Document Type


Date of Award


Degree Name

Master of Science in Chemical Engineering - (M.S.)


Chemical Engineering and Chemistry

First Advisor

Howard David Perlmutter

Second Advisor

William H. Snyder

Third Advisor

Richard B. Trattner


β,γ-Dideuteriopropylbenzene was obtained in 84% yield from deuteration of allylbenzene. Nitration of this compound resulted in o-nitro (β,γ-dideuteriopropyl)-benzene. Reduction of this compound gave o-(β,γ-aideuterio-propyl)aniline. o-(β,γ-Dideuteriopropyl)phenyl azide was prepared by dizotization of the aniline compound, followed by treatment with sodium azide.

Decomposition of the azide in isooctane solution by photolysis at room temperature gave no trace of deuterio-2-methylindoline (intramolecular insertion product).

Photolysis of the azide at the reflux temperature of the solvent (99?C) resulted in the formation of deuterated-2-methylindoline as the major product (40%) yield. The reaction is presumed to proceed through an aryl nitrene intermediate. Analysis of the nuclear magnetic resonance spectrum of this compound indicates that the nitrene shows no preference for insertion into the C-H bond versus the C-D bond (i.e. no kinetic isotope effect) (kH/kD = 1).

When the elevated temperature photolysis is carried out in the presence of a triplet photosensitizer (xanthen-9-one) the yield of 2-methylindoline is dramatically decreased.

Based on these results, arguments are presented which suggest that intramolecular C-H insertion reactions of an aryl nitrene proceeds via the intermediacy of a singlet rather than a triplet aryl nitrene.



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