CN114213469B - 一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用 - Google Patents

一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用 Download PDF

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CN114213469B
CN114213469B CN202111526857.3A CN202111526857A CN114213469B CN 114213469 B CN114213469 B CN 114213469B CN 202111526857 A CN202111526857 A CN 202111526857A CN 114213469 B CN114213469 B CN 114213469B
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陈宬
桑微
沙南
樊广高
江博文
陈原新
江民
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Wuhan University of Technology WUT
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Abstract

本发明提供了一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用，属于金属有机化学与催化技术领域。苯并咪唑的N原子含有孤对电子，它具有较强的配位能力，容易与过渡金属形成配合物，而且配位构型多样化。此外，该类配合物具有良好的刚性平面结构、丰富的π电子及优良的电子离域环境，而且苯并咪唑上芳香环的π‑π堆积作用使得该类配合物稳定性更强。本发明以式I所示结构的含苯并咪唑骨架的有机化合物作为有机配体，与过渡金属化合物反应得到以式II～VI所示结构的金属有机配合物，所得配合物能够作为催化剂催化醇脱氢制备苯甲酸的反应，且具有良好的催化活性。

Description

一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用
技术领域
本发明涉及金属有机化学与催化技术领域，特别涉及一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用。
背景技术
苯并咪唑及其衍生物是一类重要的氮杂环化合物，在染料、聚合物、金属配体、医药和材料等领域显示出独特的性能。鉴于其独特的性能以及广泛的应用前景，近年来含有苯并咪唑骨架的分子得到了越来越多科研工作者们的关注。
目前，陈宬团队成功合成了如式I所示结构的含苯并咪唑骨架的一类有机化合物(Chem.Asian J.2020,15,129-135)：
Figure BDA0003409323020000011
式I中，R1为氢、甲基或氯；
R2为甲基、乙基或异丙基；
R3为苯基或苯基衍生物。
但是，此类化合物的研究仅限于合成阶段，对于进一步开发其实际应用价值，现有技术并未进行更深入的研究。
发明内容
有鉴于此，本发明目的在于提供一种含苯并咪唑骨架的金属有机配合物及其制备方法和应用，本发明以式I所示结构的含苯并咪唑骨架的有机化合物作为有机配体，与过渡金属化合物反应得到相应的金属有机配合物，这些配合物能够作为催化剂催化醇脱氢制备羧酸的反应，且具有良好的催化活性。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种含苯并咪唑骨架的金属有机配合物，通过具有式I所示结构的有机配体与过渡金属化合物反应所得；
Figure BDA0003409323020000021
式I中，R1为氢、甲基或氯；
R2为C1～C3烷基；
R3为苯基或苯基衍生物。
优选的，所述过渡金属化合物中的过渡金属为Co、Ir、Ru、Cu和Zn中的一种。
