Europaisches Patentamt (19) European Patent Office © Publication number: 0 263 438 Office europeen des brevets A2
EUROPEAN PATENT APPLICATION
© Application number: 87114341.8 © int. ci.*: C07C 127/22 C07D , 213/64 , C07D 213/75 , A01N 47/34 © Date of filing: 01.10.87 , A01N 47/36 , C07C 93/14
© Priority: 03.10.86 JP 235857/86 © Applicant: ISHIHARA SANGYO KAISHA LTD. 11.03.87 JP 56006/87 No. 3-22, Edobori 1-chome 05.06.87 JP 141214/87 Nishi-ku Osaka(JP)
@ Date of publication of application: © Inventor: Haga, Takahiro Ishihara Sangyo 13.04.88 Bulletin 88/15 Kaisha Ltd. Chuo Kenkyusho 3-1, Nishishibukawa © Designated Contracting States: 2-chome BE CH DE ES FR GB IT LI NL Kusatsu-shi Shiga-ken(JP) Inventor: Toki, Tadaaki Ishihara Sangyo Kaisha Ltd. Chuo Kenkyusho 3-1, Nishishibukawa 2-chome Kusatsu-shi Shiga-ken(JP) Inventor: Koyanagi, To*ru Ishihara Sangyo Kaisha Ltd. Chuo Kenkyusho 3-1, Nishishibukawa 2-chome Kusatsu-shi Shiga-ken(JP) Inventor: Fujii, Yasuhiro Ishihara Sangyo Kaisha Ltd. Chuo Kenkyusho 3-1, Nishishibukawa 2-chome Kusatsu-shi Shiga-ken(JP) Inventor: Yoshida, Kiyomitsu Ishihara Sangyo Kaisha Ltd. Chuo Kenkyusho 3-1, Nishishibukawa 2-chome Kusatsu-shi Shiga-ken(JP) Inventor: Imai, Osamu Ishihara Sangyo EN Kaisha Ltd. < Chuo Kenkyusho 3-1, Nishishibukawa DO 2-chome TO Kusatsu-shi Shiga-ken(JP)
© Representative: Wachtershauser, Giinter, Dr. ID Tal 29 N D-8000 Munchen 2(DE)
LLI© Benzoylurea compounds, process for their production and pesticides containing them.
Xerox Copy Centre 0 263 438
© A benzoylurea compound having the formula:
CO -i.
(i;
wherein each of Xi and X2 is a hydrogen atom, a halogen atom or a methyl group, provided that X1 and X2 are not simultaneously hydrogen atoms, Y is independently a hydrogen atom, a halogen atom, an aikyl group which may be substituted by halogen, a -CO2R1 group wherein R1 is a hydrogen atom, a cation or an alkyl group, or a -OR1 group wherein R1 is as defined above, A1 is = N-or = C -wherein Y is as defined above, W is an oxygen atom, a sulfur atom or Y
-N- I Rl
wherein R1 is as defined above, k is an integer of from 1 to 3, I is 0 or 1 , and Ar is
A2
wherein Z is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, an alkoxy group which may be substituted by halogen, a nitro group, a cyano group or a -S(0)nR2 group wherein R2 is an aikyl group which may be substituted by halogen and n is 0, 1 or 2, A2 is -S-, -N = C -wherein Z is 1 Z as defined above, or - c = c -wherein Z is as defined above, 1 1 2 Z and m is an integer of from 1 to 3, or a salt thereof.
2 0 263 438
pcN^uYLUncA COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND PESTICIDES CONTAINING THEM
ine present invention relates to novel benzoylurea compounds, a process for their production and pesticides containing them. Benzoylurea compounds are known to be effective as insecticides, for example, from U.S Patents 3,748,356, 4,173,637, 4,173,638, 4,310,530 and 4,005,223. Further, derivatives of such benzoylurea com- 5 pounds wherein the nitrogen atom in the urea moiety bonded to an aromatic ring is substituted by an alkyl group, are known, for example, from, U.S. Patents 3,748,356, 4,607,044 and 4,659,736, Japanese Unex- amined Patent Publications No. 184151/1984 and No. 106069/1987, PCT(JP) Publication No. 501418/1987, and J. Agr. Food Chem., Vol. 21, No. 3, 348-354 (1973). Furthermore, specific benzoylurea compounds wherein the above-mentioned nitrogen atom is substituted by an alkyl group and the above-mentioned w aromatic ring is substituted by an aromatic ring are also broadly covered by the general formulas disclosed in the above publications. However, such specific benzoylurea compounds are not specifically disclosed in such publications. The present invention is based on a discovery that among such specific benzoylurea compounds, those wherein the nitrogen atom in the urea moiety bonded to an aromatic ring is substituted by a methyl group, 15 the other nitrogen atom bonded to the benzoyl group has a hydrogen atom and said aromatic ring contains an aromatic ring as a substituent, are highly safe to beneficial aquatic Crustacea and capable of being readily decomposed in soil, while exhibiting equal or superior insecticidal activities to those wherein the nitrogen atom in the urea moiety bonded to the aromatic ring is not substituted by a methyl group and has a hydrogen atom. 20 Thus, the present invention provides a benzoylurea compound having the formula:
(W)£-Ar wnerein eacn or Xi ana Xs is a hydrogen atom, a halogen atom or a methyl group, provided that Xi and X2 30 are not simultaneously hydrogen atoms, Y is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, a -CO2R1 group wherein R1 is a hydrogen atom, a cation or an alkyl group, or a -OR1 group wherein R1 is as defined above, A1 is = N-or = c -wherein Y is as defined above, W is an oxygen atom, a sulfur atom or y ti- ll. wnerein Hi is as aetined above, k is an integer of from 1 to 3, L is 0 or 1 and Ar is to , A2 (5 wherein Z is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, an alkoxy group which may be substituted by halogen, a nitro group, a cyano group or a -S(0)„R2 group wherein R2 is an alkyl group which may be substituted by halogen and n is 0, 1 or 2, A2 is -S-, -N = e -wherein Z is >o 2 as defined above, or - C = c -wherein Z is as defined above, Z 2 and m is an integer of from 1 to 3, or a salt thereof. 0 263 438 Further, the present invention provides a process for producing the compound of the formula I, a pesticide containing the compound of the formula I and an intermediate useful for the production of the compound of the formula I. Now, the present invention will be described in detail with reference to the preferred embodiments. 