CN103360242A - Preparation method of 6-hydroxy-2-naphthoic acid - Google Patents
Preparation method of 6-hydroxy-2-naphthoic acid Download PDFInfo
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Abstract
The invention discloses a preparation method of 6-hydroxy-2-naphthoic acid. A finished product with a qualified purity is acquired by carrying out Koble-Schimmit reaction in a special solvent and performing a series of processes of separating and refining. The prepared and synthesized productivity reaches about 39%; simultaneously, due to low cost and extensive source of the applied solvent, the synthesis cost of 6-hydroxy-2-naphthoic acid is effectively controlled; and meanwhile, the after treatment of the synthesized product is also facilitated and the separation and refining of the product are facilitated, so that the grade of quality of the product is improved, the additional value of the product is improved, the production efficiency is improved and the technological operation of extraction is simplified.
Description
Technical field
The present invention relates to a kind of organic synthesis of field of fine chemical, particularly a kind of preparation method who synthesizes 6-Hydroxy-2-naphthoic acid take the 2-naphthoic acid as raw material.
Background technology
Shown in the following formula I, 6-Hydroxy-2-naphthoic acid (claims again 2,6 acid) be the important source material of producing all kinds of aromatic polyester classes, and be widely used in the production of dyestuff, agricultural chemicals and medicine intermediate, particularly production have the liquid crystalline polymers of excellent processing characteristics and flowing property and have favorable elasticity and heat-resistant resin or fiber industry in institute requisite.
Formula(I)
Traditional synthetic method mainly is to utilize the Koble-Schimmit reaction by beta naphthal and CO
2Electrophilic substitution occurs, synthetic obtaining.The production method of 6-Hydroxy-2-naphthoic acid commonly used has following four kinds:
1, Koble-Schimmit reacts to prepare 6-Hydroxy-2-naphthoic acid.The carboxylation reaction of No. 6 positions occurs in this reaction with carbonic acid gas under High Temperature High Pressure take the sylvite of beta naphthal as raw material, make 6-Hydroxy-2-naphthoic acid.（U.S?Patents?Nos.1,593,816?4,287,357?4,345,095?4,329,494?and?4,345,094）。
2, the Koble-Schimmit in the high-temperature medium reacts to prepare 6-Hydroxy-2-naphthoic acid.This reaction is with carbonic acid gas 6 electrophilic substitution carboxylations to occur take the sylvite of beta naphthal as raw material under High Temperature High Pressure in high-temperature medium, makes 6-Hydroxy-2-naphthoic acid.（Japanese?Patent?Applications?Laid-Open?NO.57-95939?and?58-99436）。
3, with the synthetic 6-Hydroxy-2-naphthoic acid of the hydroxylating of aryl halide.This reaction makes 6-Hydroxy-2-naphthoic acid with reaction of carbon monoxide take 6-bromo-beta naphthal as raw material in the presence of catalyzer.（Japanese?Patent?Application?Laid-Open?NO.57-91955）。
4, with 2-(2-hydroxyl-2-propyl group) the standby 6-Hydroxy-2-naphthoic acid of naphthalene-6-carboxylic acid oxidative legal system.This reaction is take 2-(2-hydroxyl-2-propyl group) naphthalene-6-carboxylic acid makes 6-Hydroxy-2-naphthoic acid through hydrogen peroxide oxidation under the catalysis at mineral acid as raw material in second cyanogen solution.（GB2174706）。
But above-described synthetic method has respectively following shortcoming:
For method 1 and method 2, in reaction, have 2, the isomer 2-hydroxyl of 6 acid-3-naphthoic acid generates, simultaneously because the sylvite of beta naphthal is different from the phase of carbonic acid gas, it is insufficient to cause reacting the Raw contact, reaction efficiency is low, only reaches respectively 26.5% and 45% so the productive rate of reaction is all very low.The 6-Hydroxy-2-naphthoic acid of every generation a part just has the beta naphthal generation of a part in while method 1 and the method 2,, cause under the low conversion rate of beta naphthal, brought trouble also for simultaneously the aftertreatment Purification of reaction product.And for method 3, the CO (carbon monoxide converter) gas of using in reaction is relatively more dangerous, and simultaneous reactions is at 70Kg/cm
2Carry out under the high pressure, very high to the requirement of conversion unit, facility investment is large, and also more complicated of the preparation of catalyzer, and as long as the yield of reaction is 37%.And for method 4, the yield of reaction be quantitative and the condition of reaction also comparatively gentle, but the raw material of reaction is comparatively rare, the preparation trouble.
