Europaisches Patentamt European Patent Office © Publication number: 0 154 508 Office europeen des brevets A2 © EUROPEAN PATENT APPLICATION © Application number: 85301334.0 © Int. CI.4: C 07 C 149/437 A 01 N 47/34 ^ © Date of filing: 27.02.85 © Priority: 27.02.84 JP 36882/84 © Applicant: Takeda Chemical Industries, Ltd. 27, Doshomachi 2-chome Higashi-ku Osaka-shi Osaka, 541(JP) @ Date of publication of application: 11.09.85 Bulletin 85/37 @ Inventor: Nagase, Hiroshi 19-6, Daiwahigashi 1-chome © Designated Contracting States: Kawanishi Hyogo 666-OKJP) AT BE CH DE FR GB IT LI LU NL SE © Inventor: Sato, Yasuo 16-5, Ichijojihayama-cho Sakyo-ku Kyoto 606IJP) © Representative: Laredo, Jack Joseph et al, Elkington and Fife High Holborn House 52/54 High Holborn London, WC1V6SH(GB) © Thiophenylureas, their production and use. New insecticidal oriand ovicidal benzoylurea derivatives of the formula: wherein X1 is hydrogen or halogen; X2 is halogen; Y1. Y2 and Y3 are independently hydrogen, halogen or alkyl, whereby at least one of Y1, Y2 and Y3 is other than hydrogen; and R is hydrogen or a group represented by the formula -CFaZbH(3-a-d) wherein a and b are independently 0, 1, or 3, with a + b @ 3 and Z is halogen, their production and use. The present invention relates to benzoylurea derivatives of the formula: wherein X1 is hydrogen or halocgen; X2 is halogen; Y1, Y2 and Y3 are independently hydroaen, halogen or alkyl, whereby at least one of Y1, Y2 and Y3 is other than hydrogen; and R is hydrogen or a group represented by the formula -CFaZbH(3-a-b) wherein a and b are independently 0, 1, 2 or 3, with a + b < 3 and Z is halogen,which are novel compounds processina excellent insecticidal activities, to processes for producing the same, and to insecticides containing the same. Some of N-(2,6-dihalogenobenzoyl)-N'-(substituted- phenyl)urea derivatives which are benzoylurea derivatives have heretofore been known to possess insecticidal activity (e.g., British Patent Nos. 1324293 and 1501607, U. S. Patent No. 4277499, European Patent Publication Nos. 71279 and 88343, etc.). However, the insecticidal effect produced by the benzoylurea derivatives which have been concretely synthesized is far from being satisfactory. The present inventors, after extensive research and investigation into a compound exhibiting excellent insec- ticidal effect, succeeded in the synthesis of novel benzoyl- urea derivatives of the formula [I], which have not concretely been synthesized so far, through the reaction of a compound of the formula: with a compound of the formula: wherein X1, X2, Y1, Y2, Y3 and R are as defined herein- before; and one of W1 and W2 is -N=C=O (isocyanato) and the other is amino, and found that these compounds [I] unexpectedly exhibit insecticidal (particularly, molt inhibitory) and ovicidal activities superior to those of known compounds having analogous structure thereto and also are of lessened toxicities toward mammals and fishes, thus finding application as a safe insecticide exerting less adverse effects on the environment. Thus, the present invention relates to: (1) Benzoylurea derivatives [I], (2) A process for producing the benzoylurea derivatives [I], which comprises reacting a compound of the formula: wherein X1 and X2 are as defined hereinbefore, with a compound of the formula: Y3 wherein Y1, Y , and R are as defined hereinbefore, (3) A process for producing the benzoylurea derivatives [I], which comprises reacting a compound of the formula: X1 wherein and X2 are as defined hereinbefore, with a compound of the formula: wherein Y1, Y2, Y3 and R are as defined hereinbefore, and (4) Insecticidal compositions characteristically featured by containing the benzoylurea derivative [I]. In the above formulae, X is hydrogen or halogen. As the halogen represented by X1, there are used, for example, Cl, Br, F and I. Preferable examples of X1 include, for example, hydrogen, Cl and F. X2 is halogen. As the halogen represented by X2, there are used those as mentioned for X1. Preferable examples of X2 include, for example, Cl and F. Y1, Y2 and Y3 are independently hydrogen, halogen or alkyl, whereby at least one of Y1, Y2 and Y3 is other than hydrogen. As the halogen represented by yl, Y2 and Y3, there are used, for example, those as mentioned for the above X1. As the alkyl represented by Y1, Y2 and Y3, there are used, for example, straight-chain or branched chain lower alkyl of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and t-butyl. Preferable examples of Y1, Y2 and Y3 include, for example, hydrogen, Cl, F and methyl. R is hydrogen or a group represented by the formula -CFaZbH(3-a-b) wherein a and b are independently 0, 1, 2 or 3, with a - b @ 3 and Z is halogen. As the halogen represented by Z, there