CN1270826C - Fluoro comzole coordination polymer, preparation method and use - Google Patents
Fluoro comzole coordination polymer, preparation method and use Download PDFInfo
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- CN1270826C CN1270826C CN 200410010159 CN200410010159A CN1270826C CN 1270826 C CN1270826 C CN 1270826C CN 200410010159 CN200410010159 CN 200410010159 CN 200410010159 A CN200410010159 A CN 200410010159A CN 1270826 C CN1270826 C CN 1270826C
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- fluconazole
- coordination polymers
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Abstract
The present invention provides a fluconazole coordination polymer, and simultaneously, provides a polymer preparation method, namely that a product having the characteristics of high stability, insolubility in water, easy separation and repeated use is prepared from nitrogenous organic compound fluconazole and transitional metal chloride by self-assembly cultivation at room temperature. The present invention also provides a fluconazole coordination polymer use, namely that the polymer used as a catalyst for phenol hydrogen peroxide hydroxylation reaction can prepare pyrocatechol in the mode of high selectivity and effectively solve a series of problems of poor selectivity, low yield, difficult catalyst recovery, environment pollution by solvent, etc. of benzenediol generated by phenol hydroxylation reaction.
Description
Technical field:
The present invention relates to Coordination Polymers, preparation method and its usage that a kind of containing n-donor ligand and transition metal generate.
Background technology:
In recent years, the research and development of supramolecular chemistry is very fast, and utilizing crystal engineering to carry out that supermolecule constructs is one of main target of supramolecular chemistry research, particularly has the Coordination Polymers of topological structure, has obtained unprecedented gazing at especially.Coordination Polymers is that self assembly under the condition of gentleness forms by transition metal and organic ligand, combine the characteristics of composite high-molecular and complex, Coordination Polymers with multiple structures such as chain, latticed, trapezoidal, cage shapes is synthetic, because of its diversity structure, show unique character, have a extensive future at aspects such as nonlinear optical material, electrochemistry switch, magnetic, catalysis.The imidazoles of nitrogen atom and derivative thereof are because biologically active causes supermolecular scholar's interest.Wherein Fluconazole is extensive use of as medicine, but does not still appear in the newspapers as the research of organic ligand and transition metal formation Coordination Polymers.
Benzenediol comprises catechol, hydroquinones, resorcinol, and they all are the important chemical products, have application fields.Wherein catechol is the extremely wide fine chemical product of purposes, is base stock, intermediate or the auxiliary agent of industries such as rubber, medicine, agricultural chemicals, dyestuff, photosensitive material and spices, and domestic supply falls short of demand, long-term dependence on import.And catechol is difficult to separate with hydroquinones, so selectivity prepares catechol and is even more important.
The method for preparing catechol, domestic main industrialization synthetic method is the o-chlorphenol Hydrolyze method.This method is raw material with the o-chlorphenol, and copper sulphate is catalyst, and the reaction that is hydrolyzed in NaOH is the aqueous solution of alkaline medium generates catechol.This method needs press device, and operation requires high, produces 1.5 tons of sodium sulphate of 1 ton of catechol by-product.
2,4-disulfonic acid base phenol Hydrolyze method is the method that early is used to prepare catechol, the technology comparative maturity, and price is low, but uses concentrated acid sulfonation phenol, the NaOH high temperature alkali fuse, the dilute sulfuric acid hydrolysis, equipment corrosion is serious, the operating condition harshness, quantity of three wastes is big.
With hydrogen peroxide the direct hydroxylation of phenol being become dihydric phenol is the research topic of a hot topic in recent years.On the one hand, this method technology is simple, and the catabolite of oxidants hydrogen peroxide only is O
2And H
2O can not cause any environmental pollution.On the other hand, the oxidizing process in this reaction and the organism has some something in commons, so, cause chemist's extensive concern.This course of reaction is considered to 21 century one of the most promising process route.
Because hydrogen peroxide itself is not a hydroxylation reagent, must hydroxylating could take place by catalyst on phenol, generate benzenediol, therefore, to this method research maximum be catalyst, the quality of product selectivity, the height of yield all depend on activity of such catalysts to a great extent.
So far, Chinese scholars is that phenol hydroxylation technology has selected a variety of catalyst to study.External catalyst research is used comparatively ripe Japan, France, the Italy of mainly containing.They adopt the 60-70% hydrogen peroxide mostly.
