IE43695B1 - 2-substituted 5-trifluoromethyl-1,3,4-thiadiazoles and their use as fungicides and isecticides - Google Patents

Description

The present invention relates to certain new 2-substituted 5-trifluoromethyl-1,3,4-thiadiazoles, to a proeess for their preparation and to their use as fungicifes and insecticides.

It has already been disclosed that some 2-substituted thio-5-trifluoromethy1-1,3,4-thiadiazoles possess fungicidal properties (see U.'d.i’atent Specification 3,562,284). However, their activity is not always entirely satisfactory, especially when low amounts and low concentrations are Used. Insecticidal properties of these 1,3,4-thiadiazoles are not known.

The present invention provides, as new compounds, the 2-substituted 5-trifluoromethyl-1,3,4-thiadia2oles of the general formula (I) N —N in which H represents substituted alkyl, phenyl monosubstituted in the o- or m-position, polysubstituted phenyl, substituted phenylalkyl, optionally substituted phenylalkenyl, an optionally substituted 5-membered or 6-membered heterocyclic radical with 1 to 4 heteroatoms selected from N and S atoms, optionally substituted benzimidazolyl or benzthiazolyl, optionally substituted naphthyl, quinolyl, quinolyl-N-oxide, cyano or one of the groupings wherein 1 ’ H and if' conjointly represent a trimothylene, tetramethylene or pentamethylene group, X represents oxygen or sulphur, ii1 and it each represent alkyl or, together with the nitrogen atom and optionally further hetero-atoms selected from 0 and N atoms, form an optionally substituted 6-membered or 7-membered ring, and n is 0, 1 or 2, but must be 0 if R is -CX-NR'R, These compounds have been found to exhibit powerful fungicidal and insecticidal properties.

Preferably,it represents straight-chain or branched monosubstituted or polysubstituted alkyl with 1 to 6 carbon atoms, with preferred possible substituents being halogen (especially fluorine, chlorine or bromine ),cyano, isothiocyano, phenyl, carboxyl, alkylcarbonyl with 1 or 2 carbon atoms in the alkyl part, and phenylcarbonyl optionally substituted by halogen or C^-C^ alkyl; or represents phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part; or represents ohenyl monosubstituted in the ortho-position or meta-position, polysub3tituted phenyl wherein the substituents are identical or different, or monosubstituted or polysubstiruted - the substituents being identical or different - phenylalkyl with, in particular, 1 or 2 carbon atoms in the alkyl part, preferred possible substituents - 3 of phenyl in each case being alkyl with 1 to 4 carbon atoms, halogenoalkyl, halogenoalkylthio and halogenoalkylsulphonyl, each vzith 1 or 2 carbon atoms and 2 to 5 halogen atoms (especially fluorine), alkoxy, alkylcarbonyl and aikoxycarbonyl, each with 1 to 4 carbon atoms in the alkyl part, hydroxyl, carboxyl, nitro, cyano and thiocyano. Other preferred meanings of R are the following 5-membered and 6-membered heterocyclic structures; imidazol-2-yl, optionally substituted in the 1- and/or 4- and/or 5-position, with alkyl with 1 or 2 carbon atoms, optionally chlorine-substituted phenyl or nitro as substituents; thiazol-2-yl, optionally substituted in the 4- and/or 5-position, vzith alkyl vzith 1 or 2 carbon atoms, halogen or nitro as substituents; 1,2,4-thiadiazol-5-yl, optionally substituted in the 3-position, vzith alkyl or alkylthio vzith 1 to 4 carbon atoms as substituents; 1,3,4thiadiazol-5-yl, optionally substituted in the 2-position, with alkyl vzith 1 to 4 carbon atoms, amino, alkylcarbonyl, alkylamino and dialkylamino, as well as dialkylaminomethyleneimino and K,K! -dialkylureido, in each case with 1 or 2 carbon atoms in each alkyl part, optionally chlorine-substituted phenyl, alkylthio and alkylsulphonyl, in each case with 1 or 2 carbon atoms in the alkyl part, halogenoalkyl with 1 or 2 carbon atoms and 2 to 5 halogen atoms, and nitro, as possible substituents; tetrazole, optionally substituted by alkyl with 1 to 2 carbon atoms; thiophene, optionally substituted by nitro or halogen; pyridine, pyridine-N-oxide and pyrimidine, optionally substituted by alkyl vzith 1 or 2 carbon atoms or halogen; and thiazoline, tetrahydropyrimidine or tetrahydrothiazine, optionally substituted by methyl. Alternatively, R preferably represents benzimidazolyl and benzthiazolyl, optionally substituted in the benzo ring by halogen, - 4 4 3 6 8 5 especially chlorine, or alkoxy with 1 to 2 carbon atoms, or a grouping wherein ii1 and Ii1' conjointly represent a trimethylene or tetramethylene group; X represents oxygen or sulphur and R1 and ii represent alkyl with 1 or 2 carbon atoms, or form, with the N atom, a perhydrazepine, morpholine or N‘-hydroxyethyl-piperazine ring.

Furthermore, K may also preferably represent naphthyl which is optionally substituted by nitro, halogen or alkyl with 1 or 2 carbon atoms, quinolinyl, the quinolyl-N-oxide radical and cyano.

The present invention also provides a process for the preparation of a 2-substituted 5-trifluoromethyl-1,3,4thiadiazole of the general formula (I) in which (a) a 2-halogeno-5-trifluoromethyi-1 ,3,4-thiadiazole of the general formula in which ΐ represents chlorine or bromine, is reacted with a mercaptan of the general formula Ro - H (III), in which - 5 43693 R has the above-mentioned meaning in the presence of a diluent (which term herein includes a solvent) and of an acidbinding agent and, if required, the resultant 2-substituted -trifluoromethyl-1,5,4-thiadiazole of the general formula in which R has the above-mentioned meaning, is reacted with an oxidising agent (whereby, depending on the oxidising agent used, a compound of the formula (I) with n = or n = 2 is obtained), or (b) 2-mercapto-5-trifluoromethyl-1,3,4-thiadia2ole of the formula N-N K—NH li L CFr'^S-·^' (Va) (Vb) is reacted with a compound of the general formula Z - R (VI) in which R has the above-mentioned meaning and Z represents chlorine, bromine, iodine, methanesulphonyloxy or toluenesulphonyloxy, in the presence of a diluent and of an acidbinding agent and, if required, the resultant 2-substituted thio-5-trifluoromethy1-1,3,4-thiadiazole of the formula (IV) is reacted with an oxidising agent (whereby, depending on the oxidising agent, a compound of the formula (I) with n = or n = 2 is obtained), or - 6 (c) in the case of the preparation of a sulphonyl compound (wherein n = 2 in the formula (I)), a 2-halogeno-5-trifluoromethy1-1,3,4-thiadiazole of the general formula (II) is reacted in the presence of a diluent with a sulphinic acid of the general formula k-302H (VII), in which ft has the above-mentioned meaning, the sulphinic acid being used as such, in the presence of an inorganic cr organic base, or in the form of a corresponding 3ulphinate.

Surprisingly, the 2-substituted 5-trifluoromethyl1,3,4-thiadiazoles according to the invention exhibit a subtantially greater fungicidal and insecticidal action, especially a soil-insecticidal and development-inhibiting action, than the 2-substituted thio-5-trifluoromethyl1,3,4-thiadiazoles known from the state of the art which are chemically the nearest compounds. The compounds according to the invention thus represent an enrichment of the art.

