DE3208187A1 - Novel (di)thiophosphoric and -phosphonic acid derivatives, their preparation, compositions containing them and their use in crop protection, and novel chloromethyl-1,2,4-thiadiazine 1,1-dioxides as precursors, and their preparation - Google Patents

Abstract

The invention relates to compounds of the formula I which have fungicidal, acaricidal, nematicidal and insecticidal activity, in which <IMAGE> X = O or S, R and R2 = alkyl, R1 = alkyl, alkoxy or alkylamino, where, X = O, R1 can also be alkylthio.

Description

New (di) thiophosphoruride phosphonic acid derivatives,

Process for their production, agents containing them and their use in crop protection, and new chloromethyl-1,2,4-thiadiazine-1,1-dioxides as precursors and processes for their production. The present invention relates to new (di) thiophosphoric and phosphonic acid -Derivatives of the formula (I), in which X = 0 or SR and R2 = (C1-C4) -alkyl with the same or different meanings, R1 = (C1-C4) -alkyl, (C1-C4) -alkoxy or (C1-C4) -alkylamino, where in the case X = O, R1 can also be (C1-C4) -alkylthio, mean The present invention also provides a process for the preparation of compounds of the formula I, which is characterized in that compounds of the formula II in which R, R1 and X have the meanings as in formula I + and M denotes an alkali metal cation, in particular a sodium or potassium ion, or an ammonium ion, with a compound of the formula III, in which R2 has the same meaning as in formula I.

The reaction is generally carried out in the presence of inert solvents such as lower aliphatic alcohols, ketones such as acetone, nitriles such as acetonitrile, Aromatics such as toluene, benzene or water at temperatures between room temperature and the boiling point of the solvent used, preferably between 40 and 1000C.

The compounds of the formula I are considered to be tough and non-distillable Oils or obtained as crystals and can be obtained by recrystallization or chromatography be cleaned according to the usual methods.

Compounds of the formula III are new and are also the subject of the present invention. According to the invention, they can be prepared from chloroacetamidines of the formula IV, in which R2 has the abovementioned meaning through implementation with. Vinyl sulfonic acid halides of the formula V, in which CH2 = CH - SO2Hal. (V) Hal denotes a halogen atom, preferably fluorine, can be prepared in the presence of a base.

The compounds of formula IV are useful as hydrohalides for example hydrochloride used. The bases used in the reaction are for example alkali (C1-C4) alkanolates, preferably sodium methylate, which are in the form their alcoholic solutions are added, or organic bases such as pyridine and triethylamine, the reaction temperature can vary in the range from 00C to 1000C, it is preferably between 200.degree. C. and 800.degree.

The compounds of formula III are as crystals or as obtain viscous non-distillable oils.

The compounds of the formula I according to the invention have excellent properties Effect against sucking and biting insects, against acarids and against nematodes. In addition, they are also against storage pests and against species from the group of Effective hygiene pests. When used against insects that are harmful to plants, The compounds of the formula I are distinguished by mites and nematodes in addition to contact and food poison effect also through good plant tolerance and systemic Properties.

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 pest insects with sucking and biting mouthparts, which can be combated with the compounds according to the invention may be mentioned: Beetles such as the Mexican bean beetle (Epilachna varivestis), Colorado potato beetle (Leptinotarsa decemlineata), flea species (Phyllotetra spp.), strawberry stalk (Coenorrhinus germanicus), strawberry blossoms (Anthonomus rubi), cotton boll beetle (Anthonomus grandis), wireworms (Agriotes spec.); Butterflies and their larvae, like the Egyptian and the old world cotton bollworm (Earias insulana or Heliothis armigera), tobacco buttonworm (Heliothis virescens), moth, especially codling moth (Carpocapsa pomonella), oak moth (Tortrix viridana), fruit peel moth (Adoxophyesreticulana), Bud moth (Hedya nubiferana), grape moth (Eupoecilia ambiguella), European corn borer (Ostrinia nubilalis), groundworms (Agrotis spec.), Frost moth (Operophthera brumata), Nun (Lymantria monacha).

