CN112892596A - 一种钯催化剂及其在Heck反应中的应用 - Google Patents
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
本发明公开一种钯催化剂及其在Heck反应中的应用;该钯催化剂先由2,6‑二苯基苯胺和二酮反应得到二亚胺配体,二亚胺配体与PdCl2进行配位得到钯催化剂;在钯催化剂的配体的邻位引入苯基,邻位苯基的的引入对钯金属中心有一定的屏蔽作用,增大骨架上的位阻,使钯金属催化剂的位阻进一步增大,有利于稳定把金属中心,在强碱的作用下,钯催化剂能稳定的高效的催化Heck反应。
Description
技术领域
本发明属催化化学领域,具体涉及一种钯催化剂及其在Heck反应中的应用。
背景技术
传统的Heck反应一般是在PdCl2或Pd(OAc)2等均相催化剂的作用下进行的,但是它们在反应过程中易是钯离子还原生成钯黑,使催化剂失活和降低了其应用性能;为了提高催化剂寿命和效率,科学家发展了钯配合物催化剂体系,其中含有机磷配体的钯催化剂被大量研究,然而,有机膦配体具有较敏感以及毒性大的缺点;作为一类毒性较小的含氮类配体,N^N两齿钯配合物也能高活性地催化Heck反应,给钯配合物催化Heck反应提供了研究的新突破口。在Heck偶联反应中,Pd催化剂的活性受配体的影响很大。基于此,本发明制备一种钯催化剂,并将其应用于Heck反应中。
发明内容
为克服现有技术的缺点和不足,本发明提供一种钯催化剂,在钯催化剂的配体的邻位引入苯基,邻位苯基的的引入对钯金属中心有一定的屏蔽作用,增大骨架上的位阻,使钯金属催化剂的位阻进一步增大,有利于稳定把金属中心,在强碱的作用下,钯催化剂能稳定的高效的催化Heck反应。
本发明的目的在于提供一种钯催化剂。
本发明的另一目在于是提供上述钯催化剂的制备方法。
本发明的再一目的在于提供上述钯催化剂在Heck反应中的应用。
本发明上述目的通过以下技术方案实现:
一种钯催化剂,其结构式如下式(I)所示:
一种钯催化剂的制备方法,包括如下步骤:
(1)氮气气氛和室温条件下,在100mL的支口瓶中依次加入2,6-苯基苯胺、溶剂,然后用注射器缓慢加入三甲基铝,将反应温度升至110℃,反应2h后,将反应温度降至室温,然后加入二酮,110℃下继续反应6h,再降温至0℃,反应体系用5%的氢氧化钠冰水溶液终止,有机相用乙酸乙酯萃取,然后用无水MgSO4干燥,减压蒸干溶剂得到橙色油状物,在乙醇重结晶或过柱分离得到橙色的二亚胺配体。
进一步的,所述二酮的结构式如下所示:
进一步的,所述二酮与2,6-苯基苯胺、三甲基铝的摩尔比为1:2~2.5:2~2.5。
进一步的,所述反应所用的溶剂为甲苯、四氢呋喃、二氧六环中的一种。
(2)将二亚胺、氯化钯、溶剂加入支口瓶中,N2保护下60℃搅拌反应16h,冷却至室温,过柱,收集滤液,二氯甲烷/正己烷重结晶,得到的固体用正己烷洗,抽滤、重复洗涤三次得橙红色钯催化剂。
进一步的,所述的二亚胺配体的结构式为:
进一步的,溶剂为甲醇、二氯甲烷、甲苯、四氢呋喃中的一种。
进一步的,二亚胺与氯化钯的摩尔比为1~1.5:1。
本发明还提供上述钯催化剂在Heck反应中的应用。
Heck反应可参见下面的反应方程式:
进一步的,所述反应时间为12h~24h,反应温度为110℃~150℃,反应溶剂为N,N-二甲基乙酰、N,N-二甲基甲酰胺、四氢呋喃、甲苯、N-甲基吡咯烷酮、二氧六环、二甲苯、二甲基亚砜任意一种或多种,反应所用的碱为NaOH、KOH、LiOH、Ca(OH)2任意一种或多种。
与现有技术相比,本发明具有如下优点和有益效果:
本发明得到的钯催化剂在钯催化剂的配体的邻位引入苯基,邻位苯基的的引入对钯金属中心有一定的屏蔽作用,增大骨架上的位阻,使钯金属催化剂的位阻进一步增大,有利于稳定把金属中心,在强碱的作用下,钯催化剂能稳定的高效的催化Heck反应;在强碱的作用下,本发明得到的钯催化剂催化Heck反应时,24h仍然具有较高的催化效率。
附图说明
图1为本发明制备的二亚胺的单晶结构图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
本发明所有底物的转化率计算方法均通过气相色谱测试进行计算,通过查看峰积分面积,然后计算得到溴苯转化率。
实施例1
氮气气氛和室温条件下,在100mL的支口瓶中依次加入2,6-苯基苯胺(12mmol),甲苯20mL,然后用注射器缓慢加入三甲基铝12mL(1.0M,12mmol),将反应温度升至110℃反应,此时反应放出甲烷气体,反应2h后,将反应温度降至室温,然后加入二酮(5mmol),此时反应体系由无色变为深红色,并大量放热。在110℃下继续反应6h,再降温至0℃,反应体系用5%的氢氧化钠冰水溶液终止,有机相用乙酸乙酯萃取,然后用无水MgSO4干燥,减压蒸干溶剂得到橙色油状物,在乙醇重结晶或过柱分离得到橙色的二亚胺配体,产率为80.7%。
实施例2
将二亚胺配体(1mmol),氯化钯(1.1mmol),甲醇8mL加入支口瓶中,N2保护下60℃搅拌反应16h,冷却至室温,以二氯甲烷为洗脱剂干法过柱,收集滤液,旋干后用少量二氯甲烷溶解,缓慢滴加至搅拌状态的正己烷溶液中,立即析出大量黄色固体粉末,抽滤、重复洗涤三次得橙红色对位甲氧基取代的钯催化剂,产率为86.4%。
实施例3
将制备的钯催化剂在不同的反应条件下催化Heck反应。
首先将4μmol钯催化剂溶于5mL反应溶剂中,配成浓度为8×10-4mol/L的钯催化剂溶液,在氮气保护下,依次将2.0mmol溴苯,2.4mmol苯乙烯,2.2mmol的碱和4mL反应溶剂加入到干燥的50mL的施莱克管中,最后用一干净的注射器从已经配好的钯催化剂溶液中取出50μL溶液注入到上述施莱克管中,密封,将反应液置于甲基硅油中,反应温度为150℃,搅拌到中止反应时间后,取一干净的注射器(量程为50μL)从反应液中取出25μL,将取出的反应液用反应溶剂稀释3~4倍后,取1~2μL稀释液注入气相色谱中,通过查看积分面积,然后计算得到溴苯转化率。同时,将反应液冷却至室温,冷却至室温后,用乙酸乙酯(3×40mL)和去离子水(50mL)萃取三次,取有机相,然后用饱和食盐水洗涤三次后,再用无水硫酸镁干燥除去有机相中剩余的少量水,过滤除去硫酸镁,旋蒸浓缩,之后用硅胶柱色谱层析法分离,旋蒸除去溶剂,真空干燥箱中干燥24小时,最后得到纯白色的片状固体(1,2-二苯乙烯)。
表1钯催化剂催化Heck反应结果
序号 | 碱 | 溶剂 | 温度(℃) | 时间(h) | 转化率(%) |
1 | NaOH | DMSO | 130 | 12 | 31 |
2 | NaOH | DMSO | 150 | 12 | 84 |
3 | NaOH | DMSO | 150 | 24 | 96 |
4 | KOH | DMSO | 150 | 12 | 81 |
5 | LiOH | DMSO | 150 | 12 | 76 |
6 | Ca(OH)<sub>2</sub> | DMSO | 150 | 12 | 74 |
7 | NaOH | DMA | 150 | 12 | 81 |
8 | NaOH | DMF | 150 | 12 | 65 |
9 | NaOH | NMP | 150 | 12 | 71 |
10 | NaOH | Dioxane | 150 | 12 | 42 |
11 | NaOH | Xylene | 150 | 12 | trance |
12 | NaOH | THF | 150 | 12 | 36 |
13 | NaOH | Toluene | 150 | 12 | trance |
从表1的数据我们可以看出,本发明所制备的钯催化剂能高效的催化Heck,制备得到染料中间体1,2-二苯乙烯。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
2.根据权利要求1所述钯催化剂的制备方法,其特征在于,包括如下步骤:
(1)氮气气氛和室温条件下,在100mL的支口瓶中依次加入2,6-苯基苯胺、溶剂,然后用注射器缓慢加入三甲基铝,将反应温度升至110℃,反应2h后,将反应温度降至室温,然后加入二酮,110℃下继续反应6h,再降温至0℃,反应体系用5%的氢氧化钠冰水溶液终止,有机相用乙酸乙酯萃取,然后用无水MgSO4干燥,减压蒸干溶剂得到橙色油状物,在乙醇重结晶或过柱分离得到橙色的二亚胺配体;
(2)将二亚胺、氯化钯、溶剂加入支口瓶中,N2保护下60℃搅拌反应16h,冷却至室温,过柱,收集滤液,二氯甲烷/正己烷重结晶,得到的固体用正己烷洗,抽滤、重复洗涤三次得橙红色钯催化剂。
3.根据权利要求2所述钯催化剂的制备方法,其特征在于,步骤(1)中,所述二酮与2,6-苯基苯胺、三甲基铝的摩尔比为1:2~2.5:2~2.5。
4.根据权利要求2所述钯催化剂的制备方法,其特征在于,步骤(1)中,所述反应所用的溶剂为甲苯、四氢呋喃、二氧六环中的一种。
7.根据权利要求2所述钯催化剂的制备方法,其特征在于,步骤(2)中,溶剂为甲醇、二氯甲烷、甲苯、四氢呋喃中的一种。
8.根据权利要求2所述钯催化剂的制备方法,其特征在于,步骤(2)中,二亚胺与氯化钯的摩尔比为1~1.5:1。
9.根据权利要求1所述钯催化剂在Heck反应中的应用,其特征在于,所述反应时间为12h~24h,反应温度为110℃~150℃,反应溶剂为N,N-二甲基乙酰、N,N-二甲基甲酰胺、四氢呋喃、甲苯、N-甲基吡咯烷酮、二氧六环、二甲苯、二甲基亚砜任意一种或多种,反应所用的碱为NaOH、KOH、LiOH、Ca(OH)2任意一种或多种。
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