If 2-bromo-5-trifluoromethyl-1,3,4-thiadiazole and 2-mercaptobenzolc acid are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation: COOH - 7 4 3 6 3 3 If 2-chloro-5-trifluoromethyl-1,3,4-thiadiazole and 2-mercaptopyrimidine are used as starting materials in process variant (a) and chlorine is used as the oxidising agent, the course of the reaction can he represented by the following equation: CF N — N ,ark C1 -HCl N—Ν «-,. Cl^Io0 If 2-bro®o-5-trifluoromethyl-1,3,4-thiadiazole and. 3,5-dimethylthiophenol are used as starting materials in process variant (a) and hydrogen peroxide is used as the oxidising agent, the course of the reaction can be represented by the follovzing equation: N — N CFj As-^-Br -> -HBr H?O„/glacial aSetic acid - 8 4 3 6 3 5 If 2-mercapto-5-trifluoromethyl-1,3,4-thiadiazole and 2-bromo-5-nitro-thiophene are used as starting materials in process variant (b), the course of the reaction oan be represented by the following equation: CF'3 If 2-bromo-5-trifluoromethy1-1,3,4-thiadiazole and naphthalene-2-sulphinic acid, in the presence of sodium hydroxide, are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation: The 2-halogeno-5-trifluoromethyl-1,3,4-thiadiazole of the formula (11) used as the starting material for process variant (a) is already known (see German Offenlegunga15 schrift (German Published Specification) 2,162,575 and J.Het.

Chem. 11.» 343-45 (1974)). It is obtained analogously to a metnod described by Kanaoka (see Pharmaceutical Bulletin £, 385-389 (1957)) by diazotisation of the corresponding 2-amino-thiadiazole (for its preparation, see J.Het.Chem. 2.1 336-37 (1966)). Surprisingly, it has been found that the reaction described there (Sandmeyer reaction) takes - 9 place spontaneously, in high yields, even at temperatures of -5° to + 15°C and without the customary addition of copper salts.

The mercaptans which can be used according to the invention are in some cases known from Houben-Weyl, volume ,2, pages 7-48 (1955) and U.S.Patent Specification 3,798,229; they can, in any case, easily be prepared in accordance with the processes described there. Thus, for example, the aromatic mercaptans are obtained by reaction of the corresponding sulphoehloides with zinc and sulphuric acid (see also the preparative examples herein). To prepare the aliphatic and araliphatic mercaptans, for example, the corresponding bromides are heated with thiourea in ethanol under reflux, and the isothiuronium salts produced are decomposed with aqueous alkali metal hydroxide solution; the mercaptans can then be isolated by customary methods.

The following may be mentioned as examples of mercaptans of the formula (III) which can be used according to the invention: 4-mercapto-valeric acid ethyl ester, triphenylmethylmercaptan, 2-chloro-ethylmercaptan, 3-phenyl-allylmercaptan, p-methylphenacylmercaptan, 2,6-dichloro-phenylmercaptan, 2-mercaptoquinoline-N-oxide, 4-chloro-3-methyl-phenylmercaptan, 1,4-bis-mercaptomethylbenzene, 4-nitro-benzylmercaptan, pentafluoro-phenylmercaptan, 2-ethoxy-phenylmercaptan, 2-isopropylthio-5mercapto-1,3,4-thiadiazole, 4-trifluoromethoxy-benzylmercaptan, 5-chloi’o-2~mereapto-naphthalene and 4-chloro2-mercapto-pyridine-H-oxide„ The 2-mercapto-5-trifluoromethyl-1,3,4-thiadiazole of the formula (V) used as the starting material for process variant (b) is already known (see German Offenlegungs- 10 schrift (German Publish··:! .jpucification; 2,162,575)· It is ob taint'd by reaction of ;’-bromo-5-trifluoromethyl-1 ,3,4-thiadiaooif of th' formula (II) with thiourea in boiling ethanol, followed by treatment with sodium hydroxide soiution, The compounds of the formula (VI) which can be used according to the invention are compounds generally known in organic chemistry, and can te prepared in accordance with simple known methods. The following may te mentioned as examples: ?, 4-dinitrofluoroben/,ene, 2-iodo-l-methyl-5-nitroimidazole, 1-(2-chloroethyl)-?-!»·thyl-5-nitroimida-zolu, ?-bromo-5-nitro-1,3,4-thiadjaz.ol··, 5-«hi0ro-3-methylni(;rcapto-1,2,4-thiadiazole, N,Ndimi'thylcarbamoyl chloride,-, 4-nitrophenethyl bromide, chloromethylinothiocyanate, 2-bromcacetone, chloroacetonitrile, is 2,4,5-trichlorothiazole, 1,1,1 -trifluoro-2-methanesulphonyloxyethane, 4-chloro-benzyl chloride, 1,3-bis-tolueneaulphonyloxypropane , 3,4,5-trichloronitrobenzene and 2-chlorometh.ylpyridine .

The sulphinic acids and sulphinates which can be used according to the invention are compounds generally known in organic chemistry, and can be prepared in accordance with simple, known methods, for example by reduction of the corresponding culphochlorides with alkali metal sulphites in water, in which case the more stable salts of the sulphinic acids can be employed directly, without isolation, for the further reaction (see Houben-Weyl, Hethoden der organischen Chemie (Methods of Organic Chemistry), volume j), 285-343 (1955), Georg Thieme Verlag dtuttgart).

The following may be mentioned as examples: nonafluoro30 butanesulphinate s, 3,4-dimethvlbenzylsulphinates, pyridine-311 'ό δ S 5 sulphinates, thiophene-3-sulphinates, 3-bromobenzenesulphinates 3,4,5-trichlorobenzenesulphinates, 3-bromo-4-nitrobenzenesulphinates, 2-fluorobenzenesulphinates, 6-chloro-naphthalene2-sulphinates, 2,3-dichlorobenzenesulphinates, bromomethylsulphinates, benzothiazole-2-sulphinates, 1,4-butane-disulphlnates, 2-methylbenzenesulphinates, 3-methyl-4-trifluoromethylthiobenzenesulphinates, 2-(4-chlorophenol)-Vinylsulphinates, 4-methylnaphthalene-2-sulphitiates and 2,4dimethoxybenzenesulphinates.

Preferred diluents for the reaction according to the invention, in accordance with process variant (a), are water and inert organic solvents, especially ketones, such as diethyl ketone, and, more especially, acetone and methyl ethyl ketone? nitriles, such as propionitrile and especially acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxan; hydrocarbons, such as ligroin, petroleum ether, benzene, toluene and xylene; chlorinated hydrocarbons, such as chloroform, carbon tetrachloride and methylene chloride; and formamides, such as, in particular, dimethylformamide.

The reaction according to process variant (a) is carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid acceptors usually employable, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarhonate; aliphatic, aromatic or heterocyclic amines, in particular tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethyiamine, dimethylbenzyl- and cyclohexylamine and such bases as pyridine and diazabicyclooctane? alkali metal alcoholates, for example sodium methylate and potassium ethylate; or alkali 3 6 3S metal hydroxides, for example sodium hydroxide and potassium hydroxide.

In process variant (a), the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at from 0° to 120°, preferably at 20° to 100°G. In the presence of a solvent, the reaction is suitably carried out at the boiling point of the particular solvent.

