CN111732612B - 一种含双膦间位碳硼烷配体的铁配合物及其制备方法和应用 - Google Patents

一种含双膦间位碳硼烷配体的铁配合物及其制备方法和应用 Download PDF

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CN111732612B
CN111732612B CN202010512770.XA CN202010512770A CN111732612B CN 111732612 B CN111732612 B CN 111732612B CN 202010512770 A CN202010512770 A CN 202010512770A CN 111732612 B CN111732612 B CN 111732612B
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郭文
姚子健
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Abstract

本发明涉及一种含双膦间位碳硼烷配体的铁配合物及其制备方法和应用，该铁配合物经过以下方法制得：将n‑BuLi与间位碳硼烷m‑C2B10H12反应，然后加入卤代膦继续反应，再将FeCl2加入反应体系接着反应，反应结束后分离得到含双膦间位碳硼烷配体的铁配合物，并应用在催化合成反式2‑烯基氮杂芳烃化合物中。与现有技术相比，本发明在2‑甲基氮杂芳烃与芳香醛的直接缩合反应合成反式2‑烯基氮杂芳烃化合物中显示出高效的催化活性，催化剂用量低，反应条件温和，反应速率快，产率较高，在工业上有广泛的应用前景。

Description

一种含双膦间位碳硼烷配体的铁配合物及其制备方法和应用
技术领域
本发明涉及配合物合成领域，具体涉及一种含双膦间位碳硼烷配体的铁配合物及其制备方法和应用。
背景技术
2-烯基氮杂芳烃是许多天然产物和药物分子的关键骨架，也可用于合成某些具有生物活性的2-烷基氮杂芳烃化合物。该类化合物在生物医药领域应用广泛,比如含喹啉的烯烃衍生物顺尔丁(Singular)是治疗哮喘的药物，含吡啶的烯烃衍生物(CGS23113)也是一种重要的药物。合成2-烯基氮杂芳烃最经典的方法是2-甲基氮杂芳烃与芳香醛在大量乙酸酐和乙酸的存在下，通过高温反应(120-160℃)来制备,该方法虽然不需要催化剂,但用到大量的乙酸酐和乙酸，后处理麻烦，而且反应温度高、时间长、收率低。
为克服上述弊端，科学家开发了一些通过金属催化合成2-烯基氮杂芳烃的方法，但有时需要昂贵的金属催化剂或对空气和水极敏感的特殊试剂，这些缺点限制了它们的工业化应用前景。近年来一些其他方法也被报道，如铁催化的2-烷基氮杂芳烃与磺酰亚胺通过加成消除反应合成2-烯基氮杂芳烃的方法；同时研究发现该反应即使在没有催化剂存在下，加热到120-140℃也可以得到相应的产物。
与已报道的其他方法相比，这两种方法更简便，所用的原料相对廉价易得，然而通过芳香醛和对甲苯磺酰胺制备的磺酰亚胺是必需的反应物，且反应后会再生当量的对甲苯磺酰胺，为分离纯化带来不便。此外铁催化的2-甲基氮杂芳烃与芳香醛的直接缩合反应也被报道，但该方法仍需要醋酸的参与，对反应设备要求较高。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种显示出高效的催化活性，催化剂用量低，反应条件温和，反应速率快，产率较高的含双膦间位碳硼烷配体的铁配合物及其制备方法和应用。
本发明的目的可以通过以下技术方案来实现：
经研究表明，碳硼烷分子具有独特的笼状结构和电子特征被广泛应用于配位化合物的合成中。Pincer型金属配合物在有机合成及催化当中发挥着重要作用，在诸多反应中都显示出良好的催化效果。
一种含双膦间位碳硼烷配体的铁配合物，该铁配合物的结构式如下所示：
Figure GDA0003681869390000021
其中，R为-Ph、4-MeO-C6H4-、4-NO2-C6H4-或-iPr中的一种，“·”为硼氢键。
进一步地，包括铁配合物1、铁配合物2、铁配合物3、铁配合物4，其结构式如下所示：
Figure GDA0003681869390000022
