RING-OPENING REACTIONS OF PROPYLENE-OXIDE AND PROPYLENE SULFIDE WITH DIBUTYLAMINE

被引：17

作者：

KAKIUCHI, H

IIJIMA, T

HORIE, H

机构：

[1] Department of Applied Chemistry, Faculty of Engineering, Yokohama National University, Minami-ku, Yokohama

来源：

TETRAHEDRON | 1979年 / 35卷 / 03期

关键词：

D O I：

10.1016/0040-4020(79)80066-6

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The rates of ring-opening of propylene oxide (PO) and propylene sulfide (PS) with dibutylamine (DBA) were measured in the range 40°-70°. The PO-DBA reaction in toluene (Tol) was too slow to be studied in detail. The PO-DBA reaction in DMSO-benzene mixtures was quicker and found to be competitive between the second-order dependent on the first order both in the PO concentration and in the DBA concentration, and the third-order by the participation of reaction products. The PS-DBA reactions both in Tol and in DMSO-Tol mixtures were found to obey the same kinetics as the PO-DBA reaction. The order of reactivity is PSPO. The PS-DBA reaction in DMSO-Tol mixtures was accelerated and the increase in reactivity of PS was based on the selective solvation of thiolate anion by DMSO in the transition state. The pull process was shown to be an important factor in the base-catalyzed ring-opening. © 1979.

引用

页码：303 / 308

页数：6

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