HU189099B - Pesticide compositions, as well as process for the production of phosphoric acid cyanhydrin esters applicable in them as active substance - Google Patents

Abstract

Phosphoric acid cyanohydrin esters of the formula I <IMAGE> in which R represents hydrogen or an optionally substituted radical from the series comprising alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl and aryl or an optionally substituted heterocyclic radical, R<1> and R<2> are identical or different and individually represent optionally substituted radicals from the series comprising alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, alkylthio, arylthio, aralkylthio, alkylamino (mono- and dialkylamino), arylamino, aralkylamino, or together represent alkanediyl, alkanedioxy, aminoalkyloxy or alkanediamino, and X represents oxygen or sulphur, are obtained by reacting phosphoryl chlorides of the formula II <IMAGE> in which X, R<1> and R<2> have the abovementioned meanings, with aldehydes of the formula III R-CHO (III> in which R has the abovementioned meaning, in the presence of approximately equimolar amounts of water-soluble cyanides. Some of the compounds of the formula I are novel. They can be used as insecticides and acaricides.

Description

FIELD OF THE INVENTION The present invention relates to insecticidal and acaricidal compositions and to the preparation of cyanohydrin esters of phosphoric acid as active ingredients.

It is known to react with phosphoric ester chloride derivatives and cyanohydrin derivatives (N-hydroxycarboxylic acid nitriles) to produce pesticidal phosphoric acid cyanohydrin esters (U.S. Patent Nos. 1,047,776 and 1,224,307). However, according to the known process, the desired compounds are mostly formed in low yields and the effect of the known phosphoric acid cyano esters is unsatisfactory.

It is also known to prepare certain cyanohydrin esters of phosphoric acid by reacting the anhydride derivatives from carbonyl compounds and alkali metal cyanides in situ in the reaction mixture and reacting them without intermediate isolation with phosphoric ester chlorides (U.S. Pat. No. 2,965,533). However, this process is very time consuming and / or low yielding.

It has been found that the phosphoric acid cyanohydrin esters of formula (I)

R is hydrogen, (C 1 -C 12) alkyl, (C 2 -C 4) alkenyl, (C 1 -C 4) alkylthioalkyl or alkoxyalkyl (C 5 -C 6) cycloalkyl, optionally halogen, nitro, methylenedioxy a phenyl group substituted with a C 1-4 alkyl or trifluoromethyl group, a phenylalkyl group containing 1-4 carbon atoms in the alkyl optionally substituted by a halogen atom or a trifluoromethyl group, and a C 1-4 alkyl group containing alkyl; alkyl, pyridyl, thienyl, 2,2-dimethyl-3-ethoxycarbonylcyclopropyl or 2,2-dimethyl-3,3-dichlorocyclopropyl,

R 'is independently selected from C 1-4 alkyl and C 1-4 alkoxy optionally substituted with trifluoromethyl R ² , optionally substituted C 1-6 alkylthio optionally substituted with additional sulfur, monoalkylamino or dialkyl containing 1-4 carbon atoms per alkyl moiety. - amino, phenyl, chlorophenoxy or benzylthio,

X is oxygen, 'sulfur in a short reaction time can be prepared in high yield and high purity, when (ii) phosphoric acid chloride derivative of formula - in formula (II), X, R' and R ² are as defined above - ( III) an aldehyde of the formula - (III) R wherein is as defined above - water soluble cyanide in the presence of tetra (C, _ ₄ alkyl) ammonium halide fázistranszferkataíizátor presence and in the presence of water, 0 to 80 ° C water with immiscible carbon 2 in a hydrogen solvent. The above compounds have excellent insecticidal and acaricidal activity. Phosphoric acid chloride derivatives useful as starting materials in the process are defined by formula (II). Examples include O-methyl, metil-ethyl, On-propyl, and O-isopropyl-rpethyl, ethyl, propyl and phenyl-phosphoric ester chloride and the corresponding thiono compounds; Ο, Ο-dimethyl, Ο, Ο-diethyl, O, O-di-n-propyl, O-methyl, Ο-ethyl, O-methyl-O- (n-propif) -, O- methyl-Ο-isopropyl, O-ethyl-O- (n-propyl) and O-ethyl-O-isopropyl-phosphoric acid diester, as well as the corresponding thiono compounds and O, S-dimethyl, O, S- acetyl, N-S-diisopropyl, O-methyl-S-ethyl, O-methyl-S (n-propyl), O-methyl-S-isopropyl, O-ethyl-S-methyl, O-ethyl-S (n-propyl), Ο-ethyl-S-isopropyl, O- (n-propyl) -S-methyl, O- (n-propyl) -S-ethyl, O- ( n-propyl) -S-isopropyl, O-isopropyl-S-methyl, O-isopropyl-S-ethyl and 0-isopropyl-S- (n-propyl) -thiophosphoric acid diester, and the corresponding thiono compounds.

