CN121085772A - Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereof - Google Patents
Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereofInfo
- Publication number
- CN121085772A CN121085772A CN202511302575.3A CN202511302575A CN121085772A CN 121085772 A CN121085772 A CN 121085772A CN 202511302575 A CN202511302575 A CN 202511302575A CN 121085772 A CN121085772 A CN 121085772A
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- naphthol
- naphthoic acid
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of 6-hydroxy-2-naphthoic acid production, in particular to a synthetic method of 6-hydroxy-2-naphthoic acid and derivatives thereof. 2-naphthol is taken as a raw material and is subjected to esterification reaction with formic acid to obtain 2-naphthol formate with nearly quantitative yield. The compound is catalyzed by trifluoromethanesulfonic acid and subjected to classical fries rearrangement reaction to obtain 6-hydroxy-2-naphthaldehyde with higher selectivity, and simultaneously, a small amount of derivatives such as 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde and the like are obtained. The obtained 6-hydroxy-2-naphthaldehyde and 2-hydroxy-1-naphthaldehyde are oxidized to obtain 6-hydroxy-2-naphthoic acid and 2-hydroxy-1-naphthoic acid. The method is carried out in a liquid phase homogeneous system, improves the mass transfer and heat transfer problems of the traditional heterogeneous system reaction, has higher yield, better product selectivity, convenient post-treatment and environmental protection, and is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of 6-hydroxy-2-naphthoic acid production, in particular to a synthetic method of 6-hydroxy-2-naphthoic acid and derivatives thereof.
Background
The polyester is a generic name of polymers obtained by polycondensation of polyalcohol and polybasic acid, is a kind of hetero-chain polymer containing ester groups in the repeating units of the polymer molecular chain, and is widely applied to industries such as electronic appliances, agriculture, national defense science and technology, food packaging, industrial fibers and the like. Aromatic polyesters such as polyethylene terephthalate (PET) have the characteristics of friction resistance, small hygroscopicity, good dimensional stability, excellent insulating property, high chemical stability and the like, and rapidly develop into the synthetic fiber variety with the largest current yield due to the fact that the molecular chain of the aromatic polyesters contains aromatic groups, so that the rigidity of the aromatic polyesters is enhanced, the melting point of the aromatic polyesters is increased. The naphthalene ring is introduced into the polyester structure, and has a larger conjugated structure than the benzene ring, so that the rigidity is high, and the polyester material has higher performance. For example, the rigid naphthalene-containing aryl polyester synthesized by taking 6-hydroxy-2-naphthoic acid (HNA) as a main intermediate has excellent physical and mechanical properties, gas barrier properties, heat resistance, ultraviolet resistance, radiation resistance and the like, is a key intermediate for preparing Thermotropic Liquid Crystal Polymers (TLCPs), and has great application prospects in the tip fields of aviation, electronic information, petroleum exploration and the like.
Scientists as early as 1926 have adopted Kolbe-Schmitt reaction to obtain 6-hydroxy-2-naphthoic acid, namely 2-naphthol and alkali reaction to obtain 2-naphthol salt, and condensing with carbon dioxide at a certain temperature and pressure to obtain the product. However, the reaction is a gas-solid-liquid multiphase reaction, the mass transfer and heat transfer problems in the reaction are outstanding, the reaction time is longer, the side reaction is more, and the product quality stability is poor. Chinese patent application CN1569794a, published as 2005.01.26, discloses a process for the preparation of aromatic hydroxycarboxylic acids, indicating that in the presence of an alkali metal salt of an insoluble aromatic phenol in a solution system, the reactivity of carbon dioxide and 2-naphtholate