NO803509L - FUNGIZIDE SULPHONYL- RESP. SULFINYLACETANILIDER - Google Patents

Description

The invention at your disposal is a new fungicide sulfonyl-resp. sulfinyl acetanilides, methods for their production, as well as their use■ as a pest control agent, especially in plant protection see.

The compound according to the invention has it

R 1 means (C 1 -C 4 )-alkyl, halogen, (C 1 -C 4 )-alkoxy

(C 1 -C , ) -alkylthio, -(C 1 -C , ) -alkenyl,

Rg means hydrogen, (C^-C )-a,alkyl, halogen,

R0 means (C1 -C , ) -alkyl, halogen,

R^, R^ means hydrogen, methyl,

R^ denotes hydroxy, (C 1 -C 2 )-. alkoxy, (C 2 -C 2 )-alkylthio (C 1 )- alkoxyethoxy, amino, (C 2 -C 8 )-alkylamino, di'(C ^-Cg )-alkylami.no, O-cat, where cat means the cation equivalent of an inorganic or organic base, preferably Na-, K, 1/2Ca, ammonium,

R 6 means (C 1 -C 8 )-alkyl, (C 1 -C 4 )-alkyl, (C 1 -C 3 )-alkyl,

(C 1 -C 2 )-alkylthio-(C 1 -C 1 )-alkyl, (C 1 -C 8 )-alkyl-sulfinyl-(C 1 -C 2 )-alkyl, (C 1 -C 8 )-alkyl sulfonyl -

(C1-C3)-alkyl, (C3-C6)-cycloalkyl, (C^C^)-haloalkyl, (C^-C^)-hydroxyalkyl, (Cj-Cg)-alkyl carbonyl-(G^- C8)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, benzyl which is optionally substituted with one or two residues from the group (C1-C4)-alkyl, halogen, nitro, phenyl, as eventual_uelt

is substituted with one or two residues from the group (C^-C^)-alkyl, halogen,

n means 0.1

m means 0,1,2.

Preferred residues in formula I are:

means (C 2 -C 8 )'-alkyl, (C 2 -C 8 )-alkoxy, halogen,

Rg means hydrogen, (C 1 -C 8 )-alkyl, halogen

R^ means chlorine, methyl,

R^„ R^means hydrogen, methyl,

R 1 means hydroxy, (C 1 -C 8 )-alkpoxy, (C 1 -C 8 )-alkylthio,

amino, (C 1 -C 8 )-alkylamino, di-(C 1 -C 8 )-alkylamino,

R 6 means (C 1 -C 6 )-alkyl, (C 1 -C 8 )-al oxy - (C 1 -C 6 )-alkyl,

(C0-C, )-cycloalkyl,'- (C , -C )-half-genal alkyl,

yes' 4

(C 1 -C 2 )-hydroxyalkyl, (C 2 -C 8 )-hydroxycarbonyl-(C 1 -C 8 )-alkyl, (-C 1 -C 2 )-alkenyl, benzyl or with (C 1 -C 2 )-alkyl , -halogen or nitro substituted benzyl,

n means 0, 1

m means 0, 1

It is known to combat rotting diseases on plants and which are caused by fungi of the genus Phytophthora to use fungicides from a range of dithiocarbamates such as mancozeb or maneb, organotin compounds such as e.g. fentin acetate" or perchloromethyl mercaptan derivatives such as e.g. - captafol. With these active substances, phytophthora strains which attack above ground on leaves and stems can be combated, while soil-transmitted agents of the genus phytophthora and pythium, which attack the roots of the plants, are not attacked. It is further known that acylated anilinoacetic acid-, resp. propionic acid derivatives, as described in DOS no. 23 50 94-4-» 25 13 730, 25 13 789, 25 15 091', 26 43 445 and 26 43 477, in addition to a herbicide effect, also have a fungicidal effect against fungi from the family oomycetes.

It has now surprisingly been found that the compound according to the invention with formula I has an outstanding fungicidal effect, especially against oomycetes which belong to the class phycomycetes, such as e.g. pytium, phythophtora, perono-spora, p seudoperono spora and .piasmopara.

Thus, fungi on the most diverse cultivated plants such as e.g. maize, rice, cereals, sugar beets, vegetables, cucumber crops, potatoes, tomatoes, beets, hops, tobacco, citrus and paprika types, ornamental plants, cocoa, bananas, rubber, bees , resp., are inhibited, resp. their appearance on these plants is completely prevented. The compounds of formula I act partly systemically. They can also be used as a mordant to control, for example, seed-borne fungi on seed or to combat phytopathogenic fungi occurring in the soil.

