CN103145630B - Method for catalytically synthesizing quinoxaline compound - Google Patents

Method for catalytically synthesizing quinoxaline compound Download PDF

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CN103145630B
CN103145630B CN201310086879.1A CN201310086879A CN103145630B CN 103145630 B CN103145630 B CN 103145630B CN 201310086879 A CN201310086879 A CN 201310086879A CN 103145630 B CN103145630 B CN 103145630B
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reaction
compound
catalyst
quinoxaline
quinoxaline compound
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CN103145630A (en
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岳彩波
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for catalytically synthesizing a quinoxaline compound and belongs to the technical field of organic chemical synthesis. According to the method, in the condensation reaction of quinoxaline compound synthesis, the molar ratio of raw materials, namely o-phenylenediamine to a 1, 2-dicarbonyl compound is 1:1, the molar amount of a multi-sulfonic acid radical ionic liquid catalyst accounts for 5-10% of the molar amount of used o-phenylenediamine or the 1, 2-dicarbonyl compound, the reaction temperature is 40-60 DEG C, the reaction time is 20-120 minutes, the usage amount of water serving as a reaction solvent accounts for 50-90% of the total mass of the materials, and the reaction pressure is 1 atmosphere; and filtration is carried out after reaction is ended, and residues are washed by water and then are recrystallized by alcohol to obtain the pure quinoxaline compound, wherein the multi-sulfonic acid radical ionic liquid and unreacted raw materials in filtrate can be recycled for 5 times without needing treatment. Compared with other synthetic methods in which ionic liquid is taken as the catalyst, the method has the characteristics of high catalytic activity, little usage amount of the catalyst, recycling of the catalyst, little loss of the catalyst, high catalytic yield and the like.

Description

A kind of method catalyzing and synthesizing quinoxaline compound
Technical field:
The invention belongs to organic chemical synthesis technical field, be specifically related to a kind of method catalyzing and synthesizing quinoxaline compound.
Background technology:
Quinoxaline compound is the important nitrogenous Benzoheterocyclic compounds of a class, has numerous biological activity and applies widely.Many quinoxaline compounds have the biological activitys such as antibacterial, anticancer, and the quinoxaline compound of some functionalization is expected to be used as organic semiconductor, chemical switch and Supramolecular Receptors.Therefore, the preparation of quinoxaline compound comes into one's own day by day.Under normal circumstances, quinoxaline compound can carry out catalysis preparation in organic solvent by O-Phenylene Diamine and 1,2-dicarbonyl compound, and wherein organic solvent is as acetonitrile, ethanol, acetic acid, and corresponding catalyzer is CuSO 45H 2o, Ga (OTf) 3and I 2.But the use of above-mentioned organic solvent, catalyzer often can bring the disadvantage such as etching apparatus, contaminate environment, therefore, the green synthesis method developing quinoxaline compound becomes the important topic of current common concern.
Ionic liquid, as a kind of green solvent and catalyzer, has environmental friendliness, is easy to the advantages such as recycling, be widely used in synthesizing quinoxaline compounds.As Madhukar Deshmukh etc. utilizes ionic liquid [C 8dabco] Br as catalyzer, high productivity 3 (the Proficient synthesis of quinoxaline andphthalazinetrione derivatives using [C that synthesized various quinoxaline compound and ionic liquid can be recycled in aqueous phase 8dabco] Br ionic liquid as catalyst in aqueousmedia, Journal of Molecular Liquids, 2013,179:104-109).In addition, bronsted acid ionic liquid as the one in functionalized ion liquid, because it has green non-pollution, to organicly having good solubility, the acidic site be evenly distributed with mineral compound, is easy to product and is separated and can be recycled etc. advantage and being employed in the preparation of quinoxaline compound.If Fang Dong etc. is using the acidic ion liquid with single sulfonate radical as catalyzer, water is reaction medium, substituted o-phenylenediamine and 1,2-dicarbonyl compound carries out condensation reaction high yield and obtains quinoxaline compound, wherein catalyzer can recycle repeatedly (synthesis of ionic liquid aqueous phase catalysis quinoxaline compound, CN102010376A; A practical andefficient synthesis of quinoxaline derivatives catalyzed by task-specific ionic liquid, Catalysis Communications, 2008,9:317-320).
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, catalyzer usage quantity and recycle the shortcomings such as middle number of dropouts is all very large, a kind of method catalyzing and synthesizing quinoxaline compound is provided.
The structural formula of many sulfonate ions liquid catalyst 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.
A kind of method catalyzing and synthesizing quinoxaline compound provided by the present invention, its condensation reaction formula is:
Wherein react Raw O-Phenylene Diamine and 1, the mol ratio of 2-dicarbonyl compound is 1:1, the molar weight of many sulfonate ions liquid catalyst is O-Phenylene Diamine used or 1, the 5-10% of 2-dicarbonyl compound, temperature of reaction is 40-60 DEG C, and the reaction times is 20-120min, the consumption of reaction solvent water is the 50-90% of material total mass, reaction pressure is 1 normal atmosphere, and reaction product filtered after having reacted, filter residue washes rear ethyl alcohol recrystallization with water and obtains pure quinoxaline compound.In filtrate, many sulfonate ions liquid and unreacted raw material can use 5 times without cycle for the treatment of.
The present invention's 1,2-dicarbonyl compound used is
Wherein R 1, R 2for aromatic series, aliphatic substitution.
The preparation method of many sulfonate ions liquid catalyst that the present invention is used, is shown in following pertinent literature (Synthesis of a novel multi – SO 3h functionalized ionic liquid and its catalyticactivities 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 and other ionic liquid make catalyzer, there is following characteristics:
1, the sour density containing many sulfonate radicals acidic ionic liquid catalysts is high, and catalytic activity is high;
2, catalyzer usage quantity is few and to recycle middle loss amount also less;
3, the preparation of catalyzer is comparatively simple, and preparation expense is lower.
Embodiment
Embodiment 1: by 10mmol O-Phenylene Diamine, 10mmol benzil, 0.5mmol IL-SO 3h-a and 15mL water joins 50mL with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 20min at 40 DEG C, filter, filter residue ethyl alcohol recrystallization obtains 2,3-diphenylquinoxaline sterling, and productive rate is 95%, and in filtrate, many sulfonate ions liquid and unreacted raw material can without cycle for the treatment of 5 times.
Embodiment 2: by 10mmol O-Phenylene Diamine, 10mmol two (4-oxygen methylbenzene) even acyl, 0.6mmolIL-SO 3h-b and 25mL water joins 100mL with in the single port bottle of stirrer and reflux condensing tube.At 60 DEG C, vigorous stirring reaction 50min, filters, and filter residue ethyl alcohol recrystallization obtains two (4-oxygen aminomethyl phenyl) the quinoxaline sterling of 2,3-, and productive rate is 90%, and in filtrate, many sulfonate ions liquid and unreacted raw material can without cycle for the treatment of 5 times.
Embodiment 3: by 10mmol O-Phenylene Diamine, 10mmol dimethyl diketone, 0.8mmol IL-SO 3h-b and 15mL water joins 50mL with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 60min at 60 DEG C, filter, filter residue ethyl alcohol recrystallization obtains 2,3-dimethylquinoxalin sterling, and productive rate is 87%, and in filtrate, many sulfonate ions liquid and unreacted raw material can use 5 times without cycle for the treatment of.
Embodiment 4: with embodiment 1 for probe reaction, does the recycling test of catalysts, catalyst I L-SO 3h-a reuses 5 times, and the productive rate change of 2,3-diphenylquinoxaline is in table 1.
Table 1 IL-SO 3the reaction of H-a catalysis O-Phenylene Diamine and benzil synthesis 2,3-diphenylquinoxaline
IL-SO 3H-a access times 2,3-diphenylquinoxaline productive rate (%)
1 95
2 92
3 90
4 91
5 88

