JPS62502333A - Pesticide 1-(4-phenoxyphenyl)-3-benzoyl urea compound and manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention provides novel 1-(4-phenyls) useful as active poisons in agrochemical compositions. The present invention relates to (noxyphenyl)-6-benzoyl urea compounds. The present invention also provides novel Regarding the manufacturing method of 1-(4-phenoxyphenyl)-3-benzoyl urea compound do. The invention further relates to agrochemical compositions and methods of use thereof.

Background of non-invention In recent years, various benzoyl urea compounds have been reported in the literature as having pesticide activity. has been done. For example, pendiylfreid-diphenyl ether and its insecticide U.S. Pat. No. 4.005.223 (published January 25, 1977) ), No. 4,041,177 (public notice dated August 9, 1977) and No. 4. No. 068.002 (published on January 10, 1978978. Also, No. -Benzoyl-N1-phenoxyphenylurea compound and its -38357(1 56-92857 (public notice dated July 27, 1981) Publication) and No. 57-2258 (public notice dated January 7, 1982).

Furthermore, the N-benzoyl-N+-phenoxypyridyl urea compound has been granted a European patent. No. 69288 (published on January 12, 1983).

Accordingly, one or more of the following objects may be achieved by practicing the present invention: - One object of the invention is to produce novel 1-(4-phenoxyphenyl)-3-benzoyl An object of the present invention is to provide a lurea compound. Another object of the present invention is to have excellent insecticidal activity. We provide certain types of 1-(4-phenoxyphenyl)-3-pensoyl urea compounds shown below. It is to provide. Another object of the invention is 1-(2,3-dichloro-4-(2,3-dichloro-4-(2, 4-dichlorophenoxy)-6-methylphenyl)-3-(2,6-difluoro lobenzoyl) urea, 1-(2,3-dichloro-4-(2-promo 4-chloro phenoxy)-6-methylphenyl)-3-(2,ts-difluorobensoyl ) [8,1-(4-(2,4-dichlorophenoxy)-2, cucumber 6-dorimethylphenyl Novel benzoi such as enyl)-s-(z,6-difluorobenzoyl)urea, etc. An object of the present invention is to provide a lurea compound. Another object of the invention is to develop novel benzoylureas. An object of the present invention is to provide a method for producing a compound. Yet another object of the present invention is to An object of the present invention is to provide a novel hair care composition containing a novel benzoyl urea compound. . Another object of the invention is to provide a method for controlling pests by applying a novel agrochemical composition. It is to provide. For these and other purposes, please refer to the description below. will be readily apparent to those skilled in the art.

Disclosure of the invention In its broad aspects, the present invention relates to novel 1-(4-phenoxyphenyl)-3- Benzoyl urea compounds, agrochemical compositions containing the compounds, and their production and use Regarding the law. The benzoyl urea compound of the present invention can be represented by the following formula: : During the ceremony X represents halogen; Xl represents hydrogen or halogen, Xl represents fluorine or hydrogen, provided that when Xl is a halogen, Xl is hydrogen, R,, R2 and R3 are individually methyl, chlorine or bromine, provided that R1 and and one of R3 is other than chlorine or bromine, R represents methyl, chlorine, fluorine or bromine, and R1, R1 and R... individually represent water. methyl, chlorine, fluorine or bromine, but less of R', R'' and R... At least one of them is something other than hydrogen.

detailed description As already mentioned, the invention is based on the novel 1-(4-phenoxyphenyl)-3-benzoyl urea compounds, agrochemical compositions containing the compounds, and methods for producing and using the same. Ru.

Preferred benzoylurea compounds falling under the broad general formula (11) are represented by the following formula: %formula% R'' is as shown above).

Particularly preferred benzoylurea compounds have the following formula (where XSX', R1, R2, R , , R and R'' are as indicated above) and (where X%X', R and R1 are as shown above) .

The benzoyl urea compounds listed in Tables A to G below are represented by the above formulas and Illustrative examples of compounds that can be produced by practicing the invention are: Table A Table・、A (continued) Table B Table C (continued) Table D CI HBr Br Br Table E CI　P,B【Be　H HF CL CI C1 Table E (continued) Table F Table G These novel benzoyl urea compounds of the present invention can be used in one or more ways. Therefore, it can be easily manufactured.

For example, the compound of the present invention can be prepared with substituted phenoxyaniline l and benzene according to the following route l. It can be produced by reacting with zoyl isocyanate moxibustion: Here, xSx', x'', R1, R2, R3, RSR', R@ and R11 are formulas +1 1).

Alternatively, the novel compounds can be prepared using phenoxyphenylisocyanene following Route H below. It can be produced by the reaction between A and benzamide: Route ■ (where x, x', Xl, R1, R2, R3, R, R', R" and Rl 1 is a formula (having the meaning already described for 11).

