CN103709204B - A kind of cobalt complex, preparation method and its usage - Google Patents
A kind of cobalt complex, preparation method and its usage Download PDFInfo
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Abstract
The present invention provides a kind of cobalt complex, preparation method and its usage<b>,</b>belong to Metal-organic complex field of material technology.Described cobalt complex, its molecular formula is [Co (qc)2(H2O)2]·2H2O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root.The present invention also provides for the method preparing described cobalt complex, adopts 3-hydroxyl-2-quinoxaline carboxylic acid and bivalent Co to be obtained by reacting described cobalt complex in the solution.The present invention also provides for the application in catalysis 2,4-DI-tert-butylphenol compounds oxidative coupling reaction of the described cobalt complex.Cobalt complex of the present invention, has certain granularity, unique structure, has higher catalysis activity, selectivity and good stability.The preparation method of described cobalt complex is simple, and productivity is high, environmentally safe.Using cobalt complex of the present invention to prepare '-biphenyl diphenol, it is possible to be solvent with water, selectivity is good, and productivity is high, and the three wastes are few, and product is pollution-free.
Description
Technical field
The invention belongs to Metal-organic complex field of material technology, be specifically related to a kind of cobalt complex, preparation method and its usage.
Background technology
Coordination compound is used as catalyst and has lot of advantages: 1) often have the hole of definite shape and volume in the network structure of coordination compound, can optionally hold guest molecule based on void shape and size, and strong improves selectivity of catalyst；2) under chemical modification, can the coordination compound of synthesis of chiral loose structure, this is that conventional inorganic catalyst is beyond one's reach；3) organic ligand occupies part metals coordination site, improves the stability of metal ion, thus being favorably improved selectivity；4) synthetic technology that coordination compound is gentle is conducive to the industrial applications of catalyst；5) transition metal ions as catalytic active center is dispersed, not easily assembles；6) introducing of organic group makes ligand structure present the diversified catalytic selectivity likely changing metal ion.Based on these advantages, the prospect that coordination compound is used as catalyst is abnormal noticeable.
2,2 '-dihydroxybiphenyl such as 2,2 '-dihydroxy-3,3 ', 5,5 '-tetra-tert biphenyl (TBBP) is a kind of important organic synthesis intermediate, can be used for synthetic organic material stabilizer, metal catalyst complex, bidentate phosphite ester ligand and as anionic trapping agent etc..2,2 '-dihydroxybiphenyl can pass through corresponding phenol and hydroperoxidation or with oxygen with dichloroethanes for solvent, obtains under copper, cobalt, manganese salt catalytic oxidation.Abroad only two patents (WO9946227.1999 and US4380676.1983) report the synthetic method of TBBP.But the method needs to use organic solvent, environment has pollution, and product yield is only about 68%.
Along with the ambient pressure that chemical processes is growing, nowadays people increasingly advocate Green Chemistry, do not advocate use organic solvent.So, find the catalyst carrying out 2,4-DTBP (2,4-DBP) oxidative coupling reaction with water for solvent, namely carrying out so-called " cleaning procedure " reaction is the current problem that chemist has challenge meaning.
Summary of the invention
The invention aims to provide a kind of cobalt complex.
The preparation method that it is a further object of the present invention to provide cobalt complex.
Another object of the present invention is to provide the purposes of described cobalt complex.
The purpose of the present invention adopts the following technical scheme that realization.
A kind of cobalt complex, its molecular formula is [Co (qc)2(H2O)2]·2H2O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root, structural formula as shown in the formula (I):
Described cobalt complex is monoclinic system crystal, and space group is P21, and cell parameter is:
A kind of method preparing described cobalt complex, adopts 3-hydroxyl-2-quinoxaline carboxylic acid and bivalent Co to be obtained by reacting described cobalt complex in the solution.
The method of described cobalt complex, comprises the steps: that the methanol solution by 3-hydroxyl-2-quinoxaline carboxylic acid is added drop-wise to Co (ClO4)2In aqueous solution, mix homogeneously, left at room temperature 5～10 days, carry out self-assembling reaction, obtain red bulk crystals, then successively with dehydrated alcohol, washed with diethylether, dry, obtain described cobalt complex.
