CN105152849A - 一种反式二苯乙烯的合成方法 - Google Patents
一种反式二苯乙烯的合成方法 Download PDFInfo
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Abstract
本发明涉及一种制备反式二苯乙烯的方法,本发明的步骤方法如下:将一种离子液体与水混合后制备成微乳液,再在此微乳液中滴加氯化钯溶液制备成纳米级的钯催化剂,然后用此钯催化剂体系作为反应介质,加入碘苯、苯乙烯和三乙胺使体系在一定时间内发生HECK反应,从而制备得到反式二苯乙烯。采用本方法制备反式二苯乙烯的反应速度更快而且催化剂循环利用次数多,能够提升生产效率,具备较高的推广价值。
Description
技术领域
本发明涉及有机合成领域,尤其是涉及一种催化HECK反应制备反式二苯乙烯的合成方法。
背景技术
二苯乙烯又称茋,有顺反两种异构体。顺式沸点141℃,相对密度1.0143,可溶于乙醇、乙醚、丙酮、苯和氯仿。反式沸点166.7℃,相对密度0.9707,可溶于乙醚和苯。反式二苯乙烯是重要的化工中间体,可用作染料等。
HECK反应作为芳香卤代烷和含有α-吸电子基团的烯烃的偶联反应是当今有机合成中构成C-C键的重要反应之一,并已得到了广泛的应用。但与Suzuki等反应相似,HECK反应通常需要过渡金属钯的催化以及有机膦配体的辅助作用。由于钯催化剂昂贵而且有毒,同时有机膦化合物剧毒而且不能重复使用,使HECK反应没有在工业上得到深入而广泛的应用。
本发明通过一种离子液体微乳液制备的纳米级钯催化剂,成功利用HECK反应催化合成了反式二苯乙烯,使相关反应的研究推广更具价值。
发明内容
本发明的目的是要利用一种离子液体制备的钯催化剂来催化制备重要的化工中间体反式二苯乙烯,提供了一种更好的合成办法。
为了达到上述目的,本发明提供了一种反式二苯乙烯的合成方法,其制备工序如下:
1)将重量计15-25份的离子液体加入到反应瓶中,25℃条件下磁力搅拌10-15min;
2)缓慢加入重量计25-40份的表面活性剂,过程中不断向体系内通入氮气,在搅拌条件下使二者相互溶解;
3)向反应瓶中以1-3ml/min的速度缓慢滴加蒸馏水,直至整个反应体系透明澄清,开始加热到40-70℃,待温度恒定后加入6-10份的氯化钯溶液,继续搅拌;
4)当体系从浅黄色转变成深黑色,同时反应瓶内没有沉淀、体系均匀时,缓慢升温至80-90℃,向体系内加入30-40份碘苯、60-80份苯乙烯和50-80份三乙胺,搅拌3-5h;
5)反应结束后,进行产物分离,通过核磁共振分析确认产物是反式二苯乙烯并计算得率达到98%以上。
其中,所述的离子液体是指市售的[BMIM]PF6离子液体或[BMIM]PF4离子液体中的任意一种,所述的表面活性剂是指曲拉通X-100型乳化剂,所述的氯化钯溶液是按照氯化钯与盐酸物质的量之比为1:2-1:3配制的溶液,所述的产物分离方法是柱层析法。
具体实施方式
实施例1
1)将120g的[BMIM]PF6离子液体加入到反应瓶中,25℃条件下磁力搅拌15min;
2)缓慢加入160g的曲拉通X-100型乳化剂,过程中不断向体系内通入氮气,在搅拌条件下使二者相互溶解;
3)向反应瓶中以2ml/min的速度缓慢滴加蒸馏水,直至整个反应体系透明澄清,开始加热到50℃,待温度恒定后加入70g的氯化钯溶液,继续搅拌;
4)当体系从浅黄色转变成深黑色,同时反应瓶内没有沉淀、体系均匀时,缓慢升温至80℃,向体系内加入200g碘苯、220g苯乙烯和240g三乙胺,搅拌3h;
5)反应结束后,进行产物分离,通过核磁共振分析确认产物是反式二苯乙烯并计算得率达到98.6%。
实施例2
1)将150g的[BMIM]PF6离子液体加入到反应瓶中,25℃条件下磁力搅拌13min;
2)缓慢加入200g的曲拉通X-100型乳化剂,过程中不断向体系内通入氮气,在搅拌条件下使二者相互溶解;
3)向反应瓶中以1ml/min的速度缓慢滴加蒸馏水,直至整个反应体系透明澄清,开始加热到60℃,待温度恒定后加入83g的氯化钯溶液,继续搅拌;
4)当体系从浅黄色转变成深黑色,同时反应瓶内没有沉淀、体系均匀时,缓慢升温至85℃,向体系内加入240g碘苯、300g苯乙烯和250g三乙胺,搅拌3.5h;
5)反应结束后,进行产物分离,通过核磁共振分析确认产物是反式二苯乙烯并计算得率达到98.3%。
Claims (5)
1.一种反式二苯乙烯的合成方法,其特征在于包括以下工序:
1)将重量计15-25份的离子液体加入到反应瓶中,25℃条件下磁力搅拌10-15min;
