It has already been known that certain kinds of benzoylureas, bearing an aliphatic group, possess insecticidal activities (see Japanese Patent Laid-open No. Sho 60- 224667-A).

There have now been found fluoro-substituted benzoylureas of the formula (I), wherein Rl, R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen, C1-3-alkoxy,C1-3-haloalkoxy,C1-3-alkyl-thioorC1-3-alkyl,C1-3 -haloalkyl, Cl 3-haloalkylthio, with the proviso that all of Ri, R2 and R3 do not simulta- neously represent a hydrogen atom, R4 represents a hydrogen atom, nitro, cyano, halogen, C1-3-alkyl, C1-3-haloalkyl, C1-3-alkylthioorC1-3-haloalkylthio,C1-3-alkxoy,C1-3-haloalko xy, R5 represents optionally substituted C2 20-fluoroalkyl, optionally substituted C4 2carbon atoms in total) fluorocycloalkyl-alkyl, optionally substituted C3- 10-fluorocycloalkyl, optionally substituted Co' (c'on atoms in total) fluo- roalkyl-cycloalkyl or optionally substituted C3 20-fluoroalkenyl, X and Y each independently represent an oxygen atom or a sulfur atom, and

n is lor 2.

The compounds of the above formula (I) can exist as isomers and include not only an isolated isomer but also a mixture of isomers in an arbitrary ratio.

The compounds of the formula (I), according to the invention, can be prepared by a process in which a) compounds of the formula (II)

wherein RI, R2, R3, R4, X, Y and n are defined as above, are reacted with compounds of the formula (III) or their salts wherein Rs is defined as above, in the presence of inert solvents, or b) compounds of the formula (IV)

wherein RI, R2, R3, R4, X and n are defined as above, are reacted with compounds of the formula (V) wherein R5 and Y are defined as above, in the presence of inert solvents, and, if appropriate, in the presence of an in- organic alkali metal hydride or an organic lithium compound, or c) in a case where X and Y represent a sulfur atom: compounds of the formula (VI)

wherein R I, R2, R3, R4, R5 and n are defined as above, are reacted with phosphorus pentasulfide or Lawesson's reagent in the pres- ence of inert solvents.

The fluorosubstituted benzoylureas of the formula (I), according to the invention, exhibit a powerful insecticidal activity.

The fluoro-substituted benzoylureas of the formula (I) according to the invention, un- expectedly, exhibit substantially, extremely superior insecticidal activity in compari- son with the previously known compounds described in the above prior art.

In this specification, when the optionally substituted radical or the radical"which may be substituted is substituted by more than one substituent, these substituents may be same or different from one another.

In this specification, the halogen in"halogen"and halogenated substituents like in "haloalkyl","haloalkoxy and so on, represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially preferably fluorine or chlorine.

In this specification, the alkyl may be straight-chain or branched and includes, for example, methyl, ethyl, propyl, isopropyl, n-, iso-, sec-or tert-butyl, and the like.

In this specification, the haloalkyl may be straight-chain or branched and includes, for example, trifluoromethyl, 2,2,2-trifluoroethyl, and the like.

In this specification, the alkoxy may be straight-chain or branched and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec-or tert-butoxy, and the like.

In this specification, the haloalkoxy may be straight-chain or branched and includes, for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, 2,2,2-tri- fluoroethoxy, and the like.

In this specification, the"alkylthio"may be straight-chain or branched and includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-, iso-, sec-or tert- butylthio, and the like.

In this specification, the haloalkylthio may be straight-chain or branched and in- cludes, for example, trifluoromethylthio, difluoromethylthio, chlorodifluoromethyl- thio, 2,2,2-trifluoroethylthio, and the like.

