CN1597115A - Fluoro comzole coordination polymer, preparation method and use - Google Patents

Fluoro comzole coordination polymer, preparation method and use Download PDF

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CN1597115A
CN1597115A CN 200410010159 CN200410010159A CN1597115A CN 1597115 A CN1597115 A CN 1597115A CN 200410010159 CN200410010159 CN 200410010159 CN 200410010159 A CN200410010159 A CN 200410010159A CN 1597115 A CN1597115 A CN 1597115A
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fluconazole
ligand polymer
methanol solution
preparing
zncl
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CN1270826C (en
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侯红卫
韩华云
樊耀亭
孟祥茹
牛云垠
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Zhengzhou University
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Zhengzhou University
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Abstract

A fluorofurfurlazole cooling polymer used as the catalyst for preparing pyrocatechol by the hydroxylation reaction between phenol and H2O2 with high selectivity is prepared from fluorofurfurylazole and the chloride of transition metal through self assembling and culturing.

Description

Fluconazole ligand polymer, Preparation method and use
Technical field:
The present invention relates to ligand polymer, preparation method and its usage that a kind of containing n-donor ligand and transition metal generate.
Background technology:
In recent years, the researchdevelopment of supramolecular chemistry is very fast, and utilizing crystal engineering to carry out that supramolecule constructs is one of major objective of supramolecular chemistry research, particularly has the ligand polymer of topological framework, has obtained unprecedented gazing at especially.Ligand polymer is that self-assembly under the condition of gentleness forms by transition metal and organic ligand, combine the characteristics of composite high-molecular and coordination compound, ligand polymer 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 ligand polymer.
Dihydroxy-benzene comprises pyrocatechol, Resorcinol, Resorcinol, and they all are the important chemical products, have wide application field.Wherein pyrocatechol is the extremely wide fine chemical product of purposes, is basic raw material, intermediate or the auxiliary agent of industries such as rubber, medicine, agricultural chemicals, dyestuff, sensitive materials and spices, and domestic supply falls short of demand, long-term dependence on import.And pyrocatechol is difficult to separate with Resorcinol, so selectivity prepares pyrocatechol and is even more important.
The method for preparing pyrocatechol, domestic main industrialization synthesis method is the ortho chloro phenol hydrolysis method.This method is raw material with the ortho chloro phenol, and copper sulfate is catalyzer, and the reaction that is hydrolyzed in sodium hydroxide is the aqueous solution of alkaline medium generates pyrocatechol.This method needs press device, and the operational requirement height is produced 1.5 tons of sodium sulfate of 1 ton of pyrocatechol by-product.
2,4-disulfonic acid base phenol hydrolysis method is the method that early is used to prepare pyrocatechol, the technology comparative maturity, and price is low, but uses concentrated acid sulfonation phenol, the sodium hydroxide high temperature alkali fuse, the dilute sulphuric acid hydrolysis, equipment corrosion is serious, the operational 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 degradation production of oxidants hydrogen peroxide only is O 2And H 2O can not cause any environmental pollution.On the other hand, this reaction and biological intravital oxidising process have some something in commons, so, cause chemist's extensive concern.This reaction process is considered to 21 century one of the most promising operational path.
Because hydrogen peroxide itself is not a hydroxylation reagent, must hydroxylating could take place by catalyzer on phenol, generate dihydroxy-benzene, therefore, to this method research maximum be catalyzer, 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 catalyzer to study.External catalyst research is used comparatively sophisticated 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.Transformation efficiency and product selectivity and the productive rate of investigator in order to improve phenol developed multiple catalyzer, but because corrodibility is strong, cost is high, catalyst recovery difficulty etc. is multiple former thereby all not fully up to expectations.Be development ideal catalyzer, chemist is all being done unremitting effort.
Patent that Jilin University delivers adopts the polyacid title complex of Dawson structure, and to be catalyzer (patent No. 94120162.7) make oxygenant 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 contaminate 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 catalyzer (patent No. 96105181.7), and China PetroChemical Corporation is catalyzer (patent No. 99113282.3) with the copolymer pellet of vinylbenzene 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 ligand polymer as yet.Technical study about fluconazole and transition metal reaction generation ligand polymer 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 dihydroxy-benzene, the invention provides a kind of fluconazole ligand polymer of utilizing nitrogenous organic compound fluconazole and transition metal chloride self-assembling reaction to make, the method for preparing this catalyzer also is provided, this polymkeric substance can be used as catalyzer and is used for the phenol hydroxylation with hydrogen peroxide reaction, the preparation pyrocatechol.
Technical scheme of the present invention is:
The monocrystalline polymkeric substance that the fluconazole ligand polymer is made up of fluconazole and transition metal chloride, the molecular formula of the monocrystalline polymkeric substance 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 polymkeric substance of being made up of fluconazole and zinc muriate 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 ligand polymer the steps include:
A. respectively with fluconazole, FeCl 24H 2O, CdCl 22.5H 2O, ZnCl 2Be dissolved in the methyl alcohol, with CuCl 22H 2O, CoCl 26H 2O is soluble in water;
B. with the fluconazole methanol solution, be added drop-wise to FeCl respectively 24H 2O, CdCl 22.5H 2O, ZnCl 2Methanol solution and CuCl 22H 2O, 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.ml -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 2O methanol solution blended volume ratio 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 2Methanol solution blended volume ratio 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 ligand polymer: use this polymkeric substance as catalyzer, be used for the phenol hydroxylation with hydrogen peroxide reaction, the preparation pyrocatechol.
In the phenol hydroxylation with hydrogen peroxide reaction, with water as solvent, 30% hydrogen peroxide as oxidant, catalyst levels are not more than 6% of phenol, and temperature of reaction was reacted 1 hour at 40-65 ℃, can the highly-selective preparation pyrocatechol.Pyrocatechol: Resorcinol 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 ligand polymer 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 satisfactory stability.
2, using the fluconazole ligand polymer to produce pyrocatechol as catalyzer, can water be solvent, and hydrogen peroxide (30%) is an oxygenant, and not only selectivity is good, productive rate is high, and the three wastes are few, and is pollution-free to product.
3, this catalyzer 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.
Embodiment:
The present invention is described further below in conjunction with embodiment:
Embodiment 1:
Preparation fluconazole ligand polymer: 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 the xanchromatic crystal, promptly get fluconazole iron ligand polymer, productive rate 73%.Analyze through the X-single crystal diffractometer, for having the ligand polymer of two-dimensional network structure, molecular formula is: (C 28H 32Cl 2F 4FeN 12O 4) n
Be used as catalyzer: phenol 0.5g is added in the container, add 15ml water and make solvent, stir also adding fluconazole iron ligand polymer (making catalyzer) 10mg, when being heated to 40 ℃ under stirring, adding H 2O 2(30%) 0.5ml picks up counting, stopped reaction after 1 hour.With high performance liquid chromatography detection reaction product, the result shows: phenol conversion 62%, pyrocatechol content 55.3% in the product, Resorcinol content 4%.
Embodiment 2:
Methanol solution (0.04mmol.ml with the 20ml fluconazole -1) be added drop-wise to 8mlCdCl 2.2.5 H 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 ligand polymer, productive rate 79%.Analyzing through the X-single crystal diffractometer, is the ligand polymer 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 ligand polymer (making catalyzer) 10mg, when being heated to 60 ℃ under stirring, add H 2O 2(30%) 0.5ml picks up counting, and stopped reaction after 1 hour, phenol do 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 ligand polymer 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 catalyzer) 15mg, when being heated to 50 ℃ under stirring, add H 2O 2(30%) 0.5ml picks up counting, stopped reaction after 1 hour.Filtering separation is with high performance liquid chromatography detection reaction product, result: phenol conversion 78%, pyrocatechol content 63.5% in the product, Resorcinol content 9%.
Embodiment 4:
Methanol solution (0.01mmol.ml with the 5ml fluconazole -1) be added drop-wise to 1mlCoCl 2.6 H 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 ligand polymer, productive rate 79%.Analyze through the X-single crystal diffractometer, for having the ligand polymer 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 ligand polymer (making catalyzer) 20mg, when being heated to 65 ℃ under stirring, add H 2O 2(30%) 0.5ml picks up counting, stopped reaction after 1 hour.With high performance liquid chromatography detection reaction product, the result shows: phenol conversion 53%, pyrocatechol content 41.0% in the product, Resorcinol 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 ligand polymer 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%, pyrocatechol content 27.0% in the product, Resorcinol content 5%.

