CN110229080B - α-二亚胺镍金属有机配体、多孔有机聚合物及其应用 - Google Patents
α-二亚胺镍金属有机配体、多孔有机聚合物及其应用 Download PDFInfo
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Abstract
本公开提供了α‑二亚胺镍金属有机配体、多孔有机聚合物及其应用，多孔有机聚合物包括如下化学结构式：
本公开提供的多孔有机聚合物能够获得用于催化Suzuki偶联反应的催化剂，且该催化剂的催化活性高、成本低，使用量少，而且能够重复利用。
Description
技术领域
本公开属于催化剂制备技术领域，涉及α-二亚胺镍金属有机配体、多孔有机聚合物及其应用。
背景技术
这里的陈述仅提供与本公开有关的背景信息，而不必然构成现有技术。
铃木反应，也称作Suzuki偶联反应、Suzuki-Miyaura反应(铃木-宫浦反应)，是一种有机偶联反应，该反应在零价钯配合物催化下，芳基或烯基硼酸或硼酸酯与氯、溴、碘代芳烃或烯烃发生交叉偶联。铃木反应由铃木章在1979年首先报道，在有机合成中的用途很广，具有较强的底物适应性及官能团容忍性，常用于合成多烯烃、苯乙烯和联苯的衍生物，从而应用于众多天然产物、有机材料的合成中。通常情况下，铃木反应的催化剂为零价钯配合物等钯催化剂。经本公开发明人了解，钯催化剂具有催化活性低、成本高等缺点。
发明内容
为了解决现有技术的不足，本公开的目的是提供α-二亚胺镍金属有机配体、多孔有机聚合物及其应用，以α-二亚胺镍金属有机配体作为原料制备多孔有机聚合物能够获得用于催化Suzuki偶联反应的催化剂，该催化剂的催化活性高、成本低，使用量少，而且能够重复利用。
为了实现上述目的，本公开的技术方案为：
一方面，α-二亚胺镍金属有机配体，其化学结构式为：
另一方面，上述有机配体的制备方法，2,6-二异丙基对碘苯胺与2,3-丁二酮进行酮胺缩合反应获得。
第三方面，用于制备多孔有机聚合物的单体，其化学结构式为：
第四方面，上述单体的制备方法，将无水溴化镍配位至上述有机配体中，获得单体。
第五方面，多孔有机聚合物，包括如下化学结构式：
第六方面，上述多孔有机聚合物的制备方法，将上述单体与1,3,5-三乙炔苯进行sonogashira偶联反应获得。
第七方面，一种催化剂，包括活性成分，所述活性成分为上述多孔有机聚合物。
第八方面，一种上述多孔有机聚合物或上述催化剂在催化Suzuki偶联反应中的应用。
第九方面，一种联苯类化合物的合成方法，以上述多孔有机聚合物作为催化剂进行如下反应路线的Suzuki偶联反应：
其中，X为卤素(Br,I)，R1可以是-NO2,-COCH3,-OCH3,-OH,-CN,-H,-OCH3,-CF3,-CO2CH3,-CH3等一系列取代基，可以分为吸电子基和供电子基。R2可以是-CN,-OCH3,-CH3,-F,-COCH3等，也可以分为吸电子基和供电子基。
第十方面，一种上述催化剂的或上述合成方法采用的催化剂的回收方法，将反应后的物料进行离心分离，离心分离后的沉淀为回收的催化剂。
本公开提供的α-二亚胺镍金属有机配体，既能够与二价镍形成配合物，又能与1,3,5-三乙炔苯进行sonogashira偶联反应获得多孔有机聚合物，多孔有机聚合物(porousorganic polymers，POPs)是一种低骨架密度以及优异的稳定性的材料，采用多孔有机聚合物能够负载更多的二价镍配合物，同时协同多孔有机聚合物的多孔结构，能够极大的提高对Suzuki偶联反应的催化效果；而且本公开提供的多孔有机聚合物分离回收的方法更为简单，回收后的多孔有机聚合物重复多次使用后还能具有较高的催化效果。
