CN107935831B - Method for catalyzing aldol condensation reaction by copper salt - Google Patents
Method for catalyzing aldol condensation reaction by copper salt Download PDFInfo
- Publication number
- CN107935831B CN107935831B CN201711279884.9A CN201711279884A CN107935831B CN 107935831 B CN107935831 B CN 107935831B CN 201711279884 A CN201711279884 A CN 201711279884A CN 107935831 B CN107935831 B CN 107935831B
- Authority
- CN
- China
- Prior art keywords
- aldol condensation
- condensation reaction
- reactor
- benzaldehyde
- reaction
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing aldol condensation reaction by copper salt, which takes copper halide as a catalyst to catalyze benzaldehyde and butanone to generate 3-methyl-4-phenyl-3-butene-2-ketone through the aldol condensation reaction under the condition of low temperature and normal pressure. The method has the advantages of cheap and easily-obtained raw materials, mild conditions, low environmental pollution and easy separation of products, avoids the use of strong corrosive reagents such as hydrochloric acid, sodium hydroxide and the like in the prior industrial aldol condensation reaction, and is beneficial to large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of thermocatalytic organic synthesis, and particularly relates to a method for catalyzing aldol condensation reaction by copper salt.
Background
Aldol condensation is the reaction of a compound containing an active alpha-hydrogen atom, such as aldehyde, ketone, carboxylic acid, ester, and the like, undergoing nucleophilic addition with a carbonyl compound under the action of a catalyst to obtain beta-hydroxyaldehyde or acid, or further dehydrating to obtain alpha, beta-unsaturated aldehyde ketone or acid ester. Intermolecular aldol condensation is often used to synthesize some β -hydroxy compounds, which can be further used to produce polymers such as perfumes, drugs, etc.; the condensation dehydration product alpha, beta-unsaturated aldehyde is oxidized to obtain corresponding carboxylic acid which is widely used as raw materials for fine chemical production, such as preparation of polyester, photosensitive resin and liquid crystal. Therefore, the development of new and highly efficient aldol condensation reactions has long been of great interest to chemical researchers.
The traditional method for industrially carrying out aldol condensation reaction is to use a basic catalyst or an acidic catalyst, but the two methods have the remarkable disadvantages of harsh reaction conditions, complex reaction system, high cost, high pollution, low selectivity, difficult separation of products and the like. Meanwhile, the aldol condensation reaction is accompanied by a plurality of side reactions in the reaction process, alpha, beta-unsaturated aldehyde can be obtained by carrying out the aldol condensation reaction by using two different aldehyde factors, if two reactants have active alpha-hydrogen, four mixed products can be obtained, but most of the products are difficult to separate, so the value is lower. Therefore, the key to the success of the industrial application of the reaction is to reduce the reaction selectivity and improve the yield and purity of the target product. Attempts have been made to select new catalytic systems for direct aldol condensation to become a breakthrough in this reaction.
Disclosure of Invention
The invention aims to provide a method for catalyzing aldol condensation reaction by copper salt, which has the advantages of simple system, mild reaction conditions and high selectivity, and solves the problems of high pollution, high cost and difficult separation existing in the prior industrial preparation of 3-methyl-4-phenyl-3-buten-2-one.
In order to achieve the purpose, the invention adopts the following technical scheme:
a copper salt catalyzed aldol condensation reaction method uses copper halide (CuCl)2Or CuBr2) As a catalyst, benzaldehyde and butanone are catalyzed to generate 3-methyl-4-phenyl-3-butylene-2-ketone through aldol condensation reaction under the condition of low temperature and normal pressure; the method specifically comprises the following steps:
1) putting copper halide into a reactor, adding 0.1-1mmol of benzaldehyde and 1-2mL of butanone, and uniformly mixing;
2) the reactor is placed in an ultrasonic cleaner for ultrasonic treatment for 30s, and then is placed in a heat collection type constant temperature magnetic stirrer for heating reaction for 7h at 70 ℃.