The effect of the compound according to the invention with formula I is, among other things, to be described as very surprising for the corresponding alkylthioacetanilides, as they are mentioned in the above-mentioned DOS 25 15 091, only having a very small fungicidal effect against phytophthora, especially against soil-overgrown phyto.phtoriatypes and fungi of the pythium family.

The object of the invention is therefore also fungicides which are characterized by the content of a compound with formula I.

• Preparation of the compound of formula I is possible by different methods, and can e.g. take place according to the procedures 1 to 5 listed below-

The production of sulfonyl derivatives with the general formula I, in which n = 1-, can take place: 1. By alkylation of the Vsulfinic acid salt with the general formula II, in which Me is an inorganic or organic cation, preferably sodium, potassium or ammonium and R^ has the meaning' as given for formula I, in conjunction with the general formula III

in which X means a nucleophilic substitutable residue preferably from the group halogen, tosylate or mesylate, especially chlorine or bromine, and R-, R^, Rg»R^°g rn has the meaning given above for formula I, or 2. By alkylation of aniline derivatives of the general formula IV, in which R, R^, Rg, R^ and m have the meaning given above for formula I with sulfonylacetyl halides of the general formula V, in which Hal is a halogenator, preferably chlorine or bromine, and R/ has the meaning given for formula I or 3- By oxidation of mercaptoacetanyl ides with

wherein R, R^, R9, R^, R^ and m have the meaning given above for formula I.

The production of sulfinyl derivatives with the general formula I, in which n means 0, can take place: 4- By acylation of aniline derivatives with the general formula IV, in which R,. R^',. R 1 , and m have the meaning given for formula I with sulfenylacetylhalogenides with the general formula VII

in which Hal means a halogenator, preferably chlorine or bromine, and R^ has the meaning given for formula I, or

5- By oxidation of me.rkaptoacetanilides with the general formula VI

wherein R, R^, R^, R. y R^ and m have the meaning given for formula I.

The reaction according to method 1 is preferably carried out in inert towards the reaction participants, preferably polar or dipolar aprotic solvents or diluents. As. such come- it e.g. in question: alcohols, such as ethanol, propanol, butanol or glycol, dialkylated amides such as dim.ethylformamide, nitriles such as acetonitrile or propionitrile, ketones such as methyl - ethyl ketones or diisopropyl ketone, ethers such as dioxane.

The reaction temperature is preferably between 50°C and 250°C, especially between 60 and 180°C. As a literature reference for turnover according to method 1, it can e.g. mentioned -Chem;.' Pray. 13, 1272 (1880), Chem. Ber. 63, 2847, (1930), Synthesis 1979, p 733.

The reactions according to methods 2 and 4 are preferably carried out in inert dissolution or dilution media. One uses e.g. preferably hydrocarbons such as benzene, toluene, xylene, petroleum ether, cyclohexane, halogenated hydrocarbons such as chlorobenzene. carbon tetrachlorine, ethers such as dialkyl ether, dioxane or tetrahydrofuran, nitriles such as acetonitrile, dialkylated amides such as dimethylformamide or carboxylic acid esters such as acetic acid ethyl ester.

The reaction temperature is not critical and is preferably between -20°C and 60°C, especially between 0°C and 0°C.

The reaction according to methods 2 and 4 can be carried out with or without the presence of acid-binding agents. As an antacid. funds will come, e.g. in question: Tri-alkylamines such as triethylamine, pyridine, inorganic bases, such as metalloxy der or-hydr oxides, e.g. calcium oxide or sodium hydroxide, or carbonates such as calcium carbonate. Is the turnover carried out without. acid binding agent, then the work is preferably done at too high a temperature, and care must be taken to remove the halogen hydrogen from the reaction mixture.

The production of 'the' starting material used aniline derivatives with formula IV can e.g. pre-

go according to J. Org. Chem. 30,41;01 (196.5), DOS 22 12 268, US patent 4-0 12 519, tetrahedron 1 967, 4.87 and 4.93-The acid chlorides with formulas V and VII can be prepared as mercaptoacetic acid or their derivatives by oxidation and subsequent transfer into the acid chloride by reaction with thionyl chloride (cf. Chem. Ber. 29 1139, (1896).