The compound of the present invention can also be prepared by combining pencey/I/xuan and substituted urea chloride according to the following route ①. It can be produced by the reaction: (where X, X', X'', R1, R2, R 3, R, R', R1 and Rl+ are the formulas (having the meanings already stated with respect to 11) ).

i! , route 1. The reactions exemplified in II and It can be carried out in organic solvents such as hydrogen chloride, ether, and the like. Toluene, t2-dichloro Solvents such as loethane, dichloromethane are preferred. These reactions are carried out at room temperature to 150 Proceeds at temperatures in the °C range.

Route 1. The intermediates shown in II and ■ are prepared according to generally accepted procedures. It can be done. Thus, the substituted benzoyl isocyanate 3 is 5peziale etc. The following general method [J, Org, Chem, 2U, 3742 (1962) ) can be prepared from the corresponding benzamides according to: (where X%X' and Xl' has the meaning already described with respect to formula (1)).

Substituted phenoxyanilines in which R1 and R3 are not chlorine or bromine are as follows: According to Route V, which involves the reaction of substituted phenol and chloronitrobenzene, It cannot be manufactured using: Route■ (Here, R1, R2, R3, R1R', R'' and RI I + are related to formula +11. has the meaning given above, provided that R1 and R3 are not chlorine or bromine. ). Nitroether 10 is formed with phenol 9 and chloronitrobenzene. The reaction with 8 proceeds at elevated temperature in an inert solvent in the presence of a base.

Suitable bases for this reaction are potassium carbonate, sodium hydride, potassium hydroxide and sodium hydroxide. Suitable swamping agents include toluene, dimethylformamide and and dimethyl sulfoxide. The above transformation is carried out in a two-phase reaction medium in the presence of a phase transfer catalyst. Can be performed throughout the body.

Reduction of the ditroether to phenoxyaniline Z was carried out at 40-200 psi. A catalytic amount of platinum or palladium on carbon under a hydrogen atmosphere at a range of pressures and ambient temperatures. Alternatively, it can be accomplished by hydrogenation using a Raney nickel catalyst. Solvents suitable for hydrogenation The medium contains aromatic hydrocarbons or alcohols. This reduction is shown in Chem, Rev. , 65.51-68 (1965) using a metal catalyst and hydrazine. It can also be accomplished by chemical methods.

Isocyanate A is obtained by reacting substituted aniline with phosgene and 5ru. These reactions are exemplified by route ■ below: (where R1, R2, R6, R, R', R'' and R111 are with respect to formula C11 has the meaning previously stated).

Substituted phenoxyaniline in which R1 or R3 is chlorine or bromine or the following route 4-phenoxia pathway■ as described in (Here, when converting the above y to y, R, = X = chlorine or bromine, R1, R2, R SR'SR'' and R'1 have the meanings already stated in relation to formula (1), and 12 Mainly converted residue R, = X = chlorine or bromine, R2, R3, R1: al, n , 11 and R11 have the meanings already described for K in formula (1)). For such conversion Suitable solvents include aromatic hydrocarbons such as benzene or polar proteins such as acetic acid. Contains solvent. The halogenation of aniline 11 and cold exposure to chlorine or bromine in a suitable solvent or preferably benzene or vinegar. This can be accomplished by treatment with N-halosuccinimide in acid. necessary for the reaction The temperature varies depending on the types of substituents R2, R1 and R5, but is usually between 20°C and 8°C. It is in the 0°C range.・Typro and Tan phenoxyanilines are listed in route V above. It is manufactured by the method described above. However, R1 and R5 each represent hydrogen or methyl. I can do it.

Route ■ and the 4-chloro-1-nitrobenzene required for route ■ are commercially available. The Sandmeyer reaction (Mi Ller et al., J.

Med, Chem, 1980.23.1083) or known chlorobenes. It can also be produced by nitrating ZEN-14. These reactions are shown below. The type I phenoxyaniline represented by the route ■, especially the phenoxyaniline (where R,, R2, R3, R and R" have the meanings already given for the formula rll, and nl is chlorine or bromine). The reaction between this amino group and trifluoroacetic anhydride is yielding amide 18. Reduction of nitro groups, Sandmeyer rogogenation and Deprotection of the amino function produces the aniline. Details of these conversions are shown in the examples below. This is an indication.

Amine phenols of type 15 are readily available and can be prepared as shown in Route X below. ．． Nitration of 5-disubstituted phenol η''- followed by halogenation and nitro group reduction It can also be prepared as exemplified in the preparation of aminophenol 23 by: Route X (Here, R5 and R3 have the meanings already stated in relation to formula (1), and Y is bromine or chlorine). This approach to intermediate 2122 is based on Albe r t and 5ears [J, Am, Chem.

Soc, 76.4976 (1954)).

A preferred alternative to the amine phenol L''- is shown in route M below: Route M (R4, R2 and R3 here have the meanings already given for 2rll).

