DE1815939A1 - 1-cyano-vinyl-phosphoric acid ester and process for their preparation - Google Patents

Description

FARBENFABRIKEN BAYER AG 1815939

LEVlRKU SIN-B * yenmk htnt-AbttUuac Hu / HM

1-cyano-vinyl-phosphoric acid ester and process for their preparation

The present invention relates to new 1-cyano-vinyl-phosphoric acid esters, which have insecticidal and acaricidal properties, and a process for their preparation. m

From U.S. Patent 2,765,331 and British Patent 784.985 it is already known that vinyl phosphoric acid esters are characterized by an insecticidal activity.

It has now been found that 1-cyano-vinyl-phosphoric acid ester of general formula (l)

/ POC = CH ₉ (I),

^R ° CN

in which R and R 'are identical or different, straight-chain, branched or cyclic, optionally by halogen atoms or Alkoxy groups substituted alkyl radicals with a maximum of 6 carbon Atoms stand, have strong insecticidal and acaricidal properties.

LiAII 908 - 1 -

009829/1948 ORIGINAL BATHROOM

. 181593?

As has also been found, 1-cyano-vinyl-phosphoric acid esters are used of the above constitution obtained when 0,0-dialkylphosphoric acid diester halides of formula (II)

^R0 ^ P-HaI (II)

O
R ¹ O

in which R and R 'have the meaning given above and Hai stands for a halogen atom, with monochloroacetaldehyde-eyanhydrin of structure (III)

Cl-CH ₂ -CH-CN (III) OH

in the presence of acid binders.

The 1-cyano-vinylphosphoric esters according to the invention surprisingly show (I) a considerably higher insecticidal and acaricidal effect than the known vinyl phosphoric acid ester analogues Constitution and the same direction of action. The former are therefore a real asset to technology.

If OjO-diethylphosphoric acid diester chloride is used as the starting material and triethylamine as acid binder, the course of the reaction is shown by the following equation.

+ Cl-CH ₀ -CH-CN + 2 N (C _O H _K ), OH

^G 2 ^H 5 ° \ «

^{d 5} ^ POC = CH ₀ + 2 N (O ₉ H-),. HCl Π H Qr * ^d c. D ο

Le A 11 908 "2- 009829/1948

"2-

The phosphoric acid diester halides to be used as starting materials are clearly and generally defined by the formula (II). Preferably, however, R and R 'in the above formulas are identical or different, optionally chlorine-substituted straight-chain ones or branched, lower alkyl or alkoxyalkyl radicals, especially those with 1 to 6 carbon atoms or cyclohexyl groups, while Hai preferably stands for a chlorine atom. The compounds of the formula (II) are known from the literature and also in the technical field Scale easily accessible.

As examples of employable in the invention phosphoric M diesterhälogenide be mentioned are: 0,0-dimethyl, 0,0-diethyl, 0,0-di-n-propyl, 0,0-diisopropyl, 0,0 Di-n-butyl, 0,0-diisobutyl, 0,0-dihexyl (normal or branched), 0,0-dichlorodiethyl, Ο, Ο-diniethoxydiethyl, O ^ -diethoxydiethyl-phosphoric acid chloride and bromide.

0-methyl-O-isopropyl-, O-methyl-0-n-propyl-, O-methyl-0-chloroethyl, O-methyl-0-hexyl- (branched or normal), O-methyl-0-cyclohexyl-, O-methyl-O-methoxyethyl, O-methyl-0-ethoxyethyl, O-ethyl-0-chloroethyl-, O-ethyl-0-hexyl- (branched or normal), O-ethyl-O-cyclohexyl-, O-ethyl-0-methoxyethyl-, 0-ethyl-O-ethoxy- ' ethyl phosphoric acid chloride and the corresponding bromides.

The reaction is preferably carried out in the presence of solution or Diluents carried out.

Practically all inert organic solvents come as such, in question. These include, if appropriate, chlorinated ones Hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene and dichloromethane, dichloroethane, chloroform, carbon tetrachloride,

009829/1948

Ethers e.g. diethyl and dibutyl ethers, dioxane and low boiling points aliphatic ketones and nitriles, for example acetone, methyl ethyl, methyl isopropyl ketone, aceto and propionitrile.

