The present invention relates to novel compounds containing a isothiazolylamino- carbonyl group, to processes for their preparation, to their intermediates and to their use as harmful organisms controlling agents.

It is already known that certain substituted isothiazolylaminocarbonyles can be used as harmful organisms controlling agents. JP 306085/1998, US 3,454, 591 and J. Agri. Food Chem. , vol. 37 (5), p. 1438-1441, 1989, disclose certain kinds of isothiazolylaminocarbonyl-containing ureas and describe that they have harmful organism controlling or growth regulating actions. WO 95/31448, EP-A-623282 and EP-A-640597 disclose certain kinds of isothiazolylaminocarbonyl-containing amides and describe that they have harmful organism (plant diseases and pest, weeds etc.) controlling action. JP 245561/1996 and EP-A-640597 disclose certain kinds of isothiazolylaminocarbonyl-containing carbamates and describe that they have harmful organism (plant diseases and pest, weeds etc. ) controlling action.

This invention, accordingly, provides novel compounds of the general formula (I) wherein R represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, phenyl, phenoxy, cyano, nitro or alkoxycarbonyl,

X represents NH, O or S, Ri represents hydrogen or alkyl, a represents an integer of 0-5, m represents 0 or 1, and n represents 0 or 1.

In the present specification"halogen"represents fluoro, chloro, bromo or iodo, preferably represents fluoro, chloro or bromo and particularly preferably represents chloro or bromo.

"Alkyl"and alkyl part of each group"alkoxy","alkylthio","alkylsulfinyl", "alkylsulfonyl"and"alkoxycarbonyl"represents a straight-chain or branched-chain alkyl such as methyl, ethyl, n-or iso-propyl, n-, iso-, sec-or tert-butyl, n-pentyl, n- hexyl, n-heptyl, n-octyl etc. , preferably represents Cl s alkyl, more preferably represents Cl 6 alkyl and particularly preferably represents Cl 4 alkyl. Halogen part and alkyl part of each group"haloalkyl","haloalkoxy","haloalkylsulfinyl"and "haloalkylsulfonyl"represents each of the aforementioned groups, preferably represents Cl 4 alkyl, Cl 4 alkoxy, Cl 4 alkylsulfinyl and Ci_4 alkylsulfonyl substituted with 1-9 same or different halogen atom (s) selected from fluoro, chloro or bromo, and particularly preferably there can be mentioned chloromethyl, bromomethyl, trifluoromethyl, pentafluoroisopropyl, 2-bromoethoxy, difluoromethoxy, trifluoromethoxy, 3-bromopropoxy, 2-chloro-1, 1, 2-trifluoroethoxy, 1,1, 2,2- tetrafluoroethoxy, 1,1, 2,3, 3,3-hexafluoropropoxy, trifluoromethylthio, pentafluoro- ethylthio, chlorodifluoromethylthio, 2,2, 2-trifluoroethylthio, 1,1, 2,2-tetrafluoro- ethylthio, trifluoromethylsulfinyl, pentafluoroethylsulfinyl, chlorodifluorometh- ylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 1,1, 2, 2-tetrafluoroethylsulfinyl, chlorodi- fluoromethylsulfonyl, trifluoromethylsulfonyl, pentafluoroethylsulfonyl, 2,2, 2- trifluoroethylsulfonyl, 1,1, 2, 2-tetrafluoroethylsulfonyl etc.

R preferably represents halogen, C1-6 alkyl, Cl-6 haloalkyl, C1-6 alkoxy, Cl-6 haloalkoxy, Cl-6 alkylthio, C1-6 haloalkylthio, C1-6 alkylsulfinyl, Cl-6

haloalkylsulfinyl, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, phenyl, phenoxy, cyano, nitro or Cl 4 alkoxycarbonyl, Rl preferably represents hydrogen or Cl 4 alkyl.

R particularly preferably represents fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, meth- oxy, ethoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, pentafluoroethylthio, methylsulfinyl, ethyl- sulfinyl, trifluoromethylsulfinyl, pentafluoroethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, pentafluoroethylsulfonyl, phenyl, phenoxy, cyano, nitro, methoxycarbonyl or ethoxycarbonyl, Rl particular preferably represents hydrogen, methyl, ethyl or n-propyl.

Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.

Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.

Among the meanings given as preferred, particularly preferred, still greater emphasis is given to the compounds of the general formula (Ia) in which R, Rl, a and n are each as defined above. Moreover, among the meanings given as being preferred, particularly preferred, still greater emphasis is given to the compounds of the general formula (Ib)

in which R, Rl, a and n are each as defined above.

Furthermore, among the meanings given as being preferred, particularly preferred, still greater emphasis is given to those compounds of the general formula (Ic)

in which R, Rl, a and n are each as defined above.

Furthermore, among the meanings given as being preferred, particularly preferred, still greater emphasis is given to those compounds of the general formula (Id)

in which R, Rl, a and n are each as defined above.

Among the compounds of formula (Ia) particular preference is given to compounds wherein n represents 0.

Among the compounds of formula (Ic) particular preference is given to compounds wherein n represents 0.

The abovementioned general, prefered or particularly preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i. e. including combinations between the given preferred ranges.

