NO811258L - FUNGICIDE, HETEROCYCLIC SUBSTITUTED TIOGLYCOLIC ACIDANILIDES, PROCEDURES FOR THEIR PREPARATION AND PESTICIDES CONTAINING THESE - Google Patents

Description

The present invention relates to new, fungicide, heterocyclically substituted thioglycolic acid anilides, a process for their preparation, and their use as a pest control agent, especially in plant protection.

The compounds according to the invention have the general formula I,

in which

R1 = (C1-C3)-alkyl, halogen, (C1-C3)-alkoxy, (C1-C4)-alkylthio, (C2-C4)-alkenyl,

R2= hydrogen, (C1-C2)-alkyl,

= methyl, halogen,

R^, Rg = hydrogen, methyl,

R 5 = hydroxy, (C 1 -C 4 )-alkyloxy, (C 1 -C 3 )-alkylthio, (C 1 -C 2 )'-alkoxyethoxy, amino (C 2 -C 4 )-alkylamino, di-(C 2 -C ^)-alkyl-amino, O-Kat, whereby Kat stands for a cation equivalent of an inorganic or organic base, preferably Na, K, 1/2 Ca, ammonium,

Het = a 5-6 membered, saturated or unsaturated heterocyclic residue, optionally benzo-condensed, with up to 4 heteroatoms of the group N, 0, S, preferably a heterocyclic residue of the following mentioned series:

whereby each heterocyclic residue further in the carbon part can carry one or more (Cj -C^)-alkyl groups, and X = 0, S, NRQ,

Rg = hydrogen, (C1-C4)-alkyl,

R^= (C^-C^)-alkyl, halogen,

R9= (C1-C4)-alkyl,

n = 0, 1 ,

m = 0 , 1 , 2 ,

q = 0, 1 , 2.

Preferred compounds of formula I are such, i

which ones

R^ = methyl, ethyl, isopropyl, chlorine, bromine,

R 2 , R 2 = methyl,

R^, Rg = hydrogen, methyl,

R 5 = hydroxy, (C 1 -C 2 )-alkoxy, (C 1 -C 2 )-alkylthio,

Het = a 5-6 membered, saturated or unsaturated heterocyclic radical with up to 3 heteroatoms of the series N, 0, S, preferably an optionally in the carbon part one to two times (Cj-C^)-alkyl substituted heterocyclic radical of the subsequently mentioned series :

whereby

X = 0, S, NRg,

Rg = hydrogen, methyl, ethyl, isopropyl,

Rg = methyl, ethyl, isopropyl,

m = 0, 1 ,

q = 0.

It is known to use fungicides from the range of dithiocarbamates such as e.g. Mancozeb or Maneb, perchloromethylmercaptan derivatives, such as Captafol. With these active substances, the Phyto-phthora strains that attack above ground, on leaves and stems can be combated, while the disease-causing agents of the genus Phytophthora and Pythium living in the soil, which attack the plant roots, are not combated. It is further known that acylated anilinoacetic acid-, respectively propionic acid derivatives such as those described in DE-Officials 23 50 944, 25 23 730, 25 13 789, 25 15 091, 26 43 445 and 26 43 477 have, in addition to a herbicidal effect, also a fungicidal effect against fungi of the family Oomycetes. It was now surprisingly found that the compounds of formula I according to the invention exhibit an outstanding fungicidal effect, especially against those of the class of Phycomycetes belonging to Oomycetes, such as e.g. Pythium, Phytophthora,<p>eronospora, Pseudoperonospora and Plasmopara.

Thus, fungi on the most diverse cultivated plants, such as e.g. maize, rice, grain, sugar beet, vegetables, cucumber crops, potatoes, tomatoes, vines, hops, tobacco, citrus and paprika species, ornamental plants, cocoa, bananas and rubber are combated respectively. inhibited respectively 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 combat seed-dwelling fungi on semen or to combat phytopathogenic fungi occurring in the soil.

The effect of the compounds of formula I according to the invention is therefore, among other things, to be described as extremely surprising as corresponding alkylthioacetanilides, such as those described in the above-mentioned DE-OS 25 15 091, against Phytophthora, especially against soil-dwelling Phytophthora species and fungi of the family Pythium exhibit only a very small fungicidal effect.

The subject of the present invention is therefore also fungicides, which are characterized by a content of a compound of formula I.

