WO1998012184A1 - Pyrimidine compounds, process for the preparation thereof, and pest controlling agents - Google Patents

Abstract

Novel pyrimidine compounds of general formula (I), and pest controlling agents containing them as the active ingredient, wherein R?1, R2, R3, R4, R5, R8, R9, R10, R11 and R12¿ are each independently hydrogen, halogeno, C¿1?-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkoxy or the like; R?6 and R7¿ are each independently hydrogen, halogeno, C¿1?-C6 alkyl or C1-C6 haloalkyl; and R?13¿ is hydrogen, optionally substituted C¿1?-C6 alkyl, optionally substituted C2-C6 alkenyl, C2-C6 alkynyl, optionally substituted carbamoyl, COR?14¿ (wherein R14 is C1-C6 alkyl, C3-C6 cycloaklyl, C1-C6 alkoxy or the like) or SOnR15 (wherein R15 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or di(C1-C6 alkyl) amino; and n is 0, 1 or 2).

Description

 Specification

 Pyrimidine compounds, their preparation and pesticides Technical field:

 The present invention relates to a compound having a novel pyrimidine skeleton and a pesticidal composition containing the compound as an active ingredient.

Background art:

 Many insecticides and acaricides have been used in the past, but their efficacy was insufficient, their use was limited due to drug resistance problems, and phytotoxicity and contamination of plants occurred. In addition, because of their high toxicity to humans, fishes, etc., it is not always a satisfactory control agent. Therefore, there is a demand for the development of a drug that can be used safely with few such disadvantages.

 As a compound similar to the present invention, the following compound is described in WO94 / 0247-

(Wherein, Γ ¹ ~! · ¹ is a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, X ', X ² represents an oxygen atom, a sulfur atom, N r simultaneously' One represents a ^3, etc.)

The above compound弍中, 'a and X ² are the same compound, X' X and X ² is different compounds is not described at all.

 Disclosure of the invention:

 An object of the present invention is to provide a novel pesticidal agent which has a certain effect and can be used safely.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following formula [I]

[Wherein, R ′, R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ′. , Scale '' and 1 ^ "are each independently a hydrogen atom, a halogen atom, C -s alkyl group, Haroa alkyl group, C! '-S alkoxy groups, ₆ alkylthio group, C, - _fi Ha port alkoxy Group, mono- or di-substituted amino group, nitro group, cyano group, C, -κalkylalkylsulfonyl group, C, -s Represents an optionally substituted phenyl group, an optionally substituted phenyloxy group or an optionally substituted pyridyloxy group, or R ¹ and R ² or R ² and R ³ may be taken together to form an optionally substituted methylenedioxy group or a heterocyclic ring having an oxygen atom.

R ^e and R ⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a C i -S haloalkyl group,

R ¹³ represents a hydrogen atom, a (halogen atom, a C, _—B alkoxy group, a cyano group, a tri C

, - ₆ Arukirushi Li group, an alkylcarbonyl group, C, - S alkoxycarbonyl group, Te preparative La arsenide Dorofuraniru group, is also rather substituted with a conversion which may be full We two Le group) which may C,-beta alkyl group, but it may also be substituted by a halogen atom c ₂ - ₈ alkenyl group, C ₂ -B alkynyl group, and C e alkyl group, even mono optionally substituted phenylpropyl group Or a disubstituted radical group, COR ¹¹ (R ^M is an alkyl group, a C ₃ -s cycloalkyl group, a C,-«alkoxy group,

C 1 -6 haloalkyl group, alkenyl group, alkoxy C i -S alkyl groups, C physician _β alkoxycarbonyl C ₈ alkyl groups, C -! _S alkylcarbonyl Okishi alkyl group, an optionally substituted Fuweniru group, is 31 conversion Represents a good benzyl group. ^{_{), SO n R '5 (}} R 1 5 is C, - _s alkyl, C ₂ - _s alkenyl group, C ₂ -6 alkynyl group, a di C, - represents a _β alkylamine Mi amino group, eta 0, 1 Or 2) The compound represented by the formula (1) has an excellent insecticidal and acaricidal activity compared to the known compounds. Further, the present inventors have found that the compound has excellent insecticidal activity against pests that do not show insecticidal activity, and completed the present invention.

 Hereinafter, the present invention will be described in detail.

 The present invention relates to a compound having a pyrimidine skeleton represented by a pre-empirical formula [II], and an insecticide and acaricide containing the compound as an active ingredient.

