Efficient synthesis of epoxybutane from butanediol via a two-step process.
Efficient synthesis of epoxybutane from butanediol via a two-step process.
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通过两步法从丁二醇高效合成环氧丁烷
作者：
首次开发了一种通过丁二醇衍生的碳酸丁烯酯脱羧合成环氧丁烷的新方法。对于丁二醇与碳酸二甲酯的羰基化反应，NaAlO2 在温和的反应条件下表现出了优异的催化活性。碳酸丁烯酯的收率高达96.2%。 NaAlO2提供合适的酸碱活性位点来促进丁二醇和碳酸二甲酯的酯交换反应。对于碳酸丁烯酯的后续脱羧步骤，离子液体1-丁基-3-甲基溴化咪唑鎓可以有效地催化间歇或连续过程中的脱羧过程。此外，利用DFT计算探讨了1-丁基-3-甲基溴化咪唑鎓上碳酸丁烯基脱羧关键步骤的催化机制。结果表明，1-丁基-3-甲基溴化咪唑鎓的静电和氢键作用对环氧丁烷的生成起着至关重要的作用。简而言之，离子液体的Br阴离子攻击环的亚甲基，离子液体阳离子的H攻击羰基氧，这促进了五环开环和随后的脱羧形成BO。该研究不仅为生产环氧丁烷提供了一条新的绿色合成路线，而且有助于煤制乙二醇过程中不可避免地产生的副产物丁二醇的有效利用，表明在成本低廉的环氧丁烷清洁生产中具有广阔的应用前景。
A novel approach for the synthesis of epoxybutane via decarboxylation of butenyl carbonate derived from butanediol was developed for the first time. For the carbonylation of butanediol with dimethyl carbonate, NaAlO2 has exhibited excellent catalytic activity under mild reaction conditions. The yield of butenyl carbonate reached as high as 96.2%. NaAlO2 provides suitable acid–base active sites to promote the transesterification reaction of butanediol and dimethyl carbonate. For the following step of decarboxylation of butenyl carbonate, ionic liquid 1-butyl-3-methylimidazolium bromide could effectively catalyze the decarboxylation process both in batch or continuous processes. Moreover, the catalytic mechanism for the crucial step of decarboxylation of butenyl carbonate over 1-butyl-3-methylimidazolium bromide was explored using DFT calculations. The results showed that the electrostatic and hydrogen-bond effects of 1-butyl-3-methylimidazolium bromide played a crucial role for the generation of epoxybutane. Briefly, the Br anion of the ionic liquid attacks the methylene of the ring and the H of the ionic liquid cation attacks the carbonyl oxygen, which facilitated the five-ring opening and subsequent decarboxylation to form BO. This study not only provided a new and green synthetic route for producing epoxybutane, but also contributed to the effective utilization of butanediol, which is inevitably produced as by-product in the process of coal to ethylene glycol, suggesting a promising application in the clean manufacture of epoxybutane with inexpensive cost.
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影响因子：
--
作者：
Gao, Yangyan;Peng, Weicai;Sun, Yuhan
通讯作者：
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影响因子：
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作者：
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DOI：
10.1016/j.jtice.2016.10.039
发表时间：
2017-01-01
影响因子：
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作者：
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