CN108752162B - Synthetic method of trimellitic acid - Google Patents
Synthetic method of trimellitic acid Download PDFInfo
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- CN108752162B CN108752162B CN201810738849.7A CN201810738849A CN108752162B CN 108752162 B CN108752162 B CN 108752162B CN 201810738849 A CN201810738849 A CN 201810738849A CN 108752162 B CN108752162 B CN 108752162B
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention belongs to the technical field of organic chemical industry, and particularly relates to a synthetic method of trimellitic acid. Trimellitic anhydride is used as an initial raw material, and is subjected to esterification reaction to generate 1,2, 4-trimethyl benzenetricarboxylate, and the 1,2, 4-trimethyl benzenetricarboxylate is subjected to hydrolysis reaction to obtain trimellitic acid. The method has the advantages of simple operation, mild reaction conditions, cheap and easily-obtained used reagents, simple post-treatment, no need of column chromatography, easy monitoring of the reaction end point, high yield and realization of industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a synthetic method of trimellitic acid.
Background
Trimellitic acid is a white crystalline compound that is readily soluble in ethanol and dimethylformamide, soluble in acetone, sparingly soluble in water and ethyl acetate, and practically insoluble in benzene, chloroform and carbon disulfide, and has the following structural formula:
the method is mainly used for preparing trimellitic anhydride and trimellitic ester, is used for the aspects of resin, plasticizer, dye, adhesive and the like, and has wide application prospect. The existing synthesis method of trimellitic acid has the problems of harsh reaction conditions, expensive reagents, incomplete reaction, difficult monitoring of the reaction and the like.
Patent CN106187739A discloses a continuous production method of trimellitic acid, which comprises the processes of premixing, oxidation, coarse crystallization, filtration and recrystallization in sequence, wherein raw materials of trimellitic acid, solvent acetic acid, main catalysts of cobalt acetate and manganese acetate and a promoter of tetrabromoethane are mixed and preheated to 60-120 ℃ for premixing; 2-4 consecutive oxidation stages in series are carried out, and the reaction temperature of the following oxidation stage is higher than that of the preceding oxidation stage; carrying out coarse crystallization, and then carrying out centrifugal separation; dissolving crude trimellitic acid into water at the temperature of 80-100 ℃, controlling the mass percentage of trimellitic acid to be 15-35%, and filtering the hot solution while the hot solution is hot; recrystallizing and centrifuging. The method has harsh reaction conditions and expensive used reagents.
Disclosure of Invention
In order to solve the prior art existence: harsh reaction conditions, expensive used reagents, incomplete reaction, difficult monitoring of the reaction and the like. The invention uses cheap starting materials, obtains the target product with higher yield under mild reaction conditions through simple operation steps.
The method takes trimellitic anhydride (2) as a starting material, generates trimethyl 1,2, 4-benzenetricarboxylate (3) through esterification reaction, and obtains the target product trimellitic acid (1) through hydrolysis reaction of the trimethyl 1,2, 4-benzenetricarboxylate (3).
The method comprises the following specific steps:
(1) synthesis of trimethyl 1,2, 4-benzenetricarboxylate (3)
Adding trimellitic anhydride into a round-bottom flask, then adding methanol to dissolve the trimellitic anhydride, dropwise adding concentrated sulfuric acid with the mass fraction of 98%, heating to 65-80 ℃ (centigrade) for reaction, detecting by TLC (thin layer chromatography) after 24-72h (hours), and finishing the reaction. Methanol was removed by evaporation under reduced pressure at 50 ℃ and 200 mL of water was added, followed by extraction with methylene chloride (30 mL. times.10), and the organic phases were combined, washed with saturated sodium bicarbonate (100 mL. times.3), saturated brine (100 mL. times.3), and finally dried over anhydrous sodium sulfate to give trimethyl 1,2, 4-benzenetricarboxylate as a colorless oily substance.
Wherein the mass-volume ratio of the trimellitic anhydride to the methanol to the concentrated sulfuric acid is as follows: 1:4-6: 0.12-0.2; the reaction temperature is preferably 65-75 ℃, and the reaction time is preferably 48-72 h.
Because the polarity of the raw materials is high, the methanol can fully dissolve the raw materials. In addition, in the esterification reaction, the order of activity of the alcohols is that methanol is larger than primary alcohol and larger than secondary alcohol and larger than tertiary alcohol, so methanol is selected as the esterification reaction solvent and its reactants.
Concentrated sulfuric acid with the mass fraction of 98% is selected as a catalyst and a dehydrating agent for the esterification reaction, so that the forward reaction can be favorably carried out.
