CA1192912A - N-sulphenylated benzylsulphonamides, a process and their use as microbicides - Google Patents

Abstract

Abstract N-Sulphenylated benzylsulphonamides of the general formula ( I ) are novel and find use as fungicides and microbicides.
The new N-sulphenylated benzylsulphonamides can be prepared by reacting suitable benzylsulphonamides with a suitable sulphenyl chloride.

Description

Typ~e~Ia The invention relates to certain new N-sulphenylated ben~ylsulphonamides, to a process for their production and to their use as funyicides and microbicides.
Heavy metal salts of ethylene-1,2~bisdi-thiocar-bamic acid have been used for a long time in agricultureand horticulture for combating plant-pathogenic fungi (see R. Wegler, Chemie der Pflanzenschutz- und Sch~dlingsbe-k~mpfungsmittel (Chemistry of Plant Protection Agents and Pest Combating Agents), Volume 2, page 65 Springer Verlag 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 9 N-(trichloromethylthio)-tetrahydrophthalimide (see German Patent Specification 887,506) and N,N-dimethyl-N'-phenyl N'-(fluorodichloromethylthio)-sulphamide (see Angew. Chem.
76, 807 (1964)), for example, are er,lployed in practice in fruit cultivation and viticulture for combating fungal diseases. The latter compound is active, in additi~n, in the protection of timber for combating wood-discolouring fungi (see R. Wegler, Chemie der Pflanzenschutz- und Schad-lingsbek~mpfungsmittel (Chemistry of Plant Protection Agents and Pest Combating Agents), Vol. 4, page 269 (1977), Springer Verlag 8erlin).
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 formula R ~ CH- 50 ~ -N--S -CC 1 2 X ( I ) in which Le A 21 211 Rl, R2 and R3 each independently is a hydrogen, chlorine or bromine atom, a nitro radical, an a:Lkyl radical having 1 -to ~
carbon atoms, or a halogenoalkyl radical having 1 to ~ carbon atoms and 1 to 5 halogen a-toms, R4 is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, R5 is an alkyl or alkenyl radical having up to 6 carbon atoms, said alk~l or alkenyl radical being interrupted at one or more points by a hetero atom; 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; the aralkyl, phenyl and naphthyl radicals substituted by halogen, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkyl-thio ha~ing 1 to 4 carbon atoms, and X is a fluorine or chlorine atom.
According to the present inven-tion there is further pro-vided a process for the production of a compound of the present invention, characterised in that a benzylsulphonamide of the general formula R1~ ~/ CH-SO2-N-H (II) in which Rl to R5 have the meanings given above, is reacted with a sulphenyl chloride of the general formula Cl-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.
The new N-sulphenylated benzylsulphonamides possess powerful fungicidal and microbicidal properties.

2 --Su.rprisingly, the N-sulphenylated benzylsulphonamides according to the present invention possess a higher fungicidal activity in various crops, for example in rice, than the known N-trihalogenomethylthio compounds. In addition, they exhibit a higher activity than the known compounds in the case of wood-destroying fungi.

~; i - 2a -Preferred N-sulp.henylated benzylsulphonami~es according to the present invention are those in which R1, R2 and R3 independently of one another represent a hydrogen, chlorine or bromine atom, a nitro radical, an alkyl radical having l to 4 carbon atoms, or a halogenoalkyl radical having l to 4 carbon atoms and l to 5 halogen atoms, R4 represents a hydrogen atom or an alkyl radical 1û having l to 4 carbon atoms, RS represents an alkyl radical having l to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon atoms, it being possible for these radicals option-ally to be interrupted at one or more points by hetero atoms (such as oxygen or sulphur); a cyclo-alkyl radical having 3 to 7 carbon atoms; an aralkyl radical having l to 4 carbon atoms in the alkyl part and 6 to lO carbon atoms in the aryl part; or a phenyl or naphthyl radical, it being possible for 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.
Particularly preferred N-sulphenylated benzylsulphon-amides according to the present invention are those in which R1 and R2 independently of one another represent a hydrogen or chlorine atom or a nitro, methyl or trifluoromethyl radical, R3 represents a hydrogen atom, R4 represents a hydrogen atom and R5 represents an alkyl radical having l to 6 carbon atoms, an alkenyl radical having 2 to 6 carbon 35 atom.s, whic.h. option.ally can be interrupted at one Le A 21 211 Or more points from the secand 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 l to 4 carbon atoms; or represents a benzyl or phenyl radical, both of which are option-ally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkylthio having l 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.

