DE3203656A1 - Novel 1,2,3-thiadiazolylmethyl (di)thiophosphates, phosphonates and phosphoramidates, their preparation, agents containing them and their use as pesticides, as well as novel thiadiazoles as intermediates, and their preparation - Google Patents

Abstract

The invention relates to compounds of the formula I which have fungicidal, acaricidal, insecticidal and nematicidal actions, in which <IMAGE> R<1> = hydrogen, alkyl, alkoxycarbonyl, R<2> = hydrogen, alkyl, halogen, cyano, alkoxy-carbonyl, cycloalkyloxy-carbonyl, phenylalkoxy-carbonyl, alkenyloxy-carbonyl, alkynyloxy-carbonyl, alkoxy-alkoxy-carbonyl, alkylthio-carbonyl or CONR'R", where R' = alkyl and R" + alkyl or (substituted) phenyl, or where NR'R" together denote an aziridine or azetidine ring or a five- or six-membered heterocyclic ring which optionally contains an additional nitrogen atom or oxygen atom, R<3> = alkyl, alkenyl or alkynyl, R<4> = alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl and X = O or S.

Description

New 1, 2,3-Thiadiazolylmetbyl- (di) thiophosphate,

phosphonates and phosphoramidates, processes for their production, agents contained in them and their use as pesticides and new thiadiazoles as intermediates and processes for their production The invention relates to new 1,2,3-thiadiazol-4-ylmethyl (di) thiophosphates , phosphonates and phosphoramidates of the formula I, in which R1 = hydrogen, (C1-C4) -alkyl or (C1-C4) alkoxycarbonyl, R2 = hydrogen, (C1-C4) -alkyl, halogen, cyano, (C1-C4) -alkoxycarbonyl, (C3-C7) -Cycloalkyloxy-carbonyl, phenylalkoxy-carbonyl, (C3-C5) -alkenyloxy-carbonyl, (C3-C5) -alkinyloxy-carbonyl, (C1-C3) -alkoxy- (C2-C3) -alkoxy-carbonyl, (C1 - C4) -Alkylthio-carbonyl or CONR'R ", where R '= (C1-C6) -alkyl and R" = (C1-C6) -alkyl or phenyl, which is optionally substituted up to twice by halogen, methyl, methoxy or nitro is substituted, or where NR'R "together denote an aziridine or azetidine ring or a five- or six-membered heterocycle ring optionally containing an additional nitrogen atom or oxygen atom, R³ = (C1-C4) -alkyl, (C3-C4) -alkenyl or (C3-C4) -alkynyl, R4 = (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio, (C1-C4) -alkylamino, di- (C1-C4 - alkyl) amino or phenyl and X = oxygen or sulfur.

Preferred compounds of the formula I are those in which R1 = hydrogen or (C1-C2) -alkoxycarbonyl, R2 = hydrogen, chlorine, (C1-C4) -alkoxycarbonyl, (C1-C3) -Alkoxy- (C2-C3) -alkoxy-carbonyl or (C1-C4) -alkylthio-carbonyl R3 = <C1-C4) -alkyl R4 = (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio or (C1-C4) -alkylamino.

The invention furthermore relates to a process for the preparation of compounds of the formula I, characterized in that compounds of the formula II in which R1 and R2 have the meanings as in formula I and Hal denotes a halogen atom such as chlorine or bromine, in particular chlorine, with a compound of the formula III in which R3 and R4 have the same meanings as in formula I and are a proton, an alkali metal cation, in particular a sodium, potassium ion or ammonium ion.

The reaction of a compound of formula II with a compound of the formula III is expediently carried out in an inert under the reaction conditions Solvent at temperatures between 20 ° C and the boiling point of the solvent, but preferably not above 80 "C. If a proton means, it is also an acid-binding one Agents, e.g., an alkali carbonate, alkali hydroxide, ammonia, or an amine such as triethylamine added in at least a stoichiometric amount; sodium or potassium carbonate is preferred. Suitable solvents are water, lower alcohols, especially those which correspond to the radical R3, ketones such as acetone, methyl ethyl ketone, ethers such as THF or Glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene or xylene, Halogenated hydrocarbons such as dichloromethane, dichloroethane or chlorobenzene, acetonitrile, Dimethylformamide or mixtures thereof.