一种如上所述的含双膦间位碳硼烷配体的铁配合物的制备方法，该方法为：将n-BuLi与间位碳硼烷m-C2B10H12反应，然后加入卤代膦继续反应，再将FeCl2加入反应体系接着反应，反应结束后分离得到含双膦间位碳硼烷配体的铁配合物，其反应式为：
Figure GDA0003681869390000031
进一步地，所述的间位碳硼烷、n-BuLi、卤代膦和FeCl2的摩尔比为1.0:(2.2-2.5):(2.5-3.0):(0.8-1.2)。
进一步地，该方法具体包括以下步骤：
(1)在低温下，将n-BuLi溶液滴加到间位碳硼烷m-C2B10H12溶液中搅拌；
(2)升温至室温，再反应；
(3)加入卤代膦，继续反应；
(4)将FeCl2加入反应体系接着反应，反应结束后，减压抽干溶剂，再将得到的粗产物进行洗涤、抽干，得到含双膦间位碳硼烷配体的铁配合物。
进一步地，步骤(1)中所述的低温的温度为-5～5℃；所述的n-BuLi溶液为n-BuLi正己烷溶液，所述的m-C2B10H12溶液为m-C2B10H12乙醚溶液；所述的搅拌的时间为20-40min；步骤(2)中所述的再反应的时间为20-40min。
进一步地，步骤(3)中所述的卤代膦包括ClCH2PPh2、ClCH2P(4-MeO-C6H4)2、ClCH2P(4-NO2-C6H4)2或ClCH2PiPr2；所述的继续反应的时间为1-3h；步骤(4)中所述的接着反应的时间为5-8h，所述的洗涤，采用乙醚作为洗涤剂。
一种如上所述的含双膦间位碳硼烷配体的铁配合物的应用，该铁配合物应用在催化合成反式2-烯基氮杂芳烃化合物中。
进一步地，其具体应用方法为：将铁配合物、2-甲基氮杂芳烃、芳醛和K2CO3溶于甲苯，室温反应，分离纯化，即得反式2-烯基氮杂芳烃化合物。
进一步地，所述的铁配合物、2-甲基氮杂芳烃、芳醛和K2CO3的摩尔比为(0.003-0.01):1.0:(1.0-1.5):(1.5-2)，所述的反应时间为3-6h。
进一步地，所述的2-甲基氮杂芳烃包括2-甲基喹啉或2-甲基吡啶；所述的芳醛包括苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲氧基苯甲醛、4-溴苯甲醛或4-硝基苯甲醛中的一种或多种。
本发明提供了一种含双膦间位碳硼烷Pincer铁配合物，并且该配合物在2-甲基氮杂芳烃与芳香醛的直接缩合反应合成反式2-烯基氮杂芳烃化合物中显示出高效的催化活性，催化剂用量低，反应条件温和，反应速率快，产率较高，在工业上有广泛的应用前景。本发明制备方法简单绿色，一锅反应即可高收率得到的Pincer铁配合物。该方法反应条件温和，普适性好，产率高，产物分离简单，产物对空气和水均不敏感，性质稳定。
与现有技术相比，本发明具有以下优点：
(1)本发明中含双膦间位碳硼烷Pincer铁配合物制备方法简单，一锅反应即可高产率制备，且在空气中能稳定存在；
(2)本发明中Pincer铁配合物可高效催化2-甲基氮杂芳烃与芳香醛的直接缩合反应合成反式2-烯基氮杂芳烃化合物，选择性好，催化剂用量低，反应条件温和，反应速率快，产率较高，底物范围广，在工业上有广泛的应用前景。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1：铁配合物1的合成及其在催化合成2-烯基氮杂芳烃化合物中的应用
0℃下，将n-BuLi(2.2mmol)的正己烷溶液滴加到含间位碳硼烷m-C2B10H12(1.0mmol)的乙醚溶液中，滴加结束后继续搅拌30分钟，缓慢升至室温后继续反应30分钟后加入卤代膦ClCH2PiPr2(2.5mmol)，继续在室温下反应3小时，然后将FeCl2(1.0mmol)加入反应体系在50℃继续反应6小时，反应结束后，静置过滤，减压抽干溶剂，得到的粗产物进行乙醚洗涤，抽干得到目标产物1(产率76％)，其反应式为：
Figure GDA0003681869390000051
1H NMR(400MHz,CDCl3,25℃):δ＝3.11(s,4H),2.90-2.82(m,4H),1.26-1.17(m,24H).元素分析理论值C16B10H41ClP2Fe：C 38.83,H 8.35；实验值：C 38.77,H 8.39。