The compounds of formula (II) are known and / or can be prepared by known methods (Houlben-Weyl-Müller, 4th edition, Thieme-Verlag Stuttgart, 12/1, pp. 415-420 [1963]). and 560-563; 12/2 (1964), pp. 274-292 and 607-618).

The aldehydes also required as starting materials are defined by formula (III),

Examples of starting materials of formula (III) include: formaldehyde, acetaldehyde, propionaldehyde, butyrylaldehyde, iso-butyrylaldehyde, valeraldehyde, isovaleraldehyde, secalderaldehyde, capronaldehyde, isocapronaldehyde, , Croton aldehyde, Methoxyacetaldehyde, Methylthioacetaldehyde, Cyclohexanecarbaldehyde, Benzaldehyde, 4-Chlorobenzaldehyde, 4-Methylbenzaldehyde, 3,4-Methylenedioxybenzaldehyde, 4,5-Methylenedioxy-2- ~ methylbenzaldehyde, phenylacetaldehyde, N-phenylpropionaldehyde, thiophene-2-carbaldehyde, thiophene-3-carbaldehyde, pyridine-2-carbaldehyde and pyridine-3-carbaldehyde.

The compounds of formula (III) are known. Examples of water-soluble cyanides for use in the process of the present invention include alkali metal cyanides, such as sodium and calcium cyanide, but preferably sodium cyanide.

Preferably, as a water immiscible solvent, straight or branched C 5 -C 10 alkanes or cycloalkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane,

2-methylpentane, 3-methylpentane, 2-methylbutexane,

2,2,4-trimethylpentane, cyclohexane, methylcyclohexane, or methylbenzenes such as toluene or xylene, and mixtures thereof.

The catalysts used in the process of the present invention are phase transfer catalysts, i.e. compounds which are capable of transferring reactants at the interface between water and an organic solvent during reactions in biphasic systems. Such catalysts include tetraalkyl and trialkylaralkylammonium salts having 1-10 carbon atoms, preferably 1-8 carbon atoms per alkyl group.

189,099 for application. The aralkyl group preferably contains a phenyl group per aryl moiety and 1 or 2 carbon atoms in the alkyl moiety. The anions of the salts are predominantly halogen, atoms such as chlorine, bromine or iodine. Examples of phase transfer catalysts include tetrabutylammonium bromide, benzyltriethylammonium chloride, and methyltrioctylammonium chloride.

In the process of the invention, the reaction temperature is maintained at 0-80 ° C, preferably at 0-30 ° C. Preferably, atmospheric pressure is employed.

The amount of aldehyde (III), 1.0-1.5 moles, preferably 1.1 moles, per mole of phosphoric acid chloride (II) is generally 0.8-1.2 moles, preferably 0.9-1.1 moles. -1.3 moles of cyanide and 0.001-0.05 moles, preferably 0.01-0.03 moles of catalyst are calculated.

In a preferred embodiment of the process according to the invention, the starting compound (II) and (III) and the catalyst are dissolved in a water-immiscible solvent and the aqueous solution of cyanide is slowly added thereto, optionally at least at the beginning of the reaction. using external cooling, the reaction temperature is maintained between 0 ° C and 10 ° C. The entire reaction mixture was then stirred without cooling until the reaction was complete.

