56500-47-1Relevant academic research and scientific papers
Widely useful DMAP-catalyzed esterification under auxiliary base- and solvent-free conditions
Sakakura, Akira,Kawajiri, Kimio,Ohkubo, Takuro,Kosugi, Yuji,Ishihara, Kazuaki
, p. 14775 - 14779 (2008/09/17)
With regard to atom economy and E-factor, catalytic condensation of carboxylic acids with equimolar amounts of alcohols is the most desirable. Although several highly active dehydration catalysts have been reported, more efficient alternatives are still strongly needed because the dehydrative esterification of tertiary alcohols, phenols, acid-sensitive alcohols, amino acids, and hardly soluble alcohols has never proceeded satisfactorily. Here we report new insights into the classical DMAP-catalyzed acylation of alcohols: surprisingly, only a 0.05-2 mol % of DMAP can efficiently promote acylation of alcohols with acid anhydrides under auxiliary base- and solvent-free conditions to give the corresponding esters in high yields. Furthermore, we achieved the recovery and reuse of commercially available polystyrene-supported DMAP without using any solvents. These serendipitous findings provide widely useful and environmentally benign esterification methods, which might be more practical and reliable than catalytic dehydrative condensation methods, in particular, for the less reactive alcohols which hardly condense with carboxylic acid directly.
Kinetics of alcoholysis of β,β-dimethylacryloyl chloride
Marshalok,Oglashennyi,Makitra,Pirig,Yatchishin
, p. 1410 - 1418 (2007/10/03)
Rate constants and activation parameters have been determined for alcoholysis of β,β-dimethylacryloyl chloride with 14 alcohols in benzene at a reactant ratio of 1:1. The reaction proceeds via formation of H-complex or charge-transfer complex. Appropriate description of the effect of alcohol on the reaction rate requires simultaneous application of the Hammett-Taft and Koppel'-Pal'm equations.
