Photolyses of N-nitrosamides in acidic and neutral media.

Peer reviewed: 
No, item is not peer reviewed.
Date created: 
1967
Abstract: 

Photolyses of several N-nitrosamides in acidic and neutral media were studied. The photochemical decomposition of II-nitrosanides was found to involve exclusively nitrogen-nitrogen bond cleavage of the IT-nitrosamide group in contrast to the pyrolytic decomposition which involved cleavage of the acyl nitrogen bond. In acidic media, photolyses of rl-nitrosamides led to the light catalyzed denitrosation of the N-nitrosamides by photo-elimination of the [WOH] group with the formation of alkylidenimides. The alkylidenimides underwent secondary reactions to give the corresponding aldehydes. The photo-elimination products were identified as the 2 ,4-dinitrophenyl-hydrazones of the aldehydes. In neutral media, the primary photolytic process of H-nitrosa.nides was the .formation of nitroso and amide radicals. The amide radical v/as found to abstract intramolecularly a $ hydrogen atom attached to the carbon atom in the S-position^ to give a S-carbon radical. This S-carbon radical then coupled with the nitroso radical to give a C-nitroso compound which either tautomerized to form oxime or dimerized. Alternatively the amide radical underwent elimination of an alpha hydrogen to give the alkylidenimide as an intermediate. if The S-position was numbered in reference to the nitrogen atom of the amide group. For examole , the for vula of & -nitroso-n-hexylformamide would be N=0 0 Ill

Description: 

Thesis (M.Sc.) - Dept. of Chemistry- Simon Fraser University

Language: 
English
Document type: 
Thesis
Rights: 
Copyright remains with the author
File(s): 
Subject headings: 
Photochemistry.
Senior supervisor: 
Name is illegible
Department: 
Science: Chemistry Department
Thesis type: 
(Thesis) M.Sc.
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