It has already been described that certain chloropyridylcarbonyl-derivatives and cer- tain 1,2,3-benzothiadiazole-derivatives have fungicidal properties and can be em- ployed for inducing resistance to phytopathogenic diseases in plants (see JP-A Hei 9-136 887 and JP-A Hei 8-194 074). The activity of these substances, however, is not always satisfactory when they are applied at low dosages.

There have now been found novel heterocyclyl-derivatives of the formula in which Ri is imidazolyl, thiazolyl, pyrrolyl, furyl or triazolyl, which heterocyclic radi- cals optionally are substituted and/or may be benzo-condensed, R2 is hydrogen, cyano, Cl 4 alkyl, C2 4 alkenyl, phenyl or furyl, R3 is hydrogen, Cl 4 alkyl-carbonyl, benzoyl, 2,6-dichloro-pyrid-4-yl-carbonyl or Cl 4 alkoxy-Cl 4 alkyl-carbonyl, and R4 is 2-chloro-pyrid-4-yl, 2,6-dichloro-pyrid-4-yl, 1,2,3-benzothiadiazol-7-yl or 5-bromo-1,2,3-benzothiadiazol-7-yl.

It has furthermore been found that

a) heterocyclyl-derivatives of the formula in which R1 and R4 have the above-mentioned meanings, can be prepared by reacting ketones of the formula in which R 1 and R4 have the above-mentioned meanings, with reducing agents in the presence of a diluent, and b) heterocyclyl-derivatives of the formula in which Rl, R2 and R4 have the above-mentioned meanings and

R5 is Cj. 4 alkyt-carbonyl, benzoyl, 2,6-dichloro-pyrid-4-yl-carbonyl or alkyl-carbonyl,C1-4alkoxy-C1-4 can be prepared by reacting heterocyclyl-derivatives of the formula in which R I, R2 and R4 have the above-mentioned meanings, with carboxylic acid chlorides of the formula R6-CO-Cl (III) in which R6 is C1-4 alkyl, phenyl, 2,6-dichloro-pyrid-4-yl or C1-4 alkoxy-C1-4 alkyl, in the presence of a diluent and, if appropriate, in the presence of an acid- binding agent, and c) heterocyclyl-derivatives of the formula

in which R1 and R4 have the above-mentioned meanings and R7 alkylorC2-4alkenyl,C1-4 can be prepared by reacting ketones of the formula in which R I and R4 have the above-mentioned meanings, with Grignard reagents of the formula X-Mg-R7 (IV) in which R7 has the above-mentioned meaning and X is chlorine, bromine or iodine, in the presence of a diluent followed by adding water, and d) heterocyclyl-derivatives of the formula in which Rl and R4 have the above-mentioned meanings and R8 is Cl 4 alkyl, phenyl or furyl, can be prepared by reacting ketones of the formula in which RI and R4 have the above-mentioned meanings, with organolithium compounds of the formula Li-R8 (V) in which R8 has the above-mentioned meaning

in the presence of a diluent followed by adding water, and e) heterocyclyl-derivatives of the formula in which R I and R4 have the above-mentioned meanings, can be prepared by reacting ketones of the formula in which R I and R4 have the above-mentioned meanings, with trimethylsilyl cyanide of the formula (CH3) 3Si-CN (VI) in the presence of a diluent and, if appropriate, in the presence of a catalyst, followed by adding water.

Finally, it has been found that the heterocyclyl-derivatives of the formula (I) are out- standingly active as microbicides, which can be used in agriculture and horticulture.

They can either be used for directly combating undesired microorganisms, such as phytopathogenic fungi and bacteriae, or for inducing in the plant bodies themselves resistance to phytopathogenic fungi and bacteriae.

Surprisingly, the compounds according to the invention have a much better micro- bicidal activity, particularly fungicidal activity than the closest known compounds, which have the same type of action. Further, the compounds of the formula (I) are better tolerated by plants than the known compounds, which are structurally most similar.

