CN103304585A - Copper complex, preparation method and application thereof - Google Patents
Copper complex, preparation method and application thereof Download PDFInfo
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- CN103304585A CN103304585A CN2013102308154A CN201310230815A CN103304585A CN 103304585 A CN103304585 A CN 103304585A CN 2013102308154 A CN2013102308154 A CN 2013102308154A CN 201310230815 A CN201310230815 A CN 201310230815A CN 103304585 A CN103304585 A CN 103304585A
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- copper complex
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- butyl phenol
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- pyrimidine
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Abstract
The invention discloses a copper complex, a preparation method and application thereof. The chemical formula of the copper complex is [Cu(dpca)(phen)(CH3OH)]NO3.H2O, Hdpca is 2,4-dihydroxy pyrimidine-5-carboxylic acid, and phen is phenanthroline. A monocrystal complex by self assembling of molecules has certain granularity, a unique structure, high catalytic activity, high selectivity and good stability, is mild in condition, high in yield, good in reproducibility and free of pollution in production, can be prepared at normal temperature and normal pressure, and has latent economic benefit, social benefit and environmental benefit.
Description
Technical field
The invention belongs to metal-organic coordination compound material technology field, be specifically related to a kind ofly have copper complex of high-efficiency catalytic activity and preparation method thereof by what the pyrimidine carboxylic ylidene ligands was constructed.
Background technology
Become one of research focus of current coordination chemistry by on purpose designing part and selecting metal ion to synthesize metal-organic coordination compound.This more important thing is that they show superior performance in a lot of fields, as optics, magnetic, fractionation by adsorption, catalysis and biological activity etc. not only because organic-metal complexes has colourful structure.The structure of title complex is subjected to all multifactor impacts, thereby the prediction of structure also is difficult to accomplish, therefore by design with select suitable part and metal ion and control factors such as reaction conditions and come the structure of systematic study title complex and performance to have great importance.The discrete molecules copper complex had especially attracted people's extensive concern in the last few years, mainly was because this compounds is having broad application prospects aspect many metal actives of simulation metalloprotein center, molecular magnet (especially single molecular magnets), the design nano material.Be this compounds one of the most promising application direction as catalyzer.This compounds not only has good thermodynamic stability, and a fairly large number ofly has a d
9The Cu of electronic configuration (II) accumulates in the unit molecule, because synergy and transfer transport between metal center will produce unusual reactivity.In addition, this compounds has cutting, can obtain having optionally catalyzer of size or profile by suitably selecting bridgingligand.Regrettably, although some discrete molecules copper compounds are synthesized, about their but lacking very of Catalytic Performance.Simultaneously, this compounds also is in blank as the research field of heterogeneous catalyst.Therefore, the discrete molecules copper complex with good catalytic performance is prepared in design, illustrates the reactive relation of structure and active site, is a heat subject in the current research field.
Benzoquinones, two benzoquinones and derivative thereof are the synthetic multiclass speciality chemicals of industry, as the important intermediate of pharmaceuticals, dyestuff and agricultural product etc.(2,6-DBP) the oxidative coupling reaction that optionally generates benzoquinones, two benzoquinones has attracted people more and more to pay close attention to (Fig. 1) to the catalysis 2,6 di t butyl phenol in recent years.In general, homogeneous catalyst shows excellent catalytic activity and selectivity usually, yet but exists problem expensive, that be difficult to separate.On the contrary, heterogeneous catalyst has then possessed the real advantage that product is easily separated, catalyzer can be recycled.However, the catalyst system major part of reporting in the document still is homogeneous system at present, and its catalyzed polymerization is usually at organic solvent (for example benzene, toluene) or carry out in the mixed system of water-organic microemulsion and damping fluid, therefore need to reclaim solvent, removal process then will inevitably contaminate environment.Be accompanied by the growing environmental stress of chemical process, nowadays people more and more advocate Green Chemistry, do not advocate with an organic solvent.So, can be under gentle relatively reaction conditions, the design of the efficient heterogeneous catalyst that in the aqua medium, reacts, synthetic and use and understand this reaction process and have very important meaning further.On the other hand, because H
2O
2Have inexpensive, be easy to get, advantages such as cleaning, environmental protection, therefore development is with H
2O
2The research of making the catalyzer of oxygenant has important theory and is worth and wide application prospect.
