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CN106083589B - application of nitrogen-containing ordered mesoporous carbon material catalyst in ester exchange synthesis of high-grade β -ketoester - Google Patents

application of nitrogen-containing ordered mesoporous carbon material catalyst in ester exchange synthesis of high-grade β -ketoester Download PDF

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Publication number
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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catalyst
ketoester
nitrogen
reaction
carbon material
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CN106083589A (en
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许杰
马丹
薛冰
柳娜
李永昕
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Changzhou University
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

the patent relates to a reaction for synthesizing high-grade β -ketoester by catalyzing ester exchange reaction of β -ketoester and alcohol by using nitrogen-containing ordered mesoporous carbon (NOMC) as a heterogeneous catalyst, wherein NOMC is used as the catalyst in the reaction, β -ketoester and alcohol are used as raw materials, the reaction temperature is 90-110 ℃, the reaction time is 4-6 h, and the yield of the high-grade β -ketoester can reach 97% to the maximum.

Description

A kind of nitrogen-containing ordered mesopore carbon material catalyst synthesizes in advanced 'beta '-ketoester in transesterification Application
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)

1.一种含氮有序介孔碳材料催化剂在酯交换合成高级β-酮酯中的应用，其特征在于该含氮有序介孔碳材料催化剂的具体使用方法是：1. the application of a nitrogen-containing ordered mesoporous carbon material catalyst in the synthesis of high-grade β-ketoester by transesterification, it is characterized in that the concrete using method of this nitrogen-containing ordered mesoporous carbon material catalyst is: (1)将10–30摩尔份的简单β-酮酯和10摩尔份的醇，2–5摩尔份的含氮有序介孔碳材料催化剂加入到烧瓶中，在90–110℃下反应4–6h；(1) 10–30 molar parts of simple β-ketoester, 10 molar parts of alcohol, 2–5 molar parts of nitrogen-containing ordered mesoporous carbon material catalyst were added to the flask, and reacted at 90–110 °C for 4 –6h; (2)反应完毕后离心分离含氮有序介孔碳材料催化剂；(2) centrifuging the nitrogen-containing ordered mesoporous carbon material catalyst after the reaction is completed; 其中所述的含氮有序介孔碳材料催化剂是通过软模板法一步合成所得，该软模板法是以F127为软模板，均三甲苯为扩孔剂，间氨基苯酚作为碳氮前驱体，乌洛托品提供碱性条件，采用“一锅”软模板法合成的。The nitrogen-containing ordered mesoporous carbon material catalyst is synthesized in one step by a soft template method. The soft template method uses F127 as a soft template, mesitylene as a pore-enlarging agent, and m-aminophenol as a carbon-nitrogen precursor. Urotropine provides alkaline conditions and is synthesized by a "one-pot" soft template method. 2.根据权利要求1所述的一种含氮有序介孔碳材料催化剂在简单β-酮酯和醇酯交换合成高级β-酮酯中的应用，其特征在于所述的简单β-酮酯为乙酰乙酸乙酯或乙酰乙酸甲酯；所述的醇为丁醇、苯甲醇或环己醇；简单β-酮酯与醇的摩尔份数之比为3:2，催化剂与醇的摩尔比2:5。2. The application of a nitrogen-containing ordered mesoporous carbon material catalyst according to claim 1 in the synthesis of higher β-ketoesters by transesterification of simple β-ketoesters and alcohols, characterized in that the simple β-ketones Ester is ethyl acetoacetate or methyl acetoacetate; Described alcohol is butanol, benzyl alcohol or cyclohexanol; The ratio of the mole fraction of simple β-keto ester and alcohol is 3:2, and the mole of catalyst and alcohol ratio of 2:5.
CN201610422837.4A 2016-06-14 2016-06-14 application of nitrogen-containing ordered mesoporous carbon material catalyst in ester exchange synthesis of high-grade β -ketoester Expired - Fee Related CN106083589B (en)

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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

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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
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