CN113999261A - 一种邻二甲基芳香环类二膦基配体化合物及其合成方法 - Google Patents
一种邻二甲基芳香环类二膦基配体化合物及其合成方法 Download PDFInfo
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Abstract
本发明公开了一种邻二甲基芳香环类二膦基配体化合物及其合成方法,该方法以邻二卤代甲基芳香烃为原料合成相应膦酯,利用氢化铝锂还原生成相应膦氢,再和卤代、烯烃基或炔烃基配体生成相应的邻二甲基芳香环类二膦基配体化合物。根据本发明提供的合成方法,过程简单,步骤少,产物纯度和收率高,符合原子经济学和绿色化学,是一种直接且高效制备有机膦配体化合物的方法。制备的得到的目标产物是一系列邻二甲基芳香环类二膦基配体催化剂,对多种烯烃底物,如端烯,内烯,支烯,的酯化和烷氧羰基化反应,表现出了优异的催化活性和选择性,在医药、化工合成以及天然产物合成领域具有广阔的应用前景。
Description
技术领域
本发明属于有机化学合成领域,涉及一种邻二甲基芳香环类二膦基配体化合物及其合成方法,尤其是1,2-二(4-膦酮)二甲苯化合物及其合成方法。
背景技术
卞基类、芳香环类有机膦配体化合物是一种重要的催化剂,在氢甲酰化、烯烃的酯化和羰基化等反应中,有着了举足轻重的地位。近些年来,新型的配体和相应的金属配合物的快速发展,例如钯/膦配合物催化体系,在工业上已经得到广泛的应用,可以在较温和的反应条件下,高效催化烯烃的烷氧羰基化反应。
随着对有机膦配体相关性质的深入研究,催化机理的不断探索,位阻效应对有机膦配体的催化效果,起到了十分关键的作用。相比于传统的传统三苯基膦修饰的钯催化剂体系,二齿状膦配体修饰的钯催化剂体系由于其空间位阻效应而表现出更好的催化性能。
邻二甲基芳香环类二膦基配体由于其结构稳定,配体可调控,反应活性高等优势在科研界和工业界吸引了很多关注。它的发展促进了很多钯催化反应的突破,在合成功能材料、天然产物及生物活性材料中有着广阔的用途。但其生产过程一般较为复杂,合成路线长,需要使用大量难于后处理的溶剂,产率较低。
鉴于邻二甲基芳香环类二膦基配体独特的催化性质以及广阔的市场前景,因此本发明提供了一种由邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体一步生成相应的邻二甲基芳香环类二膦基配体化合物的方法,合成步骤少,产率高,有工业化大规模生产的应用前景。
发明内容
本发明的目的在于克服现有技术中的缺陷,并提供一种邻二甲基芳香环类二膦基配体化合物及其合成方法。该方法条件温和,后处理简单,适合工业化生产邻二甲基芳香环类二膦基配体化合物。
本发明所采用的具体技术方案如下:
第一方面,本发明提供了一种邻二甲基芳香环类二膦基配体化合物的合成方法,具体如下:
S1:在惰性气体氛围下,将邻二卤代甲基芳香烃和亚磷酸酯进行反应,分离后得到邻二膦酯代甲基芳香烃;
在实际应用时,该步骤可以具体采用如下方法:在室温条件下,将邻二卤代甲基芳香烃滴加到亚磷酸酯中,滴加结束后,加热至130℃,在该温度下反应过夜。这里的分离方法可以采用蒸馏。
S2:在惰性气体氛围下,将所述邻二膦酯代甲基芳香烃、三甲基氯硅烷和氢化铝锂在有机溶剂中进行反应,分离后得到邻二膦氢代甲基芳香烃;
在实际应用时,该步骤可以具体采用如下方法:在-80℃以下温度条件下,将三甲基氯硅烷滴加入含有氢化铝锂的有机溶剂,滴加结束后,恢复至室温,反应3小时,在不超过-50℃的温度条件下,加入邻二膦酯代甲基芳香烃,恢复至室温,反应3小时。这里的分离可以通过柱层析实现。
S3:在惰性气体氛围下,将所述邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体进行反应,分离后得到单取代芳香烃类膦基配体化合物;再将所述单取代芳香烃类膦基配体化合物和卤代、烯烃基或炔烃基配体进行反应,分离后得到邻二甲基芳香环类二膦基配体化合物;
在实际应用时,该步骤可以具体采用如下方法:在室温条件下,将邻二膦氢代甲基芳香烃滴加到卤代、烯烃基或炔烃基配体中,滴加结束后,加热至120℃,在该温度下反应过夜。这里的分离可以通过重结晶实现。
所述邻二甲基芳香环类二膦基配体化合物的化学结构式为
其中,R1、R2、R3、R4包括但不限于叔丁基,吡啶基,N-甲基吡咯基,N-甲基咪唑基,喹啉基,呋喃基,硫代呋喃基,金刚烷基等有机配体。
作为优选,所述邻二甲基芳香环类二膦基配体化合物为P-1至P-10中的任一种,具体化学结构式分别为:
作为优选,所述亚磷酸酯为亚磷酸三甲酯、亚磷酸三乙酯和亚磷酸三丁酯中的一种或两种以上的混合。
作为优选,所述有机溶剂为四氢呋喃、乙醚、正己烷和正庚烷的一种或两种以上的混合。
作为优选,所述亚磷酸酯和邻二卤代甲基芳香烃的摩尔比为3~5:1。
作为优选,所述邻二膦酯代甲基芳香烃、三甲基氯硅烷和氢化铝锂的摩尔比为1:3.5~5:3.5~5。
作为优选,所述步骤S3中,将所述邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体进行两次单取代反应,分离后得到邻二甲基芳香环类二膦基配体化合物;每次单取代反应过程中,卤代、烯烃基或炔烃基配体和邻二膦氢代甲基芳香烃的摩尔比均为1.9~2.1:1。
作为优选,所述步骤S3中,将所述邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体进行双取代反应,分离后得到邻二甲基芳香环类二膦基配体化合物;双取代反应过程中,卤代、烯烃基或炔烃基配体和邻二膦氢代甲基芳香烃的摩尔比为4.1~4.5:1。
上述合成方法的各步骤均可以在圆底烧瓶或Schlenk瓶中进行。
第二方面,本发明提供了一种利用第一方面任一所述合成方法合成的邻二甲基芳香环类二膦基配体化合物。
本发明相对于现有技术而言,具有以下有益效果:
本方法提供的合成方法在室温或低温条件下,以邻二卤代甲基芳香烃为原料合成相应膦酯,利用氢化铝锂还原生成相应膦氢,再和卤代、烯烃基或炔烃基配体生成相应的邻二甲基芳香环类二膦基配体化合物。实验结果表明,本发明提供的方法合成邻二甲基芳香环类二膦基配体化合物,收率在77%~92%之间,纯度大于98%,并且本发明中合成过程简单,步骤少,无污染,反应成本低,有巨大的工业化生产的应用前景。
附图说明
图1为实施例1所得1,2-二(4-膦酮)二甲苯的核磁氢谱;
图2为实施例1所得1,2-二(4-膦酮)二甲苯的核磁磷谱;
图3为实施例1所得1,2-二(4-膦酮)二甲苯的核磁碳谱。
具体实施方式
本发明公开一种邻二甲基芳香环类二膦基配体化合物及其合成方法,本领域技术人员可以借鉴本文内容,根据实际实验环境,优化相关实验参数实现。特别指出的是,本发明的许多改变和变化对本领域的技术人员来说都是显而易见的,它们都应被视为包含在本发明当中。本发明的合成路线及方法已经通过较佳的实施案例进行详细描述,这些描述仅是示范性描述,不构成对本发明范围的限制。相关技术领域的技术人员明显可以在不脱离本发明的内容和范围内对本文所述的方法进行适当改变和组合,来实现本发明的相关技术。下面结合附图和具体实施方式对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下,均可进行相应组合。
本发明提供了一种合成邻二甲基芳香环类二膦基配体化合物的合成方法,以邻二卤代甲基芳香烃为原料合成相应膦酯,利用氢化铝锂还原生成相应膦氢,再和卤代、烯烃基或炔烃基配体生成相应的邻二甲基芳香环类二膦基配体化合物。
实施例1