In carrying out process variant (a) preferably about 1<-* 1 moli? of the mercaptan of the formula (III) and about 1 mole of acid-binding agent are employed per mole of the compound of the formula (II).

To isolate the compounds of the formula (I), either the reaction mixture is poured onto ice water, the batch '5 filtered and the retained precipitate washed, if appropriate, and dried, or the reaction mixture is washed with water and the organic phase is separated off, dried and freed from tbe solvent, or the salt (by-product) which has precipitated is filtered off and the reaction product is isolated from the filtrate. The reaction products can, if desired, be purified by reerystallisation or distillation.

In accordance with process variant (a), the compounds of the formula (IV), thus obtained, can then be oxidised.

All inorganic and organic oxidising agents which can usually be employed may be considered, such as chlorine in water, per-acids, for example m-chloroperbenzoic acid, hydrogen peroxide in glacial acetic acid or in methanol, potassium permanganate and chromic acid.

The reaction temperatures for the oxidation according to process variant (a) can be varied within a fairly wide range „ In general, the reaction is carried out at - 13 4 3 6 3 3 between -30° and. +100°C, preferably at -10° to 80°C.

In carrying out the oxidation according to process variant (a), 1 to 4 moles of oxidising agent are generally employed per mole of the compound of the formula (IV). When using 1 mole of oxidising agent, such as m-chloroperbenzoic acid in methylene chloride, or hydrogen peroxide in acetic anhydride, at temperatures between -10 and +10°G, the compounds of the formula (1) wherein n = 1 arc produced preferentially. If an excess of oxidising agent and higher temperatures (say 10° to 80°C) are used, the compounds of the formula (I) wherein n = 2 are produced preferentially.

To isolate the oxidation products, either the reaction mixture is poured onto ice water, the batch filtered and the retained precipitate washed, if appropriate, and. dried, or the reaction solution is brought to pH 7 to 8 and extracted with an organic solvent, the extracted phase is dried and the solvent is distilled off. In both cases the reaction products can be purified by recrystallisation or column chromatography.

Preferred diluents for the reaction according to the invention, in accordance with process variant (b), include water and polar organic solvents, especially nitriles, such as acetonitrile; sulphoxides, such as dimethylsulphoxide; formamides, such as dimethylformamide; ketones, such as acetone; ethers, such as diethyl ether and tetrahydrofuran; and chlorohydrocarbons, such as methylene chloride and chloroform.

The reaction according to process variant (b) is carried out in the presence of an acid-binding agent, which is preferably selected from the inorganic or organic acidbinding agents already mentioned for process variant (a). - 14 4 3 ο 3 ο ΊΊΐι’ reaction ten pern tin·'·: a for proce;::': (b) correspond to those of proce;;,’ (a).

In carrying out the process variant (b) preferably about 1 mole of the halide of tho formula (VI) and about 1 mole of acid-binding agent are employed per mole of the compound of the formula (V).

The isolation of the compounds of the formula (1) is generally carried out in the same manner as that already described for process variant (a).

The conditions (oxidising agent, temperature range and isolation) of the optional oxidation in process variant (b) are the same as those already described for process variant (a). j.referred diluents for the reaction according to process variant (c) are those already mentioned for process variant (a).

The reaction according to process variant (c), if the sulphlnate is not used, is carried out in the presence of a base. It is possible to use all customary inorganic and organic bases, such as alkali metal hydroxides, for example sodium hydroxide and potassium hydroxide, or such as C^-C^ tertiary alkylamines, for example triethylamine.

The reaction temperatures for process variant (c) correspond to those of process (a).

In carrying out process variant (c), about 1 mole of the sulphinic acid of the foimula (VII) is generally employed per mole of the compound of the formula (II).

To isolate the compounds of the formula (I), the reaction mixture ia poured onto ice water and the batch is filtered. The retained precipitate is dried and purified - 15 4 3 δ 3 5 by recrystallisation.

The active compounds according to the invention exhibit a powerful fungitoxic and bacteriotoxic action. They do not damage crop plants in the concentrations required for combating fungi and bacteria. For these reasons, they are suitable for use as plant protection agents for combating fungi and bacteria. Fungitoxic agents are employed in plant protection for combating Archimycetes. Phycomycetes, Ascomvoetes. Basidiomycetes and Fungi Imperfect!.

The active compounds according to the invention have a broad spectrum of action and can be employed against parasitic fungi and. bacteria which attack above-ground parts of plants or attack the plants through the soil, and also against seed-borne pathogens. They exhibit a particularly good activity against, for example, species of Pythium, species Phytophthora. species of Fusarium, species of Fusicladium, Verticillium alboatrum. species of Botrytis. Cochllobolus miyabeanus and Phlalophora cinerescene. The compounds according to the invention are also active against cereal diseases, such as, for example, against bunt of wheat.

As plant protection agents, the active compounds according to the invention can be used for the treatment of seed and for the treatment of above-ground parts of plants.

The active compounds according to the invention furthermore exhibit a good insecticidal action, especially a powerful soil-insecticidal action. They furthermore exhibit a good development-inhibiting action on insects or spida?mites, by which action a development to the chrysalis or the sexually mature imagos is prevented. This action starts during the shedding of skin which is only typical of arthropods. In - 16 4 3 6 3 5 some cases the action ceases through several stages of development and only comes into play during the pupation or slipping sequences. The active compounds can therefore be used with good success for combating sucking and biting insects and Piptera.

To the sucking insects there belong in the main aphids such as the green peach aphid (Myzus persicae) and the bean aphid (Doralis fabae): scales, such as Aspidiotus hederae, Decanlum hesperidua and Pseudococcus maritimus; Thysanoptera, such as Hercinothrips femoralis; and bugs, such as the beet bug (Plesma quadrata) and. the bed bug (Oimex lectularius).

To the biting insects there belong in the main butterfly and moth caterpillars, such as Plutella maculipennis and Lymantria dispar; beetles, such as the granary weevil (Sitophilus granarius) and the Colorado beetle (Leptinotarsa deoemlineata). but also species living in the soil, such as the wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica); Orthoptera. such as the house cricket (Gryllus domesticus); termites, such as Reticulitermes: Hymenoptera. such as ants.

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster). fhe Mediterranean fruit fly (Oeratitis capitata), the house fly (Musca domestics) and mosquitoes, such as the yellow fever mosquito (Aedes t&S¥.PW · Tne active compounds according to the invention furthermore show good herbicidal and microbistatic actions when used, in appropriate amounts and concentrations.

The active compounds according to the present invention can be converted into the usual formulations, such as - 17 4 3 6 3 5 solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foamforming agents. In the case of the use.of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example Freon (trade mark).

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgita, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents - 18 4 3 6 0 SS include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can he present in the formulations as a mixture with other active compounds.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0,5 to 90 per cent.

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

The active compound concentrations in the ready-touse preparations can be varied within fairly wide ranges.

In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%, by weight.

In the t-eatment of seed, amounts of active compound of 0,001 to 50 g, preferably 0,01 to 10 g, per kg of seed are generally employed.