Along with the continuous development of metal-organic coordination compound research, their numerous and complicated structures, numerous transition metal centers are all evoked us and are explored them as the interest of green reaction catalyzer.We wish carrying out catalyzed oxidation 2, in the reaction of 6-DBP, not only use the oxygenant of cleaning, as O
2, H
2O
2Deng, and be that solvent reacts with water, namely carry out so-called " cleaning procedure " reaction.Unique by product of oxygenant is water in the reaction, and this is significant for the greenization of oxidising process and the Separation ﹠ Purification of product.In addition, carry out if be reflected in the out-phase, the separation of substrate and purify and will become easier, for this reason, traditional method is that catalyzer is in addition immobilized, and metal-organic coordination compound stable in properties is very big as out-phase catalysts potentiality.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, a kind of new copper title complex of heterogeneous catalysis effect to be provided.
In order to achieve the above object, the invention provides a kind of copper complex, chemical formula is that [Cu (dpca) is (CH (phen)
3OH)] NO
3H
2O, Hdpca=2 wherein, 4-dihydroxy-pyrimidine-5-carboxylic acid, phen=phenanthroline.
Above-mentioned copper complex is mononuclear structure, and it is triclinic(crystalline)system that crystal belongs to, and spacer is P-1, and unit cell parameters is:
α=63.506 (7) °, β=89.947 (6) °, γ=75.192 (6) °, V=986.54 (12)
The present invention also provides the preparation method of above-mentioned copper complex, and this copper complex utilizes N, O-part 2,4-dihydroxy-pyrimidine-5-carboxylic acid and assistant ligand phenanthroline and Cu (NO
3)
26H
2The preparation of O self-assembling reaction.
Concrete preparation process is as follows:
(1) methyl alcohol mixed liquor of preparation 2,4-dihydroxy-pyrimidine-5-carboxylic acid and phenanthroline; In the described methyl alcohol mixed liquor 2, the concentration of 4-dihydroxy-pyrimidine-5-carboxylic acid is 0.001～1molL
-1, the concentration of phenanthroline is 0.005～1molL
-1
(2) preparation Cu (NO
3)
2The aqueous solution; Described Cu (NO
3)
2Cu (NO in the aqueous solution
3)
2Concentration be 0.01～2molL
-1
(3) preparation of copper complex: described methanol mixed drips of solution is added to Cu (NO
3)
2In the aqueous solution, stir, left standstill under the room temperature 6-9 days, carry out self-assembling reaction, obtain blue bulk crystals, successively with dehydrated alcohol, ether washing, drying namely gets product then; Described methyl alcohol mixed liquor and Cu (NO
3)
2The volume ratio of the aqueous solution is 4-6:0.5-3.
The present invention also provides the application of above-mentioned copper complex aspect catalysis 2,6 di t butyl phenol oxidative coupling.2,6 di t butyl phenol oxidative coupling concrete steps are as follows: 2,6 di t butyl phenol, KOH, sodium lauryl sulphate and pure water are mixed, stir and add described copper complex, stir heating down; After rising to 40-60 ° of C to temperature, splash into concentration and be 30% H
2O
2Reactant aqueous solution 5h; The mol ratio of described copper complex and 2,6 di t butyl phenol is 2%-5%; The mol ratio of described KOH and sodium lauryl sulphate and 2,6 di t butyl phenol is 1-4:1-3:1; The add-on of described pure water is 1mmol2, and the 6-DI-tert-butylphenol compounds adds 5-8ml; Described H
2O
2The add-on of the aqueous solution is 1mmol2, and the 6-DI-tert-butylphenol compounds adds 10-30 μ l.
The present invention has the following advantages compared to existing technology:
1, the present invention's monocrystalline title complex that self-assembly forms through molecule has certain particle, and particular structure has advantages of high catalytic activity, selectivity and satisfactory stability.
2, using copper complex that the present invention constructs by pyrimidine carboxylic class part as the two benzoquinones of Preparation of Catalyst, can water be solvent, H
2O
2Be oxygenant, not only selectivity is good, the productive rate height, and also the three wastes are few, and pollution-free to product.Unique by product of oxygenant is water in the reaction, and this is significant for the greenization of oxidising process and the Separation ﹠ Purification of product.
3, copper complex of the present invention is easy to reclaim as catalyzer, can reuse.
4, copper complex of the present invention can be prepared at normal temperatures and pressures, and mild condition, productive rate height, reproducibility are good, produces pollution-freely, has potential economic benefit, social benefit and environmental benefit.