The preparation of compounds of formula I with

q = 0 is possible according to different methods and can e.g. take place by one of the following methods 1 to 3:

1. In the alkylation of mercapto-substituted heterocyclic compounds of the general formula III, in which Het has the meaning as in formula I, with compounds of the general formula II,

wherein R, R.J , , R^ and m have the meanings as in formulas I and X mean a nucleophilic substitutable starting group, preferably from the group halogen, tosylate or mesylate, especially chlorine or bromine.

The reaction according to method 1 is preferably carried out in above reactants inert, preferably polar or dipolar aprotic solvents or diluents. As such, e.g. in consideration: Water, alcohols such as methanol, ethanol, propanol, butanol or glycol; dialkylated amides such as dimethylformamide; nitriles such as acetonitrile or propionitrile; ketones such as acetone, methyl ethyl ketone or diisopropyl ketone; ether such as dioxane.

The reaction temperature is preferably between 20°C and 160°C, especially between 20°C and 120°C.

The turnover can take place with or without. addition of an auxiliary base as an acid-binding agent. Preferably, however, an auxiliary base is used. As such, e.g. in consideration: Inorganic oxides such as calcium oxide, hydroxides such as sodium hydroxide or calcium hydroxide, carbonates such as sodium or potassium carbonate and trialkylamines such as triethylamine or pyridine. 2. When reacting thioglycolic acid anilides of the general formula IV, in which R, R^, R2, Rj and m have the meanings as in formula I, with heterocyclic compounds of the general formula V,

wherein Het has the meaning as in formulas I and X means a nucleophilic substitutable starting group, preferably from the group halogen, tosylate or mesylate, especially chlorine or bromine.

The reaction conditions for method 2 are, with regard to reaction temperature, the reaction medium and the use of an auxiliary base as an acid-binding agent, identical to the conditions mentioned under 1.

3. When reacting thioglycolic acid chlorides with the general formula. VI, in which Het has the meaning as in formula I, with aniline derivatives of the general formula VII,

wherein R, R 1 , R 2 , R 2 and m have the meaning as in formula I, in the presence or absence of acid binding agents.

The conversion after 3. is preferably carried out in inert solvents or diluents. One uses e.g. preferably hydrocarbons such as benzene, toluene, xylol, petroleum ether, cyclohexane; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride; ether such as dialkyl ether, dioxane or tetrahydrofuran; nitriles such as acetonitrile; carboxylic acid ester such as acetic acid ethyl ester.

As acid-binding agents, e.g. in consideration: Trialkylamines such as triethylamine, pyridine, inorganic bases such as metal oxides or hydroxides, e.g. calcium oxide or sodium hydroxide or carbonates such as potassium carbonate. If the reaction is carried out without acid-binding agents, it is preferable to work at an elevated temperature and it must be ensured that the halogen hydrogen is removed from the reaction mixture.

The reaction temperature is between 0°C and 140°C, when using an auxiliary base as an acid-binding agent preferably between 0°C and 60°C, without an auxiliary base between 40°C

and 120°C.

The production of aniline derivatives of formula VII used as starting material can e.g. happen after: J. Org. Chem. 30, 4101 (1965); "DE-OS 22 12 268; US-PS 40 12 519; Tetra-hedron 19 6 7; 487 and 493. From these aniline derivatives, the starting materials of formula II can also be recovered by acylation, for example with chloroacetyl chloride or bromoacetyl chloride.

The preparation of compounds of formula I with

q = 1 or 2 occurs by oxidation of compounds with formula

In with q = 0 following reaction nucleus:

The oxidation of compounds of formula I with q = 0 during uptake of 1 oxygen atom to sulfoxides of formula I with q = 1 or during the absorption of 2 oxygen atoms to sulfones of formula I with q = 2 can be carried out by methods known to the person skilled in the art. As an oxidizing agent, e.g. in consideration: Hydrogen peroxide /Chem. Pray. 4J_, 2836 (1908); Houben-Weyl vol. 9, 4th edition, p. 228?>peracid such as peracetic acid, perbenzoic acid, 3-chloroperbenzoic acid or phthalmonoperic acid /Houben-Weyl, vol. 9, 4th edition, p. 228; J. prak. Chem. 131, 357 (1931) and 128, 171 (1930); Chem. Pray. 70, 379

(1937)_7, chromic or nitric acid or in the case of sulphoxides also bromine or chlorine /Synth. 1/1979 P. 3 9 7.

