CATALYTIC ACTIVITY OF VARIOUS SALTS IN THE REACTION OF 2,3-EPOXYPROPYL PHENYL ETHER AND CARBON-DIOXIDE UNDER ATMOSPHERIC-PRESSURE
CATALYTIC ACTIVITY OF VARIOUS SALTS IN THE REACTION OF 2,3-EPOXYPROPYL PHENYL ETHER AND CARBON-DIOXIDE UNDER ATMOSPHERIC-PRESSURE
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DOI：
10.1021/jo00075a011
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发表时间：
1993-11-05
影响因子：
3.6
通讯作者：
ENDO, T
中科院分区：
文献类型：
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作者：
KIHARA, N;HARA, N;ENDO, T
2，3-环氧丙基苯基醚(1)与二氧化碳在N-甲基吡咯烷酮(NMP)中于100℃下，在5mol%的各种盐的存在下反应，选择性地合成了五元环碳酸酯4-(苯氧甲基)-1，3-二氧杂环戊二酮(2)。只有卤化盐表现出较高的催化活性，其本征活性顺序为：氯>；溴>；碘，即阴离子的亲核性顺序。活性顺序为锂盐>；钠盐>；苄基三甲基铵盐，这与阳离子的Lewis酸度顺序一致。动力学分析表明，反应速率可用-d[1]/dt=k[1][cat]表示，其中二氧化碳压力对反应速率没有影响。该反应通过卤化物对环氧乙烷的亲核攻击生成β-卤代醇4，该β-卤代醇4与二氧化碳反应，然后环合。关键中间体4的存在通过1与1当量溴化锂在100℃无CO2条件下在NMP中反应2.5h间接证明，该反应以20%的产率得到重排产物1-苯氧基-2-丙酮(6)。
Reaction of 2,3-epoxypropyl phenyl ether (1) with carbon dioxide was carried out under atmospheric pressure in N-methylpyrrolidinone (NMP) at 100-degrees-C in the presence of 5 mol % of various salts to obtain a five-membered cycliccarbonate, 4-(phenoxymethyl)-1,3-dioxolan-2-one(2), selectively. Only halide salts showed high catalytic activity, and the order of intrinsic activity was found to be as follows: chloride > bromide > iodide which is the order of nucleophilicity of the anion. Furthermore, the order of the activity was found to be lithium salt > sodium salt > benzyltrimethylammonium salt, which is in accord with the order of Lewis acidity of the cation. Kinetic analyses show that the reaction rate can be represented by -d[1]/dt=k[1][cat.], where the carbon dioxide pressure shows no effect on the reaction rate. The reaction proceeds via nucleophilic attack of halide to oxirane to form beta-haloalkoxide 4 which reacts with CO2 followed by cyclization. The presence of key intermediate 4 was indirectly proved by the reaction of 1 with 1 equiv of LiBr in the absence of CO2 at 100-degrees-C for 2.5 h in NMP which leads to 1-phenoxy-2-propanone (6) in 20 % yield as the rearrangement product of 4.