Here, a diazonium salt prepared from trisubstituted phenolic acid and sulfanilic acid reacts to form the intermediate diazo compound 25, and the plate compound is atomized by reduction. It becomes minphenol-15. used in this strategy to aminophenol 15 The synthetic method is described in Payne and Weiden's US Patent No. 1,752.838 This is what is written in the number.

The uninvented compounds may be used as insecticides according to methods known to the person skilled in the art. I can do it. Pesticide compositions containing the present compound as an active poison usually include a carrier and/or Or contains a diluent (liquid or solid).

Suitable liquid diluents or carriers include water with or without surfactants, petroleum distillates or Other liquid carriers are included. Liquid concentrates contain one or more of the compounds in acetate. xylene, nitrobenzene, cyclohexanone or dimethylformamide. Dissolve this compound (poisonous substance) in a non-phytotoxic solvent such as emulsifiers or emulsifiers prepared by dispersing them in water with the aid of agents or dispersants; The selection of the dispersant and its usage amount depends on the properties of the composition and the ability of the nucleating agent to promote the dispersion of toxic substances. Rely on. Generally re-emulsified and washed away from the plant by rain after application to the plant In addition, as small a quantity as possible that is compatible with the intended toxicant dispersion in spray form. It is desirable to use an agent. Nonionic, anionic or cationic dispersants or milk A curing agent can be used. For example, alkylaryl sulfone), complex ether teral alcohols, 17th ammonium compounds, organic acids, phenols and alcohols. Examples include condensates of lekylene oxide.

When producing wettable powder, dust or granular compositions, the active ingredient is In a suitably pulverized homogeneous carrier such as Bentonite, Bentonite, Kaisou±, Fuller's earth, etc. is dispersed on a solid support. In the formulation of wettable powders, the above-mentioned dispersants are added. Contains lignosulfonate.

The required amount of toxic material contemplated by the present invention may range from 1 to 200 gallons or more per knee to be treated. or more of a liquid carrier and/or diluent or about 5 to 500 lbs. of an inert solid. It is used mixed with a carrier and/or a diluent. The concentration in liquid concentrates is typically about 1 It varies from 0 to 95% by weight, and the concentration in solid formulations ranges from about α5 to 901% by weight. It fluctuates within the range.

Perfect spray, dust or granule strength for general use is about V4-15 per unit knee car Contains bond active poison.

A concentrated drug contemplated by the invention is a drug that can be applied to a plant or other substance. Prevents insect attack on objects or other materials and also exhibits relatively high residual toxicity.

With respect to plants, non-pesticides are those used in amounts sufficient to kill or repel insects. , it has a high degree of safety as it does not burn (or damage) plants. Ru. In addition, this pesticide can be washed away by rain, exposed to ultraviolet light, oxidized, or hydrolyzed in the presence of moisture. or, at the very least, significantly reduce the desirable pesticide properties of the green plant or make it non-toxic. Weathering, including decomposition, oxidation and hydrolysis, such as imparting desired properties such as phytotoxicity resist action. Furthermore, since non-toxic substances are chemically very inert, they are It is compatible with virtually any other ingredient in the play formulation and is compatible with soil plant seeds or roots. It can be used on these seeds or roots or in the soil without damaging them.

If desired, mixtures of non-inventive active compounds can be used or Mixtures of the compound with other biologically active compounds or components can be used. .

The following examples illustrate methods used in the preparation of uninvented intermediates and compounds. example A, chemical shift of NMR spectroscopy down from internal target tetramethylsilane The number of copies per million copies of the current feed is shown.

Placed in a round bottom reaction flask equipped with a Vt magnetic stirrer, temperature needle and 15°C ice bath. A solution of sulfanilic acid (49.4 g, 2 samM) in water (25 B + rJ) was Add a2Co5 (11689, 129mM), then add Na No2 (1 A solution of 9,389,280 mM) in water (53d) was added. Another, 'N, a stirrer , concentrated HCl (4 6TIL1) and the diazonium salt solution prepared previously were charged. this mixture Stir for 45 minutes at 15°C. Meanwhile, the condenser, nitrogen inlet, thermometer, addition funnel and In a third reaction flask equipped with water and a mechanical stirrer, add water (258d), NaOH (5d) (!L8g, 142mM) and 2. Melon 5-trimethylphenol (35.5g , 259 m M) was charged. Add this mixture until the ice is completely added. The reaction mixture was heated to 52°C and solid Na2S204 (it q 9.68.3 m M) was added. Continue stirring, and when the mixture reaches 80°C, add more Na2S 204 (107, 111615, 13mM) was divided into three equal parts (35, 7, 9°2o5. o4mM) and added at 5 minute intervals. This mixture was then stirred at 80°C for 20 minutes. Mix, cool to room temperature, and filter to obtain crude product. Dissolve this in ethyl acetate and add sulfuric acid. ) It was dried on IJum. This solution was heated to 1118 ml under reduced pressure to give a crude 1! ! 4-a Mino-2,45-)limethylphenol was obtained. NMR spectroscopy showed the following results. Did: H'-Nf'a (CDCI, ): 2-1 (S, 9H), 4.6 (S, 2H), 649 (S, IH).

