SU448708A1 - The method of obtaining glycidyl esters or brocrylic acid - Google Patents

Description

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This invention relates to a process for the preparation of new glycidyl ethers of a and / or brocrylic acids, which can be found in the polymer industry.

A known method for the preparation of glycidyl esters of aromatic unsaturated acids interacts with the spin salts of corresponding acids with zichlorohydrin in the presence of a catalyst, for example triphenylbenzylammonium chloride.

The synthesis of new compounds possessing new properties is currently attracting the attention of various researchers.

According to the invention, new glycidiol esters of a and / or p-bromoacrylic acid are obtained, which have an increased reactivity. These compounds are obtained by the interaction of salts a and / / or | 3-br01macrylic acids with epichlorohydrin in the presence of an inhibitor and a catalyst, for example tetramethylammonium bromide, and the desired products are isolated by known methods.

The resulting esters are colorless, easily mobile liquids, readily soluble in acetone, alcohol, diethyl ether, chloroform, and other organic solvents that are insoluble in water.

The structure of the synthesized compounds is confirmed by the data of elementary analysis, IR spectra, purity is determined by nauseating chromatography on alumina II degree of activity. The eluent is acetone, the appearance was produced by iodine vapor.

In the IR spectra of glycidyl ethers, an intense band of 830, 920 ohms appears, which characterize the epoxy group, as well as the 1600, 1620 bands corresponding to the C – C double bond.

Example 1. Glycidyl ester of a-bromoacrylic acid.

15 ml of epichlorohydrin, 0.05 g (0.03 wt.%) Of tetramethylammonium bromide catalyst and hydroquinone are added to 10 g (0.05 mol) of the potassium salt of a-bromoacrylic acid. The reaction mixture is heated to 110 ° C with stirring for 2 hours, then cooled, the mixture is filtered, the precipitate (potassium chloride) is separated, the filtrate is distilled at 72-73 ° C / 2 m.m. The output of the glycidyl ester of a-bromacrylic acid is 47-50%.

Purity determined by thin layer chromatography. Rf 0.91 (eluent acetone).

Found,%: C 34.2; H 3.20; Br 37.2.

SbNtVgOz.

Calculated,%: C 23.8; P 3.30; Br 38.

The content of the epoxy group

found

18.5, calculated 20.1. Molecular wt.%:

.;.:,

:.; T

D. - .. to.: Gg.

found 207.0 (mass spectroscopy method), calculated 207.

Example 2. Trans-rbrOmacrylic acid glycidyl ester.

50 ml of epichlorohydrin, 0.23 g (0.2 wt.%) Of tetramethylammonium bromide catalyst and 0.05 g (0.02 wt.%) Are added to 29.8 g (0.1 mol) of the potassium salt of trans-pbromoacrylic acid. phenyl-p-naphthylamine inhibitor. The reaction mixture is stirred for 3 hours at 115 ° C.

After cooling, the reaction mixture was filtered, the precipitate was separated and the filtrate was distilled at 85-86 ° C / 2 mm. .

The output of glycidyl ether trans-p-bromoacrylic acid 48-50%.

Found,%: C 34.06; H 3.23; Br 37.5.

SbNuVgOz.

Calculated,%: C 34.8; H 3.3; Br 38.0.

Found,% 30.1.

ICD

Calculated. About 29.3.

The content of the epoxy group,%: found 19.1; calculated 20.7.

Purity determined by thin layer chromatography. Rfo, 89 (eluent acetone).

The molecular weight found was 207.0 (maos spectroscopy method), calculated 207.

Example 3. Cis-rbromacrylic acid glycidyl ester.

To 10 g (0.05 mol) of the potassium salt of cis-brocrylic acid 30 ml of epichloro448708 are added.

hydrine, 0.04 g (0.016 wt.%) of tetramethylammonium bromide catalyst and phenyl-naphthlamine inhibitor. The reaction mixture is stirred for 3 hours at 115 ° C, then the reaction mixture is filtered, the precipitate (KCl) is separated, the filtrate is distilled: ave. 72-73 ° C / 2: MiM. The yield of glycidyl ester of cis-p- | bromocrnloic acid is 46-50%. Purity determined by thin layer chromatography. R.fo.93 (element acetone).

Found,%: C 34.04; H 3.2; Br 37.6.

SbNtVgOz.

Calculated,%: C 34.80; H 3.3; Br 38.0.

Found,%: 30.

MRo.

Calculated,%: 29.3.

Content of epoxy-gruzpy,%: found 18.9, calculated 20.7. Molecular weight, found 207.0 (mass spectroscopy method), calculated 207.

Claims (1)

Invention Formula A method of producing glycidyl ethers a and / or p-bro, of macrylic acids, wherein salts of a and / or p-acrylic acid are reacted with epichlorohydrin in the presence of an inhibitor and a catalyst, for example tetramethylammonium bromide, and the desired products are isolated by known methods.