromethylthio, trichloromethylthio, and 2,2,2-trifluoroethylthio; methylsulfinyl and ethyl Alkylsulfinyl groups such as sulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, etc .; Haloalkylsulfinyl groups such as trifluoromethylsulfinyl group, trichloromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group; methylsulfonyl group, ethylsulfonyl group,
  • Examples of the halogen atom represented by Z and Z ′ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • preferred substituents X on the benzene ring include a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, and an alkoxy group.
  • Examples of Y include a halogen atom, an alkyl group, a haloalkyl group, a cyano group, and a nitro group.
  • Preferred examples of the group represented by R 1 include ( ⁇ to ( 4 haloalkyl groups, and examples of R 2 include a hydrogen atom, an alkyl group, an alkoxyalkyl group, and a haloalkoxyalkyl group.
  • the alkyl group represented by R 3 and R 3 ′ is a methyl group, an ethyl group, a propyl group, or an isopropyl group.
  • the leaving group represented by L includes a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methylsulfonyloxy group, a trifluoromethylsulfonyloxy group, Examples include substituted sulfonyloxy groups such as a phenylsulfonyloxy group and a paratrisulfonyloxy group.
  • examples of the alkyl group represented by include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. 1 ⁇
  • the 2-anilinobilimidinone derivatives of the present invention and their production intermediates can be produced by the methods exemplified in the following production methods.
  • Step 11 is a step of producing a 2-mercaptopyrimidinone derivative (2b) by reacting an isothiocynate derivative (5) with a 3-amino acrylate derivative (6).
  • the reaction can also be carried out in the presence of a base.
  • the base include triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, ⁇ , ⁇ -dimethylaniline, ⁇ , ⁇ -diamine.
  • Organic bases such as ethylaniline, 4-tert-butyl- ⁇ , ⁇ -dimethylaniline, pyridine, picolin, lutidine, diazabicycloundecene (DBU), diazabicyclooctane (DB0), imidazole, sodium carbonate, Carbonated lime, sodium bicarbonate, hydrogen hydride, sodium acetate, acetic acid, sodium methoxide, sodium methoxide, potassium tert-butoxide, sodium hydride, sodium hydride, hydrogen hydride, Alkali metal bases such as sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyllithium and lithiumhexamethyldisilazide can be used.
  • the desired product can be obtained in good yield by reacting the base with 0.1 to 2 equivalents of the substrate.
  • This reaction is preferably performed in a solvent.
  • a solvent any solvent that does not harm the reaction can be used.
  • Aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene, and aliphatic hydrocarbons such as pentane, hexane, and octane can be used.
  • Hydrogen solvents such as getyl ether, diisopropyl ether, tetrahydrofuran (THF), dimethoxetane (DME) and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; Halogen solvents such as chloroform, dichloromethane and the like; nitrile solvents such as acetonitrile and propionitol; ester solvents such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; N, N-dimethylformamide (DMF).
  • ether solvents such as getyl ether, diisopropyl ether, tetrahydrofuran (THF), dimethoxetane (DME) and 1,4-dioxane
  • ketones such as acetone, methyl ethyl ketone
  • Amide-based solvents such as ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone, etc.
  • a solvent, an alcoholic solvent such as methanol (MeOH), ethanol (EtOH), and isopropyl alcohol, dimethyl sulfoxide (DMS0), water, or a mixed solvent thereof can be used.
  • the reaction may be carried out at a temperature appropriately selected from the range of -78 ° C to the reflux temperature of the solvent, depending on the base used and the reaction conditions.
  • a part of the isothiosinate derivative (5) used as a raw material in this step is commercially available and can be easily obtained.
  • a method of reacting the corresponding aralkylamine with, for example, thiophosgene, a tertiary amine Reaction with carbon disulfide in the presence of carbon dioxide, followed by treatment with methyl chloroformate [J. Am. Chem.
  • Step 1 is a step of reacting the 2-mercaptopyrimidinone derivative (2b) with an alkylating agent (7) in the presence of a base to alkylate the sulfur atom to produce a 2-alkylthiopyrimidinone derivative (2c). It is.
