Lay J O, Evans F E, Hinson J A
Biomed Environ Mass Spectrom. 1986 Sep;13(9):495-502. doi: 10.1002/bms.1200130908.
A number of compounds associated with dichloroaniline-based herbicides were examined by high resolution mass spectrometry and high-field nuclear magnetic resonance spectroscopy. These compounds included the herbicide propanil (N-propionyl-3,4-dichloroaniline) and the related compound N-acetyl-3,4-dichloroaniline. Several possible oxidative metabolic products, including N-hydroxy-3,4-dichloroaniline, nitroso-3,4-dichlorobenzene, N-hydroxy-N-propionyl-3,4-dichloroaniline and N-hydroxy-N-acetyl-3,4-dichloroaniline were also investigated. Mass spectral fragmentation schemes were proposed, based on exact mass measurements for fragment ions from these related compounds. The change in fragmentation behavior upon oxidation of the N-acyl compounds to N-hydroxy-N-acyl derivatives was found to be quite significant. The N-hydroxy-substituted compounds showed extensive fragmentation while the analogous non-hydroxylated compounds and nitroso-3,4-dichlorobenzene showed little fragmentation. Line broadening detected in several of the high-field nuclear magnetic resonance spectra was attributed to cis-trans isomerization. The highly toxic 3,3',4,4'-tetrachloroazobenzene and 3,3',4,4'-tetrachloroazoxybenzene were also examined by high resolution mass spectrometry.
采用高分辨率质谱法和高场核磁共振光谱法对多种与二氯苯胺基除草剂相关的化合物进行了检测。这些化合物包括除草剂敌稗（N-丙酰基-3,4-二氯苯胺）和相关化合物N-乙酰基-3,4-二氯苯胺。还研究了几种可能的氧化代谢产物，包括N-羟基-3,4-二氯苯胺、亚硝基-3,4-二氯苯、N-羟基-N-丙酰基-3,4-二氯苯胺和N-羟基-N-乙酰基-3,4-二氯苯胺。基于这些相关化合物碎片离子的精确质量测量结果，提出了质谱裂解方案。发现N-酰基化合物氧化为N-羟基-N-酰基衍生物时裂解行为的变化非常显著。N-羟基取代的化合物显示出广泛的裂解，而类似的非羟基化化合物和亚硝基-3,4-二氯苯几乎没有裂解。在几个高场核磁共振光谱中检测到的谱线展宽归因于顺反异构化。还采用高分辨率质谱法对剧毒的3,3',4,4'-四氯偶氮苯和3,3',4,4'-四氯氧化偶氮苯进行了检测。
