DE4029092A1 - New fungicidal cpds. - Google Patents

Abstract

Thiolcarboxylic acid ester derivs. of formula (I) are new; X = O, S, oxymethylene, methyleneoxy, thiomethylene, methylenethio, ethylene, ethenylene or ethynylene; Y and Z = S or O, provided that they are not both O; R = 1-6C alkyl, mono- di- or tri-nuclear aryl or heteroaryl, these aryl and heteroaryl gps. opt. substd. by R1; R1 = halogen, CN, NO2, 1-6C alkyl, 3-6C cycloalkyl, 1-6C alkoxy, trifluoromethyl, mono or dinuclear aryloxy or mono, di or trinuclear aryl, these aryloxy and aryl gps. being themselves opt. susbtd. by R1.

Description

The present invention relates to new thiocarboxylic acid esters general formula I,

in which the substituents have the following meaning:
X oxygen, sulfur, oxymethylene, methyleneoxy, thiomethylene, methylene thio, ethylene, ethenylene or ethynylene,
Z oxygen or sulfur,
R C₁-C₆-alkyl, mono-, dinuclear or trinuclear aryl or heteroaryl, where aryl and heteroaryl can carry the following radicals R¹:
R¹ halogen, cyano, nitro, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, trifluoromethyl, mono- or dinuclear aryloxy or mono-, dinuclear or trinuclear aryl, aryloxy and aryl in turn by the aforementioned R¹ radicals can be substituted.

Furthermore, the invention relates to a method for producing this Compounds, the fungicidal compositions containing compounds, and a Process for combating fungi with the aid of these compounds or of these fungicidal agents.

Fungicides with a phenylglyoxylic acid oxime structure are known from EP 2 53 213, EP 2 54 426 and EP 2 99 694 are known. Much of that listed in the Writings described compounds with regard to their fungicidal Effect left something to be desired.

The invention was based on the object, fungicides with better action to provide.

Accordingly, the thiocarboxylic acid esters I defined at the outset were found.  

Of the thiocarboxylic acid esters I, preference is given to those in which the substituents have the following meaning:
X methyleneoxy, methylene thio, oxymethylene, thiomethylene, ethylene, ethenylene or ethinylene,
Z oxygen or sulfur,
R for example C₁-C₄-alkyl, methyl, ethyl, n-, iso-propyl, n-, iso-, sec- or tert-butyl, C₆-C₁₄-aryl (such as phenyl, 1-naphthyl, 2-naphthyl or phenanthranyl), heteroaromatic five- or six-membered rings which contain one, two, three or four of the heteroatoms N, O or S (such as pyridinyl, pyrimidinyl, pyrazolyl, pyridazinyl, imidazolyl, 1,2,3-, 1,2, 4-triazolyl, 1,2,4,5-tetrazinyl, furyl, pyrazolyl, thienyl, thiazolyl, thiadiazolyl) and one or two fused aromatic rings (such as benzofuryl, benzothienyl, benzothiazolyl, quinolyl, quinoxazolyl), where aryl and Heteroaryl can be substituted and can carry the following radicals R¹:
R¹ fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, for example C₁-C₄-alkyl, methyl, ethyl, n-, iso-propyl, n-, iso-, sec.-, tert.-butyl, cyclopropyl, cyclopentyl, Cyclohexyl, C₁-C₄alkoxy, methoxy, ethoxy, n-, iso-propoxy, n-, iso-, sec.-, tert.-butoxy, phenoxy, 1-naphthyloxy, 2-naphthyloxy, phenyl, 1-naphthyl, 2-naphthyl, where aryloxy and aryl may in turn be substituted by radicals which have the same preferred meaning as R¹, e.g. B. tolyl, 2-methylphenoxy.

The thiocarboxylic acid esters I according to the invention are obtained by the corresponding carboxylic acid ester II, with Z = O, or the thiolcarboxylic acid ester II, with Z = S at temperatures of 100-200 ° C with a sulfurization medium, such as B. P₄S₁₀ or Lawesson reagent, preferably with Lawesson Rea genz (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) * - for example in a diluent, such as. B. xylene or toluene implemented (see S. O. Lawesson, Bull. Soc. Chim. Belg., 87, 293 (1978)).

