CN116425607A - 一种铬催化中间炔烃选择性氢化制备顺式或反式烯烃的方法 - Google Patents

一种铬催化中间炔烃选择性氢化制备顺式或反式烯烃的方法 Download PDF

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CN116425607A
CN116425607A CN202310060760.0A CN202310060760A CN116425607A CN 116425607 A CN116425607 A CN 116425607A CN 202310060760 A CN202310060760 A CN 202310060760A CN 116425607 A CN116425607 A CN 116425607A
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曾小明
罗美明
凌亮
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Abstract

本发明公开了一种铬催化中间炔烃选择性氢化制备顺式或反式烯烃的方法，该方法以环状(烷基)(氨基)卡宾铬络合物为催化剂，镁单质为还原剂，氯硅烷和分子筛为添加剂，四氢呋喃作为溶剂，在氢气氛围下与中间炔烃在25~100℃反应，制备顺式或反式烯烃。该方法具有反应条件温和、催化剂金属廉价和丰产、底物适用范围广、操作简单、选择性高等优点。

Description

一种铬催化中间炔烃选择性氢化制备顺式或反式烯烃的方法
技术领域
本发明是关于制备顺式或反式烯烃化合物的方法，该方法利用不同的环状（烷基）（氨基）卡宾铬络合物为催化剂，在氢气氛围条件下选择性氢化中间炔烃，分别得到相应的顺式或反式烯烃。
背景技术
烯烃是一类重要的有机化合物，在材料、食品和制药等领域具有重要的应用。目前，市场上许多畅销的药品和食品添加剂含有烯烃结构。如白藜芦醇，利卡灵-A，苯烯莫德，异丁香酚，茴香脑分子中含有反式烯烃结构；康普瑞汀分子中含有顺式烯烃结构。通过过渡金属催化剂高选择性半还原中间炔烃合成顺式和反式烯烃是最实用和高效的方法之一，受到大力发展并逐渐应用到工业生产中。中间炔烃的半还原通常需要在氢气，计量的酸或其他氢源的条件下实现。与其他氢源相比较，氢气作为氢源有着原子经济性高，反应环保，体系干净等优点。虽然已有炔烃半氢化的方法可以得到相应的顺式或反式烯烃化合物，但是合成方法主要依赖昂贵金属催化剂（Pd，Ru，Rh，Ir）。对于常见廉价金属催化剂，例如：铜在催化合成顺式烯烃需要8-10 MPa的高压（Chem.Eur.J.2015,21, 15934–15938，Synthesis2017,49, 2470–2482）；铬催化合成顺式二苯乙烯衍生物存在Z/E选择性差的缺点(1/1至 10/1摩尔比) （ChemCatChem2020,12, 1–6）；采用锰催化剂只能合成含有芳基的顺式烯烃，而且存在底物受限的缺点（Org. Lett.2020,22, 5423−5428）；铁催化剂在合成顺式烯烃时，对于杂环化合物几乎不反应或产率较低（J.Am.Chem.Soc.2019,141, 17452−17458，ChemSusChem2019,12, 3864 – 3870）；镍催化剂在合成顺式烯烃时也需要120℃的高温（ChemSusChem2019,12, 3363 – 3369）。对于反式烯烃的合成更具有挑战性，常常面临过氢化产物的生成和选择性差的问题。例如：银催化合成反式烯烃需要150℃高温（J.Am.Chem.Soc.2015,137, 14598−14601）；镍催化和非金属催化合成反式烯烃则存在需要昂贵和具有毒性的氘代苯（氘代甲苯）作为溶剂或140℃高温，不利于大量的制备（J.Am.Chem.Soc.2020,142, 5396−5407，Nature Chemistry2013,5, 718–723，Chem.Eur.J.2015,21, 3495 – 3501）；铁催化合成反式烯烃对于杂环化合物比较受限，且选择性较差（Angew.Chem.Int.Ed.2013,52, 14131 –14134）；钴催化合成芳基烷基的反式烯烃，底物只能局限在烷基硅取代的炔烃，不能适用于其他烷基取代的炔烃（J.Am.Chem.Soc.2016,138, 13700−13705）。从之前的报道来看，采用廉价金属催化剂制备顺式或反式烯烃，反应条件比较苛刻，Z/E选择性差，杂环化合物不兼容，烷基烷基取代的中间炔烃均不能以很好的选择性得到反式炔烃。从上可见，高选择性合成指定构型烯烃结构的方法具有广阔的应用前景。采用廉价金属催化剂，反应条件温和，底物适用性范围广，高选择性的制备顺式或反式烯烃具有十分重要的意义。
发明内容
如前所述，虽然已有方法制备顺式或反式烯烃化合物，但是其具有局限性。本发明的目的是提供一种反应条件温和、以廉价金属为催化剂、底物适用范围广、操作简单、立体选择性高、反应体系干净的制备顺式或反式烯烃化合物的方法。
