DE3221479A1 - Novel (thiono)(dithio)phosphates/phosphonates, their preparation, and their use in pesticides - Google Patents

Abstract

The present invention relates to novel dicyanohydrine(thiono)(dithio)phosphates/phosphonates of the formula I <IMAGE> in which X represents oxygen or sulphur, R represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, alkylthio, arylthio, aralkylthio, alkylamino (mono- and dialkylamino), arylamino or aralkylamino, and R<1> and R<2> are identical or different and each represents hydrogen or optionally substituted radicals from the series comprising alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl and aryl or an optionally substituted heterocyclic radical, which can be used as synergists in pesticides, and which additionally comprise substances which are effective against arthropods, preferably against insects and arachnids, in particular against insects.

Description

New (thiono) (dithio) phosphorus (phosphonic) acid esters,

Process for their manufacture and their use in pesticides The present invention relates to new (thiono) (dithio) phosphorus (phosphonic) acid dicyanhydrin ester, Processes for their production and their use in pesticides, preferably for controlling arthropods, especially insects, mites and Spider animals.

Synergistic mixtures of insecticidal active ingredients, e.g. of pyrethroids with certain methylenedioxyphenyl derivatives, e.g. piperonyl butoxide as synergists have already become known (see e.g.

K. Naumann, Chemistry of Plant Protection Products and Pesticides, Springer Verlag Berlin, Volume 7 (1981), pages 3-6). In practice it is the effectiveness However, such preparations are not always fully satisfactory.

It has been found that the new (thiono) (dithio) phosphorus (phosphonic) acid dicyanhydrin ester of the formula I in which X stands for oxygen or sulfur, R for an optionally substituted radical from the series alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, alkylthio, arylthio, aralkylthio, alkylamino (mono- and dialkylamino), arylamino or Aralkylamino and 2 R1 and R are identical or different and individually represent hydrogen or optionally substituted radicals from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl and aryl or an optionally substituted heterocyclic radical, as synergists in Pesticides can be used which additionally contain substances effective against arthropods, preferably against insects and arachnids, in particular against insects.

Practically all common substances are effective against arthropods Active ingredients in question (see e.g. K.H. Büchel, Plant protection and pesticides, Thieme Verlag Stuttgart ,. 1977, and Farm Chemicals. Handbook 1979, Meister Publishing Co, Willougby, 1979).

It has also been found that the new (thiono) - (dithio) -phosphorus (phosphonic) acid dicyanhydrin esters of the formula (I) are obtained if a) (thiono) (dithio) -phosphorus (phosphonic) acid cyanohydrin ester chlorides of the formula II in which R and R1 have the meaning given above, with aldehydes of the formula III R2 -CHO (III) in which R2 has the meaning given above, in the presence of approximately equimolar amounts of water-soluble cyanides, in the presence of a catalyst, in the presence of water and with Water converts practically immiscible diluents at temperatures between about 0 and 80 ° C, or b) thio-phosphorus (phosphonic) acid dichlorides of the formula IV in which R has the meaning given above, either with aldehydes of the formula V R¹CHO (V) in which R1 has the meaning given above, or with aldehydes of the formula III R2 CHO (III) in which R2 has the meaning given above, in the presence of water-soluble cyanides, in the presence of a catalyst, in the presence of water and solvents which are practically immiscible with water at temperatures between about 0 and 80 ° C. or c) phosphonic (phosphoric) acid dichlorides of the formula VI in which R has the meaning given above, with substituted acetonitriles of the formula VII in which Ri has the meaning given above, and Z stands for hydrogen or an alkali metal ion, - or with substituted acetonitriles of the formula VIII in which R2 has the meaning given above, and Z 'represents hydrogen or an alkali metal ion, if appropriate in the presence of acid acceptors, if appropriate in the presence of diluents at temperatures between -800C and + 800C.

As optionally substituted alkyl R, R1 and R is straight-chain or branched alkyl with 1 to 20, preferably 1 to 10, in particular 1 to 5 Carbon atoms. Examples are optionally substituted methyl, ethyl, n- and iso-propyl, n-, iso and tert-butyl, mentioned.

The optionally substituted alkenyl R, R1 and R2 is straight-chain or branched alkenyl having preferably 2 to 5, in particular 2 to 4 carbon atoms. Examples are optionally substituted ethenyl, propenyl- (1), propenyl- (2) and butenyl- (3) called.

The optionally substituted alkynyl R, R1 and R2 is straight-chain or branched alkynyl having preferably 2 to 5, in particular 2 to 4 carbon atoms. For example, optionally substituted ethynyl, propynyl (1), propynyl (2) and butynyl- (3) called.

Optionally substituted cycloalkyl R1 and R2 are mono-, bi- and tricyclic cycloalkyl with preferably 3 to 8, in particular 3, 5 or 6 carbon atoms. Examples are optionally substituted cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo / 2,2,17-heptyl, bicyclo / 2,2,2 / octyl and called adamantyl.

Optionally substituted cycloalkenyls R1 and R2 are preferably monocyclic cycloalkenyl with 5 or 6 carbon atoms and 1 or 2 double bonds.

As optionally substituted alkoxy R is straight-chain or branched alkoxy with preferably 1 to 6, in particular 1 to. 4 carbon atoms. Optionally substituted methoxy, ethoxy, n- and iso-propoxy are exemplary and called n-, iso- and tert-butoxy.

The optionally substituted alkylthio R is straight-chain or branched alkylthio having preferably 1 to 6, in particular 1 to 4 carbon atoms.

Examples are optionally substituted methylthio, ethylthio, n- and iso-propylthio, called n-, iso- and tert-butylthio.

Aryl is optionally substituted aryl R, R1 and R preferably 6 to 10 carbon atoms in the aryl part. Examples may be substituted phenyl or naphthyl, especially called phenyl.

Optionally substituted aralkyl R, R1 and R2 are optionally all Aralkyl substituted in the aryl part and / or alkyl part with preferably 6 or 10, in particular 6 carbon atoms in the aryl part and preferably 1 to 4, in particular 1 or 2 carbon atoms in the alkyl part, the alkyl part being straight-chain or branched can be. Optionally substituted benzyl and phenylethyl are exemplary called.

Optionally substituted aralkenyl R1 and R2 corresponds in its Aryl part of the aralkyl radical R1 or R2.

In the alkenyl part it preferably contains 2 to 6, in particular 2 or 3 carbon atoms and 1 or 2, preferably 1 double bond.

Optionally substituted aryloxy, arithio and arylamino R contain preferably 6 or 10 carbon atoms in the aryl part, with phenyloxy, naphthyloxy, Phenylthio and naphthylthio, phenylamino and naphthylamino, preferably phenoxy, Phenylthio and phenylamino may be mentioned.

Optionally substituted aralkoxy, aralkylthio and aralkylamino R preferably contain 5 or 10 carbon atoms in the aryl part, with phenyl as may be mentioned as particularly preferred. The alkyl part is branched or straight-chain and preferably contains 1 to 4, in particular 1 or 2, carbon atoms. Particularly The benzyl radical is preferred as the aralkyl moiety.