In this specification, the"fluoroalkyl"represents a straight-chain or branched alkyl radical having, if not indicated otherwise, 2 to 20 carbon atoms, which is substituted by at least one fluorine, and which may further be substituted by one or more, prefer- ably one or two, substituent (s) selected from the group consisting of chlorine, bro- mine, phenyl, C3 8-cycloalkyl and C3 8-fluorocycloalkyl. Examples of"fluoroalkyl" include 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trifluoro- ethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 3,3,3- trifluoropropyl, 2,3,3-trifluoropropyl, 2,3,3,3-tetrafluoropropyl, 2,2,3,3-tetrafluoro- propyl, 2,2,3,3,3-pentafluoropropyl, 3-chloro-2-fluoropropyl, 3, 3-dichloro-2,2-di- fluoropropyl, 2,2,2-trifluoro-1-methylethyl, 2,2,2-trifluoro-1- (tri-fluoromethyl) ethyl, 3-chloro-3-fluoropropyl, 3,3-dichloro-3-fluoropropyl, 3,3-difluoropropyl, 3-chloro- 3,3-difluoropropyl, 2-fluoro-1-methylethyl, 2-fluoro-l- (fluoromethyl) ethyl, 2-chloro- 1- (fluoromethyl) ethyl, 4,4,4-trifluorobutyl, 3,3,4,4-tetra-fluorobutyl, 2,2,3,4,4,4- hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 4,4-dichloro-4-fluorobutyl, 3,4-di- chloro-3,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoro-1-methylpropyl, 2-fluoro-1,1-di- methylethyl, 2-fluoro-1- (fluoromethyl)-1-methylethyl, 2-fluoro-1,1- bis (fluoromethyl) ethyl, 2,3,3,3-tetrafluoro-1-meth- ylpropyl, 1- (trifluoromethyl) propyl, 3,3,3-trifluoro-1-methyl-propyl, 2,2,2-trifluoro- 1-methyl-1- (trifluoromethyl) ethyl, 3,3,3-trifluoro-2- (trifluoromethyl) propyl, 2,2,2-

trifluoro-1,1-bis (trifluoromethyl) propyl, 3,3-dichloro-3-fluoro-2-methylpropyl, 2- chloro-3,3,3-trifluoro-1-methylpropyl, 2,3,3,3-tetrafluoro-1-methylpropyl, 3,3-di- chloro-3-fluoro-2-methylpropyl, 3-chloro-3,3-difluoro-2-methylpropyl, 3,3,3-tri- fluoro-2-methylpropyl, 2,3-difluoro-2- (fluoromethyl) propyl, 3,3,3-trifluoro-1- (tri- fluoromethyl) propyl, 4,4,5,5,5-pentafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,4-heptafluoro-1-methylbutyl, 4,4,4- trifluoro-2-methylbutyl, 2,3-difluoro-3-methylbutyl, 3,4,4,4-tetrafluoro-3- (trifluo- romethyl) butyl, 3-pentafluoro-1,1-dimethylpropyl, 3,3,3-trifluoro-2-methyl- 2- (trifluoromethyl) propyl, 2,2,3,3-tetrafluoro-1,1- dimethylpropyl, 3,3,3-trifluoro-1,1- dimethylpropyl, 2-methyl-1- (trifluoromethyl) propyl, 3,3,4,4,5,5,6,6,6-nonafluoro- hexyl, 3,4,4,5,5,5-hexafluoro-3- (trifluoromethyl) pentyl, 4,5,5,5-tetrafluoro-4- (trifluo- romethyl) pentyl, 1 H, 1 H, 7H-dodecafluoroheptyl, 1 H, 1 H-tridecafluoroheptyl, 1 H, 1 H, 2H, 2H-perfluoro-5-methylhexyl, 3,4,4,5,5,5-hexafluoro-3- (trifluoromethyl) 1- methylpentyl, 7,7,8,8,8-pentafluorooctyl, 1 H, 1 H, 2H, 2H-perfluorooctyl, 1 H, 1 H-per- fluorooctyl, 1- (trifluoromethyl) heptyl, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecanefluorononyl, 1 H, 1 H, 9H-hexadecafluorononyl, 1 H, 1 H-perfluorononyl, 1- (trifluoromethyl) octyl, <BR> <BR> <BR> 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, 1 H, 1 H-perfluorodecyl 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro-1-(perfluorobutyl)(perfluorobutyl) hexyl, 1-butyl-3,4,4,5,5,5-hexa- fluoro3- (trifluoromethyl) pentyl, lH, lH, 11 H-perfluoroundecyl, and the like.

In this specification, the"fluorocycloalkyl"represents a cycloalkyl radical which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two, substituent (s) selected from the group consisting of chlorine, bromine and Cl 3-alkyl. Examples of"fluorocycloalkyl"include 2-fluoro- cyclopropyl, 2,2-difluorocyclopropyl, 2-fluoro-cyclohexyl, 2-chloro-2-fluorocyclo- propyl, 2-chloro-3-fluoro-cyclopropyl, 2,2-difluoro-1-methylcyclopropyl, 2-chloro- 2,3,3-trifluoro-1-methylcyclobutyl, and the like.

