DD204200A5 - FUNGICIDAL AGENTS - Google Patents

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

27 · 1 · 1983

AP A 01 Ν / 243 271/5 61 241/18

Fungicidal agent Field of application of the invention

The invention relates to fungicidal compositions containing novel N-sulfenylated benzylsulfonamides, a process for their preparation and their use as fungicides and microbicidal

Characteristic of the known technical solutions ^

For a long time heavy metal salts of ethylene-1,2-bisdithiocarbamic acid in agriculture and horticulture for the control of phytopathogenic fungi in use (Ro Wegler, Chemistry of Crop Protection and Pest Control, Volume 2, p. 65 Springer Verlag Berlin, Heidelberg ₉ New York 1970) ,

Furthermore, it has long been known that N-Trihalogenmethylthio compounds can be used as fungicides in agriculture and garden <> Thus, for example, be · Bo N- (Tr ic hl or "methylthio) -tetrahydrophthalimide (DE-PS 887 506) and N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) -sulfamide (Angew. Chem., 6, 807 (1964)) has been used in fruit and viticulture for the control of fungal diseases in practice Effect in wood preservation for controlling wood-discoloring fungi (R. Wegler, Chemie der Pflanzenschutz- und Schädlingsbekungsmittel, Vol. 4, p. 269 (1977), Springer-Verlag Berlin).

However, the effect of these compounds is not always completely satisfactory, especially at low application rates

27.1 = 1983

AP A 01 N / 243 271/5

61 241/18

Object of the invention

The aim of the invention is to provide agents with more fungicidal and microbicidal activity

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties _s are suitable as active ingredient in fungicidal and microbicidal agents «

There have been new N-sulfenylated Benzy! Sulfonamide of the general formula I.

found in which

12 3

R, R and R independently of one another represent hydrogen,

Halogen _{9 is} nitro, alkyl and haloalkyl and

ΈΓ is hydrogen or alkyl,

R is an optionally substituted ge

saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein the aliphatic

Radicals may optionally be interrupted by hetero atoms one or more times and

X is halogen.

The N-sulphenylated benzylsulfonamides of the general formula I are obtained

CH-SO, -NS-CCl ₃ X

in which

3

R, R and R independently of one another represent hydrogen, halogen, nitro, alkyl and haloalkyl

stand and

4 R is hydrogen or alkyl,

R is an optionally substituted saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or

means aromatic radical, the ali-! phatic radicals may optionally be interrupted by heteroatoms one or more times and

X means halogen,

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when Benzylsulfonamide the general formula II

CH-SO, -N-H (II)

R ³

in which

R to R have the abovementioned meaning, with a sulfenyl chloride of the formula III.

CI-StCCI ₂ X (III)

in which, X has the meaning given above,

in the presence of an acid-binding agent and optionally in the presence of a diluent.

The new N-sulfenylated benzylsulfonamides have strong fungicidal and microbicidal properties.

Surprisingly, the N-sulfenylated benzylsulfonamides according to the invention have different cultures, eg. in rice, a higher fungicidal activity than the known N-Trihalogenmethylthio-Verbindunaen. In addition, they show a higher activity in wood-destroying fungi than the known compounds.

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-S

Of the N-sulphenylated Benzylsulfonajniden of formula I according to the invention are preferably those in which

3

R, R and R independently of one another represent hydrogen, chlorine, bromine, nitro, alkyl having 1 to 4 C atoms, halogenoalkyl having 1 to 4 C atoms and

Atoms and 1 to 5 halogen atoms,

R is hydrogen or alkyl with 1 to

C atoms is,

R ^{5 is} alkyl of 1 to 6 C atoms, alkenyl

Rait 2 to 6 carbon atoms, this being

Radicals may optionally be interrupted by heteroatoms such as oxygen or sulfur one or more times, cycloalkyl having 3 to 7 carbon atoms, aralkyl having 1 to 4 carbon atoms in the alkyl moiety and 6 bis

10 C atoms in the aryl part, phenyl and naphthyl, wherein aralkyl, phenyl and naphthyl optionally with halogen, nitro, cyano, methyl, trifluoromethyl, alkoxy and alkylthio having 1 to 4 carbon atoms

may be substituted and

X is fluorine or chlorine.