5 In connection with the formula i, the alkyl group, the alkyl group which may be substituted by halogen or the alkyl moiety in the aikoxy group which may be substituted by halogen, may be an alkyl group having from 1 to 6 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a sec-butyl group, preferably a methyl group or an ethyl group, more preferably a methyl group. The halogen atom or the halogen contained in the alkyl or aikoxy group which io may be substituted by halogen, includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and it is preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl or aikoxy group which is substituted by halogen, may contain one or more halogen atoms. When it contains two or more halogen atoms, such halogen atoms may be the same or different. The salt of the benzoylurea compound of the formula I is a salt at the nitrogen atom of the urea moiety, 75 and may be a salt with an alkali metal atom. Among the compounds of the formula I, preferred are those wherein (W)t is located at the m-or p- position, preferably p-position relative to the position to which the urea moiety is attached, while (W)| is attached to Ar at the position adjacent to A2. The preferred compounds may be represented by the formula: 20 ^1 ( V-conhcon— 25 wherein Xi, X2, Y, A1, W, k, I, Z, A2 and m are as defined above, or a salt thereof. Each of Xi and X2 is preferably a hydrogen atom or a halogen atom, provided at least one of them is a halogen atom. Y is preferably independently a hydrogen atom, a halogen atom, an alkyl group which may 30 be substituted by halogen, or a -CO2R1 group wherein R1 is as defined above, and A1 is preferably = C - wherein Y is as defined above. Y Z is preferably independently a hydrogen atom, a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a -S(0)nCF3 group wherein n is as defined above, and A2 is preferably -N = C -or - C = C -. z 7. z 35 Specific preferred compounds will be given below: N-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2- pyridyloxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2,3-difluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2,5-dimethylphenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, 40 N-[3-chloro-4-(3-chioro-5-trifluoromethyl-2-pyridyloxy)-2-fluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-N'-(2-chiorobenzoyl)-N-methylurea, N-[4-(2-chloro-4-trifluoromethylphenoxy)-2,3-difluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(2-chloro-4-trifluoromethylphenoxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, 45 N-[4-(2-chloro-4-trifluoromethylphenoxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(2-chioro-4-trifluoromethylphenoxy)phenyl]-N-(2-chlorobenzoyl)-N-methyIurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-methylphenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-{4-[3-chloro-5-trifluoromethyl-2-pyridyloxy]-3-fluorophenyl}-N'-(2,6-difluorobenzoy!)-N-methylurea, N-{4-[2-chloro-4-trifluoromethylphenoxy)-3-fluorophenyl}-N'-(2,6-difluorobenzoyl)-N-methylurea, 50 N-{4-(2-chloro-4-trifluoromethylphenoxy)-3,5-difluorophenyi}-N'-(2,6-difluorobenzoyl)-N-methylurea, N-{4-[2-chloro-4-trifluoromethylphenoxy]-3-methylphenyl}-N'-(2,6-difluorobenzoyl)-N-methylurea, N-{4-[3-chloro-5-trifluoromethyl-2-pyridyloxy]-3-methylphenyl}-N'-(2-chlorobenzoyl)-N-methylurea, N-[4'-chloro-2-fluoro-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea, N-(4'-bromo-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea, 55 N-(2,5-difluoro-4'-chloro-4-biphenylyl)-N,-(2,6-difluorobenzoyl)-N-methylurea, N-(2-trifiuoromethyl-4'-chloro-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea, N-(2,5-difluoro-3'-trifluoromethylthio-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea. 4 0 263 438 ine Denzoyiurea compound of the formula I of the present invention can be prepared, for example, by the following process. (Y)k Xl V>-CO-N=C=0 H-N-^^ -j- <^ uti3 (III) (IV) @p- compound of the formula I -10 C to +100 c u.i to /i4 nours 20 In the above formulas, Xi, X2, Y, k, Ai, W, I and Ar are as defined above. The above reaction may be conducted in the presence of a solvent, if necessary. As such a solvent, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene, a cyclic or non-cyclic aliphatic hydrocarbon such as hexane or cyclohexane, an ether such as diethyl ether, dioxane or tetrahydrofuran, 25 a nitrile such as acetonitrile or propionitrile, or an aprotic polar solvent such as dimethylformamide, dimethyl- sulfoxide, sulfolane or hexamethyl phosphoric acid triamide, may be mentioned. The starting compound of the formula III can be prepared, for example, by the following process. L A j (Y)k . Acetylatinsr agent f 0 Ar (e.g. CH3COCI or /P3>-(W)rAr 1 acetic anhydride) , h3CC-NH-<^ y A- L M ethy latin g OOk O agent (e.g. CH3I) /~n\^(W) — Ar x u rr-M-/ x) ^ Compound of Base (e.g. NaH) - H3 / DeacetyMng formula CHg A-|_ agent (e.g. cone. HC1) In the above formulas, Y, k, A1, W, I and Ar are as defined above. Among the compounds of the formula III, those wherein I is 1 may be prepared, for example, also by the following process. 0 263 438 // vrw-CH3 %W-CH, Reduction °2N \ / >H2N~~^ / (e.g. by introducing'' X^-"Ai H2 in the presence of palladium /carbon) 1U In accordance with the acetylation, methylation /-y) and deacetylation steps described in as the. , \ above process [Al. // \\— -W-H ~ — -4. H-N — ( 76 ...... /TTA^W-Ar H-N-/ ^ > Base 7 1 \ / Aprotic polar solvent ^H^ — Al (III') In the above formulas, Hal is a halogen atom, and Y, k, A1, W and Ar are as defined above. 2b The reaction conditions for various reactions for the preparation of the starting compounds of the formulas III and III' such as the reaction temperature, reaction time, the solvent to be used as the case requires and the base, may be suitably selected from the reaction conditions commonly used for the reactions of this type. 30 The starting compound of the formula 35 for process [A] can be prepared in the following manner . 40 (Y)k WCH Demethylating agent WH 3 (e.g. HBr) 45 H2N- > H2N- C7\ iV-Ar CKAr J ' 2 \ 50 Base l Aprotic polar solvent ^ — A. Now, specific Examples for the preparation of the intermediates for the compounds of the present invention will be described. NTERMEDIATE PREPARATION EXAMPLE 1 3 0 263 438 preparation ot 4-Dromo-4-methylaminobiphenyl [I] A solution prepared by dissolving 0.75 g of 4-amino-4'-bromobiphenyl in 10 ml of pyridine, was cooled with ice, and 1.0 g of acetyl chloride was dropwise added thereto. The mixture was stirred over a 5 period of 30 minutes. After the completion of the reaction, the reaction solution was extracted with ethyl acetate and water. The organic layer was washed with dilute hydrochloric acid and further with a saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.8 g of N-(4'-bromo-4-biphenylyl)acetamide as colorless crystals. [II] A solution prepared by dissolving 0.80 g of N-(4'-bromo-4-biphenylyl)acetamide obtained in step [I] w in 10 ml of dimethylformamide, was dropwise added at a temperature of from 15 to 20°C to 10 ml of a dimethylsulfoxide solution in which 0.17 g of sodium hydride (60% nujol mixture) was suspended. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and then 0.78 g of methyl iodide was dropwise added thereto at a temperature of from 15 to 20°C. Then, the mixture was stirred for 3 hours at room temperature. 