WO2001029014A1

WO2001029014A1 - Isothiazole-5-carboxylic esters as microbicides

Info

Publication number: WO2001029014A1
Application number: PCT/EP2000/009851
Authority: WO
Inventors: Lutz Assmann; Yoshinori Kitagawa; Koichi Ishikawa; Haruko Sawada; Yasuo Araki; Takuma Shigyo
Original assignee: Nihon Bayer Agrochem K.K.
Priority date: 1999-10-20
Filing date: 2000-10-09
Publication date: 2001-04-26
Also published as: AU7786300A; JP2001122864A

Abstract

Novel isothiazolecarboxylic esters of formula (I) wherein R1 represents a hydrogen atom, methyl or ethyl, R2 represents a hydrogen atom or C¿1-4? alkyl, R?3¿ represents a hydrogen atom, chloro, methoxy or nitro, and R4 represents a hydrogen atom or chloro, provided that where R?1, R3 and R4¿ each represent a hydrogen atom and R2 represents methyl, then the group CO¿2R?2 is bound to the 3-position of the phenyl group. A process for the preparation of the new compounds and their use as microbicides.

Description

ISOTHIAZOLE-5-CARBOXYLIC ESTERS AS MICROBICIDES

The present invention relates to novel isothiazolecarboxylic esters, to a process for their preparation and to their use as microbicides.

It has already been known that certain isothiazolecarboxylic acid derivatives can be employed for the control of plant pests (see JP-A 59 024/1993 and DE-A 1 97 50 011). The fungicidal activity of such known compounds, however, is not always satisfactory.

There have now been found novel isothiazolecarboxylic esters of the formula

wherein

R¹ represents a hydrogen atom, methyl or ethyl,

R represents a hydrogen atom or C_1-4 alkyl,

R³ represents a hydrogen atom, chloro, methoxy or nitro, and

R > 4 represents a hydrogen atom or chloro,

provided that where R¹, R³ and R⁴ each represent a hydrogen atom and R² represents methyl, then the group CO₂R is bound to the 3-position of the phenyl group. Further, it has been found that the isothiazolecarboxylic esters of the formula (I) can be prepared by reacting 3,4-dichloro-5-isothiazolecarbonyl chloride of the formula

with compounds of the formula

in which

R¹, R², R³ and R⁴ have the above-mentioned meanings,

in the presence of an inert diluent and, if appropriate, in the presence of an acid binding agent.

Finally, it has been found that the isothiazolecarboxylic esters of the formula (I) are outstandingly active as microbicides in agriculture and horticulture, particularly as fungicides for the direct control of plant diseases or for causing resistance in plants against plant pathogens.

Surprisingly, the isothiazolecarboxylic esters according to the invention have a much better microbicidal activity than the already known compounds, which are structurally most similar and have the same type of action. In the present context, C1.4 alkyl represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso- butyl, sec-butyl and tert-butyl.

Formula (I) provides a general definition of the isothiazolecarboxylic esters according to the invention. Preferred compounds of the formula (I) are those, in which

R¹ represents a hydrogen atom, methyl or ethyl,

R" represents a hydrogen atom, methyl, ethyl or isobutyl,

R³ represents a hydrogen atom, chloro, methoxy or nitro, and

R⁴ represents a hydrogen atom or chloro,

provided that where R¹ , R³ and R each represent a hydrogen atom and R² represents methyl, then the group CO₂R is bound to the 3-posιtion of the phenyl group.

The following compounds may be mentioned as examples of particularly preferred isothiazolecarboxylic esters of the formula (I):

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-3-benzenecarboxylate,

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-propoxy}-3-benzenecarb- oxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy} -3-benzenecarboxylate,

1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy} -4-benzenecarboxylic acid isobutyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-4-benzenecarboxylate,

methyl 2-chloro-l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-4-benzene- carboxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy} -2-methoxy-4-benzene- carboxylate,

ethyl 2,6-dichloro-l-{2-[(3,4-dicUoro-5-isothiazolyl)-carbonyloxy]-ethoxy}-4-benzene- carboxylate,

ethyl l-{2-[(3,4-dicUoro-5-isothiazolyl)-carbonyloxy]-n-propoxy}-4-benzenecarboxylate,

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-propoxy}-2-methoxy-4- benzenecarboxylate,

isobutyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy}-4-benzenecarb- oxylate,

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy}-2-nitro-4-benzene- carboxylate, and

methyl 2,6-dichloro-l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy}-4- benzenecarboxylate.