X, Z and R have the meaning given above.  

The thiolcarboxylic acid esters II with Z = S are obtained, for example, by that one at a carboxylic acid ester of the general formula II, with Z = O in known manner (Organikum, 16th edition, p. 415, 622) by Ver Soap transferred into the carboxylic acid III, this then also in itself known manner (Houben-Weyl, BdE5, p. 855 ff., 1985) with methanethiol or an alkali methane thiolate to the thiolcarboxylic esters II, with Z = S implements:

X and R have the same meaning as in the formula I, Y denotes an alcohol radical, preferably a C₁-C₄ alkyl radical.

The starting compounds II with Z = O can due to the C = N double bond are present as E / Z isomer mixtures or as pure E or Z isomers, so that the corresponding secondary products, including the thiolcarbon acid ester II, with Z = S either as E / Z isomer mixtures or as E or Z isomers are obtained. The wavy line in the formulas gives this fact again. Both the individual isomeric compounds and their mixtures are encompassed by the invention. The carboxylic acid ester II, with Z = O is obtained by known methods described in EP 2 53 213, EP 2 54 426 and EP 2 99 694 are described in detail.

The carboxylic acid esters II, with Z = O are usually at temperatures of 60 to 120 ° C, preferably 90 to 110 ° C saponified by using an aqueous Alkali hydroxide solution, a KOH solution is preferred, advantageously without one brings additional solvent to react with the carboxylic acid ester. The reaction mixture is then usually concentrated Hydrochloric acid at room temperature (20 ° C) to pH 0.5 to 1.5, preferably pH 0.8 acidified to pH 1.2, the carboxylic acid III being precipitated.

The implementation of the carboxylic acids III to the thiolcarboxylic esters II, with Z = S can, for example, via carboxylic acid chlorides as an intermediate follow (cf. Houben-Weyl, Vol. 8, pp. 464 ff., 1952), but the is preferred easier way via an imidazolid or triazolid. You prefer to work with carbonyldiimidazole, but can also, for example, carbonyldi-1,2,4- Use triazole (see Houben-Weyl, Vol. E5, pp. 855 ff., 1985). The reaction is carried out in inert anhydrous solvents such as acetonitrile or Dimethyl sulfoxide, especially in dimethylformamide, at temperatures of (-20) to 10 ° C, preferably (-15) to 0 ° C, in a pH range of 6 to 8, preferably 6.5 to 7.5, through.  

After this reaction, the activated is usually without separation Acid at temperatures from (-20) to 40 ° C, in particular (-15) to 30 ° C, Methanethiol or an alkali methanethiolate, especially sodium methane thiolate or potassium methanethiolate, added to the reaction mixture, which Imidazolid or triazolid with the thiol or thiolate to the thiol carbon acid ester II, with Z = S reacts.

The following examples illustrate the preparation of the thiocarboxylic acid ester I:

Regulation 1 Preparation of methyl 2- (2-chlorophenoxymethyl) phenylthiolglyoxylate-O-methyloxim

5 g of methyl 2- (2-chlorophenoxymethyl) phenylglyoxylate-O-methyloxime were refluxed in 50 ml of 1N aqueous KOH solution for 2 hours. After cooling with conc. Hydrochloric acid adjusted a pH of 1. The the resulting precipitate was filtered off and dried. You got 4 g of 2- (2-chlorophenoxymethyl) phenylglyoxylic acid-O-methyloxime as colorless Solid which was then dissolved in 50 ml of anhydrous DMF. At (-10) ° C, 2.1 g of carbonyldiimidazole were added and the mixture was stirred for 2 h Temperature. 0.89 g of sodium methanethiolate was then added and the mixture was stirred another 90 min at (-10) ° C and then another 90 min at room temperature. After adding 100 ml of methylene chloride and 200 ml of saturated, aqueous sodium chloride solution, the organic phase was separated off, dried over magnesium sulfate and removed the solvent in vacuo. 3.8 g of crude product were obtained. This was determined by means of flash chromatography Silica gel cleaned with hexane / ethyl acetate, with 2.3 g of product as a yellow Solid with a melting point of 58 to 60 ° C were obtained.

