DE4334196A1 - Phosphoric acid derivatives - Google Patents

Description

The invention relates to new substituted thiophosphoric acid esters, a process for their manufacture and their use as pesticides, especially as insecticides, acaricides and nematicides.

It is known that certain substituted phenylthionophosphonic acid esters and Benzimidoylthionothiolphosphoric esters insecticidal, acaricidal and nematicidal Have properties (cf. EP-A 0 116 254 and DE-A-25 45 392). The effective speed of these known compounds is, however, under certain circumstances, especially at low drug concentrations and application rates, not always quite satisfactory.

There have now been the new substituted thiophosphoric esters of the general Formula (I)

in which
R represents optionally substituted alkyl,
R¹ represents optionally substituted alkyl,
R² represents optionally substituted alkyl and
R³ represents optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl,
found.

It was also found that the new substituted thiophosphoric esters general formula (I) obtained when one

• a) thiophosphoric ester chlorides of the general formula (II) in which
  R and R¹ have the meaning given above, with compounds of the general formula (III) in which
  R² and R³ have the meaning given above,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent or
• b) thiophosphoric dichlorides of the general formula (IV) in which
  R¹ has the meaning given above,
  in a first reaction stage with alcohols of the general formula (V) R-OH (V) in which
  R has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and the product of the general formula (II) obtained in which
  R and R¹ have the meanings given above, if appropriate after their isolation with compounds of the general formula (III) in which
  R² and R³ have the meanings given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.

The new compounds of general formula (I) have properties that enable their use as pesticides. They show strong ones Action against arthropods and nematodes and can be used in particular Control of insects, mites and nematodes can be used.

Preferred substituents or ranges of those mentioned in the above and below The radicals listed in formulas are explained below:

In the general formulas, alkyl means straight-chain or branched alkyl preferably 1 to 8 carbon atoms, in particular with 1 to 6 carbon atoms, particularly preferably with 1 to 5 and very particularly preferably with 1 to 4 coals atoms of matter. The following may be mentioned as preferred: methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, pentyl, hexyl and octyl.

In the general formulas, cycloalkyl preferably means monocycloalkyl preferably 3 to 7, in particular 3 to 6 and particularly preferably 5 or 6 Ring carbon atoms, cyclopentyl and cyclohexyl being preferred, in particular cyclohexyl may be mentioned.

In the general formulas, aryl is preferably aryl with 6 or 10 Carbon atoms (preferably phenyl or naphthyl); particularly preferably phenyl.

The alkyl radicals R, R¹ and R² can be one or more times (preferably one to 5- times, especially one to three times) by the same or different substituents be substituted, the preferred substituents being halogen (preferably fluorine, Chlorine, bromine and / or iodine, in particular fluorine and / or chlorine) and / or alkoxy preferably 1 to 4, in particular 1 or 2, carbon atoms may be mentioned. The alkyl radicals R, R¹ and R² and the cycloalkyl radical R³ are particularly preferred unsubstituted.

The alkyl, cycloalkyl and aryl radicals listed in R³ can be replaced by one or several, preferably 1 to 5, in particular 1 to 3 and particularly preferably 1 or  2, the same or different substituents may be substituted, being preferred Substituents are: halogen, preferably fluorine, chlorine, bromine and / or iodine, particularly preferably fluorine and / or chlorine and very particularly preferably chlorine; Alkoxy with preferably 1 to 4, particularly preferably 1 or 2 carbon atoms, very particularly preferably methoxy; Haloalkoxy with preferably 1 to 4, especially preferably with 1 or 2 carbon atoms and preferably with 1 to 5, preferably 1 to 3 identical or different halogen atoms (preferably Fluorine, chlorine and / or bromine, particularly preferably fluorine and / or chlorine and whole particularly preferably chlorine). The cycloalkyl and aryl radicals can furthermore (and optionally additionally) by one or more, preferably 1 to 3, in particular 1 or 2 of the following substituents may be substituted: alkyl with preferably 1 to 4, in particular 1 to 3 and particularly preferably 1 or 2 Carbon atoms, the alkyl radicals one or more, preferably 1 to 5, in particular 1 to 3 identical or different halogen atoms (preferably fluorine, Chlorine, bromine and / or iodine, in particular fluorine and / or chlorine, are particularly preferred Chlorine); Nitro and / or Cyano (CN). Phenyl is particularly preferred R³ is substituted by halogen (preferably chlorine) or is unsubstituted.