本实施例制备得到了一种1,2-二(4-膦酮)邻二甲苯配体(P-1),制备方法具体如下:
a)制备1,2-二磷酸丁酯邻二甲苯:在惰性气体氛围下,在50mL Schlenk瓶中,室温依次加入1.95g二溴邻二甲苯和8mL亚磷酸三丁酯,在130℃的温度条件下,反应24个小时。待反应结束后,可通过减压蒸馏进一步纯化,在5mbar条件下,取120℃的馏分,得到1,2-二磷酸丁酯邻二甲苯,收率为98%。
b)制备1,2-二膦氢邻二甲苯:在惰性气体氛围下,在50mL Schlenk中,300mg氢化铝锂分散在15mL四氢呋喃中,温度不超过-80℃,滴加1mL三甲基氯硅烷。恢复至室温,反应3小时。将1g 1,2-二磷酸丁酯邻二甲苯分散在10mL四氢呋喃中,在不超过-50℃的温度条件下,滴加到反应体系中,恢复至室温,反应三小时。待反应结束后,缓慢滴加1mL脱气去离子水和1mL 20%脱气氢氧化钠水溶液。加入脱气无水硫酸镁后过滤,滤饼用5mL脱气四氢呋喃洗涤三次,浓缩滤液,得到1,2-二膦氢邻二甲苯,产率为99%。
c)制备1,2-二(4-膦酮)邻二甲苯:在惰性气体氛围下,在50mL Schlenk瓶中,依次加入将340mg1,2-二膦氢邻二甲苯和0.65mL 2,6-二甲基-2,5-庚二烯-4-酮(烯烃基配体),加热至120℃,反应22小时。反应结束后,恢复至室温,向黄色的油状物加入少量甲醇重结晶,低温静置过夜后过滤,得到1,2-二(4-膦酮)邻二甲苯,产率为91%。
如图1~3所示,为制备所得1,2-二(4-膦酮)二甲苯的核磁氢谱、核磁磷谱和核磁碳谱,从图中可以看出,核磁数据与预设计产物结构一致,说明成功合成高纯度1,2-二(4-膦酮)二甲苯。
实施例2
本实施例制备得到了一种1,2-二((叔丁基)(2-吡啶基)膦基)邻二甲苯(P-3),制备方法具体如下:
a)制备1,2-二磷酸丁酯邻二甲苯:在惰性气体氛围下,在50mL Schlenk瓶中,室温依次加入1.95g二溴邻二甲苯和8mL亚磷酸三丁酯,在130℃的温度条件下,反应24个小时。待反应结束后,可通过减压蒸馏进一步纯化,在5mbar条件下,取120℃的馏分,得到1,2-二磷酸丁酯邻二甲苯,收率为98%。
b)制备1,2-二膦氢邻二甲苯:在惰性气体氛围下,在50mL Schlenk中,300mg氢化铝锂分散在15mL四氢呋喃中,温度不超过-80℃,滴加1mL三甲基氯硅烷。恢复至室温,反应3小时。将1g 1,2-二磷酸丁酯邻二甲苯分散在10mL四氢呋喃中,在不超过-50℃的温度条件下,滴加到反应体系中,恢复至室温,反应三小时。待反应结束后,缓慢滴加1mL脱气去离子水和1mL 20%脱气氢氧化钠水溶液。加入脱气无水硫酸镁后过滤,滤饼用5mL脱气四氢呋喃洗涤三次,浓缩滤液,得到1,2-二膦氢邻二甲苯,产率为99%。
c)1,2-二((叔丁基)(2-吡啶基)膦基)邻二甲苯:在惰性气体氛围下,在50mLSchlenk瓶中,依次加入将340mg 1,2-二膦氢邻二甲苯和396.5mg叔丁基溴,加热至120℃,反应18小时。反应结束后,恢复至室温,向黄色的油状物加入457mg 2-溴吡啶加热至120℃,反应18小时。反应结束后,恢复至室温,加入少量甲醇重结晶,低温静置过夜后过滤,得到1,2-二((叔丁基)(2-吡啶基)膦基)邻二甲苯,产率为78%。
实施例3
本实施例制备得到了一种1,2-二(1-金刚烷基)膦基邻二甲苯(P-10),制备方法具体如下:
a)制备1,2-二磷酸丁酯邻二甲苯:在惰性气体氛围下,在50mL Schlenk瓶中,室温依次加入1.95g二溴邻二甲苯和8mL亚磷酸三丁酯,在130℃的温度条件下,反应24个小时。待反应结束后,可通过减压蒸馏进一步纯化,在5mbar条件下,取120℃的馏分,得到1,2-二磷酸丁酯邻二甲苯,收率为98%。
b)制备1,2-二膦氢邻二甲苯:在惰性气体氛围下,在50mL Schlenk中,300mg氢化铝锂分散在15mL四氢呋喃中,温度不超过-80℃,滴加1mL三甲基氯硅烷。恢复至室温,反应3小时。将1g 1,2-二磷酸丁酯邻二甲苯分散在10mL四氢呋喃中,在不超过-50℃的温度条件下,滴加到反应体系中,恢复至室温,反应三小时。待反应结束后,缓慢滴加1mL脱气去离子水和1mL 20%脱气氢氧化钠水溶液。加入脱气无水硫酸镁后过滤,滤饼用5mL脱气四氢呋喃洗涤三次,浓缩滤液,得到1,2-二膦氢邻二甲苯,产率为99%。
c)1,2-二(1-金刚烷基)膦基邻二甲苯:在惰性气体氛围下,在50mL Schlenk瓶中,依次加入将340mg1,2-二膦氢邻二甲苯和1.72g 1-溴代金刚烷,加热至120℃,反应24小时。反应结束后,恢复至室温,向黄色的油状物加入少量甲醇重结晶,低温静置过夜后过滤,得到1,2-二(1-金刚烷基)膦基邻二甲苯,产率为87%。
本发明以邻二卤代甲基芳香烃为原料合成相应膦酯,利用氢化铝锂还原生成相应膦氢,再和卤代、烯烃基或炔烃基配体生成相应的邻二甲基芳香环类二膦基配体化合物。根据本发明提供的合成方法,过程简单,步骤少,产物纯度和收率高,符合原子经济学和绿色化学,是一种直接且高效制备有机膦配体化合物的方法。制备的得到的目标产物是一系列邻二甲基芳香环类二膦基配体催化剂,对多种烯烃底物,如端烯,内烯,支烯,的酯化和烷氧羰基化反应,表现出了优异的催化活性和选择性,在医药、化工合成以及天然产物合成领域具有广阔的应用前景。
以上所述的实施例只是本发明的一种较佳的方案,然其并非用以限制本发明。有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型。因此凡采取等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (10)
4.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述亚磷酸酯为亚磷酸三甲酯、亚磷酸三乙酯和亚磷酸三丁酯中的一种或两种以上的混合。
5.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述有机溶剂为四氢呋喃、乙醚、正己烷和正庚烷的一种或两种以上的混合。
6.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述亚磷酸酯和邻二卤代甲基芳香烃的摩尔比为3~5:1。
7.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述邻二膦酯代甲基芳香烃、三甲基氯硅烷和氢化铝锂的摩尔比为1:3.5~5:3.5~5。
8.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述步骤S3中,将所述邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体进行两次单取代反应,分离后得到邻二甲基芳香环类二膦基配体化合物;每次单取代反应过程中,卤代、烯烃基或炔烃基配体和邻二膦氢代甲基芳香烃的摩尔比均为1.9~2.1:1。
9.根据权利要求1所述一种邻二甲基芳香环类二膦基配体化合物的合成方法,其特征在于,所述步骤S3中,将所述邻二膦氢代甲基芳香烃和卤代、烯烃基或炔烃基配体进行双取代反应,分离后得到邻二甲基芳香环类二膦基配体化合物;双取代反应过程中,卤代、烯烃基或炔烃基配体和邻二膦氢代甲基芳香烃的摩尔比为4.1~4.5:1。
10.一种利用权利要求1~9任一所述合成方法合成的邻二甲基芳香环类二膦基配体化合物。
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