CN109096289B - 一种吡啶鎓盐类金属钴卟啉及其制备方法和应用 - Google Patents
一种吡啶鎓盐类金属钴卟啉及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种吡啶鎓盐类金属钴卟啉及其制备方法和其在高活性催化CO2环加成反应中的应用,其中,该金属钴卟啉为5,10,15,20‑四(4‑(3‑(4‑(N‑乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉,属吡啶鎓盐类,是水溶性阳离子。本发明的有益之处在于:本发明提供的金属钴卟啉,在其结构中,中心金属钴可以作为Lewis酸,***吡啶鎓盐可以作为Lewis碱,起到协同催化作用,经验证,该金属钴卟啉在二氧化碳与环氧化物的环加成反应中表现出了优异的催化活性和选择性,其催化环氧氯丙烷的TON和TOF可分别达到4320h‑1和529h‑1,选择性都超过了99%。
Description
技术领域
本发明涉及一种化合物及其制备方法和应用,具体涉及一种吡啶鎓盐类金属钴卟啉及其制备方法和其在高活性催化CO2环加成反应中的应用,属于化学技术领域。
背景技术
由金属卟啉组成的酶在动植物体内广泛存在,如动物血液中、植物叶绿素中等,但是其稳定性差、费用高、对环境灵敏、重复率低,这些都限制了其发展。因此,研究金属卟啉的仿生催化剂具有很重要的意义,合成出来的金属卟啉可以应用在生物化学、生物酶、生物模拟和光催化等方面。
由于环境以及成本等各方面的因素,CO2的固定具有非常好的发展前景,其环加成反应得到的内酯可以做为电极材料以及聚碳酸酯的底物等。因此,CO2环加成反应具有重要的研究意义。
CO2环加成反应的催化剂主要有金属配合物、离子液体及金属氧化物催化剂。其中,金属卟啉在CO2和环氧化物的加成反应中具有优良的催化活性。文献有报道,季铵盐型的金属卟啉催化活性最好,可能是金属中心(Lewis酸)和卟啉***的季铵盐(Lewis碱)起到了协同催化作用。但是文献报道的季铵盐型的金属卟啉合成较繁琐,催化剂难以回收。
发明内容
为解决现有技术的不足,本发明的目的在于提供一种季铵盐型的金属卟啉的替代物——吡啶鎓盐类金属钴卟啉,该吡啶鎓盐类金属钴卟啉不仅合成步骤简洁、易操作,而且在二氧化碳与环氧化物的环加成反应中具有优异的催化活性和选择性,并且易回收。
为了实现上述目标,本发明采用如下的技术方案:
一种金属钴卟啉,其特征在于,该金属钴卟啉为5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉,属吡啶鎓盐类,水溶性阳离子,结构式如下:
前述的金属钴卟啉的制备方法,其特征在于,以5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)卟啉和醋酸钴为原料,先通过加热回流制备得到粗产品,再通过纯化得到最终产品,反应方程式如下:
前述的金属钴卟啉的制备方法,其特征在于,具体包括以下步骤:
Step1:将5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)卟啉溶于水中,然后加入醋酸钴,加热回流,直至反应完毕;
Step2:将溶液冷却至室温,向溶液中加入过量的NH4PF6使钴卟啉沉淀完全,抽滤,固体用无水***洗涤多次,干燥,得到粗产品;
Step3:用丙酮溶解粗产品,向溶液中加入过量的四丁基溴化铵使钴卟啉以溴盐的形式沉淀完全,抽滤,固体用丙酮洗涤多次,自然干燥,得到最终产品。
本发明的有益之处在于:
1、本发明提供的金属钴卟啉,在其结构中,中心金属钴可以作为Lewis酸,***吡啶鎓盐可以作为Lewis碱,起到协同催化作用,经验证,该金属钴卟啉在二氧化碳与环氧化物的环加成反应中表现出了优异的催化活性和选择性,其催化环氧氯丙烷的TON和TOF可分别达到4320h-1和529h-1,选择性都超过了99%;
2、本发明提供的金属钴卟啉的制备方法,合成步骤简洁、易操作,污染小。
附图说明
图1是Co(TEtPyP)Br4的质谱;
图2是H2TEtPyPBr4的紫外-可见光谱;
图3是Co(TEtPyP)Br4的紫外-可见光谱;
图4是Co(TEtPyP)Br4的红外光谱。