The reaction time varies with the reaction temperature and the solvent and is 1 to 48 hours. The compounds of the formulas II and III are approximately equimolar Amounts used, with an excess of 5 to 20% of the compound of the formula III is advantageous.

Working up is carried out in the customary manner. Used with water miscible solvents, the product is made by pouring the reaction solution into Water and subsequent extraction with a water-immiscible solvent separated from its by-products. Before pouring the reaction solution into water most of the solvent can be distilled off. Not when used Water-miscible solvents can be removed by suction or by undissolved salts Remove extraction with water. The product is in each case by evaporation of the organic Phase, optionally after drying it, isolated.

The compounds of the formula I are mostly obtained as oils are sufficiently pure for the intended use. If necessary or desired, they can be distilled, i.e. by removing volatile constituents in vacuo or by chromatography, in some cases also by distillation Clean by means of a thin film evaporator or by recrystallization.

Compounds of the formula III are all known from the literature.

Of the compounds of the formula II with Hal = Br, the compounds 4-bromomethyl-1,2,3-thiadiazole-5-carboxylic acid ethyl ester f see J. Heterocycl. Chem. 13, 301 (1976) 7, 4- (1-bromoethyl) -1, 2,3-thiadiazole, 4- (1-bromopropyl) -1,2,3-thiadiazole and 4- (1-bromoethyl) - 5-methyl-1,2,3, thiadiazole fs. each J. Heterocycl. Chem. 17, 1639 (1980). The preparation of the compounds of the formula II with Hal = Br is carried out analogously to the procedures described in the two above-mentioned references from the literature by reacting compounds of the formula IV in which R1 and R2 have the same meanings as in formula I, with N-bromo-succinimide. Compounds of formula IV are in J. Amer. Chem. Soc. 77: 5359-5364 (1955), in J. Pharm.

Sci. 63 628 (1974) and in Chem. Ber. 113, 183-192 (1980).

Compounds of the formula II with Hal - Cl are new and can be prepared according to the invention by adding compounds of the formula V in which H2NNH-A VI R1 and R2 have the same meanings as in formula I, with compounds of the formula VI in which A = carbamoyl, tosyl or (C1-C4) -alkyloxycarbonyl, to compounds of the formula VII in which A, R1 and R2 have the abovementioned meanings, and these are subsequently reacted with thionyl chloride. What is surprising in the reaction of the compounds of the formula V with compounds of the formula VI is that the hydrazines of the formula VI react only with the keto group and not with the chlorine atom of the compounds of the formula V when appropriate reaction conditions are selected.

The reaction of the compounds of the formula V with compounds of the formula VI takes place in lower alcohols as solvents such as methanol or Ethanol with the addition of at least equimolar amounts of an acid, for example Acetic acid, formic acid or propionic acid. The reaction time is 1 to 20 hours, the reaction temperature is in the range between 0 and + 800C.

The implementation of the compounds of formula VII to compounds of Formula II is made with excess Thionyl chloride, optionally in the presence of inert diluents such as methylene chloride, dichloroethane, chlorobenzene or toluene. The reaction temperature can be varied between OOC and + 300C; the reaction time is 3 to 24 hours. II is isolated by vacuum distillation or by extraction and evaporation of the extract.

The compounds of the formula I according to the invention have excellent properties Effect against sucking and biting insects as well as against acarids and nematodes. Draw when used against insects, mites and nematodes that are harmful to plants they are not only due to their contact and poisonous effects, but also due to their good tolerance to plants and partly through systemic properties. In addition, they are also against storage pests as well as effective against species from the group of hygiene pests.

Different species of spider mite, such as the fruit tree spider mite, can do this (Panonychus ulmi), the citrus spider mite (Panonychus citri) and the bean spider mite (Tetranychus urticae) can be controlled well.

Among the insects to be controlled are, for example, beetles, like the Mexican bean beetle (Epilachna varivestis), Colorado potato beetle (Leptinotarsa decemlineata), earth flea beetle (Phyllotetra spp.), strawberry stalk (Coenorrhinus germanicus), strawberry blossoms (Anthonomus rubi), cotton boll beetle (Anthonomus grandis), wireworms (Agriotes spec.), butterflies and their larvae, such as the Egyptian and the old world cotton bollworm (Earias insulana or Heliothis armigera), tobacco budworm (Heliothis virescens), moth, especially codling moth (Carpocapsa pomonella), oak moth (Tortrix viridana), fruit peel moth (Adoxophyes reticulana), bud moth (edya nubifernana), grape moth (Eupoecilia ambiguella), European corn borer (Ostrinia nubilalis), groundworms (Agrotis spec.), Frost moth (Operophtera brumata), nun (Lymantria monacha), flies, like the beet fly (Pegomya betae), Mediterranean fruit fly (Ceratitis capitata), cockroaches such as the German cockroach (Blatta germanica) and the oriental cockroach (Blatta orientalis), aphids such as the black bean louse (Doralis fabae), green peach aphid (Myzus persicae) and cotton aphids (Aphis gossypii) and bed bugs, e.g. cotton bugs (Oncopeltus fasciatus and Dysdercus spp.).

