DE1050767B - Process for the production of ß-alkoxyvinylphosphonic acid alkyl ester fluorides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT LETTER 1 050767

REGISTRATION DAY:

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL:

ISSUE OF
PATENT LETTERING

DBP 1050 767 kl. 12 ο 26/01

INTERNAT. KL. C 07 f 3 JUNE 1957

FEBRUARY 19, 1959 AUGUST 6, 1959

AGREES WITH EDITORIAL

1 050 767 (F 23156 IV b / 12 o)

It is known that vinyl ethers are based on phosphorus pentachloride add. These adducts can then in a known manner with sulphurous acid to the corresponding jS-Alkoxyvinylphosphonic acid dichlorides reduced (see Anisimov and Nesmeyanov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1954, No. 4, 610, T. p. 521):

RO-CH = GH,

PCL

RO-CHCI-CH ₉ -PCl

Cl

RO-CH = CH-P;

+ HCl + SOCl ₂

Cl

It has now been found that these easily accessible β-alkoxyvinylphosphonic acid dichlorides with alkali fluorides in the presence of any alcohols into the previously unknown / 3-alkoxyvinylphosphonic acid alkyl ester fluoride the following general formula can be converted:

RO-CH = CH-P;

, OR ₁ Process for the production of

ß-alkoxyvinylphosphonic acid alkyl ester

fluoride

Patented for:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk ■

Dr. Hans-Joachim Tuppack, Leverkusen,

and Dr. Gerhard Schrader, Wuppertal-Cronenberg,

have been named as inventors

Formula obtained from Kp ^ ₀₁ 70 ⁰ C. Yield 55 ° / ₀ of theory. The ester is a colorless, water-insoluble oil which shows a mean toxicity of 25 mg / kg in rats per os.

'(R and R ₁ stand for alkyl radicals). This reaction is expediently carried out in the presence of an inert solvent

at temperatures between about 65 to 80 ⁰ C through. The following solvents have proven to be particularly effective: Benzene, toluene and chlorobenzene. The alkali fluoride used sdII expediently be anhydrous and finely divided.

The resulting / J-alkoxyvinylphosphonic acid ester fluorides are good insecticides and are characterized above all by an excellent fly effect out.

example 1

O

V OCH »Aphids (systemic

Effect)

Caterpillars

0.001

0.1 0.1

0 /

/ 0

Mortification

100

100 100

C ₂ H ₆ O-

Example 2
O

= CH-P ^

OC.H, (iso)

C ₂ H ₅ O-CH = CH-

85 g of finely powdered anhydrous sodium fluoride are suspended in 200 ecm of toluene. 20 g of anhydrous alcohol are added with vigorous stirring. Is then added dropwise with further stirring 76 g / at 80 ° C - to Äthoxyvinylphosphonsäuredichlorid (bp SS ₁₁ ⁰ C)?. It is kept at 80 to 90 ^° C. for 1 hour, then cooled to room temperature and the salts are filtered off with suction.

When fractionating the filtrate, 45 g of the / I-Äthoxyvinylphosphonsäuie äthylesterfluorides of the above 85 g of sodium fluoride are suspended in 200 ecm of toluene. 25 g of isopropyl alcohol and a drop of water are added while stirring. With vigorous stirring, 76 g / 9-ethoxyvinylphosphonic acid dichloride are added dropwise at 80.degree. The reaction is exothermic. After the reaction has subsided, the mixture is heated to 90 ^° C. for a further hour, then cooled to room temperature and the filtrate is fractionated. There are obtained 40 g of the JOE-Äthoxyvinyl fluorphosphonsäure isopropyl ester of boiling point. _OjO1 74 ⁰ C. Yield 50% of theory. The new ester is a colorless, water-insoluble oil which shows a mean toxicity of 25 mg / kg in rats per os.

