CN110790662A - Production method of 2- (4-bromomethylphenyl) propionic acid - Google Patents
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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Abstract
The invention discloses a production method of 2- (4-bromomethylphenyl) propionic acid, wherein an ionic liquid catalyst adopted by the invention can be recycled, no aluminum trichloride water is generated, materials are not required to be washed for multiple times, only layered extraction is required to obtain a required product, and the aluminum trichloride triethylamine salt ionic liquid is used for environmental protection and cost saving, so that the original complex process is simplified. The in-kettle cooling glass pipeline circulating bromination reaction is changed into by the bromination reaction in the original glass kettle, the glass pipeline reaction enables the material to increase with the area of light contact, no material is gathered on the illumination surface through circulation, thereby influencing the irradiation of light, enabling the efficiency of the reaction to be higher, shortening the reaction time, controlling the occurrence of side reactions, and enabling the product purity to be higher.
Description
Technical Field
The invention relates to the field of chemical industry, and particularly relates to a production method of 2- (4-bromomethylphenyl) propionic acid.
Background
At present, 2- (4-bromomethylphenyl) propionic acid is one of key intermediates for synthesizing loxoprofen sodium, the loxoprofen sodium belongs to novel non-steroidal anti-inflammatory drugs of aryl propionic acids, and clinical results show that the loxoprofen sodium is the most analgesic, anti-inflammatory and antirheumatic effects in the existing known aryl propionic acids, so that the loxoprofen sodium is highly popular among experts and scholars at home and abroad and advocated in the medical field and patients. However, the existing 2- (4-bromomethylphenyl) propionic acid synthesis method has the following problems:
1. the aluminum trichloride catalyst in the prior art can not be recycled, the added aluminum trichloride catalyst needs to be hydrolyzed, materials need to be washed for multiple times, and the generation amount of waste water is large.
2. The reaction efficiency of the bromination reaction in the glass kettle is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, the ionic liquid catalyst adopted by the invention can be recycled, no aluminum trichloride water is generated, the materials do not need to be washed for many times, only layered extraction is needed, the required product can be obtained, and the aluminum trichloride triethylamine salt ionic liquid is used instead, so that the environment is protected, the cost is saved, and the original complex process is simplified. The in-kettle cooling glass pipeline circulating bromination reaction is changed into by the bromination reaction in the original glass kettle, the glass pipeline reaction enables the material to increase with the area of light contact, no material is gathered on the illumination surface through circulation, thereby influencing the irradiation of light, enabling the efficiency of the reaction to be higher, shortening the reaction time, controlling the occurrence of side reactions, and enabling the product purity to be higher.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for producing 2- (4-bromomethylphenyl) propionic acid comprises the following steps:
step one, preparing ionic liquid, namely preparing aluminum trichloride: triethylamine hydrochloride in a molar ratio of 1-5: 1-10 mol ratio, adding into a reaction kettle, reacting at 10-70 ℃ for 5-12h to prepare ionic liquid;
step two, preparation of p-tolyl-2-chloro-1-ketone: adding dichloroethane, ionic liquid and anhydrous toluene into a dry acylation reaction kettle, cooling to 0-5 ℃, and dropwise adding 2-chloropropionyl chloride under stirring; the mol ratio of dichloroethane, ionic liquid, anhydrous toluene to 2-chloropropionyl chloride is 1-40: 1-15: 1-25: 1-15, stirring for 6 hours at the temperature of 0-5 ℃ after the dripping is finished for 2-3 hours, and obtaining a reaction solution after the reaction is finished; transferring the reaction liquid into an extraction kettle, standing for 3 hours for layering, separating the lower layer of ionic liquid for recycling, transferring the upper layer of dichloroethane mother liquor into a condensation reaction kettle, recovering the dichloroethane for recycling, and obtaining the residue of the condensation reaction kettle, namely the p-tolyl-2-chloro-1-ketone;
step three, 2-p-tolyl propionic acid preparation stage