The active compounds can also be used with good success in the ultra-low volume (ULV) method, where it is possible to apply formulations of up to 95% active compound or even to use the active compound by itself. - 19 4 3 6 9 5 The present invention also provides a fungicidal or insecticidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating fungi or insects which comprises applying to the fungi or insects or to a habitat thereof a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by fungi or insects by being grown in areas in j vzhich immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture vzith a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

) The pesticidal activity of the present compound is illustrated by the following biotest Examples, Example A Eusicladium test (apple )/(protective) Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether rfater: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate vzas diluted with the stated amount of water which contained - 20 4 3o&5 thi’ stated amount of the emulsifier.

Young apole seedlings in the 4-6 leaf stage were «prayed with ths spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70%. They were then inoculated ’..ith an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendrlticum) and incubated for 13 hours in a humidity chamber at 18-20°G and. at. a relative atmospheric humidity of 100/. 1θ The plants were then brought into a greenhouse for days. days after inoculation, the infection of the seedlings was determined. The assessment data were converted to per cent infection. 0% means no infection; 100/ means that thu plants were totally infected.

The active compounds, the concentrations of the active compounds and the results can be 3een from the following table; Table A Fusicladium test (apple)/protective Active compound Infection in / at an active compound concentration of 0.00062/ FjjC^S-^SOa-^-Br 16 (known/ Ν— N F,C 'V' SO, -CH, -CH, -CH, -CH, gg (known) 4360S Table A (continued) Fusicladium test (apple)/protective Active compound Infection in % at an active compound concentration of 0,00062% 4 2 6 3 5 Tab J- e_A (continued) Fusicladium test (apple)/protsctive Active compound Infection in % at an active compound concentration of 0.00062% K — N Cl (70) N —N F3C S0a ~CH=CH-£^> (71) N — N Cl F5 C-'^S-J'-SO-^^-Cl (53) Example B Phytophthora test (tomatoes)/protective Solvent; 4.7 parts hy weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Aater: 95 parts by weight The amount of the active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated amount of the emulsifier.

Young tomato plants with 2 to 4 foliage leaves were β 3 S sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70%. The tomato plants were then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants were brought into a moist chamber with an atmospheric humidity of 100% and a temperature of 18-20°G.

After 5 days the infection of the tomato plants was determined. The assessment data were converted to per cent infection: 0% means no infection; 100% means that the plants were totally infected.

The active compound, the concentrations of the active compound and the results can be seen from the following table: Table B Phytophthora test (tomatoes)/protective Active compound Infection in % at an active compound concentration of 0.00156¾ FsC^S^S02-@-Br 35 (known) N —,Ν F3C Aft>--.eo5-CH2-CH2-CHz-CH3 gl (known) Table B (c ont inued) Phytophthora test (tomatoes)/protective Active compound Infection in % at an active compound concentration of 0.00156¾ N, . Fs C -¼ CHj SOg-c ϋ (3) CHj Ν— N F, C^S^SO.

CFj (69) NF.C^E Cl ~S0g~v ' (70) Cl N” N Fj CJ' S-^S02 -CH=CK-R (71) Ν — Ν N—N F,CJ''S^S-X^S^~SCH, (24) 14 Cl kL /Πλ (53) 4 Fsc s^so-f^y-ci Example C Mycelium growth test Nutrient medium used: parts by weight of agar-agar 200 parts by weight of potato decoction parts by weight of malt 15 parts by weight of dextrose parts by weight of peptone parts by weight of disodium hydrogen phosphate 0.3 part by weight of calcium nitrate Katie of solvent mixture to nutrient medium: parts by weight of solvent mixture 100 parts by weight of agar nutrient medium Composition of the solvent mixture: 0.19 part by weight of DM? or acetone 0.01 part by weight of emulsifier (alkylaryl polyglycol ether) 1.80 parts by weight of water The amount of active compound required for the desired active compound concentration in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which had been cooled to 42°0) and was then poured into Petri dishes of 9 cm diameter, Control plates to which the preparation had not been added were also set up.

When the nutrient medium had cooled and solidified, the plates were inoculated with the species of fungi stated in the table and incubated at about 21 °C.

Evaluation vzas carried out after 4-10 daj^ dependent 69 5 upon the speed of growth of the fungi, rfhen evaluation was carried out the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient medium. In the evaluation of the fungus growth, the following characteristic values were used: no fungus growth up to 3 very-strong inhibition of growth un to 5 medium inhibition of growth up to 7 slight inhibition of growth 9 growth equal to that of untreated control.

The active compounds, the active compound concentrations and the results can be seen from the following table: - 27 3 6 9 S Mycelium growth test Fungi onxioq.o'Bo uxdqqTqcio qjftfci SU9OSe.X9UT0 ‘BJoqciox'STiqj um^q.BoqT'B ®πΐτΐΐθτ^θΛ ΒΘΛΘΠτΟ stq.A^Q.ogr snuBaqaTcra snxoqofiqooQ UmTMBSUtf nm»iourvno umT^Bsn^ Oi o ft o ϋ 0) .5 •P o cu in tn σι in in Cd in tn Bioqqifclo 3-^Ψτ SU00G3vt0UT0 j ΒίόϊίϊοΐΒτμ^ umjq.Boqit ιιτητγγτοτ^^ο^ ΏΘ,ΣΰΐίτΟ s-r^Aaiotr 3πύ·βθςυ/τπι en-roqornooo aquATu umTj:Hsndx Ό φ ΰ ci •H -P Λ uiruxourfno um CvCBSTiir o o ·>—T P ω Q) P o fi •P ω O β r-l ?υ fi § § β flj Ή 0 ο Κ Ρμ·Η EH ω θ Ρ ο >5 g£ •Ρ β Oh Φ o o c *~ o O II •P ϋ tin co in Table G (conti nued) Mycelium growth test Fungi in in in tn in tn cn tn in c\j cn CJ o w '*-<· ω 55-J I w S5=/ - 3o o «1 a. 43693 uma:oq.OBO ΰΰόϊΰφίοϊΧΐΰ •ri νϋ g „-£ su9osou:©uto τ3αοηαογΐϊΐΐΗ tn IA in ratuq.'BOqTis ΐΐτηχχτοτ^Χθ^ cn in in ΒΘΛΘίίτΟ STqXnog Cd in snuOoqHZ/ΰΰ sn^oqox^qooo p οχυΛΧίχ «Η •P d -JJ U) urn r j'ssnjf ό um.iouixno •P umpresn^ o x: P S «) rQ g § c (ti •H o o H Qt«H Eh ω a +> ι o O Hi 1 ϊ>> o in a Pt -P p. ¢) ΰ p f> P •Η Ο O -Ρ Ρ τΟ o < O II CT* cn cn O ft £ O O 0) ί> •r) -P O φ U 3 rnnjoq.o-eo susobsjbu^o BJoqaoTBTX{j nnug/Boetpe 1 Oj I tn i αιητιγτοτίμιθΑ ‘SSJBUTO in in Βηχο^οτχχ{οοο ω ρ •H «Ρ β o o βγΒΔΤΧΙ amxaBsnj πηυοωχηο tn p w φ p Jm p js umxjBsnj β o o ft-H 0P o ce OM g P ft Φ P P > Φ •H OO P Cro o < o II n T3 o ft B o Φ }> CM <· rp ι \ 2* S-ϋ =< ai CO tn vd - 32 tm.ioq.oigo! BJoqqqdo’iktH SUOOSOvEOUTO I BioqdOTBifUd umuqBoqi'B Μητχιτογ^αοΛ •rt hp οοαοοτο Γχ* sxqAaiog OnUBOQBAflU sntoqox-pPOD Ip, K\ tn tn tn rt φ G •rt •P otvatu in in C4 4-3 ω 0) •P ϊΐτη^οσΓ^ηο umTJBsn^ in oj φ H X! oi E4 P o Ph to •rl rH Φ o Pb o o Oi •rt a -P o ϋ s a •P Pi Φ Pi S> Φ •rt ο σ •P α V ϋ ο ο η C*w tn in tn <· Example ΰ Seed dressing test/bunt of wheat (seed-borne mycosis) To produce a suitable dry dressing, the active compound was extended with a mixture of equal parts by weight of talc and kieselguhr to give a finely powdered mixture with the desired concentration of the active compound.

