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Nitration of alkenes and conjugated dienes using lithium nitrate / trifluoroacetic anhydride
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Nitration of alkenes and conjugated dienes using lithium nitrate / trifluoroacetic anhydride

Stephanie Anne Costa
Master of Science (M.S.), Drexel University
Jun 2016
DOI:
https://doi.org/10.17918/etd-6841
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Abstract

Chemistry Nitrates Alkenes
Nitration of 2-methyl-2-butene in propionitrile using lithium nitrate and trifluoroacetic anhydride yielded N-(2-methyl-3-nitro-2-butyl) propionamide, in 60% yield. The product was purified using column chromatography. Nitration of cyclohexadiene in acetonitrile was unsuccessful as a mixture of indiscernible structures was obtained after attempted chromatographic separation. Nitration of 2,3-dimethyl-1,3-butadiene in acetonitrile yielded the 1,2-product, (N-(2,3- dimethyl-1-nitrobut-3-en-2-yl)acetamide), and the 1,4- product, ((E)-N-(2,3- dimethyl-4-nitrobut-2-enyl)acetamide), in low yields. Due to differences in polarity between the two products, different solvent systems were utilized. A previously unreported (Z)-isomer of the N-(2,3-dimethyl-4-nitrobut-2-enyl)acetamide was observed in the spectra of the purified N-(2,3-dimethyl-1-nitrobut-3-en-2- yl)acetamide. TLC band cutting led to successfully obtaining clean spectra of N-(2,3- dimethyl-1-nitrobut-3-en-2-yl)acetamide, which exhibited previously unreported fine structure and long-range coupling. The spectra of N-(2,3-dimethyl-1-nitrobut-3- en-2-yl)acetamide and (E)-N-(2,3-dimethyl-4-nitrobut-2-enyl)acetamide compared favorably with the literature. A solid side product, hypothesized to be a trifluoroacetate ester, was isolated during column chromatography but not identified.

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