The oxidation reactions are preferably carried out in the presence of solvents. As such can be used: Hydrocarbons such as e.g. benzene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane or trichloroethylene, ketones such as acetone or methyl ethyl ketone, carboxylic acids such as glacial acetic acid or propionic acid, anhydrides such as acetic anhydride and water or also mixtures of these solvents.

The reaction temperature for the production of sulfones is between -20°C and 160°C, preferably between 0°C and 120°C, for the production of sulfoxides between -40°C and 60°C.

If the preparation of the compounds of formula I according to the invention is carried out according to one of the methods 1 or 2 described above in such solvents, in which one of the reactants is poorly soluble, an acceleration of the reaction can be achieved by adding catalysts, like for example. crown ethers or those known as phase transfer catalysts quaternary ammonium, resp. phosphonium salts.

The compounds of formula I with

have asymmetric carbon atoms. They therefore generally exist as racemic mixtures of enantiomeric forms. The enantiomeric forms exhibit a different biological effect. A targeted synthesis of pure D-isomers can take place e.g. by fractional crystallization of salts of anilinopropionic acid of the general formula VIII with optically active bases

such as cinchonine or α-phenylethylamine or by fractional crystallization of anilinobutyrolacetones of the general formula Villa with optically active acids such as e.g. D- or L-tartaric acid. In the formulas VIII and Villa, R^, R2, R^, Rg and

m the meanings as in formula I.

But a targeted synthesis is also possible, starting from optically active halopropionic acid derivatives such as e.g.

L-2-chloropropionic acid methyl ester, optically active lactic acid ester tosylates or optically active halobutyrolacetones and anilines of the general formula IX,

in which R^, R^, R- and m have the meanings as in formula I. This reaction takes place over/or as an SN2 reaction under inversion of the configuration. Then formed from 2,6-dimethylaniline and L-2-chloropropionic acid respectively. L-2-chloropropionic acid methyl ester preferably D-2-(2,6-dimethylanilino)-propionic acid or its methyl ester.

The agent according to the invention generally contains the active ingredient of formula I to approx. 2-95% by weight, preferably 5-90% by weight. It can be used as a spray powder, emulsifiable concentrates, sprayable solutions, dusting agent, mordant, dispersions, granules or microgranules in the usual preparations.

Spray powders are similarly dispersible preparations in water which contain, in addition to the active ingredient, a diluent or inert substance and wetting agent, e.g. polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkyl or alkylphenyl sulfonates and dispersing agent, e.g. lignin sulfonic acid sodium, 2,2'-dinaphthyl-methane-6,6'-disulfonic acid sodium, dibutylnaphthalene sulfonic acid sodium or also oleoylmethyltauric acid sodium. Their production takes place in the usual way, e.g. when grinding and mixing the components. Emulsifiable concentrates can be prepared, e.g. by dissolving the active ingredient in an inert organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylol or also higher boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. In the case of liquid active substances, the solvent portion can also be completely or partially omitted. As emulsifiers can be used, for example: Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate 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 polyglycol ethers, sorbitan fatty acid esters, pbloxyethylene sorbitan fatty acid esters or polyoxyethylene - sorbitol tests.

Atomizing agent can be produced by grinding

of the active ingredient with finely distributed solids, e.g. talc, natural clays such as kaolin, bentonite, pyr<p>phyllite or diatomaceous earth.

Granules can be produced either by spraying the active substance on adsorbable, granulated inert material or by applying active substance concentrates using binders, e.g. polyvinyl alcohol, polyacrylic acid sodium or also mineral oils on surfaces of carriers such as sand, kaolinites or on granulated inert material. Suitable active substances can also be granulated in the usual way for the production of fertilizer granules - if desired in mixtures with fertilisers.

In spray powders, the active ingredient concentration is e.g. about. 10-90% by weight, the rest up to 100% by weight consists of normal formulation ingredients. In the case of emulsifiable concentrates, the active ingredient concentration can be 10-80% by weight. Dusty formulations usually contain 5-20% by weight of active ingredient, sprayable solutions approx. 2-20% by weight. In the case of granules, the active ingredient content partly depends on whether the active compound is in liquid or solid form and which granulation aids, fillers etc. are used.

In addition, the aforementioned active ingredient formulations optionally contain the usual fixing agents, wetting agents, dispersing agents, emulsifying agents, penetrating agents, solvents, fillers or carriers.

