I. The Hydration of Crotonaldehyde. II. The Coordination of Silver Ion With Unsaturated Molecules. III. Stereochemical Relationships in the Conversion of Acetates to Bromides

Citation

Winstein, Saul (1938) I. The Hydration of Crotonaldehyde. II. The Coordination of Silver Ion With Unsaturated Molecules. III. Stereochemical Relationships in the Conversion of Acetates to Bromides. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/310Z-S824. https://resolver.caltech.edu/CaltechETD:etd-04092004-093654

Abstract

I. The hydration of crotoaldehyde and the dehydration of aIdol in dilute aqueous solutions of acids are first order with respect to the organic compound and to the acid. Energies of activaton for hydration and dehydration are 18.23 and 24.48 kcal., respectively. Equilibrium is reached when 47% of the crotonaldehyde has been converted to aldol at 25° and 39% at 35°.

II. Complex formation between silver ion and a variety of unsaturated molecules in aqueous solution has been studied and equilibrium constants for the reactions of formation of several kinds of complex ions have been determined. A structure is proposed for the olefin-siver ion complex, and trends in equilibrium constants are explained in terms of steric and resonance effects.

III. The occurance of an odd number of inversions in the transformation of 2,3-diacetoxybutane to 2,3-dibrombutane has been confirmed. 1,2-Diacetoxycyclohexane fails to give 1,2-dibromcyclohexane on treatment with aqueous fuming hydrobromic acid. 2-Acetoxyoctane on treatment with fuming hydrobromic acid gives a bromide of preponderantly inverted configuration, but the retention of optical purity is only 67%.

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