75 After the completion of the reaction, the reaction solution was extracted with ethyl acetate and water. The organic layer was washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain o.76 g of N- (4'-bromo-4-biphenylyl)-N-methylacetamide as colorless crystals. [III] 10 mi of concentrated hydrochloric acid was added to a solution prepared by dissolving 0.74 g of 20 N-(4'-bromo-4-biphenylyl)-N-methylacetamide obtained in Step [II] in 20 mi of methanol, and the mixture was refluxed over a period of 18 hours. After the completion of the reaction, the reaction solution was cooled and poured into 100 ml of a 10% potassium hydroxide aqueous solution. Then, it was extracted with methylene chloride. The organic layer was washed with water and further with a saturated sodium chloride aqueous solution, and then dried over 25 anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane/ethyl acetate = 4/1) to obtain 0.30 g of 4'-bromo-4-methylaminobiphenyl having a melting point of from 127 to 129°C. 30 INTERMEDIATE PREPARATION EXAMPLE 2 Preparation of 4-(3-chloro-5-trifluoromethyi-2-pyridyloxy)-3-fluoro(N-methyl)aniline 0.8 g of 4-(N-methyl)amino-2-fluorophenol prepared in the same manner as in Steps [I], [II] and [III] of 35 Intermediate Preparation Example 1 by using 4-amino-2-fluoroanisol, 1 .2 g of 2,3-dichloro-5-trifluoromethyi- pyridine and 0.9 g of anhydrous potassium carbonate were dissolved in 20 ml of dimethylsulfoxide, and reacted in a nitrogen stream at 100° C for 1.5 hours. After the completion of the reaction, the reaction solution was poured into ice water, and then extracted with ethyl ether. The organic layer was washed with water and further with a saturated sodium chloride 40 aqueous solution, and then dried over anhydrous sodium sulfate. Then, the ethyl ether was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n- hexane/ethyl acetate = 3/2) to obtain 0.5 g of 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-3-fluoro(N-methyl)aniline. 45 INTERMEDIATE PREPARATION EXAMPLE 3 Preparation of 4-(2-chloro-4-trifluoromethyiphenoxy)-3-fluoro(N-methyl)aniline 50 [I] 2 g of 5% palladium carbon was added to a solution prepared by dissolving 10 g of 4-nitro-2- fluoroanisol in 150 ml of 1,4-dioxane, and the mixture was subjected to catalytic reduction under a hydrogen gas pressure of 4 kg/cm2 at room temperature for 30 minutes. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off under reduced pressure to obtain 8.6 g of 4-amino-2-fluoroanisol. 55 [II] 8.5 g of 4-amino-2-fluoroanisol obtained in Step [I] and 100 ml of hydrobromic acid (47%) were mixed, and the mixture was stirred under heating at 90°C for 8 hours. 0 263 438 After the completion of the reaction, excess hydrobromic acid was distilled off under reduced pressure, and the residue was neutralized by an addition of an aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layer was washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then, ethyl acetate was distilled off under reduced pressure to obtain 7.3 g of 4-amino-2-fluorophenol. [III] 2.8 g of sodium hydride (60% nujol mixture) was gradually added under cooling with ice to a solution prepared by dissolving 7.3 g of 4-amino-2-fluorophenol obtained in Step [II] in 100 ml of hexamethyl phosphoric triamide. After the addition, the liquid temperature was returned to room tempera- ture, and stirring was continued for 20 minutes. Then, to this solution, 13.6 g of 3,4-dichlorobenzotrifluoride was added, and the solution was heated to 70°C and reacted for 40 minutes. After the completion of the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and a saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. Then, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: n-hexane/ethyl acetate = 3/1) to obtain 10.4 g of 4-(2-chloro-4-trifluoromethylphenoxy)-3-fluoroaniline having a melting point of from 50 to 51 °C. [IV] By using 4-(2-chloro-4-trifluoromthylphenoxy)-3-fluoroaniline obtained in Step (III), 4(-2-chloro-4-trifluormethylphenoxy)-3-fluoro(N-methyl)aniline having a refractive index n^7'6 =1.5424 was obtained in the same manner as in steps [I], [II] and [III] of Intermediate Preparation Example I. Typical Examples of the compounds of the formula III prepared in the same manner as in the foregoing Intermediate Preparation Examples are shown in Table 1 . 8 (III) raoie i xnter- (WJ£ mediate (Y) A, Ar Physiol No. Posi- w £ properties tion 1 3-F 4 0 1 =CH- 5-trifluoro- mp. 98-99°C methyl- 2-pyridyl 2 3-F 4 0 1 =CH- 2-chloro-4- mp . 50-51°C trifluoro- methylphenyl 3 3- 4 0 1 =C- 5-trifluoro- mp.99-100°C C02CH3 | methyl- CH^ 2-pyridyl 4 • 3-F 4 0 1 =CH- 2,4-dibromo- nj8*2. D 1-563-c-- 3 phenyl 5 3-F 4 0 1 =CH- 4-trifluoro- n^8 * 2, D 1-5319_,.Q methylphenyl 6 3,6- 4 - 0 =CH- 5-bromo-2- mp. 74-77°C F 2 thienyl 7 2-CH3 4 0 1 =CH- 2-fluoro-4- mp.H2-113°C nitrophenyl 8 4 3-CH3 0 1 =C- 2-chloro-4- mp. 83-84°C | trifluoro- CH3 methylphenyl 1 9 3-CH3 4 0 | 1 =C- 3-chloro-5- mp. 105°C I trifluoro- 1 [ CH3 methyl-2- i j pyridyl i AD ORIGINAL CBJ 0 263 438 Table 1 (continued) @ ! « I •10 3-C1 ; 4 10 1 =C- 3-chloro-5- mp . 146-147~'C | trifluoro- Cl methyl-2- pyridyl 11 2,3- 4 0 1 =CH- 3-chloro-5- Oil F~ trifluoro- methyl-2- pyridyl 12 2,3- 4 0 1 =CH- 2-chloro-4- mp. 37-38°C ^2 trifluoro- methylphenyl 13 2-F 4 0 1 =CH- 3-chloro-5- Oil trif luoro- methyl-2- pyridyl 14 2-F 4 0 1 =CH- 2-chloro-4- Oil trif luoro- methylphenyl 15 3-C1 4 0 1 =CH- 2-chloro-4- Oil trif luoro- methylphenyl 16 2-F- 4 0 1 =CH- 2-chloro-4- Oil 3-C1 trifluoro- methylphenyl 17 3-C1 4 0 1 =CH- 3-chloro-5- Solid trif luoro- methyl-2- pyridyl 18 -.4 - 0 =CH-j phenyl Oil i II o 19 - 4 - 0 =CH- 4-bromophenyl S mp. 127-129 C 10 U 263 438 i'aoie i (continued) 20 " 4 ; 0 1 =CH- j 2-chIcrc-4- 62.5- mp" . j trif lucre- 63.5°C | j methvlchenyl ! 1 " ' 21 - 4 0 1 =CH- 3-chloro-5- Oil trif luoro- methyl-2- pyridyl 22 2~CH3 4 0 1 =CH- 3-chloro-5- Oil trif luoro- methyl-2- pyridyl 23 3,6- 4 0 1 =CH- 3-chloro-5- mp. 75-78°C (CH3)2 trifluoro- methyl-2- pyridyl 24 3-C1 4 0 1 =CH- 2,4-dichloro- Oil phenyl 25 3-C1 4 0 1 =CH- 4-nitro- mp. 70-72°C phenyl 26 2-F- 4 0 1 =CH- 3-chloro-5- mp. 71-73°C 3-C1 trifluoro- methyl-2- pyridyl 27 - 4 0 1 =CH- 3,5-dichloro- mp. 85-86°C 2-pyridyl 28 - 4 0 1 =CH- 5-chloro-3- mp. 86-87°C trif luoro- methyl-2- pyridyl 1 29 - 4 | 0 1 =CH- 2,3,4,5,6- Solid ; pentafluoro- j phenyl BADORJQI^,,. 0 263 438 Table 1 (continued) 30 - j 4 | Oj 1 =CK-| 2-chIoro-4- j mp . 124-125°C \ j I j : nitroohenvl j j .ill ! - ! 31 3- 4 0 1 =CH-| 3-chloro-5- mp. 86-89°C CF3 trifluoro- methyl-2- pyridyl 32 - 4 S 1 =CH- 3-chloro-5- mp! 75-76°C trifluoro- methyl-2- pyridyl 33 3-C1 4 SI =C- 3-chloro-5- mp.l37-138°C 1 trifluoro- Cl methyl-2- pyridyl 34 3-F 4 0-1 =CH- 3-chloro-5- Solid trif luoro- methyl-2- pyridyl 35 3-C1 4 0 1 =CH- 3-chloro-5- Oil trif luoro- methyl-2- pyridyl 36 3,6- 4 0 1 =CH- 4-trifluoro- F2 methylphenyl 37 4- 3 0 1 =CH- 2-chloro-4- ! 