The compounds of the formula (1) of the present invention have strong insecticidal activities against harmful organisms, particularly pests, and show good compatibility with crops. According to the present invention the compounds of the formula (I) surprisingly show very outstanding insecticidal action compared with the compounds described in the aforementioned known literatures. Moreover, a part of the compounds of the formula (I) have further controlling activities against plant diseases.

The novel substituted isothiazolylaminocarbonyles of the general formula (I) are obtained when (a) in case m represents 1: compounds of the general formula (n) wherein R, X, Rl and nare each as defined above are reacted with a compound of formula (IV)

wherein M represents-N=C=O if appropriate in the present of a diluent, or (b) in case m represents 0: compounds of the general formula (m) wherein R, Rl, a, n are each as defined above, and Hal represents haolgen, are reacted with a compound of formula (IV) wherein M represents-NH2, if appropriate in the present of a diluent and if appropriate in the presence of an acid binder.

The aforementioned preparation process a) in order to prepare a compound of the formula (I) of the present invention can be illustrated by the following reaction formula in case, for example, 3,4-dichloro-5-isothiazole isocyanate and 2,4- dichloroaniline are used as starting materials.

The aforementioned preparation process b) in order to prepare a compound of the formula (I) of the present invention can be illustrated by the following reaction formula in case, for example, 3,4-dichloro-5-isothiazolamine and 2,4-dichloro- benzoyl chloride are used as starting materials.

3,4-Dichloro-5-isothiazole isocyanate, used as starting material in the aforementioned preparation process a), is a novel compound and can be easily obtained, for example, by reacting 3,4-dichloro-5-isothiazolecarbonyl chloride with sodium azide. 3,4- Dichloro-5-isothiazolecarbonyl chloride, used in the reaction, is a known compound described in WO 99/24413. The reaction is described in a synthesis example.

Generally, 3,4-dichloro-5-isothiazole isocyanate can be obtained by reacting about 1- about 1.5 moles of sodium azide to 1 mole of 3, 4-dichloro-5-isothiazolecarbonyl chloride in using as a diluent, for example, water, hydrocarbons (examples: benzene, toluene, xylene etc. ), ethers (examples: dipropyl ether etc. ), ketones (examples: methyl ethyl ketone, methyl isobutyl ketone etc. ) in the presence of a phase transfer

catalyst (for example, triethylbenzylammonium bromide etc. ) under the condition of reaction temperature of about 20-about 170°C, preferably about 50-about 140°C.

The compounds of the formula (In, other starting materials in the preparation process a) are well-known compounds in the field of organic chemistry and as their specific examples there can be mentioned, for example, 2,4-dichloroaniline, 2-chloro-4- trifluoromethylaniline, 2-trifluoromethyl-4-trifluoromethylsulfonylaniline, 4-cyano- 2,5-difluoroaniline, 4-trifluoromethylaniline, 3,5-di (trifluoromethyl) aniline, 2-chloro- 4-cyanoaniline, 2-cyano-4-nitroaniline, 4-cyano-2-nitroaniline, 2-chloro-4-trifluoro- methylsulfonylaniline, 4-chloro-2-trifluoromethylaniline, 2,3-dichloro-4-trifluoro- methylaniline, 2-chloro-5-nitroaniline, 3-trifluoromethoxyaniline, 4-trifluoro- methoxyaniline, 2-fluoro-5-trifluoromethylaniline, 4-fluoro-3-trifluoromethylaniline, 4-bromo-2-fluoroaniline, 4-trifluoromethylthioaniline, 2-chloro-5-trifluoromethyl- aniline, 2,3, 4-trichloromethylaniline, 4-chloro-2-trifluoromethylaniline, 4-nitro-2-tri- fluoromethylaniline, 2-nitro-4-trifluoromethylaniline, 2,4-difluoro-5-trifluorometh- oxyaniline, 2,5-di (trifluoromethyl) aniline, 3,4-di (trifluoromethyl) aniline, 2,3, 5,6- tetrafluoro-4-trifluoromethylaniline, 4-bromo-2-trifluoromethylaniline, 4-bromo-2- chloroaniline, 2-bromo-4-trifluoromethylaniline, 3-bromo-4-trifluoromethylaniline, 2,4-dibromoaniline, 2-bromo-4-trifluoromethoxyaniline, 2-bromo-3,5-di (trifluoro- methyl) aniline, 4-cyano-2-trifluoroethoxyaniline, 4-bromo-2-trifluoromethoxy- aniline, 2-chloro-4-trifluoromethylthioaniline, 3-chloro-4-trifluoromethylthioaniline, 2-chloro-5-trifluoromethoxyaniline, 4-cyano-2-fluoroaniline, 3-chloro-4-trifluoro- methylaniline, 2,4-dichlorophenol, 2-chloro-4-trifluoromethylphenol, 3,4- dichlorobenzylthiol, 2,4-dichlorophenylmercaptan, benzylthiol, 2-chlorobenzylthiol, 4-chlorobenzylthiol, 4-methoxy-a-methylbenzylthiol, 2,6-dichlorobenzylthiol, 2,4- dichlorobenzylthiol, 2-chloro-4-nitrobenzylthiol etc.

