The Simultaneous First- and Second-Order Esterifications of l-Menthol by Acyl Chlorides: Autocatalyses by Menthol in Acetonitrile and in Liquid Sulfur Dioxide
- 1 January 1966
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 39 (1) , 131-137
- https://doi.org/10.1246/bcsj.39.131
Abstract
The propionylation and p-methoxybenzoylation of l-menthol in various solvents have been studied. In chloroform, benzene, ethyl methyl ketone and carbon tetrachloride, the reaction follows the second-order rate law. However, in acetonitrile or in liquid sulfur dioxide, the rate follows the second-order rate law only at the initial stage of the reaction; thereafter it gradually deviates from the second-order type to the first-order one. Moreover, the first-order rate equations both in acetonitrile and liquid sulfur dioxide are dependent on the initial concentration of the alcohol; the over-all rates being expressed as: Rate=k1°(AcCl)(ROH)0+k2(AcCl)(ROH) where(ROH)0, (ROH), (AcCl), k1° and k2 are the concentrations of the alcohol at time zero and t, that of the acyl chloride at time t, the first-order rate constant and the second-order rate constant respectively.This publication has 6 references indexed in Scilit:
- The Solvent Effects of Esterification: The Reaction of l-Menthol with Acetyl Chloride in Liquid Sulfur DioxideBulletin of the Chemical Society of Japan, 1964
- The Menschutkin Reaction in Liquid Sulfur DioxideBulletin of the Chemical Society of Japan, 1963
- The Effect of Solvent on Spectra. I. A New Empirical Measure of Solvent Polarity: Z-ValuesJournal of the American Chemical Society, 1958
- 888. Border-line mechanisms in nucleophilic displacement reactionsJournal of the Chemical Society, 1956
- Allylic Rearrangements. XIV. The Hydrolysis of Butenyl Chlorides1Journal of the American Chemical Society, 1944
- THE RATE OF REACTION OF CERTAIN ALCOHOLS WITH PARA-NITROBENZOYL CHLORIDE IN ANHYDROUS ETHER SOLUTIONJournal of the American Chemical Society, 1930