Wherein the dosage of the copper halide is 0.05 to 0.4 time of the molar weight of the benzaldehyde.
The ultrasonic treatment frequency is 40 KHz.
The invention has the advantages that:
(1) according to the invention, copper halide is used as a catalyst for low-temperature catalysis, so that the aldol condensation reaction of benzaldehyde and butanone can be carried out under the conditions of milder temperature and relatively lower temperature, and the copper halide after the reaction can be recycled after being treated, so that the cost is reduced, and the copper halide is more environment-friendly.
(2) The method adopts copper salt as a catalyst, has mild reaction conditions, and can effectively avoid pollution caused by using strong acid, strong base or heavy metal in the prior industrial aldol condensation reaction.
(3) The method has the advantages of simple and easy operation, good repeatability, simple reaction process, environmental friendliness, contribution to large-scale industrial production and suitability for popularization and application.
(4) The method can be further used for modifying organic compounds with biological activity, and has good practical application prospect and economic benefit.
Drawings
FIG. 1 is a graph showing the relationship between the amount ratio of the catalyst to the substrate and the yield of 3-methyl-4-phenyl-3-buten-2-one.
FIG. 2 is a graph showing the variation of the reaction time with respect to the yield of 3-methyl-4-phenyl-3-buten-2-one.
FIG. 3 is a graph showing the number of cycles of copper bromide dihydrate as a function of the yield of 3-methyl-4-phenyl-3-buten-2-one.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The mass spectrum detection is carried out by adopting a GC-MS 5977A mass spectrometer, and the used chromatographic column is HP-5MS (5% polymethyl silicane fixing solution, the specification is 30 m multiplied by 0.32 mm multiplied by 0.25 mu m) and is quantitatively analyzed by a GC Agilent 7890B chromatograph FID detector.
Example 1
(1) Weighing 1mmol of different salts as catalysts in sequence, adding 2mL of butanone and 0.5mmol of benzaldehyde, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer to react for 7h at 70 ℃;
(3) after the reaction was completed, the reaction mixture was centrifuged, and the supernatant was subjected to mass spectrometry, and the results are shown in Table 1.
TABLE 1 Effect of different kinds of catalysts on product yield
As can be seen from Table 1, cupric bromide has the strongest catalytic ability.
Example 2
(1) Weighing 1mmol of copper bromide dihydrate as a catalyst, adding 2mL of different organic solvents, 2mL of butanone and 0.5mmol of benzaldehyde, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer to react for 7h at 70 ℃;
(3) after the reaction was completed, the reaction mixture was centrifuged, and the supernatant was subjected to mass spectrometry, and the results are shown in Table 2.
TABLE 2 Effect of different solvents on product yield
As can be seen from Table 2, the yield was highest without the addition of the solvent.
Example 3
(1) Weighing different amounts of copper bromide dihydrate as a catalyst, adding 2mL of butanone and 0.5mmol of benzaldehyde, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer to react for 7h at 70 ℃;
(3) after the reaction is completed, the reaction mixture is centrifuged, and the supernatant is subjected to mass spectrometry, and the obtained result is shown in FIG. 1.
As can be seen from fig. 1, the yield of the product was high when the ratio of copper bromide dihydrate to benzaldehyde was 0.05 to 0.4, with the highest yield of the product when the ratio of copper bromide dihydrate to benzaldehyde was 0.2.
Example 4
(1) Weighing 1mmol of copper bromide dihydrate as a catalyst, adding 2mL of butanone and 0.5mmol of reactants, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer for reaction at 70 ℃ for a period of time;
(3) after the reaction is completed, the reaction mixture is centrifuged, and the supernatant is subjected to mass spectrometry, and the obtained result is shown in FIG. 2.
As can be seen from FIG. 2, the yield was highest when the reaction time reached 7h, while the yield decreased rather when heating was continued to 8 h.
