CN101787042A - Copper-nitrogen compound and application thereof - Google Patents
Copper-nitrogen compound and application thereof Download PDFInfo
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- CN101787042A CN101787042A CN 201010127498 CN201010127498A CN101787042A CN 101787042 A CN101787042 A CN 101787042A CN 201010127498 CN201010127498 CN 201010127498 CN 201010127498 A CN201010127498 A CN 201010127498A CN 101787042 A CN101787042 A CN 101787042A
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- copper
- complex
- nitrogen
- aminobenzylamine
- xylylenediamine
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- CMPNPRUFRJFQIB-UHFFFAOYSA-N [N].[Cu] Chemical compound [N].[Cu] CMPNPRUFRJFQIB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910017464 nitrogen compound Inorganic materials 0.000 title 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 8
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 6
- GVOYKJPMUUJXBS-UHFFFAOYSA-N 2-(aminomethyl)aniline Chemical compound NCC1=CC=CC=C1N GVOYKJPMUUJXBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006842 Henry reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- LALLFQGHVCPFCP-UHFFFAOYSA-L copper 2-(aminomethyl)aniline diacetate Chemical compound C(C)(=O)[O-].[Cu+2].NC1=C(CN)C=CC=C1.C(C)(=O)[O-] LALLFQGHVCPFCP-UHFFFAOYSA-L 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 m-xylylenediamine copper acetate Chemical compound 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XUEWIQNQPBSCOR-UHFFFAOYSA-N 2-nitro-1-phenylethanol Chemical compound [O-][N+](=O)CC(O)C1=CC=CC=C1 XUEWIQNQPBSCOR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种铜氮配合物是由邻氨基苄胺和间苯二甲胺分别与一水合醋酸铜在无水四氢呋喃溶剂中反应24小时后分离得到的邻氨基苄胺醋酸铜配合物和间苯二甲胺醋酸铜配合物。本铜氮配合物在亨利反应中显示良好的性能，转化率分别为67％、99％。A copper-nitrogen complex is obtained by reacting o-aminobenzylamine and m-xylylenediamine with copper acetate monohydrate in anhydrous tetrahydrofuran solvent for 24 hours and then separating the o-aminobenzylamine acetate copper complex and m-xylylenediamine Amine acetate copper complex. The copper-nitrogen complex shows good performance in the Henley reaction, and the conversion rates are 67% and 99%, respectively.
Description
一、技术领域1. Technical field
本发明涉及一种金属有机配位化合物(配合物)，特别涉及含氮的金属有机配合物，确切地说是一种铜氮配合物。The invention relates to a metal-organic coordination compound (complex), in particular to a nitrogen-containing metal-organic complex, specifically a copper-nitrogen complex.
二、背景技术2. Background technology
含氮的金属有机配合物具有新颖的结构以及在催化、电化学、吸附、离子交换和磁性等方面具有潜在的应用前景，这类化合物的研究越来越引起人们的浓厚兴趣，已经在备受无机化学、配位化学、金属有机化学和生物无机化学等方面的研究者的广泛重视，并取得引人瞩目的研究成果。Nitrogen-containing metal-organic complexes have novel structures and potential applications in catalysis, electrochemistry, adsorption, ion exchange, and magnetism. Researchers in inorganic chemistry, coordination chemistry, metal-organic chemistry and bioinorganic chemistry have paid extensive attention and achieved remarkable research results.
[1]徐光宪.北京大学学报，2003，38(2)：149-152。[1] Xu Guangxian. Journal of Peking University, 2003, 38(2): 149-152.
[2]丁彦滨，彭丽，等.化学工程师，2003，99(6)：42-43。[2] Ding Yanbin, Peng Li, et al. Chemical Engineers, 2003, 99(6): 42-43.
