CA2239580A1 - 1,2,3-thiadiazole carboxylic acid (thio)esters and the use thereof as a pest control agent or as a microbicide - Google Patents

Abstract

The invention relates to 1,2,3-thiadiazole carboxylic acid (thio)esters of the formula (I), in which A is a single bond or alkane diyl substituted optionally by aryl or aryl halide, wherein the alkane diyl chain can be broken by oxygen or sulphur, or is alkene diyl substituted optionally by aryl or aryl halide, wherein the alkene diyl chain can be broken by oxygen or sulphur, or is alkane diyloxy substituted optionally by aryl or aryl halide, wherein the sulphur atom is bound to the radical R2, or is alkane diylthio substituted optionally by aryl or aryl halide, wherein the sulphur atom is bound to the radical R2;
R1 is hydrogen, optionally substituted alkyl or optionally substituted aryl;
R2 is optionally substituted heterocyclyl; and Q is oxygen or sulphur. The invention also relates to the acid addition salts and metal salts complexes of said esters, and a process for the preparation of the novel substances and the use thereof for the protection of plants from attack by undesirable micro-organisms and for the control of animal pests.

Description

CA 02239~80 1998-06-04~ D~
r rl~, r~ ~ J r~.~
T~X I I RANSLATION
~ Le A 31 405-Foreign Countries / Du/by/S-P
(Ia) - 1 -1.2~3-Thiadia~oleca~oxylic (thio)estels The present invention relates to novel 1,2,3-thiadiazolecarboxylic (thio)esters, to a process for their preparation and to their use for protecting plants against attack by unwanted microorganisms and for controlling animal pests.

Certain 1,2,3-thiadiazole-5-carboxylic acid derivatives having herbicidal and plant-growth-regulating activity are already known (cf. DE-A 27 28 523). However, the use of such compounds against unwanted microorganisms and animal pests in crop protection has not yet been described.

This invention, accordingly, provides novel 1,2,3-thiadiazolecarboxylic (thio)esters of the formula Rl ~Q_A~R2 O (I) in which A represents a single bond or represents optionally aryl- or halogenoaryl-substituted alkanediyl where the alkanediyl chain may be interrupted by oxygen or sulphur, or represents optionally aryl- or halogenoaryl-substituted alkenediyl where the alkenediyl chain may be interrupted by oxygen or sulphur, or represents optionally aryl- or halogenoaryl-substituted alkanediyloxy where the oxygen atom is linked to the radical R2, or represents optionally aryl or halogenoaryl-substituted alkanediylthio where the CA 02239~80 1998-06-04 .
Le A 31 405-Foreign Countries sulphur atom is linked to the radical R2, R' represents hydrogen, optionally substituted alkyl or optionally substituted aryl, R2 represents optionally substituted heterocyclyl and Q represents oxygen or sulphur, 5 and acid addition salts and metal salt complexes thereof.

Furthermore, it has been found that 1~2,3-thiadiazolecarboxylic (thio)esters of the formula (I) and acid addition salts and metal salt complexes thereof are obtained when 1,2,3-thiadiazolecarbonyl halides of the formula /t ~f X (II) 10 in which R' is as defined above and X represents halogen are reacted with (thio)alcohols of the formula H-Q-A-R2 (III) 15 in which A, Q and R2 are as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a ~ CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries diluent, and, if appropriate, an acid or a metal salt is then added to the resulting compounds of the formula (I~.

Finally, it has been found that the 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) and acid addition salts and metal salt complexes thereof are highly suitable for protecting plants against attack by unwanted microorganisms and for controlling animal pests. The compounds according to the invention are suitable both for making plants resistant against attack by unwanted microorganisms and as microbicides for direct control of the microorganisms.

Surprisingly, the compounds according to the invention are more suitable for controlling animal pests and for protecting plants against attack by unwanted microorganisms than the constitutionally most similar prior-art substances of the same direction of action.

The compounds according to the invention may be present as mixtures of differentpossible isomeric forms, for example in the form of stereoisomers such as E and Z
isomers or else optical isomers. The invention relates both to E and Z isomers and to optical isomers, and also to any mixtures of these isomers.

Formula (I) provides a general definition of the 1,2,3-thiodiazolecarboxylic (thio)esters according to the invention.

A preferably represents a single bond or preferably represents straight-chain or branched alkanediyl having I to 4 carbon atoms where the alkanediyl chain may be interrupted by oxygen or sulphur and where the alkanediyl chain may additionally be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine and bromine, or preferably represents straight-chain or branched alkenediyl having 2 to 5 carbonatoms where the alkenediyl chain may be interrupted by oxygen or sulphur and where the alkenediyl chain may additionally be mono- or disubstituted by ~ CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or preferably represents straight-chain or branched alkanediyloxy having 1 to 4 carbon atoms where the oxygen atom is linked to the radical R2 and the alkanediyloxy chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or preferably represents straight-chain or branched alkanediylthio having I to 4 carbon atoms where the sulphur atom is linked to the radical R2 and the alkanediylthio chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine.