本公开的有益效果为：
(1)本公开提供的具有活性位点的Ni-POPS催化剂可以用来代替一些钯金属来起到催化作用，有价格便宜，催化效果好的优点
(2)采用本公开的具有活性位点的POPs催化剂进行催化，实现了异相催化；同时本发明的Ni(Ⅱ)-α-diimine-POP催化剂可以重复利用五次以上，并且做到了催化剂与碱一起回收容易，提高了催化剂的利用率，降低了成本。
(3)采用本公开的具有活性位点的POPs催化剂具有反应温度温和、反应时间较短、催化剂用量少、无其他添加剂等优点。
(4)本公开提供了一种从二亚胺配体出发通过席夫碱的反应的路径，拓宽了催化剂的领域。
附图说明
构成本公开的一部分的说明书附图用来提供对本公开的进一步理解，本公开的示意性实施例及其说明用于解释本公开，并不构成对本公开的不当限定。
图1为本公开实施例1制备的α-二亚胺镍金属有机配体(A)的1H NMR；
图2为本公开实施例1制备的α-二亚胺镍金属有机配体(A)的质谱图；
图3为本公开实施例2制备的多孔有机聚合物的单体(B)的1H NMR；
图4为本公开实施例2制备的多孔有机聚合物的单体(B)的质谱图；
图5为本公开实施例3制备的Ni(Ⅱ)-α-diimine-POP的电镜照片，a为TEM，b为SEM；
图6为本公开实施例3制备的Ni(Ⅱ)-α-diimine-POP的红外谱图；
图7为本公开实施例3制备的Ni(Ⅱ)-α-diimine-POP的TGA谱图；
图8为本公开实施例3制备的Ni(Ⅱ)-α-diimine-POP的元素分布谱图；
图9为本公开实施例4制备的联苯的1H NMR；
图10为本公开实施例5、6进行suzuki偶联反应后Ni(Ⅱ)-α-diimine-POP的PXRD谱图；
图11为本公开实施例5、6进行suzuki偶联反应后Ni(Ⅱ)-α-diimine-POP的XPS谱图，左图为催化剂催化之前镍的XPS图，右图为催化剂在催化反应五次循环之后的XPS图。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本公开提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本公开所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本公开的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
本公开中所述的sonogashira偶联反应是指由Pd/Cu混合催化剂催化的末端炔烃与sp2型碳的卤化物之间的交叉偶联反应。
本公开所述的惰性气氛是指能够防止氧气氧化的气体提供的气体氛围，该气体例如氮气、氩气等。
鉴于钯催化剂具有催化活性低、成本高等不足，为了解决如上的技术问题，本公开提出了α-二亚胺镍金属有机配体、多孔有机聚合物及其应用。
本公开的一种典型实施方式，提供了α-二亚胺镍金属有机配体，其化学结构式为：
本公开的另一种实施方式，提供了上述有机配体的制备方法，2,6-二异丙基对碘苯胺与2,3-丁二酮进行酮胺缩合反应获得。
该实施方式的一种或多种实施例中，酮胺缩合反应条件为：以甲酸作为催化剂在室温下进行反应。本公开中所述的室温是指室内温度，一般为15～30℃。
本公开的第三种实施方式，提供了用于制备多孔有机聚合物的单体，其化学结构式为：
本公开的第四种实施方式，提供了上述单体的制备方法，将无水溴化镍配位至上述有机配体中，获得单体。
该实施方式的一种或多种实施例中，具体步骤为：先将无水溴化镍和无水乙醇形成配体，得到NiBr2(EtOH)n，然后再将NiBr2(EtOH)n与1,2-二甲氧基乙烷反应，形成(DME)NiBr2，然后将(DME)NiBr2与有机配体反应。
该系列实施例中，(DME)NiBr2与有机配体反应的条件是：惰性气氛下，室温中搅拌至少48h。
本公开的第五种实施方式，提供了多孔有机聚合物，包括如下化学结构式：
本公开的第六种实施方式，提供了上述多孔有机聚合物的制备方法，将上述单体与1,3,5-三乙炔苯进行sonogashira偶联反应获得。
该实施方式的一种或多种实施例中，将上述单体、1,3,5-三乙炔苯、Pd(PPh3)4、CuI加入至三乙胺和甲苯的混合溶液中进行sonogashira偶联反应。
该实施方式的一种或多种实施例中，sonogashira偶联反应的条件为：惰性气氛下，78～82℃反应70～74h。
该实施方式的一种或多种实施例中，将sonogashira偶联反应后的沉淀依次用水、乙醇和二氯甲烷清洗，然后利用甲醇和丙酮通过索式提取进行清洗。能够将附着在产品中未反应的原料清洗干净。
本公开的第七种实施方式，提供了一种催化剂，包括活性成分，所述活性成分为上述多孔有机聚合物。
本公开的第八种实施方式，提供了一种上述多孔有机聚合物或上述催化剂在催化Suzuki偶联反应中的应用。
该实施方式的一种或多种实施例中，Suzuki偶联反应为卤苯或其衍生物与苯硼酸或其衍生物的二组分偶联反应，所述卤苯为溴苯或碘苯。
本公开的第九种实施方式，提供了一种联苯类化合物的合成方法，以上述多孔有机聚合物作为催化剂进行如下反应路线的Suzuki偶联反应：
其中，X为卤素(Br,I)，R1可以是-NO2,-COCH3,-OCH3,-OH,-CN,-H,-OCH3,-CF3,-CO2CH3,-CH3等一系列取代基，可以分为吸电子基和供电子基。R2可以是-CN,-OCH3,-CH3,-F,-COCH3等，也可以分为吸电子基和供电子基。
该实施方式的一种或多种实施例中，步骤为：卤苯或其衍生物、苯硼酸或其衍生物、K3PO4·3H2O、多孔有机聚合物，在惰性气氛下，加热至95～105℃进行回流反应，所述卤苯为溴苯或碘苯。
该系列实施例中，碘苯或其衍生物、苯硼酸或其衍生物、K3PO4·3H2O、多孔有机聚合物的比为1:1.09～1.11:2～3:50～54，mmol：mmol：mmol：mg。
该系列实施例中，卤苯为溴苯时，回流时间为11～13h；卤苯为碘苯时，回流时间为7～9h。
本公开的第十种实施方式，提供了一种上述催化剂的或上述合成方法采用的催化剂的回收方法，将反应后的物料进行离心分离，离心分离后的沉淀为回收的催化剂。
为了使得本领域技术人员能够更加清楚地了解本公开的技术方案，以下将结合具体的实施例详细说明本公开的技术方案。
实施例1：α-二亚胺镍金属有机配体(A)的制备。
(1)将2,6-二异丙基苯胺(2.54g,14.3mmol)和I2(4g,15.7mmol)的混合物装入50mL圆底烧瓶中。然后依次加入10mL环己烷和4mL饱和Na2CO3溶液。室温搅拌12h后，用EtOAc(20mL)稀释，饱和Na2S2O3(3×40mL)洗涤。用无水MgSO4干燥复合有机层。采用柱层析法(石油醚/EtOAc＝10/1)对粗品进行纯化，得到4-碘-2,6-二异丙基苯胺为黑色液体(3.90g，收率96％)。
(2)将4-碘-2,6-二异丙基苯胺(14mmol,3.7g)加入到50mL的圆底烧瓶中，再往圆底烧瓶中加入二三丁二酮(7mmol，0.611mL)，加入0.5mL甲酸做催化剂，用20mL乙醇做溶剂，在室温下搅拌5h，反应结束后，用布氏漏斗过滤，用少量乙醇洗涤，烘干后得到黄色固体A(2.2g,51％)。
制备的A的结构表征如图1～2所示。
A的晶型表征如表1所示。
表1.A的晶体学数据
A的合成路线如下：
实施例2：多孔有机聚合物的单体(B)的制备。
将A(1.1mmol,0.722g)和DME(NiBr2)(1mmol,0.308g)混合在50mL无水二氯甲烷中，置于100mL Schlenk烧瓶中。在氮气中室温搅拌2天后，将反应体系通过硅藻土垫层过滤。所得固体经无水乙醚进一步洗涤，真空干燥，得到B为砖红色固体(0.59g,68.0％)，结构表征如图3～4所示。
B的合成路线如下：
实施例3：多孔有机聚合物(Ni(Ⅱ)-α-diimine-POP)的制备。
将化合物C(0.5mmol,0.488g)、1,3,5-三乙炔苯(0.5mmol,75mg)、Pd(PPh3)4(0.25mmol,30mg)、CuI(0.1mmol,20mg)和三乙胺(25mL)在50mL甲苯中混合，在80℃氮气中加热72h。将所得的粗品冷却至室温后，分别用水(30ml)、乙醇(30ml)和二氯甲烷(30ml)清洗干净。进一步采用索氏提取甲醇和丙酮用量(50毫升:50毫升:50毫升)萃取，然后在110℃真空干燥箱中干燥得到Ni-(Ⅱ)-α-diimine-POP，产品是深灰色的固体。其中一个结构单体的相对分子质量为718.925，而此pops有无数个此循环单体，(0.247g,73％)Ni-(Ⅱ)-α-diimine-POP的结构表征如图5～8所示。
Ni(Ⅱ)-α-diimine-POP的合成路线如下：
实施例4：Ni(Ⅱ)-α-diimine-POP催化剂催化溴苯与苯硼酸的反应。
溴苯(1.0mmol,104μL)、苯硼酸(1.1mmol,0.134g)、K3PO4·3H2O(2mmol,0.533g)和Ni(Ⅱ)-α-diimine-POP(52mg)，加入2毫升甲苯在100℃搅拌12h在N2下。产率由气相色谱法测定。产率为94％。产品的结构表征如图9所示。
合成路线如下：
实施例5：Ni(Ⅱ)-α-diimine-POP催化剂催化碘苯与苯硼酸的反应。
碘苯(1.0mmol,116μL)、苯硼酸(1.1mmol,0.134g)、K3PO4·3H2O(2mmol,0.533g)和Ni(Ⅱ)-α-diimine-POP(52mg)，加入2毫升甲苯在100℃搅拌8h在N2下。产率由气相色谱法测定。产率99％。
合成路线如下：
实施例6：回收的Ni(Ⅱ)-α-diimine-POP催化剂催化碘苯与苯硼酸的反应。
将实施例5中反应结束后的物料快速离心(14800转/min)，回收催化剂，直接投入下一循环反应，按照上述条件，催化剂使用5个循环，气相色谱法测定计算产率，催化效果如表2所示。回收的催化剂通过PXRD表征，Ni(Ⅱ)-α-diimine-POP仍保持原来的框架(如图10所示)。图11中的左图表示催化剂催化之前镍的XPS图，说明镍是二价镍，图11中的右图表示催化剂在催化反应五次循环之后的XPS图，说明镍的价态没有发生变化还是二价镍，并且镍还在配体上配位着，没有掉下来，催化剂的结构稳定，没有变化。
表2 Ni(Ⅱ)-α-diimine-POP催化suzuki偶联反应5个循环的产率
实施例7：Ni(Ⅱ)-α-diimine-POP催化剂催化溴苯衍生物与苯硼酸的反应。
反应条件如实施例4，产率如表3所示。合成路线为：
表3溴苯衍生物与苯硼酸反应的产品产率
实施例8：Ni(Ⅱ)-α-diimine-POP催化剂催化碘苯衍生物与苯硼酸的反应。
反应条件如实施例5，产率如表4所示。合成路线为：