If 3,4-dichloro-5-isothiazolecarbonyl chloride and 3-chloro-4-(2-hydroxy-ethoxy)- benzoate are used as starting materials, the process according to the invention can be illustrated by the following reaction scheme:

acid binder

The 3,4-dichloro-5-isothiazolecarbonyl chloride of the formula (II) is a known compound (see JP-A 59 024/1993).

Formula (III) provides a general definition of the compounds, which are required as reaction components for carrying out the process according to the invention. In this formula, R¹, R², R³ and R⁴ preferably have those meanings, which have already been mentioned as preferred for these substituents.

The following compounds may be mentioned as examples of reaction components of the formula (III):

methyl 3-chloro-4-(2-hydroxyethoxy)-benzoate, ethyl 4-(2-hydroxypropoxy)-benzoate, methyl 3-(2-hydroxyethoxy)-benzoate, methyl 3-(2-hydroxybutoxy)-benzoate, isobutyl 4-(2-hydroxybutoxy)-benzoate, ethyl 3,5-dichloro-4-(2-hydroxyethoxy)-benzoate.

The compounds of the formula (III) are known or can be prepared by known processes (see J. Amer. Chem. Soc. 71, 1152-1156 (1949)). Thus, they can be prepared by reacting compounds of the formula

in which

R², R³ and R⁴ have the above-mentioned meanings,

with ethylene oxide, propylene oxide or 1 ,2-epoxybutane.

under basic conditions.

The compounds of the formula (IV) are known or can be prepared by known processes.

The compounds of the formula (III) in which R¹ represents a hydrogen atom, can also be prepared by the process, which is known from JP-A 140 040/1999. Thus, they can be prepared by reacting compounds of the formula (IV) with ethylene carbonate.

Further, the compounds of the formula (III) in which R¹ represents a hydrogen atom, can also be prepared by the process described in SHLΝ JIKKEΝ KAGAKU KOZA (New Lectures on Experimental Chemistry), Vol. 14 (I), pp. 461-474 (Maruzen, 1977). Thus, they can be prepared by reducing compounds of the formula

in which R², R³ and R⁴ have the above-mentioned meanings,

with metal hydrides, such as sodium boron hydride.

The compounds of the formula (III), in which Rl is methyl or ethyl, can be prepared according to the process described in SHLN JIKKEN KAGAKU KOZA (New Lectures on Experimental Chemistry), Vol. 14 (I), pp. 512-520 (Maruzen, 1977), by reacting compounds of the above-mentioned formula (V) with Grignard reagents such as methyl magnesium iodide, ethyl magnesium bromide and so on.

The compounds of the formula (V) are known or can be prepared by known processes (see "Protective Groups in Organic Synthesis", pages 116-128, John Wiley & Sons Inc. 1981). Thus, they can be prepared by de-protecting compounds of the formula

in which

R², R³ and R⁴ have the above-mentioned meanings and

R⁵ represents C_j_4 alkyl, preferably methyl or ethyl,

with inorganic acids, such as hydrochloric acid, sulfuric acid and so on.

The compounds according to the formula (VI) are known or can be prepared by known processes. Thus, they can be prepared by the process described in SHIN JIKKEN KAGAKU KOZA (New Lectures on Experimental Chemistry), Vol. 14 (I), pp. 568-571 (Maruzen, 1977) by reacting compounds of the formula (IV) with compounds of the formula

R⁵O. . CH.

CH (VII)

I ₅

OR⁵ in which

R⁵ has the above-mentioned meanings and

X represents halogen, preferably bromo or iodo.

The compounds of the formula (VII) are known organic chemicals.