Optionally, the reaction mixture is diluted with additional water immiscible solvent, the organic phase is separated off, washed with water, dried and filtered. The solvent was removed from the filtrate under reduced pressure. The crude product is obtained as an oily residue. The refractive index is given to characterize the compounds.

The active ingredients are well tolerated by plants and have low toxicity to warm-blooded animals. Therefore _; the compounds are useful in agriculture, forests and in the conservation of stock and structural materials for the control of animal pests, in particular insects, spiders and nematodes. The active ingredients are active against both normal and resistant strains of all or just a few stages of development. The pests mentioned above include:

From the order of the Isopods, for example, Oniscus asellus,

Armadillidum vulgare, Porcellio scaber. t

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

From the order of the Chilopods, for example, Geophilus carpophagus, Scutigera spp.

From the order of the Symphylaxis, for example, Scutigerella immaculata.

From the order of the Thysanuras, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus. *

From the order of Orthopteras, for example, Blatta orientalis,

Periplaneta americana, Leucophaea maderae,

Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. ^£

For example, from the order of the Dermaphores, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp. From the order of Anoplura, for example, Phylloxera vastatrix, Pemhigua spp., Pediculus humanus corporis, Haematopinus spp., Linognatus spp.

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

From the order of the Thysanoptera, for example, Hercinothrips femoral, Thrips tabaci.

From the order of heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cyptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macros. , Euscelis bilobarus, Nephotettix cincii., Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupadlus piniarius, Cheimotobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella macuypennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bymadria spp. Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiella kuehn., Gallc. Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleopteras, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius abtectus, Acanthscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotaisa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes spp., Psylliodes sp. spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligbetes aeneus, Ptinus spp. ., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocama spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fennia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypp. Stomoxys spp., Oestrus spp., Hvpoderma spp., Tabanus spp., Tannia spp., Bibin hortulanus, Oxcinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

-3189099

From the order of the Siphonapters, for example, Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnids, for example, Scorpio maurus,

Latrodectus mactans.

From the order of the Acarinas, for example, Acarus siro, Argas spp., Ornitbodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp. ., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus SPP ·

Plant-borne nematodes include:

Pratylenchus spp., Radopholus similis, Diyl Jenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The active compounds may be formulated into conventional formulations such as solutions, emulsions, soluble powders, suspensions, powders, dusts, foams, pastes, granules, aerosol formulations, suspensions and emulsifiers. They can be impregnated with natural and synthetic materials, microcapsules can be used to form polymeric materials and seed coatings, and formulations of the active ingredients with flammable fillers, such as fume cartridges, cans and spirals, and hot or cold applied by ULV processes.

The formulations are prepared in a manner known per se, for example, by mixing the active compounds with carriers, i.e., liquid solvents, pressurized liquid gases and / or solid carriers, optionally with surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. substances may also be added. When water is used as a carrier, organic solvents may also be used as co-solvents. Suitable liquid solvents are essentially aromatic compounds such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions; and alcohols such as butanol or glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strong; polar solvents such as dimethylformamide, dimethylsulfoxide and water. Liquid gaseous carriers are understood to include materials such as aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. Solid carriers include natural stone flour such as kaolin, clay earth, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, as well as synthetic stone flour such as highly dippered silica, alumina and silicates. Solid carriers for granules include crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and granules made from inorganic materials such as sawdust, coconut shells, corn cobs and tobacco stalks. Non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid ethers, polyoxyethylene fatty alcohol ethers such as alkylaryl p-glycoloyl ether, alkylsulfonates, alkylsulphonates, are emulsifiers and / or foaming agents. such as aryl sulfonates and protein hydrolysates, and lignin, sulfite impurities and methyl cellulose as dispersants.

The compositions of the present invention may contain adhesive agents such as carboxymethylcellulose, natural and synthetic, powdered, granular or latex-like polymers such as acacia, polyvinyl alcohol, polyvinyl acetate. .

