CN103159722B - Method for synthesizing coumarin compound under catalysis of multi-sulfonate acidic ionic liquid - Google Patents
Method for synthesizing coumarin compound under catalysis of multi-sulfonate acidic ionic liquid Download PDFInfo
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- CN103159722B CN103159722B CN201310086908.4A CN201310086908A CN103159722B CN 103159722 B CN103159722 B CN 103159722B CN 201310086908 A CN201310086908 A CN 201310086908A CN 103159722 B CN103159722 B CN 103159722B
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Abstract
The invention provides a method for synthesizing a coumarin compound under the catalysis of a multi-sulfonate acidic ionic liquid, belonging to the technical field of organic chemical synthesis. The method provided by the invention comprises the following steps: reacting raw materials, wherein the mol ratio of phenol and ethyl acetoacetate used as the raw materials is 1:1, the molar weight of a multi-sulfonate acidic ionic liquid catalyst accounts for 2-5% of the used phenol or ethyl acetoacetate, the reaction temperature is 80-110 DEG C, the reaction time is 50-120 minutes, and the reaction pressure is one atmosphere; after the reaction, cooling to room temperature, and filtering; and recrystallizing the filter residue with anhydrous ethanol, thus obtaining the coumarin compound, wherein the multi-sulfonate acidic ionic liquid catalyst in the filtrate can be recycled after being dried and dewatered in vacuum at 110 DEG C. Compared with the traditional synthesis method using protonic acid, Lewis acid and other acidic ionic liquids as catalysts, the method provided by the invention has high yield, and ensures that the catalyst is low in consumption and can be recycled after being subjected to simple treatment.
Description
Technical field:
The invention belongs to organic chemical synthesis technical field, be specifically related to a kind of method of many sulfonate radicals presence of acidic ionic liquid catalyst synthesizing coumarin compounds.
Background technology:
Coumarin kind compound has anticoagulation, antitumor, step-down, anti-cell hyperplasia, antibacterial, anti-AIDS, antifatigue and strengthens the effects such as autoimmunization ability.At present, coumarin kind compound can synthesize by methods such as Pechmann, Perkin and Knoevenagel condensation reactions, and wherein Pechmann condensation reaction method is most widely used.Be to find new catalysis process and catalyzer to the emphasis of coumarin kind compound preparation research in recent years, conventional catalyzer has sulfuric acid, P
2o
5, PPA and AlCl
3deng.But above-mentioned catalyzer often can cause selectivity of product poor, and yield is lower, and has the disadvantage such as etching apparatus, contaminate environment.
Acidic ion liquid due to have good thermostability, vapour pressure extremely low, organic and mineral compound are had good solubility, the acidic site being evenly distributed and are easily applied to the advantage such as product separation recovery in the synthesizing of coumarin kind compound.Such as external Manikrao M.Salunkhe etc. is with Lewis acidic ion liquid 1-butyl-3-Methylimidazole chloro-aluminate ([Bmim] Cl2AlCl
3) make catalyzer, tonka bean camphor and derivative thereof have been prepared in Pechmann condensation reaction by various phenols and methyl aceto acetate, this reaction has short and productive rate high (the Coumarin syntheses via Pechmann condensation in Lewis acidic chloroaluminate ionic liquid of mild condition, reaction times, Tetrahedron Letters, 2001,42:9285-9287).Meet water for fear of above-mentioned Lewis acidic ion liquid and occur to decompose the shortcoming that causes structural changes and can not recycle, use waterproof
it is a good selection that acidic ion liquid replaces Lewis acidic ion liquid.Based on this, domestic Zhou Zhanzhou etc. are taking methyl aceto acetate and phenol compound as raw material, at microwave and acidic ion liquid [Bmim] HSO
4under (1-butyl-3-Methylimidazole hydrosulfate ionic liquid) condition, synthesize multiple coumarin derivatives by Pechmann method of condensing, the method is compared with traditional method, get rid of the use of organic solvent, shorten the reaction times and productive rate is higher, it is simple, the eco-friendly synthetic method of a kind of condition (study on the synthesis of coumarin kind compound under microwave and ionic liquid condition, pharmacy practice magazine, 27 (6): 448-450).In addition, in order to improve the acidity of acidic ion liquid and then to reduce the consumption of acidic ion liquid in reaction, Chen Zhuo etc. utilize the acid stronger acidic ion liquid [C with a sulfonate radical
3sO
3hmim] HSO
4as the solvent catalyzer of holding concurrently, under microwave condition, effectively catalysis substituted phenol react with methyl aceto acetate and prepared 4-methylcoumarin and derivative (the solvent-free 4-of the catalyzing and synthesizing methylcoumarin of sulfonic functional ion liquid and derivative thereof under microwave radiation, fine chemistry industry, 2012,29 (8): 770-773).In order 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 made catalyzer, obtain various coumarin kind compounds by Pechmann condensation reaction high yield, and ionic liquid can be recycled at least 5 times, its catalytic activity slightly reduces (Synthesis of coumarins via Pechmann reaction in water catalyzed by acyclic acidic ionic liquids, Catalysis Letters, 2008,121:255-259).
