Spangler, Charles W.||Russell, Morley||Kevill, Dennis N.
M.S. (Master of Science)
Department of Chemistry
The nitration of 1,3,5-hexatriene with various nitrating agents was studied in detail in order to elucidate polyene substitution processes. Nitronium tetrafluoroborate in aprotic solvents, cupric nitrate trihydrate in acetic anhydride, and concentrated nitric acid in a mixture of acetic acid-acetic anhydride were utilized as nitrating media. The initial purpose of this work was to investigate the nature of the product in terms of infrared assignments, NMR analysis, and catalytic reduction behavior of the "nitrohexatriene" mixture to determine if a substitution process was, indeed, involved. Also, the nature of any substitution was to be interpreted on the basis of Huckel molecular orbital calculations, the frontier electron method, and the role of possible intermediates involved in the proposed mechanism. Conclusive evidence was obtained when catalytic reduction of the "nitrohexatriene" mixture yielded an aminohexane, which when compared to that of a calibrated mixture of the possible aminohexanes, identified the reduction product as 3-aminohexane. Nitration of 1,3,5-hexatriene with acetyl nitrate yielded 3- nitro-1,3,5-hexatriene, whereas nitronium tetrafluoroborate and cupric nitrate trihydrate yielded only polymer. Thus, the reaction of acetyl nitrate with 1,3,5-hexatriene, the only reported example of triene substitution, represents an exception to recent predictions derived from molecular-orbital theory as to the nature of linear polyene electrophilic substitution.
Hennis, Ronald P., "Nitration of 1,3,5-hexatriene" (1969). Graduate Research Theses & Dissertations. 4122.
vi, 41 pages
Northern Illinois University
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