NZ201912A

NZ201912A - N-sulphenylated benzylsulphonamide derivatives and fungicidal and microbicidal compositions

Info

Publication number: NZ201912A
Application number: NZ201912A
Authority: NZ
Inventors: E Kuhle; W Paulus; W Brandes; J Genth; V Paul
Original assignee: Bayer Ag
Priority date: 1981-09-17
Filing date: 1982-09-14
Publication date: 1984-12-14
Also published as: ATE13530T1; EP0075172A2; GR77337B; PH18247A; TR21400A; JPS5862155A; JPH0419988B2; ES8305709A1; FI823200A0; CA1192912A; EP0075172B1; NO153174B; EG15843A; PL130882B1; BR8205478A; AU8846082A; NO822972L; IL66796A; KR840001552A; ZA826788B

Abstract

1. N-Sulphenylated benzylsulphonamides of the general formula I see diagramm : EP0075172,P13,F1 in which R**1 , R**2 and R**3 independently of one another represent hydrogen, halogen, nitro, alkyl or halogenoalkyl, and R**4 denotes hydrogen or alkyl, R**5 represents alkyl with 1 to 6 C atoms, alkenyl with 2 to 6 C atoms, it being possible for these radicals optionally to be interrupted by one or more hetero atoms such as oxygen or sulphur, cycloalkyl with 3 to 7 C atoms, aralkyl with 1 to 4 C atoms in the alkyl part and 6 to 10 C atoms in the aryl part, phenyl or naphthyl, it being possible for aralkyl, phenyl and naphthyl optionally to be substituted by halogen, nitro, cyano, methyl, trifluormethyl, alkoxy or alkylthio with 1 to 4 C atoms, and X denotes halogen.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £01 91 £ 'A-' '• iS? u !■ laiiiiai PrioriL/ I'= - / 7,',^$ I •Cc- '•' • -"n- B ^ ... . w h j ^ kU -rfi a <« a o a ■ ■ r;.,C07c-\Ur7* eoicjffrboihiinto* mrm*. 41-4. KC M8* >98.; f» n : p„. lQ~la5 I • >w7 a W-# Lii x S C ..r.?f * t. ^ , • •*<>■■•••■••■■■■ 30 H N.Z. No. NEW ZEALAND Patents Act, 1953 COMPLETE SPECIFICATION "N-Sulphenylated benzylsulphonamides, a process and their use as microbicides." We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- -1- (Followed by 1A.) 201912 - lft- Ta The invention relates to certain new N-sulphenylated benzylsulphonamides, to a process for their production and to.their use as fungicides and microbicides. Heavy metal salts of ethylene-1,2-bisdithiocar-5 bamic acid have been used for a long time in agriculture and horticulture for combating plant-pathogenic fungi (see R. Wegler, Chemie der Pflanzenschutz- und SchSdlingsbe-kSmpfungsmittel (Chemistry of Plant Protection Agents and Pest Combating Agents), Volume 2, page 65 Springer Verlag 10 Berlin, Heidelberg, New York (1970). Furthermore, it has been known for a long time that N-trihalogenomethylthio compounds can be used as fungicides in agriculture and horticulture. Thus, N-(trichloromethylthio)-tetrahydrophthaiimide (see United States 15 Patent Specification 2553770) and N , N-dimethyl-N1-phenyl-N'-(fluorodichloromethylthio)-sulphamide (see Angew. Chem. 7 6, 807 (1964)), for example, are employed in practice in fruit cultivation and viticulture for combating fungal diseases. The latter compound is active, in addition, 20 in the protection of timber for combating wood-discolouring fungi (see R. Wegler, Chemie der Pflanzenschutz- und SchSd-1ingsbekSmpfungsmittel (Chemistry of Plant Protection Agents and Pest Combating Agents), Vol. 4, page 269 (1977), Springer Verlag Berlin). 25 However, the action of these compounds is not always completely satisfactory, particularly when low amounts are used. The present invention now provides, as new compounds, the N-sulphenylated benzylsulphonamides of the general 30 formula n 1 /— (I) , V // CH-SO--N —S-CC1_X R2^\Lj_y 2 15 2 r3 r r" in which Le A 21 211 201912 - 2 - 12 3 R , R and R independently of one another represent a hydrogen or halogen atom or a nitro, alkyl or halogenoalkyl radical, 4 R denotes a hydrogen atom or an alkyl radical, 5 R^ denotes an optionally substituted saturated or unsaturated aliphatic, cycloaliphatic, arali-phatic or aromatic radical, it being possible for the aliphatic radicals to be optionally interrupted at one or more points by hetero 10 atoms, and X denotes a halogen atom. According to the present invention there is further provided a process for the production of a compound of the .present invention, characterised in that a benzyl-15 sulphonamide of the general formula (II) //_<rrs°2"-sH R R in which 1 5 R to R have the meanings given above, is reacted with a sulphenyl chloride of the general formula 20 C1-S-CC12X (III) in which X has the meaning given above, in the presence of an acid-binding agent and, if appropriate, in the presence of a diluent. 