3,4-Dichloro-5-isothiazolamine, used as starting material in the aforementioned preparation process b), is a novel compound and can be easily obtained, for example, by hydrolyzing the aforementioned 3,4-dichloro-5-isothiazole isocyanate. The hydrolysis will be described specifically in a synthesis example mentioned below.

Generally, the objective 3, 4-dichloro-5-isothiazolamine can be obtained by conducting hydrolytic reaction in using as a diluent, for example, water, ethers (for example, dimethoxyethane, tetrahydrofuran, dioxane etc. ), ketones (for example, acetone, etc. ), acid amides (for example, dimethylformamide, dimethylacetamide etc. ), nitriles (for example, acetonitrile, propionitrile etc. ) carboxylic acids (for example, acetic acid etc. ) under the condition of reaction temperature of about 20- about 170°C, preferably about 60-about 150°C.

The compounds of the formula (III), other starting materials in the preparation process b) are well-known compounds in the field of organic chemistry and as their specific examples there can be mentioned, for example, 2-chloro-4- trifluoromethylbenzoyl chloride, 2,4-dichlorobenzoyl chloride, 2,4-difluorobenzoyl chloride etc.

The starting materials of the general formula (IV) wherein M represents-N=C=O or-NH2, have hitherto not been disclosed in the literature. They also form, as novel substances, part of the subject-matter of the present application.

The reaction of the preparation process a) can be conducted in the presence of an adequate diluent. As examples of the diluent usable in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons, for example, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene etc.; ethers, for example, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, dioxane, tetrahydrofuran etc.; ketones, for example, acetone, methyl ethyl ketone, methyl

isobutyl ketone etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile etc.; acid amides, for example, dimethylformamide, dimethylacetamide, N- methylpyrrolidone etc.

The reaction of the preparation process a) can be conducted in a substantially wide range of temperature. However, the temperatures in a range of generally about 0- about 170°C, preferably about 10-about 140°C are adequate.

Although said reaction is conducted desirably under normal pressure, it can be conducted optionally under elevated pressure or under reduced pressure.

In conducting the preparation process a), the aimed compound of the corresponding formula (0 can be obtained, for example, by reacting about 1-about 1.5 moles of a compound of the formula (11) to 1 mole of 3, 4-dichloro-5-isothiazole isocyanate in a diluent, for example, tetrahydrofuran and toluene.

The reaction of the preparation process b) can be conducted in the presence of an adequate diluent. As examples of the diluent usable in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, methylene chloride, chlorofonn, carbon tetrachloride, ethylene chloride, chlorobenzene etc.; ethers, for example, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran etc.; ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone etc.; nitriles, for example, acetonitrile, propionitrile etc.; acid amides, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone etc.

The reaction of the preparation process b) can be conducted in the presence of an acid binder. As the acid binder usable in that case there can be mentioned, for example, hydroxides, carbonates and alcoholates of alkali metals, or tertiary amines, for

example, triethylamine, diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4- diazabicyclo [2,2, 2] octane (DABCO), 1, 8-diazabicyclo [5,4, 0] undec-7-ene (DBU) etc.

The reaction of the preparation process b) can be conducted in a substantially wide range of temperature. However, the temperatures in a range of generally about-20- about 150°C, preferably about 0-about 110°C are adequate. Although said reaction is conducted desirably under normal pressure, it can be conducted optionally under elevated pressure or under reduced pressure.

In conducting the preparation process b), the aimed compound of the corresponding formula (I) can be obtained, for example, by reacting about 1-about 1.5 moles of a compound of the formula (E) to 1 mole of 3,4-dichloro-5-isothiazolamine in a diluent, for example, dichloromethane, in the presence of about 1-about 1.5 moles of triethylamine and a catalytic amount of 4-dimethylaminopyridine.

The compounds of the formula (I) of the present invention show strong insecticidal action. They can, therefore, be used as insecticidal agents. And the compounds of the formula (I) of the present invention can exhibit exact controlling effect against harmful insects without phytotoxicity against cultured plants. Therefore, the compounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests etc. and applied for their extermination.

As examples of such pests there can be mentioned the following pests: As insects, coleoptera, for example, Callosobruchus Clainensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptifaotarsa decemlineata, Diabrotica spp., Manochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus ;

Lepidoptera, for example, Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella ; Hemiptera, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum, Psylla spp. ; Orthoptera, for example, Blatella germanica, Periplaneta americana, Gryllotalpa africana, Locusta migratoria migratoriodes ; Homoptera, for example, Reticulitermessperatus, Coptotermesformosanus ; Diptera, for example, Musca domestic, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, etc.

Moreover, as mites there can be mentioned, for example, Tetranychus telarius, Tetranychus urticae, Panonychus citri, Aculops pelelrassi, Tarsonemus spp. etc.

Furthermore, as nematodes there can be mentioned, for example, Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides basseyi, Heterodera glycines, Pratylenchus spp. etc.

In addition, in the field of veterinary medicine, the compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes. As examples of such animal-parasitic pests there can be mentioned the following pests: As insects there can be mentioned, for example, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis etc.

