DE3520387A1 - 1,3,2-Oxathiaphospholane 2-sulphides - Google Patents

Abstract

The invention relates to novel 1,3,2-oxathiaphospholane 2-sulphides of the general formula (I) <IMAGE> in which R represents the amino group or optionally substituted radicals from the series consisting of alkyl, alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and R<1> to R<4> are identical or different and represent hydrogen or optionally halogen-substituted radicals from the series consisting of alkyl, alkoxyalkyl and alkylthioalkyl, or two of the radicals R<1> to R<4> together with the carbon atom(s) to which they are bonded also form an optionally substituted mono- or bicyclic ring with the proviso that in each case at least two of the radicals R<1> to R<4> which are bonded to a joint carbon atom (that is to say R<1> and R<2>, and R<3> and R<4>, respectively,) do not simultaneously represent hydrogen, which can be used as pesticides.o

Description

1.3.2-OxathiaDhosDholane-2-sulfide

The invention relates to substituted 1,3,2-oxathiaphospholane-2-sulfides, several processes for their production and their use as pest control agents, especially as insecticides and acaricides.

It is known that certain P-heterocycles such as e.g.

5-membered cyclic thiophosphoric acid amide diesters (M. Eto. Et al., J, Pesticide Sci, 3, 161 (1978) or dithiophosphonic acid O, S, ester (DE-PS 1 104 520) can be used to control pests.

The insecticidal and acaricidal action of the known compounds is however, especially when the active ingredient concentrations and application rates are low, not always satisfactory.

There were new 1,3,2-oxathiaphospholane-2-sulfides of the general formula (I) found, in which R stands for the amino group or for optionally substituted radicals from the series alkyl, alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and R1 to R4 are identical or different and are hydrogen or optionally halogen-substituted radicals from the series alkyl , Alkoxyalkyl, alkylthioalkyl or two of the radicals R1 to R4 together with the carbon atom or atoms to which they are bonded also form an optionally substituted mono- or bicyclic ring2 with the proviso that in each case at least two of the radicals R1 to R4 , which are bonded to a common carbon atom (i.e. R1 and R2 as well as R3 and R4) do not simultaneously represent hydrogen.

The stipulation in the definition of the radicals R1 to R4 is to be understood as that (also in the case that two of the radicals R1 to R4 are components of a ring) (a) R1 and R2 cannot be hydrogen at the same time if R3 and R4 at the same time stand for hydrogen or one of the radicals R3 and R4 stands for hydrogen and (b) R3 and R4 cannot be hydrogen at the same time if R1 and R2 are simultaneously stand for hydrogen or one of the radicals R1 and R2 stands for hydrogen.

The new compounds of the general formula (I) are obtained if (a) halides of the general formula (II) in which Hal represents halogen, in particular chlorine, and R has the meaning given above, with compounds of the general formula (III) in which R1 to R4 have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of diluents, or (b) dithioanhydrides of the general formula (IV) in which R stands for optionally substituted alkyl, with epoxides of the general formula (V) in which R1 to R4 have the abovementioned meaning, if appropriate using a diluent, or (c) initially (analogous to variant a)) thiophosphoric trichloride (PSCl3) with 2-hydroxy mercaptans of the general formula (III) to give 2-chloro-1,3 , 2-oxathiaphospholane-2-sulfides of the general formula (VI) in which R1 to R4 have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and the compounds of the general formula (VI), if appropriate after their isolation in a second reaction step, with compounds of the general formula (VII) RM ( VII) in which R stands for amino or for optionally substituted radicals from the series alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and M stands for hydrogen or an equivalent of an alkali or alkaline earth metal ion (preferably sodium, potassium or calcium) or an ammonium ion, is, optionally in the presence of acid acceptors and optionally in the presence of diluents, The new 1,3,2-oxathiaphospholane-2-sulfides of the formula (I) are characterized by high effectiveness against animal pests, preferably against arthropods, in particular by a high insecticidal and acaricidal effectiveness.

You can also use synergistic mixtures with other pesticides be used.

Surprisingly, the compounds according to the invention show the Formula (I) considerably higher insecticidal and acaricidal effects than corresponding ones known connections.