Example 5
(1) Weighing 1mmol of copper bromide dihydrate as a catalyst, adding 2mL of butanone and 0.5mmol of benzaldehyde, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer to react for 7h at 70 ℃;
(3) and (4) centrifuging after the reaction is completed, and carrying out mass spectrum detection on the supernatant. Performing primary analysis on a GC-MS spectrogram of the supernatant; and further through1The hydrogen spectrum of the product was analyzed by H NMR spectrum.
GC showed a retention time of 7.9 min; MS: 43(15%),91(8.1%),115(55%),145(10%),159 (base peak).1H NMR(400MHz,CDCl3): 7.60-7.33 (m, 5H, Ar), 2.45(s,3H),2.05(d,3H, J =1.5 Hz). The compound obtained was confirmed to be 3-methyl-4-phenyl-3-buten-2-one.
Example 6
(1) Weighing 1mmol of copper bromide dihydrate as a catalyst, adding 2mL of butanone and 0.5mmol of benzaldehyde, and uniformly mixing in a reactor;
(2) putting the reactor into an ultrasonic cleaner, carrying out ultrasonic treatment for 30s at 40KHz, and then putting the reactor into a heat collection type constant temperature magnetic stirrer to react for 7h at 70 ℃;
(3) centrifuging after the reaction is completed, and taking 2 mu l of supernatant for mass spectrometric detection;
(4) and (4) continuously adding benzaldehyde into the residual liquid in the step (3) to keep the total amount of benzaldehyde at 0.5mmol, introducing oxygen for about 2h under stirring at room temperature, and then performing recycling experiment, namely repeating the operations of the steps (1) to (4) for 5 times.
The results show that the nmr spectrum of the obtained supernatant is consistent with that obtained in example 5; as can be seen from FIG. 3, the copper bromide dihydrate is stable in property, the yield of 3-methyl-4-phenyl-3-buten-2-one is not greatly influenced by the recycling of the copper bromide dihydrate, and the copper bromide dihydrate still has a good catalytic effect after being recycled for 5 times.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A method for catalyzing aldol condensation reaction by copper salt is characterized by comprising the following steps: copper halide is used as a catalyst to catalyze benzaldehyde and butanone to generate 3-methyl-4-phenyl-3-butene-2-one through aldol condensation reaction under the condition of low temperature and normal pressure; which comprises the following steps:
1) putting copper halide into a reactor, adding 0.1-1mmol of benzaldehyde and 1-2mL of butanone, and uniformly mixing;
2) putting the reactor into an ultrasonic cleaner for ultrasonic treatment for 30s, and then putting the reactor into a heat collection type constant temperature magnetic stirrer for heating reaction for 7h at 70 ℃;
the copper halide is CuBr2。
2. The method of claim 1, wherein the copper salt catalyzes aldol condensation reaction, and wherein: the dosage of the copper halide is 0.05 to 0.4 times of the molar weight of the benzaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279884.9A CN107935831B (en) | 2017-12-06 | 2017-12-06 | Method for catalyzing aldol condensation reaction by copper salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279884.9A CN107935831B (en) | 2017-12-06 | 2017-12-06 | Method for catalyzing aldol condensation reaction by copper salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107935831A CN107935831A (en) | 2018-04-20 |
| CN107935831B true CN107935831B (en) | 2020-12-25 |
Family
ID=61945028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711279884.9A Active CN107935831B (en) | 2017-12-06 | 2017-12-06 | Method for catalyzing aldol condensation reaction by copper salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107935831B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818548A (en) * | 2019-11-21 | 2020-02-21 | 江西华宇香料化工有限公司 | Method for preparing benzylidene acetone |