Adding heptane, neopentyl glycol and TsOH into a condensation reaction kettle; heptane: neopentyl glycol: the mass ratio of TsOH is 1-20: 1-5: 1-3, heating to 80-100 ℃, stirring, performing reflux dehydration for 15-25 hours until no water drops in heptane are dehydrated, cooling the temperature in the kettle to below 70 ℃, adding zinc propionate, continuously heating to 100-150 ℃ for rearrangement reaction, wherein the mass ratio of the zinc propionate to the heptane is 1-10: 1-20, transferring the product into an alkaline hydrolysis kettle after the rearrangement reaction is finished, adding 30% NaOH solution and water under stirring for hydrolysis reaction, wherein the mass ratio of the 30% NaOH solution to the water to the zinc propionate is 1-10: 1-30: 1-10; and after hydrolysis, transferring the lower-layer water phase into an acidification kettle, transferring the upper-layer organic phase into a solvent recovery kettle to recover heptane and byproduct chloropentanol, adding 30% hydrochloric acid into the acidification kettle, wherein the mass ratio of 30% hydrochloric acid to 30% NaOH solution is 1-10: 1-5; stirring thoroughly, standing for layering, transferring the upper layer mother liquor containing 2-p-tolylpropionic acid into a distillation kettle, and distilling under reduced pressure to obtain 2-p-tolylpropionic acid; separating the lower layer water solution, and concentrating the wastewater;
step four, 2- (4-bromomethylphenyl) propionic acid stage:
the bromination reaction kettle is charged with 2-p-tolylpropionic acid: hydrogen peroxide: dichloromethane: the weight ratio of the initiator benzoyl peroxide is 1-5: 1-10: 1-15: 0.1 to 0.5; under the illumination of a sodium lamp at the temperature of 10-15 ℃, materials in a bromination reaction kettle are pumped to a bromination glass tube by a circulating pump, and hydrobromic acid is slowly dripped while the materials are circulated and stirred; the mass ratio of hydrobromic acid to 2-p-tolyl propionic acid is 0.05-0.1: 1-5; after the dropwise addition, continuing the heat preservation reaction for 1-2 hours, transferring the obtained product to a dichloroethane recovery distillation still to evaporate dichloroethane after the bromination reaction is finished, transferring the obtained product to a crystallization still, cooling to 0 ℃, stirring and crystallizing for 4-6 hours, and then putting the obtained product into a centrifuge for spin-drying to obtain a crude 2-p-bromomethylphenylpropionic acid crystal; putting the 2-p-bromomethylphenyl propionic acid crystal crude product into a refining kettle, adding dichloromethane with the weight of 1-5 times of that of the 2-p-bromomethylphenyl propionic acid crystal crude product, repeatedly crystallizing and refining for 2 times, and centrifugally drying to obtain the 2- (4-bromomethylphenyl) propionic acid finished product.
In a further improvement, the first step is summarized as follows: triethylamine hydrochloride in a molar ratio of 1-5: 1-10 mol ratio, adding into a reaction kettle, and reacting at 10-70 ℃ for 5-12 h.
The main equation is as follows:
the invention has the advantages that:
1. the aluminum trichloride catalyst in the original process technology can not be recycled, the added aluminum trichloride catalyst needs to be hydrolyzed, materials need to be washed for multiple times, the generation amount of waste water is large, the existing ionic liquid catalyst can be recycled, no aluminum trichloride water is generated in the working section, the materials do not need to be washed for multiple times, only layered extraction is needed, the needed products can be obtained, the aluminum trichloride triethylamine salt ionic liquid is used for being friendly to the environment, the cost is saved, and the original complex process is simplified.
2. The method is changed from the original bromination reaction in the glass kettle into the circulating bromination reaction of the cooling glass pipeline in the kettle, the glass pipeline type reaction increases the contact area of materials and light, and no materials are gathered on the illuminated surface through circulation, so that the illumination of light is influenced, the reaction efficiency is higher, the reaction time is shortened, the occurrence of side reactions is controlled, and the product purity is higher.
3. Compared with toluene in the prior art, the toluene in the prior art has higher solubility in water, a small amount of toluene is blended into water generated in a corresponding section, the loss of the toluene is increased, the boiling point of the toluene is higher than that of the water, the energy consumption for use is higher, and the toluene is not beneficial to bringing out water generated in the reaction in the section. And heptane is used as a solvent, the boiling points of the heptane and water are closer, the energy consumption in production and use is lower, the heptane is insoluble in water, the produced water cannot be mixed with the heptane solvent, the solvent loss cannot be caused, the water produced in the reaction can be more completely taken out, the reaction is more complete, and the time is shorter.