7R p CH3 trifluoro- | n^B'a1.5344 methylphenyl j 38 3- 4 - 0 =CH- 4-chloro- | mp. 86-88°C CH3 phenyl I t —————— ' 1 @ 1 @ i.. j ... i. @@ 1 39 - 4-0 =CH- 2,4-dichloro-; n28,21.5870 phenyl ! 12 U 263 438 Taoie i ( continued ) 40 - ! i 1 | 4 | - 0 =CH-| 4-chIoro- nro . 1I7-118°C | ; |! phenyl j 1 I'll 1 41 2- 4-0 =CH- 4-brorao- mp. 68-70°C CH^ phenyl 42 3,6- 4 - 0 =CH- 4-trif luoro- Solid F2 methyl- phenyl 43 3- 4 0 1 =C- 3-chloro-5- Oil C02~ | trifluoro- CH3 CH3 methyl-2- pyridyl 44 3- 4 0 1 =CH- 3-chloro-5- Oil c02~ trifluoro- CH3 methyl-2- pyridyl 45 2,3,6-4 0 1 =C- 3-chloro-5- Oil F3 | trifluoro- F methyl-2- pyridyl 46 3- 4 0 1 =CH- 2-chloro-4- Oil C02~ trifluoro- CH3 methyl- phenyl 47 6-F 4 - 0 =CH- 4-chloro- Oil phenyl 48 3- 4-0 =CH- 4-chloro- Oil CF3 phenyl 49 3,6- 4 - 0 =CH- 3-trif luoro- Oil F2 methylthio- phenyl 3 0 263 438 Table I (continued) 50 - 4 - | 0 =N- 4-chloro- Oil phenyl j 51 3-F 4 - 0 =CH- 4-bromo- Oil phenyl 52 - 4-0 =CH- 5-bromo- Oil 2-thienyl 53 3- 4 0 1 =CH- 2-chloro-4- C02H trifluoro- methylphenyl 54 - 4 0 1 =CH- 4-cyano- Oil phenyl 55 - 4 0 1 =CH- 4-trifluoro- Oil methyl- thiophenyl 56 - 4 0 1 =CH- 4-trifluoro- Oil me thy 1- sulf onyl- phenyl 57 3-F 4 0 1 =CH- phenyl Oil 58 3- 4 0 1 =CH- 2-chloro-4- Oil 0CH3 trifluoro- methylphenyl 59 3- 4 0 1 =CH- 3-chloro-5- C02H trifluoro- methyl-2- pyridyl 60 3- 4 0 1 =CH- 3-chloro-5- Oil 0CH3 trifluoro- methyl-2- pyridyl 14 0 263 438 Table 1 (continued) i 1 ol j 3-F 4 0 1 =CH- 4-bromo- j Oil phenyl j j j 62 - 4 0 1 =CH- 2-fluoro-4- trif luoro- methylphenyl 63 - 4 0 1 =CH- 3-fluoro-5- trif luoro- methyl-2- pyridyl 64 3-F 4 0 1 =C- 3-chloro-5- | trifluoro- F methyl-2- pyridyl 65 3- 4-0 =CH- 4-bromo- C0~- phenyl CH3 66 - 4-0 =CH- 4-methyl- phenyl 67 - 4-0 =CH- 4-trifluoro- methoxy- phenyl 68 - 4-0 =CH- 2,4,6-tri- chlorophenyl 69 - 4-0 =CH- 2,3,4,5,6- pentaf luoro- phenyl 5 0 263 438 Table 1 (continued) 70 3,6- 4 - 0 =CH- 4-bromo- (CH3)2 phenyl i 71 - 4-0 =CH- 4-methoxy- phenyl 72 - 4-0 =CH- 4-methyl- thiophenyl 73 - 4-0 =CH- 5-chloro-2- thienyl 74 3-C1 - 0 1 =CH- 4-methoxy- Oil phenyl 75 4- 3 0 1 =CH- 2-chloro-4- Oil CH, trifluoro- methylphenyl 76 - 4 0 1 =CH- 4-trifluoro- methoxy- phenyl 77 3- 4 0 1 =CH- 2-chloro-4- CH^ trifluoro- methoxyphenyl 78 3- 4 0 1 =CH- 2-chloro-4- C02~ trifluoro- Na methylphenyl 79 3- 4 0 1 =CH- 2-chloro-4- CO-- trifluoro- ^2 5 methylphenyl 80 4-C1 3 0 1 =CH- 2-chloro-4- trif luoro- methylphenyl 16 0 263 438 Taole 1 (continued) ; i 81 | 4 0 1 =CH- 2-chloro-5- trifluoro- methyl-3- pyridyl 82- 4 -N- 1 =CH- 3-chloro-5- Oil 1 trifluoro- CH3 methyl-2- pyridyl 83- 4 -N- 1 =CH- 2-chloro-4- 9fl 1 u1.5838 trifluoro- n^ CH^ methylphenyl now, specific Examples for the preparation of the compounds of the present invention will be described. However, it should be understood that the present invention is by no means restricted to these specific Examples. rnErAHA I IUN EXAMPLE 1 Preparation of N-(4'-bromo-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea (Compound No. 29) A solution prepared by dissolving 0.27 g of 2,6-difluorobenzoyl isocyanate in 5 ml of dioxane was added at room temperature to a solution prepared by dissolving 0.20 g of 4-bromo-4-methylaminobiphenyi in 5 ml of dioxane, and the mixture was stirred at room temperature for 15 hours. After the completion of the reaction, the reaction solution was poured into 100 ml of water, and Drecipitated crystals were collected by filtration and dried under reduced pressure. The solid thus obtained was suspended in 50 ml of ethyl ether. The insoluble substance was collected by filtration to obtain 0.26 g Df N-(4'-bromo-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea as crystals having a melting point of from 183 to 185°C. @"HtPAHAI ION EXAMPLES 2 to 9 In the same manner as in Preparation Example 1, the compounds as identified in Table 2 were jrepared by using the reagents and reaction conditions as identified in Table 2. 7 I i ! *c — | C C C j — - 3 3 CN — r m «— i CO Q T ^ CJO^CN ~ CN C — m KO ft CN C T C- C\! * £ * * £E * * sis • • * O O 0 en OOC O O C fcOJJ^ OZ—— O Z — CJ Z — uzO Z — • 5 CU — « C £ S-i CN CN r—i-H CN C O -H H •H -P 5 4-> -H 0 TJ • (0 C ft — E ft CUOEU OE = = = gs o cu 0 o cu &* -~ « -p ' U CD CU O C +> — m -h rax; -P > r-l c c c -P r-t >i to 3 in o min in CUCOO>iO CN cu o c CM-I-H XS CU (0 > cu c r-i x +j i-i c 3 o o in o 3 XJOCO-HO i-iiH iH (0 'H 3 MH ft— E-i Q O Sl'H £H E -H C O E en -P I c — o 5 CU D> U m cu— o cu to 4-> 3 -pro-P CQ tnCQ ra CU (0 T3 i—)(0 in (0 co(0 c o •l-i +J to cu UH CN enm •*}<-=f in (0 ft - ft E 3 CU (0 • U x o cu w z 18 C CN — C — CN « U -C L. U UC O O O O 0 H 00C tu^- U Z - U Z — CJ Z — U z — 0) — m C E S-i r}< . ^ C 0 -H X5 O O -h E-i — @H JJ 4-> *H 1 0 TJ • U CD CU O C 4J — > <4-l -H (0 13 jJ ^ , | £ £ C4->i-i><(dd t in o in cu c o o >. o — > 3 CO N O CL— TJ r-HOCOCOEr-i CU O E —1 CU CO O E d cn 19 0 263 438 Note: Intermediate Nos . in the column for "aniline 5 compound" and Compound Nos. in the column for "Product" are identified in Tables 1 and 3, respectively. w Typical examples of the compound of the present invention will be given in Table 3. 75 20 25 30 35 40 45 50 55 20 M BAD OHKallMAL O If I I /-i r- \J >-> r» rH n-r— 1 JO, KO r-> •H CU fiT! CO rH rH OuTD rH CO CU— U -H >i O O 0 <-i • • • OH d a— rH 1 I in I I c 1 O 1 1 0 CU 0 S-i CN O S-i X3 U 0 1 SfLlf^V O jH 1 h E EE B i ^yl^ ll II II II II 1 « ^ 1 J33 o? i—1 i—! i—1 i —1 ,—| z-o O O O O O O £ — 1 O COO"* @>*^rrt< —j Q O *H j \ iH 1 | CJ m fc. fa m 1 ^ CN 1 I - CN ' CN fa fa fa fa fa X rH fa fa [u fa fa • X c 3 0 rH cn rn -=r in 0j E • O O CJ 2 3A0 ORIGINAL J| r- r- < S h r-i ij t c r- i Z —" CN - CN - 0 CN- CN- i—; - 1 ~rH -cn @ co o 'Co -cn • cn 70 r—* m-— ro — ro 00— ro — ro — CO O cu cn cj en cn o r-f -H 3 O 3 3 I r- ro+JO lo o 0 US'* u u x: mr- x: x; rH •i-. CU O-i'O <43 ftt3 ftX! rH 75 CO ft— S-i -H S-i -H S-J -H >i O CJ 0 rH • Oh OrH x. s-i Q e o ft EO eo ft pu ft— i i i 20 1 0 1 o o in i u in i u s-i IOI Oi IOI 01 01 OS-.CN 3 CN 0 U CN 3 CN 3 CN 5-1 O 1 iH i—ilrH S-t 0 1 <— 1 ri 1 H rH 1 rH S-I O 3 rH >1 """•H C (fl O "tf -tf "* "* ** O -H ft-P 40 _^ 1 II 1 — CN 00 CNro cn ro cn ro fa >i IOE IOE IOX IOCS 1 — ro CJ CJ ro CJ O roCJCJ ro CJ CJ ro 45 CN fa fa fa fa fa X! rH fa fa fa fa fa 3° X T3 C 3 O U3 r> 00 cr. o 55 ft i-r E • O O O Z 22 - I o i ^ -S -5 = .5 .5 2. c o ro cn m _ j 2 — • ro - CN- CN- rH- CN- CN - = — -co -co • co • co -co -"cn 0 r— < * cn — * m —. ro — ro — ro — - ro — wo o 0 0 03 O 03 O [Q ' — ' *h 1 \D 3 03 1"* 3 co jJ ro r- 0 IVX50 ro uO o -h cu 5 rH aT3 vo at3 rH at3 03 O,— S_ -H i-4 -H U -H >i O O • OH • OH • OH CU Cu— E <03 E < 03 E < 03 '° 1 1 H 1 1 >, mi i jx in i "* I c IOI IOC IOI 100 OSuCN 01-40 0 U(N 0 U JZ ^ 2 1 H ^ 0 -S : = u o i h u o a. 5-4 03H>i 0 3 Cu 03H>i 03H < H H >h-TJ H H H H H Sx^O Hi —1 tx — fi'W £'H X. -Q^so O OO o o CO — .5 Eh .5 @" @H C CQO^ "* "tf"* ftf 0 "H Qu4J (0 1 I <£> ro H I | rH — ro O Cu cNroO Cu >-! 