Cycloaddition of Oxirane Group with Carbon Dioxide in the Supercritical Homogeneous State
Cycloaddition of Oxirane Group with Carbon Dioxide in the Supercritical Homogeneous State
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DOI：
10.1021/ie020164j
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发表时间：
2002-09
影响因子：
4.2
通讯作者：
T. Sako;Toshiyuki Fukai;Ryo Sahashi;M. Sone;Mitsuo Matsuno
中科院分区：
文献类型：
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作者：
T. Sako;Toshiyuki Fukai;Ryo Sahashi;M. Sone;Mitsuo Matsuno
在超临界均相区和汽液共存区，对2-甲基氧环烷或2,2-二甲基氧环烷与二氧化碳进行了环加成反应，得到了4-甲基-1,3-二恶氧烷-2- 1或4,4-二甲基-1,3-二恶氧烷-2- 1的环状碳酸盐化合物。当反应在超临界均匀条件下进行时，环状碳酸盐的收率超过95%。另一方面，当反应发生在两相区时，产率小于5%。几乎所有种类的碱金属卤化物在极性液体溶剂中都表现出较高的催化活性，但在超临界二氧化碳中发现有少数卤化物具有较高的催化活性。这可能是由于超临界溶剂和液体溶剂在极性和溶解力等溶剂性质上的差异。通过控制温度和压力，研究了环碳酸盐与超临界反应物和产物混合物的选择性分离。当德……
Cycloaddition of an oxirane group of 2-methyloxirane or 2,2-dimethyloxirane with carbon dioxide was carried out in both supercritical homogeneous and vapor−liquid coexisting regions to produce a cyclic carbonate compound of 4-methyl-1,3-dioxolan-2-one or 4,4-dimethyl-1,3-dioxolan-2-one. The yield of the cyclic carbonate exceeded 95%, when the reaction proceeded in the supercritical uniform condition. On the other hand, the yield was less than 5%, when the reaction occurred in the two-phase region. While almost all kinds of alkali metal halides exhibited the high catalytic activity in a polar liquid solvent, limited numbers of halides were found to have much activity in supercritical carbon dioxide. This might be due to differences in solvent properties such as polarity and dissolving power between the supercritical and liquid solvents. The selective separation of cyclic carbonate from the supercritical mixture of reactants and products was investigated by manipulating the temperature and pressure. When de...