In the optionally substituted alkylamino R contains the amino group 1 or 2 alkyl groups, each of which can be straight-chain or branched and preferably contain 1 to 5, in particular 1 to 3 carbon atoms, methyl, Ethyl, n- and iso-propyl may be mentioned. Examples are monomethylamino and dimethylamino listed.

R 1 and R 2 are optionally substituted heterocyclic radicals heteroparaffinic, heteroaromatic and heteroolefinic 5- to 7-membered, preferably 5- or 6-membered rings with preferably 1 to 3, in particular 1 or 2 identical or different heteroatoms. The heteroatoms are oxygen, Sulfur or nitrogen. Examples are optionally substituted pyrrolidinyl, Piperidinyl, furyl, thiophenyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, Oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, Azepinyl, pyrrolyl, pyridyl, piperazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, Thiepinyl and 1,2,4-diazepinyl called.

The substituted radicals mentioned in the definition of R, R1 and R2 can be one or more, preferably 1 to 3, in particular 1 or 2 identical or carry different substituents. Examples of substituents include: Alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and iso-propyl and n-, iso- and tert-butyl; Alkoxy with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and iso-propyloxy and n-, iso- and tert-butyloxy; Alkylthio with preferably 1 to 4, especially 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and iso-propylthio and n-, iso- and tert-butythio; Haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, especially 1 to 3 halogen atoms, where the halogen atoms are identical or different and as halogen atoms, preferably Fluorine, chlorine or bromine, especially fluorine, such as trifluoromethyl; Halogen, preferably fluorine, chlorine, bromine and iodine, especially chlorine and bromine; Cyano; Nitro; Alkoxycarbonyl with preferably 2 to C 4, in particular 2 or 3 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl and phenoxybenzyloxycarbonyl. In case of Radicals containing aryl moieties can pass through the aryl moieties, e.g., the phenyl rings Alkylenedioxy groups, which are preferably 1 to 3, in particular Containing 1 or 2 carbon atoms and having 1 to 4 identical or different Halogen atoms (fluorine, chlorine, bromine and iodine) can be substituted.

In the definition of the radicals of the compounds, halogen means Formulas I to Xla each (unless otherwise stated) * fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Preference is given to compounds of the formula (I) in which X is oxygen or sulfur, R is a radical which is optionally substituted by halogen from the series C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, phenyl, benzyl, C1-C5-alkoxy, Phenoxy, benzyloxy, C1-C5-alkylthio, phenylthio, benzylthio, Cl -C5-alkylamino (mono- and Dialkylamino), phenylamino or benzylamino and R1 and R2 are identical or different are and individually for hydrogen or for one optionally by halogen, cyano, C1-C4-alkoxy or Cl -C4-alkylthio-substituted alkyl radical with 1 to 20 carbon atoms, for C2-C5-alkenyl or C2-C5-alkynyl which is optionally substituted by halogen, for optionally by C1-C4-alkyl, C1-C4-alkoxycarbonyl, phenoxybenzyloxycarbonyl and / or halogen-substituted C3-C8-cycloalkyl, for optionally by halogen, C1-C4-alkyl or C1-C4-alkoxy-substituted phenyl-C1-C4-alkyl, for optionally by halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, trifluoromethyl and / or substituted by optionally halogen-substituted C1-C2-alkylenedioxy Phenyl, furyl, thienyl or pyridyl.

The invention relates in particular to compounds of the formula (I) in which X stands for oxygen or sulfur, R for one optionally by fluorine or chlorine-substituted radical from the group consisting of C1-C5-alkyl, phenyl, C1-C5-alkoxy, phenoxy, Benzyloxy, C1-C5 * alkylthio, phenylthio, benzylthio and C1-C5-alkylamino (mono- and dialkylamino) and R¹ and R² are identical or different and individually represent Hydrogen or for one optionally by fluorine, chlorine, methoxy or methylthio substituted alkyl radical with 1 to 10 carbon atoms, for C2-C5-alkenyl, w3-C6-cycloalkyl, for phenyl-C1-C2-alkyl optionally substituted by chlorine, for optionally by fluorine, chlorine, cyano, nitro, methyl, methoxy, trifluoromethyl and / or methylenedioxy substituted phenyl, thienyl or pyridyl.

Halogen means fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

If, in process variant (a), for example, O-ethyl-O- (1-cyano-2-methylpropyl) -thiophosphoric acid ester chloride, acetaldehyde and sodium cyanide are used as starting materials, the reaction of these compounds can be outlined by the following equation: If, in the process according to the invention, variant (b) is used as starting materials, for example ethanethiophosphonic acid dichloride, acetaldehyde and sodium cyanide, the reaction of these compounds can be outlined by the following equation: If, for example, ethanephosphonic acid dichloride and 2-hydroxypropionic acid nitrile are used as starting materials in process variant (c), the reaction of these compounds can be outlined by the following equation: The (thi.ono) (dithio) phosphorus (phosphonic) acid cyanohydrin ester chlorides to be used as starting materials in process variant (a) according to the invention are defined by the formula (II). In this formula, R and R1 stand for those radicals which are given above in the definition in formula (I).

Examples of the compounds of the formula (II) include: Table 1 -R R7 2HãS CH- CH3 n-CfH7S C3H7-iso C387-iso C2HsO Cl H CH- n-C3H7SCH- CH3 C2HsO N (CH) a I. C2HSO C3H7'iSO Table 1 continued R. O C3H7-iso CH. C3H7-iso C2H5 to C3H7-iso C2H5 O Cl C2H5 C2H5 CzHs CH3 n-CH7S CH3 C2H50. CH3 CH3. CH3 C2HSOCH- CH iso-C3H7S, CH3 n-C3H7S C2H5 The compounds of the formula (II) can be prepared by reacting aldehydes with thio-phosphorus (phosphonic) acid dichlorides in the presence of equimolar amounts of water-soluble cyanides such as sodium cyanide, in the presence of water and organic solvents which are practically immiscible with water such as n -Hexane and optionally in the presence of catalysts, which are usually used in reactions in two-phase systems of water and water-immiscible organic solvents for the phase transfer of reactants, such as tetrabutylammonium bromide, at temperatures between 0 and 80 ° C.

The further-in the inventive method variants (a) .- and (b) Aldehydes to be used as starting materials are represented by the formulas (III) and (V) defined. In this formula, R2 or R1 stands for those radicals which are listed above are given in the definition of R2 and R¹ in formula (I).