  • Bases include sodium carbonate, carbon dioxide, sodium hydrogen carbonate, hydrogen carbonate, sodium acetate, sodium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium hydride, potassium hydride.
  • This reaction is preferably performed in a solvent.
  • a solvent any solvent that does not harm the reaction can be used.
  • Aromatic solvents such as benzene, xylene, and benzene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ethers such as getyl ether, diisopropyl ether, THF, ME, and 1,4-dioxane Solvents, ketones such as acetone, MEK, cyclohexanone, halogen solvents such as chloroform, dichloromethane, etc., nitrile solvents such as acetonitrile, propionitrile, etc., ethyl acetate, propyl acetate, butyl acetate, propion Ester solvents such as methyl acrylate, DMF, amide solvents such as ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrroli
  • the reaction may be carried out at a temperature appropriately selected from the range of 0 ° C to the reflux temperature of the solvent, although it varies depending on the base used and the reaction conditions.
  • Step 13 is a step of oxidizing the 2-alkylthiopyrimidinone derivative (2c) to produce a 2-alkylsulfonylpyrimidinone derivative (2d).
  • the oxidation can be carried out using an oxidizing agent.
  • the oxidizing agent used is an oxidizing agent generally used for oxidizing a sulfur atom, for example, a peracid such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, or the like.
  • an oxidizing agent such as hydrogen peroxide, nitric acid, and potassium permanganate can be used.
  • This reaction is preferably carried out in a solvent, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane; dimethyl ether; Ether solvents such as isopropyl ether, THF, DME and 1,4-dioxane, ketones such as acetone, MEK, cyclohexanone, halogen solvents such as chloroform and dichloromethane, water, or a mixture thereof Any solvent can be used as long as it does not harm the reaction of the solvent.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene
  • aliphatic hydrocarbon solvents such as pentane, hexane, and octane
  • dimethyl ether Ether solvents such as isopropyl ether, THF, DME
  • the reaction may be carried out at a temperature appropriately selected from the range of 0 ° C. to the solvent reflux temperature, although it varies depending on the oxidizing agent used and the reaction conditions.
  • Steps 1-4 and 5 are carried out by reacting the 2-alkylthiopyrimidinone derivative (2c) and the 2-alkylsulfonylpyrimidinone derivative (2d) with the aniline derivative (3), respectively, as starting materials. This is a step of producing an anilinobilimidine derivative (la).
  • Bases include sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyllithium, tert-butyllithium, trimethylsilyllithium, lithiumhexamethyldisilazide, sodium carbonate, Carbonic acid sodium, sodium acetate, sodium acetate, sodium methoxide, sodium methoxide, sodium tert-butoxide and other metal bases, triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine
  • organic bases such as, ⁇ , ⁇ -dimethylaniline, ⁇ , ⁇ -ethylaniline, 4-tert-butyl- ⁇ , ⁇ -dimethylaniline, pyridine, picoline, lutidine, DBU, DBO, imiguzole, etc. be able to.
  • the target compound can be a sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diiso
  • This reaction can be carried out in a solvent, and any solvent that does not harm the reaction can be used.
  • the solvent include amide solvents such as DMF, ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone, nitrile solvents such as acetonitrile and propionitol, benzene, toluene, xylene, Aromatic hydrocarbon solvents such as benzene, etc., aliphatic hydrocarbon solvents such as pentane, hexane, octane, etc., ethers such as getyl ether, diisopropyl ether, THF, DME, 1,4-dioxane Any solvent that does not harm the reaction, such as a solvent, S0, or a mixed solvent thereof can be used.
  • the reaction is carried out at a temperature appropriately selected from the range of -78 ° C to the solvent reflux temperature.
  • a temperature appropriately selected from the range of -78 ° C to the solvent reflux temperature is appropriately selected from the range of -78 ° C to the solvent reflux temperature.
