CN101974110B - 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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Abstract
一种水溶性二茂铁超分子包合物的制备方法，本发明属于超分子材料技术领域水溶性金属有机材料的制备工艺，先以β-环糊精为原料，在强碱性条件下与环氧氯丙烷发生交联生成β-环糊精聚合物。再以β-环糊精聚合物为主体分子，二茂铁为客体分子，乙二醇为反应溶剂，发生均相超分子反应生成水溶性二茂铁超分子包合物。制备方法操作简便，条件易控，环境污染小，易于工业化。该材料的优点在于不但水溶性高，而且结构稳定，不破坏二茂铁自身的结构。其良好的水溶性使得这种二茂铁超分子包合物可应用于水相电分析化学、生物传感器、水相有机合成、生物医药等领域。A preparation method of a water-soluble ferrocene supramolecular clathrate, the invention belongs to the preparation process of water-soluble metal-organic materials in the technical field of supramolecular materials. Epichlorohydrin cross-links to form β-cyclodextrin polymers. Then take the β-cyclodextrin polymer as the host molecule, ferrocene as the guest molecule, and ethylene glycol as the reaction solvent to generate a water-soluble ferrocene supramolecular clathrate through a homogeneous supramolecular reaction. The preparation method has the advantages of simple operation, easy control of conditions, little environmental pollution and easy industrialization. The material has the advantages of high water solubility and stable structure without destroying the structure of ferrocene itself. Its good water solubility makes the ferrocene supramolecular clathrate applicable to the fields of aqueous phase electroanalytical chemistry, biosensor, aqueous phase organic synthesis, biomedicine and the like.
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 combine the systematism entity of realization high complexity through Intermolecular Forces 26S Proteasome Structure and Function.Main object has special selected property, 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 verivate 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, oleophilicity, electrochemical redox property, therefore all has a wide range of applications in fields such as electroanalytical chemistry, petrochemical complex, macromolecular material, biological medicine, organometallic catalytics.Ferrocene is one type of 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 verivate 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 through 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 penicillium mould, ferrocene cephalo element etc.Ferrocene and verivate thereof also are widely used 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 through in organic phase, ferrocene being carried out organic reaction, obtain some water-soluble ferrocene deriv, the most more complicated of these compound 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 terepthaloyl moietie 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 prone to control, and environmental pollution is little, is easy to industriallization.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 following:
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 absolute ethyl alcohol then and separate out white solid, through filtering, through 50 ℃ of vacuum-dryings, obtain beta cyclo dextrin polymer again.
Beta cyclo dextrin polymer, ferrocene and terepthaloyl moietie 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, filter cake is used absolute ethanol washing, again with solid in 50 ℃ of vacuum-dryings, obtain water-soluble ferrocene super molecule inclusion compound.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer, the present invention is at length explained 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 absolute ethyl 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 terepthaloyl moietie (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, filter cake is used 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 (1)
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 terepthaloyl moietie is reaction solvent, and the reaction of homogeneous phase supramolecule takes place, and generates water-soluble ferrocene super molecule inclusion compound;
It is characterized in that in the said 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 absolute ethyl alcohol then and separate out white solid, through filtering, through 50 ℃ of vacuum-dryings, obtain beta cyclo dextrin polymer again;
Said step 2) in, beta cyclo dextrin polymer, ferrocene and terepthaloyl moietie 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, filter cake is used absolute ethanol washing, again with solid in 50 ℃ of vacuum-dryings, obtain water-soluble ferrocene super molecule inclusion compound.
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| CN113943197B (en) * | 2021-11-10 | 2022-06-28 | 南京理工大学 | A kind of ferrocene-based macrocyclic composite combustion rate catalyst and its preparation method and use |
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