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CD 3 fCu "*Cu CNCu TfCu TfCu CN 4-1 E C •H 4J C II 1 rn | | O H 53 rn 53 15353 53 0 < CJ CJ CJ CJ — CJ CJ CJ — II II II II 11 II m erf H O O O OH CD H Jd O 1 1 1 1 O ro • —• Eh us H C COO"* Tf _p —,h —-, O "H Cu+J rn m r-i 53 53 — CJ U CJ >-" 1 ! 1 1 II — m cn Tf CN El i 6-1 Eu Eli Eli Eli H 6u 6u Eu Ecu 6u 6u X TO C 3 0 O H CN m IT) CU H r-i r-i r-i r-i H E • H H H H H H o o CJ z 39 z — co CD rH H CO -P O w •H CD CO Cu— >i O CJ £ u0 CU Cm — rH rH 1 > S* rH O C 1 C 1 >1 U CD tp | CD tp 1 c ox: 1 0 x: 1 0 cd 3 a 0 u a oux: rH>1 - S-i 0 >i = S-i 0 Q-, - j-i »w x onx oar-i f< -HO rirl O HH >i — s-i x: x: "H x: x^hx nj 4J4J 0 H JJ O-HJJ CD 1 CD 1 S-i CD 1 S-i CD 3 TPS CNJJE CNJJE c •H JJ C 1 1 I II 1 v r*~i1 Hr H O H H H H CO H Xi ^3 OlO OO O cn — Eh 3 " ' H C COOtP TP TP TP TP TP O H QjJJ CN 1 1 ro — cn cn cn 1 m 0 0 in — cj in x U cj x Sh I 1 I -CJ 1 ro 1 cn ~— ro ro — ro Z ro CJ CN fa fa fa fafa fa X H fa fa fa fafa fa x • C 3 O co r— 00 cn 0 h Oj h h h h cn cn E • H H H H H H 0 0 CJ z 40 E C CU 1 i j C2 s 2 — >. Eh _j - Hr—I *-K CUCD J -H 0O cnto o e cu u o iH — i H 0O O COrtJ ro jj4-) r*r~- iI o cu O S-iS-l Tf CO HrH S-l •H CDCU H 41 0 263 438 The compounds of the present invention show excellent activities as active ingredients for pesticides, especially insecticides, acaricides and pesticides for slugs and snails. For instance, they are effective against plant parasitic mites such as two-spotted spider mite (Tetranychus urticae), carmine spider mite 5 (Tetranychus cinnabarinus), citrus red mite (Panonychus citri) or bulb mite (Rhizoglyphus echinopus); agricultural insect pests such as diamondback moth (Plutella xylostella ), cabbage armyworm (Mamestra brassicae), common cutworm (Spodoptera litura), Colorado potato beetle (Leptinotarsa decemlineata), codling moth (Laspeyresia pomonella), ballworm ( Heliothis zea), tobacco budworm (Heliothis virescens), ball weevil (Anthonomus grandis), gypsy moth (Lymantria dispar), cucurbit leaf beetle (Aulacophora 10 femoralis), thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Agrotis ipsilon) or cutworm (Agrotis segetum), hygienic pests such as cockroaches, housefly (Musca domestica) or house mosquito ( Culex pipiens pallens); stored grain insect pests such as angoumois grain moth (Sitotroga cerealella), confused flour beetle (Tribolium confusum) or mealworms; household goods insect pests such as casemak- ing clothes moth (Tinea pellionella), black carpet beetle (Anthrenus scrophularidae), or subterranean 75 termites; and other parasites on domestic animals such as flies. Further, they are effective also against mites having the resistance to dicofol and organophosphorus insecticides and against insect pests such as diamondback moth and housefly having the resistance to organophosphorus and/or pyrethroid insecticides. Furthermore, they are effective also against slugs and snails. The compounds of the present invention exhibit particularly excellent larvicidal activities against larvae 20 of insects and mites. However, they are effective also against adults of pests. Namely, they inhibit the reproduction of pests in such a manner that when taken in by the adult pests, the compounds of the present invention are effective to destroy the ability of the adult pests to lay eggs or to prevent laid eggs from hatching. Thus, they show excellent pesticidal effects over a long period of time. The compounds of the present invention serve mainly as stomach poison. Therefore, they do not affect 25 beneficial organisms including beneficial insects that do not feed on crop plants. Further, they will be decomposed satisfactorily in soil, and they do not affect aquatic beneficial organisms. Thus, they have preferable characteristics as pesticides. When used as active ingredients for pesticides, the compounds of the present invention may be formulated together with agricultural adjuvants into various forms such as liquids, dusts, granules, wettable 30 powders, emulsifiable concentrates, flowabies, aerosols, pastes or ultra low-volume formulations just like conventional agricultural chemicals. When such formulations are to be actually used, they may be used as they are or after being diluted with suitable diluents such as water to a predetermined concentration. Such formulations are usually composed of 0.5 - 90 parts by weight of active ingredient and 1 0 - 99.5 parts by weight of agricultural adjuvants. 35 As the agricultural adjuvants, there may be mentioned carriers, emuisifiers, suspending agents, dispersants, extenders, penetrating agents, wetting agents, thickeners or stabilizers. They may be added as the case requires. The carriers may be divided into solid carriers and liquid carriers. As the solid carriers, there may be mentioned powders of animal and plant origin, such as starch, activated carbon, soybean flour, wheat flour, wood powder, fish powder or milk powder; or mineral powders such as talc, kaolin, 40 bentonite, calcium carbonate, zeolite, diatomaceous earth, fine silica, clay, alumina or sulfur powder. As the liquid carriers, there may be mentioned water; alcohols such as methyl alcohol or ethylene glycol; ketones such as acetone or methyl ethyl ketone; ethers such as dioxane or tetrahydrofuran; aliphatic hydrocarbons such as kerosine or the like; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane or solvent naphtha; halogenated hydrocarbons such as chloroform or chlorobenzene; acid 45 amides such as dimethylformamide; esters such as ethyl acetate or glycerine ester of a fatty acid; nitriles such as acetonitrile; or sulfur-containing compounds such as dimethyl sulfoxide. Further, the compounds of the present invention may be used in combination with other agricultural chemicals such as insecticides, miticides, nematocides, fungicides, antiviral agents, attractants, herbicides or plant growth regulators, as the case requires. In some cases, the effectiveness will be improved by such so combination. For instance, as such insecticides, miticides or nematocides, there may be mentioned or- ganophosphorus compounds, carbamate compounds; organic chlorine compounds, organic metal com- pounds, pyrethroide compounds, benzoyl urea compounds, other compounds and juvenile hormone-like compounds. Further, microbial insecticide such as Bacillus thuringiensis agent or nuclear polyhedrosis 55 virus may also be used in combination with the compounds of the present invention. 