From existing document, though the industrialization abroad of phenol hydroxylation preparing benzenediol, owing to reasons such as technical know-hows, the domestic industrialization of failing so far to realize.Conversion ratio and product selectivity and the productive rate of researcher in order to improve phenol developed multiple catalyst, but because corrosivity is strong, cost is high, catalyst recovery difficulty etc. is multiple former thereby all not fully up to expectations.For developing desirable catalyst, chemist is all being done unremitting effort.
Patent that Jilin University delivers adopts the polyacid complex of Dawson structure, and to be catalyst (patent No. 94120162.7) make oxidant at 70 ℃, hydrogen peroxide, acetonitrile is under the condition of solvent, though good selectivity is arranged by the phenol preparing benzenediol, but phenol conversion is low, and the acetonitrile contaminated environment.The patent (patent No. 94120019.1) of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences's invention adopts the Y shaped molecular sieve, according to the preparation difference of molecular sieve, can react in different solvents.Jilin University adopts micro-porous resin embedding nano particle to make catalyst (patent No. 96105181.7), and China PetroChemical Corporation is catalyst (patent No. 99113282.3) with the copolymer pellet of styrene and maleic anhydride.In fact, seeking with water is that solvent carries out the phenol hydroxylation catalyst for reaction, and promptly carrying out so-called " cleaning procedure " reaction is the current problem that chemist is had the challenge meaning.
Find the document of home and abroad according to us, do not see the report of making catalyst hydroxylation with hydrogen peroxide phenol of Coordination Polymers as yet.Technical research about Fluconazole and transition metal reaction generation Coordination Polymers does not more appear in the newspapers.
Summary of the invention:
For solving low, a series of problems such as catalyst recovery is difficult, solvent contamination environment of poor selectivity, productive rate that the phenol hydroxylation reaction generates benzenediol, the invention provides a kind of Fluconazole Coordination Polymers of utilizing nitrogenous organic compound Fluconazole and transition metal chloride self-assembling reaction to make, the method for preparing this catalyst also is provided, this polymer can be used as catalyst and is used for the phenol hydroxylation with hydrogen peroxide reaction, the preparation catechol.
Technical scheme of the present invention is:
The monocrystalline polymer that the Fluconazole Coordination Polymers is made up of Fluconazole and transition metal chloride, the molecular formula of the monocrystalline polymer of being made up of Fluconazole and copper, iron, cobalt, cadmium transition metal chloride is (C
28H
32Cl
2F
4MN
12O
4)
n, wherein M is Cu or Fe or Co or Cd; The molecular formula of the monocrystalline polymer of being made up of Fluconazole and zinc chloride is: (C
14H
16Cl
2F
2ZnN
6O
2)
n
Wherein: transition metal chloride is CuCl
22H
2O, CoCl
26H
2O, FeCl
24H
2O, CdCl
22.5H
2O, ZnCl
2
A kind of method for preparing the Fluconazole Coordination Polymers the steps include:
A. with Fluconazole, FeCl
24H
2O, CdCl
22.5H
2O or ZnCl
2Be dissolved in the methyl alcohol, with CuCl
22H
2O or CoCl
26H
2O is soluble in water;
B. with the Fluconazole methanol solution, be added drop-wise to FeCl
24H
2O, CdCl
22.5H
2O or ZnCl
2Methanol solution, or be added drop-wise to CuCl
22H
2O or CoCl
26H
2In the O aqueous solution, stir, leave standstill under the room temperature, carry out self-assembling reaction, generate monocrystalline, promptly get product.
In above-mentioned preparation method:
The concentration of Fluconazole methanol solution is 0.001-1mmol.ml
-1, FeCl
24H
2O, CdCl
22.5H
2O, ZnCl
2The concentration of methanol solution is 0.01-1mmol.m
-1, CuCl
22H
2O, CoCl
26H
2The concentration of the O aqueous solution is 0.01-2mmol.ml
-1
Fluconazole methanol solution and FeCl
24H
2O, CdCl
22.5H
2The volume ratio that the O methanol solution mixes is 3-6: 1-3, Fluconazole methanol solution and CuCl
22H
2O, CoCl
26H
2The volume ratio of O aqueous solution is 3-6: 0.5-3, Fluconazole methanol solution and ZnCl
2The volume ratio that methanol solution mixes is 3-6: 3-6;
After the mixing, the mol ratio of Fluconazole and copper, iron, cobalt, cadmium is 2-3: 1-2, the mol ratio of Fluconazole and zinc is 1-4: 1-3.
The purposes of Fluconazole Coordination Polymers: use this polymer as catalyst, be used for the phenol hydroxylation with hydrogen peroxide reaction, the preparation catechol.