  • Step 1 is a method for preparing a 2-anilinopyrimidine derivative (If) or (lh) of the present invention by halogenating the 5-position of the pyrimidine ring using the 2-anilinobilimidinone derivative (la) or (lg) as a raw material. This is the manufacturing process.
  • Halogenation can be carried out by using a halogenating agent.
  • a halogenating agent examples include chlorine, bromine, iodine, potassium fluoride, sulfurinolechloride, N-chloro succinic acid imid, and N- Bromosuccinic acid imid, N-iodine succinic acid imid, tert-butyl hypochlorite, dimethylaminosulfur trifluoride, carbon tetrachloride / triphenylphosphine, carbon tetrabromide / triphenylphosphine And the like.
  • the target compound can be obtained in high yield by using 1 to 2 equivalents of the base with respect to the substrate.
  • This reaction can be carried out in a solvent, and any solvent that does not harm the reaction can be used.
  • the solvent include aromatic hydrocarbon solvents such as benzene and dichlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, getyl ether, diisopropyl ether, THF, E, 1, It is possible to use ether solvents such as 4-dioxane, halogen solvents such as chloroform, methylene chloride and carbon tetrachloride, organic acid solvents such as acetic acid and propionic acid, or mixed solvents thereof. it can.
  • the reaction can be carried out at a temperature appropriately selected from the range of o ° C to the reflux temperature of the solvent to obtain the desired product in good yield.
  • step-7 the 2-anilinobilimidine derivative (lg) or (lg) of the present invention is reacted with the reagent (4) in the presence of a base, using the 2-anilinobilimidine derivative (la) or (If) as a raw material. lh).
  • Bases include sodium hydride, potassium hydride, lithium amide, sodium amide, and lithium diamide. Sopropylamide, butyllithium, tert-butyllithium, trimethylsilyllithium, lithium hexamethyldisilazide, sodium carbonate, carbonated lime, sodium acetate, acetated lime, sodium methoxide, sodium ethoxide, power Alkali metal bases such as lium-tert-butoxide, triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N, N-dimethylaniline, N, N-methylethylaniline, 4-tert-butyl Organic bases such as -N, N-dimethylaniline, pyridin, picoline, lutidine, DBU, DB0, imidazole and the like can be used. By using 1 to 2 equivalents of the base with respect to the
  • Solvents include amide solvents such as DMF, N, N-dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, benzene, toluene, xylene, and benzene.
  • Aromatic solvents such as pentane, hexane, octane, etc .; ether solvents such as getyl ether, diisopropyl ether, THF, ME, 1,4-dioxane, DMS0, Alternatively, a mixed solvent thereof can be used.
  • the desired product By conducting the reaction at a temperature appropriately selected from the range of 0 ° C. to the reflux temperature of the solvent, the desired product can be obtained in high yield.
  • polyethers such as 18-crown-6, 15-crown-5, 12-crown-4, tetrabutylammonium bromide, tetrabutylammonium sulfate, and tetraethylammonium
  • a quaternary ammonium salt such as mozide
  • the 2-anilino bilimidine derivative (1) of the present invention is useful for sanitary pests or pests harmful to agricultural and horticultural crops, particularly insects and mites, and for agricultural and horticultural crops. It shows high control effect at low drug concentration on harmful diseases and weeds.
  • the pests to be controlled include Lepidoptera such as Lotus monarch, Konaga, Cyanococcus monhamaki, Konomeiga and Nikameichiyu; Pelphins such as Tobirumoka, Segurounka, etc .; Aphids such as aphids, whiteflies such as whitefly, whitefly such as stink bugs; Larvae and adults of insects of the order Orthoptera, as well as eggs and larvae of the order Acarina, such as the mites spider mites, the red mites, the red mites, and the cynopodidae.
  • the compound of the present invention includes ascomycetes such as powdery mildew fungi on various crops, rust fungi on various crops, basidiomycetes such as rice sheath blight fungus, downy mildew fungi on various crops, plague fungi on various crops and the like. It has a high bactericidal effect against a wide range of phytopathogenic fungi such as blast fungi and incomplete fungi parasitic on various crops such as blast fungus and gray mold, and is an active ingredient of fungicides for agricultural and horticultural use. Useful.