Tertiary amines are preferably used as acid-binding agents. Particularly suitable are: triethylamine, tributylamine, dimethylbenzylamine, diethylaniline and Pyridine.

The reaction temperatures can be varied within relatively wide ranges. In general, the reaction is preferably carried out between -10 ° and + 40 °, between 0 ° .and 2O ⁰ C

To carry out the process, 2 moles of the tertiary amine in question are gradually added to the mixture of 1 mole each of phosphoric acid diester halide and monochloroacetaldehyde cyanohydrin, dissolved in one of the above-mentioned diluents, whereby a certain internal temperature is ensured by external cooling of the mixture (generally 10 ⁰ C) is not exceeded. After the addition the mixture is left for a few hours at about 20 ° to 3O ⁰ G react and then removes the precipitated salt by filtration. The piled up is washed until neutral, dried and freed from the solvent under reduced pressure. The liquid that remains - usually dark in color - is the desired 1-cyano-vinylphosphoric acid ester. In most cases it can be further purified by distillation under reduced pressure and obtained colorless.

he A 11 908 - 4 - - ■

9829/194 6

1815039

As already mentioned above, - the products are characterized by excellent insecticidal and acaricidal properties. she at the same time have only a low phytotoxicity. Besides that Some of them have fungotoxic properties and a certain rodenticidal effect Side effect on. For this reason, the erfindungegemäisen Successful connections in crop and stored product protection as well as in the hygiene sector to combat harmful sucking and biting insects and dipteras as well as against strokes (Acarina) can be applied.

The sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Myzus persicae), the black bean (Poralis fabae), oat (Hhopalosiphum padi.), Pea (Macrosiphum pisi) and potato mousse (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphie mali), floury plum (Hyalopterus arundinis) and black cherry leaf leek (Myzus cerasi), as well Scale and mealybugs (Ooccina), e.g. the ivy shield (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) like Hercinothrips femoralis and bedbugs for example the Beet (Piesma quadrata), cotton (Dysdercus intermediua), bed (Cimex lectularius), predatory bug (Rhodnius prolixua) and Chagas bug (Triatoma infeetan.s), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus *

The most common insects are caterpillars (Lepidoptera) like the coal cockroach (Plutella maouliptnnis), the Schwamaepinner (Lymantria diapar), Goldafter (Euproctie ohry- ■ orrhoea) and single-winged moth (Malaoosoma neuetria), furthermore “Le A 11 908”. - 5 -

001829/1948

Cabbage (Mamestra braesicae) and the seed owl. (Agrotis segetum), Large cabbage whitefly (Pieris brassicae), small Frostapanner (Cheimatobia brumata), oak moth (Tortrix viridana), the Army (Laphygma frugiperda) and Egyptian cottonworm (Prödenia litura), also the web (Hyponomeuta padella), flour (Ephestia Kühniella) and large watch moth (Galleria mellonella).

- 6 - ORIGINAL INSPECTED

009829/1948

The biting insects also include beetles (Coleoptera), for example corn (Sitophilue granariua = Calandra granaria), potato (Leptinotaree decetnlineata), dock (Gastrophyaa viridula), horseradish leaf (Phaedon cochleariae), rapaglance (Meligethea aerus) - (Byturue touentoaus), table beans (Bruchidius = Acanthoscelidee obtectua), bacon (Dertnestee frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneuni), corn (Calandra or Sitophilue zeamais), bread (Stegobium) paniceum), common burrow beetles (Tenebrio nolitor) and flat grain beetles (Oxyzaephilus surinaTDensie), but also species living in the ground such as wireworms (Agriotes spec.) and white grubs (Melolonthe melolontha); Cockroaches like the German (Bletella gertnanica), American (Feriplaneta anericana), Madeir © - (Laucophaea or Hhyparobia madeirae), Oriental (Blatta orientalie), giant (Blnberus giganteus) and black Rieeenachabe (Blabsrus f ^ scus) iouedlenia amchowtlenia flexivitta? furthermore orthoptera eg iae H © i @ eb © n (A © fe © fe ö © Q3stieua) | Termites such as the terrestrial termites (RetieulltesOies fla ^ ipea) and Hymenoptera such as ants, for example the ¥ l «eenae © iee (Lesiue niger).

