CN101654412B - Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate - Google Patents
Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate Download PDFInfo
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- CN101654412B CN101654412B CN2009101676044A CN200910167604A CN101654412B CN 101654412 B CN101654412 B CN 101654412B CN 2009101676044 A CN2009101676044 A CN 2009101676044A CN 200910167604 A CN200910167604 A CN 200910167604A CN 101654412 B CN101654412 B CN 101654412B
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Abstract
The invention provides a method for preparing 2,7-dicarboxylic-3,6-naphthalenedicarboxylate. The method comprises the following steps: firstly, converting 2,7-dicarboxylic naphthalinum into 2,7-dicarboxylic potassium salt by alkalization; then adding a high-temperature heat medium of hydrogenated terphenyl, obtaining naphtholate; afterwards introducing carbon dioxide, reacting for 4 hours at the temperature of 300-330 DEG C and the pressure of 4-6MPa and obtaining a yellow solid product of the 2,7-dicarboxylic-3,6-naphthalenedicarboxylate by the post-treatment steps of dissolving, filtering, drying and the like. The invention has less synthesis steps, easy operation and low cost. Compared with the prior art, the yield is enhanced by more than 4 times.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic hydroxy-carboxylic, especially a kind of employing liquid gas biphase Kolbe-Schmitt prepared in reaction 2,7-dihydroxyl-3, the method for 6-naphthalene diacid.
Background technology
Aromatic hydroxy-carboxylic can be through known Kolbe-Schmitt reaction, is obtained by aromatic hydroxy compound and carbon dioxide reaction.With 2,4-dihydroxyl-1,5-phthalic acid are example, under the alkaline condition of saleratus, adopt 110 ℃ of temperature, pressure carbon dioxide 0.3Mpa, react 3 hours, and the product productive rate is up to 99.7%; Under the alkaline condition of salt of wormwood, 200 ℃ of temperature, pressure carbon dioxide 0.3Mpa, the reaction times is 4 hours, also obtains 93% productive rate (referring to patent DE3832076,1932-06-08).For the aromatic hydroxy compound that with the naphthalene nucleus is the basis; Though can be by traditional Kolbe-Schmitt reaction system with the single naphthoic acid that replaces of high yield; As being that raw material can be produced 2-hydroxyl-3-naphthoic acid with the β-Nai Fen; The productive rate of this method reaches 41.2% (referring to Japanese publication JP2004323475A, 2004-11-18.).But because the singularity of naphthalene nucleus promptly replaces the difficult substituted in variety and β position, preparation 2,7-dihydroxyl-3, the productive rate of 6-naphthalene diacid is not high all the time.In patent US1896457, introduced Synthetic 2,7-dihydroxyl-3, the method for 6-naphthalene diacid is not mentioned concrete productive rate.Press the document repeated experiments, productive rate is less than 5%.
As everyone knows, 2,7-dihydroxyl-3,6-naphthalene diacid has purposes widely, as can be used as organic raw material, staining agent, pharmaceutical intermediate and plastics additive etc.But up to now, the route of synthetic naphthoic acid only has two: the one, and be raw material with the hydroxyl naphthalene, directly introduce carboxyl; Another is to be raw material with the naphthalene halide, changes into naphthoic acid.Two lines are compared, and article one route is introduced carboxyl, and synthesis step is few, are convenient to implement; The second route reaction time is totally shorter, could introduce carboxyl but will pass through a few step reactions, and operation easier is big, and step is many, and cost is high.Therefore, the expectation exploitation is a raw material with the dihydroxy naphthlene, and adopting improved Kolbe-Schmitt reaction is liquid gas two phase reaction, directly introduces an one-step preparation method of carboxyl, to improve productive rate.