All inert organic solvents customary for such reactions can be used as diluents for carrying out the process according to the invention. Suitable solvents preferably include aliphatic alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromefhane, chloroform, carbon tetrachloride, 1,2- dichloroethane, chlorobenzene, dichlorobenzene etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK) etc.; nitriles, for example, acetonitrile, propionitrile, acrylo- nitrile etc.; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol etc.; esters, for example, ethyl acetate, amyl acetate etc.; acid amides, for example, dimefhylformamide (DMF), dimethylacetamide (DMA), N-methylpyr- rolidone, l,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) etc.; sulfones, sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane etc.; and bases, for example, pyridine etc. Water can also be used as a diluent for carrying out the process according to the invention. In the process according to the invention, acid binding agents are used as condensing agents. Suitable compounds of this type are all inorganic and organic acid acceptors.

The following can preferably be used: inorganic bases such as hydrides, hydroxides, carbonates, bicarbonates etc. of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide etc.; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide etc.; and organic bases such as alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylamino- pyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo- [5,4,0]undec-7-ene (DBU) etc.; organolithium compounds, for example, methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, dimethyl copper lithium, lithium diisopropylamide, lithium cyclohexyl isopropyl- amide, lithium dicyclohexylamide, n-butyl lithium DBACO, n-butyl lithium DBU, n- butyl lithium TMEDA etc.

When carrying out the process according to the invention, the reaction temperatures can be varied within a substantially wide range. The reaction is generally carried out at a temperature between about -20°C and about +150°C, preferably between about 0°C and about 80°C.

The process according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under elevated or reduced pressure.

When carrying out the process according to the invention, in general 1 mole of a 3,4- dichloro-5-isothiazolecarbonyl chloride of the formula (II) is reacted with 1 to 1.2 moles of a compound of the formula (III) in the presence of 1 to 1.2 moles of an acid binding agent, such as triethylamine, and in the presence of a diluent, such as dichlorome hane.

The isothiazolecarboxylic esters according to the present invention exhibit a strong microbicidal activity. Thus, they can be used for combating undesired microorganisms, such as phytopathogenic fungi and bacteriae, in agriculture and horticulture. The compounds are suitable for the direct control of undesired microorganisms as well as for generating resistance in plants against attack by undesirable plant pathogens.

Resistance-inducing substances in the present context are to be understood as those substances which are capable of stimulating the defence system of plants such that the treated plants, when subsequently inoculated with undesirable microorganisms, display substantial resistance to these microorganisms.

Undesirable microorganisms in the present case are to be understood as phytopathogenic fungi and bacteriae. The substances according to the invention can thus be employed to generate resistance in plants against attack by the harmful organisms mentioned within a certain period of time after the treatment. The period of time within which resistance is brought about in general extends from 1 to 10 days, preferably 1 to 7 days, after treatment of the plants with the active compounds.

Generally, the compounds according to the invention can be used as fungicides for combating phytopathogenic fungi, such as Plasmodioph^'oromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deutero- mycetes, and can also be used as bactericides for combating bacteriae, such as Pseudomonoadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. The compounds according to the present invention are particularly suitable for causing resistance against infection of plants by plant pathogens, such as Pyricularia oryzae, Phythophthora infestans etc.

The good toleration, by plants, of the active compounds, at the concentrations required for combating plants diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

The compounds according to the invention do also show an insecticidal activity.

The compounds according to the present invention have a low toxicity against warmblooded animals and therefore can be used safely.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main, aromatic hydro- carbons such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or 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 or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl-isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimefhyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such as kaolings, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products.

Dispersing agents include, for example, lignin sulphite waste liquors and methyl- cellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and poly- vinyl acetate, can be used in the formulation. 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 or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and agents for improving soil structure.

In many cases, synergistic effects are achieved, i.e. the activity of the mixture exceeds the activity of the individual components.

Examples of co-components in mixtures are the following compounds:

Fungicides: aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chloro- thalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimo h, fentin acetate, fentin hydroxide, ferbam, ferimzone, fiuazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole- cis, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, immoctadine, immoctadine albesilate, immoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), quinoxyfen, sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, uniconazole, validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801, α-( 1 , 1 -dimethylethyl)-β-(2-phenoxyethyl)- 1 H- 1 ,2,4-triazole- 1 -ethanol, α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-lH-l,2,4-triazole-l -ethanol, α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-lH-l,2,4-triazole-l-ethanol, -(5-methyl-l,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-lH- 1,2,4- triazole- 1 -ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l-yl)-3-octanone, (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl {2-methyl-l -[[[ 1 -(4-memylphenyl)-emyl]-amino]-carbonyl]-propyl} -carbamate, l-(2,4-dichlorophenyl)-2-(lH-l,2,4-triazol-l-yl)-ethanone O-(phenylmethyl)-oxime,