42 0 263 438 As the fungicides, there may be mentioned organophosphorus compounds, organic chlorine com- pounds, N-halogenothioalkyl compounds, dicarboxy imide compounds, benzimidazole compounds, azole compounds, carbinol compounds, benzanilide compounds, acylalanine compounds, pyridinamine com- pounds, and other compounds. 5 The pesticides of the present invention are effective for the control of various noxious insects, noxious mites, and other noxious pests. They are applied in an active ingredient concentration of from 1 to 20,000 ppm, preferably from 20 to 2,000 ppm. The active ingredient concentration may be optionally changed depending upon the formulation, the manner, purpose, timing or place of the application and the condition of the insect pests. For instance, aquatic noxious insects can be controlled by applying the formulation w having the above-mentioned concentration to the site of the outbreak, and thus, the concentration of the active ingredient in water is less than the above-mentioned range. The amount of the application of the active ingredient per unit surface area is usually from about 0.1 to 5,000 g, preferably from 5 to 1,000 g, per 10a. However, in a certain special case, the amount of the application may be outside the above range. 75 Various formulations containing the compounds of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a feed containing the above 20 active ingredient and to control the outbreak or growth of pests, particularly insect pests, with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient. Now, Test Examples of the present invention will be described. ZD I -SI EXAMPLE 1: Miticidal test against two-spotted spider mite 30 Each formulation containing an active ingredient was dispersed in water to obtain a dispersion of each active ingredient having a concentration of 800 or 200 ppm. Each of French bean seedlings with only on primary leaf left, was transplanted to a cup having a diameter of 7 cm and a height of 4 cm. About 30 larvae and nimphs of two-spotted spider mite (Tetranychus urticae) were infested to the leaf of the French bean. Then, the French bean was dipped in the dispersion having the concentration of 800 ppm or 200 ppm for 35 about 10 seconds, then dried in air and kept in a constant temperature chamber with lightening at 26°C. On the 5th day after the treatment, dead mite's were counted, and the mortality was calculated by the following eqution: Number of dead mites Mortality (%) = @* Number of total mites I he results are shown in Table 4. 45 so r3 0 263 438 Table 4 Compound No. Mortal! tv (%} 800 ppm 200 ppm 10 4 90 - 12 100 100 15 13 - 99 20 18 - 100 TEST EXAMPLE 2; 25 Insecticidal test against diamondback moth Each formulation containing an active ingredient was dispersed in water to obtain a dispersion of each active ingredient having a concentration of 10 ppm. Leaves of cabbage were dipped in the respective 30 dispersions for about 10 seconds, and then dried in air. A sheet of moistened filter paper was placed in a Petri dish having a diameter of 9 cm, and the dried leaves of cabbage were put on the filter paper. Larvae of diamondback moth (Plutella xylostella) in second or third instar were released on the leaves, and the Petri dishes were covered and kept in a constant temperature chamber with lightening at a temperature of 26 °C. On the 7th day after release, dead insects were counted, and the mortality was calculated by the 35 following equation: The mortality was 100% with each of Compounds Nos. 1-10, 12-36, 39, 41, 43-47, 49-57, 62-74, 76-77, 80-86, 108-109, 111-115, 125 and 126, and 90% with each of Compounds Nos. 40 and 75. 40 Number of dead insects (%) = 100 Mortality Number of total insectsx TEST EXAMPLE 3: 45 Insecticidal test against common cutworm The tests were conducted in the same manner as in Test Example 2 except that larvae of common cutworm (Spodoptera litura) in second or third instar were used instead of larvae of the diamondback moth 50 in second or third instar, and the concentration of the active ingredient was changed from 1 0 ppm to 800 ppm or 1 ppm. At the concentration of 800 ppm, the mortality was 100% with each of Compounds Nos. 1-86, 108-109, 111-115, 125 and 126. At the concentration of 1 ppm, the mortality was 100% with each of Compounds Nos. 1-8, 11-27, 29, 55 31-36, 39-41, 43-47, 49-60, 62-63, 65-66, 68-72, 74, 76-78, 80, 82-86, 108-109, 111-113, 115, 125 and 126, and 90% with each of Compunds Nos. 64 and 75. 44 0 263 438 I E5 I EXAMPLE 4: Larvicidal test against larvae of house fl_ Powder feed for test animals (manufactured by Oriental Kobo Kogyo K.K.) and bran were mixed in a weight ratio of 1 : 1 and pulverized, and 10 g of the mixture was packed in an ice cream cup. Each of the formulations containing the active ingredients, was dispersed in water, and 10 ml of the dispersion was added to the mixture in the ice cream cup and thoroughly mixed to adjust the concentration of the active ingredient to 10 ppm. Into the ice cream cup, 20 larvae of house fly (Musca domestica) in second instar were released, and kept in a constant temperature chamber with lightening at 26°C. On the 10th day after the release, the emerged adults were counted, and the mortality was calculated in accordance with the following equation. Mortality (%) = 7S Number of released larvae - Number of emerged adults Number of released larvae x 100 The mortality was 100% with each of Compounds Nos. 1-5, 12-13 and 24, and 90% with Compound No. 6. I Eo I EXAMPLE 5: Larvicidal test against larvae of house mosquito Two hundreds ml of a diluted solution containing 2.5 ppb of each active ingredient was poured into a jar and 20 larvae of house mosquito (Cullex pipiens pallens) were released into the jar. Then, the jar was kept in a constant temperature chamber with lightening at 26°C. Larvae were fed every other day with 1 - 2 mg of powdered feed. On the 9th day after the release, dead insects were counted, and the mortality was calculated in the same manner as in Test Example 2. The results are shown in Table 5. as Table 5 Compound No. Mortality (%) 2.5 ppb 1 100 to 2 90 3 100 OU 4 100 30 TEST EXAMPLE 6: r5 0 263 438 Egg hatch inhibition test by the treatment of adults of house fly Sugar and skim milk were mixed in a weight ratio of 1 : 1 , and 2 g of the mixture was put into a Petri dish having a diameter of 5.5 cm. 0.5 ml of an acetone solution containing the active ingredient was added 5 to the mixture in the Petri dish. After acetone evaporated, the treated mixture was thoroughly mixed, and the concentration of the active ingredient was adjusted to 1 00 ug/g. Twenty non-mating females of house fly (Musca domestica) were allowed to feed on the poisoned diet (the treated mixture) in a cage. After 3 days, the diet was changed to the untreated mixture, then 20 non-mating males were released into the cage for mating. On the 3rd day after release, a cup of the medium for rearing fly larvae was set in the cage for 70 oviposition for 7 hours. The egg laid on the medium were collected and kept on the moistened filter paper in a Petri dish. One day later, unhatched eggs were assessed and the ratio of the egg hatch inhibition (REM) was calculated by the following equation: Number of unhatched eggs rfhtK£iHX {o)(9.