Hydrolysis, Nitrosyl Exchange, and Synthesis of Alkyl Nitrites

Article abstract of DOI:10.1021/jo00168a002

Alkyl nitrites undergo relatively slow hydrolysis in phosphate-buffered aqueous media under neutral conditions with small but significant dependence of reactivity on structure.However, rapid nitrosyl exchange with alcohols is observed, and equilibrium constants for this transformation exhibit remarkable correlation with equilibrium constants for nitrosyl exchange of alcohols with nitrosyl chloride and with nitrous acid. tert-Butyl nitrite has the greatest driving force for nitrosyl transfer among the 12 alkyl nitrites examined, and this capability is used for the synthesis of alkyl nitrites derived from steroidal alcohols and of alkyl thionitrites.