The general formulas say
R preferably for C₁-C₆-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R¹ preferably for C₁-C₆-alkyl) which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R² preferably for C₁-C₆-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R³ preferably for C₁-C₆-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy; for C₃-C₇-cycloalkyl, optionally by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkyl and / or C₁-C₄-alkoxy, the C₁-C₄-alkyl and C₁-C₄-alkoxy Residues may be substituted by halogen (preferably fluorine and / or chlorine); or for phenyl, which can carry one or more, identical or different of the following substituents:
Halogen (preferably fluorine and / or chlorine); C₁-C₄ alkyl and / or C₁-C₄ alkoxy, where the C₁-C₄ alkyl and C₁-C₄ alkoxy radicals can be substituted by halogen (preferably fluorine and / or chlorine); Nitro and / or Cyano (CN).

The general formulas say
R particularly preferably for C₁-C₄-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R¹ is particularly preferred for C₁-C₄-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R² is particularly preferably for C₁-C₄-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy.

The general formulas say
R³ is particularly preferably for C₁-C₅-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkoxy; for C₃-C₆-cycloalkyl, optionally by halogen (preferably fluorine and / or chlorine) and / or C₁-C₄-alkyl and / or C₁-C₄-alkoxy, the C₁-C₄-alkyl and C₁-C₄-alkoxy Residues may be substituted by halogen (preferably fluorine and / or chlorine); or for phenyl, which can carry one or more, identical or different of the following substituents:
Halogen (preferably fluorine and / or chlorine); C₁-C₄ alkyl and / or C₁-C₄ alkoxy, where the C₁-C₄ alkyl and C₁-C₄ alkoxy radicals can be substituted by halogen (preferably fluorine and / or chlorine); Nitro and / or Cyano (CN).

The general formulas say
R very particularly preferably for C₁-C₄-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₂-alkoxy.

The general formulas say
R¹ very particularly preferably for C₁-C₄-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₂-alkoxy.

The general formulas say
R² very particularly preferably for C₁-C₄-alkyl) which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₂-alkoxy.

The general formulas say
R³ very particularly preferably for C₁-C₅-alkyl, which is optionally substituted by halogen (preferably fluorine and / or chlorine) and / or C₁-C₂-alkoxy; for C₃-C₆-cycloalkyl, which may be halogen (preferably fluorine and / or chlorine) and / or C₁-C₂-alkyl and / or C₁-C₂- alkoxy, the C₁-C₂-alkyl and C₁-C₂-alkoxy Residues may be substituted by halogen (preferably fluorine and / or chlorine); or for phenyl, which can carry one or more, identical or different of the following substituents:
Halogen (preferably fluorine and / or chlorine); C₁-C₂-alkyl and / or C₁-C₂- alkoxy, where the C₁-C₂-alkyl and C₁-C₂-alkoxy radicals can be substituted by halogen (preferably fluorine and / or chlorine); Nitro and / or Cyano (CN).

The general formulas say
R especially highlighted for C₁-C₄ alkyl.

The general formulas say
R¹ especially highlighted for C₁-C₄ alkyl.

The general formulas say
R² especially highlighted for C₁-C₄ alkyl.

The general formulas say
R³ is particularly emphasized for C₁-C₅-alkyl, which is optionally substituted by chlorine and / or C₁-C₂-alkoxy; for C₃-C₆-cycloalkyl or for phenyl, which is optionally substituted by chlorine.

The general formulas say
R very particularly emphasized for methyl, ethyl or n-propyl, in particular for ethyl or n-propyl.

The general formulas say
R¹ particularly emphasized for n-propyl, i-propyl or sec-butyl, especially for sec-butyl.

The general formulas say
R² particularly emphasized for methyl, ethyl and i- and n-propyl, especially for methyl.

The general formulas say
R³ particularly emphasized for methyl, ethyl, n-propyl, iso-propyl, sec-butyl, tert-butyl, 1-ethyl-propyl, methoxymethyl, cyclohexyl, phenyl or chlorophenyl.

The general or priority ranges listed above nitions or explanations can be among each other, that is, between the respective Areas and preferred areas can be combined as desired. They apply to the End products as well as for the preliminary and intermediate products accordingly.

According to the invention, preference is given to the compounds of the general formula (I), in which are a combination of those listed above as preferred (preferred) Meanings exist.