The Diptera comprise essentially fly as the FAU> (Droeophila melan © gaet © r) "Mitteliseerfrucht" COo ^ ttltis cepitsta), houseflies (Mueca donestica) ₉ small © houseflies (Femmle eanicularig) _β gloss (Phoroia a © gima) mü Sefeiaeiflfliege

Le A H 9 0β ■ = 7

ß S p.2 9/1 S 4 8

also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes • egypti), HauB (Culex pipiene) and malaria mosquito (Anopheles Stephensi).

The mites (Acari) include especially the spider mites (Tetranychidae) such as the bean (Tetranychue telarius « Tetranychue althaeae or Tetranychus urticae) and the Obetbeuospinnoilbe (Paratetranychue pilosus = Panonychus ulmi), Gall mites e.g. the currant gall mite (Eriophyes ribis) and tarsonemids, for example, the shoot tip mite (HemitarsoneiDus latue) and Cyclaneninilbe (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 ones Documents from.

Le A 11. 9DB - θ -

009829/1948

Depending on their intended use, the new active ingredients can be added to the common 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 and / or carriers, optionally with the use of surface-active substances Agents that are emulsifiers and / or dispersants, with e.g. in the case of the use of water as an extender, organic solvents may be used as auxiliary solvents can be. The main liquid solvents that can be used are: aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. Chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; as solid carriers: natural Ground rock (e.g. kaolins, clays, talc, chalk) and synthetic ground rock (e.g. highly dispersed silica, Silicates); as an emulsifier; non-ionic and anionic emulsifiers emulsifiers such as polyoxyethylene fatty acid ethers, polyoxyethylene fatty alcohol ethers, e.g., alkyl aryl polyglycol ethers, alkyl sulfonates, and aryl sulfonates; as a dispersant: e.g. Lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations in Mixture with other known active ingredients are present »

LeA H 9 0S »9.

9 8 29/1948

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

90 %. ■

The active ingredient concentrations can be varied over a wide range. In general, concentrations are used
from 0.00001 " to 20 #, preferably from $ 0.01 to 5 #.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granulates be applied. It is used in the usual way, e.g. by pouring, spraying, atomizing, gasifying, smoking, Scattering, dusting, etc.

The excellent effect of the products comes from the following
Test results

Le A 11 908-10 .

009829/1948

Example A Phaedon larvae test

Solvent: Emulsifier:

3 parts by weight of acetone

1 part by weight of alkylaryl polyglycol

ether

To produce a suitable active ingredient preparation, 1 part by weight of the active ingredient in question is mixed Substance with the specified amount of the respective solvent, which contains the above-mentioned amount of emulsifier, and dilute the concentrate obtained with water to the desired concentration

This active ingredient preparation is used to make cabbage leaves (Brassica o ^ eraeea) sprayed until dripping wet and then jj4t horseradish leaf beetle larvae (Phaedon cochleariae) occupied.

After the times given in the table below, the degree of destruction of the pests is determined and expressed in #. 100 means that all and £ 0 means that no larvae of beetles were killed.

Tested active ingredients, applied active ingredient concentrations, Evaluation times and test results obtained go from the following table 1?

A 11 908

9/1

/ ♦ 4

Table 1 (Phaedon larva test)

Active ingredients
(Constitution) active ingredient concentration degree of destruction in fo in $ after

- 3 days

Il

(CH ₃ O) ₂ PO-CH = CH ₂

(known)

0.1

0 CN (CH, 0) J-O-C = CH,

0 CN (C ₂ H ₅ O) ₂ POC = CH ₂

0.1 100 0.01 100 0.1 100 0.01 90

0 CN

ti I

UC ₃ H ₇ O) ₂ POC = CH ₂ 0.1

100

_n 0 CN ' ^ POC = CH,

• CH ₃ O

0.1

0.01

100 50

Cl-CH ₀ -CHJJ O CN ^ ^ \ ti »

^ P-O-C = CH, CH, 0

0.1

0.01

100

70

Le A 11 908 - 12 -

00982 9/1948

SAD ORiGINAL

Example B.