Q preferably represents oxygen or sulphur.

lS R~ preferably represents hydrogen, straight-chain or branched alkyl having I to 6 carbon atoms, straight-chain or branched halogenoalkyl having I to 6 carbon atoms and 1 to 5 halogen atoms or preferably represents aryl having 6 to 10 carbon atoms, where these aryl radicals may be mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen, cyano,nitro, straight-chain or branched alkyl having I to 6 carbon atoms, straight-chain or branched alkoxy having I to 6 carbon atoms, straight-chain or branched halogenoalkyl having I to 6 carbon atoms and I to 5 identical or different halogen atoms and/or straight-chain or branched halogenoalkoxy having I to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

25 R2 preferably represents optionally benzo-fused, saturated or unsaturated mono-, bi-or tricyclic heterocyclyl having 3 to 8 ring members and I to 3 oxygen, sulphur and/or nitrogen atoms, where the heterocycle may be mono- to pentasubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, amino, hydroxyl, formyl, carboxy, carbamoyl, CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries _ 5 thiocarbamoyl, respectively straight-chain or branched alkyl, alkoxy, alkylthio,alkylsulphinyl or alkylsulphonyl having in each case I to 6 carbon atoms;

respectively straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in S each case 1 to 6 carbon atoms and 1 to S identical or different halogen atoms;

respectively straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl,alkylcarbonyloxy, alkoxycarbonyl, arylsulphonyloxy, hydroximinoalkyl or alkoximinoalkyl having in each case I to 6 carbon atoms in the individual alkyl moieties;

cycloalkyl having 3 to 6 carbon atoms;

phenyl which itself may be mono- to trisubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, phenoxy which itself may be mono- to trisubstituted by identical or different l S substituents from the group consisting of halogen and, alkyl having I to 4 carbon atoms, dioxolanyl which itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of alkyl having I to 4 carbon atoms, dioxanyl which itself may be mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of alkyl having I to 4 carbon atoms.

and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on carbocyclic ring having S or 6 ring members, where the carbocycle itself may be mono- to tetrasubstituted by identical or CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries different substituents from the group consisting of halogen and alkyl having I
to 4 carbon atoms, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on heterocyclic ring having 5 or 6 ring members and 1 or 2 oxygen, sulphur and/or nitrogen atoms, where the heterocycle itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms.

A particularly preferably represents a single bond or particularly preferably represents straight-chain or branched alkanediyl having 1 to 4 carbon atoms, where the alkanediyl chain may be interrupted once by oxygen or sulphur and where the alkanediyl chain may be mono- or disubstituted by identical or different substituents from the group consisting of phenyl and phenyl which it~elf is m.ono- o~ disubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or lS particularly preferably represents straight-chain or branched alkenediyl having

2 to 4 carbon atoms, where the alkenediyl chain may be interrupted once by oxygen or sulphur and where the alkenediyl chain may be mono- or disubstituted by identical or different substituents from the group consisting of phenyl and phenyl which itself is mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or particularly preferably represents straight-chain or branched alkanediyloxy having I to 3 carbon atoms, where the oxygen atom is linked to the radical R2 and the alkanediyloxy chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or particularly preferably represents straight-chain or branched alkanediylthio having I to 3 carbon atoms, where the sulphur atom is linked to the radical R2 and the alkenediylthio chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- or disubstituted by identical or different CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries substituents from the group consisting of fluorine, chlorine and bromine.

Q also particularly preferably represents oxygen or sulphur.

R' particularly preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having I
to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, particularly preferably represents phenyl or naphthyl, where each of these two last-mentioned radicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms and/or straight-chain or branched halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

15 R2 particularly preferably represents optionally benzo-fused, saturated or unsaturated mono-, bi- or tricyclic heterocyclyl having 3 to 8 ring members and 1 to 3 oxygen, sulphur and/or nitrogen atoms, where the heterocycle may be mono- to pentasubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbamoyl, respectively straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinylor alkylsulphonyl having in each case 1 to 4 carbon atoms, respectively straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case I to 4 carbon atoms and I to 5 fluorine, chlorine and/or bromine CA 02239~80 1998-06-04 Le A 31 40S-Foreign Countries atoms, respectively straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl,alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 4 carbon atoms in the individual alkyl S moieties, cycloalkyl having 3 to 6 carbon atoms, phenyl, which itself may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl and isopropyl, phenoxy, which itself may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl and isopropyl, dioxolanyl, which itself may be mono- or disubstituted by identical or differentsubstituents from the group consisting of methyl, ethyl and propyl, lS dioxanyl, which itself may be mono- or disubstituted by identical or different substituents from the group consisting of methyl, ethyl and propyl, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on carbocyclic ring having S or 6 ring members, where the carbocycle itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromme, methyl, ethyl and propyl, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on heterocyclic ring having five or six ring members and one or two oxygen, sulphur and/or nitrogen atoms, where the heterocycle CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries g itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl, ethyl and propyl.