The concentration of the methanol solution of described 3-hydroxyl-2-quinoxaline carboxylic acid is 0.01～2mol L-1, described Co (ClO4)2Co (ClO in aqueous solution4)2Concentration be 0.001～1mol L-1, the methanol solution of described 3-hydroxyl-2-quinoxaline carboxylic acid and Co (ClO4)2The volume ratio of aqueous solution is (3～5): (0.4～2).
The present invention also provides for the application in catalysis 2,4-DI-tert-butylphenol compounds oxidative coupling reaction of the described cobalt complex.
Described application, comprises the steps: to mix 2,4-DTBP, KOH, sodium lauryl sulphate and water, and stirring is lower adds described cobalt complex, the lower heating of stirring；After rising to 30-60 DEG C to temperature, instilling mass percentage concentration is the H of 30%2O2Aqueous solution, reacts 3～5h.The mol ratio of described cobalt complex and 2,4-DI-tert-butylphenol compounds is 1%～5%；The mol ratio of described KOH, sodium lauryl sulphate and 2,4-DI-tert-butylphenol compounds is (1～4): (1～3): 1；Amount of water corresponding to every mM of 2,4-DI-tert-butylphenol compounds is 5-10ml；The H that every mM of 2,4-DI-tert-butylphenol compounds is corresponding2O2The addition of aqueous solution is 10-30 μ l.
The present invention has the advantage that compared to existing technology
1, the present invention is through the monocrystalline cobalt complex of molecular self-assembling, has certain granularity, unique structure, has higher catalysis activity, selectivity and good stability.
2. the preparation method of cobalt complex of the present invention is simple, and productivity is high, environmentally safe.
3, use the cobalt complex constructed by quinoxaline carboxylic acid's class part of the present invention as catalyst preparing '-biphenyl diphenol, it is possible to be solvent with water, H2O2For oxidant, not only selectivity is good, and productivity is high, and the three wastes are few, and product is pollution-free.In reaction, unique by-product of oxidant is water, and this is significant for the greenization of oxidizing process and the Separation & Purification of product.
4, cobalt complex of the present invention is easily recycled as catalyst, it is possible to reuse.
5, cobalt complex of the present invention can be prepared at normal temperatures and pressures, and mild condition, productivity are high, reproducibility is good, produce pollution-free, has potential economic benefit, social benefit and environmental benefit.
Accompanying drawing explanation
Fig. 1 is 2,4-DTBP oxidative coupling reaction route map, and wherein But represents the tert-butyl group.
Fig. 2 is the X-ray single crystal diffraction figure of cobalt complex of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Room temperature in the present invention refers to 25 °.
Embodiment one
It is 0.1mol L by 10ml, concentration-1The methanol solution of 3-hydroxyl-2-quinoxaline carboxylic acid, being dropwise added drop-wise to 5ml concentration is 0.05mol L-1Co (ClO4)2.6H2In O aqueous solution, shake up, obtain a red limpid solution, stand in room temperature and carry out self-assembling reaction in 8 days, obtain red bulk crystals, then successively with dehydrated alcohol, washed with diethylether, dry, obtain molecular formula for [Co (qc)2(H2O)2]·2H2The cobalt complex of O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root, structural formula such as formula (I), productivity 54%.Analyzing through X-single crystal diffractometer, cobalt complex prepared by the present embodiment is the coordination compound of mononuclear structure.Elementary analysis: by theoretical structural formula C18H18CoN4O10, value of calculation: C42.45, H3.56, N11.00%；Measured value: C42.53, H3.37, N10.88%.
The structure determination of coordination compound:
The monocrystalline choosing suitable size under the microscope at room temperature carries out X ray diffraction experiments.On BrukerSmart1000CCD diffractometer, with the Mo K alpha ray through graphite monochromator monochromatization WithMode collects diffraction data.Respectively with BrukerSAINT(BrukerAXS, SAINTSoftwareReferenceManual, Madison, WI, 1998) and SHELXTL(G.M.Sheldrick, G.M.SHELXTLNTVersion5.1.ProgramforSolutionandRefinemenof CrystalStructures, UniversityofGermany, 1997) program carries out data convert and structure elucidation.The diffraction data SADABS program of part-structure carries out absorption correction.Crystal structure is solved in conjunction with difference Fourier synthesis by direct method.Whole non-hydrogen atom coordinates and anisotropic parameters carry out complete matrix least square refinement, and hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and the methanol method of difference Fourier peak-seeking processes.Detailed axonometry data are in Table 1 and table 2.Crystal structure is shown in Fig. 2.