Summary of the invention
For addressing the above problem, the invention discloses a kind of preparation method of 6-Hydroxy-2-naphthoic acid, guaranteed that the synthetic productive rate of preparation reaches about 39%, simultaneously because the solvent cost of selecting is cheap, wide material sources have been controlled 2,6 synthetic cost effectively, also be convenient to simultaneously the aftertreatment of synthetic after product, it is refining to be beneficial to product separation, thereby has promoted the grade of product, has improved value-added content of product, and improved the efficient of producing, simplified the technological operation of purifying.
The preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention comprises the steps:
(1), step of reaction:
Add successively beta naphthal, KOH, solvent in a, the autoclave, solvent is n-tetradecane or 3# white oil or DMF;
B, reactor are heated to temperature T under nitrogen atmosphere
1, stirring, the fractionator solvent reacts complete to the abundant fractionation of product water;
C, pass into CO
2, stir, keep reaction pressure P
1, temperature of reaction T
2, reaction times t
1
D, the reaction complete, the removal reaction pressure is cooled to temperature T
3
(2), separation phase:
E, add entry in the steps d product, fully mix, the water oil mixt that obtains is shifted out reactor, standing demix separates and also retains water while hot;
F, adjusting water PH to A are warming up to T4 again, add the first naphtho-and stir, and extract also while hot standing demix, and water is also retained in separation;
G, stirring water add the first naphthalene and extract also while hot standing demix, separate also retention water;
H, cooling water add acetic acid solution to T5, use the PH to B of dilute sulphuric acid regulator solution again, are cooled to T6 again, filter, and obtain crude product;
(3), refining stage:
I, with step the h crude product that obtains and the gac that accounts for crude product massfraction w1, add in the solvent, stir temperature rising reflux to crude product and dissolve fully, and insulation t2 hour;
J, suction filtration while hot slowly are cooled to T with filtrate
7, crystallization, suction filtration obtain wet product;
K, with the wet product of suction filtration, in temperature T
8Lower oven dry.
The invention discloses a kind of preparation method of 6-Hydroxy-2-naphthoic acid, the oble-Schimmit reaction is carried out in utilization in specific solvent n-tetradecane or 3# white oil or DMF, and through a series of separation and purification process, obtained the qualified finished product of purity, the raw materials cost wide material sources are cheap, and guaranteed that the synthetic productive rate of preparation reaches about 39%, simultaneously because the solvent cost of selecting is cheap, wide material sources have been controlled 2,6 synthetic cost effectively, also be convenient to simultaneously the aftertreatment of synthetic after product, it is refining to be beneficial to product separation, thereby has promoted the grade of product, has improved value-added content of product, and improved the efficient of producing, simplified the technological operation of purifying, so that the repayment of the production of 6-Hydroxy-2-naphthoic acid input is larger.
A kind of improvement of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention, T
1Be 252-254 ℃, P
1Be 0.2-0.4MPa, T
2Be 260-270 ℃, t
1Be 16-20h, T
3Be 100-120 ℃, A is Ph=7-8, T
4Be 90-95 ℃, T
5Be 65-75 ℃, B is Ph=3.0-4.0, T
6Be 20-30 ℃, w
1For being not more than 10%, t
2For being not more than 2h, T
7Be 0-10 ℃, T
8Be 60-100 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods is to optimizing the zone, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved the output of 6-Hydroxy-2-naphthoic acid, and effectively controlled 2, the production cost of 6 acid, thus the input-output ratio that 6-Hydroxy-2-naphthoic acid is produced improved.