The compositions of the present invention also include colorants such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo-metal phthalocyanine dyes, and printing materials such as iron, manganese, boron, copper, cobalt, mohodene and zinc. salts may ^b.

The compositions generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The active ingredients used in the compositions is commercially candidate ₃₀ and / or the use forms prepared therefrom form.

The formulations and the uses for which they are prepared are, in addition to these active substances. They may contain active ingredients such as insecticides, acaricides, non-motocides, fungicides, attractants, sterilizers and growth promoters. Insecticidal agents include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, microorganisms, and the like.

In addition to the active compounds of the present invention, the compositions or formulations thereof may also contain synergizing agents. Synergizing agents are compounds that enhance the action of the active ingredients without the synergizing agent itself being active.

The active ingredient content of the formulations prepared from the formulations may be varied within wide limits. The concentration of the active compounds in the forms of use is between 0.000,000 and 95% by weight, preferably 0.0001-1% by weight.

Use is made in a manner appropriate to the particular formulation.

When used against insects harmful to health and pests of stored products which attack the active ingredients of formula (I) are distinguished by their effects on wood and fabric ⁶⁰ is extremely durable, and good to alkali on limed substrates.

The compounds of the present invention are also useful in veterinary medicine for controlling ecto- and endoparasites. Parasite-free herds achieve better milk yield, longer life and greater weight.

-4189,099

In veterinary medicine, the active compounds may be administered in the usual manner, i.e. orally, for example in the form of tablets, capsules, granules, liquids for drinking, or dermally, such as by spraying, spraying, pouring and powdering, and parenterally, such as by injection.

The efficacy of the compounds of the present invention is compared below with the activity of the O, O-diethyl-O- (1-cyanoethyl) -dithiophosphoric acid ester. In the pharmacological examples, this compound is referred to as the "reference compound".

Example A)

Demonstration of the action against the owlbill

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient formulation, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and the indicated amount of emulsifier, and the concentrate is diluted with water to a concentration of 0.1%.

Cabbage leaves (Brassica oleracea) are dipped in the above preparation, and the still wet leaves are introduced with the caterpillars of the bagolypille (Laphygma frugiperda).

days later, the percent mortality is determined. 100% means that all caterpillars are dead, while 0% means that no caterpillars are destroyed.

The comparator compound was ineffective at concentrations of 0.1%, while Compounds 1, 2, 7, 8, 11,

12, 14, 15, 17, 18, 24-26, 28, 29, 32, 34, 36,

The compounds of Examples 38, 41, 42 and 43 had a 100% death rate.

Example B)

Detection of resistant spider mites

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient formulation, 1 part by weight of the active ingredient is admixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to a concentration of 0.1%.

Bean plants (Phaseolus vulgaris) heavily infected with all stages of development of common spider mite (Tetranychus urticae) are dipped in the above preparation.

days later, the percent mortality is determined. 100% means that all spider mites have been killed, while 0% means that no mites have died. The comparator compound was ineffective at 0.1% (0%), whereas under the same conditions, 1, 11, 12, 14,

The compounds of Examples 17, 18, 24, 25, 26, 32, 34, 38 and 43 produced 100% mortality.

Example C)

Demonstration of action against soil-borne insects

Experimental insect: Phorbia antiqua larvae in soil Solvent: 3 parts by weight acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient formulation, 1 part by weight of the active ingredient is admixed with a specified amount of solvent and a specified amount of emulsifier, and the concentrate is diluted with water.

The active compound formulation is carefully mixed with the soil. The active ingredient content of the preparation does not play a role here, only the amount of active ingredient per unit volume per soil is decisive. This amount is given in ppm (e.g. mg / l). The soil is filled into flower pots and allowed to stand at room temperature.

After 1 hour, the experimental insects are introduced into the treated soil and after a further 2 to 7 days, the efficacy of the active ingredient is determined by counting live and dead insects. The efficiency is 100% if all insects are killed and 0% if the same number of insects survived as in the untreated control.