As examples of the compounds of formula (III) -bzw. (V) are called: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, Valeraldehyde, iso-valeraldehyde, sec.-valeraldehyde, capronaldehyde, iso-capronaldehyde, sec.-capronaldehyde, PivaXaldehyd, acrolein, crotonaldehyde, methoxyacetaldehyde, methylthioacetaldehyde, Cyclohexane-carbaldehyde, benzaldehyde, 4-chlorobenzaldehyde, 4-methylbenzaldehyde, 3,4-methylenedioxy-benzaldehyde, 4,5-methylenedioxy-2-nitro-benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, Thiophene-2-carbaldehyde, Thiophene-3-carbaldehyde, pyridine-2-carbaldehyde and pyridine-3-carbaldehyde.

The starting compounds of the formulas (III) and (V) are known.

Water-soluble cyanides, which in the process according to the invention (a) Can be used are, for example, alkali metal cyanides, such as sodium cyanide and potassium cyanide; Sodium cyanide is preferred.

As a water-immiscible solvent in the invention Process variant (a) preferably hydrocarbons, in particular straight-chain or branched alkanes or cycloalkanes having 5 to 10 carbon atoms, e.g. n-pentane, n-fxane, n-heptane, n-octane, n-nonane, n-decane, 2-methylpentane, 3-methylpentane, 2-methylhexane, 2,2, 4-trimethylpentane, cyclohexane, methylcyclohexane, or also methylbenzenes, such as toluene or xylenes, as well as mixtures of these hydrocarbons are used.

As catalysts in the process variant according to the invention (a) preferably uses compounds which are usually used in reactions in two-phase systems from water and water-immiscible organic solvents for phase transfer from Serving reactants (phase transfer catalysts).

As such, tetraalkyl and trialkyl aralkyl ammonium salts are above all with preferably 1 to 10, in particular 1 to 8, carbons per alkyl group, preferably Phenyl as an aryl component of the aralkyl group and preferably 1 to 4, in particular 1 or 2 carbon atoms in the alkyl part of the aralkyl groups are preferred.

Here come mainly the halides, such as chlorides, bromides and Iodides, preferably the chlorides and bromides in question. Examples are tetrabutylammonium bromide, Benzyl-triethylammonium chloride and methyltrioctylammonium chloride called.

The reaction temperature is in the process variant according to the invention (a) Maintained between about 0 and 80 ° C, preferably between about 0 and 30 "C. The The process is preferably carried out at normal pressure.

On 1 mole of thiono (dithio) phosphorus (phosphonic) acid cyanohydrin ester chloride of the formula (II) are generally used between about 0.6 and 1.1 mol, preferably about 0.75 to 1.0 moles of aldehyde of formula (III), between about 1.0 and 1.5 moles, preferably about 1.1 to 1.3 moles of cyanide and optionally between about 0.001 and 0.05 moles, preferably about 0.01 to 0.03 moles of catalyst.

In a preferred embodiment of the process variant according to the invention (A) the starting compounds of the formulas (II) and (III), the catalyst and the cyanide dissolved in the water-immiscible solvent and added to this Solution is slowly added to water, optionally initially by external cooling the reaction temperature is brought to about 0 to 100C. The reaction mixture is then stirred at about 20 ° C. for several hours.

For work-up, if necessary, no further water is used diluted with a miscible solvent, the organic phase separated off, washed with water, dried and filtered. The filtrate is reduced by distillation Freed from the solvent under pressure, the crude product being obtained as an oily residue.

In the process variant (b) according to the invention as the starting point substances to be used thio-phosphorus (phosphonic) acid dichlorides are represented by the formula (IV) defined. In this formula, R stands for those radicals which are mentioned above in the Definition given in formula (I).

Examples of the compounds of the formula (IV) include: Methane, ethane, propane, butane and benzene thionophosphonic acid dichloride; O-methyl, O-ethyl-, O-n- and O-iso-propyl-, O-n-, O-iso- and O-sec.-butyl-, O-phenyl- and O-benz.yl-thi.onophosphoric acid ester dichloride; 5-methyl-, 5-ethyl, S-n- and S-iso-propyl, S-n-, S-iso- and S-sec-butyl-, S-phenyl- and S-benzyldithiophosphoric acid ester dichloride.

The compounds of the formula (IV) are known and / or can be used in a customary manner Way to be produced by processes known per se (cf. methods of organic Chemie (Houben-Weyl-Müller), 4th ed., Volume 12/1 (1963), pp. 387-406 and pp. 552-557; 12/2 (1964), pp. 212-225, 590-S94 and 682-683; Thieme-Verlag Stuttgart).

As water-soluble cyanides, which in the process variant according to the invention (b) can be used, the cyanides are preferably used in the Process variant (a) have already been mentioned.

The solvent used for the reaction according to the process variant (b) Preferably the solvents in question that are already used in process variant (a) were called.

The catalysts used for the reaction are in accordance with the process variant (B) preferably the catalysts in question, which in process variant (a) have already been mentioned.

The reaction temperature is in process (b) according to the invention between about 0 and 80 "C, preferably between about 0 and 30" C. The procedure is preferably carried out at normal pressure.

Relies on 1 mole of thiophosphorus (phosphonic) acid dichloride of the formula (IV) generally between about 2.5 to 4.0 moles, preferably between about 3.0 and 3.5 mol of aldehyde of the formula (II.I) or (V), between about 2.0 and 3.0 mol, preferably about 2.2 to 2.6 mol of cyanide and optionally between about 0.002 to 0.1 moles, preferably between 0.02 to 0.06 moles of catalyst.

In a preferred embodiment of the process variant according to the invention (b) the starting compounds of the formulas (IV) and (V) or (III), the catalyst and the cyanide dissolved in and added to the water-immiscible solvent Solution is slowly added to water, optionally initially by external cooling the reaction temperature is brought to about 0 to 50C. The reaction mixture is then several hours at around 200C.

For work-up, if necessary, no further water is used diluted with a miscible solvent, the organic phase separated off, washed with water, dried and filtered. The filtrate is reduced by distillation under Freed from the solvent under pressure, the crude product being obtained as an oily residue.

The at. process variant (c) according to the invention as starting materials Phosphonic acid dichlorides to be used are defined by the formula (VI).

In this formula, R stands for those radicals which are mentioned above in the Definition of R in formula (I) are given.

Examples of the compounds of the formula (VI) include: Methane, ethane, propane, butane and benzene phosphonic acid dichloride; O-methyl-, O-ethyl-, O-n- and O-iso-propyl, O-n-, O-iso- and O-sec-butyl, O-phenyl and O-benzyl-phosphoric acid ester dichloride; S-methyl-, S-ethyl-, S-n- and S-iso-propyl-, S-n-, S-iso- and S-sec-butyl-, S-phenyl- and S-benzyl thiophosphoric acid ester dichloride.

The compounds of the formula (VI) are known and / or can be used in a customary manner Way to be produced by processes known per se (cf. methods of organic Chemie (Houben-Weyl-Müller), 4th ed., Volume 12/1 (1963), p. 387 ff; Volume 12/2 (1964), P. 212-225, p. 383 and p. 596; Thieme-Verlag Stuttgart).