~ C,4SO2 N5SCCl~ (I) 15 H H H H -CH2-CH=CX2 F

H H H H C~2CX2SC2H5 F

H H H H ~Cl F

H H H H -CH2~) F

4-Cl H H H ~CX3 F

Le A 21 211 R1 R2 R3 . R4 R5 X

4-Cl H H H -CH3 Cl 4-CF3 H H H -C H -tert. F
4-CF3 2-Cl H H -CH3 F
4-CF3 H H H -CH2-CH=CH2 F
4-C1 2-C1 5-Cl H -CEI3 F

3 -N02 H H H -C 2~5 F
2-C1 6-Cl H H -C3H7i F
H H EI CH3 -C,~ F
H H H C~I3 ~ 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~CH2 SO2 ~IE ~ ClSCFCl 2 .?

Cl~-CH 2 SO 2 NSCFCl 2 Preferred benzylsulphonamides of formula (II) required as starting materials are those in which R1 to R5 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, or are obtainable in a manner which is in itself known when .
Le A 21 211 a banzylsulphonyl chloride of the general formula R~ cH-so2cl ( I V ) in which R1 to R4 have the meaninys given above, is reacted with a primary amine of the general formula R NH2 (~) in which R5 has the meaning given above, if appropria-te in the presence of a base and of a diluent.
(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 precursor of formula (II) are those in which R1 to R4 have the meanings which have already been mentioned in connect-ion with preferred and particularly preferred compounds of formula (I).
Examples of suitable benzylsulphonyl chlorides of 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, Methoden der organischen Chemie (Methods of Organic Chemistry), 4th Edition, Volume 9, page 395 (1955)).
Preferred amines of formula (V) also required a~ starting materials for the production of precursors of formula (I) are those in which R5 has meanings which have already been mentioned in connection with the preferred and oarticularly preferred compounds of formula (I).
Examples of suitable amines of the formula (V) are Le A 21 211 2~

methylamine) ethylamine, isooropylamine, allylamine, tert.-butylamine~ methoxyethylamine, methylmercapto-ethylamine J cyclopentylamine, 4-methylcyclohexylamine, benzylamine, 4-nitrobenzylamine, aniline, 4-chloro-aniline, 3-fluoroaniline, 2-toluidine, 3-chloro-4-tri-fluoromethylaniline and l-naphthylamine. They are known compounds.
If, for example, 4-chloro benzylsulphonyl 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:

Cl~CH2S02Cl + NH2 ~ Cl~C~2-S(:)2~H

In carrying out this process, any of the inert organic solvents are suitable diluents. These include, as prefer-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 triethylamine) can be used as acid-binding agents.
Aoout l 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 relatively wide range. In general, the reaction is carried out at a temperature btween 0 and 100C, preferably between 20 and 50C.
The process can be carried out as follows: the benzylsulphonyl chloride of the formula (IV) is initially Le A 21 211 introduced into a diluent and heated to ~0C. The primary amine of the formula (V) is added in portions.
Isolation and puri~ication of the benzylsulphonamide of the formula (III) is effected in the customary manner.
Fluorodichloromethane-sulphenyl chloride and trichloromethane-sulphenyl chloride can be employed as sulph~nyl chlorides of the formula (III).
In carrying out the process according to the present invention3 any of the inert organic solvents are suitable 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 sodium carbonate) or tert.-amines (such as pyridine and triethylamine) 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 100C, preferably at a temperature between 20 and 50C.
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 40C.
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.
3D The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganismsO
The active compounds are suitable for use as plant pro-tection agents.
Fungicidal agents in plant protection are employed Le A 21 211 for comba~ing Plasmodiophoromycete`s, Oonlyce~es, Chy-tridio-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 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.
Examples of microorganisms which can cause degra-dation or modification of industrial materials are bac-teria, 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 mucila-ginous organisms.
Microorganisms of the following genera may be mentioned as examples: Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, 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 Pul].ularia pullulans, Sclerophoma~ such as Sclerophoma pityophila and Staphy-lococcus, such as Sta~hylococcus aureus.