Another improvement of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention, T
1Be 252 ℃, P
1Be 0.2MPa, T
2Be 260 ℃, t
1Be 16h, T
3Be 100 ℃, A is Ph=7, T
4Be 90 ℃, T
5Be 65 ℃, B is Ph=3.0, T
6Be 20 ℃, w
1For being not more than 8%, t
2For being not more than 1.5h, T
7Be 0 ℃, T
8It is 60 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
Another improvement of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention, T
1Be 253 ℃, P
1Be 0.3MPa, T
2Be 265 ℃, t
1Be 18h, T
3Be 110 ℃, A is Ph=8, T
4Be 95 ℃, T
5Be 70 ℃, B is Ph=4.0, T
6Be 30 ℃, w
1For being not more than 5%, t
2For being not more than 1h, T
7Be 5 ℃, T
8It is 80 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
Another improvement of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention, T
1Be 254 ℃, P
1Be 0.4MPa, T
2Be 270 ℃, t
1Be 20h, T
3Be 120 ℃, A is Ph=7.5, T
4Be 92.5 ℃, T
5Be 75 ℃, B is Ph=3.5, T
6Be 25 ℃, w
1Be 5%, t
2Be 1h, T
7Be 10 ℃, T
8It is 100 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
Another of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention improved, and the stirring velocity among step b and the step c is 60-80round/min.The stirring velocity in the reaction process is set in this improvement, so that the abundant contact reacts of the raw material in the solvent has avoided again stirring to overrun, and normally carrying out of impact reaction so that raw material is in good reaction contact condition, guaranteed the efficient of reaction, improved the output of product 6-Hydroxy-2-naphthoic acid.
Another of the preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention improved, and the solvent in the step I is the mixture of acetone or water or acetone and water.It is refining solvent that the mixture of acetone, water or acetone and water is adopted in this improvement, and the solvent wide material sources are with low cost, are conducive to the refining purification operations to 6-Hydroxy-2-naphthoic acid, reduced the production cost of enterprise.
The invention discloses a kind of preparation method of 6-Hydroxy-2-naphthoic acid, the oble-Schimmit reaction is carried out in utilization in specific solvent n-tetradecane or 3# white oil, and through a series of separation and purification process, obtained the qualified finished product of purity, the raw materials cost wide material sources are cheap, and guaranteed that the synthetic productive rate of preparation reaches about 39%, simultaneously because the solvent cost of selecting is cheap, wide material sources have been controlled 2,6 synthetic cost effectively, also be convenient to simultaneously the aftertreatment of synthetic after product, it is refining to be beneficial to product separation, thereby has promoted the grade of product, has improved value-added content of product, and improved the efficient of producing, simplified the technological operation of purifying, so that the repayment of the production of 6-Hydroxy-2-naphthoic acid input is larger, set simultaneously the stirring velocity in the reaction process, so that the abundant contact reacts of the raw material in the solvent avoided again stirring and overrun, and normally the carrying out of impact reaction, so that raw material is in good reaction contact condition, guarantee the efficient of reaction, improved the output of product 6-Hydroxy-2-naphthoic acid.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention, should understand following embodiment and only be used for explanation the present invention and be not used in and limit the scope of the invention.
The preparation method of 6-Hydroxy-2-naphthoic acid disclosed by the invention comprises the steps:
(1), step of reaction:
Add successively beta naphthal, KOH, solvent in a, the autoclave, solvent is n-tetradecane or 3# white oil or DMF;
B, reactor are heated to temperature T under nitrogen atmosphere
1, stirring, the fractionator solvent reacts complete to the abundant fractionation of product water;
C, pass into CO
2, stir, keep reaction pressure P
1, temperature of reaction T
2, reaction times t
1
D, the reaction complete, the removal reaction pressure is cooled to temperature T
3
(2), separation phase:
E, add entry in the steps d product, fully mix, the water oil mixt that obtains is shifted out reactor, standing demix separates and also retains water while hot;
F, adjusting water PH to A are warming up to T4 again, add the first naphtho-and stir, and extract also while hot standing demix, and water is also retained in separation;
G, stirring water add the first naphthalene and extract also while hot standing demix, separate also retention water;
H, cooling water add acetic acid solution to T5, use the PH to B of dilute sulphuric acid regulator solution again, are cooled to T6 again, filter, and obtain crude product;
(3), refining stage:
I, with step the h crude product that obtains and the gac that accounts for crude product massfraction w1, add in the solvent, stir temperature rising reflux to crude product and dissolve fully, and insulation t2 hour;
J, suction filtration while hot slowly are cooled to T with filtrate
7, crystallization, suction filtration obtain wet product;
K, with the wet product of suction filtration, in temperature T
8Lower oven dry.
