CN102617490A - Process for preparing pyrazine-2-formic acid through metalloporphyrin catalytic oxidation of 2-methylpyrazine - Google Patents
Process for preparing pyrazine-2-formic acid through metalloporphyrin catalytic oxidation of 2-methylpyrazine Download PDFInfo
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- CN102617490A CN102617490A CN2012100526785A CN201210052678A CN102617490A CN 102617490 A CN102617490 A CN 102617490A CN 2012100526785 A CN2012100526785 A CN 2012100526785A CN 201210052678 A CN201210052678 A CN 201210052678A CN 102617490 A CN102617490 A CN 102617490A
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- methylpyrazine
- formic acid
- pyrazine
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Abstract
The invention relates to a process for preparing pyrazine-2-formic acid through metalloporphyrin catalytic oxidation of 2-methylpyrazine. The process comprises the steps of using 2-methylpyrazine as raw materials; using a mixed solution of ethanol or 60% - 90% (by volume) of ethanol and water as a solvent; using monokaryon metalloporphyrin having a structure represented by formula (I) or formula (II) or dicaryon metalloporphyrin having a structure represented by formula (III) as a catalytic agent with the using amount accounting for 0.02% - 0.07% of raw material weight; reacting for 0.5 - 8 hours at a temperature between 80 DEG C - 140 DEG C under the oxygen pressure of 0.5 - 2.5 MPa in the presence of alkali sodium hydroxide or potassium hydroxide; subjecting the reacted product to acidification, filtration, extraction and hot water recrystallization; and obtaining the pyrazine-2-formic acid finally. According to the process, a small amount of the catalytic agent is consumed and the catalytic agent does not require to be separated, the reaction temperature is low, the solvent environment is friendly, and the process has wide application prospects in industry.
Description
Technical field
The present invention relates to the method that a kind of catalysis of metalloporphyrin oxidation 2-methylpyrazine prepares pyrazine-2-formic acid.
Background technology
Pyrazine-2-formic acid is a kind of important medicine intermediate, is mainly used in a synthetic cancer therapy drug RP 35972 and a line antitubercular agent pyrazinoic acid amide.Simultaneously, it still is a kind of widely used bridge ligand.The preparation method of pyrazine-2-formic acid mainly contains chemical oxidization method, intermolecular cyclization method, decarboxylation method and hydrolysis method etc. at present.Air or oxygen oxidation 2-methylpyrazine prepares pyrazine-2-formic acid and has the flow process weak point, and simple to operate, raw material is easy to get, and separates advantages such as simple, compares other compound methods and has more wide prospect in industrial application.
US 3154549 (open day: on October 27th, 1964) disclosing a kind of was oxygenant with the sodium dichromate 99, and the 2-methylpyrazine is the method for feedstock production pyrazine-2-formic acid, 225 ℃ of temperature of reaction, and pyrazine-2-formic acid yield is 74%.The shortcoming of this method is to use expensive chemical oxidizing agent, and temperature of reaction is higher, has increased energy consumption, has increased running cost.
People (Zhurnal Prikaladnoi Khimii.1992 such as Iovel I.G.; 65 (9): 2075-2078) reported with 1; The 2-glycol dimethyl ether is a solvent; With the potassium tert.-butoxide is alkali, is that catalyst oxygen interface oxidation 2-methylpyrazine prepares pyrazine-2-formic acid with the 18-of weight ratio 2～3% hat-6.The shortcoming of this method is that catalyst levels is bigger, and the non-close friend of solvent environment.
What report in the prior art at present in sum, is that the method for feedstock production pyrazine-2-formic acid has following shortcoming with the 2-methylpyrazine:
(1) need to use chemical oxidizing agent usually, oxygenant produces a large amount of poisonous waste water, waste liquid generally than costliness and large usage quantity in the preparation process, environment is polluted;
(2) generally need increase energy consumption and equipment cost, and increase the danger of operation in high temperature (225 ℃) reaction down;
(3) catalyst levels big (weight ratio 2～3%) also must separate after using, and has increased the input of equipment cost;
(4) use the friendly solvent (1, the 2-glycol dimethyl ether) of non-ambient, increased environmental pollution.