are used, for example, those as mentioned for X1. In the case of b being not less than 2, the halogen represented by Z may be the same or different. As concrete examples of the group represented by the formula -CFaZbH(3-a-b), there are used, for example, CF3, CC13, CBr3, CI3, CF2Cl, CF2Br, CFCl2, CFI2, CFBr2, CFClBr, CC12Br, CClBr2, CHF2, CHFCl, CHFBr, CHClBr, CHC12, CHBr2, CH2F, CH2Cl, CH2Br and CH3. Preferable examples of R include, for example, CF3, CHF2, CHFC1, CHFBr and CEC12. Preferable examples of the benzoylurea derivatives [I] or the object products of the present invention include, for example, compounds represented by the formula: wherein X1a is F or Cl; X2a is F or Cl in the case of Xla being F, or hydrogen or Cl in the case of Xla being Cl; yla is Br, Cl, F or methyl; Y2a is hydrogen, Cl or methyl; and Z' is F or Cl , compounds represented by the formula: wherein Xla, X2a and Z' are as defined hereinbefore; Y1b is hydrogen or F; Y2b is Br, Cl, F or methyl; and Y3a is hydrogen, Cl, F or methyl , and compounds represented by the formula: wherein Xla, X2a and Z' are as defined hereinbefore; y2c Y3b is Br, Cl or F; and is F or Cl. Particularly preferable examples of the derivatives [I] are, for example, compounds represented by the formula wherein X2b is F or Cl; Y1c is F or Cl; and Y2d is hydrogen or Cl , compounds represented by the formula: wherein the symbols are as defined hereinbefore , compounds represented by the formula: wherein X2b and Y3b are as defined hereinbefore , and compounds represented by the formula: wherein the symbols are as defined hereinbefore. The objective product [I] of the present invention. can exist in isomers, when an asymmetric carbon is present in R, and may consist of individual isomers or a mixture thereof. The benzoylurea derivatives [I] of the present invention possess enhanced insecticidal and ovicidal effects, and can produce adequate insecticidal and ovicidal effects in less used amount as compared with known analogous compounds. Besides offering the economical advantage that the applied amount can be reduced, the benzoylurea derivatives [I] of the present invention are exceedingly low in toxicity toward mammals and also low in fish toxicity, with less adverse effects on the environment, and are therefore effective for exterminating and preventing household insect pests, harmful insects parasitic on animals and plants, forest insect pests, etc. They demonstrate powerful insecticidal activities, particularly molt inhibitory activities against larvae, by allowing insect pests to directly contact, or to ingest, the compounds [I], for example, by spraying them directly on animals and plants parasitized with insect pests. In addition, the compounds [I] of the present inyention exhibit ovicidal and sterilizing activities and the like. The compounds [I] of the present invention , with their reduced phytotoxicity and lowered fish toxicity, provide combined characteristics of safety and advantage in utilizing for example as an agent for exterminating and preventing forest insect pests. The compounds [I] of the present invention and insecticidal compositions containing them are effective for exterminating and preventing, for example, insect pests of the order Lepidoptera, such as Spodopteralitura, Plutella xylostella, Pieris rapae crucivora, Chilo suppressalis, Plusia nicrisiana, Halicoverpa assulta, Pseudaletia separata, Mamestra brassicae, Adoxophyes orana, Pleuroptya derogata, Cnaphalocrocis medinalis, Phthorimaea operculella, Hvphautria cunea and Lvmantria dispar; insect pests of the order Coleoptera, such as Henosepilachna vigintiocto- punctata, Aulacophora femoralis, Phyllotreta striolata, Onlema oryzae, Echinocnemus scruameus, Leptinotorsa decemlineata, Lissorhcptrus oryzophilus and Anthonomus arandis; insect pests of the order Diptera, such as Musca domestica, Culex pipiens pallens, Tabanus triaonus, Hvlemva antiaua and Hylemva platura; insect pests of the order Orthoptera, such as Locusta miqratoria and Gryllotalpa africana; insect pests of the order Dictyptera such as Blattella aermanica and Periplaneta fuliginosa; insect pests of the order Isoptera, such as Reticulitermes soeratus; and nematodes, such as Aphelenchoides bessevi. In utilizing the benzoylurea derivatives [I] of the present invention as an insecticide or/and ovicide, such derivatives may be formulated into the application forms which general agricultural chemicals can take; namely, one or not less than two kinds of the compounds [I], depending upon the purpose of application, are dissolved or suspended in a suitable liquid carrier, or mixed or adsorbed with an appropriate solid carrier to process into forms of preparations, such as emulsifiable concentrate (emulsion), oil or solvent