DE2409462A1 - 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES - Google Patents

Description

Bayer Aktiengesellschaft 2 4 ο 9.4 6 2

Central area of patents, trademarks and licenses

Hu / Hg 5Q ₉ Leverkusen, Bayerwerk

O-ethyl-on-propyl-O-vinyl-thionophosphoric acid ester, process for their preparation and their use as insecticides and _N acaricides

The present invention relates to new O-ethyl-O-n-propyl-O-vinyl-thiophosphoric acid ester, Process for their preparation and their use as insecticides and acaricides.

It is already known that 0,0-dialkyl-0-cyano-vinyl (thiono) -phosphoric acid ester, e.g. 0,0-diethyl-0- / T- (4 ^f -methyl- or -4'-chlorophenyl) - 2-cyano-vinyl7-phosphoric acid ester and O, O-diethyl-0- / T- (2'-methyl- or -2'-Chlor- or -2 ', 5'-dichloro- or -4'-methoxyphenyl ) -2-cyanovinyl7-thionophosphoric acid esters have insecticidal and acaricidal properties (cf. German Offenlegungsschrift 2 030 509).

It has been found that the new O-ethyl-0-n-propyl-O-vinylthionophosphoric acid ester the formula

(D

. S I \ n I.

^ P-O-C = CH-CN

in which

R and R ¹ identical or different alkyl or alkoxy

radicals each with 1 to 4 carbon atoms or halogen

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mean, and
K also stands for hydrogen,

have an excellent insecticidal, also soil insecticidal and acaricidal effect.

The general formula (I) includes the corresponding cis and trans isomers of the constitution (II) and (III) and Mixtures of these components:

C ₂ H ₅ OS

J Γ \ C * Π XJ Γ \ Q

^ ^£ 5 ° \ fi ^C 2 ^H 5 ° \ J

P-O, CN P-O H

/ "<y * pi TT f \ ' C * Γ *

\ _H 3 7

R R '

(H) (III)

It has also been found that the new O-ethyl-0-n-propyl-O-vinyl-thionophosphoric acid ester of constitution (I) can be obtained when using O-ethyl-0-n-propylthionophosphoric acid diester halides the formula

^N P-HaI

in which

Hal is a halogen, preferably chlorine atom,

with CJ-cyanoacetophenone derivatives (benzoylacetonitriles) der Formula (V) or its enol form of the formula (Va)

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NC-CH ₂ -C = O. NC-CH = C-OM

"respectively.

(V) (Va)

in which

R and R ^{1 have} the meaning given above and M is an alkali, alkaline earth or ammonium equivalent,

optionally in the presence of an acid acceptor and optionally reacts in the presence of a solvent.

Surprisingly, those according to the invention stand out O-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid ester (i) a better insecticidal, also soil insecticidal and acaricidal effect with low warm-blooded toxicity compared to previously known ones Compounds of analogous constitution and the same direction of action. The substances according to the invention thus represent a a real asset to technology.

If, for example, O-ethyl-0-n-propyl-thionophosphoric acid diester chloride is used and cJ-cyano-2-methylacetophenone or the corresponding If sodium salt is used as the starting material, the course of the reaction can be represented by the following formulas will:

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P-C1 + NC-CH ₂ -C-

CH,

P-O-C = CHCN

P-Cl + NC-CH = C-

CH

■ A

The O-ethyl-0-n-propylthionophosphoric acid diester halide to be used as the starting material (IV), the keto compounds (V) and its enol form are clear from the above formulas generally defined. However, the formulas (V) and (Va) preferably contain:

R for hydrogen, methyl, ethyl, methoxy, ithoxy, chlorine,

Bromine or fluorine and
R ^{1 represents} methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine;

in particular means
R hydrogen and
R ¹ methyl, ethyl, methoxy, ethoxy, chlorine, bromine, fluorine

or

R methyl, ethyl and
R 'methyl, ethyl, chlorine, bromine, fluorine,

or R and R ^{f are} chlorine, bromine and fluorine.

