Acrylyl chloride

A mixture of 1 kg. (18.9 moles) of acrylonitrile (Caution—volatile toxic material), 6 g. of hydroquinone, 14 g. of copper powder, 648 g. of ice, and 1012 ml. of concentrated sulfuric acid is heated gradually under a reflux condenser on a steam bath. The exothermic reaction is controlled by cautious application of heat, particularly during the first hour. Heating is continued for 48 hours, after which the mixture is cooled and the precipitated ammonium bisulfate is filtered off. The crude acid is distilled by dropping it into a distilling flask loosely packed with fine copper wire and heated to a bath temperature of 250°. The system is maintained under a pressure of about 10 mm., and the distillation receiver is packed in ice. Approximately 1 kg. of clear, colorless distillate is obtained which is shown by analysis to be 86% acrylic acid free of sulfur and nitrogen. 

A mixture of 216 g. (3.0 moles) of acrylic acid (p. 3), 844 g. (6.0 moles) of benzoyl chloride, and 0.5 g. of hydroquinone is heated under an efficient fractionating column. The distillation receiver contains 0.5 g. of hydroquinone and is immersed in an ice bath. The reaction mixture is distilled rather rapidly., and the distillate boiling up to 85° is collected (most boils in the range 60-70°). The distillate (215-225 g.) is redistilled through the same column, and the 

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Chemical properties. As already stated, Petrin is an intermediate in the prepn of numerous mixed esters. Marans et al (Ref 2) prepd a series of Petrin-nitrobenzoate esters by reacting Petrin with the appropriate nitrobenzoyl chloride. They also prepd Petrin-formate, acetate, propionate, oxalate, glutarate, succinate, adipate, and phthalate. An especially important Petrin derivative is Petrin-acrylate. It is prepared by reacting Petrin with a mixt of acrylyl chloride and dimethylaniline (Ref 4)... 

Because of the high cost and hygroscopic nature of trifluoroacetic anhydride, a new process, based on dimethylaniline and acrylyl chloride, was considered. Yields averaged 46% and product purities averaged 93.5% (Refs 2, 3 4) ... 

The condensation of biguanide with acrylate esters [e.g. methyl acrylate in presence of sodium methoxide 484)1 was expected to afford a vinyl-triazine (LXXXIV, R = R = H), but gave in fact 2-( 3-methoxy-ethyl)guanamine (LXXXVI) (51%). The desired vinyl-triazine was finally synthesised 486) from phenylbiguanide and acrylyl chloride in aqueous acetonitrile and its structure proved by its hydrogenation to 2-ethyl-6-phenylguanamine. 

Poly-N-[l-carbetoxy-3-methyl-butyl]-acrylamide (XXVIII) has been prepared from poly-acrylyl-chloride (XXIX) and leucine ethyl ester (XXX) ([a]f)° + 13.1) according to Scheme 5. 

Acetyl chloride adds to /3-propiolactone in the presence of sulfuric acid to give /3-acetoxypropionyl chloride, CH,COjCH,CHjCOCl (67%). The lactone ring is also opened by thionyl chloride to give /3-chloro-piopionyl chloride, from which acrylyl chloride may be obtained by heating with anhydrous barium chloride. 

A number of methods employ an imidazole-2-thione or related compound with a bifunctional reagent to build the thiazine ring in one or two steps. Treatment of (682) with acrylyl chloride directly produced (683) (64JOC1720). Substituting acrylic acid under catalysis allows isolation of the S-alkylated intermediate, which cyclized to (683) upon heating (64JOC1715). 

One hundred grams (1.11 moles) of acrylyl chloride (p. 2) is dissolved in 1 1. of benzene, and dry ammonia gas is bubbled through... 

TIus was obtained by Ville 119] by acting with acrylyl chloride on 2 trinitro ethanol (Chapter VIH). No infonnation was given on the possible polymerization. 

Aliphatic acid chlorides (Cj to C ) can be prepared in 80-90% yield by mixing the acid with excess benzoyl chloride and distilling the volatile RCOCl. Other examples acrylyl chloride (70%)," propionyl chloride (80%), isovaleryl chloride."... 

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