In this specification, the"fluoroalkyl-cycloalkyl"represents a cyclo, alkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by

alkyl which is substituted by at least one fluorine, and which may further be substi- tuted by one or more, preferably one or two substituent (s) selected from the group consisting of chlorine, bromine and Cl 3-alkyl. Examples of fluoroalkyl-cycloalkyl include 1- (1, 1-difluoroethyl) cyclohexyl, 1- (1,1,2,2-tetrafluoroethyl) cyclohexyl, 3-tri- fluoromethylcyclohexyl, 2-trifluoromethylcyclohexyl, 1- (trifluoromethyl) cyclo- propyl, 2- (trifluoromethyl) cyclopentyl, 2,4-bis (trifluoromethyl) cyclohexyl, 2- (tri- fluoromethyl)-1-methylcyclohexyl, and the like.

In this specification, the"fluorocycloalkyl-alkyl"represents an alkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by cyclo- alkyl substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two) substituent (s) selected from the group consisting of chlorine, bromine and C l 3-alkyl. Specific examples thereof include, for example, (perfluorocyclohexyl) methyl, 2- (1-fluorocyclohexyl) ethyl, 2- (1,2-difluorocyclo- hexyl) ethyl, and the like.

In this specification, the"fluoroalkenyl"represents astraight-chain or branched alkenyl radical with, if not indicated otherwise, 3 to 20 carbon atoms, which is sub- stituted by at least one fluorine, and which may further be substituted by one or more (preferably one or two) substituent (s) selected from the group consisting of chlorine, bromine and alkoxycarbonyl. Specific examples thereof include, for example, 2,3,3- trifluoro-2-propenyl, 3,4,4-trifluoro-3-butenyl, 4,4,4-trifluoro-2-butenyl, 4,4-di- fluoro-3-methylbutenyl, 4,4,5,5,6,6,7,7,7-nonafluoro-2-heptenyl, 4-trifluoromethyl- 4,5,5,6,6,6-hexafluoro-2-hexenyl, 3- (perfluorohexyl)-2-propenyl, and the like.

In this specification"examples"are given without limiting the scope of the invention.

Preferred compounds of the above formula (I) are compounds, wherein Ri, R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, tri-

fluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-tri- flu- oroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, di- fluoromethylthio or 2,2,2-trifluoroethylthio, with the proviso that all of RI, R2 and R3 do not simultaneously represent a hydrogen atom, R4 represents a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, chloro- difluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, tri- fluoromethylthio, chlorodifluoromethylthio, difluoromethylthio or 2,2,2-tri- fluoroethylthio, R5 represents C2_i l-fluoroalkyl which may be substituted by one or more, (prefer- ably one or two, especially preferably one) substituent (s) selected from the group consisting of chlorine and bromine or represents C4 8-fluorocycloalkyl- alkyl which may be substituted by one or more (preferably one or two, espe- cially preferably one) substituent (s) selected from the group consisting of chlorine and bromine or represents C3 l0-fluorocycloalkyl which may be sub- stituted by one or more (preferably one or two, especially preferably one) substituent (s) selected from the group consisting of chlorine, bromine and methyl, or represents C4_to-fluoroalkyl-cycloalkyl or represents C3 5-fluoro- alkenyl, X and Y each independently represent an oxygen atom or asulfur atom, (preferably an oxygen atom) and n is 1 or 2 (preferably 1).

Particularly preferred compounds of the above formula (I) are compounds, wherein

RI, R2 and R3 each independently represent a hydrogen atom, fluorine, chlorine, bromine, methoxy, trifluoromethyl, nitro or methyl, with the proviso that all of Rl, R2 and R3 do not simultaneously represent a hydrogen atom, R4 represents a hydrogen atom, fluorine or trifluoromethyl, RS represents 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2-fluoro-1- methylethyl, 2-chloro-l- (fluoromethyl) ethyl, 2-fluoro-l- (fluoromethyl) ethyl, 2,2,2-trifluoro-1-methylethyl, 2-fluoro-1,1-dimethylethyl, 2-fluoro-1,1-bis- (fluoromethyl) ethyl, 3, 3, 3-trifluoro-1, 1-di- methylpropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 1 H, 1 H, 7H-dodecafluoro- heptyl, 1 H, 1 H-perfluorooctyl, 2-fluorocyclopropyl, 2-chloro-2-fluorocyclo- propyl, 2,2-difluorocyclopropyl, 2,2-difluoro-1-methylcyclopropyl, 2- (trifluo- romethyl) cyclopentyl, 2,4-bis (trifluoromethyl) cyclohexyl, 2,3,3-trifluoro-2- propenyl or 3,4,4-trifluoro-3butenyl, 2-chloro-2,2-difluoroethyl, 2-chloro-3- fluorocyclopropyl, 2,2,2-trifluoro-1-methyl-1-trifluoromethyl-ethyl, 3,3,3-tri- fluoro-2-trifluoromethyl-propyl, 2,2,3,3,4,4,4-heptafluoro-1-methyl-butyl, 3,3,3-trifluoro-2-methyl-2-trifluoromethyl-propyl, 4,4-difluoro-3-methyl-3- butenyl, 3-trifluoromethyl-cyclohexyl, 2-ethoxycarbonyl-1-trifluoromethyl- ethylenyl, 2-tri-fluoromethylcyclohexyl, 2-fluoro-1-fluoromethyl-1-methyl- ethyl, 1 H, 1 H, 2H, 2H-perfluorooctyl, 1-trifluoromethyloctyl, 3,4-dichloro- 3,4,4-trifluorobutyl, 2-fluorocyclohexyl, 2,3-difluoropropyl, 2,3,3-trifluoro- propyl, 1H, lH-perfluorononyl, 1H, lH, 1 lH-perfluoroundecyl.