The oxidation of mercaptoacetanilides with formula VI according to method 5 resp- 3' to sulfoxide, resp. sulfones, can be carried out according to methods common to those skilled in the art. As an oxidizing agent, for example: Hydrogen peroxide/(Chem-Ber. 4-1-, 28:36 (1 908), Houben-Weyl. Vol. 9. 4- edition, 2. 228/, peracids as peracetic acid, perbenzoic acid, 3-chloroperbenzoic acid, or phthalic acid /Houben-Weyl vol. 9 4- oppi. 2. 228, J. Prak.- Chem. 131, 357 (1 931 ) and 128, 171, (1 930), Chem. Ber'. 70, 379, (1 937)/, Chromic or nitric acid or in the case of sulphoxides also bromine or chlorine /Synth 1 /1 979 p. 397.

The turnover according to procedure 3 and

5, is preferably carried out in the presence of solvents. As such, it can be used: Hydrocarbons such as benzene, halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetra-

chloride, dichloroethane or trichloroethylene, ketones such as acetone or methyl ethyl ketone, carboxylic acid such as glacial acetic acid or propionic acid, anhydrides such as acetic anhydride, alcohols such as methanol, ethanol and water, or also mixtures of these solvents with each other.

The reaction temperatures in process 3 for the production of sulphones are between -20 and 160°C, preferably between 0 and 120°C. in process 5 for the production of sulfoxides between -40 and 100°C, preferably between -40 and 60C

Those for the conversion of used mercaptoacetanilides of formula VI are partially known /cf. DOS 25 15 091/- Their production can e.g. take place by reaction of aniline derivatives with formula IV with mercaptoacetic acid chlorides or by reaction of hal and enac e tanyl ides, with mercaptans, resp. their al kal.i salts.

If the preparation of the compound according to the invention with formula I is carried out according to one of the methods 1 to 5 in such solvents in which one of the reaction participants is only slightly soluble, an acceleration of the reaction can be achieved by adding catalysts , like for example. crown nethers or those known as phase-transfer catalyst quaternary ammonium-, resp. phosphonium

sa,l ter.

The connections with. 'formula'1with R

and has asymmetric carbon atoms. They therefore usually exist as racemic mixtures of enantiomeric forms. The enantiomeric forms have a different biological activity. A meter after synthesis of the pure D-isomer can e.g. take place by fractional crystallization of salts of anilinopropionic acid with the general formula VIII with optically active bases such as cinchonine or et-phenylethylamine or by fractional crystallization of anilinothiobutyrylactones with the general formula. Villa with optical; active acids such as D- or L-tartaric acid. In formula VIII and Villa, R^, Rg, R^, and m have the meanings given in formula I.

However, it is also possible with a targeted synthesis starting from optically active halopropionic acid derivatives such as e.g. L-2-chloropropionic acid methyl ester, optically active lactic acid ester bisylates or optically active halobutyrothiolactones and anilines of the general formula IX, in which R^, R^ > R^ and'mhar has the meaning given for the compound of formula I.<:>This reaction takes place mainly as SN2 reaction during inversion of the configuration. Thus arises from 2,-6-dimethylaniline and L-2-chloropropionic acid, resp. L-2-chloropropionic acid methyl ester, preferably D-2-(2,6-dimethylanilino)-propionic acid or

its methyl ester.

The agents according to the invention usually contain the active substances of formula I to approx. 2-95

wt%, preferably 5-90 wt%. They can be used as spray powders, emulsifiable concentrates, sprayable solutions, dusting agents, mordants, dispersions, granules or microgranules in usual preparations.

Spray powders are preparations that are evenly dispersible in water and, in addition to the active substance, possibly contain a diluent or inert substance, without a wetting agent, e.g. polyoxytylated alkylphenols, polyoxytylated fatty alcohols, alkyl or alkylphenyl sulfonates, and dispersing agents, e.g. 1igninesulfonic acid sodium, 2,21-dinaphthyl methane-6,61-disulfonic acid sodium, dibutylnaphthalene sulfonic acid sodium or also oleoylmethyl-tauric acid sodium. Their production takes place in the usual way, e.g. when grinding or mixing the components.

