CN106083589B - A kind of nitrogen-containing ordered mesopore carbon material catalyst synthesizes the application in advanced 'beta '-ketoester in transesterification - Google Patents
A kind of nitrogen-containing ordered mesopore carbon material catalyst synthesizes the application in advanced 'beta '-ketoester in transesterification Download PDFInfo
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- CN106083589B CN106083589B CN201610422837.4A CN201610422837A CN106083589B CN 106083589 B CN106083589 B CN 106083589B CN 201610422837 A CN201610422837 A CN 201610422837A CN 106083589 B CN106083589 B CN 106083589B
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- C07—ORGANIC CHEMISTRY
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- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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Abstract
This patent is related to being catalyzed the reaction that simple 'beta '-ketoester synthesizes advanced 'beta '-ketoester with the ester exchange reaction of alcohol as heterogeneous catalyst using nitrogen-containing ordered mesopore carbon (NOMC).The reaction is using NOMC as catalyst, and using 'beta '-ketoester and alcohol as raw material, reaction temperature is 90-110 DEG C, and the reaction time is 4-6h, and the yield of advanced 'beta '-ketoester reaches as high as 97%.Compared with homogeneous catalyst common before catalysis reaction, have many advantages, such as catalyst recycling and convenient product separation.
Description
Technical field
The invention belongs to heterogeneous catalysis fields, and in particular to one kind is using nitrogen-containing ordered mesopore carbon as catalyst, catalysis letter
The method that single 'beta '-ketoester and alcohol transesterification reaction prepare advanced 'beta '-ketoester.
Background technique
'beta '-ketoester is a kind of important intermediate in Chemical Manufacture.'beta '-ketoester can be used as Material synthesis thiolactone mycin
(thiolactomycin), the biochemical reagents such as prostaglandin (prostaglandin), conjunction carpel sour (syncarpic acid).
Transesterification is the universal synthesis method of 'beta '-ketoester, that is, uses simple 'beta '-ketoester (such as formyl acetic acid ethyl ester and ethyl acetoacetate)
Transesterification occurs with higher alcohol and synthesizes advanced 'beta '-ketoester and rudimentary alcohol.Reaction equation is as shown below, wherein R1=H,
CH3；R2=CH3, C2H5；R3≥C2H5。
Since the ester exchange reaction of 'beta '-ketoester and alcohol is the reaction of chemical kinetics control, generally required in actually synthesis
Catalyst is added to improve the rate of the reaction, so as to shorten the time of reaction.Current developed catalyst system can be divided into
Homogeneous catalyst and heterogeneous catalyst.By taking homogeneous catalyst as an example, Wang etc. (Tetrahedron Letters, 2003,34,
5037-5039) use ionic liquid and sulfamic acid as synergistic catalyst, the ester exchange reaction for 'beta '-ketoester and alcohol.As a result
Display: when the ratio between ester and alcohol are 5:6, reaction temperature is 80 DEG C, and after 3-4.5h of reaction time, the conversion ratio of 'beta '-ketoester is up to
95% or more.In addition, the reports such as Ribeiro are catalyzed ethyl acetoacetate using methenamine (Synthesis, 2007,61-64)
73% is up to the yield of 1- isopropyl, 5- methyl cyclohexanol, target product.Although above-mentioned catalyst has high reactivity
It is not easy to carry out the recycling of catalyst and again but since catalyst and reactant/product are in same phase with highly selective advantage
It is multiple to utilize, while in the presence of many difficult in terms of product separation and purification.
Compared to homogeneous catalyst, heterogeneous catalyst has many advantages, such as catalyst/product separation is simple.Kantam etc.
Organic base is anchored on mesopore silicon oxide MCM-41 material by (Catalysis Letters, 1999,62,67-69).In acetyl
In the transesterification of ethyl acetate and n-butanol, butanol high conversion rate is up to 100%.It should be noted that the caltalyst ties up to conjunction
It needs at middle using expensive silane coupling agent, and catalyst preparation cost is very high.Recently, this seminar (Catalysis
Science&Technology, 2014,4,2126-2133) report uses methenamine for presoma, mesoporous SBA-15
As hard mould agent, mesoporous carbonitride has been synthesized.Using it as heterogeneous catalyst, in the transesterification of ethyl acetoacetate, performance
Preferable catalytic activity out.But the mesoporous carbonitride is prepared by nanometer casting method, manufacturing cycle is very long, Er Qiezhong
Between be related to removing template process.In addition, Madje et al. report uses B2O3/ZrO2Transesterification as catalyst 'beta '-ketoester is anti-
It answers.The high income of its target product 'beta '-ketoester in 110 DEG C, reaction time 3h, the reaction of methyl acetoacetate and cyclohexanol
Up to 78%.The deficiencies of although catalytic activity of this metal oxide is very high, and there are metallic pollutions.In consideration of it, it is necessary to
A kind of efficient heterogeneous catalyst is designed and developed to be catalyzed the reaction.