Wheat seed, was contaminated with 5 g of the chlamydospores of Tilletia caries per kg of seed. To apply the dressing, the seed was shaken with the dressing in a closed glass flask. The seed, on moist loam under a cover of a layer of muslin and 2 m of moist compost soil, was exposed to optimum germination conditions for the spores for 10 days at 10°C in a refrigerator.

The germination of the spores on the wheat grains, each of which was contaminated with about 100,000 spores, was subsequently determined microscopically. The smaller the number of spores which had germinated, the more effective was the active compound.

The active compounds, the concentrations of the active compounds in the dressing, the amounts of dressing used and the percentage spore germination can be seen from the following table; - 34 4 ii 6 9 5 c o •rt +3 £3 uL o rt ft O £ '0 tO-rt in O in o o c •rt Ό rD O n> Ό Λ5 O CJ -Ρ -rt OOO β CO O «3 s ω deed dressing test/bunt of whea· t.3 I •rt £ 0 0 £ ϋ o c~< i>3 Tj P P £ w< O Ή ft £ β £ •rt o O o •rt P £ o rf •rt > Js to •rt P co •P £ a; ϋ 0 P 0 rd in CJ in m m cj in cj xi o ft a o o o > •rt -P ϋ CG ω o in *d -p ΰ o •p •rt ta o •m ffi O ι Al £ ffi o J zS, CM a V O J CM o O ca ca £ £ ox ' I'=\ M I w -fSd O o *) Kl fo fo fo O I J? ω U5 o cu ν C? SS co « ο •Η •Ρ tfl rf ο. α) α CO ttbrl in Ο Ο ιη Ο Ο tt? •3 to Ch 0] ο φ ίπ tt) Ό Λί «Η U0 0 Ρ rf Η § Ό Ο Φ Φ S 03 Φ •5 rf 03 Ρ Ρ Λ co tt φ I •Η ρ « Φ Ο »5 tiO φ φ rf Λ Ή TJP rQ 03 rt (0 3 ΰ <5 o'* Ο -Η ft £ rf Ο Ο ϋ Ή ._, φ-£·3] > μ ω •Η -Ρ 03 ρ rf ω ϋ Φ ?Η <ή ϋ'd ιηο ιη OJ νin C\! ιη ιη CM OJ tt co •rf ο ft I ϋ φ ί> •Η Ρ ϋ <ί Q ο γ*° fa Example 1·.

Critical concentration test/soil insects Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglyeol ether To produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with the soil. Tho concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight of active compound per unit volume of soil, which is quoted hereinafter in ppm (=mg/l). The soil was filled into pots and the pots were left to stand at room temperature.

After 24 hours the test insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and live test insects. The degree of effectiveness is 100% if all the test insects had been killed and is 0% if exactly as many test insects were still alive as in the case of the untreated control.

The active compounds, amounts used and results can be seen from the table which follows: - 37 Table fi Soil insecticides Tenebrio molitor larvae in the soil Active compound Active com- Degree of pound con- destruction centration in % in ppm Κ—(N F3 C A S^SOj -^j^-βγ (known) F3C N,—N -U S0aCH2CHs CHeCH, (known) 100 100 (32) 4 3 6 0 S The Examples F and 0 given in the text which follows show the action of the compounds according to the invention in inhibiting the development of arthropods, without it being wished to impose a limitation with regard to the breadth of action of these compounds. Luring the entire stated development of the test animals, the morphological changes, such as half-pupated animals, incompletely slipped larvae or caterpillars, defective wings and pupal cuticles in imagos, as well as the mortality,we re assessed. The sum of the morphological malformations and of the destruction during development is shown as a percentage of the test animals employed.

Example F Development-inhibiting action/ingestion test Test animals ;Plutella maculipennis (caterpillars, Feed plants solvent Emulsifier 4th stage), 20 individuals Phaedon cochleariae (larvae), 20 individuals :Cabbage plants (Brassica oleracea) :10 parts hy weight of acetone :2.5 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, parts by weight of active compound were mixed with the stated amount of solvent and emulsifier and sufficient water to give a 1% strength mixture, which was diluted with water to the desired concentration.

The test animals were fed with leaves of the feed plant, which were provided with a uniform spray coating of the active compound mixture, of the stated concentration, until - 39 3 Ώ D ΐ) the imago developed..

For control, the animals were fed with leaves treated only with solvent and emulsifier of the stated concentration The results can be seen from the table which follows: Table F Development-inhibiting action/ingestion test Active compound Inhibition of development in % at an active compound concentration of 0.01% Plutella Phaedon FscAs/-S08-@-N020 20 (known) F3C-Vs/h3O2-CH=CH-^2^ 100 40 (71 ) (77) 100 100 - 40 43633 Example 0 Development-inhibiting action/Laphygma test Test animals Feed Solvent Emulsifier : Laphygma exigua (caterpillars) : 1 cm thick discs, of 3 cm diameter, of airdried synthetic feed consisting of shredded bean seeds, yeast, vitamin mixture, powdered leaves, agar and preservative : 10 parts by weight of acetone : 2.5 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, parts by weight of active compound were mixed with the stated amount, of solvent and emulsifier and sufficient water to give a 1/- strength mixture, which was diluted with water to the desired concentration.

Test animals were placed each on a separate feed disc moistened with 1.2 ml of active compound solution of the stated concentration and observed until the imago slipped.