The radicals listed in the general formulas should, as follows, explained: The alkyl group in the alkylamino radical R is straight-chain or branched and contains 1 to 8, preferably 1 to 6 and especially 1 to 4 carbon atoms, Examples include methyl, ethyl, n- and i-propyl, and they are preferred unsubstituted, The alkyl groups in the dialkylamino radical R are the same or different and straight-chain or branched and preferably contain 1 to 6, especially 1 to 4 carbon atoms. Examples are methyl, ethyl and called n- and i-propyl. They are preferably unsubstituted.

As optionally substituted alkyl R is straight-chain or branched alkyl having preferably 1 to 6, in particular 1 to 4 carbon atoms. Examples are optionally substituted methyl, ethyl * n- and i.-propyl, n.-, i.- and t.-butyl called. The alkyl groups are preferably unsubstituted.

As optionally substituted alkoxy R is straight-chain or branched alkoxy having preferably 1 to 6, in particular 1 to 4 carbon atoms. Optionally substituted methoxy, ethoxy, n.- and i.-propoxy are exemplary and called n.-, i.- and t.-butoxy. These radicals are preferably unsubstituted before.

The optionally substituted alkenyloxy R is straight-chain or branched alkenyloxy having preferably 2 to 6, in particular 2 to 4 carbon atoms. Optionally substituted propenyloxy and butenyloxy may be mentioned as examples. These radicals are preferably unsubstituted.

The optionally substituted alkylthio R is straight-chain or branched alkylthio having preferably 1 to 6, in particular 1 to 4 carbon atoms. Exemplary are optionally substituted methylthio, ethylthio, n4- and i.-Propylthio, called n.-, i.- and t.-Butylthio.

These radicals are preferably unsubstituted, In if appropriate by Halogen-substituted alkyl R1 to R4 denotes straight-chain or branched alkyl Alkyl having preferably 1 to 6, in particular 1 to 4 carbon atoms. Exemplary are optionally substituted by halogen, preferably fluorine, chlorine or bromine Methyl, ethyl, n.- and i.-propyl, n.-, i.- and t.-butyl, mentioned, with chloromethyl and bromomethyl should be particularly emphasized.

The halogen (preferably fluorine, chlorine or bromine) Substituted alkoxyalkyl and alkylthioalkyl radicals R1 to R4 preferably contain 2 to 8, especially 2 to 6 carbon atoms. Examples include halogen substituted methoxymethyl, ethoxymethyl, methoxymethyl, methylthiomethyl, methylthioethyl and called ethylthiomethyl.

Two of the radicals R1 to R4 can together with the carbon atom (s) to which they are attached, 5- to 7-membered cycloalkyl or cycloalkenyl rings form, which are also bridged by a methylene or ethylene group can and which furthermore by 1 or 2, preferably 1, alkyl group, preferably Methyl or ethyl can be substituted.

The optionally substituted radicals R can be one or more preferably 1 to 3, in particular 1 or 2 same or different Carry substituents. The following are exemplified as substituents: alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and i.-propyl and n.-, i.- and t, -butyl; Alkoxy with preferably 1 to 4, especially 1 or 2 carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, i.- and t-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n4- * and t.-butylthio: haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being the same or are different and as halogen atoms, preferably fluorine, chlorine or bromine, in particular Are fluorine, such as trifluoromethyl: halogen, preferably fluorine, chlorine, bromine and iodine, especially chlorine and bromine; Cyan; Nitro: alkylcarbonyl with preferably 2 to 5 Carbon atoms and alkoxycarbonyl with preferably 2 to 5 carbon atoms.

Halogen means everywhere, unless otherwise stated, fluorine, chlorine, Bromine and iodine, preferably fluorine, chlorine and bromine, especially chlorine and bromine.

Preference is given in the general. Formulas R for methyl, ethyl, methylamino, Dimethylamino or methoxy.

It can be beneficial to the effectiveness of the new compounds of the general formula (I) have an effect when at least one of the radicals R1 to R4 represents a branched alkyl radical, such as i-propyl, i.-, sec, - and tert-butyl.

Preference is given to compounds of the general formula (I) in which R for amino, C1-C6-alkylamino, di- (C1-C6-alkyl) -amino, for optionally by Halogen-substituted radicals from the series C1-C6-alkyl, C2-C6-alkenyloxy, C1-C6-alkoxy and C1-C6-alkylthio, and R1 to R4 are identical or different and are hydrogen, C1-C6-alkyl, which can be substituted by halogen, C1-C4-alkoxy-Cl-C4-alkyl or C1-C4-alkylthio-C1-C4-alkyl to alkylthio-C1-C4-alkyl or in which 2 of the radicals R1 to R4 together with the carbon atom or atoms to which they are attached are bonded to form a C5-C7 cycloalkyl or cycloalkenyl ring, which through Methyl or ethyl can be substituted and which by a methylene or ethylene group can be bridged to a bicyclic ring with the proviso that two the radicals R1 to R4, which are bonded to a common carbon atom, do not simultaneously stand for hydrogen.