铜氮金属有机配合物具有一些优良的催化性能，与材料科学、有机合成、生命科学等学科密切相关，含Cu-N的金属有机配合物在高分子和有机合成不对称催化领域具有重要意义。成为国内外研究的热点之一，已经有大量的文献报道。Copper-nitrogen metal-organic complexes have some excellent catalytic properties, which are closely related to materials science, organic synthesis, life science and other disciplines. Cu-N-containing metal-organic complexes are of great significance in the field of asymmetric catalysis in polymer and organic synthesis. It has become one of the research hotspots at home and abroad, and there have been a lot of literature reports.
[3]M.del Carme Castellano，Josefina Pons，Jordi García-Antón，et al.InorganicaChimica OActa，2008，361：2923-2928[3] M. del Carme Castellano, Josefina Pons, Jordi García-Antón, et al. Inorganica Chimica OActa, 2008, 361: 2923-2928
[4]Dennis A.Walker，Timothy J.Woodman，Mark Schormann，et al.Organometallics，2003，22：797-803[4] Dennis A. Walker, Timothy J. Woodman, Mark Schormann, et al. Organometallics, 2003, 22: 797-803
三、发明内容3. Contents of the invention
本发明旨在提供一种Cu-N金属有机配合物以应用于不对称催化领域，所要解决的技术问题遴选合适的芳胺作为配体并合成铜氮配合物。The present invention aims to provide a Cu-N metal-organic complex for application in the field of asymmetric catalysis, and the technical problem to be solved is to select a suitable aromatic amine as a ligand and synthesize a copper-nitrogen complex.
本发明所称的铜氮配合物其中一种是由邻氨基苄胺与一水合醋酸铜制备的由以下化学式所示的配合物：One of the copper-nitrogen complexes referred to in the present invention is a complex represented by the following chemical formula prepared by o-aminobenzylamine and copper acetate monohydrate:
下简称邻氨基苄胺醋酸铜，记为配合物(I)。Hereinafter referred to as o-aminobenzylamine copper acetate, denoted as complex (I).
本发明所称的铜氮配合物另一种是由间苯二甲胺与一水合醋酸铜制备的、由以下化学式所示的配合物：Another copper-nitrogen complex referred to in the present invention is prepared by m-xylylenediamine and copper acetate monohydrate, and is a complex shown in the following chemical formula:
下简称间苯二甲胺醋酸铜，记为配合物(II)Hereinafter referred to as m-xylylenediamine copper acetate, denoted as complex (II)
本配合物(I)和(II)的合成方法是由邻氨基苄胺和间苯二甲胺分别与一水合醋酸铜在无水四氢呋喃溶剂中回流反应24小时。The synthesis method of the complexes (I) and (II) is to react respectively o-aminobenzylamine and m-xylylenediamine with copper acetate monohydrate in anhydrous tetrahydrofuran solvent for 24 hours under reflux.
配合物(I)自反应液中析出蓝色固体便是配合物(I)。The complex (I) is the complex (I) when the blue solid is precipitated from the reaction solution.
配合物(II)当反应液冷却、于THF溶液中静止得无色透明的晶体配合物(II)。配合物(I)、(II)在亨利反应中显示良好的催化性能见下表。Complex (II) is colorless and transparent crystal complex (II) when the reaction liquid is cooled and static in THF solution. The complexes (I) and (II) show good catalytic performance in the Henry reaction as shown in the table below.
四、附图说明4. Description of drawings
图1是配合物(I)的X射线衍射单晶结构图。Fig. 1 is an X-ray diffraction single crystal structure diagram of complex (I).
图2是配合物(II)的X射线衍射单晶结构图。Fig. 2 is an X-ray diffraction single crystal structure diagram of complex (II).