A very particularly preferably represents a single bond, very particularlyS preferably represents methylene, ethane-l,l-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,3-diyl, ethene-1,2-diyl, propene-1,3-diyl, phenylmethane-1,1-diyl, 1 -(2,4-dichloro-phenyl)-ethane- 1 ,2-diyl, 1 -phenyl-propane- I ,3-diyl where the radical R2 is attached in position 3, 1-(4-fluorophenyl)-propane-1,3-diyl where the radical R2 is attached in position 3, furthermore very particularly preferably represents the groups -CH.-O-CH2-, -CH2-S-CH2-, -CH-O-CH2-, -CH-S-CH2-, -CH=CH-CH2-O-CH2- and -CH=CH-CH2-S-CH2-, and very particularly preferably represents the groups -CH2-O-, -CH2-CH2-O-, -CH2-S- and -CH2-CH2-S-, where the hetero atom is in each case attached to the radical R2.

15 Q also very particularly preferably represents oxygen or sulphur.

Rl very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, trichloromethyl, trifluoromethyl, fluoromethyl, difluoromethyl or very particularly preferably represents phenyl or naphthyl, where each of these two last-mentioned radicals may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, trichloromethyl, trifluoromethyl and trifluoromethoxy.

R2 very particularly preferably represents pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries indolyl, benzimidazolyl, benzothiazolyl, benzotriazolyl or benzodioxanyl, oxetanyl, tetrahydrofuryl, perhydropyranyl, pyrrolidinyl, piperidinyl, morpholinyl, dioxolanyl, dioxanyl, hexahydrozepinyl, quinuclidinyl, benzofuranyl, benzothienyl, quinolinyl, isoquinolinyl, oxiranyl, thiazinyl, S dihydrothiazinyl or tetrahydrothiazinyl, where these radicals may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbamoyl,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl, phenyl, chlorophenyl, methylphenyl, phenoxy, chlorophenoxy, fluorophenoxy, methylphenoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, dioxalanyl which itself may be mono- or disubstituted by methyl, and dioxanyl which itself may be mono- or disubstituted by methyl, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on carbocyclic ring having five or six ring members, where the carbocycle itself may be mono- to tetrasubstituted by fluorine, chlorine, bromine and/or methyl, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on heterocyclic ring having five or six ring members and I or 2 oxygen, sulphur and/or nitrogen atoms, where the heterocycle itself may be mono- or disubstituted by fluorine, chlorine, bromine and/or methyl.

CA 02239~80 1998-06-04 ., Le A 31 405-Foreign Countries I I
Preferred compounds according to the invention are also the addition products of acids and those 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) in which A, Q, R' and R2 each have those meanings which have been mentioned as being preferred forthese radicals.

5 The acids which can be subjected to an addition reaction preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, sulphuric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, cataric acid, citric acid, salicylic acid, 10 sorbic acid and lactic acid, and also sulphonic acids, such as, for example, p-toluene sulphonic acid and 1,5-naphthalene disulphonic acid, and also saccharin and thiosaccharin.

Other preferred compounds according to the invention are adducts of salts of metals of main groups II to IV and sub-groups I and II and IV to VIII of the Periodic Table of 15 the Elements and those 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) in which A, Q, Ri and R2 each have those meanings which have been mentioned as being preferred for these radicals.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred in this context. Suitable anions of these salts are those which are derived 20 from acids which lead to physiologically acceptable adducts. Particularly preferred acids of this type are, in this context, the hydrohalic acids, such as, for example hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulphuric acid Examples of compounds according to the invention which may be mentioned are the 25 1,2,3-thiadiazolecarboxylic (thio)esters listed in the tables below.

Le A 31 405-Forei~n Countries Table 1:

1/ ~~ R2 O (I-l) where R2 represents the following substituents:

N ~ H3C~

~N ~C N~ ~ ~ ~N 3 H C~-- N ~5 Table 2 CH
Il ~, o R2 O (I-2) where R~ represents the substituents mentioned in Table 1.

Le A 31 405-Foreign Countries Table 3 1~ ~o R2 O (I-3) where RZ represents the substituents mentioned in Table 1.

Table 4 i-C3H7 o R2 O (I-4) where R2 represents the substituents mentioned in Table 1.

Table 5 o ~ R2 o 3 (I-5) where R2 represents the substituents mentioned in Table 1.

10 Table 6 CH3 O ; (I-6) ., Le A 31 405-Foreign Countries where R2 represents the substituents mentioned in Table 1.

Table 7 o ~ R2 o 3 (I-7) where R2 represents the substituents mentioned in Table 1.

5 Table 8 N~
// ~ ~--R2 O (I-8) where R2 represents the following substituents:

~N 3/

Table 9 /1 ~O_R2 O (I-9) where R2 represents the following substituents:

-Le A 31 405-Foreign Countries N~ ,N3 Table 10 N~
~--R2 ~ (I-10) where R2 represents the substituents mentioned in Table 8.