Emulsifiable concentrates can e.g. is produced by dissolving the active substance in an inert organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. In the case of liquid active substances, the solvent part can also be completely or partially removed. As an emulsifier, for example: Alkylaryl sulphonic acid can be used: calcium salts such as Ca-dodecylbenzenesulphonate, or non-ionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, fatty alcohol-propylene oxide-ethylene oxide condensation products, alkyl polyglycols, sorbitan acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethyl sorbitan esters.

Samples can usually be obtained by grinding the active substance with finely divided solids, e.g. talc, natural clay, such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Granules can either be produced by atomizing the active substance, adsorbing, granulated inert material or by applying active substance concentrates using binders, e.g. polyvinyl alcohol, sodium polyacrylic acid or also mineral oil on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active substances can also be granulated in the usual way for the production of fertilizer granules, if desired in a mixture with fertilisers.

In spray powders, this constitutes the active substance concentration

e.g. approx. 10 to 90% by weight, the rest to 100% by weight consists of normal formulation ingredients. In the case of emulsifiable concentrates, the active substance concentration can amount to approx. 10 to 80% by weight. Powdered formulations mostly contain 5 to 20% by weight of active substance, sprayable solutions approx. 2 to 2'Q wt%. In the case of granules, the active substance content partly depends on whether the active compound is liquid or solid, and which granulation aids, fillers, etc. are used.

In addition, the aforementioned active ingredient formulations possibly contain the usual adhesive-moistening-dispersing-emulsifying-penetrating-solvent-filling or carrier substances.

For use, the commercially available concentrates are optionally diluted in the usual way,

e.g. by spray powders,. emulsifiable concentrates, dispersions and partly also with microgranules using water. Powdered and granulated preparations as well as sprayable solutions are usually not further diluted with additional inert substances before use.

Also mixtures or mixed formulations with other pesticide active substances such as e.g. Insecticides, acaricides, herbicides, growth regulators or fungicides are possibly possible. Particularly in the case of mixtures with fungicides, energetic effects can also be partially achieved.

The invention shall be explained in more detail by means of the following examples:

A. Manufacturing examples

Example 1

Methyl 2-N-(methylsulfonylacetyl)-N-(2,6-dimethyl-phenyl)-amino-N-propanoate.

U.75 g (0.05 mol) of methyl 2-[N-(methylthioacetyl)-N-(2,6-dirnetylphenyl)-amino_7-propanoate in 60 ml of methylene chloride are mixed over the course of 1 hour with. a suspension of 27.1 g (0,

11 mol) 3-chloroperbenzo acid. ( 80%- ±g) in 100 ml of methylene chloride. After the addition has been made, the mixture is heated for 2 hours at 4.0°C, the separated 3-chlorobenzoic acid is filtered off and the filtrate is vigorously stirred with 200 ml. saturated sodium bicarbonate solution. The methylene chloride phase is separated and dried over sodium sulfate. The methylene chloride is then distilled off. The residue is recrystallized from ■ toluene/cyclohexane. Mon

gives H.1 g ( = 8.6.3# of the theoretical) Methyl -2-[ N-(methyl - sulfonylacetyl ) -N - (2, 6 - dime tylphenyl ) -amino_/-propanoate with melting point 115 - 116°C, "pg formula:

Example 2

Methyl 2-[N-(stylsulfonylacetyl)-N-(2,6-dimethyl-phenyl)-amino]-propanoate.

28.3 g (0.1 mol) methyl 2-[N-(chloroacetyl)-N-(2,6-dimethylphenyl)-amino_7-propanoate, 1 g TEBA (=triethyl-benzylammonium bromide) and 14.0' g ( 0.12 mol) of sodium ethyl sulphonate is heated in 100 ml of anhydrous dimethylformamide at 120 C for 40 hours. The mixture is then filtered off, dimethylformamide is distilled off, the residue is digested in water and extracted with methylene chloride. The methylene chloride phase is dried and the methylene chloride is distilled off. The residue is recrystallized from toluene/cyclohexane. You get 23.5 g (69% of the theoretical) methyl-2-TN-(ethyl sulfonylacetyl)-N-(2,6-dimethyl-phenyl )-aminoj7-propanoate with melting point 128 - 129°C and

formula:

