DE2545028A1 - (1,3)-Dithiacyclohexyl (thio)phosphates and (thio)phosphonates - with insecticidal and acaricidal activity - Google Patents

Abstract

New (thio)phosph(on)ate derivs. are of formula (I): (where R and R2 are 1-5C alkyl; R1 is 1-6C alkyl, alkoxy or alkylthio, or phenyl; X is O or S). They possess insecticidal and acaricidal activity, e.g. giving 100% kill of soil insect larvae (Phorbia antiqua and Tenebrio molitor) at a concn. of 2.5-5 ppm. In an example, (I; R = R2 = Et, R1 = OEt, X = S) is prepd. by reacting 4-ethoxycarbonyl-5-oxo-1,3-dithiacyclohexane with (EtO)2PSCl.

Description

1,3-dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid

esters, process for their preparation and their use as insecticides The present invention relates to new 1,3-dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid esters, a process for their production and their use as insecticides.

It is already known that O, O-dialkyl-O- (i-oxocyclohexenyl) -thionophosphoric acid ester, z. 2. O, O-di-isopropyl-O- [1-oxo-2-cyclohexen (3) yl] thionophosphoric acid ester insecticidal Have properties (compare German patent specification 864 252).

It has now been found that the new 1,3-dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid esters of the formula in which R and R2 stand for identical or different alkyl radicals with 1 to 5, R1 for alkyl, alkoxy or alkylthio with 1 to 6 carbon atoms per alkyl radical, also for phenyl and X for oxygen or sulfur, are characterized by particularly strong insecticidal properties.

It has also been found that the new 1,3-dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid esters of the formula (I) are obtained if (thiono) (thiol) phosphorus (phosphonic) acid ester halides of the formula in which R, R1 and X have the meaning given above and Hal is halogen, preferably chlorine, with 1,3-dithia-4-carbalkoxy-5-oxo-cyclohexane derivatives of the formula in which R2 has the meaning given above, reacts if appropriate in the presence of acid acceptors and if appropriate in the presence of solubilizers.

Surprisingly, the 1,3-dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid esters according to the invention show a better insecticidal wirinirig than the corresponding known O, F-dialkyl-0- (1-oxo-cyclohexenyl) thionophosphoric acid esters of similar constitution and the same Direction of action. The products according to the present invention thus represent a real one Enrichment of technology.

If, for example, O-ethyl-S-sec.-butyl-thiolphosphoric acid diester chloride and 1,3-dithia-4-carbo-n-propoxy-5-oxo-cyclohexane are used as starting materials, the course of the reaction can be represented by the following equation: C02C, H, -n C2H5 ° \ 11 C02C3H7-n acid- C2H50 \ 0fl pS P'C1 + sec.-C4H9 1 + = 0 tor sec.-C4HgS x - HCl The starting materials to be used are generally defined by the formulas (II) and (iii). Preferably, however, R and R2 therein stand for identical or different, straight-chain or branched alkyl radicals with 1 to 3, R1 for straight-chain or branched alkyl or alkoxy each with 1 to 3, or alkylthio with 1 to 4 carbon atoms, also for phenyl and X for Sulfur.

The (thiono) (thiol) phosphorus (phosphonic) acid ester halides to be used as starting materials (II) are known and can be produced by customary processes.

Examples include: 0,0-dimethyl-, OsO-diethyl-, 0, O-di-n-propyl, 0, O-di-isopropyl, 0-ethyl-O-n-propyl, O-ethyl-O-iso-propylphosphoric acid diester chloride and the corresponding thiono analogs, also 0, S-dimethyl, O, S-diethyl, O, S-di-n-propyl, O, S-di-isopropyl-, O-ethyl-S-n-propyl-, O-ethyl-S-iso-propyl-, 0-ethyl-S-n-butyl-, O-ethyl-S-sec.-butyl-, O-n-propyl-S-ethyl-, O-n-propyl-S-iso-propyl-, O-methyl-S-n-propyl- and O-methyl-S-äthylthiolphosphorsäurediesterchlorid and the corresponding thiono analogs, also 0-methyl-, 0-ethyl-, 0-n-propyl-, 0-iso-propyl-methane or

-ethane-, -n-propane, -iso-propane or -phenylphosphonic acid ester chloride and the corresponding thiono analogs.

The 1,3-dithia-4-carbalkoxy-5-oxo-cyclohexane derivatives to be used as starting materials (III) can be prepared by processes known from the literature, for example by Methylene-bis-thioglycolic acid dialkyl ester cyclized in the presence of potassium tert-butoxide.