Particular preference is given to the N-sul enylated benzylsulfohamides of the formula I in which

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-δι ο

R and R independently of one another represent hydrogen, chlorine,

Nitro, methyl and trifluoromethyl,

R is hydrogen _Λ

4 R is hydrogen and

R. is alkyl having 1 to 6 carbon atoms, alkenyl having '2 to 6 carbon atoms, which may optionally be interrupted by heteroatoms such as oxygen or sulfur from the second carbon atom one or more times, for cycloalkyl with 3 to 7 C atoms · which optionally with alkyl

· is benzyl and phenyl, both optionally substituted with fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, alkoxy and alkylthio substituted with 1 to 4 carbon atoms

can be and

X is fluorine.

Specifically, in addition to the preparation examples, the following N-sulfenylated benzylsulfonamides of the formula I may be mentioned:

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-CHSO ₀ -N-SCCUx 5

• ₄ ^, c

(D

H H H H -CH ₂ -CH = CH ₂ F H H H H -CH ₂ CH ₂ OCH ₃ F H H H H , -CH ₂ CH ₂ SC ₂ H ₅ F H H H H F

H4-C1

4-Cl 4-CF.

4-CF.

4-CF.

4-Cl 3-NO.

2-Cl

H H H H 2-Cl H H H 2-Cl 5-Cl H H 6-Cl H H- H H , H

H H

H .

CH-

CH-

-CIL

CH ₃ Cl C ₄ H ₉ -tert. F CH ₃ F CH ₂ -CH = CH ₂ F CH ₃ F ^C 2 ^H 5 F C η H fi 1 F ^C l3 F F

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If, for example, 4-chlorobenzylsulfonyl-N-methylamide and fluorodichloromethanesulfenyl chloride are used as starting components, the course of the reaction can be represented by the following formula scheme:

Cl-K ^ j) -CH ₂ SO ₂ NH + ClSCFCl ₂ ^{N (C, HH} . 1 1 ³ > CH ₃

Cl- <Q> .- CH ₂ SO ₂ NSCFCl ₂

CH ₃

The required as starting materials Benzylsulfonylsäureamide are generally defined by the formula II. In this formula, R to R 'preferably and more preferably have the meanings which have already been mentioned as preferred and particularly preferred in the description of the compounds of the formula I according to the invention for these substituents.

The benzenesulfonamides are known or obtainable in a manner known per se when benzylsulfochlprides of the formula IV

in which

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14

R to R have the meaning given for formula I,

with a primary amine of the formula. V

R ⁵ -NH ₂ (V),

in which

R has the meaning given above,

if appropriate in the presence of a base and a diluent.

(Compare Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 9, page 39 5 (1955)).

The benzylsulfonyl chlorides required as starting materials are generally defined by formula IV. In this formula

1-4, R.sup.1 to R.sup.4 preferably and particularly preferably have the meanings which have already been mentioned as preferred and particularly preferred in connection with formula I.

Suitable benzylsulfochlorides of the formula IV are, for example, benzyl, 4-methyl, 4-chloro, 2,4-dichloro, 4-nitro, 4-fluoro, 3-trifluoromethylbenzylsulfochloride. The compounds are known or accessible in a manner known per se from corresponding benzyl chlorides (compare Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 9, page 395 (1955) ).

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The amines required as starting materials are by. Formula V is generally defined. In this formula, R is preferably and more preferably the meanings which have already been mentioned as preferred and particularly preferred in connection with formula I.

Examples of suitable amines of the formula V are methyl, ethyl, isopropyl, allyl, tert-butyl, methoxyethyl / methylmercaptoethyl, cyclopentyl, 4-methylcyclohexyl, benzyl, 4-nitrobenzylamine, aniline, 4 Chloroaniline, 3-fluoroaniline, 2-toluidine, 3-chloro-4-trifluoromethylaniline and 1-naphthylamine. They are known compounds.

If, for example, 4-chlorobenzylsulfochloride and methylamine are used as starting materials, the course of the reaction can be represented by the following formula scheme:

CH ₃

When carrying out the process, suitable diluents are all inert organic solvents. These include preferably hydrocarbons such as toluene, chlorinated hydrocarbons such as methylene chloride and chlorobenzene, or ethers such as dioxane.

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As acid-binding agents, inorganic bases such as sodium hydroxide and sodium carbonate or tertiary amines such as pyridine and triethylamine can be used.

About 1 mole of primary amine of formula V is used per mole of benzenesulfonyl chloride of the formula IV.

The reaction temperatures can be varied over a wider range. In general, from 0 to 100 ⁰ C, preferably from 20 to 50 ⁰ C.

The process may be carried out as follows: The Benzylsulfochlorid of formula IV is placed in a diluent and heated to 4O ⁰ C. This is the primary amine. the formula V added in portions. Isolation and purification of the Benzylsulfonamids of formula III is carried out in the usual manner.

