I. The Synthesis of Spiro(3,5)Nonane. II. The Presumed Synthesis of 1,3-Cyclobutanedicarboxylic Acid by Markownikoff and Krestownikoff. III. The Synthesis of Cis and Trans-1,3-Cyclobutanedicarboxylic Acids

Citation

Deutsch, Daniel Harold (1951) I. The Synthesis of Spiro(3,5)Nonane. II. The Presumed Synthesis of 1,3-Cyclobutanedicarboxylic Acid by Markownikoff and Krestownikoff. III. The Synthesis of Cis and Trans-1,3-Cyclobutanedicarboxylic Acids. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/K23E-7793. https://resolver.caltech.edu/CaltechTHESIS:10122017-111506286

Abstract

Spiro(3,5)nonane was prepared by methods indicative of structure.

The historically The historically important acid reported in 1881 by Markownikoff and Krestownikoff and assigned the structure 1,3-cyclobutanedicarboxylic acid (a structure which has never subsequently been questioned) was shown to be 1-methyl- 1,2-cyclopropanedicarboxylic acid. The mechanism of the for­mation of the Markownikoff-Krestownikoff acid is discussed.

The previously unknown cis- and trans-1,3-cyclobutane­- dicarboxylic acids were synthesized. After numerous unsuc­cessful attempts the synthesis was achieved starting from pentaerythritol. The reaction between the benzylidene der­ivative of 2,2-bis(bromomethyl)-1,3-propandiol and sodium malonic ester gave a condensation product which after hydrolysis and oxidation with nitric acid yielded 1,1,3,3-cyclobutanetetracarboxylic acid. On decarboxylation of the latter, the desired acids were obtained.

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