Example 3

Methyl -2-/N-(n-propylsulfonylacetyl)-N-(2-,6-dimethylphenyl)-amino 7-propanoate

To a suspension of 20.7 g (0.1 mol) of methyl 2-[N-2,6-dimethylphenyl)-amino_7--propanoate and 13» 8 g (0.1 mol) potassium carbonate in 100 ml of dry acetonitrile is added at room temperature to 18.5 g (0.1 mol) of n-propylsulphonyl acetyl chloride. After stirring the mixture for 12 hours at room temperature, the precipitate from potassium hydrogen carbonate is filtered off, the filtrate is poured into 1 liter of ice water, and extracted with methylene chloride Methylene chloride if the phase is t-dried, then methylene chloride is removed, and the residue is recrystallized from toluene. 22.4 g (63% of the ■ theoretical) methyl-2-/N-(n-propyl-sulfone) is obtained sylacetyl)-N-(2,6-dimethylphenyl)-amine ol-propanoate with melting point 124.5 - 125.5°C, and formula:

Examples 4 to 112.

Examples 4 to 112 listed below in Tables 1 and 2 are prepared analogously to Examples 1 to 3. There are in Table 1 for those in Examples 4 to 95 and in Table "'2 for the compounds prepared in Examples 96 to 112 with formula I reproduced the residues for R^fn and m in summarized form, and each time in the last column of the table listed in the available physical-mechanical data.

. Example 113

Methyl-2-N-(n-propyl sulfinylacetyl)-N-(2-dimethyl-phenyl)-amino-N-propanoate.

To a solution of 16.15 g (0.05 mol) methyl-2-TN-(n-propylthioacetyl)-N--(2,6-dimethylphenyl)-amino_ /- propanoate in 60 ml methylene chloride is dosed at -20 to -30 C

during 2 hours with stirring, a solution of 10.15 g (0.05 mol) of 85% 3-chlorobenzoic acid in 100 ml of methylene chloride. After 2 hours of further stirring at room temperature, the mixture is filtered, the methylene chloride phase is washed intensively with 200 ml of saturated aqueous sodium bicarbonate solution, and dried over sodium sulfate. Methylene chloride is then distilled off, and the residue and co-crystallizers are obtained from toluene/cyclohexane. You get 14.3 g (= 84.5% of the theoretical) -methyl-2-y\N-(n-propyl sulfinylacetyl)-N-(2,6-dimethylphenyl)-amino_7- propanoate with melting point 93 - 95°C'o:g formula:

Example 114

Methyl 2-n-(phenylsulfinylacetyl)-N-(2-dimethyl-phenyl)-amino-n-propanoate.

17.86 g (0.05 mol) of methyl-2-[N-(phenylthioacetyl)-N-(2,6-dimethylphenyl)-amino_7"-propanoate. Dissolve in 100 ml methylene chloride, and in 100 ml A 10% aqueous potassium hydrogen carbonate solution is placed in a 500 ml four-necked flask. With good stirring, 8 g of bromine are added to the mixture at room temperature, and stirred for 2 hours at room temperature. Then the methylene chloride phase is separated and dried over sodium sulfate. The methylene chloride is then distilled off and the residue is recrystallized from toluene. 15.2 g (81% of the

■ theoretical) methyl-2-[N-(phenylsulfinylacetate)-N-(2,6-dimethylphenyl)-amine o/"-prop ionate with melting point 116 - 118°c,

and formula:

Example 115 - 225

Analogous examples 113 and 114 are restated

those below in tables 3 and 4.. listed examples 115 to 225- It is in table 3 for the, in -examples 115 to 208,

and in table 4 for the compounds of formula I prepared in examples 209 to 225, the residues R^ to R^, n and m are given in summarized form, and each time in the last column of the table listed the physical-chemical data found.

In Table 5, a selection of a further 10 examples with optically active compounds of formula I from the D-series, resp. the L-series is listed. These products are distinguished from the examples' with the corresponding racemic products by the addition "AD", resp. "AL" to sample no. In Table 5, these optically active compounds are characterized next to the corresponding substituents of formula I, moreover by their specific rotation [aj. Their production takes place analogously to the corresponding racemic products.

B.' Formulation examples

Example A

A dusting agent is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of tolcum as an inert substance, and crushing in an impact mill.

Example - B

A water-dispersible, wettable powder is obtained by mixing 25 parts by weight of active substance, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignin sulphonic acid potassium and 1 part by weight, oleylmethyltauric acid sodium, as a wetting and dispersing agent and grinding into a stick -mill.

