CN101696217A - M-phenylene dimethylamine copper complex - Google Patents
M-phenylene dimethylamine copper complex Download PDFInfo
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- CN101696217A CN101696217A CN200910184967A CN200910184967A CN101696217A CN 101696217 A CN101696217 A CN 101696217A CN 200910184967 A CN200910184967 A CN 200910184967A CN 200910184967 A CN200910184967 A CN 200910184967A CN 101696217 A CN101696217 A CN 101696217A
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Abstract
The invention relates to m-phenylene dimethylamine copper complex, which is shown in the following chemical formula. The complex is prepared by performing the reflux reaction on M-phenylene dimethylamine and hydrated copper acetate in an anhydrous ethanol solvent for 24 hours, and performing separation and crystallization. The complex has the excellent catalytic performance in a Henry reaction.
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 by m-xylene diamine and hydration neutralized verdigris preparation.
Two, background technology
Part on the copper complex is divided into unidentate ligand and polydentate ligand by the number that ligating atom can be provided, cause it to synthesize multiple monokaryon or multinuclear copper complex. copper (II) can with monodentate, three teeth or polydentate ligand coordination, and then form monokaryon, double-core and polynuclear coordination compound.Ammonia is typical unidentate ligand, and the general formula that forms title complex with copper (II) is CuX
2NNH
3(n=2,4,5,6).Under the normal circumstances, copper (II) can close with four part huge legendary turtles, for example CuCl
2Close the Cu of formation (Py) with pyridine molecule huge legendary turtle
2Cl
2Can stably be present in the pyridine.At Cu (NH
3)
4(NO
3)
2In the crystal seed, 4 NH
3Approximate square (Cu-N=200pm), two O are in the position (about 250pm) of not waiting slightly.Two (dimethylaminoethyl) methylamine, three pyridines are that the typical case is two, tridentate ligand, and the title complex general formula that forms with copper (II) is: [CuLX
2] and [CuLXY], it is configured as distored trigonal bipyramid configuration.Copper (II) forms octahedra complex molecule with sterically hindered bigger three (2-aminoethyl) amine.Copper (II) all has stronger avidity with O, S in addition, copper (II) and oxine, Quercetin, perchloric acid [three (2-benzoglyoxaline methylene radical) amine] imidazoles, 1, and 4-thiophene oxane etc. all can produce stable coordination ion.
Since the mankind had historical records, copper and title complex thereof were promptly as medicine.Copper is the metallic element of needed by human.The eubolism process need of human body they, but synthetic in can't body, therefore, need every day from the diet picked-up with absorb.Biopharmacy man and investigator understand copper and the effect of title complex in living things system thereof up hill and dale with great effort, wish to obtain prevention and treatment that information more is beneficial to human diseases.Copper is one of modal metal in the daily life, also be a kind of very important life trace element is distributed in organ and organizes in human body in, bringing into play important effect for the vital movement of keeping the people, human body lacks copper can cause multiple disease, so suitable absorption copper is useful.Because copper is to the importance of human body, become noticeable research object in recent years up to now, constantly have new copper complex synthetic, the anti-microbial activity of the synthetic method of title complex and the physicochemical property of title complex, crystalline structure and title complex is to study one of focus at present
Because copper has variable valency, in life entity, can participate in a series of processes such as electron transport, redox, medicinal activity with special biological activity .Schiff alkali copper complex is the focus that people pay close attention at antibiotic, anti-tumor aspect particularly always.Synthetic filter out fungistat efficient, low toxicity, study its principle, structure activity relationship and influence factor antitumor, that suppress cell proliferation and be the main direction of research at present.Metal complexes to human body generation effect mainly be enter human body by the organic drug molecule after, with metalloprotein, metalloenzyme in the intravital trace element of people, bacterium, virus or the cancer cells nucleic acid interphase interaction is arranged, promote the recovery of body eubolism or the eubolism of destruction pathogenic agent.Current metal complexes is used widely in medical science and study of pharmacy.For example Quercetin closes the stronger antitumour activity of copper complex demonstration: CuCl
22H
2O and DNA do the time spent, can insert between the base pair of DNA, there is the bonding pattern of inserting. may be just because of the effect of this insertion bonding, influenced the endo conformation of dna molecular, the further heredity that has suppressed dna molecular with duplicate, thereby the malignancy of anticancer is to reach anticancer effect.