X and Y represent an oxygen atom, and n is 1 or 2 (preferably 1).

Specific examples of the compounds of the formula (I) according to the invention are shown in the later-described Table 1.

The course of the reaction in the above-mentioned process (a) is represented by the following reaction equation when, for example, the starting materials are 2,6-di- fluorobenzoyl isocyanate and 2,2,3,3,3-pentafluoropropylamine:

The course of the reaction in the above-mentioned process (b) is represented by the following reaction equation when, for example, the starting materials are 2,6-di- fluoro-benzamide and 2,2,3,3,3-pentafluoro-propyl isocyanate:

The course of the reaction in the above-mentioned process (c) is represented by the following reaction equation when, for example, the starting materials are 1- urea and phosphorus penta- sulfide:

In the above-mentioned process (a), the compounds of the formula (II), used as starting materials are those wherein RI, R2, R3, R4, X, Y and n are defined as above.

The compounds of the formula (II) are known compounds and can be obtained, for example, by the processes similar to those described in Journal of Organic Chemistry Vol. 27,1962,3742-3743; ib. Vol. 30,1965,4306-4307; Journal of the American Chemical Society Vol. 59,1973,2011-2013; ib. Vol. 61,1939,632-633; ib. Vol. 62, 1940,1595-1596 and Organic Syntheses Coll. Vol. 3,1955,735-736.

As examples, the compounds of the formula (II) include 2-fluorobenzoyl-isocyanate, 2-chlorobenzoyl-isocyanate, 2,4-difluorobenzoyl-isocyanate, 2-fluoro-4-chloro- benzoyl-isocyanate, 2,6-difluorobenzoyl-isocyanate, 2-chloro-6-fluorobenzoyl-iso- cyanate, 2,6-dichlorobenzoyl-isocyanate, 2,4,6-trifluorobenzoyl-isocyanate, and the like.

In the above-mentioned process (a), the compounds of the formula (III) used as starting materials are those wherein RS is defined as above.

The compounds of the formula (III) are known compounds and can be obtained, for example, by the processes described in Journal of The American Chemical Society Vol. 72,1950,2786-2788 and Organic Syntheses Coll. Vol. 3,1955,151-156.

As examples, the compounds of the formula (III) include 2,2,2-trifluoroethylamine, 2,2-difluoropropylamine, 3,3,3-trifluoropropylamine, 2,2,3, 3,3-pentafluoropropyl- amine, 2,2,3,3,4,4,4-heptafluorobutylamine, 2,2,3,3,4,4,5,5-octafluoropentylamine, 1-fluoro-2-propylamine, 1-chloro-3-fluoro-2-propylamine, 1,3-difluoro-2-propyl- amine, 1,1,1-trifluoro-2-propylamine, 1-fluoro-2-methyl-2-propylamine, 1,3-di- fluoro-2-methyl-2-propylamine, 1,3-difluoro-2- (fluoromethyl)-2-propylamine, 1, 1, 1- trifluoro-2-methyl-2-propylamine, 1,1,1-tri- fluoro-3-methyl-butylamine, 2-fluoro-1-cyclopropylamine, 2,2-difluoro-1-cyclo- propylamine, 2,2-difluoro-1-methyl-1-cyclopropylamine, 1- (trifluoromethyl)-1- cyclopropylamine, 2-chloro-2,3,3-trifluoro-1-methyl-1-cyclobutylamine, 2- (trifluo- romethyl)-1-cyclopentylamine, 2,4-di (trifluoromethyl)-1-cyclohexylamine, 3,4,4-tri- fluoro-3-buten-1-ylamine.