The reference compound was ineffective at 5 ppm, whereas the 1, 17, 18,

Compounds prepared according to Examples 29, 32, 36, 38 and 43 gave 100% efficacy at the same concentration.

Example D)

Experiment on parasitic fly larvae

Solvent: 35 parts by weight of ethylene polyglycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable active ingredient formulation, 30 parts by weight of the active ingredient are mixed with the above-mentioned amount of solvent containing the ethnulsifier, and the resulting concentrate is diluted with water to a concentration of 0.1 g / l.

Twenty larvae (Lucilia cuprina) are introduced into a test tube containing approximately 2 cm ^{3 of} lean meat. Pipette 0.5 ml of the active ingredient into the horse meat. After 24 hours, the degree of death was determined. 100% means that all larvae have died, while 0% means that no larvae have died.

In the above experiment, for example, the compounds of Examples 1, 14, 17, 18, 19, 29, 32, 34, 37 and 43 at 100 ppm resulted in 100% mortality.

The following examples illustrate the process of the invention.

-5189 099

f. example

11.6 g (0.2 mol) of propane, 43.7 g (0.2 mol) of O-ethyl-S-propyldithiophosphoric acid diester chloride and

To a mixture of 1.2 g of tetrabutylalummonium bromide in 300 ml of hexane at 0-10 ° C with vigorous stirring

A solution of sodium cyanide (11.2 g, 0.23 mol) in water (20 ml) was added dropwise. Upon completion of the addition, the temperature was slowly raised to 20 ° C and the mixture was stirred until the reaction was complete. The aqueous phase was then separated, and the organic phase was washed with water (2 x 100 mL) and dried over sodium sulfate. The solvent was distilled off under reduced pressure with a water jet pump, the less volatile constituents were distilled off at 50 ° C and 3 mbar, and then as an oily residue.

50.5 g (95% of theory) of O-ethyl-O- (1-cyano-propyl) -S-propyl-dithiophosphoric ester are obtained.

Refractive index: np = 1.5120.

The following compounds of formula (I) are prepared as described:

Table I

The serial number of the example R R ¹ 2 -CH ₂ -SCH ₃ · °% ^Η 5 3 -C ₃ H ₇ ~ taste -SC ₃ H _7, 4 a) ° C ₂ H ₅ 5 -ch ₃ “°° 2 ^Η 5 6 -C-H ^ -isomer - ^SC 3 ^H 7 · 7 -CH-CH _? CH _? CH ^! 3 CH She - ° c ₂ ^h 5 8 -CH ₂ 0CH ₃ ^0C 2 ^H 5 9 group b) -oc ₂ h ₅ 10 -C ₃ H ₇ -iso -0C ₂ ^H 5 11 ° ^ -methyl- benzyl -c ₂ h ₅ 12 oC methyl benzyl -ch ₃ 13 -methyl- benzyl -CH ₂ Cl

RX Refractive index ⁿ D

-SC, H _, - n S 1.5336

-NH-C H _? - S 1.5160

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-SC ₃ H _? -n S 1.5762

-0C H _c S 1.4664

-OCHgCF S 1.4799

-SC ₃ H _? -n S 1.4950

-SC H _? -n S 1.5109

-SC H _? -n S 1.5480 benzylthio S 1.5412

-S-CH-CH "CH_

I 2 3 ^CH 3 S 1,5496

-SC ₃ H _? -n S 1.5583

-SC ₃ H _? -n S 1.5618

-6189,099

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Ο Ο Ο

I I I ιη ιη

X X

CM

8

I ι

YOU K? ο. Η rh γΊ γ4 ω Ή • Η • Η • Η ΙΌ X) ε , C C ε ο ο ο χ I 0) 03 Ο α » ο Ν Ν Ν Ο r-i Μ- Μ- 4- 4- Ν • Η • Η Ή 1 • Γ! Ι Ι I γ4 • Η 1 1 I X j + 1- U ε Ή 1 0s Ν Ν ο 0) Ό Ό Ό υ Γ χ X X 11 ε ι-1 ι-1 rh φ X ΙΌ ΙΌ κ> X ι ν ' | JZ I ε | 1 f V 8 8 8 8 V rf I rf Β rf 1 rf 8