In addition, flies such as the beet fly (Pegmoya beta), the Mediterranean fruit fly (Ceratitis capitata) and cockroaches, such as the German cockroach (Blatta germanica) and the oriental cockroach (Blatta orientalis) and aphids, such as the black one Bean louse (Doralis fabae), green peach aphid (Myzus persicae) and cotton aphid (Aphis gossypii) and bed bugs, e.g. cotton bugs (Oncopeltus fasciatus and Dysdercus spp.).

The compounds of the formula I are against all or individual stages of development normally sensitive and resistant species 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 Aphelenchaides.

Furthermore, the claimed compounds of the formula I show a very good fungicidal, partly systemic effect against phytopathogenic fungi. the Compounds include e.g. Phytophthora infestans, Plasmopara viticola, Pythium ultimum, Venturia inaequalis, Cercospora beticola, powdery mildew mushrooms, Piricularia oryzae and rust mushrooms. The compounds have an excellent fungicidal action against Rhizoctonia solani.

The invention also relates to insecticidal, acaricidal and nematocidal and fungicidal agents, characterized in that they contain compounds of the formula I in addition to the usual formulation auxiliaries and inert substances and the use the compounds for combating phytopathogenic fungi, harmful insects, and those that damage plants Nematodes and acarids.

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, e.g. sodium lignosulfonic acid, Sodium 2,2'-dinaphthylmethane-6,6'-disulfonic acid, dibutylnaphthalenesulfonic acid Contain sodium or oleylmethyltauric acid sodium.

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

Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling ones Aromatics 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 cadodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, Alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, Alkyl polyethers, sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters or Polyoxethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.

Dusts are obtained by grinding the active ingredient with finely divided ones solid substances, e.g. talc, natural clays such as kaolin, bentonite, poryphillite or diatomaceous earth. Granules can either be sprayed on by the active ingredient adsorptive, granulated inert material are produced or by application of active ingredient concentrates by means of adhesives, e.g.

Polyvinyl alcohol, polyacrylic acid sodium or mineral oils 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 the usual way - if desired in a mixture with fertilizers - are produced.

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 around 10 ffi can be up 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 in part on whether the effective compound is liquid or solid and which granulation aids, Fillers, etc. can be used.

The commercially available concentrates are optionally used in the usual way Diluted in a way, e.g. with wettable powders and emulsifiable concentrates with water.

The ready-to-use suspensions preferably contain 0.05 to 2, in particular 0.1 to 1% active ingredient. Dust-like and granulated preparations as well Sprayable solutions are no longer mixed with other inert substances before use diluted.

The following examples are intended to explain the invention in more detail: A) Preparation Example Example 1 3- (O, O-Dimethvl-dithiophosPhorYlmethYl) -4-methyl-1,2,4-thiadiazine-1,1-oxide 20 g of 3-chloromethyl-4-methyl-1,2,4-thiadiazine-1,1-dioxide and 18 g of the ammonium salt O, O-dimethyldithiophosphoric acid are dissolved in 200 ml of methanol. The reaction mixture is stirred for 10 min.

heated to boiling. The solvent is then distilled off in vacuo. The residue is taken up in 200 ml of methylene chloride and stirred with 100 ml of water. After the organic phase has been separated off and dried with sodium sulfate, the methylene chloride is added distilled off. What remains are 30 g of a colorless oil, which at room temperature stiffens. By dissolving from cyclohexane, 20 g of 3- (O, O-dimethyldithiophosphorylmethyl) -4-methyl-1, 2,4-thiaidazin-1, 1-dioxide with a melting point of 154-1550C obtain.

Examples 2 to 21 In a manner analogous to that described in Example 1, the compounds of Examples 2 to 3 summarized in the table below 21 manufactured.