The predominant crystal data of table 1 cobalt complex
The main bond distance of table 2 cobalt complexWith bond angle [°] *
Symmetrytransformationsusedtogenerateequivalentatoms:(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
It is 2mol L by 8ml, concentration-1The methanol solution of 3-hydroxyl-2-quinoxaline carboxylic acid, being dropwise added drop-wise to 2ml concentration is 1mol L-1Co (ClO4)2·6H2The aqueous solution of O, shakes up, and obtains a red limpid solution, stands in room temperature and carry out self-assembling reaction in 9 days, obtains red bulk crystals, then successively with dehydrated alcohol, washed with diethylether, dry, obtains molecular formula for [Co (qc)2(H2O)2]·2H2The cobalt complex of O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root, structural formula such as formula (I), productivity 59%.Analyzing through X-single crystal diffractometer, cobalt complex prepared by the present embodiment is the coordination compound of mononuclear structure.Axonometry data and crystal structure are with compound in embodiment 1.
Embodiment three
It is 0.05mol L by 12ml, concentration-1The methanol solution of 3-hydroxyl-2-quinoxaline carboxylic acid, be dropwise added drop-wise to 6ml, concentration is 0.02mol L-1Co (ClO4)2·6H2The aqueous solution of O, shakes up, and obtains a red limpid solution, stands in room temperature and carry out self-assembling reaction in 6 days, obtains red bulk crystals, then successively with dehydrated alcohol, washed with diethylether, dry, obtains molecular formula for [Co (qc)2(H2O)2]·2H2The cobalt complex of O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root, structural formula such as formula (I), productivity 59%.Analyzing through X-single crystal diffractometer, cobalt complex prepared by the present embodiment is the coordination compound of mononuclear structure.Axonometry data and crystal structure are with compound in embodiment 1.
Application Example one
Under room temperature, 2 are added to equipped with in the 10ml there-necked flask of condensing tube and thermometer, 4-DI-tert-butylphenol compounds (206mg, 1mmol), potassium hydroxide (56mg, 1mmol) with sodium lauryl sulphate (SDS, 29mg, 1mmol), be subsequently adding 5mL pure water, stir and add embodiment 1 preparation cobalt complex (0.02mmol) as catalyst.The lower heating of stirring, to 50 DEG C, is the H of 30% by 10 μ l syringe holder mass percentage concentration2O2Aqueous solution is slowly added dropwise in above-mentioned mixed solution, within every 15 minutes, adds 10 μ l, drips 20 μ l altogether, and reaction 4h(is from just starting to drip H2O2Aqueous solution starts timing) stop afterwards.By TLC method reaction product isolated on previously prepared thin layer silica gel.Result shows: the conversion ratio of 2,4-DTBP is 100%, in product 2, and 2 '-dihydroxy-3,3 ', 5,5 '-tetra-tert biphenyl (TBBP) yield is 76%, and benzoquinone yield is 24%.
Application Example two
Under room temperature, 2 are added to equipped with in the 10ml there-necked flask of condensing tube and thermometer, 4-DI-tert-butylphenol compounds (206mg, 1mmol), potassium hydroxide (224mg, 4mmol) with sodium lauryl sulphate (SDS, 87mg, 3mmol), be subsequently adding 5mL pure water, stir and add embodiment 2 preparation cobalt complex (0.05mmol) as catalyst.The lower heating of stirring, to 60 DEG C, is the H of 30% by 10 μ l syringe holder mass percentage concentration2O2Aqueous solution is slowly added dropwise in above-mentioned mixed solution, within every 15 minutes, adds 10 μ l, drips 20 μ l altogether, and reaction 4h(is from just starting to drip H2O2Aqueous solution starts timing) stopped reaction afterwards.By TLC method reaction product isolated on previously prepared thin layer silica gel.Result shows: the conversion ratio of 2,4-DTBP is 100%, in product 2, and 2 '-dihydroxy-3,3 ', 5,5 '-tetra-tert biphenyl (TBBP) yield is 89%, and benzoquinone yield is 11%.