As sulfenyl chlorides of the formula III, fluorodichloromethane-sulfenyl chloride and trichloromethane-sulfenyl chloride can be used.

When carrying out the process according to the invention, suitable diluents are all inert organic solvents. These include preferably hydrocarbons such as toluene, chlorinated hydrocarbons such as methylene chloride and chlorobenzene, or ethers such as dioxane and water.

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As acid-binding agents, inorganic bases such as sodium hydroxide and sodium carbonate or tertiary amines such as pyridine and triethylamine can be used.

The reaction temperatures can be varied within a substantial range. In general, from 0 to 100 ⁰ C, preferably from 20 to 5O ⁰ C.

The process according to the invention is carried out as follows: A benzenesulfonic acid amide of the formula III and a sulfonyl chloride of the formula III are initially charged in a diluent. Dazu'wird at room temperature, the acid binder is added in portions, so that the reaction temperature rises to about 4 0 ⁰ C. After completion of the reaction, the N-sulphenylated Benzylsulfonamid of formula (I) is precipitated with water and isolated in the usual manner and purified.

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active ingredients are suitable for deTL use 2.0 as a plant protection product.

Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

In addition, the active compounds according to the invention show bactericidal and acaricidal properties.

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The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.

Furthermore, the active compounds according to the invention can be used for controlling microorganisms in industrial materials.

Technical materials which are to be protected by the substances according to the invention against microbial change and destruction are, for example, adhesives, glues, papers and cardboard, textiles, leather, wood, paints and plastic articles which can be attacked and decomposed by microorganisms.

Microorganisms which can cause degradation or alteration of the technical materials are, for example, bacteria, fungi, yeasts, algae, slimes and viruses. The substances according to the invention preferably act against molds, wood-discolouring fungi and wood-destroying fungi (Basidiomycetes) as well as against lean organisms.

There may be mentioned, for example, microorganisms of the following genera:

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,

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Penicillium such as Penicillium glaucum, Polyporus such as Polyporus versicolor, Pullularia such as Pullularia pullulans, Sclerophoma such as Sclerophoma pityophila, Staphylococcus such as Staphylococcus aureus.

Depending on their field of application, 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 into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, and also in formulations with fuel packs, such as smoke cartridges, cans, spirals, etc., as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner. , represents, for example, by mixing the active ingredients with extenders, that is liquid solvents, under pressure

optionally liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents, in the case of the use of water as extender

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can e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; By liquefied gaseous diluents or carriers are meant those liquids which are normal

" ¹ ^ temperature and under atmospheric pressure are gaseous, eg

Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifier and / or

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foaming agents are possible: Z..B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-suede and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular and latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate can be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azole metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention may be present in the formulations or in the various application forms in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, nerb_j; iden, protective substances

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against avian influenza, growth factors, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions / emulsions, suspensions, powders, pastes and granules. The application is done in the usual way, e.g. by pouring, dipping, spraying, spraying, atomizing, vaporizing, injecting, silting, spreading, dusts, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%.

In the seed treatment are generally drug amounts of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, needed.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

The novel active compounds according to the invention can also be present in a mixture with other known active compounds. For example, the following active ingredients may be mentioned:

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AP A 01 N / 243 271/5 61 241/18

Benzimidazoles 1-me thy! .Carbamate s tetramethyl-thiuram disulfide, Zn salts of dialkyldithiocarbamates, 2.4 _S 5> 6-tetrachloro-isophthalonitrile, thiazolylbenzimidazole, mercaptobenzothiazole and phenol derivatives, such as 2-phenylphenol, (2,2'-dihydroxy -5 »5 ^f -dichloro) ~ diphenylmethano

Ausführungsbe ispiel

The invention is explained in more detail below with reference to some examples

Herξtellungsbe! Games

7-

CH

13 g (0.07 mol) Benzylsulfomethylamid are dissolved in 100 ml of dioxane with the addition of 13 g (0.077 mol) Fluorordichlprmethansulfenchlorid. 7.8 g (0.077 mol) of triethylamine are added dropwise to this solution, and the temperature is allowed to rise to about 40.degree. The mixture is stirred for a while and the product is precipitated with water. Yield 16 g = 70% of theory. From toluene-petroleum ether mp. 91-92 °.

