SU473709A1 - The method of obtaining unsaturated esters of acrylic or methacrylic acid - Google Patents

Description

where R is hydrogen, alkyl;

R is hydrogen, bromine;

iR is hydrogen, alkyl;

Y - oxygen, sulfur;

p is an integer, 1-3;

t, 1, 2;

n - 1, 2,

that is, the acrylic or methacrylic acid acetyl esters are reacted with 7-bromo-acetylenoxy-substituted phenol in methanol or a mixture of methanol and tetrahydrofuran and ether. The process is carried out in the presence of a copper monochloride catalyst, the complexing agent is n-alkylamine and the reducing agent is hydroxylamine.

. The final product is isolated with known examples. The yield of the target product to 90%. Process temperature 18-22 ° С, duration 40-50 minutes.

Preferably, to obtain esters of formula I with p, p 2, the process is conducted, respectively, in methanol, methanol-tetrahydrofuran-ether (5: 1: 1), methanol-tetrahydrofuran-ether (1: 1: 1).

Example 1. 1-about-Bromophenoxy- (2,4-hexadiin) -acrylcarboxy-6

(lH2-CJ-i-0- (JH2-C dC (l-CH2-0- (a three-neck flask equipped with a gas-water tube, an auto-stirrer and a dropping funnel, load 0.05 g of copper monochloride into 7.5 ml of n-propylamine , 0.80 g of acrylic acid propargyl ester in 30 ml of dehydrated methanol 1. With an intensive stirring and under an atmosphere of dry nitrogen, 1.45 g of o-bromophenol 3-bromopargyl ether dissolved in 35 ml of dehydrated methanol is slowly added (drop by drop). Periodically, 0.2 g of hydroxylamine hydrochloride (as a reducing agent) is added periodically. . Mnatnoy temperature After the addition of all the products, the reaction mixture was further stirred for 25-30 minutes nr same temperature after which the reaction mixture was obrabaty (H2 C-C-0-CN -. (

to

A mixture of 0.80 g of acrylic acid propargyl ester, 30 ml of dry methanol, 0.05 g of copper monochloride, 7.5 ml of n-propylamine and 0.3 g of hydroxylamine hydrochloride is loaded into the above device. Then, under an atmosphere of dry nitrogen, with vigorous stirring, 1.45 g of 3-bromopropargyl ester of α-bromophenol in 40 ml of dehydrated methanol are added dropwise in 10-15 minutes. The mixture is continued to stir for another 25-30 minutes, then it is treated according to the onsanp procedure and 1.35 g (84.6% of

theory) 1- / g-bromophenoxy - (2,4 - hexadiin) acrylcarboxy - 6,

by myself

representing -99 ° C. colors with t. pl. 97crystals of yellow HbOZ. The product was purified by the method of (ethyl alcohol).

Found,%: C 56.35, 56.38; P 3.41, 3.37; Br 25.11, 25.09.

S.zNiOzVg.

Calculated,%: With 56,45; P 3.47; Br 25.03.

Example 3. 1-2,4-Dibromophenoxy- (2,4hexadiin) -acrylcarboxy-6 is prepared with 200 ml of a 5% aqueous solution of hydrochloric acid. It is extracted with sulfuric ether (several times) and the extract is dried over anhydrous K2CO3, then filtered and the ether is distilled off. A yellow color crystallizes in the precipitate (as it grows pink), which is purified by thin layer chromatography on an AO3 (ethyl alcohol). The output of 1.30 g (81.5% of theoretical), so pl. 39-41 ° C. Paydeno,%: C 56.30, 56.33; H 3.50, 3.45; Br 25.10, 25.12. CisHnOsBr. %: With 56.45; P 3.47; Br 25.03. Calculated, Example 2. 1- / g-Bromophenoxy- (2,4-hexadiin) -acrylcarbox-6 C- (H2-0-

((-0-С1Ьg (С - (- С ill2) The described method consists of 0.8 g (0.0073 mol) of acrylic acid propargyl ester (in 30 ml of methanol) and 1.85 g (0.005 mol) of 2.4 bromopropyl ether) -dibromophenol in a mixture of 25 ml of methanol, 5 ml of sulfuric ether and 5 ml of tetrahydrofuran, 0.005 g of copper monochloride as a catalyst, 8.5 ml of n-propylamine, 0.35 g of hydroxylamine hydrochloride, 1.72 g (86.4% of theory) -c-o- (1n, -y - (; CH3

1.24 g (0.01 mol) of methacrylic acid propargyl ester dissolved in 40 ml of purified methanol are placed in a three-necked flask equipped with an auto-stirrer, a gaseous feed tube and an addition funnel,