is improved. The reaction of 2-naphthol with carbon dioxide in kerosene to give 6-hydroxy-2-naphthoic acid is reported in literature (IijimaT, et al Journal of the Japan Petroleum Institute, 2008, 51 (1): 65-69.) and the reaction time, reaction temperature and influence of alkali metal cations on the reaction are investigated. The reaction of potassium 2-naphtholate is shown to be significantly better than that of sodium 2-naphtholate, and carboxylation of sodium 2-naphtholate produces only a small amount of 6-hydroxy-2-naphthoic acid. Literature (WangY, et al ADVANCED MATERIALS RESEARCH, 2013, 634-638:2044-2048.) uses 2-naphthol as a raw material, and is carboxylated after methyl protection, bromination and Grignard reaction, and then deprotected to obtain 6-hydroxy-2-naphthoic acid in 78.5% total yield. The synthetic method has longer route and higher production cost. Chinese patent application CN101045684A, with publication time 2007.04.02, discloses a method for preparing 2-hydroxynaphthalene-3, 6-dicarboxylic acid, which uses potassium 2-naphtholate and carbon dioxide as raw materials, takes aliphatic hydrocarbon as solvent at 150-400 ℃ and obtains 2-hydroxynaphthalene-3, 6-dicarboxylic acid with higher yield. The Chinese patent application CN117776901A, with the publication time 2024.03.29, discloses a method for continuously producing 6-hydroxy-2-naphthoic acid, and the main reaction is introduced into a tubular reactor, so that the method has the advantages of small occupied area, good mass transfer, difficult back mixing and the like. The literature (Nakamura R, et al Tetrahedron, 2009, 65 (18): 3577-3581.) reports a novel process for preparing 6-hydroxy-2-naphthoic acid starting from 2, 6-diisopropylnaphthalene. 2, 6-diisopropyl naphthalene is oxidized under the catalysis of Co and Mn compounds to obtain 6-acetyl-2-isopropyl naphthalene, and then is further oxidized and hydroxylated to obtain 6-hydroxy-2-naphthoic acid. Chinese patent application CN113698292A, publication time 2021.11.26, discloses a preparation method of 6-hydroxy-2-naphthoic acid, which takes 6-isopropyl-2-naphthoic acid ethyl ester as raw material, and carries out hydroxylation on isopropyl through free radical reaction to obtain 6-hydroxy-2-naphthoic acid ethyl ester, and then carries out hydrolysis and acidification to obtain the target product 6-hydroxy-2-naphthoic acid. U.S. patent application No. US5075496, publication No. 1991.12.24, discloses the production of 2, 6-hydroxynaphthoic acid (manufacturing of 2, 6-hydroxynaphthoic acid), using 2-naphthol as raw material, firstly forming naphtholate to obtain 2-naphthol cesium or 2-naphthol rubidium, condensing with carbon dioxide, and obtaining 6-hydroxy-2-naphthoic acid in good yield. The research improves the synthesis process of the 6-hydroxy-2-naphthoic acid to a certain extent, but the mass transfer problem under an inherent multiphase system is not changed at all, and some reactions have the defects of high production cost, more reaction byproducts, complex post-treatment and the like.
Disclosure of Invention
According to the defects in the prior art, the invention aims to provide a synthesis method of 6-hydroxy-2-naphthoic acid and derivatives thereof, which takes 2-naphthol as a raw material to carry out esterification reaction with formic acid to obtain 2-naphthol formate with nearly quantitative yield. The compound is catalyzed by trifluoromethanesulfonic acid and subjected to classical fries rearrangement reaction to obtain 6-hydroxy-2-naphthaldehyde with higher selectivity, and simultaneously, a small amount of derivatives such as 2-hydroxy-1-naphthaldehyde, 3-hydroxy-2-naphthaldehyde and the like are obtained. The obtained 6-hydroxy-2-naphthaldehyde and 2-hydroxy-1-naphthaldehyde are oxidized to obtain 6-hydroxy-2-naphthoic acid and 2-hydroxy-1-naphthoic acid. The method is carried out in a liquid phase homogeneous system, improves the mass transfer and heat transfer problems of the traditional heterogeneous system reaction, has higher yield, better product selectivity, convenient post-treatment and environmental protection, and is beneficial to industrial production.