Le A 21 211 Depending on their field o~ use, -the substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules.
The active compounds can be converted to the cus-tomary formulations, such as solutions, emulsions, sus-pensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound~ very fine capsules in polymeric substances and 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, 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 agent~ and/or dispersing agents and/or foam-forming 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, especially solvents, there are suitable in the main, aromatic hydro-carbons, 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 and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers is meant liquids which would be gaseous at normal temperature and Le A 21 211 under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers -there may be used ground natural 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 na-tural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synth~tic 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 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, 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 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, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from O.l to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weigh-t.
The active compounds according to the invention Le A 21 211 can be present .in th~ formulatlons or in the various use forms as a mixture with other known active compounds, such a~ fungicides, bactericides, insecticides, acari-cides, nema~icides~ herbicides, bird repellants, growth 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 for~s prepared therefrom by Further dilution, such as ready-to-use solu-1û tions, emulsions, suspensions, powders, pastes andgranules. The~ are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dus~ing, 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 l and 0. 0001o by weight, preferably between 0.5 20 and 0. 001o.
In the treatment of seed, amounts of active com-pound of O.OOl to 50 9 per kilogram of seed, preferably O.Ol to lO 9, are generally required.
For the treatment of soil, active compound con-! 25 centrations of O.OOOOl to 0~1o by weight, preferably O.OOOl to 0~02~o~ are generally required at the place of action.
The present invention also provides fungicidaland 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 batin.g fungi and microbes. which comprises applying to the Le A 21 211 fungi and mi~robes, or to a habitat thereof, a c~mpound o~ the present invention alone or in the form of a compos-ition containing as active ingrediPnt a compound of the present invention in admixture with a diluent or carrier.
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 ~arrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The new activP compounds according to the inven-- tion can also be present as a mixture with other known active compounds. The following active compounds may be 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-5,5'-dichloro)-diphenylmethane.
Preparative Examples Example l ,_ H2so2N-s -CFCl ( 1 ) - C~I3 13 9 (0.07 mol) of benzylsulphonylmethylamide were dissolved in lOû ml of dioxane, with the addition of 13 9 (0.077 mol) of fluorodichloromethanesulphenyl chloride. 7.8 9 (0.077 mol) of triethylamine were added dropwise to this solution~ and the temperature was allowed to increase to about 40C. The mixture was stirred for some time and the product was precipitated with water.
Yield 16 9 1 70O of theory. From toluene/petroleum ether: m.p. 9l to 92C.

Le A 21 211 The following compounds were obtained in an analogous manner:

R2 ~ CH~S02-N S CC12 (I), R1 R R3 4 R5X Physical ample R const-.l.nr 3 H H H H i C3H7 F 80-81 C

4 H H H H n-C3H7 E' n20 1,5434 H H H H C~H5 F 74-76 C
6 H H H H n-C4H9 F nD 1,5381 7 H H H H t-C4Hg F 65-68 C

8 2-Cl H H H C6H5 F 117-120 C

9 4-Cl H- H H CH3 F 98~100 C

4-Cl H H H C2H5 F 57 C

11 4-Cl H H H i C3H7 F 115 C

12 4-Cl H H H t-C4Hg F nD 1, 5529 13 4 -Cl HH H C5H11 F 130 C

14 4-Cl H H X C6H5 F 118-122C

Le A 212~1 Ex- 1 2 3 4 5 Physical ample R R R R R ~ constant ds-Cl 3-Cl H H CH3 F 78-81 C

