CN108467331A - 一种由烯烃制备邻二溴化合物的方法 - Google Patents
一种由烯烃制备邻二溴化合物的方法 Download PDFInfo
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Abstract
本发明涉及结构式如下所示的由烯烃制备邻二溴化合物的方法:
Description
本发明涉及一种由烯烃制备邻二溴化合物的方法。
邻二溴化合物是很多合成中间体的前体化合物,比如环丙烷类、炔烃类,以及在偶联化学中具有重要价值的烯基溴类化合物。烯烃类化合物在含溴素试剂的作用下,发生亲电加成,得到相应的邻二溴化合物。通过分子结构中的溴原子,可以引入各种不同的官能团,因此该方法广泛应用于天然产物的全合成研究中,是一种非常有效的合成方法。
鉴于邻二溴化合物的重要性,其合成方法近年来受到越来越多的关注。由烯烃类化合物制备相应的邻二溴化合物,传统的方法是在溴单质的作用下进行二溴代反应。但由于溴单质是一种有毒、有腐蚀性、挥发性的液体,不易操作,此方法的应用受到了限制。于是越来越多的研究在传统方法上进行改进,寻找可替代液溴的溴代试剂。目前主要的合成方法有以下两种:(1)烯烃在含溴素试剂,比如三溴盐、N-溴代丁二酰亚胺(NBS)及其类似物作用下进行二溴代反应;(2)烯烃在氧化剂和金属溴化物作用下进行二溴代反应。这些改进方法为烯烃的二溴代反应提供了丰富的可选择途径,但相对于烯烃在溴单质作用下的二溴代反应,这些改进方法存在不可避免的缺陷:试剂价格比较昂贵,原子经济性低,反应产生废弃物较多。
本发明的目的是提供一种由烯烃制备邻二溴化合物的新方法。其特征是以烯烃为原料,以二氯甲烷为溶剂,在二甲亚砜/草酰溴组合试剂的作用下,得到相应的邻二溴化合物。本发明的制备方法具有试剂价廉易得、操作简便、产率高、反应条件温和的优点。反应式如下:
本发明涉及结构式如下所示的由烯烃制备邻二溴化合物的方法:
其主要过程是:在-10℃先将二甲亚砜(1.5equiv)的二氯甲烷溶液滴加至草酰溴(1.5equiv)的二氯甲烷溶液中,再滴加原料烯烃,然后回至室温或加热至30-40℃反应,得到相应的邻二溴化合物,产率在79~97%。
本发明方法中由烯烃制备的邻二溴化合物的结构都通过核磁共振进行了确认。分析结果附在实施例后。
具体实施方式
(1)1,2-二溴癸烷的制备
氮气保护,在装有温度计的100mL三口烧瓶中,加入草酰溴(7.5mmol,1.1mL,1.5equiv)和无水二氯甲烷(10mL)。-10℃下,用恒压滴液漏斗缓慢滴加二甲亚砜(7.5mmol,0.53mL,1.5equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,再滴加1-癸烯(5mmol,700mg,1.0equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,然后缓慢加热至30℃,反应1h。冰浴0℃下,加入30mL蒸馏水,分液,取有机相,用饱和氯化钠水溶液(50mL)洗涤,无水硫酸钠干燥。过滤,旋蒸除去溶剂得到1,2-二溴癸烷1.38g,产率为92%。1H NMR(300MHz,CDCl3)δ4.22-4.12(m,1H),3.85(dd,J=10.2,4.5Hz,1H),3.63(t,J=9.9Hz,1H),2.19-2.08(m,1H),1.84-1.72(m,1H),1.62-1.50(m,1H),1.47-1.38(m,1H),1.36-1.24(m,10H),0.88(t,J=6.6Hz,3H)。13C NMR(75MHz,CDCl3)δ53.32,36.51,36.17,31.97,29.50,29.34,28.96,26.90,22.80,14.26。
(2)trans-1,2-二溴环戊烷的制备
氮气保护,在装有温度计的100mL三口烧瓶中,加入草酰溴(7.5mmol,1.1mL,1.5equiv)和无水二氯甲烷(10mL)。-10℃下,用恒压滴液漏斗缓慢滴加二甲亚砜(7.5mmol,0.53mL,1.5equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,再滴加环戊烯(5mmol,340mg,1.0equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,然后回至室温反应0.5h。冰浴0℃下,加入30mL蒸馏水,分液,取有机相,用饱和氯化钠水溶液(50mL)洗涤,无水硫酸钠干燥。过滤,旋蒸除去溶剂得到trans-1,2-二溴环戊烷1.03g,产率为90%。1H NMR(300MHz,CDCl3)δ4.59(dm,J=5.1Hz,2H),2.66(ddt,J=14.1,5.1,8.7Hz,2H),2.20-2.11(m,2H),2.05-1.95(m,2H)。13C NMR(75MHz,CDCl3)δ57.44,34.01,21.24。
(3)trans-1,2-二溴-1,2-二氢苊烯的制备
氮气保护,在装有温度计的100mL三口烧瓶中,加入草酰溴(7.5mmol,1.1mL,1.5equiv)和无水二氯甲烷(10mL)。-10℃下,用恒压滴液漏斗缓慢滴加二甲亚砜(7.5mmol,0.53mL,1.5equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,再滴加苊烯(5mmol,760mg,1.0equiv)的无水二氯甲烷(10mL)溶液。滴加完毕后,-10℃下继续搅拌10min,然后回至室温反应1h。冰浴0℃下,加入30mL蒸馏水,分液,取有机相,用饱和氯化钠水溶液(50mL)洗涤,无水硫酸钠干燥。过滤,旋蒸除去溶剂得到trans-1,2-二溴-1,2-二氢苊烯1.32g,产率为85%。1H NMR(300MHz,CDCl3)δ7.83(dd,J=6.6,2.1Hz,2H),7.66-7.59(m,4H),6.01(s,2H)。13C NMR(75MHz,CDCl3)δ140.62,134.95,131.11,128.98,126.01,122.69,55.03。
Claims (1)
1.一种由烯烃制备邻二溴化合物的方法,其特征是以烯烃为原料,以二氯甲烷为溶剂,在二甲亚砜/草酰溴组合试剂的作用下,得到相应的邻二溴化合物,反应式如下:
。
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CN103012050A (zh) * | 2011-09-21 | 2013-04-03 | 中国科学院大连化学物理研究所 | 一种多氯烷烃的合成方法 |
CN107353266A (zh) * | 2017-08-23 | 2017-11-17 | 北京工商大学 | 一种烯酸溴内酯化的制备方法 |
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CN107353266A (zh) * | 2017-08-23 | 2017-11-17 | 北京工商大学 | 一种烯酸溴内酯化的制备方法 |
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