CN101875640A - Method for preparing pyrazinecarboxylic acid in ionic liquid - Google Patents
Method for preparing pyrazinecarboxylic acid in ionic liquid Download PDFInfo
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- CN101875640A CN101875640A CN 201010210175 CN201010210175A CN101875640A CN 101875640 A CN101875640 A CN 101875640A CN 201010210175 CN201010210175 CN 201010210175 CN 201010210175 A CN201010210175 A CN 201010210175A CN 101875640 A CN101875640 A CN 101875640A
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Abstract
The invention discloses a method for preparing pyrazinecarboxylic acid having a structure represented by a formula (I) in ionic liquid. In the method, 2,3-pyrazinecarboxylic acid represented by a formula (II) is used as a raw material to undergo a decarboxylic reaction at 40 to 180 DEG C in the ionic liquid having a structure represented by a formula (III), and the pyrazinecarboxylic acid is obtained by post treatment after complete reaction; and in the formula (III), R1 is C1 to C10 alkyl, R2 is C1 to C10 alkylene and L may be Cl or Br. The synthesis method of the pyrazinecarboxylic acid has the advantages that: the post treatment is simple; the ionic liquid can be recycled; and the environmental pollution is light.
Description
(1) technical field
The invention provides a kind of method for preparing pyrazine carboxylic acid.
(2) background technology
Pyrazine compounds has important purposes in perfume industry and medicine industry, wherein pyrazine carboxylic acid is a kind of important spices and medicine intermediate.Traditional with 2,3-pyrazine dioctyl phthalate is that the method for feedstock production pyrazine carboxylic acid is: add thermal decarboxylation and get pyrazine carboxylic acid in acetate.Adopt acetate to make solvent in the decarboxylic reaction, and that acetate has strong impulse acid is smelly, stronger corrodibility is arranged.
(3) summary of the invention
The technical problem to be solved in the present invention be to provide a kind of simple to operate, yield is high, aftertreatment is easy, the eco-friendly method for preparing pyrazine carboxylic acid.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of method for preparing the pyrazine carboxylic acid of structure shown in formula I: with shown in formula II 2,3-pyrazine dioctyl phthalate is a raw material, in the ionic liquid of structure shown in formula III, carry out decarboxylic reaction in 40～180 ℃, fully reaction is after aftertreatment obtains pyrazine carboxylic acid;
In the formula III, R
1Be the alkyl of C1～C10, R
2Be the alkylidene group of C1～C10, L is Cl or Br.
Further, the temperature of reaction of described reaction is preferably 80～140 ℃.
Further, the reaction times of described reaction is preferably 3～8 hours.
Further, described 2,3-pyrazine dioctyl phthalate and the ion liquid mass ratio that feeds intake are 1: 5～100, preferred 1: 5～50.
Ordinary method is adopted in aftertreatment of the present invention, specifically can adopt following steps: after reaction finished, solid was separated out in cooling, suction filtration, and recrystallization can obtain pyrazine carboxylic acid.One of recrystallization solvent is preferred following: water, 10% aqueous ethanolic solution, 30% aqueous ethanolic solution, 50% aqueous ethanolic solution.The concentration of above-mentioned aqueous ethanolic solution is concentration of volume percent.The ionic liquid that obtains behind the suction filtration does not need aftertreatment can continue on for this reaction.
The present invention is concrete to recommend described method to carry out according to following steps: add 2 successively in reaction vessel, 3-pyrazine dioctyl phthalate, ionic liquid carry out decarboxylic reaction under 80～140 ℃ temperature condition, 3～8 hours reaction times; After reaction finished, solid was separated out in cooling, suction filtration, and recrystallization promptly obtains the decarboxylate pyrazine carboxylic acid; Described 2,3-pyrazine dioctyl phthalate and the ion liquid mass ratio that feeds intake are 1: 5～50.
The synthetic method of pyrazine carboxylic acid of the present invention, its beneficial effect are embodied in that aftertreatment is simple, the recyclable recycling of ionic liquid, environmental pollution are little.
(4) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL 1-methyl-3-propyloic chloro imidazole salts ([AcMIm] Cl) is heated to 40 ℃, behind the reaction 8h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.6g pyrazine carboxylic acid, yield 48.3%, fusing point: 224-225 ℃
Embodiment 2 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL1-methyl-3-propyloic chloro imidazole salts ([AcMIm] Cl) is heated to 110 ℃, behind the reaction 5h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.76g pyrazine carboxylic acid, yield 61.2%, fusing point: 224-225 ℃.
Embodiment 3 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL1-methyl-3-propyloic chloro imidazole salts ([AcMIm] Cl) is heated to 180 ℃, behind the reaction 3h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.7g pyrazine carboxylic acid, yield 56.4%, fusing point: 224-225 ℃.
Embodiment 4 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL1-butyl-3-propyloic chloro imidazole salts ([AcBIm] Cl) is heated to 80 ℃, behind the reaction 5h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.88g pyrazine carboxylic acid, yield 71%, fusing point: 224-225 ℃.
Embodiment 5 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL1-butyl-3-propyloic chloro imidazole salts ([AcBIm] Cl) is heated to 110 ℃, behind the reaction 5h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.9g pyrazine carboxylic acid, yield 72.6%, fusing point: 224-225 ℃.
Embodiment 6 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL1-octyl group-3-propyloic chloro imidazole salts ([AcOIm] Cl) is heated to 80 ℃, behind the reaction 5h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.78g pyrazine carboxylic acid, yield 62.9%, fusing point: 224-225 ℃.