16 4 -Cl 3-Cl H H C6H5 F 116-119 C

17 6-Cl 2~Cl H H C6H5 F 190-196C

18 2-CF3 H H H CH3 F n20 1,5178 4-NO, H H H CH3 E 122 C

21 Cl NO2 H H C6H5 F 99-102C

Preparation of the precursors _______________________._____ Example 22 ~ CH2-S02NHCH3 Gaseous methylamine was introduced into 20 9 of . benzylsulphonyl chloride in 100 ml of toluene at 40C.
The reaction product which was obtained together with methylamine hydrochloride was filtered of~ under suction while cold, and was washed with water. Yield 13 9, m.p.
10 118 to 119C.
The ~ollowing sulphonamides were prepared analo-gously: R1 R2 ~ ,4 S2 N5H (II), Le A 21 211 - ~6 -Ex- Melting ample R1 R2 R3 R4 R5 point ~C
23 H H H H C2H5 oily 24 H H H H i-C3H7 98-100 H H H H n~C3H7 95-96 26 H H H H C3~l5 74-75 27 H H H H n-C4H9 96-97 28 H H H H t-C4H9 102-103 2g 2-Cl H H H 6H5 98 4-Cl H H H CH3 108-110 31 4-Cl H H H C2 5 96-97 32 4-Cl H H H i C3H7 138-140 33 4-Cl H H H t-C4H9 141 34 4-Cl H H H C6H11 168-169 4-Cl H H H C6H5 89 36 4-C1 3-Cl H H CH3 117 37 4-Cl 3-Cl H H C6H5 129-132 42 C1 N0~ H H C6H5 115-119 The microbicidal and fungicidal activity of the `- compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the com,oounds 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 Solvent: lOO parts by weight of dimethylformamide Emulsifier: 0.25 part by weight oF alkylaryl polyglycol ether Le A 21 211 17 _ To produce a sui-table preparation of active com-pound, l part by weight oF active compound was mixed with the stated amounts of solvent and emulsifier 7 and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity3 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-sphaeria nodorum. The plants remained in an incubation cabin at 20C and a relative atmospheric humidity of ,- 100o for 48 hours.
- The plants were placed in a greenhouse at a temperature of about 15C and a relative atmospheric humidity of about 80o.
Evaluation was carried out lO days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by the 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 polyglycol ether To produce a suitable prsparation of active com-pound, l par-t 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, 2 small pieces of agar covered with Botrytis cinerea were placed on each leaf. The inoculated Le A 21 211 plant~ were placed in a darkened humidity chamber at 20C. 3 days after the inoculation, the si~e of the infected spots oi7 the leaves was evaluated.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by thecompounds (20~ and (9).
Example C
Phytophthora Test (tomato)/protective Solvent: 4.7 par~s by weight of acetone Emulsifier: 0.3 par-t by wPight of alkylaryl polyglycol ether -- To produce a suitable preparation of active com-pound, l part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with wa-ter to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of active compound l~ntil dripping wet. After the spray coating had dried on, 2û the plants were inoculated with an aqueous spore suspension of Phytophthora infestans.
The plants were placed in an incubation cabin at 100o relative atmospheric humidity and at about 20C.
Evaluation was carried out 3 days after the inoculation.
In this test a clearly superior activity com-pared to ~he state of the art was shown, for example, by the compounds (l), (9), (15), (2), (3), (4), (5) and (6).
Example ~
Puccinia Test (wheat)/protective Solvent: lO0 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, l part by weight of active compound was mixed with Le A 21 211 3~L~

the stated amounts ~f solvent a~d emulsifier, and the concentrate was dilu~ed with water ~o the desired concen-tration.
To test for protective activity, young plants were inoculated with a spore suspension of Puccinia recondita in a 0.1o 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 20C and 10 l00o relative atmospheric humidity for ~4 hours.
The plants were placed in a greenhouse at a tem-perature of about 20C and a relative atmospheric humidity of about 80,o in order to promote the development of rust pustules.
Evaluation was carried out lO days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by the compound (l).
~Xample 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 9 of chlamydospores of Tilletia caries per kg of seed, was shaken with the 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 10C
in a refrigerator for lO days.
lO days after sowing, the germination of spores Le A 21 211 on the wheat grains ~as evaluated.
In this test, a clearly superiDr activity com-pared with the prior art was shown, for example~ by the compound (l).
Example ~
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 com-pound, l part by waight 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 20 greenhouse at 100o relative atmospheric humidity and 25C.
Evaluation of the disease infestation was carried out 4 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art was shown, for example, by the ( 25 compounds (20), (~), (18), (5) and (6).
Example G
To demonstrate the activity against fungi, the minimum inhibitory concentrations (MIC) of active com-pounds according to the invention were determined.
Active compounds according to the invention were added, in concentrations of from O.l mg/l to 5,000 mg/l, 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 35 was effected. After storage for 2 weeks at 28~C and Le A 21 211 60 to 70O relative atmospheric humidity, the MIC was determined. The MIC was the lowest concentration of active compound at which the microbe species ~sed showed no growth.
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 O.l to lO0 mg/l in each case, in Allens nutrient solution (see Arch. Mikrobiol 17, 34 to 53 (1952)), which contained 0.2 g of ammonium chloride, ~- 4 0 9 of sodium nitrate, l.0 9 of dipotassium hydro~en phosphate, û.2 9 of calcium chloride, 2.05 9 of magnesium sulphate~ 0.02 9 of iron chloride and 1o of caprolactam in 4 litres of sterile water, dissolved in a small amount of acetone. The nutrient solution was infected shortly beforehand with mucilaginous organisms (about 106 germs/ml) which had been isolated from spinning-water cycles used in polyamide production. Nutrient solutions which 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 compound-free nutrient solutions after 3 to 4 days did not take place.
The MIC was determined in this manner for the benzylsulphonamide.