For use, the commercially available concentrates are optionally diluted in the usual way, e.g. by spray powders, emulsifiable concentrates, dispersions and partly also by microgranules using water. Dusty 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 also possible. Particularly in the case of mixtures with fungicides, synergistic increases in effectiveness can also be partially achieved.

The invention is illustrated in more detail by the following examples:

A. Manufacturing examples

Example_el_1

Methyl-2-(N-thiazolin-2-ylmercaptoacetyl)-N-(2,6-dimethylphenyl)-amino7-propanoate, 17 g (0.06 mol) methyl-2-(N-(chloroacetyl)-N-( 2,6-dimethylphenyl)-amino7-propanoate,

6.3 g (0.063 mol) of 2-mercaptothiazoline and 0.7 g (0.063 mol) of potassium carbonate are stirred in 100 ml of acetonitrile for 16 hours at 65°C. After filtering off the inorganic salt formed, the filtrate is diluted with ice and water, the precipitate formed is filtered off and recrystallized from toluene. 18.4 g (84% of theory) of methyl 2-[N-(thiazolin-2-ylmercaptoacetyl)-N-(2,6-dimethylphenyl)-amino7-propanoate with a melting point of 95°G are obtained.

Examples_2_to_28a

In an analogous manner to that described in example 1, the subsequent examples 2 to 28a indicated in table 1 are prepared. It is in table 1 for the compounds of formula I prepared in examples 2 to 28a with q = 0, the residues R, R^ to R^, m and Het are reproduced, in summarized form and in the last column of the table they are found physical-chemical characteristics listed.

Exercise; 2el_29

Methyl 2-[N-(benzthiazol-2-ylsulfonylacetyl)-N-(2,6-dimethylphenyl)amino]-propanoate.

14.50 g (0.035 mol) methyl 2-[N-(benzthiazol-2-yl-mercaptoacetyl)-N-(2,6-dimethylphenyl)-amino]-propanoate, dissolved in 100 ml methylene chloride is added at 30° C to 40°C with 0.75 mol (15.25 g) of 85% 3-chloroperbenzoic acid. After the addition, the mixture is stirred for 1 hour at reflux, then the 3-chlorobenzoic acid is filtered off and the filtrate is washed with sodium bicarbonate solution. The methylene chloride phase is dried and the methylene chloride is distilled off. The remaining residue is recrystallized from toluene/cyclohexane. 14.2 g (90.5% of theory) of methyl 2-[N-(benzthiazol-2-ylsulfonylacetyl)-N-(2,6-dimethylphenyl)-amino]-propanoate with a melting point of 181°C to 182 .5°C.

Example 30

Methyl 2-[N-(benzthiazol-2-ylsulfonylacetyl)-N-(2,6-dimethylphenyl)-amino]-propanoate.

10.7 g (0.025 mol) methyl 1-2-/N-(benzthiazol-2-yl-mercaptoacetyl)-N-(2,6-dimethylphenyl)-amino7-propanoate, dissolved in 100 ml methylene chloride is added at -20 °C in the course of 1 hour with 5.1 g (0.025 mol) of 85% 3-chloroperbenzoic acid, dissolved in 50 ml of methylene chloride. After the addition, the mixture is stirred for 2 hours at room temperature, the methyl chloride phase is washed thoroughly with aqueous sodium bicarbonate solution, dried over sodium sulfate, finally the methylene chloride is distilled off and the remaining residue is recrystallized from toluene/cyclohexane. 8.4 g (78% of theory) of methyl 2-[N-(benzthiazo1-2-ylsulfonylacetyl)-N-(2,6-dimethylphenyl)-amino7-propanoate with a melting point of 159°C to 161°C are obtained.

B. Formulation examples

Example_el_A

A nebulizing agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as inert material and fine parts in an impact mill.

Example_el_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 ligninsulfonic acid calcium and 1 part by weight of oleoylmethyltauric acid sodium as a wetting and dispersing agent and grinding in a stick mill.

Example_C

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

<*>) = number of ethylene oxide units in the polyglycol ether residue.

Eczema<p>_el_D

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of nonylphenol polyglycol ether (10 AeO) as emulsifier.

Example_el_E

For the production of a 5% active ingredient containing granules, the following components are used: 5 parts by weight active ingredient, 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 substance is mixed with the epichlorohydrin and dissolved in 6 parts by weight of acetone, then the polyethylene glycol and cetyl ether are added. The resulting solution is sprayed on

kaolin and then the acetone is evaporated under vacuum.