  • the compound of the present invention can control weeds in any of pre-emergence soil treatment, growing foliage treatment and flooding treatment.
  • the weeds targeted by the compound of the present invention include, for example, Shiroza, Akaza, Inutade, Haruyude, Inoubu, Aobu, Hakobe, Hotokenoza, Ichibi, Onamomi, Wild morning glory, Korean ginseng, Wild ginseng, Seyyosumire, Oroshigiku, Kosendangusa, Meishiba, Ohishiba, Inubie, Enokorogsa and the like.
  • the compound of the present invention can be used as a selective herbicide for cultivated crops such as corn, wheat, rye, rice, daisies, and ivy.
  • the 2-anilinobilimidine derivative (1) of the present invention is useful as an agricultural and horticultural fungicide, a herbicide, an insecticide, and an acaricide.
  • insects, mites, phytopathogenic fungi and weeds to be controlled by the compounds of the present invention are not limited to those exemplified above.
  • the 2-anilinobilimidine derivative (1) of the present invention When used as an agricultural or horticultural agricultural chemical, it may be used alone, but is preferably in the form of a composition produced using a general-purpose agricultural chemical auxiliary. use.
  • the form of the fungicide, herbicide, insecticide, and acaricide of the present invention is not particularly limited, and examples thereof include emulsions, wettable powders, powders, flowables, dry flowables, fine granules, granules, tablets, oils, It is suitable to be in the form of a spray, an aerosol, a jumbo or the like.
  • one or more of the 2-anilinopyrimidine derivatives (1) of the present invention can be blended as an active ingredient.
  • the pesticide adjuvants used for producing fungicides, herbicides, insecticides and acaricides containing the 2-anilinobilimidine derivative (1) of the present invention as an active ingredient include, for example, fungicides, herbicides and It can be used for the purpose of improving the effect of insecticides and acaricides, stabilizing and improving dispersibility.
  • a carrier for example, a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersant, a disintegrant, and the like can be used.
  • liquid carrier examples include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butyl alcohol and glycol, ketones such as acetone and cyclohexanone, and amides such as dimethylformamide. And sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like.
  • Solid carriers include clay, kaolin, talc, diatomaceous earth, silica, Calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.
  • Usable surfactants can be used as emulsifiers and dispersants, for example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and lauryl betaine.
  • anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and lauryl betaine.
  • a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.
  • a spreading agent such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl phenyl ether; a wet spreading agent such as dialkyl sulfosuccinate; a fixing agent such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate; Disintegrants such as sodium lauryl sulfate can be used.
  • the content of the active ingredient in the fungicide, herbicide, insecticide, and acaricide for agricultural and horticultural use of the present invention is selected from the range of 0.01 to 99.5! 3 ⁇ 4, and the formulation form, application method, etc.
  • the emulsion is preferably prepared so as to contain about 1 to 90% by weight, preferably 10 to 40% by weight, of the active ingredient.
  • an undiluted emulsion can be prepared by mixing a solvent and a surfactant with the 2-anilinobilimidine derivative (1) of the present invention, which is the active ingredient, and further using this undiluted solution At this time, it can be applied after being diluted with water to a predetermined concentration.
  • a stock solution is prepared by mixing the active ingredient 2-anilinobilimidine derivative (1), a solid carrier and a surfactant, and the stock solution is diluted with water to a predetermined concentration before use. Can be used.
  • the active ingredient 2-anilinopyrimidine The derivative (1), the solid carrier, etc. can be mixed and applied as it is.
  • the active ingredient 2-anilinobilimidine derivative (1), the solid support, a surfactant, etc. are mixed. It can be manufactured by granulation and applied as it is.
  • the production method of each of the above-mentioned preparation forms is not limited to the above-mentioned method, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient, the purpose of application, and the like.