The further in process variant (c) according to the invention as the starting point Substances to be used substituted acetonitriles or their alkali metal salts are defined by formulas (VII) and (VIII). In this formula, R1 or R2 for those radicals which are mentioned above in the definition of R1 or R2 in the formula (I) are indicated, and Z and Z 'respectively represent hydrogen, lithium, sodium or potassium.

Examples of the compounds of the formula (VII) and (VIII) may be called: Hydroxyacetonitrile, 2-Hydroxy-propanenitrile, 2-Hydroxy-butannïtrilt 2-Hydroxypentanenitril, 2-Hydroxy-3-methylbutannitrii, 2-Hy- droxy-hexanenitrile, 2-hydroxy-3-methyl-pentanenitrile, 2-hydroxy-4-methyl-pentanenitrile, 2-hydroxy-heptanenitrile, 2-hydroxy-3-methyl-hexanenitrile, 2-hydroxy-4-methyl-hexanenitrile, 2-hydroxy-octanenitrile, 2-hydroxy-3-methyl-heptanenitrile, 2-hydroxy-4-methyl-heptanenitrile, 2-hydroxy-3,3-dimethyl-butanenitrile, 2-hydroxy-4-butenenitrile, 2-hydroxy-3-pentenni.tril, 2-hydroxy-2-methoxy-acetonitrile, 2-hydroxy-2-methylthio-acetonitrile, 2-cyclohexyl-2-hydroxyacetonitrile, 2-hydroxy-2-phenylacetonitrile, 2- (4-chlorophenyl) -2-hydroxyacetonitrile, 2- (4-methylphenyl) -2-hydroxyacetonitrile, 2- (3,4-methylenedioxyphenyl) -2-hydroxyacetonitrile, 2- (4,5-methylenedioxy-2-nitrophenyl) -2-hydroxyacetonitrile, 2-hydroxy-3-phenyl-propanenitrile, 2-hydroxy-2-phenyl-propanenitrile, 2-hydroxy-2- (2-thienyl) acetonitrile, 2-hydroxy-2- (3-thienyl) acetonitrile, 2-hydroxy-2- (2-pyridyl) acetonitrile and 2-hydroxy-2- (3-pyridyl) acetonitrile as well as the alkali metal salts such as lithium, sodium and potassium salts of these compounds.

The starting compounds of the formula (VII) or (VIII) are known or can be prepared in a customary manner by processes known per se (see.

Methods of organic chemistry (Houben-Weyl-Müller), 4th edition, volume 8/3 (1952), pp. 274-278; Thieme-Verlag Stuttgart).

The diluents come in handy in process variant (a) all inert organic solvents in Question. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, Methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ethers such as diethyl and dibutyl ethers, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones such as acetone, Methyl ethyl, methyl isopropyl and methyl isobutyl ketone, as well as esters such as methyl acetate and ethyl esters, also nitriles, such as acetonitrile and propionitrile, above in addition to amides, such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylene phosphoric acid triamide.

Acid acceptors which can be used in process variant (c) are all customary Acid binders can be used.

These preferably include alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, Dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature is in process variant (c) between about -800C and + 800C, preferably between about -600C and -300C. The procedure is preferably kept between about -60 ° C and + 300C. The method is preferred carried out at normal pressure.

When carrying out process variant (c), one relies on about 1 mole of the compound of the formula (VI) is preferably about 1.5 to 2.5 moles of substituted Acetonitrile of the formula (VII) or (VIII), the substituted acetonitrile in the event that Z resp.

Z 'stands for sodium, potassium or lithium, preferably in situ the corresponding HyQ'oyacetonitrile and a strong base such as butyllithium, Methyl lithium, sodium, potassium, sodium hydride and sodium amide is produced. the The end products are isolated in the generally customary manner.

The new (thiono) (dithio) phosphorus (phosphonic) acid dicyanhydrin ester of formula (I) have in a mixture with substances of any constitution, which against Arthropods are effective, strong synergistic effects on what their use in pesticides made possible.

The new (thiono) (dithio) phosphorus (phosphonic) acid dicyanhydrin esters are preferred of formula (I) together with arthropodicides A) carbamic acid esters and / or B) carboxylic acid esters including natural and synthetic pyrethroids and / or C) phosphorus compounds, such as phosphoric and phosphonic esters, including the thio and dithio compounds and or D) Halogen (cyclo) alkanes, such as hexachlorocyclohexane used.

Surprisingly, the effect of the new ore is in accordance with the invention Combinations of active ingredients against arthropods are much higher than the effects of the individual components or the sum of the effects of the individual components.

It is also much higher than the effect of combinations of active ingredients with the. known synergists piperonyl butoxide. The (Thiono) according to the invention Dicyanhydrin (dithio) phosphorus (phosphonic) acid esters also show excellent synergistic effectiveness not only for one class of active ingredients, but also for active ingredients from a wide variety of chemical substance groups.

The synergistic effect of the compounds of the formula (I) is particularly preferred in the case of A) carbamic acid esters of the formula (IX) in which R3 stands for an optionally substituted carbocyclic or heterocyclic aromatic radical or for an optionally substituted oxime radical (the radicals R³ explained below are preferred), R4 stands for C1-C4-alkyl and R5 stands for hydrogen, C1-C4- Alkyl or a radical Y, where Y stands for the radical -CO-R6, in which R6 is halogen, C1-C4-alkyl, C1-C4-alkoxy, C3-C5-alkenoxy, C3-C5-alkynoxy, Ci - C4-alkylthio, C1-C4-alkyl-amino, di-C1-C4-alkylamino, C1-C4-alkyl-hydroxylamino, for optionally by halogen, nitro, Cvano, trifluoromethyl, C1-C4-alkyl, C1-C4-alkoxy , L1-C4-alkylenedioxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl-substituted phenoxy, phenylthio or phenylamino, for 2,3-dihydro-2,2-dimethyl-7-benzofuranyl or for the remainder where R7 is hydrogen, C1-C4-alkyl or di-C1-C4-alkylamino-carbonyl and R8 is C1-C4-alkyl, C1-C4-alkylthio, cyano-C1-C4-alkylthio, Cl-C4 - Alkylthio-C1-C4-alkyl, or the two radicals R7 and R8 together represent C2-C8-alkanediyl optionally interrupted by oxygen, sulfur, SO or SO2, or in which Y represents the radical -Sn (O) m-R9 where n is 1 or 2 and m is 0, 1 or 2 and R9 is optionally halogen-substituted C1-C4-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or C3-C6-cycloalkyl, for optionally phenyl, benzyl or phenylethyl substituted by halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, C1-C4-alkyl or C1-C4-alkoxy, or for the remainder where R10 is C1-C4-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, C3-C6-cycloalkyl or benzyl and R11 is C1-C4-alkyl, C3-C5-alkenyl, C3-C5- Alkynyl, C3-C6-cycloalkyl, benzyl, phenylethyl, halocarbonyl, formyl, C1-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl, Cl-C4 -alkoxyphenox-carbonyl, C3-C5-alkynox-carbonyl, C3-C5 -Alkenoxycarbonyl, C1-C4-alkylthiocarbonyl, C1-C4-alkyl-aminocarbonyl, C1-C4-alkyl-hydroxyamino-carbonyl, C1-C10-alkyl-phenoxycarbonyl, di-C1-C4-alkyl-aminocarbonyl, phenylthiocarbonyl, phenoxycarbonyl , 2,3-dihydro-2,2-dimethy.1-7-benzofuranyloxycarbonyl, is phenylsulfenyl, phenylsulphinyl, phenylsulphonyl or phenyl which is optionally substituted by halogen, cyano, nitro, trifluoromethyl, C1-C10-alkyl or C1-C4-alkoxy , or for the rest is in which R12 has the meaning given above for R7 R13 for R8, furthermore in the remainder the radicals R10 and R11 together represent a hydrocarbon chain with 3 to 8 carbon atoms optionally interrupted by oxygen or sulfur, in which furthermore R9 can also stand for the same radical to which the radical -Sn (O) m-R9 is bonded.

