CN102993091A - Preparation method of 5-amino-2-(4-amino phenoxy)-pyridine - Google Patents
Preparation method of 5-amino-2-(4-amino phenoxy)-pyridine Download PDFInfo
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- CN102993091A CN102993091A CN2012104923859A CN201210492385A CN102993091A CN 102993091 A CN102993091 A CN 102993091A CN 2012104923859 A CN2012104923859 A CN 2012104923859A CN 201210492385 A CN201210492385 A CN 201210492385A CN 102993091 A CN102993091 A CN 102993091A
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Abstract
The invention discloses a preparation method of 5-amino-2-(4-amino phenoxy)-pyridine, which comprises the steps of: 1) stirring 2-chloro-5-nitro-pyridine, 4-nitro-phenol, potassium carbonate and dimethyl formamide (DMF) and heating for reaction to obtain 5-nitro-2-(4-nitro- phenoxy)-pyridine; and 2) stirring the 5-nitro-2-(4-nitro- phenoxy)-pyridine, palladium carbon catalyst and absolute ethyl alcohol or methanol, and carrying out reaction under the hydrogen flow to obtain 5-amino-2-(4-amino phenoxy)-pyridine. The preparation method disclosed by the invention is simple in preparation process, easy in aftertreatment and high in yield, the total yield exceeds 85%, and the product purity exceeds 99wt%.
Description
Technical field
The invention belongs to the organic synthesis field, specifically relate to the preparation method of 5-amino-2-(4-amino-benzene oxygen)-pyridine.
Background technology
The rigid backbone of polyimide uniqueness and stronger Interchain interaction power so that it has very high fusing point or softening temperature, cause its solvability in most of organic solvents relatively poor, these limitations restrict its application in some field.In order to overcome these deficiencies, when design and synthetic new monomer, generally introduce large suspension side group, flexible ether chain, polyfluoro alkoxy grp at molecular chain, and introduce the method such as unsymmetrical structure unit.
Wherein, 5-amino-2-(4-amino-benzene oxygen)-pyridine just has These characteristics, but because in its preparation process, product yield is low, product is not easily separated after the reaction.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that 5-amino-2-(4-amino-benzene oxygen) that a kind of yield is high, reactor product is easy to separate-pyridine is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of a kind of 5-amino-2-(4-amino-benzene oxygen)-pyridine, and its preparation process is:
1) 5-nitro-2-(4-nitro-phenoxy)-pyridine (NNP):
In reactor, add 2-chloro-5-nitropyridine, 4-nitrophenols, salt of wormwood and DMF; Stir, heat 85 ~ 90 ℃, keep this temperature condition reaction 3 ~ 4h; Then, reaction solution is cooled to 20 ~ 25 ℃, reaction mixture is poured in 0 ~ 5 ℃ the frozen water and left standstill 12 ~ 15h, collect the solid that produces, water cleans, and is dried to water content≤2%, and column chromatography for separation obtains 5-nitro-2-(4-nitro-phenoxy)-pyridine;
2) 5-amino-2-(4-amino-benzene oxygen)-pyridine (AAP):
In reactor, add 5-nitro-2-(4-nitro-phenoxy)-pyridine, palladium-carbon catalyst and dehydrated alcohol or methyl alcohol, stir room temperature under hydrogen stream (20 ~ 25 ℃) reaction 90 ~ 95h, HPLC detects, raw material 5-nitro-2-(4-nitro-phenoxy)-and pyridine reacts completely, and reaction finishes, solids removed by filtration, ethanol or methyl alcohol are removed in decompression, get solid, column chromatography is purified, and gets 5-amino-2-(4-amino-benzene oxygen)-pyridine.
Reaction equation is:
In the step 1), the mol ratio of described 2-chloro-5-nitropyridine, 4-nitrophenols and salt of wormwood is 1:1 ~ 1.2:1.1 ~ 1.4.
Step 2) in, described palladium carbon accounts for 5-nitro-2-(4-nitro-phenoxy)-mass percent of pyridine is 4 ~ 5%.
Beneficial effect of the present invention: preparation method disclosed by the invention, preparation process is simple, and aftertreatment is easy, and yield is high, and total recovery surpasses 85%, and product purity surpasses 99Wt.%.
Embodiment
Embodiment 1
1) 5-nitro-2-(4-nitro-phenoxy)-pyridine (NNP):
In the 250ml four-hole round-bottomed flask of magneton, prolong, nitrogen conduit and thermometer is housed, add the DMF solvent of 6.32g (0.04mol) 2-chloro-5-nitropyridine, 6.67g (0.048mol) 4-nitrophenols and 6.08g (0.044mol) salt of wormwood and 150mL.Start stirring, mixture solution is heated to 86 ℃ and react 4h under this temperature.Then, reaction solution is cooled to room temperature.This reaction mixture poured into to the frozen water of q.s spend the night.Collect the solid that produces, water cleans three times, and use sherwood oil: ethyl acetate=4:1 mixed solvent separates thick product with the method for column chromatography and obtains faint yellow solid product 9.64g as leacheate again; Productive rate is 92.3%.
2) 5-amino-2-(4-amino-benzene oxygen)-pyridine (AAP):
At 250mL, magnetic stirring bar is housed, in the four-hole round-bottomed flask of prolong and thermometer, adds 7.84g(0.03mol) 5-nitro-2-(4-nitro-phenoxy)-pyridine (NNP), 0.32g palladium-carbon catalyst and the absolute dehydrated alcohol of 100ml, violent stirring, room temperature reaction 95h under hydrogen stream, solids removed by filtration reduces pressure and removes ethanol afterwards, get faint yellow solid, column chromatography is purified, AAP5.7g, productive rate 94.8%.
