Photochemistry of Pivalaldehyde in Solution Studied by CIDNP

The n.m.r. spectrum observed during irradiation of pivalaldehyde dissolved in perfluoromethylcyclohexane indicates the formation of several compounds whose hydrogens are spin polarized. These compounds are 2-methylpropane, 2-methylpropene, and pivalaldehyde. A mechanism involving radical reactions w...

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Bibliographic Details
Published in:Canadian journal of chemistry 1973-09, Vol.51 (18), p.3032-3038
Main Authors: Chen, Holger E. C, Groen, Arend, Cocivera, Michael
Format: Article
Language:English
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Summary:The n.m.r. spectrum observed during irradiation of pivalaldehyde dissolved in perfluoromethylcyclohexane indicates the formation of several compounds whose hydrogens are spin polarized. These compounds are 2-methylpropane, 2-methylpropene, and pivalaldehyde. A mechanism involving radical reactions which is consistent with these results is presented. According to this mechanism, the primary photochemical step is cleavage of the bond between the carbonyl carbon and the tertiary carbon of the t-butyl group. In contrast, this step does not appear to be important for acetaldehyde. As a test of the proposed mechanism CCl 4 is added to trap free radicals. In this case, one of the products is CCl 3 COH. A mechanism for the formation of this and the other products having nuclear spin polarization is presented.
ISSN:0008-4042
1480-3291
DOI:10.1139/v73-452