CN105854935A - Preparation method of solid alkali catalyst for Knoevenagel reaction - Google Patents
Preparation method of solid alkali catalyst for Knoevenagel reaction Download PDFInfo
- Publication number
- CN105854935A CN105854935A CN201610214744.2A CN201610214744A CN105854935A CN 105854935 A CN105854935 A CN 105854935A CN 201610214744 A CN201610214744 A CN 201610214744A CN 105854935 A CN105854935 A CN 105854935A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- graphene oxide
- preparation
- literary composition
- solid alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a solid alkali catalyst for a Knoevenagel reaction. The catalyst takes graphene oxide and ammonia gas as raw materials; and effective grafting of ammonium ions on the surface of the graphene oxide can be realized through room-temperature gas-solid contact, so that the solid alkali catalyst for the Knoevenagel reaction is obtained. The method is simple to operate and has no influences on the structure of the graphene oxide; the obtained solid alkali catalyst can be continually and circularly utilized after the catalyst reacts and is filtered; and the catalyst is long in service life, good in stability and low in preparation cost. When the prepared solid alkali catalyst is used for the Knoevenagel reaction, a good catalytic effect is obtained.
Description
Technical field
The present invention relates to the preparation field of solid base catalyst, react the preparation method of solid base catalyst particularly to one for brain literary composition lattice (Knoevenagel).
Background technology
Brain literary composition lattice (Knoevenagel) condensation reaction is the reaction that a kind of important " C=C " is formed, and is widely used in preparing α, and beta-unsaturated carbonyl compound, such as spice and the intermediate of medicine.Many application are suffered from fields such as work, agriculture, biological medicine industry.This type of catalyst used by reaction generally can be divided into homogeneous and heterogeneous catalysis.Traditional homogeneous catalyst is mainly organic base, such as fatty amine, aromatic amine etc.；And heterogeneous catalysis is mainly Lewis alkali (such as molecular sieve) and solid alkaline thing.Although homogeneous catalysis and catalytic efficiency are the highest, but this kind of catalyst cannot utilization and recycle, the most economically impractical, but also product purity can be affected, separate to subsequent product and bring huge burden.Heterogeneous catalysis, such as zeolite molecular sieve, although solves catalyst and separates the problem that difficulty is the highest with product purity, but gap is bigger on catalytic performance with homogeneous catalyst.Therefore, generally requiring raising reaction temperature to obtain higher catalysis activity or extend the response time, this can cause again new energy consumption problem.Ionic liquid has the most special physicochemical property, as strong in non-combustible, solvability, good conductivity, good stability etc..As a kind of " green solution ", ionic liquid can have a wide range of applications at numerous areas such as electrochemistry, organic synthesis, catalysis.Having research to be successfully used in brain literary composition reaction grid by ionic liquid, within the shorter response time, productivity nearly reaches 100%.But, ionic liquid equally exists the problem separating difficulty as catalyst.Although also there being document report that by the method for silane coupler, ionic liquid is grafted in pure silicon molecular sieve, such as SBA-15, MCM-41 etc., as the catalyst of brain literary composition reaction grid, the most all obtain preferable catalytic effect.But the template used by silane coupler and synthesis pure silicon molecular sieve is expensive, and the most this method does not the most possess industrial applications prospect.
In sum, a kind of solid catalyst for brain literary composition reaction grid with low cost, that catalyst reclaims and recycles simply, catalysis activity is high is found significant.
Summary of the invention
The technical problem to be solved in the present invention is to reclaim difficulty, high in cost of production defect for current brain literary composition reaction grid used catalyst.
In order to solve the problems referred to above, the present invention provides a kind of solid catalyst preparation method, it is possible to achieve this solid catalyst high catalytic activity in brain literary composition reaction grid, high selectivity, and catalyst reclaims and recycles conveniently, catalyst preparation cost is low, and method is simple.