Particularly preferred are compounds of the general formula (I), in which R stands for C1-C4-alkyl, C1-C4-alkoxy, C2-C5-alkenyloxy, C1-C4-alkylthio, C1-C4-alkylamino or di- (C1-C4-alkyl) -amino, R1 to R4 the same or are different and for hydrogen, optionally substituted by halogen C1-C4-alkyl or two of the radicals R1 to R4 together with the carbon atom (s), to which they are attached, a 5- or 6-membered cycloalkyl or cycloalkenyl ring form, which through a methylene or ethylene group to a bicyclic ring can be bridged, with the proviso that in each case at least two of the radicals R1 to R4, which are bonded to a common carbon atom, not at the same time stand for hydrogen.

Compounds of the general formula are very particularly preferred (I), in which R is C1-C4-alkyl or C1-C4-alkoxy, C1-C4-alkylamino or di- <C1-C4-alkyl) -amino R 1 to R 4 are identical or different and represent hydrogen or optionally C1-C4-alkyl substituted by chlorine or bromine (preferably unsubstituted) stands, with the proviso that in each case at least two of the radicals R1 to R4, which are bonded to a common carbon atom, not at the same time for hydrogen stand.

Compounds of the general formula are particularly preferred (I) highlighted in which R stands for methyl, ethyl, methoxy, methythio, methylamino or dimethylamino, preferably methyl, ethyl or methoxy and R1 to R4 for hydrogen, methyl, ethyl * n-propyl or i.-propyl, preferably for Is hydrogen, methyl or i, -propyl, with the proviso given here as well The following applies: The compounds of the general formula (I) contain one or more centers of asymmetry and can thus be in the form of diastereomers or mixtures of diastereomers.

If, for example, methanthiophosphonic acid dichloride and 2,2-dimethyl-2-hydroxyethyl mercaptan are used as starting materials for process variant (a), the reaction of these compounds can be outlined by the following equation: If the starting materials used for process variant (b) are ethanthiophosphonic dithioanhydride and 2-methylpropene-1-oxide, the reaction of these compounds can be outlined using the following equation: If thiophosphoric trichloride, 2,2-dimethyl-2-hyaroxyethyl mercaptan and sodium methoxide are used as starting materials for process variant (c), the two-stage reaction of these compounds can be outlined by the following equation: The compounds of the general formulas (II), (III), (IV), (V) and (VII) required as starting materials are generally known compounds of organic chemistry or can be prepared by known processes and methods.

The compounds of the formula (VI) which can be used as starting materials are new and belong to the present invention. The production takes place as below Process (c) described (see also preparation examples).

Examples of the compounds of the general formula (VI) include: R1 R2 R3 R4 CH3 CH3 HH CH3 C2H5 HH CH3 C3H7 HH CH3 i-C3H7 HH C2H5 C2H5 HH R1 R2 R3 R4 C2H5 C3H7 HH C2H5 i-C3H7 HH C3H7 C3H7 HH C3H7 i-C3H7 HHHH CH3 CH5 HH CH3H C3 CH3 i-C3H7 HH C2H5 C2H5 HH C2H5 C3H7 HH C2H5 i-C3H7 HH C3H7 C3H7 HH C3H7 i-C3H7 CH3 H CH3 CH3 CH3 H CH3 C2H5 CH3 H CH3 C3H7 CH3 H CH3 i-C3H7 CH3 H C2H5 CH3H5 CH3 H7 C2 H C2H5 i-C3H7 CH3 H C3H7 C3H7 CH3 H C3H7 i-C3H7 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 C2H5 CH3 CH3 CH3 C3H7 CH3 CH3 CH3 i-C3H7 CH3 CH3 C2H5 C2H5 CH3 CH3 C2H5 CH3H7 CH3 CH3 C2H7 CH3. C3H C3H C3H C3H7 CH3 CH3 C3H7 i-C3H7 Suitable diluents for process variants a), b) and c) according to the invention, including the process for preparing the compounds of general formula (VI), are practically all inert organic diluents. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl - and dibutyl ethers, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide and, for example, dimethylformamide -Methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide, the process variants a), b) and c) according to the invention, including the process for the preparation of the compounds of general formula (VI), are generally carried out at temperatures between -50 ° C. and 120 ° C.

