Acrylates of Difficultly Esterified Alcohols

Aryl (meth)acrylates and polymers based on them

“…Earlier methods for the synthesis of aryl (meth)acrylates were rather complicated and were not of a general character. Thus phenyl acrylate (PA) was prepared by direct esterification of phenol with acrylic acid in the presence of trifluoroacetic anhydride 1 and also by the Reppe reaction, i.e., by the reaction of acetylene and carbon monoxide with phenol. 2 Phenyl 3 and naphthyl acrylates 4 were obtained by pyrolysis of 2-acetoxypropionates MeCH 2 (OAc)CO 2 Ar.…”

The Use Of Trifluoroacetic Anhydride And Related Compounds In Organic Syntheses

“…The stability of unsaturated molecules is shown by the preparation of monomeric esters which normally polymerize in the presence of strong acids (1, 2). Thus phenyl acrylate has been prepared in good yield directly from phenol and acrylic acid, using trifluoroacetic anhydride (1).…”

“…Later workers prepared mixed anhydrides by treating various acids with acetic anhydride (4, 5, 6); by mixing two symmetrical anhydrides together (22,25); by treating the solution of one acid in a tertiary base, with the acid chloride of another acid (77,142,200) [this method has also recently been used in connection with peptide syntheses (32,203)]; and by treating the sodium salt of a monoacyl sulfonate (RCOSG2ONa) with the sodium salt of a different carboxylic acid (161,162,163). Ketene has been used extensively in more recent times to prepare mixed anhydrides of acetic acid (106,108,127,129), and /3-benzoylacrylic acid mixed anhydrides have been 1 Considerable confusion has arisen in the literature through the failure of workers to be sufficiently precise when discussing reactions of molecules of the type RCO-O-COR', which have variously been called "mixed anhydrides," "asymmetric anhydrides," and "unsymmetric anhydrides." In an attempt to clear up some of this confusion the following terms will be employed throughout this discussion: "unsymmetrical anhydride" to refer only to the actual molecule RCO-O-COR'; "mixed anhydride" to refer to any system which analyzes for RCO • • COR' but which may contain equimolecular mixtures of the two symmetrical anhydrides (RCO)20 and (R'CO)20 or a mixture of these together "with the unsymmetrical anhydride.…”

Partially Fluorinated Esters and Ethers as Temperature Stable Liquids. Part I. Synthesis and Characterization

“…Heretofore, this has been considered an impractical procedure (16). Trifluoroacetic anhydride has been used as a catalyst in the preparation of $'-butyl acrylates (31), but this catalyst was not used here because of its high cost and the difficulty of removing trace quantities of the trifluoroacetic acid from the productFor the types of esters presented here the direct esterification method is preferred and was employed in all instances. To assure complete esterification an excess of the fluoroalcohol was used in reactions with aliphatic acids while an excess of the fluoroacids was reacted with aliphatic alcohols.…”