CN113896624B - Method for preparing salicylic acid from 2, 3-benzofuran - Google Patents
Method for preparing salicylic acid from 2, 3-benzofuran Download PDFInfo
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- CN113896624B CN113896624B CN202111251298.XA CN202111251298A CN113896624B CN 113896624 B CN113896624 B CN 113896624B CN 202111251298 A CN202111251298 A CN 202111251298A CN 113896624 B CN113896624 B CN 113896624B
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- C07C51/41—Preparation of salts of carboxylic acids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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Abstract
The invention discloses a method for preparing salicylic acid from 2, 3-benzofuran, which comprises the steps of adding 2, 3-benzofuran and additive alkali into a temperature-resistant and pressure-resistant glass tube, sequentially adding a solvent and an oxidant tert-butyl hydroperoxide, sealing the glass tube at normal temperature and normal pressure, and placing the glass tube into an oil bath kettle preheated at the temperature of 45-150 ℃ for stirring reaction; after reacting for 1-20 h, quenching to room temperature, and detecting the concentration of 2, 3-benzofuran in the organic phase and the concentration of salicylate in the water phase; and acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid. The reactant used by the invention can be prepared from biomass, and the source is green; the reaction time is short, and the reaction temperature is moderate; the reaction condition is mild, the reaction system is simple, no gas filling body is needed, the reaction is carried out at normal pressure, and the safety is high; the yield is moderate; the post-treatment is simple; has very important application value.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing salicylic acid from 2, 3-benzofuran.
Background
Salicylic acid is an important medicine and a prodrug, has the functions of antisepsis and sterilization, sweat odor removal, itching relieving and swelling subsiding, pain relieving and inflammation diminishing and the like, and can also be used for preparing medicines such as acetylsalicylic acid (aspirin), salicylamide, o-ethoxybenzoic acid amine (acesodyne) and the like. It is a naturally occurring substance found mainly in willow bark, beautyberry leaves and sweet birch. At present, the salicylic acid is industrially prepared mainly by a phenolic acid synthesis method, wherein phenol reacts with sodium hydroxide to obtain sodium phenolate, the sodium phenolate is dried and then reacts with carbon dioxide to obtain sodium phenolate, and finally, a salicylic acid crude product is obtained after sulfuric acid acidification. The raw material phenol is mainly from non-renewable petrochemical resources. In recent years, salicylic acid can also be prepared from 2, 3-benzofuran or benzyl alcohol and salicylaldehyde which are upstream products of the benzofuran. With [ Fe (TF) 5 PP)Cl]The catalyst is hydrogen peroxide as an oxidant, and 2, 3-benzofuran can be oxidized into ethyl salicylate (Chemistry Select,2018,3 (5): 1392-1403) in ethanol at 90 ℃; using nano magnet modified trivalent cobalt complex as catalyst, oxidizing o-hydroxyphenylcarbinol by sodium hypochlorite at normal temperature to obtain salicylic acid (Green Chemistry,2020, 22 (19): 6600-6613); taking a trivalent iron-cobalt complex as a catalyst, and oxidizing benzyl alcohol into salicylic acid at a low temperature in an oxygen atmosphere (Angew Chem,2017, 56, 3867-3871).No one-step method for preparing salicylic acid from 2, 3-benzofuran by metal-free catalytic conversion has been reported.
Disclosure of Invention
In view of the deficiencies and problems of the prior art, the present invention is directed to a process for the preparation of salicylic acid from 2, 3-benzofuran.
The invention is realized by the following technical scheme:
a process for the preparation of salicylic acid from 2, 3-benzofuran, the process comprising the steps of:
s1, adding 2, 3-benzofuran and additive alkali into a temperature-resistant and pressure-resistant glass tube, sequentially adding a solvent and an oxidant tert-butyl hydroperoxide, sealing the glass tube at normal temperature and normal pressure, and putting the glass tube into an oil bath kettle preheated at the temperature of 45-150 ℃ for stirring reaction, wherein the molar ratio of the 2, 3-benzofuran to the alkali is 0.1-10: 1; the molar volume ratio (mol/L) of the 2, 3-benzofuran to the solvent is 0.1-10: 1; the mol ratio of the 2, 3-benzofuran to the tert-butyl hydroperoxide is 0.05-4: 1;
s2, reacting for 1-20 hours in the step S1, quenching to room temperature, and detecting the concentration of organic phase 2, 3-benzofuran and the concentration of water phase salicylate, wherein the upper layer liquid is organic phase reaction liquid, a proper amount of filtration is adopted for detection by a gas chromatograph, the lower layer liquid is water phase reaction liquid, and a proper amount of filtration is adopted for detection by a high performance liquid chromatograph;
and S3, acidifying the water phase collected in the step S2, concentrating, filtering, washing and drying to obtain crude salicylic acid.
