CN101974110A - Preparation method of water-soluble ferrocene supramolecular inclusion compound - Google Patents
Preparation method of water-soluble ferrocene supramolecular inclusion compound Download PDFInfo
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- CN101974110A CN101974110A CN 201010506173 CN201010506173A CN101974110A CN 101974110 A CN101974110 A CN 101974110A CN 201010506173 CN201010506173 CN 201010506173 CN 201010506173 A CN201010506173 A CN 201010506173A CN 101974110 A CN101974110 A CN 101974110A
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Abstract
The invention relates to a preparation method of a water-soluble ferrocene supramolecular inclusion compound, belonging to the field of preparation processes of water-soluble metal organic materials in the technical field of supramolecular materials. The preparation method comprises the following steps of: firstly crosslinking beta-cyclodextrin as a raw material with epoxy chloropropane to generate a beta-cyclodextrin polymer under a strong alkaline condition; and then carrying out homogeneous supramolecular reaction on the beta-cyclodextrin polymer as a subject molecule, ferrocene as an object molecule and glycol as a reaction solvent to generate the water-soluble ferrocene supramolecular inclusion compound. The preparation method has the advantages of easy and convenient operation, easy control of conditions, little environmental pollution and easy industrialization; the material not only has high water solubility, but also has stable structure without damaging the self structure of the ferrocene; and in addition, the water-soluble ferrocene supramolecular inclusion compound can be used in the fields of aqueous-phase electroanalytical chemistry, biological sensors, aqueous-phase organic synthesis, biological medicine, and the like because of good water solubility.
Description
Technical field
The invention belongs to the fabricating technology field of the water-soluble organic materials of supramolecule technical field.
Background technology
Supramolecular chemistry is the chemistry of inter-molecular linkage, thereby studies two or more molecules by the 26S Proteasome Structure and Function of Intermolecular Forces in conjunction with the systematism entity of realizing high complexity.Main object has special selectivity, and the synthetic of host molecule is the key point of supramolecular chemistry with using all the time.Though synthesizing with the beta-cyclodextrin at Harada in 1984 etc. is the ferrocene super molecule inclusion compound of host molecule, water-soluble very little.
Since synthetic ferrocene such as nineteen fifty-one Pauson, synthetic and the application of ferrocene and derivative thereof are studied widely.Ferrocene has unique sandwich-like structure, ferrous ion is sandwiched between two planar rings staggered configuration each other, the specific molecule structure makes it have characteristics such as aromaticity, hypotoxicity, lipophilicity, electrochemical redox, therefore all has a wide range of applications in fields such as electroanalytical chemistry, petrochemical complex, macromolecular material, biological medicine, organometallic catalytics.Ferrocene is a class electron rich system, and the redox characteristic that it is unique is widely used in aspects such as electroanalysis, electrochemical synthesis, electrocatalysis and biosensor.Ferrocene has 2 cyclopentadiene π key bonded laminate structures, and its aromatic ring character makes ferrocene have very high octane value and anti-knocking property, at aspects such as fuel-economizing, smoke elimination, knot charcoal, antiknock, boosting of octane rating vital role is arranged.In processing of high molecular material, add 1% ~ 5% ferrocene and derivative thereof, the course of processing is eliminated smoke, and the easy demoulding of goods, and smooth surface, and it is aging to prevent that ultraviolet radiation from causing, increases the service life.Ferrocene by the same tertiary alkyl of methylene radical, secondary alkyl and the homologue that links to each other of base have anti-anaemia property, be a kind of medicine of very effective, low toxicity, also can be used for synthesizing glutathion, ferrocene penicillin, ferrocene cephalo element etc.Ferrocene and derivative thereof also are extensive use of in reactions such as asymmetry catalysis, aldol condensation, alkene normal pressure hydrogenation, benzophenone hydrosilylation.
But ferrocene is water insoluble, has limited its use at aqueous phase greatly.Though people by in organic phase ferrocene being carried out organic reaction, obtain some water-soluble ferrocene deriv, the most more complicated of these synthetic methods, cost is higher, is detrimental to health, and environmental pollution is very big.