The radicals R, R1, R2 and X given in the table relate to formula I. Ex. R R1 R2 X Physical No data 2 C2H5 C2H5O CH3 O M.p. 66-67 ° 3 C2H5- C2H5O CH3 s m.p. 94-95 4 C2H5 C2H5 CH3 s m.p. 108-109 5 n-C3H7 n-C3H7 CH3 S nD40 = 1.5638 6 i-C3H7 n-C3H7 CH3 S nD40 = 1.5604 7 C2H5 n-C3H7S CH3 O nD40 = 1.5538 8 C2H5 CH3NH CH3 O nD40 = 1.5385 9 CH3 i-C3H7NH CH3 O nD40 = 1.5374 10 C2H5 C2H50 C2H5 ° nD40 = 1.5139 11 C2H5 C2H5O CH3 S nD40 = 1.5429 12 C2H5 C2H5 CH3 S 13 C2H5 C2H5 n-C3H7 O nD21 = 1.5178 14 C2H5 C2H5O CH3 S nD21 = 1.5473 15 C2H5 C2H5 CH3 S nD40 = 1.5585 16 C2H5 C2H5O i-C3H7 O nD40 = 1.5015 17 C2H5 C2H5O CH3 S 18 C2H5 C2H5 CH3 S 19 CH3 i-C3H7 CH3 O 20 C2H5 C2H50 n-C4H9 S. 21 C2H5 C2H5 CH3 S nD40 = 1.5274

The compounds according to Examples 12, 17, 18, 19 and 20 are in the form of highly viscous resins. The following analysis data were determined for these compounds: Vbg analysis data Example no. (% N) calc. (% N) 12 7.7 8.1 17 7.8 7.5 18 7.9 7.8 19 11.5 11.8 20 7.5 7.2 Example 22 3-Chloromethyl-4-methyl-1,2,4-thiadiazine-1,1-dioxide 72.0 g of chloroacetmethylamidine hydrochloride are dissolved with methanol. Sodium methylate (prepared from 11.5 g of sodium and 200 g of methanol) was added. After stirring for half an hour, 55.0 g of vinyl sulfofluoride are added, the temperature of the reaction mixture rising to 60.degree. The mixture is stirred with methanol at 45 ° -500 ° C. over the course of half an hour.

Sodium methylate (from 11.5 g of sodium and 100 ml of methanol) was added. The mixture is allowed to stand for 12 hours at room temperature, and the precipitated material is filtered off with suction Salt and concentrate the filtrate. The product crystallizes out, which crystallizes out a little acetone is redissolved. 67.0 g of the title compound with a melting point of 140 are obtained. 1410C.

Further compounds of the formula III with R2 = C2H5, n-C3H7, i-C3H7 and n-C4Hg are prepared analogously to the procedure described in Example 22. They are obtained in the form of highly viscous oils.

B) Formulation Examples Example A An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient of the formula I 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of nonylphenol polyglycol ether (10 AeO) +) as an emulsifier +) = Number of ethylene oxide units in the polyglycol ether residue Example B A in water Easily dispersible wettable powder is obtained by adding 25 parts by weight Active ingredient of the formula I 64 parts by weight of koalin-containing quartz as an inert substance and 1 part by weight oleoylmethyltaurinsaures Sodium as a wetting and dispersing agent mixes and in one Pin mill grinds.

Example C A dust is obtained by adding 10 parts by weight Active ingredient of the formula I and 90 parts by weight of talc as an inert substance and mixed in one Impact mill crushed Example D Granules are obtained by Granulation of a mixture of 2-15 parts by weight of active ingredient of formula I and 98 - 85 parts by weight of inert granulate carrier material, optionally containing binders, e.g.

Attapulgite, pumice granules, quartz sand.

C. Biological Examples Example I In a uniform and strong Soil contaminated with Rhizoctonia solani became the compounds listed in Table I. evenly mixed in and distributed. The treated soil was put in plastic pots filled and each pot then sown with 10 bean seeds. 8-10 days after After sowing, the tests were evaluated by counting the number of accrued, healthy plants are determined and the degree of effectiveness of the compound used is calculated became. Pots with infected, untreated soil were used as controls.

Table I. Compound efficiency in% at mg active ingredient / kg soil according to example 200 100 50 25 (mg / kg) 11 100 100 100 100 (%) 12 100 100 100 100-97 (%) 15 100 100 100 100 (%) 17 100 100 100 100 (%) 18 100 100 100 100 (%) 20 100 100 100 100-97 (%) untreated infected 0 (%) floor EXAMPLE II Field beans (Vicia faba) heavily infested with customer bean aphid (Aphis craccivora) were sprayed with aqueous dilutions of wettable powder concentrates containing 0.0125% by weight of active ingredient until the drip-off stage began. After 3 days, the mortality was 100% in each case for the preparations with the active ingredients of Examples 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16w 17, 18, 20, 21.

