DEF0010679MA - - Google Patents

Description

Federal Republic of Germany

Registration day: December 22, 1952 Announced on March 29, 1956

GERMAN PATENT OFFICE

PATE NTAN M E LD UNG

CLASS 12o GROUP 5o4 F 10679 IVb / 12 ο

Dr. Gerhard Schrader, Opladen

has been named as the inventor

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk Process for the preparation of derivatives of cyanophosphoric acid

It is known that phosphorus trichloride easily reacts with ethylene glycol to form glycol phosphorous acid chloride can be implemented (P. A. R ο s s i s s k a j a and

PCl ₃ + HO-CH ₂ -CH ₂ -OH

... In the Glykolphosphorigsäurechlolo thus obtained rid, the last chlorine can easily be compared with the rest of an alcohol, the rest of a phenol, the rest of an aliphatic or aromatic mercaptan or finally the remainder of a secondary. base

,. change. This way you get connections of the all-15 common formula:

M. J. Kabatschnik, Chemisches Zentralblatt 1949, I, p. 487):

ei -p:

, 0- CH ₀

- CH,

+ 2 HCl.

x - p .:

.0-CH,

¹ O-CH,

in the X for RO-, Ar - 0-, ES- and Ar-S -

as well as * ^) N -, R, R ₁ and R ₂ any ali- R ₂ /

509 699/495

F 10679 IVb / 12 ο

Phatic radicals, where R ₁ and R ₂ can be linked to form a cyclic ring system, and Ar is an optionally substituted one; aromatic radical is understood. ,

It has now been found that the compounds of the formula

x-p:

, O · CH,

"O · CH,

so react with cyanogen halides that, with splitting of the ring, the halogen migrates to the glycol residue and the cyano to φετι phosphorus: r -.

\ A

x-p;

, 0-CH ₉

'C CH,

BrCN

; p-cn

Br-CH ,. CH,

The implementation takes place at room temperature. To alleviate the reaction, the Implementation in an inert solvent, such as. B. ether, benzene, toluene, etc. performed will. The process products are distillable, water-insoluble oils, which are used as pesticides Should be used. · .. -

It is already known to react alkyl chlorides with cyclic phosphorous acid esters (see: Ar b u s ο w and S oroa's'trowa, Chemisches Zentralblatt 1951,11, p.34). Here are 'alkyl phosphonic acid esters receive. In contrast to those available according to the process. Phpephorsäurecyanestern the known phosphonic acid esters have no noticeable insecticidal effect.

Example ι

27 g glycol phosphorous & acid dimethylamide (bp. 12 mm 65 °) are 'in 300 ecm dry ether solved. At 20 °, 22 g of cyanogen bromide are added to the solution with stirring; those in 100 ecm dry ether are resolved. When the crude product is fractionated, 26 g of dimethylamino-cyano-phosphoric acid - /? - bromoethyl ester are obtained of bp 2 mm 131 °. The new ester is a pale yellow, water-insoluble one Oil that is characterized by strong insecticidal properties.

■ ■ ■ ^! '- "Example 2

27 g of ethyl glycol phosphate (boiling point 12 mm 52 °) are dissolved in 200 ecm of ether. at At 20 to 25 °, 22 g of cyanogen bromide in 50 ecm of dry ether are added to this solution. After the reaction is complete the crude product obtained is fractionated. There are 15 g of ethyl cyano-phosphoric acid - /? - bromoethyl ester obtained as a colorless, water-insoluble oil. The new ester shows strong insecticidal properties.

- ■ B ei sρ ie 1 3.

38 g Glykolphosphorigsäurediethylamid (bp 10 mm 88 to 90 °) are dissolved in 300 ecm dry ether. To this solution one gives. under .-. Stirring at 20 ° 26 g of cyanogen bromide, which was dissolved in 100 ecm of ether. The specified temperature is maintained for another hour, the ether is then distilled off and, in the subsequent vacuum distillation, 33 g of the diethylaminocyanophosphoric acid /? - bromoethyl ester with a b.p. 3 mm 145 ^{0 are obtained} .

Example 4

20 g Glykolphosphorigsäurepyrrolydid are dissolved in 300 ecm dry ether. One inserts Stirring at 20 ° 13 g of cyanogen bromide, dissolved in 50 ecm Ether, and keep the specified temperature at 2o °. After the ether has been distilled off 14g des: Pyrrolydyl-cyano-phosphoric acid - ^ - obtained bromoethyl ester. Kp. 2 mm i6i °.

Example 5 O

Br-CH ₂ -CH ₂ -OP;

, SCH,

'CN

28 g of glycolphosphorous acid thiol-methyl ester (b.p. 14 mm 78 to 79 ⁰ ) are dissolved in 250 ecm of ether with the exclusion of air. At 15 ° nian södänn adds a solution of 22 g of cyanogen bromide in 100 ecm of dry ether. ... During fractionation, after distilling off the ether, 20 g of the new ester vdm'Kp.i mm 119 ⁰ are obtained.

Br-CH ₉ -CH ₉ -OP

CN

Br-CH, -CH, -0-P

Br-CHV-CH ₉ -OP:

-Cl

• ON

, 0

Cl

40 g of Glykolphosphorigsäure-thiol-phenylester (Kp. , 2 rrmi 123 ⁹ ) are dissolved in 215 ecm dry ether. At 25 ° one gives a solution of 22 g of cyanogen bromide in 100 ecm of ether. After removing the solvent by vacuum distillation, 35 g of a viscous, colorless,> water-insoluble ester are obtained which cannot be distilled even in a high vacuum.

Similarly, from the Glykolphosphorigsäure-2,4-dichlorophenyl ester (Kp.s 135 mm ⁰⁾ and from the Glykolphosphorigsäure-4-chlorophenyl ester (b.p. 110 ° 2 mm.) Is obtained the following compounds: -> * ■

699/495

F 10679 IVb / 12 ο

These esters are viscous, water-insoluble liquids that are also not in a high vacuum let distill.

Claims (1)

PATENT CLAIM: Process for the preparation of derivatives of cyanophosphoric acid, characterized in that that cyanogen halides with compounds of the formula , 0-CH ₉ x-p: - CH, in which X is RO—, Ar — O—, RS—, Ar — S— or ¹ ^) N -, where R, R ₁ and R _{2 are} any ali- R ₂ / Phatic radicals, where R ₁ and R ₂ can be linked to form a cyclic ring system, and Ar means an optionally substituted aromatic radical, can be reacted. Referred publications: Arbusow and Soroastrowa, “Chemicals Zentralblatt «, 1951, II, p. 34.