Formula:... In ^{1], 1¾ R 2 R 3, R} 4 R 5, R 8, R ° R 10, R u及beauty R ¹² are each independently a hydrogen atom, full Tsu containing chlorine , Bromine and other halogen atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, etc., C1 alkyl groups, trifluoromethyl groups, etc. C ₆ Alkyl groups, Cs alkoxy groups such as methoxy, ethoxy, n-propoxy, and isopropoxy groups; Cis alkylthio groups such as methylthio, ethylthio, propylthio, and isopropylthio groups; C, such as butoxy group, Bruno, mouth alkoxy group, a Mi amino group, two collected by filtration group, Shiano group, main Chirusuruhoniru, Echirusuruhoniru, n -. Pro Pirusuruhoniru Lee Sopuro Pirusuruhoniru of group C> - ₆ Alkylsulfonyl group, C such Furuorome Chirusuruhoniru group, haloalkylsulfonyl group,

(Full Tsu element in any position of the benzene璟, chlorine, a halogen atom such as bromine, methylation, 0 ₆ alkyl group such Echiru, main butoxy, etc. d butoxy group C, - s alkoxy group, two collected by filtration group A phenyl group, a halogen atom such as fluorine, chlorine, or bromine at any position of the benzene ring; a C ^ s alkyl group such as methyl. A methoxy group such as a ethoxy group or the like, a methoxy group, a nitro group or the like; a phenyl group; Halogen atom such as bromine, C, _-B alkyl group such as methyl and ethyl, methoxy. Ethoxy group, etc. (may be substituted with _6- alkoxy group, nitro group, etc.) 2 — pyri Ziloxy group, (Hydroxy, chlorine, bromine, etc. Emissions atoms, methylation, alkyl groups such as Echiru, main butoxy, ₆ alkoxy group such as e butoxy group, may be substituted with two collected by filtration group) 3 - pyridyl Jiruokishi group, arbitrary in (pyridinium Jin ring Substituted with a halogen atom such as fluorine, chlorine, odor purple, etc., a C, -s alkyl group such as methyl and ethyl, a methoxy group, an ethoxy group, etc. An alkoxy group, a nitrogen group, etc. may also be) 4 one pyridinium Jiruokishi or represents a group, or, R 'and R ² also rather is R 2 and R ³ since it conversion is good main switch which may have been down Jiokishi group or Te preparative la together It may form a hydrofuranyl ring.

R ^e, R ⁷ are each independently a hydrogen atom, full Tsu-containing, chlorine, Ha androgenic atom such as a bromine atom, methylation, Echiru, C etc. propyl Lee Sopuro propyl group, -. ₆ alkyl group, Or represents a ₆ haloalkyl group such as a trifluoromethyl group ₌

R ^'3 represents a hydrogen atom, methylation, Echiru propyl, i Sopuro pills, heptyl, t -.. Heptyl, pentyl, hexyl, Application Benefits Furuoro methylation main Bok carboxymethyl methylation, main butoxy Echiru, main Tokishipuro pill Methoxybutyl, ethoxymethyl. Ethoxyxetil, propoxymethyl, propoxethyl, cyanomethyl, trimethylsilylmethyl, trinitilsilinomethyl, methylcanolebonylmethyl, methyloxy Carbonyl, tetrahydrofuranylmethyl. Benzyl, phenethyl. P-chloro C-alkyl which may have a substituent such as benzyl, vinyl, arylalkyl. lower Li Le, 4. 4-difluoro-2, 3 - Bed evening may be substitution with a halogen atom such as a Jeniru C ₂ - ₆ alkenyl group, E Ji Le, C _2, such propargyl group -. ₆ alkynyl group, dimethyl Chirukarubamoi Le, Jefferies Ji carbamoyl, main Chirufu et two force Luba乇I le groups such as carbamoyl group, formyl, Asechiru, pro Pioniru, t Buchiroiru consequent Ropuro Pillcarbonyl, methoxycarbonyl, trifluoromethylcarbonyl, dichloromethylcarbonyl, vinylcarbonyl, methoxymethylcarbonyl, methoxycarbonylmethylcarbonyl, acetyloxymethylcarbonyl, benzoyl, p-pi benzoyl, p - main Chirubenzoi Le, Ben Jirukaruho 'sulfonyl, p - click throat base down Jill carbonyl, p - main Chiruben Jirukarubo two Le group C 0 R ¹⁴ represented by groups such as, main Chirusuruhoniru, such Echirusuruhoniru group a group represented by S 0 R ^'5, main Chirusuru Represents the I nil. Echirusurufu I alkenyl group group represented by SOR 1 ⁵ etc., main Chiruchio. Echiruchio group represented by SR ^{1 5} such groups.

Among the compounds of the present invention, R ⁴ , R ⁵ .R ⁹ and R ¹² represent a hydrogen atom, and R′.R ² , R ³ , R ⁸ , R′o and R ¹¹ each independently represent a water purple atom And a halogen atom. Compounds having a C haloalkyl group, a _β- haloalkoxy group, a cyano group, or a nitro group have particularly excellent insecticidal activity as compared with the compound described in WO94 / 02470. Show.

 (Production of compounds)

The compound of the present invention can be produced, for example, as follows. Manufacturing method 1

(Wherein, R ′, R ² , R ³ , R ¹ , R ⁵ , R ⁶ , R ⁷ , R ^s , R ′, R ′., R ′ ′, R ¹ R ′ ³ have the same meanings as described above. Represents.)