ω ε X Ό3 ι — 1 Ν ό ιη Ο. U ο <ω ιη ιο ro ιό ro ω

ιό σ> ο> —ι

ΙΌ rf rf rf

ΙΌ rf

-9189 099 • o

4->

ra + ->

a e

ra '03

L. O: O CM Q H c

n ro She She ' She n She She cn tendon CM She st • CM n RRI st L ' n n CM RRI CM tendon n n tendon n tendon n n «. · " * * · » RRI pH pH RRI RRI r-1 r-l Ri ω ω ω (0 ω ω ω ω

continued Table n

CM 0 ω ro X CM 0 W tendon X tendon X tendon X ro CM She CM CM CM CM U. X CM X, 0 0 ro 0 0 She X cf 1 ro 1 ! CM ro CM 0 ro CM X X X X X X X X X X 0 - 0 ο- 0 ο- 0 She 0 0 - She 0 l ι ι w She ω w ω ω ω ω

rri (Z h

N <

Qí ra i tj -ra rri N - <ü OT DL D

O CD <ω ε ro

X t

CM ro

X ro in

CM n

x

CM n

x

CM!

n x

CM n

x

CM

I

RRI RRI RRI RRI Ή • Ή • ri -R N N N N r-l C c c C ri SHE to to to C _Q n JD -Q < » RRI RRI RRI RRI <4_ rl • ri • ri • ri Ι- + J 4-> 4-> 4-> Ό to to to to RRI ε H ε ε V 1 l 1 l 1 st 4

rf η n ix St Sf co cn

St st n

x

CM ro x

Y x

She

II

X

I

-10189 099 '

-o jj {0 JJ □ ε ω Ό u Ο: O CJ Ο 1- C

tendon tn tn CD She CD tn tn | X She the tendon tn rd rí ω tn fs r4 co rd 04 10 She · rí r ¹ tendon rí tendon tendon tendon tendon · » s ·, * * * rd r-1 rd r4 rd r4 I-I i-l She She ω CD CD CD CD CD

Continue Table

0I

DC m

E c

I

N

X tn o

ω r

m tendon tendon tendon X X X X C 04> 04 04 04 | SHE She SHE SHE · Γ - tendon i tn 1 tn ι tn i X X X X X X X X X tn 04 O O Ο- She 0-0 ο- She She 1 Ι I ι ω She CD ω CD ω

in in tn x x x,

C4 04 04

8 8

I I t in x

I in ~ c \ 2 o

in x

SHE

I in x

SHE

I in x

SHE

I

1 u u Ό Ό r4 ι-1 I 1 _X -X • 4 Ή rl Ή X 1 X I X X 1 r4 1 r4 t 1 m rt tn -π tn tn «· Ex - CL · * tn o tn o tn tn ι 1 t- 1 u I * —I I r-4 r4 CL r-4 CL r4 * 4 rd r4> 4 4 O • 4 O • 4 CL r4 • H • 4 Q- JJ r4 JJ r4 JJ O • 4 C + J O Φ <B ZZ <D L. tn X She Φ Ι- ε -rí Ert E CL · Z- ω M c Ε ex • rt O • 4 O • 4 O tD X U 1 • rl O X 1 X I X r X SHE ^k O h ' X r4 I t- l u ι zz She i-1 rd X Λ -X 04 Ό 04 X 04 -4 \ z V tn 'rl 'r4 - 1-1 'Ü Q • 4 1 She 04 O 04 ZZ 04 OZ 04 1 1 SHE ¹

(C I X '(0 r4 N 4U (!)