1 -(2-methyl- 1 -naphthalenyl)- 1 H-pyrrol-2,5-dione, l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione, 1 -[(diiodomethyl)-sulphonyl]-4-methyl-benzene, l-[[2-(2,4-dichlorophenyl)-l,3-dioxolan-2-yl]-methyl]-lH-imidazole, l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole, l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole,

1 -methyl-5 -nonyl-2-(phenylmethyl)-3 -pyrrolidinole, 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-l,3-thiazole-5- carboxanilide,

2,2-dichloro-N-[l-(4-chlorophenyl)-ethyl]-l-ethyl-3-methyl- cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(l -methyl ethyl)-sulphonyl]-5-(trichloromethyl)-l, 3, 4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4- methoxy-lH-pyrrolo[2,3-d]pyrimidine-5-carbonitrile, 2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP), 3,4-dichloro-l-[4-(difluoromethoxy)-phenyl]-lH-pyrrol-2,5-dione,

3,5-dichloro-N-[cyano[(l-methyl-2-propinyl)-oxy]-methyl]-benzamide,

3-( 1 , 1 -dimethylpropyl- 1 -oxo- 1 H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5 -(4-methylphenyl)- 1 H-imidazole- 1 -sulphonamide, 4-methyl-tetrazolo[l,5-a]quinazolin-5(4H)-one,

8-(l , 1 -dimethylethyl)-N-ethyl-N-propyl- 1 ,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-(l-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy] 2,5-thiophenedicarboxylate, cis- 1 -(4-chlorophenyl)-2-(l H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4-[3-[4-(l,l-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-moφholine- hydrochloride, ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate, methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)- 1 -methyl-cyclohexanecarboxamide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide, N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide, N-(4-cyclohexylphenyl)- 1 ,4,5 ,6-tetrahydro-2-pyrimidineamine, N-(4-hexylphenyl)- 1 ,4,5,6-tetrahydro-2-pyrimidineamine, N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N- [2,2 ,2-tri chloro- 1 - [(chloroacetyl)-amino] -ethyl] -benzamide, N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1 ,2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1 -benzopyran-2 , 1 ' (3 ' H)-isobenzofuran] -3 ' -one,

Bactericides: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides / acaricides / nematicides: abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha- cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloφyrifos, chloφyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S -methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn, eflusilanate, emamectin, empenthrin, endosulfan, Entomopf hora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb, granulosis viruses, halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, isazophos, isofenphos, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, naled, nitenpyram, nithiazine, novaluron, nuclear polyhedrosis viruses, omethoat, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, ribavirin, salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, vamidothion, vaniliprole, Verticillium lecanii, YI 5302, zeta-cypermethrin, zolaprofos,

(lR-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanyl- idene)-methyl] 2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)-methyl 2,2,3, 3-tetramethylcyclopropanecarboxylate, l-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazine-2-

(lH)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(l,l-dimethylethyl)phenyl]-4,5-dihydro-oxazole,

2-(acetyloxy)-3-dodecyl-l,4-naphthalenedione,

2-chloro-N-[[[4-(l-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide, 2-chloro-N-[[[4-(2,2-dichloro-l,l-difluoroethoxy)-phenyl]-amino]-carbonyl]- benzamide,

3-methylphenyl propylcarbamate

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-l-fluoro-2-phenoxy-benzene,

4-chloro-2-(l,l-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]- 3(2H)-pyridazinone,

4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyri- dazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyri- dazinone, Bacillus thuringiensis strain EG-2348,

[2-benzoyl- 1 -( 1 , 1 -dimethylethyl)-hydrazinobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-l-oxaspiro[4.5]dec-3-en-4-yl butanoate,

[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide, dihydro-2-(nitromethylene)-2H-l,3-thiazine-3(4H)-carboxaldehyde, ethyl [2-[[l ,6-dihydro-6-oxo-l -(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,

N-(3 ,4,4-trifluoro- 1 -oxo-3 -butenyl)-glycine, N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-lH-pyra- zole- 1 -carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine, N-methyl-N'-( 1 -methyl-2-propenyl)- 1 ,2-hydrazinedicarbothioamide, N-methyl-N'-2-propenyl- 1 ,2-hydrazinedicarbothioamide,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, tablets, pastes, microcapsules and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporizing, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compounds concentration in the use forms can be varied within a substantial range. They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 and 0.001%.