The invention discloses a kind of preparation method of 6-Hydroxy-2-naphthoic acid, the oble-Schimmit reaction is carried out in utilization in specific solvent n-tetradecane or 3# white oil or DMF, and through a series of separation and purification process, obtained the qualified finished product of purity, the raw materials cost wide material sources are cheap, and guaranteed that the synthetic productive rate of preparation reaches about 39%, simultaneously because the solvent cost of selecting is cheap, wide material sources have been controlled 2,6 synthetic cost effectively, also be convenient to simultaneously the aftertreatment of synthetic after product, it is refining to be beneficial to product separation, thereby has promoted the grade of product, has improved value-added content of product, and improved the efficient of producing, simplified the technological operation of purifying, so that the repayment of the production of 6-Hydroxy-2-naphthoic acid input is larger.
As a kind of preferred, T
1Be 252-254 ℃, P
1Be 0.2-0.4MPa, T
2Be 260-270 ℃, t
1Be 16-20h, T
3Be 100-120 ℃, A is Ph=7-8, T
4Be 90-95 ℃, T
5Be 65-75 ℃, B is Ph=3.0-4.0, T
6Be 20-30 ℃, w
1For being not more than 10%, t
2For being not more than 2h, T
7Be 0-10 ℃, T
8Be 60-100 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods is to optimizing the zone, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved the output of 6-Hydroxy-2-naphthoic acid, and effectively controlled 2, the production cost of 6 acid, thus the input-output ratio that 6-Hydroxy-2-naphthoic acid is produced improved.
As a kind of preferred, T
1Be 252 ℃, P
1Be 0.2MPa, T
2Be 260 ℃, t
1Be 16h, T
3Be 100 ℃, A is Ph=7, T
4Be 90 ℃, T
5Be 65 ℃, B is Ph=3.0, T
6Be 20 ℃, w
1For being not more than 8%, t
2For being not more than 1.5h, T
7Be 0 ℃, T
8It is 60 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
As a kind of preferred, T
1Be 253 ℃, P
1Be 0.3MPa, T
2Be 265 ℃, t
1Be 18h, T
3Be 110 ℃, A is Ph=8, T
4Be 95 ℃, T
5Be 70 ℃, B is Ph=4.0, T
6Be 30 ℃, w
1For being not more than 5%, t
2For being not more than 1h, T
7Be 5 ℃, T
8It is 80 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
As a kind of preferred, T
1Be 254 ℃, P
1Be 0.4MPa, T
2Be 270 ℃, t
1Be 20h, T
3Be 120 ℃, A is Ph=7.5, T
4Be 92.5 ℃, T
5Be 75 ℃, B is Ph=3.5, T
6Be 25 ℃, w
1Be 5%, t
2Be 1h, T
7Be 10 ℃, T
8It is 100 ℃.This improvement is by limiting 2, reaction parameter among the 6 sour preparation methods, be conducive to promote abundant contact and the reaction of raw material, thereby effectively improved the production efficiency of product, improved 2, the output of 6 acid, and effectively controlled the production cost of 6-Hydroxy-2-naphthoic acid, thereby improved 2, the input-output ratio that 6 acid are produced has reduced production cost and production difficulty.
As a kind of preferred, the stirring velocity among step b and the step c is 60-80round/min.The stirring velocity in the reaction process is set in this improvement, so that the abundant contact reacts of the raw material in the solvent has avoided again stirring to overrun, and normally carrying out of impact reaction so that raw material is in good reaction contact condition, guaranteed the efficient of reaction, improved the output of product 6-Hydroxy-2-naphthoic acid.