 That is, a dihalogenobilimidine such as dichloropyrimidine represented by the formula [II] is added to the formula [II! Is reacted in the presence of a base to obtain an intermediate (IV), and then the aniline represented by the formula (V) is reacted in the presence of a base. It is what makes them.

 Manufacturing method 2

 Further, in the reaction of the halogeno virimidine represented by the formula [IV] with the aniline represented by the formula [V], the compound is reacted in the presence of a palladium catalyst and a base to give a compound. [I] can also be obtained.

Palladium catalysts that can be used in this reaction include palladium chloride, bis (triphenylphosphine) dichloroharadium, and tetrakis (triphenyl). Phosphine) palladium, tris (dibenzylideneacetate) diparadium.chloroform adducts, and the like. The amount of the catalyst is preferably from 1 mol% to 20 mol% with respect to 1 mol of the halogeno pyrimidine represented by the formula [IV]: When a palladium catalyst is used, the triflic acid is preferably used. Production method 3 in which the reaction can be carried out in the co-presence of a phosphorus compound such as triaryl phosphine such as enyl phosphine or tritril phosphine.

 Further, the compound of the present invention can also be produced by the following method.

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ RR ⁷ , RRRRR ¹² and R ¹³ represent the same meaning as described above.)

That is, an aniline represented by the formula (V) is allowed to act on a dihalogeno pyrimidine such as a dicyclopyrimidine represented by the formula (II) in the presence of a base to form an intermediate (V). After obtaining, then, the funinols represented by the formula [111] are reacted in the presence of a base. Manufacturing method 4

Further, among the compounds of the present invention, those in which R ¹³ is a group other than a hydrogen atom can also be produced by the method represented by the following reaction formula.

^{(Wherein, R ', R 2, R} 3, R 4, R 5, R 8, R 7, R 8, R 9, R'., R 1 1. R 1 2 are the same as defined above, R ^'3' is the table as defined above R ^{1 3} except hydrogen atom, X represents a leaving group.)

 That is, it can be produced by reacting a compound represented by the formula [I-11] with a compound represented by the formula [VI] in the presence or absence of a base. Examples of the compound represented by the formula [νπ] include, for example, halogenated alkyls such as methyl iodide, isopropyl iodide, isopropyl bromide, and aryl chloride; and dialkyl sulfates such as dimethyl sulfate. Esters, alkyl sulfonic acid esters such as propyl tosylate and butyl methyl sulphate; phosphoric acid esters such as trimethyl phosphite; ortho esters such as ethyl ethyl formate; dimethylformyl Alkylating agents such as formamide salts such as amide dimethyl acetal, etc., onium salts such as diazomethane and dimethyloxosulfonium salt,

Carboxylic acid derivatives such as acetyl chloride, acetic anhydride, formic acid, and methyl acetate; dimethylation; acylation agents such as potassium rubavamoyl chloride; and acylation agents such as haematogen compounds such as methansulfinyl chloride; Nilchloride, methane sulfone Sulfonylating agents such as sulfur halides such as chlorochloride; sulfinylating agents; sulfenylating agents; and the like. Further, the sulfinyl-sulfonylation can also be produced by sequentially oxidizing the corresponding sulfinyl compound with an oxidizing agent.

 Bases that can be used in the reactions of these production methods i to 4 are, for example, triethylamine, diisopropylethylamine, pyridine, and 1,8-diazabicyclo. -[5,4.0]-7- ゥ decane (DBU), carbonates such as potassium carbonate and sodium carbonate, hydroxides such as sodium hydroxide and potassium hydroxide, and water Hydrides such as sodium hydride, sodium methoxide ', metal alkoxides such as sodium ethoxide, and calcium-t-butoxide. You.

Solvents that can be used in these reactions include N, N ^: —dimethylformamide (DMF), N, N—dimethylacetamide (DMA), N— Pads such as methylpyrrolidone, ethers such as tetrahydrofuran (THF), and ethyl ether, alcohols such as methanol and ethanol, benzene, toluene, and xylene Examples thereof include aromatic hydrocarbons such as butane, esters such as ethyl acetate, nitriles such as acetonitril, dimethyl sulfoxide (DMSO), and the like. These reactions proceed smoothly within the temperature range of the boiling point of the solvent used after zero. In any of the reactions, after completion of the reaction, the desired product can be obtained by performing post-operations by a usual synthetic chemistry technique.

 The structure of the reaction product was identified by measuring various spectra such as NMR, 1R, and MASS.

 (Insecticide · Acaricide)

 The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphalidic, larvicidal, and ovicidal action. The following are typical examples.

Lepidopteran pests, for example, scutellaria spp. , Kinmonhosoga, Myimaga, Jiyadokuga, Nikkameiga, Kobunomeiga, Yoichichi Biancon Borra-, Americana Horitori, Sujimadara Mega, Heliotisu, Helicobelpa, Aggrotis II, Iga, Kodlinga, Ichimami Mimi, etc.