Synthesis of trimellitic acid (1)
Adding 1,2, 4-trimethyl benzenetricarboxylate into a round-bottom flask, adding methanol to dissolve the trimethyl benzenetricarboxylate, adding 40 mass percent of sodium hydroxide, heating to 65-80 ℃, performing reflux reaction, detecting by TLC after 24-60 h, and finishing the reaction. Methanol was removed by evaporation under reduced pressure at 50 ℃ and 200 mL of water was added, hydrochloric acid was added to the mixture to strongly acidic, the mixture was extracted with ethyl acetate (30 mL. times.10), the organic phases were combined, washed with saturated brine (100 mL. times.3), and finally dried over anhydrous sodium sulfate to give trimellitic acid as a white solid powder.
Wherein, the mass-volume ratio of the 1,2, 4-trimethyl benzenetricarboxylate to the methanol and sodium hydroxide solution is as follows: 1:4-6: 2-4; the reaction temperature is 65-75 ℃, and the reaction time is 40-50 h.
According to the invention, strong alkali sodium hydroxide with good water solubility and mass fraction of 40% is selected for hydrolysis, so that the reaction time is reduced, and the yield of the product is ensured.
Has the advantages that:
the method selects methanol as an esterification reaction solvent and a reactant thereof, and concentrated sulfuric acid with the mass fraction of 98 percent as a catalyst and a dehydrating agent for the esterification reaction, and obtains the trimethyl 1,2, 4-benzenetricarboxylate with high yield under mild conditions. The reaction degree can be easily monitored by esterification reaction and then hydrolysis reaction, the reaction condition is mild, and the yield of the reaction product is high.
The method has the advantages of simple operation, mild reaction conditions, no need of high-temperature and high-pressure reaction, cheap and easily-obtained used reagents, simple post-treatment, no need of column chromatography, easy monitoring of reaction end point, high yield and realization of industrial production.
Detailed Description
The following describes in detail specific embodiments of the present invention.
Example 1
Synthesis of trimethyl 1,2, 4-benzenetricarboxylate
Trimellitic anhydride (100.0 g (g), 520.48 mmol (mmol)) was added to a 1L (liter) round-bottomed flask, and then dissolved in 500mL of methanol, 16 mL of 98% concentrated sulfuric acid was added dropwise thereto, and the mixture was heated at 70 ℃ for reflux reaction at 48 hours and then detected by TLC (thin layer chromatography), and the reaction was completed. Methanol was removed by evaporation under reduced pressure at 50 ℃ and 200 mL of water was added, followed by extraction with methylene chloride (30 mL. times.10), and the organic phases were combined, washed with saturated sodium bicarbonate (100 mL. times.3), saturated brine (100 mL. times.3), and finally dried over anhydrous sodium sulfate to give 118.4g of trimethyl 1,2, 4-benzenetricarboxylate as a colorless oily substance in 90.20% yield.
1H NMR (400 MHz, CDCl3) δ：8.43(s，1H), 8.21(d，J=8.0Hz，1H), 7.76(d，J=8.0Hz，1H), 3.96(s，3H), 3.94(s，6H); 13C NMR (300 MHz, CDCl3) δ：167.63, 166.83, 165.37, 136.23, 132.44, 132.29, 131.59, 130.28, 128.89, 52.95, 52.87, 52.65。
(2) Synthesis of trimellitic acid
1,2, 4-trimethyl benzenetricarboxylate (100.0 g, 396.48 mmol) is added into a 1L (liter) round-bottom flask, then 500mL of methanol is added to dissolve the trimethyl benzenetricarboxylate, 250mL of sodium hydroxide with the mass fraction of 40% is added, the mixture is heated at 70 ℃ for reflux reaction, and after 48 hours, the reaction is finished by TLC detection. Methanol was removed by evaporation under reduced pressure at 50 ℃ and 200 mL of water was added, hydrochloric acid was added to make it strongly acidic, extraction was performed with ethyl acetate (30 mL. times.10), the organic phases were combined, washed with saturated brine (100 mL. times.3), and finally dried over anhydrous sodium sulfate to give a white solid powdery substance (75.1 g, yield 90.16%).
1H NMR (400 MHz, DMSO) δ：13.46(brs，3H), 8.22(s，1H), 8.12(d，J=8.0Hz，1H), 7.76(d，J=8.0Hz，1H)。
Example 2
In the step (1), the mass-to-volume ratio of trimellitic anhydride, methanol and concentrated sulfuric acid is as follows: 1:4.5: 0.15, the reaction temperature is 75 ℃, the reaction time is 50h, and the yield of the trimethyl 1,2, 4-benzenetricarboxylate is as follows: 89.88 percent.
In the step (2), the mass-to-volume ratio of the trimethyl 1,2, 4-benzenetricarboxylate to the methanol to the sodium hydroxide is as follows: 1:4.5:3.0, the reaction temperature is 75 ℃, the reaction time is 40h, and the yield of trimellitic acid is as follows: 90.02 percent.
