WO1997023471A1

WO1997023471A1 - 5-difluoromethoxy-3-aryl-1,2,4-thiadiazol derivatives, their preparation and their use as nematicide agents

Info

Publication number: WO1997023471A1
Application number: PCT/EP1996/005520
Authority: WO
Inventors: Ralf Klintz; Reinhard Kirstgen; Hartmann König; Michael Rack; Gerhard Hamprecht; Peter Schäfer; Elisabeth Heistracher; Cyrill Zagar; Volker Harries; Jacobus Jan De Kramer
Original assignee: Basf Aktiengesellschaft
Priority date: 1995-12-21
Filing date: 1996-12-11
Publication date: 1997-07-03
Also published as: DE19547882A1

Abstract

Thiadiazols have the formula (I), in which the index and the substituents have the following meaning: n equals 1, 2, 3, 4 or 5, whereas the R substituents may differ from each other when n is higher than 1; R stands for alkyl, alkenyl or alkinyl, nitro, cyano, halogen, C1-C4-alkyl halide, C1-C4-alkoxy, C1-C4-alkoxy halide, C1-C4-alkylthio, C1-C4-alkyl sulfonyl, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl and when n ⊃ 1 a 1,3-butadien-1,4-yl or oxy-(C1-C2-alkylidene)-oxy group bonded to two adjacent C atoms of the phenyl radical, whereas said group may be partially or completely halogenated. Also disclosed is a process for preparing these compounds, mixtures containing the same and their use for controlling nematodes.

Description

5-DIFLU0RMETH0XY-3-ARYL-l, 2, 4-THIADIAZ0L DERIVATIVES, THEIR PRODUCTION AND THE USE THEREOF AS A NEMATICIDE AGENT.

5 Description

The present invention relates to thiadiazoles of the formula I.

in which the index and the substituents have the following meaning:

n is 0, 1, 2, 3, 4 or 5, where the substituents R can be different if n is greater than 1;

20 R alkyl, alkenyl or alkynyl, nitro, cyano, halogen,

Cχ-C ₄ haloalkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ haloalkoxy, Cι-C ₄ alkylthio, Cι-C ₄ alkylsulfonyl, Cι-C ₄ alkylcarbonyl, Cι-C ₄ alkoxycarbonyl and for n> l is a 1,3-butadien-1,4-yl- or bonded to two adjacent C atoms of the phenyl radical

25 an oxy- (-C ₂ alkylidene) -oxy group, which in turn can be partially or completely halogenated.

The invention also relates to processes for the preparation of these compounds, mixtures containing them and their use in combating nematodes.

JP 06100550-A discloses thiadiazoles with an insecticidal action. EP-A 273534 discloses specifically substituted thiazides which are suitable as pesticides. The action of these thiadiazoles against certain pests is not always satisfactory.

The present invention was therefore based on compounds with improved effects, in particular against nematodes.

Accordingly, the compounds I defined at the outset were found. Furthermore, processes for their preparation, mixtures containing them and processes for controlling nematodes 45 using compounds I have been found. The compounds I can be obtained by various methods known per se from the literature.

For example, the compounds I are obtained by reacting the derivative of the formula II with a 3-hydroxy-1,2,4-thiadiazole or the tautomeric 1,2,4-thiadiazolinone form of the formula III in the presence of a base.

L in formula II represents a nucleophilically exchangeable group, e.g. halogen, e.g. Chlorine, bromine and iodine, or an alkyl or aryl sulfonate, e.g. Methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate and 4-methylphenyl sulfonate.

The reaction is usually carried out at from 0 ° C. to the boiling point of the reaction mixture, preferably from 20 ° C. to 60 ° C.

Suitable solvents are water, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol, ketones such as acetone and methylethyl ketone and dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidine -2-one and l, 2-dimethyltetrahydro-2 (IH) - pyrimidine, preferably water, dioxane, methylene chloride, acetone and dimethylformamide. Mixtures of the solvents mentioned can also be used.