Summary of the invention
The objective of the invention is to propose that a kind of environmental pollution is little, the preparation method of the water-soluble ferrocene super molecule inclusion compound that is easy to suitability for industrialized production.
The present invention includes step:
1) under strong alkaline condition, beta-cyclodextrin and epoxy chloropropane generation is crosslinked, generate beta cyclo dextrin polymer;
2) with the beta cyclo dextrin polymer be host molecule, ferrocene is a guest molecule, and ethylene glycol is reaction solvent, and the reaction of homogeneous phase supramolecule takes place, and generates water-soluble ferrocene super molecule inclusion compound.
The present invention is easy and simple to handle, and condition is easily controlled, and environmental pollution is little, is easy to industrialization.The ferrocene super molecule inclusion compound good water solubility of preparation, in 25 ℃ of water, solubleness is 54.60 g/L, and Stability Analysis of Structures, does not destroy the structure of ferrocene self.Its water-soluble ferrocene that makes has incomparable wide application prospect in fields such as water electroanalytical chemistry, biosensor, water organic synthesis, biological medicine, catalysis.
Concrete scheme of the present invention is as follows:
Under the normal temperature condition, sodium hydroxide, beta-cyclodextrin and water are mixed earlier in container, add epoxy chloropropane then, finish in 30 ℃ of stirring in water bath reacting by heating to reaction; After the question response system temperature is reduced to room temperature, solution is dialysed, show neutral until the pH value of solution value; Again that solution evaporation is extremely thick, add dehydrated alcohol then and separate out white solid, after filtration, through 50 ℃ of vacuum-dryings, obtain beta cyclo dextrin polymer again.
Beta cyclo dextrin polymer, ferrocene and ethylene glycol stirring at normal temperature in container is mixed, leave standstill 12 h then; Question response with the inclusion complex in solution suction filtration, is removed excessive ferrocene after finishing, and makes orange-yellow solution; In orange-yellow solution, add acetone again, separate out yellow solid, the suction filtration solid, the filter cake absolute ethanol washing, again with solid in 50 ℃ of vacuum-dryings, obtain water-soluble ferrocene super molecule inclusion compound.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is described in detail below in conjunction with embodiment.
Embodiment:
1, preparation beta cyclo dextrin polymer:
In 250 mL there-necked flasks, add sodium hydroxide (19.7 g), beta-cyclodextrin (25 g) and water (40 mL).Stirring at normal temperature to solid all dissolves, and then adds epoxy chloropropane (12 mL), and 30 ℃ of heating in water bath stir 24 h.
Question response finishes, and after temperature of reaction system is reduced to room temperature, solution is dialysed, and shows neutral until the pH value of solution value.Solution is rotated evaporation, steams, add dehydrated alcohol and separate out white solid, filter 50 ℃ of vacuum-drying 24h to thick.Obtain the beta cyclo dextrin polymer (15 g) of white at last.
2, the water-soluble ferrocene super molecule inclusion compound of preparation:
In 250 mL round-bottomed flasks, add beta cyclo dextrin polymer (4 g), ferrocene (2 g) and ethylene glycol (100 mL).Stirring at normal temperature 24 h leave standstill 12 h.
Question response with the inclusion complex in solution suction filtration, is removed excessive ferrocene after finishing, and gets orange-yellow solution.In solution, add 100 mL acetone, yellow solid is separated out, the suction filtration solid, the filter cake absolute ethanol washing then with 50 ℃ of vacuum-drying 24 h of solid, obtains yellow solid (3 g), promptly water-soluble ferrocene super molecule inclusion compound.
Claims (3)
1. the preparation method of a water-soluble ferrocene super molecule inclusion compound comprises step:
1) under strong alkaline condition, beta-cyclodextrin and epoxy chloropropane generation is crosslinked, generate beta cyclo dextrin polymer;
2) with the beta cyclo dextrin polymer be host molecule, ferrocene is a guest molecule, and ethylene glycol is reaction solvent, and the reaction of homogeneous phase supramolecule takes place, and generates water-soluble ferrocene super molecule inclusion compound.