As mites there can be mentioned, for example, Ornithodoros spp., Ixodes spp., Boophilus spp. etc.

In the present specification substances having insecticidal action against pests, which include all of them, are in some cases called collectively as insecticides The active compounds of the present invention can be made into customary formulation forms, when they are used as insecticides. As such formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, suspensions, powders, foaming agents, pastes, granules, aerosols, active compound- impregnated natural and synthetic substances, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans and coils), ULV [cold mist, warm mist] etc.

These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents, liquefied gas diluents, solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents. In case water is used as extender, for example, organic solvents can be used as auxiliary solvents.

As liquid diluents or carriers there can be used, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc. ), chlorinated aromatic or

chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc. ), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc. )], alcohols (for example, butanol, glycols and their ethers, esters etc. ), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide etc. ), and water.

Liquefied gas diluents or carriers are liquefied substances that are gases at normal temperature and pressure and as their examples there can be mentioned aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons etc.

As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc. ), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.).

As solid carriers for granules there can be mentioned crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc. ) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks etc. ) etc.

As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates etc. ) ], albumin hydrolysis products etc.

Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.

Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers there can be mentioned, for example, carboxymeth-

yl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate etc.).

Colorants can also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further traces nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc. can be added Said formulations can contain the active compounds of the formula (I) in the range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight.

The active compounds of the formula (I) of the present invention can exist also as a mixed agent with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides etc. in the form of their commercially useful formulations or in the application forms prepared from such formulations. Here, as the above-mentioned insecticides, there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microbes etc.

Further, the active compounds of the formula (I) of the present invention can exist also as a mixed agent with a synergist and such formulations and application forms can be mentioned as commercially useful. Said synergist itself must not be active, but is a compound that enhances the action of the active compound.

The content of the active compounds of the formula (I) of the present invention in a commercially useful application form can be varied in a wide range.

The concentration of the active compounds of the formula (I) of the present invention at the time of application is, for example, in the range of 0.0000001-100 % by weight

and preferably in the range of 0.00001-1 % by weight. The compounds of the formula (I) of the present invention can be applied by usual methods suitable to the application forms.

In case of application against hygienic pests and stored grain pests the active compounds of the formula (I) of the present invention has a good stability against alkali on a calcific substance and an excellent residual effectiveness in wood and soil.

The preparation and the use of the active compounds according to the invention can be seen from the examples below.

EXAMPLES Synthesis Example 1

0. 5g of 2, 4-dichloroaniline was added to 20ml of tetrahydrofuran and mixed with a solution of 3,4-dichloro-5-isothiazole isocyanate in toluene (a solution containing 0. 5g of 3,4-dichloro-5-isothiazole isocyanate) at room temperature. After refluxing the mixed solution for 2 hours, the solvent was distilled off under reduced pressure.

Then the residue was purified by column chromatography (eluent: toluene: ethyl acetate = 4: 1) to obtain 0. 8g of N- (3, 4-dichloro-5-isothiazolyl)-N'- (2, 4-dichloro- phenyl) urea as white crystals (yield 76%, mp higher than 250°C).

Synthesis Example 2 0.4g of 2,4-dichlorobenzyl alcohol was added to 20ml of tetrahydrofuran and mixed with a solution of 3,4-dichloro-5-isothiazole isocyanate in toluene (a solution containing 0. 5g of 3,4-dichloro-5-isothiazole isocyanate) at room temperature. After refluxing the mixed solution for 2 hours, the solvent was distilled off under reduced pressure. Then the residue was purified by column chromatography (eluent: toluene: ethyl acetate = 9: 1) to obtain 0.7g of 2', 4'-dichlorobenzyl-3,4-dichloro-5-isothiazole carbamate as white crystals (yield 73%, mp 165-167°C).

Synthesis Example 3

0. 5g of 3,4-dichloro-5-isothiazolamine and 0.4g of triethylamine were dissolved in 30ml of dichloromethane and a solution of 0.7g of 2,4-dichlorobenzoyl chloride in 20ml of dichloromethane was added therein under ice bath cooling. After addition of 0. 05g of 4-dimethylaminopyridine, the mixed solution was stirred at room temperature for 7 hours. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (eluent : toluene) to obtain 0. 8g of 2, 4-dichloro-N- (3, 4-dichloro-5-isothiazole) benzamid as white crystals (yield 79%, mp 152-153°C).

Synthesis Example 4 0.5 g of 2,4-dichlorobenzylthiol was added to 30 ml of toluene and mixed with a solution of 3, 4-dichloro-5-isothiazole isocyanate in toluene (a solution containing 0.5 g of 3,4-dichloro-5-isothiazole isocyanate) at room temperature. After adding a catalystic amount of dimethylaminopyridine (about 0.05 g) to the mixed solution and refluxing it for 2 hours, the solvent was distilled off under reduced pressure. Then the residue was purified by column chromatography (eluent: toluene: ethyl acetate = 9.1) to obtain 0.6 g of 2', 4'-dichlorobenzyl-3,4-dichloro-5-isothiazole thiocarbamate as white crystals (yield 60%, mp 156-157°C).