  • the fungicides, herbicides, insecticides, and acaricides for agricultural and horticultural use of the present invention include, in addition to the 2-anilinobilimidine derivative (1) of the present invention, which is an effective component, other fungicides, insecticides, and acaricides. Any active ingredient such as a herbicide, an insect growth regulator, a fertilizer, and a soil conditioner may be blended.
  • the method of application of the agricultural and horticultural fungicide, herbicide, insecticide, and acaricide of the present invention is not particularly limited, and may be applied by any method such as foliage application, water application, soil treatment, seed treatment, and the like. it can.
  • foliage application or soil treatment use a solution in a concentration range of 0.001 to 1000 ppm, preferably 0.01 to 500 ppm, at an application rate of about 0.1 to 5000 L, preferably about 10 to 2000 L per 10 ares.
  • the application rate is usually 0.1 to 1 OKg per 10 ares for granules containing 0.01 to 15% of active ingredient.
  • about 10 to 100 mL of a solution in a concentration range of 10 to 1000 ppm per 1 kg of seed weight can be applied.
  • Example Example 1 1 1
  • the reaction solution was concentrated under reduced pressure, water (300 mL) and ethyl acetate (300 mL) were added to the residue, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (100 mL ⁇ 3). The organic layers were combined, washed with water (300 mL ⁇ 3) and saturated saline (500 mL), and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure to give a light yellow color of 3- (4-fluorobenzyl) -2-methylthio-6-trifluoromethyl-4 (3H) -pyrimidinone [No. 23].
  • reaction solution was concentrated under reduced pressure, water (100 mL) and ethyl acetate (100 mL) were added to the residue, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (100 mL). The organic layers were combined, washed with water (100 mL) and saturated saline (100 RaL), and dried over anhydrous sodium sulfate. After filtering off the desiccant, the solvent was distilled off under reduced pressure.
  • the reaction solution was concentrated under reduced pressure, water (80 mL) and ethyl acetate (80 mL) were added to the residue, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (40 mL ⁇ 3). The organic layers were combined, washed with water (80 raLx3) and saturated saline (200 mL), and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure.
  • the organic layer was washed with a mixed solution (75raLx2) of saturated saline and water (1: 1), and the aqueous layer was extracted with ethyl acetate (75raL). And washed.
  • the organic layers were combined, dried over anhydrous sodium sulfate, the desiccant was filtered, and the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed sequentially with a mixed solution of saturated saline and water (1: 1) (80 mL ⁇ 2) and saturated saline (80 mL), and the aqueous layer was extracted with ethyl acetate (80 mL). The previous organic layer was washed with washed saline and saturated saline. The organic layers were combined, dried over anhydrous sodium sulfate, and after filtering the drying agent, the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed three times with a mixed solution of saturated saline and water (1: 1), and the aqueous layer was extracted with ether (80 mL). The organic layer was washed with the washed saline, and the organic layers were combined, dried over anhydrous sodium sulfate, the desiccant was filtered, and the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed successively with a mixed solution of saturated saline and water (1: 1) (130 mL ⁇ 2) and saturated saline, and then the aqueous layer was extracted with ether (130 mL) and washed with saturated saline and saturated saline. did.
  • the organic layers are combined, dried over anhydrous sodium sulfate, the desiccant is filtered, and the solvent is distilled off from the filtrate under reduced pressure.
  • the organic layer was washed successively with a mixed solution of saturated saline and water (1: 1) (70 mL x 2) and saturated saline (70 mL), and the aqueous layer was extracted with ether (70 mL). And washed.
  • the organic layers were combined, dried over anhydrous sodium sulfate, and after filtering the drying agent, the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed with a mixed solution of saturated saline and water (1: 1) (75raLx2), and then the aqueous layer was extracted with ether (75mL) and washed with saturated saline (75mL).
  • the organic layers were combined, dried over anhydrous sodium sulfate, and after filtering the drying agent, the solvent was distilled off from the filtrate under reduced pressure.