The compounds of the formula I according to the invention are against all or individual stages of development of normally sensitive and resistant species are effective.

Furthermore, the compounds of the formula I have an action against those which are harmful to plants Nematodes, for example against those of the genera Meloidogyne, Heterodera, Ditylenchus and aphelenchoides.

The compounds of formula I also show a very good fungicidal, partially systemic action against phytophathogenic fungi. Capture the connections e.g.

Phytophthora infestans, Plasmopara viticola, Pythium ultimum, Venturia inaequalis, Cercospora beticola, powdery mildew, Pyricularia oryzae and rust fungi.

The compounds have an excellent funigizde effect Rhizoctonia solani on The invention also relates to insecticides, acaricidal, nematicidal and fungicidal agents, characterized by a content of Compounds of the formula I in addition to the customary formulation auxiliaries and inert substances and the use of the compounds for combating insects, animals of the order Acarina, nematodes and phytopathogenic fungi.

The agents according to the invention contain the active ingredients of the formula I. generally 1 to 95% by weight. They can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations be applied.

Wettable powders are preparations that can be dispersed evenly in water, which, in addition to the active ingredient, apart from a diluent or inert substance, also wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants such as sodium lignin sulfonic acid, 2,2'-dinaphthylmethane-6,6'-disulfonic acid Sodium, sodium dibutylnaphthalenesulfonic acid or oleylmethyltauric acid Contain sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g.

Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling ones Aromatic or hydrocarbons with the addition of one or more emulsifiers manufactured. Examples of emulsifiers that can be used are: alkylarylsulfonic acid Calcium salts such as calcium dodecylbenzenesulfonate, or nonionic 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 polyethers, sorbitan fatty acid esters, Polyoxethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.

Dust is obtained by grinding the active ingredient with finely divided, solid substances, e.g. talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.

Granules can either be sprayed onto adsorptive, Granulated inert material can be produced or by applying active ingredient concentrates by means of adhesives, e.g. polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the surface of carrier materials such as sand, kaolinite, or granulated Inert material. Suitable active ingredients can also be used for the production of fertilizer granules in the usual way - if desired in a mixture with fertilizers.

In wettable powders, the active ingredient concentration varies between, for example about 10% and 80%, the remainder consists of the formulation additives given above. In the case of emulsifiable concentrates, the active ingredient concentration can also be approximately 10 to 80%. Dust-like formulations usually contain 5 - 20% Active ingredient, sprayable solutions about 2 - 20%. In the case of granules, the active ingredient content depends partly on whether the active compound is liquid or solid and which one Granulating aids, fillers, etc. can be used.

The commercially available concentrates are optionally used for use diluted in the usual way, e.g. with wettable powders and emulsifiable concentrates by means of Water. The ready-to-use dilutions contain the Active ingredient in concentrations from 1 to 0.0001%, preferably from 0.2 to 0.01%. Dust-like and granulated preparations as well as sprayable solutions are before no longer diluted with other inert substances after application. The invention Active ingredients can be combined with other insecticides, acaricides and fungicides will.

Production examples A) 4-halomethyl-1,2,3-thiadiazoles of the formula II Example 1 4-Chloromethyl-1,2,3-thiadiazole-5-carboxylic acid methyl ester 138.8 is dissolved g (1 mol) γ-chloroacetoacetate in 1 1 methanol and 60 ml (1 mol) Glacial acetic acid.

90 g (1 mol) of methyl hydrazinoformate are added and the mixture is stirred 1 h under reflux and left to stand overnight at room temperature. Then steams one in vacuo and the residue crystallized with ether. Yield 164.8 g (74 %) methyl t-chloroacetoacetate methoxycarbonylhydrazone; yellow crystals with Melting point 85-87 ° C.