Basically, inorganic compounds such as alkali metal and alkaline earth metal hydroxides (for example lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metal and alkaline earth metal oxides (for example lithium oxide, sodium oxide, calcium oxide and magnesium oxide), alkali metal and alkaline earth metal hydrides (for example lithium hydride) are generally used , Sodium hydride, potassium hydride and calcium hydride), alkali metal amides (for example lithium amide, sodium amide and potassium amide), alkali metal and alkaline earth metal carbonates (for example lithium carbonate, potassium carbonate and calcium carbonate) and alkali metal bicarbonates (for example sodium bicarbonate), organometallic compounds, in particular alkali metal alkyls (for example like methyl lithium, butyllithium and phenyllithium), alkylmagnesium halides (for example methylmagnesium chloride) and alkali metal and alkaline earth metal alcoholates (for example sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium), and also organic bases such as tertiary Trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines are considered.

Sodium hydroxide, potassium carbonate and potassium tert-butoxide are particularly preferred.

The bases are generally used in equimolar amounts, in excess or, if appropriate, as a solvent.

It may be advantageous for the reaction to add a catalytic amount of a crown ether (e.g. 18-crown-6 or 15-crown-5).

The reaction can also be carried out in two-phase systems consisting of a solution of alkali or alkaline earth metal hydroxides or carbonates in water and an organic phase (e.g. aromatic and / or halogenated hydrocarbons). Examples of phase transfer catalysts here are ammonium halides and tetrafluoroborates (e.g. benzyltriethylammonium chloride, benzyltributylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide or terabutylammonium tetrafluoroboridyl) and phosphonium halobutyl chloride (e.g. phosphonium halobutyl chloride) and, for example, phosphonium halobutyl chloride.

It may be advantageous for the reaction to first react the 3-hydroxy-1,2,4-thiadiazole with the base into the corresponding hydroxylate, which is then reacted with the derivative II.

In the definitions of the symbols given in the formulas above, collective terms were used which generally represent the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals, in particular with 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl , 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, Hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methyl- propyl and l-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above), these groups being able to partially or completely replace the hydrogen atoms by halogen atoms as mentioned above, for example C ₁ -C ₂ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl , Difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2 , 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, *

Alkoxy: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);

Haloalkoxy: straight-chain or branched alkyl groups with 1 to 4 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the structure via an oxygen atom;

Alkoxycarbonyl: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);

Alkylcarbonyl: straight-chain or branched alkyl groups with 1 to 4 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);

Alkylthio: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);

Alkylsulfonyl: straight-chain or branched alkyl groups with 1 to 4 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-S0 ₂ -);

Alkenyl: unsaturated straight-chain or branched hydrocarbon ^¬ radicals, in particular having 2 to 6 carbon atoms and a double bond in any position, for example ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2- Methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-l-butenyl, 3-methyl-l-butenyl, 1-methyl- 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl- 2-propenyl, 1,2-dimethyl-l-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3- Hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4- Methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, l, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl;

Alkynyl: straight-chain or branched hydrocarbon groups, in particular with 2 to 6 carbon atoms and a triple bond in any position, e.g. Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl- 2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2- Methyl-4-pentinyl, 3-methyl-1-pentinyl, 3-methyl-4-pentinyl, 4-methyl-l-pentinyl, 4-methyl-2-pentinyl, 1, l-dimethyl-2-butinyl, 1, l-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l- Ethyl 3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

Compounds of the general formula I in which the index and the substituents have the following meaning are preferred: n 1, 2 or 3,

R alkyl, -CC ₄ alkoxy, -C-C ₄ haloalkyl, C -.- C ₄ haloalkoxy or halogen.

5 Also preferred are compounds of the general formula I in which

n stands for 1, 2 or 3 and

R is alkyl, -CC ₄ -haloalkyl or halogen. 0

In addition, compounds of the general formula I are preferred in which

n is 1, 2 or 3 and 5 is R CH ₃ , CF ₃ , C ₂ F ₅ , F, Cl or Br.

Compounds of the general formula I with combinations of the preferred substituents are also preferred.

