SU432127A1 - Method of producing a-acyloxy, a- (alkoxycarbonyloxy) aryl acrylates - Google Patents

Description

one

This invention relates to the preparation of a-acyloxy-a- (alkoxycarbonyloxy) aryl acrylates, which can be used for polymer materials.

A method is known for preparing, for example, aacyl-alkyl alkyl acrylates by reacting Pxls-p-lactic acid with alcohol, followed by treating the resulting p-chloractate with anhydride or chloral hydride. Having obtained α-acyloxychloropropionate, it is subjected to dehydrochlorination and the desired product is isolated by known technological methods and.

Using the known chemical reactions, according to the proposed method, it is possible to obtain new, not described in the literature, compounds of the formula

.СН2 С-СООА1

o- C- 2 C

where Z - Alk, OAlk, which in comparison with the known have new properties. Colorless transparent polymeric materials with a temperature of about 200 ° C are obtained on their basis.

The proposed method consists in the fact that p-chloro-lactic acid is reacted with chlorine hydrides of the formula

C1-C-Z O

where Z is Alk, OAlk, in the presence of opraiiji oskovan of the organic solution of the body. The resulting salt of a-acyloxy-a (alkoxycarbop; loco) 1-) p - chloropropionic acid is treated with hydrochloric acid, and the a-Herbone-who-xyxyl derivatives of chloropropio are separated; -; interaction with aromatic alcohols in the presence of an organic base in an organic solution ;; tel; The resulting Ari is m. p-chloropropionate is depirochlorinated in the presence of 1 and an organic base in an organic solvent medium at 20-80 ° C in the presence of radical gland inhibitors and a-adyloxy, a- (alkoxyncarbonyloxy) aryl acrylate is isolated.

In the case of Cl-p-chloropropionate C1, nridine is used as the organic base.

In the dehydrochlorination stage, triethylamine is used as an organic acid.

Example 1. Synthesis of a-methylcarbonyloxyphenyl acrylate. To 124.50 g (1.0 mol of p-chloromolic acid in 500 ml of sulfuric ether at 15 ° C, 158.2 g (2 mol) of lyridide a are added. The mixture is cooled to 5 ° C. With stirring. For 2 hours 94.5 g (1.0 mol) of methyl chloroformate are added to 100 ml of sulfuric ether. The reaction mixture is left to stand at room temperature for 2 hours. treated with an aqueous solution (82.4 ml) of 37% hydrochloric acid in 300 ml of distilled WATER. the native salt of pyridine and the resulting a-meth, ilcarbonyloxy (3-chloropropionic acid), which is separated from the aqueous layer by repeated extraction with small amounts of m and sulfuric ether. The serium is removed, the iCymaT IB residue is removed. 109.5 g (60 %) a-methylcarbonyloxy-chloroprotational acid, the latter is heated with 72.2 g (50% excess) of thionyl chloride for 14 hours at 80 ° C. The excess of thionyl chloride is removed and the residue is distilled under vacuum. Get 60,25 g (50%) of chlorine "hydride with t. Kip. PO-11574.5 mm Hg v .; content of the main substance is 91%; determined chlorine content.

To a solution of 60.25 g (0.3 mol) of α-methylcarboxyloxy-p-chloropropionic acid chloride cooled to 5 ° C in 200 ml of sulfuric acid, add 28.2 g (0.3 mol) of phenol and 23.73 (0.3 mol) pyridine in 100 ml of sulfuric ether, incubated for 10 hours at room temperature, the resulting iiridine hydrochloride salt is separated. The filtrate is washed with 5% hydrochloric acid solution, 5% sodium bicarbonate solution and water until neutral. The washing solutions are prepared with an 8% aqueous solution of common salt. Dried over sulfate "at. S or magnesium. Sulfur is removed, the residue is fractionated under vacuum, 45 g (58%) of amethyl carbonyloxyphenyl-p-chloropropionate (m.p.) are separated. 164 ° / 4 mmHg Art. T. pl. 60-62 ° C.

Found,%: C 50.51; H 4.09; C1 14.09. Mol weight 254.5.

StsNtsOES.

Calculated,%: C 50.9; H 4.25; C1 13.7. Mol weight. 258.5.

To 20.2 g (D, 2 mol) of triethylamine in 150 ml of dry benzene, and 60 ° C, 45 g (0.175 mol) of amethylcarboyloxy-p-chlorophenylpropnonate and 0.001 g of di-naphthyl-l are added dropwise with stirring. -phenylenediamine. The temperature was raised to 80 ° C and the mixture was stirred for 5 hours at 80 ° C. The ohlal was allowed to reach room temperature, the hydrochloric triethylamine was filtered off. The filtrate is washed as above. Dry the scale with sodium sulfate, remove benzene and argon in an atmosphere of argon.

vacuum in a vacuum. 21.2 g (55%) of a-methylcarbonyloxyphenyl acrylate are recovered. T. KCP 132 ° / 3 mmHg Art. 1.5028; d 1,213.