Example B A 500 g round bottom reaction flask equipped with a magnetic stirrer and a nitrogen inlet was prepared in Example A. 4-Amino-2,3,5-)limethylphenol (3Q, , Og, 175mM ), dimethyl sulfoxide (110d), 3,4-dichloronitropenzey ( 28,0171146mM) and potassium t-butoxide (1 & 1g, 161 (mM). The reaction mixture was stirred at room temperature overnight, then diluted with toluene. I interpreted it. The organic phase is water C’L5! ), saturated NH4Cl (200 m/) and 2 ．． Washed with 5X NaOH until the aqueous layer was almost colorless. Then, The organic phase was washed with brine, dried over N a 2 SO a and concentrated under reduced pressure to give the crude Product 4-(2-chloro-4-nitrophenoxy)-2,3,6-)limethyl Aniline was obtained as a brown oil (1tsJF). NMR spectroscopic analysis gave the following results. Shown: H'-M (CDCl, ): 8.36 (d, J=2H2, IH) , &0 (d, d: J=2, 9Hz: IH), &73 (S, iH ), fh 65 (d, J = 9 Hz p I H), 166 (brS.

2H), 2.50.2.47, z36(3-3,9H).

4-(2-chloro-4-nitropheno 54.2-3mM) prepared in Example B and tolu Add raw trifluoroacetic anhydride to a magnetically stirred solution of ene (50, w/) (74,359,35A9mM) was added. Stir the reaction mixture overnight at room temperature. During this time, precipitation of the product occurred. Filter the mixture through a glass plate and Washed with sun. This allows Mltx4-<2-chloro-4-nitrophenoki )-2,16-trimethyl-N-)lifluoroacetanilide (29 g, 7. 2mM, 27.6%) was obtained as an off-white powder. NMR spectroscopy showed the following results: H'-NPa (CDCIs) 8.37 (d, J= 2 Hz, IH), a, o 5 (d, d:ty=z, 9Hz , IH), Z71 (br S, IH), 677 (S, IH), 470 (s ,1)().

In a 250 g Parr bottle, add 4-(2-chloro-4-nitrofluoropropylene) prepared in Example C. (phenoxy)-2,16-)dimethyl-N-trifluoroacetanilide (2,8 2g, 7.56mM) and ethyl acetate (50mj) were charged. Nitrogen the bottle 5% platinum on carbon (280 cm) was added. The reaction mixture was heated in a rocking Parr. Hydrogenation equipment 4% μm15. , /, rx” hydrogenated for 45 minutes at room temperature. I let it happen. The catalyst was removed by filtration through Celite, and the F solution was concentrated under reduced pressure to obtain pure 4-( 4-amino-2-chlorophenoxy)-2,5,6-trimethyl-N-)ria off-white Obtained as a powder.

NMR spectroscopy showed the following results: H’-h”MR (CDCI,) 1 (L23 (br s, IH), t, ao-as6 (m, 3H), a32 (s, 1H), 4.41 (brs.

2H), 2.29 (S, 3H), 2.20 (S, iH), 2.10 (S, IH) .

Cooled on ice and stirred magnetically, NaN02 (455 rnl, t57mM)-concentrated mimetic acid (52 rnl) solution, add 4-(4-amino-2-chlorophenoxy) prepared in the example. )-Z3.6-)dimethyl-N-trifluoroacetanilide (2-259,6 A solution of acetic acid (14,7d) at 0.036 mM) was added dropwise. This reaction mixture was heated at 15°C. I was shocked by the following. After the dropwise addition, the reaction mixture was stirred at room temperature for 2 hours. Meanwhile, chloride A solution of stannous was prepared as follows. That is, CuSO4・5H20(5,26 a, 088mM), NaOH (485, 2mg, 1113mM) and water (N 96 mJ) was added. The mixture was stirred to obtain a white precipitate. Kamisumi's enemy is big The precipitate was washed with water. Add concentrated HC1 (1, am) to turn green and black. A colored solution was obtained. Add the diazonium salt in acetic acid/H2SO4 prepared earlier to the solution. Add dropwise without stirring and stir the mixture for 30 minutes at room temperature. the reaction The mixture was diluted with acetic acid, washed three times with H2O, once with brine, and diluted with sodium sulfate. Dry on a rack. Concentrate under reduced pressure to obtain crude fi4-(2,4-dichlorophenoxy)- 2,16-trimethyl-N-)lifluoroacetanilide (10,9) in orange oil Obtained as a solid. Add methanol (zone) to this product, then N)f2 NH2.H2O (3 oi) was added. The reaction mixture was brought to reflux and stirred for 5.5 hours. Mix, cool, dilute with water and then extract with toluene. organic phase was washed twice with saturated NH4Cl, once with H2O, once with brine and dried over sodium sulfate. It was dried. Concentrate under reduced pressure to obtain crude 94-(2゜4-dichlorophenoxy)-2,h 6-trimethylaniline (t49fI) was obtained as an oil. Flush the reaction mixture. column chromatography (load ratio 70:1, hexane to ethyl acetate ratio s : 1) Pure 4-(2,4-dichlorophenoxy)-2 purified from Ic, &6-) Limethylaniline (810In9.2.73mM, IZ45X), mp8 (L) Obtained as off-white crystals at 5°C to 84°C.