Myzus-Teat (contact effect) Solvent: 3 parts by weight of acetone Emulsifier: 1 Oewiohtstelle Alkylarylpolyglykoläther

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

Cabbage plants (Brassica oleracea), which are heavily infested by the peach aphid (Myzus persicae), sprayed with drip nose.

After the specified times, the degree of destruction is determined in%. Here, 100% means that all aphids have been abgetütet _t, 0% means that no aphids were abgetütet.

Active ingredients, active ingredient concentrations, evaluation times and Results go from the table below? stands out

Le A 11 908 '- 73.

009829/1948

BASS QRlQlHAL

Table 2 (Myzus test)

Active ingredients (constitution)

Active ingredient concentration degree of destruction in $> in # after __ 24 hours

It

(CH ₃ O) ₂ PO-CH = CH ₂ (known)

0.1

Il I 0.1 100 (CH ₃ O) ₂ POC = CH ₂ 0.01 98 0.001 40 O CN. (C ₂ H ₅ O) ₂ POC = CH ₂ 0.1
0.01 100
80 O CN UC ₃ H ₇ OJ ₂ POC = CH ₂ 0.1 100 0.01 45 iC H OvJJ? ^{N
3 7} ^, POC = CH ₂
CH ₃ O 0.1
0.01
0.001 100
100
40 0 CN
CnIC ₄ H ₉ O) ₂ POC = CH ₂ 0.1
0.01 99
30th 0 CN
Il 1
/ rti λ TJ fill _Λ ^ V Λ C-. PU
CCC C 0.1
0.01 100
90 Cl-CH-CH ₉ O ^ S? ^Ν
CH ₃ Q * 0.1
0.01
0.001 100
100
50 Lt A 11 908 -H-

m »,

009829/1948

■■ · * ■ »

Example C Tetranychus test

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

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

Bean plants (Phaseolus vulgaris) which are approximately 10-30 cm in height are sprayed to runoff with the preparation of the active compound. These bean plants are strong with 'all Bai' Winding stages of the bean spider mite (Tetranyehus telBrius) infested.

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 spider mites have been killed, 0 % means that none of the spider mites have been killed.

Active ingredients, active ingredient concentrations »Evaluation« times% mü Results are taken from the following table 3h @ r:

Le A 11 908 »15» © 0S829 / 'ii48 BAD

Table 3 (Te tranychus-Tes t)

Active ingredients
(Constitution) Active substance concentration degree of destruction in $ in $ after 48 hours

0
(CH ^ O) ₀ PO-CH = CH,

(known)

0 CN

(CH ₃ O) ₂ POC = CH ₂

0 CN

^l 2

95

60

0 CN

CH ₃ O

60

CH ₃ -O

POC = CH ₂

45

Le A 11 908

- 16

009829/1948

Example D

LT ₁₀₀ -Test for Diptera

Test animals: Musca dornestica (housefly) Solvent: acetone

2 parts by weight of active ingredient are in 1000 parts by volume of solvent recorded. The solution obtained in this way is adjusted to the desired lower concentrations with further solvent diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. There is a filter paper on the bottom of the Petri dish with a diameter of about 9.5 cm. The petri dish remains Stand open until the solvent has completely evaporated is. Depending on the concentration of the active ingredient solution

ρ
the amount of active ingredient per m of filter paper varies. Then you put about 25 test animals in the Petri dish and cover them with an Olas lid «

The condition of the test animals is continuously monitored. The time it takes for a 100 # knock down effect is necessary.