5 Table 11 O R
O (I-1 1) where R2 represents the substituents mentioned in Table 1.

Table 1 2 // ~o R

~ (I-12 10 where R2 represents the substituents mentioned in Table 1.

Le A 31 405-Forei~n Countries Table 13 ~C2H5 N ~ S ~ R2 O (I-13) where R2 represents the substituents mentioned in Table 1.

Table 14 S _ R2 O (I-14) where R2 represents the following substituents:

H3C--~S [3~H ~~ CH~

H~ N~ICH>-- [~ S H CJ ~N~

~N 3/

CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries Table 15 O (I-15) where R2 represents the substituents mentioned in Table 14.

Table 1 6 O (I-16) where R2 represents the substituents mentioned in Table 14.

Table 1 7 O (I-17) where R2 represents the substituents mentioned in Table 14.

10 Using 4-methyl-1,2,3-thiadiazolecarbonyl chloride and furfuryl alcohol as starting materials, the course of the process according to the invention can be illustrated by the following equation:

CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries Il ~CI + ~ OH

base - HCI

N ~

The formula (II) provides a general definition of the 1,2,3-thiadiazolecarbonyl halides required as starting materials for carrying out the process according to the invention.
In this formula, R' preferably or in particular has those meanings which have already S been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for R'.
X preferably represents chlorine.

The starting materials of the formula (II) are known or can be prepared by knownprocesses (cf. for example DE-A 2728523 or J. Heterocyclic Chem. 1976, 301).

10 The formula (III) provides a general definition of the (thio)alcohols furthermore required as starting materials for carrying out the process according to the invention.
In this formula, A, Q and R2 each preferably or in particular have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being 15 particularly preferred for A, Q and R2.

The (thio)alcohols of the formula (III) are known reagents of organic chemistry.
Suitable acid binders for carrying out the process according to the invention are all customary inorganic and organic bases Preference is given to using alkaline earth CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide,sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium 5 carbonate, potassium bicarbonate, sodium bicarbonate, further ammonium compounds, such as ammonium hydroxide, ammonium acetate and ammonium bicarbonate, and additionally tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), 10 diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated15 hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisol; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as 20 acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane.

When carrying out the process according to the invention, the reaction temperatures can 25 be varied within a relatively wide range. In general, the reaction is carried out at temperatures between -20~C and +180~C, preferably at temperatures between 20~C and 1 30~C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under elevated or reduced . CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries pressure.

When carrying out the process according to the invention, generally 0.5 to 10 mol, preferably 0.8 to 3 mol, of (thio)alcohol of the formula (III) are employed per mole of 1,2,3-thiadiazolecarbonyl halide of the formula (II). Work-up is carried out by 5 customary methods (cf. also the Preparation Examples).

The 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) can be converted into acid addition salts and metal salt complexes.

For the preparation of acid addition salts of the compounds of the formula (I), preference is given to using those acids which have already been mentioned in 10 connection with the description of the acid addition salts according to the invention as being preferred acids.

The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compoundof the formula (I) in a suitable inert solvent and adding the acid, for example 15 hydrochloric acid, and they can be isolated in the known manner, for example by filtering off, and, if appropriate, be purified by washing with an inert organic solvent.

Suitable salts for the preparation of metal salt complexes of the compounds of the formula (I) are preferably those of metals which have already been mentioned in connection with the description of the metal salt complexes according to the invention 20 as being preferred metal salts.

The metal salt complexes of the compounds of the formula ('i) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compounds of the formula (I). Metal salt complexes can be isolated in the known manner, for example by filtering 25 off, and, if appropriate, be purified by recrystallization.

CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries The active compounds according to the invention have strong resistance-inducing activity in plants. They are therefore suitable for generating resistance in plants against attack by unwanted microorganisms.

In the present context, resistance-inducing compounds are those substances which are S capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with unwanted microorganisms, are largely resistant against these microorganisms.

In the present case, unwanted microorganisms are phytopathogenic fungi, bacteria and viruses. Thus, the compounds according to the invention can be employed to induce, 10 for a certain period of time after the treatment, resistance in plants against attack by the abovementioned harmful organisms. The period of time for which resistance is generated generally extends over I to 10 days, preferably I to 7 days, after thetreatment of the plants with the active compounds.

In addition to the resistance-inducing activity, the active compounds according to the 15 invention also have strong microbicidal activity, and they are also employed in practice for the direct control of unwanted microorganisms. The active compounds are suitable for use as crop protection agents, in particular fungicides.

In crop protection, the unwanted microorganisms include fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, 20 Basidiomycetes, Deuteromycetes and furthermore bacteria, such as Pseudomon~ re~ 7 Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come under the generic names listed above are mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. ory~ae;
25 Pseudomonas species, such as, for example, Pseudomonas syringae pv. Iachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;

CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
5 Bremia species, such as, for example, Bremia lactucae, Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
10 Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);
15 Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
20 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;
25 Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae; and Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
The fact that the active compounds are well tolerated by plants at the concentrations 30 required for controlling plant diseases permits the treatment of aerial parts of plants, of propagation stock and seeds, and of the soil.