155.9 g (0.7 mol) of these crystals are added in portions with stirring at 15-20 ° C. for 1 h to 400 ml of thionyl chloride. The mixture is stirred for a further 2 h at room temperature, allowed to stand overnight and the excess thionyl chloride was distilled off in vacuo away. The residue is distilled in vacuo. Yield 94.3 g (70%), boiling point 105 - 1100C / 2 mbar; Melting point 49-520C.

Example 2 5-chloro-4-chloromethyl-1,2,3-thiadiazole Solution of 42.5 g (0.335 mol) of 1,3-dichloroacetone in 50 ml of methanol at 200C Stirring with a solution of 30 g (0.334 mol) of methyl hydrazinoformate and 21 ml of glacial acetic acid in 150 ml of methanol, stirred for 0.5 h and left to stand for a further 1.5 h. then is filtered off with suction and washed with a little methanol. Yield 50.6 g (78%) of white crystals with a melting point of 136 ° C.

These crystals (50.6 g = 0.254 mol) become at approx.

150C added in portions with stirring to 120 ml of thionyl chloride. The mixture is stirred for a further 3 hours, left to stand overnight and the excess thi-onyl chloride is distilled off in vacuo away. The residue is dissolved in ether and neutralized with water and bicarbonate solution washed, dried and evaporated in a rotary evaporator. Yield 36.8 g (92 %) light brown liquid that slowly crystallizes. Melting point 38 ° C.

Example 3 2-Chloro-2- (1,2,3-thiadiazol-4-yl) -acetic acid methyl ester 45.5 g (0.3 mol) of methyl α-chloroacetoacetate, 20 ml of glacial acetic acid and 27 g (0.3 mol) of methyl hydrazinoformate are dissolved in 200 ml of methanol and over night left to stand at 20 to 250C. Evaporate in vacuo a, the residue is taken up in dichloromethane, washed with bicarbonate solution, dried and the resulting solution is added dropwise to 80 ml of thionyl chloride at 15-200C with stirring. After stirring for 6 hours and standing overnight, the mixture is evaporated in vacuo and extracted the oily residue with petroleum ether. Evaporation of the extract yields the product with 29.9 g (52%) yield as an oil of 86% purity (GC).

Examples 4 to 13 The procedure is analogous to that in Examples 1 to 3 procedures described, the following compounds of formula II Example no. Hal R1 R2 Yield (%) 4 Cl H C02-i-C4H9 73 5 C1 H C02CH2CH20 CH3 60 6 Cl H COSC3H7 (n) 49 7 Cl H C02-cycl o-C6H11 8 C1 H CON (CH3) 2 9 Cl H CON (CH2) 4 10 Cl H CON (CH3) C6H6 17 11 Br C2H5 C02C2H5 12 Cl C02C2H5 H 13 C1 C02C2H5 C2H5 B. 1,2,3-Thiadi-azol-4-ylmethyl (di) thiophosphate (one) ate of the formula I Example 14 0.0-Dimethyl-S- (5-methoxycarbonyl-1,2,3-thiadiazole- 4-ylmethyl-dithioEhose has: 5.8 g (30 mmol) of the thiadiazole obtained according to Example 1 and 6.3 g are stirred (36 mmol) ammonium 0.0-dimethyldithiophosphate in 60 ml THF for one day at room temperature, lets stand for two more days and then pours on water.

The combined extracts are extracted three times with dichloromethane are shaken with bicarbonate solution, dried and evaporated in vacuo.

Yield 8.5 g (90%) of yellow oil with nD30 = 1.5630.

Example 15 O.N-Dimethyl S- (5-methoxycarbonyl-1.2.3-thiadiazol-4-ylmethyl) amidothiophosphate 5.8 g (30 mmol) of the thiadiazole obtained according to Example 1 and 5.9 g (33 mmol) Potassium 0.-N-dimethylamidothiosphate is added to 70 ml of DMF for 2 days at room temperature stirred and evaporated. The residue is taken up in dichloromethane and shaken with 20 ml of semi-saturated sodium bicarbonate solution, dry and evaporate in vacuo a. Yield 6.2 g (78%) oil with nD30 = 1.5567 Example 16 O-Ethyl S- (5-methoxycarbonyl-1,2,3-thiadiazol-4-ylmethyl) -S-n -propyldithiophosphate 5.2 g (27 mmol) of the thiadiazole obtained according to Example 1 and 7.1 g (30 mmol) Potassium O-ethyl-S-n-propyldithiophosphate is heated in 70 ml of acetonitrile for 7 hours stirred to reflux and then, as described in Example 15, worked up. yield 8.0 g (83%) brown oil.