Found,%: C 59.73; H 4.51, mol. weight 217. SiNuOb.

Calculated,%: C 59.5; H 4.5, mol. weight. 22

The resulting monomer compound is a syrupy liquid, which is distilled in vacuum without much decomposition.

PRI mme R 2. Synthesis of a-acetoxyphenyl acrylate.

To 124.50 g (1.0 mol) of p-chloro-molar acid in 500 ml of seroyl ether at G5 ° C, 159.2 g (2 mol) of pyridine are added, the mixture is cooled to 5 ° C and stirred for 2 hours. 78.5 g (1.0 mol) of acetyl chloride in 200 ml of sulfuric ether, incubated for 2 hours at room temperature. The hydrochloride salt of pyridine and the pyridinium salt of a-acetoxy-chloropropionic acid are isolated. The resulting reaction mass is treated with a solution of 98.4 g 37% hydrochloric acid in 300 ml of distilled water. Water passes to the aqueous layer pyridine chloride a and a-acetoxy-p-chloropropionic acid, which is obtained in this way, which is extracted by repeated extraction in small portions of the sero ether. The ether is removed, the residue is dried in a vacuum. 100 g (60%) of the acetoxy-p-chloroproxide is isolated. acid. It is mixed with 119 g (50% excess) of thionyl chloride and agglomerated for 14-15 hours at 80 ° C. The excess of thionyl chloride is removed, the residue is distilled in vacuum. 61.5 g (55%) of a-acetoxy chloride is obtained p-chloropropionic acid. T. Kip. 95 ° C / 5 mm. Hg Art. “About 1,81550; the content of the basic substance is 92%, as determined by the percentage of chlorine.

To a solution of 61.5 g (0.35 mol) of a-acetoxy-chloropropionic acid chloride, cooled to 5 ° C, in a mixture of 250 ml of sulfuric ester is added 28.6 g (0.33 mol) of phenol and 24.9 (0 , 33 mol) p.iridine in 50 ml of sulfuric ether. The mixture is kept for 10 hours at room temperature, the resulting iridium hydrochloride salt is separated. The filtrate is washed with the method described in Example 1 and the iad is dried with sodium sulfate. Sulfur is removed, the residue is fractionated in vacuo. 44 g (55%) of phenyl-a-acetoxy-p are obtained - chloropionate. T. cues. 158 ° at 1 mm Hg. Art. n 1 1.5050.

Found,%: C 54.58; P 4.50; C1 44.58. Mol weight 239.8.

CnHir04Cl.

Calculated,%: C 54.5; H 4.54; C1 14.61. Mol weight. 242.5.

To 21.3 g (0.21 mol) of triethylamine in 100 l. 44 g (0.182 mol) of phenyl-a-acetoxy-p-chloropropionate and 0.001 g of di-p-naphthyl-lfenylenediamine are added with stirring at dry at 60 ° C. The temperature was raised to 80 ° C and the mixture was stirred for 5 hours at 80 ° C. The mixture was cooled to room temperature, the precipitated triethylamine hydrochloride was filtered off. The filtrate is washed as described in Example 1. It is dried over sodium sulfate, benzene is removed under argon and the residue is distilled in vacuo. 23 g (60%) of a-acetoxyphenyl acrylate are recovered. T. Kip. 118 ° / 1 mm. Hg Art. nf 1.5085, d 20 1.166.

Found,%: C 64.17; H 4.84. Mol weight 202.3

CiilHioO4.

Calculated,%: C 64.2; H 4.82. Mol weight 206.

(The monomer compound obtained is a viscous, colorless liquid that is distilled without appreciable decomposition.

Subject invention

The method of obtaining a-acyloxy-, a- (alkoxycarbonyloxy) aryl acryl atoms, characterized by

the fact that p-chlorobiol acid is subjected to interaction with the acid chloride of the General formula

C1-c-g

It is about

where Z is an alknl or O-alkyl, at a temperature up to 5 ° C in an organic solvent medium, for example sulfuric ether, in the presence of an organic base, for example pyridine, the salt thus obtained is successively treated with hydrochloric acid, thionyl chloride, and an aromatic alcohol in organic medium the solvent in the presence of an organic base and the p-chloroproshunatat thus obtained are dehydrochlorinated at 20-80 ° C in an environment of an organic solvent and a radical polymerization inhibitor, followed by isolation of the target product known; tricks.