0 The compounds listed in Table 1 are very particularly preferred.

Table 1

Examples

Example 1: 3- ⁽ 4-chlorophenyl) -5-difluoromethoxy-1,2,4-thiadiazole

Sodium hydroxide (4.0 g dissolved in 50 ml of water) was added to a solution of 3- (4-chlorophenyl) -5-hydroxy-1,2,4-thiadiazole (4.3 g) in 100 ml of dioxane. Chlorine difluoromethane was then gassed in at 60-65 ° C. for 6 h, with sodium hydroxide (a total of 4.0 g in two portions) being added again. After cooling, the reaction mixture was extracted twice with 100 ml each of methyl tert-butyl ether. The combined organic phases were washed twice with water and dried over sodium sulfate. After removal of the solvent, the titanium compound was obtained (mp. 60-63 ° C.).

Connections shown analogously

Table 2

The 1,2,4-thiadiazoles of the formula I according to the invention are suitable for controlling animal pests from the class of the nematodes. They can be used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.

The class of nematodes includes, for example, root-gall nematodes, for example Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, for example Globodera pal- lida, Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera endoparachia -endoparasitic nematodes, for example Heliocotylenchus multicinc- tus, Hirschmanniella oryzae, Hoplolaimus spp, Pratylenchus bra- chyurus, Pratylenchus fallax, Pratylenchus penetrans, Pratylen¬ chus vulnus, Radopholus similis, Rotylenchus Terniformnematus, Scolipenuseniformans, Scolipenuseniformis, Scolipenus nematodes, Scolipenus bromiformes, Scoliformus nematodes, Scolipenus nematodes, Scol - eg Anguina tritici, Aphelenchoides besseyi, Ditylenchus angustus, Ditylenchus dipsaci, virus vectors, eg Longidorus spp, Trichodorus christei, Trichodorus viruliferus, Xiphinema index, Xiphinema mediterraneum.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the intended use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The new compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions,

Dusts, powders, pastes or granules. The application forms depend on the respective intended use; in any case, they should ensure the finest possible distribution of the active ingredients.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where, in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents.

The following are essentially considered as auxiliary substances:

- 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, clay, 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

Dispersing agents such as lignin sulfite leaching and methyl cellulose. The surface-active substances are the alkali, alkaline earth, and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols, as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl, or nonylphenol, or nonylphenol Tributylphenyl polyglycol ether, alkyl aryl 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 waste liquor or methyl cellulose.

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or old dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.

Solid carriers are mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. The active substance concentrations in the ready-to-use preparations can be varied over a wide range. In general, the agents contain between 0.0001 and 95% by weight of active ingredient.

Formulations with more than 95% by weight of active ingredient can be applied successfully with the ultra-low-volume process (ULV), and even the active ingredient can be used without additives.

Formulations with 0.0001 to 10% by weight, preferably 0.01 to 1% by weight of active ingredient are suitable for use in combating nematodes.

The active compounds are normally used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of such preparations are:

I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for use in the form of tiny drops;

II. A solution of 20 parts by weight of a compound I according to the invention in a mixture of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoetha- nolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil; a dispersion is obtained by finely distributing the formulation in water.

III. a solution of 20 parts by weight of a compound I according to the invention in a mixture of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isoctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil; A dispersion is obtained by finely distributing the formulation in water.

IV. An aqueous dispersion of 20 parts by weight of a compound I according to the invention, in a mixture of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of Addition product of 40 mol ethylene oxide to 1 mol Castor oil; A dispersion is obtained by finely distributing the formulation in water.

V. a mixture, milled in a hammer mill, of 20 parts by weight of a compound I according to the invention, 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite liquor and 60 parts by weight .- Share powdered silica gel; A spray liquor is obtained by finely distributing the mixture in water;

VI, an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of a compound I according to the invention, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which was sprayed onto the surface of this silica gel; this preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt of a phenosulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of a compound I, 2 parts by weight of the

Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil;

a mixture ground in a hammer mill from 10 parts by weight of a compound I according to the invention, 4 parts by weight of the sodium salt of diisobutyl-naphthalene-α-sulfonic acid, 20 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite liquor, 38 parts by weight . Parts of silica gel and 38 parts by weight of kaolin. By finely distributing the mixture in 10,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient. The application rate of active ingredient for controlling nematodes is 0.02 to 10, preferably 0.1 to 2.0 kg / ha of active ingredient under field conditions.