As a control, test animals were placed each on a separate feed disc moistened with 1.2 ml of solvent and emulsifier of the corresponding concentration and observed until the imago slipped. The results can be seen from the table which follows: Λ 3 δ & 5 Table G Development-inhibiting action/laphygma test Active compound Inhibition of development in % at an active compound concentration of 0.1% 0.01% '2 (known) The process according to the present invention is illust rated by the following preparative Examples: Example 1 (process variant (a)) Ν— M •Cl (1) Cl 130.5 g (0.66 mole) of 2-bromo-5-trifluoromethyl-1,3,4thiadiazole were added dropwise to a solution of 98.1 g (0,66 mole) of 3,4-dichloro-thiophenol and 57.6 g (0.66 mole) of triethylamine in 5θ0 ml of ethanol. An exothermic effect was observed and a white precipitate separated out. The mixture was stirred for a further 2 hours under reflux, concentrated to half in vacuo and introduced into 1 litre of ice water. The white precipitate was filtered off, dried over phosphorus pentoxide and recrystaliised from about 300 ml of petroleum ether. 147 g (76% of theory) of 2-(31,4’dichlorophenylthio)-5-trifluoromethyl-1,3,4-thiadiazole of melting point 46°0 were obtained. - 42 4 3 6 3 3 Preparation of the starting material; (a) A solution of 69 g (1.0 mole) of sodium nitrite in 150 ml of water wa3 added dropwise over the course of 1.5 hours, whilst stirring, to a solution, cooled to +5 °C, of 84.5 g (0.5 mole) of 2-amino-5-trifluoromethy1-1 ,3,4-thiadiazole in a mixture of 400 ml of hydrogen bromide (48% strength) and 100 ml of water. Thereafter, the evolution of the nitrous guurjij and of the nitrogen was completed by stirring at 25°C (1 hour). The product separated out as a dark brown, heavy liquid and was abstracted from the reaction mixture by repeated extraction with a total of 500 ml of methylene chloride. After washing with 2 x 100 ml of water, drying over sodium sulphate ana careful distillation of the solvent, the residue was fractionated in vacuo through a short column. 101 g (87% of theory) of 2-bromo-5-trifluoromethyl-1,3,4thiadiazole of boiling point 55°O/1O mm Hg were obtained. (b) HS Cl Cl 37.5 g (0.15 mole) of 3,4-dichlorobenzenesulphochloride were added dropwise over the course of 30 minutes to a stirred mixture of 400 g of ice and 60 ml of concentrated sulphuric acid at 0°C. Thereafter, 54.5 g (0.84 g atom) of zinc dust were introduced in portions. The mixture wa3 stirred for 1 hour at room temperature and 6 hours under reflux. The thiophenol was steam-distilled, extracted with - 43 & 3 © S «5 chloroform and subsequently distilled in vacuo. 13.1 g (47% of theory) of 3,4-dichlorothiophenol of b.p. 114-115°θ/θ·θ8 mm Hg were obtained.

Sxample 2 (process variant (a) with oxidation); N—.N (2) CF. 22.6 g (0.223 mole) of triethylamine, 25 g (0.223 mole) of 2-mercapto-pyrimidine and 52,2 g (0.223 mole) of 2-bromo-5trifluoromethyl-1,3,4-thiadiazole in 250 ml of tetrahydrofuran were stirred for 3 hours under reflux, concentrated to half in vacuo and introduced into 500 ml of ice water. The precipitate was filtered off, dried and recrystallised from petroleum ether/ethyl acetate (3:1). 44.1 g (75% of theory) of 2-pyrimidyl-(2)-thio-5-trifluoromethyl-1,3,4-thiadiazole of melting point 102°0 were obtained. 31.9 g (0.121 mole) thereof were suspended in 30 ml of water. Chlorine was slowly passed in at 0° to 5°C until.the mixture was saturated, during which time a precipitate separated out. After 2 hours at 0°C, the mixture was adjusted to pH 8 with potassium carbonate solution and extracted with chloroform, the extract was concentrated and the residue was recrystallised from ethyl acetate. 17.4 g (51% of theory) of 2-pyrimidyl-(2)-sulphinyl 5-trifluoromethyl-1,3,4-thiadiazole of melting point 184°C were obtained.

Sxample 3 (process variant (a) with oxidation) (3) ΪΪ—N 'CHS - 44 fi.5 g (0.061 mole) of 3,5-dimethylthiophenol, 6.2 g (0.061 mole) of triethylamine and 14.5 g (0.061 mole) of 2bromo-5-trifluox’omethyl-1,3,4-thiadiazole in 150 mole of tetrahydrofuran were stirred for 30 minutes under reflux. The salt (by-product) which had precipitated was filtered off and washed thoroughly with tetrahydrofuran. After distilling off the solvent in vacuo. a colourless oil passed over on distillation. 16.8 g (95% of theory) of 2-(3',5'dimethylphenylthio)-5-trifluoromethyl-1,3,4-thiadiazole of I boiling point 107-108°C/10.2 nan Hg were ohtained. 22.8 g (0.201 mole) of hydrogen peroxide (30y strength) in 100 ml of glacial acetic acid were added thei’eto and the reaction mixture was stirred for 15 hours at 60°C, and poured onto ice water. The precipitate was filtered off and recrystallised from ethanol. 12.7 g (54% of theory) of 7-(3',5'-dimethylphenyl3ulphonyl)-5-trifluoromethyl-1,3,4thiadiazole of melting point 110°C were obtained.

Sxample 4 (process variant (b)) (4) A mixture of 18.6 g (0.1 mole) of 2-mercapto-5-trifluoromethyl-1,3,4-thiadiazole and 5.6 g (0.1 mole) of powdered potassium hydroxide in 100 ml of absolute dimethylformamiue va., stirred for 30 minutes. 20.8 g (0.1 mole) of 2-bromo-5~nitru-thiophene were added in a single portion.

The mixture was stirred for 3 hours at 50°C, diluted with watei· and extracted with methylene chloride and after drying the organic phase was evaporated over sodium sulphate.

Vacuum distillation gave 24.4 g of crude product of boiling - 45 4 3 6 S S> point 160-163°C/0.3 mm Hg, which was recrystallised from hexane/ethyl acetate (10:1). After further recrystallisation ether/petroleum ether (4:3), 17.3 g (55/ of theory) of pure 2-(5’-nitro-thiophen-2'-yl-thio)-5-trifIuoromethyl-1,3,4thiadiazole of melting point 57°C were obtained.

.Preparation of the starting material W—NH (Vb) CFj; SH (V) (Va) 699 g (3 moles) of 2-bromo-5-trifIuoromethyl-1,3,4thiadiazole and 248 g (3.3 moles) of thiourea in a mixture of 600 ml of ethanol and 75 ml of water Were heated for 2 hours under reflux. A solution of 223 g of potassium hydroxide in 2 litres of water was rapidly added dropwise to the reaction solution whilst it was still hot, and the mixture was once more heated under reflux, for 5 minutes. The cooled solution was adjusted to pH 5«with dilute hydrochloric acid and extracted repeatedly with methylene chloride. After drying and concentrating, the residue was recrystallised from a little petroleum ether. The mother liquor yielded further product. 330 g (59/ of theory) of 2-mercapto-5trifluoromethyl-1,3,4-thiadiazole of melting point 73°C were obtained.

Example 5 (process variant (b) with oxidation) CF: N—N AJCl S0.-CHBA (5) - 46 436S5 9.5 g (0.05 mole) of 2-mercapto-5-trifluorome1:hyl-1,3,4thiadiazole, 5.1 g (0.05 mole) of triethyiamine and 8.1 g (0.05 mole) of o-chlorobenzyl chloride in 80 ml of absolute ethanol were stirred for 2 hours under nitrogen at 50°C and then poured onto ice. The precipitate was filtered off and purified by low temperature crystallisation from petroleum ether. 10 g (64% of theory) of 2-(o-chlorobenzylthio)-5trifluoromethyl-1,5,4-thiadiazole of melting point 36-37°C were obtained. A solution of 9.8 g (0.048 mole) of m-chloroperbenzoie aeid (85% pure) in 85 ml of methylene chloride was added dropwise to 5 g (0.016 mole) of the above compound in 10 ml of methylene chloride. The mixture was stirred for 4.5 hours under reflux and then mixed successively with a solution of 6.4 g of sodium sulphite in a little water, followed by a solution of 2.7 g of sodium carbonate in a little water, and stirred thoroughly for 15 minutes. The organic phase, after concentration and recrystallisation from cyclohexane/ethyl acetate, gave colourless crystals. 4.8 g (87% of theory) of 2-(o-chlorobenzylsulphonyl)-5-trifluoromethyl-1,3,4-thiadiazole of melting point 103°C were obtained.