In the present context,"halogen"represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. <BR> <BR> <BR> <BR> <BR> <BR> <P>The term"C, 4 alkyl"represents straight-chain or branched alkyl and includes, for example, methyl, ethyl, propyl, isopropyl, n-, iso-, tert-or sec-butyl.

The term"C2 4 alkenyl"represents, for example, vinyl, allyl, 1-propenyl, isopropenyl, 1-, 2-or 3-butenyl. <BR> <BR> <BR> <BR> <BR> <BR> <P>The term"C, 4 alkoxy"represents C, includes, for example, methoxy, ethoxy, propoxy, and the like. <BR> <BR> <BR> <BR> <BR> <BR> <P>The term"C, 4 alkyl-carbonyl"represents C, alkyl-CO-and includes, for example, acetyl, propionyl, and the like. <BR> <BR> <BR> <BR> <BR> <BR> <P> The term"C, 4 alkoxy-C, 4 alkyl-carbonyl"represents C, _4 alkyl-carbonyl which is<BR> <BR> <BR> <BR> <BR> <BR> substituted by C, 4 alkoxy, and includes, for example, methoxy-acetyl, ethoxy-acetyl, methoxy-propionyl, and the like.

The term"C, 4 haloalkyl"represents C 4 alkyl in which one or more of the hydrogen atoms is (are) substituted by halogen, and includes, for example, trifluoromethyl, difluoromethyl, chloromethyl, dichloromethyl, and the like.

Formula (I) provides a general definition of the heterocyclyl-derivatives according to the invention.

Preferred compounds of the formula (I) are those, in which R'represents 2-imidazolyl, 2-thiazolyl, 5-thiazolyl, 2-pyrrolyl, 2-furyl, 1,2,4- triazol-5-yl or 2-triazolyl, which heterocyclic radicals are optionally sub- stituted by one or two radicals selected from halogen, C1-4 alkyl, C1-4 halo- alkyl, alkoxy-C1-4alkyl,C1-4cyanoalkyl,C1-4alk-C1-4 oxy-carbonyl-CI4 alkyl, phenyl and/or C24 alkenyl and/or may be benzo- condensed, R2 represents hydrogen, cyano, Cl 4 alkyl, C2 4 alkenyl, phenyl or 2-furyl, <BR> <BR> R3 represents hydrogen, C, 4 alkyl-carbonyl, benzoyl, 2,6-dichloro-pyrid-4-yl-<BR> carbonyl or C, 4 alkoxy-CI 4 alkyl-carbonyl, and R4 represents 2-chloro-pyrid-4-yl, 2,6-dichloro-pyrid-4-yl, 1,2,3-benzothiadia- zol-7-yl or 5-bromo-1,2,3-benzothiadiazol-7-yl.

Particularly preferred compounds of the formula (I) are those, in which R'represents 2-imidazolyl, 2-thiazolyl, 5-thiazolyl, 2-pyrrolyl, 2-furyl, 1,2,4- triazol-5-yl or 2-triazolyl, which heterocyclic radicals are optionally substi- tuted by one or two radicals selected from fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, t-butyl, difluoromethyl, trifluoromethyl, tri-

fluoromethoxy, methoxymethyl, cyanomethyl, methoxycarbonylmethyl, phenyl and/or allyl, and/or may be benzo-fused, R2 represents hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyano, vinyl, allyl, phenyl or 2-furyl, R3 represents hydrogen, acetyl, propionyl, benzoyl, 2,6-dichloropyrid-4-yl- carbonyl, methoxymethyl-carbonyl or ethoxymethyl-carbonyl, and R4 represents 2-chloro-pyrid-4-yl, 2,6-dichloro-pyrid-4-yl, 1,2,3-benzothiadia- zol-7-yl or 5-bromo-1,2,3-benzothiadiazol-7-yl.

Specific examples of the formula (I) according to the invention, which may be mentioned, are the compounds shown in the following Tables.