Carbamic acid esters of the formula (IX), in which R³ is optionally substituted by C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-C4-alkoxymethyl, C1-C4-alkylthio, are very particularly preferred as active ingredient components , C1-C4-alkylthio-methyl, C1-C4-alkylamino, di- (C1-C4-alkyl) -amino, di- (C3-C4-alkenyl) -amino, halogen, dioxolanyl, methylenedioxy and / or by the rest -N = CH (CH3) 2 substituted radicals from the series phenyl, naphthyl, 2, 3-dihydro-7-benzofuranyl, pyrazolyl or pyrimidinyl, or in which R3 represents an alkylidene amino radical of the formula (IXa) in which R14 and R15 have the meanings given above for R7 and R8, respectively, and R4 stands for C1-4-alkyl and R5 stands for hydrogen or C1-C4-alkyl (preferably for hydrogen).

Examples of the carbamic acid esters of the formula (IX) are: 2-methyl-phenyl-, 2-ethyl-phenyl-, 2-iso-propyl-phenyl-, 2-sec-butyl-phenyl-, 2-methoxyphenyl-, 2-ethoxyphenyl-, 2-iso-propoxyphenyl-, 4-methyl-phenyl-, 4-ethyl-phenyl-, 4-n-propyl-phenyl-, 4-methoxyphenyl, 4-ethoxyphenyl, 4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 3,5-dimethyl-4-methylthio-phenyl-, 3-methyl-4-dimethylaminophenyl-, 2-ethylthiomethyl-phenyl-, 1-naphthyl-, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, 2,3- (dimethyl-methylenedioxy) -phenyl-, 2- (4,5-dimethyl-1,3-dioxolan-2-yl) -phenyl-, 1-methylthio-ethylidene-amino-, 2-methylthio-2-methylpropylideneamino-, 1 - 1- (2-cyano-ethylthio) -ethylideneamino- and 1-methylthiomethyl-2,2-dimethylpropyl idenamino-N-methyl-carbamic acid ster.

The synergistic effect of the compounds of the formula (I) is shown more preferably in the case of B) carboxylic acid esters of the formula (X) in which R16 stands for an open-chain or cyclic alkyl radical which is optionally substituted by halogen, alkyl, cycloalkyl, by alkenyl optionally substituted by halogen, alkyl and / or alkoxy, by phenyl or styryl, which is optionally substituted by halogen, optionally halogen substituted radicals from the series alkyl, alkoxy, alkylenedioxy and / or alkylthio are substituted by spirocyclically linked, optionally halogen-substituted cycloalk (en) yl, which is optionally benzannellated, in which R17 is also hydrogen, alkyl, haloalkyl, alkenyl, alkynyl or cyano, and R18 stands for an optionally substituted alkyl or aryl radical or for a heterocycle, or together with R17 and the carbon atom to which both radicals are bonded forms a cyclopentenone ring.

Carboxylic acid esters of the formula (X), in which R16 is the remainder, are very particularly preferred as active ingredient components in which R19 represents hydrogen, methyl, fluorine, chlorine or bromine and R20 represents methyl, fluorine, chlorine, bromine, C1-C2 fluoroalkyl or C1-C2 chlorofluoroalkyl or radicals optionally substituted by halogen and / or optionally halogenated Series C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and / or C1-C2-alkylenedioxy-substituted phenyl, or in which both radicals R19 and R20 are C2-C5-alkanediyl (alkylene); or in which R16 for the rest where R21 is phenyl optionally substituted by halogen and / or by optionally halogen-substituted grates of the series C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C2-alkylenedioxy and R22 is isopropyl or Cyclopropyl; or in which R16 for one of the radicals where the dotted lines are intended to indicate possible double bonds or represent methyl, and in which R17 represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, cyano or ethynyl and 18 radicals from the series phenyl, furyl, which are optionally substituted by halogen or tetrahydrophthalimido, where these radicals can in turn be substituted by optionally halogen and / or by an optionally halogen-substituted radical from the series C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy, C2-C4-alkenoxy, C1-C4-alkylthio, C1-C2-alkylenedioxy, phenoxy and / or benzyl, where R is preferably pentafluorophenyl, 3, 4-dichlorophene, enyl, phenoxyphenyl, which can be substituted by halogen in one or both phenyl rings or is tetrahydrophthalimido.

Next are the naturally occurring pyrethroids (like pyrethreum) particularly preferred as the carboxylic acid ester of the formula (X).

Examples of the carboxylic acid esters of the formula (X) are: Acetic acid (2, Z, 2-trichloro-1- (3,4-dichloro-phenyl) -ethyl) ester, 2, 2-dimethyl-3- (2-methyl-propen-1 -yl) - cyclopropane carboxylic acid (3,4,5,6-tetrahydro-phthalimido-methyl) ester, 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-carboxylic acid- (3-phenoxy-benzyl) -ester, 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid ((Q & -cyano-3-phenoxy-benzyl) ester, 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid (α-cyano-4-fluoro-3-phenoxy-benzyl) ester, 2,2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylic acid (pentafluorobenzyl) ester, 2,2-Dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarboxylic acid (-cyano-3-phenoxybenzyl) ester and 3-methyl-2- (4-chloro-phenyl) -butanoic acid (cyano-3-phenoxy-benzyl) ester.

The synergistic effect of the compounds of the general formula (I) is also shown, preferably in the case of C) phosphoric acid and phosphonic acid esters of the general formula (XI) in which X each represents O or S and Y represents O, S, -NH- or a direct bond between the central P atom and R25 and R and R are identical or different and represent optionally substituted alkyl or aryl, R25 represents hydrogen, optionally substituted alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or an oxime radical or represents the same radical to which it is bonded.