Detailed Description
Example 1
A method for producing 2- (4-bromomethylphenyl) propionic acid comprises the following steps:
step one, preparing ionic liquid, namely preparing aluminum trichloride: triethylamine hydrochloride in a molar ratio of 1-5: 1-10 mol ratio is added into a reaction kettle to react at 10-70 ℃ to prepare ionic liquid;
step two, preparation of p-tolyl-2-chloro-1-ketone: adding dichloroethane, ionic liquid and anhydrous toluene into a dry acylation reaction kettle, cooling to 0-5 ℃, and dropwise adding 2-chloropropionyl chloride under stirring; the mol ratio of dichloroethane, ionic liquid, anhydrous toluene to 2-chloropropionyl chloride is 1-40: 1-15: 1-25: 1-15, stirring for 6 hours at the temperature of 0-5 ℃ after the dripping is finished for 2-3 hours, and obtaining a reaction solution after the reaction is finished; transferring the reaction liquid into an extraction kettle, standing for 3 hours for layering, separating the lower layer of ionic liquid for recycling, transferring the upper layer of dichloroethane mother liquor into a condensation reaction kettle, and recycling dichloroethane for recycling;
step three, 2-p-tolyl propionic acid preparation stage
To the condensation reactor was added heptane: neopentyl glycol: TsOH is 1-20: 1-5: 1-3, heating, stirring, performing reflux dehydration for 15-25 hours until no water drops in heptane are dehydrated, reducing the temperature in the kettle to below 70 ℃, adding zinc propionate, continuously heating for rearrangement reaction, transferring to an alkaline hydrolysis kettle after the rearrangement reaction is finished, adding 1-10 parts of 30% NaOH and 1-30 parts of water under stirring for hydrolysis reaction, transferring the lower water phase to an acidification kettle after the hydrolysis is finished, transferring the upper organic phase to a solvent recovery kettle for recovering heptane and byproduct chloropentanol, adding 1-5 parts of 30% hydrochloric acid into the acidification kettle, fully stirring, standing for layering, and transferring the upper mother liquor containing 2-p-tolylpropionic acid into a distillation kettle to evaporate 2-p-tolylpropionic acid under reduced pressure; separating the lower layer water solution, and concentrating the wastewater;
step four, 2- (4-bromomethylphenyl) propionic acid stage:
the bromination reaction kettle is charged with 2-p-tolylpropionic acid: hydrogen peroxide: dichloromethane: the weight ratio of the initiator benzoyl peroxide is 1-5: 1-10: 1-15: 0.1 to 0.5; under the illumination of a sodium lamp at the temperature of 10-15 ℃, materials in a bromination reaction kettle are pumped to a bromination glass tube by a circulating pump, and hydrobromic acid is slowly dripped while the materials are circulated and stirred; the mass ratio of hydrobromic acid to 2-p-tolyl propionic acid is 0.05-0.1: 1-5; after the dropwise addition, continuing the heat preservation reaction for 1-2 hours, transferring the obtained product to a dichloroethane recovery distillation still to evaporate dichloroethane after the bromination reaction is finished, transferring the obtained product to a crystallization still, cooling to 0 ℃, stirring and crystallizing for 4-6 hours, and then putting the obtained product into a centrifuge for spin-drying to obtain a crude 2-p-bromomethylphenylpropionic acid crystal; and (3) putting the crude 2-p-bromomethylphenyl propionic acid crystal into a refining kettle, adding dichloromethane, repeatedly crystallizing and refining for 2 times, and centrifugally drying to obtain a finished product of the 2- (4-bromomethylphenyl) propionic acid.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention.
Claims (2)
1. A production method of 2- (4-bromomethylphenyl) propionic acid is characterized by comprising the following steps:
step one, preparing ionic liquid, namely preparing aluminum trichloride: triethylamine hydrochloride in a molar ratio of 1-5: 1-10 mol ratio, adding into a reaction kettle, reacting at 10-70 ℃ for 5-12h to prepare ionic liquid;
step two, preparation of p-tolyl-2-chloro-1-ketone: adding dichloroethane, ionic liquid and anhydrous toluene into a dry acylation reaction kettle, cooling to 0-5 ℃, and dropwise adding 2-chloropropionyl chloride under stirring; the mol ratio of dichloroethane, ionic liquid, anhydrous toluene to 2-chloropropionyl chloride is 1-40: 1-15: 1-25: 1-15, stirring for 6 hours at the temperature of 0-5 ℃ after the dripping is finished for 2-3 hours, and obtaining a reaction solution after the reaction is finished; transferring the reaction liquid into an extraction kettle, standing for 3 hours for layering, separating the lower layer of ionic liquid for recycling, transferring the upper layer of dichloroethane mother liquor into a condensation reaction kettle, recovering the dichloroethane for recycling, and obtaining the residue of the condensation reaction kettle, namely the p-tolyl-2-chloro-1-ketone;