The compounds I, alone or in combination with herbicides or fungicides, can also be applied jointly with other crop protection agents, for example with growth regulators or with agents for controlling pests or bacteria. Also of interest is the miscibility with fertilizers or with mineral salt solutions which are used to remedy nutritional and trace element deficiencies.

The crop protection agents and fertilizers can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1, if appropriate also only immediately before use (tank mix). When mixed with fungicides or insecticides, the fungicidal spectrum of activity is increased in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain the possible combinations, but not to limit it:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylenediamin-bis-dithiocarbamate, tetramethylthiurium -diamid-dibi-ethamidulfide ), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thio- carbamoyl) disulfide; Nitroderivate, such as dinitro- (1-methyl-heptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitro-phenyl-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, 0.0-diethyl-phthalimidophosphonothioate, 5-amino-1-ß- tbis- (dimethylamino) phosphinyl] -3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo-ß- [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-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-rhodanmethylthiobenzthiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-l-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-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-dirnethyl-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-talc, piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide, 1- (3,4-dichloroanilino) -1-formylamino-2 , 2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cy-clodedecyl-morpholine or its salts, N- [3- (p -tert.-butylphenyl) -2-methylpropyl1 -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [ 2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-yl-ethyl] -lH-l, 2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) ) -N'-imidazol-yl-urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (lH-l, 2,4-triazol-l-yl) -2-butanone, 1 - (4-chlorophenoxy) -3,3-dimethyl-l- (lH-l, 2,4-triazol-l-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-pyridine-methanol, 1,2-bis- (3-ethoxy- carbonyl-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-dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine-methyl ester, N- (2,6-dimethylphenyl) -N -chloracetyl- D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylace tyl ^■) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlor¬ phenyl) -2,4-dioxo-l, 3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3, 5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-l, 2-dicarboxylic acid imide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino ] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-di-fluoro-α- (1H-l, 2,4-triazolyl -l-methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4th -Fluorophenyl) methylsilyl) methyl) -1 H-1,2,4-triazole.

Claims

1. Thiadiazoles of the formula I.

^Q

in which the index and the substituents have the following meaning:

n is 1, 2, 3, 4 or 5, where the substituents R can be different if n is greater than 1;

R alkyl, alkenyl or alkynyl, nitro, cyano, halogen, Cχ-C ₄ -haloalkyl, Cι-C ₄ -alkoxy, Cι-C ₄ -haloalkoxy, Cι-C ₄ -alkylthio, Cι-C ₄ -alkylsulfonyl, Cι- C ₄ -alkylcarbonyl, Cχ-C ₄ -alkoxycarbonyl and for n> l a 1,3-butadiene-l, 4-yl- or an oxy- (Cι-C. ₎ Bonded to two adjacent C atoms of the phenyl radical ₂ -Alkyliden) -oxy group, which in turn can be partially or completely halogenated.

2. thiadiazoles of the formula I according to claim 1, in which the index and the substituents have the following meaning:

n 1, 2 or 3

R alkyl, -CC ₄ alkoxy, C; _L -C ₄ haloalkyl, C -.- C ₄ haloalkoxy or halogen.

3. thiadiazoles of the formula I according to claim 1 or 2, in which the substituents have the following meaning:

R alkyl, -CC ₄ haloalkyl or halogen.

4. thiadiazoles of the formula I according to any one of claims 1 to 3, in which the substituents have the following meaning:

R CH ₃ , CF ₃ , C ₂ F ₅ , F, Cl or Br. A process for the preparation of the thiadiazoles of the formula I according to claim 1, characterized in that a compound of the formula II with a 3-hydroxy-1,2,4-thiadiazole or the tautomeric 1,2,4-thiadiazolinone of the formula III

converts to the thiadiazoles of the formula I in the presence of a base.

6. Mixture suitable for controlling nematodes, comprising an inert additive and an effective amount of a thiaziazole of the formula I according to claim 1.

7. A method for combating nematodes, characterized in that the nematodes, their habitat or the plants, surfaces, materials or spaces to be kept free of nematodes are treated with an effective amount of a thiadiazole of the formula I according to claim 1.

8. Use of the thiadiazoles of the formula I according to claim 1 for the preparation of a mixture suitable for controlling nematodes.

9. Use of the thiadiazoles of the formula I according to claim 1 for combating nematodes.