In the phenol hydroxylation with hydrogen peroxide reaction, with water as solvent, 30% hydrogen peroxide as oxidant, catalyst amount are not more than 6% of phenol, and reaction temperature was reacted 1 hour at 40-65 ℃, can the highly-selective preparation catechol.Catechol: hydroquinones mol ratio=5-8: 1-2.Catalysis is carried out in heterogeneous.After reaction finished, separating catalyst was reused.
Compared with prior art, the present invention has following advantage:
1, the monocrystalline Coordination Polymers of the present invention for cultivating through the molecule self assembly, pore structure and pore-size distribution with certain particle, uniqueness have very high catalytic activity, selectivity and good stable.
2, using the Fluconazole Coordination Polymers to produce catechol as catalyst, can water be solvent, and hydrogen peroxide (30%) is an oxidant, and not only selectivity is good, productive rate is high, and the three wastes are few, and is pollution-free to product.
3, this catalyst is easy to reclaim, and can reuse.
4, this method for preparing catalyst is simple, produces pollution-freely, has potential economic benefit, social benefit and environmental benefit.
The specific embodiment:
The present invention is described further below in conjunction with embodiment:
Embodiment 1:
Preparation Fluconazole Coordination Polymers: with the methanol solution (0.04mmol.ml of 15ml Fluconazole
-1) be added drop-wise to 6mlFeCl
2.4H
2Methanol solution (the 0.05mmol.ml of O
-1) lining, stir, leave standstill under the room temperature, after one month, generate yellow crystal, promptly get Fluconazole iron Coordination Polymers, productive rate 73%.Analyze through the X-single crystal diffractometer, for having the Coordination Polymers of two-dimensional network structure, molecular formula is: (C
28H
32Cl
2F
4FeN
12O
4)
n
Be used as catalyst: phenol 0.5g is added in the container, add 15ml water and make solvent, stir also adding Fluconazole iron Coordination Polymers (making catalyst) 10mg, when being heated to 40 ℃ under stirring, adding H
2O
2(30%) 0.5ml picks up counting, and stops reaction after 1 hour.With high performance liquid chromatography detection reaction product, the result shows: phenol conversion 62%, catechol content 55.3% in the product, hydroquinones content 4%.
Embodiment 2:
Methanol solution (0.04mmol.ml with the 20ml Fluconazole
-1) be added drop-wise to 8mlCdCl
2.2.5H
2(0.05mmol.ml in the methanol solution of O
-1), stir, leave standstill under the room temperature, after 3 days, generate colourless monocrystalline, promptly get Fluconazole cadmium Coordination Polymers, productive rate 79%.Analyzing through the X-single crystal diffractometer, is the Coordination Polymers of two-dimensional network structure, and molecular formula is: (C
28H
32Cl
2F
4CdN
12O
4)
n
Phenol 0.5g is added in the container, add 15ml water and make solvent, stir and adding Fluconazole cadmium Coordination Polymers (making catalyst) 10mg, when being heated to 60 ℃ under stirring, add H
2O
2(30%) 0.5ml picks up counting, and stops reaction after 1 hour, and phenol does not have conversion substantially.
Embodiment 3:
Methanol solution (0.02mmol.ml with the 15ml Fluconazole
-1) be added drop-wise to 3mlCuCl
22H
2The aqueous solution (the 0.05mmol.ml of O
-1) lining, shaking up, room temperature leaves standstill, and has blue monocrystalline to occur after 3 days, promptly gets the Fluconazole copper coordination polymer, productive rate 77%.Through X-single crystal diffractometer analysis and characterization, for having the Coordination Polymers of two-dimensional network structure, molecular formula is (C
28H
32Cl
2F
4CuN
12O
4)
n
Phenol 0.5g is added in the container, add 15ml water and make solvent, stir and adding Fluconazole copper coordination polymer (making catalyst) 15mg, when being heated to 50 ℃ under stirring, add H
2O
2(30%) 0.5ml picks up counting, and stops reaction after 1 hour.Isolated by filtration is with high performance liquid chromatography detection reaction product, result: phenol conversion 78%, catechol content 63.5% in the product, hydroquinones content 9%.