The invention is realized by adopting the following technical scheme:
The synthesis method of the 6-hydroxy-2-naphthoic acid and the derivatives thereof comprises the following steps:
(1) Dropwise adding formic acid into acetic anhydride to obtain a mixture, stirring the mixture, dropwise adding the mixture into a dichloromethane solution in which 2-naphthol and sodium bicarbonate are suspended, stirring the mixture at room temperature, adding a saturated sodium carbonate aqueous solution to quench the reaction, extracting the reaction product, combining the dichloromethane solution, drying the dichloromethane solution, and removing the solvent under reduced pressure to obtain 2-naphthol formate;
。
(2) Adding 2-naphthol formate into trifluoromethanesulfonic acid, stirring, detecting the reaction of raw materials by thin layer chromatography, evaporating the solution, and separating and purifying the obtained product to obtain 6-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde and 3-hydroxy-2-naphthaldehyde;
。
(3) ① adding 6-hydroxy-2-naphthaldehyde and sodium hydroxide into water, stirring until raw materials are dissolved, gradually adding hydrogen peroxide and sodium chlorite, continuing stirring at room temperature, detecting that the raw materials are reacted through thin layer chromatography, adjusting the pH value of reaction liquid to 3, separating out solid, filtering to obtain a crude product, and recrystallizing the crude product to obtain 6-hydroxy-2-naphthoic acid;
。
② Adding 2-hydroxy-1-naphthaldehyde and sodium hydroxide into water, stirring until the raw materials are dissolved, gradually adding hydrogen peroxide and sodium chlorite, continuously stirring at room temperature, detecting the reaction of the raw materials by thin layer chromatography, adjusting the pH value of the reaction solution to 3, separating out solid, filtering to obtain a crude product, and recrystallizing the crude product with ethanol to obtain 2-hydroxy-1-naphthoic acid;
。
In the step (1), the molar ratio of formic acid to acetic anhydride is 1 (1-1.5), the molar ratio of formic acid to 2-naphthol is (3-4) 1, the molar ratio of 2-naphthol to sodium bicarbonate is 1 (2-3), the molar ratio of 2-naphthol formate to trifluoromethanesulfonic acid is 1 (14-16) in the step (2), the molar ratio of 6-hydroxy-2-naphthol formaldehyde to sodium hydroxide is 1:1 in the step ①, and the molar ratio of 2-hydroxy-1-naphthol formaldehyde to sodium hydroxide is 1:1 in the step ②.
In the step (1), the mixture is stirred for 40-45 minutes at 58-60 ℃ and then cooled to room temperature, the molar ratio of dichloromethane to 2-naphthol is (15-16): 1, the stirring time at room temperature is 4.5-5 hours, and the dosage of saturated sodium carbonate aqueous solution is 2-2.5 times of that of dichloromethane solution.
In the step (2), stirring is carried out for 1-1.5 hours at room temperature, heating the reaction mixture to 60-90 ℃ gradually, stirring for 6-8 hours, separating and purifying the product by a silica gel column chromatography column, wherein the mobile phase is ethyl acetate/petroleum ether=1/15 v/v.
In the step ①, the concentration of the hydrogen peroxide is 30%, the adding amount is 2-3 times of the adding amount of the 6-hydroxy-2-naphthaldehyde by mol, and the mol ratio of the hydrogen peroxide to the sodium chlorite is 3:2.
In the step ②, the concentration of the hydrogen peroxide is 30%, the adding amount is 3 times of the adding amount of the 6-hydroxy-2-naphthaldehyde by mol, and the mol ratio of the hydrogen peroxide to the sodium chlorite is (3-4): 2.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention synthesizes 6-hydroxy-2-naphthoic acid and derivatives thereof by adopting a novel route and method. The compound takes 2-naphthol as a raw material, and is subjected to esterification reaction with formic acid to obtain naphthol formate with nearly quantitative yield. Under the action of a catalyst, 6-hydroxy-2-naphthaldehyde, a small amount of 2-hydroxy-1-naphthaldehyde and a trace amount of 3-hydroxy-2-naphthaldehyde are obtained through fries rearrangement reaction with higher selectivity. The obtained 6-hydroxy-2-naphthaldehyde is oxidized to obtain the high-performance polyester synthetic monomer 6 hydroxy-2-naphthoic acid. The derivative 2-hydroxy-1-naphthoic acid can be obtained after the oxidation of 2-hydroxy-1-naphthoaldehyde.
