CN103193607B - Method for preparing chalcone and directive through multi-sulfonate ion liquid catalysis - Google Patents
Method for preparing chalcone and directive through multi-sulfonate ion liquid catalysis Download PDFInfo
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- CN103193607B CN103193607B CN201310086922.4A CN201310086922A CN103193607B CN 103193607 B CN103193607 B CN 103193607B CN 201310086922 A CN201310086922 A CN 201310086922A CN 103193607 B CN103193607 B CN 103193607B
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Abstract
The invention provides a method for preparing chalcone and a directive through multi-sulfonate ion liquid catalysis, and belongs to the technical field of organic chemistry synthesis. In the condensation reaction of the method, the mole ratio of raw material aldehyde to ketone is 1:1, the molar weight of a multi-sulfonic acid group ion liquid catalyst is 8%-10% of the used ketone or aldehyde, the reaction temperature is 120-140 DEG C, the reaction time is 8-20 hours, the reaction pressure is 1 atmospheric pressure, an upper layer product separated through standing layering after the reaction is recrystallized to obtain products, namely the chalcone and the derivative; and a separated lower layer which contains the multi-sulfonate ion liquid catalyst can be subjected to vacuum drying treatment at 110 DEG C for 2 hours and then can be recycled. Compared with the traditional preparation method which takes bronsted acid, Lewis acid and other acidic ion liquids as catalysts, the method provided by the invention has the advantages that catalytic activity is high, catalyst usage amount is small, the separation of the catalyst and the products is simple and convenient, the catalyst is recycled, and the catalytic activity of the catalyst is not obviously reduced.
Description
Technical field:
The invention belongs to organic chemical synthesis technical field, be specifically related to the method that phenyl styryl ketone and derivative are prepared in the catalysis of a kind of many sulfonate ions liquids.
Background technology:
Phenyl styryl ketone is a kind of flavonoid compound, the natural compounds being parent with it is present in the plant such as Radix Glycyrrhizae, safflower, be the precursor of synthesis flavones in plant materials, there is very strong pharmacological action, show as the effects such as anti-oxidant, antitumor, anti-inflammatory activity, anti-liver are viral, antibacterial.At present, this compounds has been widely used in the treatment of the common diseases such as cardiovascular disorder, cancer, disease of immune system, and meanwhile, it is also a kind of important organic synthesis intermediate, can be used for the synthesis of the fine chemicals such as spices and medicine.Phenyl styryl ketone and derivative thereof adopt the Claisen-Schmidt condensation reaction under highly basic or strong acid to be prepared usually, and these acid or alkali comprise AlCl
3, dense H
2sO
4, solid super-strong acid, solid alkali etc.But the use of above-mentioned strong acid, alkali catalyst often can cause selectivity of product poor, and yield is lower, and there is the disadvantage such as etching apparatus, contaminate environment.Therefore, the environment-friendly preparation method thereof developing phenyl styryl ketone and derivative thereof becomes the important topic of current common concern.
Acidic ion liquid, particularly bronsted acid ionic liquid owing to having green non-pollution, to organicly there is good solubility, the acidic site be evenly distributed with mineral compound, be easy to product and be separated and can be recycled etc. advantage and being used in the preparation of phenyl styryl ketone and derivative.Such as Shen Jianghan etc. hold concurrently using the imidazoles containing sulfonate radical or pyridinium salt acidic ion liquid as solvent catalyzer, the phenyl aldehyde of catalysis efficiently and methyl phenyl ketone by Claisen-Schmidt condensation reaction prepare phenyl styryl ketone (
acidic ionicliquids as dual catalyst and solvent for environmentally friendly synthesis of chalcone, Journal of Molecular Catalysis A:Chemical, 2008,280:24-28; Use a method for ionic liquid synthesizing chalcone and derivative thereof, CN101289378A).In order to reduce the above-mentioned expense produced owing to using glyoxaline ion liquid, Qian Hua etc. use sulfation N, N, N-triethyl-N-fourth sulfonic acid ammonium salt ionic liquids etc. are as catalyzer, various phenyl styryl ketone and derivative is obtained by Claisen-Schmidt condensation reaction high yield, and ionic liquid can be recycled at least 5 times, its catalytic activity (Synthesis ofchalcones via Claisen-Schmidt reaction catalyzed by sulfonic acid-functional ionicliquids in a slight decrease, Industrial & Engineering Chemistry Research, 2011, 50:1146-1149).In order to reduce the preparation expense of ionic liquid further, Fang Dong etc. use sulfation N, N, N-trimethylammonium-N-propanesulfonic acid Ammonium Salt Ionic Liquid is as catalyzer, under condition of no solvent, various different phenyl styryl ketone and derivative (Synthesis of chalcones via Claisen-Schmidt condensation reactioncatalyzed by acyclic acidic ionic liquids thereof have been prepared in catalysis effectively, Catalysis Communications, 2008,9:1924-1927).
Summary of the invention:
The object of the invention is to overcome that the environmental pollution existed in prior art is serious, severe reaction conditions, product separation difficulty, catalyzer usage quantity and recycle the shortcomings such as middle number of dropouts is all very large, provide a kind of many sulfonate ions liquid catalyst to prepare the method for phenyl styryl ketone and derivative.
The structural formula of many sulfonate ions liquid used in the present invention is:
In formula, n is 3 or 4.As n=3, acidic ion liquid is designated as IL-SO
3h-a; As n=4, acidic ion liquid is designated as IL-SO
3h-b.