  • Ether (20 mL) and a saturated aqueous solution of ammonium chloride (10 mL) were added to the obtained mixture, the organic layer was separated, and the aqueous layer was further extracted with ether (10 mL ⁇ 2). After the organic layers were combined and washed with saturated saline (10 mL), the solvent was removed under reduced pressure.
  • the organic layer was washed with a mixed solution of saturated saline and water (1: 1) (60 mL ⁇ 2), and then the aqueous layer was extracted with ether (60 raL) and washed with saturated saline (60 mL).
  • the organic layers were combined, dried over anhydrous sodium sulfate, and after filtering the desiccant, the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed with a mixed solution of saturated saline and water (1: 1) (6 After washing with 0 mL ⁇ 2), the aqueous layer was extracted with ether (60 mL), and washed with saturated saline (6 OmL). The organic layers were combined, dried over anhydrous sodium sulfate, and after filtering the drying agent, the solvent was distilled off from the filtrate under reduced pressure.
  • the organic layer was washed twice with water and saturated saline (1: 1), and then with saturated saline. And washed.
  • the aqueous layer was extracted with ether (50 mL), and the previous organic layer was washed with washed brine.
  • the organic layers were combined and dried over anhydrous sodium sulfate. Dry After the desiccant was filtered off, the filtrate was concentrated under reduced pressure.
  • the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (15 mL ⁇ 3).
  • the organic layers were combined, washed with water (40 mL ⁇ 2), a saturated aqueous solution of sodium hydrogen carbonate (80 mL), and a saturated saline solution (80 mL), and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure.
  • the reaction solution was concentrated under reduced pressure, ether (10 mL) was added, and the filtrate obtained by filtering the insoluble material was washed with saturated aqueous sodium hydrogen carbonate (15 mL) and saturated saline (15 mL), and dried over anhydrous magnesium sulfate. Was. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure.
  • reaction solution was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After filtering off the drying agent, the filtrate was concentrated under reduced pressure to give 5-chloro-3- (3-chlorobenzyl) -2- (2-dimethoxy-4-trifluoromethylphenyl) amino-.
  • a yellow viscous liquid (1.20 g) of 6-trifluoromethyl-4 (3H) -pyrimidinone [No. 2-117] was obtained.
  • the filtrate obtained by filtering the insolubles was washed with saturated aqueous sodium hydrogen carbonate (15 iaL) and saturated brine (15 mL), dried over anhydrous magnesium sulfate, and the desiccant was filtered off, and the filtrate was concentrated under reduced pressure.
  • potassium carbonate 0.21 g, 1.52 ol
  • 18-crown-6-ether 26 mg, 0.10 ol
  • chloroethyl (co-methyl) ether 0.78 g, 6 ol). .05 marl ol
  • Hydrogenated sodium (2-methylthio-3-S-phenethyl-6-trifluoromethyl-4 (3H) _pyrimidinone (3.10g, 9.86 ol) and aniline (0.65niL) were added to a F (lOraL) solution.
  • 60% oily, 0.36 g, 9. Oramol) was added at room temperature, and the mixture was stirred at the same temperature for 13 hours, and then stirred at 70 ° C for 2 hours.
  • Ether (20 mL) and a saturated aqueous solution of ammonium chloride (aOraL) were added to the obtained mixture, the organic layer was separated, and the aqueous layer was further extracted with ether (10 mL ⁇ 2).
  • Example 1 By a method similar to that described in 200, the reaction was carried out by reacting 2-methylthio-6-trifluoromethyl-4 (3H) -pyrimidinone having an aralkyl group at the 3-position with a substituted aniline. To 2-anilino-3-aral Kill-6-trifluoromethyl-4 (3H) -pyrimidinone [No. 2-158 to 164] was obtained. The compound name, compound number, yield, melting point and 1 H-NMR spectrum data are shown below. Example—20 1
  • Example 1 By a procedure similar to that described in 186, 2- (2,4-bistrifluoromethylphenyl) amino-3- (4-chlorobenzyl) -6-trifluoromethyl- 4 By chlorinating (3H) -pyrimidinone (0.52 g, 1.0 marl) with N-chloro succinic acid imide (0.13 g, L0mniol), 2- (2,4-bistriol) is obtained. Fluoromethylphenyl) amino-5-chloro-3- (4-chlorobenzene) -6-trifluoromethyl-4 (3H) -pyrimidinone [No. 2-165] white solid ( 0.36 g).