Claims (2)

1. catalyze and synthesize a method for quinoxaline compound, it is characterized in that the method is specific as follows:
The condensation reaction Raw O-Phenylene Diamine of synthesizing quinoxaline compounds and 1, the mol ratio of 2-dicarbonyl compound is 1:1, the molar weight of many sulfonate ions liquid catalyst is O-Phenylene Diamine used or 1, the 5-10% of 2-dicarbonyl compound, temperature of reaction is 40-60 DEG C, reaction times is 20-120min, the consumption of reaction solvent water is the 50-90% of material total mass, reaction pressure is 1 normal atmosphere, reaction product filtered after having reacted, filter residue washes rear ethyl alcohol recrystallization with water and obtains pure quinoxaline compound; The described structural formula containing many sulfonate ions liquid catalyst is:
In formula, n is 3 or 4.
2. a kind of method catalyzing and synthesizing quinoxaline compound according to claim 1, is characterized in that 1,2-described dicarbonyl compound is
Wherein R 1, R 2for aromatic series, aliphatic substitution.
CN201310086879.1A 2013-03-18 2013-03-18 Method for catalytically synthesizing quinoxaline compound Expired - Fee Related CN103145630B (en)

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Publication number Priority date Publication date Assignee Title
CN103787991B (en) * 2014-01-21 2016-04-20 同济大学 Yb/NaY molecular sieve catalyst catalyzes and synthesizes the method for quinoxaline compound
CN104311484B (en) * 2014-09-11 2016-05-11 安徽工业大学 A kind of method that catalyzes and synthesizes quinoline derivatives
CN105017167B (en) * 2015-07-20 2017-10-20 新乡医学院 A kind of preparation method of quinoxaline compound
CN110592157B (en) * 2019-10-09 2021-01-01 吉林大学 Method for synthesizing quinoxaline compound by double-protein catalytic cascade reaction

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318938A (en) * 2008-07-14 2008-12-10 苏州大学 Method for synthesizing quinoxaline derivant
WO2011000481A1 (en) * 2009-07-02 2011-01-06 Merck Patent Gmbh Synthesis of pyrazine derivates
CN102010376A (en) * 2009-09-08 2011-04-13 盐城师范学院 Synthesis of ionic liquid aqueous phase catalysis quinoxaline compound
WO2011147067A1 (en) * 2010-05-24 2011-12-01 海洋王照明科技股份有限公司 Quinoxaline conjugated polymer containing fused-ring thiophehe unit, preparation method and uses thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318938A (en) * 2008-07-14 2008-12-10 苏州大学 Method for synthesizing quinoxaline derivant
WO2011000481A1 (en) * 2009-07-02 2011-01-06 Merck Patent Gmbh Synthesis of pyrazine derivates
CN102010376A (en) * 2009-09-08 2011-04-13 盐城师范学院 Synthesis of ionic liquid aqueous phase catalysis quinoxaline compound
WO2011147067A1 (en) * 2010-05-24 2011-12-01 海洋王照明科技股份有限公司 Quinoxaline conjugated polymer containing fused-ring thiophehe unit, preparation method and uses thereof

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