 Hemiptera pests, for example, peach aphid, petal aphid, Nisedai kombi, wheat bilea aphid, scorpion worm, mosquito mosquito, yano okaigamurashi, kukonakaigaramushi, konshika nagamurashibushi, shikomi shikoku , Tobi-iron power, Hime-to-bin power, Sedge lownka, Tsumagurokonokoi, etc.

 Coleopteran pests, for example, Leaf beetle, Leaf beetle, Colorado beetle, Rice mud beetle, Red beetle, Azuki beetle, Bean beetle, Brown beetle, Japrotica genus, Evening beetle, Leaf beetle Mikiri, sesame power, agriculture, nervous system, coconut, pork, etc.

 Nuptera pests, for example, house flies, oak fly, sentinella flies, flies, flies, flies, rice flies, rice flies, flies, flies, flies, flies The power of swords, the power of shinahamadara, etc.

 Orthoptera pests, for example, southern blue thistle, cyano thistle, etc., Lepidopteran insects, for example, blue ants, hornets, wasps, etc., orthopterous insects, for example, japonicus Panic cockroaches, red cockroaches, black cockroaches, black cockroaches, etc.

 Pests of the order Isoptera, for example, Yeshiroa, Yamatoshiro

 Laminariae pests, for example, human fleas, lice Pests, for example, human louse, etc. Mites, for example, Namihadani, Kanzahadaji, Micani spider mite, Lingo spider mite, Mikansabida (2) Lingo Savidani, Chino Hoko Ridani, Blevi Palpa 厲, Je te Tranikas, Kobinedani, Kenagakonadani, Konahi-y ヒ mikomi, Oshishima mite, Scarabidae, etc.

 Plant-parasitic nematodes, such as sweet potato nematode, nexarecenti, soybean ciscentium, rice singarecenti, matsunosaisenyu and the like.

In addition, in recent years, many insect pests such as Japanese moth, pinworm, leafhopper, aphid, etc. have developed resistance to organic phosphorus agents, carbamates, and acaricides, causing a problem of insufficient efficacy of those agents. There is a need for a drug that is effective against pests and mites that are resistant to strains. The compound of the present invention has an excellent insecticidal and acaricidal effect against not only susceptible strains but also insect pests of organic phosphorus, carbamate or pyrethide-resistant strains and mites of acaricide-resistant strains. It is a drug.

 In addition, the compound of the present invention is a highly safe drug with low phytotoxicity, low toxicity to fish poisons and mixed animals.

 The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.

 When the compound of the present invention is applied as an insecticide or acaricide, it can be used in a pure form without adding other components, and it can be used in general agricultural chemicals for use as a broad medicine. That is, they can be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, powders, flowables and the like. When solid additives are used as additives and carriers, soybean grains, vegetable powders such as flour, diatomaceous earth, limestone, gypsum, talc, bentonite, pyrophyllite, clay And organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol , Acetone, trichloroethylene, methyl isoptyl ketone, mineral oil, vegetable oil, water, etc. are used as solvents. To obtain a uniform and stable form in these preparations, a surfactant can be added if necessary. The amount of the active ingredient is preferably 5 to 70%. The wettable powder, emulsion and flowable obtained in this manner are diluted with water at a predetermined temperature to prepare a suspension or emulsion, and the powder and granules are sprayed as they are. Is done.

 It goes without saying that the compound of the present invention is sufficiently effective alone, but it can also be used in combination with one or more of various fungicides, insecticides, acaricides, or synergists. .

 Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.

 Fungicide :

Captan, Forpet, Thiuram, Jiram, Zineb, Maneb, Mancozeb, Provineb, Polycarbamate, Chlorotalonil, Quintzensen, Capita Hor, iplodione, procymidone, vinclozolin, fluorimide, thymoxanil, mepronil, furtranil, penciclone, oxycarboxynin, josetyl aluminum, propamocarb, triadimene Phone, Triadimenol, Propiconabul, Diclobtrazol, Bitertanol, Hexaconazole, Microcrobyl, Flusilazole, Ethaconazole, Fluotrimazole, Full Triafene, benconazole, diconazole, cyproconazoles, fenarymol, triflumisol, prochloraz, imazalil, perfrazoate, tridemorph, fenpropimorph, trifoliol , Petiovert, pyri-knox, anilazine, Polyoxin, metalaxyl, oxadixyl, furalaxil, isoprothiolane, probenazole, pyrrolnitrile, blastidine

S, kasugamycin, validamycin, dihydrostreptotomycin sulfate, benomyl, carbendazim, thiophanenetyl methyl, himexazole, basic copper chloride, basic sulfate Net, funintin acetate, triphenyltin hydroxide, jetfuncarb, methasulfocarb, quinomethionate, pinapacryl, lecithin, baking soda, dithianon, zinocap, fena Minosulf, dicromedin, guazatine, dozine, IBP, edifenphos, mepanipyrim, fermzon, trichloramide, methasulfocalp, fluazinam, ethoxyquin, dimethomorph, pilokirone , Tech mouth phthalam, fusaride, phenazine oxide, thiabendaburu, tricycle, bottle Clozolin, simoxanil, cyclobutanyl, guatatin, probamocarb hydrochloride, oxolinic acid.