Further, the molar ratio of the 2, 3-benzofuran to the alkali in the step S1 is 0.25-1: 1; the molar volume ratio (mol/L) of the 2, 3-benzofuran to the solvent is 0.5-2: 1; the mol ratio of the 2, 3-benzofuran to the tert-butyl hydroperoxide is 0.0833-0.25: 1; the preheating temperature of the oil bath pot is 80-130 ℃.
Further, the solvent is one or more of water, ethanol, tert-butyl alcohol and n-hexane.
Further, the additive alkali is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and hydroxyapatite.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for preparing salicylic acid by using biomass-based 2, 3-benzofuran as a raw material, which has the advantages of mild reaction conditions, simple reaction system, no need of any metal catalyst, and capability of oxidizing the 2, 3-benzofuran into salicylate by adding a certain amount of solvent in an alkaline environment by using tert-butyl hydroperoxide as an oxidant, and obtaining the salicylic acid after acidification.
(2) The reactant used by the invention can be prepared from biomass, and the source is green; the reaction time is short, and the reaction temperature is moderate; no inflation body is needed, the reaction is carried out at normal pressure, and the safety is high; the yield is moderate; the post-treatment is simple; has very important application value.
Drawings
FIG. 1 is a schematic diagram of the reaction of 2, 3-benzofuran to produce salicylic acid according to the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1.
2mmol of sodium hydroxide, 2mmol of sodium carbonate, 0.5ml of water, 12mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in the atmosphere of normal pressure, and the glass tube is put into an oil bath kettle preheated to 120 ℃ for stirring reaction and kept for 2 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a conversion of 86.3% of 2, 3-benzofuran, and the aqueous phase was collected and examined for a yield of 41.7% of salicylate. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid, wherein the reaction formula is shown in figure 1.
The 2, 3-benzofuran conversion, salicylate yield were measured and calculated according to the following methods.
The apparatus for measuring the concentration of 2, 3-benzofuran was an Agilent 7820A series gas chromatograph (Agilent HP-5,0.32mm ID X30 m gas chromatography column), the apparatus for measuring the concentration of salicylate was a Watts H-Class series high performance liquid chromatograph (PDA detector, 234.2nm wavelength, ICSep Coregel 107H,7.8mm ID X300 mm liquid chromatography column, mobile phase was 0.2g/L dilute sulfuric acid).
Calculation of the conversion of 2, 3-benzofuran:
conversion of 2, 3-benzofuran =1- (2, 3-benzofuran remaining mol/2, 3-benzofuran input mol) × 100%
Calculation of yield of salicylate:
yield of salicylate = (salicylate molar amount/2,3-benzofuran molar amount charged) × 100%
Example 2.
2mmol of sodium hydroxide, 2mmol of sodium carbonate, 1ml of water, 12mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in normal pressure air, and the glass tube is placed into an oil bath kettle preheated to 130 ℃ for stirring reaction and kept for 1 hour. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for 2, 3-benzofuran conversion of 87.4%, the aqueous phase was collected and examined for salicylate yield of 41.9%. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 3.
3mmol of sodium hydroxide, 1ml of water, 12mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in the atmosphere of normal pressure, and the glass tube is placed into an oil bath kettle preheated to 120 ℃ for stirring reaction and kept for 1 hour. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a conversion of 80.0% of 2, 3-benzofuran, the aqueous phase was collected and examined for a yield of 35.3% of salicylate. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 4.
4mmol of sodium hydroxide, 1ml of normal hexane, 8mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in normal pressure air, and the glass tube is put into an oil bath kettle preheated to 80 ℃ to be stirred and reacted for 10 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a 2, 3-benzofuran conversion of 62.8%, the aqueous phase was collected and examined for a salicylate yield of 18.0%. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 5.