The compounds of the formula (I) of the present invention, which are obtained by the similar process to the above-mentioned Synthesis Examples 1,2, 3 and 4, are shown collectively in the following Tables 1-4. The compounds of the present invention

obtained in the above-mentioned Synthesis Examples 1-4 are also shown in Tables 1- 4 together.

In the tables, Me represents methyl, Et represents ethyl, n-Pr represents n-propyl, iso- Pr represents isopropyl, tert-Bu represents tert-butyl, and Ph represents phenyl.

Table 1 Compound No. (R) a n mp. ornez Ia-1 H O 249-250 Ia-2 2-F O 238-241 Ia-3 3-F O 248-250 Ia-4 4-F O 238-240 (decomp. ) Ia-5 2-C1 O 228-233 Ia-6 3-Cl O 217-221 Ia-7 4-C1 O >250 Ia-8 2-Br O Ia-9 4-Br Ia-10 2-I O 233-235 Ia-11 4-I O 248-249 (decomp.) Ia-12 2-Me O 221-225 Ia-13 3-Me O 225-226 Ia-14 4-Me O 231-233 Ia-15 4-Et Ia-16 4-n-Pr O Ia-17 4-iso-Pr O Ia-18 4-tert-Bu O >250 Ia-19 2-CF3 O 219-221 Ia-20 3-CF3 O 220-224 Ia-21 4-CF3 O >250 Ia-22 4-MeO O Compound No. (R) a n mp. or nD20 Ia-234-EtO0 Ia-24 4-iso-PrO O Ia-25 4-CF2HO O 213-216 Ia-26 2-CF30 O 151-152 Ia-27 3-CF30 O 213-214 Ia-28 4-CF30 O 233-234 Ia-29 4-MeS O Ia-30 4-EtS O Ia-31 4-CF3S O 253-254 Ia-32 2-CF3CH2S O >250 Ia-33 4-CF3CH2S O Ia-34 4-MeSO O Ia-35 4-MeSO2 O Ia-36 4-EtSO Ia-37 4-EtSO2 O Ia-38 4-Ph O Ia-39 2-PhO O >250 Ia-40 3-PhO O 213-214 Ia-41 4-PhO O 219-220 Ia-42 2-CN O >250 Ia-43 3-CN O >250 Ia-44 4-CN O >250 Ia-45 2-NO2 O 229-231 Ia-46 3-NO2 O >250 Ia-47 4-NO2 O >250 Ia-48 2-COOMe O >250 Ia-49 4-COOMe O >250 Ia-50 2-COOEt Compound No. (R) a n mp. or nD20 Ia-51 2, 3-F2 O 207-209 Ia-52 2, 4-F2 O 247-250 (decomp.) Ia-53 2, 5-F2 O 237-240 Ia-54 2,6-F2 O 230-233 Ia-55 3, 4-F2 O 232-234 (decomp.) Ia-56 3, 5-F2 O 227-229 (decomp.) Ia-57 2, 3-Cl2 O Ia-58 2, 4-Cl2 O >250 Ia-59 2, 5-Cl2 O Ia-60 2, 6-Cl2 O 237-240 Ia-61 3, 5-Cl2 O 217-219 Ia-62 2,4-Br2 O >250 Ia-63 2, 5-(CF3)2 O >250 Ia-64 3, 4-(CF3)2 O 203-204 Ia-65 3, 5- (CF3) 2 O 192-194 Ia-66 2, 4-(Me)2 O 206-207 Ia-67 2, 6- (Me) 2 O Ia-68 3, 5-(Me)2 O 227-228 Ia-69 3, 4-(MeO) 2 O 199-204 Ia-70 3, 5-(MeO) 2 O 204-206 Ia-71 2-F, 4-Cl O 247-248 Ia-72 2-F, 4-Br O >250 Ia-73 2-F, 5-CF3 O >250 Ia-74 2-F, 6-CF3 O 224-226 Ia-75 2-Cl, 4-Br O >250 Ia-76 2-Cl, 4-Me O 246-248 2-Cl, 4-CF3 O >250 Ia-78 2-Cl, 4-CF3 O >250 Compound No. (R) a n mp. or nD20 Ia-79 2-Cl, 4-CF3SO2 O 221-227 Ia-80 2-Cl, 4-NO2 O >250 Ia-81 2-Cl, 5-NO2 O >250 Ia-82 2-Cl, 6-NO2 O Ia-83 2-Cl, 4-CN O >250 Ia-84 3-Cl, 4-MeO O 231-233 Ia-85 3-Cl, 4-CN O 240-242 Ia-86 2-Br, 4-F O 239-240 Ia-87 2-Br, 4-CF3 O >250 Ia-88 2-Br, 4-CF30 O 226-228 Ia-89 3-Br, 4-CF3 O >250 Ia-90 2-Me, 4-Cl O 240-245 Ia-91 2-Me, 4-I O 247-248 Ia-92 2-Me, 4-CF30 O 