CN107827913B - 含1,10-菲啰啉状的n-杂环卡宾铜（i）配合物及用途 - Google Patents

含1,10-菲啰啉状的n-杂环卡宾铜（i）配合物及用途 Download PDF

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CN107827913B
CN107827913B CN201711179428.7A CN201711179428A CN107827913B CN 107827913 B CN107827913 B CN 107827913B CN 201711179428 A CN201711179428 A CN 201711179428A CN 107827913 B CN107827913 B CN 107827913B
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phenanthroline
heterocyclic carbene
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刘桂艳
韩方外
刘成鑫
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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Abstract

本发明公开了1,10‑菲啰啉状的N‑杂环卡宾铜（I）配合物（以及配合物单晶）及用途。本发明所述的1,10‑菲啰啉状的N‑杂环卡宾铜（I）配合物是以1,10‑菲啰啉状的N‑杂环卡宾为配体。本发明所述含1,10‑菲啰啉状的N‑杂环卡宾铜（I）配合物（以及配合物单晶）具有较高的稳定性，它还能作为催化剂很好的催化氯代芳烃和咪唑的偶联反应。

Description

含1,10-菲啰啉状的N-杂环卡宾铜（I）配合物及用途
本发明得到天津市自然科学基金（16JCYBJC19700）的资助。
技术领域
本发明涉及一种新型金属有机配位化合物及其用途，特别涉及金属铜有机配合物及用途，确切地说是一种新型的含1,10-菲啰啉状的N-杂环卡宾铜（I）配合物及用途。
背景技术
在现在的社会生产实践中，配合物的存在已经极为普遍，配合物的应用也逐渐增多，例如在化学反应中需要的催化剂等。 N-杂环卡宾具有给电子能力强、制备简便、易于修饰等等优点,近些年来引起了人们很大的研究兴趣。N-杂环卡宾过渡金属化合物已经被广泛应用于烯烃复分解、偶联反应、氢化反应等等的有机反应。
发明内容
新型的含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物并将它应用于催化领域。
本发明是通过以下技术方案实现的：
含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物具有如下结构式：
Figure 771932DEST_PATH_IMAGE001
本发明进一步公开了含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的单晶数据如下：
本发明更进一步公开了含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的合成方法：
主要包括反应、分离和纯化，含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的合成方法包括反应、分离和纯化，其特征是以萘啶基团修饰的咪唑氯代盐为原料与氯化亚铜在碱性条件下反应，得到所述含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物。将所得含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物溶于二氯甲烷/石油醚混合溶剂中慢慢挥发得到相应的单晶。
Figure 921154DEST_PATH_IMAGE002
本发明更进一步公开了含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及的配合物单晶）在氯代芳烃和咪唑的偶联反应中有较好的催化性能。实验结果显示，当选用碳酸钾作为碱，DMF作为溶剂，以含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物作为催化剂，催化氯代芳烃和咪唑的偶联反应，其中氯代芳烃，咪唑和碳酸钾的投料比为：1:1.2:2，在120℃条件下，反应1-12小时，仅用0.01当量催化剂，反应产率就能达到95%以上。
本发明公开的含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的特点在于：
(a)含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物结构新颖，目前未见和其结构完全相同的报道。
(b) 本发明所制备的含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及配合物单晶）可很好的应用于催化氯代芳烃和咪唑的偶联反应，并显示出较好的催化性能。目前还未发现任何一种N-杂环卡宾铜（I）配合物能催化该反应。
附图说明
图1：含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的晶体结构图。
具体实施方式
下面通过具体的实施方案叙述本发明。除非特别说明，本发明中所用的技术手段均为本领域技术人员所公知的方法。另外，实施方案应理解为说明性的，而非限制本发明的范围，本发明的实质和范围仅由权利要求书所限定。对于本领域技术人员而言，在不背离本发明实质和范围的前提下，对这些实施方案中的物料成分和用量进行的各种改变或改动也属于本发明的保护范围。
实验中所有的原料都是从国内的化学试剂公司进行购买，没有经过继续提纯而直接使用。本发明所使用的核磁共振仪器的型号为BrukerAvance III 400 M小时z，单晶衍射仪型号为APEX II CCD。
实施例1
含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物的合成路线和步骤如下：
Figure 801385DEST_PATH_IMAGE003
取以萘啶基团修饰的咪唑氯代盐（50 mg, 0.14 mmol），氯化亚铜(13.6 mg, 0.14mmol)和碳酸钾(38 mg, 0.38 mmol)发生反应，保持温度为60 ℃，用丙酮回流24小时后，沉淀用二氯甲烷洗涤，过滤干燥，得到最终晶体530 mg (产率:75%)。
产物核磁共振数据：1H-NMR (400 MHz, CDCl3) δ (ppm): 1.12 (d, 12H), 2.27(m, 2H), 7.21 (d, 3H), 7.30 (d,1 H), 7.39-7.46 (m, 3H), 8.0 (d,1 H), 8.66 (s,1 H)。
实施例2
含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及配合物单晶）催化氯代芳烃和咪唑的偶联反应的应用：
在120度条件下，选用碳酸钾作为碱，DMF作为溶剂，以含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物作为催化剂，催化氯代芳烃和咪唑的偶联反应 ，其中氯代芳烃，咪唑和碳酸钾的投料比为：1:1.2:2。反应结束后，反应液用水洗，以二氯甲烷萃取三次，有机层合并，加无水硫酸镁干燥，浓缩，产物用柱色谱法提纯，得到相应产率。反应结果如下表1所示:
表1：含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及配合物单晶）在氯代芳烃和咪唑的偶联反应中的应用
Figure 160691DEST_PATH_IMAGE004
结论：从表中可以看出，当选用碳酸钾作为碱，DMF作为溶剂，以含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及配合物单晶）作为催化剂，催化氯代芳烃和咪唑的偶联反应 ，其中氯代芳烃，咪唑和碳酸钾的投料比为：1:1.2:2，在120度条件下，用0.01当量催化剂，反应1-12小时，反应产率就能达到95%以上。目前还未发现任何一种N-杂环卡宾铜（I）配合物能催化该类反应。
本发明的方法，考察了现有的金属铜配合物催化氯代芳烃和咪唑的偶联反应，并进行了比较，在相同的反应条件下结果如下：
比较试验
结论：只有本发明专利报道的含有1,10-菲啰啉状的N-杂环卡宾铜（I）配合物（以及配合物单晶）作为催化剂，在上述反应条件下，反应产率才能达到95%以上，其他催化剂产率都低于90%。