Summary of the invention
The objective of the invention is to overcome shortcoming of the prior art, provide a kind of catalyst levels few and need not to separate, temperature of reaction is low, and the friendly catalysis of metalloporphyrin oxidation 2-methylpyrazine of solvent environment prepares the method for pyrazine-2-formic acid.
A kind of catalysis of metalloporphyrin oxidation 2-methylpyrazine provided by the present invention prepares the method for pyrazine-2-formic acid; The steps include: that with the 2-methylpyrazine be raw material, is solvent with the mixing solutions of ethanol or 60～99% (volume) ethanol and water, and the dinuclear metalloporphyrin of selecting the monokaryon metalloporphyrin of have formula (I), formula (II) structure for use or having a formula III structure is as catalyzer; Catalyst levels accounts for raw material weight 0.02～0.07%; In the presence of highly basic sodium hydroxide or Pottasium Hydroxide, under 0.5～2.5MPa oxygen pressure, reacted 0.5～8 hour down in 80～140 ℃; Reacted product obtains pyrazine-2-formic acid behind acidifying, filtration, extraction and hot water recrystallization
Wherein, M
1Or M
2Represent manganese, iron, cobalt, copper, zinc, chromium or nickel, preferred manganese, iron, cobalt, copper or zinc; M
3Or M
4Represent manganese, iron or cobalt, preferred M
3Or M
4Be manganese, preferred M
3Be iron, M
4Be manganese; Substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32, R
33Represent nitro, halogen, carboxyl, hydrogen, methyl, methoxyl group or hydroxyl, preferred chlorine or hydrogen; Dentate X represents halogen, preferred chlorine.
Aforesaid method sodium hydroxide or Pottasium Hydroxide consumption account for raw material weight 50～180%; Preferable reaction temperature is 80～120 ℃; The preferred reaction time is 1～4 hour, and the preferred oxygen atmospheric pressure is 0.5～2MPa; Preferred solvent is the mixing solutions of 70～99% (volume) ethanol and water.
The inventive method is compared with existing method has following beneficial effect:
(1) does to replace the serious and expensive chemical oxidizing agent of environmental pollution with cleaning and oxygen cheap and easy to get, reduced reaction cost and environmental friendliness;
(2) the inventive method temperature of reaction is 80～140 ℃, and low-temp reaction has not only reduced energy consumption and process cost, and has reduced the danger of operation;
(3) the inventive method is catalyzer with the metalloporphyrin, its consumption few (accounting for raw material weight 0.02～0.07%), and metalloporphyrin is degraded automatically after the reaction, does not need Separation and Recovery;
(4) to select the mixing solutions of ethanol or ethanol and water for use be solvent to the inventive method, eliminated the pollution of harmful poisonous solvent to environment.
Embodiment
Embodiment 1
In the autoclave of 200mL, add 5.04g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0014g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=Gl, M
1=Mn), feed the oxygen of 1.5MPa, reacted 2 hours down at 120 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 34.9%, and the yield of pyrazine-2-formic acid is 20.0%.
Embodiment 2
In the autoclave of 200mL, add 4.20g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0014g has the monokaryon metalloporphyrin (R wherein of formula (II) structure
21=R
22=H, R
23=NO
2, M
2=Fe, X=Cl), the oxygen of feeding 2.0MPa reacted 0.5 hour down at 120 ℃, obtained pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 14.1%, and the yield of pyrazine-2-formic acid is 9.2%.
Embodiment 3
In the autoclave of 200mL, add 3.36g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 29.7mL ethanol, 0.3mL water, 0.0010g have the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=COOH, M
1=Co), feed the oxygen of 2.5MPa, reacted 1 hour down at 100 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 16.3%, and the yield of pyrazine-2-formic acid is 10.1%.