The compounds of formula (III) can be used in form of salts, for example as hydro- chlorides, hydrobromides or acetates.

In the above process (b), the compounds of the formula (IV) used as the starting ma- terial are those wherein RI, R2, R3, R4, X and n are defined as above.

The compounds of the formula (IV) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of Medicinal Chemistry Vol. 11,1963,814-819 or Organic Syntheses Coll. Vol. 3,1955,490-492.

In the above process (b), the compounds of the formula (V) used as the starting mate- rial are those wherein R3 and Y are defined as above.

The compounds of the formula (V) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of The American Chemical Society Vol. 72,1950,1888-1891 or Organic Syntheses Coll. Vol 3,1955, 599-600.

In the above process (c), the compounds of the formula (VI) used as the starting ma- terial, which may be mentioned, are those wherein RI, R2, R3, R4, R5 and n are de- fined as above.

The compounds of the formula (VI) are the compounds of the invention, which are synthesized by the above processes (a) or (b).

In the process (c), Lawesson's reagent is 4-methoxyphenylthionophosphine sulfide dimer.

The reaction of the above-mentioned process (a) can be carried out in an appropriate diluent. Examples of usable diluents, which may be mentioned, are: aliphatic, alicyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chloroben- zene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and di- ethylene glycol dimethyl ether (DGM); nitriles such as acetonitrile, propionitrile and acrylonitrile; esters such as ethyl acetate and amyl acetate; acid amides such as di- methylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3- dimethyl-2-imidazolidinone and hexamethylphosphoric triamide (HMPA); sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolan; and bases such as pyridine.

When the compound of the formula (III) is a salt, the reaction of the process (a) can be carried out in the presence of an organic base or an organic lithium compound.

Examples of usable organic bases include tertiary alcoholates, tertiary amines, dial- kylaminoanilines and pyridines, such as triethylamine, 1,1,4,4-tetramethylethylene- diamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4-dimeth- ylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-diazabi- cyclo [5,4,0] undec-7-ene (DBU). Examples of organic lithium compounds include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, n- butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.

The reaction of the process (a) can be carried out at a temperature within a substan- tially broad range, but it can generally be carried out at a temperature of about-10 to about 120°C, preferably about 0 to about 100°C. Further, the reaction should pref- erably be conducted under atmospheric pressure but it may optionally be operated under elevated or reduced pressure.

For carrying out the process (a), for instance, when the compounds of the formula (III) is not a salt, 1 mole of the compounds of the formula (II) can be reacted with 1 to 1.3 molar amounts of the compounds of the formula (III) in a diluent such as tolu- ene to obtain the desired compounds.

For carrying out the process (a), for instance, when the compounds of the formula (III) is a salt, 1 mole of the compounds of the formula (II) can be reacted with 1 to 1.3 molar amounts of the compounds of the formula (III) in a diluent such as tetrahy- drofuran in the presence of an organic base to thereby obtain the desired compounds.

The reaction of the above process (b) is known per se orcan be carried out by a proc- ess similar to a known one.

The reaction of the above-mentioned process (b) can be carried out in an appropriate diluent. Examples of usable diluents, which may be mentioned, are: aliphatic, ali- cyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pen- tane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichlo-

romethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene gly- col dimethyl ether (DGM); nitriles such as acetonitrile, propionitrile and acryloni- trile; esters such as ethyl acetate and amyl acetate; acid amides such as dimethyl- formamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl- 2-imidazolidinone and hexamethylphosphoric triamide (HMPA); sulfones and sulf- oxides such as dimethyl sulfoxide (DMSO) and sulfolan; and bases such as pyridine.

The reaction of the process (b) can be carried out in the presence of an inorganic al- kali metal hydride or an organic lithium compound. Examples of usable inorganic alkali metal hydrides include lithium hydride, sodium hydride and potassium hy- dride. Examples of organic lithium compounds include methyllithium, n-butyl- lithium, sec-butyllithium, tert-butyllithium, phenyllithium, n-butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.

The reaction of the process (b) can be carried out at a temperature within a substan- tially broad range, but it can generally be carried out at a temperature of about-80 to about 200°C, preferably about-60 to about 150°C. Further, the reaction should preferably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.

For carrying out the process (b), for instance, 1 mole of the compounds of the for- mula (IV) can be reacted with 1 to 1.3 molar amounts of the compounds of the for- mula (V) in a diluent such as toluene, if desired in the presence of an inorganic alkali metal hydride or an organic lithium compound to obtain the desired compounds.

The reaction of the above process (c) is known per se or can be carried out by a proc- ess similar to a known one.