Example 6 (process variant (c))i i solution of 75.6 g (0.6 mole) of analytically pure sodium sulphite in 300 ml of water was pre-warmed to 60-70°C in a beaker. 122.8 g (0.5 mole) of 3,5-dichlorobenzenesulphochloride, and a solution of 40 g (1 mole) of sodium hydroxide - 47 i 3 6 3 5 in 200 ml of water were synchronously added dropwise from two dropping funnels in such a way tha- the pH value (measured with an electrode in the reaction solution) was always between 7 and 9; during the addition the mixture was stirred magnetically. The saline solution of the 3,5-dichlorobenzenesulphinate (about 600 ml) was then diluted with 1.8 litries of dimethylformamide and after adding 116.5 g (0.5 mole) of 2-bormo-5-trifluoromethyl-1,3,4-thiadiazole the whole was stirred for 15 hours at 50°C. The sulphone was precipitated completely by adding ice water and was recrystallised from ethanol. 121 g (70% of theory) of 2-(31,5'-dichlorophenylsulphonyl )-5-trifluoromethy1-1,3,4-thiadiazole of melting point 123°C were obtained.

Preparation of the sulphoohloride Cl —SO.

‘Cl 40.5 g (0.25 mole) of 3,5-dichloroaniline were dissolved in a mixture of 110 ml of glacial acetic acid and 135 ml of concentrated hydrochloric acid, A solution of 17.7 g (0.256 mole) of sodium nitrite in 35 ml of water was metered in under the surface of the reaction solution, whilst stirring at 0 to 5°C, in such a way that no nitrous gases were evolved. At the same time, a saturated solution of sulphur iioxide in 140 ml of glacial acetic acid was prepared and introduced, together with 4 g of copper(I) chloride into a 2 litre vessel. The diazotised solution was introduced in portions (foaming occurred) and when the evolution of nitrogen had subsided, the mixture was diluted with 500 - 48 43605 ml of ice water. It was then extracted twice with methylene chloride, the extract was filtered, dried over sodium sulphate and concentrated, and the sulphochloride was distilled in vacuo 49.2 g (80% of theory) of 3,5-dichloro5 benzenesulphochloride of boiling point 83-84°C/0.1 mm Hg were obtained.

The compounds in the table which follows could be prepared analogously to Examples 1 to 6: - 49 ο ο «Ρ -Ρ β ρ ♦Η Ή Ο Ο Pt Ρ Ρ •Η ‘Η •ΡΗ r-J Ή a> 2 Ο Ο ιη I σι οτ *^& ίΛ ΕΛ tn CZ fi χ—·» ο οοο ο-ϊ ixP ο S—/ ο s-< <ϋ Η Χ3 «S ε-< Η Pt · a ο §S3 CQ σ» 4360s •p -p β β •Η Ή Ο Ο ft ft eu β β •ri ·Η •Ρ Η Η ·Η Φ Ο ί£.ο ο σ\ Ε> οο co ω co Ρί b 1 e (continued) φ Η a co avaa ν ν Μ a 6! 2-0 V - 51 a ® o g P P rf rf •ri Ή O O ft ft hOttl •S3 Ρ rri Η «Η Φ O *d Φ rf rf •ri P rf O o *** Φ rri 0 rri X ft « a o d M E4 o Cd Cd cn O <* S> o m CM ά o oa S-// ? O s & o II s a. . cn U=/ s \ ΓΛ s oa Y ?4 I Y isF< o CM CM CM CM CM Ρ Ρ £ £ «Η Ο Ο ft Ο iiDtl £ £ •Η ·Η «Ρ Η Η 'Η Φ Ο CO M3 OJ in ΟΟΟ ΟΟΟ ( continued) Η rf Η Cy fo χ* in M3 OJ OJ Ol c- co σν OJ OJ C\J »95 «Ρ -Ρ α β •Η Ή Ο Ο ft ft fctO tiO -PH Η H Φ O SH CM co CM VD VO VD IA **-— CVJ 4369s •Ρ -Ρ ΰ ϋ •Η Ή Ο Ο ΆΛ gjgj •Η ·Η •Ρ Η Η ·Η Φ Ο & Xj ε* CM Ι> co ffl CM © κ\ co (continued) - 56 4363S -Ρ-Ρ ri ri •rt -rt O O ft ft ηοΛο β a •rt *rt -Ρ H Η ·Η Φ Ο (continued) « H -°ί ell J Ιίλ > o in tt m » «0 o co tn CTi ««— te o ι cu tn LC\ in in kO co Lf\ o o cn σ\ CM CM in xo in in - 57 •ΡΡ ·5·5 ο ο ft ft S' S' •Η ·Η -PH H H Q O S co vo tn o-. tn co ϊλ m tn e- oo *- 3S5S ρ Ρ I £ £ •Η ·Η | Ο Ο ftftj •Η Ή Ρ Η Η Ή Q) Ο KrG ί> ο~ tn tn οο tn in κο cn cn OJ cm oj m CM CM 0- GO σ KO KO ko 43S0S - 3 (3 y Q -P -P β β Ή Ή Ο Ο ft ft Η ·Η Ρ Η Η Ή Φ Ο SH Table (continued) Exampl f· CM £·— r“ CM σ\ ί<Λ CO CM CM i> vo CM Λ rl Cti HO CO tcn CM CO co 3 S S 5

Claims (36)

1. 2-Substituted 5-trifluorometbyl-1,3,4-thiadiazoles of the general formula (I) CF. 3. S(0) ft -R j in which R represents substituted alkyl, phenyl monosubstituted in the o- or m-position, polysubstituted phenyl, substituted phenylalkyl, optionally substituted phenylalkenyl, an optionally substituted 5-membered or 6IO membered heterocyclic radical with 1 to 4 heteroatoms selected from R and S atoms, optionally substituted benzimidazolyl or benzthiazolyl, optionally substituted naphthyl, quinolyl, quinolyl-N-oxide, cyano or one of the groupings wherein 1 2 R and R conjointly represent a trimethylene, tetramethylene or pentamethylene group, v reprenents oxygen or sulphur, 20 R* and R each represent alkyl, or togetherwith the nitrogen atom and optionally further hetero-atoms selected from 0 and N atoms, form an optionally substituted 6-membered or 7-membered ring, and n is 0, 1 or 2, but must be 0 if R is -CX-NR'R. - 62 438SS

