CN103193607A - 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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- CN103193607A CN103193607A CN2013100869224A CN201310086922A CN103193607A CN 103193607 A CN103193607 A CN 103193607A CN 2013100869224 A CN2013100869224 A CN 2013100869224A CN 201310086922 A CN201310086922 A CN 201310086922A CN 103193607 A CN103193607 A CN 103193607A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 the organic chemical synthesis technical field, be specifically related to the method for a kind of many sulfonate ions liquids catalytic preparation phenyl styryl ketone and derivative.
Background technology:
Phenyl styryl ketone is a kind of flavonoid compound, be that the natural compounds of parent is present in the plants such as Radix Glycyrrhizae, safflower with it, be the precursor of synthetic flavones in the plant materials, have very strong pharmacological action, show as anti-oxidant, antitumor, anti-inflammatory activity, anti-liver virus, effect such as antibiotic.At present, this compounds has been widely used in the treatment of common diseases such as cardiovascular disorder, cancer, disease of immune system, and simultaneously, it also is a kind of important organic synthesis intermediate, can be used for the synthetic of fine chemicals such as spices and medicine.Phenyl styryl ketone and derivative thereof adopt the Claisen-Schmidt condensation reaction under highly basic or the 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 causes selectivity of product relatively poor through regular meeting, and yield is lower, and has disadvantages such as etching apparatus, contaminate environment.Therefore, the environment-friendly preparation method thereof of exploitation phenyl styryl ketone and derivative thereof becomes the important topic of current common concern.
Acidic ion liquid, particularly bronsted acid ionic liquid owing to have green non-pollution, to organicly having good solubility, the acidic site that is evenly distributed with mineral compound, being easy to that product separates and advantage such as can be recycled is used in the preparation of phenyl styryl ketone and derivative.Such as Shen Jianghan etc. with the imidazoles that contains sulfonate radical or pyridinium salt acidic ion liquid as the solvent catalyzer of holding concurrently, catalysis efficiently phenyl aldehyde and methyl phenyl ketone by the Claisen-Schmidt condensation reaction prepare phenyl styryl ketone (
Acidic ionic liquids as dual catalyst and solvent for environmentally friendly synthesis of chalcone, Journal of Molecular Catalysis A:Chemical, 2008,280:24-28; A kind of method of using ionic liquid synthesizing chalcone and derivative thereof, CN101289378A).Above-mentioned owing to the expense of using glyoxaline ion liquid to produce in order to reduce, Qian Hua etc. use sulfation N, N, N-triethyl-N-fourth sulfonic acid ammonium salt ionic liquids etc. are as catalyzer, obtain various phenyl styryl ketone and derivative by Claisen-Schmidt condensation reaction high yield, and ionic liquid can be recycled 5 times at least, its catalytic activity has reduction (Synthesis of chalcones via Claisen-Schmidt reaction catalyzed by sulfonic acid-functional ionic liquids, Industrial﹠amp slightly; Engineering Chemistry Research, 2011,50:1146-1149).In order further to reduce the preparation expense of ionic liquid, Fang Dong etc. use sulfation N, N, N-trimethylammonium-N-propanesulfonic acid ammonium salt ionic liquid is as catalyzer, under the condition of no solvent effectively catalytic preparation various phenyl styryl ketone and derivative (Synthesis of chalcones via Claisen-Schmidt condensation reaction catalyzed by acyclic acidic ionic liquids thereof, Catalysis Communications, 2008,9:1924-1927).
Summary of the invention:
The objective of the invention is to overcome that the environmental pollution that exists in the prior art is serious, severe reaction conditions, product separation difficulty, catalyzer usage quantity and recycle in the equal shortcoming such as very big of number of dropouts, 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:
N is 3 or 4 in the formula.When n=3, acidic ion liquid is designated as IL-SO
3H-a; When n=4, acidic ion liquid is designated as IL-SO
3H-b.
The method of a kind of many sulfonate ions liquid catalyst catalytic preparation phenyl styryl ketone provided by the present invention and derivative, its Claisen-Schmidt condensation reaction formula is:
Wherein the mol ratio of raw ketone (I) and aldehyde (II) is 1:1 in the reaction, the molar weight of many sulfonate ions liquid catalyst is the 8-10% of used ketone or aldehyde, temperature of reaction is 120-140 ℃, reaction times is 8-20h, reaction pressure is 1 normal atmosphere, reaction back standing demix obtains product phenyl styryl ketone and derivative behind the upper strata product recrystallization of telling.The lower floor that tells contains many sulfonate ions liquid catalyst and can recycle behind 110 ℃ of vacuum drying treatment 2h.
The used ketone (I) of the present invention is any in methyl phenyl ketone, 4-methoxyacetophenone, the acetone.
The used aldehyde (II) of the present invention is any in phenyl aldehyde, 4-methoxybenzaldehyde, 3-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-chlorobenzaldehyde, the 4-chlorobenzaldehyde.
Method of the present invention, wherein said Claisen-Schmidt condensation reaction is reflected under nitrogen or the argon shield to be carried out.
The preparation method of many sulfonate ions liquid that the present invention is used sees pertinent literature (Synthesis of a novel multi – SO
3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis, Green Chemistry, 12 (2010), 201-204; A kind of preparation method of multi-sulfonic functional ion liquid, CN101348487A).
The synthetic method that the present invention and traditional protonic acid, Lewis acid and other acidic ion liquid are made catalyzer is compared has following characteristics:
1, the sour density height that contains many sulfonate radicals acidic ion liquid, the catalytic activity height;
2, the catalyzer usage quantity few and recycle in loss amount also less;
3, catalyzer is more convenient with separating of reaction product, can separate by modes such as decants.