  • Example 1 2- (2,4-Bistrifluoromethylphenyl) amino-3- (4-fluorobenzyl) -6-trifluoromethyl-4 (3H) -pyrimidinone (2- (2,4-bistrifluoromethylphenyl) amino-3- (4-fluorobenzyl) -4-pyrimidinone) 0,50 g, 1.0 bandol ol), 2- (2,4-bistrifluoromethylphenyl) amino-3- (3,5-dichlorobenzene) -6-trifluoromethyl-4 ( 3H) -Pyrimidinone (0.55 g, 1.

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

Abstract

Cette invention se rapporte à des dérivés de 2-anilinopyrimidinone représentés par la formule générale (1), qui possèdent d'excellents effets contre divers champignons pathogènes, les insectes parasites, les mites et les mauvaises herbes en agriculture et en horticulture.
PCT/JP1999/001976 1998-04-15 1999-04-14 Derives de 2-anilinopyrimidinone, intermediaires utilises dans la production de ceux-ci, procede de production correspondant et pesticides contenant ces derives comme principe actif WO1999052881A1 (fr)

Priority Applications (2)

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JP2000543442A JP4478854B2 (ja) 1998-04-15 1999-04-14 ２−アニリノピリミジノン誘導体及び製造中間体、それらの製造方法並びにそれらを有効成分として含有する農薬
AU33438/99A AU3343899A (en) 1998-04-15 1999-04-14 2-anilinopyrimidinone derivatives, intermediates in the production thereof, process for producing the same and pesticides containing the same as the active ingredient

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JP10/119917 1998-04-15
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JP2001131156A (ja) * 1999-11-08 2001-05-15 Sagami Chem Res Center ２−置換アミノピリミジノン誘導体、それらの製造方法並びにそれらを有効成分とする殺虫、殺ダニ剤
JP2001354659A (ja) * 2000-06-13 2001-12-25 Kureha Chem Ind Co Ltd 新規ピラゾリン誘導体、その製造方法、及び有害生物防除剤
JP2002338551A (ja) * 2001-05-22 2002-11-27 Sagami Chem Res Center ２−アニリノ−４（３ｈ）−ピリミジノン誘導体及び製造中間体、それらの製造方法、並びにそれらを有効成分とする有害生物防除剤
WO2013118855A1 (fr) * 2012-02-09 2013-08-15 塩野義製薬株式会社 Noyau hétérocyclique et dérivé carbocyclique
WO2013144223A1 (fr) 2012-03-30 2013-10-03 Basf Se Composés de pyrimidinylidène n-substitués et dérivés destinés à lutter contre les animaux nuisibles
EP2604260A4 (fr) * 2010-08-10 2015-01-07 Shionogi & Co Nouveaux dérivés hétérocycliques, et composition pharmaceutique comprenant ceux-ci
US9150546B2 (en) 2009-02-13 2015-10-06 Shionogi & Co., Ltd. Triazine derivative and pharmaceutical composition comprising the same
US9718790B2 (en) 2010-08-10 2017-08-01 Shionogi & Co., Ltd. Triazine derivative and pharmaceutical composition having an analgesic activity comprising the same
US9732060B2 (en) 2013-06-14 2017-08-15 Shionogi & Co., Ltd. Aminotriazine derivative and pharmaceutical composition comprising the same

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JPH0288655A (ja) * 1988-07-29 1990-03-28 Ciba Geigy Ag 塩素含有ポリマー用安定剤としてのチオウラシル