The following compounds are obtained in an analogous manner

CH-SO ₉ -NS-CCl ₉ X

i.4

: R ⁵

Ex. R ¹ R ² R ³ R ⁴ R ⁵

(D,

X Phys.Konst,

H HH H

C ₂ H ₅

59-61 ⁰ C

HHHH 1-C ₃ H ₇

H HH

F 80-81 ⁰ C ^{F n}

1/5434

HHHH C ₃ H ₅

74-76 ⁰ C

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Ex. R

R ² R ³ R ⁴ R ⁵ X Phys. const

HHHH

1, 5381

• 7 HH HH tC ₄ H ₉ F 6 5-68 ⁰ C.

8 2-Cl H H H

117-120 ⁰ C

4-Cl H ¹ HH CH.

98-100 ⁰ C

10 4-Cl HHH C ₂ H ₅

57 ° C

11 4-Cl HHH ^± ~ ° 3 ^Ε η ^F 115 ⁰ C

12 4-Cl HHH tC ₄ H _g F n ^ 1.5529

13 4-Cl HHH

ρ 13O ⁰ C

14 4-Cl HHH 118-122 ⁰ C

15 4-Cl 3-Cl H H CH-

78-81 ⁰ C

16 4-Cl 3-Cl HHC _c He

O

F 116-119 ⁰ C

17 6-Cl 2-Cl H H-

190-196 ⁰ C

18 2 - CF ₃ HHH CH ₃ F n ²⁰ 1.5178

19 2-CF., HHH 134-136 ⁰ C

20 4-NO ₂ HHH CH ₃

122 ° C

21 Cl NO ₀ HHC, H _C

99-102 ° C

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I) Preparation of precursors V 1 (/ \\ _ CH ₂ -SO ₂ NHCH ₃

20 g of benzylsulfonyl chloride are added in 100 ml of toluene with gaseous methylamine 40 °. The resulting together with the methylamine hydrochloride reaction product is filtered off with suction in the cold and washed with water. Yield 13 g, mp 118-119 °.

The following sulfonamides are prepared analogously:

CH-SO -, - Ν-Η R ⁵ ·

(ID,

Ex. R ¹ R ² R ³ R ⁴ R ⁵

HHHH-C ₂ H ₅

Schmp. ⁰ C oily

V 3 HHHH ⁱ ~ ^C 3 ^H 7 98-100 °

V 4 HHHH ⁿ ~ ^C 3 ^H 7 .95-96 °

HHHH

74-75 °

V. 6 HHHH HC ₄ H ₉ 96-97 °

H H H H

102-103 °

V 8 2-Cl HHH C _C H _C 98 °

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Ex. R ¹ R ²

V 9 4-Cl H

V 10 4-Cl H

V 11 4-Cl H

V 12 4-Cl H

V 13 4-Cl H

V 14 4-Cl H

V 15 4-Cl 3 Cl

V 16 4-Cl 3-Cl

V 17 6-Cl 2 Cl

V 18 '2-CF ₃ H

V 19 2-CF ₃ H

V 20 4-NO ₂ H

V 21 Cl NO "

R ³ R ⁴ R ⁵

Schmp. ⁰ C

H CH.

H H

H H

H H

HHC _C H _C bb

H CH.

HHC H _{6. 5}

HHC ₅ H ₅

H CH-

HHC _C H _C

D D

H CH.

108-110 '

96-97 °

HH 1-C ₃ H ₇ 138-140 °

H H

'6 5

141 °

168-169 °

89 °

117 °

129-132 °

179 °

96-98 °

107-109 °

141-143 °

115-119 °

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-23- L u u ι ι y

Application Examples Example A Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier:. 0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Leptosphaeria nodorum. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin.

The plants are placed in a greenhouse at a temperature of about 15 ⁰ C and a relative humidity of about 80%.

10 days after the inoculation the evaluation takes place.

Significant superiority in efficacy over the prior art is demonstrated in this assay, e.g. the compounds according to the following preparation examples: 9, 15, 2, 3, 4, 5, 6.

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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 prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ^° C. 3 days after the inoculation, the size of the infestation spots on the leaves is evaluated.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compounds according to the following preparation examples: 20, 9.

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^r )

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 prepare a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans.

The plants are placed in an incubation cabin with 100% relative humidity and about 20 ⁰ C.

3 days after the inoculation the evaluation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compounds according to the following preparation examples: 1, 9, 15, 2, 3, 4, 5, 6.

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-2T-

Example D

Puccinia test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are inoculated with a spore suspension of Puccinia recondita in a 0.1% aqueous agar solution. After drying, the plants are sprayed with the active ingredient preparation dewy. The plants remain for 24 hours at 20 ⁰ C and 100% rel. Humidity in an incubation cabin.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80% to promote the development of rust pustules.