(2) The synthesis reaction of the invention is safe and reliable, the process is simple and easy to control, the reaction yield is high, the selectivity is good, and the three wastes are less discharged.
Drawings
FIG. 1 is a hydrogen spectrum of 2-naphthol formate obtained in the step (1) of example 1 of the present invention;
FIG. 2 is a graph showing the carbon spectrum of 2-naphthol formate obtained in the step (1) of example 1 of the present invention;
FIG. 3 is a hydrogen spectrum of 6-hydroxy-2-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 4 is a carbon spectrum of 6-hydroxy-2-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 5 is a hydrogen spectrum of 2-hydroxy-1-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 6 is a carbon spectrum of 2-hydroxy-1-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 7 is a hydrogen spectrum of 3-hydroxy-2-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 8 is a carbon spectrum of 3-hydroxy-2-naphthaldehyde obtained in step (2) of example 1 of the present invention;
FIG. 9 is a hydrogen spectrum of 6-hydroxy-2-naphthoic acid obtained in step ① of example 1 of the present invention;
FIG. 10 is a carbon spectrum of 6-hydroxy-2-naphthoic acid obtained in step ① of example 1 of the present invention;
FIG. 11 is a hydrogen spectrum of 2-hydroxy-1-naphthoic acid obtained in step ② of example 1 of the present invention;
FIG. 12 is a carbon spectrum of 2-hydroxy-1-naphthoic acid obtained in step ② of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below in order to make the objects and technical solutions of the present invention more apparent.
Example 1
The synthesis method of the 6-hydroxy-2-naphthoic acid and the derivatives thereof comprises the following steps:
(1) 13.8 g (0.3 mol) of formic acid are gradually added dropwise to 30.6 g (0.3 mol) of acetic anhydride, the resulting mixture is stirred at 60℃for 40 minutes and then cooled to room temperature, and then gradually added dropwise to 100mL of a dichloromethane solution in which 14.4 g (0.1 mol) of 2-naphthol and 16.8 g (0.2 mol) of sodium hydrogencarbonate are suspended, after stirring at room temperature for 5 hours, 200mL of saturated aqueous sodium carbonate solution is added to quench the reaction, the dichloromethane organic phase solution is separated, the aqueous phase is extracted 2 times with 100mL of dichloromethane, the dichloromethane solution is combined, after drying over anhydrous Na 2SO4, the solvent is removed under reduced pressure, 16.3 g (0.095 mol) of 2-naphthoate as a colorless oily liquid is obtained in a yield of 95%. The hydrogen spectrum of the 2-naphthol formate is shown in figure 1 (figure ,1H NMR (500 MHz, Chloroform-d) 8.28 (s, 1H), 7.75 (t, J = 8.4 Hz, 2H), 7.70 (d, J = 7.7 Hz, 1H), 7.49 (d, J = 2.2 Hz, 1H), 7.39 (pd, J = 6.9, 1.4 Hz, 2H), 7.15 (dd, J = 8.9, 2.3 Hz, 1H).）;2-. The carbon spectrum of the naphthol formate is shown in figure 2 (figure ：13C NMR (126 MHz, Chloroform-d) δ 158.37, 146.48, 132.62, 130.59, 128.78, 126.78, 126.62, 125.83, 125.00, 119.39, 117.15.）.