Test animals, active ingredients, active ingredient concentrations and tents with a 100% knock-down effect are shown in the following table :

Le A 11 906 '- 17 -

009829/1948

Tabel

■ (LT ₁₀₀ -Test for Diptera)

Active ingredients (constitution)

Active ingredient concentration ^{LT i00} 7 ' tration in # 15 '
45 '
8 ^h = 70 0.2 5 |
8 ^h = 30 0.02
0.002-
0.0002 5 ¹
35 '
h ¹⁶⁰ '
6 ⁿ = 70 0.2
0.02
0.002
0.0002 15 '
h ³⁰ '
6 ^h = 95 0.2
0.02
0.002
0.0002 35 '
v, 140 '
8 ⁿ = 50 0.2
0.02
0.002 5 '
h ⁶ ^
6 ⁿ = 50 $> 0.2
0.02
0.002 0.2
0.02
0.002
0.0002

GH O

° ^CN "^ POC = CH

7th
^G 2 ^H 5 °

0 CN

0 CN i -G H O "'

CH, 0

0 CN

ti *

CH ₃ O

O (CH ₃ O) ₂ -PO-CH = CH ₂

(known) 0

'2

-O - CH-CH ₂

(known)

Le A 11 908

0.2

0.2 0.02

v, 90 '

8 ⁿ »30

- 18 009829/1948

BATH

example

LT, ₀₀ test for Diptera
Test animals: Aedee aegypti

Acetone solvent

2 parts by weight of active ingredient are in 1000 parts by volume of solvent recorded. The solution obtained in this way is adjusted to the desired lower concentrations with further solvent diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9 * 5 cm. The petri dish remains Stand open until the solvent has completely evaporated is. Depending on the concentration of the active ingredient solution

p
the amount of active ingredient per m of filter paper varies. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. It will the time determined for a 100 # knock down effect is necessary.

Test animals, active ingredients, active ingredient concentrations and times, who have a 100 $ knoek down effect, go from Table 5 below;

LeA 1t 90 8 '- 19 -

009829/1948 _{ßAD oWG1NA} u

Tabel

for dipteras)

Active ingredient
(Constitution)

Active ingredient concentrations ^LT 10C tration in i ° 0.2
0.02
0.002
0.0002
0.00002 60 '
60 '
60 '
120 '
180 ' 0.2
0.02
0.002
0.0002
0.00002 60 '
60 '
60 '
120 '
180 ' 0.2
0.02
0.002
0.0002
0.00002 60 '
60 '
120 '
120 '
180 0.2
0.02
0.002
0.0002
0.00002 60 «
60 '
60 '
120 '
180 ' 0.2
0.02
0.002 35 '
, HO '
8 ⁿ = 50 0.2
0.02
0.002
0.0002 60 '
60 '
⁶ OU
> 3 ^h 0.2
0.02 18Oi
> 3 ^h 0.2
0.02 150 '

UtL,

CH ₃ O

P-O-O = CH,

0 CN

CN

11-C ₃ H ₇ O

0 CN

• i π η η »ι 'ι ^ 3 7 ^ POC = CH, / <■

ΟΗ, Ο

^{4 3} ^ POC = CH

P-O-C = CH

0 P.

(CH ₃ O) ₂ PO-CH-CH ₂ (known)

(C ₂ H ₅ O) ₂ PO-CH-CH ₂ (known)

Le A 11 908 - 20 -

009829/1948

Example. ¹ * LD ₁₀₀ test

Test animals: Sitophilus granarius Solvent: acetone

2 parts by weight of active ingredient are in 1000 parts by volume

Solvent added. The solution thus obtained is

with further solvent to the desired concentrations diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. There is a filter paper on the bottom of the Petri dish with a diameter of about 9.5 cm · The petri dish remains Stand open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution

ο
the amount of active ingredient per m of filter paper varies.

Then about 25 test animals are placed in the Petri dish and covers them with a glass lid.

The condition of the test animals is checked after 1 and 5 days after the experiments have been started. The knock down effect is determined in %.