For the treatment of seed, amounts of active compound of 0.001 to 50 g, especially 0.01 to 10 g, are generally employed per kilogram of seed.

For the treatment of soil, active compound concentrations, at the point of action, of 0.00001 to 0.1% by weight, especially of 0.0001 to 0.02%, are generally employed.

The preparation and use of the active compounds according to the invention can be seen from the following examples. Svnthesis Example 1

(Compound No. 6)

Methyl 3-chloro-4-(2-hydroxyethoxy)-benzoate (1.04 g) and triethylamine (0.55 g) were dissolved in 1,2-dichloroethane (30 ml), to which a solution of 3,4-dichloro-5- isothiazolylcarbonyl chloride (1.05 g) in 1,2-dichloroethane (10 ml) was added drop by drop while stirring under ice-cooling. After that the mixture was brought to room temperature and stirred further for 16 hours. After washing with a saturated aqueous solution of sodium hydrogen carbonate (30 ml x twice) and drying over unhydrous magnesium sulfate, the solvent was distilled off. The concentrate was purified by silica gel column chromatography (eluent: dichloromethane/efhanol = 99/1) to obtain methyl 2-chloro-l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-4-benzene- carboxylate (0.75 g) in the form of colorless crystalls. mp 81-84°C.

The compounds shown in the following Table 1 were also prepared according to the method described in Synthesis Example 1.

Table 1

Compound

No. R' CO₂R^z R^> R Physical Constant

1 H 3-CO₂CH₃ H H mp 77-78°C

2 CH₃ 3-CO₂CH₃ H H n_D ²⁰ 1.5532

3 C₂H₅ 3-CO₂CH₃ H H n_D ²⁰ 1.5540

4 H 4-CO₂H H H mp 130-135°C

5 H 4-C0₂CH₂CH(CH₃)2 H H n_D ²⁰ 1.5449

6 H 4-CO₂CH₃ Cl H mp 81-84°C

7 H 4-CO₂CH₃ OCHβ H mp 128°C

8 H 4-CO₂C₂H₅ Cl Cl mp 108-109°C

9 CH₃ 4-CO₂C₂H₅ H H mp 72-73°C

10 CH₃ 4-CO₂CH₃ OCH₃ H mp 134-135°C

11 C₂H₅ 4-C0₂CH₂CH(CH₃)₂ H H n_D ²⁰ 1.5370

12 C₂H₅ 4-CO₂CH₃ NO₂ H mp l l5-119°C

13 C₂H₅ 4-CO₂CH₃ Cl Cl n_D ²⁰ 1.5710

Synthesis Example 2 (Preparation example of an intermediate)

Methyl 3-chloro-4-(formylmethoxy)benzoate (5.2 g) was dissolved in ethanol (30 ml), to which sodium boron hydride (0.43 g) was gradually added while stirring. The reaction mixture was further stirred at room temperature for 4 hours. ^εr distilling off ethanol under reduced pressure and adding water (50 ml), the solution was extracted with dichloromethane (50 ml x twice) and washed with a saturated aqueous solution of sodium hydrogen carbonate (50 ml x once). The residue, obtained by distilling off the solvent under reduced pressure after drying with unhydrous magnesium sulfate, was purified by silica gel column chromatography (eluent: dichloromethane/ethanol = 97/3) to obtain methyl 3-chloro-4-(2-hydroxy- ethoxy)-benzoate (4.0 g) in the form of colorless crystalls. mp 70-74°C.