Summary of the invention:
The object of the invention is to overcome that the environmental pollution that exists in prior art is serious, severe reaction conditions, product separation difficulty, catalyzer usage quantity and recycle all shortcomings such as very large of middle number of dropouts, a kind of method of many sulfonate radicals presence of acidic ionic liquid catalyst synthesizing coumarin compounds is provided.
The structural formula of many sulfonate radicals acidic ion liquid used in the present invention is:
In formula, n is 3 or 4.In the time of n=3, acidic ion liquid is designated as IL-SO
3h-1; In the time of n=4, acidic ion liquid is designated as IL-SO
3h-2.
The method of a kind of many sulfonate radicals presence of acidic ionic liquid catalyst synthesizing coumarin compounds provided by the present invention, its reaction formula is:
The mol ratio of wherein reacting Raw phenol and methyl aceto acetate is 1:1, the molar weight that contains many sulfonate radicals acidic ionic liquid catalysts is the 2-5% of phenol used or methyl aceto acetate, temperature of reaction is 80-110 DEG C, reaction times is 50-120min, reaction pressure is 1 normal atmosphere, after reaction, be cooled to room temperature, reaction product filtered filtration residue is obtained to coumarin kind compound with dehydrated alcohol recrystallization, and the many sulfonate radicals acidic ionic liquid catalysts in filtrate can recycle after 110 DEG C of vacuum-dryings dewater.
The present invention's phenol used is any in Resorcino, o-phenol, pyrogallol, Phloroglucinol monomethyl ether, m-methyl phenol, meta-methoxy phenol, hydroxyanisole, para-chlorophenol, m-nitrophenol, ortho chloro phenol, m-Chlorophenol, naphthyl alcohol.
The preparation method of the present invention's many sulfonate radicals acidic ion liquid used, see following pertinent literature (Synthesis of a novel multi – SO3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis, 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 makes catalyzer with traditional protonic acid, Lewis acid and other acidic ion liquid, there is following characteristics:
1, the sour density that contains 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, catalyzer can recycle after simple process, and catalytic efficiency does not have obvious reduction.
Embodiment
Embodiment 1: by 20mmol Resorcino, 20mmol methyl aceto acetate and 0.4mmol IL-SO
3h-1 joins in the single port bottle of 50mL with stirrer and reflux condensing tube.At 80 DEG C, vigorous stirring reaction 50min, is cooled under room temperature and filters, and filter residue obtains corresponding coumarin kind compound 3.35g with ethyl alcohol recrystallization, and productive rate is 95%, and filtrate recycles after 110 DEG C of vacuum-drying 8h dewater.
Embodiment 2: by 20mmol Phloroglucinol monomethyl ether, 20mmol methyl aceto acetate and 0.5mmol IL-SO
3h-1 joins respectively in the single port bottle of 50mL with stirrer and reflux condensing tube.At 80 DEG C, vigorous stirring reaction 1h, is cooled under room temperature and filters, and filter residue obtains corresponding coumarin kind compound 3.54g with ethyl alcohol recrystallization, and productive rate is 92%, and filtrate recycles after 110 DEG C of vacuum-drying 8h dewater.
Embodiment 3: by 20mmol naphthyl alcohol, 20mmol methyl aceto acetate and 0.8mmol IL-SO
3h-2 joins respectively in the single port bottle of 50mL with stirrer and reflux condensing tube.At 110 DEG C, vigorous stirring reaction 2h, is cooled under room temperature and filters, and filter residue obtains corresponding coumarin kind compound 3.28g with ethyl alcohol recrystallization, and productive rate is 78%, and filtrate recycles after 110 DEG C of vacuum-drying 8h dewater.