优选的，当R3为苯基衍生物时，所述苯基衍生物为
Figure BDA0003409323020000022
Figure BDA0003409323020000023
优选的，所述过渡金属化合物为过渡金属卤化物或过渡金属有机卤化物；
所述过渡金属卤化物为六水合氯化钴、溴化铜或溴化锌；
所述过渡金属有机卤化物为二氯(五甲基环戊二烯基)合铱二聚体、二氯双(4-甲基异丙基苯基)钌二聚体、二氯双(六甲基苯基)钌二聚体或二氯双苯基钌二聚体。
优选的，所述有机配体与过渡金属化合物的摩尔比为(1～2)：(1～3)。
优选的，具有式II～VI任意一项所示结构：
Figure BDA0003409323020000031
Figure BDA0003409323020000032
式IV中，R4为氢、六甲基或1-甲基-4-异丙基；
Figure BDA0003409323020000033
本发明提供了上述含苯并咪唑骨架的金属有机配合物的制备方法，包括以下步骤：
将具有式I所示结构的有机配体、过渡金属化合物和有机溶剂混合后反应，得到含苯并咪唑骨架的金属有机配合物。
优选的，所述有机溶剂为醇类溶剂。
优选的，所述反应的温度为20～80℃，反应的时间为1～15h。
本发明提供了上述含苯并咪唑骨架的金属有机配合物作为催化剂在催化醇脱氢制备羧酸反应中的应用。
苯并咪唑的N原子含有孤对电子，它具有较强的配位能力，容易与过渡金属形成配合物，而且配位构型多样化。该类配合物具有很好的刚性平面结构和丰富的π电子，以及优良的电子离域环境，而且苯并咪唑上芳香环的π-π堆积作用使得该类配合物稳定性更强。本发明提供了一种含苯并咪唑骨架的金属有机配合物，其通过具有式I所示结构的有机配体与过渡金属化合物反应所得。本发明所得金属有机配合物能够作为催化剂催化醇脱氢制备羧酸的反应，且具有良好的催化活性。实施例结果表明，本发明提供的含苯并咪唑骨架的金属有机配合物用于催化苯甲醇脱氢偶联反应制备苯甲酸时，苯甲酸的产率为51.3～88.5％。
附图说明
图1为Co-1的单晶结构图；
图2为Co-2的单晶结构图；
图3为Ru-1的单晶结构图；
图4为Cu-1的单晶结构图；
图5为Zn-1的单晶结构图。
具体实施方式
本发明提供了一种含苯并咪唑骨架的金属有机配合物，通过具有式I所示结构的有机配体与过渡金属化合物反应所得；
Figure BDA0003409323020000041
式I中，R1为氢、甲基或氯；
R2为C1～C3烷基，优选为甲基、乙基或异丙基；
R3为苯基或苯基衍生物，所述苯基衍生物优选为
Figure BDA0003409323020000042
Figure BDA0003409323020000043
在本发明中，所述过渡金属化合物中的过渡金属优选为Co、Ir、Ru、Cu和Zn中的一种。
在本发明中，所述过渡金属化合物优选为过渡金属卤化物或过渡金属有机卤化物；
所述过渡金属卤化物优选为六水合氯化钴、溴化铜或溴化锌；
所述过渡金属有机卤化物优选为二氯(五甲基环戊二烯基)合铱(III)二聚体(结构：
Figure BDA0003409323020000051
)，二氯双(4-甲基异丙基苯基)钌(II)二聚体(结构：
Figure BDA0003409323020000052
)，二氯双(六甲基苯基)钌(II)二聚体(结构：
Figure BDA0003409323020000053
)或二氯双苯基钌(II)二聚体(结构：
Figure BDA0003409323020000054
)。
在本发明中，所述有机配体与过渡金属化合物的摩尔比优选为(1～2)：(1～3)，进一步优选为1:1、2:1。
在本发明中，所述含苯并咪唑骨架的金属有机配合物，优选具有式II～VI任意一项所示结构：
Figure BDA0003409323020000061
Figure BDA0003409323020000062
式IV中，R4为氢、六甲基或1-甲基-4-异丙基；
Figure BDA0003409323020000063
作为本发明的具体实施例，所述含苯并咪唑骨架的金属有机配合物具有表1中式a～式o任意一项所示结构。