As a kind of preferred, the solvent in the step I is the mixture of acetone or water or acetone and water.It is refining solvent that the mixture of acetone, water or acetone and water is adopted in this improvement, and it is large to crystallize into crystalline substance, and the solvent wide material sources are with low cost simultaneously, are conducive to the refining purification operations to 6-Hydroxy-2-naphthoic acid, reduced the production cost of enterprise.
Embodiment 1
The beta naphthal (2.91mol, 99%) that adds successively 420g in the autoclave of 2000ml, the KOH(2.79mol of 170g, 92%); behind the 550ml solvent n-tetradecane, be warming up to 254 ℃ under the nitrogen protection, make its backflow; steam certain water, minute water is complete, passes into CO
2, keeping 0.3Mpa pressure, reaction is 16 hours under 265 ℃ of temperature; After reaction finished, removal pressure was cooled to 100 ℃; Add 500 mL water to reaction mixture; Extract still internal reaction thing out, standing demix while hot, water layer is retained.Water layer drips dilute sulphuric acid, makes its pH=7; Be warming up to 90 ℃, stir and the extraction of adding 500mL first naphthalene; While hot layering, water layer is retained.Water layer stirs and adding 500mL first naphthalene reextraction; While hot layering, water layer is retained.Water layer is cooled to 65 ℃, adds 15% acetic acid solution 100g, drips dilute sulphuric acid, makes its pH=3.5, separates out the light yellow solid powder, be cooled to 20 ℃ after suction filtration.Obtain the wet product 300g of crude product, HPLC content: 98.53%.
Crude product 150g, acetone 400g, water 100g; The gac that adds crude product weight 5%; Stirring is warming up to reflux crude product is dissolved fully, insulation 1h; While hot press filtration; Filtrate is slowly cold to be cooled to 0 ℃; The suction filtration product that must wet; Dry to get 109g for 80 ℃.HPLC content: 99.88%, yield: 40%.
Embodiment 2:
Charging capacity is consistent with case study on implementation 1 with feeding sequence, only makes reaction solvent into the 3# white oil, and other conditions are constant, and the result gets 219g.HPLC content: 99.92%, yield: 40%.
Embodiment 3
Charging capacity is consistent with case study on implementation 1 with feeding sequence, only makes reaction solvent into DMF, and other conditions are constant, and the result gets 219g.HPLC content: 99.92%, yield: 40%.
Embodiment 4
The beta naphthal (2.91mol, 99%) that adds successively 420g in the autoclave of 2000ml, the KOH(2.79mol of 170g, 92%); behind the 550ml solvent n-tetradecane, be warming up to 253 ℃ under the nitrogen protection, make its backflow; steam certain water, minute water is complete, passes into CO
2, keeping 0.2Mpa pressure, reaction is 18 hours under 260 ℃ of temperature; After reaction finished, removal pressure was cooled to 110 ℃; Add 500 mL water to reaction mixture; Extract still internal reaction thing out, standing demix while hot, water layer is retained.Water layer drips dilute sulphuric acid, makes its pH=7.5; Be warming up to 93 ℃, stir and the extraction of adding 500mL first naphthalene; While hot layering, water layer is retained.Water layer stirs and adding 500mL first naphthalene reextraction; While hot layering, water layer is retained.Water layer is cooled to 70 ℃, adds 15% acetic acid solution 100g, drips dilute sulphuric acid, makes its pH=3.0, separates out the light yellow solid powder, be cooled to 25 ℃ after suction filtration.Obtain the wet product 298g of crude product, HPLC content: 98.33%.
Crude product 150g, water 300g; The gac that adds crude product weight 5%; Stir 50-60 ℃ of intensification, use liquid caustic soda to transfer PH to 9-10, then heat to backflow, crude product is dissolved fully, insulation 1h; While hot press filtration; Filtrate is slowly cold to be cooled to 0-5 ℃; Drip dilute sulphuric acid, make its pH=3.5-4.0, separate out the light yellow solid powder, the suction filtration product that must wet; Dry to get 107g for 80 ℃.HPLC content: 99.97%, yield: 38.7%.
Enforcement case 5:
Charging capacity is consistent with case study on implementation 4 with feeding sequence, only makes reaction solvent into the 3# white oil, and other conditions are constant, and the result gets 217g.HPLC content: 99.92%, yield: 39.6%.