\ - x 1UUinn 75 Number of collected eggs The egg hatch inhibition was 100% with each of Compounds Nos. 1, 5, 12-13, 15, 20, 24, 29 and 31, and 88% with Compound No. 3. 20 TEST EXAMPLE 7: Insecticidal tests: 25 In the same manner as in Test Examples 2 and 3, insecticidal tests against diamondback moth and common cutworm were conducted with respect to each compound, and the minimum concentrations at which no less than 90% of insects are killed (hereinafter referred to as C-value), were obtained. 30 II. Acute Immobilisation Test against Daphnia magna Straus An acetone solution of each compound was dispersed in water to obtain test solutions having various concentrations of the active ingredient. 250 ml of each test solution was introduced into a 430 ml glass beaker. Into each beaker, 1 0 first instar larvae born within 24 hours were released and kept at the solution 35 temperature of 23 ±1 °C. The immobilisation up to 48 hours after the release of the larvae was investigated in accordance with the OECD test guideline. The test was repeated 2-3 times in two series for each concentration. The 50% immobilisation concentration (EC50, ppb) was obtained by Probit method. III. Residual test in soil Upland soil (volcanic ash soil) was screened through a sieve with a mesh size of 5 mm, and 20 g by dry weight basis of the soil was put into a 100 ml Erlenmeyer flask. Then, distilled water was introduced to simulate an irrigated condition with a water depth of 1 cm. An aluminum foil was put on the top of the flask, and the flask was left to stand still for 1 week in an incubator (dark place) at 30°C. 0.5 ml of a 200 ppm dispersion in acetone of each compound (100 jxg) was added to the flask by means of a pipet (to a concentration of 5 ppm). The flask was closed and thoroughly shaked, and the soil attached to the closure was washed into the flask with a small amount of water. Then, the top of the flask was covered with an aluminum foil, and the flask was subjected to incubation in a growth cabinet (30°C, humidity: 60%, continuously lighted with a fluorescent lamp with 9,000 lux). 20 Days later, the total 20 g of the soil was subjected to analysis, and the remaining amount of the compound was measured. The results of tests I, II and III are shown in Table 6. 55 46 (0 CD r- E _> — CD (0 C! CC - Oil 1 cn _ — ra ro _ 'r| U Tf -P CO a c jj .. 0 Ou sz co o oo o o tr> •— a ud ir> _4 10 15] V rH V V o Q d ID Dl CJ MH CCS _ OS 9" Cu _JJ a. o — E CD _ _ CJ rH ro (0 J_ CO CO CO CN CN > — o oo o ro o 1 c • . CJOO oo oo o E >i (0 4J -H " •HQ . > •H VO JJ ~ — 1 —— 0 CD ra rH X! rH E to ro u Er> _0 @h S O +J -J< Tf CO CN •H30 OO OVO O -P 0 • .. 0 O OO ,o O CD C O cn o C E M E o CJ ro CC EC CC CC ro CC ro CJ CC CC CJ CJ „ <"* "m o c *• cd L u i •on..?. ? J - ^ 1 * ~^°) @ 1 S g— 5— i— 5 o o "Sir ^rjf ^ 47 0 263 438 Now, the Formulation Examples of the present invention will be described. However, the compounds of the present invention, the amount of the active ingredients or the types of the formulations are not restricted to these specific Examples. FORMULATION EXAMPLE 1 (a) Compound No. 18 20 Parts by weight (b) Kaoline 72 Parts by weight (c) Sodium lignin sulfonate 8 Parts by weight The above components are uniformly mixed to obtain a wettable powder. FORMULATION EXAMPLE 2 (a) Compound No. 24 5 Parts by weight (b) Talc 95 Parts by weight The above components are uniformly mixed to obtain a dust. FORMULATION EXAMPLE 3 (a) Compound No. 3 20 Parts by weight (b) N,N'-dimethylformamide 20 Parts by weight (c) Polyoxyethylenealkylphenyl ether 10 Parts by weight (d) Xylene 50 Parts by weight The above components are uniformly mixed and dissolved to obtain an emulsifiable concentrate. FORMULATION EXAMPLE 4 (a) Kaoline 78 Parts by weight (b) Sodium lignin sulfonate 2 Parts by weight (c) Polyoxyethylealkylaryl sulfate 5 parts by weight (d) Fine silica powder 15 Parts by weight A mixture of the above components and Compound No. 31 were mixed in a weight ratio of 4 : 1 to obtain a wettable powder. FORMULATION EXAMPLE 5 (a) Compound No. 46 40 Parts by weight (b) Oxylated polyalkylphenol phosphatetriethanolamine 2 parts by weight (c) Silicon 0.2 Part by weight (d) Xanthan gum 0.1 Part by weight (e) Ethylene glycol 5 Parts by weight (f) Water 52.7 Parts by weight The above components are uniformly mixed and pulverized to obtain a flowable. FORMULATION EXAMPLE 6 (a) Compound No. 3 50 Parts by weight (b) Oxylated polyalkylphenyl phosphatetriethanoline 2 Parts by weight (c) Silicon 0.2 Part by weight 48 0 263 438 \a) water parts Dy weignt The above components are uniformly mixed and pulverized to obtain a base liquid, and (e) Sodium polycarboxylate 5 Parts by weight (f) Anhydrous sodium sulfate 42.8 Parts by weight were added, and the mixture was uniformly mixed and dried to obtain a dry flowable. rUnMULA I IUIN EXAMPLE / (a) Compound No. 49 5 Parts by weight (b) Glycerin 20 Parts by weight (c) Milk powder 3 Parts by weight (d) Fish powder 72 Parts by weight The above components are uniformly kneaded to obtain a paste. rUniVIIJLA I HJIN EXAMPLE _ (a) Compound No. 57 5 Parts by weight (b) Wheat bran 1 0 Parts by weight (c) Rice bran 80 Parts by weight (d) Molasses 5 Parts by weight The above components are uniformly mixed and kneaded together with a small amount of water, and then the mixture was molded by extrusion molding into a granular form, followed by drying to obtain granules. @UHMULA I IUIN EXAMPLE » (a) Compound No.76 2.5 Parts by weight (b) N-methyl-2-pyrrolidone 2.5 Parts by weight (c) Soybean oil 95.0 Parts by weight The above components are uniformly mixed and dissolved to obtain an ultra low-volume formulation. 