The two-step photodissociation mechanism of 1,3-cyclohexane dinitrite is confirmed by observation of the laser-induced fluorescence spectrum of the intermediate 3-nitrosooxy cyclohexoxy radical.
Alkyl dinitrites have attracted attention as an important type of nitrosating agent and a pollution source in atmosphere. The reactivity and chemistry of alkyl dinitrites induced by the two ONO functional groups are relatively unknown. In this work, decompositions of 1,3- cyclohexane dinitrite and 1,4-cyclohexane dinitrite are studied by electron impact ionization mass spectroscopy (EI-MS). Apart from NO+ (m/z=30), fragment ions m/z=43 and 71 are the most abundant for the 1,3-isomer. On the other hand, fragments m/z=29, 57, 85, and 97 stand out in the EI-MS spectrum of 1,4-isomer. Possible dissociation mechanisms of the two dinitrites are proposed by theoretical calculations. The results reveal that the ring-opening of 1,3-cyclohexane dinitrite mainly starts from the intermediate ion (M-NO)+ by cleavage of two αC-βC bonds. For 1,4-cyclohexane dinitrite, in addition to the decomposition via intermediate (M-NO)+, cleavage of βC-βC bonds can occur directly from the parent cation M+. The results will help to understand the structural related chemistry of alkyl dinitrites in atmosphere and in NO transfer process.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.