表1含苯并咪唑骨架的金属有机配合物的具体结构
Figure BDA0003409323020000064
Figure BDA0003409323020000071
Figure BDA0003409323020000081
本发明提供了上述含苯并咪唑骨架的金属有机配合物的制备方法，包括以下步骤：
将具有式I所示结构的有机配体、过渡金属化合物和有机溶剂混合反应，得到含苯并咪唑骨架的金属有机配合物。
在本发明中，所述具有式I所示结构的有机配体的制备方法，优选包括以下步骤：
在催化剂与碱的作用下，具有式A所示结构的苯并咪唑化合物与具有式B所示结构的氨基化合物进行碳氮偶联反应，得到具有式I所示结构的有机配体。
Figure BDA0003409323020000091
R3-NH2式B；
式A和式B中，R1为氢、甲基或氯；
R2为C1～C3烷基；
R3为苯环或苯环衍生物。
在本发明中，所述催化剂优选为PdCl2，所述碱优选为Cs2CO3；在本发明中，所述PdCl2的用量优选为式B所示反应原料摩尔数的5～10％，所述Cs2CO3的用量优选为式B所示反应原料摩尔数的4倍。
在本发明中，所述具有式A所示结构的苯并咪唑化合物与具有式B所示结构的氨基化合物的摩尔比优选为2:1。
在本发明中，所述碳氮偶联反应优选在有机溶剂中进行，所述有机溶剂优选为甲苯。
在本发明中，所述碳氮偶联反应的温度优选为120℃，时间优选为16h。
在本发明中，所述碳氮偶联反应完成后，本发明采用柱层析法对产物进行提纯，得到式I所示结构的有机配体纯品。本发明对所述柱层析提纯的方式没有特殊的要求，使用本领域技术人员熟知的提纯方式即可。
在本发明中，所述过渡金属化合物优选为金属卤化物或金属有机卤化物。
在本发明中，所述有机溶剂优选为醇类溶剂。在本发明中，所述醇类溶剂优选为甲醇。本发明对所述有机溶剂的用量没有特殊的要求，能够将所述有机配体和过渡金属化合物溶解即可。
在本发明中，合成金属有机配合物的反应温度优选为20～80℃，更优选为30～70℃；时间优选为1～15h，更优选为2～12h。
本发明提供了上述含苯并咪唑骨架的金属有机配合物作为催化剂的应用。在本发明中，所述催化剂优选为醇脱氢制备羧酸反应的催化剂。
下面结合实施例对本发明提供的含苯并咪唑骨架的金属有机配合物及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
有机配体与过渡金属化合物分别溶解在甲醇中，然后将过渡金属化合物的甲醇溶液加入到回流的有机配体甲醇溶液中，将混合溶液继续回流反应4h后冷却至室温，过滤出蓝色固体沉淀即为粗产物。将粗产物加入DMF(使完全溶解)中，然后通过乙醚缓慢地向DMF溶液中扩散得到相应的单晶纯产品。该方法得到Co-1和Co-2。
Co-1的制备过程如式(1)所示，Co-2的制备过程如式(2)所示。
Figure BDA0003409323020000101
其中，Co-1的单晶结构图如图1所示；Co-2的单晶结构图如图2所示。
实施例2
有机配体与过渡金属化合物比例为2:1，溶解在甲醇中，然后将混合溶液回流反应4h后冷却到室温，过滤出黄色固体沉淀即为粗产物，再用乙醚与乙酸乙酯的混合溶剂润洗3次后得到纯产品。该方法得到Ir-1和Ir-2。
Ir-1的制备过程如式(3)所示，Ir-2的制备过程如式(4)所示。
Figure BDA0003409323020000111
其中，Ir-1的核磁数据为：
1H NMR(500MHz,DMSO-d6)δ7.86(d,J＝8.3Hz,2H),7.66(d,J＝8.3Hz,2H),7.53(t,J＝7.6Hz,2H),7.47(t,J＝7.7Hz,4H),7.24(t,J＝7.4Hz,1H),7.03(d,J＝7.8Hz,2H),4.01(s,6H),1.39(s,15H).13C NMR(126MHz,DMSO-d6)δ145.1,142.3,137.1,134.4,131.3,125.3,124.7,124.4,119.5,114.6,113.2,88.0,32.4,9.2.