Table 1 Ri R2 R3 2-imidazolyl H H Table 2

R3R1R2 H2-imidazolylH H1-methyl-2-imidazolylH H1-methyl-2-imidazolylmethyl H1-methyl-2-imidazolylethyl H1-methyl-2-imidazolylisopropyl H1-methyl-2-imidazolylt-butyl H1-methyl-2-imidazolylvinyl H1-methyl-2-imidazolylphenyl H1-methyl-2-imidazolyl2-furyl acetyl1-methyl-2-imidazolylH benzoyl1-methyl-2-imidazolylH 2,6-dichloropyrid-4-1-methyl-2-imidazolylH yl-carbonyl H1-difluoromethyl-2-imidazolylH H1-ethyl-2-imidazolylH H1-propyl-2-imidazolylH H1-isopropyl-2-imidazolylH H1-t-butyl-2-imidazolylH H1-trifluoromethoxy-2-imidazolylH H1-methoxymethyl-2-imidazolylH Table 2 (continued) Rl R2 R3 1-cyanomethyl-2-imidazolyl H H I-methoxycarbonylmethyl-2-H H imidazolyl H1-phenyl-2-imidazolylH 1-allyl-2-imidazolyl H H H1-methyl-5-triazolylH 1-methyl-5-triazolyl methyl H 1-methyl-5-triazolyl isopropyl H H1-methyl-5-triazolylphenyl H1-isopropyl-5-triazolylH 2-triazolyl H H 2-triazolyl methyl H 2-triazolyl ethyl H 2-triazolyl isopropyl H 2-triazolyl t-butyl H 2-triazolyl phenyl H 2-triazolyl allyl 2-triazolyl cyano H 5-methyl-2-triazolyl H H 4-methyl-2-triazolyl H H H1-methyl-2-pyrrolylH 2-furyl 2-furyl H Table 3 RI R2 R3 2-imidazolyl H H 2-imidazolyl methyl H 1-methyl-2-imidazolyl H H H1-methyl-2-imidazolylmethyl 1-methyl-2-imidazolyl isopropyl H 2,6-dichloropyrid-4-1-methyl-2-imidazolylH yl-carbonyl 1-isospropyl-2-imidazolyl methyl H 5-chloro-1-methyl-2-imidazolyl H H 1-methyl-5-triazolyl H H 1-difluoromethyl-5-triazolyl H H 2-thiazolyl H H 2-thiazolyl H 2,6-dichloropyrid-4- yl-carbonyl 2-thiazolyl H acetyl 2-thiazolyl H methoxymethyl- carbonyl Table 4

Rl R2 R3 1-methyl-5-triazolyl H H 1-methyl-2-benzoimidazolyl H H If 1,2,3-benzothiadiazol-7-yl- (2-thiazolyl)-methanone is used as starting material and sodium tetrahydroborate is used as reducing agent, the course of process (a) accord- ing to the invention can be illustrated by the following formula scheme.

If 1,2,3-benzothiadiazol-7-yl- (2-thiadiazolyl)-methanol and 2,6-dichloro-isonicotinic acid chloride are used as starting materials, the course of process (b) according to the invention can be illustrated by the following formula scheme.

If 2,6-dichloro-pyrid-4-yl- (l-methyl-2-imidazolyl)-methanone and allyl-magnesium bromide are used as starting materials, the course of process (c) according to the invention can be illustrated by the following reaction scheme.

If 2,6-dichloro-pyrid-4-yl- (l-methyl-2-imidazolyl)-methanone and methyl lithium are used as starting materials, the course of process (d) according to the invention can be illustrated by the following reaction scheme.

If 2,6-dichloro-pyrid-4-yl- (l-methyl-2-imidazolyl)-methanone and trimethylsilyl cyanide are used as starting materials, the course of process (e) according to the invention can be illustrated by the following reaction scheme.

Formula (II) provides a general definition of the ketones, which are required as starting materials for carrying out processes (a), (c), (d) and (e) according to the invention. In this formula, RI and R4 preferably have the meanings, which have already been mentioned as preferred for these radicals.

The following compounds may be mentioned as examples of ketones of the formula (II).