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The O-ethyl-0-n-propylthionophosphoric acid diester chloride to be used as the starting material (IV) is described in the literature and accessible by customary methods, as well like the iij-cyanoacetophenones (V) or their enol form (Va) (see German Offenlegungsschrift 2 o3o 5o9)> which after methods known in principle can be produced, e.g. B. by

a) Acetonitrile with phenyl carboxylic acid esters in the presence of alcoholates at elevated temperatures, if appropriate in a solvent and then the reaction mixture is treated with acids:

R. 1) alcoholate 0

s. * ——— »Il

CH, -CN + <* ^ -CO ₉ AIk 2) heating NC-CH ₉ -C

π ι ^ x- '

3)

or

b) the corresponding phenyl compounds with acetyl chloride in Reacts the presence of aluminum chloride, the intermediate product is brominated and finally the bromine is exchanged for the cyano group:

P ₁ , AlCl, fj , * R Br ₉

-H + CH ₃ -C-Cl I ^ CH ₃ -C - // -%

H ₀ C C - //

- ^ = ^ R ¹ RR ¹

f ^r ? l r- ^ * NaCN

HoC b - (/ ^ V _v NC-CH = C-ONa

2 \ V ^

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c) reacting appropriately substituted aromatic nitriles with acetonitrile in the presence of an alkali metal and that resulting ketimine splits with acid:

NH j

NH

Na R, ^ [j acid

, -C-C

\ V-CN + CH ₅ CN. ^ V ^ -C-CH ₂ -CN.

R ¹ 'R

R M

AC-CH ₂ -CN
R.

As examples of the usable cj-cyanoacetoph'enone derivatives (V) or their enol form (Va) are mentioned in detail:

2-methyl, 2-ethyl, 2-methoxy, 2-ethoxy, 2-chloro, 2-bromine, 2-fluoro, 3-methyl, 3-ethyl, 3-methoxy , 3-ethoxy, 3-chlorine, 3-bromine, 3-fluorine, 4-methyl, 4-ethyl, 4-methoxy, 4-ethoxy, 4-chlorine, 4-bromine , 4-fluoro, 2,5-dichloro, 2,5-dibromo, 4,5-dibromo, 4,6-dimethyl, 4,6-diethyl-W-cyano-acetophenone and the corresponding sodium salts of Enol form.

The production process is preferably carried out using suitable solvents and diluents. Practically all inert organic solvents can be used as such. These include in particular aliphatic ^ and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ethers, e.g. B.

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Diethyl and dibutyl ethers, dioxane, and also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as aceto- and propionitrile.

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

The reaction temperature can be varied within a relatively wide range. Generally one works between 0 and loo, preferably at 2o to 55 C.

The reaction can generally proceed at normal pressure.

To carry out the process, the starting materials are generally employed in equimolar proportions. An excess one or the other reaction component generally has no significant advantages. The implementation is preferred in the presence of one of the abovementioned solvents, if appropriate in the presence of an acid acceptor for the specified ones Temperatures made. After a reaction time of one to several hours, usually at an elevated temperature, the is cooled Approach and pour the reaction mixture into an organic solvent, for. B. toluene. The reaction mixture is then in the usual manner by washing with a saturated Sodium bicarbonate solution and water, drying of the organic phase, evaporation of the solvent and optionally Worked up distillation of the residue.

The new compounds are obtained in the form of oils which, in most cases, cannot be distilled undecomposed, but through

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so-called "Andes tillieren", d * h. prolonged heating under reduced pressure to moderately elevated temperatures freed from the last volatile constituents and cleaned in this way. The refractive index is used to characterize them.

As already mentioned several times, the O-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid esters according to the invention are distinguished by an excellent insecticidal, also soil insecticidal and acaricidal effectiveness. They act against plant, hygiene and "storage pests" and contribute to very low phytotoxicity and a good effect against sucking as well as eating insects.

For this reason, the compounds according to the invention can be used successfully in crop protection as well as on hygiene and before Council protection sector are used.

In the following application examples A to F, the active ingredients according to the invention were tested in terms of their effectiveness against a number of plant pests in comparison to the known O, O-dialkyl-0-cyanovinyl (thiono) phosphoric acid esters designated with (A) to (F) the following constitution tested:

OCH,

S η

(A) (C ₂ H ₅ O) ₂ POC = CH-CN (B) (C ₂ H ₅ O) ₂ POC = CH-CN

CH,

(C) (C ₂ H ₅ O) ₂ POC = CH-CN (D) (C ₂ H ₅ O) ₂ POC = CH-CN

(E) (C ₂ H ₅ O) ₂ POC = CH-CN (F) (C ₂ H ₅ O) ₂ POC = CH-CN

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The sucking insects mainly include aphids
(Aphidae) such as the green peach aphid (Myzus persicae),
the black bean (Doralis fabae), oat (Rhopalosiphum
padi), pea (Macrosiphum pisi) and potato peas (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mall), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as black cherry aphid (Myzus cerasi) - and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well as the mealybug (Pseudococcus maritimus);
Bladder feet (Thysanoptera) such as Hercinothrips femoralie and
Bed bugs, for example beet bugs (Piesma quadrata), cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and chagas bugs (Triatoma infestans),
also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar) and golden juices should be mentioned in particular
(Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frost moth (Cheimatobia brumata), oak moth (Tortrix viridana), the Army (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),

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Furthermore, the biting insects include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes Frischl), Khapra- (Trogoderma granarium), red-brown Rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground such. B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like that German (HLsttella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially include flies such as the dew (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy (Phormia regina) and blowfly (Calliphora erythrocephala) as well the calf stick (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles stephensi) _etc.