Synthesis Example 3 (Preparation example of an intermediate)

Methyl 3-chloro-4-(2,2-diethoxyethoxy)-benzoate (12 g) was dissolved in 1,4- dioxane (50 ml), to which 1-N hydrochloric acid (50 ml) was added. The mixture was stirred at 80°C for 2 hours. After bringing the mixture to room temperature, sodium chloride was dissolved up to the saturation. The mixture was then extracted with dichloromethane (50 ml x twice) and washed with water (100 ml x once). The residue, obtained by distilling off the solvent under reduced pressure after drying with unhydrous magnesium sulfate, was purified by silica gel column chromato- graphy (eluent: dichloro-methane/ethanol = 99/1) to obtain methyl 3-chloro-4- (formylmethoxy)-benzoate (5.3 g) in the form of colorless crystalls. mp 84-89°C.

Synthesis Example 4 (Preparation example of an intermediate)

OC₂H₅

Methyl 3-chloro-4-hydroxybenzoate (9.3 g) was added to a suspension of 60% sodium hydride (2.1 g) in N,N-dimethylformamide (50 ml) while stirring under ice- cooling. After stirring for 1 more hour, bromoacetaldehyde diethylacetal (10.8 g) was added, and the resulting mixture was stirred at 120°C for 8 hours. After distilling off N,N-dimethylformamide under reduced pressure, the residue was dissolved in dichloromethane (150 ml) and washed with IN aqueous solution of sodium hydroxide (50 ml x twice). The residue, obtained by distilling off the solvent under reduced pressure after drying with unhydrous magnesium sulfate, was purified by silica gel column chromatography (eluent: dichloromethane/ethanol = 99/1) to obtain methyl 3-chloro-4-(2,2-diethoxyethoxy)-benzoate (12 g) in the form of pale yellow crystalls. mp 44-45°C.

Synthesis Example 5 (Preparation example of an intermediate)

CH,

A mixture of ethyl 4-hydroxybenzoate (5.15 g), powdered potassium hydoxide (0.35 g), water (0.6 ml) and propylene oxide (3.60 g) was heated and stirred at 60-65. for 4 hours. Propylene oxide (1.80 g) was then added and the mixture was heated and stirred at the same temperature for 4 hours. After bringing the mixture to room temperature, water (100 ml) was added and resulting mixture was extracted with dichloromethane (100 ml x twice). The extract was dried with unhydrous magnesium sulfate. The residue, obtained by distilling off the solvent under reduced pressure, was purified by silica gel column chromatography (eluent: dichloromethane/ethanol = 98/2) to obtain ethyl 4-(2-hydroxypropoxy)-benzoate (4.4 g) in the form of colorless crystalls. mp 57-60°C.

Biological Test Examples

Test Example A

Test of foliar spray effect against Pyricularia oryzae

Preparation of formulations of the compounds tested

Active compound: 30 - 40 parts by weight

Carrier: mixture of diatomaceous earth and kaolin (1 :5), 55-65 parts by weight

Emulsifier: polyoxyethylene alkyl phenyl ether, 5 parts by weight

The above-mentioned amounts of active compound, carrier and emulsifier are crushed and mixed to make a wettable powder. A portion of the wettable powder comprising the prescribed amount of active compound is diluted with water and used for testing.

Testing procedure

Seedlings of paddy rice (cultivar: Kusabue) were cultured in plastic pots each having a diameter of 6 cm. The previously prepared solution of the prescribed concentration of active compound was sprayed over the seedlings in the 1.5 - 2 leaf stage, at a rate of 20 ml per 3 pots. 5 days after the application, a suspension of spores of artificially cultured Pyricularia oryzae sprayed on the test plants once for inoculation, and the plants were kept at 25°C and 100% relative humidity for infection. 7 days after the inoculation, the infection rate per pot was classified and evaluated according to the following standard and the control value (%) was calculated. Phytotoxicity was tested at the same time. This test is an average of the results of 3 pots for 1 section.

The evaluation of the infection rate and the calculation method of the control value are identical in each of the Test Examples A-D. Infection rate Percentage of lesion area in (%)

0 0

0.5 less than 2

1 2-less than 5

2 5 -less than 10

3 10-less than 20

4 20-less than 40

5 more than 40

Control value (%) =

x 100 infection rate o untreated section '

Test results

Compounds No. 1, 2, 3, 4, 5, 8, 9, 10 and 11 showed control values of more than 80% at an active compound concentration of 500 ppm. No phytotoxicity was observed.

