SU390070A1 - A method of producing cyanogen-containing derivatives of acrylic acid. 12 The invention relates to the field of production of [Personalized lIl'functional Compounds of Cyanogenic Acrylic Acids-Acids. ^ ^ - _ _ 7-o-, Y = -S, -S-07 -So. - Google Patents

Description

, 2, RbRs-H, Alk.

The compounds described in the literature

of the class are effective light-stabilized. The obtained compounds containing polymer isolators and how many functional groups are obtained are synthesized by condensation of ketones or aldehydes according to Knovengel.

(2)

esters of cyanoacetic acid by Kohvengs10.

The proposed method consists in the acylation of hydroxy aromatic compounds containing -NH, -S, -SO2, SO, CO-groups with the acid chloride of cyan-containing acrylic acid derivatives in the presence of a hydrogen chloride acceptor at a temperature of 25-35 ° C and holding at 40-60 ° C With the selection of products known methods.

The yield of the desired products is 75-85%, considered the corresponding acid chloride.

The resulting compounds and / are identified by elemental analog and spectroscopic methods.

In all the joints, there are marked intensive absorption bands at 1730-1755 cm; 3370-3400 cm and 2205-2215, confirming the presence of ester, secondary amine and cyanoographer.

Example 1. Preparation of cc-cyan10-p 4-apilinophenyl ester of | 3-diphenyl acrylic acid.

A 1.85 g (0.01 g-mol) p-oxydiphyl amine, 20 ml of absolute dioxane, 1.4 ml (0.01 g-mol) of triethylamine and at a temperature of 20–25 ° C, chloroanhydride of α-cyano-p, p-diphenylacrylic acid is added.

After the addition of the acid chloride has been completed, the mixture is maintained at 40-45 ° C for 3 hours and dry at 55-60 ° C for 1 hour. After cooling the reaction mass to room temperature, the precipitated hydrochloric acid salt of triethylamine is filtered off, and the filtrate is poured into 150 ml of distilled water. The precipitated oil quickly crystallizes upon washing with 2% sodium carbonate solution and water. The crystals are filtered and dried. The yield is 3.37 g (81% of theory, based on acid chloride), m.p. 151-152 ° C (from ethanol).

Calculated,%: C, 80.77; H 4.81; N 6.73.

C28H2oN2O2.

Found,%: C 80.79; H 4.73; N 6.74.

The product is highly soluble in dioxane, benzene, chloroform, dichloroethane, poorly soluble in ethanol, practically insoluble in hexane and water.

IRS: VCO 1740 cm-, VNII 3370 El-, VCN 2210 slg-1.

Example 2. Preparation of a-cyano-p, p-diphenylacrylic acid 4-amino-naphthylphenyl ester.

Under the conditions of example 1, of 2.35 g (Q, 0 g mol) α-oxyneosia and 2.67 g (0.01 g-mol) of a-cyano-p chloride, p-diphenyl acrylic acid in 20 ml of absolute dioxane in the presence of 1.4 ml (0.01 g-mol) of triethylamine, 3.63 g (77.8% of theory) of a-cyano-p-3-diphenyl acrylic acid 4-aminonaphthylphenyl ester with m.p. 159-160 ° C (from ethanol).

Calculated by-,%: C 8.3; H 4.73; N 6.01.

C32H22N2O2.

Found,%: C 82.71; H 4.78; N 6.58.

The solubility of the product is similar to the previous P1, it is a sample.

IR: VCO 1730 cm-VNH 3410 cc-i, VCN 2205 cm-.

Example 3. Preparation of the product of l-aminophenol adylation with α-cy0 apo- (3, | 3-diphenylacrylic acid) chloral hydride.

Under the conditions of Example 1, from 0.545 g (0.005 g-mol) p-aminophenol, 2.67 g (0.01 g-mol) of a-cyano-p chloride, p-diphenyl acrylic acid in 20 ml of dioxane in the presence of 1.4 ml of 5 (0.01 gmol) of triethylamine give the product of acylation. The output of 2.72 g (80% of theory), so pl. 238-239 ° C (from benzene).

Calculated,%: C 79.8; H 4.38; N 7.35.

Sz8N2bMzOz.