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The mites (Acari) include especially the spider mites (Tetranychidae) such as the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), Gall mites, e.g. the currant gall mite (Eriophyes ribis) and tarsoneraids, e.g. the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

When used against hygiene and storage pests, especially flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.

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The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solids Carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Using water as an extender, organic solvents, for example, can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride,

aliphatic hydrocarbons such as cyclohexane or paraffins, for example 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; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, for example freon; as solid carrier substances: natural rock powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as emulsifiers and / or foam-producing agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose. The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds. Le a. 15 5oo - 12 -

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

The active ingredients can be used as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, Powders, pastes, soluble powders, dusts and granules can be applied. The application happens in the usual way, e.g. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10 %, preferably between 0.01 and 1 %.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100 % active ingredient alone «

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Example A.
Drosophila test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

1 cm of the active compound preparation is pipetted onto a filter paper disk with a diameter of 7 cm. One Ie ■ this wet to the Öffnung.eines glass vessel located in the si h ^r jG fruit flies (Drosophila melanogaster) and be. jI; - * - them with a glass plate.

After the specified times, the A ^ t: L, ng is determined in %. 100 % means that all flies have been killed --Ien.

Active ingredients, active ingredient concentrations, evaluation.,. The degree of death can be found in the following table

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Table 1
(Drosophila test)

Active ingredient active ingredient kill rate

concentration in # after in generally 1 day

(A) o, o1 20

(5) o, o1 1oo

o, oo1 100

(2) o, o1 1oo

o, oo1 100

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Example ^B.
Plutella test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

For the production of an appropriate preparation of active substance mixed 1 part by weight of active ingredient is diluted with the stated amount of solvent and the stated amount of emulsifier the concentrate with water to the desired concentration.

Cabbage leaves are sprayed with the active compound preparation (Brassica oleracea) becomes dewy and populates them with caterpillars of the cabbage moth (Plutella maculipennis).

After the specified times, the degree of destruction is determined in % . 100% means that all of the caterpillars have been killed, while 0 % indicates that no caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below:

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Table 2

(Plutella test) Active ingredient
concentration
in <? » Degree of destruction
in io after
3 days Active ingredient o, o1
o, oo1 1oo
0 (C) o, o1
o, oo1 90
0 (B) o, o1
o, oo1 1oo
9o (1) o, o1
o, oo1 1oo
1oo (7) o, o1
o, oo1 1oo
1oo (5) o, o1
o, oo1 1oo
1oo (8th) o, o1
o, oo1 1oo
9o (2) o, o1
ο, οοϊ 1oo
1oo (4) o, o1
o, oo1 1oo
8o (6)

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Example C

Myzus test (contact effect)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage plants (Brassica oleracea), which are heavily infested by the peach aphid (Myzus persicae), sprayed until dripping wet.

After the specified times, the degree of destruction is determined in % . 100 % means that all aphids have been killed, 0 % means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below:

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Tabel

(Myzus test) "Active ingredient
concentration
in io From the degree of mortality
in $ after
1 day Active ingredient o, 1
o, o1 48 ·
50 (B) o, 1
o, o1
o, oo1 I00
I00
I00 (5) o, 1
o, o1
o, oo1 I00
I00
95 CD o, 1
, ο, ο 1
o, oo1 I00
I00
7o (7) o, 1
o, o1
o, oo1 I00
I00
I00 (8th) 0.1
o, o1
o, oo1 I00
I00
95 (2) o, 1
o, o1
ο, ο ο 1 I00
I00 ■
■ 9o U) o, 1
o, o1
O.oo1 I00
I00
95 (6)

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7409462

Example i)

Tetranychus test (resistant)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which are approximately 10 to 30 cm in height, sprayed to runoff. These bean plants are strong with everyone Developmental stages of the common spider mite or bean spider mite (Tetranychus urticae).

