顺式-1,2-环己烷二甲醇合成工艺的优化
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摘要
介绍了硼氢化钠在有机合成中的应用以及影响硼氢化钠还原体系的因素,并探讨了采用硼氢化钠还原体系制备顺式-1,2-环己烷二甲醇两种方法的可行性.方法一,采用硼氢化钠直接还原顺式-1,2-环己烷二甲酸制备顺式-1,2-环己烷二甲醇,其收率很低;方法二,采用硼氢化钠还原顺式-1,2-环己烷二甲酸二甲酯制备顺式-1,2-环己烷二甲醇,收率可达87%.在此基础上,重点考察了不同硼氢化钠还原体系对反应的影响.
In this paper, we introduce the application of sodium borohydride in organic synthesis reactions as well as the factors which affect the sodium borohydride reduction system. The feasibility of using sodium borohydride reduction system to prepared cis-1, 2-cyclohexanedimethanol are discussed, and the cis-1, 2-cyclohexanedimethanol are prepared by the following two methods. The first method was directly using the sodium borohydride into the reaction, and this method turned out to be failed because the extremely low production rate; the second method was using the dimethyl cis-1, 2-Cyclohexanedicarboxylate to prepared the cis-1, 2-cyclohexanedimethanol via sodium borohydride reduction system, the yield reached 87%. In this work, we focus on the effects of the different sodium borohydride reduction system on the reaction.
In this paper, we introduce the application of sodium borohydride in organic synthesis reactions as well as the factors which affect the sodium borohydride reduction system. The feasibility of using sodium borohydride reduction system to prepared cis-1, 2-cyclohexanedimethanol are discussed, and the cis-1, 2-cyclohexanedimethanol are prepared by the following two methods. The first method was directly using the sodium borohydride into the reaction, and this method turned out to be failed because the extremely low production rate; the second method was using the dimethyl cis-1, 2-Cyclohexanedicarboxylate to prepared the cis-1, 2-cyclohexanedimethanol via sodium borohydride reduction system, the yield reached 87%. In this work, we focus on the effects of the different sodium borohydride reduction system on the reaction.
引文
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[2]赵开荣,王芳,丁克鸿.高效还原剂双(2-甲氧基乙氧基)二氢铝钠[J].广东化工,2013,40(21):102~103
[3]靳立人,刘宝丽,时晓军,等.双(2-甲氧乙氧基)铝氢化钠还原芳杂环酯的研究[J].厦门大学学报(自然版),2004,43(3):352~355
[4]白银娟,路军,马怀让.硼氢化钠在有机合成中的研究进展[J].应用化学,2002,19(5):409~415
[5]韩卫华,李浩然,邓东顺,等.硼氢化钠还原潜手性酮反应机理的量子化学研究[J].化学学报,2006,64(16):1723~1729
[6]时憧宇,杜玲枝.手性二茂铁基β-氨基醇的合成及其在催化硼氢化钠/碘对潜手性酮的不对称还原反应中的应用[J].河南大学学报(自然版),2008,38(5):479~482
[7]黄世文,彭伟立,单自兴,等.丙二酰氧基硼氢化钠介入的醛、酮还原胺化反应[J].化学试剂,2000,22(2):65~67
[8]林世博,李喆宇,罗刚,等.羧酸酯还原制备醇的方法研究进展[J].化工进展,2014,33(5):1276~1284
[9]宋超,何杰,李杰,等.羧酸及其衍生物的Na BH4还原体系研究进展[J].化学通报,2012,75(7):614~620
[10]陈翠,徐松森,刘卫兵.硼氢化钠选择性还原乙酰乙酰苯胺至不饱和烯胺和β-羟基酰胺[J].有机化学,2016,36(8):1890~1894
[11]林荣辉,张永敏,周子牛.复合还原剂硼氢化钠/铁盐对腈的还原[J].高等学校化学学报,1990,11(8):889~890
[12]Saeed A,Ashraf Z.Sodium borohydride reduction of aromatic carboxylic acids via methyl esters[J].Journal of Chemical Sciences,2006,118(5):419~423
[13]Yamakawa T,Masaki M,Nohira H.Chem Inform Abstract:A New Reduction of Some Carboxylic Esters with Sodium Borohydride and Zinc Chloride in the Presence of a Tertiary Amine[J].Cheminform,1991,22(52):102
[14]王伟,杨玉琼,赵军,等.硼氢化钠/氯化钙新法还原乙酰基二茂铁合成1-二茂铁基乙醇[J].精细化工中间体,2011,41(5):70~72
[15]蔡良珍,李明珠,陶晓春,等.Na BH4/Lewis酸体系室温下还原反式环己基羧酸及酯的反应[J].液晶与显示,2007,22(6):652~656
[16]陈蔚,潘毅,康江鹏,等.一种手性中间体环己烷二甲醇的制备方法:中国,102952001A[P].2013