step three, 2-p-tolyl propionic acid preparation stage
Adding heptane, neopentyl glycol and TsOH into a condensation reaction kettle; heptane: neopentyl glycol: the mass ratio of TsOH is 1-20: 1-5: 1-3, heating to 80-100 ℃, stirring, performing reflux dehydration for 15-25 hours until no water drops in heptane are dehydrated, cooling the temperature in the kettle to below 70 ℃, adding zinc propionate, continuously heating to 100-150 ℃ for rearrangement reaction, wherein the mass ratio of the zinc propionate to the heptane is 1-10: 1-20, transferring the product into an alkaline hydrolysis kettle after the rearrangement reaction is finished, adding 30% NaOH solution and water under stirring for hydrolysis reaction, wherein the mass ratio of the 30% NaOH solution to the water to the zinc propionate is 1-10: 1-30: 1-10; and after hydrolysis, transferring the lower-layer water phase into an acidification kettle, transferring the upper-layer organic phase into a solvent recovery kettle to recover heptane and byproduct chloropentanol, adding 30% hydrochloric acid into the acidification kettle, wherein the mass ratio of 30% hydrochloric acid to 30% NaOH solution is 1-10: 1-5; stirring thoroughly, standing for layering, transferring the upper layer mother liquor containing 2-p-tolylpropionic acid into a distillation kettle, and distilling under reduced pressure to obtain 2-p-tolylpropionic acid; separating the lower layer water solution, and concentrating the wastewater;
step four, 2- (4-bromomethylphenyl) propionic acid stage:
the bromination reaction kettle is charged with 2-p-tolylpropionic acid: hydrogen peroxide: dichloromethane: the weight ratio of the initiator benzoyl peroxide is 1-5: 1-10: 1-15: 0.1 to 0.5; under the illumination of a sodium lamp at the temperature of 10-15 ℃, materials in a bromination reaction kettle are pumped to a bromination glass tube by a circulating pump, and hydrobromic acid is slowly dripped while the materials are circulated and stirred; the mass ratio of hydrobromic acid to 2-p-tolyl propionic acid is 0.05-0.1: 1-5; after the dropwise addition, continuing the heat preservation reaction for 1-2 hours, transferring the obtained product to a dichloroethane recovery distillation still to evaporate dichloroethane after the bromination reaction is finished, transferring the obtained product to a crystallization still, cooling to 0 ℃, stirring and crystallizing for 4-6 hours, and then putting the obtained product into a centrifuge for spin-drying to obtain a crude 2-p-bromomethylphenylpropionic acid crystal; putting the 2-p-bromomethylphenyl propionic acid crystal crude product into a refining kettle, adding dichloromethane with the weight of 1-5 times of that of the 2-p-bromomethylphenyl propionic acid crystal crude product, repeatedly crystallizing and refining for 2 times, and centrifugally drying to obtain the 2- (4-bromomethylphenyl) propionic acid finished product.
2. The process for producing 2- (4-bromomethylphenyl) propionic acid according to claim 1, wherein the first step is carried out by mixing aluminum trichloride: triethylamine hydrochloride in a molar ratio of 1-5: 1-10 mol ratio, adding into a reaction kettle, and reacting at 10-70 ℃ for 5-12 h.
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| US20040133056A1 (en) * | 2002-11-12 | 2004-07-08 | Zhichang Liu | Method for manufacturing alkylate oil with composite ionic liquid used as catalyst |
| CN101921189A (en) * | 2010-08-27 | 2010-12-22 | 黎明化工研究院 | Preparation method of 2-(4'-amyl-benzoyl) benzoic acid |
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| CN104513177A (en) * | 2014-12-12 | 2015-04-15 | 上海应用技术学院 | Preparation method for 5-(N, N-dibenzylamino)acetylsalicylamide |
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2019
- 2019-11-19 CN CN201911125399.5A patent/CN110790662A/en active Pending
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| WO1998003454A1 (en) * | 1996-07-22 | 1998-01-29 | Akzo Nobel N.V. | Linear alkylbenzene formation using low temperature ionic liquid and long chain alkylating agent |
| US20040133056A1 (en) * | 2002-11-12 | 2004-07-08 | Zhichang Liu | Method for manufacturing alkylate oil with composite ionic liquid used as catalyst |
| CN101921189A (en) * | 2010-08-27 | 2010-12-22 | 黎明化工研究院 | Preparation method of 2-(4'-amyl-benzoyl) benzoic acid |
| CN103342636A (en) * | 2013-06-27 | 2013-10-09 | 南通泰通化学科技有限公司 | Preparation method for 2-(4-brooethylphenyl) propionic acid |
| CN104513177A (en) * | 2014-12-12 | 2015-04-15 | 上海应用技术学院 | Preparation method for 5-(N, N-dibenzylamino)acetylsalicylamide |
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