Example 17 O-Ethyl S- (5-iso-butoxycarbonyl-1,2,3-thiadiazol-4-ylmethyl) -S-n -propyldithiophosphate 5.7 g (25 mmol) of the compound from Example 4 and 6.4 g (27 mmol) of potassium O-ethyl-S-n-propyldithiophosphate are stirred in 70 ml of acetone for 2 days at room temperature and 4 lI at reflux and then worked up as in Example 15. Yield 9.4 g (94%) oil with 30 nD = 1.5317.

Example 18 O-Isobutyl-S-z5- (2-methoxy-ethoxy-carbonyZ-1,2,3-thiadiazol-4-ylmethyl-7-methyl-thiophosphonate 5.9 g (25 mmol) of the compound from Example 5 and 5.0 g (27 mmol) of ammonium O-isobutyl methylthiophosphonate are stirred in 50 ml of water and 50 ml of acetone for three days at room temperature and as in Example 15 described, worked up. Yield 9.2 g of 30 (100%), oil with nD = 1.5141.

Example 19 0.0 Dimethyl S- (5-n-propylthiocarbonyl-1,2,3-thiadiazol-4-ylmethyl) dithophosphate 7.1 g (30 mmol) of the compound from Example 6 and 5.8 g (33 mmol) of ammonium 0.0-dimethyldithiophosphate are gertillrt in 60 ml of acetone for 2 days at room temperature and then poured out of water.

It is extracted three times with dichloromethane, dried and evaporated in vacuo and thereby purify Ciiromatographie over a silica gel column with dichloromethane as a solvent. Yield 4.3 g (40 O) oil with 50 nD = 1.5893.

Examples 20-63 If the procedure is analogous to the procedures described in Examples 14 to 19, the following compounds of the formula I can be obtained: Example No. R¹ R² R³ R4 X Refractive index / ° C 20 H CO2CH3 CH3 CH3 S 1.5877 / 30 21 H CO2CH3 C2H5 CH3 O 1.5303 / 30 22 H CO2CH3 i-C4H9 CH3 O 1.5250 / 21 23 H CO2CH3 CH3 CH3 S 1.5821 / 21 24 H CO2CH3 C2H5 CH3 S 1.5551 / 30 25 H CO2CH3 CH3 CH3 O 1.5567 / 30 26 H CO2CH2CH2OCH3 CH3 CH3 S 1.5460 / 30 27 H CO2CH2CH2OCH3 C2H5 CH3 O dark oil1 28 H CO2CH2CH2OCH3 C2H5 CH3 O dark oil1 29 H CO2C4H9- (i) CH3 CH3 S 1.5355 / 30 30 H COSC3H7- (n) C2H5O CH3 O 1.5660 / 30 31 H CON (CH3) C6H5 CH3 CH3 S 1.6032 / 31 32 H Cl C2H5 CH3 O 1.5632 / 31 33 H Cl CH3 CH3 S 1.5830 / 31 34 H Cl C2H5 CH3 S dark oil1 35 H Cl C2H5 CH3 O 1.5423 / 31 Example No. R¹ R² R³ R4 X Refractive index / ° C 36 CO2CH3 H C2H5 C2H5O S 1.540 / 21 37 CO2CH3 H C2H5 i-C3H7NH O 1.5212 / 22 38 CO2CH3 H C2H5 n-C3H7 S 1.5620 / 22 39 CO2CH3 H C2H5 n-C3H7S O 1.5451 / 25 40 CO2CH3 H CH3 CH3O S 41 CO2C2H5 C2H5 CH3 CH3O S 42 CO2C2H5 C2H5 CH3 CH3 S 43 CO2C2H5 C2H5 C2H5 n-C3H7S O 44 CO2C2H5 C2H5 C2H5 CH3NHO 45 H CO2CH3 C2H5 n-C3H7S S 46 C2H5 CO2C2H5 CH3 CH3O S 47 CH3 CO2C2H5 CH3 CH3O S 48 CH3 CH3 CH3 CH3O S 49 CH3 CH3 C2H5 CH3 S 50 H CN CH3 CH3O S 51 H CN CH3 CH3NHO Ex. No.- R1 R2 R3 R4 X 52 H CN C2H5 n-C3H7S O 53 H CO2-cyclo- CH3 CH3O S C5H9 54 H CO2CH2C6H5 CH3 CH3O S 55 H CO2CH2CH # CH3 CH3 CH3O S 56 H CO2CH2-C # CCH3 CH3 CH3O S 57 H CON (CH3) 2 CH3 CH3O S 58 H CON (CH2) 4 CH3 CH3O S 59 -CH2-CH2 CH3 CH3O S 60 -CH2-CH2-CH2- CH3 CH3O S 61 C2H5 H CH3 CH3O S 62 CH3 H CH3 CH3O S 63 HH CH3 CH3O S Formulation Examples 6 g of active ingredient are premilled with 6 g of highly dispersed silica and then with 48 g of a mixture containing 13.3% cell pitch, 65.4% (R) Sillithin Z (quartz + Al-silicate), 15.3% highly dispersed e Silicic acid, 4.7% polypropylene glycol P 750 and 1.3% oleoylmethyltauride Na mixed in a mixer. This gives 60 g of a 10% against spray powder.

