3-Bromo-3-methyl-1-butyne, 1-Bromo-3-methyl-1,2-butadiene, and 1-Bromo-3-methyl-1,3-butadiene1
3-Bromo-3-methyl-1-butyne, 1-Bromo-3-methyl-1,2-butadiene, and 1-Bromo-3-methyl-1,3-butadiene1
复制标题
3-溴-3-甲基-1-丁炔、1-溴-3-甲基-1,2-丁二烯和1-溴-3-甲基-1,3-丁二烯1
DOI：
10.1021/jo01040a051
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发表时间：
1963
影响因子：
3.6
通讯作者：
W. L. Petty
中科院分区：
文献类型：
--
作者：
T. L. Jacobs;W. L. Petty
以2-甲基-3-丁-2- oi为原料，与三溴化磷或亚硫基溴化合成3-溴-3-甲基- 1 -丁炔（IV）。它被溴化亚铜或溴离子重排成l-溴-3-甲基- 1,2 -丁二烯(V)。在60-80时，后者产生52%的顺式- 1 -溴-3-甲基- 1,3-丁二烯，28%的二聚体<反式- 1,2 -二溴- 3,4 -二异丙基环丁烷，20%的其他二聚体和聚合物。考察了IV和V与碘离子、噻吩氧离子和二乙胺的置换反应。研究了氢化铝锂对IV、V和二聚体的脱卤反应。Alíenle卤化物最常用的合成方法是将相应的丙炔卤化物重排，或由丙炔醇通过置换反应生成重排的卤化物。已知有许多氯烯，但在本工作完成时只报道了两种溴烯：溴烯本身和3-溴-5-苯基- 2,2,6,6 -
3-Bromo-3-methyI-l-butyne (IV) was obtained from 2-methyl-3-butyn-2-oI by reaction with phosphorus tri-bromide or thionyl bromide. It was rearranged by cuprous bromide or bromide ion to l-bromo-3-methyl-I, 2-butadiene (V). At 60-80 the latter gave 52% of cis-and irans-l-bromo-3-methyl-l, 3-butadiene, 28% of the dimer< rans-l, 2-dibromo-3, 4-di-isopropylidenecyclobutane, and 20% of other dimers and polymers. Displace-ment reactions of IV and V with iodide ion, thiophenoxide ion, and diethylamine were examined. Dehalogena-tion of IV, V, and the dimer by lithium aluminum hydride was also studied.Alíenle halides havebeen synthesized most frequently by rearrangement of the corresponding propargyl halides or from propargyl alcohols by displacement reac-tions which often yield rearranged halides. A number of chloroallenes are known but only two bromoallenes had been reported2 when the present work was com-pleted: bromoallene itself3 and 3-bromo-5-phenyl-2, 2, 6, 6-