. 909 573/403

Grain beetle

Colorado potato beetle

To fly

Aphids

Aphids (systemic

Effect)

Caterpillars

0.01
0.01
0.001
0.01

0.1
0.1

0 / / 0

Mortification

100
100
100
100

100
100

Example 3
O

C ₂ H ₆ O-CH = CH-P

OCH,

210 g of sodium fluoride are suspended in 500 ecm of benzene and 32 g of methanol are added with stirring. 190 g of β-ethoxyvinylphosphonic acid dichloride are then added dropwise at 65.degree. C. and the mixture is kept at 65.degree. C. for a further 1 hour. After the salts formed have been suctioned off, it is distilled. The new esters have a Kp.j80 g to 81 ⁰ C, yield 52nd The / S-ethoxyvinylfluorophosphonic acid methyl ester is a pale yellow, water-insoluble oil. Yield 30 ° / ₀ of theory. The new ester has an oral toxicity of 250 mg / kg in rats.

aqueous
emulsion 0 /
/ 0
Mortification Grain beetle 0.01
0.01
0.1 100
100
100 Aphids Caterpillars

Example 4

o-ch:

C ₂ H ₅ O-CH = CH-

CH,

C, H _S

76 g of β-ethoxyvinylphosphonic acid dichloride are added dropwise at 80.degree. It is kept at 90 ° C. for 1 hour and then worked up in the usual way. 63 g of the new fluorophosphonic acid ester with a boiling point of _{0> 01} 96 ° C. are obtained. Yield 65% of theory. Rat per os DL ₅₀ 50 mg / kg.

Example 6
O

C ₉ ILO-CH = CH-P

0-CH ₉ -CH ₀ -Cl

85 g of sodium fluoride are suspended in 200 ecm of toluene. 34 g of ethylene chlorohydrin are added. Is then added dropwise at 80 ° C 76 g / 3 to Äthoxyvinylphosphonsäuredichlorid and the reaction product maintains for 1 hour at 9O ⁰ C. After the usual work-up, _{0) 01} 87 ⁰ C. Yield 60 g is obtained of the new ester, bp. 60% of the Theory. Rat per os DL ₅₀ 25 mg / kg.

Example 7
O

CH,

OCH-.

C ₂ H ₅ O-CH = CH-P ^ C (CH ₃ ) ₃

F.

85 g of sodium fluoride are suspended in 200 ecm of toluene. Add 41 g of pinacolin alcohol. 76 g / 9-ethoxyvinylphosphonic acid dichloride are then added dropwise at 80.degree. It is kept at 90 ^° C. for 1 hour and then worked up in the usual way. 82 g of the new ester are obtained. Yield 86% of theory. Even in a high vacuum, the ester can only be distilled with decomposition. Rat per os DL ₉₅ 500 mg / kg.

Claims (1)

Claim: Process for the preparation of / S-alkoxyvinylphosphonic acid alkyl ester fluorides the formula 85 g of sodium fluoride are suspended in 200 ecm of toluene. Add 30 g of secondary butyl alcohol. At 80 ° C., 76 g / S-ethoxyvinylphosphonic acid dichloride are then added dropwise with vigorous stirring. It is kept at 90 ° C. for a further hour, then cooled to room temperature and the salts are filtered off. At the. Fractionation of the filtrate gives 70 g of the new ester fluoride with a boiling point of _{0> 01} 80 ° C. Yield 81% of theory. Rat per os DL ₆₀ 25 mg / kg. RO-CH = CH-P; , OR ₁ Example 5
O C ₂ H ₅ O-CH = CH-P ^ OC ₆ H ₁₃ (η) wherein R and R ₁ denote alkyl radicals, characterized in that jS-alkoxyvinylphosphonic acid dichlorides of the formula Cl RO —CH = CH- Cl 85 g of sodium fluoride are suspended in 200 ecm of toluene. 41 g of n-hexyl alcohol are added to this. then wherein R represents an alkyl radical, reacted with anhydrous alkali metal fluorides in the presence of alcohols will.