| CN112425610A (en) * | 2021-01-22 | 2021-03-02 | 深圳市洛奇机电科技有限公司 | Preparation system and application of pesticide suspending agent for preventing and treating kaffir lily leaf spot disease |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009050345A1 (en) * | 2009-10-22 | 2011-06-01 | Süd-Chemie AG | Preparing alpha, beta-unsaturated carbonyl compounds, comprises reacting aldehydes and/or ketones in the presence of hydrotalcite catalyst and preparing the hydrotalcite catalyst |
| CN104987284A (en) * | 2015-06-16 | 2015-10-21 | 天长市天佳化工科技有限公司 | Organic nonlinear optical compound chalcone dibromide synthetic method |
| CN106810519A (en) * | 2015-12-02 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method for being catalyzed aldol reaction |
-
2017
- 2017-12-06 CN CN201711279884.9A patent/CN107935831B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| "RuCl3 Catalyses Aldol Condensations of Aldehydes and Ketones";Nasser Iranpoor et al;《Tetrahedron》;19980611;第54卷;第9478页Table-2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107935831A (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Palladium-catalyzed direct oxidation of alkenes with molecular oxygen: general and practical methods for the preparation of 1, 2-diols, aldehydes, and ketones | |
| Howell | Asymmetric and diastereoselective conjugate addition reactions: C–C bond formation at large scale | |
| Panish et al. | A Mixed‐Ligand Chiral Rhodium (II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B | |
| Azizi et al. | Natural deep eutectic salt promoted regioselective reduction of epoxides and carbonyl compounds | |
| Palmisano et al. | Heck reactions with very low ligandless catalyst loads accelerated by microwaves or simultaneous microwaves/ultrasound irradiation | |
| Wiles et al. | Solid‐Supported Gallium Triflate: An Efficient Catalyst for the Three‐Component Ketonic Strecker Reaction | |
| CN107935831B (en) | Method for catalyzing aldol condensation reaction by copper salt | |
| Vivekanand et al. | Sonocatalyzed synthesis of 2-phenylvaleronitrile under controlled reaction conditions–A kinetic study | |
| Ashfeld et al. | Features and applications of [Rh (CO) 2Cl] 2-catalyzed alkylations of unsymmetrical allylic substrates | |
| Ammar et al. | Green condensation reaction of aromatic aldehydes with active methylene compounds catalyzed by anion-exchange resin under ultrasound irradiation | |
| Laroche et al. | Basic anion-exchange resin-catalyzed aldol condensation of aromatic ketones with aldehydes in continuous flow | |
| Kuhwald et al. | Matteson reaction under flow conditions: iterative homologations of terpenes | |
| Lan et al. | On the Mechanism of the Palladium Catalyzed Intramolecular Pauson− Khand-Type Reaction | |
| Fulton et al. | Global Diastereoconvergence in the Ireland–Claisen Rearrangement of Isomeric Enolates: Synthesis of Tetrasubstituted α-Amino Acids | |
| CN108002968B (en) | Method for preparing carboxylic acid compounds by oxidizing and breaking carbon-carbon bonds of ketone compounds | |
| CN109456161A (en) | A kind of method of visible light catalytic oxidation fracture carbon-carbon bond | |
| Titova et al. | Metal oxides and silica as efficient catalysts for the preparative organic chemistry | |
| Chen et al. | Chiral vanadyl (V) complexes enable efficient asymmetric reduction of β-ketoamides: application toward (S)-duloxetine | |
| Srivastava et al. | Catalytic investigations of calix [4] arene scaffold based phase transfer catalyst | |
| CN109746042B (en) | Catalyst for synthesizing 3-methoxy methyl acrylate and solid-supported and using method | |
| CN103626810A (en) | Method for catalyzing glucose by using magnetic solid acid to produce methyl glucoside | |
| CN113698337B (en) | Preparation method of alpha-oxo acetophenone compound | |
| Wiles et al. | Evaluation of the heterogeneously catalyzed Strecker reaction conducted under continuous flow | |
| CN111701621B (en) | Synthesis of coordination type zirconium o-benzenetrisol and application of coordination type zirconium o-benzenetrisol in preparation of cyclohexanol | |
| Wang et al. | Kinetic study of dichlorocyclopropanation of 4-vinyl-1-cyclohexene by a novel multisite phase transfer catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |