CN102093427B - Nickel-nitrogen complex - Google Patents
Nickel-nitrogen complex Download PDFInfo
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- CN102093427B CN102093427B CN 201110005822 CN201110005822A CN102093427B CN 102093427 B CN102093427 B CN 102093427B CN 201110005822 CN201110005822 CN 201110005822 CN 201110005822 A CN201110005822 A CN 201110005822A CN 102093427 B CN102093427 B CN 102093427B
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- complex
- nickel
- phenylene diamine
- acetate tetrahydrate
- nickel acetate
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Abstract
The invention discloses a nickel-nitrogen complex, which is synthesized by a method comprising: reacting o-phenylenediamine and nickel acetate tetrahydrate, which serve as raw materials, by refluxing in absolute methanol solvent for 24 hours; separating and dissolving to obtain green oily liquid; adding mixed solvent of chloroform and absolute ether to obtain saturated solution; and standing and separating to obtain crystals, namely the target product. The method makes process simple, only adopts an organic solvent which can be recycled, and avoids emission of waste gas, waste water and waste residues. The complex can demonstrate high catalytic performance in the Henry reaction of benzaldehyde with yield reaching 99 percent.
Description
One, technical field
The present invention relates to a kind of organometallic complex (title complex) and preparation method thereof, particularly nitrogenous a metal-organic complex and preparation method thereof, be exactly a kind of O-Phenylene Diamine nickel complex and synthetic method thereof.
Two, background technology
Contain nickel complex usually because different valence state and the variable coordination ability of Ni have multifarious structure, thereby present multifrequency nature and function, all have a wide range of applications at aspects such as biological chemistry, Materials science, catalytic chemistries.Scientist has synthesized many nickel metal complexess in recent years, has 1994, Anthony J.Arduengo, the people such as III as all joining type N-heterocyclic carbine Ni (O) Complex synthesis
[1]With nomadic nitrogen heterocycle carbine and Ni (COD)
2Be under the condition of solvent at tetrahydrofuran (THF), ligand exchange reaction occurs, obtain first dinitrogen heterocycle carbine Ni (O) title complex with higher productive rate (70.80%).Mixed matching N-heterocyclic carbine Ni (O) Complex synthesis has 1997, the people such as Wolfgang A.Herrmann
[2]Predecessor's one imidazole salts of nitrogen heterocycle carbine ligand of chirality of having utilized Chiral Amine, oxalic dialdehyde and paraformaldehyde one-step synthesis, then and Ni (CO) deprotonation under the condition of sodium hydride liquefied ammonia (33 ℃) (for preventing racemization) generates free N-heterocyclic carbine,
3Ligand exchange reaction occurs generate N-heterocyclic carbine Ni (O) carbonyl compound,, the people such as Matthew S.Sigman in 2003
[3]With Nj (COD)
2, the reaction of chlorallylene and nomadic nitrogen heterocycle carbine obtains N-heterocyclic carbine Ni (O) allyl chloride etc.[1-3]。
Reference:
[1]Arduengo，III?A.J.，Siegfried?F.Camper，Joseph?C.，Calabrese，FredricD.J.Am.Chem.Soc.，1994，116：43914394.
[2]Herrmann，Wolfgang?A.，Goossen，Lukas?J.，Artus，Georg?R.J.，Christian?Ko-cher.Organometallics，1997，16：2472-2477.
[3]Dible，Benjamin?R.，Sigman，Matthew?S.，J.Am.Chem.Soc.，2003，125：872-873.
Three, summary of the invention
The present invention aims to provide a kind of Ni-N a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected O-Phenylene Diamine as part and synthetic nickel nitrogen complex.
The alleged nickel nitrogen complex of the present invention is a kind of be by O-Phenylene Diamine and nickel acetate tetrahydrate preparation by the title complex shown in following chemical formula:
Chemical name: the O-Phenylene Diamine nickelous acetate, be called for short title complex.
This Complex synthesis method be by O-Phenylene Diamine and with nickel acetate tetrahydrate back flow reaction 24 hours in the anhydrous methanol solvent.Obtain green oily liquids after separation, precipitation.Green liquid is mixed with the standing volatilization of saturated solution (trichloromethane+anhydrous diethyl ether) obtains green crystal.This title complex shows good catalytic performance in the Henry of phenyl aldehyde reaction, its productive rate is up to 99%.
Four, description of drawings
Fig. 1 is the single crystal diffraction figure of this title complex.