Active ingredients, active ingredient concentrations, tea animals and results are shown in Table 6 below:

009829/1948

Le A 11 908 -21-

T a belle 6 Mortification · < (LD _{1 00} test) in 1o Active ingredients Active ingredient 100
100
80 (Constitution) tration in i ° 100
100 0 CN
CH ₃ O ^ »_ _O _ _{C '= CH}
CH ₃ O 0.2
0.02
0.002 0 CN 0.2
0.02

C ₂ H ₅ O

0 CV

CH-O 5

GN

0.2 0.02

0.2

0.02

0.002

100 100

100

100

^CN -OC-CH,

0.2 0.02

100 100

Λ Λ1Ι

^ P-O-C = CH

(CH ₃ O) ₂ PO-CH = CH ₂

(known) 0

(C ₂ H ₅ O) ₂ PO-CH = CH ₂ (known)

0.2 0.02

0.2

0.2

100 100

Le A 11

- 22 -

009829/1948

BATH

example

LD ₁₀₀ -Test

Test animals: Blatta orientalis

Acetone solvent

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution thus obtained is diluted with further solvent to the desired concentrations.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9 * 5 cm. The petri dish remains Stand open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution 1st the amount of active ingredient per m of filter paper varies. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is checked after 1 and 3 days after the experiments have been started. The knock down effect is determined in %.

Active ingredients, active ingredient concentrations, test animals and results are shown in the table below:

00982 9/1948

^{Le A 11}

CH ₃ O

(CH ₃ O) ₂ PO-CH = CH ₂ (known)

(C ₂ H ₅ O) ₂ -PO-CH = CH, (known)

Table 7 Mortification (LD ₁₀₀ -TeSt) in 1o Active ingredients Active ingredient concentrations 100
100 (Constitution) tration in 'fo 100
100
100
30th ³ ^ POC = CH ₀
f \ TT (\ ^
\ J Xl «^ V / 0.2
0.02 100
30th
100
100 0 CN
^C 2 ^H 5 °> P-O-C = CH ₂
C ₂ H ₅ O 0.2
0.02
0.002
0.0002 0 CN
η -C ₃ H ₇ O
0 CN 0.2
0.02
0.2
0.02

0.2

0.2 0.02

100 0

Le A 11 9OB

009829/1948

ORJG / ΝΑς

Example 1:. q

Of

Is added to a mixture of 43.4 g (0.3 mol) of 0,0-dimethyl-phosphOrsäurediesterchlorid, 31.7 g (0.3 mol) Monochloracetaldehydcyanhydrin and 300 cc of toluene at an inner temperature of door 1O ⁰ C with stirring and external cooling, a Solution of 62.0 g (0.6 mol) of triethylamine in 60 ecm of toluene was added dropwise. After the addition is complete, the mixture is left to react at 20 to 30 ° C. for a further 2 hours. The deposited salt-like precipitate is removed by filtration and the piltrate is washed using a little water and sodium bicarbonate solution until it reacts neutral. After drying over sodium sulfate, the solvent is distilled off under reduced pressure and, by distilling the residue, 35.0 g (66 % of theory) O ₁ O-dimethyl-δ-d-cyano-vinyl) phosphoric acid ester is obtained in the form of a colorless liquid from Kpp 88 G and the refractive index n ^ = 1.4259.

Analysis? PN

Calculated for a molecular weight of 177.11: 17.49 %; 7.91 i ° \ Found:. $ 17.34; $ 7.84.

Example 2:

C ₂ H ₅ O

Under the same conditions as described in the previous example, 62.0 g of triethylamine, dissolved in 60 com of toluene, are added dropwise to a mixture of 52.0 g (0.3 mol) of 0,0-diethyl-phoB-

Le A 11 906 - -25- 009829/1948

phosphoric acid diester chloride, 31.7 g (0.3 mol) of monochloroacetaldehyde hydrogen chloride and 300 ecm of toluene. After a two-hour reaction, the batch is worked up as described. Distillation under reduced pressure gives 39.4 g (64 $> of theory) 0,0-diethyl-0- (1-cyano-vinyl) -phosphoric acid ester in the form of a color

o 22

-free liquid from the Kp.q. 84 C and the refractive index np = 1.4249

Analysis: .PN

Calculated for a molecular weight of 205.17: 15.10 #; 6.83 #; Found: 15.00 #j 6.72 #.