NMR spectroscopy showed the following results: H'-AiR (CDCI3) near, 27 (d, J=2Hz, IH), 493 (d, d: J=2.9Hz, I H), &57 (s, IH), 6.42 (d, J=9Hz, IH), Eng36 (br s, 2H), 2. o6 (s, 6H), t96 (s, 5H).

A1 1-(2,!idichloro--(2,4-dichlorophenoxy)-6-methyl Production of phenyl)-5-(2,6-difluorobenzoyl)urea -6-Methylnitrobenzene production Magnetic stirrer, reflux condenser, thermometer and Add 4,5-dichloro-2-methylnitrochloride to a round-bottomed reaction flask equipped with a nitrogen inlet. Trobenzene 5 & 4. y (17a7mM), 2,4-dikuoa7znor35. 9g (22α2mM), potassium carbonate 2t1,9 (152,5mM) and dimethyl 350 d of chillformamide was charged. The reaction mixture was stirred and refluxed for 2 hours. The mixture was filtered while still warm, then cooled to room temperature, and concentrated under reduced pressure. Dilute the residue with methylene chloride , the organic phase was washed with brine, dried over anhydrous N az SOa, and concentrated under reduced pressure. The crude product was obtained as a viscous dark brown liquid at °C. Light brown by adding hexane and toluene A colored solid was obtained which was purified by flash column chromatography (hexane vs. toluene). pure 3-chloro-4-(2,4-dichlorophenol) with a ratio of 4:1 to 2:1). xy)-6-methylnitrobenzene (24,59,757mM), 42%) was obtained. Ta. NM'R spectroscopy showed the following results: H' → 4m (CDCI3) = 8.26 (br s, IH), 7.60 (d, J=2Hz.

IH), 7.35 (d, d: 2.9Hz: IM), 7.06Cd, J=9H1° IH), &59 (s, IH), 2.55 (S, 3H).

In a 2501 L parr bottle, 3-chloro-4-(2,4- dichlorophenoxy)-6-methylnitrobenzene 2444.9 (75 aamM ) and 150 d of toluene were charged. The bottle was purged with nitrogen and washed with carbon at room temperature. Hydrogenation was carried out for 1 hour. The catalyst was removed by filtration through Celite, and the furnace liquid was concentrated under reduced pressure. The product was obtained as a dark yellow oil. Pure 6-chloro-4- by adding hexane (2,4-dichlorophenoxy)-6-methylaniline (2α41Ji’, 67 ．． 5mM, 92X) was obtained as a light brown solid. NMR spectroscopic analysis gave the following results. Shown: H'-'Nhm (CDCIs): 7.41 (d, J=2 Hz, IH), 710 (d.

d: J=2.9Hz: IH), &7B(S, IH), a72(s, 1H), 6.55 (d, J=9Hz, IH), x59 (br s, 2H), 2.10 (s.

Prepared in Step B in a 100 nine-bottom reaction flask equipped with a magnetic stirrer and a nitrogen inlet. 3-chloro-4-(2,4-dichlorophenoxy)-6-methylaniline 9 ．． 41! ! (xtlomM), acetic acid 62- and N-chlorosuccinimide 4 ．． (Sg (34, 21mM) was charged. This mixture was incubated at ambient temperature for 45 minutes. Stir and dilute with toluene and saturated Na2SO3 bath. Saturates the toluene layer Na　3 times with 2305 bath solution, 3 times with 30.5% NaOH solution in water, and once with water. Wash with water and salt water, dry with N a 2 So 4, and under reduced pressure! 111m and raw The product was obtained as a dark brown oil. Flash column chromatography (load ratio 1oo:1. 2,3-dichloro-4- (2,4-dichlorophenoxy)-6-methylaniline (ta 7g, 4.36 mM, 14X) was obtained. NMR spectroscopy showed the following results: ) I'-NMR (CDCI, ) 7.43 (d, J=2H2, IH), 7 ．． 30 (d.

d: J=2.9Hz, IH), 474 (S, IH), &56 (d, J=9 Hz, IH), 4.08 (brs, 2H), 2.18 (S, 5H).