Embodiment 4:
Methanol solution (0.01mmol.ml with the 5ml Fluconazole
-1) be added drop-wise to 1mlCoCl
2.6H
2(0.025mmol.ml in the aqueous solution of O
-1), shake up, leave standstill under the room temperature, after 3 days, generate peach crystal, promptly get Fluconazole cobalt Coordination Polymers, productive rate 79%.Analyze through the X-single crystal diffractometer, for having the Coordination Polymers of two-dimensional network structure, molecular formula is: (C
28H
32Cl
2F
4CoN
12O
4)
n
Phenol 0.5g is added in the container, add 15ml water and make solvent, stir and adding Fluconazole cobalt Coordination Polymers (making catalyst) 20mg, when being heated to 65 ℃ under stirring, add H
2O
2(30%) 0.5ml picks up counting, and stops reaction after 1 hour.With high performance liquid chromatography detection reaction product, the result shows: phenol conversion 53%, catechol content 41.0% in the product, hydroquinones content 8%.
Embodiment 5:
Methanol solution (0.08mmol.ml with the 25ml Fluconazole
-1) be added drop-wise to 20ml ZnCl
2Methanol solution in (0.1mmol.ml
-1), shake up, leave standstill under the room temperature, after one month, generate clear crystal, promptly get the Fluconazole zinc coordination polymer, productive rate 73%.Analyze through the X-single crystal diffractometer, for having the cancellated Coordination Polymers of one dimension, molecular formula is: (C
14H
16Cl
2F
2ZnN
6O
24)
n
With embodiment 3 identical conditions under, use the Fluconazole zinc coordination polymer instead as catalyst reaction, phenol conversion is 39%, catechol content 27.0% in the product, hydroquinones content 5%.
Claims (12)
1, Fluconazole Coordination Polymers cooperates the monocrystalline polymer of forming by Fluconazole and transition metal chloride, it is characterized in that: the molecular formula of the monocrystalline polymer that Fluconazole and copper, iron, cobalt, cadmium transition metal chloride are formed is (C
28H
32Cl
2F
4MN
12O
4)
n, wherein M is Cu or Fe or Co or Cd.
2, Fluconazole Coordination Polymers cooperates the monocrystalline polymer of forming by Fluconazole and transition metal chloride, and it is characterized in that: the molecular formula of the monocrystalline polymer that Fluconazole and zinc chloride are formed is: (C
14H
16Cl
2F
2ZnN
6O
2)
n
3, the described Fluconazole Coordination Polymers of claim 1, it is characterized in that: transition metal chloride is CuCl
22H
2O, CoCl
26H
2O, FeCl
24H
2O, CdCl
22.5H
2O.
4, the described Fluconazole Coordination Polymers of claim 2, it is characterized in that: transition metal chloride is ZnCl
2
5, a kind of method for preparing claim 1 or 2 described Fluconazole Coordination Polymers is characterized in that:
A. with Fluconazole, FeCl
24H
2O, CdCl
22.5H
2O or ZnCl
2Be dissolved in the methyl alcohol, with CuCl
22H
2O or CoCl
26H
2O is soluble in water;
B. with the Fluconazole methanol solution, be added drop-wise to FeCl
24H
2O, CdCl
22.5H
2O or ZnCl
2Methanol solution, or be added drop-wise to CuCl
22H
2O or CoCl
26H
2In the O aqueous solution, stir, leave standstill under the room temperature, carry out self-assembling reaction, generate monocrystalline, promptly get product.
6, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, the concentration that it is characterized in that the Fluconazole methanol solution is 0.001-1mmo1.m1
-1, FeCl
24H
2O, CdCl
22.5H
2O, ZnCl
2The concentration of methanol solution is 0.01-1mmo1.ml
-1, CuCl
22H
2O, CoCl
26H
2The concentration of the O aqueous solution is 0.01-2mmo1.ml
-1
7, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, it is characterized in that: Fluconazole methanol solution and FeCl
24H
2O, CdCl
22.5H
2O, ZnCl
2The volume ratio that methanol solution mixes is 3-6: 1-3.
8, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, it is characterized in that: Fluconazole methanol solution and CuCl
22H
2O, CoCl
26H
2The volume ratio of O aqueous solution is 3-6: 0.5-3.
9, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, it is characterized in that: Fluconazole methanol solution and ZnCl
2The volume ratio that methanol solution mixes is 3-6: 3-6.
10, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, it is characterized in that: the mol ratio of mixing back Fluconazole and copper, iron, cobalt, cadmium is 2-3: 1-2.
11, according to the described method for preparing the Fluconazole Coordination Polymers of claim 5, it is characterized in that: the mol ratio of mixing back Fluconazole and zinc is 1-4: 1-3.
12, the purposes of claim 1 or 2 described Fluconazole Coordination Polymers is characterized in that: this polymer is used for the phenol hydroxylation with hydrogen peroxide reaction as catalyst, the preparation catechol.
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