Embodiment 4: taking embodiment 1 as probe reaction, make the active replica test of catalysts, catalyzer is reused 4 times, and its catalysis productive rate changes in table 1.
Table 1IL-SO
3the reaction of H-1 catalysis Resorcino and methyl aceto acetate synthesizing coumarin compounds
| IL-SO 3H-1 access times | Coumarin kind compound productive rate (%) |
| 1 | 95 |
| 2 | 93 |
| 3 | 95 |
| 4 | 92 |
Claims (2)
1. a method for the presence of acidic ionic liquid catalyst of sulfonate radical more than synthesizing coumarin compounds, is characterized in that the method is specific as follows:
The Pechmann reaction Raw phenol of synthesizing coumarin compounds and the mol ratio of methyl aceto acetate are 1:1, the molar weight that contains many sulfonate radicals acidic ionic liquid catalysts is the 2-5% of phenol used or methyl aceto acetate, temperature of reaction is 80-110 DEG C, reaction times is 50-120min, reaction pressure is 1 normal atmosphere, after reaction, be cooled to room temperature, reaction product filtered filtration residue is obtained to coumarin kind compound with dehydrated alcohol recrystallization; The described structural formula that contains many sulfonate radicals acidic ion liquid is:
In formula, n is 3 or 4; Described phenol is any in Resorcino, o-phenol, pyrogallol, Phloroglucinol monomethyl ether, m-methyl phenol, meta-methoxy phenol, hydroxyanisole, para-chlorophenol, m-nitrophenol, ortho chloro phenol, m-Chlorophenol.
2. the method for a kind of many sulfonate radicals presence of acidic ionic liquid catalyst synthesizing coumarin compounds according to claim 1, is characterized in that the many sulfonate radicals acidic ionic liquid catalysts in filtrate can recycle after 110 DEG C of vacuum-dryings dewater after described filtration.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348487A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of multi-sulfonic functional ion liquid |
| WO2009157020A1 (en) * | 2008-06-23 | 2009-12-30 | Delhi University | Coumarin compounds for the treatment of cardiovascular diseases and process for preparing the same |
| CN102311414A (en) * | 2011-07-01 | 2012-01-11 | 广东石油化工学院 | Method for synthesizing 7-hydroxy-4-methylcoumarin with solvent-free catalysis of ionic liquid |
| CN102584569A (en) * | 2011-12-15 | 2012-07-18 | 北京林业大学 | Method for preparing diphenolic acid in ionic liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4658512B2 (en) * | 2004-04-27 | 2011-03-23 | 日本臓器製薬株式会社 | Coumarin derivative and Maillard reaction inhibitor containing the derivative |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157020A1 (en) * | 2008-06-23 | 2009-12-30 | Delhi University | Coumarin compounds for the treatment of cardiovascular diseases and process for preparing the same |
| CN101348487A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of multi-sulfonic functional ion liquid |
| CN102311414A (en) * | 2011-07-01 | 2012-01-11 | 广东石油化工学院 | Method for synthesizing 7-hydroxy-4-methylcoumarin with solvent-free catalysis of ionic liquid |
| 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 (6)
| Title |
|---|
| JP特开2005-314240A 2005.11.10 |
| N-甲基吡咯烷酮硫酸氢盐催化合成7-羟基-4-甲基香豆素;滕俊江 等;《化工进展》;20120630;第31卷(第6期);1321-1324 * |
| Shirin Safaei,等.Application of a multi-SO3H Bronsted acidic ionic liquid in water: a highly efficient and reusable catalyst for the regioselective and scaled-up synthesis of pyrazoles under mild conditions.《RSC Advances》.2012,第2卷5610-5616. * |
| 微波促进下新型离子液体催化的香豆素无溶剂合成研究;翁璐丹 等;《广东化工》;20111130;第38卷(第11期);34-35 * |
| 滕俊江 等.N-甲基吡咯烷酮硫酸氢盐催化合成7-羟基-4-甲基香豆素.《化工进展》.2012,第31卷(第6期),1321-1324. |
| 翁璐丹 等.微波促进下新型离子液体催化的香豆素无溶剂合成研究.《广东化工》.2011,第38卷(第11期),34-35. |
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