C. Biological examples

Example_el_I

YiElSSi22_§Y_f2E^i2^§i§ene_med_f ormel_I_against_PYthium_ultimum on_pea

a) YiElS?}i52_§tt?E_i2<r>^5EEli^;§Si2Si

The mushroom is grown in a sand culture and mixed with soil.

The thus infected soil is filled in cultivation pots and sown with sow peas. After sowing, the fungicidal compounds to be tested are poured as aqueous suspensions onto the surface of the culture soil. Thereby, active substance concentrations of 200 to 12 ppm (calculated from the soil volume) are used. The pots are set up for 2-3 weeks in a greenhouse at 20°C to 22°C and the culture soil is kept uniformly slightly moist. When assessing Pythium attack, the germination of the pea plants and the proportion of healthy and diseased plants are determined in comparison to the corresponding control plants and the corresponding efficiency.

The compounds of formula I according to the invention lead, at an application amount of 200 ppm, to extensive control of the Pythium ultimum attack (efficiency on average >80%). A number of compounds with formula I are excellently effective at an even lower active ingredient concentration. As the trial results compiled in the subsequent table I show.

Table I

Effect against Pythium ultimum after treatment of inoculated soil and subsequent sowing of fresh seed. 1st day: Inoculation of soil with Pythium ultimum and treatment with a fungicide compound, sowing.

14th day: Evaluation.

Example_II

Preventive effect2_of the compounds_with_formula_I_against El}YÉ2Ehtl}2E§_£§2§iSi_ii2E^§2Eii}S§s ion)_

Phytophthora capsici is raised in sand cultures and mixed with test soil. The thus infected soil is filled in cultivation pots and sown with paprika (Capsicum annuum). After sowing, the compounds according to the invention are poured as aqueous suspensions on the soil surface or incorporated into the cover soil. In this way, active substance concentrations from 200 to 12 ppm (calculated on the soil volume) are used. The jars are then lined up approx. 3 weeks in a greenhouse at 22°C to 24°C and the culture soil is kept uniformly moist. When assessing the Phytophthora capsici attack, the germination of paprika plants is determined as well as the proportion of healthy and diseased plants in comparison to corresponding controls and the corresponding degree of effectiveness is calculated.

The compounds of formula I provide, at an application rate of 200 ppm, an almost complete control of the Phytophthora capsici attack. A number of compounds of formula I lead to a substantially even smaller amount of use in a likewise almost complete reduction of the fungal attack, as the compiled test results in the following table II show.

Table II

Effect against Phytophthora capsici after treatment of inoculated soil with fungicidal compounds of formula I and sowing of fresh paprika seedstock. 1st day: Inoculation of the soil and treatment with a fungicide compound, sowing.

about. 21st day: Evaluation.

Example_III

iDl§§tans_2å_Solanum_lYgo2ersicum Preventive_virknin2^

Tomato plants (Solanum lycopersicum) of the variety Rheinlandsruhm are sprayed dripping wet in the 3-leaf stage with the compounds of formula I according to the invention. The application concentrations were. 500, 250 and 125 mg active ingredient per liter of spray liquid.

After the drying of the spray coating, the plants are heavily inoculated with a Zoosporangien suspension of Phytophthora infestans and are kept dripping wet for a day in a climate chamber with a temperature of 16°C and a relative humidity of almost 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 seen in the form of typical leaf spots, the number and size of which serve as a yardstick for evaluating the tested active substance. The degree of attack is expressed in % of the infested leaf surface in comparison with untreated, infected control plants (= 100% attack). In this test, the compounds of formula I at an application rate of 500 mg/liter of spray liquid effect an almost complete prevention of the attack. From some test results compiled in Table II, it can be shown that many compounds of formula I also lead to a complete control of attack by harmful fungi even with a significantly smaller amount of use.

