Photochemical Processes due to n-π* and π-π* Transitions of 3-Picoline N-Oxide in the Vapor Phase

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Abstract
Gaseous photolysis of 3-picoline N-oxide was attempted by irradiation with the 3261Å (Cd 3P1) or 2537Å (Hg 3P1 resonance line corresponding to an n-π* or a π-π* absorption region, respectively, of this substance. In either case, the photolytic products were mainly 3-picoline, and we observed a remarkable temperature-dependence for the quantum yield of 3-picoline in the case of 3261Å irradiation but not in the case of 2537Å irradiation. This observation suggests that an activation energy would be required for the production of 3-picoline at 3261Å only. The activation energy estimated from the relation between the quantum yield of produced 3-picoline and the temperature at 3261Å irradiation was about 11.5 kcal. mol−1, which is almost about the same value as that of pyridine N-oxide. The reactions succeeding to an n-π* or a π-π* transition of 3-picoline N-oxide were considered to be similar to the case of pyridine N-oxide.

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