表4碘苯衍生物与苯硼酸反应的产品产率
以上所述仅为本公开的优选实施例而已，并不用于限制本公开，对于本领域的技术人员来说，本公开可以有各种更改和变化。凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
Claims (16)
1.多孔有机聚合物，其特征是，包括如下化学结构式：
2.权利要求1所述的多孔有机聚合物的制备方法，其特征是，将用于制备多孔有机聚合物的单体与1,3,5-三乙炔苯进行sonogashira偶联反应获得，单体的化学结构式为：
所述的单体的制备方法是将无水溴化镍配位至α-二亚胺镍金属有机配体中，α-二亚胺镍金属有机配体化学结构式为：
3.如权利要求2所述的多孔有机聚合物的制备方法，其特征是，α-二亚胺镍金属有机配体由2,6-二异丙基对碘苯胺与2,3-丁二酮进行酮胺缩合反应获得。
4.权利要求3所述的多孔有机聚合物的制备方法，其特征是，酮胺缩合反应条件为：以甲酸作为催化剂在室温下进行反应。
5.权利要求2所述的多孔有机聚合物的制备方法，其特征是，单体的制备方法具体步骤为：先将无水溴化镍和无水乙醇形成配体，得到NiBr2(EtOH)n，然后再将NiBr2(EtOH)n与1,2-二甲氧基乙烷反应，形成(DME)NiBr2，然后将(DME)NiBr2与有机配体反应。
6.权利要求5所述的多孔有机聚合物的制备方法，其特征是，(DME)NiBr2与有机配体反应的条件是：惰性气氛下，室温中搅拌至少48h。
7.权利要求2所述的多孔有机聚合物的制备方法，其特征是，将单体、1,3,5-三乙炔苯、Pd(PPh3)4、CuI加入至三乙胺和甲苯的混合溶液中进行sonogashira偶联反应。
8.权利要求7所述的多孔有机聚合物的制备方法，其特征是，sonogashira偶联反应的条件为：惰性气氛下，78～82℃反应70～74h。
9.权利要求7所述的多孔有机聚合物的制备方法，其特征是，将sonogashira偶联反应后的沉淀依次用水、乙醇和二氯甲烷清洗，然后利用甲醇和丙酮通过索式提取进行清洗。
10.一种催化剂，其特征是，包括活性成分，所述活性成分为权利要求1所述的多孔有机聚合物。
11.一种权利要求1所述的多孔有机聚合物或权利要求10所述的催化剂在催化Suzuki偶联反应中的应用。
12.如权利要求11所述的催化Suzuki偶联反应中的应用，其特征是，Suzuki偶联反应为卤苯或其衍生物与苯硼酸或其衍生物的二组分偶联反应，所述卤苯为溴苯或碘苯。
13.一种联苯类化合物的合成方法，其特征是，以权利要求1所述的多孔有机聚合物作为催化剂进行如下反应路线的Suzuki偶联反应：
其中，X为卤素，R1选自-NO2、-COCH3、-OH、-CN、-H、-OCH3、CF3、-CO2CH3、-CH3，R2选自-CN、-OCH3、-CH3、-F、-COCH3。
14.如权利要求13所述的联苯类化合物的合成方法，其特征是，步骤为：卤苯或其衍生物、苯硼酸或其衍生物、K3PO4·3H2O、多孔有机聚合物，在惰性气氛下，加热至95～105℃进行回流反应，所述卤苯为溴苯或碘苯。
15.如权利要求14所述的联苯类化合物的合成方法，其特征是，碘苯或其衍生物、苯硼酸或其衍生物、K3PO4·3H2O、多孔有机聚合物的比为1:1.09～1.11:2～3:50～54，mmol：mmol：mmol：mg。
16.如权利要求14所述的联苯类化合物的合成方法，其特征是，卤苯为溴苯时，回流时间为11～13h；卤苯为碘苯时，回流时间为7～9h。
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