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WO2000029388A1 - Derives de 2-(phenylimino substitue) pyrimidine, intermediaires dans la production de ces derniers, procede de production de ces derniers et pesticides contenant ces derniers comme ingredient actif - Google Patents

Derives de 2-(phenylimino substitue) pyrimidine, intermediaires dans la production de ces derniers, procede de production de ces derniers et pesticides contenant ces derniers comme ingredient actif Download PDF

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Publication number
WO2000029388A1
WO2000029388A1 PCT/JP1999/006208 JP9906208W WO0029388A1 WO 2000029388 A1 WO2000029388 A1 WO 2000029388A1 JP 9906208 W JP9906208 W JP 9906208W WO 0029388 A1 WO0029388 A1 WO 0029388A1
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group
trifluoromethyl
alkyl group
alkoxy
alkyl
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PCT/JP1999/006208
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English (en)
Japanese (ja)
Inventor
Kenji Hirai
Natsuko Okano
Ryuta Ohno
Maho Nagaoka
Atsushi Uchida
Chikako Ota
Toshiki Fukuchi
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Sagami Chemical Research Center
Mitsubishi Chemical Corporation
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Priority to AU10791/00A priority Critical patent/AU1079100A/en
Priority to JP2000582375A priority patent/JP4600621B2/ja
Publication of WO2000029388A1 publication Critical patent/WO2000029388A1/fr

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    • 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- (substituted furimino) pyrimidine derivatives, intermediates for producing them, methods for producing them, and pesticides containing them as active ingredients.
  • the present invention relates to a pesticidal agent containing a 2- (substituted furimino) pyrimidine derivative as an active ingredient, and in particular, to arthropods (insects) in the fields of agriculture and horticulture, clothing and dwelling-related or livestock and pets. And mites), nematodes, helminths and protozoa.
  • a pesticidal agent containing a 2- (substituted furimino) pyrimidine derivative as an active ingredient, and in particular, to arthropods (insects) in the fields of agriculture and horticulture, clothing and dwelling-related or livestock and pets. And mites), nematodes, helminths and protozoa.
  • insecticides and acaricides for example, organophosphorus agents (hue nitrothion, malathion, protifoss, DDVP, etc.), pyrethroids ( Acquired resistance to pesticides, such as permethrin, cypermethrin, humvalerate, cyhalothrin, benzoinoleurea (difluvenzuron, tefluvenzuron, chlorofunorazuron, etc.), and nereistoxin (cartap, bensultap, etc.) It is becoming more difficult year after year to control pests.
  • organophosphorus agents hue nitrothion, malathion, protifoss, DDVP, etc.
  • pyrethroids Acquired resistance to pesticides, such as permethrin, cypermethrin, humvalerate, cyhalothrin, benzoinoleurea (diflu
  • Japanese Kokai Tokkyo Koho JP 06/157478 discloses a pyrimidine derivative having insecticidal and acaricidal activity.
  • the substituted phenylimino group is substituted with a pyrimidine. It is present at the 4-position of the ring, and is different from the compound of the present invention.
  • Japanese Kokai Tokkyo Koho JP 07/002799 discloses a 2- (substituted funinilimino) pyrimidine derivative having a herbicidal activity and a plant growth regulator.
  • the above publication does not mention any physiological activity other than herbicidal activity and action as a plant growth regulator, such as insecticidal, acaricidal and fungicidal activities of these compounds.
  • derivatives having two trifluoromethyl groups on the phenyl ring on the 2-position imino group and derivatives having one or two halogen atoms introduced into two trifluoromethyl groups are specifically described. Examples are shown No mention is made of their biological activity.
  • no 2- (substituted phenylimino) pyrimidine derivatives having a nitro group as a substituent on the fuynyl ring on the 2-position imino group have been reported so far. Disclosure of the invention
  • An object of the present invention is to provide a high control effect on various pests that are resistant to conventional insecticides, acaricides, nematicides, etc. for agricultural and horticultural use, clothing and shelter-related or livestock and pets, Another object of the present invention is to provide a novel pest control agent having high safety for crops.
  • a novel 2- (substituted phenylimino) pyrimidine derivative represented by the following general formula (1) is a compound having the above characteristics. This led to the completion of the present invention. That is, the present invention provides a compound represented by the general formula (la) ⁇ i a)
  • R 1 represents a hydrogen atom; a halogen atom; ⁇ alkyl group; - (8 a cycloalkyl group; ⁇ (:! 6 Ha port alkyl group; ( ⁇ - ( ⁇ Arukokishi ⁇ ⁇ Arukiru group;
  • ⁇ ⁇ Ararukiru group represents a optionally substituted Fuweniru group or an optionally substituted C 2 -C 6 vinyl groups
  • R 3 a is ( ⁇ ⁇ (: 6 alkyl; C 3 -C 8 cycloalkyl group; ⁇ Haroa Kill groups; human Dorokishi C 2 -C 6 7 alkyl group; ( ⁇ - ( ⁇ alkoxy) - alkyl group; (Ci ⁇ haloalkoxy) Cl to c 6 alkyl group; ⁇ (6 alkoxy ( ⁇ (6 alkoxy) ⁇ !
  • Kiriden an amino group and X is (to display the] ⁇ ⁇ haloalkyl group, Y a is hydrogen atom or a (:. Representing the ⁇ alkyl group) 2- (substituted phenylene Ruimino) pyrimidine derivative represented by the effective It relates to pesticides as components, especially insecticides and acaricides.
  • R 3 b is ⁇ C 6 alkyl group; ⁇ Ji 8 cycloalkyl group; ⁇ (:. 6 haloalkyl group; ( ⁇ C 6 alkoxy ) -C 6 alkyl group; (( ⁇ - (6 haloalkoxy) - (- 6 alkyl group; ⁇ C 6 alkoxy ( ⁇ C 6 alkoxy) - (- 6 alkyl group; (( ⁇ - (6 alkylthio) ⁇ alkyl group; (C ⁇ alkoxy) carboxamide sulfonyl (: ⁇ (6 alkyl group; ( ⁇ (:!
  • n is an integer of 0 to 4. However, when n is 2 to 4 integer ⁇ is be the same or different A 2- (substituted phenylimino) pyrimidine derivative represented by the general formula (lc):
  • R la is a hydrogen atom, a halogen atom, - (6 alkyl group; C 3 - Shikuroa alkyl group; ⁇ ⁇ Ha port alkyl group; ( ⁇ C 6 alkoxy) - (- 6 alkyl group; C 3
  • R 3 c is a C 3 to C 8 cycloalkyl group; a hydroxy C 2 to C 6 alkyl group; ((:!
  • R 2, R 3 ⁇ X , Y a represents.
  • Z represents a halogen atom as defined above, p is 0, 1 or 2.
  • the present invention relates to a production intermediate represented by the general formula (le):
  • R 3b has the same meaning as described above, and L represents a leaving group).
  • R 3d is, R 2 is - (6 Ha port alkyl group; alkoxy) - (6 ⁇ alkyl group; C 3 -C 6 haloalkenyl group; C 3 - C port alkynyl; substituted Good ⁇ ( ⁇ . Aralkyl group; optionally substituted phenyl group or optionally substituted ⁇ In the case of C 6 vinyl group, ⁇ C 6 alkyl group; 3 ⁇ cycloalkyl group; ⁇ (: 6 Ha port alkyl group; (- (6 alkoxy) ⁇ - (6 Al kill group; ( ⁇ C, Roarukokishi) - (6 alkyl group; ⁇ (6 alkoxy (
  • R la, R 2, R 3 d, X, Y a and m are as defined above.
  • 2 represented by - relates to a process for preparing (substituted phenylene Ruimino) pyrimidine derivative.
  • R 3 e is ⁇ ⁇ (: 6 alkyl group; C 3 -C 8 cycloalkyl group; ⁇ : 2- (: 6 alkyl group; hydroxy C 2 -alkyl group; (( ⁇ ⁇ ( ⁇ alkoxy) C 2 ⁇ C 6 alkyl Group; (( ⁇ - (6 alkoxy) carbonyl ( ⁇ ⁇ (:! 6 alkyl group; (C ⁇ Ashiruoki Shi) - c 6 alkyl group; Shiano-c 6 alkyl group; ⁇ c 6 alkenyl group; c 3 ⁇ halo alkenyl; hydroxy C 3 -C 6 alkenyl group; c 3 to c 6 alkynyl
  • R ⁇ R 3 ⁇ X , Y b and m are as defined above.
  • 2 represented by - about (substituted phenylene Ruimino) pyrimidine derivative.
  • the present invention provides a compound represented by the general formula (3d 3)
  • the present invention relates to a method for producing a 2- (substituted furimino) pyrimidine derivative represented by the formula:
  • a 2- (substituted furimino) pyrimidine derivative represented by the formula:
  • substituent represented by R 1 include a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom and a halogen atom of an iodine atom; a methyl group and an ethyl group , Propyl, isopropyl, cyclopropyl, butyl, isobutyl, S-butyl, alkyl or cycloalkyl such as t-butyl, cyclopentyl and cyclohexyl; fluoromethyl, chloromethyl, bromomethyl, trichloromethyl, trifluoromethyl, trichloroethyl, 2 -Haloalkyl groups such as chloroethyl group and 3-chloropropyl group; alkoxyalkyl groups such as methoxymethyl group, 2-methoxyethyl group,
  • alkoxy group fluoromethyoxy group, difluorome Toxic group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, chloromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2-chloro-1-methylethoxy
  • Haloalkoxy groups such as methoxy ethoxy, ethoxy methoxy, 2-chloroethoxy methoxy, 2-methoxy ethoxy methoxy, isopropoxy methoxy, 2-methoxy ethoxy and other alkoxyalkoxy groups; cyano methoxy, A cyanoalkoxy group such as a 1-cyanoethoxy group; a 2-propenyloxy group, a 2-methyl-2 Alkenyloxy groups such as -propenyloxy group, 2-butenyloxy group, 3-methyl-2-butenyloxy group, 1-butene-3-yloxy group; 2-chloro-2-propenyloxy group; Haloal
  • substituents as a pesticide include a halogen atom, a haloalkyl group and a nitro group, among which a chlorine atom, a bromine atom and a trifluoromethyl group are preferred.