Example III With fruit tree spider mite (Panonychus ulmi, more resistant Trunk) heavily populated plants (apple trees) were with the aqueous suspension a wettable powder concentrate containing 0.0125% by weight of the active ingredient from Example 2 contained, injected to the stage of beginning dripping and at approx. 22 OC im Greenhouse set up.

The acaricidal effectiveness was determined eight days after treatment and for the compounds from Examples 3, 4, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, and 21 100% mortality.

Example IV Carrying out the experiment: analogous to Example III experimental animal: Tetranychus urticae (bean spider mite) Test plant: Phaseolus vulgaris (French bean) The activity determined after 8 days was shown for the compounds from the examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and 21 100 % Mortality.

Example V Root balls of potted field beans (Vicia faba) were made surrounded with foil and after infection with bean aphids (Aphis craccivora) treatment was carried out by uniformly distributing 1 mg of the respective active ingredient in the root area, 8 days after the treatment, it was possible for the in Examples 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 18 and 20 each 100 % Mortality can be determined.

Example VI Carrying out the experiment: analogous to Example v Test animal: Tetranychus urticae (bean spider mite) Test plant: Phaseolus vulgaris (French bean) The efficacy determined after 8 days for compounds 1, 2, 3, 4, 5, .6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 each 100% mortality.

SeisPiel VII A powdery formulation was mixed with earth, which was contaminated with Meloidogyne incognita. Then the filling took place in pots and planting them with tomatoes. After a standing time of 4 weeks in the greenhouse the values were determined according to the following scheme: galls / plant Value number 0 1 1-2 2 3-5 3 6 -10 4. .

. .

. .

over 150 9 in the table below is the effectiveness of the following Preparations shown: Preparation according to the amount of active ingredient / value number Example area unit 3 20 kg / ha 1 4 "1 11" 1 12 "1 15 II 1 18" 1 21 11 1 Example VIII On the inside of the lid and bottom of a Petri dish was made using a pipette 1 ml from Example 7 as the active ingredient in acetone at a concentration of 0.025 wt .-% applied evenly and until the complete evaporation of the Leave the pans open with the solvent. Then 10 houseflies (Musca domestica) are placed in the Petri dishes, the dishes are closed with the lid and 100% death of the test animals was found after 3 hours.

The compounds according to Example 10 were found to be just as effective, 12 and 19.

Example IX Leaves of the bean (Phaseolus vulgaris) were with a aqueous emulsion of the compound from Example 4 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 5, 7, 8, 12, 15 and 18.

Claims (10)

Claims: 1. Compounds of the formula I, in which X = 0 or SR and R2 = (C1-C4) -alkyl with the same or different meanings, R1 = (C1-C4) -alkyl, (C1-C4) -alkoxy or (C1-C4) -alkylamino, where in the case X = O, R1 also mean. 2. Process for the preparation of compounds of the formula I according to claim 1, characterized in that compounds of the formula II in which R, R1 + and X have the same meanings as in formula I and M denotes an alkali or ammonium ion, with a compound of the formula III, in which R2 has the same meaning as in formula I. 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. Use of compounds of the formula I according to Claims 1, 3 and 4 for pest control in crop protection. 6. Methods of combating insect pests, acarids and nematodes, characterized in that an effective amount is applied to the infected plants a compound of formula I applies. 7. 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. 8. Compounds of the formula III, wherein K2 = (C1-C4) -alkyl. 9. A process for the preparation of compounds of the formula III, characterized in that compounds of the formula III in which R2 has the same meaning as in formula III with vinylsulfonic acid halides of the formula V, CH2 = CH-SO2Hal (V) in which Hal denotes a halogen atom, is reacted in the presence of a base. 10. Use of compounds of the formula III for the preparation of Pesticides and fungicides.