氯化铜参与的制备对称二硫化合物的新方法.pdf

第21卷第5期
化学研究
中国科技核心期刊
2010年9月
CHEMICAL RESEARCH
hxy@henu.edu.cn
A New Approach to the Synthesis of Symmetrical Disulfides
Using Copper Chloride
TIAN Xin-yong, LI Chun-li, WANG Zhi-hua, WU Wei, WANG Hua
( Key Lab for Stecial Functional Materials of Ministry of Education, Henan University, Kaifeng 475004, Henan, China
Abstract: A new and efficient procedure for the oxidation of thiols to generate symmetrical di
sulfides in presence of r Buli/ copper chloride is described. Total ten samples are employed in
good to excellent yields.
eywords: copper chloride; oxidation thiols; symmetrical disulfides
CLC number: O 625
Document code
Article ID:10081011(2010)05-0025--05
氯化铜参与的制备对称二硫化合物的新方法
田新勇,李春丽,王治华,吴伟,王华
(河南大学教育部特种功能材料重点实验室,河南开封475004)
摘要:报道了在正丁基锂和氯化铜条件下氧化硫醇生成对称的二硫化合物的新方法.所实施的十个例子都具
有很高的产率
关键词:氯化铜;氬化;硫醇;对称二硫化合物
Disulfides have attracted considerable interest because of their importance in biochemistry as well as in
synthetic chemistry 3). With thiols as the precursors, the oxidation processes for making disulfides have
been extensively investigated for many years. The oxidation reagents such as cetyltrimethylammonium di-
chromate*, 2, 6-dicarboxy-pyridinium chlorochromate], 1, 3-dibromo-5, 5-dimethyl-hydantoinl6l, bis
muth (Il )nitrate pentahydrate], molybdate sulfuric acid (MSA)[], air with manganese(IT) Schiff base
complex, potassium fluoride supported on alumina],2-polyvinylpyridine/bromine complex, hydro
gen peroxide 12, iodine, CECL7H2 O in graphite and Cu(N 3H,11 have been utilized for oxi
dation of thiols to disulfides. In addition, Kim reported the synthesis of alkyl polysulfides by treatment of
thiols, disulfides, and thionitrites with anhydrous copper(I chloride 5], but the yields of the target di
sulfides were poor in many cases, In our work, we have found that copper chloride could be used for effi-
cient oxidative coupling of thiol anions to form disulfides with high yields
Copper chloride is a cheap, commercially available reagent. The formation of C-C bond Cucl2-pro-
moted has been studied widely for oxidative coupling". We found the first example of S-S coupling pro
ed by Cucl2 in our previous work in the formation of the derivative of thienosilole(12]. Our continuing
interest is in the new method of formation of S-S bond promoted by Cucl2 In this paper, the efficient
synthesis of symmetrical disulfides with thiols as raw materials in presence of -Buli/Cucl, is described
Received date: 2010-07-06
Foundation item: T his research was supported by the NSFC (20972041, 20672028), Program for Innovation Scientists and Technicians
Troop Construction Projects of Henan Province (104100510011), Program for NCET-05-0610 and SRF for ROCS-SEM
Biography: TIAN Xin-yong( 1985-), male, research field: organic synthesis. "Corresponding author