DEF0010673MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: December 20, 1952. Advertised January 5, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 12ο GROUP 2601

F 10673 IVb / 12 ο

Dr. Gerhard Schrader, Opladen

has been named as the inventor

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Process for the preparation of phosphonic acid derivatives

It is known that phosphorus trichloride easily reacts with ethylene glycol to form glycolphosphorous acid chloride

PCL + HO-CH ₉ -CH ₉ -OH

In the glycolphosphorous acid chloride thus obtained

the last chlorine can easily be compared to the rest of one

ίο alcohol, a phenol, an aliphatic or

can be implemented (P. A. Rossisskaja and M. J. Kabatschnik, Chemisches Zentralblatt, 1949, I, p. 487):

ei - p:

, 0-CH ₉

O- CH ₉

2 HCl

in the X for RO, ArO, RS, Ar-S as well as

R ₂ /
stands, where R, R ₁ and R _{2 represent} aliphatic radicals substituting aromatic mercaptans or a secondary base. Compounds of the general formula are obtained in this way.

, 0-CH ₉

0-CH ₂

and Ar is understood to be an optionally substituted, aromatic radical.

509 627/41

F 10673 IVb / 12 ο

It has now been found that the compounds of the formula

Q) - CH ₂

^X O - CH ₂

in which X has the above meaning with dichloro or trichloroacetic acid esters, thiol esters or amides react. With simultaneous splitting and chlorination of the glycol ring bound to the phosphorus the corresponding phosphonic acid derivatives of the general formula are formed in good yield

! I

X-P

0-CH ₂ -CH ₂ -Cl

(H)
I.
^X C —CO —R ₄

Cl

wherein R _{4 represents} the ester or amide radical of the above acid esters or amides.

The implementation runs, for example, according to the following equation:

x-p:

Il
xp:

, 0-CH ₉

O - CH,

CCL-CO- OC ₂ H,

, 0-CH ₂ -CH ₂ -Cl

CCL-CO- OC ₉ H.

The implementation takes place easily when heated; it can also be used in the presence of inert solvents be made. The products of the process are high-boiling, mostly distillable oils, which are used as Pesticides should be used.

It is already known that cyclic phosphorous acid esters react with alkyl chlorides at elevated temperatures convert with simultaneous splitting and chlorination of the glycol ring bound to the phosphorus : '■

x-p;

, OCH ₉

¹ OCH ₉

(RHaI) X-P:

, 0-CH ₂ -CH ₂ Hal

While with alkyl chlorides alkylphosphonic acid

Esters which have no insecticidal property are α-phosphonic acid derivatives according to the invention obtained, which are characterized by their effect as pesticides.

example 1

31 g Glykolphosphorigsäure-jS-chloräthylester (Kp. 91 _g ⁰⁾ are heated with 36 g Trichloressigsäureäthylester I ¹ I ₂ hour at 70 to 80 °. When the crude product is fractionated, 18 g of a new ester of the following constitution are obtained:

Cl-CH ₂ -CH ₂ -O,

Cl -CH ₉ -CH ₉ -O '

Ii ■ ■■

"P-CCl ₂ -CO-OC ₂ H ₅

The ester boils under a pressure of 2 mm at 158 to 160 °.

Example 2

42 g of trichloroacetic acid-thioläthylester (Kp. ₁₄ ° 89) are heated with 29 g Glykolphosphorigsäureäthylester (Kp. ₁₂ 52 ⁰⁾ 120 ⁰ briefly. The temperature continues to rise by itself to 21c ⁰ . When the crude product is fractionated, 20 g of the ester are obtained:

Cl-CH ₉ -CH ₉ -O

C ₂ H ₅ O '

: P-CCl ₂ -CO-SC ₂ H ₆

from Kp. ₂ 150 to 152 ⁰ . The new ester shows a good effect against flies.

Example 3

31 g of ß-chloroethyl glycol phosphate (boiling point ₉ 91 °) are heated to 160 ° with 42 g of thiol ethyl trichloroacetate (boiling point ₁₄ 89 ^0). The temperature rises by itself to 210 ⁰ . When the crude product is fractionated, 35 g of the following ester are obtained:

Cl-CH ₉ -CH ₉ -O

Cl-CH ₉ -CH ₉ -O-

Kp. ₂ 188 °. The ester shows a good effect against flies and aphids.

Example 4

42 g of trichloroacetic acid thiolethyl ester are heated to 10 ° for ¹ Z ₂ hours with 28 g of glycolphosphorous acid dimethylamide (boiling point ₁₂ 65 °), which are diluted with 60 ecm of toluene. When the crude product is fractionated, 54 g of the following ester are obtained:

CI-CH ₂ -CH ₂ -O _n

: P-CCl ₂ -CO- SC ₂ H ₆

from Kp. ₁ 167 to 169 ⁰ .

627/41

F 10673 IVb / 12 ο

Example 5

39 g of ethyl trichloroacetate are heated to 10 ° for ¹ Z ₂ hours with 28 g of dimethyl glycol phosphorous acid dissolved in 40 ecm 5 of toluene. When the crude product was fractionated, 30 g of the following ester were obtained:

Cl-CH ₉ -CH ₉ -O

: p - CCi ₉ -co -OC ₉ H ,;

KP 0.05153 ⁰

Example 6

29 g glycol phosphorous acid ethyl ester (bp ₁₂ 52 ⁰ )

thioläthylester dichloroacetic acid with 35 g (bp. 47 ° ₂₎ 20 minutes heated to 140 ^0th After fractionating the crude product, 12 g of the following ester are obtained:

-CHCl

Cl • CH, • CH ₉ • O

Kp. _S i ₄ o °.

Claims (1)

PATENT CLAIM: Process for the preparation of phosphonic acid derivatives of the general formula: 0-CH ₂ -CH ₂ -Cl ₃₅ _p / ci (H) ^ C-CO-R ₄ Cl wherein R _{4 is} an ester, thiolester or an amide radical and X is RO, ArO, RS, ArS or R ₂ ' 'N- are, where R, R ₁ and R _{2 are} aliphatic radicals, and Ar is understood to be an optionally substituted aromatic radical, characterized in that compounds of the general formula: x-p: 0-CH ₉ 0-CH ₉ in which X has the above meaning, with dichloro or trichloroacetic acid esters, thiol esters or 60 -amides are reacted at elevated temperature. Referred publications: Chemisches Zentralblatt, 1951, II, p. 34 - A. Jl. 65 Arbusow and W. M. Soroasstrowa.