The range between OC and 110 "C. is preferred. The reactions are generally carried out at normal pressure.

Process variants a) and c), including the process for Preparation of the compounds of the general formula (VI) can in the presence of Acid acceptors are carried out. As acid acceptors, all of the lichen Find acid binders use. Alkali carbonates have proven particularly useful 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 Acid acceptors are usually used in an amount that is sufficient is to bind the acid formed, with an excess of acid acceptors can be used without disadvantage for carrying out the process variant according to the invention a) one puts on one mole of (di) thiophore (n) s-boric dichloride (formula II) 1 to 1.6 moles, preferably 1 to 1.4 mol of the compounds of the general formula (III).

To carry out process variant b) according to the invention, sets one mole of dithiophosphonic anhydride of the formula (IV) is preferably 1 to 50 Moles, preferably 1 to 20 moles, of the compounds of the general formula (V).

To carry out process variant c) according to the invention and to prepare the compounds of the general formula (VI), one mole is used Thiophosphoric trichloride 1 to 1.6 moles, preferably 1 to 1.4 moles, of the compounds of the general formula (III). On one mole of the compounds of the general formula (VI) 1 to 1.6 mol, preferably 1 to 1.4 mol of the compounds of the general Formula (VII), where in the case that R is amino, alkylamino or dialkylamino stands, M stands for hydrogen and no acid acceptor is used, 2 to 2.8 Mol of the compounds of the formula (VII) are used.

Working up is carried out by customary methods, for example by Extraction of the products with toluene or methylene chloride from the diluted with water Reaction mixture, washing the organic phase with water, drying and distilling or so-called "partial distillation", i.e. prolonged heating under reduced pressure to moderately elevated temperatures to keep them from the last volatile constituents to free, or by chromatographic purification over silica gel. For characterization the compounds serve refractive index, melting point Rf value, boiling point or the 3tP NMR chemical shift.

The active ingredients are suitable and cheaper if they are well tolerated by plants Warm-blooded toxicity for the control of animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector, you are against normal sensitive and resistant species as well as against all or individual stages of development effective. The pests mentioned above include: From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scraper.

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

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

From the order of the Symphyla e.g. Scutigerella immaculata, the end of the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola, e.g. Onychiurus armature.

From the order of the Orthoptera, e.g. 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, e.g. Forficula auricularis.

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

From the order of the Mallophaga, e.g. Trichodectes spp., Damalinea spp, From the order of the Thysanoptera, e.g. Hercinothrips femoralis and Thrips tabaci.

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

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma 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, e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp ,, Euxoa sps4, Feltia spp ,, Earias insulana, Heliothis sps., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris sps., Chilo sps., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, e.g., Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria sps., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp ,, Trogoderma spp ,, Anthrenus sps., 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, e.g. Diprion spp., Hoplocampa spp ,, Lasius spp., Monomorium pharaonis, Vespa spp, Out of the order of Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca sps., Fannia spp., Calliphora erythrocephala, Lucilia sps., Chrysomyia spp., Cuterebra spp., Gastrophilus sps., 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, for example, Scorpio maurus, Latrodectus mactans.

From the order of the Acarina z, B, 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 plant-parasitic nematodes include Pratylenchus spp ,, Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Active ingredient-impregnated Natural and synthetic materials, finest encapsulation in polymer materials and in Enveloping compounds for seeds, also in formulations with burning charges, such as smoking cartridges, - cans, spirals and the like, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if applicable using surface-active agents, i.e. emulsifiers and / or dispersants and! or foam-generating agents. In the case of using water as an extender For example, 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, chloroethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their 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 are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly dispersed silica, aluminum oxide and silicates: as solid carriers for granulates there are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granulates made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks come as emulsifiers and / or foam-producing agents in question: e.g. 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 hydrolyzates are used as dispersants in question: z, B, lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latex are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils4 Colorants such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes substances and micro-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%, The active ingredients according to the invention can in their customary formulations as well as in those from these formulations prepared application forms mixed with other active ingredients, such as insecticides, Attractants, sterilants, acaricides, nematicides, fungicides, growth regulators Substances or herbicides are present. The insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, through Substances produced by microorganisms u, a, The active ingredients according to the invention can also in their customary formulations as well as in the formulations derived from these formulations prepared use forms are present as a mixture with synergists. Are synergists Compounds by which the effect of the active ingredients is increased without the added synergist must itself be actively effective.