The technical solution adopted for the present invention to solve the technical problems is:
The solid base catalyst for brain literary composition reaction grid prepared by the present invention is with graphene oxide and ammonia as raw material, and ammonia is passed through at 0-20 DEG C the hermetic container equipped with graphene oxide, stands 10-120min, the most i.e. can be used for being catalyzed brain literary composition reaction grid.
As limitation of the invention, the concentration of ammonia of the present invention is 5%-40% (with the volume ratio of air), and ammonia is 10:1-80:1 with the volume ratio of graphene oxide.
Graphene oxide of the present invention is prepared by the following method:
In ice-water bath, 5g crystalline flake graphite and 2.5g sodium nitrate are mixed homogeneously with the concentrated sulphuric acid of 115mL, stirring is slowly added to 15gKMnO4, keep less than 2 DEG C sustained responses 1h, transfer them to 35 DEG C of water-bath 30min, be gradually added 250mL deionized water, after temperature rises to 98 DEG C of continuation reaction 1h, can substantially observe that mixture is become glassy yellow by sepia.Further continuously dilute, and with the H of mass fraction 30%2O2Solution processes.By above-mentioned solution sucking filtration, with the washing of 5%HCl solution to neutral, filter cake is put in baking oven 80 DEG C and is fully drying to obtain graphite oxide.Take 0.1g graphite oxide and put in 50mL deionized water, supersound process 1.5h (180W, 60Hz), carry out sucking filtration subsequently, filter cake is put into 40 DEG C (10Pa) in vacuum drying oven dry 6h and i.e. obtains required graphene oxide.
The present invention, with graphene oxide as raw material, can realize the effective grafting on graphene oxide of the ammonium radical ion by gas-solid contact under room temperature, thus obtain the solid base catalyst of a kind of function admirable.Concrete advantage has following 2 points:
1. graphene oxide derives from native graphite, and therefore source is wide, and production cost is low, with tradition immobilized AlCl_3 catalyst carrier, compares such as molecular sieve and has obvious price advantage；
2. surface of graphene oxide has a considerable amount of carboxyl functional group, and the reaction of amino and carboxyl is the reaction being very easy in chemical reaction carry out, therefore this reaction is in room temperature, even below all can carry out under conditions of room temperature, and this is that the preparation of catalyst provides energy-saving and cost-reducing probability.(this process uses gas-solid contact can realize the grafting of ammonium radical ion, and the material after ammonia processes can be directly used for being catalyzed brain literary composition reaction grid, it is not necessary to the processing procedure such as be dried, therefore easier in operation)；It is shown below:
The solid catalyst of the present invention is applied to brain literary composition reaction grid, obtains and arrived good effect.In course of reaction, solid catalyst is not only catalyzed activity height, the most i.e. reusable edible, good stability, greatly reduces the preparation cost of catalyst for ester exchange reaction.
Detailed description of the invention
The present invention will be described further with regard to following example, be used however, it should be noted that these embodiments only illustrate, and be not necessarily to be construed as the restriction that the present invention implements.
Embodiment 1
Take 0.25mL graphene oxide and put in 50mL round-bottomed flask, at 20 DEG C, be passed through the ammonia that 50mL concentration is 20%, airtight standing 30min, subsequently gained catalyst be used for brain literary composition reaction grid, be designated as Cat1.
Embodiment 2
Take 0.25mL graphene oxide and put in 50mL round-bottomed flask, at 20 DEG C, be passed through the ammonia that 50mL concentration is 40%, airtight standing 30min, subsequently gained catalyst be used for brain literary composition reaction grid, be designated as Cat2.
Embodiment 3
Take 0.25mL graphene oxide and put in 50mL round-bottomed flask, at 10 DEG C, be passed through the ammonia that 50mL concentration is 5%, airtight standing 120min, subsequently gained catalyst be used for brain literary composition reaction grid, be designated as Cat3.
Embodiment 4
Take 0.25mL graphene oxide and put in 50mL round-bottomed flask, at 0 DEG C, be passed through the ammonia that 50mL concentration is 20%, airtight standing 10min, subsequently gained catalyst be used for brain literary composition reaction grid, be designated as Cat4.