. CA 02239~80 1998-06-04 t Le A 31 405-Forei~n Countries The active compounds according to the invention can be employed particularly successfully for controlling rice diseases, such as Pyricularia species, and also very successfully again cereal diseases, such as powdery mildew.

Depending on their particular physical and/or chemical properties, the active 5 compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixing the active 10 compounds with extenders, that is, liquid solvents, liquefied gases under pressure and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, organic solvents can, for example, also be used as auxiliary solvents. Essentially, the following are suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated 15 aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl 20 sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, 25 montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco 30 stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

5 Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

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

The formulations generally comprise between 0.1 and 95 per cent by weight of active 15 compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also mixed with known fungicides, bactericides, acaricides, nematicides or insecticides in order thus, for example, to widen the spectrum of action or to prevent development of resistance. In many cases, synergistic effects are achieved, i.e. the 20 activity of the mixture exceeds the activity of the individual components Suitable mixing partners are, for example, those listed below:

Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl- 1 ,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-25 trifluoromethylbenzyl)-benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries pyrimidin-4-yloxy]-phenyl }-3-methoxyacrylate; methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, ~nil~7.ine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, 5 bromuconazole, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, 10 difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, flu~7.in~m, 15 fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, im~7~1il, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, 20 kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram, metsulphovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, 25 ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), 30 sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole, validamycin A, vinclozolin, zineb, ziram.
Bactericides:
5 bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides/Acaricides/Nematicides:
abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoro-methyl)-lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, beta-cyluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, 15 cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl]-N'-cyano-N-methyl-ethaneimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, 20 deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulphoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, 25 fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, flll~7in~rn, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb.
HCH, heptenophos, hexaflumuron, hexythiazox, 30 imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, CA 02239~80 1998-06-04 .

Le A 31 40~-Foreign Countries malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, S omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, 1 0 quinalphos, salithion, sebufos, silafluofen, sulphotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, 1 5 trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, is also possible.

The active compounds according to the invention can be used as such, in the form of 20 their commercial formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts andgranules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active 25 compound formulation or the active compound itself into the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants, the concentrations of active compound in the use forms can vary within a relatively wide range: they are in general between I and0.0001% by weight, preferably between 0.5 and 0.001% by weight.

CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries - 2~ -In the treatment of seeds, amounts of active compound of from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 10 g, are generally required.

In the case of the treatment of soil, active-compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, are required at the site 5 of action.

The compounds according to the invention also have activity against animal pests, in particular against leaf insects.

The active compounds according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against 10 animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

15 From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., D~m~lin~ spp., Trichodectes spp. and Felicola spp.

From the order Diptera and the sub-orders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., 20 Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp, Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp, Morellia spp., Fannia spp.,Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., 25 Lipoptena spp. and Melophagus spp.

CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.

5 From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma 10 spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., 15 Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Octodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
and Laminosioptes spp.

The compounds according to the invention have, for example, excellent activity against Musca domestica.

20 The active compounds according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals, such as, for example, dogs, cats, cage birds, aquarium fish, and so-called experimental animals such as, for example, hamsters, 25 guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce mortality and decreased performance (in meat, milk, wool, hides, eggs, honey and the CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.

In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral :~llminictration, for example in the form of tablets, capsules, 5 drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral ~tlmini.stration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal a-lminictration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which 10 comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, marking devices and the like.

When aflminictered to livestock, poultry, domestic animals and the like, the active compounds according to the invention can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of lS 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10,000, or they may be used in the form of a chemical bath.

The preparation and the use of the active compounds according to the invention are illustrated by the following examples.

CA 02239~80 1998-06-04 Le A 31 405-Foreign Countries Preparation Examples ~,y:~mple 1:
CH3 ~\

N/ ~~~~

A solution of 30.5 g (0.28 mol) of 3-hydroxymethylpyridine and 40 ml of triethylamine in 150 ml of toluene is mixed with 40 g of (0.246 mol) of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride and stirred at 100~C for 18 hours. After cooling, the reaction mixture is admixed with water and the organic phase is separated off, dried over magnesium sulphate and concentrated by evaporation. The resulting oil slowly crystallizes. 45.5 g (79% of theory) of pyrid-3-ylmethyl 4-methyl- 1 ,2~3-thiadiazole-5-carboxylate of melting point 48~C are obtained.

The compounds of the formula (I) listed in the table below are also prepared by the method mentioned above.