The active ingredient content prepared from the commercially available formulations Application forms can vary within wide ranges. The active ingredient concentration the use forms can range from 0.0000001 up to 95% by weight of active ingredient, preferably are between 0.0001 and 1% 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 compounds according to the invention are also suitable for combating undesirable pests such as insects, ticks and mites in the animal husbandry field and cattle diving, with better results by controlling the pests, e.g. higher milk yield, higher weight, nicer animal fur, longer lifespan etc. can be achieved.

The active compounds according to the invention are used in these areas in a known manner, such as by external application in the form of, for example, immersion (dipping), spraying (spraying) and pouring on (pour-on and spot-on). The biological effectiveness of the compounds according to the invention generally Formula (I) is intended to be illustrated by the following examples. As a comparison compound, the compound of the formula (A) known from DE-PS 1 104 520 was used in some tests.

Example A LD100 test test animals: Leucophaea maderae Number of test animals: 5 Solvent: Acetone 2 parts by weight of active ingredient are in 1000 parts by volume of solvent recorded. The solution obtained in this way is adjusted to the desired with further solvent Concentrations diluted.

2.5 ml of active ingredient solution are pipetted into a Petri dish, Auf at the bottom of the petri dish is a filter paper with a diameter of about 9.5 cm.

The petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution Different levels of active ingredient per m3 of filter paper. Then you give the specified Place the number of test animals in the Petri dish and cover it with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction is determined in%.

100% means that all test animals were killed: 0% means that no test animals were killed.

In this test, for example, at an active ingredient concentration of 0.2% the compounds of preparation examples 1, 4 and 6 a destruction of 100 %, while the comparison compound (A) gave no kill (Oó).

EXAMPLE B LT100 test for Diptera test animals: Musca domestica number of the test animals: 25 solvent: acetone 2 parts by weight of active ingredient are in 1000 Parts by volume of solvent added. The solution thus obtained is with further Solvent diluted to the desired lower concentrations.

2.5 ml of active ingredient solution are pipetted into a Petri dish, Auf at the bottom of the petri dish is a filter paper with a diameter of about 9.5 cm.

The petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution Different levels of active ingredient per m3 of filter paper. Then you give the specified Number of test animals in the Petri dish and covered with a glass lid, the The condition of the test animals is continuously monitored.

The time it takes to knock a 100 Xigen down effect (LT100) is necessary.

In this test, at an exemplary active ingredient concentration of 0.002 X with the compounds from Preparation Examples 3, 5, 7, 8 and 9 of the LT100 reached after 70 minutes, while the comparison compound (A) after 6 hours had no effect.

Example C Limit Concentration Test / Soil Insect Test Insect: Phorbia antiqua maggots (in the soil) solvent: 3 parts by weight acetone emulsifier: 1 part by weight Alkylaryl polyglycol ethers For the production of an expedient active ingredient preparation mixing 1 part by weight of active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the desired concentration.

The active ingredient preparation is intimately mixed with the soil, thereby the concentration of the active ingredient in the preparation is practically irrelevant, The only decisive factor is the amount of active substance by weight per unit volume of soil, which is given in ppm (= mgll). You fill the bottom in pots and leave them at Stand room temperature.

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

In this test, for example, with an active ingredient concentration of 20 ppm kill the compounds of Preparation Examples 1, 3, 4, 6, 8 and 9 of 100 X, while the comparative compound (A) had no effect at this concentration (O%).

EXAMPLE D Limit Concentration Test 1 Soil Insect Test Insect: Diabrotica balteata larvae (in the soil) solvent: 3 parts by weight acetone emulsifier: 1 part by weight Alkylaryl polyglycol ethers For the production of an expedient active ingredient preparation mixing 1 part by weight of active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the desired concentration.

The active ingredient preparation is intimately mixed with the soil. Included the concentration of the active ingredient in the preparation is practically irrelevant, The only decisive factor is the amount of active substance by weight per unit volume of soil, which is given in ppm (= mgll>. The soil is filled into pots and these are left Stand room temperature, After 24 hours, the test animals are in the treated soil given and after a further 2 to 7 days, the effectiveness of the active ingredient is through Counting the dead and living test insects in X is determined. The efficiency is 100 X if all test insects have been killed, it is 0 X if still accurate as many test insects are alive as in the untreated control.