1,2,3-benzothiadiazol-7-yl (2-thiazolyl) methanone, 2,6-dichloro-4-pyridyl (2-thiazolyl) methanone, 1,2,3-benzothiadiazol-7-yl (2-imidazolyl) methanone, 2,6-dichloro-4-pyridyl (2-imidazolyl) methanone, 1,2, 3-benzothiadiazol-7-yl (l-methyl-2-imidazolyl) methanone, 2,6-dichloro-4-pyridyl (l-methyl-2-imidazolyl) methanone, 1,2,3-benzothiadiazol-7-yl (l-isopropyl-2-imidazolyl) methanone, 2,6-dichloro-4-pyridyl (1-isopropyl-2-imidazolyl) methanone, and the like.

The ketones of the formula (II) are known or can be prepared by known methods (see JP-A Hei 9-136 887 and JP-A Hei 8-194 074).

All customary compounds for the hydrogenation of carbonyl groups can be used as reducing agents for carrying out process (a) according to the invention. As examples of such reducing agents, there may be mentioned sodium tetrahydroborate, lithium aluminum hydride, diborane, and the like.

Formula (Ic) provides a general definition of the heterocyclyl-derivatives, which are required as starting materials for carrying out process (b) according to the invention. In this formula, RI, R2 and R4 preferably have the meanings, which have already been mentioned as preferred for these radicals.

The heterocyclyl-derivatives of the formula (Ic) are compounds according to the invention. They can be prepared by processes (a), (c), (d) and (e) according to the invention.

The following compounds may be mentioned as examples of heterocyclyl-derivatives of the formula (Ie).

Obtainable by process (a) according to the invention: 1, 2,3-benzothiadiazol-7-yl (2-thiazolyl) methanol, 2,6-dichloro-4-pyridyl (2-thiazolyl) methanol, 1, 2,3-benzothiadiazol-7-yl (2-imidazolyl) methanol, 2,6-dichloro-4-pyridyl (2-imidazolyl) methanol, 1,2, 3-benzothiadiazol-7-yl (l-methyl-2-imidazolyl) methanol, 2,6-dichloro-4-pyridyl ( 1-methyl-2-imidazolyl) methanol, 1,2,3-benzothiadiazol-7-yl (l-isopropyl-2-imidazolyl) methanol, 2,6-dichloro-4-pyridyl (1-isopropyl-2-imidazolyl) methanol, and the like.

Obtainable by processes (c), (d) or (e) according to the invention : l-(l', 2', 3'-benzothiadiazol-7'-y l)-l-(2"-thiazolyl) ethano l, 1- (2', 6'-dichloro-4'-pyridyl)-l- (2"-thiazolyl) ethanol, 1- (1', 2', 3'-benzothiadiazol-7'-yl)-1- (2"-imidazolyl) ethanol, 1-(2',6'-dichloro-4'-pyridyl)-1-(2"-imidazolyl)ethanol, I- (I', 2', 3'-benzothiadiazol-7'-yl)-1-(1"-methyl-2"-imidazolyl) ethanol,

1-(2', 6'-dichloro-4'-pyridyl)-l-(1"-methyl-2"-imidazolyl)(2', 6'-dichloro-4'-pyridyl)-l-(1"-methyl-2"-imidazolyl) ethanol, 1- (1', 2', 3'-benzothiadiazol-7'-yl)-l-(l"-isopropyl-2"-imidazolyl) ethanol, l-(2', 6'-dichloro-4'-pyridyl)-l-(1"-isopropyl-2"-imidazolyl)(2', 6'-dichloro-4'-pyridyl)-l-(1"-isopropyl-2"-imidazolyl) ethanol, cyano- (2, 6-dichloro-4-pyridyl)- (1-methyl-2-imidazolyl) methanol, and the like.

Formula (III) provides a general definition of the carboxylic acid chlorides, which are also required as starting materials for carrying out process (b) according to the invention. In this formula, R6 preferably is methyl, ethyl, phenyl, 2,6-dichloro-pyrid- 4-yl, methoxy-methyl or ethoxy-methyl.

