Radical-Catalyzed Oxidation of Thiols by Trithiocarbonate and Dithioester RAFT Agents: Implications for the Preparation of Polymers with Terminal Thiol Functionality

被引：38

作者：

Harrisson, Simon ^{[1
]}

机构：

[1] CSIRO Mol & Hlth Technol, Clayton, Vic 3168, Australia

来源：

MACROMOLECULES | 2009年 / 42卷 / 04期

关键词：

FRAGMENTATION-CHAIN-TRANSFER; TRANSFER POLYMERIZATION; COPOLYMERS; POLY(N-ISOPROPYLACRYLAMIDE); POLYMETHACRYLATES; CHEMISTRY;

D O I：

10.1021/ma900075v

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

A study was conducted to demonstrate the implications of radical-catalyzed oxidation of thiols by trithiocarbonate and dithioester reversible addition fragmentation chain transfer (RAFT) agents for the preparation of polymers with terminal thiol functionality. The oxidation of thiols proceeded through a base-catalyzed radical in which thiolate anions were oxidized to form thiyl radicals that coupled to form disulfides. Thiyl radicals were generated in the presence of the RAFT agents dibenzyl trithiocarbonate and benzyl dodecyl trithiocarbonate by the thermal decomposition of 2,2'-azobis(isobutyronitrile) (AIBN) at 80 °C in degassed solutions of benzyl mercaptan. The reactions were carried out in flame-sealed NMR tubes and followed by 1H NMR NMR spectroscopy. It was observed that the presence of an equimolar quantity of trithiocarbonate RAFT agent caused a significant increase in the rate of conversion of thiol to disulfide.

引用

页码：897 / 898

页数：2

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