'UnlVIULA I IUIN EXAMPLE 1Q 1 . A benzoylurea compound having the formula: merem eacn or xi ana X2 is a nydrogen atom, a halogen atom or a methyl group, provided that Xi and X2 ire not simultaneously hydrogen atoms, Y is independently a hydrogen atom, a halogen atom, an alkyl iroup which may be substituted by halogen, a -CO2R1 group wherein R1 is a hydrogen atom, a cation or an 9 0 263 438 alkyl group, or a -ORi group wherein Ri is as defined above, Ai = N-or = C -wherein Y is as defined above, W is an oxygen atom, a sulfur atom or y -N- i Rl wherein Ri is as defined above, k is an integer of from 1 to 3, I is 0 or 1 , and Ar is wherein Z is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, an aikoxy group which may be substituted by halogen, a nitro group, a cyano group or a -S(0)nR2 group wherein R2 is an alkyl group which may be substituted by halogen and n is 0, 1 or 2, A2 is -S-, -N = C -wherein Z is 1 Z as defined above, or - C = C -wherein Z is as defined above, 1 1 z z and m is an integer of from 1 to 3, or a salt thereof. 2. The compound according to Claim 1, which has the formula: V _/'\\ -CONHCON-/(Twer/— n\T y-TW)7/3~CZ)- % (ID CH3X=Ai A2 wherein Xi, X2, Y, A1, W, k, I, Z, A2 and m are as defined above, or a salt thereof. 3. The compound according to Claim 1 , wherein each of Xi and X2 is a hydrogen atom or a halogen atom, provided at least one of them is a halogen atom. 4. The compound according to Claim 1, wherein Y is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, or a -CO2R1 group wherein Ri is as defined above, and A1 is = C - Y wherein Y is as defined above. 5. The compound according to Claim 1, wherein Z is independently a hydrogen atom, a halogen atom, a trifluoromethyi group, a trifiuoromethoxy group or a -S(O) nCF3 group wherein n is as defined above, and A2 is -N = c -wherein Z is as defined above, or - c = c - z z z wherein Z is as defined above. 6. The compound according to Claim 1, which is N-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2- pyridyloxy)pheny1]-N'-(2,6-difluorobenzoyI)-N-methyiurea. 7. The compound according to Claim 1, which is N-[4-(3-chloro-5-trifiuoromethyl-2-pyridyloxy)-2,3- difluorophenylJ-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2,5-dimethylphenyl]-N-(2,6-difIuorobenzoyl)-N-methylurea, N-[3-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-fluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-N'-(2-chlorobenzoyl)-N-methylurea, N-[4-(2-chloro-4-trifluoromethyiphenoxy)-2,3-difluorophenyl]-N'-(2,6-difluorobenzoyl)-N-methyiurea, N-[3-chloro-4-(2-chloro-4-trifluoromethylphenoxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chloro-4-(2-chloro-4-trifluoromethylphenoxy)-2-fluoropheny!]-N'-(2,6-djfluorobenzoyl)-N-methylurea, N-[4-(2-chloro-4-trifluoromethylphenoxy)phenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[3-chioro-4-(2- chloro-4-trifluoromethylphenoxy)phenyl]-N'-(2-chlorobenzoyl)-N-methylurea, N-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-methylphenyl]-N'-(2,6-difluorobenzoyl)-N-methylurea, 50 0 263 438 N-{4-[3-chloro-5-trifluoromethyl-2-pyrid N-{4-t2-chloro-4-trifluoromethylphenoxy]-3-fluorophenyl}- N'-(2,6-difluorobenzoyl)-N-methylurea, N-{4-(2-chloro-4-trifluoromethylphenoxy)-3,5-difluoro^ N-{4-[2- chloro-4-trifluoromethylphenoxy]-3-methylphenyI}-N'-2,6-difluoroben or N-{4-[3-chloro-5-trifluoromethyl-2-pyridyloxy]-3-methylphenyl}-N'-(2-chl^ 8. The compound according to Claim 1, which is N-(4'-chloro-2-fluoro-4-biphenylyl)-N'-(2,6-difluoroben- zoyl)-N-methylurea, N-(4'-bromo-4-biphenyiyl)-N'-(2,6-difluorobenzoyl)-N-methylurea, N-[2,5-difluoro-4'-chloro-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea, N-(2-trifluoromethyl-4'-chloro-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea or N-(2,5-difiuoro-3'-trifiuoromethylthio-4-biphenylyl)-N'-(2,6-difluorobenzoyl)-N-methylurea. 9. A process for producing a benzoylurea compound having the formula: wherein each of Xi and X2 is a hydrogen atom, a halogen atom or a methyl group, provided that Xi and Xa are not simultaneously hydrogen atoms, Y is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, a -CO2R1 group wherein Ri is a hydrogen atom, a cation or an alkyl group, or a -OR1 group wherein Ri is as defined above, A1 is = N-or = c -wherein Y is as defined above, W is an oxygen atom, a sulfur atom or Y wherein Ri is as defined above, k is an integer of from 1 to 3, I is 0 or 1 , and Ar is N-2T wherein 2 is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, an aikoxy group which may be substituted by halogen, a nitro group, a cyano group or a -S(0)nR2 group wherein R2 is an alkyl group which may be substituted by halogen and n is 0, 1 or 2, A2 is -S-, -N = C -wherein Z is Z as defined above, or - C = C -wherein Z is as defined above, z z and m is an integer of from 1 to 3, or a salt thereof, which comprises reacting an aniline compound having the formula: // \\- CWK - A y \^(W)£-Ar ^A'l (III) wherein A1, Y, W, k, I and Ar are as defined above, with a benzoyl isocyanate compound having the formula: 51 0 263 438 (IV) 5 wherein Xi and X2 are as defined above. 10. The process according to Claim 9, wherein the reaction is conducted in the presence of a solvent at 70 a temperature of from -10°C to + 100°C. 1 1 . A pesticidal composition comprising a pesticidally effective amount of a benzoylurea compound as defined in Claim 1 and an agriculturally acceptable adjuvant. 1 2. The pesticidal composition according to Claim 1 1 , which comprises from 0.5 to 90 parts by weight of the benzoylurea compound and from 1 0 to 99.5 parts by weight of the adjuvant. 75 13. A method for controlling a pest, which comprises applying a pesticidally effective amount of a benzoylurea compound as defined in Claim 1 to a locus to be protected. 14. An aniline compound having the formula: (V) wherein Y is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, a -CO2R1 group wherein Ri is a hydrogen atom, a cation or an alkyl group, or a -OR1 group wherein Ri is as defined above, A1 is = N-or = C -wherein Y is as defined above, 30 W is an oxygen atom, a sulfur atom or y -N- wherein Ri is as defined above, k is an integer of from 1 to 3, t is 0 or 1 , and Ar is 40 Xa7(z) ra wherein Z is independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted by halogen, an aikoxy group which may be substituted by halogen, a nitro group, a cyano group or a -S(0)nR2 45 wherein R2 is an alkyl group which may be substituted by halogen and n is 0, 1 or 2, A2 is -S-, -N = c - wherein Z is as defined above, or - C = C - Z 1 i z z wherein Z is as defined above, and m is an integer of from 1 to 3, or a salt thereof. 55 52