The following compounds may be mentioned as examples of carboxylic acid chlorides of the formula (III): 2,6-dichloro-isonicotinic acid chloride, acetyl chloride, propionyl chloride, benzoyl chloride, methoxy-acetyl chloride, and the like.

The carboxylic acid chlorides of the formula (III) are known or can be prepared by known processes.

Formula (IV) provides a general definition of the Grignard reagents, which are re- quired as reaction components for carrying out process (c) according to the invention.

In this formula, R7 preferably is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, vinyl or allyl and X preferably is bromine or iodine.

The following compounds may be mentioned as examples of Grignard reagents of the formula (IV): isopropylmagnesium bromide, allylmagnesium bromide, methylmagnesium iodide, and the like.

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

Formula (V) provides a general definition of the organolithium compounds, which are required as reaction components for carrying out process (d) according to the invention. In this formula R8 preferably is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl or furyl.

The following compounds may be mentioned as examples or organolithium com- pounds of the formula (V): methyl lithium, ethyl lithium, butyl lithium, phenyl lithium, 2-furyl lithium, and the like.

The organolithium compounds of the formula (V) are known or can be prepared by known methods.

Diluents which are suitable for carrying out process (a) according to the invention are all customary organic solvents as well as water. The following can preferably be used:

water; aliphatic, alicyclic or aromatic hydrocarbons (which may optionally be chlo- rinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chlorobenzene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxy- ethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl- pyrrolidone, 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 carrying out process (a) 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 +100°C, preferably between 0°C and 50°C.

Process (a) according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under reduced or elevated pressure.

When carrying out process (a) according to the invention, in general 1 mole of a ke- tone of the formula (II) is reacted with 0.3 to 20 molar amounts of a reducing agent in the presence of a diluent, such as ethanol. Working up is carried out by customary methods.

Diluents which are suitable for carrying out process (b) according to the invention are all customary organic solvents. The following can preferably be used: 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, chlorobenzene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran

(THF) and diethylene glycol dimethyl ether (DGM); ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK); nitriles such as acetonitrile, propionitrile and acrylonitrile; esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (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.

Process (b) according to the invention can be carried out in the presence of an acid binding agent. Suitable acid binders are inorganic bases, for example, hydrides, hydroxides, carbonates and bicarbonates of alkali metals or alkaline earth metals, such as sodium hydride, lithium hydride, sodium hydrogencarbonate, potassium hy- drogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; inorganic alkali metal amides, such as lithium amide, sodium amide and potassium amide; and organic bases, for example, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethyl- aniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-dia- zabicyclo [2,2,2] octane (DABCO) and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU).

When carrying out process (b) 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-50°C and about +150°C, preferably between 0°C and 100°C.

Process (b) according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under reduced or elevated pressure.

When carrying out process (b) according to the invention, in general 1 mole of a het- erocyclyl derivative of the formula (Ic) is reacted with 0.1 to 20 moles of a carbox- ylic acid chloride of the formula (III) in the presence of a diluent, such as dichlo-

romethane, and in the presence of a base, such as triethylamine. Working up is carried out by customary methods.

When carrying out process (c) according to the invention, all inert organic solvents customary for such reactions can be used as diluents. Suitable diluents preferably are aliphatic, alicyclic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene and xylene; and ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM).

When carrying out process (c) 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-100°C and about +100°C, preferably between 0°C and +100°C.

Process (c) according to the invention is generally carried out under atmospheric pressure.

When carrying out process (c) according to the invention, in general 1 mole of a ke- tone of the formula (II) is reacted with 1 to 20 moles of a Grignard reagent of the formula (IV) in the presence of a diluent, such as tetrahydrofuran. Water is then added to the reaction mixture, and working up is carried out by customary methods.

When carrying out process (d) according to the invention, all inert organic solvents customary for such reactions can be used as diluents. Suitable diluents preferably are aliphatic, alicyclic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene and xylene; and ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM).