Embodiment 6
Charging capacity is consistent with case study on implementation 4 with feeding sequence, only makes reaction solvent into DMF, and other conditions are constant, and the result gets 218g.HPLC content: 99.92%, yield: 39.8%.
Embodiment 7
The beta naphthal (2.91mol, 99%) that adds successively 420g in the autoclave of 2000ml, the KOH(2.79mol of 170g, 92%); behind the 550ml solvent n-tetradecane, be warming up to 252 ℃ under the nitrogen protection, make its backflow; steam certain water, minute water is complete, passes into CO
2, keeping 0.4Mpa pressure, reaction is 20 hours under 270 ℃ of temperature; After reaction finished, removal pressure was cooled to 120 ℃; Add 500 mL water to reaction mixture; Extract still internal reaction thing out, standing demix while hot, water layer is retained.Water layer drips dilute sulphuric acid, makes its pH=8; Be warming up to 95 ℃, stir and the extraction of adding 500mL first naphthalene; While hot layering, water layer is retained.Water layer stirs and adding 500mL first naphthalene reextraction; While hot layering, water layer is retained.Water layer is cooled to 75 ℃, adds 15% acetic acid solution 100g, drips dilute sulphuric acid, makes its pH=4.0, separates out the light yellow solid powder, be cooled to 30 ℃ after suction filtration.Obtain the wet product 299g of crude product, HPLC content: 98.43%.
Crude product 150g, acetone 400g, water 100g; The gac that adds crude product weight 10%; Stirring is warming up to reflux crude product is dissolved fully, insulation 2h; While hot press filtration; Filtrate is slowly cold to be cooled to 5 ℃; The suction filtration product that must wet; Dry to get 108g for 100 ℃.HPLC content: 99.87%, yield: 39.3%.
Embodiment 8:
Charging capacity is consistent with case study on implementation 7 with feeding sequence, only makes reaction solvent into the 3# white oil, and other conditions are constant, and the result gets 218g.HPLC content: 99.92%, yield: 39.8%.
Embodiment 9
Charging capacity is consistent with case study on implementation 7 with feeding sequence, only makes reaction solvent into DMF, and other conditions are constant, and the result gets 217g.HPLC content: 99.92%, yield: 39.6%.
The invention discloses a kind of preparation method of 6-Hydroxy-2-naphthoic acid, the oble-Schimmit reaction is carried out in utilization in specific solvent n-tetradecane or 3# white oil, and through a series of separation and purification process, obtained the qualified finished product of purity, the raw materials cost wide material sources are cheap, and guaranteed that the synthetic productive rate of preparation reaches about 39%, simultaneously because the solvent cost of selecting is cheap, wide material sources have been controlled 2,6 synthetic cost effectively, also be convenient to simultaneously the aftertreatment of synthetic after product, it is refining to be beneficial to product separation, thereby has promoted the grade of product, has improved value-added content of product, and improved the efficient of producing, simplified the technological operation of purifying, so that the repayment of the production of 6-Hydroxy-2-naphthoic acid input is larger, set simultaneously the stirring velocity in the reaction process, so that the abundant contact reacts of the raw material in the solvent avoided again stirring and overrun, and normally the carrying out of impact reaction, so that raw material is in good reaction contact condition, guarantee the efficient of reaction, improved the output of product 6-Hydroxy-2-naphthoic acid.
The disclosed technique means of the present invention program is not limited only to the disclosed technique means of above-mentioned technique means, also comprises the technical scheme that is comprised of above technical characterictic arbitrary combination.