Le A 31 405-Foreign Countries Table 18 N ~Q ~ R2 (I) o Ex.R' Q A R2 phys. data No.
2-CH3 ~ -CH2- Cl NMR*): 3.80 (3H);
2.30 (3H) --~ N--CH3 ~J= N

3-CH3 O -CH2- ~ ~CH3 3.78 (3H) N_N~CH

4-CH3 O -CH2- H3C~ bpo I mb: 180~C
<~
t-Bu

5-CH3 ~ -CH2- N NMR*): 8.51 (IH);
~Cl 7.95 (IH); 7.53 (IH)

6-CH3 ~ -CH2- Cl NMR*): 8.12 (IH);
>= N 7.67 ( I H) ~CI

7-CH3 ~ -CH2- Cl NMR*): 7.69 (2H) ~N

Le A 31 405-Foreign Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.

8 -CH3 ~ -CH2- /~N mp.: 75~C
--N~g~

9 -CH3 ~ -CH2- ,N CH3 NMR*): 2.40 (3H);
--N~ 8.17 (IH); 2.19 (3H) -CH3 O -CH2- ~ mp.: 44~C

Il -CH3 O -CH2 ~ mp.: 55~C

~, 12 -CH3 o CH3 ,~ NMR*): 8.64 (2H);
J~ ~N 7.31 (2H) 13 -CH3 O -cH2- ~ bpo l mb 160 C

14 -CH3 O -CH2- ~3 bpo I mb 160 C
o -Le A 31 405-Foreign Countries Table 18 (continuation) Ex. Rl Q A R2 phys. data No.
-C2Hs O -CH2-CH2- ~ bPo 2 mb 190 C

16 -CH3 ~ -CH2 ~=N NMR*): 8.40 (IH);
~Cl 7.88 ( I H) 17 -C3H7 ~ -CH2- ~3 bpo.l mb 170 C

18 -CH3 O -CH2-CH2- ~N~ NMR*): 8.08 (IH);
W N 7.55-7.53 (2H);
7 44-7.40 ( I H) 19 -CH3 O - r--N NMR*): 8.61-8.58 (2H); 7.66-7.62 ( I H); 7.47-7.42 (IH) -CH3 ~ CH3 /=N NMR*): 8.70; 8.60;
J~ ~ 7.74;7.34 21 -CH3 O - Br NMR*): 8.38 (IH);
>~N 7.65 (IH);
7.41 (IH) . CA 02239580 1998-06-04 .

Le A 31 405-Foreign Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.
22 -CH3 ~ -CH2- / =N mp.: 43~C
~ CH3 23 -CH3 ~ -CH2- ,CH3 NMR*): 2.80; 2.28;
~ 1.95-1.61 24 -CH3 0 - H,C~ O ~XCH NMR*): 5.89;
H3C O ~Xo CH3 4.98 (2H);
4.3-3.83 (4H); 1.54;
1.42; 1.34; 1.33 -CH3 ~ -CH2- C, H3 NMR*): 2.45;
2.61-1.78; 3.10 26 -CH3 0 - H3C NMR*): 2.50; 8.49;
>=N 7.53; 7.26 ~Y

27 -CH3 0 - Cl mp.: 77-78~C
~>= N

Le A 31 405-Foreign Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.
28 -CH3 ~ -CH2- Cl mp.: 51~C

29 -CH3 O -(CH2)3- N NMR*): 8.48 (2H);
7.53 (IH);
7.25 (IH); 4.39;
2.13 -CH3 O -(CH2)2- N NMR*): 8.57 (IH);
7.66 (IH);
7.23-7.17 (2H);
4.76; 3.24 31 -CH3 O - /=N mp.: 64-66~C
~1 32 -CH3 O -(CH2)3- N NMR*): 8.54 (IH);
7.61 (IH);
7.18-7.11 (2H) 33 -CH3 O -(CH2)2 OCl mp.: 108-110~C
~=N

Le A 31 405-Foreign Countries Table 18 (continuation) Ex. Rl Q A R2 phys. data No.
34 -CH3 O - ~ bpo 2 mb: 200~C

~N~

-CH3 O -(CH2)2- ~3 NMR*): 7.38 (IH);
S 6.98 (2H); 4.52;
3.26 36 -CH3 O -CH2- ~ NMR*):
4.194.13 (IH) 37 -CH3 ~ -CH2- ~CH3 NMR*): 5.03; 2.21;
H 3 54; 7.36-6.98 (4H) f~
Cl 38 -CH3 O ~ ,N~ NMR*): 8.51 (lH);
--N 7.96 (IH) F

-Le A 31 405-Foreign Countriçs Table 18 (continuation) Ex. R' Q A R2 phys. data No.
39 -CH3 O -(CH2)2- ~ NMR*): 4.42; 2.89;
N ~ 2.80-2.71 (4H);
1.63-1.53 (8H) -CH3 O -CH2- O~ mp.: 41~C
~0~