(2) 6.88G (40.0 mmol) of 2-naphthol formate was added to 50mL of trifluoromethanesulfonic acid, stirred at room temperature for 1 hour, the reaction mixture was heated gradually to 60℃and stirred for 6 hours, the reaction of the starting materials was detected by thin layer chromatography, the solution was evaporated to dryness under reduced pressure, and the obtained product was purified by column chromatography on silica gel (mobile phase: ethyl acetate/petroleum ether=1/15 v/v) to give 5.65 g (32.8 mmol) of 6-hydroxy-2-naphthol formaldehyde with a yield of 82%, 0.62 g (3.6 mmol) of 2-hydroxy-1-naphthol formaldehyde with a yield of 9%, and 0.21 g (1.2 mmol) of 3-hydroxy-2-naphthol formaldehyde with a yield of 3%. The hydrogen spectrum of 6-hydroxy-2-naphthaldehyde is shown in FIG. 3（1H NMR (500 MHz, DMSO-d6) δ 10.34 (s, 1H), 10.04 (s, 1H), 8.42 (s, 1H), 8.01 (d, J = 8.6 Hz,1H), 7.86 – 7.74 (m, 2H), 7.22 (dd, J = 8.8, 2.5 Hz, 2H).）;6-, the carbon spectrum of hydroxy-2-naphthaldehyde is shown in FIG. 4（13C NMR (126 MHz, DMSO-d6) δ 168.11, 157.94, 137.43, 131.60, 131.02, 127.12, 126.66, 125.97, 125.27, 119.94, 109.16.）.2-, the hydrogen spectrum of hydroxy-1-naphthaldehyde is shown in FIG. 5 (the carbon spectrum of ：1H NMR (500 MHz, Chloroform-d) δ 13.08 (s, 1H), 10.72 (s, 1H), 8.25 (d, J = 8.5 Hz, 1H), 7.89 (d, J = 9.1Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.53 (t, J = 7.7 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 9.1 Hz, 1H).）;2- hydroxy-1-naphthaldehyde is shown in FIG. 6（13C NMR (126 MHz, Chloroform-d) δ 192.25, 163.91, 138.12, 131.86, 128.45, 128.10, 126.77, 123.48, 118.15, 117.56, 110.25.）.3-, the hydrogen spectrum of hydroxy-2-naphthaldehyde is shown in FIG. 7 (the carbon spectrum of ：1H NMR (500 MHz, Chloroform-d) δ 10.24 (s, 1H), 9.98 (s, 1H),8.04 (s, 1H), 7.77 (d, J = 8.3 Hz, 1H), 7.62 (d, J = 8.4 Hz, 1H), 7.47(t, J = 7.3 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 7.19 (s, 1H).）;3- hydroxy-2-naphthaldehyde is shown in FIG. 8 (the carbon spectrum of ：1H NMR (500 MHz, Chloroform-d) δ 10.24 (s, 1H), 9.98 (s, 1H),8.04 (s, 1H), 7.77 (d, J = 8.3 Hz, 1H), 7.62 (d, J = 8.4 Hz, 1H), 7.47(t, J = 7.3 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 7.19 (s, 1H).）;3- hydroxy-2-naphthaldehyde is shown in the drawing) ,13C NMR (126 MHz, Chloroform-d) δ 195.64, 154.79, 137.16, 136.82, 129.25, 128.33, 126.37, 125.64, 123.38, 121.25, 110.90.）.
(3) ① 1.72G (10.0 mmol) of 6-hydroxy-2-naphthanaldehyde and 0.4g (10.0 mmol) of sodium hydroxide are added to 60mL of water and the mixture is stirred at room temperature for 20 minutes until the starting material is completely dissolved. Then, 3.4 g (30.0 mmol) of 30% hydrogen peroxide and 1.80g (20.0 mmol) of sodium chlorite are gradually added, stirring is continued for 5 hours at room temperature, after the thin layer chromatography detects that the raw material reaction is finished, the pH value of the reaction solution is adjusted to 3 by 37% hydrochloric acid, solids are separated out, the solid is filtered, a crude product is obtained, and after the crude product is recrystallized by ethanol, 1.73 g (9.2 mmol) of 6-hydroxy-2-naphthoic acid is obtained, and the yield is 92%. The hydrogen spectrum of 6-hydroxy-2-naphthoic acid is shown in FIG. 9 (the carbon spectrum of ,1H NMR (500 MHz, DMSO-d6) δ 12.82 (s, 1H), 10.16 (s, 1H), 8.50 (s, 1H), 7.97 (d, J = 8.9 Hz, 1H), 7.89 (dd, J = 8.6, 1.7 Hz, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.24 – 7.15 (m, 2H).）;6- hydroxy-2-naphthoic acid is shown in the figure) 10（13C NMR (126 MHz, DMSO-d6) δ 168.11, 157.94, 137.43, 131.60, 131.02, 127.12, 126.66, 125.97, 125.27, 119.94, 109.16.）.