According to the invention, particular preference is given to the compounds of the general Formula (I) in which a combination of the above is particularly preferred listed meanings is present.

According to the invention, the compounds of general formula (I) used, in which a combination of these as above very particularly preferred meanings are present.

According to the invention, the compounds of the general my formula (I), in which a combination of the above as special highlighted meanings is present.

According to the invention, the compounds of general formula (I) in which a combination of the above as special highlighted meanings is present.

If, for example, thiophosphoric acid S-sec-butyl-O-ethyl diester chloride is used and O-methyl acethydroxamic acid as starting materials, so the reaction can  the process variant (a) according to the invention by the following formula as are given:

For example, use is made of thiophosphoric acid S-propyl ester dichloride, ethanol and O-methyl-benzhydroxamic acid as starting materials, so the reaction can in process variant (b) according to the invention using the following formula are reproduced:

The starting materials of the general formulas II, III, IV and V are known or can be obtained by known methods and methods.

The process variants according to the invention for producing the new compounds of formula (I) are preferably used using diluents  carried out. Practically all inert ones come as diluents organic solvents in question. These preferably include 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-di chlorobenzene, ethers such as diethyl and dibutyl ether, 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 ester, nitriles such as B. acetonitrile and propionitrile, amides such as. B. Dimethyl formamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetra methylene sulfone and hexamethylphosphoric triamide.

All of them can be used as acid acceptors in the process variants according to the invention Acid binders which can usually be used for such reactions are used become. Alkali metal and alkaline earth metal hydrides, such as Lithium, sodium, potassium and calcium hydride, alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium and calcium hydroxide, alkali metal and Alkaline earth metal carbonates and bicarbonates, such as sodium and potassium carbo nate or bicarbonate and calcium carbonate, alkali metal acetates such as Na trium and potassium acetate, alkali metal alcoholates, such as sodium and potassium tert butylate, also basic nitrogen compounds, such as trimethylamine, triethylamine, Tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropyl amine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1, 8-diazabi cyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] octane (DABCO).

The reaction temperatures in the process variants according to the invention can be varied over a wide range. Generally one works at Tempera structures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.  

The process variants according to the invention are generally below normal printing done. However, it is also possible to increase or decrease it Pressure to work.

To carry out the process variants according to the invention, the respective be necessary starting materials preferably used in approximately equimolar amounts. It However, it is also possible to use one of the components used in one to use larger excess. The reactions are in an appropriate Diluent carried out in the presence of an acid acceptor, and that Reaction mixture is several hours at the temperature required in each case touched. The processing takes place in the process variants according to the invention in each case according to customary methods (cf. the production examples).

In process variant (b), the compounds of the general formula (II) preferably not isolated.

In most cases, the new compounds are obtained in the form of oils that are Do not allow some to be distilled without decomposing, but using so-called "Distill", i.e. H. by prolonged heating under moderate pressure to moderate elevated temperatures freed from the last volatile components and in this way getting cleaned. The refractive index is used to characterize them.

The active ingredients are suitable for good plant tolerance and inexpensive warmth blood toxicity to control animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in stock and Material protection and in the hygiene sector. You can preferably can be used as pesticides. They are sensitive to normal and resi constant species and effective against all or individual stages of development. To the Pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasum 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 z. B. 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 spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera sppi, Trichoplapsia s., Trichoplapsia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia po dana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidanana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., 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 z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of 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.

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, granules, aerosols, Active ingredient-impregnated natural and synthetic substances, very fine encapsulation in poly meren substances and in coating compositions for seeds, also in formulations with Brenn sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and Warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients are under pressure with extenders, i.e. liquid solvents the liquefied gases and / or solid carriers, if necessary with use formation of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as a stretch means can e.g. B. also used organic solvents as auxiliary solvents become. The following are essentially suitable as liquid solvents: aromatics, such as Xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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, and water; With Liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. B. aerosol propellant, such as halogenated hydrocarbons and butane, propane, Nitrogen and carbon dioxide; as solid carriers come into question: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite,  Montmorillonite or diatomaceous earth and synthetic rock powder, how high disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stalks; as an emulsifier and / or foamer Witnesses are possible: B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydro lysates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as Gunimiarabicum, polyvinyl alcohol, polyvinyl acetate, and natural phospholipi de, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

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

The active compounds according to the invention can be in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, Ne maticidal, fungicidal, growth-regulating substances or herbicides are present. Insecticides include, for example, phosphoric acid esters, carbamates, carbon acid esters, chlorinated hydrocarbons, phenylureas, by microorganisms manufactured fabrics u. a.  