10 days after the inoculation the evaluation takes place.

A clear superiority in the efficiency over the prior art shows in this test, for example, the compounds according to the following preparation examples:

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- 2β - L "^ i II

Example E -

Tilletia caries test (wheat) / seed treatment

The application of the active ingredients is carried out as a dry dressing. They are prepared by stripping the respective active ingredient with rock flour to a fine powdery mixture, which ensures a uniform distribution on the seed surface.

For pickling, shake the seed previously contaminated with 5 g of Tilletia caries chlamydospores per kg of seed with the seed dressing in a sealed glass bottle for 3 minutes.

The seed is placed on moist clay under a cover layer of a layer of gauze and 2 cm wet vermiculite in the refrigerator for 10 days at 10 ⁰ C optimal germination conditions for the spores.

10 days after sowing, the evaluation is based on spore germination on the wheat grains.

Significant superiority in efficacy over the prior art is demonstrated in this assay, e.g. the compounds according to the following preparation examples:. 1 .

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ns

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 is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Subsequently, the plants are grown in a greenhouse at 100%. rel. Humidity and 25 ⁰ C set up.

4 days after the inoculation, the evaluation of the disease infestation takes place.

Significant superiority in efficacy over the prior art is demonstrated in this assay, e.g. the compounds according to the following preparation examples: 20, 9, 18, 5, 6.

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Example G

To demonstrate the effectiveness against fungi, the minimum inhibitory concentrations (MIC) of active compounds according to the invention are determined:

An agar, which is prepared from wort and peptone, is added to active compounds according to the invention in concentrations of 0.1 mg / 1 to 5000 mg / l. After solidification of the agar contamination occurs with pure cultures of the test organisms listed in the table. After 2 weeks of storage at 28 ⁰ C and 60 to 70% relative humidity, the MIC is determined. MIC is the lowest concentration of active substance that does not undergo any growth by the microbial species used, it is given in the table below.

In this test, compounds according to the following preparation examples are used: 9.

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- 3-r -

At game H

Effect on mucus organisms

The compound according to Table G is administered in concentrations of 0.1 to 100 mg / l. In aliens nutrient solution (Arch.

.5 microbiol. V7, 34-53 (1952)) prepared in 4 L of sterile water, 0.2 g ammonium chloride, 4.0 g sodium nitrate, 1.0 dipotassium hydrogen phosphate, 0.2 g calcium chloride, 2.05 g magnesium sulfate, 0.02 g Contains ferric chloride and 1% caprolactam, dissolved in a little acetone, brought to the table. Shortly before, the nutrient solution is infected with slime organisms (about 10 germs / ml) isolated from spinning water circuits used in polyamide production. Nutrient solutions having the minimum inhibitory concentration (MIC) or greater drug concentrations are still perfectly clear after 3 weeks of culture at room temperature, i. the noticeable in active ingredient-free nutrient solutions after 3 to 4 days noticeable proliferation of microbes and slime formation.

For the Benzylsulfonarnid according to Table G was determined in this way the MIC.

Le A 2 \ 211

Claims (2)

invention claim Fungicidal agent, characterized by a content of at least one N-sulphenylated benzylsulfonamide of general formula I. CH-SO ₉ -NS-CCl ₉ X (I) ₁ ⁴ R ⁵ in which R, R and R ^ are each independently hydrogen, Halogen, nitro, alkyl and haloalkyl are and R is hydrogen or alkyl, R is an optionally substituted saturated or unsaturated aliphatic, cycloaliphatic _s araliphatic or aromatic radical meansj wherein the aliphatic radicals may optionally be interrupted by hetero atoms one or more times, and X means halogen , in addition to extenders and / or surface-active agents » 27.1 "1983 AP A 01 N / 243 271/5 61 241/18 2. A method of combating fungi, characterized in that N-sulfenylated Benzylsulfonami.de act according to point 1 on fungi or their habitat ο Use of N-sulfenylated benzylsulfonamides according to item 1, characterized in that they are used for controlling fungi 4 * A process for the preparation of fungicidal agents, characterized by mixing N-sulfenylated Benzylsulfonamide according to item 1 with extenders and / or surface-active agents Use of U-sulfenylated benzylsulfonamides according to item 1, characterized in that they are used for the protection of technical materials « 6ο Agent for the protection of industrial materials, characterized by a content of at least one N-sulfenylated benzylsulfonamide according to item 1 in addition to extenders and / or surface-active agents »