41 -CH3 ~ -CH2- Cl ~,N NMR*): 8.38 (IH);
~CI 7.80 (IH) 42 -CH3 O -(cH2)2-s ~CI mp.: 45-46~C

43 -CH3 O -CH2- ~ mp.: 63~C

44 -CH3 O -CH2- N~ bpo l mb 210 C

N

-CH3 O -CH2- N bpo I mb:l70~C
~--CH3 Le A 31 405-Foreign Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.
46 -CH3 ~ -CH2- H3C NMR*) N~ 230 (3H);
N 6.14 (IH);
7.63 (1 H) 47 -CH3 O -CH2-CH2- A NMR*) --N 0 3.70 (4H);
2.54 (4H) 48 -CH3 0 --ICH-CH2 A NMR*) CH3 --N 0 2.39-2.64 (8H) 49 -CH3 ~ -CH2- F3C NMR*) 6.63 (1 H);
N 7.85 (lH) S 50 -CH3 O -CH2- ~ mp.: 100~C
N

51 -CH3 O --CH--CHz N~ NMR*) ~, J N 6.87-7.75 (6H) r Le A 31 405-Foreign Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.
52 -CH3 O - /~ NMR*) 2.30 (3H);
~CH3 5.10 (IH) 53 -CH3 O -CHz- H3CCl mp.: 97~C

~(CH3 54 -CH3 O -CH2-CH2- \ mp.: 46~C
~3 -CH3 ~ -CH2- CH3 mp.: 44~C

56 -CH3 O -(CH2)2 O N mp.: 110~C
~3 NO2 57 -CH3 O --CH-- N NMR~) 7.11 (lH);
~"~ 7.68 (1 H);
8.59 (lH);
8 69 (IH) Le A 31 405-Forçi~n Countries Table 18 (continuation) Ex. R' Q A R2 phys. data No.
58 -CH3 ~ -CH2- H3C Br mp.: 61~C
N~ IN CH3 59 -CH3 ~ -CH2- H3C NMR*) \l~N 2.80 (3H) /~ S

-CH3 O -CH2 ~\ bpolmb:220~C
H3C~
N~ IN CH3 61 -CH3 O --CH--(CH~)2 ~ bpo I mb 170 C
CH3 N~N
I

62 -CH3 O -CH2- ~ bpol mb: 200~C

CI~S Cl *) The IH N MR spectra were recorded in deuterochloroform (CDC13) or hexadeuterodimethylsulphoxide (DMSO-d6) using tetramethylsilane (TMS) as internal standard. Stated is the chemical shift for the radical R2 as o value in ppm.

CA 02239~80 1998-06-04 Le A 31 4Q5-FQrçign Countries Use Fy~mrles li'Y~rnrle A
Pyricularia Test (rice)/protective Solvent: 12.5 parts by weight of acetone 5 Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of activecompound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

To test for protective activity, young rice plants are sprayed to run off point with the

10 active compound preparation. 5 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are subsequently placed in a greenhouse at 100% relative atmospheric humidity at 25~C.

The extent of the disease is evaluated 4 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of 100% means that 15 no disease is observed.

In this test, the compounds according to the invention disclosed in Examples 1, 2 and 4 show, at an active compound concentration of 0.0125% by weight in the spray liquor, an efficacy of 70% or more.

-Le A 31 405-Foreign Countries Table A
Pyricularia Test (rice)/protective Active compound Active com- Efficacy in %
pound concen-tration in the spray liquor in %
According to the invention 0.0 1 25 80 (1) N ~
O 0.0125 70 (2) Cl ,CH3 CH3 \ I N
O ~f N
CH3 0.0125 80 (4) H3C~

N ~ C(CH3)3 . . CA 02239~80 1998-06-04 I~e A 31 405-Foreign Countries ~x~nple B
Pyricularia Test (rice)/systemic Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, I part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

To test for systemic properties, 40 ml of the active compound preparation are poured onto standard soil in which young rice plants were grown. 7 days after the treatment, 10 the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Until the evaluation, the plants remain in a greenhouse at a temperature of 25~C and arelative atmospheric humidity of 100%.

The extent of the disease is evaluated 4 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of 100% means that 15 no disease is observed.

In this test, the compounds according to the invention disclosed in Examples 8, 9, 11 and 13 show, at a concentration of 100 mg of active compound per 100 cm2, an efficacy of more than 60%.

. CA 02239580 1998-06-04 ., Le A 31 405-Foreign Countries Table 13 Pyricularia Test (rice)/systemic Active compound Application rate in Efficacy in %
mg of active com-pound per 100 cm2 According to the invention CH3 r= N
// ~o N~ lOO 89 cl (8) CH3 N =/
o ~1 100 72 (9) N~ ~ N 100 67 10 (1 1) N~ ~ ~ 100 80 (13) . CA 02239~80 1998-06-04 -Le A 31 405-Foreign Countries )le C
Test with flies (Musca domestica) Test ~nim~ Adult Musca domestica, Reichswald strain (OP, SP, carbamate-resistant) Solvent: 35 parts by weight of ethylene glycol monomethyl ether 5 Emulsifier: 35 parts by weight of nonylphenyl polyglycol ether To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts of the abovementioned solvent-emulsifier mixture, and the resultingemulsion concentrate is diluted with water to the concentration desired in each case.