When carrying out process (d) 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-100°C and about +150°C, preferably between-78°C and+25°C.

Process (d) according to the invention is generally carried out under atmospheric pressure.

When carrying out process (d) according to the invention, in general 1 mole of a ke- tone of the formula (II) is reacted with 1 to 20 moles of an organolithium compound of the formula (V) in the presence of a diluent, such as tetrahydrofuran. Water is then added to the reaction mixture, and working up is carried out by customary methods.

When carrying out process (e) according to the invention, all inert organic solvents customary for such reactions can be used as diluents. Suitable diluents preferably are aliphatic, alicyclic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene and xylene; and ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); nitriles such as acetonitrile.

Process (e) according to the invention can be carried out in the presence of a catalyst.

Suitable catalysts preferably are Lewis acids, such as zinc chloride.

When carrying out process (e) 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-78°C and about +150°C, preferably between-20°C and +100°C.

Process (e) according to the invention is generally carried out under atmospheric pressure.

When carrying out process (e) according to the invention, in general 1 mole of a ke- tone of the formula (II) is reacted with 1 to 10 moles of trimethylsilyl cyanide of the formula (VI) in the presence of zinc chloride as a catalyst and in the presence of a diluent, such as acetonitrile. Water is then added to the reaction mixture and working up is carried out by customary methods.

The compounds according to the present invention exhibit a strong microbicidal ac- tivity without causing phytotoxicity to cultivated plants. They can be used for com- bating undesired microorganisms, such as phytopathogenic fungi and bacteriae, in agriculture and horticulture. The compounds are suitable for the direct control of un- desired microorganisms as well as for generating resistance in plants against attack by undesirable microorganisms.

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

Generally, the compounds according to the invention can be used as fungicides for combating phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromyce- tes, and can also be used as bactericides for combating bacteriae, such as Pseudo- monoadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomy- cetaceae.

Some causative organisms of fungal and bacterial diseases included under the above- mentioned main headings, are mentioned below as non-limiting examples: Xantho- monas species, such as, for example, Xanthomonas campestris pv. oryzae; Pseudo- monas species, such as, for example, Pseudomonas syringae pv. lachryrnans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for

example, Pythium ultimum; Phytophthora species, such as, for example, Phytoph- thora infestans; Pseudoperonospora species, such as, for example, Pseudoperono- spora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Perono- spora pisi or Peronospora brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Po- dosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea; (Conidial form; Drechslera, Synonym: Helmin- thosporium); Cochliobolus species, such as, for example, Cochliobolus sativus; (Co- nidial form: Drechslera, Synonym: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puc- cinia recondita; Tilletia species, such as, for example, Tilletia caries; Ustilago spe- cies, such as, for example, Ustilago nuda or, Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Lep- tosphaeria nodorum; Cercospora species, such as, for example, Cercospora canes- cens; Alternaria species, such as, for example, Alternaria brassicae; Pseudocerco- sporella species, such as, for example, Pseudocercosporella herpotrichoides, and the like.

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

Furthermore, the compounds according to the invention are low toxic to warm- blooded animals, thus they can be used safely.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granu- les, tablets (jumbo agents), aerosols, natural and synthetic materials impregnated with active compounds, very fine capsules in polymeric substances, coating compo- sitions for use on seed, and formulations used with burning equipment, such as fumi- gating 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 chlo- rinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methyl- ene 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 dimethyl- 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 kaolins, 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 methylcel- lulose.

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 com- pound, 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 repel- lents, growth factors, plant nutrients and agents for improving soil structure.

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, pastes and granules. They are used in the custom- ary manner, for example by watering, immersion, spraying, atomizing, misting, va- porizing, 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 compound 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.

