SUBSTITUTION-REACTIONS WHICH PROCEED VIA RADICAL-ANION INTERMEDIATES .20. REPLACEMENT OF THE NITRO-GROUP BY HYDROGEN
SUBSTITUTION-REACTIONS WHICH PROCEED VIA RADICAL-ANION INTERMEDIATES .20. REPLACEMENT OF THE NITRO-GROUP BY HYDROGEN
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DOI：
10.1021/ja00497a028
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发表时间：
1979-01-01
影响因子：
15
通讯作者：
SMITH, RG
中科院分区：
文献类型：
--
作者：
KORNBLUM, N;CARLSON, SC;SMITH, RG
脂肪族硝基化合物与甲硫醇钠盐的反应可以在硝基被氢完全取代的情况下发生。这是如此，尽管存在一个竞争性的过程-取代硝基的硫代甲基。证据支持的观点，这两个转换是电子转移过程，并提出了一个自由基阴离子自由基链机制。本文叙述了控制硝基化合物与甲硫醇钠盐反应过程的因素，并提出了简单的理论依据。直到1954年，还没有一种合成叔硝基烷烃的有效方法。从那时起，已经发现了许多反应，其给出了优异的纯脂族和双环叔硝基化合物的产率;这些反应采用温和的条件，并且大多数反应都是在室温下进行的。
The reaction of an aliphatic nitro compound with the sodium salt of methanethiol can occur with clean replacement of the nitro groupby hydrogen. This is so despite the existence of a competitive process—replacement of nitro by thiomethyl. Evidence in support of the view that both transformations are electron transfer processes is presented and a radical anion-free radical chain mechanism is proposed. The factors which control the course of reaction of a nitro compound and the sodium salt of methanethiol are described and a simple rationale is presented.Until 1954 a synthetically useful method for the preparation of tertiary nitroparaffins did not exist. Since that time a number of reactions have been discovered which give excellent yields of pure aliphatic and alicyclictertiary nitro compounds; 2™ 1 1 these reactions employ mild conditions and most