Example 3 '»

nC, H ₇ O. "

⁰ '"2P-OO = CH ₉

Leaving 60.2 g (0.3 mol) of 0,0-di-n-propyl-phosphoric acid diester chloride in the same manner as indicated in Example 1, with 31.7 g (0.3 mol) of monochloroacetaldehyde cyanohydrin and 62.0 g (0.6 mol) of triethylamine react, so after working up the mixture 50.8 g (72.6% of theory) of 0,0-di-n-propyl-0- (1-cyano-vinyl) phosphoric acid ester in form of an almost colorless liquid from Kp.Q ..75 ⁰ C and the refractive index nn obtain = 1.4279.

Analysis: ρ _Ν

Calculated for a molecular weight of 233.22: $ 13.29; 6.01 #; Found: 13.74 #; 5.91 #.

Le A 11 908 - 26 -

00982 9/1948

BATH ORIGINAL

In a manner analogous to that in Example 1, when the corresponding phosphoric acid diester chlorides are used, the following 1-cyanovinyl phosphoric acid esters are obtained available:

,

CH ₃ O 'CN

Yield: 51 % of theory;

colorless liquid of boiling point _{Q Q1} ^{90 0} C;

25 refractive index: n-p = 1.4224;

Analysis: ρ _Ν

Calculated for a molecular weight of 205.16: $ 15.10; $ 6.83; Found: 15.10 #; 6.69 #.

Cl-CH ₉ -CH ₉ -O

> P-OC = CH ₉ ^CH 3 ° CN

Yield: $ 56 of theory;

colorless liquid of boiling point _{Q O1} 98 ° C;

20 refractive index: η _Ώ = 1.4525;

Analysis:

Calculated for a molecular weight of 225.59:

P Cl N

13.73%; $ 15.72 > \ 6.21

Found: $ 13.69; 15.65 #; 6.21

> ^nG 4 ^H 9 ° CN

Yield: $ 78> of theory;

almost colorless liquid with a boiling point of _{Q O1} 96 ° C;

Le A 11 908 -27- "'009829/1948

Refractive index n ^ = 1 »4319;

Analysis: ρ _Ν

Calculated for a molecular weight of 261.27s 11.86 #; 5.36 #;

Found: 12.25 1 ° \ 5.39 #.

Cl-CH ₉ -CH ₉ -O.

^ P-OC = CH ₉

- ° CN

Yield: 68 ^ of theory; almost colorless liquid of bp, _{Q 01} H3 ° C;

Refractive index n ^ ⁷ = 1.4680;

Analyzes

i - ρ Cl N

Calculated for a molecular weight of 274.06: $ 11.30>; 25.88%; $ 5.11 > \ Found: 11.45? Sj26.57 ^; 5.09%.

Le A t1 908 - 28 -

00 9 829/1948

ORIGINAL

Claims (6)

Patent claims: 1-cyano-vinyl-phosphoric acid ester of the formula: 0
R ¹ O in which R and R 'for the same or different, straight-chain, branched or cyclic, optionally substituted by halogen atoms or alkoxy groups with alkyl radicals up to 6 carbon atoms. 2) Process for the preparation of 1-cyano-vinyl-phosphoric acid esters, characterized in that 0,0-dialkyl-phosphorus acid diester halides of the formula J
R ¹ O in which R and R 'have the meaning given in claim 1. and Hai stands for a halogen atom, with monochloroacetaldehyde-eyanhydrin in the presence of acid binders implements. 3) insecticidal and acaricidal agents, characterized by a Content of i-cyano-vinyl-phosphoric acid esters according to claim 4) A method for combating insects and mites, characterized in that 1-Oyan-vinyl-phoBphör acid ester is used ιλ A 11 qoa - 2'9 - 0 0 9 8 2 9/1948 according to claim 1 to insects and / or mites or their Let the roughness of life take effect. 5) Process for the production of insecticides and acaricides Agents, characterized in that 1-cyano-vinyl-phosphoric acid ester according to claim 1 mixed with extenders and / or surface-active agents. 6) Use of 1-cyano-vinyl-phosphoric acid esters according to claim 1 to control insects and mites. Le A 11 908 - 30 - 009829/1948