Production of urea (difluorobenzoyl) 2,3-dichloro-4-(2,4-dichlorophenoxy)-6 prepared in Step C -Methylaniline (143g, 4.24mM)) and hexa 7 (4 ml) and stir electromagnetically. (780μ, 424mM) and leave this mixture overnight. Stir at room temperature. The resulting precipitate was collected by Pa, washed with hexane, and dried. Pure 1-(2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methane) tylphenyl)-3-(2,6-difluorobenzoyl)urea (670■, 1 29mM, 28X) was obtained as a white solid, mp 196<0>C to 199<0>C. white solid Elemental analysis of showed the following results: Analysis: C2,■(,2C14F2N203 Calculated value: C4&49, H253, N5.39, actual value: C4B, 1B, H2,45, N5. s 4 example 2 and 6 Using the same procedure used in the previous example but using one of the synthetic routes described above, other urine An elementary compound was produced. The types of substituents and analytical data regarding the general formula are shown in Table 1 below. Post on: Book 1～～ did. We are also applying the new compound to heavy crops including beans, soybeans, corn, tomatoes and cotton. The plant was tested for phytotoxicity in important crops. Furthermore, new compounds can be used in mammals. It was evaluated for toxicity.

Dissolve 100 μ of the compound in 15 ml of dimethylformamide, then add an emulsifier or Alkylphenoxypolyethoxyethanol surfactant α25% as a dispersant A suspension of the test compound was prepared by adding 8.5 d of an acetone solution containing . The solution formed is mixed with 30 g of water to form a suspension containing the compound in finely divided form. Got 0 goals. The compound content of the raw material suspension prepared by Tonoyo 5K was 2.53% by weight. there were. The weight ppm concentration used in the following test is determined by appropriately diluting the above raw material suspension with water. This is what I got. Sonication was used when necessary to form a homogeneous turbidity. . The test procedure is as follows: Leaf plants for southern armyworm (5 outnern armyworm) Larvae of fall armyworm in the southern United States (5podopte) reared on tengu green. ra eridania, (Cram, )) was used as the test insect.

The raw material suspension is diluted with water to obtain a concentration (per million parts of final formulation) as indicated in the table below. The number of kites containing the test compound is treated with the test compound. By using a Devilbiss spray gun with 100 g of the above test compound formulation was sprayed.

Continued spraying for 25 seconds is sufficient to wet the plant enough to drip. Met. As a control, plants similarly infested with larvae were treated without any test compound. 100 g of a fresh water-acetone-emulsifier solution was sprayed. When this is dry, Separate the remaining leaves and place each one in a 9cm vetri dish lined with moistened F paper. I put it inside. Each. The larvae could easily consume the whole leaf within 24 hours, but after that The above food was not given. Larvae that cannot move their body length even if stimulated by prodding will die. It was deemed that Mortality was recorded at each concentration level.

Legume tender green at 80 ± 5’l’ and relative humidity 50 ± 5X The fourth instar larva (Epi lachnavarivestis, Muls, ) was used as the test insect.

Dilute the raw material suspension with water and make it as shown in the table below! (per million parts of final formulation) The test compound is treated by forming a suspension containing the test compound in I did it. Rotating standard-season legume tender greens cultivated by bee milling Using a Dew Bilvis spray gun placed on the board and with air pressure set to 40 psig. 100 g of the test compound formulation described above was sprayed. The liquid is dripping Rg, mist for 25 seconds was sufficient to wet the plants. contrast and Similarly, plants infested with larvae were treated with the test compound (without water, acetone, and Emulsifier solution 100- was sprayed. When this dries, separate the paired leaves Then, each was placed in a 9-epee (IJ) dish lined with humidified F paper. each Five randomly selected larvae were introduced into the dish, covered, labeled and identified. It was kept at 80±5'F for 5 days. Larvae easily consume entire leaves within 24-48 hours I was able to do that, but I didn't give him any more food. Unable to move body length even if stimulated Young larvae were considered dead.

Commercially obtained and fed on artificial food at a temperature of 80 ± 5'F and a relative humidity of 50 ± 5X Heliothis virescens.

F, (weight approximately 2.s rq) and He1iothis zea, (B oddie) (body weight 2.5 cm) was used as the test insect.

Follow the same procedure as above, except use cotton or other material instead of legumes, and 9c of dried cotton leaves! was introduced into an IL Petri dish. This test consists of 10 Petri dishes. It is included in a batch of sets. 1 randomly selected for each plate of 10 pieces One larva was introduced and the lid was placed. Label and identify, 5 to 80 ± 5’F It was kept for days.

Larvae that were unable to move their body length upon stimulation were considered dead. Death to concentration mother The rate was recorded.

The biological properties of specific examples representative of the compounds of the present invention are listed in Tables ■, Table ■, and Table ■ below. I will post it.

(1) Armyworm in the southern United States (2) Insects of the genus Chimrididae (3) Code: Insect killing rate of A-71 to 100X B-31 - 70% insect killing rate C = O ~ 30X insect killing rate Kaoru Tested at 25 ppm.