0.1 g of SiaCI in 17 ml of n-nropylamine and 0.4 g of a pale-yellow crystalline substance with mp. 95-96 ° C. Paydeno,%: C 45.21, 45.19; P 2.45, 2.47; Br 40.08, 40.06. S15P, oZVG2. Calculated,%: C 45.27; P 2.53; Vg 40.15. Example 4. 1 - -Bromophenoxy- (2,4-hexadiin) -methacrylcarboxy-6 C- (n2-o- {br

hydroxylamine sulfate. Under a nitrogen atmosphere, 2.90 g (0.01 mol) of l-bromophenol 3-bromopropargyl ester in 40 ml of purified methanol is added dropwise over 15-20 minutes with stirring. After that, the reaction mixture is stirred for another 25-30 minutes. Then the contents of the flask were poured into a beaker with 200 ml of a 1: 2 solution of hydrochloric acid and extracted with sulfuric ether. The ether extract is dried over dehydrated potash. After evaporation of the solvent with PBS C-C-0 SI2-C (- (- 1 -CH2-0- / -B1 1

: siz

0.62 g (0.005 mol) of methacrylic acid propargyl ester is charged into the device described in example 4 in 25 ml of methanol, 0.05 g of copper monochloride in 8 ml of n-propylamine and added dropwise during 10-15 minutes 1.85 g (0.005 mol) of 2,4-dibromophenol 3-bromiopargyl ether in a mixture of 25 ml of methanol, 5 ml of sulfuric ether and 5 ml of tetrahydrofuran are added. Then the mixture is stirred for 30–40 minutes at room temperature. Next, the mixture is treated with a 5% solution of Sol acid

CH, rC-C-0-CH, r (-S.g O

From 0.62 g of methacrylic propargyl ester in 30 ml of methanol, 2.24 g of 2,4,6-tribromophenol 3-bromopropargyl ether in a mixture of 15 ml of methanol, 15 ml of sulfuric ether and 15 ml of tetrahydrofuran in the presence of 0.06 g of monochloride copper, 8.5 ml of n-propylamine and 0.4 g of hydroxylamine hydrochloric acid in a nitrogen atmosphere according to the method described in example 4, 1.97 g (80.2% of theory) of the main crystalline product with

A crystalline color, yellow color, shines. The product is cleaned, ayut by TLC on ABOZ, so pl. 79-81 ° C. The output of 2.86 g (86,0% of theoretical).

Found,%: C57.59, 57.56; H 3.89, 3.91; Br 23.90, 23.91.

CieHiaOsBr.

Calculated,%: C 57.68; H 3.93; Br 23.98.

Example 5. 1-2,4-Dibromophexy - (2,4hexadiin) -methacrylcarboxy-6

and extracted with ether. After distilling off the solvent, a crystalline substance was obtained with mp. 72-74 ° C. Purification was performed by TLC on ABOz.

The output of 1.83 g (89.0% of theory).

Found,%: C 46.56, 46.58; H 2.91, 2.87; Br 38.67, 38.69.

С1бН12ОзВг2.

Calculated,%: C 46.64; H 2.93; Br 38.78.

Example 6. 1-2,4,6-Tribromphenoxy- (2,4hexadiin) -methacrylcarboxy-6

m.p. 127-129 0.

Found,%: C 39.11, 39.06; H 2.19, 2.17; Br 48.77, 48.76.

С1бН11ОзВгз.

Calculated,%; C 39.13; H 2.25; Br 48.82.

Under similar conditions, 1-2,4,6-tribromophenoxy- (2,4-hexadiine) -acrylcarboxy-6 and 1-o-bromophenoxy- (2,4-hexadiine) methacrylcarboxy-6 (see table) were obtained.

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Claims (2)

I t: -V I ABOUT about i w -w Oh i sh with. K bJ and The subject of the invention 1. The method of obtaining the unsaturated esters of the formula I 12 acrylic or methacrylic acid total (dH2) n - {() 2 - ((H2U-o where R is hydrogen, alkyl; R is hydrogen, bromine; R is hydrogen, alkyl; Y - oxygen, sulfur; p is an integer, 1-3; t, 1, 2; n-, 2, characterized in that acetyl esters of acrylic or methacrylic acid are reacted with α-bromo-acetylenoxy-substituted phenols in methanol or a mixture of methanol, tetrahydrofuran and ether in the presence of copper monochloride as a catalyst, followed by separation of the target product by known techniques. 2. The method according to claim 1, characterized in that, in the case of preparing esters of formula I, at p 2, the process is carried out, respectively, in methanol, methanol-tetrahydrofuran-ether medium in a ratio (5: 1: 1), methanol-tetrahydrofuran ester F; ratio (1: 1: 1).