キハラ ノブヒロ   Kihara Nobuhiro
  木原 伸浩
   所属   神奈川大学  理学部 化学科
   職種   教授
言語種別 英語
発行・発表の年月 1993/11
形態種別 学術雑誌
査読 査読あり
標題 Catalytic Activity of Various Salts in the Reaction of 2,3-Epoxypropyl Phenyl Ether and Carbon Dioxide under Atmospheric Pressure
執筆形態 共著
掲載誌名 J. Org. Chem.
巻・号・頁 58(23),pp.6198-6202
著者・共著者 Nobuhiro Kihara, Nobutaka Hara, and Takeshi Endo
概要 Reaction of 2,3-epoxypropyl Ph ether (I) with CO2 was carried out under atm. pressure at 100° in the presence of salts to obtain 4-(phenoxymethyl)-1,3-dioxolan-2-one (II) selectively. Only halide salts showed high catalytic activity, and the order of intrinsic activity was the order of nucleophilicity of the anion. Furthermore, the order of the activity was in accord with the order of Lewis acidity of the cation. The reaction rate can be represented by -d[I]/dt = k[I][catalyst], where the carbon dioxide pressure shows no effect on the reaction rate. The reaction proceeds via nucleophilic attack of halide on oxirane to form β-haloalkoxide (III), which reacts with CO2, followed by cyclization. The presence of key intermediate III was indirectly proved by the reaction of I with 1 equiv of LiBr in the absence of CO2 at 100° for 2.5 h in NMP, which leads to 1-phenoxy-2-propanone in 20% yield as the rearrangement product of III.
DOI 10.1021/jo00075a011
ISSN 0022-3263