In this test, for example, with an active ingredient concentration of 20 ppm the compounds of Preparation Examples 1, 3, 8 and 9 kill 100 X, while the comparison compound (A) has no effect at this concentration (O X) revealed.

Example E Test with Lucilia cuprina resistant larvae emulsifier: 35 Parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether To produce an appropriate preparation of active ingredient, three parts by weight are mixed Active ingredient with seven parts by weight of the above mixture and diluted the concentrate obtained in this way with water to the desired concentration, About 20 Lucilia cuprina res, larvae are placed in a test tube, which contains approx. 1 cmt horse meat and 0.5 ml of the preparation of the active compound, after 24 hours the degree of destruction is determined.

In this test, for example, with an active ingredient concentration of 30C ppm the compounds of Preparation Examples 1, 5, 6 and 8 have a degree of destruction of 100%.

Example F LT100 test Test animals: Sitophilus granarius Solvent: Acetone 2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent, The solution obtained in this way is reduced to the desired lower levels with further solvent Concentrations diluted, 2.5 ml of the active ingredient solution are pipetted into a Petri dish, There is a filter paper with a diameter on the bottom of the Petri dish of about 9.5 cm, the Petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution Different levels of active ingredient per m2 of filter paper. Then about 25 test animals are given into the petri dish and cover it with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction in X is determined. B, for an active ingredient concentrate ion of 0.02 X the compounds of Preparation Examples 3, 7, 8 and 9 kill of 100 X, while at the same concentration the comparative compound (A) only resulted in a kill of 60X.

Example G Laphygma test Solvent: 7 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether for the production of an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the preparation of active compound the desired concentration and treated with caterpillars of the owl moth (Laphygma frugiperda) occupied as long as the leaves are still moist.

After the desired time, the destruction is determined in%.

100% means that all the caterpillars have been killed; 0% means that no caterpillars were killed.

In this test, for. B. at an active ingredient concentration of 0.01% of the compounds of Preparation Examples 6, 8 and 9 had a kill of 100 %, while the comparison compound (A) does not kill at the same concentration (O%).

Example H Doralis test (systemic effect) Solvent: 7 parts by weight Acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether Appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and diluted the concentrate with water to the desired concentration.

With 20 ml each of the active ingredient preparation of the desired concentration Bean plants (vicia faba), which are heavily influenced by the black bean louse (Doralis fabae) are infested, poured on, so that the active ingredient preparation penetrates the soil, without wetting the shoot, the active ingredient is absorbed by the roots and in the sprout passed on, after the desired time, the kill in X is determined, 100% means that all aphids have been killed.

In this test, for example, the compounds of the preparation examples showed 3, 4 and 9 with an active ingredient concentration of 0.01 X a kill of 100 X, while the comparative compound (A) does not kill at the same concentration (O X) resulted in Example J Tetranychus test (resistant) solvent: 7 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether for production 1 part by weight of active ingredient is mixed with an appropriate active ingredient preparation the specified amount of solvent and the specified amount of emulsifier and diluted the concentrate with water to the desired concentration, bean plants <Phaseolus vulgaris), which is strongly influenced by all stages of development of the common spider mite or Bean spider mite (Tetranychus urticae) are infested by diving into the Treated active ingredient preparation of the desired concentration.

After the desired time, the destruction is determined in%.

100 X means that all spider mites have been killed; 0% means that no spider mites have been killed.

In this test showed, for example, at an active ingredient concentration of 0.01% of the compound of Preparation Example 9 had a kill of 98%, while the comparison compound (A) at the same concentration does not kill (O X) revealed.

The preparation of the compounds according to the invention will be explained in more detail using the following preparation examples: Example 1 16 g (0.1 mol) of ethanethiophosphonic acid dichloride are dissolved in 250 ml of toluene and slowly a mixture of 24 g (0.22 mol) of triethylamine and 12 g of 3-hydroxy-3-methyl-2-mercapto-butane in 200 ml at 200 ° C. Tetrahydrofuran was added dropwise. The mixture is then heated to reflux temperature for 2 days, the solvent is distilled off in a water jet vacuum, the residue is taken up with methylene chloride, washed with water, the organic phase is dried with magnesium sulfate, filtered and freed from the solvent first in a water jet vacuum and then in an oil pump vacuum, 15.7 g are obtained (75X of theory) 2-ethyl-5,5-dimethyl-4-methyl-oxathiaphospholane-2-sulfide with a refractive index n = 1.5698.

