CN113735883B - 一种含氮杂环衍生n,o-双齿配位单核铜催化剂的制备方法及其用途 - Google Patents
一种含氮杂环衍生n,o-双齿配位单核铜催化剂的制备方法及其用途 Download PDFInfo
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Abstract
本发明公开了一种含氮杂环衍生N,O‑双齿配位单核铜催化剂的制备方法，该方法将N‑(2‑喹啉基甲基)N‑氧化吗啡啉溶解在无水乙醇中，加入无水CuCl2，室温搅拌反应3~10个小时，析出的绿色沉淀经过滤，无水乙醇洗涤，真空抽干溶剂得到绿色固体Cu[C14H16N2O2]Cl2，通过气相扩散法将乙醚扩散到该固体的甲醇溶液，获得适合X‑ray衍射分析的N,O‑双齿配位单核铜催化剂的晶体。本发明方法具有反应速度快、制备操作和后处理简单，催化剂活性高等优点。该铜配合物在苯并咪唑与芳基硼酸的Chan‑Lam偶联反应中表现出很高的催化活性，产率高达96%。
Description
技术领域
本发明属于有机合成领域，其中涉及到含氮杂环(喹啉、吗啡啉)衍生N,O-双齿配位单核铜催化剂的制备方法。
技术背景
铜配合物是一类具有多变配位结构的化合物，根据配体的不同可合成结构多样的单核或多核铜配合物。而不同结构的铜配合物往往表现出特殊的性能，例如许多金属酶和金属蛋白的活性部位均含有双核铜结构单元，某些具有新颖拓扑结构的铜配合物，对于探索和研究药物分子抗菌、抗肿瘤的作用机制具有重要意义。同时，含不同配体骨架的铜配合物在材料科学、生物、医学、催化、能源方面也表现出优良的性能，尤其在催化烯烃氧化、醇氧化、水氧化、聚合反应等方面取得了巨大的成就，受到研究者广泛的持续关注。
另一方面，Chan-Lam反应是指在铜催化下芳基硼酸(或锡烷、硅氧烷等)与含氮/氧/硫亲核体的氧化偶联反应。自1998年Chan，Evans和Lam课题组分别独立报道了铜盐促进的芳基硼酸与含氮/氧亲核体的芳基化反应后，由于其温和的反应条件、宽广的底物范围以及弱碱和铜盐的使用，该反应已成为构筑C-N、C-O、C-S等化学键强有力的合成策略(J.X.Qiao,P.Y.S.Lam,Synthesis 2011,829-856.)。然而，这些反应大多数是铜盐直接促进或催化的Chan-Lam偶联反应，关于铜配合物催化的Chan-Lam反应研究仍然面临重大挑战和机遇。许多课题组已经在这方面进行了有益的探索。例如2000年Collman首次报道了[Cu(OH)(TMEDA)]2Cl2催化下芳基硼酸与咪唑的Chan-Lam偶联反应(Org.Lett.2000,2,1233-1236；J.Org.Chem.2001,66,7892-7897).。2014年Onaka利用[Cu(OH)(TMEDA)]2Cl2发展了5-取代四唑与芳基硼酸的区域选择性芳基化反应，但需要12mol％催化剂在氧气存在下进行(J.Org.Chem.2014,79,6703-6707.)。2016年Phukan成功合成[Cu(DMAP)4I]I配合物，以较低催化量(2mol％)实现了胺、酰胺、磺酰基叠氮、硫酚与芳基硼酸的C-N和C-S偶联(Chem.Commun.2016,52,1170-1173.)。2017年Schaper系统地开展了含磺酸基亚胺骨架铜配合物的合成及催化芳基硼酸与胺的Chan-Lam偶联反应研究，并对其催化反应机理进行了详细研究(Organometallics 2017,36,3053-3060；ACS Catal.2018,8,7308-7325.)。2018年，张占辉课题组发展了聚酰亚胺共价有机骨架固载的铜配合物作为有效和可循环使用的异相催化剂，用于芳基硼酸和胺的Chan-Lam偶联反应(Green Chem.2018,20,4891-4900)。2020年，Emerson课题组报道了一例新型四齿配位氮杂环卡宾铜配合物的合成及其在Chan-Lam偶联反应中的催化活性(Organometallics 2020,39,4457-4464)。
尽管铜配合物催化的Chan-Lam偶联反应取得了一定的进展，但仍存在催化剂用量高、配体结构单一、催化体系少等缺点。因此，设计合成新型的含氮杂环衍生的铜配合物，并发展其高效催化Chan-Lam偶联反应新体系是十分必要的。
通过检索，尚未发现与本发明申请相同的公开专利文献。
发明内容
本项发明的目的是针对Chan-Lam偶联反应中铜配合物催化剂结构单一、催化体系较少等问题，提供一种合成新型含氮杂环(喹啉、吗啡啉)衍生的N,O-双齿配位单核铜催化剂的制备方法，以期在Chan-Lam偶联反应中发挥催化作用，发展实用高效的催化体系，提供构建C-N键的新方法。
本发明的设计思路如下：
1.设计合成了喹啉、吗啡啉杂环骨架衍生的新型N,O-双齿配体，将其与无水CuCl2作用制备N,O-双齿配位单核铜配合物，借助配体的杂环骨架调控中心铜原子的催化活性；
2.利用重结晶、挥发、扩散等常规结晶方法获得上述铜配合物的单晶，并确定其结构；
3.将具有明确结构的喹啉杂环衍生N,O-双齿配位的单核铜催化剂应用于Chan-Lam偶联反应，实现高效催化构建C-N键的目标。
这类催化剂的晶体结构信息通过如下方法获得的：
通过常规法合成得到N,O-双齿配位单核铜配合物的晶体，具体的描述实验方法如下：
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(0.5～8mmol)和无水乙醇(10～40mL)，使其完全溶解，再加入无水氯化铜(0.5～6mmol)，室温下搅拌反应，10～30分钟后析出绿色沉淀，继续反应3～10个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体，产率约65～75％。
适合于X-ray衍射分析的单晶通过气相扩散法，将乙醚扩散到铜配合物的甲醇溶液中获得。晶体结构的准确信息经X-ray衍射分析确定如下：
晶体的分子式为Cu[C14H16N2O2]Cl2，属P21/n空间群单斜晶系，不对称单元含有一个配体分子和CuCl2，二者按1:1配位，中心铜原子分别与配体中喹啉环的N2、N-氧化吗啡啉部分的O2以及两个氯原子以双齿配位模式形成结构稳定的四配位铜配合物。通过结构分析，金属铜是活性位点，对Chan-Lam偶联反应具有催化作用，配体的存在有可能增强中心铜原子的催化活性。
这项发明主要是设计合成了一种新型的N,O-双齿配位的铜催化剂，期望能在实际应用中实现高效催化Chan-Lam偶联反应。
本发明提供N,O-双齿配位单核铜催化剂具有以下特点：
1.使用的配体容易合成，配合物制备方法简单，并且催化剂具有明确的分子结构，有助于了解N,O-双齿配体与金属铜的配位方式，研究催化反应机理。
2.催化剂价格低廉，对Chan-Lam偶联反应表现出很高的催化活性，产率高，具有实际应用价值。
附图说明
图1.铜配合物Cu[C14H16N2O2]Cl2的晶体结构示意图(为了结构清晰,没有画氢原子)；
图2.铜配合物Cu[C14H16N2O2]Cl2的IR谱图。
具体实施方式
具体实例1：铜配合物Cu[C14H16N2O2]Cl2的制备
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(0.5mmol)和无水乙醇(10mL)，使其完全溶解，再加入无水氯化铜(0.5mmol)，搅拌10分钟后析出绿色沉淀，室温继续反应3个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体。产率约70％。
具体实例2：铜配合物Cu[C14H16N2O2]Cl2的制备
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(2mmol)和无水乙醇(20mL)，使其完全溶解，再加入无水氯化铜(4mmol)，搅拌30分钟后析出绿色沉淀，室温继续反应5个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体。产率约75％。
具体实例3：铜配合物Cu[C14H16N2O2]Cl2的制备
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(5mmol)和无水乙醇(30mL)，使其完全溶解，再加入无水氯化铜(6mmol)，搅拌20分钟后析出绿色沉淀，室温继续反应6个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体。产率约72％。
具体实例4：铜配合物Cu[C14H16N2O2]Cl2的制备
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(6mmol)和无水乙醇(30mL)，使其完全溶解，再加入无水氯化铜(4mmol)，搅拌30分钟后析出绿色沉淀，室温继续反应8个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体。产率约65％。
具体实例5：铜配合物Cu[C14H16N2O2]Cl2的制备
在一个50mL干燥的圆底烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉(8mmol)和无水乙醇(40mL)，使其完全溶解，再加入无水氯化铜(4mmol)，搅拌30分钟后析出绿色沉淀，室温继续反应10个小时后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体。产率约68％。
如表1所示：铜配合物Cu[C14H16N2O2]Cl2的晶体学数据
具体试验例：含氮杂环衍生N,O-双齿配位单核铜催化剂应用于Chan-Lam偶联反应
在干燥的25mL Schlenk反应管中，加入苯并咪唑(0.2～1mmol)、芳基硼酸(0.6～1.2mmol)，再加入CH3OH(1～5mL)，搅拌下加入铜催化剂(5～8mol％)，将反应管密封，在50℃的条件下反应12～24h，通过TLC监测反应过程。待反应结束后，冷却到室温，减压除去部分溶剂，残余物用柱色谱分离纯化得到偶联产物。具体Chan-Lam偶联反应的实验数据见表2。
Claims (4)
1.含氮杂环衍生N,O-双齿配位单核铜催化剂的制备方法，其特征在于：步骤为：在干燥的烧瓶中加入N-(2-喹啉基甲基)N-氧化吗啡啉和溶剂，使其完全溶解，再加入无水氯化铜，搅拌反应，10~30分钟后析出绿色沉淀，继续反应后，过滤，无水乙醇洗涤，洗涤后的固体真空抽干溶剂得到绿色固体的铜配合物；通过气相扩散法，将乙醚扩散到铜配合物的甲醇溶液中获得晶体；晶体的分子式为Cu[C14H16N2O2]Cl2，属P21/n空间群单斜晶系，不对称单元含有一个配体分子和CuCl2，二者按1:1配位，中心铜原子分别与配体中喹啉环的N、N-氧化吗啡啉中氧化部分的O以及两个氯原子以双齿配位模式形成结构稳定的四配位铜配合物。
2.根据权利要求1所述的含氮杂环衍生N,O-双齿配位单核铜催化剂的制备方法，其特征在于：N-(2-喹啉基甲基)N-氧化吗啡啉：氯化铜物质的量之比为0.5~8: 0.5~6，所用溶剂为无水乙醇。
3.根据权利要求1所述的含氮杂环衍生N,O-双齿配位单核铜催化剂的制备方法，其特征在于：搅拌反应温度为室温，继续反应时间为3~10个小时。
4.一种按照权利要求1-3任一所述制备方法获得的含氮杂环衍生N,O-双齿配位单核铜催化剂在Chan-Lam偶联反应中的应用。
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| Four N,O-Bidentate-Chelated Ligand-Tunable Copper(II) Complexes: Synthesis, Structural Characterization and Exceptional Catalytic Properties for Chan-Lam Coupling Reactions;Xuefeng Jia等;《Asian J.Org.Chem.》;20180502;第7卷;1093-1100 * |
| Synthesis and Characterization of a Tetradentate, N-Heterocyclic Carbene Copper(II) Complex and Its Use as a Chan-Evans-Lam Coupling Catalyst;James D.Cope等;《Organometallics》;20201211;第39卷;4457-4464 * |
| 含氮杂环衍生双齿配体及其铜和钯配合物的合成、表征与催化研究;崔婧;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20170415(第04期);B014-145 * |
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