Ir-2的核磁数据为：
1H NMR(500MHz,DMSO-d6)δ7.87(d,J＝8.2Hz,2H),7.68(d,J＝8.1Hz,2H),7.54(t,J＝7.6Hz,2H),7.50–7.46(m,2H),6.91–6.78(m,4H),4.01(s,6H),2.89(s,6H),1.44(s,15H).13C NMR(126MHz,DMSO-d6)δ145.5,137.1,134.4,125.2,124.3,119.4,115.4,113.0,92.6,92.3,89.7,88.0,32.4,9.3,8.7.
实施例3
有机配体与过渡金属化合物的比例为2:1，将有机配体与过渡金属化合物溶解于乙醇中，氩气氛围下60～70℃反应10～15h。该方法得到Ru-1到Ru-9，制备过程如式(5)所示。
Figure BDA0003409323020000121
其中，Ru-1的单晶结构图如图3所示；
Ru-1的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.92(d,J＝7.9Hz,2H),7.66(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,2H),7.51(t,J＝7.5Hz,2H),7.47(t,J＝7.5Hz,2H),7.32–7.28(m,1H),6.98(d,J＝7.9Hz,2H),5.68(d,J＝5.6Hz,2H),5.42(d,J＝5.4Hz,2H),4.13(s,6H),2.29–2.23(m,1H),1.92(s,3H),1.06(d,J＝6.8Hz,6H).13C NMR(126MHz,CDCl3)δ144.9,142.4,139.0,133.8,131.6,126.0,125.5,125.0,119.7,114.1,112.2,106.0,100.7,83.0,82.7,32.2,30.9,22.8,18.8.
Ru-2的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.88(d,J＝7.7Hz,2H),7.63(d,J＝7.6Hz,2H),7.49–7.37(m,4H),6.81(d,J＝8.4Hz,2H),6.71(d,J＝8.4Hz,2H),5.64(d,J＝5.2Hz,2H),5.39(d,J＝5.2Hz,2H),4.04(s,6H),2.92(s,6H),2.31–2.25(m,1H),1.88(s,3H),1.03(d,J＝6.5Hz,6H).13C NMR(126MHz,CDCl3)δ148.4,145.6,139.1,133.8,132.0,125.8,124.9,119.7,115.5,114.4,112.0,105.8,100.8,83.3,82.6,40.7,32.1,30.8,22.8,18.9.
Ru-3的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.90(d,J＝7.8Hz,2H),7.64(d,J＝7.5Hz,2H),7.51–7.40(m,4H),7.33(s,2H),7.06(s,2H),5.72(d,J＝4.5Hz,2H),5.47(d,J＝4.5Hz,2H),4.09(s,6H),2.32–2.24(m,1H),1.91(s,3H),1.06(d,J＝6.4Hz,6H).13C NMR(126MHz,CDCl3)δ159.7(d,J＝246.6Hz),144.9,139.0,138.4(d,J＝2.6Hz),133.8,125.8,124.9,119.7,118.6(d,J＝23.3Hz),116.3(d,J＝7.9Hz),112.3,106.1,100.4,82.9,82.9,32.5,30.9,22.7,18.8.
Ru-4的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.91(t,J＝6.5Hz,4H),7.65(d,J＝7.9Hz,2H),7.52(t,J＝7.5Hz,2H),7.47(t,J＝7.6Hz,2H),7.38(d,J＝8.2Hz,2H),5.75(d,J＝5.5Hz,2H),5.52(d,J＝5.4Hz,2H),4.13(s,6H),2.24–2.15(m,1H),1.96(s,3H),1.04(d,J＝6.7Hz,6H).13CNMR(126MHz,CDCl3)δ145.0,144.2,139.1,133.9,128.9(q,J＝3.6Hz),127.6(q,J＝33.7Hz),126.1,125.1,123.5(q,J＝272.1Hz),119.8,115.1,112.2,106.2,100.4,83.0,82.8,32.2,30.9,22.7,18.8.
