CN104744237A - Preparation method of 2-(4-bromomethylphenyl) propionic acid - Google Patents
Preparation method of 2-(4-bromomethylphenyl) propionic acid Download PDFInfo
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- CN104744237A CN104744237A CN201510083872.3A CN201510083872A CN104744237A CN 104744237 A CN104744237 A CN 104744237A CN 201510083872 A CN201510083872 A CN 201510083872A CN 104744237 A CN104744237 A CN 104744237A
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- bromomethylphenyl
- propionic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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Abstract
The invention discloses a preparation method of 2-(4-bromomethylphenyl) propionic acid. The preparation method is characterized by comprising a preparation stage of 2-phenyl propionitrile, a preparation stage of 2-phenyl propionic acid and a preparation stage of 2-(4-bromomethylphenyl) propionic acid. The preparation stage of 2-phenyl propionitrile comprises the following steps: mixing benzyl cyanide, dimethyl carbonate and potassium carbonate; heating to 100-300 DEG C and carrying out thermal reaction for 5-50h under the pressure of 0.5-6MPa; and by the end of the reaction, carrying out filter pressing and rinsing to be neutral; distilling to removal excessive dimethyl carbonate; and carrying out high-vacuum rectification to obtain 2-phenyl propionitrile. Compared with the prior art, the preparation method disclosed by the invention has the following advantages and effects that the main raw material is benzyl cyanide which is subjected to methylation, hydrolysis reaction and bromomethylation to finally obtain the finished product; the purity of the finished product is high and the yield is up to 90% or above; and in addition, the preparation method has the advantages of simple production process, low production cost and low environment pollution.
Description
Technical field
The present invention relates to a kind of 2-(4-2-bromomethylphenyl) propionic acid preparation method.
Background technology
At present, 2-(4-2-bromomethylphenyl) propionic acid is one of key intermediate of synthesis loxoprofen sodium, loxoprofen sodium belongs to the novel non-steroid antiinflammatory drug of arylprop acids, clinically show that it is that analgesia in current known arylprop acids medicine, anti-inflammatory, antirheumatic effect are best, thus dark in domestic and international expert and the favor of scholar and the high praise of the world of medicine and patient.Pharmaceutical Co., Ltd was in development listing in 1986 altogether by Japan three for these product, and at present in the listing of many countries such as Japan, Korea S, America and Europe, and growth is powerful.According to statistics, within 1992, the market sales revenue reaches 1.8 hundred million dollars, within 1994, reaches 25,000,000,000 yen in the sales volume of Japan, belongs to the medicine of first 20 of annual sales amount.China also in recent years starting to produce and in clinical application, but the complex manufacturing of prior art, production cost large, pollute large, and its product yield is low.
Summary of the invention
The object of the invention is to overcome above shortcomings in prior art, and 2-(4-2-bromomethylphenyl) the propionic acid preparation method that a kind of production technique is simple, product purity is high, yield is high is provided.
The present invention's adopted technical scheme that solves the problem is:
A kind of 2-(4-2-bromomethylphenyl) propionic acid preparation method, is characterized in that: comprise 2-phenylpropanenitrile preparatory phase, 2-phenylpropionic acid preparatory phase and 2-(4-2-bromomethylphenyl) propionic acid stage, concrete steps are as follows:
1) 2-phenylpropanenitrile preparatory phase
Benzyl cyanide, methylcarbonate, salt of wormwood mixing after, be warming up to 100 ~ 300 DEG C, pressure-controlling at 0.5 ~ 6MPa, insulation reaction 5 ~ 50 hours; Reaction terminate after, then by press filtration, be washed to neutrality; Then distillation removes excessive methylcarbonate, and high vacuum rectification obtains 2-phenylpropanenitrile;
2) 2-phenylpropionic acid preparatory phase
After the mixing of liquid caustic soda, water, 2-phenylpropanenitrile, be warming up to 80 ~ 120 DEG C, back flow reaction 5 ~ 20 hours; After reaction terminates, be cooled to 20 ~ 60 DEG C and pass through to drip sulfuric acid, until PH < 5; Layering obtains 2-phenylpropionic acid crude product, and high vacuum rectification obtains 2-phenylpropionic acid;
3) 2-(4-2-bromomethylphenyl) the propionic acid stage
Hydrogen bromide, formaldehyde drip sulfuric acid after mixing with above-mentioned 2-phenylpropionic acid at 20 ~ 50 DEG C of temperature; Be warming up to 60 ~ 120 DEG C subsequently, insulation reaction 3 ~ 20 hours, it is neutral for dividing sub-cloud sour water and washing material to aqueous phase, obtains 2-(4-2-bromomethylphenyl) propionic acid crude product; Add dimethylbenzene, repeat crystal refining 3 ~ 5 times, centrifugal, wash, be drying to obtain 2-(4-2-bromomethylphenyl) propionic acid finished product.