Example C

A water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of active substance with 6 parts by weight of nonylphenol polyglycol ether (10Ae0)<*>), 3 parts by weight of isotridecanol polyglycol ether (8AeO-)<*>) and 71 parts by weight of paraffin mineral oil, (boiling range e.g. approx. 255 to above 377°C) and ground in a friction ball mill to a fineness of less than 5 microns.

Number of ethylene oxide units in polyglycol ether residue.

Example D

An emulsifiable concentrate is obtained. of 15 parts by weight of active substance, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of nonylphenol polyglycol ether (lOAeO) as an emulsifier.

Example E

For the production of a granule containing 5% active substance, the following components are used: 5 parts by weight active substance, 0.25 parts by weight epichlorohydrin, 0.25 parts by weight cetyl polyglycol ether, 3.5 parts by weight polyethylene glycol, 91 parts by weight kaolin. The active ingredient is mixed with the epichlorohydrin and dissolved in 6 parts by weight of acetone, then polyethylene glycol and cetyl ether are added. The resulting solution is sprayed onto the kaolin, and then the acetone is evaporated under vacuum.

C. Biological examples

Example I

Effect of additives with formula I against Pythium ultimum on peas.

a) Effect after soil application.

Mushrooms are grown in a sand culture and mixed with soil.

The thus infected soil is filled in growing pots and sown

with pea seeds. After sowing, the fungicidal compounds to be examined are filled s,qm aqueous suspensions each time on the surface of the cool soil. Thereby, active substance concentrations from 200 to 12 ppm are used; (referred to soil volume).. The pots are set up for 2-3 weeks in a greenhouse at 20 - 22°C and the cool potting soil is kept evenly slightly moist. When assessing pythium infestation, the number of pea plants affected is determined by the proportion of healthy and diseased plants compared to the corresponding controls and the corresponding degree of effectiveness is calculated.

The compounds according to the invention with formula I lead to a strong control of the pythium ultimum attack (efficiency average y80%) at an applied amount of 20.0 ppm. A number of compounds of formula I are excellently effective at even significantly less effective substance concentrations, as the test results summarized in the following Table Ia show.

Table Ia

Effect against py thiuni-ultimum after treatment

of inoculated soil' and subsequent sowing of fresh seed.

■ 1st day: Inoculation of the soil with pythium-ultimum and treatment with a fungicide compound, sowing

14th day: Assessment.

b) Effect after stain application.

The fungus is cultivated as described in example Ia, and mixed

with search terms. This is filled in growing pots and sown with pea seeds that have been stained in advance with the experimental preparations to be examined and formulated: as a mordant. Thereby, effective substance concentrations of 1000 - 250 ppm (referred to seed weight) are used. The pots are set up for 2 -3 weeks in a greenhouse at 20 - 22°C, and the soil is kept evenly slightly moist. The assessment is carried out as mentioned in example Ia.

The compound of formula I shows an average efficiency of y 80% at 1000 ppm. A number of compounds with formula I give, at even significantly lower concentrations, complete attack control, as the test results summarized in the following table I b show.

Table Ib

Effect against pythium ultimum after treatment (pickling) of pea seed material and subsequent sowing in inoculated soil. 1st day: Inoculation of the test soil and sowing of stained pea seeds, as well as unstained control trials.

14-. day: Assessment.

Example II

Preventive effect of compound of formula I

mother phyto<p>htora capsici (soil application).

Phytophtora capsici is grown in sand culture and mixed with experimental soil. The thus infected soil is filled in growing pots and sown with paprika (Capsicum annuum). After out-

sowing, the compound according to the invention is poured as aqueous suspensions on the soil surface or. incorporate ideas into the topsoil.

Thereby, active substance concentrations are used

from 200 to 12 ppm (referred to j ord volume t),. The pots are then placed approx. 3 weeks in a greenhouse at 22 - 24°C, and the culture soil is kept evenly moist'.- When assessing Phytophthora capsicum infestation, the growth of paprika plants as well as the proportion of fresh and healthy plants compared to the corresponding controls, and the efficiency is calculated accordingly.

The compound of formula I gives, at an amount used of 200 pprn, an approximately full termite. control of phytophtora capsici infestation. A number of compounds of formula I lead to a similarly almost complete reduction of the fungal attack (0 - 5%) at even significantly smaller amounts used, as shown below in Table II The test results listed below.

Example III

Effect of compounds of formula I rnot phytop-htora inf est ans on solan.um lycopersicum.

a) Preventive effect.