Embodiment 5
Take 0.25mL graphene oxide and put in 50mL round-bottomed flask, at 20 DEG C, be passed through the ammonia that 50mL concentration is 20%, airtight standing 60min, subsequently gained catalyst be used for brain literary composition reaction grid, be designated as Cat5.
The solid base catalyst Cat1-Cat5 that embodiment 1～5 obtains is applied to brain literary composition lattice (Knoevenagel) condensation reaction of Cyanoacetyl-Cyacetazid and benzaldehyde, and reaction equation is as follows:
Concrete operation method is: the Cyanoacetyl-Cyacetazid of 5mmol and the benzaldehyde of 5mmol are joined in two mouthfuls of flasks of 25mL, appropriate n-decane (internal standard) and 5mL acetonitrile (solvent) is added again toward it, add 0.1g catalyst, stir evenly, 50 DEG C of reaction 4h.The sample taken out is analyzed after being performing centrifugal separation on gas chromatograph.
The condition of chromatography is: OV-101 capillary chromatographic column, vaporizer and detector temperature 250 DEG C, column oven temperature 100-180 DEG C temperature programming, determines yield and the selectivity of product, and concrete outcome is as shown in table 1.
The experimental result of table 1 catalysis of solid catalyst brain literary composition reaction grid
| Catalyst | Benzaldehyde conversion ratio (%) | Target product yield (%) |
| Cat1 | 87.6 | 85.5 |
| Cat2 | 91.4 | 87.7 |
| Cat3 | 75.2 | 80.3 |
| Cat4 | 80.9 | 81.4 |
| Cat5 | 82.1 | 84.8 |
As it can be seen from table 1 be applied in brain literary composition reaction grid by the catalyst of the present invention, catalyst all has higher activity.
Using the method filtered to be reclaimed by the solid catalyst in reactant liquor, directly reuse (without dried), it is as shown in table 2 that catalyst Cat 2 reuses result in brain literary composition reaction grid.
The repeat performance result of table 2 catalyst
| Cycle-index | Benzaldehyde conversion ratio (%) | Target product yield (%) |
| 1 | 91.4 | 87.7 |
| 2 | 91.0 | 86.5 |
| 3 | 90.2 | 85.4 |
From table 2 it can be seen that this catalyst is after three times recycle, catalyst activity is basicly stable, illustrates that this catalyst can reuse and not reduce its catalysis activity, has good effect.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, relevant staff can carry out various change and amendment completely in the range of without departing from this invention technological thought.The content that the technical scope of this invention is not limited in description, it is necessary to determine its technical scope according to right.
Claims (2)
1. the preparation method for brain literary composition reaction grid solid base catalyst, it is characterised in that this catalyst
Preparation is with graphene oxide and ammonia as raw material, is passed through ammonia equipped with graphene oxide at 0-20 DEG C
Hermetic container, stands 10-120min, the most i.e. can be used for being catalyzed brain literary composition reaction grid.