WO1993021162A1 (fr) * 1992-04-15 1993-10-28 Nissan Chemical Industries, Ltd. Derive de 2-arylaminopyrimidinone, et herbicide et regulateur de la croissance vegetale contenant ce compose
JPH0789941A (ja) * 1993-09-27 1995-04-04 Nissan Chem Ind Ltd フェニルグアニジン誘導体および除草剤

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JPH0288655A (ja) * 1988-07-29 1990-03-28 Ciba Geigy Ag 塩素含有ポリマー用安定剤としてのチオウラシル
WO1993021162A1 (fr) * 1992-04-15 1993-10-28 Nissan Chemical Industries, Ltd. Derive de 2-arylaminopyrimidinone, et herbicide et regulateur de la croissance vegetale contenant ce compose
JPH0789941A (ja) * 1993-09-27 1995-04-04 Nissan Chem Ind Ltd フェニルグアニジン誘導体および除草剤

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4674676B2 (ja) * 1999-11-08 2011-04-20 公益財団法人相模中央化学研究所 ２−置換アミノピリミジノン誘導体、それらの製造方法並びにそれらを有効成分とする殺虫、殺ダニ剤
JP2001131156A (ja) * 1999-11-08 2001-05-15 Sagami Chem Res Center ２−置換アミノピリミジノン誘導体、それらの製造方法並びにそれらを有効成分とする殺虫、殺ダニ剤
JP2001354659A (ja) * 2000-06-13 2001-12-25 Kureha Chem Ind Co Ltd 新規ピラゾリン誘導体、その製造方法、及び有害生物防除剤
JP2002338551A (ja) * 2001-05-22 2002-11-27 Sagami Chem Res Center ２−アニリノ−４（３ｈ）−ピリミジノン誘導体及び製造中間体、それらの製造方法、並びにそれらを有効成分とする有害生物防除剤
US9150546B2 (en) 2009-02-13 2015-10-06 Shionogi & Co., Ltd. Triazine derivative and pharmaceutical composition comprising the same
US9688643B2 (en) 2009-02-13 2017-06-27 Shionogi & Co., Ltd. Triazine derivative and pharmaceutical composition comprising the same
JP2017081969A (ja) * 2010-08-10 2017-05-18 塩野義製薬株式会社 新規複素環誘導体およびそれらを含有する医薬組成物
EP2604260A4 (fr) * 2010-08-10 2015-01-07 Shionogi & Co Nouveaux dérivés hétérocycliques, et composition pharmaceutique comprenant ceux-ci
US9212130B2 (en) 2010-08-10 2015-12-15 Shionogi & Co., Ltd. Heterocyclic derivative and pharmaceutical composition comprising the same
US9718790B2 (en) 2010-08-10 2017-08-01 Shionogi & Co., Ltd. Triazine derivative and pharmaceutical composition having an analgesic activity comprising the same
JPWO2013118855A1 (ja) * 2012-02-09 2015-05-11 塩野義製薬株式会社 複素環および炭素環誘導体
US20160024072A1 (en) * 2012-02-09 2016-01-28 Shionogi & Co., Ltd. Heterocyclic Ring and Carbocyclic Derivative
US9550763B2 (en) 2012-02-09 2017-01-24 Shionogi & Co., Ltd. Heterocyclic ring and carbocyclic derivative
WO2013118855A1 (fr) * 2012-02-09 2013-08-15 塩野義製薬株式会社 Noyau hétérocyclique et dérivé carbocyclique
WO2013144223A1 (fr) 2012-03-30 2013-10-03 Basf Se Composés de pyrimidinylidène n-substitués et dérivés destinés à lutter contre les animaux nuisibles
US9732060B2 (en) 2013-06-14 2017-08-15 Shionogi & Co., Ltd. Aminotriazine derivative and pharmaceutical composition comprising the same
US10065941B2 (en) 2013-06-14 2018-09-04 Shionogi & Co., Ltd. Aminotriazine derivative and pharmaceutical composition comprising the same

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