针对上述目的，本发明采用的技术方案是：将下面反应式所示的中间炔烃化合物、环状(烷基)(氨基)卡宾铬络合物催化剂、镁、氯硅烷以及分子筛加入四氢呋喃中，通入氢气，在25～100℃下搅拌反应，得到反应式所示的Z-3或E-3烯烃化合物。该方法具有如下反应通式：
Figure SMS_1
式中，R1,R2代表连在炔碳上的C1～C20烷基、呋喃基，噻吩基，吡啶基，芳基（芳基上含C1～C10烷基、烷氧基、酰胺基、酯基、卤代烃基、呋喃基，噻吩基，吡啶基，烯基，硅基，频哪醇硼酸酯基，氨基，羟基，取代炔基）任意一种或任意两种取代的组合。
上述环状(烷基)(氨基)卡宾铬络合物催化剂的结构式如下所示：
Figure SMS_2
上述环状(烷基)(氨基)卡宾铬络合物催化剂的加入量为中间炔烃化合物摩尔量的0.5%～10%。
上述镁的加入量为中间炔烃化合物毫摩尔量的1~3倍。
上述的氯硅烷为三甲基氯硅烷、三乙基氯硅烷或三丁基基氯硅烷中任意一种。氯硅烷的加入量为中间炔烃化合物摩尔量的0.2～2倍。
上述的分子筛为4Å分子筛或5Å分子筛中任意一种。
上述的有机溶剂为四氢呋喃。
上述方法中，通入氢气的压力为0.1～6 MPa。
上述方法中，在25～100℃下搅拌反应12~24小时。
顺式烯烃的合成步骤：
在有搅拌子的反应管中依次加入36 mg (0.2 mmol) 1,2-二苯乙炔、7 mg (0.01mmol)环状(烷基)(氨基)卡宾铬络合物催化剂1b、10 mg (0.4 mmol)镁，22 mg (0.1 mmol)三甲基氯硅烷，25 mg 4 Å MS，2 mL四氢呋喃，将反应管放入高压釜中，通入5 MPa的氢气。反应体系放置于40℃搅拌24 h。反应用盐酸水溶液淬灭，用乙酸乙酯萃取，萃取液在减压下除去挥发性溶剂。再经硅胶柱层析得到顺式烯烃化合物。
反式烯烃的合成步骤：
在有搅拌子的反应管中依次加入36 mg (0.2 mmol) 1,2-二苯乙炔、6 mg (0.01mmol)环状(烷基)(氨基)卡宾铬络合物催化剂1a，10 mg (0.4 mmol)镁，11 mg (0.05mmol)三甲基氯硅烷，2 mL四氢呋喃，将反应管防入高压釜中，通入1 MPa的氢气。反应体系放置于100℃搅拌24 h。反应用盐酸水溶液淬灭，用乙酸乙酯萃取，萃取液在减压下除去挥发性溶剂。再经硅胶柱层析得到反式烯烃化合物。
与已有的方法比较，本发明具有如下的优点：反应条件温和，廉价金属催化剂，反应快速且产率较高，底物适用范围广，产物E/Z选择性高，反应体系干净，适合顺式或反式烯烃化合物的生产。
具体实施方式
以下的实施例，在于详细的说明本发明而非限制本发明。
实施例1~23
实施例1
在有搅拌子的反应管中依次加入36 mg (0.2 mmol) 1,2-二苯乙炔、7 mg (0.01mmol)环状(烷基)(氨基)卡宾铬络合物催化剂1b、10 mg (0.4 mmol)镁，22 mg (0.1 mmol)三甲基氯硅烷，25 mg 4 Å MS，2 mL四氢呋喃，将反应管放入高压釜中，通入5 MPa的氢气。反应体系放置于40℃搅拌24 h。反应用盐酸水溶液淬灭，用乙酸乙酯萃取，萃取液在减压下除去挥发性溶剂。再经硅胶柱层析（洗脱剂为石油醚与乙酸乙酯体积比100:1的混合液），得到顺式-1,2二苯乙烯，产率88%，Z/E=93:7。
对比实施例1
用等摩尔量的1c替换实施例1中的1b，其他步骤与实施例1相同，得到顺式-1,2二苯乙烯，产率90%，Z/E=70:30。
对比实施例1
用等体积三乙基氯硅烷替换实施例1中的三甲基氯硅烷，其他步骤与实施例1相同，得到顺式-1,2二苯乙烯，产率83%，Z/E=92:8。
对比实施例1
用等体积三丁基基氯硅烷替换实施例1中的三甲基氯硅烷，其他步骤与实施例1相同，得到顺式-1,2二苯乙烯，产率85%，Z/E=90:10。
对比实施例1
用等质量的5Å分子筛替换实施例1中的4Å分子筛，其他步骤与实施例1相同，得到顺式-1,2二苯乙烯，产率81%，Z/E=93:7。
实施例2
本实施例中，用等摩尔4-(苯乙炔基)氯苯替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到4-氯-顺-二苯乙烯，产率86%，Z/E=97:3。
实施例3
本实施例中，用等摩尔4-(苯乙炔基)苯基特戊酸酯替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到4-特戊酰氧基-顺-二苯乙烯，产率92%，Z/E=97:3。
实施例4
本实施例中，用等摩尔4-(苯乙炔基)苯甲醇替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到4-羟甲基-顺-二苯乙烯，产率72%，Z/E=99:1。
实施例5
本实施例中，用等摩尔3-(苯乙炔基)苯胺替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到3-氨基-顺-二苯乙烯，产率88%，Z/E>99:1。
实施例6
本实施例中，用等摩尔2-(己-1-炔基)萘替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到顺-2-(1-己烯基)萘，产率90%，Z/E=98:2。
实施例7