Phosphoric and phosphonic esters of the formula (XI), in which R23 and R24 are identical or different and are C1-C4-alkyl or phenyl, R25 is hydrogen, alkyl having 1 to 4 carbon atoms, which is optionally replaced by halogen, are particularly preferred. Hydroxyl, cyano, optionally halogen-substituted phenyl, carbamoyl, alkylsulfonyl, alkylsulfinyl, alkylcarbonyl, alkoxy, alkylmercapto, alkoxycarbonyl, alkylaminocarbonyl, the latter with up to 6 carbon atoms each, for alkenyl with up to 4 carbon atoms, which is optionally substituted by halogen, optionally halogen-substituted phenyl or C1-C4-alkoxycarbonyl is substituted, or for the remainder of the general formula (XIa) R26 and R27 are as defined above for R7 and R8, where R26 and have the meaning given, or are cyano or phenyl, and in which R25 is also dioxanyl, which is substituted by the same radical to which R25 is bonded, or R25 is the same Radical to which it is bonded or R25 stands for phenyl, which is optionally substituted by methyl, nitro, cyano, halogen and / or methylthio and k25 also particularly preferably stands for optionally by C1-C4-alkoxy, C1-C4-alkylthiomethyl, C1-C4-alkyl and / or halogen-substituted heteroaromatic radicals, such as pyridinyl, quinolinyl, quinoxalinyl, pyrimidinyl or benzo-1,2,4-triazinyl.

The following may be mentioned in detail: 0,0-dimethyl- or 0,0-diethyl-0- (2,2-dichloro- respectively.

2,2-dibromovinyl) phosphoric acid ester, O, O-diethyl-0- (4-nitro-phenyl) -thionophosphoric acid ester O, O-Dimethyl-O- (3-methyl-4-methylthio-phenyl) -thionophosphoric acid ester O, O-dimethyl-O- (3-methyl-4-nitro-phenyl) -thionophosphoric acid ester, O-ethyl-S-n-propyl-O- (2,4-dichlorophenyl) -thionophosphoric acid ester, O-ethyl-S-n-propyl-O- (4-methylthio-phenyl) -thionophosphoric acid ester, O, O-dimethyl-S- (4-oxo-1,2,3-benzothriazin (3) yl-methyl) -thionothiolphosphoric acid ester, O-methyl-O- (2-iso-propyl-6-methoxy-pyrimidin (4) yl) -thionomethanephosphonic acid ester, O, O-Diethyl-O- (2-iso-propyl-6-methyl-pyrimidin (4) yl) -thionophosphoric acid ester, O, O-diethyl-O- (3-chloro-4-methyl-coumarin (7) yl ) thionophosphoric acid ester, O, O-dimethyl-2, 2, 2-trichloro-1-hydroxy-ethane-phosphonic acid ester, O, O-dimethyl-S- (methylaminocarbonyl-methyl) -thionophosphoric acid ester.

Furthermore, the synergistic effect of the compounds is shown general formula (I) preferably for D) halogen (cyclo) alkanes, such as hexachlorocyclohexane, 1,1,1-trichloro-2,2-bis- (4-chlorophenyl) -ethane, 1,1,1-trichlor-2,2-bis- (4-methoxyphenyl) -ethane and 1,1-dichloro-2,2-bis (4-ethylphenyl) ethane.

The weight ratios of the synergists and active ingredients can be in can be varied over a relatively wide range.

In general, the compounds used as synergists of formula (I) with the other active ingredients in mixing proportions between 1: 100 and 100: 1, preferably between 1: 5 and 5: 1 (parts by weight) used.

The active ingredient combinations according to the invention do not have just one quick knock-down effect, but also cause the sustained killing Ci animal Pests, in particular of insects and mites, which are found in agriculture in Forests, in store and material protection as well as in the hygiene area. they are against normally sensitive and resistant species as well as against all or individual stages of development effective.

Among the animal pests which use the compounds of the formula (I) can be combated include, for example: From the order of the Isopoda e.g. Oniscus asellus, Porcellio scaber.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Orthoptera, e.g. Blatta orientalis, Periplaneta maericana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Schistocerca gregaria.

From the order of the Dermaptera, e.g. Forficula auricularia.

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

From the order of the Anoplura, e.g. Pediculus humanus corporis, Haematopinus spp., Linograthus spp.

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

From the order of the Heteroptera e.g. Cimex lectularius, Phodnius prolixus, Triatoma spp.

From the order of the Homoptera, for example, Myzus spp., And Psylla spp.

From the order of the Lepidoptera, e.g. Ephestia kuehniella and Galleria mellonella.

From the order of the Coleoptera, e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bejulus, Oryzaephilus surinamensis, Sitophilus spp., Dermestes spp., Trogoderma spp. , Anthrenus spp., Attagenus spp. Lyctus spp.

Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp. and Tenebrio molitor.

From the order of the Hymenoptera, e.g. Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, e.g. Aädes spp. R Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypderma spp. and Tabanus spp.

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, Boophilus spp., Rhipicephalus spp., Amblyomma spp.

Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.

The active ingredient combinations from the compounds of the formula (I) and the other active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, Pastes, soluble powders, aerosols, suspension emulsion concentrates, impregnated agents Natural and synthetic materials, finest encapsulation in polymer materials, furthermore in formulations with burning charges, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredient mixtures with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using 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 be used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as Xylene, toluene, or Alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylene 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 such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and 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 minerals 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 emulsifying and / or foam-generating agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates; as dispersants: 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.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and 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% by weight Combination of active ingredients, preferably between 0.5 and 90%.

The active ingredient combinations according to the invention are used in the form of their commercially available formulations and / or those from these formulations prepared application forms.

The total active ingredient content (including the synergist) of the Use forms prepared from commercially available formulations can be used in a wide range vary. The active ingredient concentration of the use forms can range from 0.0001 to 100% by weight active ingredient combination, 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 ingredient combinations due to an excellent residual effect on wood and Clay as well as good alkali stability on limed substrates.

The following examples are intended to illustrate the effectiveness of the compounds of the formula (I) which can be used according to the invention: I. Examples of active substances which can be used according to the invention A) (Propoxur) 2) (Carbofuran) C) (Bendiocarb) (Methomyl) E) Pyrethrins of natural origin as a 25% extract.

(Tetramethrin) (Permethrin) (Decamethrin) (Penfenate) (γ-hexachlorocyclohexane) (DDPV) II. Examples of synergists which can be used according to the invention 9) piperonyl butoxide (known) III. Carrying out the LT100 test Test animals: Female Musca domestica (Weymanns strain) resistant to phosphoric acid esters and carbamates Solvent: Acetone Solutions are made of the active ingredients, synergists and mixtures of active ingredients and synergists and 2.5 ml of them are prepared in Petri dishes on filter paper discs of 9.5 cm Pipetted diameter.

The filter paper soaks up the solutions. The petri dishes remain Stand open until the solvent has completely evaporated. Afterward 25 test animals are placed in the Petri dishes and covered with a glass lid.