 Insecticide · Acaricide:

 Organophosphorus and power-based insecticides:

Funinthion, phenytrothion, diazinone, chlorpyrifos, ESP, bamidione, phenate, dimethate, formotione, malathone, trichlorfon, thiomethone, phosmene , Dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicion, cyanophos, isoxathion, bilidafenthion, hosalon, methidathion, sulprophos, chlorfenbinephos Trachlorbinphos, dimethyltilbinphos, propaphos, isofenphos, ethylthiomethone, propenophos, pyraclophos, monochlorotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, carbomil Flann, Carbosulfan, Benfracarb, Fratiocalp, Propoquisl, BPMC, MTMC, MIPC, Levalvalil, Pirimicarb, Ethofencarb, Phenyloxyrubbe, etc.

Pyrethroid insecticides:

 Permethrin, cypermetryn, deltamethrin, fembrelate, fempronotrine, pyrethrin, arelesline, tetrameline, resmetrine , Dimethrin, propasulin, phenotrin, protrin, full variate, cyflutrin, cyhalotrin, full citrine, ethomprox, siclin Loprotoline, trolamethrin, sirafluorfen, profenprox, akrinatrin, etc.

Benzoyl Rare Other Insecticides:

 Difluvenzuron, Chronolefrazuron, Hexaflumuron, Trifnoremuron, Tetravenzuron, Furfenoxuron, Funoresicuroxuron, Buprofegzine, Pyri Proxyfene, Methoprene, benzepin, jafenthiuron, acetapride, imidacloprid, nitenbiram, fipronil, cartap, zeocyclam, bensultap, nicotinic sulfate, rotenon, metaaldehyde , Machine oil, microbial pesticides such as fish and insect pathogenic viruses.

Nematicide:

 Phenamiphos, phostiazetate, etc.

Acaricide:

 Chlorbenzilate, fenisobromolate, dicophor, amitraz, Β Ρ ΡS, benzomate, hexithiaxox, phenoxide, tin oxide, polyactin, quinomethionate, CPCBS, Tetradiphone, Avermectin, Milbemectin Clofendentin, Sihexatin, Pyridaven, Fenpyroxime, Tebufenvirad, Pyrimidiphene, Fenochocalp, Dienochlor and others.

 Plant growth regulator:

Jibere Li emissions (such Jibere Li down A _3, Jibere Li down A 4, Jibere Li down A:) IAA, NAA. BEST MODE FOR CARRYING OUT THE INVENTION: Next, the present invention will be described in more detail with reference to examples.

 (Implementing cold 1)

 Production of 4- (3-fluoro-3 -trifluorometylanilino) -16- (4-fluoro-13-trifluorometylphenoxy) pyrimidine (Compound N 0.13)

4 1-chloro 6-(4-fluoro-3-trifluoromethyl thioxy) pyrimidine 0.30 g (i. 0. 3 mmol) is dissolved in 10 ml of ethanol and then there. -4 —Fluoro-3 — Trifluoramylamine 0.20 g (l.12 mm 0 1) and triethylamine 0.13 g (l.28 mmol) The mixture was heated under reflux for T2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.30 g of the desired product. Yield 67%

 Melting point 1 0 8 — i 10 ° C

 (Reference example 1)

 Manufacture of 4-chloro-6- (4-fluoro-3-tritrifluoromethyl) pyrimidine

4.Dissolve 1.36 g (7.55 mmoI) of monofluoro-3-trifluoromethylphenol in 60 ml of DMF and add 4,6-dichloropyrimidine i Add 13 g (7.58 mmo1) and 49 g (10.8 mmol) to potassium carbonate under ice, and add 20 minutes at 0 ° C and 1 minute at room temperature. The mixture was stirred for 7.5 hours. The reaction mixture was poured into water and extracted with getyl ether. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 94 g of the title compound. Yield 8 8% Melting point 5 3-5 6

 In addition, Haruto's 41-fluoro-3-trifluoromethyl was synthesized as follows.

_{F 3 C, 1) c.} HzSO, F 3 C

 2) NaN0

-NH: F -NH ₂ BF

3) HBF ₄ \\ //

4 Dissolve 15.0 g (83.7 mm 0 1) of monofluoro-3 — trifluormethylethylaniline in 69 ml of concentrated sulfuric acid, and add sodium nitrite to the solution. g (92.1 mm 01) was added under ice-cooling, and the mixture was stirred at the following temperature for 30 minutes. Further, 6.45 g (92.1 mm 01) of borohydrofluoric acid was added under ice cooling, and the mixture was stirred at 5 ° C or lower for 10 minutes. To the resulting reaction solution was added 202 g of nitric acid trihydrate (836 mm 0 1), and further, 12.0 g of secondary oxide (83.9 mm 0 1) Was added little by little, and the mixture was stirred for 2 hours after the addition was completed. The reaction foamed violently. After completion of the reaction, insolubles were filtered off, and 5,000 ml of getyl ether was added to the filtrate to separate the layers. Then, To the organic layer, 500 ml of a 2.5 N aqueous sodium hydroxide solution and 300 ml of a 0.1 N aqueous sodium hydroxide solution were sequentially added, followed by washing. Alkaline solution)! The mixture was acidified with concentrated hydrochloric acid, extracted with getyl ether, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography to obtain 7.91 g of 4-fluoro-3 -trifluoromethylphenol, yield 5 2%

