Date of Award:


Document Type:


Degree Name:

Master of Science (MS)


Chemistry and Biochemistry


Richard K. Olsen


The reaction of dimethylcopper lithium and di-n-butylcopper lithium with 3-bromo-2-(2-phenylacetamido) acrylic acid, mp 174 - 175°, produced as major products 3-methyl-2-(2-phenylacetamido) acrylic acid and 3-n-butyl-2-(2-phenylacetamido) acrylic acid, respectively. The dimethylcopper lithium reaction was stereospecific for the E geometrical isomer, mp 198 - 199°, and produced 3-methyl-2-(2-phenylacetamido) acrylic acid and 2-(2-phenylacetamido) acrylic acid in a 3:1 molar ratio, respectively. The di-n-butylcopper lithium reaction produced as the main products 3-n-butyl-2-(2-phenylacetamido) acrylic acid and 2-(2- phenylacetamido) acrylic acid in a 7:1 molar ratio, respectively, with the 3-n-butylacrylic acid comprising 83% of the product. The reaction produced the E isomer, mp 205 - 206°, and the Z isomer, mp 164 - 165°, in the approximate ratio of 2:1, respectively. The configuration of the products of both reactions was determined by the comparison of the nuclear magnetic resonance spectra with spectra of model compounds of known configuration.

Nuclear magnetic resonance evidence relating to the stereochemistry of 3-bromo-2-(2-phenylacetamido) acrylic acid based on the single isomers of this acid and the corresponding methyl ester reported in the literature was inconclusive. In order that a comparison of the properties of both isomers could be made, an attempt was made to prepare the uncommon isomer of methyl 3-bromo-2-(2-phenylacetamido) acrylate from (a) the common isomer by hydrobromination-dehydrobromination with triethylamine and (b) from methyl 2-(2-phenylacetamido) acrylate by bromination-dehydrobromination with triethylamine. Both attempts were unsuccessful.



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