CL ΙΟ C0 <(!) G in m rí in in io in co σ>

in

-11189 099 'O + j ro

4- * □

ε ro 'Φ ι- Ο: Ο CM Q l · - C

She tendon She co She tendon m CO rt tn CD CO She CO SHE CO SHE She CM CO CD tendon CO She tendon tendon tendon tendon rt rt rt tendon «» * • t - «% - · » r-l 4-r i-l i-4 4-r 4-r 1-1 co ω ω ω She SHE SHE ω

Continue Table

CM

QI

H

IM <í i — 1

CZ

Oí ro ι ό ~ ro r4 IM ro ro CL ΙΟ ro <w E ¥

tendon

X tendon tendon tendon 1 X X X CM CM CM CM SHE SHE SHE cn 1 m ι rn ι · sn I tn X X X X X X T X o ~ ( She ο, υ o-o 1 7 ' She ω ω ω w

Ilii in x

C C CM l I CJ is. rs ι m

X X XX tn tn ο — ο υ ο ι w ω ω

I I ι c

I rs x

in o

ω

I in x

CM

SHE

I in x

CM

SHE

I in

X X

CM CM o o

I ι in x

CM

SHE

SHE

I in

CM in x

CM

O ι

m x

CM

SHE

I

CM tn x

o x

CM

X o

CO tn ίΟ

CL

SHE

0) o

the ι

rn

CM

X!

tn

OO o

I

CM

X

V: O • l-J ro r — I CL -ro

V tn x

• H

I rs x

tn • <4

Is tn ro

1-4 co cm tn co co sj- in co cO co cO

also

X in rco

-12189 099 • o

4->

to

Σ3 ε

<o ra u o: O CM Q H C

CM σι She to CM She tendon to fs fs She to CD to She to She 4-r rt tendon tendon to to lt> to lf) « «► * 1 ι-l I-1 r-l r-l r-l to to ra ' to to to to

Continuing CM ra ι — 1 in ra table

CM

Q £ <X

QC ra ι TJ '{0 rH N ra ω α. Ίο ro <Φ E in

E

CM ra x x o-ra ra in

X

CM o

ι ra ra ra in x

CM CJ

I

X X 0-0

I ra ι

in r — t

X -H

CM C

SHE . «• rl

I ra • rl

I fs ra σι o ra is ra in in

X CM ^X CM JL CM CM SHE' 1 X ro X to X CM SHE 1 X SHE i ro X X SHE 1 X 9 ~ She 9 9 7 '° θ ' 1 1 ω 1 ω to ω 1 to 1

ra ra

X o

I in x

CM

O ra x

in x

CM

SHE

I in x

CM

O • rl

I fs

<?

ι — ι fs

I

• H 1 TJ • H 1 r-l X to -rl She - CL LJ to O to l E E i-1 EL u • rl O She LJ r-l □ © ZZ • rl r-l r-l Er | • rl M-r-1 • Η CJ rs X IO LJ to c • rl -rl L. C LJ ra tj 1 1 E cm She 1 to q l urt I - ι-1 CM zz

cm ra ts rs

Ft in fs

-13189 099 ra ε <n ♦ ra I- o Ό CM o H C

CM She ί- 10 lake 00 CM ο rt tendon SHE r- IO rt She tendon RT_ tendon tn tendon * » ·, rd ι-1 1 "t rd rd (0 She co CO. CO

Continue Table

CM

CZ

H

N <

ι — I Taste c

s

S ' ¹

I ω

i in m

X X c CM c • CM c c 1 SHE 1 She 1 1 Γ- 1 to s 1 lake ο- r- X X X X X T χ T ro o o lake ο- SHE IO lake SHE Ύ She ι She She (0 co co ω ω co

II II II in

I in ι ι ι ο ι o c>

in in in in

XX XX

04 04 04

Ο O Ο O

Ή • rl rd 1 X X • id • rl She SHE 4-r X 4J 4-1 to She ω (0 ε 4-1 ι — 1 ε ε CM CM 1 ra -rd ί- u z * u ε m ο She lake lake T> u c 3 3 X X 1 o ra rd rd She She tendon 1d □ XJ M rq μ- rd X L. · Η rd 1 • rd ♦ H η • rd X CM Ό N Md L_ C u C 1 1 She rd C • rd rd 4- < She 4-i ω N CM 1 ro -u: cu U 4-r 1 Μ- I Μ- τ- X X X 1 -Q , 4J ra rt Ι rt Ι Ο SHE She She rt ι 1 E rt ι

ra ra e ό -CD rd M · © co Cu ΙΟ <ω cn | x co

0) o

N 00 rd CM

CO. Co

-14189,099

Presentation examples

1. Dusting agent

0.5 parts by weight of active ingredient (1, 2, 7, 8, 11, 5)