The method of phenyl styryl ketone and derivative is prepared in a kind of many sulfonate ions liquid catalyst provided by the present invention catalysis, and its Claisen-Schmidt condensation reaction formula is:
Wherein reacting Raw ketone (I) is 1:1 with the mol ratio of aldehyde (II), the molar weight of many sulfonate ions liquid catalyst is the 8-10% of ketone used or aldehyde, temperature of reaction is 120-140 DEG C, reaction times is 8-20h, reaction pressure is 1 normal atmosphere, stratification after reaction, obtains product phenyl styryl ketone and derivative after the upper strata product recrystallization separated.The lower floor separated contains many sulfonate ions liquid catalyst and can recycle after 110 DEG C of vacuum drying treatment 2h.
The present invention's ketone (I) used is methyl phenyl ketone, any one in 4-methoxyacetophenone, acetone.
The present invention's aldehyde (II) used is phenyl aldehyde, any one in 4-methoxybenzaldehyde, m-methoxybenzaldehyde, Benzaldehyde,2-methoxy, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde.
Method of the present invention, wherein said Claisen-Schmidt condensation reaction reaction is carried out under nitrogen or argon.
The preparation method of many sulfonate ions liquid that the present invention is used, is shown in pertinent literature (Synthesis of anovel multi – SO
3h functionalized ionic liquid and its catalytic activities for biodieselsynthesis, Green Chemistry, 12 (2010), 201-204; A preparation method for multi-sulfonic functional ion liquid, CN101348487A).
Compared with the synthetic method that the present invention and traditional protonic acid, Lewis acid and other acidic ion liquid make catalyzer, there is following characteristics:
1, the sour density containing many sulfonate radicals acidic ion liquid is high, and catalytic activity is high;
2, catalyzer usage quantity is few and to recycle middle loss amount also less;
3, the segregation ratio of catalyzer and reaction product is more convenient, can be separated by modes such as decants.
Embodiment
Embodiment 1: under nitrogen protection by 10mmol phenyl aldehyde, 10mmol methyl phenyl ketone and 0.8mmolIL-SO
3h-a joins 50mL with in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 120 DEG C, and reaction 8h, is cooled to room temperature, and reaction soln is divided into two-layer after leaving standstill, separate upper solution by decant, it is 94% that recrystallization purifying can obtain benzylideneacetophenone (phenyl styryl ketone) productive rate.Containing IL-SO
3lower floor's solution of H-a can be recycled after 110 DEG C of vacuum-drying 2h.
Embodiment 2: under nitrogen protection by 10mmol4-methoxybenzaldehyde, 10mmol methyl phenyl ketone and 1mmol IL-SO
3h-a joins 50mL with in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 140 DEG C, and reaction 9h, is cooled to room temperature, and reaction soln is divided into two-layer after leaving standstill, separate upper solution by decant, it is 90% that recrystallization purifying can obtain 4-methoxy chalcones productive rate.Containing IL-SO
3lower floor's solution of H-a can be recycled after 110 DEG C of vacuum-drying 2h.
Embodiment 3: by 10mmol3-chlorobenzaldehyde, 10mmol methyl phenyl ketone and 1mmolIL-SO under argon shield
3h-b joins 50mL with in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 140 DEG C, and reaction 8h, is cooled to room temperature, and reaction soln is divided into two-layer after leaving standstill, separate upper solution by decant, it is 87% that recrystallization purifying can obtain 3-chlorine phenyl styryl ketone productive rate.Containing IL-SO
3lower floor's solution of H-b can be recycled after 110 DEG C of vacuum-drying 2h.
Embodiment 4: with embodiment 1 for probe reaction, make the active replica test of catalysts, catalyzer reuses 4 times.The yield data of reaction is in table 1.
Table 1IL-SO
3the reaction of H-a catalysis phenyl aldehyde and methyl phenyl ketone synthesis phenyl styryl ketone
| IL-SO 3H-a access times | Phenyl styryl ketone productive rate (%) |
| 1 | 94 |
| 2 | 92 |
| 3 | 93 |
| 4 | 90 |
Claims (2)
1. the liquid catalyst of sulfonate ion more than prepares a method for phenyl styryl ketone and derivative, it is characterized in that the method is specific as follows:
Prepare the Claisen-Schmidt condensation reaction Raw aldehyde of described phenyl styryl ketone and derivative and the mol ratio of ketone is 1:1, the molar weight of many sulfonate ions liquid catalyst is the 8-10% of ketone used or aldehyde, temperature of reaction is 120-140 DEG C, reaction times is 8-20h, reaction pressure is 1 normal atmosphere, stratification after reaction, obtains product phenyl styryl ketone and derivative after the upper strata product recrystallization separated; The described structural formula containing many sulfonate ions liquid is:
In formula, n is 3 or 4; Described aldehyde is any one in phenyl aldehyde, 4-methoxybenzaldehyde, 3-chlorobenzaldehyde, and described ketone is methyl phenyl ketone.
2. a kind of many sulfonate ions liquid catalyst according to claim 1 prepares the method for phenyl styryl ketone and derivative, it is characterized in that described Claisen-Schmidt condensation reaction is carried out under nitrogen or argon.
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| CN105566234A (en) * | 2015-12-24 | 2016-05-11 | 南阳市天华制药有限公司 | Quinocetone preparation method |
| CN107162970B (en) * | 2017-06-30 | 2019-12-20 | 马鞍山市泰博化工科技有限公司 | Method for synthesizing 2-aryl-2, 3-dihydro-4 (1H) -quinolinone derivative under catalysis of high-acidity ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101289378B (en) * | 2007-04-18 | 2011-04-20 | 中国科学院大连化学物理研究所 | Process for synthesizing chalcone and derivates thereof by using ion liquid |
| CN101348487A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of multi-sulfonic functional ion liquid |
| CN101927182B (en) * | 2010-07-05 | 2012-11-07 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
| CN102584569B (en) * | 2011-12-15 | 2015-01-14 | 北京林业大学 | Method for preparing diphenolic acid in ionic liquid |
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