The reaction of the above-mentioned process (c) can be carried out in an appropriate diluent as, for example, inert solvents. Examples of usable diluents are: aromatic hydrocarbons such as benzene, toluene, xylene and pyridine; and ethers such as di- oxane, dimethoxyethane (DME) and tetrahydrofuran (THF).

The reaction of the process (c) can be carried out at a temperature within a substan- tially broad range, but it can generally be carried out at a temperature of about 30 to about 200°C, preferably about 50 to about 150°C. Further, the reaction should pref- erably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.

For carrying out the process (c), for instance, 1 mole of the compounds of the for- mula (VI) can be reacted with 0.5 to 2 molar amounts of phosphorus pentasulfide or Lawesson's reagent to obtain the aimed compounds.

The compounds of the formula (I) according to the invention exhibit a powerful in- secticidal activity. Further, the active compounds of the formula (I) according to the invention exhibit penetrating and translocating properties, and exhibit precise effects for combating injurious insects without causing phytotoxicity against cultivated plants.

Further, the compounds according to the invention can be used for combating a broad range of various insects, particularly injurious sucking insects, biting insects, soil insects and other plant-parasitic insects as well as insects of stored cereals and hy- giene insects, and can be used for destructing them.

Examples of such insects are as follows: Insects from the order of the Coleoptera, for example, Callosobruchus chinensis, Si- tophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotrarsa decemlineata, Diabrotica spp., Mono-

chamus alternatus, Lissorhoptrus oryzophilus, Aulacophora femoralis and Lyctus bruneus; insects from the order of the Lepidoptera, for example, Lymantria dispar, Mala- cosoma maneustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo sup- pressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Heliothis vires- cens and Phyllocnistis citrella; insects from the order of the Hemiptera, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Lipaphis erysimi, Stephanitis nashi, Nezara spp., Cimex lectularius, Trialeurodes vaporariorum and Psylla spp.; insects from the order of the Orthoptera, for example, Blattela germanica, Periplaneta americana, Gryllotralpa africana and Locusta migratorioides; insects from the order of the Isoptera, for example, Deucotermes speratus and Cop- totermes formosanus; and insects from the order of the Diptera, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis and Culex tritaeniorhynchus.

As acarina, there may be mentioned, for example, Tetranychus kanzawai, Tetrany- chus urticae, Panonychus citri, Aculops pelekassi and Tarsonemus spp.

As nematodes, there may be mentioned, for example, Meloidogyne incognita, Bursa- phelenchus xylophilus, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp.

Further, in the pharmaceutical field of veterinary medicine, there may be mentioned various injurious animal parasites (endoparasites and ectoparasites), such as insects and helminths.

Examples of such animal parasites include the following insects: As insects, there may be mentioned, for example, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp. and Ctenocephalides spp.

As tick, there may be mentioned, for example, Ornithodoros spp., Ixodes spp. and Boophilus spp.

In this specification, the compounds useful for combatting all the insects as men- tioned above, are often referred generically to as"insecticide (s)".

In the case of the use as insecticides, the active compounds of the invention can be converted into customary formulations, such as solutions, wettable powders, emul- sions, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, very fine capsules and coating compositions for seed, furthermore in formulations used with buring equip- ment, such as fumigating cartridges, fumigating cans and fumigating coils and the like, as well as ULV cold-and warm-mixed formulations.

These formulations are produced in a manner known per se, for example, by mixing the active compounds with extenders, for example, liquid solvents, liquefied gas di- luents under pressure, solid diluents or carriers, optionally with the use of surface- active agents, for instance emulsifying agents and/or dispersing agents and/or foam- forming agents.

As liquid solvents or carriers, there are suitable: for example, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes; chlorinated aromatic hydrocarbons and

chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as butanol and glycol as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ke- tone or cyclohexanone; strongly polar solvents, such as dimethylformamide and di- methylsulfoxide; as well as water.

In the case of the use of water as the extender, organic solvents can be used as auxil- iary solvents.

"Liquefied gaseous diluents or carriers"means liquids obtained by liquefying gase- ous substances which are gaseous at room temperature and under atmospheric pres- sure, for example aerosol propellants, such as butane, propane, nitrogen, carbon di- oxide and halogenohydrocarbons.

As solid diluents or carriers there are suitable: for example, ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma- ceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

As solid carriers for granules there are suitable: for example, crushed and frac- tionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic mate- rial such as sawdust, coconut shells, maize cobs and tobacco stalks.

As emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene- fatty acid alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as protein hydrolysation products.

As dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives may also be used in formulations such as powders, granules and emul- sions, and the followings are examples of usable adhesives: for example carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of metals, for example iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general can contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of the above active compounds.

The active compounds of the formula (I) according to the invention can be present in their commercially available formulations and in the use forms prepared with these formulations, as a mixture with other active compounds, such as insecticides, attrac- tants, sterilants, miticides, nematocides, fungicides, growth-regulating substances or herbicides. The above insecticides include, for example, organic phosphate, carba- mates, carboxylates, chlorinated hydrocarbons, chloronicotinyls and insecticidal sub- stances produced by microorganisms.

The active compounds of the formula (I) according to the invention can further be present as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.

The content of the active compounds of the formula (I) according to the invention in their commercially available use form can be varied within wide limits, for instance

within the range of from 0.0000001 to 100% by weight, preferably between 0.00001 and 1 % by weight.

The compounds of the formula (I) according to the invention can be employed against insects, in a customary manner appropriate for the use forms. For combating hygiene insects and insects of stored cereals, the active compounds according to the invention are extremely excellent in stability to alkali on limed substances and in residual activity on wood and soil.

Then, the following Examples illustrate the invention, but they should not be re- garded as limiting the scope of the invention.

Examples Example 1

To a suspension of 2,6-difluorobenzamide (1.57 g) in 1,2-dichloroethane (15 ml), oxalyl chloride (1.65 g) is added dropwise. The mixture is heated under reflux for 30 minutes and the solvent is distilled off. To the residue, toluene (20 ml) is added and a toluene (10 ml) solution of 2,2,3,3,3-pentafluoropropylamine (1.64 g) is added drop- wise under cooling with ice. The mixture is stirred at room temperature for 5 hours, and then it is diluted with hexane (60 ml). The precipitates are filtered off and air- dried to obtain 1- (2,2,3,3,3-pentafluoropropyl)-3- (2,6-difluorobenzoyl) urea (3.02 g) as colorless crystals. melting point: 156-158°C Example 2 To a suspension of 3,4,4-trifluoro-3-butenylamine hydrochloride (0.89 g) in anhy- drous tetrahydrofuran (20 ml), sodium tert-butoxide (0,62 g) is added at room tem- perature. A solution of 2,6-difluorobenzoyl isocyanate prepared from 2,6-difluoro- benzamide (0.79 g) in anhydrous tetrahydrofuran (10 ml) is added dropwise under cooling with ice. After stirring the mixture at room temperature for 12 hours, the sol- vent is distilled off under reduced pressure. Then, water is added and the mixture is

extracted with ethyl acetate. The extract is dried over anhydrous sodium sulfate. Af- ter distilling off the solvent, the residue is subjected to column chromatography on silica gel (ether: hexane = 1: 4) to obtain 1- (3,4,4-trifluoro-3-butenyl)-3- (2,6-di- fluorobenzoyl) urea (0.94 g) as colorless crystals. meltingpoint: 149-151°C The following Table 1 shows the compounds of Examples 1 and 2 together with the compounds produced in a manner similar to those of the above Examples 1 or 2 as well as the compounds which can be synthesized in a manner similar to those of the above Examples 1 or 2.

