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Thesis (M.S.)—University of Nebraska—Lincoln, 1959. Department of Chemistry.


Copyright 1959, the author. Used by permission.


Diphenyl N-cyclohexyl-, diphenyl N-(2-ethylhexyl)-, diphenyl N-hexyl-, and diphenyl N-decylphosphoramidates were prepared by reaction of the corresponding amine with diphenyl phosphoryl chloride with cyclohexylamine in carbon tetrachloride. An additional preparation of diphenyl N-decylphosphoramidate was made by reaction of diphenyl phosphoryl chloride with Cyclohexylamine in carbon tetrachloride.The experimental details and results are presented with an analysis of the infrared spectra of the compounds prepared. Pyrolysis of the prepared diphenyl N-alkylphosphoramidates gave the expected olefin and primary and/or secondary amine with little indication of formation of a tertiary amine. Identification of the olefins obtained was made by gas chromatography.The hexene isomers formed were identified by available techniques and were compared to hexenes formed from dehydration of n-hexyl alcohol with sulfuric acid.It was found that more rearranged olefins were formed than terminal olefins in the pyrolysis and no parallel could be drawn between the ratio of fraction isomerized and temperature of pyrolysis. Mechanisms involving an ionic intermediate are suggested for the formation of the many olefinic isomers during the pyrolysis reaction.It is believed this mechanism proceeds through a carbonium ion, thus explaining the rearrangement of the olefin.Due to the rearranged products formed during the course of the reaction, it is concluded that although olefin yields were high, this reaction would not be of value for the preparation of pure olefins, except in a few instances, such as preparation of cyclohexene.

Advisor: H. E. Baumgarten