220-222 Ia-93 2-Me, 4-NO2 O 243-246 Ia-94 2-MeO, 5-Cl O >250 Ia-95 2-MeO, 4-NO2 O >250 Ia-96 2-CF3, 4-F 0 209-211 Ia-97 2-CF3, 4-Cl O 234-236 Ia-98 2-CF3,4-Br O >250 Ia-99 2-CF3, 4-CF3SO2 O 203-206 Ia-100 2-CF3, 4-NO2 O >250 Ia-101 2-CF3,4-F O 216-218 (decomp.) Ia-102 3-CF3, 4-Cl O >250 Ia-103 3-CF3, 4-NO2 O >250 Ia-104 2-MeS, 5-CF3 O 142-148 Ia-105 2-NO2, 4-F O >250 Ia-106 2-NO2, 4-Cl O 248-249 Compound No. (R) a n mp. ornez Ia-107 2-NO2, 4-Me O 209-213 Ia-108 2-NO2, 4-MeO O >250 Ia-109 2-NO2, 4-CF3 O 233-234 Ia-110 2-NO2, 4-CN O >250 la-Ill 2-CN, 5-Cl O >250 Ia-112 2-CN, 4-NO2 O >250 Ia-113 2-COOMe, 4-Cl O >250 Ia-114 2,4, 5-F3 O >250 Ia-115 2,3, 4-C13 O >250 Ia-116 2,4, 5-Cl3 O >250 Ia-117 2,4, 6-C13 O 225-227 Ia-118 2, 4-F2, 5-CF30 O 237-238 Ia-119 2,5-F2, 4-CN O >250 Ia-120 2,6-F2, 4-Br O 217-219 Ia-121 2, 3-Cl2, 4-CF3 O >250 Ia-122 2-Cl, 4-tert-Bu O 242-243 Ia-123 2, 6-C12, 4-Br O >250 Ia-124 2, 6-C12, 4-CF3 0 >250 Ia-125 3, 5-(CF3)2, 2-Br O 162-163 Ia-126 2-Cl, 4-CF3,6-Br O >250 Ia-127 2,3, 4,5, 6-F5 O 213-218 Ia-128 2,3, 4,5, 6-Cl5 O >250 Ia-129 2,3, 5,6-F4, 4-Br O 236-237 Ia-130 2,3, 5,6-F4, 4-CF3 O >250 Ia-131 3-CHF20 O 193-194 Ia-132 2, 4-(NO2) 2 O 241-243 Ia-133 2-Me, 4-CF (CF3) 2 O 234-238 (decomp.) Ia-134 2-F, 4-I O >250 Compound No. (R) a n mp. or nD20 Ia-135 2-F, 4-CN O >250 Ia-136 2-F, 5-CN O >250 Ia-137 2-Cl, 4-I O >250 Ia-151 3-CN, 4-F O >250 Ia-152 3-CN, 4-CF3 O >250 Ia-153 3-CF3,4-CN O >250 Ia-154 2, 4-C12, 6-CF3 O >250 Ia-155 2, 6-Cl2, 4-NO2 O 222-223 Ia-156 2, 4-C12, 6-CN O >250 Ia-157 2, 4-C12, 4-CN O >250 Ia-158 2, 6-Br2, 4-CF30 O 204-209 Ia-159 2, 6-I2, 4-NO2 O 232-235 (decomp.) Ia-160 2, 6-(NO2)2, 5-F O >250 Ia-161 3, 5-Cl2, 4-CHF2CF2S O 213-215 Ia-162 2-F, 4-Br, 5-CF30 O >250 Ia-163 2,4-F2, 3, 5-Cl2 O >250 Ia-164 2,3, 5,6-F4, 4-CN O 157-158 Table 2 Compound No. (R) a n Rl mp. or nD20 Ib-1 H 0-193-195 Ib-2 3-F 0- Ib-3 4-Cl 0- Ib-4 2-Me 0 - Ib-5 3-CF3 0 - Ib-6 4-CF3 0->250 Ib-7 2, 4-Cl2 0-217-218 Ib-8 H 1 H Ib-9 2-F 1 H Ib-10 3-F 1 H Ib-11 4-F 1 H Ib-12 2-C1 1 H Ib-13 3-C1 1 H Ib-14 4-C1 1 H Ib-15 2-Br 1 H Ib-16 4-Br 1 H Ib-17 4-I 1 H Ib-18 2-Me 1 H Ib-19 4-Me 1 H Ib-20 4-Et 1 H Ib-21 4-n-Pr 1 H Ib-22 4-iso-Pr 1 H Ib-23 4-tert-Bu 1 H Ib-24 2-CF3 1 H Ib-25 3-CF3 1 H Ib-26 4-CF3 1 H 174-175 Ib-27 4-MeO 1 H Ib-28 4-EtO 1 H Ib-29 4-iso-PrO 1 H Ib-30 4-CF2HO 1 H Ib-31 4-CF30 1 H Ib-32 4-MeS 1 H Ib-33 4-EtS 1 H Ib-34 4-CF3S 1 H Ib-35 4-CF3CF2S 1 H Ib-36 4-MeSO 1 H Ib-37 4-MeS02 1 H Ib-38 4-EtSO 1 H Ib-39 4-EtS02 1 H Ib-40 4-Ph 1 H Ib-41 4-PhO 1 H Ib-42 4-CN 1 H Ib-43 4-NO2 1 H Ib-44 2-COOMe 1 H Ib-45 2-COOEt 1 H Ib-46 2, 3-F2 1 H Ib-47 2, 4-F2 1 H Ib-48 2, 6-F2 1 H Ib-49 2, 3-C12 1 H Ib-50 2, 4-C12 1 H 