Octyl nitrite photolysis

The photolysis of 1-octyl nitrite 6 yields 4-nitroso-l-octanol 8 in 45% yield, via cyclic transition state 7—the formation of regioisomeric nitroso alcohols is not observed ... 

The involvement of an intramolecular hydrogen abstraction in the Barton reaction is not necessarily limited to those molecules with rigid stereochemistry. In fact, simple aliphatic nitrites undergo the Barton reaction with equal ease. Thus, the principal product obtained from the photolysis of ra-octyl nitrite20 in benzene solution is the dimer of 4-nitroso-l-octanol however, photolysis of n-octyl nitrite in n-heptane20 produced a mixture of 7/-nitroso heptanes in addition to 4-nitroso-l-octanol in the ratio l 4.5,f respectively. The formation of y-nitroso heptane obviously results from an attack of the intermediate alkoxy radical on the solvent molecule. The intermediate alkyl radical then collapses, according to eq. 2. For the sake of convenience we have indi-... 

The photolysis of n-octyl nitrite in n-heptane provides a favorable situation for comparing the tendency of an alkoxyl radical to undergo the Barton-type intramolecular reaction or, alternatively, the intermolecular reaction as indicated in eqs. 1 and 2. Calculations23 reveal that both intramolecular and intermolecular hydrogen abstraction involving a second-... 

Nitrate esters can also be made by the oxidation of nitrite esters (Vol. I, p.2). This reaction can also be carried out through a photolysis of nitrite esters. Such is, for example, the photolysis of octyl nitrite in heptane saturated with oxygen of the probable mechanism as below [47, 48] ... 

For an early study, see Xanaka, M., Xanaka J., and Nagakura, S., Xhe electronic structures and electronic spectra of some aliphatic nitroso compounds. Bull. Chem. Soc. Jpn., 39, 766, 1966. Kabasakalian, P. and Xownley, E.R., Photolysis of nitrite esters in solution. 1. Photochemistry of n-octyl nitrite,/. Am. Chem. Soc., 84, 2711, 1962. 

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