Table 1 Com-melting R2R3R4nR5XYpointpoundR1 No.(°C) HFHCH2CF2ClOO1F HFHCH2CF3OO180-1832F HFHCH2CH2FOO125-1333F HFHCH2CHFCH3OO4F HFHCH2CH2CH3OO5F HFHCH2CH2CF3OO164-1696F HFHCHCF2CHF2OO143-1457F HFHCH2CF2CF3OO156-1588F HHHCH2CF2CF3OO165-1669F HHHCH2CF2CF3OO147-15010Cl HClHCH2CF2CF3OO127-13111F Com-melting pound R1 R2 R3 R4n R5 X Y point No. (°C) X Cl _ Cl H CH2CF2CF3 O O 126-130 13 F H CF3 H CH2CF2CF3 O O 145-146 14 F F H H CH2CF2CF3 0 0 120-123 F Cl H H CH2CF2CF3 O O 133-136 X Cl F H C'i O O 171-173 17 Cl Cl H H CH2CF2CF3 O O 161-163 18 F CF3 H H CH2CF2CF3 O O 164-166 t F No2 H H CH2CF2CF3 O O 172-175 X Cl NO2 H CH2tF2CF3 O O 156-159 21 F F F H CH2CF2CF3 O O 153-154 t F H F H CH (CH2F) (CH2F O O 23 F H F H CH (CH2Ci) CH2F O O 24 F H F H CH (CH3) CF3 O O 164-167 25 F H F H CH (CF3) CF3 O O 26 F H F H ß O O Com-melting pound R'R2 R3 R4n R5 X Y point No. (°C) 27 F H F H F o o 28 F H F H O O cri 29 F H F H CH2CF=CF2 O O 30 F H F H CH2CH2CH2CF3 O O 181-187 31 F H F H CH2CF2CHFCF3 O O 32 F H F H CH2CF2CF2CF3 O O 156-159 33 F H F H C (CH3) (CH2F) CH30 0 34 F 1-1 F H C (CH2F) (CH2F) CH3 O O 175-177 35 F H F H C (CH2F) (CH2F) CH2F O O 36 F H F H C (CH3) (CF3) CF3 O O 37 F H F H CH2CH (CF3) CF3 O O 38 F H F H F 0 0 F CH 3 39 F H F H CH2CH2CF=CF2 O O 149-151 40 F H F H CH2CF2CF2CF2CHF2 O O 41 F H F H CH (CH3) CF2CF2CF3 O O Com-melting pound R'R2 R3 R4n RS X Y point No. (°C) 42 F H F H CH2C (CH3) (CF3) CF3 O O 43 F H F H CH2CH2C (CH3) =CF2 O O 44 F H F H CH2CH2CF2CF2CF2CF3 O O 45 F H F H CH2CF2CF2CF2CF2CF2CHF2 O O 46 F H F H C F3 o o 204-207 47 F H F H CH2CF2CF2CF2CF2CF2CF2C O O 141-144 F3 48 F H F H CHCF2CF3 o O 120-125 b 49 H F H H CH2CF2CF3 O O 147-150 50 F F H H CF3 0 0 117-121 L C CHCOOC2H5 _ 51 F H F H O O 204-207 CF3 52 P CH3 H 5-F CH2CF2CF3 O O l32-134 53 F 11 H H CH2CF2CF3 O O 155-158 | Com-_ = melting pound R'R2 R3 R4n R5 X Y point No. (°C) 54 F H H 5-F CH2CF2CF3 O O 146-148 7 OCH3 H OCH3 H CH2CF2CF3 O O 153-158 | 56 F H F 3, 5- CH2CF2CF3 0 0 166-174 F2 57 F H H 3-CH2CF2CF3 O O 171-174 CF3 58 CF3 H Cl H CH2CF2CF3 O O 142-148 59 F H F 3-F CH2CF2CF3 O O 148-149 | 60 F F F H CH2 (CF2) 6CF3 O O 137-138 61 F F F H CH2F O O 180-182 .. _ CHEF 62 F F F H CH3 o o 177-179 CCF3 I 63 F F F H CH3 o o 191-194 CAF. CCF3 Com-melting pound R'R2 R3 R4n R5 X Y point No. (°C) 64 F F H 3-F CH2CF2CF3 O O 139-141 65 F H F H iCHCH2F o o 122-124 CH3 66 F F H H CH2CF2CF3 O O 119-120 '67TTtT"HCHCHFCFg0 0 67 F H F H CH2CH2 (CF2) 5CF3 0 0 68 F H F H i H (CHZ) 6CH3 o O 61-62 CF3 69 F F F H tH3 o o 195-197 ICCH2F CH3 70 F _} CH2CH2CCIFCCIF2 O O 145 146 71 Br F H H CH2CF2CF3 O O 120-127 72 F H F H 0 0 F 73 F F F H CH2CHFCH2F O O = 74 F F F H CH2CHFCHF2 O O 75 F H F H CH2CHFCH2F O O 76 F H F H CH2CHFCHF2 O O 77 F IJ F H CH2 (CF2) 7CF3 O O 78 F H F H CH2 (CF2) 9CHF2 O O

Biological Test Examples: Test against Spodoptera litura larvae Preparation of test solutions Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether To produce a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier, and the mixture was diluted with water to the prescribed con- centration.

Testing procedure Leaves of cabbage (Bassica oleracea) were dipped into the water solution of the ac- tive compound at the prescribed concentration. After air-drying of the solution, the treated leaves of cabbage were placed in a Petri dish (diameter: 9 cm), and ten of the third-instar larvae of common cutworms (Spodoptera litura) were released. The dish was then placed at an incubation chamber of 28°C. After 7 days, the number of dead larvae was examined to calculate mortality in %. Tests was successively conducted three times and the mortality in % is shown in their average.

Results Compounds Nos. 2,10,11,16,21,30 and 32 as test examples exhibited 100 % of destruction at the concentration of 100 ppm.