Emulsion concentrate 2 g active ingredient, 16 g cyclohexanone and 2 g nonylphenol decaglycol ether are mixed together. 20 g of a 10% emulsion concentrate are obtained.

Biological examples Example I With bean spider mites (Tetranychus urticae, normally sensitive) strongly infested bean plants (Phaseol us vulgaris) with the aqueous dilution of a wettable powder concentrate, the 0.025 wt .- ° ,, des Active ingredient from Example 14 contained up to the stage of beginning dripping injected. At the r, the microscopic control showed eight days after the treatment that all mobile and immobile stages of the population were killed. Tested in the same way, the compounds according to Examples 15, 16, l7, 20-30, 32, 34, 35 and 38 are equally effective.

Example II Heavily infested with customer bean aphids (Aphis craccivora) Field beans (Vicia faba) were mixed with the aqueous suspension of a wettable powder concentrate, which contained 0.0l25% by weight of the active ingredient from Example 14, up to the stage of Splashed to drain. After placing the plants in the greenhouse it was three days 100% death of the test animals was found after the treatment. as well The compounds according to Examples 15-34, 36, 37 and 39 proved to be effective.

Example III With whitefly (Trialeurodes vaporariorum, larvae) heavily populated bean plants (Phaseolus vulgaris) were found with an active ingredient content of 0.025% by weight sprayed until it starts to drain. After placing the plants in the greenhouse at 20 ° -25 ° C. and 40-50% humidity, the microscopic procedure took place after 7 days Control with the result of 100% mortality in each case for the preparations with the Active ingredients of Examples 14, 18, 20-24, 33 and 34.

Example IV A powdery formulation was mixed with soil, which was contaminated with Meloidogyne incognita. Then the filling took place in pots and planting them with tomatoes.

After a period of 4 weeks in the greenhouse, the values were determined according to the following scheme: Gallen / plant value number 0 1 l - 2 2 3 - 5 3 6-10 4 over 150 9 The following table I shows the effectiveness of the following compounds: Active ingredient according to the example Amount of active ingredient / value number Area unit No. 16 20 kg / ha 1 17 "" 1 28 "Ii 1 30 "II 1 35 "II 1 Example V Using a pipette, 1 ml from Example 28 was uniformly applied as active ingredient in acetone at a concentration of 0.025% by weight to the inside of the lid and bottom of a Petri dish, and the dishes were left open until the solvent had completely evaporated. Then 10 houseflies (Musca domestica) were placed in each of the Petri dishes, the dishes were closed with the lid and after 3 hours 100% death of the test animals was determined.

The compounds according to Example 16 were found to be just as effective, 17, 20, 22, 23, 28, 30 and 32.

Example VI As described in Example V, the compound according to Example 23 as an active ingredient in acetone at a concentration of 0.025% by weight uniformly applied to the inside of the lid and the bond of a Petri dish and let dry. Then 10 larvae (L 4) of the German cockroach were per Petri dish (Blatella germanica) inserted, -the bowls closed with the lid and after 72 hours a 100% death of the test animals was found.

The compounds according to the example proved to be equally effective 14, 16, 17, 18, 19, 20, 22, 23, 28, 30, 32, 33 and 34.

