间氯过氧化苯甲酸可控性氧化2-巯基萘醌类化合物的合成与鉴定  

Synthesis and Identification of 2-Thio Naphthoquinones by Controlled Oxidation of m-chloroperoxybenzoic Acid

作　　者：申贵男 郝莹莹 张雷 曹立明 韩英浩[1] 王伟东[1] 李婧[1] 金成浩[1] Shen Guinan;Hao Yingying;Zhang Lei;Cao Liming;Han Yinghao;Wang Weidong;Li Jing;Jin Chenghao(College of Life Science and Technology,Heilongjiang Bayi Agricultural University,Daqing 1633192.College of Animal Science and Technology,Heilongjiang Bayi Agricultural University)

机构地区：[1]黑龙江八一农垦大学生命科学技术学院,大庆163319 [2]黑龙江八一农垦大学动物科技学院

出　　处：《黑龙江八一农垦大学学报》2020年第2期68-73,90,共7页journal of heilongjiang bayi agricultural university

基　　金：黑龙江省自然科学基金项目(QC2015121);黑龙江省大学生创新训练项目(201910223027);黑龙江省海外学人科研资助项目(1253HQ008);黑龙江省普通本科高校青年创新人才培养计划(CXRC2017016)。

摘　　要：间氯过氧化苯甲酸(meta-Chloroperoxybenzoic acid,mCPBA)是一种良好的氧化剂,能氧化多种官能团,反应温和条件可控,是可控性氧化的优选试剂。研究采用mCPBA为氧化剂,通过控制反应条件,氧化2-巯基萘醌类化合物制备萘醌类衍生物。实验以两个2-巯基萘醌化合物为底物,控制反应物与氧化剂的比例、反应温度和反应时间,研究不同条件下氧化产物的分子结构和产量。反应产物经柱层析分离纯化后利用质谱、核磁共振等波谱学方法进行结构鉴定。研究发现产物包括亚硫酰化合物、磺酰基化合物和2,3-二氢-2,3-环氧化亚硫酰基化合物。反应温度在0℃,反应物与mCPBA的物料比为1∶1时,产物以亚硫酰化合物为主;室温下、物料比为1∶2,反应时间在4~6 h时,主产物为磺酰基化合物;反应时间超过6 h,产物全部为2,3-二氢-2,3-环氧化亚硫酰基化合物。研究结果为以mCPBA为氧化剂制备萘醌类衍生物奠定实验基础。m-Chloroperoxybenzoic acid(mCPBA)was an extraordinary oxidant that could oxidize many functional groups under a mild and controllable condition,and was used in controllable oxidation reaction often.mCPBA was used as oxidant to react with 2-mercaptonaphthoquinone derivatives to obtain novel naphthoquinone derivatives under various conditions.The oxidation reactions were carried out on two 2-mercaptonaphthoquinones substrates by varying the ratio of substrate and mCPBA,temperature and reaction time.The products were purified by chromatography,measured yield and analyzed structures by NMR and MASS spectroscopy.The results showed that the products included sulfoxides,sulfones and 2,3-dihydro-2,3-epoxidized sulfones.When the reaction temperature was 0℃,the ratio of substrate and mCPBA was 1∶1,the major products were sulfoxides;at room temp-erature,the ratio of substrate and mCPBA was 1∶2,and reaction time was 4~6 h,the main products were sulfones.When the reaction time exceeded 6 h,all the products were transformed to 2,3-dihydro-2,3-epoxidized sulfones.It provided solid supports for preparing naphthoquinone derivatives by mCPBA.

关 键 词：间氯过氧化苯甲酸 巯基 氧化 

分 类 号：TQ245[化学工程—有机化工]