Nitrogen-containing ordered mesopore carbon material (NOMC) has very high specific surface area, uniform adjustable mesoporous pore size (2-
50nm).In recent years, NOMC absorption with separate, be catalyzed, gas storage, electrochemistry, energy storage and conversion, or even biological cure
The various fields such as medicine highlight wide application prospect.Due to being rich in a large amount of amido functional group, NOMC is undoubtedly a kind of typical case
Catalyzed by solid base.NOMC belongs to non-metal catalyst, avoids metallic pollution in catalysis reaction.Secondly, NOMC is solid,
It can be used as heterogeneous catalyst in liquid-phase reaction system.Up to the present, document and patent report is not had to be catalyzed β-using NOMC
The ester exchange reaction of ketone ester and alcohol.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to urging currently used for the catalyst of 'beta '-ketoester and alcohol transesterification reaction
Change the problems such as activity is low, expensive, stability is poor, metallic pollution, a kind of catalytic activity is provided and product yield is higher, reaction
After separate simple and reuse the good novel catalyst of effect.
In order to solve the above technical problems, the technical solution adopted by the present invention is that being catalyzed β -one as catalyst using NOMC
The ester exchange reaction of ester and alcohol synthesizes advanced 'beta '-ketoester.
NOMC preparation method used in the present invention be according to Su Dangsheng (Chemical Communications, 2014,
50,9182-9184) synthesis step carries out.NOMC is using F127 as soft template, and mesitylene is as expanding agent, amino
Phenol provides alkaline condition as carbon nitrogen presoma, methenamine, synthesizes the invention institute using easy " one pot " soft template method
Catalyst n OMC material.
Above-mentioned prepared catalyst is applied in the ester exchange reaction of 'beta '-ketoester and alcohol, specific reaction condition and step
It is as follows:
(1) by the alcohol of the 'beta '-ketoester of 10-30 molar parts and 10 molar parts, the catalyst of 2-5 molar parts is added in flask,
4-6h are reacted at 90-110 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product is through gas chromatographic analysis, target product, i.e., advanced 'beta '-ketoester
Yield be 60-97%.
As to of the invention preferred, simple 'beta '-ketoester of the present invention is ethyl acetoacetate and acetoacetate first
Ester, wherein it is preferred that ethyl acetoacetate.The alcohol is higher alcohol (such as butanol, benzyl alcohol and cyclohexanol), wherein it is preferred that fourth
Alcohol.110 DEG C of reaction condition preferable temperature, reaction time 6h.
As limitation of the invention further, the ratio between molfraction of 'beta '-ketoester and alcohol of the present invention is 3:2, is urged
The molar ratio 2:5 of agent and higher alcohol.
After adopting the above technical scheme, the present invention and common catalyst such as strong acid, highly basic, the catalyst phase such as ionic liquid
Than having the advantage that
(1) NOMC is the solid catalyst of no metal, does not have metallic pollution in reaction process, and after reaction, letter
After single separation of solid and liquid, it can reuse.
(2) yield of 'beta '-ketoester is 65-97%.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1
(1) by the butanol of the ethyl acetoacetate of 30 molar parts and 10 molar parts, the catalyst of 4 molar parts is added to flask
In, 6h is reacted at 110 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product through gas chromatographic analysis, target product butyl-acetoacetate
Yield is 97%.
Embodiment 2
(1) by the butanol of the ethyl acetoacetate of 30 molar parts and 10 molar parts, the catalyst of 4 molar parts is added to flask
In, 4h is reacted at 110 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product through gas chromatographic analysis, target product butyl-acetoacetate
Yield is 90%.