Ru-5的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.96(d,J＝8.0Hz,2H),7.69(d,J＝7.9Hz,2H),7.61(t,J＝7.3Hz,2H),7.51(t,J＝7.5Hz,2H),7.49–7.44(m,2H),7.30(t,J＝7.0Hz,1H),6.93(d,J＝7.7Hz,2H),5.64(d,J＝5.5Hz,2H),5.32(d,J＝5.5Hz,2H),4.81–4.68(m,2H),4.56–4.39(m,2H),2.27–2.17(m,1H),1.88(s,3H),1.52(t,J＝6.8Hz,6H),1.05(d,J＝6.7Hz,6H).13CNMR(126MHz,CDCl3)δ144.2,142.9,139.3,132.5,131.4,125.9,125.6,124.9,112.0,114.3,112.5,105.6,101.2,83.4,82.3,41.2,30.7,22.7,18.9,14.7.
Ru-6的核磁数据为：
1H NMR(500MHz,CDCl3)δ8.07–7.92(m,2H),7.76–7.68(m,2H),7.64(t,J＝7.7Hz,2H),7.52–7.40(m,4H),7.34(t,J＝7.3Hz,1H),6.90(d,J＝8.1Hz,2H),5.68(d,J＝5.7Hz,2H),5.32(d,J＝5.7Hz,2H),5.12–5.00(m,2H),2.38–2.23(m,1H),2.01(d,J＝6.8Hz,6H),1.89(s,3H),1.54(d,J＝6.8Hz,6H),1.10(d,J＝6.8Hz,6H).13C NMR(126MHz,CDCl3)δ143.8,143.5,139.7,131.4,131.2,125.8,125.6,124.5,120.7,114.1,113.5,105.5,101.4,83.8,82.1,50.8,30.8,22.8,21.9,21.1,19.1.
Ru-7的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.91(d,J＝8.0Hz,2H),7.66(d,J＝7.8Hz,2H),7.49(t,J＝7.5Hz,2H),7.45(t,J＝7.6Hz,2H),7.37(d,J＝7.5Hz,2H),6.80(d,J＝7.6Hz,2H),5.66(d,J＝5.4Hz,2H),5.39(d,J＝5.3Hz,2H),4.10(s,6H),2.36(s,3H),2.32–2.24(m,1H),1.88(s,3H),1.06(d,J＝6.7Hz,6H).13C NMR(126MHz,CDCl3)δ145.1,140.0,139.0,135.4,133.8,131.9,125.9,124.9,119.7,114.1,112.2,105.8,100.8,83.3,82.5,32.3,30.8,22.7,20.6,18.9.
Ru-8的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.71(d,J＝8.1Hz,2H),7.67–7.55(m,4H),7.46(t,J＝7.5Hz,2H),7.41(t,J＝7.6Hz,2H),7.30(t,J＝7.4Hz,1H),7.02(d,J＝8.0Hz,2H),4.02(s,6H),1.96(s,18H).13C NMR(126MHz,CDCl3)δ144.3,139.9,137.5,134.2,130.9,125.6,125.0,124.2,120.2,114.0,112.1,93.6,89.5,32.6,16.4,15.8.
Ru-9的核磁数据为：
1H NMR(500MHz,CDCl3)δ7.97(d,J＝8.1Hz,2H),7.65(d,J＝7.9Hz,2H),7.61(d,J＝7.4Hz,2H),7.57–7.50(m,4H),7.31(d,J＝5.1Hz,1H),6.92(d,J＝8.5Hz,2H),5.73(s,6H),4.17(s,6H).13C NMR(126MHz,DMSO-d6)δ146.0,143.6,139.6,134.1,131.2,125.1,124.7,124.3,120.5,114.6,112.6,85.2,31.8.
