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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- benzylamine
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Abstract
The invention relates to a copper-nitrogen compound, which comprises an o-amino-benzylamine copper acetate compound and an m-xylene diamine copper acetate compound which are prepared by respectively performing the reaction of o-amino-benzylamine and hydrated copper acetate and performing the reaction of m-xylene diamine and the hydrated copper acetate in an anhydrous tetrahydrofuran solvent for 24 hours and then respectively carrying out separation on the reaction solution. The copper-nitrogen compound shows good performance in the Henry reaction. The conversion rate of the o-amino-benzylamine copper acetate complex and the m-xylene diamine copper acetate compound are respectively 67 percent and 99 percent.
Description
One, technical field
The present invention relates to a kind of metal organic coordination compounds (title complex), particularly nitrogenous a metal-organic complex exactly is a kind of copper-nitrogen compound.
Two, background technology
Nitrogenous a metal-organic complex has novel structure and has the potential application prospect at aspects such as catalysis, electrochemistry, absorption, ion-exchange and magnetic, the research of this compounds more and more causes people's great interest, in the investigator's who enjoys aspects such as inorganic chemistry, coordination chemistry, Organometallic Chemistry and bio-inorganic chemistry extensive attention, and obtain noticeable achievement in research.
[1] Xu Guangxian. Peking University's journal, 2003,38 (2): 149-152.
[2] Ding Yanbin, Peng Li, etc. chemical engineer, 2003,99 (6): 42-43.
Copper nitrogen a metal-organic complex has some excellent catalytic performance, and closely related with subjects such as Materials science, organic synthesis, life sciences, a metal-organic complex that contains Cu-N is significant at polymer and organic synthesis asymmetric catalysis field.Become one of focus of domestic and international research, a large amount of bibliographical informations has been arranged.
[3]M.del?Carme?Castellano，Josefina?Pons，Jordi?García-Antón，et?al.InorganicaChimica?OActa，2008，361：2923-2928
[4]Dennis?A.Walker，Timothy?J.Woodman，Mark?Schormann，et?al.Organometallics，2003，22：797-803
Three, summary of the invention
The present invention aims to provide a kind of Cu-N a metal-organic complex to be applied to asymmetric catalysis field, and technical problem to be solved is selected suitable arylamine as part and synthetic copper-nitrogen compound.
The alleged copper-nitrogen compound of the present invention is wherein a kind of be by o-amino-benzylamine and hydration neutralized verdigris preparation by the title complex shown in the following chemical formula:
Under be called for short the o-amino-benzylamine neutralized verdigris, be designated as title complex (I).
The alleged copper-nitrogen compound another kind of the present invention is by m-xylene diamine and hydration neutralized verdigris preparation, by the title complex shown in the following chemical formula:
Under be called for short the m-xylene diamine neutralized verdigris, be designated as title complex (II)
This title complex (I) and synthetic method (II) be by o-amino-benzylamine and m-xylene diamine respectively with hydration neutralized verdigris back flow reaction 24 hours in the anhydrous tetrahydro furan solvent.
Separating out blue solid in title complex (I) the autoreaction liquid is title complex (I).
Title complex (II) is when reaction solution cools off, the static water white crystal title complex (II) that gets in THF solution.Title complex (I), (II) show that in Henle reaction good catalytic performance sees the following form.
Four, description of drawings
Fig. 1 is the X-ray diffraction single crystal structure figure of title complex (I).
Fig. 2 is the X-ray diffraction single crystal structure figure of title complex (II).