Example 2 6.2 g (0.05 mol) of ethanethiophosphonic dithioanhydride are added in portions to 40 ml of 2,3-dimethyl-butene-1-oxide at 20C. The reaction is followed by thin layer chromatography (approx. 20 h>. Then 30 ml of toluene are added, extracted several times with ice water, the toluene phase is dried and freed from the solvent in a water jet vacuum or an oil pump vacuum (bath temperature 20-30 ° C.) 1 CH2Cl2 taken up and filtered through 600 g of silica gel. After distilling off the solvent, 9.3 g (83% of theory) of 2-ethyl-4-methyl-4-i-propyl-1,3,2-oxathiaphospholan 2-sulfide with a refractive index n = 1.522 Example 3 17.0 g (0.1 mol) of thiophosphoric acid trichloride are dissolved in 1 l of toluene and between -5 and OC internal temperature 10.6 g (0.1 mol) of 2-hydroxy-2-methylpropyl mercaptan and 24 g (0.22 mol) triethylamine, dissolved in 200 ml of tetrahydrofuran, was added dropwise. The mixture is warmed to 20 ° C. and stirred for 1 day.

Then the solid is suctioned off, the solvent is distilled off in vacuo, taken up in methylene chloride, washed with water, dried and the solvent distilled off in vacuo. It is then filtered through 500 g of silica gel (mobile solvent (Parts by volume): cyclohexane, acetone = 10: 1). After distilling off the Solvent 9.6 g (48X of theory) of 2-chloro-5,5-dimethyl-1,3,2-oxathiaphospholane-2-sulfide with the refractive index n = 1.5678.

2 g (0.01 mol) of the chloride obtained in this way are dissolved in 100 ml of toluene dissolved and at 20 ° C with rapid stirring 1.9 g of 47.5% dimethylamine solution (in Water) is added dropwise, the mixture is stirred for 2 days at 20 ° C. and then another 2 g of dimethylamine solution are added added. It is then worked up as described above. 1.8 g of 2-dimethylamino-5,5-dimethyl-1,3,2-oxathiaphospholane-2-sulfide are obtained with a melting point of 63-64 * C.

The following compounds of the general formula (I) can be prepared analogously to Examples 1 to 3: Example R R1 R2 R3 R4 Physics.

No., data 4 C2H5 CH3 CH3 CH3 CH3 nD2 ° = 1.5345 5 C2H5 CH3 CH3 H H ni50 nD2 ° = 1.5523 6 C2H5 CH3 i-C3H7 H H nD2 ° = 1.5337 7 CH3 CH3 CH3 H H nD2 ° = 1.562 8 CH3O CH3 CH3 H H nD2 ° = 1.5408 9 CH3NH CH3 CH3 H H 10 CH3S CH3 CH3 H H

Claims (1)