A kind of preparation method for brain literary composition reaction grid solid base catalyst, its
The volumetric concentration being characterised by described ammonia is 5%-40%, and ammonia with the volume ratio of graphene oxide is
10:1-80:1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610214744.2A CN105854935A (en) | 2016-04-07 | 2016-04-07 | Preparation method of solid alkali catalyst for Knoevenagel reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610214744.2A CN105854935A (en) | 2016-04-07 | 2016-04-07 | Preparation method of solid alkali catalyst for Knoevenagel reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105854935A true CN105854935A (en) | 2016-08-17 |
Family
ID=56637129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610214744.2A Pending CN105854935A (en) | 2016-04-07 | 2016-04-07 | Preparation method of solid alkali catalyst for Knoevenagel reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854935A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818592A (en) * | 2019-11-26 | 2020-02-21 | 华侨大学 | Tandem reaction synthesis method of 2- (phenylmethylene) malononitrile or derivatives thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120225A (en) * | 1982-12-27 | 1984-07-11 | Mitsubishi Heavy Ind Ltd | Method and apparatus for deodorizing waste gas |
| CN103691471A (en) * | 2013-12-19 | 2014-04-02 | 南开大学 | Preparation method of nitrogen-doped graphene material |
| CN104084230A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of solid catalyst for Knoevenagel reaction |
-
2016
- 2016-04-07 CN CN201610214744.2A patent/CN105854935A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120225A (en) * | 1982-12-27 | 1984-07-11 | Mitsubishi Heavy Ind Ltd | Method and apparatus for deodorizing waste gas |
| CN103691471A (en) * | 2013-12-19 | 2014-04-02 | 南开大学 | Preparation method of nitrogen-doped graphene material |
| CN104084230A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of solid catalyst for Knoevenagel reaction |
Non-Patent Citations (2)
| Title |
|---|
| LINFEI LAI等: "Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction", 《ENERGY ENVIRON. SCI.》 * |
| 黄志桂等: "《有机化学》", 30 June 1999, 西南师范大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818592A (en) * | 2019-11-26 | 2020-02-21 | 华侨大学 | Tandem reaction synthesis method of 2- (phenylmethylene) malononitrile or derivatives thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104084230B (en) | A kind of preparation method reacting solid catalyst for Knoevenagel | |
| CN104368384B (en) | A kind of preparation method for the Knoevenagel organic diamine modified graphene oxide solid catalysts reacted | |
| CN104069882A (en) | Method for preparing carbon-nitrogen material loaded nano metal catalyst | |
| CN103191780A (en) | Functionalized carbon nitride photocatalyst capable of performing catalytic oxidization on benzene to synthesize phenol | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN110280238A (en) | A kind of carbon quantum dot@MIL-125-NH2The preparation method and applications of/Pt photochemical catalyst | |
| CN109970555A (en) | The preparation method of electron level n propyl propionate | |
| CN105521825A (en) | Catalyst for preparing phenol by benzene oxidation and preparation method and application thereof | |
| CN105854935A (en) | Preparation method of solid alkali catalyst for Knoevenagel reaction | |
| CN114436893B (en) | Production process of deuterated acetonitrile | |
| CN111875493A (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN107790191B (en) | Preparation method of solid acid catalyst for cyclohexanone and ethylene ketal reaction | |
| CN106905161B (en) | A kind of synthetic method of 2- chlorine-4-fluorine-5-nitro benzoic acid | |
| CN108499592A (en) | One kind being used for CO2Catalyst of cycloaddition reaction and preparation method thereof | |
| CN107694610A (en) | A kind of phase transfer catalyst for cyclohexanol synthesizing cyclohexanone and preparation method thereof | |
| CN113416114A (en) | Method for preparing 2-chloro-4-fluoro-trichlorotoluene by catalyzing photochlorination of 2-chloro-4-fluorotoluene through supported phosphorus trichloride | |
| CN109369476A (en) | A kind of preparation method of medicine intermediate parachloroben-zenesulfonyl chloride | |
| CN102070404B (en) | Method for synthesizing 3,4-hexanediol through photocatalysis | |
| CN104945223B (en) | A kind of method that load molecular sieve catalysis toluene synthesizes ortho-chlorotolu'ene | |
| CN108080027A (en) | A kind of resin catalyst treatment process of liquid phase Beckmann rearrangement caprolactam | |
| CN105289722B (en) | It is a kind of for catalyst of ester exchange Catalysts of Preparing Methyl Ethyl Carbonate and preparation method thereof | |
| CN104646053B (en) | A kind of preparation method and applications of solid super acid catalyst | |
| LU501713B1 (en) | Biomass-based Carbon-silicon Material Supported Heteropoly Acid Catalyst and Preparation Method and Application Thereof | |
| CN107556188A (en) | A kind of method of phase-transfer Wittig reaction benzyl ester | |
| CN109437168B (en) | Graphene hydrogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160817 |