具体实施方式
以下结合附图和具体实施例对本发明作具体的介绍。
一、Co(TEtPyP)Br4的化学结构
本发明提供的金属钴卟啉为5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉(Co(TEtPyP)Br4),属吡啶鎓盐类的金属卟啉,水溶性阳离子,结构式如下:
在该金属钴卟啉的结构中,中心金属钴可以作为Lewis酸,***吡啶鎓盐可以作为Lewis碱,起到协同催化作用,所以该催化剂在二氧化碳与环氧化物的环加成反应中具有很好的催化效果。
中心金属钴可以活化环氧化物,***的吡啶鎓盐能够吸附活化CO2,这样两个活化的反应物在比较温和的条件下就可以高效率生成相应的环加成产物,反应中没有其他副产物,选择性很高。
由于该金属钴卟啉在乙酸乙酯中不溶,所以反应结束后,用乙酸乙酯将产物萃取出来,这样金属钴卟啉就沉淀出来,与产物分离。
二、Co(TEtPyP)Br4的制备方法
Co(TEtPyP)Br4是以5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)卟啉和醋酸钴为原料制备而来的,先通过加热回流制备得到粗产品,再通过纯化得到最终产品。
Co(TEtPyP)Br4的合成路线如下:
Co(TEtPyP)Br4的制备方法具体如下:
Step1:在100mL三颈瓶中,加入0.4055g(0.25mmol)5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)卟啉(H2TEtPyPBr4),溶于60mL水中,然后加入0.6227g(2.5mmol)醋酸钴(Co(OAc)2·4H2O),加热回流,TLC检测反应进程,直至反应完毕(用时24h)。
Step2:待反应完毕后,将溶液冷却至室温,向溶液中加入过量的NH4PF6使溶液沉淀完全,抽滤,固体用无水***洗涤多次,干燥,得到粗产品。
Step3:用丙酮溶解粗产品,向溶液中加入过量的四丁基溴化铵使溶液沉淀完全,抽滤,固体用丙酮洗涤多次(除去过量的四丁基溴化铵),自然干燥,得到最终产品。
最终产品为紫黑色的粉末。经计算,产品的产率为92%。
三、Co(TEtPyP)Br4的表征
熔点:>250℃。
UV-vis(H2O):λmax/nm,430(Soret带)546,584(Q带)。
MS:m/z,340.1[(M-4Br-)/4]。
元素分析实测值(%,C84H68N16CoBr4理论值):C 60.08(60.05);H 4.11(4.08);N13.29(13.34)。
FT-IR(KBr压片):v,cm-1,2966,1637,1510,1371,1176,1002,840,555。
1、质谱分析
我们采用电喷雾四级杆飞行时间串联质谱仪(ESI-MS)在阳离子模式下测定了实验所合成的金属钴卟啉Co(TEtPyP)Br4的质谱,得到的质谱如图1所示。
在该质谱中,CoTEtPyP在溶液中带四个正电荷的阳离子,所以在质谱中出现了[(M4+)/4]峰,对应340.1。
质谱测试的数据结果可以认为是目标化合物的佐证。
2、紫外-可见光谱分析
我们以水为溶剂,测试了金属钴卟啉Co(TEtPyP)Br4的紫外-可见光谱,得到的紫外-可见光谱如图3所示。
在该紫外-可见光谱中,所合成的金属钴卟啉Co(TEtPyP)Br4包含了两类吸收谱带:
(1)处于430nm处的特别强的吸收带(称作Soret带或者B带);
(2)处于546nm,584nm处的两个弱吸收带(称作Q带)。
依据Gouterman四轨道模型,Soret带认为是卟啉大环分子中从a2u(π)到eg(π*)的跃迁,Q带归属于a1u(π)到eg(π*)的跃迁,一般会出四个峰值。当自由卟啉与金属离子Co(II)形成金属卟啉配合物后,对称性明显增加,在可见区,Q带的出峰个数会减少。与反应物自由卟啉相比,Co(TEtPyP)Br4的Soret带发生红移,Q带由自由卟啉的四个减少到两个。根据以上分析,可以判断自由卟啉和金属钴已经发生了配位。
3、红外光谱分析
我们在400~4000cm-1波数范围内,采用KBr压片法测定了Co(TEtPyP)Br4的红外光谱,得到的红外光谱如图4所示。