The condition of the test animals is continuously monitored for up to 6 hours. The time is determined which is necessary for a 100% knock-down effect is.

If the LT100 is not reached after 6 hours, the percentage of Knocked down test animals were found.

Concentrations of the active ingredients, synergists and mixtures and their Effects are shown in the table below.

IV. Test results LT100 test with female Musca domestica (strain Weymanns) resistant to phosphoric acid ester active ingredients / concentrations in% LT-100 in minutes or synergists active ingredient / synergist at 3'0 'in% A) 1.0 360' = 0% B) 1.0 360 '= 0% C) 1.0 360' = 0% D) 0.04 360 '= 0% E) 0.04 360' = 0 x F) 0.008 360 '= 60% G) 0, 04 180 'H) 0.0016 60' I) 0.04 45 'J) 1.0 360' = 70 x K) 0.008 360 'L) 0.008 360' = 95% M) 0.04 60 '1) 1 , 0 360 '= 0 X 2) 1.0 360' = 0% 3) 1.0 360 '= 0% 4) 1.0 360' = 0% 5) 1.0 360 '= 0% 6) 1 , 0 360 '= 0% 7) 1.0 360' = 0% 8) 1.0 360 '= 0% 9) (known) 1.0 360' = 0% active ingredient / synergist concentrations in% LT 100 in minutes Active ingredient / synergist or at 360 'A + 2 0.2 + 0.2 240' A + 4 0.2 + 0.2 150 'A + 5 0.2 + 0.2 150' A + 6. 0, 04 + 0.04 120 'AA + 8 0.04 + 0.04 180' A + 9 0.2 + 0.2 360 '= 95% B + 2 0.04 + 0.04 150' B + 4 1 , 0 + 1.0 150 '8 + 5 1.0 + 1.0 210' B + 6 0.04 + 0.04 8 + 7 0.04 + 0.04 90 '8 + 9 0.04 + 0 '04 360' = 7575% C + 5 1.0 + 1.0 C + 6 0.04 + 0.04 C + 7 0.04 + 0.04 210 'C + 9 0.04 + 0.04 360' = 10% D + 2 0.04 + 0.04 210 'D + 4 0 , 04 + 0.04 240 'D + 6 0.04 + 0.04 180' 0 + 7 0.04 + 0.04 180 'D + 9 0.04 + 0.04 360' = 6 E + 7 0 .04 + 0.04 180 'E + 6 0.04 + 0.04 180' F + 2 0.008 + 0.008 F + 3 0.008 + 0.008 150 'F + 6 0.008 + 0.008 120' F + 7 0.008 + 0.008 180 ' F + 9 0.008 + 0.008 360 '= 10 XG + 1 0.04 + 0.04 90' G + 2 0.04 + 0.04 1051 G + 3 0.04 + 0.04 150 'G + 4 0, 04 + 0.04. 90 'G + 5 0, C4 + 0.04 120' G + 6 0.04 + 0.04 G + 7 0.04 + 0.04 90 'Active ingredient / synergist concentrations in% LT 100 in minutes Active ingredient / synergist at 360 'H + 2 0.0016 + 0.0016 45' H + 3 0.0016 + 0.0016 45 'H + 6 0.0016 + 0.0016 45' H + 7 0.0016 + 0.0016 45 ' 1 + 3 0.04 + 0.04 30 'I + 6 0.04 + 0.04 I + 7 0.04 + 0.04 J + 1 0.2 + 0.2 240' J + - 2 0, 2 + 0.2 240 'J + 5 0.2 + 0.2 J + 7 0.2 + 0.2 210' J + 9 0.2 + 0.2 360 '= 95 x K + 1 0.008 + 0.008 K + 2 0.008 + 0.008 120 'K + 3 0.008 + 0.008 150' K + 4 0.008 + 0.008 K + 5 0.008 + 0.008 K + 6 0.008 + 0.008 120 'K + 7 0.008 + 0.008 150' K + 9 0.008 + 0.008 180 'L + 1 0.008 + 0.008 180' L + 4 0.008 + 0.008 L + 7 0.008 + 0.008 1051 L + 9 0.008 + 0.008 360 '= 85 XM + 3 0.04 + 0.04 45' M + 6 0.008 + 0.008 45 'M + 7 0.04 + 0.04 45' The preparation of the compounds of the formula (I) is explained using the following preparation examples: Example 1: Process variant (a) 14.1 g (0.1 mol) 4-chlorobenzaldehyde, 22.6 g (0.1 mol) 0- (1-cyano-2-methyl-propyl) -ethyl-thiophosphonic acid ester chloride, 0.6 g tetrabutylammonium bromide and 5 , 6 g (0.12 mol) of sodium cyanide are placed in 300 ml of toluene and, at an internal temperature between 0 and 100 ° C., 10 ml of water are added dropwise with vigorous stirring. After the addition has ended, the temperature is slowly increased to 200 ° C. and stirring is continued until the reaction has ended. The aqueous phase is then separated off, the organic phase is washed twice with 100 ml of water each time and dried over sodium sulfate. After the solvent has been stripped off in a water jet vacuum and less volatile constituents have been distilled off at 50 ° C./3 mm Hg, 31 g (86.9% of theory) of 0- (1-cyano-1- (4-chlorophenyl) methyl) - are obtained as an oily residue 0- (1-cyano-2-methyl-propyl) -ethyl-thiophosphonic acid diester with a refractive index nD20: 1.5357.

Example 2 process variant (b) (Synergist No. 3) 20.9 g (0.1 mol) of Sn-propyl-dithiophosphoric acid dichloride, 13.2 g (0.3 mol) of acetaldehyde, 11.2 g (0.23 mol) of sodium cyanide and 1 g of tetrabutylammonium bromide placed in 200 ml of hexane and added dropwise at an internal temperature of 0 and 5 ° Cg 20 ml of water with vigorous stirring. After the addition has ended, the temperature is slowly increased to 20 ° C. and stirring is continued until the end of the reaction. After the organic phase has been separated off, the residue is extracted twice with 200 ml of methylene chloride, and the combined organic phases are washed twice with 100 ml of water and dried over sodium sulfate. After removing the solvent in a water jet vacuum and distilling off less volatile constituents at 50 ° C./3 mm Hg, 19.4 g (70% of theory) of bis-0,0- (1-cyanoethyl) -Sn-propyl-dithiophosphoric acid ester are obtained as an oily residue a refractive index nD20: 1.5013.

Example 3: Process variant (c) 64 g (0.2 mol) of a 15% solution of butyllithium in hexane was added dropwise. This mixture is then added dropwise at -500C to a solution of 16.3 g (0.1 mol) of phosphoric acid O-ethyl ester dichloride in 50 ml of tetrahydrofuran. When the addition is complete, the mixture is heated to 200 ° C. and stirred for a further 12 hours at this temperature. After the solvent has been removed in a water jet vacuum, the mixture is taken up in methylene chloride, washed with water and the organic phase is dried over sodium sulfate. After distillation, 3.8 g (20% of theory) of bis-0,0- (cyano-methyl) -0-ethyl-phosphoric acid ester with a boiling point of 1460 ° C./0.5 mm Hg and a refractive index nD20: 1.4325 are obtained.