2. Compounds according to claim 1, in which R represents 3traight-chain or branched alkyl with 1 to 6 carbon atoms which may be monosubstituted or polysubstituted by halogen, cyano, isothiocyano, phenyl, carboxyl, alkylcarbonyl with 1 or 2 carbon atoms in the alkyl part or phenylcarhonyl which may be substituted by halogen or by 0^ -0^ alkyl; phenylalkenyl with 2 to 4 carbon atoms in the alkenyl part; phenyl monosubstituted in the m or o-position, polysubstituted phenyl or phenyl-alkyl with 1 or 2 carbon atoms in the alkyl part and which is mcnosubstituted or polysubstituted in the phenyl part, the substituents being selected from alkyl with 1 to 4 carbon atoms, halogenoalkyl, halogenoalkylthio or halogenoalkylsulphonyl each with 1 or 2 carbon atoms and 2-5 halogen atoms, alkoxy, alkylcarbonyl or alkoxycarbonyl each with 1 to 4 carbon atoms in the alkyl part, hydroxyl, carboxyl, nitro, cyano and thiocyano; imidazol-2-yl, optionally substituted in the 1- and/or 4- and/or 5-position by alkyl with 1 or 2 carbon atoms, optionally chlorine-substituted phenyl or nitro; thiazol-2-yl optionally substituted in the 4- and/or 5position by alkyl with 1 or 2 carbon atoms, halogen or nitro; 1,2,4-thiadiazol-b-yl, optionally substituted in the 3position by alkyl or alkylthio with 1 to 4 carbon atoms; 1 »3,4~thiadiazol-5-yl, optionally substituted in the 2-position by alkyl with 1 to 4 carbon atoms, amino, alkylcarbonyl, alkylamino, diaikylamino, dialkylaminomethyleneimino or NjN'-dialkylureido each with 1 or 2 carbon atoms in the or 'each alkyl moiety, optionally chlorine-substituted phenyl, alkylthio or alkylsulphonyl with 1 or 2 carbon atoms in the alkyl part, nalogenoalkyl with 1 or 2 carbon atoms and 2 to 5 halogen atoms, or nitro; tetrazole, optionally substituted by - 65 4 3 6 & 3 alkyl with 1 or 2 carbon atoms; thiophene, optionally substituted by nitro or halogen; pyridine, pyridine-N-oxide or pyrimidine, each optionally substituted by alkyl with 1 or 2 carbon atoms or halogen; thiazoline, tetrahydropyrimidine or tetrahydrothiazine, optionally substituted by methyl; benzimidazole or benzthiazolyl, optionally substituted in the benzo ring by halogen or alkoxy with 1 to 2 carbon atoms; naphthyl, which is optionally substituted by nitro, halogen or alkyl with 1 or 2 carbon atoms; quinolyl; quinolyl-lJθ oxide, cyano; or a grouping of the formula R tetramethylene group; X represents oxygen or sulphur and R' and R represent alkyl with 1 or 2 carbon atoms, or form, with the ϊί atom,, a perhydrazepine-, morpholine or Ν'-hydroxyethyl-piperazine ring.

3. The compound of the formula (24)

4. Ths compound of the formula (25) - 64 4 3 63S

5. The compound of the formula N—Ν N-jt -.cAsAs /AAo, (42)

6. The compound of the formula Ν—N F. !t /s\ A (43) 5

7. The compound of the formula Cl Η—N !1 (53)

8. The compound of the formula Cl (55)

9. The compound of the formula (57)

10. The compound of the formula (61) - 65 «3S85

11. The oompound of the formula (70) ‘1

12. The compound of the formula (71)

13. The oompound according to claim 1 that is hereinbefore disclosed in any one Examples 1-23, 26-41, 44-52, 54, 56, 58-60, 62 69 and 72-82.

14. A process for the preparation of a 2-substituted 5trifluoromethy1-1,3,4-thiadiazole according to claim 1, in which (a) a 2-halogeno-5-trifluoromethyl-1,3,4-thiadiazole of the general formula CF. in which Y represents chlorine or bromine, is reacted, in the presence of a diluent and of an acidbinding agent, with a mercaptan of the general formula RS - H (III) in which R has the meaning stated in claim 1, and, if required, the resultant 2-substituted 5-trifluoromethyl-1,3,4-thiadiazole of the general formula R - 66 in which R has the meaning stated in claim 1, is reacted with an oxidising agent, or (b) 2-mercapto-5-trifluoromethyl-1,3,4-thiadiazole,of the formula (Va) (Vb) is reacted, in the presence of a diluent and of an acidbind agent, with a compound of the general formula Z-R (VI), in which R has the meaning stated in claim 1, and Z represents chlorine, bromine, iodine, methanesulphonyloxy or toluenesulphonyloxy, and, if required, the resultant 2-substituted thio-5-trifluoromethyl-1,3,4-thiadiazole of the formula (IV) is reacted with an oxidising agent, or (c) in the case of the preparation of a sulphonyl compound (wherein n = 2 in the formula (I)), a 2-halogeno-5-trifluoromethyl-1,3,4-thiadiazole of the general formula (II) is reacted in the presence of a diluent with a sulphinic acid of the general formula R-SO 2 H (VII), in which R has the meaning stated in claim 1 the sulphinic arid being used as such, in the presence of an inorganic or organic base, or in the form of a corresponding sulphinate. - 67

15. A process according to claim 14 (a) or 14(b), in which the acid-binding agent is an alkali metal carbonate, an alkali metal alcoholate, an alkali metal hydroxide or an aliphatic, aromatic or heterocyclic ainine.

16. A process according to claim 14(a) or (b) or claim 15, in which the compound (IV) is oxidised at a temperature between -30°C and +100°C.

17. A process according to claim 16, in which the compound (IV) is oxidised at a temperature of from -10° to 80°C.

18. A process according to any of claims 14(a) Or (b) and 15 to 17, in which the compound (IV) is oxidised using chlorine in water, a per-acid, hydrogen peroxide in glacial acetic acid or in methanol, potassium permanganate or chromic acid.

19. A process according to any of claims 14(a) or (b) and 15 to 18, in which the compound (IV) is exidised using 1 to 4 moles of oxidising agent per mole of the compound (IV).

20. A process according to claim 14(c), in which the reaction is effected in the presence, as the said base, of an alkali metal hydroxide or a C^-C^ tertiary amine.

21. A process according to any of claims 14 to 20, in which the reaction is effected at from 0° to 120°C.

22. A process according to claim 21, in which the reaction is effected at from 20° to 1OO°C.

23. A process according to any of claims 14 to 22, in which the reaction is effected in the presence of water or an inert organic solvent. - 68 43685

24. A process according to any of claims 14 to 23, in which the reactants are employed in substantially equimolar amounts.

25. A process for the preparation of a compound according to claim 1, substantially as described in any one of Examples 1 to 5.

26. Compounds according to claim 1, whenever prepared by a process according to any of claims 14 to 25.

27. A fungicidal or insecticidal composition containing as active ingredient a compound according to any of claims 1 to 13 and 26 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

28. A composition according to claim 27 containing from 0.1 to 95% of the active compound, by weight.

29. A composition according to claim 28 containing from 0.5 to 90% o£ the active compound, by weight.

30. A method of combating fungi or insects which comprises applying to the fungi or insects or to a habitat thereof a compound according to any of claims 1 to 13 and 26 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 13 and 26 in admixture with a diluent or carrier.

31. A method according to claim 30 in which a composition is used containing from 0.0001 to 10% of the active compound, by weight.

32. A method according to claim 31 in which a composition is used containing from 0.01 to 1% of the active compound, by weight.

33. A method according to claim 30, 31 or 32 in which the active compound is applied to seed in an amount of 0.001 to 50 g per kg seed. GSS©8S

34. A method according to claim 33 in which the active compound is applied in an amount of 0.01 to 10 g per kg seed.

35. A method according to any of claims 30 to 34, in which the active compound is one of those hereinbefore mentioned 5 in any of Examples A to G.

36. Harvested crops protected from damage by fungi or insects by being grown in areas in which immediately prior to and/or during the time of the growing a compound according to any of claims 1 to 13 and 26 was applied alone or in admixture with a 10 diluent or carrier.