Example VII Leaves of cotton (Gossypium sp.) Were with a aqueous emulsion of the compound according to Example 17 in a concentration of 0.025 % By weight based on active ingredient, sprayed (= 600 l spray mixture / ha) and treated in the same way Caterpillars (10 pieces, stage L 3 - 4) of the common cotton worm (Prodenia litura) added. Leaves and caterpillars were put together in observation cages and after 48 h, 100% death of the test animals was found.

Example VIII Leaves of the bean (Phaseolus vulgaris) were used with a aqueous emulsion of the compound from Example 16 in a concentration of 0.05 % By weight (based on active ingredient) treated and treated identically to larvae of the Mexican Bean beetle (Epilachna varivestis) placed in observation cages. An evaluation after 48 hours, the test animals were killed off 100%.

The compounds proved to be comparatively just as effective Example 14, 16, 17, 20, 21, 22, 24 and 33.

Example IX In a uniform and strong with Rhizoctonia solani contaminated soil were the compounds of the invention in the following Table I examples are evenly mixed in and distributed. So treated Soil was filled into plastic pots and then each pot was filled with 10 bean seeds sown. 8-10 days after sowing, the tests were evaluated by the number of emerged, healthy plants and the efficiency of the claimed connection was established. Pots with infected, untreated soil. The efficiency is given in percentage values in Table I below (Specify ten healthy plants per pot 100 8).

Table I. Application rate (mg active ingredient / kg soil) 200 100 50 25 Example no. Efficiency (%) 16 100 100 100 100 28 100 100 100 100 29 100 100 100 100 34 100 100 100 100 36 100 100 100 100 38 100 100 100 100 39 100 100 100 97 underhandled infected soil 0

Claims (10)

Claims 1. Compounds of the formula I, in which R1 = hydrogen, (C1-C4) -alkyl or (C1-C4) alkoxycarbonyl, R2 = hydrogen, (C1-C4) -alkyl, halogen, cyano, (C1-C4) -alkoxycarbonyl, (C3-C7) Cycloalkyloxycarbonyl, phenylalkoxycarbonyl, (C3-C5) alkenyloxycarbonyl, (C3-C5) alkynyloxycarbonyl, (C1-C3) -alkoxy- (C2-C3) -alkoxycarbonyl, (C1-C4) alkylthio -carbonyl or CONR'R ", where R '= (C1-C6) -alkyl and R" = (C1-C6) -alkyl or phenyl, which is optionally substituted up to twice by halogen, methyl, methoxy or nitro, or where NR'R "together denote an azir.idine or azetidine ring or a five- or six-membered heterocyclic ring optionally containing an additional nitrogen atom or oxygen atom, R3 = (C1-C4) -alkyl, (C3-C4) -alkenyl or (C3-C4) -alkynyl, R4 = (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio, (C1-C4) -alkylamino, di- (C1-C4- alkyl) amino or phenyl and X = oxygen or sulfur. 2. A process for the preparation of compounds of the formula I of claim 1, characterized in that a compound of the formula II in which R1 and R2 have the meanings as in formula T and Hal denotes a halogen atom with a compound of the formula III in which R3 and R4 have the same meanings as in forms I and denotes a proton, an alkali metal cation or an ammonium ion. 3. Insecticidal, acaricidal and nematocidal agents, characterized by a content of a compound of the formula I. 4. Fungicidal agents, characterized in that they contain a compound of formula I. 5. methods of combating insect pests, acarids and nematodes, characterized in that an effective amount is applied to the infected crops a compound of formula I applies. 6. A method for combating harmful fungi, characterized in that that they infested areas, plants or substrates with a fungicide brings effective amount of active ingredients of the formula I into contact. 7. Use of compounds of the formula I according to claims 1, 3 and 4 for pest control in crop protection. 8. Compounds of the formula II of claim 2, characterized characterized in that Hal is a chlorine atom and R1, R2 have the meanings as in formula I. 9. A process for the preparation of compounds of the formula II of claim 8, characterized in that a compound of the general formula V, wherein R1 and R2 have the meanings we have in formula I, with a H2N - NH -VI Compound of the formula VI, in which A = carbamoyl, tosy; or (C1-C4) -alkyloxy-carbonyl, to a compound of the formula VII, in which A, R1 and R2 have the abovementioned meanings, and reacts them with thionyl chloride. 10. Use of compounds of formula II according to claim 8 for Manufacture of connections of the formula I.