I. Derivatives of Spiro (3,3) Heptanetetra Carboxylic Acid. II. Attempted New Synthesis of Cis-2 Butene-1, 4-Diol

Author: Monroe, Emmett Paul

Year: 1949

Degree: Master's thesis

Advisor: Buchman, Edwin Raphael

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/VB67-1R54

Abstract

I. DERIVATIVES OF SPIRO(3,3) HEPTANETETRACARBOXYLIC ACID:

The isolation of the isoamyl ester of spiroheptanetetra-carboxylic acid, prepared by the condensation of sodiomalonic ester with pentaerythrityl tetrabromide in isoamyl alcohol is reported. The synthetic method is that of Fecht as modified by Backer and Schurink. Pentaerythrityl benzenesulfonate is substituted for the bromide in the reaction with the malonic ester, but the yield is found to be much poorer. Attempts to prepare the ethyl ester of spiroheptanetetracarboxylic acid by using pentaerythrityl benzenesulfonate in ethyl alcohol solvent, and pentaerythrityl bromide in excess malonate and xylene solvents are described. These experiments did not produce a practical synthesis of the ethyl ester.

The unsuccessful attempt to reduce the isoamyl ester of spiroheptanetetracarboxylic acid with lithium aluminum hydride is described.

II. ATTEMPTED NEW SYNTHESIS OF CIS-2-BUTENE-,4-DIOL:

A synthesis of cis-2-butene-1,4-diol by the reduction of maleic anhydride with lithium aluminum hydride is attempted. Two experiments are described, one of which employs an aqueous system in the isolation of the product, the other a non-aqueous system. No amount of any consequence of the diol was obtained. A discussion of lithium aluminum hydride as a reducing agent is included.

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