一、具体实施方式1. Specific implementation
1、邻氨基苄胺醋酸铜配合物(I)的合成1. Synthesis of o-aminobenzylamine acetate copper complex (I)
将1.1023g邻氨基苄胺与0.9001g的一水合醋酸铜加入100毫升的圆底烧瓶中，加入40毫升的四氢呋喃，加热搅拌24小时。热过滤得到蓝色固体，用少量无水乙醇溶解后，静置挥发得到蓝色针状晶体。Anal.Calc.for Cu[C9H13N2O2]2：C，50.70；H，6.10；N，13.15％.Found：C，50.55；H，6.43；N，13.38％.).IR(KBr pellet)：3451，3342，3230，3183，3113，3067，3028，2950，2886，2349，1576，1496，1468，1454，1418，1394，1334，1279，1223，1159，1121，1087，1041，1020，995，945，860，846，754，664，650，623，587，492，472.Add 1.1023g of o-aminobenzylamine and 0.9001g of copper acetate monohydrate into a 100ml round bottom flask, add 40ml of tetrahydrofuran, and heat and stir for 24 hours. After hot filtration, a blue solid was obtained. After dissolving with a small amount of absolute ethanol, it was left to evaporate to obtain a blue needle-like crystal. Anal.Calc.for Cu[C 9 H 13 N 2 O 2 ] 2 : C, 50.70; H, 6.10; N, 13.15%.Found: C, 50.55; H, 6.43; N, 13.38%.).IR( KBr pellet): 3451, 3342, 3230, 3183, 3113, 3067, 3028, 2950, 2886, 2349, 1576, 1496, 1468, 1454, 1418, 1394, 1334, 1279, 1223, 1159, 1121, 1087, 1041, 1020, 995, 945, 860, 846, 754, 664, 650, 623, 587, 492, 472.
2、间苯二甲胺醋酸铜配合物(II)的合成2. Synthesis of m-xylylenediamine acetate copper complex (II)
将1.5mL间苯二甲胺与1.1174g的一水合醋酸铜加入100ml的圆底烧瓶中，加入40毫升四氢呋喃，加热搅拌24小时。而后倒出部分上层溶夜，封口静置，数天后得到无色晶体。Yield：38％(0.62g).Anal.Calc.for ZnC12H18N2O4：C，45.14；H，5.64；N，8.78％.Found：C，44.58；H，5.76；N，8.84％.1HNMR(300MHz，CDCl3，27℃)，δ(ppm)＝(s，8H)，δ(ppm)＝(s，8H)，δ(ppm)＝(s，6H).IR(KBr pellet)：.3476，3235，3130，3030，3007，2979，2956，2887，2548，2333，2149，1957，1589，1491，1396，1335，1248，1158，1089，1001，929，882，794，770，748，701，677，623，595，485.Add 1.5mL of m-xylylenediamine and 1.1174g of copper acetate monohydrate into a 100ml round bottom flask, add 40ml of tetrahydrofuran, and heat and stir for 24 hours. Then part of the upper solution was poured out, sealed and left to stand, and colorless crystals were obtained after a few days. Yield: 38% (0.62g). Anal. Calc. for ZnC 12 H 18 N 2 O 4 : C, 45.14; H, 5.64; N, 8.78%. Found: C, 44.58; H, 5.76; N, 8.84% .1 HNMR (300MHz, CDCl 3 , 27°C), δ(ppm)=(s, 8H), δ(ppm)=(s, 8H), δ(ppm)=(s, 6H).IR(KBr pellet ):.3476, 3235, 3130, 3030, 3007, 2979, 2956, 2887, 2548, 2333, 2149, 1957, 1589, 1491, 1396, 1335, 1248, 1158, 1089, 1001, 929, 882, 794, 770 , 748, 701, 677, 623, 595, 485.
