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Reaction of atomic oxygen with alkanes. Regioselective alcohol formation on. gamma. -radiolysis of liquid carbon dioxide solutions of alkanes

Journal Article · · J. Org. Chem.; (United States)
DOI:https://doi.org/10.1021/jo00433a026· OSTI ID:7312620

Gamma-radiolysis of liquid carbon dioxide in the presence of cyclohexane, methylcyclohexane, and cis- or trans-decalin has been studied at 0/sup 0/C. The main products were corresponding alcohols and carbonyl compounds. The oxidizing species from carbon dioxide apparently shows selective attack on C--H bonds of alkane in the order tertiary greater than secondary greater than primary. The observed tendency could be rationalized in terms of the reaction of ground state triplet oxygen atoms, O(/sup 3/P), with alkane in liquid carbon dioxide. In the case of cis- and trans-decalin, highly configurational retention of decalol-9 was observed. The formation of a dimer of alkane was negligibly small. The rapid recombination of radical pairs initially formed by the reaction of O(/sup 3/P) atoms with alkane in a solvent cage is proposed. In addition, the production of cyclohexanone from cyclohexanol is described.

Research Organization:
Osaka Univ., Suita, Japan
OSTI ID:
7312620
Journal Information:
J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 42:13; ISSN JOCEA
Country of Publication:
United States
Language:
English