The active compounds according to the invention can also be in their commercially available Formulations as well as in the application prepared from these formulations forms in a mixture with synergists. Synergists are connections through which increases the effectiveness of the active ingredients without the added synergist must be actively active itself.

The active substance content of the users prepared from the commercially available formulations Forms of application can vary widely. The drug concentration of the An Application forms can range from 0.0000001 to 95% by weight of active ingredient, preferably are between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

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

The preparation of the compounds of formula (I) according to the invention should be based on following examples are explained:

Unless otherwise stated, percentages relate to Percentages by weight.  

Manufacturing examples: Example 1 (process variant a)

To a solution of 11.7 g (0, 131 mol) of O-methyl acethydroxamic acid in 100 ml Acetonitrile is added at room temperature to 15.2 g (0.136 mol) of potassium tert-butoxide and stir the mixture for 20 minutes at room temperature (approx. 20 ° C). Then drips one at 10 to 15 ° C 27.7 g (0.128 mol) thiophosphoric acid-S-sec.-butyl-O-ethyl diester chloride and the mixture is stirred for 18 hours at room temperature. The Solvent is distilled off in vacuo, the residue is mixed with 300 ml Toluene and shake 3 times with 100 ml of water. The organic phase will dried and evaporated in vacuo. The residue is distilled at 60 ° C in High vacuum. This gives 22.2 g (64% of theory) Thiophosphoric acid S-sec.-butyl-O-ethyl-O- (1-methoxyimino) ethyl ester - in the form of a yellow oil with the refractive index n1.4731.

Example 2 (process variant b)

To a solution of 4.8 g (0.025 mol) of thiophosphoric acid S-propyl ester dichloride in 30 ml of toluene are added dropwise at -10 ° C. 2.7 g (0.027 mol) of triethylamine and then 1.2 g (0.026 mol) of ethanol. The reaction mixture is 3 hours at 10 ° C. stirred and then at -10 ° C with a mixture of 4 g (0.0265 mol) of O-methyl benzhydroxamic acid, 2.8 g (0.028 mol) of triethylamine and 20 ml of acetone were added. Man the reaction mixture is stirred overnight at room temperature (approx. 20 ° C.) then washes once with 20 ml of water, once with 20 ml of 5 percent  (Weight percent) hydrochloric acid and again with 20 ml of water. The organic phase is dried and evaporated in vacuo. The residue is at 60 ° C in High vacuum distilled. 4.7 g (59% of theory) of thiophosphorus are thus obtained Acid-O-ethyl-S-propyl-O- (methoxyiminophenyl) methyl ester in the form of a yellow Oil.

The following compounds are analogous to both Example 1 and Example 2 of formula (I)

receive:

Table I

The biological activity of the compounds of the general formula (I) should using the following biological examples:  

Example A Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae were killed.

In this test, e.g. B. the compounds according to Preparation Examples 3, 5, 9 and 17, with an exemplary active ingredient concentration of 0.01%, killing from 100% after 3 days.  

Example B Plutella test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella maculipennis) as long as the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this test, e.g. B. the compounds according to Preparation Examples 3, 4, 5, 8, 9, 16, 17 and 18 with an exemplary active ingredient concentration of 0.01% 100% kill after 3 days.  

Example C Nephotettix test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Rice seedlings (Oryzae sativa) are immersed in the active ingredient preparation desired concentration and treated with larvae of green rice leafhopper (Nephotettix cincticeps) occupied while the seedlings are still moist.

After the desired time, the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas are killed were.

In this test, e.g. B. the compounds according to the preparation examples 12th and 16 at an exemplary drug concentration of 0.01% after 6 days a kill rate of 100%.  

Example D Myzus test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea), heavily from the peach aphid (Myzus persicae) are infested, by dipping into the active ingredient preparation of the desired Concentration treated.

After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids are killed were.

In this test, e.g. B. the connection of preparation example 5 in a exemplary drug concentration of 0.01% after one day an effect of 100%.  