2. according to the preparation method of the described water-soluble ferrocene super molecule inclusion compound of claim 1, it is characterized in that in the described step 1), under the normal temperature condition, sodium hydroxide, beta-cyclodextrin and water are mixed earlier in container, add epoxy chloropropane then, finish in 30 ℃ of stirring in water bath reacting by heating to reaction; After the question response system temperature is reduced to room temperature, solution is dialysed, show neutral until the pH value of solution value; Again that solution evaporation is extremely thick, add dehydrated alcohol then and separate out white solid, after filtration, through 50 ℃ of vacuum-dryings, obtain beta cyclo dextrin polymer again.
3. according to the preparation method of the described water-soluble ferrocene super molecule inclusion compound of claim 1, it is characterized in that described step 2) in, beta cyclo dextrin polymer, ferrocene and ethylene glycol stirring at normal temperature in container is mixed, leave standstill 12 h then; Question response with the inclusion complex in solution suction filtration, is removed excessive ferrocene after finishing, and makes orange-yellow solution; In orange-yellow solution, add acetone again, separate out yellow solid, the suction filtration solid, the filter cake absolute ethanol washing, again with solid in 50 ℃ of vacuum-dryings, obtain water-soluble ferrocene super molecule inclusion compound.
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| CN2010105061732A CN101974110B (en) | 2010-10-14 | 2010-10-14 | Preparation method of water-soluble ferrocene supramolecular inclusion compound |
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| CN101974110A true CN101974110A (en) | 2011-02-16 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302786A (en) * | 2011-08-01 | 2012-01-04 | 扬州大学 | Preparation method for beta-cyclodextrin polymer-paclitaxel inclusion compound |
| CN102516739A (en) * | 2011-12-13 | 2012-06-27 | 中国科学院成都生物研究所 | Multiple sensitive hydrogel material and preparation method thereof |
| CN102813938A (en) * | 2012-09-14 | 2012-12-12 | 扬州大学 | Llex A-cyclodextrin polymer medicine composition for preventing and curing atherosclerosis and preparation method thereof |
| CN105267975A (en) * | 2015-10-10 | 2016-01-27 | 扬州大学 | Preparation method of poly gamma cyclodextrin-paclitaxel supermolecular anticancer drug |
| CN106474485A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | A kind of voltage-stimuli responsive type intelligent nano container and preparation method thereof |
| CN109671966A (en) * | 2018-12-19 | 2019-04-23 | 中国科学技术大学 | The organic fluid cell electrolyte of water system, preparation method and the organic flow battery of water system |
| CN110028601A (en) * | 2019-04-23 | 2019-07-19 | 济宁医学院 | A kind of beta-cyclodextrin derivative, preparation method and the method for preparing supermolecule vesica |
| CN110707327A (en) * | 2019-10-13 | 2020-01-17 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN110801863A (en) * | 2019-11-12 | 2020-02-18 | 北京单原子催化科技有限公司 | Cyclodextrin-based transition metal monoatomic catalytic material and preparation method thereof |
| CN113527543A (en) * | 2021-06-23 | 2021-10-22 | 西安交通大学 | Aqueous neutral piperidine nitrogen-oxygen free radical organic flow battery electrolyte, battery and preparation method |
| CN113651901A (en) * | 2021-08-20 | 2021-11-16 | 成都工业学院 | Preparation method of water-soluble polymer cyclodextrin |
| CN113788903A (en) * | 2021-10-08 | 2021-12-14 | 福建工程学院 | Bio-based smoke suppressant and preparation method and application thereof |
| CN113943197A (en) * | 2021-11-10 | 2022-01-18 | 南京理工大学 | Ferrocenyl macrocyclic composite burning rate catalyst and preparation method and application thereof |
| CN115232319A (en) * | 2021-04-22 | 2022-10-25 | 四川大学 | Supermolecule polyaldehyde compound based on poly-beta-cyclodextrin and ferrocene host-guest action and preparation method thereof |