25 The new N-sulphenylated benzylsulphonamides possess powerful fungicidal and microbicidal properties. Surprisingly, the N-sulphenylated benzylsulphonamides according to the present invention possess a higher fungicidal activity in various crops, for example in 30 rice, than the known N-trihalogenomethy1thio compounds. In addition, they exhibit a higher activity than the known compounds in the case of wood-destroying fungi. Le A 21 211 > f (?) .f - .3 - Preferred N-sulp.henylated benzylsulphonamides according to the present invention are those in which 12 3 R , R and R independently of one another 5 represent a hydrogen, chlorine or bromine atom, a nitro radical, an alkyl radical having 1 to 4 carbon atoms, or a halogenoalky1 radical having 1 to 4 carbon atoms and 1 to 5 halogen atoms, 4 R represents a hydrogen atom or an alkyl radical 10 having 1 to 4 carbon atoms, 5 R represents an alkyl radical having 1 to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon atoms, it being possible for these radicals optionally to be interrupted at one or more points by 15 hetero atoms (such as oxygen or sulphur); a cyclo- alkyl radical having 3 to 7 carbon atoms; an aralkyl radical having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part; or a phenyl or naphthyl radical, it being possible for 20 aralkyl, phenyl and naphthyl radicals optionally to be substituted by halogen, nitro, cyano, methyl, trifluoromethyl, alkoxy and alkylthio having 1 to 4 carbon atoms, and X represents a fluorine or chlorine atom. 25 Particularly preferred N-sulphenylated benzylsulphon amides according to the present invention are those in which 1 2 R and R independently of one another represent a hydrogen or chlorine atom or a nitro, methyl or 30 trifluoromethyl radical, R^ represents a hydrogen atom, R^ represents a hydrogen atom and R"* represents an alkyl radical having 1 to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon 35 atoms, which, optionally, can be interrupted at one La fl-,.8'1 711 201912 10 - A - or. more points from the second carbon atom by hetero atom(s) selected from oxygen and sulphur; or represents a cycloalkyl radical which has 3 to 7 carbon atoms and which is optionally substituted by alkyl having 1 to 4 carbon atoms; or represents a benzyl or phenyl radical, both of which are optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkylthio having 1 to 4 carbon atoms, and X represents a fluorine atom. In addition to those of the preparative Examples, the following N-sulphenylated benzylsulphonamides of the formula (I) may be mentioned individually: R. )Oi chs09-n-scc1„x t,4 „5 r r (I) r, R R R~ r" x 1 5 h h h h -ch2-ch=ch2 f h h h h -ch2ch2och3 f h h h h -ch2ch2sc2h5 f h h h h 1—1 f h h h h -ch2^0 f ■ci h h h ^Q^CH3 f 201912 - 5 - r1 r2 r3 . r4 r5 x 4-CI H H H -ch3 CI 4-CF3 H H H -C.Ho-tert. 4 9 F 4-CF3 2-Cl H H -ch3 F 4-CF3 H H H -ch2-ch=ch2 F 4-Cl 2-Cl 5-C1 H -ch3 F . 3-no, H H H ~C2H5 F 2-Cl 6-CI H H -C3H^i (isoprofyl) F H H H ch3 -CH^ F H H H ch3 F If, for example, 4-chlorobenzylsulphonyl- N- methylamide and fluorodichloromethanesulphenyl chloride are used as the starting components, the course of the reaction according to the present invention is illustrated by the following equation: ci-^^-ch2so2ne + ciscfci2 n (c;hs} 3 > ch3 C1^0>"CH2S02NSCFC12 ck3 Preferred benzylsulphonamides of formula (II) 1 5 required as starting materials are those in which R to R 10 have the meanings which have already been mentioned for these substituents in the description of the preferred and particularly preferred compounds according to the present invention. The benzylsulphonamides of formula (II) are known, 15 or are obtainable in a manner which is in itself known when Le A 21 211' ' - 6 - a benzylsulphony1 chloride of the general formula R1 R2 CH-SO,Cl 'IV) R4 in which 1 4 R to R have the meanings given above, is reacted with a primary amine of the general formula r5-nh2 (v) in which R^ has the meaning given above, if appropriate in the presence of a base and of a diluent. 10 (See Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry), ,4th Edition, Volume 9, page 395 ( 1955)) . Preferred benzylsulphonyl chlorides of formula (IV) required as starting materials for the production of 1 4 15 precursor of formula (II) are those in which R to R have the meanings which have already been mentioned in connection with preferred and particularly preferred compounds of formula (I) . Examples of suitable benzylsulphonyl chlorides of 20 the formula (IV) are benzyl-, 4-methyl-, 4-chloro-, 2 , 4-dichloro-, 4-nitro-, 4-fluoro- and 3-trifluoromethyl-benzylsulphonyl chloride. The compounds are known, or are obtainable from the corresponding benzyl chlorides in a manner which is in itself known (see Houben-Weyl, 25 Methoden der organischen Chemie (Methods of Organic Chemistry), 4th Edition, Volume 9, page 395 (1955)). Preferred amines of formula (V) also required as starting materials for the production of precursors of formula (I) are those in which R has meanings which 30 have already been mentioned in connection with the preferred and particularly preferred compounds of formula (I). Examples of suitable amines of the formula (V) are 2019 12 - 7 - methylamine,. ethylamine,. isopropylamin'e , allylamine, tert.