在反应管中将铁配合物1(0.005mmol)、2-甲基氮杂芳烃(1.0mmol)、芳醛(1.1mmol)和K2CO3(1.5mmol)溶于甲苯2mL，室温反应5小时，反应结束后浓缩反应液，粗产物通过柱层析分离纯化，淋洗液为石油醚：乙酸乙酯＝8:1，即得缩合产物，具体结果见表1，其反应式为：
Figure GDA0003681869390000052
表1
Figure GDA0003681869390000053
Figure GDA0003681869390000061
实施例2：铁配合物2的合成
0℃下，将n-BuLi(2.4mmol)的正己烷溶液滴加到含间位碳硼烷m-C2B10H12(1.0mmol)的乙醚溶液中，滴加结束后继续搅拌30分钟，缓慢升至室温后继续反应30分钟后加入卤代膦ClCH2PPh2(2.8mmol)，继续在室温下反应3小时，然后将FeCl2(1.0mmol)加入反应体系在50℃继续反应8小时，反应结束后，静置过滤，减压抽干溶剂，得到的粗产物进行乙醚洗涤，抽干得到目标产物2(产率80％)，反应式为：
Figure GDA0003681869390000071
1H NMR(400MHz,CDCl3,25℃):δ＝7.72-7.61(m,8H),7.48-7.40(m,12H),3.19(s,4H).元素分析理论值C28B10H33ClP2Fe：C 53.30,H 5.27；实验值：C53.36,H 5.25。
实施例3：铁配合物3的合成
0℃下，将n-BuLi(2.5mmol)的正己烷溶液滴加到含间位碳硼烷m-C2B10H12(1.0mmol)的乙醚溶液中，滴加结束后继续搅拌30分钟，缓慢升至室温后继续反应30分钟后加入卤代膦ClCH2P(4-MeO-C6H4)2(3.0mmol)，继续在室温下反应3小时，然后将(COD)PdCl2(1.0mmol)加入反应体系在80℃继续反应5小时，反应结束后，静置过滤，减压抽干溶剂，得到的粗产物进行乙醚洗涤，抽干得到目标产物3(产率82％)，反应式为：
Figure GDA0003681869390000072
1H NMR(400MHz,CDCl3,25℃):δ＝7.79-7.65(m,8H),7.56-7.44(m,8H),3.56(s,12H),3.12(s,4H).元素分析理论值C32B10H41ClO4P2Fe：C 51.18,H 5.50；实验值：C 51.22,H5.56。
实施例4：铁配合物4的合成
0℃下，将n-BuLi(2.2mmol)的正己烷溶液滴加到含间位碳硼烷m-C2B10H12(1.0mmol)的乙醚溶液中，滴加结束后继续搅拌30分钟，缓慢升至室温后继续反应30分钟后加入卤代膦ClCH2P(4-NO2-C6H4)2(2.8mmol)，继续在室温下反应3小时，然后将(COD)PdCl2(1.0mmol)加入反应体系在60℃继续反应6小时，反应结束后，静置过滤，减压抽干溶剂，得到的粗产物进行乙醚洗涤，抽干得到目标产物4(产率81％)，反应式为：
Figure GDA0003681869390000081
1H NMR(400MHz,CDCl3,25℃):δ＝7.80-7.75(m,8H),7.62-7.55(m,12H),3.17(s,4H).元素分析理论值C28B10H29ClN4O8P2Fe：C 41.47,H 3.60,N 6.91；实验值：C 41.55,H3.63,N 6.86。
将铁配合物1-4催化2-甲基喹啉和苯甲醛的缩合反应，具体步骤如下：
在反应管中将Pincer铁配合物、2-甲基喹啉(1.0mmol)、苯甲醛(1.1mmol)和K2CO3(1.5mmol)溶于甲苯2mL，室温反应3-6小时，反应结束后浓缩反应液，粗产物通过柱层析分离纯化，淋洗液为石油醚：乙酸乙酯＝8:1，即得缩合产物，具体结果见表2，反应式为：
Figure GDA0003681869390000082
表2
序号 催化剂 催化剂用量(mmol) 反应时间(h) 产率(％)
1 实施例1 0.003 3 65
2 实施例1 0.003 5 82
3 实施例1 0.003 6 83
4 实施例1 0.005 6 93
5 实施例1 0.010 6 93
6 实施例2 0.005 5 89
7 实施例3 0.005 5 92
8 实施例4 0.005 5 91