Example 3
In the step (1), the mass-to-volume ratio of trimellitic anhydride, methanol and concentrated sulfuric acid is as follows: 1:5.5: 0.18, reaction temperature 68 ℃, reaction time 65h, yield of trimethyl 1,2, 4-benzenetricarboxylate: 89.92 percent.
In the step (2), the mass-to-volume ratio of the trimethyl 1,2, 4-benzenetricarboxylate to the methanol to the sodium hydroxide is as follows: 1:5.5:3.5, reaction temperature of 68 ℃, reaction time of 45h, yield of trimellitic acid: 89.78 percent.
Comparative example 1
Trimellitic anhydride (0.5 g, 2.60 mmol) was added to a 50mL (milliliter) round-bottomed flask, then 2.5mL of methanol was added to dissolve the trimellitic anhydride, 1.25mL of 40% by mass sodium hydroxide was added, the mixture was heated at 70 ℃ for reflux reaction, and after 48 hours, the reaction was stopped by detecting by TLC. Since the reaction amount was extremely small, no treatment was performed.
Comparative example 2
And (2) converting the methanol in the step (1) into ethanol, wherein the mass-to-volume ratio of the trimellitic anhydride to the ethanol to the concentrated sulfuric acid is as follows: 1:5.0: 0.16, reaction temperature of 70 ℃, reaction time of 48h, and yield of triethyl 1,2, 4-benzenetricarboxylate: 73.56 percent.
In the step (2), the mass-to-volume ratio of the triethyl 1,2, 4-benzenetricarboxylate to the methanol to the sodium hydroxide is as follows: 1:5.0:2.5, reaction temperature of 70 ℃, reaction time of 48h, yield of trimellitic acid: 87.58 percent.
Comparative example 3
And (2) changing the concentrated sulfuric acid in the step (1) into p-toluenesulfonic acid, wherein the mass-volume ratio of trimellitic anhydride to methanol to p-toluenesulfonic acid is as follows: 1:5.0: 0.16, reaction temperature 70 ℃, reaction time 48h, yield of trimethyl 1,2, 4-benzenetricarboxylate: 70.28 percent.
In the step (2), the mass-to-volume ratio of the trimethyl 1,2, 4-benzenetricarboxylate to the methanol to the sodium hydroxide is as follows: 1:5.0:2.5, reaction temperature of 70 ℃, reaction time of 48h, yield of trimellitic acid: 89.12 percent.
Comparative example 4
And (2) changing the temperature of 70 ℃ in the step (1) into room temperature reaction, wherein the mass-to-volume ratio of trimellitic anhydride, methanol and concentrated sulfuric acid is as follows: 1:5.0: 0.16, reaction time 48h, yield of trimethyl 1,2, 4-benzenetricarboxylate: 23.56 percent.
In the step (2), the mass-to-volume ratio of the trimethyl 1,2, 4-benzenetricarboxylate to the methanol to the sodium hydroxide is as follows: 1:5.0:2.5, reaction temperature of 70 ℃, reaction time of 48h, yield of trimellitic acid: 89.42 percent.
Claims (2)
1. A synthetic method of trimellitic acid is characterized by comprising the following steps: the synthesis method comprises the following specific processes:
(1) synthesis of trimethyl 1,2, 4-benzenetricarboxylate
Adding trimellitic anhydride into a round-bottom flask, adding methanol to dissolve the trimellitic anhydride, dropwise adding 98% concentrated sulfuric acid, heating to 65-80 ℃ for reflux reaction, detecting by TLC after 24-72 hours, ending the reaction, removing the methanol by decompression at 50 ℃, adding 200 mL of water, extracting by dichloromethane, combining organic phases, washing by saturated sodium bicarbonate, washing by saturated salt water, drying by anhydrous sodium sulfate, and spin-drying to obtain a colorless oily substance, namely trimethyl 1,2, 4-benzenetricarboxylate;
the mass-volume ratio of the trimellitic anhydride to the methanol to the concentrated sulfuric acid is as follows: 1:4-6: 0.12-0.2;
(2) synthesis of trimellitic acid (1)
Adding 1,2, 4-trimethyl benzenetricarboxylic acid into a round-bottom flask, adding methanol to dissolve the trimethyl benzenetricarboxylic acid, adding 40 mass percent of sodium hydroxide, heating to 65-80 ℃ for reflux reaction, detecting by TLC after 24-60 h, ending the reaction, removing the methanol by decompression at 50 ℃, adding 200 mL of water, adding hydrochloric acid to adjust to be strongly acidic, extracting by using ethyl acetate, combining organic phases, washing by using saturated saline solution, finally drying by using anhydrous sodium sulfate, and spin-drying to obtain a white solid powdery substance trimellitic acid.
2. The method for synthesizing trimellitic acid according to claim 1, wherein: the mass-volume ratio of the 1,2, 4-trimethyl benzenetricarboxylate in the step (2) to the methanol to the sodium hydroxide solution is as follows: 1:4-6:2-4.
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