Hydrophobic vitamin B12.: Part 19:: Electroorganic reaction of DDT mediated by hydrophobic vitamin B12
Hydrophobic vitamin B12.: Part 19:: Electroorganic reaction of DDT mediated by hydrophobic vitamin B12
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DOI：
10.1039/b315170k
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发表时间：
2004-01-01
影响因子：
4
通讯作者：
Hisaeda, Y
中科院分区：
文献类型：
--
作者：
Shimakoshi, H;Tokunaga, M;Hisaeda, Y
1，1-二(4-氯苯基)-2，2，2-三氯乙烷(DDT)在疏水性维生素B-12高氯酸七甲酯存在下，在-1.4V与Ag-AgCl的电压下进行了控制电位电解。将滴滴涕脱氯生成1，1-双(4-氯苯基)-2，2-二氯乙烷、1，1-二(4-氯苯基)-2，2-二氯乙烯、1-氯-2，2-双(4-氯苯基)乙烯和1，1，4，4-tetrakis(4-chlorophenyl)-2，3-dichloro-2-butene(TTDB)(E/Z)，并用电子能谱确定了催化剂的定量回收。用电子能谱对电解过程中形成的钴-碳键的光敏中间体进行了表征。用重水溶剂和UV-Vis、EPR自旋捕获等光谱技术研究了各种脱氯产物的形成机理。
The controlled-potential electrolysis of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) was carried out at -1.4 V vs. Ag-AgCl in the presence of a hydrophobic vitamin B-12, heptamethyl cobyrinate perchlorate. DDT was dechlorinated to form 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloro-ethylene (DDE), 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU) and 1,1,4,4-tetrakis(4-chlorophenyl)-2,3-dichloro-2-butene (TTDB) (E/Z), and quantitative recovery of the catalyst after the electrolysis was confirmed by electronic spectroscopy. A photo-sensitive intermediate having a cobalt-carbon bond formed during the electrolysis was characterized by electronic spectroscopy. A mechanism for the formation of various dechlorinated products was investigated by using deuterium solvents and various spectroscopic measurements such as UV-VIS and the EPR spin-trapping technique.