Claims (9)

1.一种含双膦间位碳硼烷配体的铁配合物，其特征在于，该铁配合物的结构式如下所示：
Figure FDA0003681869380000011
其中，R为-Ph、4-MeO-C6H4-、4-NO2-C6H4-或-iPr中的一种，“·”为硼氢键。
2.一种如权利要求1所述的含双膦间位碳硼烷配体的铁配合物的制备方法，其特征在于，该方法为：将n-BuLi与间位碳硼烷m-C2B10H12反应，然后加入卤代膦继续反应，再将FeCl2加入反应体系接着反应，反应结束后分离得到含双膦间位碳硼烷配体的铁配合物。
3.根据权利要求2所述的一种含双膦间位碳硼烷配体的铁配合物的制备方法，其特征在于，所述的间位碳硼烷、n-BuLi、卤代膦和FeCl2的摩尔比为1.0:(2.2-2.5):(2.5-3.0):(0.8-1.2)。
4.根据权利要求2所述的一种含双膦间位碳硼烷配体的铁配合物的制备方法，其特征在于，该方法具体包括以下步骤：
(1)在低温下，将n-BuLi溶液滴加到间位碳硼烷m-C2B10H12溶液中搅拌；
(2)升温至室温，再反应；
(3)加入卤代膦，继续反应；
(4)将FeCl2加入反应体系接着反应，反应结束后，减压抽干溶剂，再将得到的粗产物进行洗涤、抽干，得到含双膦间位碳硼烷配体的铁配合物。
5.根据权利要求4所述的一种含双膦间位碳硼烷配体的铁配合物的制备方法，其特征在于，步骤(1)中所述的低温的温度为-5～5℃；所述的n-BuLi溶液为n-BuLi正己烷溶液，所述的m-C2B10H12溶液为m-C2B10H12乙醚溶液；所述的搅拌的时间为20-40min；步骤(2)中所述的再反应的时间为20-40min。
6.根据权利要求4所述的一种含双膦间位碳硼烷配体的铁配合物的制备方法，其特征在于，步骤(3)中所述的卤代膦包括ClCH2PPh2、ClCH2P(4-MeO-C6H4)2、ClCH2P(4-NO2-C6H4)2或ClCH2PiPr2；所述的继续反应的时间为1-3h；步骤(4)中所述的接着反应的时间为5-8h，所述的洗涤，采用乙醚作为洗涤剂。
7.一种如权利要求1所述的含双膦间位碳硼烷配体的铁配合物的应用，其特征在于，该铁配合物应用在催化合成反式2-烯基氮杂芳烃化合物中；其具体应用方法为：将铁配合物、2-甲基氮杂芳烃、芳醛和K2CO3溶于甲苯，室温反应，分离纯化，即得反式2-烯基氮杂芳烃化合物。
8.根据权利要求7所述的一种含双膦间位碳硼烷配体的铁配合物的应用，其特征在于，所述的铁配合物、2-甲基氮杂芳烃、芳醛和K2CO3的摩尔比为(0.003-0.01):1.0:(1.0-1.5):(1.5-2)，所述的反应时间为3-6h。
9.根据权利要求7所述的一种含双膦间位碳硼烷配体的铁配合物的应用，其特征在于，所述的2-甲基氮杂芳烃包括2-甲基喹啉或2-甲基吡啶；所述的芳醛包括苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲氧基苯甲醛、4-溴苯甲醛或4-硝基苯甲醛中的一种或多种。
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