As examples of the derivatives (III) are mentioned in detail: 4-Carbomethoxy- and 4-carbethoxy, 4-carb-n-propoxy and 4-carb-iso-propoxy-5-oxo-1,3-dithiacyclohexane.

The process for making the compounds of the invention is preferably carried out with the use of suitable solvents and diluents. Practically all inert organic solvents can be used as such. For this include in particular aliphatic and aromatic, optionally chlorinated Hydrocarbons such as benzene, toluene, xylene gasoline, methylene chloride, chloroform, Carbon tetrachloride, chlorobenzene, or; ethers, e.g. diethyl and dibutyl ethers, Dioxane, also ketones, for example acetone, methylethyl, methylisopropyl and Methyl isobutyl ketone, as well as nitriles such as aceto- and propionitrile.

All customary acid binders can be used as acid acceptors Find. Alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, Dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can vary within a relatively wide range will. In general, one works between 0 and 100OC, preferably at 20 to SOOC.

The reaction is generally allowed to proceed under normal pressure.

The reaction components are used to carry out the process preferably in equimolar proportions. An excess of one or the other Component does not have any significant advantages. Preference is given to using 4-carbalkoxy-1,3-dithia-5-oxo-cyclohexane optionally together with an acid acceptor in one of the solvents mentioned usually at room temperature and the (thiono) thiol-phosphorus (phosphonic) acid ester halide is added dropwise to the mix. After one to several hours of reaction at elevated temperature the batch is poured into an organic solvent, e.g. toluene, and the organic Phase worked up as usual by washing, drying and distilling off the solvent.

The new compounds occur in the form of oils, which are partly do not allow to distill without decomposition, but by so-called 'distillation2w, i.e. by prolonged heating under reduced pressure to moderately elevated temperatures freed from the last volatile components and cleaned in this way. The refractive index is used to characterize them.

As already mentioned several times, the inventive 1, 3-Dithiacyclohexenyl (thiono) (thiol) phosphorus (phosphonic) acid ester by a excellent insecticidal effectiveness. They work against plant, hygiene and storage pests. With low phytotoxicity, they have both a good one Effect against sucking as well as eating insects.

The active ingredients are suitable if they are well tolerated by plants and are cheaper Warm-blooded toxicity for combating animal pests, in particular insects and arachnids, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector. They are sensitive and resistant to normal Species as well as effective against all or individual stages of development. To the above mentioned Pests include: From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, for. B. Blaniulus guttulatus.

From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola, for. B. Onychiurus armatus.

From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, for. B. Forficula auricularia.

From the order of the Isoptera, for. B. Reticulitermes spp ..

From the order of the Anoplura, e.g. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp, Linognathus spp.

From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrats, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Erio.soma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp.

Psylla spp ..

From the order of the Lepidoptera, for example, Pectinophora gossypiella and Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, for. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus - spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp. Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for. B. Diprion spp., Hoplocampa spp., Lasius spp. Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp. ' Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina, e.g. Acarus siro, Argas spp.

Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

The active compounds according to the invention are used in the form of them commercial formulations and / or those prepared from these formulations Application forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges.

The active ingredient concentration of the use forms can range from 0.0000001 up to 100% by weight of active ingredient, preferably between 0.01 and 10% by weight.

They are used in a customary manner adapted to the use forms Way.

When used against hygiene and storage pests stand out the active ingredients through an excellent residual effect on wood and clay as well as through good alkali stability on limed substrates.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspenders, powders, dusts, foams, Pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, Active ingredient-impregnated natural and synthetic materials, fine encapsulation in polymers Substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, coils, etc. as well as ULV cold and warm mist formulations These formulations are prepared in a known manner, 7. 3. by mixing the active ingredients with extenders, i.e. liquid solvents, are under pressure liquefied gases ur, d / or solid carriers, optionally using of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g.

organic solvents can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or Glycol or ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons as Butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic barley in flours, such as fumed silica, alumina and Silicates; as solid carriers for granules: broken and fractionated natural Rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granulates made from inorganic and organic flours and granulates made from organic material such as sawdust, coconut shells, corn cobs, and tobacco stalks; as an emulsifier and / or Foaming agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. Lignin, sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, There can be dyes such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan blue and organic Dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90 96.

Example A Limit concentration test / soil insects 1 test insect: Phorbia antiqua maggots in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether preparation of an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the healthy concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The bottom is filled into pots and left read stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after a further 2 to 7 days wea the degree of effectiveness of the active ingredient by counting of the dead and living test insects determined in%. The efficiency is 100% wen all test insects have been killed; it is O% if there are just as many test insects live like in the untreated control.