Test Example B

Test of water surface application effect against Pyricularia oryzae.

Testing procedure

Seedlings of paddy rice (cultivar: Kusabue) in the 1.5 leaf stage were cultivated in plastic pots each having a diameter of 6 cm. The seedlings were then transplanted into irrigated plastic cups each having a diameter of 10 cm, one seedling per pot, and the water just covering the soil. The solution of the prescribed concentration of the active compound, which had been prepared in the same manner as that of Test Example A, was dropped to the water surface with a pipette at a rate of 5 ml per pot. 7 days after the chemical treatment, a suspension of spores of artificially cultured

Pryricularia oryzae was sprayed once on the test plants for inoculation, and the plants were kept at a temperature of 25°C and a relative atmospheric humidity of 100%. Seven days after the inoculation, the infection rate per pot was classified and evaluated, and further the control value (%) was calculated. Phytotoxicity was tested at the same time.

This test is an average of the results of 3 pots for 1 section.

Test results

Compounds No. 5, 8 and 11 showed control values of more than 80% at an active compound rate of 8 kg/ha. No phytotoxicity was observed.

Test Example C

Test for the effect of seed treatment against Pyricularia oryzae

Testing procedure

Seeds of paddy rice (cultivar: Kasabue) were soaked in a diluted solution of an active compound having the prescribed concentration. 5 ml of such solution, which had been prepared in the same manner as that of Test Example A, were used per 150 grains of seed. Soaking was conducted at a temperature of 20°C for 5 days. After the soaking, the air-dried seeds were sown in 2 plastic pots, each having a diameter of 9 cm, and the seeds were germinated by placing the pots in a warmed nursery box (32°C) for 3 days. After cultivating the seedlings for 2 weeks, the plants reached the 2 - 2.5 leaf stage. A spore suspension of artificially cultured Pyricularia oryzae was then sprayed on the test plants once, and the plants were kept at a temperature of 25°C and a relative atmospheric humidity of 100% for infection. Seven days after the inoculation, the infection rate per pot was classified and evaluated and the control value (%) was calculated. Phytotoxicity was tested at the same time.

This test is an average of the results of 2 pots for 1 section. Test results

Compounds No. 4, 6, 8, 10, 12 and 13 showed control values of more than 80% at an active compound concentration of 500 ppm. No phytotoxicity was observed.

Test Example D

Spraying test against Phytophthora infestans.

Testing procedure

About 1 seed of tomato (cultivar: Regina) was sown in each plastic pot of a diameter of 6 cm, and raised in a greenhouse at 15-25°C. The solution obtained by diluting the prepared formulation of the test compound to the prescribed concentration as mentioned above, was sprayed at a rate of 20 ml per 3 pots over seedlings which had reached the 4 leaf stage. Zoosporangia formed on the lesion of tomato plants, which previously had been infected with Phytophthora infestans, were washed down with a brush into distilled water to make a suspension. Five days after the tomato plants had been sprayed with the solution of active compound, the suspension was sprayed on the plants once for inoculation, and the treated plants were kept at a temperature of 20°C and a relative atmospheric humidity of 100%. Four days after the inoculation, the infection rate per pot was classified and the control value (%) was calculated. Phytotoxicity was tested at the same time.

This test is an average of the results of 3 pots for 1 section.

Test results Compounds No. 5, 9 and 11 showed control values of more than 80% at an active compound concentration of 500 ppm. No phytotoxicity was observed. Formulation Examples

Formulation Example I (Granules)

25 parts by weight of water were added to a mixture of 10 parts by weight of Com- pound No. 4 according to the invention, 30 parts by weight of bentonite (mont- morillonite), 58 parts by weight of talc and 2 parts by weight of lignin sulphonic acid salt, and the mixture was kneaded thoroughly. The resulting product was granulated by means of an extrusion granulator to form granules having a size of from 10 to 40 meshes. The granules were dried at a temperature between 40 and 50°C.

Formulation Example II (Granules)

95 parts by weight of a clay mineral having a particle size distribution within a range of from 0.2 to 2 mm were introduced into a rotary mixer. This product was uniformly wetted by spraying thereto under rotation a mixture of 5 parts by weight of Com- pound No. 5 according to the invention and a liquid diluent. The granules obtained in this manner were dried at a temperature between 40 and 50°C.