Be further used as preferably, in 2-phenylpropanenitrile preparatory phase, the mol ratio of benzyl cyanide, methylcarbonate and salt of wormwood is: 1 ~ 10:1 ~ 40:0.01 ~ 3,
Be further used as preferably, in 2-phenylpropionic acid preparatory phase, the weight part of liquid caustic soda, water and 2-phenylpropanenitrile is respectively: 1 ~ 10 part, 1 ~ 5 part, 1 ~ 5 part.
Be further used as preferably, 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the weight part of 2-phenylpropionic acid, Hydrogen bromide and formaldehyde is respectively 1 ~ 5 part, 1 ~ 10 part, 0.1 ~ 1 part.
Be further used as preferably, 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the weight part of sulfuric acid is 1 ~ 5 part.
Be further used as preferably, 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the dropping temperature of sulfuric acid is 40 DEG C.
The present invention compared with prior art, has the following advantages and effect: the present invention take benzyl cyanide as main raw material, and finally make finished product through the reaction of methylation reaction, hydrolysis reaction and bromomethylation, its finished product purity is high, and yield is up to more than 90%.In addition, production technique of the present invention is simple, production cost is low, it is little to pollute.
Embodiment
Principal reaction equation of the present invention is:
1) 2-phenylpropanenitrile preparatory phase:
2) 2-phenylpropionic acid preparatory phase:
3) 2-(4-2-bromomethylphenyl) the propionic acid stage:
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment one:
The preparation method of the present embodiment 2-(4-2-bromomethylphenyl) propionic acid, comprise 2-phenylpropanenitrile preparatory phase, 2-phenylpropionic acid preparatory phase and 2-(4-2-bromomethylphenyl) propionic acid stage, concrete steps are as follows:
1) 2-phenylpropanenitrile preparatory phase
By benzyl cyanide: methylcarbonate: salt of wormwood is that the mol ratio of 10:40:2 adds in dry autoclave, under stirring, be slowly warming up to 180 DEG C, pressure-controlling, at below 2MPa, is incubated reaction in 30 hours and terminates; Reaction solution is by press filtration, washed reaction liquid to neutral, and then distillation removes excessive methylcarbonate, and high vacuum rectification obtains 2-phenylpropanenitrile;
2) 2-phenylpropionic acid preparatory phase
In hydrolytic reaction pot, add liquid caustic soda: water: 2-phenylpropanenitrile is that then 2:1:1 weight part is warming up to 95 DEG C, stir, back flow reaction 15 hours, is cooled to 40 DEG C and proceeds to acidification reaction still; Slowly sulfuric acid is dripped, until PH < 5 in acidification reaction still; Layering obtains 2-phenylpropionic acid crude product, and high vacuum rectification obtains 2-phenylpropionic acid;
3) 2-(4-2-bromomethylphenyl) the propionic acid stage
In bromomethylation reactor, drop into above-mentioned 2-phenylpropionic acid: Hydrogen bromide: paraformaldehyde is 1:1.5:0.25 weight ratio, open and stir, then slowly dripping weight part is the sulfuric acid of 1.5, and temperature controls below 40 DEG C; Sulfuric acid to be dripped, is warming up to 80 DEG C, insulation reaction 12 hours, and it is neutral for dividing sub-cloud sour water and washing material to aqueous phase, obtains 2-(4-2-bromomethylphenyl) propionic acid crude product; In reactor, add parts by weight of xylene 3 repeat crystal refining 3 times, centrifugal, wash, be drying to obtain 2-(4-2-bromomethylphenyl) propionic acid finished product.After testing, the high purity 98% of 2-(4-2-bromomethylphenyl) propionic acid finished product, yield is up to 99%.
