SU523077A1 - The method of obtaining the 9-anthrylmethyl esters of acrylic or methacrylic acid - Google Patents

Description

one

The invention relates to methods for the preparation of anthracene containing monomers, namely, 9-anthrylmetropic acrylic or methacrylic acid esters used to prepare scintillation and photoconductive properties of polymers and radiation-resistant materials.

A method of producing anthrylmethyl esters of acrylic and methacrylic acids is known by reacting 9-anthrylmethyl alcohol with the corresponding acid chlorides in the presence of triethylamine and the inhibitor (phenyl-α-naphtylamine) 1.

The substances obtained according to the indicated method are a complex mixture of anthracene-containing compounds with m.p. 105-119 ° C, which does not allow to isolate the target products in pure form.

There is also known a method for producing 9-anthrylmethyl esters of acrylic and methacrylic acids by reacting the corresponding acid with 9-anthryldiazomethane in a solution of saturated hydrocarbons 2. The use of this method is limited by the need to obtain and use low stable and toxic compounds such as aryl diazomethanes.

In order to simplify the process technology, a method has been proposed for producing acrylic acid anthrylmethyl esters, which consists of

in that acrylic or methacrylic acid is reacted with chloromethyl anthracene derivative, preferably with 9 chloromethylanthracene, or 9 chloromethyl 10 methylanthracene, or 9,10 bis (chloromethyl) anthracene in a polar antrotic solvent, for example acetonitrile, the presence of a tertiary amine, such as triethylamine, at a temperature of 80-85 ° C and at a weight ratio of chlorine methyl anthracene derivative, acrylic or methacrylic acid and tertiary amine 1: 1-4: 1-4, respectively, followed by release target product.

The proposed method for the preparation of anthrylmethyl esters of acrylic acids is more technological and does not require the use of complex synthesized, toxic and unstable anthryldiazomethanes.

The proposed method is illustrated by the examples below. In all examples, the structure of the compounds obtained was confirmed by the methods of elementary analysis, IR and UV spectroscopy.

Example 1. Getting 9-anthrylmethyl ester of methacrylic acid.

The reaction mixture of 200 mg of 9-chloromethylanthracene, 0.75 ml of methacrylic acid, and 1.23 ml of triethylamine in 3.7 acetonitrile is intermixed for 1 hour at 80-85 ° C. The resulting dark yellow solution is cooled and poured into ten times the volume of water. The product which precipitated out as a yellow powder was filtered off, washed with water and dried in vacuo at room temperature.

Yield of methacrylic acid 9-anthrylmethyl ester 180, 5 mg (74.2% of theoretical); m.p. 84-86 ° C. After crystallization from a mixture of ether - ethanol m. Pl. 85.5 -86 ° C.

Example 2. Preparation of 9-anthrylmeti.: Acrylic acid ester.

From 0.6 ml of acrylic acid in Example 1, 174 mg of 9-anthrylmethyl acrylic ester is obtained (78.3% of the theoretical); m.p. 78-82 ° C. After crystallization t. Il. 86.5 -87,

Example 3. Preparation of 10-methyl-9-anthrylmethyl methacrylic ester.

The reaction mixture of 600 mg of 9-chloromethyl 1-methylanthracene, 1.1 ml of methacrylic acid and 1.74 ml of triethylamine in 18 ml of acetonitrile is stirred for 2 hours at 80-85 ° C. The resulting solution is cooled, filtered and poured into a ten-fold volume of water. The product isolated as a yellow powder was washed with water and dried under vacuum at room temperature.

The yield of 10-methyl-9-anthrylmethyl ester of methacrylic acid 480 mg (66.6% of theoretical); m.p. 100-104 ° C. After crystallization from ethanol, m.p. 106.5-107 ° C.

Example 4. Obtaining 9,10-b “c- (methacryloxymethyl) anthracene. The reaction mixture of 497 mg of 9.10-bc-chloromethyl anthropate, 1.53 ml of methacrylic acid and 2.52 ml of triethylamine in 31 ml of acetonitrile is unmixed for 1 hour at 80-85 ° C. The resulting orange solution is cooled, filtered and poured into 300 ml of water. The product, in the form of a light yellow powder, is isolated, washed with water and dried in vacuo at room temperature.

Yield 9,10-byc- (methacryloxymethyl) -anthracene 46.3 mg (68.7% of theoretical); t, pl.

152-156 ° C. After crystallization from benzene and t. Pl. 158-G60 ° C.

Example 5. Getting 9,10-b “c- (acryloxymethyl) -antrone.

The reaction mixture of 208 mg of 9,10-bms (chloromethyl) anthracene, 0.2 ml of acrylic acid, 0.4 ml of triethylamine in 12.6 ml of acetonitrile is stirred for 2 hours at 80-85 ° C. Isolation of the product is carried out according to Example 4.

Yield 9,10-byc- (acryloxymethyl) -antracene 213 mg (84.9% of theoretical); m.p. 151 - 152 ° С. After crystallization from ethanol, m.p. 159-160,5 ° C.

Claims (2)

Invention Formula The method of obtaining the 9-anthrylmethyl esters of acrylic or methacrylic acid by reacting the reactive derivatives of 9-anthrylmethane with acrylic or methacrylic acid in a solvent environment, characterized in that, in order to simplify the process, chloromethyl derivatives of the anthracene are used as reactive derivatives of 9-anthrylmethane, and A polar aprotic solvent, for example acetonitrile, is used as a solvent, and the process is carried out at a temperature of 80-85 ° C in the presence of a tertiary amine. and, for example triethylamine, at a weight ratio chloromethyl derivative of anthracene, fire metakrplovoy acrylic acid and a tertiary amine, = 1: 1-4: 1-4, respectively. 2. A method according to claim 1, characterized in that 9-chloromethylanthracene, or 9-chloromethl-10-methylanthracene or 9.10 bis- (chloromethyl) anthracene is used as anthracene chloromethyl derivatives. Sources of information taken into account at the examination: 1. US patent 9,331,687, cl. 96-1; 1967 2. Auth. St. USSR №292956 CL 07c 69/54; 10/13/1969