  • Derivatives having two trifluoromethyl groups or derivatives in which two trifluoromethyl groups are further substituted with a halogen atom have high biological activity and reduced toxicity to mammals. Thus, these substituents are particularly preferred.
  • substituents represented by R la can be mentioned exemplified substituents R 1 except nitro group.
  • substituent represented by R 2 include a methyl group, an ethyl group, a propyl group, Alkyl groups such as isopropyl, butyl, isobutyl, S-butyl, t-butyl, cyclopropylmethyl, pentyl, isopentyl, neopentyl, hexyl, and isohexyl; Methyl group, 2-bromoethyl group, 2-chloropropyl group, 2-bromopropyl group, 1-chloro-2-propyl group, 1-bromo-2-propyl group, 3-fluoropropyl group, etc.
  • Haloalkyl group alkoxyalkyl group such as methoxymethyl group, 2-methoxyl group, ethoxymethyl group and 2-ethoxylethyl group; 2-propenyl group, 2-methyl-2-propenyl group, 2-butenyl group Alkenyl groups such as, 3-methyl-2-butenyl group and 1-butene-3-yl group; 2-octopen-2-propenyl group, 3-octopen-2-propenyl group 2-propynyl group, 1-butyn-3-yl group, 2 Alkynyl groups such as 3-butynyl group and 3-butynyl group; alkynyl groups such as 3-bromo-2-propynyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group, 3-methylcyclopentyl group and cyclohexyl group Groups: benzyl group, 2-chlorobenzyl group, 3-chlorobenzene group,
  • substituent of the optionally substituted fuunyl group represented by K 2 Halogen atom of fluorine atom, chlorine atom, bromine atom, iodine atom; Ci-alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, S-butyl group, t-butyl group, etc.
  • 6 alkoxy) alkoxyl group 6 alkoxyl group; cyano group; hydroxyl group; Ci to C such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, S-butoxy, t-butoxy, etc. 6 alkoxy groups; trifluoromethoxy group, difluoromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2-chloro-1-methylethoxy group, 2,2,2-trifluoroethoxy group, etc.
  • -Alkoxy) carbonyl-alkoxy) groups such as (methoxycarbonyl) ethoxy group; 2-propenyloxy group, 2-methyl-2-propenyloxy group, 2-butenyloxy group, 3-methyl -Cs alkenyloxy group such as 2-butenyloxy group and 1-butene-3-yloxy group; 2-propynyloxy group, 1-methyl-2-propynyloxy group, 2-butynyloxy group and the like ⁇ C 6 ⁇ Ruquinyloxy group; phenyloxy group, 4-methylphenyloxy group, 3-chlorophenyloxy group, 2-fluorophenyloxy group, 4-fluorophenyloxy group, etc.
  • substituents represented by R 3 a is a methyl group, Echiru group, a propyl group, an isopropyl group, a butyl group, Isopuchiru group, alkyl groups such as s-butyl group and t-butyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; fluoromethyl group, chloromethyl group, bromomethyl group, trichloromethyl group, trifluoromethyl group Haloalkyl groups such as 1-chloroethyl group, 2-chloroethyl group, and 3_chloroethyl propyl group; 2-hydroxyethyl group, trihydroxy-2-propyl group, 3-hydroxypropyl group, etc.
  • Hydroxyalkyl group methoxymethyl group, ethoxymethyl group, propyloxymethyl group, butyloxymethyl group, 1-methoxyxethyl
  • Alkoxyalkyl groups such as 2-methoxyethoxyl, 2-ethoxyethyl, and tetrahydrofuran-3-yl; trifluoromethoxymethyl, trichloromethoxymethyl, 2,2,2-trifluoro Haloalkoxyalkyl groups such as ethoxymethyl group and 2-chloroethoxymethyl group
  • alkoxyalkoxyalkyl groups such as 2-methoxyethoxymethyl group, 2-methoxyethoxymethyl group and 2-ethoxyethoxymethyl group
  • Alkylthioalkyl groups such as methylthiomethyl group, ethylthiomethyl group, 1_ (methylthio) ethyl group and 2- (methylthio) ethyl group
  • a thiocyanatoalkyl group such as a thiocyanatomethyl group and a thiocyanatoethyl group; a 2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-methyl-2-butenyl group; Alkenyl groups such as 1-butene-3-yl group; haloalkenyl groups such as 2-chloro-2-propenyl group and 3-chloro-2-propenyl group; Hepta-hydroxyalkenyl group such as 4-hydroxy-2-butenyl group; 2-propynyl group, 1-butyn-3-yl group, 2-butynyl group, 3-butynyl group, 3 Alkynyl groups such as -pentynyl group; haloalkynyl groups such as 3-butamo-2-propynyl group; hydroxyalkynyl groups such as 4-hydroxy-2-butynyl group; 2- (methyl
  • R 3 b Each substituent represented by R 3 b, R 3 ⁇ R 3 d or R 3 e is its described in R 3 a Each corresponding substituent can be exemplified.
  • X include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a trichloromethyl group, a trifluoromethyl group, a 1-chloroethyl group, Examples thereof include haloalkyl groups such as a 2-chloroethyl group, a 3-chloropropyl group, and a pentafluoroethynole group.
  • Y a or alkyl group represented by Y b can be exemplified a methyl group, Echiru group, a propyl group, a butyl group or the like.
  • Y b or Upsilon epsilon in represented Ru halogen atom it can be exemplified fluorine atom, chlorine atom, bromine atom and the like.
  • Specific examples of the halogen atom represented by ⁇ include a fluorine atom, a chlorine atom, and a bromine atom.
  • the 2- (substituted furimino) pyrimidine derivatives of the present invention can be produced by the methods exemplified in the following Production Methods 11 to 4.
  • the production method 1 and the production method 1 use the 2-anilino-4 (3-)-pyrimidinone derivative (3a) or (3b) as a raw material, and the compound represented by the general formula (4a) or (4b) in the presence of a base. And producing the 2- (substituted phenylimino) -3H-pyrimidine derivative (lb ') or (lc), respectively, of the present invention.
  • Step one 1 and step one 2 in these manufacturing methods in the presence of a base.
  • the base include sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide (LM), butyllithium, t-butyllithium, trimethylsilyllithium, lithium hexamethyldisilazide, sodium carbonate, and carbonated lithium.
  • Metal bases such as sodium acetate, sodium acetate, sodium acetate, sodium acetate, sodium methoxide, sodium ethoxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydro
  • Organic bases such as 4. 0] penta-5-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABC0) and imidazole can be used.
  • the target product can be obtained in good yield by using 1 to 2 equivalents of the base relative 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 amide solvents such as ⁇ , ⁇ -dimethylformamide (DMF), ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone ( ⁇ ), and nitrile-based solvents such as acetonitrile and propionitrile.
  • Solvents Aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Jetyl ether, diisopropyl ether, tetrahydrofuran (THF), and dimethoxetane (E), an ether solvent such as 1,4-dioxane, dimethyl sulfoxide (DMS0), or a mixed solvent thereof can be used.
  • the reaction varies depending on the base to be used and the like, and the target compound can be obtained in good yield by performing the reaction at a temperature appropriately selected from the range of -78 ° C to the solvent reflux temperature.
  • polyethers such as 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether and the like, tetrabutylammonium bromide Quaternary ammonium salts such as tetrabutylammonium sulfate, tetraethylammonium sulfate, metal salts such as lithium bromide, sodium bromide, potassium iodide, sodium iodide, silver oxide, etc.
  • Step one 1 and step one 2 (4a) or the like substituents previously exemplified for the reactant represented by formula (4b) Oite, as substituents represented by R 3 b, or R 3 d
  • substituents represented by R 3 b, or R 3 d substituents represented by R 3 b, or R 3 d
  • the leaving group represented by L include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a P-toluenesulfonyloxy group, and a substituted sulfonyloxy group. And the like.
  • alkylating agents such as dialkyl sulfates such as dimethyl sulfate and diethyl sulfate and trimethyl oxonium tetrafluoroborate are also included in the reactant represented by the general formula (4a) or (4b).
  • Steps 11 and 12 the compound of the present invention, 2- (substituted phenylimino) -4, having a substituent introduced on the 1-position nitrogen atom, as shown in the following general formula: (1H, 3H) -pyrimidinone derivatives and 2-anilino-4 (3H) -pyrimidinone derivatives (lb ") and (1c"), in which a substituent is introduced on the nitrogen atom of the 2-position anilino group, are secondary.
  • These compounds may be produced by a general separation and purification method such as silica gel column chromatography, etc., using the 2- (substituted phenylimino) -3H-pyrimidine derivative of the present invention which is the target of the reaction And can be easily separated.
  • step one 1 and step one 2 for example, the general formula (4a) or (4b)
  • a product in which the 5-position of the pyrimidine ring is alkylated may be obtained depending on the type of the substituent group and the reaction conditions (see below). See Examples).
  • the 2- (substituted phenylimino) -3H-pyrimidine derivatives thus obtained are also included in the compound of the present invention.
  • Production method 3 is to chlorinate a 2-anilino-4 (3H) -pyrimidinone derivative (3c) to give a 2- (substituted phenylimino) -4-chloro-3H-pyrimidine derivative (le), A method for producing a 2- (substituted phenylimino) -3H-pyrimidine derivative (If) of the present invention by reacting with an alcohol (5) in the presence of a base.
  • Step-3 comprises chlorinating the 4-position carboxy group of the 2-anilino-4 (3H) -pyrimidinone derivative (3c) to form the 2- (substituted phenylimino) -4-cyclo-3H-pyrimidine derivative of the present invention. This is the step of manufacturing (le).
  • Halogenation can be performed by using a halogenating agent.
  • a halogenating agent a chloride such as phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride can be used.
  • the chlorinating agent in an excess of at least 1 equivalent relative to the substrate, the desired product can be obtained in good yield.
  • 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, ME, and 1,4.
  • -Ether solvents such as dioxane, halogen solvents such as chloroform, dichloromethane and carbon tetrachloride, organic acid solvents such as acetic acid and propionic acid, and mixed solvents thereof can be used.
  • Step 14 is a step of reacting the 2- (substituted phenylimino) -4-chloro-3H-pyrimidine derivative (le) with an alcohol (5) in the presence of a base. This is a step of producing a (2,2,3-amino) -3H-pyrimidine derivative (If).
  • Bases include sodium hydride, lithium hydride, lithium amide, sodium amide, LDA, butyllithium, t-butyllithium, trimethylsilyllithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, Alkali metal bases such as sodium acetate, acetate acetate, sodium methoxide, sodium methoxide, sodium phosphate-1-butoxide, sodium hydroxide, hydroxide hydroxide, metal base, triethylamine, diisopropylethylamine , Tributylamine, N-methylmorpholine, MA, N, N-methylethylaniline, 4- 1-butyl- ⁇ , ⁇ -dimethylaniline, pyridine, ⁇ , picoline, noretidine, DBU, DAB CO, imidazole, etc.
  • Organic base and the like can be used.
  • the base binds to the substrate
  • the desired product can be obtained in good yield.
  • This reaction can be carried out in a solvent, and any solvent that does not harm the reaction can be used.
  • Solvents include amide solvents such as MF, N, N-dimethylacetamide and NMP, nitrile solvents such as acetonitrile and propionitrile, and aromatic solvents such as benzene, toluene, xylene, and benzene.
  • Hydrocarbon solvents such as pentane, hexane, octane, etc., ether solvents such as diethyl ether, diisopropyl ether, THF, DME, 1,4-dioxane, DMS0, or a mixture thereof
  • ether solvents such as diethyl ether, diisopropyl ether, THF, DME, 1,4-dioxane, DMS0, or a mixture thereof
  • a solvent or the like can be used.
  • the reaction varies depending on the alcohols, bases, and the like used, and the desired product can be obtained in good yield by performing the reaction at a temperature appropriately selected from the range of -78 ° C to the solvent reflux temperature.
  • alcohols used in this step include methanol, ethanol, propyl alcohol, isopropyl alcohol, cyclopropyl alcohol, butyl alcohol, isobutyl alcohol, s-butyl alcohol, pentanol, 3-pentanol, and neopentyl.
  • Ru can Shimesuru. Further, glycidyl alcohol, tetrahydrofuran-3-ol, tetrahydrovirane-2-methanol, 1,3-dioxan-5-ol and the like can also be exemplified, but the alcohols that can be used are not limited to these examples. Not something.
  • Production method-4 (Step 1-5) is to react a 2-anilino-4 (3H) -pyrimidinone derivative (3d) with a reactant represented by the general formula (4a) in the presence of a base, This is a method for producing the 2- (substituted phenylimino) -4 (1H, 3H) -pyrimidinone derivative (2a) of the present invention.
  • Step-15 is performed in the presence of a base.
  • the base the base described in Step 11 and Step 12 can be used.
  • the target product can be obtained in high yield by using 1 to 2 equivalents of the base relative to the substrate.
  • This reaction can be carried out in a solvent and is a solvent that does not harm the reaction. If you can use it.
  • the solvent the solvents described in Step 11 and Step 12 can be used.
  • the reaction varies depending on the base to be used and the like, and the target compound can be obtained in good yield by performing the reaction at a temperature appropriately selected from the range of -78 ° C to the solvent reflux temperature.
  • polyethers such as 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, tetrabutylammonium bromide, sulfuric acid Coexistence of quaternary ammonium salts such as tetrabutylammonium and tetraethylammonium, metal salts such as bromoammonium, sodium bromide, potassium iodide, sodium iodide, and silver oxide By reacting below, the target product can be obtained with higher yield.
  • Step 15 is a reaction under the same conditions as the reactions of Step 1 and Step 12.
  • a 2- (substituted phenyl) in which a substituent was introduced on the 4-position oxygen atom was also used.
  • they can be easily separated by a common separation and purification method such as silica gel column chromatography.
  • R 4 and R 5 represent a C 6 alkyl group, and also represent a halogen atom.
  • R 2 , X, Y ⁇ L and m represent the same meaning as described above.
  • Step 16 is a step of producing the 2-mercapto-4 (3H) _pyrimidinone derivative (8) by reacting the isothiosane derivative (7) with the 3-aminoacrylic acid ester derivative (6). .
  • the reaction can be carried out in the presence of a base.
  • a base examples include triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, DMA, N, N-methylethylaniline, and 4--1-butyl- ⁇ , ⁇ -dimethylaniline, pyridine, DMAP, picoline, lutidine, DBU, MBC0, imidazole, and other organic bases, sodium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium acetate, potassium acetate, Sodium methoxide, sodium methoxide, potassium hydroxide, sodium hydride, sodium hydride, lithium hydride, lithium amide, sodium amide, butyllithium, t-butyllithium, LDA, trimethylsilyllithium, lithiumhexamethyldisilazide Alkali such as sodium hydroxide, potassium hydroxide A metal base or the like can be used.
  • the desired product By reacting the base with 0.1 to 2.0 equivalents to the substrate, the desired product can be obtained in high yield.
  • 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, toluene, xylene, and benzene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, getyl ether, diisopropyl ether, THF, and the like.
  • Ether-based solvents such as DME and 1,4-dioxane; ketones such as acetone, methylethylketone (MEK) and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitriles such as acetonitrile and propionitrile Solvent, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, etc., amide solvents such as F, ⁇ , ⁇ -dimethylacetamide, ⁇ , etc., methanol (MeOH), ethanol (EtOH) ), Alcohol solvents such as isopropyl alcohol, DMS0, water, or a mixture of these. it can.
  • ketones such as acetone, methylethylketone (MEK) and cyclohexanone
  • halogen-based solvents such as chloroform and dichloromethane
  • 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 isothiocyanate derivative (7) used as a raw material in this step is commercially available and can be easily obtained. Also, a method of reacting the corresponding amines with, for example, thiophosgene, a method of isomerizing thiosyanate [Japan Kokai Tokkyo Koho JP 05/43541 (Chemical Abstracts 130: 72256)], disulfide in the presence of a tertiary amine Reaction with carbon followed by treatment with methyl chloroformate [J. Am. Chem.
  • Step 1 the 2-mercapto-4 (3H) -pyrimidinone derivative (8) is reacted with an alkylating agent (9) in the presence of a base to alkylate the sulfur atom to form a 2-alkylthio-4 (3H ) -Pyrimidinone derivative (10a).
  • Bases include sodium carbonate, carbon dioxide, sodium bicarbonate, hydrogen bicarbonate, sodium acetate, gallium acetate, sodium methoxide, sodium methoxide, sodium 1-butoxide, sodium hydride, hydrogenation Potassium, sodium amide, butyllithium, t-butyllithium, LM, trimethylsilyllithium, alkali metal bases such as lithiumhexamethyldisilazide, sodium hydroxide, potassium hydroxide, etc., triethylamine, diisopropylethylenoleamine, tributyl , N-methylmorpholine, MA, N, N-Jetylaniline, 4- 1-butyl-N, N-dimethylaniline, pyridine, MAP, picolin, lutidine, DBU, DABC0, imidazole, etc.
  • a base or the like can be used. Although the stoichiometric amount of the base is sufficient for
  • 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, ether solvents such as dimethyl ether, diisopropyl ether, THF, DME, 1,4-dioxane, ketones such as acetone, MEK, cyclohexanone, halogen solvents such as chloroform, dichloromethane, etc.
  • Nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; amide solvents such as DMF, ⁇ , ⁇ -dimethylacetamide and ⁇ , MeOH, EtOH, alcoholic solvents such as isopropyl alcohol, DMS0, water, or a mixture of these It is possible.
  • the reaction varies depending on the base used and the reaction conditions. It can be performed at a temperature appropriately selected from the range up to the temperature.
  • examples of the leaving group represented by L include a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a P-toluenesulfonyloxy group.
  • a chlorine atom a bromine atom
  • a halogen atom such as an iodine atom
  • methanesulfonyloxy group such as an xy group
  • Step 18 is a step of oxidizing the 2-alkylthio-4 (3H) -pyrimidinone derivative (10a) to produce a 2-alkylsulfonyl-4 (3H) -pyrimidinone derivative (10b).
  • This step can be carried out using an oxidizing agent.
  • the oxidizing agent used include oxidizing agents commonly used for oxidizing sulfur atoms, such as peracetic acid, perbenzoic acid, and m-chloroperbenzoic acid.
  • An oxidizing agent such as peracid or hydrogen peroxide, nitric acid, 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; getyl ether; Ether solvents such as diisopropyl ether, THF, DME and 1,4-dioxane; ketones such as acetone, MEK and cyclohexanone; halogen solvents such as chloroform and dichloromethane; water; and mixed solvents thereof Any solvent that does not harm the reaction can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene
  • aliphatic hydrocarbon solvents such as pentane, hexane, and octane
  • getyl ether Ether solvents such as diisopropyl ether, THF, DME and 1,
  • the reaction can 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.
  • Step 9 the 2-alkylthio-4 (3H) -pyrimidinone derivative (10a) or the 2-alkylsulfonyl-4 (3H) -pyrimidinone derivative (10b) is used as a raw material to react with the aniline (11).
  • This is a step of producing a 2-anilino-4 (3H) -pyrimidinone derivative (3c).
  • the reaction of Step 19 is preferably performed in the presence of a base in terms of good yield.
  • Bases include sodium hydride, potassium hydride, lithium amide, Thorium amide, LDA, butyllithium, t-butyllithium, trimethylsilyllithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium methoxide, Potassium-butoxide, sodium hydroxide, alkali metal bases such as potassium hydroxide, triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, DMA, ⁇ , ⁇ -ethylaniline, 4- Organic bases such as -butyl- ⁇ , ⁇ -dimethylaniline, pyridine, DMAP, picoline, lutidine, DBU, MBC0, and imidazole can be used.
  • the desired amount of the base can be obtained in
  • 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 and ⁇ , butritol solvents such as acetonitrile and propionitrile, and aromatic hydrocarbons such as benzene, toluene, xylene, and benzene.
  • Hydrogen solvents aliphatic hydrocarbon solvents such as pentane, hexane, octane, etc., ether solvents such as getyl ether, diisopropyl ether, THF, DME, 1,4-dioxane, MS0, or a mixed solvent thereof Any solvent can be used as long as it does not harm the reaction such as the above.
  • the reaction can be carried out at a temperature appropriately selected from the range of -78 ° C to the reflux temperature of the solvent, whereby the desired product can be obtained in high yield.
  • Step one 1 0 2 Anirino - 4 (3H) -
  • Y a is used as the hydrogen atoms in the raw material, and halogenated pyrimidine ring 5-position, 2 - ⁇ two Reno -
  • the halogenation can be carried out by using a halogenating agent.
  • the halogenating agent used include chlorine, bromine, iodine, potassium fluoride, sulfuryl chloride, N-chloro mouth succinate imid, and N-bromoamber.
  • Acid imid N-iodine succinic acid imid, t-butyl hypochlorite, getylaminosulfur Halogenating agents such as trifluoride, carbon tetrachloride / triphenylphosphine, and carbon tetrabromide / triphenylphosphine can be used.
  • getylaminosulfur Halogenating agents such as trifluoride, carbon tetrachloride / triphenylphosphine, and carbon tetrabromide / triphenylphosphine can be used.
  • the desired product can be obtained in good yield by using 1 to 2 equivalents of the base relative 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, ME, 1,4 -Ether solvents such as dioxane, halogen solvents such as chloroform, dichloromethane and carbon tetrachloride, organic acid solvents such as acetic acid and propionic acid, and mixed solvents thereof can be used.
  • the desired product when the reaction is carried out at a temperature appropriately selected from the range of 0 ° C. to the reflux temperature of the solvent, the desired product can be obtained with high yield.
  • the pest control agent containing the compound of the present invention as an active ingredient is useful for repelling, controlling, and controlling pests in a wide range of fields such as agriculture, forestry, livestock industry, fisheries, and product preservation and public health in these industries. It is effective for etc.
  • the compound of the present invention is particularly useful for repelling and controlling pests in agriculture, forestry, etc., specifically when cultivating crops, harvests, trees, ornamental plants, etc., and in public health situations. Excellent effect as insecticide and acaricide used for control and the like.
  • target pests are shown below, but the present invention is not limited to the following description.
  • the more specifically exemplified pests do not limit the target pests, and the exemplified pests also include their adults, larvae, eggs and the like.
  • the compound of the present invention can be used for agricultural crops such as food crops (rice, wheat, corn, Potatoes, sweet potatoes, beans, etc.), vegetables (brassic crops, sea urchins, eggplants, tomatoes, leeks, etc.), fruit trees (citrus, apples, grapes, peaches, etc.), special crops (tobacco, tea, sugar beet) , Sugar cane, cotton, olive, etc.), grass and forage crops (sorghum, grass, legumes, etc.) and ornamental plants (herbaceous, flowers, garden trees, etc.) during the growing season. It is effective for repelling and controlling pests such as arthropods, molluscs, nematodes, and various fungi.
  • agricultural crops such as food crops (rice, wheat, corn, Potatoes, sweet potatoes, beans, etc.), vegetables (brassic crops, sea urchins, eggplants, tomatoes, leeks, etc.), fruit trees (citrus, apples, grapes, peaches, etc.), special crops (
  • the compounds of the present invention are harmful when storing harvested products from the above-mentioned crops, such as cereals, fruits, tree nuts, spices and tobacco, and products that have been subjected to drying, powdering, etc. It is also effective for repelling and extermination of living things. It is also effective in protecting standing trees, fallen trees, processed timber, and stored timber from damage by pests such as termites and beetles.
  • Specific pests include, for example, those belonging to the arthropod phylum, mollusc phylum, and linear animal phylum as follows.
  • arthropod phylum Insecta examples include the following.
  • the order Lepidoptera there are, for example, the family Noctuidae such as Spodoptera litura, Tobacco beetle, Noctuida, and Tamanaginba; the stagflies such as Konaga; the anthracidae such as Cyanococcus terrestris; Laminariaceae, such as Papilionidae; Limpetidae, such as Papilionidae; Scarabaeidae, such as Negi-koga; Scarabaeidae, such as Scarabaeidae; Iridaceae, such as moths; Mesinaceae, such as Kobomimeiga, Nikameichiyu, and P.
  • the stagflies such as Konaga
  • the anthracidae such as Cyanococcus terrestris
  • Laminariaceae such as Papilionidae
  • Limpetidae such as
  • Coleoptera for example, Douganebuuibu, Scarabaeidae such as beetles; beetles such as beetles; beetles such as marc beetles; beetles such as marc beetles; tents such as tentacles; And beetles, such as Chrysomelidae; Pterodactylidae, such as peach beetle; Pterodactylidae, such as arimodokibushi;
  • Hemiptera examples include, for example, stink bugs such as Coleoptera and Stinging bugs; Sting bugs such as pear bugs; Helicopteridae such as Coleoptera; Sting bugs such as Spider Helicopter; Gastropodidae such as Nashigumbai, etc .; Coleoptera, such as Usumi dori-mekuragame; Cicada, such as Nichiniizemi; Coleoptera, such as grapevine; Coleoptera, such as Coleoptera; Lepidoptera, such as Leafhoppers; Lepidoptera, such as brown beetle; Tonidae, such as Tobira-noka; Phyllophoridae, such as Apohagoromo; Phyllomorphidae, such as pear lice; Whitefly, Silverleaf whitefly, etc.
  • stink bugs such as Coleoptera and Stinging bugs
  • Sting bugs such as pear bugs
  • Helicopteridae such as Coleoptera
  • Sting bugs such
  • Lamiaceae Lamiaceae; Filophyllaceae such as cricket brassicae; Lentaceae such as apple beetles; Aphids such as L. aphid, peach aphid, and okabonoa force aphid; And the insects of the family Pterodactylidae; ruber beetles; etc .;
  • a thrips family such as Citrus thrips, Chrysanthemum thrips, and a thrips thrips
  • Hymenoptera include, for example, honeybees such as the power wasp; apple wasps And other honeybees; honeybees and the like; honeybees and the like.
  • the diptera for example, the flies that belong to the order of the flies such as soybean flies and the fly; Engineering can be mentioned.
  • the Orthoptera includes, for example, grasshoppers such as crickets; crickets such as pine beetles; ceraceae such as kerataceae; and grasshoppers such as kobaneinago.
  • grasshoppers such as crickets
  • crickets such as pine beetles
  • ceraceae such as kerataceae
  • grasshoppers such as kobaneinago.
  • bryozoan family such as brown bryozoan
  • the termites include, for example, termites such as Taiwan termites, and the example of the earwigs include, for example, the earwigs such as the earworms.
  • arthropod phylum crustaceae and spider webs The following can be exemplified as arthropod phylum crustaceae and spider webs.
  • Examples of isopods of the crustacean include the family Oxodidae, such as the Okadan Bug.
  • acarid mites of the class Arachnid include, for example, Dermatophagoids, such as Cyanomycidae and Cyclamenidae; Dermatophagoides, such as barley mites; Berberidae, such as Bud ⁇ Himehadada2; Rubiaceae; Rubiaceae; Rutaceae, Apple Rabbitii, and 2 Pseudomonidae; Rubiaceae; Rubiaceae; Rubiaceae;
  • the gastropods of the gastropods include, for example, Scutellaria mussels, and the peduncles include, for example, African snails, slugs, Nycophora methaji, Chacolana slugs, and U.S. it can.
  • Examples of the genus Coleoptera include, for example, Anguinaceae, such as Imogusarecentiyu; Tirenkorinkusu, such as Namiikusekisenyu; Bratyrenx, such as Kitanegu Salenchiyu, Minamigusarechinyu; Family: Heteroderidae such as potato cysts; Melodydaceae such as sweet potatoes; Cliconiaceae such as ⁇ ⁇ ; Notorenidae such as strawberry; and Aflencoides such as strawberry And the like.
  • Examples of the order Coleoptera Longidoridae, such as P. elegans;
  • the compound of the present invention is also effective for repelling, controlling and controlling pests that damage trees or affect the vigor of natural forests, plantations and urban green spaces.
  • specific pests include the following.
  • arthropod insects and spider webs examples include the following.
  • Lepidoptera for example, Scutellariae such as Sugidokuga and Gypsy moth; Kalehagaceae such as Makakareha and Gigakareha; Meigataceae such as Larix sylvestris; Gagaceae such as L. brajaga; Kamamatsui Tohikihamaki, Kurimiga, Sugigasa etc. Family: Hirrigidae, such as Amerikashi-Mori, and Moglitiviga, such as Shimogliticiga;
  • the Coleoptera for example, Scarabaeidae, such as Scarabae beetle, and Nagachacogane; Tenebrionidae, such as Pleurotus terrestris; Etc .; Ossomoptidae such as Ozomuushi; Psyllididae such as pine bark beetle, Itayan bark beetle; For example, a family of Nagashininushi, such as cypress.
  • Scarabaeidae such as Scarabae beetle, and Nagachacogane
  • Tenebrionidae such as Pleurotus terrestris
  • Etc . Ossomoptidae
  • Ozomuushi such as Ozomuushi
  • Psyllididae such as pine bark beetle, Itayan bark beetle
  • a family of Nagashininushi such as cypress.
  • Hemiptera for example, aphid family such as Aphididae; aphid family such as ezomacca sabra; marsupiidae family such as cedar round scale; etc .; Can be.
  • Hymenoptera include honeybees, such as the stag beetle; scabies, such as the pine sawfly;
  • dipterans include the genus Dermatidae, such as P. terrestris, the genus Dermatidae, such as L. japonicus, and the flies that include adults, larvae, and eggs.
  • spiders of the order Acarina include Suginohadani and Todoma nohadani.
  • the Nematodes of the Nematodes of the Nematoda there may be mentioned, for example, the parasitafenelidae family such as the pine wood mosquito.
  • the pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in addition to other active compounds such as insecticides, pesticides, and the like in the above-mentioned preparations effective in agriculture and forestry, and in any use form prepared by the preparations. It can be used in combination or as a mixture with mites, nematicides, fungicides, synergists, plant regulators, herbicides, baits and the like.
  • the form of use is arbitrary, for example, wettable powders, wettable powders for granules, aqueous solvents, emulsions, solutions, suspensions in water ⁇ ⁇ ⁇ Floables such as emulsions in water, capsules, powders, granules, aerosols, etc. Can be mentioned.
  • the content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but is usually from 0.001 to 95% by weight, preferably from 0.1 to 60% by weight as the total amount of the active ingredients. is there.
  • the method of use depends on the type and amount of pests, the target crops, trees and other species, the cultivation form, and the state of growth.For example, for arthropods, gastropods, nematodes, etc. Generally, the area where damage is caused by these pests, or where damage may occur, is The amount of the active ingredient may be 0.1 to 1000 g, preferably 1 to 100 g.
  • Specific application methods include, for example, the above-mentioned wettable powders, wettable powders for granules, aqueous solvents, emulsions, liquids, suspensions in water, and flowables such as emulsions in water, capsules, etc. It may be diluted and sprayed on crops, trees, etc. in the range of 10 to 1000 liters per 10 ares, depending on the type of crop, tree, etc., cultivation form, and growth condition. In the case of powders and aerosols, the preparations may be applied to crops, trees, etc. within the range of the above-mentioned usage.
  • the target pest mainly infects crops, trees, etc. in soil
  • the flowables, capsules, etc. can be diluted with water and applied generally in the range of 5 to 500 liters per 10 ares.
  • the medicine may be sprayed on the soil surface so as to be evenly applied to the entire application area, or the medicine may be irrigated into the soil.
  • the form of the preparation is a powder or granules
  • the preparation may be sprayed as it is on the soil surface so as to be uniform over the entire area to be applied.
  • spraying or irrigation it may be applied only around seeds, crops, trees, etc. that you want to protect from damage by pests, or plowed during or after spraying to disperse the active ingredient mechanically. You may.
  • a pesticidal composition containing the compound of the present invention as an active ingredient may be adhered around plant seeds by a known method. Such treatment not only prevents damage by pests in the soil after sowing the seeds, but also reduces the foliage, flowers, fruits, etc. of the plant from pest damage after growth. It can also be protected.
  • the pesticidal composition containing the compound of the present invention as an active ingredient may be used alone or separately.
  • Can be used in combination or as admixture with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents and synergists.
  • the content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but it is usually 0.0001 to 95% by weight of the total amount of the active ingredient, and it is not preferable for oils, powders, granules, etc. 0.005 to 10% by weight, preferably 0.01 to 50% by weight in emulsions, wettable powders and sols. Specifically, for example, in the case of controlling and controlling termites and beetles, 0.01 to 100 g of the active ingredient compound per lm 2 may be sprayed on the soil or wood surface.
  • the pesticidal composition containing the compound of the present invention as an active ingredient is infested internally or externally with animals such as pets bred in the livestock industry, the fishery industry, and the home, and eats and sucks blood from the skin.
  • animals such as pets bred in the livestock industry, the fishery industry, and the home, and eats and sucks blood from the skin.
  • Effective for repelling, controlling and controlling pests such as arthropods, nematodes, trematodes, tapeworms, protozoa, etc. that cause direct harm such as spreading disease, etc. It can also be used to prevent and treat diseases associated with these pests.
  • the target animals include vertebrates, such as warm-blooded vertebrates such as cattle, sheep, goats, horses, pigs, and other livestock and farmed fish; and poultry, dogs, cats, and other mice, rats, and hamsters. And rodents such as squirrels; carnivores such as furlets; and pet animals such as fish.
  • vertebrates such as warm-blooded vertebrates such as cattle, sheep, goats, horses, pigs, and other livestock and farmed fish
  • poultry, dogs, cats, and other mice, rats, and hamsters rodents
  • rodents such as squirrels; carnivores such as furlets; and pet animals such as fish.
  • the following can be exemplified as the arthropod phylum Insecta and spider webs.
  • dipterans examples include the Afidae family, for example, amabutab, ummetogebu, and akaushiab; the housefly family, such as blowfly, housefly, and flies; the ⁇ manoc engineering department, such as the fly; the ⁇ shiba engineering department, such as the fly; Pterodactylae, such as Pterodactyla fossils, etc .; Phytospermaceae, such as P. serrata; Pteridophyta, such as Pterodactyla and Dermatophagidae; And the squid family, such as Nichinori-Nukanuka.
  • Afidae family for example, amabutab, ummetogebu, and akaushiab
  • the housefly family such as blowfly, housefly, and flies
  • the ⁇ manoc engineering department such as the fly
  • the ⁇ shiba engineering department such as the
  • examples of the Lapidoptera include human fleas such as cat flea and flea flea.
  • examples of the lice include lice of the family Lepidoptera nits, such as lice and lice; lice, such as Mahle lice; lice of the family Lice, such as white lice; and lice of the family Lice, such as white lice.
  • acarids of the arthropod spiders include the tick family, for example, tick ticks, sick ticks, red ticks, swelling ticks, etc .; trifoliaceae, such as Trissidae; And Dermatophagoids such as Dermatophagoides farinae and Acarinae; and Dermatophagoids such as Dermatophagoides farinae.
  • the following can be illustrated as examples of the nematodes of the nematode phylum.
  • Examples of the order Coleoptera include hookworms, pig nematodes, pig lungworms, ciliate nematodes, and caterpillar nodules.
  • As the roundworms for example, roundworm, roundworm, etc. can be mentioned.
  • Examples of the flatworm fluke include, for example, Schistosoma japonicum, Hepatic fluke, Schistosoma japonicum, P. westermani, and Japanese egg fluke.
  • Examples of the tapeworm include foliate tapeworms, tapeworms, Beneden tapeworms, square tapeworms, striated tapeworms, and tapered tapeworms.
  • the order of the root flagellates is, for example, Histomonas
  • the order of the protoflagellate is, for example, Leishmania, Trypanosoma, etc.
  • the order of the multiflagellate is, for example, Giardia, etc. Is, for example, Trichomonas, etc. o
  • amoeba of the fleshytes for example, Entamoeba and the like
  • sporeworm Piroplasma subclasses for example, Theilaria and Babesia
  • live sporozoa subclasses for example, Eimeria Plasmodiunu Toxoplasma Cite be able to.
  • the pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in another active compound such as an insecticide in a formulation effective in the livestock industry or the aquatic industry described above, and in any use form prepared by the formulation. It can be used in combination or as a mixture with acaricides, nematicides, fungicides, fungicides, synergists, plant regulators, herbicides and poison baits.
  • Specific methods of application include, for example, a pharmaceutical composition that can be mixed with feed for livestock pets or the like, or that can be orally ingested, such as tablets or pills containing a pharmaceutically acceptable carrier-coating substance.
  • a pharmaceutical composition that can be mixed with feed for livestock pets or the like, or that can be orally ingested, such as tablets or pills containing a pharmaceutically acceptable carrier-coating substance.
  • it can be administered transdermally as spray, powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo, etc.
  • a device eg, a collar, a medallion, a tag, etc.
  • an animal e.g., a device attached to an animal to control arthropods locally or systemically can be used.
  • Beverage preparations When administered orally as a medicinal beverage preparation, it is usually dissolved in a suitable non-toxic solvent or water together with a suspending agent such as bentonite or a wetting agent or other excipients, or the suspension or What is necessary is just to make a dispersion liquid, and may contain an antifoaming agent as needed.
  • Beverage preparations generally contain the active ingredient compound in an amount of 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight.
  • capsules, pills or tablets containing a predetermined amount of the active ingredient compound are usually used.
  • These use forms include diluents, fillers, disintegrants and / or Alternatively, it is produced by homogeneously mixing with a binder, for example, starch, lactose, talc, magnesium stearate, vegetable gum and the like.
  • a binder for example, starch, lactose, talc, magnesium stearate, vegetable gum and the like.
  • the weight and content of the anthelmintic may be appropriately determined according to the type of host animal to be treated, the degree of infection and the type of parasite, and the weight of the host.
  • the final feed When administered via feed, there may be mentioned, for example, a method in which the active ingredient compound is homogeneously dispersed in the feed, or a method in which the drug is used as top dressing or in the form of a bellet.
  • the final feed usually contains 0.0001 to 0.05% by weight, preferably 0.0005 to 0.01% by weight of the active ingredient compound.
  • the active ingredient compound When dissolved or dispersed in a liquid carrier excipient, it may be administered parenterally to animals by intraruminal, intramuscular, intratracheal or subcutaneous injection. Because of parenteral administration, the active ingredient compound is preferably mixed with vegetable oils such as peanut oil and cottonseed oil. In such a formulation, the active ingredient compound is generally contained in an amount of 0.05 to 50% by weight, preferably 0 .; ⁇ 0.2% by weight.
  • a preparation mixed with a carrier such as dimethyl sulfoxide or a hydrocarbon solvent can be directly or locally applied to the external surface of a livestock animal by spraying or direct injection.
  • the pesticidal agent containing the compound of the present invention as an active ingredient has adverse effects on clothes, food, and living environment, further harms the human body, and carries and transmits pathogens in public health situations and the like. It is also effective in repelling, controlling and controlling pests for maintaining public health.
  • pest control agents containing the compound of the present invention as an active ingredient include, for example, wood products such as wood in and inside and outside the house, wooden furniture, stored foods, clothing, books, animal products (skin, hair, etc.). , Wool, feathers, etc.) and plant products (clothing, paper, etc.), etc., which have an adverse effect on sanitary life such as lepidoptera, beetles, spots, cockroaches, flies, mites, etc. Repellent, eradication 'Effective in controlling.
  • this Specific examples of pests in such public health situations include the following.
  • Examples of the arthropod phylum Insecta include the following.
  • Examples of the Lepidoptera include, for example, Pterodaceae such as Monshiro dokuga; Psychophyllidaceae such as Kunugikareha; Iragidae such as Aoilaga; Madagalaceae such as Takenohosokuroba; And the like; and the genus Higashikoga, such as Iga and Koiga.
  • Pterodactylidae such as Pterodactyla
  • Pterodactylidae such as Mamehanmyo
  • Flocketidae such as Pterodactyla
  • Occidental pterodactyl such as Pterodactyla and Pterodactyla
  • Beetles such as endophus beetles, broad beetles, etc .
  • Tenebrionidae such as kokunustomodoki
  • Beetle family such as beetle beetles
  • beetle family such as beetle beetle
  • beetle family such as beetle beetle
  • long beetle family such as beetle beetle, beetle beetle
  • Hymenoptera examples include hornets, such as wasps, hornets, etc .;
  • dipterans include: A family of stag beetles such as stag beetle; a family of stag beetles such as brassicae;
  • technics include a fly engineering, such as black fly, and a blow fly, such as black flies; a two-flies engineering, such as a fly; a fly engineering, such as a fruit fly; and a chisuba engineering, such as a cheese fly.
  • Examples of the order Lepidoptera include a flea family such as flea flea.
  • the viscera for example, Murasakito Occidental beetles, such as vivid beetles.
  • the cockroaches include, for example, cockroaches such as German cockroaches and European cockroaches; cockroaches such as cockroaches, black cockroaches, and black cockroaches.
  • the Orthoptera includes, for example, the family Corrugidae, such as the Madara Powered Madoma and the Camadidae.
  • the louse include, for example, the lice of the lice such as the head lice; the lice of the lice such as the lice.
  • bed bugs such as bed bugs; and bugs such as sand turtles can be mentioned.
  • Examples of the termites include the termites of the termites such as the termites and termites; termites such as the termites of the termites; termites such as the termites of the termites, such as the termites of the termites and the termites of the termites. Can be mentioned.
  • Examples of the order Staphylococcus may include, for example, spots such as stag beetles and scorpions o.
  • arthropod spiders The following can be exemplified as arthropod spiders.
  • mites examples include, for example, ticks, such as Schurz ticks; mites, such as house dust mites; Pterodaceae, such as house dust mites; two families of lice, such as lice mites; two families of acrids, such as Acrididae; And the family Dermatidae, such as the stag beetle, such as the stag beetle; the mites, such as the mites Dermatophagidae and the mites;
  • Examples of the true spiders include, for example, the spiders, such as the birch spider; the spiders, such as the spider spider; the spiders, such as the spider, the spiders; And the like.
  • scorpiones there may be mentioned, for example, the scorpion family, such as the scorpion.
  • Other arthropod phylums For example, the order Pterodaceae such as Centipede and Azumkade may be mentioned.
  • Examples of the arthropod polypodes Ophiaceae include, for example, Rhododendrons such as Tokayasude, and examples of the arthropod phylum crustacea include the Parasitoids such as Waradinae.
  • examples of the annelid fauna, Lepidoptera include the family Lamavir, such as Lamavir.
  • the pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in combination with other active compounds such as insecticides, acaricides in any of the above-mentioned preparations effective in public health, and in any use form prepared by the preparation. It can be used in combination or as an admixture with agents, nematicides, fungicides, synergists, plant regulators, herbicides, baits and the like.
  • the form of use is optional.
  • the amount of the active ingredient compound in these preparations is 0.0001 to 95% by weight! 3 ⁇ 4 It is preferable to contain.
  • Application methods include pests, such as arthropods that directly harm or arthropods that are vectors of disease, etc. ⁇ Injection ⁇ Irrigation ⁇ Applying, Spraying powders, fumigants, mosquito coils ⁇ Self-burning smokers ⁇ Heat fogs such as chemical reaction type fogs, smokers such as fogging, ULV agents, etc. And the method of treatment with such a preparation. In addition, they are applied in other forms such as granules, tablets or poison bait, or by dripping floating powder, granules, etc. into waterways, wells, reservoirs, water tanks and other running or stationary water. Just do it.
  • formulations in these forms of use can also be present as a mixture with other active compounds, for example insecticides, acaricides, nematicides, fungicides, repellents or synergists, These preparations preferably contain the active ingredient compound in a total amount of 0.0001 to 95% by weight.
  • the compounds of the present invention may be used alone or in combination with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents, synergists and the like or as a mixture. You can do it.
  • the content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but is usually from 0.0001 to 95% by weight of the total amount of the active ingredient. 005 to 10% by weight
  • the content is preferably 0.01 to 50% by weight.
  • 0.01 to 100 g of the active ingredient compound per lm 2 may be sprayed around or directly on the surface.
  • compositions such as pharmaceuticals Acceptable carriers-tablets, pills, capsules, pastes, gels, beverages, medicated feed, medicated drinking water, medicated bait, sustained release large pills, etc. It can be administered orally as a sustained release device or the like, or transdermally as a spray, powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo, etc. Specific formulation and the like can be prescribed in the same manner as the method described in the section of “(B) Livestock industry, fishery industry, etc.”.
  • the compound of the present invention can be used in combination with other active compounds or as a mixture.
  • the following are examples of more specific active compounds, but are not limited thereto.
  • organic phosphorus agents include, for example, dichlorvos, phennitrothion, malathion, naled, chlorpyrifos, diazinon, tetrachlorvinphos, fenthion, isoxathion, methidathion, salithion, caseit, Dimeton-S-methyl, disulfone, monocrotophos, azinphos-mesyl, parathion, hosalone, pirimiphos-methyl, prothiophos and the like.
  • Examples of the carbamate include metocarb, fenuobcalp, propoxur, carbarinole, ethiofopenkalp, piriimicarb, bendiocalp, carbosulfan, carbofuran, mesomil, thiodicarp and the like.
  • Examples of the organic chlorine agent include lindane, DDT, endosulfan, aldrin, chlordane and the like.
  • Pyrethroids include, for example, permethrin, cypermethrin, deltamethrin, cyhalothrin, cyflutrin, acrinatrine, fenvalerate, ethopropox, silafluofen, flunolinate, flucitrinate, biphentrin, arrestrin, phenothrin , Fuenpronotrine, sihuenotrin, flamethrin, resmethrin, transfluthrin, praletrin, flufenprox, halofanprox, imiprothrin and the like.
  • Neonicotinoid agents include, for example, imidacloprid, nitrene bilam, acetamiprid, tefuranitodine, thiamethoxam, thiacloprid and the like.
  • insect growth regulators such as flupenzyl perea agents include diflubenzuron, black mouth fluazuron, triflumuron, and flufenox mouth. , Hexaflumuron, lufenuron, tefluvenzuron, buprofezine, tebufenozide, chromaphenozide, methoxfenozide, siromadine and the like.
  • juvenile hormone preparations include pyriproxyphen, phenoxycarb, mesoprene, and hydroprene.
  • Insecticidal substances produced by microorganisms include, for example, abamectin, minorebemectin, nikkomycin, emamectin benzoate, iveremectin, spinosad-1 and the like.
  • insecticides include, for example, cartap, bensultap, chronorefenapyr, diafanturon, nicotine sulfate, methaldehyde, fipronil, pimetrozine, indoxacarp, tolfenpyrad and the like.
  • Active compounds for acaricides include, for example, dicophor, phenisobromolate, benzomate, tetradiphone, polynactin complex, amitraz, propargyl, fenbutatin oxide, trihexylhydroxide hexyltin, tebufenpyrad, pyridaben, fenpyroximate, pyrimidifene And phenazaquin, clopentezine, hexithizox, acequinosyl, quinomethionate, pentochalp, ethoxazole, bifenazetate and the like.
  • Examples of the nematicide active compound include methyl isocyanate, phosthiazate, oxamil, and mesulfonphos.
  • Examples of the bait include monofluoroacetic acid, perfurin, coumatetralyl, difacine and the like.
  • Active compounds of fungicides include, for example, inorganic copper, organocopper, sulfur, maneb, thiuram, thiadiazine, capbutane, chlorothalonil, iprobenphos, thiophanate methyl, benomyl, thiabendazolyl, iprodione, procimidon, pencyclon, metalaxyl, sandax Fans, bileton, Triflumizole, fenarimol, triforine, dithianon, triazine, fluazinam, probenazole, jetfencap, isoprothiolane, pyroquilon, iminoctadine acetate, echromemethol, dazomet, clesoxime methyl and the like.
  • active compounds such as herbicides include bialaphos, sethoxydim, trifluralin, mefunaset and the like.
  • active compounds for plant regulators include indolebutyric acid, ethephon, 4-CPA and the like.
  • Active compounds for repellents include, for example, karan-3,4-diol, N, N-ethyl-m-triamide (Deet), limonene, linalool, citronellal, menthone, hinokitiol, menthol, graniol, eucalyptol And the like.
  • Examples of the active compound of the synergist include bis- (2,3,3,3-tetrachloropropyl) ether and N- (2-ethylhexyl) bisc [2,1,1] hept-5- Ene-2,3-dicarboximide, ⁇ - [2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene, and the like.
  • the present invention will be described more specifically with reference to Examples, Reference Examples, and Test Examples. However, the present invention is not limited to the following Examples and Test Examples.
  • Example Example 1 1 1
  • the reaction solution was concentrated under reduced pressure, water (10 mL) and ethyl acetate (10 mL) were added, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (5 mL x 2). The organic layers were combined, washed with saturated saline (20 inL), and dried over anhydrous magnesium sulfate. After filtering off the drying agent, the filtrate was concentrated under reduced pressure.
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.24 g, 0.55 mmol) with sodium hydride (60 oily, 23 mg, 0.58 bandol) and 3-pentanole (0.06 mL), and the resulting crude product is subjected to silica gel ram ( ⁇ ).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.44 g, 1 .01 marl ol) with sodium hydride (60 oily, 4 mg, 1.1 mmol) and 2-chloroethanol (0.07 mL), and the resulting crude product was subjected to a silica gel column ( ⁇ -gel C-gel).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-cyclobut-3-ethyl-6-trifluoromethyl-3H-pyrimidine (1.00 g) , 2.21 dragonol), sodium hydride (60% oily, 97 mg, 2.43 bandolol) and ethylene glycol (IraL), and the resulting crude product was subjected to a silylation gel column (Merck Kieselgel 60, chromatography 2- (2,4-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4- (2-hydroxyethyloxy) -6-trifluoromethyl A yellow viscous oil of -3H-pyrimidine (1.05 g) was obtained.
  • Example—Similar to 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ di Mino-4-chloro-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.18 g, 0.41 ol), sodium hydride (60% oily, 20 mg, 0.50 mmol) and 2-ethoxyethanol (0.04 mL), and the resulting crude product is purified by a silica gel column ( ⁇ -gel C-200, ethyl acetate: hexane 1: 10 to 1: 8) to give 2- A yellow solid of ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4- (2-ethoxyhexyloxy) -3-ethyl-6-trifluoromethyl-3H-pyrimidine (90 mg) was obtained.
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.94 g, 2 .15) with sodium hydride (60% oil, 86.Omg, 2.15mmol) and 1-methoxy-2-butanol (0.25mL), and the resulting crude product was treated with silica gel.
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (1.07 g) , 2.44 mmol) with sodium hydride (60% oily, 120 mg, 2.93 mmol) and 3-methoxybutanol (0.33 mL).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g , 0.88 mmol) with sodium hydride (60% oily, 0.04 g, 1.00 marl) and methyl hydroxypivalate (130 mg, 0.97 mmol), and the resulting crude product was subjected to a silica gel column (Merck). Purification by Kieselgel 60, chloroform-form) gives 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4- (2-methoxycarbonyl-2-methylpropyloxy).
  • Example 1 As in 36, '2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4- (2-hydroxyethoxy) -6-trifluoro Methyl-3H-pyrimidine (0.30 g, 0.63 bandol) was reacted with cyclopropylcarbonyl chloride (79 mg, 0.75 mmol) and triethylamine (0.1 mL), and the resulting crude product was subjected to silica gel chromatography. ( ⁇ Merck Kieselgel 60, black form) ⁇ to give 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4- ⁇ 2- (cyclopropylcarbonyloxy) ethoxy ⁇ -.
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0 40 g, 0.88 g ol) was reacted with sodium hydride (60% oil, 0.05 g, 1.27 mmol) and transcrotonyl alcohol (76 mg, 1.06 ol).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenylinamino) amino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g, 0 .88 mmol) with sodium hydride (60% oily, 0.05 g, 1.27 mmol) and 3-buten-1-ol (76 mg, 1.06 mmol), and the resulting crude product was subjected to silica gel chromatography (Merck).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.58 g, 1.33 mmol) and 2-butene-1,4-diol (0.12 mL) and sodium hydride (60% oily, 58 mg, 1.45 mol / l) were reacted.
  • Example 13 Similarly to Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g) , 0.88 mmol) and 2-butyn-: I-ol (74 mg, 1.06 marl ol) and sodium hydride (60! Oily, 0.05 g, 1.27 marl ol) were reacted, and the resulting crude product was silica gel.
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g) , 0.88 title ol) with 3-butyn-1-ol (74 rag, 1, 06 mmol) and sodium hydride (60 g oily, 0.05 g, 1.27 ol) to obtain the crude product.
  • Example 11 As in Example 13, 2- ⁇ 2,4-bis (methyl trifluo) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.30g, 0 .69 marl ol) and 1-pentyn-3-ol (0.06 mL) and sodium hydride (60% oily, 30 mg, 0.75 t ol), and the resulting crude product was subjected to a silica gel column ( ⁇ CO-gel).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0 ⁇
  • the crude product obtained by reacting 58 g, 1.33 bandol) with 2-butyne-1,4-diol (0.13 g, 1.46 mmol) and sodium hydride (60% oily, 58 mg, 1.45 mmol) was purified on a silica gel column (Cogel C-200, black form) to give 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4- (4-hydroquinone).
  • Example 13 As in Example 13, 2- ⁇ 2,4-bis (trifluoromethyl) phenyl ⁇ imino-4-chloro-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0. 88 g, 2. Olmmol), 3- (dimethylamino) propanol (2.
  • the aqueous layer was further extracted with ethyl acetate (20 mL ⁇ 2), and the organic layers were combined, washed with saturated saline (100 mL ⁇ 3), and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified with a silica gel column ( ⁇ co-gel C-200, black form) to give 2- ⁇ 2,4-bis A yellow oil (0.79 g) of (trifluoromethyl) phenyl ⁇ imino-3-butyl-4-chloro-4-6-trifluoromethyl-3H-pyrimidine was obtained.
  • aqueous layer was extracted with ethyl acetate (50 mU). The layers were combined, washed with a saturated saline solution (100 mL x 3), dried over anhydrous sodium sulfate, filtered to remove the desiccant, and the filtrate was concentrated under reduced pressure. A crude product of 3,5-bis (trifluoromethyl) fluoro ⁇ imino-3-methyl-6-trifluoromethyl-3H-pyrimidine was obtained.
  • the product was added to a solution of sodium methoxide (126 mg, 2.33 mol) in methanol (20 mL) and heated under reflux for 1 hour After the reaction was completed, saturated saline (80 mL) and ethyl acetate (60 mU) were added, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate (60 raL), and the organic layers were combined, washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. After filtering off the the. Desiccant, the filtrate was concentrated under reduced pressure.
  • Example 1 4- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ amino-3-methyl-6-trifluoromethyl-4 (3H)- Pyrimidinone (0.70 g, 1.59 mmol) was allowed to react with chloromethyl butyrate (0.26 1.91 bandol) and silver oxide (0.74 g, 3.19 mmol). 4-butyryloxymethyloxy-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-methyl-6-trifluoro A yellow solid of methyl-3H-pyrimidine (0.15 g) was obtained. Yield: 17%; melting point: 64-66. ⁇ ; 1 8- 1 00?
  • Example 1 In the same manner as in Example 63, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl) imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine ( 0.86 g, 1.80 mmol) and sodium methoxide (0.12 g, 2.16 mmol) were reacted, and the resulting crude product was purified by a silylation gel column (Keizergel 60, chloroform, manufactured by Merck).
  • Example 1 As in Example 64, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine ( 0.50 g, 1.02 mmol) and sodium ethoxide (0.08 g, 1.22 ol) were reacted, and the resulting crude product was purified using a sily gel ram (Merck Kieselgel 60, Kuguchiguchi form).
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H -Pyrimidine (1.69 g, 3.56 mmol) was reacted with trimethoxy-2-propanol (0.39 mL) and sodium hydride (60% oily, 0.16 g, 4.0 OO mmol). Purification on a force gel column ( ⁇ -gel C-200, ethyl acetate: hexane-1: 8) yielded 22-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3.
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g, 0.82 bandol) with 2-butyn-1-ol (0.2 mL) and sodium hydride (60% oily, 50 mg, 1.23 iMol). 4- (2-butynyloxy) -2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl- A yellow solid (0.24 g) of 6-trifluoromethyl-3H-pyrimidine was obtained.
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H -Pyrimidine (0.40 g, 0.82 ol) and propargyl alcohol (0.5 mL) and sodium hydride (60% oily, 40 mg, 0.984 ol) were reacted, and the resulting crude product was applied to a silica gel column (Merck).
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.50 g, 1.02 dragonol) with benzyl alcohol (0.13 g, 1.22 dragonol) and sodium hydride (60 oily, 0.05 g, 1.22 nmol), and the resulting crude product is subjected to a silica gel column. (Benzyl Merck Kieselgel 60, chloroform-form) to give 4-benzyloxy-2- ⁇ 2-chloro-3,5-bis (trifluoromethyl).
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H -Pyrimidine (0.50 g, 1.02 ramol) was reacted with phenol (0.1 llg, 1.22 mmol) and sodium hydride (60% oily, 0.05 g, 1.22 mmol). 2- (2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4 -phenoxy-6- A yellow solid of trifluoromethyl-3H-pyrimidine (0.36 g) was obtained. Yield: 64%; mp: C; 1 !!
  • Example 1-13 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g, 0.82 mmol) with acetoxime (0.2 mL) and sodium hydride (60% oily, 40 mg, 0.984 mmol), and the resulting crude product was subjected to a silica gel column (Merck Kieselgel 60, chromatogel). Form- A yellow solid of trifluoromethyl-3H-pyrimidine (0.38 g) was obtained. Yield: 98; mp: ⁇ ⁇ ⁇ ; 1 !!
  • Example 13 As in Example 13, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethylinole) phenyl ⁇ imino-3-ethyl-6-trifluoromethyl-3H-pyrimidine (0.40 g, 0.82 mraol) and 2-butanone oxime (0.2 mL) and sodium hydride (60% oily, 40 mg, 0.984 bandol) were reacted, and the resulting crude product was subjected to silica gel chromatography (Merck Kieselgel).
  • Example 18 As in Example 2, 2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ amino-3-prosel-6-trifluoromethyl-4 (3H) -pyrimidinone (H .70 g, 1.50 ramol) and trimethyloxodimethyltetrafluoroborate (0.70 g, 4.73 bandol) and the resulting crude product was passed through a silica gel column (Merck Kieselgel 60, chromatogel).
  • Example 1 Similarly to 63, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-isobutyl-6-trifluoromethyl-3H-pyri
  • the crude product obtained was reacted with pyridine (0.76 g, 1.52 mmol) and sodium methoxide (0.09 g, 1.67 mmol).
  • 2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-isobutyl-4-methoxy-6-trifluoromethyl-3H-pyrimidine yellow solid (0.54 g). Yield: 72! 3 ⁇ 4; melting point:
  • Example 1 As in the case of 3, 3-benzyl-4-chloro-2-2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-6-trifluoromethyl-3H- Pyrimidine (0.32 g, 0.58 bandol) is reacted with sodium methoxide (53 mg, 0.98 mmol), and the resulting crude product is subjected to a silica gel column ( ⁇ -gel C-200, ethyl acetate: hexane).
  • Example 1 63 As in Example 3, 4-chloro-2--2- ⁇ 2-chloro-3,5-bis (trifluoromethylinole) phenyl ⁇ imino-3- (4-fluorobenzyl) -6-trifluoromethyl -Reaction of 3H-pyrimidine (0.17 g, 0.31 mol ol) with sodium methoxide (55 mg, 1.02 mmol), and the resulting crude product is converted to a silica gel column ( ⁇ Kogel C-200, hexane to acetic acid).
  • Example 18 As in the case of 2, 2- ⁇ 2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ amino-6-trifluoromethyl-3-vinyl-4 (3H) -pyri
  • the reaction of midinone (0.50 g, 1.20 mmol) with trimethyloxodimethyltetrafluoroborate (1.00 g, 6.76 inmol) was carried out, and the resulting crude product was subjected to a silica gel column (Merck Kieselgel 60, 2- (2-chloro-3,5-bis (trifluoromethyl) phenyl ⁇ imino-4-methoxy-6-trifluoromethyl-3-vinyl-3H-pyridin.
  • Example-8 As in 2, 2- ⁇ 2-bromo-3,5-bis (trifluoromethyl) pheninole) amino-3-ethyl-6-trifluoromethyl-4 (3H)- Pyrimidinone (2.0 Og, 4.01 marl ol) is reacted with trimethyloxodimethyltetrafluoroborate (2.97 g, 20.lramol). The product was purified by gel column (Cogel C-200, black form) and purified by 2- ⁇ 2-bromo-3,5-bis (trifluoromethyl) phenyl ⁇ imino-3-ethyl-4- methoxy-6-trifluoro. Oromethyl-3H-pyrimidine was obtained as a yellow oil (1.13 g).
  • Example-2 2- ⁇ 2-bromo-3,5-bis (trifluoromethyl) phenyl ⁇ imino-4-imino-3-ethyl-3-6-trifluoromethyl-3H- Pyrimidine (0 .20 g, 0.39 mmol) and sodium hydride (60% oily, 16 mg, 0.40 mmol) were reacted in methanol, and the resulting crude product was subjected to a silylation gel column ( ⁇ -gel C-200, acetic acid).
  • reaction solution was concentrated under reduced pressure, water (10 mL) and ethyl acetate (10 mL) were added to the residue, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (5 mL). The organic layers were combined, washed with a saturated saline solution (20 mL), and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure.
  • potassium carbonate (0.25 g, 1.81 mraol)
  • 18-crown-6_ether 40 mg, 0.15 mmol
  • methyl iodide (1.28 g, 9.02 mmol
  • Aqueous sodium thiosulfate solution (100 mL) and ethyl acetate (100 mL) were added, the organic layer was separated, and the aqueous layer was extracted with 50 mL of ethyl acetate.
  • the organic layers were combined, and saturated sodium bicarbonate solution (100 mL) and saturated After washing with brine (100 mL) and drying over anhydrous magnesium sulfate, the desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure.
  • Phosphorus oxychloride (2. OmL) was added to 3- (2-methoxethyl) -2-methylthio-6-trifluoromethyl-4 (3H) -pyrimidinone (0.50 g, 1.87 ramol), and the mixture was added at 100 ° C. For 4 hours. After completion of the reaction, excess phosphorus oxychloride and the like were removed under reduced pressure, and the obtained residue was poured into an aqueous sodium hydrogen carbonate solution (50 mL) and extracted with ethyl acetate (30 mL).

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Abstract

L'invention concerne des dérivés de 2-(phénylimino substitué)pyrimidine représentés par la formule générale suivante (1a) et (2a) . Ces dérivés permettent de repousser, d'exterminer ou de contrôler des pesticides comme des arthropodes (insectes et acariens), nématodes, helminthes et protozoaires qui endommagent les cultures et le bétail dans les cultures en croissance et récoltées. Ces dérivés présentent une grande utilité dans l'agriculture et l'élevage des animaux, les bois et les plantes d'ornement.
PCT/JP1999/006208 1998-11-12 1999-11-08 Derives de 2-(phenylimino substitue) pyrimidine, intermediaires dans la production de ces derniers, procede de production de ces derniers et pesticides contenant ces derniers comme ingredient actif WO2000029388A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU10791/00A AU1079100A (en) 1998-11-12 1999-11-08 2-(substituted phenylimino)pyrimidine derivatives, intermediates in the production thereof, process for producing the same and pesticides containing the same asthe active ingredient
JP2000582375A JP4600621B2 (ja) 1998-11-12 1999-11-08 ２−（置換フェニルイミノ）ピリミジン誘導体及びそれらの製造中間体、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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP32118398 1998-11-12
JP10/321183 1998-11-12

Publications (1)

Publication Number Publication Date
WO2000029388A1 true WO2000029388A1 (fr) 2000-05-25

Family

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Application Number Title Priority Date Filing Date
PCT/JP1999/006208 WO2000029388A1 (fr) 1998-11-12 1999-11-08 Derives de 2-(phenylimino substitue) pyrimidine, intermediaires dans la production de ces derniers, procede de production de ces derniers et pesticides contenant ces derniers comme ingredient actif

Country Status (3)

Country Link
JP (1) JP4600621B2 (fr)
AU (1) AU1079100A (fr)
WO (1) WO2000029388A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072799A (ja) * 1993-06-18 1995-01-06 Nissan Chem Ind Ltd ２−アリールイミノピリミジノン誘導体および除草剤、植物生長調節剤
EP0636615A1 (fr) * 1992-04-15 1995-02-01 Nissan Chemical Industries, Limited Derive de 2-arylaminopyrimidinone, et herbicide et regulateur de la croissance vegetale contenant ce compose
WO1998051675A1 (fr) * 1997-05-15 1998-11-19 Sagami Chemical Research Center Derives de l'anilinopyrimidinone, leur procede de production, et insecticides/acaricides dont ils constituent le principe actif

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0636615A1 (fr) * 1992-04-15 1995-02-01 Nissan Chemical Industries, Limited Derive de 2-arylaminopyrimidinone, et herbicide et regulateur de la croissance vegetale contenant ce compose
JPH072799A (ja) * 1993-06-18 1995-01-06 Nissan Chem Ind Ltd ２−アリールイミノピリミジノン誘導体および除草剤、植物生長調節剤
WO1998051675A1 (fr) * 1997-05-15 1998-11-19 Sagami Chemical Research Center Derives de l'anilinopyrimidinone, leur procede de production, et insecticides/acaricides dont ils constituent le principe actif
WO1998051152A1 (fr) * 1997-05-15 1998-11-19 Sagami Chemical Research Center Insecticides/acaricides

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AU1079100A (en) 2000-06-05
JP4600621B2 (ja) 2010-12-15

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