12, 14, 15, 17, 18, 24-26, 28, 29, 32, 34, 36,

Any of the active compounds of Examples 38, 41, 42 and 43) is mixed with 99.5 parts by weight of ground limestone and the resulting mixture is finely ground.

2. Emulsifiable concentrate by weight of active ingredient (1, 2, 7, 8, 15,

The active compounds of Examples 24, 25, 26 or 42) are dissolved in 15 parts by weight of xylene and 10 parts by weight of cyclohexane. 10 parts by weight of a mixture of dodecylbenzenesulfonic acid calcium and nonylphenol polyglycol ether are added as emulsifiers.

3. Wettable powder ² θ parts by weight of active ingredient (1, 2, 7, 8, 11, 12,

14, 28 or 29), parts by weight of dibutyl naphthalene sulfonate, 25 parts by weight of lingin sulfonate, parts by weight of highly dispersed silica, and parts by weight of natural stone powder.

The above components are mixed and ground to a fine _3Q powder.

4. ULV preparation in parts by weight of active ingredient (1, 2, 7, 8, 11, 12, ₃₅₎

14, 15, 17, 18, 24, 25, 26, 28, 29, 41 or 43) and 3 parts by weight of polyethylene oxide in 7 parts by weight of aromatic mineral oil. fraction, and the resulting solution is vigorously stirred.

Claims (2)

Claims ⁴⁰ Insecticidal and acaricidal compositions, characterized in that they contain from 0.1 to 95% by weight, as active ingredient, of phosphoric acid cyanohydrin ester derivatives having the general formula (I): R is hydrogen, (C 1 -C 12) alkyl, (C 2 -C 4) alkenyl, (C 1 -C 4) alkylthioalkyl or alkoxyalkyl, (C 5 -C 6) cycloalkyl, optionally halogen, nitro, methylenedioxy phenyl substituted with C 1-4 alkyl or trifluoromethyl, phenylalkyl containing 1-4 carbon atoms in the alkyl moiety, optionally substituted with halogen or trifluoromethyl, and alkyl having 1-4 carbon atoms per alkyl moiety; alkyl, pyridyl, thienyl, 2,2-dimethyl-3-ethoxycarbonylcyclopropyl or 2,2-dimethyl-3,3-dichlorocyclopropyl; R ¹ is independently C 1-4 alkyl and C 1-4 alkoxy optionally substituted with C 1 -C 4 alkyl optionally substituted by trifluoromethyl R ² , optionally substituted C 1-6 alkylthio optionally substituted with 1 to 4 carbon atoms per moiety of C 1-6 alkylthio. - or dialkylamino, phenyl, chlorophenoxy or benzylthio, X represents oxygen or sulfur atoms with solid carriers, preferably natural or synthetic powders such as limestone and highly dispersed silica, and liquid carriers, preferably hydrocarbons such as cyclohexane or petroleum fraction and optionally alkyl-aryl, preferably alkyl-aryl, mixed with lignin sulfonate or polyethylene oxide. 2. A process for preparing cyanohydrin esters of phosphoric acid as an active ingredient in the compositions of claim 1 wherein R, R ¹ , R ² and X are as defined in claim 1, wherein the phosphoric acid of formula II is a chloride derivative - wherein X, R ¹ and R ^{2 in} formula (II) are as defined above - an aldehyde of formula (III) - in formula (III) R is a water-soluble cyanide as defined in claim 1, The reaction is carried out in the presence of a ( _4- alkyl) ammonium halide phase transfer catalyst and water in the presence of a water-immiscible hydrocarbon solvent at 0-80 ° C.