Description of drawings
Fig. 1 is 2,6 di t butyl phenol oxidative coupling route map;
Fig. 2 is the X-ray single crystal diffraction figure of copper complex of the present invention.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment one
With 15ml2, the methanol solution of 4-dihydroxy-pyrimidine-5-carboxylic acid and phenanthroline (is 0.02molml
-3) dropwise be added drop-wise to 4mlCu (NO
3)
26H
2The aqueous solution (the 0.06molml of O
-3), shake up, obtain a blue limpid solution, after leaving standstill 6 days, room temperature obtains blue bulk crystals, namely get pyrimidine carboxylic base copper complex, productive rate 68%.Analyzing through the X-single crystal diffractometer, is the title complex of mononuclear structure.Ultimate analysis: by theoretical structural formula C
18H
17CuN
5O
9, calculated value: C42.32, H3.35, N13.71%; Measured value: C42.45, H3.17, N13.78%.
The structure determination of title complex:
The monocrystalline of choosing suitable size at microscopically at room temperature carries out the experiment of X – ray diffraction.On Bruker Smart1000CCD diffractometer, use the K through the Mo of graphite monochromator monochromatization –
αRay
With
Mode is collected diffraction data.Use Bruker SAINT(Bruker AXS respectively, SAINT Software Reference Manual, Madison, WI, 1998) and SHELXTL(G.M.Sheldrick, G.M.SHELXTL NT Version5.1.Program for Solution and Refinemen of Crystal Structures, University of
Germany, 1997) program is carried out reduction of data and structure elucidation.The diffraction data of part-structure carries out absorption correction with the SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out the complete matrix least-squares refinement, and the hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and the methyl alcohol is handled with the method for difference Fourier peak-seeking.Detailed axonometry data see Table 1 and table 2.Structure is seen Fig. 2.
The main crystallographic data of table 1 copper complex
aR=Σ(||F
o|-|F
c||)/Σ|F
o|,wR=[Σw(|F
o|
2-|F
c|
2)
2/Σw(|F
o|
2)
2]
1/2,where?F
o=observed?and?F
c=calculated?structure?factors,respectively.
The main bond distance of table 2 copper complex
And bond angle [°] *
Symmetry?transformations?used?to?generate?equivalent?atoms:(i)-x-1,-y,-z;(ii)x-1,y,z;(iii)-x,-y,-z;(iv)-x-1/2,y-1/2,-z+1/2.
Embodiment two
With 8ml2, the methanol solution of 4-dihydroxy-pyrimidine-5-carboxylic acid and phenanthroline (is 1molml
-3) dropwise be added drop-wise to 1mlCu (NO
3)
26H
2The aqueous solution (the 2molml of O
-3), shake up, obtain a blue limpid solution, after leaving standstill 9 days, room temperature obtains blue bulk crystals, namely get pyrimidine carboxylic base copper complex, productive rate 65%.
Embodiment three
With 12ml2, the methanol solution of 4-dihydroxy-pyrimidine-5-carboxylic acid and phenanthroline (is 0.005molml
-3) dropwise be added drop-wise to 6ml Cu (NO
3)
26H
2The aqueous solution (the 0.01molml of O
-3), shake up, obtain a blue limpid solution, after leaving standstill 9 days, room temperature obtains blue bulk crystals, namely get pyrimidine carboxylic base copper complex, productive rate 65%.
Application Example one
Under the room temperature, in the 10ml there-necked flask that prolong and thermometer are housed, add 2 respectively, the 6-DI-tert-butylphenol compounds (206mg, 1mmol), potassium hydroxide (56mg, 1mmol), sodium lauryl sulphate (SDS, 29mg, 1mmol), add the 5mL pure water then, stirring also adds copper complex (0.02mmol) as catalyzer.Be heated to 50 ℃ under stirring, with 10 μ l syringe holder H
2O
2(30%) slowly splashes in the above-mentioned mixing solutions, added 10 μ l, and be total to secondary, stopped reaction behind the 5h in per 15 minutes.With TLC method reaction product isolated on previously prepared thin layer silica gel.The result shows: the transformation efficiency of 2,6 di t butyl phenol is 100%, and two benzoquinones content are 79% in the product, and biphenyl two quinone contents are 21%.
Application implementation two
Under the room temperature, in the 10ml there-necked flask that prolong and thermometer are housed, add 2 respectively, the 6-DI-tert-butylphenol compounds (206mg, 1mmol), potassium hydroxide (224mg, 4mmol), sodium lauryl sulphate (SDS, 87mg, 3mmol), add the 5mL pure water then, stirring also adds copper complex (0.05mmol) as catalyzer.Be heated to 60 ℃ under stirring, with 10 μ l syringe holder H
2O
2(30%) slowly splashes in the above-mentioned mixing solutions, added 10 μ l, and be total to secondary, stopped reaction behind the 5h in per 15 minutes.With TLC method reaction product isolated on previously prepared thin layer silica gel.The result shows: the transformation efficiency of 2,6 di t butyl phenol is 100%, and two benzoquinones content are 90% in the product, and biphenyl two quinone contents are 10%.
Claims (6)
1. copper complex is characterized in that: the chemical formula of described copper complex is for [Cu (dpca) is (CH (phen)
3OH)] NO
3 .H
2O, Hdpca=2 wherein, 4-dihydroxy-pyrimidine-5-carboxylic acid, phen=phenanthroline.
2. copper complex according to claim 1, it is characterized in that: described copper complex is the triclinic(crystalline)system crystal, spacer is P-1, unit cell parameters is: a=8.8459 (6), b=11.1643 (8), c=11.6449 (9), α=63.506 (7) °, β=89.947 (6) °, γ=75.192 (6) °
V=986.54 (12)
3
3. the preparation method of claim 1 or 2 described copper complexes, it is characterized in that: described copper complex utilizes N, O-part 2,4-dihydroxy-pyrimidine-5-carboxylic acid and assistant ligand phenanthroline and Cu (NO
3)
2 .6H
2The preparation of O self-assembling reaction.
4. preparation method according to claim 3, it is characterized in that: described preparation method may further comprise the steps:
(1) methyl alcohol mixed liquor of preparation 2,4-dihydroxy-pyrimidine-5-carboxylic acid and phenanthroline; In the described methyl alcohol mixed liquor 2, the concentration of 4-dihydroxy-pyrimidine-5-carboxylic acid is 0.001 ~ 1 mol L
-1, the concentration of phenanthroline is 0.005 ~ 1 mol L
-1
(2) preparation Cu (NO
3)
2The aqueous solution; Described Cu (NO
3)
2Cu (NO in the aqueous solution
3)
2Concentration be 0.01 ~ 2 mol L
-1
(3) preparation of copper complex: described methanol mixed drips of solution is added to Cu (NO
3)
2In the aqueous solution, stir, left standstill under the room temperature 6-9 days, carry out self-assembling reaction, obtain blue bulk crystals, successively with dehydrated alcohol, ether washing, drying namely gets product then; Described methyl alcohol mixed liquor and Cu (NO
3)
2The volume ratio of the aqueous solution is 4-6:0.5-3.
5. claim 1 or the 2 described copper complexes application aspect catalysis 2,6 di t butyl phenol oxidative coupling.
6. application according to claim 5, it is characterized in that: described 2,6 di t butyl phenol oxidative coupling concrete steps are as follows: 2,6 di t butyl phenol, KOH, sodium lauryl sulphate and pure water are mixed, stirring also adds described copper complex, stirs heating down; After rising to 40-60 ℃ to temperature, splash into concentration and be 30% H
2O
2Reactant aqueous solution 5h; The mol ratio of described copper complex and 2,6 di t butyl phenol is 2%-5%; The mol ratio of described KOH and sodium lauryl sulphate and 2,6 di t butyl phenol is 1-4:1-3:1; The add-on of described pure water adds 5-8ml for the 1mmol 2,6 di t butyl phenol; Described H
2O
2The add-on of the aqueous solution adds 10-30 μ l for the 1mmol 2,6 di t butyl phenol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440581A (en) * | 2018-05-08 | 2018-08-24 | 宁波大学 | A kind of 5- nitroorotic acids mononuclear zinc complex and its preparation method and application |
| CN112341478A (en) * | 2020-11-20 | 2021-02-09 | 池州学院 | Mononuclear copper complex and preparation method and application thereof |
-
2013
- 2013-06-09 CN CN201310230815.4A patent/CN103304585B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 朱学文: "氮杂环/羧酸/Schiff碱配合物的合成与结构表征", 《中国博士学位论文全文数据库工程科技I辑》, no. 1, 15 January 2011 (2011-01-15), pages 014 - 4 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440581A (en) * | 2018-05-08 | 2018-08-24 | 宁波大学 | A kind of 5- nitroorotic acids mononuclear zinc complex and its preparation method and application |
| CN112341478A (en) * | 2020-11-20 | 2021-02-09 | 池州学院 | Mononuclear copper complex and preparation method and application thereof |
| CN112341478B (en) * | 2020-11-20 | 2023-10-13 | 池州学院 | Mononuclear copper complex and preparation method and application thereof |
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