Claims (11)

1, fluconazole ligand polymer cooperates the monocrystalline polymkeric substance of forming by fluconazole and transition metal chloride, it is characterized in that: the molecular formula of the monocrystalline polymkeric substance 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 ligand polymer cooperates the monocrystalline polymkeric substance of forming by fluconazole and transition metal chloride, and it is characterized in that: the molecular formula of the monocrystalline polymkeric substance that fluconazole and zinc muriate are formed is: (C 14H 16Cl 2F 2ZnN 6O 2) n
3, claim 1 and 2 described fluconazole ligand polymer, it is characterized in that: transition metal chloride is CuCl 22.5H 2O, CoCl 26H 2O, FeCl 24H 2O, CdCl 22.5H 2O, ZnCl 2
4, a kind of method for preparing claim 1 and 2 described fluconazole ligand polymer is characterized in that:
A. respectively with fluconazole, FeCl 24H 2O, CdCl 22.5H 2O, ZnCl 2Be dissolved in the methyl alcohol, with CuCl 22H 2O, CoCl 26H 2O is soluble in water;
B. with the fluconazole methanol solution, be added drop-wise to FeCl respectively 24H 2O, CdCl 22.5H 2O, ZnCl 2Methanol solution and CuCl 22H 2O, CoCl 26H 2In the O aqueous solution, stir, leave standstill under the room temperature, carry out self-assembling reaction, generate monocrystalline, promptly get product.
5, according to the described method for preparing phenol fluconazole ligand polymer of claim 4, the concentration that it is characterized in that the 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.ml -1, CuCl 22H 2O, CoCl 26H 2The concentration of the O aqueous solution is 0.01-2mmol.ml -1
6, according to the described method for preparing the fluconazole ligand polymer of claim 4, it is characterized in that: fluconazole methanol solution and FeCl 24H 2O, CdCl 22.5H 2O, ZnCl 2Methanol solution blended volume ratio is 3-6: 1-3.
7, according to the described method for preparing the fluconazole ligand polymer of claim 4, it is characterized in that: fluconazole methanol solution and CuCl 22.5H 2O, CoCl 26H 2The volume ratio of O aqueous solution is 3-6: 0.5-3.
8, according to the described method for preparing the fluconazole ligand polymer of claim 4, it is characterized in that: fluconazole methanol solution and ZnCl 2Methanol solution blended volume ratio is 3-6: 3-6.
9, according to the described method for preparing the fluconazole ligand polymer of claim 4, it is characterized in that: the mol ratio of mixing back fluconazole and copper, iron, cobalt, cadmium is 2-3: 1-2.
10, according to the described method for preparing the fluconazole ligand polymer of claim 4, it is characterized in that: the mol ratio of mixing back fluconazole and zinc is 1-4: 1-3.
11, the purposes of claim 1 and 2 described fluconazole ligand polymer is characterized in that: this polymkeric substance is used for the phenol hydroxylation with hydrogen peroxide reaction as catalyzer, the preparation pyrocatechol.
CN 200410010159 2004-03-26 2004-03-26 Fluoro comzole coordination polymer, preparation method and use Expired - Fee Related CN1270826C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053817A (en) * 2018-07-10 2018-12-21 济宁学院 A kind of nickel-antifungal drug functionalization polyacid compound, preparation method and application
CN110215179A (en) * 2019-06-20 2019-09-10 京东方科技集团股份有限公司 The medicament release device and capsule endoscope of capsule endoscope

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053817A (en) * 2018-07-10 2018-12-21 济宁学院 A kind of nickel-antifungal drug functionalization polyacid compound, preparation method and application
CN109053817B (en) * 2018-07-10 2020-11-03 济宁学院 Nickel-antifungal drug functionalized polyacid compound, preparation method and application
CN110215179A (en) * 2019-06-20 2019-09-10 京东方科技集团股份有限公司 The medicament release device and capsule endoscope of capsule endoscope
CN110215179B (en) * 2019-06-20 2022-02-25 京东方科技集团股份有限公司 Medicine releasing device of capsule endoscope and capsule endoscope

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