Five, embodiment
1, O-Phenylene Diamine nickel acetate title complex (I) is synthetic
1.0823g O-Phenylene Diamine (0.015mmol) and the four hydration nickel acetates of 1.2389g (0.005mol) are added the round-bottomed flask of 100 milliliters, add the anhydrous methanol of 60 milliliters, heated and stirred 24 hours.Evaporate liquid and get green oily matter, use CHCl
3After the anhydrous diethyl ether dissolving, standing volatilization obtains green crystal.Productive rate 30%.Ultimate analysis: measured value: Found:N:13.91%, C:48.63%; H, 5.677%; 1R (KBr, pellet): 3320,3140,1564,1505,1404,1334,1269,1044,849,752,656,484.
2, Henle reaction is used
Reaction principle:
The Henry reaction is that Louis Henry found the earliest and named in 1895.It is based on carbonyl and contains C―C bond formation reaction between the nitroparaffins compounds of α-reactive hydrogen, and its product is the bifunctional compound that a class contains β-nitroalcohol.Up to the present it remains a kind of C―C bond formation reaction of classics.In Henry reaction, the nitro-compound that contains α-reactive hydrogen is taken by force at alkali etc. and is become carbanion under the proton reagent effect, then the attack carbonyl forms new carbon-carbon bond, and obtains bifunctional compound β-nitroalcohol.
The preparation of 2-Nitro-1-phenylethanol
The preparation of 2-nitro-1-phenylethyl alcohol
Get 0.15mmol title complex (catalytic amount is 15%) in the little flask of 25mL, the methanol solution that adds 2 milliliters, then, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL in mentioned solution, stirring at normal temperature was reacted 72 hours, with sherwood oil/eluent methylene chloride, carry out column chromatography, productive rate 99%
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 (2)
1. nickel nitrogen complex is characterized in that: by O-Phenylene Diamine and nickel acetate tetrahydrate preparation, by the title complex shown in following chemical formula:
2. by Complex synthesis method claimed in claim 1, O-Phenylene Diamine and nickel acetate tetrahydrate are raw material, comprise synthetic, separation, crystallization and washing, it is characterized in that: O-Phenylene Diamine and with nickel acetate tetrahydrate back flow reaction 24 hours in the anhydrous methanol solvent; Obtain green oily liquids after separation, precipitation; Add trichloromethane and anhydrous diethyl ether mixed solvent to form standing separation after saturated solution.
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| CN 201110005822 CN102093427B (en) | 2011-01-12 | 2011-01-12 | Nickel-nitrogen complex |
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| CN 201110005822 CN102093427B (en) | 2011-01-12 | 2011-01-12 | Nickel-nitrogen complex |
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| CN102093427A CN102093427A (en) | 2011-06-15 |
| CN102093427B true CN102093427B (en) | 2013-06-05 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101550155A (en) * | 2009-05-11 | 2009-10-07 | 合肥工业大学 | Phenylene diamine zinc nitrogen complex |
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| US4518488A (en) * | 1983-02-28 | 1985-05-21 | Standard Oil Company (Indiana) | Metal-containing active carbon and methods for making and using same |
| JP2010001281A (en) * | 2008-05-23 | 2010-01-07 | Fujitsu Ltd | Ligand, metal complex compound containing the ligand, method for producing the same, and method for producing molecular device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101550155A (en) * | 2009-05-11 | 2009-10-07 | 合肥工业大学 | Phenylene diamine zinc nitrogen complex |
Non-Patent Citations (4)
| Title |
|---|
| A. E. Malkov等,.Reactions of ortho-phenylenediamine with a nickel trimethylacetate complex.《Russian Journal of Coordination Chemistry》.2001,第27卷(第9期),第677–684页, 尤其是第637页左栏第2段和第639页结构式. |
| R.C.Aggarwal等,.Synthesis and structural studies of some diamine complexes of cobalt(II) and nickel(II) amino and hydroxy benzoates.《Journal of Inorganic and Nuclear Chemistry》.1978,第41卷第1057-1061页. |
| Reactions of ortho-phenylenediamine with a nickel trimethylacetate complex;A. E. Malkov等,;《Russian Journal of Coordination Chemistry》;20010930;第27卷(第9期);第677–684页, 尤其是第637页左栏第2段和第639页结构式 * |
| Synthesis and structural studies of some diamine complexes of cobalt(II) and nickel(II) amino and hydroxy benzoates;R.C.Aggarwal等,;《Journal of Inorganic and Nuclear Chemistry》;19781221;第41卷;第1057-1061页 * |
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