CS209333B1 - Process for preparing acrylic and methacrylic esters of p-acylated 2-phenoxyethanes - Google Patents

Abstract

The invention relates to a method for the preparation of p-acylated acrylic and methacrylic esters of 2-phenoxyethanol of the general formula 1 where R1 is hydrogen or methyl, R2 is alkyl with 1 to 9 carbon atoms, 2-chloroethyl, phenyl, benzyl. The essence of the invention lies in the fact that 1-acryloyloxy- or 1-methacryloyloxy-2-phenoxyethane is acylated in the presence of aluminum chloride with aliphatic acid chlorides, aromatic or aromatic-aliphatic acid chloride. The substances prepared according to the invention are used for the preparation of light-sensitive polymers and polymer sensitizers.

Description

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The present invention relates to a novel process for the preparation of β-acylated acrylic and methacrylic esters of 2-phenoxyethanol of the general formula 1. 0¾ = C - COO - ch2 - ch2 - O - <O> - 00 -R, (1) where Rp is hydrogen or methyl, R 2 is alkyl of 1 to 9 carbon atoms, 2-chloroethyl, phenyl benzyl.

Some acrylic and methacrylic esters of p-acylated 2-phenoxyethanes have been prepared in the past;

The process for the preparation of β-acylated acrylic and methacrylic esters is carried out as follows: γ-acrylic and methacrylic esters of the general formula 2, ch 2 = C - COO - CH 2 --O - o - O / (2) * 1 in / where is hydrogen or methyl; they acylate in the presence of aluminum chloride with chloride-aliphatic acids, in -haloaliphatic acids, with an aromatic or aromatic-aliphatic acid chloride, wherein the alkyl, c-haloalkyl, aryl and arylalkyl moieties of these acids are as defined above for R2.

The preparation process simplifies the process of preparing the compounds of formula (I) and also makes it possible to prepare novel substances which are very difficult to obtain by the original process, e.g., cu-haloalkyl derivatives. The new method of preparation utilizes acylation in the presence of an ester-like double agent which is retained. A similar example of preserving double penetration is known. The prepared substances can be used for the preparation of light-sensitive polymers and polymeric sensitizers. Example 1) 1-methacryloyloxy-2- (4-acetylphenoxy) ethane 15 g acetyl chloride (0.19 mol) in 15 ml carbon disulphide was added at 0 ° C and stirred to 30.6 g (0.23 g). mol) of aluminum chloride in 30 ml of carbon disulfide. Thereafter, 1-methacryloyloxy-2-phenoxyethane (39.4 g, 0.19 mol) was added in 40 ml of sulfuric acid with stirring. After addition of all 1-metacroyloxy-2-phenoxyethane, the reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was carefully quenched with ice and hydrochloric acid and extracted with chloroform. The chloroform layer was washed 4 times with water and the chloroform was evaporated in vacuo. The product was crystallized from petroleum ether. A white crystalline solid of m.p. 49.5-50.5 ° C in 69% yield.

Allowing 1-acryloyloxy-2-phenoxyethane with acetyl chloride under the same reaction conditions affords 1-acryloyloxy-2- (4-acetyloxy) ethane in 30% yield. Example 2 1-Methacryloyloxy-2- (4-propionylphenoxy) ethane 10 g propionyl chloride (0.108 mol) in 10 ml carbon disulfide (0 ° C) 88a were added to 17.3 g (0.13 mol) aluminum chloride in 20 ml with stirring. carbon disulphide. Then, with cooling and stirring, 22.3 g (0.108 mol) of 1-methacryloyloxy-2-phenoxyethane in 25 ml of carbon disulfide are added. After addition of all 1-methacryloyloxy-2-phenoxyethane, the reaction mixture was stirred for 30 minutes at room temperature. Then, the reaction mixture is decomposed by pouring it into acid, hydrochloric acid, and ice and extracted with chloroform. The chloroform layer was washed 4 times with water and the chloroform was evaporated in vacuo. The product was dissolved in ethanol, slightly warmed with charcoal, filtered and allowed to crystallize. A white crystalline substance with m.p. 68-69 ° C (53%).

Similarly, by aeylation with 1-methacryloyloxy-2-phenoxyethane decanoyl chloride, 45% yield is obtained. Example 3 1-Methacryloyloxy-2- [4- (3-chloropropionyl) phenoxyJetane 12.3 g (0.0969 mol) of i-chloropropionyl chloride in 20 ml of carbon disulphide was added to 15.5 g under cooling (0 ° C) and stirring. Of aluminum chloride in 20 ml of carbon disulphide. Thereafter, 20 g (0.0969 mol) of 1-methacryloyloxy-2-phenoxyethane in 20 ml of sulfuric acid was added to the mixture and stirred. After all of the 1-methacryloyloxy-2-phenoxyethane was added, the reaction mixture was stirred for 30 minutes. Then the reaction mixture was carefully poured onto ice / hydrochloric acid and extracted with chloroform. The chloroform layer was washed 4 times with water. The chloroform was evaporated in vacuo and the viscous product was shaken. Dissolved in benzene, and passed through a pad of silica gel (3 cm x 5 cm). Then the benzene was evaporated. The material was dissolved in ether and frozen at 70 ° C. After drying, a white crystalline solid with m.p. 85.5-87 ° C, 66% yield. y * - Example 4 1-Methacryloyloxy-2- (4-benzoylphenoxy) ethane To a suspension of 17.5 g (0.131 mol) of anhydrous aluminum chloride in 10 ml of carbon disulphide was added a solution of 18.45 g (1 h). 0.131 mol) benzyl chloride in 20 ml carbon disulfide. The 1-methacryloyloxy-2-phenoxyethane solution was then added at a slightly elevated temperature as it reacted. Then stir for 15 minutes at room temperature spread out with l'ad and hydrochloric acid. Organic portion separated by chloroform extraction, neutralized with 5% sodium carbonate solution. The chloroform extract was partially evaporated and dried over a fritted silica gel. After evaporation of the chloroform, 37 g of material were obtained. The material was extracted hot with 3 times 200 mL petroleum ether. Over time, the petroleum ether extract thickened and contained mainly benzoic acid. The extraction residue was dissolved in diethyl ether and boiled with activated charcoal and filtered through a pad of silica gel. Crystals were obtained from the solution only at low temperatures. The product so prepared was almost the desired compound in a yield of 17.7 g. The product was purified by chromatography on silica gel and eluted with benzene. A viscous colorless liquid was obtained which was the desired pure product.

Claims (1)

Sp6sob the preparation of acrylic and methacrylic esters of p-acylated 2-phenoxyethanol of the formula 1, wherein R · ^ is hydrogen or methyl and R ₂ is alkyl of up to β _$ »2-chloroethyl, phenyl, and benzyl, vyznačujúei in that 1-acryloyloxy or 1-methacryloyloxy-2-phenoxyethane of formula (2), wherein R R is as in 1, is acylated in the presence of aluminum chloride with aliphatic acid chlorides, ω-haloaliphatic acids, aromatic or aromatic-aliphatic acid chloride, the alkyl The ω-haloalkyl, aryl and arylalkyl moieties of these acids correspond to the above meanings for Bg.