After the specified times, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in % . 100% means that all the spider mites have been killed _s 0% means that none of the spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 4 below:

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Table 4 (Tetranychus test)

Active ingredient

Active ingredient
concentration
in <fo From the degree of mortality
in fo after
2 days o, 1
o, o1 9o
O o, 1
o, o1 6o
O o, 1
o, o1 98
95 o, 1
o, o1. 1oo
98 ■ o, 1
o, o1 95
9o o, 1
o, o1 99
95

(D)

(E) (3) (5) (2) (4)

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Example E.

Limit concentration test / soil insects

Test insect: Tenebrio molitor larvae in the soil

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the stated amount of solvent, the stated amount of emulsifier and dilutes the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient by weight per volume unit of soil, which is given in ppm (e.g. mg / 1). You fill the soil in pots and leaves the pots at room temperature. The test animals are placed in the treated soil for 24 hours after a further 48 hours, the effectiveness of the active ingredient is determined by counting the dead and living test insects in $. The efficiency is $ 100 when all test insects have been killed; it is $ 0 if there are exactly that many Test insects live as in the control.

Active ingredients, application rates and results are based on the following Table 5 shows:

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Table 5

(Soil insecticide test / Tenebrio molitor - larvae in the soil)

Active ingredient kill rate in %

at an active ingredient concentration of 2ο ppm

(F) 0

(5) 100

(7) 100

(8) 100

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Example F

Limit concentration test / soil insects

Test insect: Phorbia antiqua maggots in the soil

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

For the production of an appropriate preparation of the active substance If 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation plays practically no role here; the only decisive factor is the amount by weight of the active ingredient per unit volume of soil, which is given in ppm (e.g. mg / l). The bottom is filled into pots and the pots are left to stand at room temperature. After 24 hours the test animals are placed in the treated soil and after a further 48 hours the degree of effectiveness of the active ingredient is determined by counting the dead and living test insects in fo . The efficiency is 1oo fo _f if all the test insects had been killed; it is $ 0 if just as many test insects are still alive as in the control.

Active ingredients, application rates and results are based on the following Table 6 shows:

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Table 6

(Soil insecticide test / Phorbia antiqua - larvae Degree of destruction in%
at an active ingredient concentration
of 2ο ppm Active ingredient O (F) 100 (2) 100 (5) 100 (7) 100 (8th)

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Manufacturing examples

example 1

NC-CH-

S OC ₂ H ₅

ο-κ

χ r \ rt TT

To a mixture of 15.9 g (0.1 mol) of Gu -cyan-2-methylacetophenone, 14.2 g (0.11 mol) of potassium carbonate and 150 ml of acetonitrile are 2o.2 g (0.1 mol) of O-ethyl-O-n-propyl-thionophosphoric acid diester chloride dripped. The reaction mixture is then heated to 50 ° C. for 3 hours and then cooled and pour the batch into 300 ml of toluene. The toluene solution is washed with saturated sodium bicarbonate solution and water, dried over sodium sulfate and then the solvent is removed under reduced pressure. 28 g ($ 86 of the Theory) O-ethyl-0-n-propyl-0- / ~ 1- (2'-methylphenyl) -2-cyanovinyl_7-'fchionophosphorsäureester as yellow oil with that

25th
Refractive index n _D : 1.532o.

The following connections can be established in an analogous manner:

at
game
No, constitution NC-CH = C S ^ OC ₂ H ₅ Refractive
index yield
{ia the
Theory) 2 Cl
> } n £ ³ : 1.5427 81

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On constitution refractive yield

game index (# the

No theory)

: 1.535o 77

NC-CH = C "
ο-P
\ ₍

Example 4

Cl
NC-CH = C

\ S 0C _o H _c

To a suspension of 23.6 g (0.1 mol) of the sodium salt of <L7-cyano-2,5-dichloroacetophenone in 2oo ml of acetonitrile, 2o.2 g (0.1 mol) of O-ethyl-on-propyl- thionophosphoric acid diester chloride was added dropwise. The reaction mixture is heated to 50 ° C. for 3 hours, cooled and the batch is poured into 300 ml of toluene. The toluene solution is washed with saturated sodium bicarbonate solution and water, dried over sodium sulfate, then the solvent is removed under reduced pressure. This gives 28.5 g (75 i ° of theory) of O-ethyl-On-propyl-0- / ~ 1 - (2 ', 5' -dichlorphenyl) -2-cyanovinyl / - "thionophosphorsaureester as an oil with the refractive index np ι 1.5245.

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The following connections are made in the same way:

example
No.