② 0.52G (3.0 mmol) of 2-hydroxy-1-naphthaldehyde and 0.12g (3.0 mmol) of sodium hydroxide were added to 15mL of water and the mixture was stirred at room temperature for 20 minutes until the starting material was completely dissolved. Then, 1.0g (9.0 mmol) of 30% hydrogen peroxide and 0.54g (6.0 mmol) of sodium chlorite are gradually added, stirring is continued for 5 hours at room temperature, after the thin layer chromatography detects that the raw materials are reacted, the pH value of the reaction solution is adjusted to 3 by 37% hydrochloric acid, solids are separated out, the solid is filtered, a crude product is obtained, and after the crude product is recrystallized by ethanol, 0.49 g (2.6 mmol) of 2-hydroxy-1-naphthoic acid is obtained, and the yield is 88%. The hydrogen spectrum of 2-hydroxy-1-naphthoic acid is shown in FIG. 11 (the carbon spectrum of ,1H NMR (500 MHz, DMSO-d6) δ 12.78 (s, 1H), 8.48 (d, J = 8.6Hz, 1H), 8.00 (d, J = 8.9 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.56(ddd, J = 8.5, 6.9, 1.4 Hz, 1H), 7.38 (ddd, J = 8.0, 6.9, 1.0 Hz,1H), 7.21 (d, J = 8.9 Hz, 1H).）;2- hydroxy-1-naphthoic acid is shown in the figure) 12（13C NMR (126 MHz, DMSO-d6) δ 172.69, 160.24, 135.03, 131.89,129.17, 128.43, 128.33, 124.90, 123.80, 119.28, 108.90.）.
Example 2
The synthesis method of the 6-hydroxy-2-naphthoic acid and the derivatives thereof comprises the following steps:
(1) 4.6 g (0.1 mol) of formic acid are gradually added dropwise to 10.2 g (0.1 mol) of acetic anhydride, the resulting mixture is stirred at 60℃for 45 minutes and then cooled to room temperature, and then gradually added dropwise to 100mL of a dichloromethane solution in which 14.4 g (0.1 mol) of 2-naphthol and 16.8 g (0.2 mol) of sodium hydrogencarbonate are suspended, after stirring at room temperature for 5 hours, 200mL of saturated aqueous sodium carbonate solution are added to quench the reaction, the dichloromethane organic phase solution is separated, the aqueous phase is extracted 2 times with 100mL of dichloromethane, the dichloromethane solution is combined, after drying over anhydrous Na 2SO4, the solvent is removed under reduced pressure, 11.7 g (0.068 mol) of 2-naphthoate as a colorless oily liquid is obtained in a yield of 68%.
(2) 6.88G (40.0 mmol) of 2-naphthol formate was added to 50mL of trifluoromethanesulfonic acid, stirred at room temperature for 1.5 hours, the reaction mixture was heated gradually to 90℃and stirred for 8 hours, the reaction of the starting materials was detected by thin layer chromatography, the solution was evaporated to dryness under reduced pressure, and the obtained product was purified by column chromatography on silica gel (mobile phase: ethyl acetate/petroleum ether=1/15 v/v) to give 4.20 g (24.4 mmol) of 6-hydroxy-2-naphthoaldehyde in a yield of 61%, 1.57 g (8.8 mmol) of 2-hydroxy-1-naphthoaldehyde in a yield of 22%, and 0.69 g (4.0 mmol) of 3-hydroxy-2-naphthoaldehyde in a yield of 10%.
(3) ① 1.72G (10.0 mmol) of 6-hydroxy-2-naphthanaldehyde and 0.4g (10.0 mmol) of sodium hydroxide are added to 60mL of water and the mixture is stirred at room temperature for 20 minutes until the starting material is completely dissolved. Then, 2.27 g (20.0 mmol) of 30% hydrogen peroxide and 0.90g (10.0 mmol) of sodium chlorite were gradually added, stirring was continued at room temperature for 8 hours, the reaction solution was adjusted to pH 3 with 37% hydrochloric acid, solids were precipitated, and filtration was carried out to obtain a crude product, which was recrystallized with ethanol to obtain 1.22 g (6.5 mmol) of 6-hydroxy-2-naphthoic acid in 65% yield.