Embodiment 2:
1) 5-nitro-2-(4-nitro-phenoxy)-pyridine (NNP):
In the 250ml four-hole round-bottomed flask of magneton, prolong, nitrogen conduit and thermometer is housed, add the DMF solvent of 6.32g (0.04mol) 2-chloro-5-nitropyridine, 5.56g (0.04mol) 4-nitrophenols and 7.78g (0.056mol) salt of wormwood and 150mL.Start stirring, mixture solution is heated to 86 ℃ and react 4h under this temperature.Then, reaction solution is cooled to room temperature.This reaction mixture poured into to the frozen water of q.s spend the night.Collect the solid that produces, water cleans three times, and use sherwood oil: ethyl acetate=4:1 mixed solvent separates thick product with the method for column chromatography and obtains faint yellow solid product 9.68g as leacheate again; Productive rate is 92.7%.
2) 5-amino-2-(4-amino-benzene oxygen)-pyridine (AAP):
At 250mL, magnetic stirring bar is housed, in the four-hole round-bottomed flask of prolong and thermometer, adds 7.84g(0.03mol) 5-nitro-2-(4-nitro-phenoxy)-pyridine (NNP), 0.39g palladium-carbon catalyst and the absolute anhydrous methanol of 100ml, violent stirring, room temperature reaction 92h under hydrogen stream, solids removed by filtration reduces pressure and removes ethanol afterwards, get faint yellow solid, column chromatography is purified, AAP5.67g, productive rate 94.3%.
Claims (3)
1. the preparation method of a 5-amino-2-(4-amino-benzene oxygen)-pyridine, its preparation process is:
1) 5-nitro-2-(4-nitro-phenoxy)-pyridine:
In reactor, add 2-chloro-5 nitropyridines, 4-nitrophenols, salt of wormwood and DMF; Stir, heat 85 ~ 90 ℃, keep this temperature condition reaction 3 ~ 4h; Then, reaction solution is cooled to 20 ~ 25 ℃, reaction mixture is poured in 0 ~ 5 ℃ the frozen water and left standstill 12 ~ 15h, collect the solid that produces, water cleans, and is dried to water content≤2%, and column chromatography for separation obtains 5-nitro-2-(4-nitro-phenoxy)-pyridine;
2) 5-amino-2-(4-amino-benzene oxygen)-pyridine:
In reactor, add 5-nitro-2-(4-nitro-phenoxy)-pyridine, palladium-carbon catalyst and dehydrated alcohol or methyl alcohol, stir room temperature reaction 90 ~ 95h under hydrogen stream, HPLC detects, raw material 5-nitro-2-(4-nitro-phenoxy)-and pyridine reacts completely, and reaction finishes, solids removed by filtration, ethanol or methyl alcohol are removed in decompression, get solid, column chromatography is purified, and gets 5-amino-2-(4-amino-benzene oxygen)-pyridine.
2. the preparation method of a kind of 5-amino-2-according to claim 1 (4-amino-benzene oxygen)-pyridine, it is characterized in that: in the step 1), the mol ratio of described 2-chloro-5 nitropyridines, 4-nitrophenols and salt of wormwood is 1:1 ~ 1.2:1.1 ~ 1.4.
3. the preparation method of a kind of 5-amino-2-according to claim 1 (4-amino-benzene oxygen)-pyridine is characterized in that: step 2) in, described palladium carbon accounts for 5-nitro-2-(4-nitro-phenoxy)-mass percent of pyridine is 4 ~ 5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372581A (en) * | 2019-08-19 | 2019-10-25 | 南通嘉禾化工有限公司 | A method of preparing 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2002103A (en) * | 1932-06-30 | 1935-05-21 | Standard Oil Co | Pipe anchor |
| WO2002053150A1 (en) * | 2000-12-27 | 2002-07-11 | Ajinomoto Co., Inc. | Preventives for wound adhesion |
| CN1372548A (en) * | 1999-07-01 | 2002-10-02 | 味之素株式会社 | Heterocyclic compounds and medicinal use thereof |
-
2012
- 2012-11-28 CN CN2012104923859A patent/CN102993091A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2002103A (en) * | 1932-06-30 | 1935-05-21 | Standard Oil Co | Pipe anchor |
| CN1372548A (en) * | 1999-07-01 | 2002-10-02 | 味之素株式会社 | Heterocyclic compounds and medicinal use thereof |
| WO2002053150A1 (en) * | 2000-12-27 | 2002-07-11 | Ajinomoto Co., Inc. | Preventives for wound adhesion |
Non-Patent Citations (3)
| Title |
|---|
| HARRIS L.FRIEDMAN,等: "Tuberculostatic compounds. I. Ethers of 2-hydroxy-5-aminopyridine", 《J.AM.CHEM.SOC.》, vol. 69, no. 5, 31 May 1947 (1947-05-31), pages 1204 - 1206 * |
| INSIK IN,等: "Soluble wholly aromatic polyamides containing unsymmetrical pyridyl ether linkages", 《POLYMER》, vol. 47, no. 2, 15 December 2005 (2005-12-15), pages 547 - 552 * |
| 杨逢春: "新型系列化不对称芳香二胺及其可溶性聚酰亚胺的设计，合成与性能研究", 《兰州大学博士研究生学位论文》, 13 September 2010 (2010-09-13), pages 43 - 45 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372581A (en) * | 2019-08-19 | 2019-10-25 | 南通嘉禾化工有限公司 | A method of preparing 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine |
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Application publication date: 20130327 |