3.亨利反应应用3. Henry Reaction Application
2-硝基-1苯基乙醇的制备Preparation of 2-nitro-1-phenylethanol
分别取0.15mmol的间苯二甲胺醋酸铜及邻氨基苄胺醋酸铜(催化用量为15％)于两只25mL的小烧瓶中，各加入2毫升的甲醇溶液，然后，向上述溶液中各加入0.1mL的苯甲醛与0.5mL的硝基甲烷，常温搅拌，反应72小时，进行液相色谱测定，转化率分别为99％，67％。1HNMR(300MHz，CDCl3)7.28～7.32(m，5H，Ar-H)，5.32～5.35(d，J＝9.18Hz，1H，-CH)，4.38～4.56(m，2H，-CH2)，3.89(br，1H，-OH).Get respectively 0.15mmol of m-xylylenediamine copper acetate and o-aminobenzylamine copper acetate (the catalytic amount is 15%) in two 25mL small flasks, respectively add 2 ml of methanol solution, and then add each 0.1 mL of benzaldehyde and 0.5 mL of nitromethane were added, stirred at room temperature, reacted for 72 hours, and determined by liquid chromatography, the conversion rates were 99% and 67%, respectively. 1 HNMR (300MHz, CDCl 3 ) 7.28～7.32(m, 5H, Ar-H), 5.32～5.35(d, J=9.18Hz, 1H, -CH), 4.38～4.56(m, 2H, -CH 2 ) , 3.89 (br, 1H, -OH).
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Cited By (8)
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| CN102030782A (en) * | 2010-11-16 | 2011-04-27 | 罗梅 | Nickel/nitrogen complexes |
| CN102702236A (en) * | 2012-05-31 | 2012-10-03 | 合肥工业大学 | Copper nitrogen complex and application thereof |
| CN102718782A (en) * | 2012-07-10 | 2012-10-10 | 罗梅 | Copper nitrogen complex and application thereof |
| CN102875579A (en) * | 2012-05-17 | 2013-01-16 | 罗梅 | Copper and nitrogen complex and application thereof |
| CN103285924A (en) * | 2013-07-03 | 2013-09-11 | 罗梅 | Application of chiral copper complex |
| CN103467500A (en) * | 2013-09-09 | 2013-12-25 | 合肥工业大学 | Copper complex |
| CN106083901A (en) * | 2016-06-03 | 2016-11-09 | 合肥工业大学 | A kind of copper complex |
| CN106902887A (en) * | 2017-03-14 | 2017-06-30 | 山东管理学院 | It is a kind of can the copper complex catalyst and preparation method and application that reclaims of magnetic force |
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| CN102030782B (en) * | 2010-11-16 | 2013-08-14 | 罗梅 | Nickel/nitrogen complexes |
| CN102030782A (en) * | 2010-11-16 | 2011-04-27 | 罗梅 | Nickel/nitrogen complexes |
| CN102875579B (en) * | 2012-05-17 | 2015-06-03 | 罗梅 | Copper and nitrogen complex and application thereof |
| CN102875579A (en) * | 2012-05-17 | 2013-01-16 | 罗梅 | Copper and nitrogen complex and application thereof |
| CN102702236B (en) * | 2012-05-31 | 2015-03-25 | 合肥工业大学 | Copper nitrogen complex and application thereof |
| CN102702236A (en) * | 2012-05-31 | 2012-10-03 | 合肥工业大学 | Copper nitrogen complex and application thereof |
| CN102718782A (en) * | 2012-07-10 | 2012-10-10 | 罗梅 | Copper nitrogen complex and application thereof |
| CN102718782B (en) * | 2012-07-10 | 2014-11-05 | 罗梅 | Copper nitrogen complex and application thereof |
| CN103285924A (en) * | 2013-07-03 | 2013-09-11 | 罗梅 | Application of chiral copper complex |
| CN103467500A (en) * | 2013-09-09 | 2013-12-25 | 合肥工业大学 | Copper complex |
| CN106083901A (en) * | 2016-06-03 | 2016-11-09 | 合肥工业大学 | A kind of copper complex |
| CN106902887A (en) * | 2017-03-14 | 2017-06-30 | 山东管理学院 | It is a kind of can the copper complex catalyst and preparation method and application that reclaims of magnetic force |
| CN106902887B (en) * | 2017-03-14 | 2019-06-14 | 山东管理学院 | A kind of copper complex catalyst which can be recovered by magnetic force and its preparation method and application |
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