Embodiment 3
(1) by the butanol of the ethyl acetoacetate of 25 molar parts and 10 molar parts, the catalyst of 3 molar parts is added to flask
In, 6h is reacted at 100 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product through gas chromatographic analysis, target product butyl-acetoacetate
Yield is 85%.
Embodiment 4
(1) by the butanol of the ethyl acetoacetate of 30 molar parts and 10 molar parts, the catalyst of 2 molar parts is added to flask
In, 4h is reacted at 110 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product through gas chromatographic analysis, target product butyl-acetoacetate
Yield is 76%.
Embodiment 5
(1) by the benzyl alcohol of the ethyl acetoacetate of 30 molar parts and 10 molar parts, the catalyst of 4 molar parts is added to burning
In bottle, 6h is reacted at 100 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product is through gas chromatographic analysis, target product acetoacetate benzene methyl
Yield be 75%.
Embodiment 6
(1) by the cyclohexanol of the ethyl acetoacetate of 30 molar parts and 10 molar parts, the catalyst of 4 molar parts is added to burning
In bottle, 5h is reacted at 100 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product is through gas chromatographic analysis, target product acetoacetate cyclohexyl
Yield be 65%.
Embodiment 7
(1) by the cyclohexanol of the methyl acetoacetate of 20 molar parts and 10 molar parts, the catalyst of 5 molar parts is added to burning
In bottle, 4h is reacted at 110 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product is through gas chromatographic analysis, target product acetoacetate cyclohexyl
Yield be 67%.
Embodiment 8
(1) by the cyclohexanol of the ethyl acetoacetate of 10 molar parts and 10 molar parts, the catalyst of 2 molar parts is added to burning
In bottle, 4h is reacted at 90 DEG C.
(2) it is centrifugated catalyst after completion of the reaction.Product is through gas chromatographic analysis, target product acetoacetate cyclohexyl
Yield be 66%.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (2)
1. a kind of nitrogen-containing ordered mesopore carbon material catalyst synthesizes the application in advanced 'beta '-ketoester in transesterification, it is characterised in that should
The specifically used method of nitrogen-containing ordered mesopore carbon material catalyst is:
(1) by the alcohol of the simple 'beta '-ketoester of 10-30 molar parts and 10 molar parts, the nitrogen-containing ordered mesopore carbon material of 2-5 molar parts
Catalyst is added in flask, and 4-6h are reacted at 90-110 DEG C；
(2) it is centrifugated nitrogen-containing ordered mesopore carbon material catalyst after completion of the reaction；
Wherein the nitrogen-containing ordered mesopore carbon material catalyst is as obtained by soft template method one-step synthesis, which is
Using F127 as soft template, mesitylene is expanding agent, and for m-aminophenol as carbon nitrogen presoma, methenamine provides alkaline item
Part, using the synthesis of " one pot " soft template method.
2. a kind of nitrogen-containing ordered mesopore carbon material catalyst according to claim 1 is closed in simple 'beta '-ketoester and alcohol transesterification
At the application in advanced 'beta '-ketoester, it is characterised in that the simple 'beta '-ketoester is ethyl acetoacetate or methyl acetoacetate；
The alcohol is butanol, benzyl alcohol or cyclohexanol；The ratio between molfraction of simple 'beta '-ketoester and alcohol is 3:2, catalyst and alcohol
Molar ratio 2:5.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102320589A (en) * | 2011-05-20 | 2012-01-18 | 天津大学 | Preparation of ordered mesoporous carbon doped with nitrogen atom and preparation and application in immobilized laccase sensor thereof |
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| CN102320589A (en) * | 2011-05-20 | 2012-01-18 | 天津大学 | Preparation of ordered mesoporous carbon doped with nitrogen atom and preparation and application in immobilized laccase sensor thereof |
Non-Patent Citations (3)
| Title |
|---|
| Highly Ordered Mesoporous Carbon Nitride Nanoparticles with High Nitrogen Content: A Metal-Free Basic Catalyst;Xin Jin等;《Angew. Chem.》;20091231;第121卷;第8024-8027页 |
| Synthesis of nitrogen-containing ordered mesoporous carbon as a metal-free catalyst for selective oxidation of ethylbenzene;Jia Wang等;《ChemComm》;20140704;第50卷;第9182-9184页 |
| Transesterification of ethylacetoacetate catalysed by metal free mesoporous carbon nitride;Chokkalingam Anand等;《Catalysis Today》;20120830;第204卷;第164-169页 |
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