-butylamine , methoxyethylamine, methylmercapto-ethylamine, cyclopentylamine, 4-methylcyclohexylamine, benzylamine, 4-nitrobenzylamine, aniline, 4-chloro-aniline, 3-fluoroaniline, 2-toluidine, 3-chloro-4-tri-fluoromethylaniline and 1-naphthylamine. They are known compounds. If, for example, 4-chloro-benzylsulphony1 chloride and methylamine are used as starting materials, the course of the reaction for the production of precursors of formula (II) is illustrated by the following equation: ci-u /Vch2so2ci + nh2 7 CE3 ci^r\c*2-so2m ch. In carrying out this process, any of the inert organic solvents are suitable diluents. These include, as prefer-15 ences, hydrocarbons (such as toluene), chlorohydrocarbons (such as methylene chloride and chlorobenzene) and ethers (such as dioxane). Inorganic bases (such as sodium hydroxide and sodium carbonate) or tert.-amines (such as pyridine and 2q triethylamine) can be used as acid-binding agents. About 1 mol of primary amine of the formula (V) is employed per mol of benzylsulphonyl chloride of the formula (IV). The reaction temperatures can be varied within a 25 relatively wide range. In general, the reaction is carried out at a temperature btween 0 and 10Q°C, preferably between 20 and 50°C. The process can be carried out as follows: the benzylsulphonyl chloride of the. formula (IV) is initially - .8 introduced into a diluent and heated to 40°C. The primary amine of the formula (V) is added in portions. Isolation and purification of the benzylsulphonamide of the formula (III) is effected in the customary manner. 5 Fluorodichloromethane-sulphenyl chloride and trichloromethane-sulphenyl chloride can be employed as sulphenyl chlorides of the formula (III). In carrying out the process according to the present invention, any of the inert organic solvents are suitable 1 g diluents. These include, as preferences, hydrocarbons (such as toluene), chlorohydrocarbons (such as methylene chloride and chlorobenzene) and, ethers (such as dioxane) and also water. Inorganic bases (such as sodium hydroxide and 15 sodium carbonate) or tert.-amines (such as pyridine and triethyl amine) can be used as acid-binding agents. The reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between 0 and 100°C, preferably 20 at a temperature between 20 and 50°C. The process according to the invention is generally carried out as follows: a benzylsulphonic acid amide of the formula (II) and a sulphenyl chloride of the formula (III) are initially introduced into a diluent. The 25 acid-binding agent is added in portions at room temperature, so that the reaction temperature increases to about 4Q°C. After the end of the reaction, the N-sulphenylated benzyl-sulphonamide of the formula (I) is precipitated with water, and isolated and purified in the customary manner. 3Q The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms. The active compounds are suitable for use as plant protection agents. 35 Fungicidal agents in plant protection, are employed i 21i3 '' V ^ 10 - 9 - ' for combating Plasmodiophoromycete's, Oomycete's, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. In addition, the active compounds according to the invention possess bactericidal and acaricidal properties. The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil. Furthermore, the active compounds according to the invention can be used for combating microorganisms in industrial materials. Examples of industrial materials intended to be 15 protected by the substances according to the invention, against microbial modification and destruction are adhesives, glues, papers and cardboards, textiles, leather, wood, coating agents and plastic articles which can be attacked and decomposed by microorganisms. 2o Examples of microorganisms which can cause degra dation or modification of industrial materials are bacteria, fungi, yeasts, algae, slimes and viruses. The substances according to the invention are preferably active against moulds, wood-discolouring fungi and wood-25 destroying fungi (Basidiomycetes) and against mucilaginous organisms. Microorganisms of the following genera may be mentioned as examples: Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, 30 such as Chaetomium globosum, Coniophora, such as Coniophora cerebella, Lentinus, such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Pullularia, such as Pullularia pullulans, Sclerophoma, such as Sclerophoma pityophila and Staphy-35 loc.occus, such as Staphylococcus aureus. ■Le A 21 21 1 201912 - 10 - Depending on their field of use, the substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. 