本实施例中，用等摩尔6-十二炔替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到顺-6-十二烯，产率88%，Z/E=99:1。
实施例8
本实施例中，用等摩尔4-甲氧基苯丙炔替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到顺式-茴香烯，产率96%，Z/E=95:5。
实施例9
本实施例中，用等摩尔3-甲氧基-4-羟基苯丙炔替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到顺式-异丁香酚，产率84%，Z/E=96:4。
实施例10
本实施例中，用等摩尔1-(3,5-二甲氧基苯基)-2-(4-甲氧基苯基)乙炔替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到3,4',5-三甲氧基-顺-二苯乙烯，产率88%，Z/E=99:1。
实施例11
本实施例中，用等摩尔(E)-4,4'-(hex-3-ene-3,4-diyl)bis(hex-1-yn-1-ylbenzene)替换实施例1中的1,2-二苯乙炔，其他步骤与实施例1相同，得到1-((Z)-hex-1-en-1-yl)-4-((E)-4-(4-(hex-1-yn-1-yl)phenyl)hex-3-en-3-yl)benzene,产率44%，Z/E=99:1。
实施例12
在有搅拌子的反应管中依次加入36 mg (0.2 mmol) 1,2-二苯乙炔、6 mg (0.01mmol)环状(烷基)(氨基)卡宾铬络合物催化剂1a，10 mg (0.4 mmol)镁，11 mg (0.05mmol)三甲基氯硅烷，2 mL四氢呋喃，将反应管防入高压釜中，通入1 MPa的氢气。反应体系放置于100℃搅拌24 h。反应用盐酸水溶液淬灭，用乙酸乙酯萃取，萃取液在减压下除去挥发性溶剂。再经硅胶柱层析（洗脱剂为石油醚与乙酸乙酯体积比100:1的混合液），得到反式-1,2二苯乙烯，产率85%，E/Z=99:1。
实施例13
本实施例中，用等摩尔3-(苯乙炔基)苯酚替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-3-羟基二苯乙烯，产率87%，E/Z=90:10。
实施例14
本实施例中，用等摩尔4-(三甲硅基)二苯乙炔替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-4-(三甲基硅基)二苯乙烯，产率87%，E/Z=90:10。
实施例15
本实施例中，用等摩尔4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)二苯乙炔替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-4-(频哪醇硼酸酯基)二苯乙烯，产率65%，E/Z=86:14。
实施例16
本实施例中，用等摩尔3-(3-(苯乙炔基)苯基)呋喃替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-3-(3-呋喃基)二苯乙烯，产率95%，E/Z=98:2。
实施例17
本实施例中，用等摩尔3-(苯乙炔基)噻吩替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-3-苯乙烯基噻吩，产率84%，E/Z=92:8。
实施例18
本实施例中，用等摩尔3-(苯乙炔基)吡啶替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-3-苯乙烯基吡啶，产率39%，E/Z=94:6。
实施例19
本实施例中，用等摩尔1,3-二甲基-5-(辛-1-炔基)苯替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反-1,3-二甲基-5-(辛-1-烯基)苯，产率85%，E/Z=99:1。
实施例20
本实施例中，用等摩尔4-甲氧基苯丙炔替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反式-茴香脑，产率92%，E/Z=97:3。
实施例21
本实施例中，用等摩尔3-甲氧基-4-羟基苯丙炔替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反式-异丁香酚，产率87%，E/Z=98:2。
实施例22
本实施例中，用等摩尔(E)-4,4'-(hex-3-ene-3,4-diyl)bis(hex-1-yn-1-ylbenzene)替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到(E)-4,4'-((E)-hex-3-ene-3,4-diyl)bis(((E)-hex-1-en-1-yl)benzene), 产率76%，E/Z=99:1。
实施例23
本实施例中，用等摩尔1-三甲基硅基-1-辛炔替换实施例14中的1,2-二苯乙炔，其他步骤与实施例14相同，得到反式-1-三甲基硅基-1-辛烯, 产率78%，E/Z=96:4。