One, embodiment
1, o-amino-benzylamine neutralized verdigris title complex (I) is synthetic
The hydration neutralized verdigris of 1.1023g o-amino-benzylamine and 0.9001g added in 100 milliliters the round-bottomed flask, add 40 milliliters tetrahydrofuran (THF), heated and stirred 24 hours.Heat filtering obtains blue solid, behind a small amount of anhydrous alcohol solution, leaves standstill volatilization and obtains blue needle-like crystal.Anal.Calc.for?Cu[C
9H
13N
2O
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, m-xylene diamine neutralized verdigris title complex (II) is synthetic
The hydration neutralized verdigris of 1.5mL m-xylene diamine and 1.1174g is added in the round-bottomed flask of 100ml, add 40 milliliters of tetrahydrofuran (THF)s, heated and stirred 24 hours.Then pour out part upper strata molten night, seal and leave standstill, obtain clear crystal after a couple of days.Yield：38％(0.62g).Anal.Calc.for?ZnC
12H
18N
2O
4：C，45.14；H，5.64；N，8.78％.Found：C，44.58；H，5.76；N，8.84％.
1HNMR(300MHz，CDCl
3，27℃)，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.
3. Henle reaction is used
The preparation of 2-nitro-1 phenylethyl alcohol
Get the m-xylene diamine neutralized verdigris of 0.15mmol and o-amino-benzylamine neutralized verdigris (catalytic amount is 15%) respectively in the little flask of two 25mL, each adds 2 milliliters methanol solution, then, in above-mentioned solution, respectively add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature was reacted 72 hours, carried out liquid chromatogram measuring, transformation efficiency is respectively 99%, 67%.
1HNMR(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).
Claims (4)
1. copper-nitrogen compound, it is characterized in that by o-amino-benzylamine and hydration neutralized verdigris preparation by the title complex shown in the following chemical formula:
2. the purposes of copper-nitrogen compound as claimed in claim 1, it is characterized in that this copper-nitrogen compound in Henle reaction as Application of Catalyst.
3. copper-nitrogen compound, it is characterized in that by m-xylene diamine and hydration neutralized verdigris preparation, by the title complex shown in the following chemical formula:
4. copper-nitrogen compound purposes as claimed in claim 3, it is characterized in that this copper-nitrogen compound in Henle reaction as Application of Catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429212A (en) * | 2008-07-23 | 2009-05-13 | 合肥工业大学 | Zinc-nitrogen, copper-nitrogen complex of alpha-phenylethylamine and synthesis thereof |
| CN101550155A (en) * | 2009-05-11 | 2009-10-07 | 合肥工业大学 | Phenylene diamine zinc nitrogen complex |
-
2010
- 2010-03-17 CN CN201010127498XA patent/CN101787042B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429212A (en) * | 2008-07-23 | 2009-05-13 | 合肥工业大学 | Zinc-nitrogen, copper-nitrogen complex of alpha-phenylethylamine and synthesis thereof |
| CN101550155A (en) * | 2009-05-11 | 2009-10-07 | 合肥工业大学 | Phenylene diamine zinc nitrogen complex |
Non-Patent Citations (4)
| Title |
|---|
| 《Journal of Applied Polymer Science》 20011231 IAN HAMERTON et al. The Development of Controllable Complex Curing Agents for Epoxy Resins. I. Preparation, Characterization, and Storage Behavior of Transition Metal-Diamine Complexes 1489-1503 1-4 第80卷, 2 * |
| 《Journal of Applied Polymer Science》 20021231 IAN HAMERTON et al. The Development of Controllable Complex Curing Agents for Epoxy Resins. II. Examining the Dissociation and Thermal Behavior of Transition Metal-Diamine Complex-Epoxy Blends 第2411-2424页 1-4 第84卷, 2 * |
| 《Transition Met. Chem.》 19831231 Dimitra Kovala-Demertzi et al. Complexes of Aminobenzylamines. Part I. Complexes of o-Aminobenzylamine with Copper(II), Cobalt(II) and Nickel(II) 第140-146页 1-4 第8卷, 2 * |
| 《有机化学》 20081231 甘昌胜等 不对称催化Henry 反应研究进展 第1193-1198页 1-4 第28卷, 第7期 2 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | It is a kind of can magnetic force recycling copper complex catalyst and the preparation method and application thereof |
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| CN101787042B (en) | 2012-01-18 |
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