Claims (7)
1. a cobalt complex, its molecular formula is [Co (qc)2(H2O)2]·2H2O, wherein qc represents 3-hydroxyl-2-quinoxaline carboxylic acid's root, shown in structural formula such as formula (I):
Described cobalt complex is monoclinic system crystal, and space group is P21, and cell parameter is: α=90.00 °, β=100.916 (6) °, γ=90.00 °,
2. the method preparing cobalt complex described in claim 1, it is characterised in that 3-hydroxyl-2-quinoxaline carboxylic acid and bivalent Co are obtained by reacting described cobalt complex in the solution.
3. the method preparing described cobalt complex according to claim 2, it is characterised in that comprise the steps: that the methanol solution by 3-hydroxyl-2-quinoxaline carboxylic acid is added drop-wise to Co (ClO4)2In aqueous solution, mix homogeneously, left at room temperature 5～10 days, carry out self-assembling reaction, obtain red bulk crystals, then successively with dehydrated alcohol, washed with diethylether, dry, obtain described cobalt complex.
4. the method preparing described cobalt complex according to claim 3, it is characterised in that the concentration of the methanol solution of described 3-hydroxyl-2-quinoxaline carboxylic acid is 0.01～2mol L-1, described Co (ClO4)2Co (ClO in aqueous solution4)2Concentration be 0.001～1mol L-1, the methanol solution of described 3-hydroxyl-2-quinoxaline carboxylic acid and Co (ClO4)2The volume ratio of aqueous solution is (3～5): (0.4～2).
5. the application in catalysis 2,4-DI-tert-butylphenol compounds oxidative coupling reaction of the cobalt complex described in claim 1.
6. applying according to claim 5, it is characterised in that comprise the steps: to mix 2,4-DTBP, KOH, sodium lauryl sulphate and water, stirring is lower adds described cobalt complex, the lower heating of stirring；After rising to 30-60 DEG C to temperature, instilling mass percentage concentration is the H of 30%2O2Aqueous solution, reacts 3～5h.
7. apply according to claim 6, it is characterised in that the mol ratio of described cobalt complex and 2,4-DTBP is 1%～5%；The mol ratio of described KOH, sodium lauryl sulphate and 2,4-DI-tert-butylphenol compounds is (1～4): (1～3): 1；Amount of water corresponding to every mM of 2,4-DI-tert-butylphenol compounds is 5-10ml；The H that every mM of 2,4-DI-tert-butylphenol compounds is corresponding2O2The addition of aqueous solution is 10-30 μ l.
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| US3725068A (en) * | 1970-04-17 | 1973-04-03 | Ciba Geigy Ag | Process for the photographic development of silver salts |
| CN101260122A (en) * | 2007-03-08 | 2008-09-10 | 中国科学院化学研究所 | 2-(6'-iminopyridyl)quinoxaline metal complex compound and its preparing method and application |
| WO2010123046A1 (en) * | 2009-04-21 | 2010-10-28 | 住友化学株式会社 | Modified metal complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725068A (en) * | 1970-04-17 | 1973-04-03 | Ciba Geigy Ag | Process for the photographic development of silver salts |
| CN101260122A (en) * | 2007-03-08 | 2008-09-10 | 中国科学院化学研究所 | 2-(6'-iminopyridyl)quinoxaline metal complex compound and its preparing method and application |
| WO2010123046A1 (en) * | 2009-04-21 | 2010-10-28 | 住友化学株式会社 | Modified metal complex |
Non-Patent Citations (1)
| Title |
|---|
| THE USE OF QUINQXALINE-2-CARBUXYLIC ACID AND ITS DERIVATIVES AS ANALYTICAL REAGENTS;N.KDUTT等，;《Anatlytica Chimica Acta》;19681231;第41卷;第331-339页，尤其是第333页表1 * |
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