Active ingredients, application rates and results are shown in Table 1 below: Table 1 Limit concentration test / soil insects I (Phorbia antiqua maggots in the soil) Active ingredient kill rate in% with one Active ingredient concentration of 5 ppm 0 (OC3H7-iso) 2 O (known) CO-05C2H5 100 -OP P (OC2H5) 2 Example B Limit concentration test / soil insects II test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To create an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier is added and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / 1). The bottom is filled into pots and left read stand at room temperature.

After 24 hours, the test animals are treated in the. Given soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of dead and living TostT insects determined in%. The efficiency is 100%, all test insects have been killed; it is 0% if there are just as many Test insects live as in the untreated cantilever roll.

Active ingredients, application rates and results are shown in the following table 2: Table 2 border control test / soil insects II (Tenebrio molitor larvae in the soil) Active ingredient kill rate in% with one Active ingredient concentration of 2.5 ppm 0 ) -P (OC3H7iso) 2 (known) CO-OC2H5 CS ) -P (OC2Hg) 2 100 Production examples Example 1 a: 22.4 g (0.2 mol) of potassium tert-butoxide are added in portions at 20 ° to 250 ° C. to a solution of 50.4 g (0.2 mol) of methylene-bis-thioglycolic acid diethyl ester in 50 ml of ethanol. The reaction mixture is stirred for a further 5 hours at 20 to 25 ° C., poured into 200 ml of water and extracted with 100 ml of ethylene chloride. The aqueous phase is then acidified while cooling with ice and extracted several times with methylene chloride. The combined organic extracts are dried over sodium sulfate and then concentrated. 21.5 g (52.5% of theory) of 4-carbethoxy-5-oxo-1,3-dithiacyclohexane are obtained in the form of a yellow oil with a boiling point of 150 OC / 2 Torr.

nD22: 1.5549.

Example 1b: To a mixture of 20.6 g (0.1 mol) of the 4-carbethoxy-5-oxo-1,3-dithiacyclohexane obtained under 1 a), 14.5 g (0.15 mol) of anhydrous potassium carbonate and 200 ml of acetonitrile 18.8 g (0.1 mol) of O, O-diethylthionophosphoric acid diester chloride are added dropwise at 20 ° C. The reaction mixture is allowed to react for a further 3 hours at 40 ° C. and is then poured into 300 ml of toluene.

The toluene layer is washed with saturated sodium bicarbonate solution and Washed with water, dried over sodium sulfate and then concentrated. 23.5 is obtained g (65% of theory) O, O-diethyl-O- [4-carbethoxy-1,3-dithiacyclohex (4) en- (5) yl] -thionophosphoric acid ester in Form of a yellow oil with the refractive index nD26: 1.5449.

The following compounds of the formula are produced: Example Yield physical data game (% of (refraction no. XR R1 R2 theory) index) 2 S -C2H5-SC3H7-n -C2H5 52 nD26: 1.5618 3 S -C2H5-C2H5 -C2H5 69 nD26 : 1.5451 4 O -C2H5-OC2H5 -C2H5 53 nD26: 1.5255 5 S -C2H5- # -C2H5 69 nD26: 1.5850

Claims (6)

Claims: 6) 1,3-Dithiacyclohexenyl (thiono) - (thiol) -phosphorus (phosphonic) acid ester of the formula in which R and R2 stand for identical or different alkyl radicals with 1 to 5, R1 for alkyl, alkoxy or alkylthio with 1 to 6 carbon atoms per alkyl radical, also for phenyl and X for oxygen or sulfur. 2) Process for the preparation of 1,3-dithiacyclohexenyl (thiono) - (thiol) phosphorus (phosphonic) acid esters, characterized in that one (thiono) (thiol) phosphorus (phosphonic) acid ester halides of the formula in which R, R1 and X have the meaning given in claim 1, Hal represents halogen, preferably chlorine, with 1,3-dithia-4-carbalkoxy-5-oxo-cyclohexane derivatives of the formula in which R2 has the meaning given in claim 1, if appropriate reacts in the presence of acid acceptors and if appropriate in the presence of solvents. 3) Insecticidal agents characterized by a content of compounds according to claim 1. 4) method for combating insects, characterized in that that one compounds according to claim 1 on the said pests or their habitat can act. 5) Use of compounds according to claim 1 for combating Insects. 6) Process for the production of insecticidal agents, characterized in that that one compounds according to claim 1 with extenders and / or surface-active Means mixes.