Example E Tetranychus test (OP-resistant)

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with emulsifier Water to the desired concentrations.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development of the ge my spider mite (Tetranychus urticae) are infected in an active ingredient immersion of the desired concentration.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites are killed were tested.

In this test, e.g. B. the compounds of Preparation Examples 5 and 16 an exemplary active ingredient concentration of 0.1% had an effect after 7 days of 100%.  

Example F Limit concentration test / nematodes

Test nematode: Meloidogyne incognita
Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent gives the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is mixed intimately with soil, that with the test nematodes is heavily contaminated. The concentration of the active ingredient in the preparation plays a role practically no role, the decisive factor is the amount of active ingredient per unit volume Soil, which is given in ppm (= mg / l). The treated soil is filled in Pots, seeds lettuce and keeps the pots at a greenhouse temperature of 20 ° C.

After six weeks, the lettuce roots are attacked by nematodes (root galls) examined and the effectiveness of the active ingredient determined in%. The efficiency is 100% if the infestation is completely avoided, it is 0% if the infestation is ge is exactly as high as in the control plants in untreated, but in the same way contaminated soil.

In this test, the compounds according to the invention showed good activity.

Claims (9)

1. Substituted thiophosphoric esters of the general formula (I) in which
R represents optionally substituted alkyl,
R¹ represents optionally substituted alkyl,
R² represents optionally substituted alkyl and
R³ represents optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl. 2. Compounds according to claim 1, in which
R represents C₁-C₆-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy,
R¹ is C₁-C₆-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy,
R² is C₁-C₆-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy and
R³ stands for C₁-C₆-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy, for C₃-C₇-cycloalkyl, which is optionally substituted by halogen and / or C₁-C₄-alkyl and / or C¹-C₄- Alkoxy, where the C₁-C₄-alkyl and C₁-C₄-alkoxy radicals may be substituted by halogen; or for phenyl, which can carry one or more, identical or different of the following substituents:
Halogen; C₁-C₄-alkyl and / or C₁-C₄-alkoxy, where the C₁-C₄-alkyl and C₁-C₄-alkoxy radicals can be substituted by halogen; Nitro and / or Cyano (CN). 3. Compounds according to claim 1, in which
R represents C₁-C₄-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy,
R¹ is C₁-C₄-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy,
R² is C₁-C₄-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy and
R³ stands for C₁-C₅-alkyl, which is optionally substituted by halogen and / or C₁-C₄-alkoxy, for C₃-C₆-cycloalkyl, which is optionally substituted by halogen and / or C₁-C₄-alkyl and / or C₁-C₄- Alkoxy, where the C₁-C₄-alkyl and C₁-C₄-alkoxy radicals may be substituted by halogen; or for phenyl, which can carry one or more, identical or different of the following substituents:
Halogen; C₁-C₄-alkyl and / or C₁-C₄-alkoxy, where the C₁-C₄-alkyl and C₁-C₄-alkoxy radicals can be substituted by halogen; Nitro and / or Cyano (CN). 4. Compounds according to claim 1, in which
R represents C₁-C₄ alkyl,
R¹ is C₁-C₄ alkyl,
R² is C₁-C₄ alkyl and
R³ represents C₁-C₅-alkyl, which is optionally substituted by chlorine and / or C₁-C₂-alkoxy, represents C₅-C₆-cycloalkyl or phenyl, which is optionally substituted by chlorine. 5. A process for the preparation of the substituted thiophosphoric esters of the general formula (I) according to claim 1, characterized in that

• a) thiophosphoric acid ester chlorides of the general formula (II) in which
  R and R¹ have the meaning given above,
  with compounds of the general formula (III) in which
  R² and R³ have the meaning given above,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent or
• b) thiophosphoric dichlorides of the general formula (IV) in which
  R¹ has the meaning given above,
  in a first reaction stage with alcohols of the general formula (V) R-OH (V) in which
  R has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and the product of the general formula (II) obtained in which
  R and R¹ have the meanings given above, if appropriate after their isolation, with compounds of the general formula (III) in which
  R² and R³ have the meanings given above,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

6. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1.   7. Use of compounds of formula (I) according to claim 1 for Pest control. 8. A method for controlling pests, characterized in that Compounds of formula (I) according to claim 1 on the pests and / or let their living space take effect. 9. Process for the preparation of pesticides, characterized is characterized in that compounds of formula (I) according to claim 1 Extenders and / or surfactants mixed.