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PHOTOLYSIS OF 1-(4-AZIDOMETHYL-PHENYL)-ETHANONE AND MATRIX/LFP STUDIES OF 2-BENZOYL-3-METHYL-2H-AZIRINE

by KELLER, CHRISTOPHER

Abstract (Summary)
The photolysis of 1-(4-Azidomethyl-phenyl)-ethanone with wavelengths greater than 300 nm yielded two products: a minor product 4-acetyl-benzaldehyde, and a major product 1-{4[5-(4-Acetyl-phenyl)-[1,2,4]oxadiazol-3-yl]-phenyl}-ethanone. The formation of the aldehyde can be attributed to a variety of possible mechanistic pathways. The formation of the oxydiazol product can be attributed to the reaction of a triplet alkyl nitrene with an adduct resulting from the photooxidation of the azide. Laser flash studies of 1-(4-azidomethyl-phenyl)-ethanone demonstrate the formation of a triplet ketone, which then decays via a transfer of energy to produce a triplet alkyl nitrene. Time-dependent Gaussian studies using DFT-B3LYP-631* level of theory support the formation of a triplet alkyl nitrene intermediate. Low temperature isolation matrix studies of 2-Benzoyl-3-methyl-2H-azirine produced a ketene imine product that was confirmed via IR stretches, which were also supported by the use of Gaussian IR frequency studies. The production of the ketene imine is generated by the production of the triplet vinyl nitrene intermediate. Transcient UV spectra, when in argon, demonstrate a sharp absorbance detected in the region of 340-430 nm. The transcient UV spectrum of 2-Benzoyl-3-methyl-2H-azirine in the presence of O2 shows a significant decrease in absorbance intensity and in lifetime, indicating a mixture of excited species. A kinetic trace at 420 nm shows a short-lived (400 ns) intermediate suspected to be a vinyl triplet nitrene. TD-DFT calculations support the formation of a triplet alkyl nitrene.
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School:University of Cincinnati

School Location:USA - Ohio

Source Type:Master's Thesis

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ISBN:

Date of Publication:01/01/2005

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