5 The active compounds can be converted to the cus tomary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and 10 in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations. These formulations may be produced in known manner, 15 for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the 20 use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, 25 chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers 30 and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone , or strongly polar solvents, such as dimethy1formamide and dimethylsulphoxide, as well as water. By liquefied gaseous diluents or carriers is meant 35 liquids which would be gaseous at normal temperature and 2019 1 - 11 - under normal pressure, for example aerosol prope 1'1'ant's, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid carriers there may be used ground natural 5 minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural 1 g rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there may 15 be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, 20 for example, lignin sulphite waste liquors and methyl-cellulose . Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or. latices, such as gum arabic, polyvinyl alcohol 25 and polyvinyl acetate, can be used in the formulations. It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, 3g and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight. 35 The active compounds according to the invention - -.12 - can be present in. the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acari-cides, nematicides, herbicides, bird repellants, growth 5 factors, plant nutrients and agents for improving soil structure. The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solu-10 tions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, 15 wet dressing, slurry dressing or encrusting. Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 20 and 0.001%. In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required. For the treatment of soil, active compound con-25 centrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are generally required at the place of action. The present invention also provides fungicidal and microbicidal composition containing as active ingredient 30 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 com-35 bating fungi and microbes, which comprises applying to the " 13 - fungi and microbes, 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. 5 The present invention further provides crops protected from damage by fungi and microbes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. 10 It will be seen that the usual methods of providing a harvested crop may be improved by the present invention. The new active compounds according to the invention can also be present as a mixture with other known active compounds. The following active compounds may be 15 mentioned as examples: benzimidazolyl-methyl carbamates, tetramethyl-thiuramdisulphide, Zn salts of dialkyl-dithiocarbamates, 2,4,5,6-tetrachloro-isophthalonitrile, thiazolylbenzimidazole, mercaptobenzthiazole and phenol derivatives, such as 2-phenylphenol and (2 , 2 '-dihydroxy-2o 5,5'-dichloro)-diphenylmethane. Preparative Examples Example 1 £3"ch2so2n-s -cfci2 (!) ch3 13 g (0.07 mol) of benzylsulphonylmethylamide 25 were dissolved in 100 ml of dioxane, with the addition of 13 g (0.077 mol) of fluorodichloromethanesulphenyl chloride. 7.8 g (0.077 mol) of triethylamine were added dropwise to this solution, and the temperature was allowed to increase to about 40°C. The mixture was stirred for 30 some time and the product was precipitated with water. Yield 16 g 1 70% of theory. From toluene/petroleum ether.: m.p. 91 to 92°C. 2019 12 _ 14 The following compounds were obtained in an analogous manner: .1 CH-SO2 -N-s-cci^ R (I), ■. R" Ex* 1 2 3 4 5 ample R R • R R R Physical constant H H H H C2H5 59-61°C 3 H H H H i-C3H7 F 80-81°C 4 H H H H n-C3H7 P 20 n£U 1,5434 5 H H H H C^H5 F 6 H H H H n-C4H9 F 74-76 °C n20 1,5381 7 H H H H t-C4H9 F 6 5-68°C 8 2-Cl H H H CeEc 6 5 F 117-120 °C 4-Cl H H H CH. F 98-100 °C 10 4-Cl H H H C2E5 57°C 11 4-Cl H H H i-C3H? 115°C 12 4-Cl H H H t"C4Hg 20 1,5529 13 4-Cl H H H C6H11 F 1 30 °C 14 4-Cl H H H C-.H- 6 5 F 118-122°C -15- 12 3 4 5 ample R R R , R R Physical X constant 15 