实施例4
有机配体与过渡金属化合物的比例为1:1，将有机配体与过渡金属化合物分别溶解于乙醇中，在室温下将有机配体的乙醇溶液缓慢倒入过渡金属化合物的乙醇溶液中，反应2h过滤出固体即可。该方法得到Cu-1和Zn-1。
Cu-1的制备过程如式(6)所示，Zn-1的制备过程如式(7)所示。
Figure BDA0003409323020000151
其中，Cu-1的单晶结构图如图4所示；
Zn-1的单晶结构图如图5所示；
Zn-1的核磁数据为：
1H NMR(500MHz,DMSO-d6)δ7.49(d,J＝7.8Hz,4H),7.38(t,J＝7.5Hz,2H),7.26–7.15(m,5H),6.98(d,J＝7.8Hz,2H),3.39(s,6H).13C NMR(126MHz,DMSO-d6)δ150.0,143.3,140.4,135.2,130.2,125.4,122.8,122.6,122.1,118.7,110.7,30.5.
应用例1
将实施例1～4所得含苯并咪唑骨架的金属有机配合物作为催化剂，在无任何氧化剂和添加剂的存在下用于催化苯甲醇的脱氢偶联反应。该反应是一种绿色与环境友好的过程，反应生成的苯甲酸是一种重要的化工原料与医药中间体，而唯一的副产物是氢气，具体过程为：
在氩气气氛下，将苯甲醇(1，1.5mmol)、KOH(1.8mmol)、苯甲醇摩尔数0.2％的催化剂与甲苯混合，加热至回流进行脱氢偶联反应，反应16h后加入盐酸酸化即可得到苯甲酸。
反应过程如式(8)：
Figure BDA0003409323020000161
不同催化剂催化下所得苯甲酸与剩余苯甲醇的产率见表2。
表2不同催化剂催化下所得苯甲酸与剩余苯甲醇的产率
Figure BDA0003409323020000162
由表2可以看出，本发明提供的含苯并咪唑骨架的金属有机配合物用于催化苯甲醇脱氢偶联反应制备苯甲酸时，具有良好的催化活性，苯甲酸的产率为51.3～88.5％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

1.一种含苯并咪唑骨架的金属有机配合物，通过具有式I所示结构的有机配体与过渡金属化合物反应所得；
Figure FDA0004022149970000011
式I中，R1为氢、甲基或氯；
R2为C1～C3烷基；
R3为苯基或苯基衍生物；
当R3为苯基衍生物时，所述苯基衍生物为
Figure FDA0004022149970000012
所述过渡金属化合物为过渡金属卤化物或过渡金属有机卤化物；
所述过渡金属卤化物为六水合氯化钴、溴化铜或溴化锌；
所述过渡金属有机卤化物为二氯(五甲基环戊二烯基)合铱二聚体、二氯双(4-甲基异丙基苯基)钌二聚体、二氯双(六甲基苯基)钌二聚体或二氯双苯基钌二聚体。
2.根据权利要求1所述的含苯并咪唑骨架的金属有机配合物，其特征在于，所述有机配体与过渡金属化合物的摩尔比为(1～2)：(1～3)。
3.根据权利要求1所述的含苯并咪唑骨架的金属有机配合物，其特征在于，具有式II～VI任意一项所示结构：
Figure FDA0004022149970000013
Figure FDA0004022149970000021
式IV中，R4为氢、六甲基或1-甲基-4-异丙基；
Figure FDA0004022149970000022
4.权利要求1～3任意一项所述含苯并咪唑骨架的金属有机配合物的制备方法，包括以下步骤：
将具有式I所示结构的有机配体、过渡金属化合物和有机溶剂混合后反应，得到含苯并咪唑骨架的金属有机配合物。
5.根据权利要求4所述的制备方法，其特征在于，所述有机溶剂为醇类溶剂。
6.根据权利要求4或5所述的制备方法，其特征在于，所述反应的温度为20～80℃，反应的时间为1～15h。
7.权利要求1～3任意一项所述的含苯并咪唑骨架的金属有机配合物或权利要求4～6任意一项所述制备方法制备得到的含苯并咪唑骨架的金属有机配合物作为催化剂在催化醇脱氢制备羧酸反应中的应用。
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