在该红外光谱中,卟啉环内N-H键的伸缩振动吸收峰出现在3500-3300cm-1,但是由于合成的水溶性卟啉易吸水,在3400cm-1附近出现的水峰很强,容易将其掩盖,所以卟啉环内N-H键的伸缩振动吸收峰不能作为卟啉的特征吸收峰。卟啉环内N-H键的弯曲振动在960cm-1左右,而当与金属离子进入卟啉环内配位形成金属卟啉时,此特征峰消失,在1002cm-1出现了N-M键的特征吸收峰,这是判断金属是否进入卟啉环内配位的一个重要标志,被称作“氧化态标示带”。苯环的骨架υC=C振动吸收峰主要在1625-1450cm-1范围内,以1639cm-1和1510cm-1处的两个吸收为主。根据以上分析,红外光谱也证明了金属卟啉的合成。
四、Co(TEtPyP)Br4催化CO2与环氧化物的环加成反应
1、催化实验
CO2与环氧化物的环加成反应如下:
我们选取了以下环氧化物分别与CO2进行环加成反应:
精确量取环氧化物0.01mol(环氧丙烷0.7mL,环氧丁烷0.86mL,环氧氯丙烷0.78mL,烯丙基缩水甘油醚1.19mL,环氧丙基苯基醚1.35mL),直接加入到聚四氟乙烯内衬中,然后精确称取Co(TEtPyP)Br4催化剂7.5mg加入到聚四氟乙烯内衬中,将聚四氟乙烯内衬加入到高温高压反应釜中,向反应釜中缓慢充入CO2排除反应釜中其他气体的干扰,然后再充入2MPa CO2,磁力搅拌加热至120℃,反应8h。催化反应结束后,将反应釜冷却至室温,打开釜,将溶液吸出,加入8mL乙酸乙酯萃取产物,催化剂由于不溶于乙酸乙酯,以沉淀析出在管底部,离心洗涤后回收催化剂。将上清液吸出,利用GC1100型普析通用气相色谱仪对上清液进行测试,用外标法对上清液进行定量分析。
2、催化活性分析
表1 催化剂Co(TEtPyP)Br4的催化活性数据表
从上面的催化结果我们可以看出,Co(TEtPyP)Br4在催化环氧化物与CO2的环加成反应中表现出了优良的催化活性,选择性也都超过了99%,对环氧氯丙烷的催化更是表现出了非常好的效果,TON和TOF分别达到了4230和529h-1。
五、总结
本发明提供的5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉(Co(TEtPyP)Br4),是一种吡啶鎓盐类的金属卟啉,并且属水溶性阳离子。通过对其进行MS、UV-vis、FT-IR表征,证明我们确实成功的合成了Co(TEtPyP)Br4;对其进行催化环氧化物与CO2的环加成反应,证明了该催化剂具有很好的催化活性和选择性。
另外,本发明提供的Co(TEtPyP)Br4的制备方法,是用水作溶剂,环保,污染小;得到的钴卟啉通过加入沉淀剂就可从水溶液中沉淀分离出来,方法简单,较一般的金属卟啉合成需用有机溶剂(如二氯甲烷),且分离需要过柱的方法相比,此合成方法简单易操作。
需要说明的是,上述实施例不以任何形式限制本发明,凡采用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 (2)
1.5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉在催化CO2与环氧化物的环加成反应中的应用,其特征在于,所述环氧化物包括:环氧丙烷、环氧丁烷、环氧氯丙烷、烯丙基缩水甘油醚和环氧丙基苯基醚。
2.根据权利要求1所述的应用,其特征在于,所述5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉的应用方法如下:
(1)将环氧化物和5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉加入到聚四氟乙烯内衬中;
(2)将聚四氟乙烯内衬加入到高温高压反应釜中,向反应釜中缓慢充入CO2排除反应釜中其他气体的干扰,然后再充入2MPa CO2,磁力搅拌加热至120℃,反应8h;
(3)催化反应结束后,将反应釜冷却至室温,打开釜,将溶液吸出,向溶液中加入乙酸乙酯萃取产物,5,10,15,20-四(4-(3-(4-(N-乙基)溴化吡啶)吡唑基)苯基)钴(II)卟啉不溶于乙酸乙酯,以沉淀析出在管底部,离心洗涤后回收。
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