Example 1 Production of 2- [2-methylphenoxymethyl] phenylthio-glyoxylic acid methyl ester-O-meth-yloxime (Verb. 24 Tab. 12)

10.2 g (33 mmol) of 2- [2-methylphenoxymethyl] phenylglyoxylic acid methyl ester-O-methyloxime in 50 ml of xylene are mixed with 16.6 g (41 mmol) of Lawesson's reagent. The mixture is heated under reflux for 24 hours and the solvent is removed in vacuo. Chromatography on silica gel with ethyl acetate / hexane gives 6.3 g (59%) of the compound 24 Table 3 as a black oil.
1 H-NMR (CDCl₃): δ = 2.27 (s, 3H), 4.03 (s, 3H), 4.19 (s, 3H), 4.95 (s, 2H), 6.78-7 , 61 ppm (m, 8H).

Example 2 Preparation of 2- (2-methylphenoxymethyl) phenyldithio-glyoxylic acid methyl ester-O-methyloxime (Verb. 24 Tab. 3)

A solution of 5 g (15 mmol) of 2- (2-methylphenoxymethyl) -phenylthio-glyoxylic acid methyl ester-O-methyloxime in 20 ml of toluene is mixed with 3.6 g (9 mmol) of Lawesson's reagent. The mixture is heated under reflux for 24 hours and concentrated. The residue is chromatographed on silica gel with ethyl acetate / hexane. 2.8 g (54%) of compound 24 Table 12 are obtained as a black oil.
1 H-NMR (CDCl₃): δ = 2.25 (s, 3H), 2.60 (s, 3H), 4.02 (s, 3H), 4.91 (s, 2H), 6.78-7.61 ppm (m, 8H).

Similarly, those listed in the following tables Connections are obtained:  

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

Table 14

Table 15

Table 16

Table 17

Table 18

The new compounds are suitable as fungicides.

The new fungicidal compounds or the compositions containing them can for example in the form of directly sprayable solutions, powders, Sus pensions, including high-proof aqueous, oily or other suspensions sions or dispersions, emulsions, oil dispersions, pastes, dusts means, sprinkling agents or granules by spraying, atomizing, ver dusting, scattering or pouring can be used. The application forms depend on the purposes; they should be possible in any case the finest possible distribution of the active ingredients according to the invention Afford.

Usually the plants are sprayed with the active ingredients or pollinated or treated the seeds of the plants with the active ingredients.

The formulations are prepared in a known manner, e.g. B. by Stretching the active ingredient with solvents and / or carriers, if desired, using emulsifiers or dispersants means, but in the case of water as a diluent also other orga African solvents can be used as auxiliary solvents. As Auxiliaries are essentially considered here: solvents such as Aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. Cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, Chalk) and synthetic stone powder (e.g. highly disperse silica, Silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquor and methyl cellulose.

The alkali, alkaline earth, ammonium salts come as surface-active substances of aromatic sulfonic acids, e.g. B. lignin, phenol, naphthalene and di butylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its deri vate with formaldehyde, condensation products of naphthalene or naphtha thalin sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, Tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, Polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite liquor or methyl cellulose in Consider.  

Powders, materials for spreading and dusts can be mixed or combined Grinding the active substances with a solid carrier be put.

Granules, e.g. B. coating, impregnation and homogeneous granules by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica gel, silica, and pebbles gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, Dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ge ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, Tree bark, wood and nutshell flour, cellulose powder or other solid Carriers.