Summary of the invention
The present invention is intended to overcome above-mentioned defective, provides a kind of with traditional solid and gas Kolbe-Schmitt reaction, changes into liquid gas biphase Kolbe-Schmitt prepared in reaction 2,7-dihydroxyl-3, the method for 6-naphthalene diacid of adopting.For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
2,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid is characterized in that being undertaken by following process step:
A, in autoclave, add 2,7 dihydroxy naphthalene, add the methanol solution of Pottasium Hydroxide again in nitrogen protection down, behind the inflated with nitrogen of finding time under room temperature stirring reaction 9～13 hours;
B, in the reaction solution of steps A, add hydrogenated terphenyl, be warming up to 90～110 ℃ after, extract through decompression again that solution obtains anhydrous naphtholate in the autoclave;
C, under nitrogen protection, the anhydrous naphtholate that step B is made is warming up to 250～280 ℃, feeds carbonic acid gas simultaneously;
D, continue to feed carbonic acid gas, reach 4Mpa～6Mpa to pressure, simultaneously temperature is risen to 300～330 ℃, reacted 4～6 hours;
After E, reaction finish, temperature is cooled to room temperature, inclines to going out hydrogenated terphenyl, residual solids is with 80～100 ℃ of hot water dissolvings; Suction filtration, filtrating is acidified to pH 1～3 with concentrated hydrochloric acid, and have a large amount of white solids to separate out this moment, once more suction filtration; Filter cake is used acetone solution, through filtering, steams and removes filtrating solvent, drying; Promptly get yellow solid product 2,7-dihydroxyl-3,6-naphthalene diacid.
The methanol solution of Pottasium Hydroxide described in the steps A is to be dissolved in 16～20 milliliters the methyl alcohol formulated by 1～1.2 gram Pottasium Hydroxide.
The add-on of hydrogenated terphenyl described in the step B is that 1 gram 2,7 dihydroxy naphthalene adds 15～20 milliliters of hydrogenation terphenyls.
The concentration of the used hydrochloric acid of acidifying is in the step e: 30～37%, and W/W.
The add-on of acetone described in the step e is that 1 gram product adds 15～25 milliliters in acetone.
The invention has the advantages that:
Synthesis step is few, easy handling, and cost is low, and compared with prior art, productive rate improves more than 3～4 times.
Embodiment
Embodiment 1:
With 5 grams 2; The 7-dihydroxy naphthlene joins in the autoclave that electric mixing device is housed, and under nitrogen protection, adds the 80 ml methanol solution contain 5 gram Pottasium Hydroxide, the inflated with nitrogen three times of finding time then; To get rid of oxygen in the solution, stirring at room is 12 hours under nitrogen protection.Add 100 milliliters of hydrogenated terphenyls then, be warming up to 100 ℃ after, decompression extracts methyl alcohol and volatile small molecule in the autoclave.Be warming up to 270 ℃, feed dioxide gas, be warmed up to 310 ℃ again, reaction is 4 hours under pressure carbon dioxide 4Mpa condition.After being cooled to room temperature, toppling over and hydrogenated terphenyl, remaining solid is with 80～100 ℃ of hot water dissolvings, suction filtration; Filtrating with concentrated hydrochloric acid (35%, W/W) be acidified to pH 1～3, suction filtration is used acetone solution then once more; Filter, remove the filtrating solvent, drying gets yellow solid product 2; 7-dihydroxyl-3,6-naphthalene diacid, productive rate 20.3%.
1H?NMR(400MHz，DMSO-d
6)δ8.617(s，2H)，7.831(s，2H)。
Embodiment 2:
With 10 grams 2; The 7-dihydroxy naphthlene joins in the autoclave that electric mixing device is housed, and under nitrogen protection, adds the 160 ml methanol solution contain 10 gram Pottasium Hydroxide, the inflated with nitrogen three times of finding time then; To get rid of oxygen in the solution, stirring at room is 12 hours under nitrogen protection.Add 100 milliliters of hydrogenated terphenyls then, be warming up to 100 ℃ after, decompression extracts methyl alcohol and volatile small molecule in the autoclave.Be warming up to 275 ℃, feed dioxide gas, be warmed up to 316 ℃ again, reaction is 4 hours under pressure carbon dioxide 6Mpa condition.After being cooled to room temperature, toppling over and hydrogenated terphenyl, remaining solid is with 80～100 ℃ of hot water dissolvings, suction filtration; Filtrating with concentrated hydrochloric acid (37%, W/W) be acidified to pH 1～3, suction filtration is used acetone solution then once more; Filter, remove the filtrating solvent, drying gets yellow solid product 2; 7-dihydroxyl-3,6-naphthalene diacid, productive rate 22.5%.