Embodiment
Embodiment 1: under nitrogen protection with 10mmol phenyl aldehyde, 10mmol methyl phenyl ketone and 0.8mmol IL-SO
3H-a joins 50mL and has in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 120 ℃, and reaction 8h is cooled to room temperature, is divided into two-layerly after reaction soln leaves standstill, and tells upper solution by decant, and it is 94% that recrystallization purifying can get 1,3-phenylbenzene-2-propylene-1-ketone (phenyl styryl ketone) productive rate.Contain IL-SO
3Lower floor's solution of H-a can be recycled after through 110 ℃ of vacuum-drying 2h.
Embodiment 2: under nitrogen protection with 10mmol4-methoxybenzaldehyde, 10mmol methyl phenyl ketone and 1mmol IL-SO
3H-a joins 50mL and has in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 140 ℃, and reaction 9h is cooled to room temperature, is divided into two-layerly after reaction soln leaves standstill, and tells upper solution by decant, and it is 90% that recrystallization purifying can get 4-methoxyl group phenyl styryl ketone productive rate.Contain IL-SO
3Lower floor's solution of H-a can be recycled after through 110 ℃ of vacuum-drying 2h.
Embodiment 3: under argon shield with 10mmol3-chlorobenzaldehyde, 10mmol methyl phenyl ketone and 1mmol IL-SO
3H-b joins 50mL and has in the there-necked flask of stirrer and reflux condensing tube.Vigorous stirring is warming up to 140 ℃, and reaction 8h is cooled to room temperature, is divided into two-layerly after reaction soln leaves standstill, and tells upper solution by decant, and it is 87% that recrystallization purifying can get 3-chlorine phenyl styryl ketone productive rate.Contain IL-SO
3Lower floor's solution of H-b can be recycled after through 110 ℃ of vacuum-drying 2h.
Embodiment 4: be probe reaction with embodiment 1, make the active replica test of catalysts, catalyzer is reused 4 times.The productive rate data of reaction see Table 1.
Table 1IL-SO
3The reaction of the synthetic phenyl styryl ketone of H-a catalysis phenyl aldehyde and methyl phenyl ketone
| IL-SO 3The H-a access times | Phenyl styryl ketone productive rate (%) |
| 1 | 94 |
| 2 | 92 |
| 3 | 93 |
| 4 | 90 |
Claims (4)
1. sulfonate ion liquid catalyst more than a kind prepares the method for phenyl styryl ketone and derivative, it is characterized in that this method is specific as follows:
Prepare that the mol ratio of raw material aldehyde and ketone is 1:1 in the Claisen-Schmidt condensation reaction of described phenyl styryl ketone and derivative, the molar weight of many sulfonate ions liquid catalyst is the 8-10% of used ketone or aldehyde, temperature of reaction is 120-140 ℃, reaction times is 8-20h, reaction pressure is 1 normal atmosphere, reaction back standing demix obtains product phenyl styryl ketone and derivative behind the upper strata product recrystallization of telling; The described structural formula that contains many sulfonate ions liquid is:
N is 3 or 4 in the formula.
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 ketone is any in methyl phenyl ketone, 4-methoxyacetophenone, the acetone.
3. 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 aldehyde is any in phenyl aldehyde, 4-methoxybenzaldehyde, 3-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-chlorobenzaldehyde, the 4-chlorobenzaldehyde.
4. 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 carries out under nitrogen or argon shield.
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| CN201310086922.4A CN103193607B (en) | 2013-03-18 | 2013-03-18 | Method for preparing chalcone and directive through multi-sulfonate ion liquid catalysis |
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| CN201310086922.4A CN103193607B (en) | 2013-03-18 | 2013-03-18 | Method for preparing chalcone and directive through multi-sulfonate ion liquid catalysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566234A (en) * | 2015-12-24 | 2016-05-11 | 南阳市天华制药有限公司 | Quinocetone preparation method |
| CN107162970A (en) * | 2017-06-30 | 2017-09-15 | 马鞍山市泰博化工科技有限公司 | A kind of ionic liquid-catalyzed synthesis dihydro 4 of 2 aryl 2,3 of highly acidity（1H）The method of qualone derivative |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289378A (en) * | 2007-04-18 | 2008-10-22 | 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 |
| CN101927182A (en) * | 2010-07-05 | 2010-12-29 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
| CN102584569A (en) * | 2011-12-15 | 2012-07-18 | 北京林业大学 | Method for preparing diphenolic acid in ionic liquid |
-
2013
- 2013-03-18 CN CN201310086922.4A patent/CN103193607B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289378A (en) * | 2007-04-18 | 2008-10-22 | 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 |
| CN101927182A (en) * | 2010-07-05 | 2010-12-29 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
| CN102584569A (en) * | 2011-12-15 | 2012-07-18 | 北京林业大学 | Method for preparing diphenolic acid in ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| XUEZHENG LIANG等: "Synthesis of a novel multi –SO3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis", 《GREEN CHEM.》, vol. 12, 27 November 2009 (2009-11-27) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566234A (en) * | 2015-12-24 | 2016-05-11 | 南阳市天华制药有限公司 | Quinocetone preparation method |
| CN107162970A (en) * | 2017-06-30 | 2017-09-15 | 马鞍山市泰博化工科技有限公司 | A kind of ionic liquid-catalyzed synthesis dihydro 4 of 2 aryl 2,3 of highly acidity（1H）The method of qualone derivative |
| 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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| CN103193607B (en) | 2015-03-04 |
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