Examples 4 and 5 and Comparative Example A In order to demonstrate enhanced biological activity against insects of the genus Chrysophyllum, the present invention A typical 1-(4-phenoxyphenyl)-3-benzoyl urea compound of Comparisons were made with known compounds. The results are shown in the table ■ below: From the data shown in Table 1, the 1-(4-phenoxyphenyl)-6-ben Comparison of known compounds shows that zoyl urea compounds have a positive effect on insects of the genus P. chinensis. It is clear that they exhibit enhanced biological activity. In Table ■, Comparative Example A used The compound was prepared in a similar manner to the procedure described in Japanese Patent Application No. 56-92857. Ta.

Examples 6 and 7 and Comparative Example B To demonstrate enhanced biological activity against Heliothis Spp. Representative 1-(4-phenoxyphenyl)-3-benzoyl urea compounds of the present invention was compared with known compounds. The results are shown in the table ■ below: From the data shown in Table 2, the 1-(4-phenoxyphenol)-3-benzene of the present invention In comparison with known compounds, Nzoyl urea compounds were compared with Heliothis spp. It is clear that it shows enhanced biological activity against . Comparisons used in the table The compound of Example B was prepared in a similar manner to the procedure described in Japanese Patent Application No. 56-92857. Manufactured.

Although the invention has been illustrated by the examples above, it is not intended to be limited to the materials used in these examples. Rather, the invention is represented by the general formula shown above. Therefore, various modifications Other embodiments may be made without departing from the spirit and scope of the invention.

international search report ;GB,'EX:OT=E D;'E:'u'! Enter TIC:! AL　5=AR C5 R3 FORT 0NZN NAT! ONA, LA? PL engineering CATrONN o, PCT/l; S86100319 (SA12350)

Claims (61)