Claims (8)

1.一种铬催化中间炔烃选择性氢化制备顺式或反式烯烃的方法，其特征在于：将下列反应式所示的中间炔烃化合物、环状(烷基)(氨基)卡宾铬络合物催化剂、镁、氯硅烷和分子筛加入四氢呋喃(THF)溶剂中，通入氢气，搅拌反应，得到顺式或反式烯烃化合物；R1,R2代表连在炔碳上的C1～C20烷基、呋喃基，噻吩基，吡啶基，芳基(芳基上含C1～C10烷基、烷氧基、酰胺基、酯基、卤代烃基、呋喃基，噻吩基，吡啶基，烯基，硅基，频哪醇硼酸酯基，氨基，羟基，取代炔基)任意一种或任意两种取代基的组合。
Figure QLYQS_1
2.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：所述通入氢气的压力为0.1～6MPa。
3.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：所述环状(烷基)(氨基)卡宾铬络合物催化剂的加入量为中间炔烃化合物摩尔量的0.5％～10％。
4.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：所述镁的加入量为中间炔烃化合物摩尔量的1～3倍。
5.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：所述氯硅烷为三甲基氯硅烷(TMSCl)、三乙基氯硅烷或三丁基氯硅烷。氯硅烷的加入量为中间炔烃化合物摩尔量的0.2～2倍。
6.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：所述分子筛为
Figure QLYQS_2
分子筛或者/>
Figure QLYQS_3
分子筛。分子筛加入量按每摩尔量的中间炔烃化合物加入25～200mg。
7.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：溶剂为四氢呋喃。
8.根据权利要求1所述的以铬催化中间炔烃选择性氢化合成顺式或反式烯烃的方法，其特征在于：在25～100℃下搅拌反应12～24小时。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120130086A1 (en) * 2010-03-03 2012-05-24 Sk Global Chemical Co., Ltd. Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same
CN112661653A (zh) * 2020-12-28 2021-04-16 四川大学 一种环状（烷基）（氨基）卡宾铬络合物催化还原硝基化合物制备胺的方法
CN113443952A (zh) * 2021-07-15 2021-09-28 南通大学 水供氢铱催化炔烃半还原选择性合成顺、反式烯烃的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120130086A1 (en) * 2010-03-03 2012-05-24 Sk Global Chemical Co., Ltd. Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same
CN112661653A (zh) * 2020-12-28 2021-04-16 四川大学 一种环状（烷基）（氨基）卡宾铬络合物催化还原硝基化合物制备胺的方法
CN113443952A (zh) * 2021-07-15 2021-09-28 南通大学 水供氢铱催化炔烃半还原选择性合成顺、反式烯烃的方法

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