Examples of such preparations are:

• I. a solution of 90 parts by weight of compound no Table 3 and 10 parts by weight of N-methyl-α-pyrrolidone, the An application in the form of tiny drops is suitable;
• II. A mixture of 20 parts by weight of compound no Table 12, 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-mono ethanolamide, 5 parts by weight of calcium salt of the dodecylbenzenesulfone acid, 5 parts by weight of the adduct and 40 mol of ethylene oxide on 1 mol castor oil; by finely distributing the solution in Water gives a dispersion.
• III. an aqueous dispersion of 20 parts by weight of compound no. 24 from Table 3, 40 parts by weight of cyclohexanone, 30 parts by weight of iso butanol, 20 parts by weight of the adduct of 40 mol Ethylene oxide in 1 mol castor oil;
• IV. An aqueous dispersion of 20 parts by weight of compound no. 24 from Table 12, 25 parts by weight of cyclohexanol, 65 parts by weight of one Mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil oil;
• V. a mixture of 80 parts by weight ground in a hammer mill Compound No. 24 from Table 3, 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of Sodium salt of a lignin sulfonic acid from a sulfite waste liquor and  7 parts by weight of powdered silica gel; by fine Ver dividing the mixture into water gives a spray mixture;
• VI. an intimate mixture of 3 parts by weight of compound no Tables 12 and 97 parts by weight of finely divided kaolin; this dust medium contains 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of compound no Table 3, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil on the surface of this pebble acid gel was sprayed; this preparation gives the active ingredient good adhesion;
• VIII. A stable aqueous dispersion of 40 parts by weight of the compound No. 24 from Table 12, 10 parts by weight of the sodium salt one Phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight Silica gel and 48 parts by weight of water, which are further diluted can;
• IX. a stable oily dispersion of 20 parts by weight of the compound No. 24 from Table 3, 2 parts by weight of the calcium salt of Dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid urea-formaldehyde condensate and 68 parts by weight of one paraffinic mineral oil.

The new compounds are characterized by excellent effectiveness against a wide range of phytopathogenic fungi, especially from the class of Ascomycetes and Basidiomycetes. They are partly systemically effective and can be used as leaf and soil fungicides will.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, Corn, grass, cotton, soy, coffee, sugar cane, wine, fruit and ornaments plants and vegetables such as cucumber, beans and squash, as well on the seeds of these plants.

The compounds are applied by looking at the mushrooms or the front Fungus to protect seeds, plants, materials or the Soil treated with a fungicidally effective amount of the active ingredients.

The application takes place before or after the infection of the materials, Plants or seeds through the mushrooms.  

The compounds I are particularly suitable for controlling the following plants Diseases:

Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Pososphaera leucotricha on apples,
Uncinula necator on vines,
Puccinia species on cereals,
Rhizoctonia species on cotton and lawn,
Ustilago species on cereals and sugar cane,
Venturia inaequalis (scab) on apples,
Helminthosporium species on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, vines,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes,
Fusarium and Verticillium species on different plants,
Plasmopara viticola on vines,
Alternaria species in vegetables and fruits.

The new connections can also be used in material protection (wood protection) be set, e.g. B. against Paecilomyces variotii.

The fungicidal compositions generally contain between 0.1 and 95 preferably between 0.5 and 90 wt .-% active ingredient.

Depending on the type of effect desired, the application rates are between 0.02 and 3 kg of active ingredient per ha.

In the seed treatment, amounts of active ingredient are generally 0.001 up to 50 g, preferably 0.01 to 10 g per kilogram of seed is required.

The agents according to the invention can be used as fungicides also be present together with other active ingredients, the z. B. with herbicides, Insecticides, growth regulators, fungicides or even with fertilizers.

When mixed with fungicides, you get one in many cases Enlargement of the fungicidal spectrum of activity.