Embodiment two:
The preparation method of the present embodiment 2-(4-2-bromomethylphenyl) propionic acid, comprise 2-phenylpropanenitrile preparatory phase, 2-phenylpropionic acid preparatory phase and 2-(4-2-bromomethylphenyl) propionic acid stage, concrete steps are as follows:
1) 2-phenylpropanenitrile preparatory phase
By benzyl cyanide: methylcarbonate: salt of wormwood is that the mol ratio of 5:30:3 adds in dry autoclave, under stirring, be slowly warming up to 220 DEG C, pressure-controlling, at below 2.5MPa, is incubated reaction in 20 hours and terminates; Reaction solution is by press filtration, washed reaction liquid to neutral, and then distillation removes excessive methylcarbonate, and high vacuum rectification obtains 2-phenylpropanenitrile;
2) 2-phenylpropionic acid preparatory phase
In hydrolytic reaction pot, add liquid caustic soda: water: 2-phenylpropanenitrile is that then 5:2:1 weight part heats up 110 DEG C, stir, back flow reaction 8 hours, is cooled to 40 DEG C and proceeds to acidification reaction still; Slowly sulfuric acid is dripped, until PH < 5 in acidification reaction still; Layering obtains 2-phenylpropionic acid crude product, and high vacuum rectification obtains 2-phenylpropionic acid;
3) 2-(4-2-bromomethylphenyl) the propionic acid stage
In bromomethylation reactor, drop into above-mentioned 2-phenylpropionic acid: Hydrogen bromide: paraformaldehyde is 2:5.5:0.5 weight ratio, open and stir, then slowly dripping weight part is the sulfuric acid of 4.5, and temperature controls below 50 DEG C; Sulfuric acid to be dripped, is warming up to 70 DEG C, insulation reaction 20 hours, and it is neutral for dividing sub-cloud sour water and washing material to aqueous phase, obtains 2-(4-2-bromomethylphenyl) propionic acid crude product; In reactor, add parts by weight of xylene 2 repeat crystal refining 4 times, centrifugal, wash, be drying to obtain 2-(4-2-bromomethylphenyl) propionic acid finished product.After testing, the high purity 97% of 2-(4-2-bromomethylphenyl) propionic acid finished product, yield is up to 98.5%.
Embodiment three:
The preparation method of the present embodiment 2-(4-2-bromomethylphenyl) propionic acid, comprise 2-phenylpropanenitrile preparatory phase, 2-phenylpropionic acid preparatory phase and 2-(4-2-bromomethylphenyl) propionic acid stage, concrete steps are as follows:
1) 2-phenylpropanenitrile preparatory phase
By benzyl cyanide: methylcarbonate: salt of wormwood is that the mol ratio of 2:35:3.5 adds in dry autoclave, under stirring, be slowly warming up to 250 DEG C, pressure-controlling, at below 4MPa, is incubated reaction in 15 hours and terminates; Reaction solution removes solid carbonic acid potassium by press filtration and washed reaction liquid is extremely neutral, and then distillation removes excessive methylcarbonate, and high vacuum rectification obtains 2-phenylpropanenitrile;
2) 2-phenylpropionic acid preparatory phase
In hydrolytic reaction pot, add liquid caustic soda: water: 2-phenylpropionic acid is that then 7:3:1 weight part heats up 100 DEG C, stir, back flow reaction 8 hours, is cooled to 40 DEG C and proceeds to acidification reaction still; Slowly sulfuric acid is dripped, until PH < 5 in acidification reaction still; Layering obtains 2-phenylpropionic acid crude product, and high vacuum rectification obtains 2-phenylpropionic acid;
3) 2-(4-2-bromomethylphenyl) the propionic acid stage
In bromomethylation reactor, drop into above-mentioned 2-phenylpropionic acid: Hydrogen bromide: paraformaldehyde is 1:2:0.27 weight ratio, open and stir, then slowly dripping weight part is the sulfuric acid of 2, and temperature controls below 35 DEG C; Sulfuric acid to be dripped, is warming up to 70 DEG C, insulation reaction 11 hours, and it is neutral for dividing sub-cloud sour water and washing material to aqueous phase, obtains 2-(4-2-bromomethylphenyl) propionic acid crude product; In reactor, add parts by weight of xylene 1.1 repeat crystal refining 5 times, centrifugal, wash, be drying to obtain 2-(4-2-bromomethylphenyl) propionic acid finished product.After testing, the high purity 98.5% of 2-(4-2-bromomethylphenyl) propionic acid finished product, yield is up to 99%.