2)缓慢加入重量计25-40份的表面活性剂,过程中不断向体系内通入氮气,在搅拌条件下使二者相互溶解;
3)向反应瓶中以1-3ml/min的速度缓慢滴加蒸馏水,直至整个反应体系透明澄清,开始加热到40-70℃,待温度恒定后加入6-10份的氯化钯溶液,继续搅拌;
4)当体系从浅黄色转变成深黑色,同时反应瓶内没有沉淀、体系均匀时,缓慢升温至80-90℃,向体系内加入30-40份碘苯、60-80份苯乙烯和50-80份三乙胺,搅拌3-5h;
5)反应结束后,进行产物分离,通过核磁共振分析确认产物是反式二苯乙烯并计算得率达到98%以上。
2.根据权利要求1所述一种反式二苯乙烯的合成方法,其特征在于步骤1)中离子液体是指市售的[BMIM]PF6离子液体或[BMIM]PF4离子液体中的任意一种。
3.根据权利要求1所述一种反式二苯乙烯的合成方法,其特征在于步骤2)中的表面活性剂是指曲拉通X-100型乳化剂。
4.根据权利要求1所述一种反式二苯乙烯的合成方法,其特征在于步骤3)中的氯化钯溶液是按照氯化钯与盐酸物质的量之比为1:2-1:3配制的溶液。
5.根据权利要求1所述一种反式二苯乙烯的合成方法,其特征在于步骤5)中的产物分离方法是柱层析法。
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CN108658718A (zh) * | 2018-06-21 | 2018-10-16 | 温州大学 | 一种反式二苯乙烯化合物的制备方法 |
Citations (3)
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CN1845889A (zh) * | 2003-09-05 | 2006-10-11 | 帝斯曼知识产权资产管理有限公司 | 二苯乙烯衍生物的制备方法 |
WO2010113005A2 (en) * | 2009-03-27 | 2010-10-07 | Council Of Scientific & Industrial Research | One pot multicomponent synthesis of some novel hydroxy stilbene derivatives with alpha, beta-carbonyl conjugation under microwave irradiation |
CN102503763A (zh) * | 2011-11-28 | 2012-06-20 | 上海工程技术大学 | 二苯乙烯类化合物的制备方法 |
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CN1845889A (zh) * | 2003-09-05 | 2006-10-11 | 帝斯曼知识产权资产管理有限公司 | 二苯乙烯衍生物的制备方法 |
WO2010113005A2 (en) * | 2009-03-27 | 2010-10-07 | Council Of Scientific & Industrial Research | One pot multicomponent synthesis of some novel hydroxy stilbene derivatives with alpha, beta-carbonyl conjugation under microwave irradiation |
CN102503763A (zh) * | 2011-11-28 | 2012-06-20 | 上海工程技术大学 | 二苯乙烯类化合物的制备方法 |
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GUOPING ZHANG ET AL.: "Pd nanoparticles catalyzed ligand-free Heck reaction in ionic liquid microemulsion", 《GREEN CHEMISTRY》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108658718A (zh) * | 2018-06-21 | 2018-10-16 | 温州大学 | 一种反式二苯乙烯化合物的制备方法 |
CN108658718B (zh) * | 2018-06-21 | 2020-12-18 | 温州大学 | 一种反式二苯乙烯化合物的制备方法 |
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