Embodiment 7 is by 2, and 3-pyrazine dioctyl phthalate prepares pyrazine carboxylic acid
In the 50mL there-necked flask, add 1.68g (0.01mol) 2,3-pyrazine dioctyl phthalate, 20mL 1-octyl group-3-propyloic chloro imidazole salts ([AcOIm] Cl) is heated to 110 ℃, behind the reaction 5h, cooling is separated out solid, suction filtration, the hot water recrystallization, get the 0.86g pyrazine carboxylic acid, yield 69.3%, fusing point: 224-225 ℃.
Claims (8)
1. method for preparing structure suc as formula the pyrazine carboxylic acid shown in (I), it is characterized in that described method is: with suc as formula 2 shown in (II), 3-pyrazine dioctyl phthalate is a raw material, structure suc as formula the ionic liquid shown in (III) in, carry out decarboxylic reaction in 40 ℃～180 ℃, fully reaction is after aftertreatment obtains pyrazine carboxylic acid;
In the formula (III), R
1Be the alkyl of C1～C10, R
2Be the alkylidene group of C1～C10, L is Cl or Br.
2. the method for preparing pyrazine carboxylic acid as claimed in claim 1, the temperature of reaction that it is characterized in that described reaction is 80～140 ℃.
3. the method for preparing pyrazine carboxylic acid as claimed in claim 1, the reaction times that it is characterized in that described reaction is 3～8 hours.
4. the method for preparing pyrazine carboxylic acid as claimed in claim 1 is characterized in that describedly 2, and 3-pyrazine dioctyl phthalate and the ion liquid mass ratio that feeds intake are 1: 5～100.
5. the method for preparing pyrazine carboxylic acid as claimed in claim 1 is characterized in that describedly 2, and 3-pyrazine dioctyl phthalate and the ion liquid mass ratio that feeds intake are 1: 5～50.
6. the method for preparing pyrazine carboxylic acid as claimed in claim 1, it is characterized in that described aftertreatment employing following steps: after reaction finished, solid was separated out in cooling, suction filtration, recrystallization can obtain pyrazine carboxylic acid.
7. the method for preparing pyrazine carboxylic acid as claimed in claim 6, it is one of following to it is characterized in that recrystallization solvent is selected from: water, 10% aqueous ethanolic solution, 30% aqueous ethanolic solution, 50% aqueous ethanolic solution.
8. the method for preparing pyrazine carboxylic acid as claimed in claim 1, it is characterized in that described method carries out according to following steps: in reaction vessel, add 2 successively, 3-pyrazine dioctyl phthalate, ionic liquid carry out decarboxylic reaction under 80～140 ℃ temperature condition, 3～8 hours reaction times; After reaction finished, solid was separated out in cooling, suction filtration, and recrystallization promptly obtains the decarboxylate pyrazine carboxylic acid; Described 2,3-pyrazine dioctyl phthalate and the ion liquid mass ratio that feeds intake are 1: 5～50.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477044A (en) * | 2010-11-26 | 2012-05-30 | 苏州凯达生物医药技术有限公司 | Synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) |
| CN104591989A (en) * | 2015-01-05 | 2015-05-06 | 上海华谊（集团）公司 | Method for preparing 5-[(4-chlorophenyl)methyl]-2,2-dimethyl-cyclopentanone |
| CN111763193A (en) * | 2020-07-21 | 2020-10-13 | 河北美星化工有限公司 | Synthesis method of 1, 4-cyclohexanedione monoethylene glycol ketal |
| CN113387890A (en) * | 2021-06-17 | 2021-09-14 | 中国科学院过程工程研究所 | Ionic liquid, polyionic liquid and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101469145A (en) * | 2007-12-28 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Process for preparing attapulgite based composite material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101469145A (en) * | 2007-12-28 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Process for preparing attapulgite based composite material |
Non-Patent Citations (3)
| Title |
|---|
| 《Advanced Synthesis & Catalysis》 20081215 Abhishek Sharma et al. Unique Versatility of Ionic Liquids as Clean Decarboxylation Catalyst Cum Solvent: A Metal- and Quinoline-Free Paradigm towards Synthesis of Indoles, Styrenes, Stilbenes and Arene Derivatives under Microwave Irradiation in Aqueous Conditions 2910-2920 1-8 第350卷, 第18期 2 * |
| 《The Journal of Organic Chemistry》 20040421 Dongmei Li et al. Application of Functional Ionic Liquids Possessing Two Adjacent Acid Sites for Acetalization of Aldehydes 3582-3585 1-8 第69卷, 第10期 2 * |
| 《云南化工》 19921231 殷彩霞等 吡嗪类化合物的合成研究 7-8 1-8 , 第4期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477044A (en) * | 2010-11-26 | 2012-05-30 | 苏州凯达生物医药技术有限公司 | Synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) |
| CN104591989A (en) * | 2015-01-05 | 2015-05-06 | 上海华谊（集团）公司 | Method for preparing 5-[(4-chlorophenyl)methyl]-2,2-dimethyl-cyclopentanone |
| CN111763193A (en) * | 2020-07-21 | 2020-10-13 | 河北美星化工有限公司 | Synthesis method of 1, 4-cyclohexanedione monoethylene glycol ketal |
| CN113387890A (en) * | 2021-06-17 | 2021-09-14 | 中国科学院过程工程研究所 | Ionic liquid, polyionic liquid and preparation method and application thereof |
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Assignee: Zhejiang Xianju Litian Chemical Co. Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2012330000026 Denomination of invention: Method for preparing pyrazinecarboxylic acid in ionic liquid Granted publication date: 20111228 License type: Exclusive License Open date: 20101103 Record date: 20120217 |
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