2 ml of this active compound preparation are pipetted onto filter paper dishes (9.5 cm) 10 situated in Petri dishes of corresponding size. After the filter discs have dried, 25 test ~nim~l~ are transferred into the Petri dishes and covered.

The activity of the active compound preparation is determined after 24 hours. 100%
means that all the flies have been killed; 0% means that none of the flies have been killed.

15 In this test, the compound according to the invention disclosed in Example 10 shows, at an active compound concentration of 1000 ppm, an efficacy of 100%.

Le A 31 405-Foreign Countries Table C
Test with flies (Musca domestica) Active compound Active compoundEfficacy in %
concentration in ppm According to the invention S N/ ~~~~ 1000 100 (10)

Claims (7)

Claims

1. 1,2,3-thiadiazolecarboxylic (thio)esters of the formula in which A represents a single bond or represents optionally aryl- or halogenoaryl-substituted alkanediyl where the alkanediyl chain may be interrupted by oxygen or sulphur, or represents optionally aryl- or halogenoaryl-substituted alkenediyl where the alkenediyl chain may be interrupted by oxygen or sulphur, or represents optionally aryl- or halogenoaryl-substituted alkanediyloxy where the oxygen atom is linked to the radical R2, or represents optionally aryl or halogenoaryl-substituted alkanediylthio where the sulphur atom is linked to the radical R2, R1 represents hydrogen, optionally substituted alkyl or optionally substituted aryl, R2 represents optionally substituted heterocyclyl and Q represents oxygen or sulphur, and acid addition salts and metal salt complexes thereof.

2. 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim 1, in which A represents a single bond or represents straight-chain or branched alkanediylhaving 1 to 4 carbon atoms where the alkanediyl chain may be interrupted by oxygen or sulphur and where the alkanediyl chain may additionally be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or represents straight-chain or branched alkenediyl having 2 to 5 carbon atoms where the alkenediyl chain may be interrupted by oxygen or sulphur and where the alkenediyl chain may additionally be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or represents straight-chain or branched alkanediyloxy having 1 to 4 carbon atoms where the oxygen atom is linked to the radical R2 and the alkanediyloxy chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, or represents straight-chain or branched alkanediylthio having 1 to 4 carbon atoms where the sulphur atom is linked to the radical R2 and the alkanediylthio chain may be mono- or disubstituted by phenyl and/or by phenyl which itself is mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, Q represents oxygen or sulphur, R1 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms or represents aryl having 6 to 10 carbon atoms, where these aryl radicals may be mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and/or straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, and R2 represents optionally benzo-fused, saturated or unsaturated mono-, bi- or tricyclic heterocyclyl having 3 to 8 ring members and 1 to 3 oxygen, sulphur and/or nitrogen atoms, where the heterocycle may be mono- to pentasubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, amino, hydroxyl, formyl, carboxy, carbamoyl, thiocarbamoyl, respectively straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms;

respectively straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms;

respectively straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, arylsulphonyloxy, hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in the individual alkyl moieties;

cycloalkyl having 3 to 6 carbon atoms;

phenyl which itself may be mono- to trisubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, phenoxy which itself may be mono- to trisubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, dioxolanyl which itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of alkyl having 1 to 4 carbon atoms, dioxanyl which itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of alkyl having 1 to 4 carbon atoms, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on carbocyclic ring having 5 or 6 ring members, where the carbocycle itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, and/or may also be substituted in such a manner that in each case two adjacent substituents form a fused-on heterocyclic ring having 5 or 6 ring members and 1 or 2 oxygen, sulphur and/or nitrogen atoms, where the heterocycle itself may be mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms.

Process for preparing 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim 1 and acid addition salts and metal salt complexes thereof, characterized in that 1,2,3-thiadiazolecarbonyl halides of the formula in which R1 is as defined above and X represents halogen are reacted with (thio)alcohols of the formula H-Q-A-R2 (III) in which A, Q and R2 are as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, and, if appropriate, an acid or a metal salt is then added to the resulting compounds of the formula (I).

4. Composition for protecting plants against attack by unwanted microorganisms and for controlling animal pests, characterized in that it comprises at least one 1,2,3-thiadiazolecarboxylic (thio)ester of the formula (I) according to Claim 1 or one acid addition salt or metal salt complex of a 1,2,3-thiadiazolecarboxylic(thio)ester of the formula (I).

5. Use of 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim 1 or of acid addition salts and metal salt complexes thereof for protecting plants against attack by unwanted microorganisms and for controlling animal pests.

6. Method for protecting plants against attack by unwanted microorganisms and for controlling animal pests, characterized in that 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim I or acid addition salts or metal salt complexes thereof are applied to the unwanted microorganisms or animal pests and/or their habitat.

7. Process for preparing compositions for protecting plants against attack by unwanted microorganisms and for controlling animal pests, characterized in that 1,2,3-thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim 1or acid addition salts or metal salt complexes thereof are mixed with extenders and/or surfactants.