165-167 Ib-51 2, 5-Cl2 1 H Ib-52 2, 6-Cl2 1 H Ib-53 2,4-Br2 1 H Ib-54 2, 4- (Me) 2 1 H Ib-55 2, 6- (Me) 2 1 H Ib-56 2-F, 4-Cl 1 H Ib-57 2-Cl, 4-Me 1 H Ib-58 2-C1, 4-CF3 1 H 142-144 Ib-59 2-Cl, 4-NO2 1 H Ib-60 2-Cl, 6- NO2 1 H Ib-61 H 1 Me Ib-62 H 1 Et Ib-63 H 1 n-Pr Ib-64 4-Cl 1 Me Ib-65 4-Cl 1 Et Ib-66 4-MeO 1 Me Ib-67 2, 4-Cl2 1 Me Ib-68 2, 4-C12 1 Et Table 3 Compound No. (R) a n mp. or nD20 Ic-1 H O Ic-2 2-F O Ic-3 3-F O Ic-4 4-F O Ic-5 2-Cl O 169-170 Ic-6 3-Cl O Ic-7 4-Cl O Ic-8 2-Br O Ic-9 4-Br O Ic-10 2-I O Ic-11 3-Me O Ic-12 4-Me O Ic-13 4-Et O Ic-14 4-n-Pr O Ic-15 4-iso-Pr O Ic-16 4-tert-Bu O Ic-17 2-CF3 O 195-196 Ic-18 3-CF3 O Ic-19 4-CF3 O Ic-20 3-MeO O Ic-21 4-EtO O Ic-22 4-iso-PrO O Ic-23 4-CF2HO O Ic-24 4-CF30 O Ic-25 4-MeS O Ic-26 4-EtS O Ic-27 4-CF3S O Ic-28 4-CF3 CF2S O Ic-29 4-MeSO O Ic-30 4-MeSO2 0 Ic-31 4-EtSO O Ic-32 4-EtSO2 O Ic-33 4-Ph O Ic-34 4-PhO O Ic-35 4-CN O Ic-36 4-NO2 O Ic-37 2-COOMe O Ic-38 2-COOEt O Ic-39 2, 3-F2 O Ic-40 2,4-F2 O 146-147 Ic-41 2, 6-F2 O Ic-42 2, 3-Cl2 O Ic-43 2, 4-Cl2 O 152-153 Ic-44 2, 5-Cl2 O Ic-45 2, 6-Cl2 O Ic-46 2, 4-Br2 O Ic-47 2, 4-(Me)2 O Ic-48 2, 6-(Me)2 O Ic-49 2-F, 4-Cl O Ic-50 2-Cl, 4-Me O Ic-51 2-Cl, 4-CF3 O 164-465 Ic-52 2-Cl, 4-NO2 O 144-151 Ic-53 2-Cl, 6-NO2 O 236-237 Table 4 Compound No. (R)a R1 n mp. or nD20 Id-1 H - 0 Id-2 3-F-0 Id-3 4-Cl-0 Id-4 2-Me-0 Id-5 3-CF3-0 Id-6 4-CF3-0 Id-7 2, 4-Cl-0 201-202 Id-8 H H 1 168-170 Id-9 H Me 1 Id-10 H Et 1 Id-11 H n-Pr 1 Id-12 2-F H 1 Id-13 3-F H 1 Id-14 4-F H 1 Id-15 2-Cl H 1 193-194 Id-16 3-Cl H 1 Id-17 4-Cl H 1 209-210 Id-18 4-C1 Me 1 Id-19 4-C1 Et 1 Id-20 2-Br H 1 Id-21 4-Br H 1 Id-22 4-1 H 1 Id-23 2-Me H 1 Id-24 4-Me H 1 Id-25 4-Et H 1 Id-26 4-n-Pr H 1 Id-27 4-iso-Pr H 1 Id-28 4-tert-Bu H 1 Id-29 2-CF3 H 1 Id-30 3-CF3 H 1 Id-31 4-CF3 H 1 Id-32 4-MeO H 1 Id-33 4-MeO Me 1 161-163 Id-34 4-EtO H 1 Id-35 4-iso-PrO H 1 Id-36 4-CF2HO H 1 Id-37 4-CF30 H 1 Id-38 4-MeS H 1 Id-39 4-EtS H 1 Id-40 4-CF3S H 1 Id-41 4-CF3CF2S H 1 Id-42 4-MeSO H 1 Id-43 4-MeS02 H 1 Id-44 4-EtSO H 1 Id-45 4-EtS02 H 1 Id-46 4-Ph H 1 Id-47 4-PhO H 1 Id-48 4-CN H 1 Id-49 4-NO2 H 1 Id-50 2-COOMe H 1 Id-53 2, 4-F2 H 1 Id-54 2, 6-F2 H 1 Id-55 2, 3-Cl2 H 1 Id-56 2,4-Cl2 H 1 156-157 Id-57 2, 4-C12 Me 1 Id-58 2, 4-C12 Et 1 Id-59 2, 5-Cl2 H 1 Id-60 2, 6-C12 H 1 193-194 Id-61 3, 4-Cl2 H 1 208-210 (decomp. ) Id-62 3, 5-Cl2 H 1 Id-63 2,4-Br2 H 1 Id-64 2, 4- (Me) 2 H 1 Id-65 2, 6- (Me) 2 H 1 Id-66 2-F, 4-C1 H 1 Id-67 2-Cl, 4-Me H 1 Id-68 2-Cl, 4-MeO H 1 Id-69 2-Cl, 4-CF3 H 1 184-185 Id-70 2-Cl, 4-CF30 H 1 Id-71 2-Cl, 4-NO2 H 1 159-161 Id-72 2-Cl, 4-CN H 1 Id-73 2-Cl, 6-NO2 H 1 Id-51 2-COOEt H 1 Id-52 2, 3-F2 H 1 Synthesis Example 5 (Intermediate Synthesis)