4-Cl 3-Cl H H CH- 78-81°C 16 4-Cl 3-CI H H CgH5 116-119 °C 17 6-Cl 2-Cl H H CgH5 190-196 °C 18 2-CF3 H H H CH3 F n20 1 ,5178 19 2-CF3 H H H CgH5 134-136°C 20 4-no2 h h h ch3 1 22 °C 21 CI N02 H H CgH5 99-102 °C Preparation_of_the precursors Example 22 (/ \\-ch2-so2nhch3 5 Gaseous methylamine was introduced into 20 g of benzylsulphonyl chloride in 100 ml of toluene at 40°C. The reaction product which was obtained together with methylamine hydrochloride was filtered off under suction while cold, and was washed with water. Yield 13 g, m.p 1Q 118 to 119°C. The following sulphonamides were prepared analogously : ch-so7-n-h 1 4 1 5 R RD (II) 2 019 12 Example R1 R2 R3 R4 R5 Melting ( point 23 H H H H c2h5 oily 0 24 H H H H i-cjh, 98-100 25 H H H H n-C3H7 95-96° 26 H H H H C3H5 74-75° 27 H H H H n-P4H9 96-97° 28 H H H H t-C4H9 102-103° 29 2-Cl H H H C6H5 98° 30 4-Cl H H H CH 108-110° 31 4-Cl H H H <=2h5 96-97° 32 4-Cl H H H i-C3H7 138-140° 33 4-Cl H H H fc-C4H9 141° 34 4-Cl H H H C6H11 168-169° 35 4-Cl H H H C6H5 89° 36 4-Cl 3- CI H H ch3 117° 37 4-Cl 3- CI H H C6H5 129-132° 38 6-C1 2- CI H H C6H5 179° 39 . 2-CF-j H H H ch3 96-98° 40 2-CF3 H H H C6H5 107-109° 41 4-N02 H H H ch3 141-143° 42 CI NO 2 H H C6H5 115-119° The microbicidal and fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples. 5 In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example. Example A Leptosphaeria nodorum Test (wheat)/protective 1Q Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether *■?> 0 ! 9 1 2 - 17 - To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-5 tration. To test for protective activity, young plants were sprayed with the preparation of active compound until dew moist. After the spray coating had dried on, the plants were sprayed with a conidia suspension of Lepto-10 sphaeria nodorum. The plants remained in an incubation cabin at 2Q°C and a relative atmospheric humidity of 100% for 48 hours. The plants were placed in a greenhouse at a temperature of about 15°C and a relative atmospheric 15 humidity of about 80?o. Evaluation was carried out 10 days after the inoculation. In this test, a clearly superior activity compared with the prior art was shown, for example, by the 20 compounds (9), (15), (2), (3), (4), (5) and (6). Example B Botrytis test (bean)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyg.lycol 25 ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired 30 concentration. To test for protective activity, young plants were sprayed with the preparation of active compound until dripping wet. After the spray coating had dried on, 2 small pieces of agar covered with Botrytis 35 cinerea. were placed, on each leaf. The inoculated LannA i ai -ei** //_. iu J. '& k ^ 10 1 5 - 18 - plants were placed in a darkened humidity chamber at 20°C. 3 days after the inoculation, the size of the infected spots on the leaves was evaluated. In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (20) and (9). Example C Phytophthora Test (tomato)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration. To test for protective activity, young plants were sprayed with the preparation of active compound until dripping wet. After the spray coating had dried on, 20 the plants were inoculated with an aqueous spore suspension of Phytophthora infestans. The plants were placed in an incubation cabin at 100% relative atmospheric humidity and at about 20°C. Evaluation was carried out 3 days "after the 2 5 i noculation. In this test a clearly superior activity compared to the state of the art was shown, for example, by the compounds (1), (9), (15), (2), (3), (4), (5) and (6). Example D 30 Puccinia Test (wheat)/protective Solvent: 100 parts by weight of dimethy1formamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-35 pound, 1 part by weight of active compound was mixed with a s1 "-gt-l 9 1 2 - 19 - the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration. To test for protective activity, young plants were 5 inoculated with a spore suspension of Puccinia recondita in a 0.1% strength aqueous agar solution. After the spore suspension had dried on, the plants were sprayed with the preparation of active compound until dew-moist. The plants remained in an incubation cabin at 20°C and 10 100% relative atmospheric humidity for 24 hours. The plants were placed in a greenhouse at a temperature of about 20°C and a relative atmospheric humidity of about 80% in order to promote the development of rust pustules. 15 Evaluation was carried out 10 days after the inoculation. In this test, a clearly superior activity compared with the prior art was shown, for example, by the compound (1). 