1H?NMR(400MHz，DMSO-d
6)δ8.618(s，2H)，7.832(s，2H)。
Claims (5)
1.2,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid is characterized in that being undertaken by following process step:
A, in autoclave, add 2,7 dihydroxy naphthalene, add the methanol solution of Pottasium Hydroxide again in nitrogen protection down, behind the inflated with nitrogen of finding time under room temperature stirring reaction 9～13 hours;
B, in the reaction solution of steps A, add hydrogenated terphenyl, be warming up to 90～110 ℃ after, extract through decompression again that solution obtains anhydrous naphtholate in the autoclave;
C, under nitrogen protection, the anhydrous naphtholate that step B is made is warming up to 250～280 ℃, feeds carbonic acid gas simultaneously;
D, continue to feed carbonic acid gas, reach 4MPa～6MPa to pressure, simultaneously temperature is risen to 300～330 ℃, reacted 4～6 hours;
After E, reaction finish, temperature is cooled to room temperature, inclines to going out hydrogenated terphenyl, residual solids is with 80～100 ℃ of hot water dissolvings; Suction filtration, filtrating with hcl acidifying to pH 1～3, after solid is separated out, suction filtration once more; Filter cake is used acetone solution, and is assorted through filtering, steams and removes filtrating solvent, drying; Promptly get yellow solid product 2,7-dihydroxyl-3,6-naphthalene diacid.
2. as claimed in claim 12,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid, the methanol solution that it is characterized in that Pottasium Hydroxide described in the steps A is to be dissolved in 16～20 milliliters the methyl alcohol formulated by 1～1.2 gram Pottasium Hydroxide.
3. as claimed in claim 12,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid, the add-on that it is characterized in that hydrogenated terphenyl described in the step B are that 1 gram 2,7 dihydroxy naphthalene adds 15～20 milliliters of hydrogenation terphenyls.
4. as claimed in claim 12,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid is characterized in that the concentration of the used hydrochloric acid of acidifying in the step e is: 30～37%, W/W.
5. as claimed in claim 12,7-dihydroxyl-3, the preparation method of 6-naphthalene diacid, the add-on that it is characterized in that acetone described in the step e are that 1 gram product adds 15～25 milliliters in acetone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101676044A CN101654412B (en) | 2009-09-11 | 2009-09-11 | Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate |
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| CN2009101676044A CN101654412B (en) | 2009-09-11 | 2009-09-11 | Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate |
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| CN101654412A CN101654412A (en) | 2010-02-24 |
| CN101654412B true CN101654412B (en) | 2012-07-04 |
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| CN2009101676044A Expired - Fee Related CN101654412B (en) | 2009-09-11 | 2009-09-11 | Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate |
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| CN110776411B (en) * | 2019-11-07 | 2021-01-19 | 北京师范大学 | Method for preparing 2, 7-dihydroxy-3, 6-naphthalene diacid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1896457A (en) * | 1931-01-12 | 1933-02-07 | Gen Aniline Works Inc | 2.7-dihydroxynaphthalene-3.6-dicarboxylic acid |
| CN1569794A (en) * | 2003-04-28 | 2005-01-26 | 株式会社上野制药应用研究所 | Method for preparing aromatic hydroxyl carboxylic acid |
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- 2009-09-11 CN CN2009101676044A patent/CN101654412B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1896457A (en) * | 1931-01-12 | 1933-02-07 | Gen Aniline Works Inc | 2.7-dihydroxynaphthalene-3.6-dicarboxylic acid |
| CN1569794A (en) * | 2003-04-28 | 2005-01-26 | 株式会社上野制药应用研究所 | Method for preparing aromatic hydroxyl carboxylic acid |
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