Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

作者：Correra Thiago C; Riveros Jose M^*

来源：Journal of Physical Chemistry A, 2010, 114(44): 11910-11919.

DOI：10.1021/jp107500s

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH- and F- with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO3- is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH- at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (OH-)-O-18 showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH2- and SH- to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

• 出版日期2010-11-11