Claims (7)
1. the preparation method of a 6-Hydroxy-2-naphthoic acid, it is characterized in that: the preparation method of described 6-Hydroxy-2-naphthoic acid comprises the steps:
(1), step of reaction:
Add successively beta naphthal, KOH, solvent in a, the autoclave, solvent is n-tetradecane or 3# white oil or DMF;
B, reactor are heated to temperature T under nitrogen atmosphere
1, stirring, the fractionator solvent reacts complete to the abundant fractionation of product water;
C, pass into CO
2, stir, keep reaction pressure P
1, temperature of reaction T
2, reaction times t
1
D, the reaction complete, the removal reaction pressure is cooled to temperature T
3
(2), separation phase:
E, add entry in the steps d product, fully mix, the water oil mixt that obtains is shifted out reactor, standing demix separates and also retains water while hot;
F, adjusting water PH to A are warming up to T4 again, add the first naphtho-and stir, and extract also while hot standing demix, and water is also retained in separation;
G, stirring water add the first naphthalene and extract also while hot standing demix, separate also retention water;
H, cooling water add acetic acid solution to T5, use the PH to B of dilute sulphuric acid regulator solution again, are cooled to T6 again, filter, and obtain crude product;
(3), refining stage:
I, with step the h crude product that obtains and the gac that accounts for crude product massfraction w1, add in the solvent, stir temperature rising reflux to crude product and dissolve fully, and insulation t2 hour;
J, suction filtration while hot slowly are cooled to T with filtrate
7, crystallization, suction filtration obtain wet product;
K, with the wet product of suction filtration, in temperature T
8Lower oven dry.
2. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 1 is characterized in that: described T
1Be 252-254 ℃, P
1Be 0.2-0.4MPa, T
2Be 260-270 ℃, t
1Be 16-20h, T
3Be 100-120 ℃, A is Ph=7-8, T
4Be 90-95 ℃, T
5Be 65-75 ℃, B is Ph=3.0-4.0, T
6Be 20-30 ℃, w
1For being not more than 10%, t
2For being not more than 2h, T
7Be 0-10 ℃, T
8Be 60-100 ℃.
3. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 2 is characterized in that: described T
1Be 252 ℃, P
1Be 0.2MPa, T
2Be 260 ℃, t
1Be 16h, T
3Be 100 ℃, A is Ph=7, T
4Be 90 ℃, T
5Be 65 ℃, B is Ph=3.0, T
6Be 20 ℃, w
1For being not more than 8%, t
2For being not more than 1.5h, T
7Be 0 ℃, T
8It is 60 ℃.
4. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 2 is characterized in that: described T
1Be 253 ℃, P
1Be 0.3MPa, T
2Be 265 ℃, t
1Be 18h, T
3Be 110 ℃, A is Ph=8, T
4Be 95 ℃, T
5Be 70 ℃, B is Ph=4.0, T
6Be 30 ℃, w
1For being not more than 5%, t
2For being not more than 1h, T
7Be 5 ℃, T
8It is 80 ℃.
5. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 2 is characterized in that: described T
1Be 254 ℃, P
1Be 0.4MPa, T
2Be 270 ℃, t
1Be 20h, T
3Be 120 ℃, A is Ph=7.5, T
4Be 92.5 ℃, T
5Be 75 ℃, B is Ph=3.5, T
6Be 25 ℃, w
1Be 5%, t
2Be 1h, T
7Be 10 ℃, T
8It is 100 ℃.
6. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 1, it is characterized in that: the stirring velocity among described step b and the step c is 60-80round/min.
7. the preparation method of 6-Hydroxy-2-naphthoic acid according to claim 1, it is characterized in that: the solvent in the described step I is the mixture of acetone or water or acetone and water.
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Cited By (5)
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| CN112707808A (en) * | 2020-12-25 | 2021-04-27 | 宿迁思睿屹新材料有限公司 | Preparation process of 2-hydroxy-6-naphthoic acid |
| CN113698292A (en) * | 2021-09-16 | 2021-11-26 | 宿迁思睿屹新材料有限公司 | Preparation method of 6-hydroxy-2-naphthoic acid |
| CN114057566A (en) * | 2021-12-09 | 2022-02-18 | 宁夏清研高分子新材料有限公司 | Preparation method of 2-hydroxy-6-naphthoic acid |
| CN114524723A (en) * | 2022-01-29 | 2022-05-24 | 宿迁思睿屹新材料有限公司 | 2-hydroxy-6-naphthoic acid preparation process capable of continuous production and control device thereof |
| CN115536515A (en) * | 2022-10-13 | 2022-12-30 | 衢州英特高分子材料有限公司 | Preparation method of 2-hydroxy-6-naphthoic acid |
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