DE1006414B - Process for the preparation of vinylphosphonic acid bis (ª ‰ -chloroethyl) ester - Google Patents

Description

GERMAN

The present invention relates to a method for the production of vinyl phosphonic acid bis (/ 9-chloroethyl) ester the formula

Il

(Cl - CH ₂ - CH ₂ - O) ₂ == P - CH = CH ₂

from / J-chloroethyl phosphonic acid bis - ^ - chloroethyl ester the formula

Ii

(Cl - CH ₂ - CH ₂ - O) ₂ = P - CH ₂ - CH ₂ - Cl

If one of / S-chloroethyl-phosphonic acid bis - ^ - chloroethyl) ester splits off hydrogen chloride in a known manner through the action of organic or inorganic bases, a mixture of various vinyl compounds and their composition is obtained that is very difficult to separate on the one hand on the amount of the organic or inorganic base used, on the other hand on their Character depends, since various side reactions - for example alcoholysis, aminolysis - can occur.

The present invention now relates to the use of basic salts of organic compounds Acids, especially of alkali acetates, as agents that split off hydrogen chloride, at elevated temperatures. Other suitable salts are, for. B. the alkali propionates and the butyrate alkali salts. The usage The acetates and propionates is therefore particularly advantageous because the free acids pass through allow simple evaporation to remove from the reaction mixture.

In the process according to the invention, surprisingly, there is a selective effect with regard to the elimination of hydrogen chloride in such a way that, even when a large excess of the salts mentioned is used, hydrogen chloride is only eliminated from the chloromethyl group bonded directly to phosphorus. When working between 90 and 140 °, for example, a crude product is obtained from which the pure vinyl ester can be obtained by simple distillation under reduced pressure. The reaction can be carried out in an inert solvent, for example dioxane, o-dichlorobenzene or tetrahydronaphthalene, although the reaction takes a long time. Air oxygen is expediently excluded by working under an N ₂ or CO ₂ atmosphere.

The reaction product can be worked up by various obvious methods. If you work in the presence of a solvent, you can simply filter off after the reaction and that The filtrate can be purified by multiple fractionation if necessary. Do you work in the absence of one Solvent, you can, after cooling, the process for the preparation of bis (/ 9-chloroethyl) vinylphosphonate

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Dr. Ernst O. Leupold, Hofheim (Taunus),

and Dr. Hermann Zorn, Vienna,
have been named as inventors

Add water to the reaction mixture until the salt has dissolved, and it is advisable to add a little more to the reaction mixture Wash out water and then distill. You can also suck off and remove the residue immediately after cooling with solvents, e.g. B. carbon tetrachloride, wash out and, optionally after washing out with Distill water and the filtrate combined with the solution.

For the subject matter of the invention, it is irrelevant

whether the elimination of the hydrogen chloride takes place directly or whether the chlorine is primarily replaced by the carboxyl group of the organic acid takes place, for example, through the acetoxy group and only secondarily through The acid is split off and the vinyl compound is formed.

When working according to the invention, it is not necessary to use pure / I-chloroethyl-phosphonic acid bis (β-chloroethyl) ester to use; Rather, you can also use the raw product or the raw solution, that or which one in the implementation of, for example, crude tris (jÖ-chloroethyl) phosphite z. B. according to Patent application F 16621 IVb / 12o has received.

The compound is polymerizable by itself and with other suitable compounds and as an intermediate for the production of other organic compounds, e.g. B. of insecticides, plasticizers, can be used.

example 1

27 g of bis-chloroethyl-phosphonic acid bis - ^ - chloroethyl) ester (0.1 mol) are boiled with 24.6 g (0.3 mol) of sodium acetate in 100 ecm of dioxane under gentle reflux for 10 hours. After cooling, it is suction filtered and the filtrate is distilled in vacuo. 17.6 g (= 75% yield) of a _{fraction which passes over at bp 0) 2} 112 to 145 ° are obtained, the repeated distillation of which is 15.6 g (= 66% yield) of vinyl phosphonic acid bis - (/? - chloroethyl ) -ester of bp. _{0) 4} 110 to 112 ° results.

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Example 2

A crude product obtained by heating a water-white ethoxylation product obtained at 0 ° from 138 parts of phosphorus trichloride and 3 mol of ethylene oxide at 140 ° for 12 hours with stirring is kept at 110 ° for 2 hours with 110 parts of sodium propionic acid. After cooling, add enough water until all the salt has dissolved and two layers form. The reaction product, which forms the lower layer, is separated off and extracted twice with a little water. The distillation gives 123 parts (= 52% yield, based on PCl ₈ ) of the vinyl ester; Kp. _{0) 4} 110 to 112 °.

Example 3

Vacuum fractionated. This gives 400 parts of pure Vinylester (= 86 ° / ₀ of theory).

Example 5

A solution that had been obtained by keeping an ethoxylation product obtained at 0 to 25 ° from 825 parts of phosphorus trichloride with 817 parts of ethylene oxide (103% of theory) in the presence of 1640 parts of o-dichlorobenzene at 180 to 190 ° for 3 hours, 550 parts of sodium acetate (112% of theory) are added at 90 ° and the mixture is then heated to 115 ° to 120 ° for 3 hours. After cooling, the mixture is stirred with water and the reaction product is fractionated in vacuo. 1008 parts of vinyl ester with a _{boiling point of 0.16} ° to 110 °, which is 72% of theory, are obtained

The same amount of the crude product used in Example 2 is obtained after the addition of 105 parts of potassium acetate Heated to 100 ° for 5 hours and suction filtered after cooling. The residue is dissolved in water and shaken out with carbon tetrachloride. This solution is combined with the Filtxat and twice with water washed out. Distillation gives 115 parts of the vinyl ester.

Example 4

539 parts / I-chloroethyl-phosphonic acid bis - ^ - chloroethyl) ester are treated in the presence of 539 parts of o-dichlorobenzene with 164 parts of sodium acetate for 3 hours at 120 ° to 130 °. After cooling, the mixture is stirred with water and the crude product in PCl ₃ .
analysis

Calculated Cl 30.5%, P 13.3%, HJ number 109.0;

found ... Cl 30.58%, P 12.97%, HJ number 109.3.

Claims (1)

PATENT CLAIM: Process for the production of vinyl-phosphonic acid-bis (ß-chloroethyl) ester by splitting off hydrogen chloride from / 3-chloroethyl-phosphonic acid bis (/? ~ chloroethyl) ester at elevated temperatures, characterized in that the splitting off with the aid of basic salts of organic acids, preferably by means of alkali acetates or propionates, and optionally in the presence of solvents is made. © 6OJ 569/428 4.57