Claims:? Di. I, 3,2-Oxathiaphospholan-2-sulfide of the general formula (I) in which R represents the amino group or optionally substituted radicals from the series alkyl, alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and R1 to R4 are identical or different and represent hydrogen or radicals from the series alkyl, alkoxyalkyl optionally substituted by halogen , Alkylthioalkyl or two of the radicals R1 to R4 together with the carbon atom or atoms to which they are bonded also form an optionally substituted mono- or bicyclic ring, with the proviso that in each case at least two of the radicals R1 to R4, which are bonded to a common carbon atom (i.e. R1 and R2 as well as R3 and R4) do not simultaneously represent hydrogen. 2, compounds of the general formula (I) according to claim 1, in which R. for amino, C1-C6-alkylamino, di-CC1-C6-alkyl) -amino, for optionally by halogen substituted radicals from the series C1-C6-alkyl, C2-C6-alkenyloxy, C1-C6-alkoxy and C1-C6-alkylthio, and R1 to R4 are identical or different and are hydrogen, C1-C6-alkyl, which can be substituted by halogen, C1-C4-alkoxy-Cl-C4-alkyl or C1-C4-alkylthio-Cl-C4-alkyl or ir; which 2 of the radicals R1 to R4 have in common with the carbon atom or atoms to which they are attached, a C5-C7 cycloalkyl or form a cycloalkenyl ring which may be substituted by methyl or ethyl can and which through a methylene or ethylene group to a bicyclic ring can be bridged with the proviso that in each case at least two of the radicals R1 to R4, which are bonded to a common carbon atom, not at the same time stand for hydrogen. 3, compounds of the general formula (I) according to claim 1, in which R is C1-C4-alkyl, C1-C4-alkoxy, C2-C5-alkenyloxy, C1-C4-alkylthio, C1-C4-alkylamino or di- <C1-C4-alkyl) - amino, R1 to R4 are identical or different and represent hydrogen, optionally halogen-substituted C1-C4-alkyl, or two of the radicals R1 to R4 together with the carbon atom (s) to which they are attached are bonded to form a 5- or 6-membered cycloalkyl or cycloalkenyl ring which can be bridged by a methylene or ethylene group to form a bicyclic ring, with the proviso that in each case at least two of the radicals R1 to R4, which are attached to a common carbon atom are bonded, do not simultaneously represent hydrogen, 4. Process for the preparation of the compound of the general formula (I) in which R stands for the amino group or for optionally substituted radicals from the series alkyl, alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and R1 to R4 are identical or different and represent hydrogen or radicals from the series alkyl, alkoxyalkyl optionally substituted by halogen , Alkylthioalkyl or two of the radicals R1 to R4 together with the carbon atom (s) to which they are bonded also form an optionally substituted mono- or bicyclic ring, with the proviso that in each case at least two of the radicals R1 to R4, which are bonded to a common carbon atom (i.e. R1 and R2 as well as R3 and R4) do not simultaneously represent hydrogen. characterized in that (a) halides of the general formula (II) in which Hal represents halogen, in particular chlorine, and R has the meaning given above, with compounds of the general formula (III) in which R1 to R4 have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of diluents, or (b) dithioanhydrides of the general formula (IV) in which R stands for optionally substituted alkyl, with epoxides of the general formula (V) in which R1 to R4 have the abovementioned meaning, if appropriate using a diluent, or (c) initially (analogous to variant a)) thiophosphoric acid trichloride (PSCl3) with 2-hydroxy mercaptans of the general formula (III) to give 2-chloro-1,3 , 2-oxathiaphospholane-2-sulfides of the general formula (VI) in which R1 to R4 have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and the compounds of the general formula (VI), if appropriate after their isolation in a second reaction step, with compounds of the general formula (VII) RM (VII) in which R stands for amino or for optionally substituted radicals from the series alkylamino, dialkylamino, alkoxy, alkenyloxy and alkylthio, and M for hydrogen or one equivalent of an alkali or alkaline earth metal ion or an ammonium ion, optionally in the presence of acid acceptors and optionally reacts in the presence of diluents. 5. Pesticides, characterized by a content of at least one compound of the general formula (I) according to Claim 1 or 4th 6. Use of compounds of general formula (I) according to claim 1 or 4 for the control of pests, preferably arthropods, in particular Insects and arachnids. 7. A method for combating pests, characterized in that that compounds of the general formula (I) according to claim 1 or 4 on pests, preferably arthropods, especially insects or arachnids or their habitat can act. 8, Method of making pesticides, thereby characterized in that compounds of the general formula (1) according to claim 1 or 4 mixed with extenders and / or surfactants. 9, compounds of the general formula (VI) in which R1 to R4 are identical or different and represent hydrogen or optionally halogen-substituted radicals from the series alkyl, alkoxyalkyl, alkylthioalkyl or two of the radicals R1 to R4 together with the carbon atom (s) to which they are bonded, also form an optionally substituted mono- or bicyclic ring, with the proviso that in each case at least two of the radicals R1 to R4 which are bonded to a common carbon atom (ie R1 and R2 as well as R3 and R4) do not simultaneously represent hydrogen. 10. Process for the preparation of compounds of the general formula (VI) in which R1 to R4 are identical or different and represent hydrogen or optionally halogen-substituted radicals from the series alkyl, alkoxyalkyl, alkylthioalkyl or two of the radicals R1 to R4 together with the carbon atom (s) to which they are bonded, also form an optionally substituted mono- or bicyclic ring, with the proviso that in each case at least two of the radicals R1 to R4 which are bonded to a common carbon atom (ie R1 and R2 as well as R3 and R4) do not simultaneously represent hydrogen. characterized in that thiophosphoric acid trichloride (PSCl3) with 2-hydroxy mercaptan of the general formula (III) in which R1 to R4 have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.