Synthesis Example 1 (Compound No. 10)

Sodium tetrahydroborate (0.4 g) was added to a solution of 1,2,3-benzothiadiazol-7- yl (2-thiazolyl) methanone (2.5 g) in ethanol (100 moles) at a temperature of 4°C within 10 minutes whilst stirring. The mixture was stirred at room temperature for 5 hours. The solvent was distilled off then, and water was added. The resulting reaction mixture was neutralized with IN hydrochloric acid and then extracted with dichlo- romethane. The combined organic phases were washed with saturated aqueous so- dium chloride solution and then dried over anhydrous sodium sulfate. After concen- trating the organic phase under reduced pressure, 1,2,3-benzothiadiazol-7-yl (2- thiazolyl) methanol (2.1 g) was obtained as a solid substance.

Melting point: 127-128.5°C Synthesis Example 2 (Compound No. 11)

2,6-Dichloro-isonicotinic acid chloride (0.6 g) was added dropwise to a solution of 1,2,3-benzothiadiazol-7-yl- (2-thiazolyl) methanol (1.25 g) and triethylamine (0.6 g) in dichloromethane (50 ml) whilst stirring at room temperature.

The mixture was stirred at room temperature for 3 hours, and then it was washed successively with IN hydrochloric acid (20 ml) and a saturated aqueous sodium chloride solution (20 ml). The solvent was distilled off then.

1,2,3-benzothiadiazol-7-yl (2-thiazolyl) methyl 2,6-dichloro-isonicotinoate (2.0 g) was obtained in this manner.

Melting point: 145-146.5°C.

Synthesis Example 3 (Compound No. 3)

A solution of methyl lithium (0, 3 g) in tetrahydrofuran (20 ml) was added dropwise within 15 minutes to a solution of 2,6-dichloro-4-pyridyl (1-methyl-2-imidazolyl)- methanone (2.6 g) in tetrahydrofuran (200 ml) whilst stirring at-70°C. The reaction mixture was stirred at room temperature for 9 hours, and then the solvent was distilled off under reduced pressure.

Water was added to the residue, and the resulting mixture was neutralized with IN hydrochlorid acid and then extracted with dichloromethane. The combined organic phases were concentrated under reduced pressure, and the remaining product was purified by column chromatography on silica gel (eluting solvents: chloro- form: ethanol = 19: 1). 1- (2', 6'-Dichloro-4'-pyridyl)-1- (1"-methyl-2"-imidazolyl) etha- nol (1.7 g) was obtained in this manner.

Melting point: 192-193°C.

Table 5 Com-Melting point pound RI R2 R3 R4 (°C) or refrac- No. tive index 1 2-imidazolyl H H 2,6-dichloro- pyridyl 2 1-methyl-2-imidazolyl H H 2,6-dichloro- pyridyl 3 1-methyl-2-imidazolyl methyl H 2, 6-dichloro- 192-193 pyridyl 4 I-methyl-2-imidazolyl isopropyl H 2,6-dichloro- pyridyl 2-furylH2,6-dichloro-52-furyl pyridyl HH1,2,3,-benzo-65-chloro-1-methyl-2- imidazolyl thiadiazol-7-yl 7 1-methyl-1,2,4-triazol- H H 1,2,3-benzo- 5-ylthiadiazol-7-yl 8 1-difluoromethyl-H H 1,2,3-benzo- 1, 2,4-triazol-5-yl thiadiazol-7-yl 9 1-methyl-1,2,4-triazol- H H 7-bromo-1, 2, 3- 5-yl benzothiadiazol-7- yl 10 2-thiazolyl H H 1,2,3-benzo-127-128.5 thiadiazol-7-yl 11 2-thiazolyl H 2,6-dichloro 1, 2,3-benzo- 145-146.5 pyridylcarbonyl thiadiazol-7-yl Table 5 (continued) Com-Melting point pound R3R4(°C)orrefrac-R2 No. tive index 12 2-thiazolyl H methylcarbonyl 1,2,3-benzo- thiadiazol-7-yl 13 2-thiazolyl H methoxycarbonyl 1,2,3-benzo- thiadiazol-7-yl 14 1-methyl-2-H H 7-bromo-1, 2, 3- benzoimidazolyl benzothiadiazol-7- Yl 15 I-isopropyl-2-H H 2, 6-dichloro-153-155 imidazolyl pyridyl 16 1-methyl-2-imidazolyl H H 1,2,3-benzothia->250 diazol-7-yl

Biological Test Examples Test Example 1 Test of foliar spray effect against rice blast 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 Each of the wettable powders is prepared by pulverizing and mixing the above amounts of active compound, carrier and emulsifier. A portion of the wettable powder containing the prescribed amount of the active compound is diluted with water.