Tomato plants (solanum, lycopersicum) of the type

Rheinlandsruhm is sprayed in the 3-leaf stage with a compound according to the invention of formula I dropwise. -Use carefully, the doses are each time ■500, 250 and 125 mg of active substance per Oxygen spray fluid. -After drying the spray coating, the plants are strongly inoculated with a zoosporangia suspension of Phytophtora infestans, and placed 'drop-moist for a day' in a kl i rna chamber at a temperature of 16°C and a relative humidity of approximately 100%. They are then placed in a cold greenhouse with a temperature of 15°C and a relative humidity of 90 - 95%. After an incubation period of 7 days, the plants are examined for attack by phytophthora. The latter is made visible in the form of typical bl/adf leaks, the number and size of which serve as an assessment of narrow sticks for the investigated active substances. The degree of attack is expressed in % infested leaf surfaces - compared to untreated, infected control plants (100% attack). In this test, the compounds of formula I at an applied amount of 500 mg per liters of spray liquid, an almost complete attack barrier. With some of the test results summarized in Table Illa, it can be shown that many compounds of formula I, even with significantly smaller amounts used, lead to a complete fungal attack control.

b) Curative effect

Tomato plants (solanum lycopersicum) of the type

Rheinlaridsruhm is strongly inoculated in the 3-leaf stage with a Zoo sporangia suspension of phytophtora infestans and incubated for 24 hours in a climate chamber at a temperature of 15°C and a relative humidity of approximately 100%.

After drying the plants, they are sprayed with the compounds of formula I formulated as spray powder at active substance concentrations of 500, 250 and 125 mg/l injection liquid. The plants are then reset again in a greenhouse - with a temperature of approx. 16 - 18°C, and a relative humidity of approx. 90 - 95%. '•

A few days later, the plants are examined for infestation with phytophtora infestans. The number and size of the typical phytophthora leaf spots serve as a yardstick for assessing the investigated company's substances.

The degree of attack is expressed in % of infested leaf surfaces compared to untreated, infected control plants (=100% attack).

In connection with formula I, the infection is almost completely stopped at an applied quantity of 500 mg/l of injection fluid. As the experimental results listed in Table IIIb show, many forbindel ser V with formula I at still significantly smaller applied quantities lead to a full attack control.

c) Preventive systemic effect

Those that spray powders .formulated compounds

with formula I has as aqueous suspensions in active substance - concentrations of 200, 100, 50 and 25 ppm (referred to soil volume) on the soil surface of approx. 3~4 weeks old inoculated tomato plants of the Rheinlandsruhm type. Three days later, the plants are inoculated with a Zoosporangia suspension of phytophtora infenstans, and incubated as indicated in Example Illa. After an incubation period of 6-7 days, the plants are examined for infestation with phytophtora infestans. The number and size of the typical phytophthora leaf spots formed on the leaves form a yardstick for assessing the effect of the investigated compounds.

The degree of attack is expressed in % infested leaf surfaces compared to untreated, infected control plants (100% attack).

With the compound of formula I, the attack is almost completely prevented when an amount of 200 ppm is used.

as a substance (referred to soil volume). As we see in table Ille summarized research results, many compounds with formula I lead to a complete attack control with still significantly smaller amounts used.

Example IV

Effect of the compounds of formula I against Plasrnopara viticola on beet.

.Preventive effect.''"

Vines grown from cuttings of plasma-paratending types, Muller-Thurgau, are sprayed at the droplet-moist 4-leaf stage with aqueous suspensions of the compounds of formula I to be investigated. The concentrations used are 500, 250 and 125 mg of active substance/l of spray liquid.

After drying the spray coating, . the plants are inoculated with Zoosporangia suspension of Plasrnopara viticola and placed in a drop-moist chamber at a temperature of 20°C, and a relative humidity of approx. 100% After 24 hours, the infected plants are removed from the climate chamber and placed in a greenhouse with a temperature of 23°C and a humidity of

approx. 98%. After an incubation period of 7 days, the plants are moistened and placed overnight in the climate chamber and the disease is brought to an outbreak. Attack assessment then takes place. The number and size of infection sites on/mixtures of the inoculated and treated plants serve as a measure of the effect of the compound according to the invention. The degree of attack is expressed in % infested leaf surfaces, compared to untreated infected control plants (= 100% attack)■'..