The compounds of the formula (I) listed in the table below can be prepared analogously to process variant (a) or (b) or (c): Table 2 Example XR R1 R2 Physical data Synergist No. Refractive index n20 no. D. 4 S --OC2Hs -CH3 -CH3 1.4702 2) 5 S -C.93 -CH3 -CH3, 1.4770 6) 6 S -C2H5 -CH3 o Cl 1.5262 8) 7 S -OCpHs o Cl -CH3 1.4280 8 S o -C3H7i -CK3 1.5190 9 S -OC2Hg HH 1.4863 1) 10 S -CH3 HH 1.5100 4) 11 S -C2H5 HH 1.4993 '5) 12 S -C2H5 -CX3 -CH3 1.4783 7) 13 0 -C2Hs HH 1.4500 The preparation of compounds of the formula (II) is explained using the following example: Example for the preparation of the compounds of the formula (II): 233 g (1.3 mol) of 0-ethyl-thiophosphoric acid ester dichloride 72 g (1.0 mol) of isobutyraldehyde and 6 g of tetrabutylammonium bromide are placed in 1 l of hexane and a solution of 56 g (1, 1 mol) of sodium cyanide in 100 ml of water was added dropwise with vigorous stirring. After the addition has ended, the temperature is slowly increased to 200 ° C. and the H <s mixture is stirred for a further 12 hours. The aqueous phase is then separated off, the organic phase is washed with 100 ml of water and dried with sodium sulfate.

After removing the solvent in a water jet vacuum and distilling off of the excess starting material, 173 g (71% of theory) of 0-ethyl-0- (1-cyano-2-methyl-propyl) are obtained -thio-phosphoric acid diester chloride as a 2 oily residue from the refractive index nD: 1.4806.

Analogously to this example, the other compounds of the formula (II) can be produced.

Claims (9)

Claims: (»(Thiono) (Dithio) -Phosphor- (phosphonic) -dicyanhdrinester of the formula I in which X represents oxygen or sulfur, R represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, alkylthio, arylthio, aralkylthio, alkylamino (mono- and dialkylamino), arylamino or Aralkylamino and R¹ and R² are identical or different and individually represent hydrogen or optionally substituted radicals from the series consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl and aryl or an optionally substituted heterocyclic radical. 2. Compounds according to claim 1, in which X is oxygen or Represents sulfur, R represents a radical which is optionally substituted by halogen the series C C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, phenyl, benzyl, C1-C5-alkoxy, Phenoxy, benzyloxy, C1-C5-alkylthio, phenylthio, benzylthio, C1-C5-alkylamino, (mono- and dialkylamino), phenylamino or benzylamino and R1 and R2 are identical or different are and individually for hydrogen or for one optionally by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio substituted alkyl radical with 1 to 20 carbon atoms, for C2-C5-alkenyl or C2-C5-alkynyl which is optionally substituted by halogen, for optionally by C1-C4-alkyl, C1-C4-alkoxycarbonyl, phenoxybenzyloxycarbonyl and / or halogen-substituted C3-C8-cycloalkyl, for optionally by halogen, C1-C4-alkyl or C1-C4-alkoxy-substituted phenyl-C1-C4-alkyl, for optionally by halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, trifluoromethyl and / or substituted by optionally halogen-substituted C1-C2-alkylenedioxy Phenyl, furyl, thienyl or pyridyl. 3. Compounds according to claim 1, in which X is oxygen or Represents sulfur, R represents one which is optionally substituted by fluorine or chlorine Remainder from the series C1-C5-alkyl, phenyl, C1-C5-alkoxy, phenoxy, benzyloxy, C1-C5-alkylthio, Phenylthio, benzylthio and C1-C5-alkylamino (mono- and dialkylamino) and R1 and R2 are identical or different and individually for hydrogen or for one alkyl radical optionally substituted by fluorine, chlorine, methoxy or methylthio with 1 to 10 carbon atoms, for C2-C5-alkenyl, C3-C6-cycloalkyl, for optionally phenyl-C1 -C2-alkyl substituted by chlorine, for optionally by fluorine, Substituted chlorine, cyano, nitro, methyl, methoxy, trifluoromethyl and / or methylenedioxy Phenyl, thienyl or pyridyl. 4. Process for the preparation of (thiono) (dithio) phosphorus (phosphonic) acid dicyanhydrin esters of the formula 1 in which X represents oxygen or sulfur, R represents an optionally substituted radical from the series alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, alkylthio, arylthio, aralkylthio, alkylamino (mono- and dialkylamino), arylamino or Aralkylamino and R1 and R2 are identical or different and individually represent hydrogen or optionally substituted radicals from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl and aryl or an optionally substituted heterocyclic radical, characterized in that one a) (Thiono) (Dithio) -Phosphor- (phosphonic) -säurecyanhydrinesterchloride of the formula II in which R and R1 have the meaning given above, with aldehydes of the formula III R2-CHO (III) in which R2 has the meaning given above, in the presence of approximately equimolar amounts of water-soluble cyanides, in the presence of a catalyst, in the presence of water and with Water converts practically immiscible diluents at temperatures between about 0 and 80 ° C or b) thio-phosphorus (phosphonic) acid dichlorides of the formula IV in which R has the meaning given above, either with aldehydes of the formula V R1CHO (V) in which R1 has the meaning given above, or with aldehydes of the formula III R2CHO (III) in which R2 has the meaning given above, in the presence of water-soluble cyanides, in the presence of a catalyst, in the presence of water and virtually water-immiscible solvents at temperatures between about 0 and 80 ° C. or c) phosphonic (phosphoric) acid dichlorides of the formula VI in which R has the meaning given above, with substituted acetonitriles of the formula VII in which R1 has the meaning given above, and Z represents hydrogen or an alkali metal ion, - or with substituted acetonitriles of the formula VIII in which R2 has the meaning given above, and Z 'stands for hydrogen or an alkali metal ion, optionally in the presence. of acid acceptors, optionally in the presence of diluents at temperatures between -800C and. + 800C converts. 5. Pesticides, characterized by a content of at least one compound of formula 1 according to claim 1. 6. Pesticides containing at least one synergist and at least one other substance effective against anthropods, characterized by a content of at least one compound of the formula I according to claim 1. 7. Use of compounds of the formula I according to claim 1 as synergists in the control of pests, especially insects and arachnids. 8. A method for combating pests, characterized in that that one compound of formula 1 according to claim 1 and other active ingredients which are effective against arthropods, on the pests, preferably insects or arachnids or let their living space act. 9. Process for making pesticides thereby characterized in that compounds of the formula I according to claim 1 with other active ingredients, which are effective against arthropods and with diluents and / or surface-active substances Means mixed up.