Testing procedure Seedlings of paddy rice (cultivar: Kusabue) were cultured in unglazed pots each having a diameter of 12 cm. The previously prepared solution of the prescribed concentration of active compound was sprayed at a rate of 50 ml per 3 pots over the foliages of the seedlings in the 3-4 leaf stage. 5 Days after the application, a suspension of artificially cultured Pyricularia oryzae spores was spray-inoculated once on the seedlings, and the seedlings were maintained at 25°C and 100% relative humidity for infection. 7 Days after the inoculation, the degree of infection per pot was examined and rated according to the criteria mentioned below. Further, the control value (%) was calculated.

The data are an average of the results of 3 pots in one plot.

Degree of Infection Percentage of Lesion Area (%) <BR> <BR> <BR> <BR> 0 0<BR> <BR> <BR> <BR> <BR> <BR> <BR> 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 40 or more degree of infection in treated plot control vlaue (%) _ (1-) x 100 degree of infection in non-treated plot Test results Each of Compounds Nos. 1,2,10,11,13,15 and 16 exhibited a control value of 80% or higher at an active compound concentration of 500 ppm.

Test Example 2 Test of water surface application effect against rice blast.

Testing procedure Seedlings of paddy rice (cultivar: Kusabue) in the 1.5 leaf stage were transplanted into irrigated plastic pots (100 cm2), one seedling per pot. 7 Days after the trans- planting (when the seedlings were in 3-4 leaf stage), the solution of the prescribed concentration of the active compound, which had been prepared in the manner similar to that of the above Test Example 1, was dropped to the water surface with a pipette at a rate of 10 ml per pot, to the water surface. 7 Days after the chemical treatment, a suspension of artificially cultured rice blast (blast fungus race C) spores

was spray-inoculated once on the seedlings, and the seedlings were maintained in the inoculation box at 25°C and 100% relative humidity for 12 hours for infection.

Thereafter, the seedlings were transferred to the greenhouse for management. 7 Days after the inoculation, the degree of infection per pot was evaluated, and further the control value (%) was calculated in the manner similar to that of the above Test Example 1.

Test results Each of Compounds Nos. and 15 exhibited a control value of 80% or higher at an active compound concentration of 8 kg/ha.

Test Example 3 Test of foliar spray effect against tomato late blight Preparation of formulations of active compounds 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 Each of the wettable powders is prepared by pulverizing and mixing the above amounts of active compound, carrier and emulsifier. A portion of the wettable powder containing the prescribed amount of the active compound is diluted with water.

Testing procedure About 5 seeds of tomato (cultivar: Kurihara) were sown in each vinyl plastic pot of a diameter of 7cm, and were raised in a greenhouse (at 15-25°C). The solution

obtained by diluting the prepared formulation of the testing compound to the prescribed concentration as mentioned above, was sprayed at a rate of 25 ml per 3 pots over small seedlings reaching the 4 leaf stage. 10 Days after the spraying, the zoosporangia formed on leasions, which had previously been infected and diseased with Phytophthora infestans, were washed down with a writing-brush into distilled water to prepare a suspension. The suspension was spray-inoculated on the treated plants and they were maintained in a greenhouse at 15-20°C. 4 Days after the inoculation, the degree of infection per pot was evaluated and the control value was calculated in the manner similar to that of the above Test Example 1. The results are an average of 3 pots.

Test results Each of Compounds Nos. and 13 exhibited a control value of 80% or higher at an active compound concentration of 250 ppm.

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. 3 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. 1 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 obtained by mixing 30 parts by weight of Compound No. 1 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 Com- pound No. 1 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. 15 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.