2mmol of sodium carbonate, 1ml of ethanol, 12mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in normal pressure air, and the glass tube is put into an oil bath kettle preheated to 120 ℃ to be stirred and reacted for 1 hour. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a 2, 3-benzofuran conversion of 49.8%, the aqueous phase was collected and examined for a salicylate yield of 21.5%. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 6.
2mmol of sodium hydroxide, 2mmol of sodium carbonate, 1ml of tertiary butanol, 12mmol of 70wt% of tertiary butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in normal pressure air, and the glass tube is placed into an oil bath kettle preheated to 120 ℃ for stirring reaction and kept for 2 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a 2, 3-benzofuran conversion of 68.4%, the aqueous phase was collected and examined for a salicylate yield of 29.1%. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 7.
2mmol of sodium hydroxide, 2mmol of sodium carbonate, 1ml of water, 1ml of tert-butyl alcohol, 12mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant and pressure-resistant glass tube, the glass tube is sealed in normal pressure air, and the glass tube is placed into an oil bath kettle preheated to 120 ℃ for stirring reaction and kept for 3 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a conversion of 86.2% of 2, 3-benzofuran, and the aqueous phase was collected and examined for a yield of 46.7% of salicylate. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 8.
2mmol of potassium hydroxide, 1ml of water, 4mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml of temperature-resistant and pressure-resistant glass tube, the glass tube is sealed in the air under normal pressure, and the glass tube is put into an oil bath kettle preheated to 80 ℃ for stirring reaction and kept for 5 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for a 2, 3-benzofuran conversion of 39.9%, the aqueous phase was collected and examined for a salicylate yield of 17.4%. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
Example 9.
2mmol of potassium carbonate, 1ml of water, 8mmol of 70wt% of tert-butyl hydroperoxide and 1mmol of 2, 3-benzofuran are sequentially added into a 15ml temperature-resistant pressure-resistant glass tube, the glass tube is sealed in the air at normal pressure, and the glass tube is put into an oil bath kettle preheated to 80 ℃ for stirring reaction and kept for 5 hours. The glass tube was cooled to room temperature in a water bath, the organic phase was collected and examined for 54.8% conversion of 2, 3-benzofuran and the aqueous phase was collected and examined for 24.5% yield of salicylate. And then acidifying, concentrating, filtering, washing and drying the collected water phase to obtain crude salicylic acid.
The foregoing description merely represents preferred embodiments of the present invention, which are described in some detail and detail, and should not be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A process for the preparation of salicylic acid from 2, 3-benzofuran, characterised in that it comprises the following steps:
s1, adding 2, 3-benzofuran and additive alkali into a temperature-resistant and pressure-resistant glass tube, sequentially adding a solvent and an oxidant tert-butyl hydroperoxide, sealing the glass tube at normal temperature and normal pressure, and putting the glass tube into an oil bath kettle preheated at the temperature of 80-130 ℃ for stirring and reacting, wherein the molar ratio of the 2, 3-benzofuran to the additive alkali is 0.1-10: 1; the mol/L ratio of the 2, 3-benzofuran to the solvent is 0.1-10: 1; the molar ratio of the 2, 3-benzofuran to the tert-butyl hydroperoxide is 0.05-4: 1; the solvent is one or more of water, ethanol and tertiary butanol; the additive alkali is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate
S2, reacting for 1-20 hours in the step S1, quenching to room temperature, detecting the concentration of organic phase 2, 3-benzofuran and the concentration of water phase salicylate, wherein the upper layer liquid is organic phase reaction liquid, taking a proper amount of filtration to detect by using a gas chromatograph, and the lower layer liquid is water phase reaction liquid, taking a proper amount of filtration to detect by using a high performance liquid chromatograph;
and S3, acidifying the water phase collected in the step S2, concentrating, filtering, washing and drying to obtain crude salicylic acid.
2. A process according to claim 1 for the preparation of salicylic acid from 2, 3-benzofuran, characterised in that: in the step S1, the molar ratio of the 2, 3-benzofuran to the alkali is 0.25-1: 1; the mol/L ratio of the 2, 3-benzofuran to the solvent is 0.5-2: 1; the molar ratio of the 2, 3-benzofuran to the tert-butyl hydroperoxide is 0.0833-0.25: 1.
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