[Claims] 1. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the ceremony X represents halogen; X' represents hydrogen or halogen, X'' represents fluorine or hydrogen, provided that when X' is a halogen, X'' is hydrogen. the law of nature, R1, R2 and R3 are individually methyl, chlorine or bromine, provided that R1 and and one of R3 is other than chlorine or bromine, R represents methyl, chlorine, fluorine or bromine; R', R'' and R''' are individually , hydrogen, methyl, chlorine, fluorine or bromine, with the proviso that R', R'' and R' A compound in which at least one of ′′ is other than hydrogen. 2. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R, R', R'' and R''' are 2. The compound according to claim 1, wherein the compound has the following range (as shown in claim 1). 3. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R and R■ are shown in claim 1. 2. A compound according to claim 1, wherein the compound has the following formula: 4. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R and R' are shown in claim 1. 2. A compound according to claim 1, wherein the compound has the following formula: 5. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R and R''' are defined in claim 1. 2. A compound according to claim 1, wherein the compound has the following properties: 6. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R, R' and R'' are 2. A compound according to claim 1, which has the following properties: 7. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R, R' and R''' are 2. A compound according to claim 1, which has the following properties: 8. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, X', R1, R2, R3, R, R'' and R''' are within the scope of the claims. 2. A compound according to claim 1, having the following properties: as shown in claim 1). 9. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, X, R1, R2, R3, R and R'' are the same as shown in claim 1. The compound according to claim 1, which has the following. 10. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where X, X', R and R'' are as shown in claim 1) The compound according to claim 1, which has. 11. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where X, R and R'' are as shown in claim 1) , the compound according to claim 1. 12. X' is halogen, R and R are individually methyl, bromine or chlorine; The compound according to claim 3, wherein 13. X' is hydrogen and R and R'' are individually methyl, bromine or chlorine , the compound according to claim 3. 14. X and X' are fluorine, R and R'' are individually methyl, bromine or salt 4. The compound according to claim 3, which is 15. Claim 5, wherein R and R''' are individually methyl, bromine or chlorine. Compounds described in Section. 16. Claims where R, R' and R'' are individually methyl, bromine or chlorine Compound according to item 6. 17. Claims in which R, R'' and R''' are individually methyl, bromine or chlorine A compound according to Scope Item 8. 18. X is fluorine and R and R'' are individually methyl, bromine or chlorine; A compound according to claim 9. 19. X and X' are fluorine, R and R'' are individually methyl, bromine or salt 11. The compound according to claim 10, which is 20. X and X' are fluorine, R is chlorine or bromine, and R'' is chlorine; 11. The compound according to claim 10. 21. X is fluorine and R and R'' are individually methyl, bromine or chlorine; A compound according to claim 11. 22. In the claimed case, X is fluorine, R is chlorine or bromine, and R'' is chlorine. A compound according to Range 11. 23.1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methyl tylphenyl]-3-(2,6-difluorobenzoyl)urea. A compound according to item 1. 24.1-[2,3-dichloro-4-(2-promo-4-chlorophenoxy)- 6-methylphenyl]-3-(2,6-difluorobenzoyl)urea, A compound according to item 1 of the claimed scope. 25.1-[4-(2,4-dichlorophenoxy)-2,36-trimethylphenylene [Claim 1]-3-(2,6-difluorobenzoyl)urea Compounds described. 26.1-[3-chloro-4-(2,4-dichlorophenoxy)-2,6-dime tylphenyl]-3-(2,6-difluorobenzoyl)urea. A compound according to item 1. 27.1-[3-chloro-4-(2-bromo-4-chlorophenoxy)-2,6 -dimethylphenyl]-3-(2,6-difluorobenzoyl)urea, A compound according to item 1 of the claimed scope. 28.1-[2,3-dichloro-4-(2,4-dichlorophenoxy)-6-methyl tylphenyl]-3-(2-fluorobenzoyl)urea, Claim 1 Compounds described in Section. 29.1-[2,3-dichloro-4-(2-promo-4-chlorophenoxy)- 6-methylphenyl]-3-(2-fluorobenzoyl)urea A compound according to item 1. 30.1-[4-(2,4-dichlorophenoxy)-2,36-trimethylphenylene ]-3-(2-fluorobenzoyl)urea according to claim 1. Compound. 31. comprising an acceptable carrier and a pesticidally effective amount of a compound according to claim 1. Pesticide composition. 32. comprising an acceptable carrier and a pesticidally effective amount of a compound according to claim 2. Pesticide composition. 33. comprising an acceptable carrier and a pesticidally effective amount of a compound according to claim 3. Pesticide composition. 34. a compound according to claim 4 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 35. a compound according to claim 5 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 36. a compound according to claim 6 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 37. a compound according to claim 7 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 38. a compound according to claim 8 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 39. a compound according to claim 9 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 40. a compound according to claim 10 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 41. a compound according to claim 11 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 42. a compound according to claim 23 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 43. a compound according to claim 24 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 44. a compound according to claim 25 in an acceptable carrier and a pesticidally effective amount. Pesticide composition. 45. By subjecting pests to an agrochemically effective amount of the compound according to claim 1. Pest control methods. 46. by subjecting pests to an agrochemically effective amount of the compound according to claim 2. Pest control methods. 47. comprising subjecting pests to an agrochemically effective amount of the compound according to claim 3. , pest control methods. 48. By subjecting pests to an agrochemically effective amount of the compound according to claim 4. Pest control methods. 49. By subjecting pests to an agrochemically effective amount of the compound according to claim 5. Pest control methods. 50. By subjecting pests to an agrochemically effective amount of the compound according to claim 6. Pest control methods. 51. By subjecting pests to an agrochemically effective amount of the compound according to claim 7. Pest control methods. 52. By subjecting pests to an agrochemically effective amount of the compound according to claim 8. Pest control methods. 53. By subjecting pests to an agrochemically effective amount of the compound according to claim 9. Pest control methods. 54. By subjecting pests to an agrochemically effective amount of the compound according to claim 10. A pest control method. 55. By subjecting pests to an agrochemically effective amount of the compound according to claim 11. A pest control method. 56. By subjecting pests to an agrochemically effective amount of the compound according to claim 23. A pest control method. 57. By subjecting pests to an agrochemically effective amount of the compound according to claim 24. A pest control method. 58. By subjecting pests to an agrochemically effective amount of the compound according to claim 25. A pest control method. 59. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A method for producing a compound of the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Phenoxyaniline and the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A method comprising reacting with benzoyl isocyanate [During the ceremony X represents halogen; X' represents hydrogen or halogen, X'' represents fluorine or hydrogen, provided that when X' is a halogen, X'' is hydrogen. the law of nature, R1, R2 and R3 are individually methyl, hetero or bromine, provided that R1 and and one of R3 is other than chlorine or bromine, R represents methyl, chlorine, fluorine or bromine; R, R'' and R''' are individually , hydrogen, methyl, chlorine, fluorine or bromine, with the proviso that R', R'' and R'' ′, at least one of which is other than hydrogen]. 60. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A method for producing a compound of the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Phenoxyphenyl isocyanate and formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method consisting of reacting with benzamide [in the formula X represents halogen; X' represents hydrogen or halogen, X'' represents fluorine or hydrogen, provided that when X' is a halogen, X'' is hydrogen. the law of nature, R1, R2 and R3 are individually methyl, chlorine or bromine, provided that R1 and and one of R3 is other than chlorine or bromine, R represents methyl, chlorine, fluorine or bromine; R', R'' and R''' are individually , hydrogen, methyl, chlorine, fluorine or bromine, with the proviso that R', R'' and R' At least one of ′′ is other than hydrogen]. 61. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A method for producing a compound of the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Substituted urea and formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A method comprising reacting with benzoyl chloride [in the formula X represents halogen; X' represents hydrogen or halogen, X'' represents fluorine or hydrogen, provided that when X' is a halogen, X'' is hydrogen. the law of nature, R1, R2 and R3 are individually methyl, chlorine or bromine, provided that R1 and and one of R3 is other than chlorine or bromine, R represents methyl, chlorine, fluorine or bromine; R', R'' and R''' are individually , hydrogen, methyl, chlorine, fluorine or bromine, with the proviso that R', R'' and R' At least one of ′′ is other than hydrogen]. Detailed explanation of the invention■