Eczema]Part_i<y>

YiElSJ}il22_§y_f 2£2iQd2iser_with_f 2£m§i_I_m2t_Ei§§S2E5E§_Yi£il co1a_go_vines^

Preventive_effect_:_

Vines raised from cuttings of the Plasmopara-susceptible variety Miiller-Thurgau are sprayed wet at the 4-leaf stage with aqueous suspensions of compounds of formula I to be tested. Application concentrations are 500, 250 and 125 mg of active substance/litre of spray liquid. After drying the spray coating, the plants are inoculated with a Zoosporangien suspension of Plasmopara viticola and placed dripping wet in a climate chamber with 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 brought into a greenhouse with a temperature of 23°C and a humidity of 98%. After an incubation period of 7 days, the plants are moistened, placed overnight in the climate chamber and the disease is brought to an outbreak. Then follows the assessment of the attack. The number and size of the infection sites on the leaves of the inoculated and treated plants serve as a measuring stick for the effect of the compounds according to the invention. The degree of attack is expressed in % of the attacked leaf surface in comparison to untreated, infected control plants (= 100% attack). The compounds of formula I provide an average attack control of >80% at an application amount of 500 mg of active ingredient/litre of spray liquid. As can be seen from some of the test results compiled in Table IV, many compounds of formula I can lead to a complete control of the attack by harmful fungi with a significantly smaller amount of use.

Claims (6)

1. Compounds of the general formula I, in which R 1 = (■C)-C 3 )-alkyl, halogen, (C 1 -C 3 )-alkoxy, (C 1 -C 2 )-alkylthio, . (C 2 -C 4 )-alkenyl, R2 = hydrogen, (C₁-C₁)-alkyl, R3 = methyl, halogen, R^ , Rg = hydrogen, methyl, R 5 = hydroxy, (C 1 -C 3 )-alkyloxy, (C 1 -C 3 )-alkylthio, (C 1 -C 3 )-alkoxyethoxy, amino, (C 3 -C 4 )-alkylamino, di-(C 3 -C 2 )-alkyl-amino, O-Kat, whereby Kat stands for a cation equivalent to an inorganic or organic base, preferably Na, K, 1/2 Ca, ammonium, Het = a 5-6 membered, saturated or unsaturated heterocyclic residue, optionally benzo-condensed, with up to 4 heteroatoms of the group N, 0, S, preferably a heterocyclic residue of the following mentioned series: whereby each heterocyclic residue further in the carbon part can carry one or more (C^ -C^ )-alkyl groups, and X = 0, S, NRg, Rg = hydrogen, (C1-C4)-alkyl, R7 = (C1~ C4 )-alkyl, halogen, Rg = (C1 -C4 )-alkyl, n = 0, 1, m = 0 , 1 , 2 , q = 0, 1,2. 2. Process for the preparation of compounds of formula I according to claim 1, characterized by , I. that for the preparation of compounds of formula I, in which q = 0, a) react compounds of the general formula II, in which R, R^ , R^ , R^ oc3 m when the meaning as in formulas I and X means a nucleophilic substitutable starting group, preferably of the group halogen, tosylate or mesylate, especially chlorine or bromine, with heterocyclic compounds of the general formula III, in which Het has the meaning as in formula I, possibly with the addition of acid-binding agents, preferably in inert solvents or diluents and preferably at temperatures between 20 and 160°C, or b) that one reacts thioglycolic acid anilides with the general formula IV, in which R, R^, R^, R^ and m have the meanings as in formula I, with heterocyclic compounds of the general formula V, in which Het has the meaning as in formulas I and X means a nucleophilic substitutable starting group, preferably from the group halogen, tosylate or mesylate, especially chlorine or bromine, optionally with the addition of acid binding agents, preferably in inert solvents or diluents and preferably at temperatures between 20 and 160°C, or c) that one reacts aniline derivatives with the general formula VII, in which R, R^ , R^' R3°? m has the meanings as in formula I, with thioglycolic acid chlorides of the general formula VI, in which Het has the meaning as in formula I, optionally with the addition of acid-binding agents, preferably in inert solvents or diluents and preferably at temperatures between 0 and 140°C, and II. that for the preparation of compounds of formula I, in which q = 1 or 2, compounds of formula I, in which q = 0, are converted with corresponding amounts of an oxidizing agent either to compounds of formula I, in which q = 1, or to compounds with formula I, in which q = 2, preferably optionally in solvents or diluents and preferably at temperatures between -40 and 60°C for compound with formula I with q = 1, resp. between -20 and 160°C for compound of formula I with q = 2. 3. Fungicidal agent, characterized by a content of a compound of formula I according to claim 1 as active ingredient. 4. Fungicidal agent, characterized by a content of 2-95% by weight, preferably 5-90% by weight, of a compound of formula I according to claim 1 as active ingredient and common formulation aids. 5. Use of compounds of formula I according to requirements 1, 3 and 4 for pest control in plant protection. 6. Method for combating harmful fungi, characterized by bringing the surfaces, plants or substrates infested by the fungi into contact with a fungicidally effective amount of active substances of formula I according to requirements 1, 3 and 4.