Example 3
The difference from example 1 is that:
the synthesis method of the 6-hydroxy-2-naphthoic acid and the derivatives thereof comprises the following steps:
(1) 9.2 g (0.2 mol) of formic acid were gradually added dropwise to 20.4 g (0.2 mol) of acetic anhydride, the resulting mixture was stirred at 60℃for 40 minutes, then cooled to room temperature, and then gradually added dropwise to 100mL of a dichloromethane solution in which 14.4 g (0.1 mol) of 2-naphthol and 16.8 g (0.2 mol) of sodium hydrogencarbonate were suspended, after stirring at room temperature for 5 hours, 200mL of saturated aqueous sodium carbonate solution was added to quench the reaction, the dichloromethane organic phase solution was separated, the aqueous phase was extracted 2 times with 100mL of dichloromethane, the dichloromethane solution was combined, and after drying over anhydrous Na 2SO4, the solvent was removed under reduced pressure, 14.1 g (0.082 mol) of 2-naphthoate as a colorless oily liquid was obtained in 82% yield.
Comparative example 1
The difference from example 1 is that:
6.88g (40.0 mmol) of 2-naphthol formate and 6.0 g (40.0 mmol) of trifluoromethanesulfonic acid are added to 100mL of toluene and stirred at room temperature for 1 hour, the reaction mixture is heated to 60℃and stirred for 12 hours, a large amount of starting material remains, the solution is evaporated to dryness under reduced pressure, and the resulting product is purified by column chromatography on silica gel (mobile phase: ethyl acetate/petroleum ether=1/15 v/v) to give 3.03 g (17.6 mmol) of 6-hydroxy-2-naphtalenecarboxaldehyde in a yield of 44%, 0.89 g (5.2 mmol) of 2-hydroxy-1-naphtalaldehyde in a yield of 13%, 0.28 g (1.6 mmol) of 3-hydroxy-2-naphtalaldehyde in a yield of 4%.
Comparative example 2
The difference from example 1 is that:
6.88g (40.0 mmol) of 2-naphthol formate is added to 50mL of trifluoromethanesulfonic acid, stirred at room temperature for 24 hours, a large amount of raw material remains, the solution is evaporated to dryness under reduced pressure, and the obtained product is purified by column chromatography on silica gel (mobile phase: ethyl acetate/petroleum ether=1/15 v/v) to obtain 2.20 g (12.8 mmol) of 6-hydroxy-2-naphtalenecarboxaldehyde in a yield of 32%, 0.28 g (1.6 mmol) of 2-hydroxy-1-naphtalaldehyde in a yield of 4%.
Comparative example 3
The difference from example 1 is that:
1.72g (10.0 mmol) of 6-hydroxy-2-naphthaldehyde and 0.4g (10.0 mmol) of sodium hydroxide were added to 60mL of water and the mixture stirred at room temperature for 20 minutes until the starting material was completely dissolved. Then, 2.27 g (30.0 mmol) of 30% hydrogen peroxide was gradually added and stirring was continued at room temperature for 4 hours, the conversion of the raw material was low, the temperature was raised to 60℃and stirring was carried out for 8 hours, the pH of the reaction solution was adjusted to 3 with 37% hydrochloric acid, solids were precipitated, and filtration was carried out to obtain a crude product, which was recrystallized with ethanol to obtain 0.60 g (3.2 mmol) of 6-hydroxy-2-naphthoic acid with a yield of 32%.
Comparative example 4
The difference from example 1 is that:
1.72g (10.0 mmol) of 6-hydroxy-2-naphthaldehyde and 0.4g (10.0 mmol) of sodium hydroxide were added to 60mL of water and the mixture stirred at room temperature for 20 minutes until the starting material was completely dissolved. Then, 1.80g (20.0 mmol) of sodium chlorite was gradually added thereto, and the mixture was stirred at room temperature for 8 hours, the pH of the reaction solution was adjusted to 3 with 37% hydrochloric acid, a solid was precipitated, and the solid was filtered to obtain a crude product, which was recrystallized from ethanol to obtain 0.77 g (4.1 mmol) of 6-hydroxy-2-naphthoic acid in a yield of 41%.