 The 4-fluoro-3-trifluoromethyl phenol can also be obtained by the method described in Japanese Unexamined Patent Publication No. 1-268685.

(Example 2)

 4-1 (4-Fnoroleol 3 — trifluorene methyl arino) 1 6— [4-1 fluorene _3 — trifluorene tyl enoxy) Production of pyrimidine (Production method 3)

41 1-chloro-6- (4-fluoro-3-trifluoromethyarilino) pyrimidine (50 g, l.71 mmol) was dissolved in DMF (5 ml), and the solution was added to the solution.ー 3— Add 0.37 g (2.05 mm 0 1) of trifluoromethyl phenol and 0.71 g (5.14 mm 0 1) of potassium carbonate, and add 90. Stirred overnight at C. The reaction solution was poured into water and extracted twice with 40 ml of getyl ether. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.69 g of the desired product. Yield 93%

(Reference example 2) 4 Production of 1-chloro-6- (4-fluoro-3-tritrifluoromethyl-lino) pyrimidine

CF ₃

 N, N

4 Fluoro-3 — trifluorene tyraline 3.00 g (16.4 mm 01) and 4,6-cyclopyrimidine 2.45 g (16.4 mmol ) Was dissolved in 15 ml of ethanol, and 2.0 g (19.8 mmo 1) of triethylamine was added thereto at room temperature, and the mixture was stirred under reflux overnight. The solvent was distilled off under reduced pressure, 80 ml of water was added to the residue, and the mixture was extracted twice with ethyl acetate 100 ml 1. The organic layer was dried over magnesium sulfate anhydride, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 2.9 g of the desired product.

 This sublimed at 16 ° C.

 (Implementation ^ 3)

 4 1 (N-methino 1 -4 1-chloroaniline) 1 6— (4—funoleol 3—trifluoromethylfurinoxy) Pyrimidine (compound N 0.48) Manufacture

In 10 ml of toluene, 41-chloro-6- (4-fluorinated-3-3-trifluoromethylphenoxy) pyrimidine 0.40 g (1.37 mm 01), N-methyl- 4 1-chloroaniline 0.25 g (1.66 mm 0 1), tris (dibenzylidene) diparadium / clo-form adduct 0.15 g (0.14 5 mm 0 1), tri-o-trilyl phosphine 0.19 g (0.605 mmol) and t; monobutyric acid sodium 0.19 g (l. 9 8 mmol), and the mixture was stirred under a nitrogen atmosphere at 60-70 for 1 hour and further at 100 ° C for 3 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted with 20 ml of getyl ether. The ether layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 6: 1 to 4: 1) to give the title compound as a viscous oily substance 0.38 g was obtained. 70% yield

 NMR data: NMR-5

 (Example 4)

 4-[N-acetyl-(4-fluoro-3-trifluoromethyl phenyl) amino] 1-6-(4-Fluoro-3-trifluoromethyltylphenoxy) pyrimidine (Compound No. 21) Manufacturing of

F ₃

4- (4-Fluoro-3—trifluorme tyruarino) 1 6— (4-fluoro-3—trifluorme tylophenoxy) bilimidine 0.60 g (1.38 mm o 1) 60% sodium hydride lig (2.75 mmo 1) was added to a 6 ml solution of DMF, and the mixture was stirred at room temperature. After confirming that the generation of hydrogen gas had stopped, 0.22 g (2.80 mm 01) of acetyl chloride was added dropwise to the mixture, and the mixture was added to the chamber. The mixture was stirred at room temperature. The reaction mixture was poured into water and extracted twice with geetyl ether. The obtained getyl ether / i was dried over anhydrous magnesium sulfate, filtered, and concentrated under i Ham pressure. The resulting residue was purified by silica gel column chromatography and recrystallization to obtain 0.444 g of the title compound as crystals. Yield 67%

 Melting point 1 1 0-i 1 2

 Table 1 summarizes the compounds of the present invention that can be produced as described above.

 Table 1

A C

Table 1 (continued)

Table 1 (Puki)

Table 1

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Table (Puki)

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1 Table

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1 Table

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 A B C Physical properties

1 6 4 1 _cl _ / ^r V; -ΝΗ ~ <·,, Vci;:

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 1 7 0 society \ N N

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^{1 7 2} 1 / —! I ^Χ ί- ^NH "_Z [146-148]

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Table 1 (Puki)

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(Insecticide and acaricide)

 Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, but can be changed in a wide range. Parts in Formulation Examples indicate overlapping parts.

Conduct ^ 5 wettable powder

 Compound of the present invention 40 parts

 Diatomaceous earth 5 3 parts

 Higher alcohol sulfate 4 parts

 Alkyl naphthalene sulfonate 3 parts

 If the top is mixed uniformly and finely crushed, a 40% active ingredient in water is obtained: ^ 6 Emulsion

 Compound of the present invention 30 parts

 Xylene 3 3 parts

 Dim Chilholm Amid 30

 Polyoxyethylene alkyl ether 7 parts

 By mixing and dissolving the above, an emulsion containing 30% of the active ingredient is obtained.

Example 7 Dust

 Compound of the present invention 10 parts

 Talc 8 9 parts

 Polyoxyethylene alkyl aryl ether 1 part

 If the above are uniformly mixed and finely powdered, a powder of the active ingredient 10¾ is obtained: done ^ 8

 5 parts of the compound of the present invention

 Cray 7 3 copies

 Bentonite 20

 Dioctyl sulfosak sine sodium salt 1 copy

 1 part of sodium phosphate

 The above is well ground and mixed, water is added, and the mixture is kneaded well.

Example 9 Compound of the present invention 10 parts

 Ligninsul; sodium phosphate 4 parts

 1 part of sodium decylbenzenesulfonate

 Kisanta Ngam 0.2 parts

 Water 84.8 parts

 The above ingredients are mixed and wet-pulverized until the abundance is 1 micron or less, whereby a suspension of 10¾ of the active ingredient is obtained.

The invention's effect :

Trial ^ 1 Efficacy against Namihadaji

 After inoculating 17 female adults of Nami-Nadadani, which are resistant to organic phosphoric acid, on the first true leaf 7 to 10 days after germination of kidney beans after sowing in 2 inch pots, Follow the wettable powder formulation shown in the end of the procedure, and spray a chemical diluted with water so that the compound concentration becomes 丄 25 ppm: place in a thermostatic chamber at a temperature of 25 and a humidity of 65%. Three days after spraying, the adults were removed, and the eggs laid during these three days were examined on day 11 to determine whether they could develop into adults, and the acaricidal efficacy was determined. Table 2 summarizes the results.

 The acaricidal effectiveness was calculated by the following formula.

 Non-treated adult-Number of treated adult

Acaricidal effectiveness (= X 1 0 0

 Number of adults in untreated plots

According to the formulation of the wettable powder described in Example 7 of the above-mentioned drug, it was diluted with water so that the compound concentration was 125 ppm. Corn leaves were immersed in the chemical solution for 30 seconds and air-dried, and then the leaves were placed in a scale containing five second instar larvae. They were placed in a thermostatic chamber at a temperature of 25 ° C and a humidity of 65% with a glass lid, and the insecticidal rate was examined 6 days later. The results are summarized in Table 2. Younger brother

 8 1 0 0

 1 9 1 0 0 1 0 0 2 1 1 0 0 1 0 0 2 3 1 0 0 1 0 0 4 7 1 0 0 1 0 0 4 8 1 0 0 1 0 0

4 9 1 0 0 1 0 0

5 0 1 0 0

 5 2 1 0 0 1 0 0 5 3 1 0 0 1 0 0 5 4 1 0 0 1 0 0 5 7 1 0 0 1 0 0

5 8 1 0 0 1 0 0

6 0 1 0 0 1 0 0 6 1 1 0 0 6 3 1 0 0 1 0 0 6 4 1 0 0 1 0 0

(Compound Α: compound described in WO 94/0247)

Test ^ 3 Hasmonyo tow

According to the formula of wettable powder shown in Example 7 of the above-mentioned drug, it was diluted with water so that the compound concentration became 31 pm. The cabbage leaves were soaked in the chemical for 30 seconds, air-dried, and then put into a petri dish containing five tomato larvae: 5 caps, a glass lid, a temperature of 25, and a humidity of 6 5 % In a constant temperature room, and 3 Two reactions. The results are summarized in Table 3.

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 Compound No. 3 says post-mortem,

 υ ^ 1 π n m 1 "1

 (%) 1

 1 3 l o o!

 1 7 1 0 0!

 I

 2 1 1 0 0!

 1 No.

 1 1 4! l o o!

 Asefut 1 2 0

 table

 Compound A 0 1 Industrial applicability:

 As described above, the compound represented by the formula [I] has an excellent insecticidal and acaricidal effect, and the composition containing the compound of the present invention is useful as an insecticide and acaricide.

Claims

Range of finished product

1.