Along with vitochemical development, the application of organometallics in organic synthesis is more and more wide, is one of field very active in the present organic chemistry, is widely used in the organic synthesis.Use chiral ligand and the catalytic asymmetric catalysis synthesis of transition metal complex that the later stage sixties 20 century occurs have quickened the research of chiral drug greatly.The important content of chemical catalysis asymmetric synthesis method is chiral ligand and containing metal catalyst design, thereby makes reaction have efficient and high enantioselectivity.
1, the one metal complexes catalysis of chirality bisoxazoline part is asymmetric Cyclopropanated
The asymmetric cyclopropane of catalysis promptly utilizes the cycloaddition reaction of chiral ligand one metal complexes catalysis diazonium compound and alkene than reaction, is the important means of synthetic photolytic activity cyclopropane structural compounds.Nineteen ninety,
Masmune etc. utilize chirality bisoxazoline part-copper complex catalysis cyclopropanization reaction respectively, have all obtained very high enantioselectivity.
2, asymmetric cyclopropanization reaction takes place in chiral copper catalyst one catalyzed alkene
Asymmetric cyclopropanization reaction takes place with the chiral copper catalyst catalyzed alkene in SUMITOMO CHEMICAL company, has synthesized dipeptides inhibitor C ilastatin.
Reference:
[1]Holmes?F，Jones?K?M，et?al.Complex-forming?agents?similar?to?2，2’-bipyridyl.Part?I.Some?ligands?containing?imidazole[J].J?Chem?Soc，1961，4790-4794
[2] Fan Zhi, Wen Xin, Zhou Weihong, Liu Xiaolan, Miu Fangming. synthetic, the crystalline structure of three (2-benzoglyoxaline methylene radical) amine copper (II) title complex and quantum Chemical Study. Chinese Journal of Inorganic Chemistry, in September, 1999, the 5th phase: 602-606
[3] Tan Jun. Quercetin closes the coordination chemistry research of copper (II) title complex. Chongqing College of Education journal, in November, 2006, the 19th volume the 6th phase: 11-15
[4] Li Qinling. the application of transition metal complex in chiral drug is synthetic. Qinghai science and technology, 2007 the 1st phase: 45-49
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 m-xylene diamine as part and synthetic copper-nitrogen compound.
The alleged copper-nitrogen compound of the present invention is by m-xylene diamine and hydration neutralized verdigris preparation, by the title complex shown in the following chemical formula:
Call m-xylene diamine neutralized verdigris title complex in the following text, be called for short title complex.
This title complex meets the definition of coordination compound (title complex),
The synthetic method of this title complex is and m-xylene diamine and hydration neutralized verdigris back flow reaction 24 hours in anhydrous ethanol solvent.
After the title complex reaction finishes, gained solution is spin-dried for, has the blue-greenish colour viscous liquid to be attached on bottle wall.Can find that it cools off a little and promptly has small amount of crystal to occur, and for obtaining comparatively purified crystal, adds small amount of ethanol in bottle, viscous liquid dissolves just at the bottom of making bottle, be placed on then under the room temperature and volatilize, can find after 5 hours that the Erlenmeyer flask bottom has a certain amount of crystal to separate out
Title complex shows good catalytic performance in Henry reaction and nitrile silicification reaction.
Four, description of drawings
Fig. 1 is the single crystal diffraction figure of this title complex.
Five, embodiment
1, m-xylene diamine neutralized verdigris title complex is synthetic
Take by weighing 1.9965g one hydration neutralized verdigris (0.01mol) and put into the round-bottomed flask of 100mL, adding 40ml anhydrous methanol solvent dissolves it, then, the m-xylene diamine (0.01mol) that in above-mentioned solution, adds 1.3mL with syringe, put into stirrer, reflux 8 hours, the m-xylene diamine (0.01mol) of injection 1.3mL in flask continues reflux and obtained navy blue liquid in 8 hours again.
After reaction finishes, gained solution is spin-dried for, has the blue-greenish colour viscous liquid to be attached on bottle wall.Can find that it cools off a little and promptly has small amount of crystal to occur, for obtaining comparatively purified crystal, in bottle, add small amount of ethanol, viscous liquid dissolves just at the bottom of making bottle, be placed on then under the room temperature and volatilize, can find after 5 hours that the Erlenmeyer flask bottom has a certain amount of crystal to separate out, recording its fusing point is 64-66 ℃. under the ultimate analysis data: theoretical value: C:52.91%; H:6.66%; N:12.34%; Experimental value: C:52.55%; H:6.78%; N:12.33%.Infrared data: 3334,3219,2926,2878,1571,1444,1401,1332,1174,1158,1090,1055,993,919,791,755,734,703,651,639,616.
2. the application of this title complex in the nitrile silicification reaction
Reaction principle is as follows:
The preparation of 2-(4-phenyl)-2-(trimethylsilyloxy) acetonitrile
The preparation of 2-4-phenyl-2-trimethylsiloxy group acetonitrile
M-xylene diamine and neutralized verdigris (2: the 1) title complex (catalytic amount is 15%) of getting 0.0681g (0.15mmol) are dissolved in the 5mL tetrahydrofuran solution, add 0.1ml phenyl aldehyde (1mmol) and TMSCN 0.2ml (2.2mmol), react after 30 hours, with liquid chromatography monitoring, transformation efficiency: 78%.
1H?NMR(300MHz，CDCl3)7.56-7.59(m，0.9Hz，2H)，7.31-7.34(m，3H)，5.43(s，1H)，0.16(s，9H).
13C?NMR(75MHz，CDCl3)136.1，128.8(x2)，126.2(x2)，119.1，63.5，-0.39(x3).
3. the application of this title complex in Henle reaction
Reaction principle is as follows:
The preparation of 2-Nitro-1-phenylethanol
The preparation of 2-nitro-1 phenylethyl alcohol
Get the m-xylene diamine of 0.0681g (0.15mmol) and neutralized verdigris (2: 1) title complex (catalytic amount is 15%) in the little flask of 25mL, the methanol solution that adds 2 milliliters, then, in above-mentioned solution, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature, reacted 72 hours, and carried out liquid chromatogram measuring, transformation efficiency 69%.
1H?NMR(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 (1)
1. M-phenylene dimethylamine copper complex is characterized in that: by m-xylene diamine and hydration neutralized verdigris preparation, by the title complex shown in the following chemical formula:
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941991A (en) * | 2010-07-28 | 2011-01-12 | 罗梅 | Cobalt nickel complex of m-xylylenediamine and synthesis method thereof |
| CN101973939A (en) * | 2010-09-25 | 2011-02-16 | 罗梅 | Chiral nitrogen heterocyclic heptane compound and preparation method thereof |
| CN102875391A (en) * | 2010-07-28 | 2013-01-16 | 罗梅 | Cobalt complex of m-xylylenediamine and synthesis method of m-xylylenediamine |
| CN111592660A (en) * | 2020-06-15 | 2020-08-28 | 平顶山学院 | One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell |
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2009
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941991A (en) * | 2010-07-28 | 2011-01-12 | 罗梅 | Cobalt nickel complex of m-xylylenediamine and synthesis method thereof |
| CN101941991B (en) * | 2010-07-28 | 2012-12-26 | 罗梅 | Cobalt nickel complex of m-xylylenediamine and synthesis method thereof |
| CN102875391A (en) * | 2010-07-28 | 2013-01-16 | 罗梅 | Cobalt complex of m-xylylenediamine and synthesis method of m-xylylenediamine |
| CN101973939A (en) * | 2010-09-25 | 2011-02-16 | 罗梅 | Chiral nitrogen heterocyclic heptane compound and preparation method thereof |
| CN111592660A (en) * | 2020-06-15 | 2020-08-28 | 平顶山学院 | One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell |
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