20 Example E Tilletia carries test (wheat)/seed treatment The active compounds were based on dry dressings. These were prepared by extending the particular active compound with a ground mineral to give a finely pul-25 verulent mixture, which ensured uniform distribution on the seed surface. To apply the dressing, the seed, which had been contaminated beforehand with 5 g of chlamydospores of Tilletia caries per kg of seed, was shaken with the 30 dressing in a closed glass flask for 3 minutes. The seed, on moist loam under a cover of a layer of muslin and 2 cm of moist vermiculite, was exposed to optimum germination conditions for the spores at 10°C in a refrigerator for 10 days. 35 10 days after sowing, the germination of spores 1—u^A 01 01 1 "01912 - 20 - on the wheat grains was evaluated. In this test, a clearly superior activity compared with the prior art was shown, for example, by the compound (1) . Example F . Pyricularia test (rice)/protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsifier, to the desired concentration. To test for protective activity, young rice plants were sprayed with the preparation of active compound until dripping wet. After the spray coating had dried off, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants were then placed in a greenhouse at 100% relative atmospheric humidity and 25°C. Evaluation of the disease infestation was carried out 4 days after the inoculation. In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (20), (9), (18), (5) and (6). Example G To demonstrate the activity against fungi, the minimum inhibitory concentrations (MIC) of active compounds according to the invention were determined. Active compounds according to the invention were added, in concentrations of from 0.1 mg/1 to 5,000 mg/1, to an agar prepared from beer-wort and peptone. After the agar had solidified, contamination with pure cultures of the test organisms listed in the following table was effected. After storage for 2 weeks at 28°C and </div>

Claims

<div class="application article clearfix printTableText" id="claims"> •' :\s) £ # fc! te*;- 21 -;60 to 70?o relative, atmospheric humidity, the MIC was determined. The MIC was the lowest concentration of active compound at which the microbe species used showed no growth.;5 In this test, compound (9) was used.;Example H;Action on mucilaginous organisms;The compound according to following Table G was used, in concentrations of 0.1 to 100 mg/1 in each case, 10 in Aliens nutrient solution (see Arch. Mikrobiol. 1_7, 34 to 53 (1952)), which contained 0.2 g of ammonium chloride, 4.0 g of sodium nitrate, 1.0 g of dipotassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulphate, 0.02 g of iron chloride and l?o of caprolactam 15 in 4 litres of sterile water, dissolved in a small amount of acetone. The nutrient solution was infected shortly beforehand with mucilaginous organisms (about 10^ germs/ml) which had been isolated from spinning-water cycles used in polyamide production. Nutrient solutions which 20 had the minimum inhibitory concentration (MIC) or higher active compound concentrations were still completely clear after 3 weeks of culture at room temperature, that is to say the pronounced multiplication of the microbes and formation of slime which are noticeable in active 25 compound-free nutrient solutions a.fter 3 to 4 days did not take place.;The MIC was determined in this manner for the benzylsulphonamide.;imtt A 01 011;2 019 12;- 22 -;what^ve claim is:;1. N-Sulphenylated benzylsulphonamides of the general formula;ch-s02-n -s-cc12;x;(I);in which;10;15;2.;that;20;25;30;R";R and R^ independently of one another represent a hydrogen or halogen atom or a nitro,;alkyl or halogenoalkyl radical,;4;R denotes a hydrogen atom or an alkyl radical,;5;denotes an optionally substituted saturated or unsaturated aliphatic, cycloaliphatic, arali-phatic or aromatic radical, it being possible for the aliphatic radicals to be optionally interrupted at one or more points by hetero atoms, and X denotes a halogen atom.;Compounds according to claim 1, characterised in;12 3 •;R , R and R^ independently of one another represent a hydrogen, chlorine.or bromine atom, a nitro radical,;an alkyl radical having 1 to 4 carbon atoms, or a halogenoalkyl radical having 1 to 4 carbon atoms and;1 to 5 halogen atoms,;4;R represents a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms,;C;R^ represents an alkyl radical having 1 to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon atoms, it being possible for these radicals optionally to be interrupted at one or more points by hetero atoms j a cycloalkyl radical having 3 to 7 carbon .atoms; an aralkyl radical