硒格氏试剂反应研究
摘要
有机硒化合物通常具有较好的生物活性,而硒醚又是其中一种很重要的有机硒化合物。目前合成硒醚的方法尚有很多不足之处,我们在总结前人经验的基础上,用硒格氏试剂作反应物,直接与卤代物或烯烃反应制得一系列硒醚。主要研究结果如下：
1.用此法成功合成了对甲氧苯基硒醚、邻甲氧苯基硒醚、2-噻吩基硒醚、1-萘基硒醚和环已基硒醚等一系列对称硒醚,获得的GC产率分别为94%,51%,13%,19%和20%。
2.用此法成功合成一系列不对称硒醚,但因副产物较多,于是考察了不同反应条件对反应的影响并探讨了从RSeMgBr合成硒醚的反应机理：从R1Br制备出R1SeMgBr后,加入的R2Br与过量镁生成R2MgBr, R1SeMgBr的Se又有部分转移到R2MgBr形成R2SeMgBr,同时留下部分R1MgBr,最后几种硒格氏试剂和格氏试剂在催化剂的作用下相互发生反应生成了不同的硒醚。
3.利用苯基硒格氏试剂与苯乙烯进行了加成反应应制得苯乙基苯基硒醚,并确定了在四氢呋喃和水混合溶剂下,CuI作催化剂等因素有利苯基硒格氏试剂与苯乙烯反应,产物收率达40%以上
Organoselenium compounds show good biological activity, and selenides are important compounds of them. There are many disadvantages for methods of selenides synthesis so far. Based on the former research works, we used magnesium selenolate as reactant to react with RX or styrene to synthesize a series of selenide. Followings are the main research results:
1. Some symmetrical selenides, such as di-4-methoxyphenyl selenide, di-2-methoxyphenyl selenide,2-(2-thienylseleno)thiophene, di-1-naphthyl selenide and di-cyclohexyl selenide were successfully synthesized by this method in yields of 94%,51%,13%,19%and 20%, respectively.
2. Some unsymmetrical selenides were successfully synthesized by this method, but complex products were given. The effects of different conditions on the reaction were investigated. We also discuss the reaction mechanism. After R1SeMgBr was prepared from R1Br, then the added R2Br reacted with excess Mg to afford R2MgBr. Se of R1SeMgBr could exchange to R2MgBr to form R2SeMgBr. Finally, the magnesium selenolates could react with Grignard reagents to generate complex selenides.
3. (1-Phenyl)ethyl phenyl selenide was successfully synthesized from PhSeMgBr and styrene. It was found that magnesium selenolates reacting with styrene via the catalysis of CuI in the THF-H2O mixed solvent leaded to 40%yield of target product.
1.用此法成功合成了对甲氧苯基硒醚、邻甲氧苯基硒醚、2-噻吩基硒醚、1-萘基硒醚和环已基硒醚等一系列对称硒醚,获得的GC产率分别为94%,51%,13%,19%和20%。
2.用此法成功合成一系列不对称硒醚,但因副产物较多,于是考察了不同反应条件对反应的影响并探讨了从RSeMgBr合成硒醚的反应机理：从R1Br制备出R1SeMgBr后,加入的R2Br与过量镁生成R2MgBr, R1SeMgBr的Se又有部分转移到R2MgBr形成R2SeMgBr,同时留下部分R1MgBr,最后几种硒格氏试剂和格氏试剂在催化剂的作用下相互发生反应生成了不同的硒醚。
3.利用苯基硒格氏试剂与苯乙烯进行了加成反应应制得苯乙基苯基硒醚,并确定了在四氢呋喃和水混合溶剂下,CuI作催化剂等因素有利苯基硒格氏试剂与苯乙烯反应,产物收率达40%以上
Organoselenium compounds show good biological activity, and selenides are important compounds of them. There are many disadvantages for methods of selenides synthesis so far. Based on the former research works, we used magnesium selenolate as reactant to react with RX or styrene to synthesize a series of selenide. Followings are the main research results:
1. Some symmetrical selenides, such as di-4-methoxyphenyl selenide, di-2-methoxyphenyl selenide,2-(2-thienylseleno)thiophene, di-1-naphthyl selenide and di-cyclohexyl selenide were successfully synthesized by this method in yields of 94%,51%,13%,19%and 20%, respectively.
2. Some unsymmetrical selenides were successfully synthesized by this method, but complex products were given. The effects of different conditions on the reaction were investigated. We also discuss the reaction mechanism. After R1SeMgBr was prepared from R1Br, then the added R2Br reacted with excess Mg to afford R2MgBr. Se of R1SeMgBr could exchange to R2MgBr to form R2SeMgBr. Finally, the magnesium selenolates could react with Grignard reagents to generate complex selenides.
3. (1-Phenyl)ethyl phenyl selenide was successfully synthesized from PhSeMgBr and styrene. It was found that magnesium selenolates reacting with styrene via the catalysis of CuI in the THF-H2O mixed solvent leaded to 40%yield of target product.
引文
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[3]牟维鹏.不同化学形式硒的毒性作用机制[J].国外医学卫生学分册.2001,28(4)：202-210.
[4]郑文杰,欧阳政.植物有机硒的化学及其医学应用[M].广州：暨南大学出版社,2001.
[5]李东,周元军,范新国,等.硒与人及畜禽动物健康[J].医学动物防制.2004,20(3)：183-186.
[6]Schwarz K, Foltz C M. Selenium as an integral part of factor 3 against dietary necrotic liver degeneration[J]. J. Am. Chem. Soc.1957,79(12):3292-3293.
[7]薛君武,李申田.硒与癌症的化学预防[J].国际耳鼻咽喉头颈外科杂志.1987(01)：7-10.
[8]关玉群,朱磊,王充,等.硒与人体健康[J].现代预防医学.2003,30(5)：700-703.
[9]Philip B M, Kenneth O. Fulminant heart failure due to selenium deficiency cardiomyopathy (Keshan disease).[J]. Medicine, science, and the law.2002,42(1): 10-13.
[10]萧进,袁倚盛,方明,等.微量元素铬、锰、锌、铜、硒与中老年人常见病的关系[J].微量元素与健康研究.1990(01)：30-33.
[11]李景岩,张爱君.硒与心血管疾病[J].中国地方病防治杂志.2007,22(6)：424-426.
[12]左钱飞,沈香琴,万仁玲.微量元素硒与人体健康[J].科学之友.2010(3)：96-98.
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