Röper H, Heyns K
IARC Sci Publ (1971). 1976(14):27-40.
Nitrosamines (R1R2NO) containing a certain R groups yield mass spectra with M+-OH fragments which can be accounted for by intramolecular hydrogen shift with subsequent cleavage of OH-radicals. As can be shown with mass spectra of specifically deuterated derivatives of nitrosobenzylmethylamine - nitrosobenzyltrideuteriomethylamine, alpha,alpha-nitrosodideuteriobenzylmethylamine and o,o',p-nitrosotrideuteri0-benzylmethylamine - hydrogen transfer within the molecular ion of nitrosobenzylmethylamine occurs selectively onto the oxygen of the nitroso group from the benzylethylene group, probably via a five-membered cyclic transition state. Cleavage of OH radicals leads to formation of M+-17 ions, the stability of which can be explained by mesomerically stabilized cyclic diazirinium ions.
含有特定R基团的亚硝胺（R1R2NO）产生的质谱图中，M+-OH碎片可以通过分子内氢转移以及随后OH自由基的裂解来解释。正如亚硝基苄基甲胺的特定氘代衍生物——亚硝基苄基三氘代甲胺、α,α-亚硝基二氘代苄基甲胺和邻,邻',对-亚硝基三氘代苄基甲胺的质谱图所示，亚硝基苄基甲胺分子离子内的氢转移选择性地从苄基乙烯基转移到亚硝基的氧上，可能是通过五元环状过渡态。OH自由基的裂解导致形成M+-17离子，其稳定性可以通过中介稳定的环状二氮烯鎓离子来解释。