Formulation Example III (Emulsifiable Concentrate)

An emulsifiable concentrate was prepared by mixing 30 parts by weight of Compound No. 8 according to the invention, 55 parts by weight of xylene, 8 parts by weight of polyoxyethylene alkyl phenyl ether and 7 parts by weight of calcium alkylbenzene sulphonate with stirring.

Formulation Example IV (Wettable Powder) A wettable powder was prepared by thoroughly mixing 15 parts by weight of Compound No. 9 according to the invention, 80 parts by weight of a mixture (1:5) of White Carbon (fine powder of hydrated non-crystalline silicon oxide) and powdery clay, 2 parts by weight of sodium alkylbenzene sulphonate and 3 parts by weight of a condensate of sodium alkylnaphthalene sulphonate and formaldehyde in powdery state. Formulation Example V (Wettable Granules)

20 parts by weight of Compound No. 11 according to the invention, 30 parts by weight of sodium lignin sulphonate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatomaceous earth powder were thoroughly mixed with water. The resulting product was granulated by means of extrusion through a 0.3 mm screen. After drying the product, wettable granules were obtained.

Claims

Patent Claims

1. Isothiazolecarboxylic esters of the formula

wherein

R¹ represents a hydrogen atom, methyl or ethyl,

R² represents a hydrogen atom or C alkyl,

R represents a hydrogen atom, chloro, methoxy or nitro, and

R⁴ represents a hydrogen atom or chloro,

provided that where R¹, R³ and R⁴ each represent a hydrogen atom and R represents methyl, then the group CO R² is bound to the 3-position of tht phenyl group.

2. Isothiazolecarboxylic esters of the formula (I) according to claim 1, in which

R¹ represents a hydrogen atom, methyl or ethyl,

R² represents a hydrogen atom, methyl, ethyl or isobutyl,

R³ represents a hydrogen atom, chloro, methoxy or nitro, and

R⁴ represents a hydrogen atom or chloro, provided that where R¹, R³ and R⁴ each represent a hydrogen atom and R² represents methyl, then the group CO R² is bound to the 3-position of the phenyl group.

3. Isothiazolecarboxylic esters of the formula (I) according to claim 1, said compounds being

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-3-benzene- carboxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-propoxy} -3-benzene- carboxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy} -3-benzene- carboxylate,

1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy } -4-benzenecarboxylic acid

isobutyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy} -4-benzene- carboxylate,

methyl 2-chloro-l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-4- benzenecarboxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy} -2-methoxy- 4-benzenecarboxylate,

ethyl 2,6-dichloro-l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-ethoxy}-

4-benzenecarboxylate, ethyl 1 - {2-[(3 ,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-propoxy} -4-benzene- carboxylate,

methyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-propoxy}-2-meth- oxy-4-benzenecarboxylate,

isobutyl 1 - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy} -4-benzene- carboxylate,

methyl l-{2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy}-2-mtro-4- benzenecarboxylate, and

methyl 2,6-dichloro-l - {2-[(3,4-dichloro-5-isothiazolyl)-carbonyloxy]-n-butoxy} - 4-benzenecarboxylate.

4. Process for the preparation of isothiazolecarboxylic esters of the formula (I) according to Claim 1, characterized in that 3,4-dichloro-5-isothiazolecarbonyl chloride of the formula

is reacted with compounds of the formula

in which

R¹, R², R³ and R⁴ have the above-mentioned meanings,

5. Microbicidal compositions, characterized in that they contain at least one isothiazolecarboxylic ester of the formula (I) according to claim 1 plus extenders and/or surface active agents.

6. Process for combating undesired microorganisms, characterized in that isothiazolecarboxylic esters of the formula (I) according to claim 1 are applied to the microorganisms and/or to their habitat.

7. Use of isothiazolecarboxylic esters of the formula (I) according to claim 1 for combating undesired microorganisms.

8. Process for the preparation of microbicidal compositions, characterized in that isothiazolecarboxylic esters of the formula (I) according to claim 1 are mixed with extenders and/or surface-active agents.