ORGANIC SULFUR COMPOUNDS .8. ADDITION OF THIOLS TO CONJUGATED DIOLEFINS
ORGANIC SULFUR COMPOUNDS .8. ADDITION OF THIOLS TO CONJUGATED DIOLEFINS
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DOI：
10.1021/ja00879a020
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发表时间：
1962-01-01
影响因子：
15
通讯作者：
HUDSON, BE
中科院分区：
文献类型：
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作者：
OSWALD, AA;THALER, WA;HUDSON, BE
简单脂肪族和芳族硫醇以及硫乙酸自由基加成成1,3 -丁二烯、2,3 -二甲基- 1、3-丁二烯、异戊二烯和氯丁二烯主要生成1,4 -#稀有单加合物。在不对称取代的丁二烯（异戊二烯、氯丁二烯和胡椒烯）的情况下，芳香噻基自由基的加成对第一个碳原子具有高度选择性。脂肪族巯基自由基选择性较低；它们与碳四的添加会产生大量的“反向加合物”作为副产品。加合物是由中间的烯丙基自由基通过反应性更强的伯碳原子从硫醇中提取氢而得到的。硫醇与胡椒烯加成生成1,2 -和1,4 -加合物。这是预料之中的，因为中间烯丙基的两个活性碳都是仲型的。
Radical addition of simple aliphatic and aromatic thiols and of thiolacetic acid to 1, 3-butadiene, 2, 3-dimethyl-l, 3-butadiene, isoprene and chloroprene yieldspredominantly the 1, 4-# rares-monoadducts. In the case of unsymmetrically substituted butadienes (isoprene, chloroprene and piperylene), the addition of aromatic thiyl radicals is highly selective to the first carbon atom. Aliphatic thiyl radicals are less selective; their addition to carbon four leads to significant amounts of the “reverse adducts" as by-products. The adducts are derived from the intermediate allylic radical through subsequent hydrogen abstraction from the thiol by the more reactive primary carbon atom. Thiols addto piperylene to yield both 1, 2-and 1, 4-adducts. This is expected since both reactive carbons of the inter-mediate allylic radical are of the secondary type.