Kinetics and Stereochemistry of the Hydrolysis of Esters of Nitric, Sulfuric and p-Toluenesulfonic Acids

Citation

Leroux, Pierre Jean (1951) Kinetics and Stereochemistry of the Hydrolysis of Esters of Nitric, Sulfuric and p-Toluenesulfonic Acids. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/SCPZ-H386. https://resolver.caltech.edu/CaltechTHESIS:10032017-105106793

Abstract

Unlike the hydrolysis of carboxylic esters or that of alkyl halides, the hydrolysis of esters derived from oxygenated acids of nitrogen, phosphorus, sulfur and the halogens has not been subjected to a systematic investigation.

This work represents an attempt to clarify the mechanism operating in the hydrolysis of alkyl sulfonates, sulfates and nitrates.

2-Butanol and 2,3-butanediol were chosen as the alcoholic constituents because they afforded easily obtainable optical isomers and also because of their intermediate position as secondary alkyl derivatives.

The study of the kinetics and stereochemistry of their hydrolysis has revealed that sec-butyl p-toluenesulfonate and sec-butyl nitrate resemble the secondary halides while sec-butyl hydrogen sulfate behaves much like the corresponding carboxylic esters.

The study of 3-hydroxy-sec-butyl hydrogen sulfate has afforded a reasonable explanation of the complex behavior of cyclic sulfate of 2,3-butanediol upon hydrolysis.

An improvement in the synthesis of D(+)-sec-butyl bromide has lead to the preparation of L(-)-sec-butyl nitrate with a relatively high degree of optical activity.

Finally a new preparation of L(-)-2-butanol from D(-)-2,3-butanediol is described.

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