To a mixed solution of 200ml of water and 100ml of toluene 5g of sodium azide and 0. 3g of triethylbenzylammonium chloride were added. To the strongly stirred solution a solution of 14g of 3, 4-dichloro-5-isothiazolecarbonyl chloride in 100ml of toluene was added drop by drop under ice bath cooling. After the solution was stirred for further 30 minutes at room temperature, the organic layer was separated and dried with anhydrous magnesium sulfate. The filtrate was heated for 2 hours at 80°C to obtain 3,4-dichloro-5-isothiazole isocyanate solution in toluene, which was used for further reactions without purification.

Synthesis Example 6 (Intermediate Synthesis) From a solution of 3,4-dichloro-5-isothiazole isocyanate in toluene (a solution containing 8g of 3,4-dichloro-5-isothiazole isocyanate) the solvent was distilled off under reduced pressure. The residue was dissolved in 50ml of THF and added to a mixture of 100ml of acetic acid and 100ml of water under ice bath cooling. After refluxing the mixed solution for 30 minutes, 300ml of water was added to the reaction mixture and extracted by using 500ml of ethyl acetate. The separated organic layer was washed with water and then with an aqueous solution of sodium hydrogen carbonate and dried with anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was treated by column chromatography (eluent : toluene: ethyl acetate = 9: 1) to obtain 6.4g of 3, 4-dichloro- 5-isothiazolamine as white crystals (yield 92%, mp 129-130°C).

Synthesis Example 7 (Intermediate Synthesis)

105g of 3, 4-dichloro-5-isothiazolecarboxylic acid was dissolved in 200ml of 1,2-di- chloroethane, to which 0. 5ml of dimethylformamide was added. 80g of thionyl chloride was further added drop by drop thereto under ice bath cooling and the mixed solution was refluxed for 8 hours on an oil bath. After the reaction mixture was brought to room temperature, the solvent and excess thionyl chloride were distilled off under reduced pressure. The residue was purified by distillation under reduced pressure to obtain 96. 5g of 3,4-dichloro-5-isothiazolecarbonyl chloride (yield 84%).

Biological Test Example: Test against larva of Spodoptera litura Preparation of test agent: Solvent: Dimethylformamide 3 parts by weight Emulsifier : Polyoxyethylene alkyl phenyl ether 1 part by weight In order to make an appropriate formulation of an active compound 1 part by weight of the active compound was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier and the mixture was diluted with water to a prescribed concentration.

Test method: A leaf of sweet potato is soaked in the test agent diluted to a prescribed concentration with water, dried in the air and put in a dish of 9 cm diameter. 10 larvae of Spodoptera litura at the third instar were placed on the leaf and kept in a room at constant temperature of 28°C. After 2 or 7 days the number of dead larvae is counted and the rate of death is calculated.

Results As specific examples the compounds No. Ia-58, Ia-63, Ia-64, Ia-65, Ia-77, Ia-79, Ia- 80, Ia-83, Ia-87, Ia-88, Ia-99, Ia-112, Ia-115, Ia-121, Ia-125, Ib-58, Ic-43, Ic-51, Id- 17, Id-56, Id-61 and Id-69 showed 100% of rate of death at 100ppm concentration of effective component.

Formulation Example 1 (Granular) To a mixture of 10 parts of the compound of the present invention No. Ia-58,30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water was added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.

Formulation Example 2 (Granules) 95 Parts of clay mineral particles having particle diameter distribution in the range of 0.2-2mm are put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention No. Ia-65 are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.

Formulation Example 3 (Emulsifiable concentrate) 30 Parts of the compound of the present invention No. Ia-80, 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzene- sulfonate are mixed and stirred to obtain an emulsifiable concentrate.

Formulation Example 4 (Wettable powder) 15 Parts of the compound of the present invention No. Ia-112, 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1: 5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkyl- naphthalenesulfonate-formalin-condensate are crushed and mixed to make a wettable powder.

Formulation Example 5 (Water dispersible granule) 20 Parts of the compound of the present invention No. Ia-99,30 parts of sodium ligninsulfonate, 15 parts of bentonite and 35 parts of calcined diatomaceous earth are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.