Constitution refractive yield index (^ der

Theory)

NC-CH = C S

^N 0-P

n ^: 1.519o 76

Cl

NC-CH = C

S OCX P

It ₁ ³ : 1.54o7 58

CH

NC-CH = C

S.
Il

Ii / OCpH ₅

: 1.5272 71

NC-CH = C

Cl 0C _o H _c

0-P

n ^: 1.5372

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The CL> -cyanacetophenone derivatives to be used as starting compounds (V) or its enol form (Ta) can be obtained, for example, by the following method:

NC-OH = C-ONa

A solution is added dropwise with stirring to 26.8 g (0.1 mol) of 2 ', 5 ^f- dichloro-2-bromoacetophenone (prepared from p-dichlorobenzene and acetyl chloride according to Friedel-Crafts and then bromination in ether) in 3o ml of ethanol of 10.8 g of sodium cyanide in 2o ml of water and 2o ml of ethanol, the temperature of the mixture rising to 5o ° C. The batch is stirred for 15 minutes, cooled to 10 ° C. and the precipitated salt is sharply filtered off with suction. It is washed with ether and dried for 5 hours at 1oo to 11O ⁰ C under reduced pressure. Are thus obtained 19.5 g (85 io of theory) of a beige powder of melting point> 3oo ° C.

The following Qj -cyanacetophenones and their sodium salts are also accessible in an analogous manner:

constitution

Yield {<fo the theory)

Physical properties (boiling point,
Melting point)

NC-CH ₂ -CO-

68

53

Le A 15 5oo

- 29 -

129 ⁰ C

75-78 ⁰ C

509840/1100

Constitution yield (io of theory)

Physical properties (boiling point, melting point)

NC-CH ₂ -CO-

43

125

NC-CH ₂ -CO-

35 15o-16o ° C / 4 Torr

NC-CH ₂ -CO-

Vy-CH. 33

100 ° C

NC-CH ₂ -CO - //

72 ⁰ C

CH

NC-CH ₂ -CO-

37

84-85 C.

ONa NC-CH = C- //

77

NC-CH ₂ -CO- ^

OCH, 71

88 ⁰ C

ΟΗ, Ο

NC-CH ₂ -CO-

5o

67 ⁰ C

Le A 15 5oo

- 3o -

509840/1 1 00

7409462

Constitution Yield Physical

($ of the property theory) (boiling point, Melting point)

NaO

NC-CH = C- / Vci 51

Cl

NaO
NC-CH = C- / ~ Λ -F 75 284 ° C

Well (J
NC-CH = C- / 'VBr 82

Le A 15 5oo - 31 -

509840/1100

(Decomposition)

yield 2409462 (fo the constitution Theory) Physical properties (Boiling point, 37 Melting point) NaO
ι NC-CH = C - //% -Br 272 ⁰ C (Decomposition)

'Br

NaO NC-CH = C - //

77

NC-CH ₂ -CO-

-CH

CH,

2o

74 ⁰ C

NC-CH ₂ -CO-

-C ₃ H ₇ -I

18th

56 ⁰ C

NC-CH ₂ -CO-

CH,

CH,

Le A 15 5oo

22nd

71 ⁰ C

509840/1 100

Claims (6)

Pat entana proverbs 2409Λ62 1. O-ethyl-0-n-propyl-O-vinyl-thionophosphoric acid ester of formula R ¹ J ^ Jk R C ₂ H ₅ ° \ S '-0-C = CH-CN in which R and R ^{1 are} identical or different alkyl or alkoxy residues each with 1 to 4 carbon atoms or Mean halogen and R also stands for hydrogen. 2. Process for the preparation of O-ethyl-0-n-propyl-O-vinylthionophosphoric acid esters, characterized in that 0-ethyl-O-n-propylthionophosphoric acid diester halides of formula O ₂ H ₅ OS P-HaI in which Hai means a halogen, preferably a chlorine atom, with CJ -cyanacetophenone derivatives of the formula NC-CH ₂ -Q = O RR ¹ Le A 15 5oo - 33 - 509840/1100 2Λ09462 Sy or their enol form of the formula
NC-CH = G-OM in which R and R 'have the meaning given in claim 1 and M is an alkali, alkaline earth or ammonium equivalent, optionally in the presence of an acid acceptor and optionally reacts in the presence of a solvent. 3 · Insecticidal and acaricidal agents, characterized by a content of compounds according to claim 1. 4. Method for combating insects and mites, characterized in that compounds according to Claim 1 are allows the pests mentioned or their habitat to act. 5. Use of compounds according to Claim 1 for combating from insects and mites. 6. A process for the preparation of insecticides and acaricidal agents, characterized in that compounds according to Claim 1 mixes with extenders and / or surface-active agents. Le A 15 5oo - 34 - 509 8AO / 1 1 00