The Mechanisms of Some Reactions of Optically Active 2,3-Butanediol and its Derivatives

Citation

Garner, Harold Karl (1949) The Mechanisms of Some Reactions of Optically Active 2,3-Butanediol and its Derivatives. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/fwfg-wr89. https://resolver.caltech.edu/CaltechTHESIS:06022025-183255549

Abstract

Dextrorotatory 2,3-epoxybutane has been shown to belong to the D family by a consideration of the mechanisms of the reactions involved in its preparation from D(-)-2,3-butanediol. Similar considerations show dextrorotatory erythro-3-chloro-2-butanol to belong to the L family. The latter compound was oxidized by hypobromite to L(-)-α-chloropropionic acid, giving additional proof of its configuration.

The stereochemical results of, (a) the acetolysis of the p-toluenesulfonates of D(-)-2,3-butanediol, and (b) the reactions of the optically active erythro- and threo-3-iodo-2-butanols with the hydrohalic acids, can be satisfactorily explained only by assuming neighboring group participation in the replacement process. This participation is by way of the cyclic intermediate ions, I and II respectively.

See PDF of abstract for Figs. I and II.

A number of cyclic acetals and esters of D(-)-2,3-butanediol were prepared, namely, the formal, acetal, carbonate, sulfite, sulfate, borate, and several phosphite derivatives. All of these behaved normally on hydrolysis except the sulfate, which gave the meso-glycol on acid hydrolysis, and the DL-glycol on basic hydrolysis.

The effect of 3-acetyl-6-methoxybenzaldehyde in inhibiting the growth of tomato plants was reduced somewhat by removing the roots from the test plants. The compound was also shown to inhibit germination and root growth of tomato seedlings.

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