Rainey W T, Christie W H, Lijinsky W
Biomed Mass Spectrom. 1978 Jun;5(6):395-408. doi: 10.1002/bms.1200050606.
The preparation of a series of N-nitrosamines for carcinogenicity studies presented an opportunity to study mass spectral fragmentation schemes in detail. Condensed spectra are listed for 146 N-nitrosamines of widely differing structures, including nitroso derivatives of commercial drugs and insecticides. Aliphatic nitrosamines were generally characterized by molecular ions and loss of OH. Subsequent fragmentation via alpha-cleavage is similar to that of aliphatic amines. The loss of OH is believed to result in a cyclic ion. Subsituted aliphatic nitrosamines varied in fragmentation schemes with structure and position of the substitutent groups. However, most showed alpha-cleavage at some point in fragmentation. When substituted with aromatic groups prominent peaks due to the aromatic moiety were observed. The alicyclic nitrosamines showed losses of NO, NOH and OH and subsequent alpha-cleavages. Nitrosamides were characterized by rupture of the carbonyl to nitrogen bond. Spectra of substituted ureas usually showed charge retention by the carbonyl fragment, while carbamate esters showed ions from both fragments.
制备一系列用于致癌性研究的N-亚硝胺为详细研究质谱碎裂模式提供了契机。列出了146种结构差异很大的N-亚硝胺的缩合光谱，包括商业药物和杀虫剂的亚硝基衍生物。脂肪族亚硝胺的特征通常是分子离子和OH的丢失。随后通过α-裂解的碎裂与脂肪族胺相似。OH的丢失被认为会产生一个环状离子。取代脂肪族亚硝胺的碎裂模式因取代基的结构和位置而异。然而，大多数在碎裂的某个阶段显示出α-裂解。当被芳基取代时，会观察到由于芳基部分产生的突出峰。脂环族亚硝胺显示出NO、NOH和OH的丢失以及随后的α-裂解。亚硝酰胺的特征是羰基与氮键的断裂。取代脲的光谱通常显示羰基片段保留电荷，而氨基甲酸酯则显示来自两个片段的离子。