(In the formula, R ′, R ² , R ³ , R ′, R ³ , R ⁸ , R ⁹ , R ⁱⁿ , R ¹ ′ and R ′ ² are each independently a hydrogen atom, a halogen atom, C, ^ Alkyl group, haloalkyl group, C, alkoxy group, C,-, alkylthio group, C, haloalkoxy group, mono- or di-substituted amino group, nitro group, cyano group Or an alkylsulfonyl group, (: a _6- haloalkylsulfonyl group, a phenyl group which may have a substituent, a phenyl group which may have a substituent or a substituent which may have a substituent. Represents a pyridyloxy group, or R ¹ and R ² or R ² and R ³ are linked together to form an optionally substituted methylenedioxy group or a heterocyclic ring having an oxygen atom. Often

R ^6, R ⁷ are each independently a hydrogen atom, a halogen atom, C, - represents ₆ alkyl group or C, and -s haloalkyl group,

R ^{1 3} represents a hydrogen atom, (halogen atom, C alkoxy group, Shiano group, Application Benefits C, - ₆ Arukirushi Li Le group, C _i-6 alkyl group, C, - ₆ alkoxycarbonyl group, Te DOO La May be substituted with a hydrofuranyl group or a substituted or unsubstituted phenyl group) C,-^ alkyl group, C _{2 -S} alkenyl group optionally substituted with a halogen atom, alkynyl group , (C, - ₆ alkyl, optionally substituted disubstituted can rather also mono which may phenylpropyl group) force Rubamoiru ^{group, C 0 R 1 (R 1} 4 is <: I ₆ alkyl group , C ₃ - ₆ a cycloalkyl group, ₆ alkoxy groups, C haloalkyl groups, C ₂ - ₆ alkenyl group, (:. ₆ alkoxy C, - _s alkyl le group, epsilon,-beta alkoxycarbonyl alkylsulfonyl c alkyl group,

Alkylcarboxy, represents an _e- alkyl group, an optionally substituted phenyl group, and an optionally substituted benzyl group. ), S 〇 _n R ^{1 3} (R ^{1 5} is an alkyl group, C ₂ - _u alkenyl Groups, C ₂ - represents _β alkynyl group, a di-C "alkylamine Mi amino group, eta represents 0, 1 or 2. )]

2. In the formula 门, R ¹ , R ⁵ , R ⁸ and R ″ represent a hydrogen atom, and R ′, R ^2. R ³ , R °, R ^1} and R ¹ ′ each independently represent hydrogen atom, halogen atom, C, - ₆ haloalkyl group, C ₆ haloalkoxy group, a Shiano group or a Tokomoto compound of claim 1, wherein

 3. Nin [1

(In the formula, R ^B and R ⁷ represent the same meaning as described above, hal represents a halogen atom, and may be the same or different.)

 Pyrimidines represented by the formula:

8

(Wherein, R ¹ , R ² , R ³ , R ¹ , and R ⁵ represent the same meaning as described above.)

 Is reacted in the presence of a base to give the formula πν]

(IV)

(Wherein, R ′, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ represent the same meaning as described above,

) After the compound represented by the formula,

Η

Wherein R ⁸ , R ⁹ , R ″ R ^M , R ¹² , and R ¹³ have the same meanings as described above. ]

R ^{1 1}

 Ν

■! '

a ¹

^{(Wherein, R 1, R 2, R} 5, R, R 5, R, R 7, R ", RRR, R, 2, R 13 are as defined above.)

A method for producing a compound represented by the formula:

4. Equation [m

 hal- hal

(Wherein, R ^s , R ⁷ and ha 1 have the same meanings as described above).

(Wherein, R ^e , R ⁹ , R ^{, 0} , R ^M , R ¹² , and R ¹³ have the same meanings as described above.) The aniline represented by the formula is reacted in the presence of a base. And formula (VI) VI:

^{(Wherein, R s, R:, R} B, R ", RR M, R 1 R '' are as defined above:)

And then formula (Πί j

H

(Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above.)

Characterized by reacting a finolol represented by the following formula [I:

(In the formula, R ¹ , R ² , R ³ , R, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R °, R ^lu , R, R ′ ² , R ¹³ represent the same meaning as the preceding self. . )

A method for producing a compound represented by the formula:

5. Nin 门

I one 1

 [I-1]

(Where, RRR ³ ,, RRR ⁷ RR ⁰ , RR

, R ¹² represents the same meaning as described above, and a compound represented by the formula [VI RX (wherein, R ′, R −, R ^J , R ¹ , R ⁵ , R ″, R ⁷ , R ^{s , R, R '11, R} 11, R 12 are as defined above, R' ¹ 'represent the same taste as R except hydrogen atom, X represents a leaving group: represented by) Reacting the compound with a compound in the presence or absence of a base;

^{Wherein, ', [¾ 2, 1¾} 3, 1 ^, 1 ^, 1¾, RR ", R 3, R' R, R 1 R 13 ' have the same meanings as defined above -)

A method for producing a compound represented by the formula:

 6Equation (I)

^{Wherein, R ', R 2, R} 3, R, R 5, R S R 7, RRRR, c R 12, R 13 is of the same meaning as defined above)

A pesticidal agent characterized by containing a compound represented by the formula (1) as an active ingredient