Le A 21 211

Claims (21)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An N-sulphenylated benzylsulphonamide of the formula in which R1, R2 and R3 each independently is a hydrogen, chlor-ine 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, R4 is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, R5 is an alkyl or alkenyl radical having up to 6 carbon atoms, said alkyl or alkenyl radical being interrupted at one or more points by a hetero atom; 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; the aralkyl, phenyl and naphthyl radicals substituted by halogen, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkylthio having 1 to 4 carbon atoms, and X is a fluorine or chlorine atom.

2. A compound according to claim 1, in which R1 and R2 each independently is a hydrogen or chlorine atom or a nitro, methyl or trifluoromethyl radical, R3 is a hydrogen atom, R4 is a hydrogen atom and R is an alkyl or alkenyl radical having up to 6 carbon atoms and optionally interrupted at one or more points from the second carbon atom by an oxygen and/or sulphur atom; or is a cyclo-alkyl radical which has 3 to 7 carbon atoms and which is optionally substituted by alkyl having 1 to 4 carbon atoms; or is a benzyl or phenyl radical optionally substituted by fluorine, chlorine, brom-ine, nitro, cyano, methyl, trifluoromethyl, alkoxy or alkylthio having 1 to 4 carbon atoms, and X is a fluorine atom.

3. N-Dichlorofluoromethylsulphenyl-N-methyl-benzylsulphona-mide of the formula

4. N-Dichlorofluoromethylsulphenyl-N-isopropyl-benzylsul-phonamide of the formula

5. N-Dichlorofluoromethylsulphenyl-N-propyl-benzylsulphona-mide of the formula

6. N-Dichlorofluoromethylsulphenyl-N-methyl-4-chlorobenzyl-sulphonamide of the formula

7. N-Dichlorofluoromethylsulphenyl-N-methyl-4-nitrobenzyl-sulphonamide of the formula

8. A process for the production of a compound according to claim 1, characterised in that a benzylsulphonamide of the general formula (II) in which R1 to R5 have the same meanings as in claim 1, is reacted with a sulphenyl chloride of the general formula Cl-S-CCl2X (III) in which X has the same meaning as in claim 1, in the presence of an acid-binding agent.

9. A method of combating fungi or microbes comprising apply-ing to the fungi or microbes or to a habitat thereof, a fungici-dally or microbicidally effective amount of a compound according to claim 1.

10. A method according to claim 9 wherein the compound is applied in the form of a composition containing said compound as active ingredient, in admixture with a suitable diluent or carrier.

11. A method according to claim 10, wherein a composition is used containing from 1 to 0.0001% of said compound, by weight.

12. A method according to claim 11, wherein a composition is used containing from 0.5 to 0.001% of said compound, by weight.

13. A method according to claim 9, 10 or 12, wherein said compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.

14. A method according to claim 9, 10 or 12, wherein said compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight.

15. A method according to claim 9, 10 or 12, wherein said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

16. A method according to claim 9, 10 or 12, wherein said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

17. The method according to claim 9, 10 or 12, wherein such compound is N-dichlorofluoromethylsulphenyl-N-methyl-benzylsulphon-amide.

18. The method according to claim 9, 10 or 12, wherein such compound is N-dichlorofluoromethylsulphenyl-N-isopropyl-benzylsul-phonamide.

19. The method according to claim 9, 10 or 12, wherein such compound is N-dichlorofluoromethylsulphenyl-N-propyl-benzylsulphon-amide.

20. The method according to claim 9, 10 or 12, wherein such compound is N-dichlorofluoromethylsulphenyl-N-methyl-4-chlorobenzyl-sulphonamide.

21. The method according to claim 9, 10 or 12, wherein such compound is N-dichlorofluoromethylsulphenyl-N-methyl-4-nitrobenzyl-sulphonamide.