Embodiment 4
In the autoclave of 200mL, add 2.52g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0010g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=Cl, R
12=R
13=H, M
1=Zn), feed the oxygen of 1.0MPa, reacted 3 hours down at 140 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 30.7%, and the yield of pyrazine-2-formic acid is 13.6%.
Embodiment 5
In the autoclave of 200mL, add 1.68g sodium hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0006g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=CH
3, M
1=Cu), feed the oxygen of 0.5MPa, reacted 4 hours down at 80 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 19.5%, and the yield of pyrazine-2-formic acid is 11.0%.
Embodiment 6
In the autoclave of 200mL, add 3.36g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0018g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=R
13=H, M
1=Mn), feed the oxygen of 2.0MPa, reacted 2 hours down at 120 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 36.8%, and the yield of pyrazine-2-formic acid is 21.7%.
Embodiment 7
In the autoclave of 200mL, add 3.36g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 29.7mL ethanol, 0.3mL water, 0.0014g have the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=NO
2, M
2=Cr), feed the oxygen of 1.0MPa, reacted 6 hours down at 120 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 38.1%, and the yield of pyrazine-2-formic acid is 12.9%.
Embodiment 8
In the autoclave of 200mL, add 3.36g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0010g has the monokaryon metalloporphyrin (R wherein of formula (II) structure
21=R
23=H, R
22=Cl, M
2=Ni, X=Cl), the oxygen of feeding 2.5MPa reacted 4 hours down at 120 ℃, obtained pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 24.2%, and the yield of pyrazine-2-formic acid is 11.5%.
Embodiment 9
In the autoclave of 200mL, add 1.68g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0006g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=OH, M
2=Mn), feed the oxygen of 2.0MPa, reacted 8 hours down at 100 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 17.8%, and the yield of pyrazine-2-formic acid is 10.5%.
Embodiment 10
In the autoclave of 200mL, add 4.20g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0010g has the monokaryon metalloporphyrin (R wherein of formula (I) structure
11=R
12=H, R
13=OCH
3, M
2=Co), feed the oxygen of 2.5MPa, reacted 2 hours down at 120 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 30.1%, and the yield of pyrazine-2-formic acid is 18.3%.
Embodiment 11
In the autoclave of 200mL, add 4.20g sodium hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0010g has the dinuclear metalloporphyrin (R wherein of formula (III) structure
31=R
32=H, R
33=NO
2, M
3=M
4=Mn), feed the oxygen of 2.0MPa, reacted 2 hours down at 140 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 33.3%, and the yield of pyrazine-2-formic acid is 19.7%.
Embodiment 12
In the autoclave of 200mL, add 3.36g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0018g has the dinuclear metalloporphyrin (R wherein of formula (III) structure
31=R
32=H, R
33=Cl, M
3=Fe, M
4=Mn), feed the oxygen of 2.5MPa, reacted 2 hours down at 100 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 36.8%, and the yield of pyrazine-2-formic acid is 21.0%.
Embodiment 13
In the autoclave of 200mL, add 4.20g Pottasium Hydroxide successively, 2.82g 2-methylpyrazine, 30mL ethanol, 0.0018g has the dinuclear metalloporphyrin (R wherein of formula (III) structure
31=NO
2, R
32=R
33=H, M
3=Mn, M
4=Co), feed the oxygen of 1.0MPa, reacted 2 hours down at 120 ℃, obtain pyrazine-2-formic acid.Through efficient liquid phase chromatographic analysis, the transformation efficiency of 2-methylpyrazine is 29.9%, and the yield of pyrazine-2-formic acid is 17.2%.