Comparative example 5
6-Hydroxy-2-naphthoic acid comprising the steps of:
42.0g (0.29 mol) of 2-naphthol and 16.4g (0.29 mol) of potassium hydroxide are added into 50mL of n-tetradecane base oil, the temperature is raised and reflux is carried out under the protection of nitrogen, the generated water is separated, CO 2 is introduced, the pressure of 0.3Mpa is kept, after the reaction is carried out for 18 hours at 265 ℃, the temperature is cooled to 100 ℃, 50mL of water is added into the reaction mixture, the temperature is kept at 70 ℃ for standing and layering, the pH of the separated water layer is regulated to 3.5 by dilute sulfuric acid, pale yellow solid is separated out, the solution is cooled to 20 ℃, after the solid is fully separated out, suction filtration is carried out, thus obtaining crude product, and after the crude product is recrystallized by ethanol, 20.8 g (0.11 mol) of 6-hydroxy-2-naphthoic acid is obtained, and the yield is 38%.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511302575.3A CN121085772A (en) | 2025-09-12 | 2025-09-12 | Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511302575.3A CN121085772A (en) | 2025-09-12 | 2025-09-12 | Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN121085772A true CN121085772A (en) | 2025-12-09 |
Family
ID=97891551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202511302575.3A Pending CN121085772A (en) | 2025-09-12 | 2025-09-12 | Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN121085772A (en) |
-
2025
- 2025-09-12 CN CN202511302575.3A patent/CN121085772A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111905828B (en) | Naphthyl ligand MOF activated carbon composite catalyst and preparation method and application thereof | |
| CN114605363B (en) | A preparation method of 3,3',4,4'-benzophenone tetracarboxylic dianhydride | |
| CN112876359A (en) | Preparation method of dimethyl 2, 6-naphthalenedicarboxylate | |
| CN121085772A (en) | Synthesis method of 6-hydroxy-2-naphthoic acid and derivative thereof | |
| CN114773299A (en) | Preparation method of 2, 5-disubstituted furan compound | |
| CN111205261B (en) | A kind of method of synthesizing naphthopyran-2-one compounds | |
| CN114907211B (en) | Polyester degradation method | |
| CN108299352B (en) | Preparation method of furan dicarboxylate compound | |
| CN118666652A (en) | Synthesis of glycolide and lactide based on abundant petrochemical raw materials and their co-production with carbonates | |
| CN121554378B (en) | Preparation method of 2-methacrylic acid | |
| CN117362165A (en) | Preparation method of ibuprofen | |
| CN116332889B (en) | Preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride | |
| CN119661431B (en) | A method for synthesizing a 3-hydroxyquinoline derivative | |
| CN115925656B (en) | A method for industrial synthesis of 5-HMF and its derivatives | |
| CN116199659B (en) | Preparation method of 4, 4-difluoro-3, 4-dihydrocoumarin compound | |
| CN115433065B (en) | A kind of preparation method of 1,3-butanediol | |
| CN116283538B (en) | A preparation method of 9-phenanthroline formic acid | |
| CN120605737A (en) | Application of sulfonic acid/sulfuric acid and zinc salt in polyester chemical recovery and polyester chemical recovery method | |
| CN115466199B (en) | A method for dehydrogenation esterification of aldehydes and aromatic phenols by light/nickel dual catalytic system | |
| JP2567705B2 (en) | Process for producing biphenyl compound and novel biphenyl compound | |
| US8871966B2 (en) | Regiospecific synthesis of terephthalates | |
| CN109678822B (en) | Preparation method of 2, 5-furan diformic acid ester compound | |
| CN120208784A (en) | A kind of synthetic method of methyl cyclopentylcarboxylate | |
| CN119798027A (en) | Triarylmethylonium ion compounds and their application in polyester degradation | |
| CN118724718A (en) | A kind of preparation method of trimethyl hydroquinone diester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |