CN108148062A - 一种2-(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用 - Google Patents

一种2-(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用 Download PDF

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CN108148062A
CN108148062A CN201611127762.3A CN201611127762A CN108148062A CN 108148062 A CN108148062 A CN 108148062A CN 201611127762 A CN201611127762 A CN 201611127762A CN 108148062 A CN108148062 A CN 108148062A
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pyridine bromide
bromide base
imidazole compound
benzo
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柴会宁
余正坤
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Dalian Institute of Chemical Physics of CAS
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
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Abstract

本发明公开了一种2‑(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用。以6‑溴‑2‑吡啶甲酸和四氨基苯盐酸盐为起始原料，经缩合反应生成2‑(溴代吡啶基)苯并双咪唑化合物。该化合物可用于合成高效的双金属催化剂。本发明具有原料价廉易得、操作简便以及效率高等优点。

Description

一种2-(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用
技术领域
本发明涉及一种2-(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用。以6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3为原料，经缩合反应生成2-(溴代吡啶基)苯并双咪唑化合物。该化合物可用于合成高效的双金属催化剂。本发明具有原料价廉易得、操作简便以及效率高等优点。
背景技术
双齿NN化合物作为一类用途广泛的N-杂环化合物，不仅具有潜在的生物活性，也可用于制备高活性配合物催化剂。上世纪九十年代Noyori小组报道了单对甲苯磺酰手性二胺配体(Ts-DPEN)和β-氨基醇类化合物，在Ru催化的不对称转移氢化反应中获得了非常优秀的结果，具有划时代的意义(Noyori,R.et al.J.Am.Chem.Soc.2006,128,8724.)。这些工作有力的推动了不对称转移氢化反应的发展，为配体的设计提供了指导思想。Baratta小组报道了2-氨甲基吡啶(Ampy)系列的NN配体，它们在Ru和Os催化的不对称转移氢化反应中也表现出很高的催化活性和对映选择性，是二齿配体中的优秀代表(Baratta,W.etal.Organometallics 2005,24,1660.)。
近年来，双齿NN化合物也引起了人们的重视，它可作为双金属的载体，通过金属与金属之间的协同作用，制备出比单金属催化活性更高的双金属配合物(Takeuchi,D.etal.Organometallics 2014,33,5316.)。
本发明所合成的2-(溴代吡啶基)苯并双咪唑化合物不仅可以发出荧光，作为一种潜在的荧光材料，而且还可以作为双金属配体与金属配位得到高活性的金属催化剂，此外，该发明还具备原料价廉易得、操作简便、效率高、步骤少等优点。
发明内容
本发明的目的在于提供一种原料易得、适应性广、能高效地合成2-(溴代吡啶基)苯并双咪唑化合物。
为了实现上述目的，本发明的技术方案如下：
以6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3为起始原料，经缩合反应生成2-(溴代吡啶基)苯并双咪唑化合物。(反应式1)。
技术方案为：
1.6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3为合成子。
2.6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3发生缩合反应制备2-(溴代吡啶基)苯并双咪唑化合物1，反应溶剂为多聚磷酸(PPA)或冰醋酸；反应过程中6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3的摩尔比2:1-4:1；反应温度为70-230℃；反应时间为5-32小时。
本发明具有以下优点：
1)原料来源广泛，便宜易得或者易于制备。
2)2-(溴代吡啶基)苯并双咪唑化合物1合成方法简单、制备效率高、产物用途广泛、易于衍生化。
3)2-(溴代吡啶基)苯并双咪唑化合物1用途较广，可用于制备高活性配合物催化剂或配合物发光材料的配体。
总之，本发明利用一步合成方法制备吡啶基桥联NNN双金属配体，合成方法简便、制备效率高、产物易于衍生化且应用广泛。
具体实施方式
本发明以6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3为原料，经缩合反应生成2-(溴代吡啶基)苯并双咪唑化合物。该配体可用于合成高效的双金属催化剂。本发明具有原料价廉易得、操作简便以及效率高等优点。通过下述实施例有助于进一步理解本发明，但本发明的内容并不仅限于此。
原料四氨基苯盐酸盐3(Jin,Ningren et al.Huagong Xuebao,2012,63,2092.)按文献方法制备。
实施例1
6-溴-2-吡啶甲酸2(0.40g,2.00mmol)、四氨基苯盐酸盐3(0.28g,1.00mmol)在冰醋酸中，70℃下搅拌反应12小时。冷至室温后先硅藻土过滤，二氯甲烷多次洗涤直至无产物为止，旋干溶剂并柱层析分离，得到黄色固体1为目标产物(0.11g，收率23％)。目标产物通过核磁共振谱得到确认。
应用例1
在氮气保护下，往25mL Schlenk反应瓶中依次加入配体1(47.0mg，0.1mmol)、PdCl2(35.4mg，0.2mmol)和3mL二甲亚砜，50度下反应4h。冷至室温后，加入乙醚使之沉淀，固体用乙醚洗涤(3×20mL)。真空干燥后得到黄色固体产品4(68.0mg，收率85％)。金属配合物4通过核磁共振谱与元素分析测定得到确认。

Claims (4)

1.一种2-(溴代吡啶基)苯并双咪唑化合物，其结构式如下式1所示，
2.一种权利要求1所述2-(溴代吡啶基)苯并双咪唑化合物的合成方法，其特征在于：以6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3为原料，经缩合反应得到2-(溴代吡啶基)苯并双咪唑化合物1；
合成路线如下述反应式所示：
3.按照权利要求2所述的合成方法，其特征在于：
其中：6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3发生缩合反应制备2-(溴代吡啶基)苯并双咪唑化合物1，反应溶剂为多聚磷酸(PPA)或冰醋酸；反应过程中6-溴-2-吡啶甲酸2和四氨基苯盐酸盐3的摩尔比2:1-4:1；反应温度为70-230℃；反应时间为5-32小时。
4.一种权利要求1所述2-(溴代吡啶基)苯并双咪唑化合物在作为荧光材料或金属配合物催化剂中的应用。
CN201611127762.3A 2016-12-09 2016-12-09 一种2-(溴代吡啶基)苯并双咪唑化合物的制备方法及其应用 Pending CN108148062A (zh)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635416A (zh) * 2020-06-30 2020-09-08 哈尔滨工业大学（威海） 一种咪唑类化合物的制备方法及应用
CN111848624A (zh) * 2019-04-30 2020-10-30 上海和辉光电有限公司 一种苯并二咪唑类的化合物、空穴注入材料、oled器件及其制备方法和应用
CN112679507A (zh) * 2021-01-18 2021-04-20 邓颖菁 一种共轭苯并咪唑缓蚀剂及其制备方法
CN112876483A (zh) * 2021-01-18 2021-06-01 邓颖菁 一种双阳离子苯并咪唑缓蚀剂及其制备方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848624A (zh) * 2019-04-30 2020-10-30 上海和辉光电有限公司 一种苯并二咪唑类的化合物、空穴注入材料、oled器件及其制备方法和应用
CN111635416A (zh) * 2020-06-30 2020-09-08 哈尔滨工业大学（威海） 一种咪唑类化合物的制备方法及应用
CN112679507A (zh) * 2021-01-18 2021-04-20 邓颖菁 一种共轭苯并咪唑缓蚀剂及其制备方法
CN112876483A (zh) * 2021-01-18 2021-06-01 邓颖菁 一种双阳离子苯并咪唑缓蚀剂及其制备方法
CN112679507B (zh) * 2021-01-18 2024-03-05 河北中天兰清环境科技有限公司 一种共轭苯并咪唑缓蚀剂及其制备方法

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Application publication date: 20180612