Claims (1)

1.一种含1,10-菲啰啉状的N-杂环卡宾铜（I）配合物作为催化剂在氯代芳烃和咪唑的偶联反应中的应用；所述的1,10-菲啰啉状的N-杂环卡宾铜（I）配合物具有如下结构式：
Figure 760246DEST_PATH_IMAGE001
。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1518534A (zh) * 2001-04-24 2004-08-04 麻省理工学院 铜-催化的碳-杂原子键和碳-碳键的形成
CN102558024A (zh) * 2012-01-16 2012-07-11 山东盛华电子新材料有限公司 一种催化体系催化芳胺n-烷基化的方法
CN104910195A (zh) * 2015-04-21 2015-09-16 福州大学 一种二氟卡宾铜试剂及其制备和应用
CN105944762A (zh) * 2016-05-09 2016-09-21 武汉工程大学 菲啰啉类铜配合物催化剂及其制备方法和应用
CN106478687A (zh) * 2016-09-26 2017-03-08 广西师范大学 以1‑(2‑吡啶)‑9‑乙基‑β‑咔啉为配体的氯化铜配合物及其合成方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1518534A (zh) * 2001-04-24 2004-08-04 麻省理工学院 铜-催化的碳-杂原子键和碳-碳键的形成
CN102558024A (zh) * 2012-01-16 2012-07-11 山东盛华电子新材料有限公司 一种催化体系催化芳胺n-烷基化的方法
CN104910195A (zh) * 2015-04-21 2015-09-16 福州大学 一种二氟卡宾铜试剂及其制备和应用
CN105944762A (zh) * 2016-05-09 2016-09-21 武汉工程大学 菲啰啉类铜配合物催化剂及其制备方法和应用
CN106478687A (zh) * 2016-09-26 2017-03-08 广西师范大学 以1‑(2‑吡啶)‑9‑乙基‑β‑咔啉为配体的氯化铜配合物及其合成方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Silver and Gold Complexes with a New 1,10-Phenanthroline Analogue NHeterocyclic Carbene: A Combined Structural, Theoretical, and Photophysical Study;Margit Kriechbaum et al.;《Chem. Eur. J.》;20121231;第18卷;page: 5506-5509 *
串联的铜、钯催化偶联-环化合成二芳胺基芴;蔡良珍等;《有机化学》;20151231;第1682-1690页 *

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