CN103113347B - Method for preparing acetal or ketal under catalytic action of metal-organic frameworks - Google Patents
Method for preparing acetal or ketal under catalytic action of metal-organic frameworks Download PDFInfo
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- CN103113347B CN103113347B CN201310042438.1A CN201310042438A CN103113347B CN 103113347 B CN103113347 B CN 103113347B CN 201310042438 A CN201310042438 A CN 201310042438A CN 103113347 B CN103113347 B CN 103113347B
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Abstract
The invention provides a method for preparing acetal or ketal under the catalytic action of metal-organic frameworks, belonging to the technical field of organic chemistry synthesis. In the acetal or ketal reaction, the mol ratio of aldehyde or ketone to alcohol is 1:(1-6), the molar weight of the metal-organic frameworks calculated on the basis of -SO3H is 10% of the aldehyde or ketone, the reaction temperature is 80-100 DEG C, the reaction time is 1-3 hours, and the reaction pressure is one atmosphere; the temperature is reduced to room temperature after the reaction; and the metal-organic framework catalyst obtained by filtration can be recycled after being subjected to vacuum dehydration at 120 DEG C. The method provided by the invention is environment-friendly; and the catalyst has the advantages of high conversion rate and high selectivity, and can be recycled many times while the catalytic activity is not obviously lowered.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, be specifically related to a kind of method that metallic organic framework compound for catalysis is prepared acetal or ketal.
Background technology
Metallic organic framework compound (MOFs) is a kind of new function material that is subject at present extensive concern, claim again Porous coordination polymer, typically refer to metal ion or metal cluster and organic ligand and form and there is the periodically crystalline material of infinite network structure by self assembling process.It is similar with molecular sieve as heterogeneous solid catalyst, has the duct of systematicness and specific dimensions and the shape of special topological framework, internal arrangement.But in chemical property, metallic organic framework compound is different from inorganic molecule sieve, and its duct consists of jointly metal and organic constituent, and organic molecule and organic reaction are had to larger activity and selectivity.And, prepare the metal ion of metallic organic framework compound and the range of choice of organic ligand is very large, can, according to the performance of material requested, as the size and dimension in duct etc., select suitable metal ion and there is particular functional group and the organic ligand of shape.In addition, its preparation is simple, generally adopts one-step synthesis, i.e. metal ion and organic ligand self-assembly forms, and need not exchange processing, therefore easier than synthesizing of the materials such as inorganic molecule sieve.At present, exploitation has the functional metal organic backbone of catalytic applications prospect, comprise and found active metallic ion site and functionalization organic ligand, become the focus of metallic organic framework compound for catalysis research field, be subject to concern and the favor of domestic and international chemosynthesis man, obtained good achievement.Such as domestic Xu Chunming etc. utilizes metallic organic framework compound after salicylic acid is modified as Schiff's base, with NaAuCl
4synthesized and there is the unsaturated Au of coordination
3+iRMOF-3-SI-Au, and using it as heterogeneous catalyst, apply in phenyl aldehyde, phenylacetylene and piperidines three component linked reactions.Find that this catalyzer has higher catalytic activity and 100% selectivity of product, and can reuse catalytic activity substantially remain unchanged (preparation of Au/MOF catalyzer, sign and catalyzed three-component linked reaction thereof, catalysis journal 3 times, 33 (2012), 833-841); The external people such as Martin Hartmann have synthesized three kinds with-NH by one-step synthesis
2metallic organic framework compound (Al-MIL-101-NH
2, Fe-MIL-101-NH
2and CAU-1), and they apply in the Knoevenagel condensation reaction of phenyl aldehyde and the third two eyeballs or ethyl cyanacetate, and the highest yield of product can reach 95%, and highly selective is 99%.In addition, Al-MIL-101-NH
2can recycle repeatedly, catalytic activity does not obviously reduce (Amino-functionalized basic catalysts with MIL-101 structure, Microporous and Mesoporous Materials, 164 (2012), 38-43).
Aldehydes or ketones reacts with alcohol prepares acetal or ketal is the method for an important carbonyl-protection in organic synthesis, and the method is usually used in the synthetic of steroid, glucide.In addition, acetal can be used as reaction intermediate, can prepare the compound that adopts ordinary method to be difficult to preparation, thereby has further expanded the Application Areas of acetal compound.In traditional method, conventional various inorganic, organic protonic acids, Lewis acid or containing the mixture of the metals such as Rh, Pd and Pt, make the catalyzer of acetal or ketal reaction.But such catalyzer has a lot of shortcomings, such as etching apparatus, difficult separation and recycling and operational condition are complicated, the more important thing is that environmental pollution is serious.Therefore development of new catalyzer just become synthetic family study hotspot.
Summary of the invention
The shortcoming such as the object of the invention is to overcome that the environmental pollution that exists in prior art is serious, severe reaction conditions, product separation difficulty and catalyzer can not recycle, and provide a kind of metallic organic framework compound for catalysis to prepare the method for acetal or ketal.
A kind of metallic organic framework compound for catalysis provided by the present invention is prepared the method for acetal or ketal, and the skeleton symbol of described metallic organic framework compound is:
In formula, n is 3 or 4, and when n=3, metallic organic framework compound is designated as IRMOF-3-1; When n=4, metallic organic framework compound is designated as IRMOF-3-2.Wherein the metal ion of metallic organic framework is Zn ion, and part is the amino terephthalic acid of 2-.
