【摘要】 用气相色谱-质谱法,发现河南林县酸菜中存在一种以甲硫基为桥、亚硝基配位的含铁化合物:Roussin红甲酯(二-μ-甲硫基-四亚硝基-二铁)。结构测定用单离子检测、低分辨质谱和峰匹配等方法。最后,与合成Roussin红甲酯的低分辨质谱进行比较,进一步证实了它的结构。本文还通过对亚稳离子的测定,提出并讨论了Roussin红甲酯在电子轰击下的碎裂机理。更多还原

【Abstract】 In the study of the aetiological factors of esophageal cancer in Linxian County of North China, a pure compound was isolated from some kind of pickled vegetable and identified as Roussin red methyl ester (di-μ-methanethiolate-tetranitrosodiiron). The chemical structure of the compound is as follows:Since Roussin first synthesized Roussin’s red and Roussin’s black salts in 1858, compounds of this kind of structure in which both NO groups and sulfur atoms are coordinated to a transition metal have aroused great interest in structural chemistry. But identification of this type of compounds in nature has not yet been reported in literature so far. Recently, it was also found that the structure of the active centers in proteins containing iron-sulfur cluster bears a certain resemblance to the cyclic structure of Roussin’s red. The discovery of this compound in pickled vegetable might be of some significance in the study on its possible association with proteins containing iron-sulfur cluster,its mechanism of formation and its biological activities in plants.It was shown that Roussin red methyl ester reacted readily with secondary amines to form nitrosoamines. It was also found that the pickled vegetable in Linxian County contains a certain kind of mutagenic substance. Investigation on the carcinogenic property of Roussin red methyl ester is now being carried out.GC/MS, mono-ion detection and peak matching techniques were used for the identification of this compound. As there was significant difference between the low resolution mass spectrum obtained for the isolated compound and that of Roussin red methyl ester reported in literature, the accurate masses of ten intensive peaks were measured and the corresponding elementary compositions calculated. The data obtained agree nicely with that of Roussin red methyl ester.Roussin red methyl ester was also synthesized and its IR, NMR and MS were taken. The data of IR and NMR, and the coincidence between the mass spectra of the synthetic product and the isolated compound show that the identification of the latter is reliable.The fragmentation pathway of the compound has been worked out using the high resolution MS data and the information from metastable scans.更多还原