0 Found,%: C 79.36; H 4.55; N 7.73.

The product is highly soluble in acetone, dioxane; it is poorly soluble in benzene, practically insoluble in hexane and water. IR: VCO 1750 cm-, VCN 2215 cm-.

5 Example 4. Preparation of thiobis (a-cyano-phenyl ester, | 3-diphenyl acrylic acid).

In a three-necked flask with a stirrer, a thermometer and a calcium chloride cooler, 1.09 g (0.05 gmol) of 4,4-diphenylenesulfide, 20 ml of dioxane, 1.4 ml (0.01 gmol) of triethylamine are charged and 20 to 25 ° C. 2.67 g (0.01 gmol) of a-cyano-p, p-dIfeiyl acrylic acid chloride are added. After

The 5 ends, and the acid chloride acidification is maintained for 2 hours at 35-40 ° C, 2 hours at 45-50 ° C and 1 hour or 60 ° C. After cooling the reaction mass to room temperature. Perature is filtered out the precipitated salt of 0 "oxidized triethylamine salt. The filtrate is poured into water. The precipitated crystals are filtered, washed with 2% sodium carbonate solution and with water until neutral.

5 Yield 3.08 g (75% of theory, calculated on acid chlorohydride), so pl. 180-182 ° C (from acetic acid).

Calculated,%: C 77.7; . H 4.12; N 4.12; S 4.71.

0C44H28N2SO4.

Found,%: C, 77.32; H 3.97; N 4.01; S 4.35.

The product is highly soluble in dioxane, badly soluble in ethanol and acetic acid;

practically insoluble in water and hexane.

5 IKS: VCO 1755 cl, VCN 2215 cm-.

Example 5. Preparation of thiobis- (3-methyl-bg / e7-butylphenyl ester a-cyano-p, p-diphenyl acrylic acid).

Under the conditions of Example 4, 1.79 g (0.005 g0 mol) of bis- (2-methyl-5-greg-butyl-4-hydroxyphenyl) sulfide and 2.67 e of α-cyano-p chloride, rdiphenyl acrylic acid in 20 ml dioxane

in the presence of 1.4 ml (0.01 gmol) of triethylamine. 2.91 g (71% of theory) of the acylation product are obtained, m.p. 204-205 ° С (from

acetic acid). Calculated,%: G 79.02; H 5.85; N 3.4; S 3.9.

C54H38N2SO4.

Found,%: C 78.66; H 5.89; N 3.04; S 4.05.

The solubility of the product is similar to the previous sample.

IR: VCO 1740 cm-, VGN 2205 cm-, vco 1688 (amide I).

Example 6. Preparation of 3-hydroxy-4-benvoylphenyl ester of sb-cyano-p, p-diphenylacrylic acid.

Under the conditions of Example 4, of 2.15 g (0.01 g-mol) of 2,4-dioxybenzaphenone and 2.67 g (0.01 g-mol) of chloro anhydride a-cyano-p, p-diphenyl acrylic acid in 20 ml of dioxane in the presence of 1.4 ml (0.01 g-mol) of triethylamine give 2.35 g (53% of theory) of 3-hydroxy-3-benzoylphenyl ester a-cyano- 3, p-diphenylacrylic acid; m.p. 138-139 ° C (from ethanol).

Ri Cg, -so- -SOj;

Calculated,%: C 78.4; H 4.28; N 3.15.

CsgH.gno.

Found,%: C 78.3; H 4.20; N 3.05. The product is well soluble in most organic solvents (dioxane, benzene, dichloroethane), poorly soluble in ethanol. IKS: VCO 1755 cm-, VCN 2210 with -.

Subject matter of the HI and

ten

Claims (2)

1. The method of obtaining cyanogen-containing acrylic acid derivatives, formula 15 C where R is hydrogen, alkyl, aryl or aralkyl;  ; - b nl, 2, Ri and Cr-hydrogen, alkyl, characterized by the fact that hydroxyaromatic compounds (containing -NH, -S-, -SO, -S02, CO groups, are reacted with dianhydrochloride acid derivative of acrylic acid in the presence of hydrogen chloride acceptor in the environment of organic the solvent when heated with the subsequent, their selection of the target product by known methods. 2. A method according to claim 1, characterized in that the process is carried out at a temperature of 25-35 ° C, followed by aging at a temperature of 40-60 ° C.