Claims (10)
1. a catalysis of metalloporphyrin oxidation 2-methylpyrazine prepares the method for pyrazine-2-formic acid; The steps include: that with the 2-methylpyrazine be raw material, is solvent with the mixing solutions of ethanol or 60～99% (volume) ethanol and water, and the dinuclear metalloporphyrin of selecting the monokaryon metalloporphyrin of have formula (I), formula (II) structure for use or having a formula III structure is as catalyzer; Catalyst levels accounts for raw material weight 0.02～0.07%; In the presence of highly basic sodium hydroxide or Pottasium Hydroxide, under 0.5～2.5MPa oxygen pressure, reacted 0.5～8 hour down in 80～140 ℃; Reacted product obtains pyrazine-2-formic acid behind acidifying, filtration, extraction and hot water recrystallization
Wherein, M
1Or M
2Represent manganese, iron, cobalt, copper, zinc, chromium or nickel, M
3Or M
4Represent manganese, iron or cobalt; Substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32, R
33Represent nitro, halogen, carboxyl, hydrogen, methyl, methoxyl group or hydroxyl; Dentate X represents halogen.
2. according to the process of claim 1 wherein M
1Or M
2Represent manganese, iron, cobalt, copper or zinc.
3. according to the process of claim 1 wherein M
3Or M
4Be manganese.
4. according to the process of claim 1 wherein M
3Be iron, M
4Be manganese.
5. according to the process of claim 1 wherein substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32, R
33Represent chlorine or hydrogen.
6. according to the process of claim 1 wherein that dentate X represents chlorine.
7. according to the method for claim 1, it is characterized in that sodium hydroxide or Pottasium Hydroxide consumption account for raw material weight 50～180%.
8. according to the method for claim 1, it is characterized in that temperature of reaction is 80～120 ℃.
9. according to the method for claim 1, it is characterized in that the reaction times is 1～4 hour.
10. according to the method for claim 1, it is characterized in that oxygen pressure is 0.5～2MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775357A (en) * | 2012-08-09 | 2012-11-14 | 石家庄学院 | Air oxidation method for preparing acetylpyrazine under catalytic action of metalloporphyrin |
| CN102924389A (en) * | 2012-10-30 | 2013-02-13 | 北京工业大学 | Preparation method of 5-methylpyrazinyl-2-carboxylic acid |
| CN103193654A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst |
| CN104311483A (en) * | 2014-10-27 | 2015-01-28 | 北京工业大学 | Method for preparing quinoline-2-carboxylic acid |
| CN105061776A (en) * | 2015-08-10 | 2015-11-18 | 北京工业大学 | Metal organic framework material of Fe porphyrin ligand, preparation method therefor and application thereof |
| CN106831612A (en) * | 2017-01-14 | 2017-06-13 | 河南工程学院 | A kind of carboxylic acids complex and its synthetic method |
| CN109206388A (en) * | 2018-11-11 | 2019-01-15 | 北京工业大学 | A kind of preparation method of coumarilic acid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775357A (en) * | 2012-08-09 | 2012-11-14 | 石家庄学院 | Air oxidation method for preparing acetylpyrazine under catalytic action of metalloporphyrin |
| CN102775357B (en) * | 2012-08-09 | 2015-01-07 | 石家庄学院 | Air oxidation method for preparing acetylpyrazine under catalytic action of metalloporphyrin |
| CN102924389A (en) * | 2012-10-30 | 2013-02-13 | 北京工业大学 | Preparation method of 5-methylpyrazinyl-2-carboxylic acid |
| CN103193654A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst |
| CN104311483A (en) * | 2014-10-27 | 2015-01-28 | 北京工业大学 | Method for preparing quinoline-2-carboxylic acid |
| CN105061776A (en) * | 2015-08-10 | 2015-11-18 | 北京工业大学 | Metal organic framework material of Fe porphyrin ligand, preparation method therefor and application thereof |
| CN106831612A (en) * | 2017-01-14 | 2017-06-13 | 河南工程学院 | A kind of carboxylic acids complex and its synthetic method |
| CN109206388A (en) * | 2018-11-11 | 2019-01-15 | 北京工业大学 | A kind of preparation method of coumarilic acid |
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Application publication date: 20120801 |