| CN115340634A (en) * | 2022-08-19 | 2022-11-15 | 扬州朗轩科技有限公司 | Host-guest cladding-based monatomic material and preparation method thereof |
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| US5432274A (en) * | 1993-07-28 | 1995-07-11 | National Research Council Of Canada | Redox dye and method of preparation thereof using 2-hydroxypropyl-β-cyclodextrin and 1,1'-dimethylferrocene |
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2010
- 2010-10-14 CN CN2010105061732A patent/CN101974110B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5432274A (en) * | 1993-07-28 | 1995-07-11 | National Research Council Of Canada | Redox dye and method of preparation thereof using 2-hydroxypropyl-β-cyclodextrin and 1,1'-dimethylferrocene |
Non-Patent Citations (3)
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| 《Carbohydrate Polymers》 20030506 Bjorn Ekberg et al. The synthesis of water-soluble polymers of beta-cyclodextrin and their use in aqueous two-phase systems 第183-188页 1-3 第10卷, 第3期 2 * |
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Cited By (20)
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| CN102302786A (en) * | 2011-08-01 | 2012-01-04 | 扬州大学 | Preparation method for beta-cyclodextrin polymer-paclitaxel inclusion compound |
| CN102516739A (en) * | 2011-12-13 | 2012-06-27 | 中国科学院成都生物研究所 | Multiple sensitive hydrogel material and preparation method thereof |
| CN102813938A (en) * | 2012-09-14 | 2012-12-12 | 扬州大学 | Llex A-cyclodextrin polymer medicine composition for preventing and curing atherosclerosis and preparation method thereof |
| CN106474485A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | A kind of voltage-stimuli responsive type intelligent nano container and preparation method thereof |
| CN106474485B (en) * | 2015-08-28 | 2019-06-21 | 南京理工大学 | A kind of voltage-stimuli responsive type intelligent nano container and preparation method thereof |
| CN105267975A (en) * | 2015-10-10 | 2016-01-27 | 扬州大学 | Preparation method of poly gamma cyclodextrin-paclitaxel supermolecular anticancer drug |
| CN109671966A (en) * | 2018-12-19 | 2019-04-23 | 中国科学技术大学 | The organic fluid cell electrolyte of water system, preparation method and the organic flow battery of water system |
| CN110028601A (en) * | 2019-04-23 | 2019-07-19 | 济宁医学院 | A kind of beta-cyclodextrin derivative, preparation method and the method for preparing supermolecule vesica |
| CN110707327B (en) * | 2019-10-13 | 2020-10-23 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN110707327A (en) * | 2019-10-13 | 2020-01-17 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN110801863A (en) * | 2019-11-12 | 2020-02-18 | 北京单原子催化科技有限公司 | Cyclodextrin-based transition metal monoatomic catalytic material and preparation method thereof |
| CN110801863B (en) * | 2019-11-12 | 2023-03-14 | 北京单原子催化科技有限公司 | Cyclodextrin-based transition metal monoatomic catalytic material and preparation method thereof |
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| CN113527543B (en) * | 2021-06-23 | 2022-12-09 | 西安交通大学 | Aqueous neutral piperidine nitrogen-oxygen free radical organic flow battery electrolyte, battery and preparation method |
| CN113651901A (en) * | 2021-08-20 | 2021-11-16 | 成都工业学院 | Preparation method of water-soluble polymer cyclodextrin |
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| CN113943197A (en) * | 2021-11-10 | 2022-01-18 | 南京理工大学 | Ferrocenyl macrocyclic composite burning rate catalyst and preparation method and application thereof |
| CN113943197B (en) * | 2021-11-10 | 2022-06-28 | 南京理工大学 | Ferrocenyl macrocyclic composite combustion rate catalyst and preparation method and application thereof |
| CN115340634A (en) * | 2022-08-19 | 2022-11-15 | 扬州朗轩科技有限公司 | Host-guest cladding-based monatomic material and preparation method thereof |
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