The compounds of formula 1 give an average attack control of ^> 80..% at an applied quantity of 500 mg of active substance/l•spray liquid. ' As it may appear on

some test results summarized in Table IV, many compounds of formula I can also lead to a complete fungal attack control at significantly smaller amounts used.

Claims (1)

Patent claim1. Connection with the general formula I, R^ means (C^-C^)-alkyl, halogen, (C^-C^ )-alkoxy, (C,-C, )-alkylthio, '(C 0-C,)-alkene <y>l , ■ R means hydrogen, (C1-C , )alkyl, halogen, 2 .14 ■■■■ R. j means (C 1 -C 4 )-alkyl, halogen, R^ , Rrj mean hydrogen, methyl, R 1 means hydroxy, (C 1 -C 1 )-alkoxy, (C 1 -C 2 )-alkylthio, (C 2 -C 5 )-alkoxyethoxy, amino, (C 2 -C 8 )-alkylamino, di-(C 3 -C9 )-alkylamino, O-ka.t, where kat means a cation equivalent of an inorganic or organic base, R 6 means (C 1 -C 8 )-alkyl, (C 1 -C 4 )-alkoxy-(C 1 -C 6 )-alkyl, (C 1 -C 2 )-alkylthio-(C 1 -C 3 )-alkyl, (C 1 -C 8 )-alkyl-sulfinyl-(C 1 -C 3 )-alkyl. , -Cg ) _sulf onyl _ _ C^ )-alkyl, (C_-C6 )'-cycloalkyl, (C1-C^ )-halo-alkyl, (C^ -C^ )-hydroxyalkyl, (C^ -C9 )-Alkoxy-Carbonyl-(C1 -CQ )-alkyl, (CQ-C , )-alkenyl, (C„-C4 ,)-alkynyl, benzyl, which is optionally substituted with one or two residues from the group (C-j-C4 .)-alkyl, halogen, nitro,-phenyl, which is optionally substituted with one or two residues from the group (C^-C^)-alkyl, halogen, n means 0, 1 and m means 0, 1,2. 2.. Process for the preparation of a compound of formula I according to claim 1, characterized by ata) Compound of the general formula III in which R, R., R0, R„ and m have the above meaning, and X means a nucleophilic substitutable leaving residue, preferably from the group halogen, tosylate or mesylate, especially chlorine or bromine, is reacted with. sulfinure salts of the general formula II Where Me means an inorganic or <:> organic cation, preferably sodium, potassium, calcium or ammonium, and R^ has the above-mentioned meaning, is converted to a compound of formula I in which n=1, preferably in inert solvents or diluents, and preferably at temperatures between 50 and 250°C, or'b) Acylinder derivatives with the general formula IV wherein R, R^ . R 0 , R 1 and m have the aforementioned meanings, are reacted with sulfonyl acetyl halides of the general formula V R6 - SO2 - CH2 - COHal (V ) in which Hal means a halogen atom, preferably chlorine or ■bromine, and R^ means a compound of formula I in which n=1, or is reacted with sulfinylacetyl halides of the general formula VII, in which R^ and Hal have the meaning indicated under f.rmel V for compounds of formula I in which & =0, possibly each time during the addition of acid-binding agents, preferably each time inert dissolving or thinning agents, and preferably each time at temperatures between - 20 and 160°C, oro) More cap toacetanil ides "of the general formula VI": in which R, R^ , Rg, Ry R^ and m have'-the one under formula I indicated meaning, is reacted with corresponding amounts of an oxidizing agent either to a compound of formula I in which n = 0, or to a compound of formula I in which n = T, preferably each time in solvents or emollients, and preferably at temperatures between - 40 and 100 C- for compounds of formula I, in which n = 0, resp. between - .20' and 160°C, tor compounds of formula I, where n=1. 3. Fungicides, characterized by a content of a. compound with formula I according to claim 1 as active substance.. 4/ Fungicidal agents characterized by a content of 2 to 95% by weight, preferably 10 to 90% by weight, of a compound of formula I' according to claim 1 as active substance as well as common formulation aids. 5. Use of compound with formula I according to claims 1, 3 and 4 "for pest control in planted shuttles see . 6. Procedure for combating common fungi, . characterized by bringing the affected surfaces, plants or substrates into contact with a fungicidally effective amount of active substances of formula I according to claims 1, 3 and 4 ..'•