It is as follows that described metallic organic framework compound for catalysis is prepared the method particular content of acetal or ketal:
In acetal or ketal reaction, the mol ratio of aldehydes or ketones used and alcohol is 1:(1-6), with-SO
3the molar weight that H calculates metallic organic framework compound used is 10% of aldehydes or ketones used, temperature of reaction is 80-100 ℃, reaction times is 1-3h, reaction pressure is a normal atmosphere, after reaction, be cooled to room temperature, the metallic organic framework catalyzer obtaining after filtration can recycle after 120 ℃ of vacuum-dryings dewater.
Described aldehydes or ketones is selected from
In a kind of, wherein a is the integer between 0-6; R is a kind of in alkyl, alkoxyl group, nitro, halogen, hydroxyl.
Described alcohol is selected from
In a kind of, wherein b is the integer between 1-6; C is the integer between 0-4; X=O.
The preparation method of the metallic organic framework compound that the present invention is used, see document (Ring-opening reactions within porous metal-organic frameworks, Inorganic Chemistry, 49 (2010), 6387-6389).
The reaction method that the present invention and traditional protonic acid, Lewis acid and acidic ion liquid are made catalyzer is compared has following characteristics:
1, the inventive method is environmentally friendly, and transformation efficiency and selectivity are high, and the simple and catalyzer of technique can be recycled repeatedly and catalytic activity does not have obvious attenuating.
2, the sour density of metallic organic framework compound is high, and catalytic activity is high, and usage quantity is few;
3, catalyzer easy, cheaply operation separated with reaction system;
4, the aperture of catalyzer has shape selective catalysis ability for reactant or product, and reaction preference is higher.
Embodiment:
Embodiment 1: 10mmol butyraldehyde-n, 10mmol 1,3-PD and 20mg IRMOF-3-1 are joined in the single port bottle of 25ml with stirrer and reflux condensing tube.At 80 ℃, vigorous stirring reaction 1h, is cooled under room temperature and filters, and filtrate gas chromatographic detection obtains transformation efficiency 98%, and selectivity is 100%, and productive rate is 98%, and filter residue recycles after 120 ℃ of vacuum-drying 8h dewater.
Embodiment 2: by 10mmol 1-butanone, 10mmol 2,2-dimethyl propylene glycol and 20mg IRMOF-3-1 join respectively in the single port bottle of 25ml with stirrer and prolong.At 90 ℃, vigorous stirring reaction 2h, is cooled under room temperature and filters, and filtrate gas chromatographic detection obtains transformation efficiency 97%, and selectivity is 100%, and productive rate is 97%, and filter residue recycles after 120 ℃ of vacuum-drying 8h dewater.
Embodiment 3: by 10mmol pimelinketone, 10mmol 2,2-dimethyl propylene glycol and 22mg IRMOF-3-2 join respectively in the single port bottle of 25ml with stirrer and prolong.At 100 ℃, vigorous stirring reaction 2h, is cooled under room temperature and filters, and filtrate gas chromatographic detection obtains transformation efficiency 93%, and selectivity is 100%, and productive rate is 93%, and filter residue recycles after 120 ℃ of vacuum-drying 8h dewater.
Embodiment 4: take embodiment 1 as probe reaction, make the active replica test of catalysts, catalyzer is reused 4 times.
The data such as transformation efficiency of embodiment 1-4 reaction are in Table 1.
The aldolization of table 1 IRMOF-3-1 catalysis butyraldehyde-n and 1,3-PD
| Access times | Transformation efficiency (%) | Selectivity (%) | Productive rate (%) |
| 1 | 98 | 100 | 98 |
| 2 | 95 | 100 | 95 |
| 3 | 96 | 100 | 96 |
| 4 | 91 | 100 | 91 |
Claims (3)
1. metallic organic framework compound for catalysis is prepared a method for acetal or ketal, and the skeleton symbol of described metallic organic framework compound is:
In formula, n is 3 or 4, and wherein the metal ion of metallic organic framework is Zn ion, and part is the amino terephthalic acid of 2-, and it is as follows that described metallic organic framework compound for catalysis is prepared the method particular content of acetal or ketal:
In acetal or ketal reaction, the mol ratio of aldehydes or ketones used and alcohol is 1:(1-6), with-SO
3the molar weight that H calculates metallic organic framework compound used is 10% of aldehydes or ketones used, temperature of reaction is 80-100 ℃, reaction times is 1-3h, reaction pressure is a normal atmosphere, after reaction, be cooled to room temperature, the metallic organic framework catalyzer obtaining after filtration can recycle after 120 ℃ of vacuum-dryings dewater.
2. method according to claim 1, is characterized in that described aldehydes or ketones is selected from
In a kind of, wherein a is the integer between 0-6; R is a kind of in alkyl, alkoxyl group, nitro, halogen, hydroxyl.
3. method according to claim 1, is characterized in that described alcohol is selected from
In a kind of, wherein b is the integer between 1-6; C is the integer between 0-4; X=O.
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| CN104084237B (en) * | 2014-07-18 | 2016-01-20 | 山东大学 | A kind of synthetic method of aqueous phase click-reaction catalyst of high efficiency high stable |
| CN104327038B (en) * | 2014-10-15 | 2016-04-27 | 安徽工业大学 | A kind of containing-SO 3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H |
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