The following list of fungicides with which the Ver bindings can be used together, the combination explain the possibilities, but do not restrict them:

Sulfur,
Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthiuram disulfide, ammonia-complex-dith-ammonium-dithi-ammonium-dithi-ammonium-complex-dith-ammonium-complex-dith-ammonium-dithi-ammonium-complex-dit-ammonium-complex-dit-ammonium-complex-dit-ammonium-dithi-ammonium-complex-di- (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl) disulfide; Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate, 5-nitro -isophthalic acid di-isopropyl ester; heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- ( dimethylamino) -phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (Butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,1,2,2 -Tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3 thiadiazole, 2-rhodanmethylthiobenzthiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2 -Methyl-5, 6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N- Formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis- (1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1 -formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p -tert.-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine-, N- [3- (p-tert.-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-t-riazole, 1- [2- (2,4-dichlorophenyl) -4- n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N ′ -imidazol-yl-urea-, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H -1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, - α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p -chlorophenyl) -3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, and various fungicides, such as dodecylguanidine acetate , 3- [3- (3,5-Dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) - alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone , DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine , 3- [3,5-dichlorophenyl- (5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-d-ion, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid d, - 2-Cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4 -Difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chlorine -2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Claims (7)

1. Thiocarboxylic acid esters of the general formula I in which the substituents have the following meaning:
X oxygen, sulfur, oxymethylene, methyleneoxy, thiomethylene, methylene thio, ethylene, ethenylene or ethynylene,
Z oxygen or sulfur
R C₁-C₆-alkyl, mono-, dinuclear or trinuclear aryl or heteroaryl, where aryl and heteroaryl can carry the following radicals R¹:
R¹ halogen, cyano, nitro, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, trifluoromethyl, mono- or dinuclear aryloxy or mono-, dinuclear or trinuclear aryl, aryloxy and aryl in turn by the aforementioned R¹ radicals can be substituted. 2. Process for the preparation of thiocarboxylic acid esters of the formula I. in which the substituents have the following meaning:
X oxygen, sulfur, oxymethylene, methyleneoxy, thiomethylene, methylene thio, ethylene, ethenylene or ethynylene,
Z oxygen or sulfur,
R C₁-C₆-alkyl, mono-, dinuclear or trinuclear aryl or heteroaryl, where aryl and heteroaryl can carry the following radicals R¹:
R¹ halogen, cyano, nitro, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, trifluoromethyl, mono- or dinuclear aryloxy or mono-, dinuclear or trinuclear aryl, aryloxy and aryl in turn by the aforementioned Radicals R 1 can be substituted,
characterized in that a carboxylic acid or thiol carbonate of the formula II in a manner known per se with a sulfurizing agent to give the thio carboxylic esters I. 3. Fungicidal compositions comprising a fungicidally effective amount of a thiocarboxylic acid ester of the formula I. in which the substituents have the following meaning:
X oxygen, sulfur, oxymethylene, methyleneoxy, thiomethylene, methylene thio, ethylene, ethenylene or ethynylene,
Z oxygen or sulfur
R C₁-C₆-alkyl, mono-, dinuclear or trinuclear aryl or heteroaryl, where aryl and heteroaryl can carry the following radicals R¹:
R¹ halogen, cyano, nitro, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, trifluoromethyl, mono- or dinuclear aryloxy or mono-, dinuclear or trinuclear aryl, aryloxy and aryl in turn by the aforementioned R¹ radicals can be substituted
and usual additives. 4. A method for combating harmful fungi, characterized in that the fungi or the plants, seeds, materials or areas threatened by fungal attack with a fungicidally effective amount of a thiocarboxylic acid ester of the formula I. treated in which the substituents have the following meaning:
X oxygen, sulfur, oxymethylene, methyleneoxy, thiomethylene, methylene thio, ethylene, ethenylene or ethynylene,
Z oxygen or sulfur,
R C₁-C₆-alkyl, mono-, dinuclear or trinuclear aryl or heteroaryl, where aryl and heteroaryl can carry the following radicals R¹:
R¹ halogen, cyano, nitro, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, trifluoromethyl, mono- or dinuclear aryloxy or mono-, dinuclear or trinuclear aryl, aryloxy and aryl in turn by the aforementioned R¹ radicals can be substituted. 5. A compound of formula I according to claim 1, in which R 2-methylphenyl, X Methyleneoxy and Z mean oxygen. 6. A compound of formula I according to claim 1, in which R 2-methylphenyl, X Methyleneoxy and Z mean sulfur. 7. A compound of formula I according to claim 1, in which R 2-chlorophenyl, X Methylenthio and Z mean oxygen.