having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part; or a phenyl or naphthyl radical, it. being possible;201912;- 23 -;for aralkyl3 phenyl and naphthyl radicals optionally to be substituted by halogen, nitro, cyano, methyl, trifluoromethyl, alkoxy and alkylthio having 1 to 4 carbon atoms, and;X represents a fluorine or chlorine atom. 3. Compounds according to claim 1, characterised :in that;1 2;R and R independently of one another represent a hydrogen or chlorine atom or a nitro, methyl or 10 trifluoromethyl radical,;R^ represents a hydrogen atom,;R represents a hydrogen atom and;R represents an alkyl radical having 1 to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon atoms, /radicals;-L-> which /optionally can be interrupted at one or more points from the second carbon atom by hetero atom(s) selected from oxygen and sulphur; or represents a cycloalkyl radical which has 3 to 7 carbon atoms and which is optionally substituted by alkyl having 1 20 to 4 carbon atoms; or represents a benzyl or phenyl radical, both of which are optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkylthio having 1 to 4 carbon atoms, and 25 X represents a fluorine atom.;4. Any one of the compounds according to claim 1 which are hereinbefore specifically identified.;5. A process for the production of a compound according to any of claims 1 to characterised in that a benzyl-;30;sulphonamide of the general formula;.1;CK-SO,-N-H (II);.4 « 5;R R;Le A 21 211;^ P *fi Q - 24 - in which' 1 5 R to R have the same meanings as in claim 1, is reacted with a sulphenyl chloride of the general formula C1-S-CC12X (III) 5 in which X has the same meaning as in claim 1, in the presence of an acid-binding agent. 6. A process according to claim 5, characterised in that the reaction is carried out in the presence of a diluent. 10 7. A process according to claim 6, characterised in that the diluent is an inert organic solvent. 8. A process according to any of claims 5 to 7, charac terised in that the reaction is carried out at. a temperature between 0 and 100°C. 15 9- A process according to any of claims 5 to 8, charac terised in that the benzylsulphonamide of formula (II) has been obtained by reacting a benzylsulphonyl chloride of the general formula ^ R^ r2 R- ^ ch - s02c1 (iv) R 20 in which

1-4 • r to r have the same meanings as in claim 1, with a primary amine of the general formula r5-nh2 (v) in which 25 R^ has the same meaning as in claim 1. 10. A process according to claim 9, characterised in that the reaction between the benzylsulphonyl chloride of formula (IV) and the primary amine of formula (V) is carried out in the presence of a base and of a diluent. 30 11. A process for the preparation of a compound according . to. claim 1}. .substantially as. described in. any. of Examples. 1 201912 - 25. - to 21. 12. A compound according to claim 1, characterised in that it is prepared by a process according to any of claims 5 to ll. 5 15- A fungicidal or microbicidal composition, characterised in that it contains as active ingredient a compound according to any of claims 1 to 4 and 12 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a sur-10 face-active agent. 14. A composition according to claim 13, characterised in that it contains from 0.1 to 95$ of the active compound, by weight. 15. A method of combating fungi or microbes characterised 15 in that there is applied to the fungi or microbes or to a habitat thereof, a compound according to any of claims 1 to 4 and 12 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 4 and 12, in admixture with a diluent or carrier. 20 16. A method according to claim 15, characterised in that a composition is used containing from 1 to 0.0001$ of the active compound, by weight. 17. A method according to claim 16, characterised in that a composition is used containing from 0.5 to 0.001 25 of the active compound, by weight. 18. A method according to claim 15, characterised in that the active compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight. 19. A method according to claim 18, characterised in 30 that the active compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight. 20. A method' according to claim 15, characterised in that the active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed. 35 21. A method according to claim 20, characterised in kotfil 26 that the active compound is applied to seed in an amount of 0.01 to 10 g per kg of seed. 22. A compound according to any one of claims 1 to 4 and 12, alone or in admixture with a diluent or carrier when in contact with a crop and/or crop growing area'. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED </div>