Above content described in this specification sheets is only made for the present invention illustrating.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment; only otherwise depart from the content of specification sheets of the present invention or surmount this scope as defined in the claims, protection scope of the present invention all should be belonged to.
Claims (6)
1. 2-(4-2-bromomethylphenyl) propionic acid preparation method, is characterized in that: comprise 2-phenylpropanenitrile preparatory phase, 2-phenylpropionic acid preparatory phase and 2-(4-2-bromomethylphenyl) propionic acid stage, concrete steps are as follows:
1) 2-phenylpropanenitrile preparatory phase
Benzyl cyanide, methylcarbonate, salt of wormwood mixing after, be warming up to 100 ~ 300 DEG C, pressure-controlling at 0.5 ~ 6MPa, insulation reaction 5 ~ 50 hours; Reaction terminate after, then by press filtration, be washed to neutrality; Then distillation removes excessive methylcarbonate, and high vacuum rectification obtains 2-phenylpropanenitrile;
2) 2-phenylpropionic acid preparatory phase
After the mixing of liquid caustic soda, water, 2-phenylpropanenitrile, be warming up to 80 ~ 120 DEG C, back flow reaction 5 ~ 20 hours; After reaction terminates, be cooled to 20 ~ 60 DEG C and pass through to drip sulfuric acid, until PH < 5; Layering obtains 2-phenylpropionic acid crude product, and high vacuum rectification obtains 2-phenylpropionic acid;
3) 2-(4-2-bromomethylphenyl) the propionic acid stage
Hydrogen bromide, formaldehyde drip sulfuric acid after mixing with above-mentioned 2-phenylpropionic acid at 20 ~ 50 DEG C of temperature; Be warming up to 60 ~ 120 DEG C subsequently, insulation reaction 3 ~ 20 hours, it is neutral for dividing sub-cloud sour water and washing material to aqueous phase, obtains 2-(4-2-bromomethylphenyl) propionic acid crude product; Add dimethylbenzene, repeat crystal refining 3 ~ 5 times, centrifugal, wash, be drying to obtain 2-(4-2-bromomethylphenyl) propionic acid finished product.
2. 2-according to claim 1 (4-2-bromomethylphenyl) propionic acid preparation method, it is characterized in that: in 2-phenylpropanenitrile preparatory phase, the mol ratio of benzyl cyanide, methylcarbonate and salt of wormwood is: 1 ~ 10:1 ~ 40:0.01 ~ 3,
3. 2-according to claim 1 (4-2-bromomethylphenyl) propionic acid preparation method, it is characterized in that: in 2-phenylpropionic acid preparatory phase, the weight part of liquid caustic soda, water and 2-phenylpropanenitrile is respectively: 1 ~ 10 part, 1 ~ 5 part, 1 ~ 5 part.
4. 2-according to claim 1 (4-2-bromomethylphenyl) propionic acid preparation method, it is characterized in that: 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the weight part of 2-phenylpropionic acid, Hydrogen bromide and formaldehyde is respectively 1 ~ 5 part, 1 ~ 10 part, 0.1 ~ 1 part.
5. 2-according to claim 4 (4-2-bromomethylphenyl) propionic acid preparation method, is characterized in that: 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the weight part of sulfuric acid is 1 ~ 5 part.
6. 2-according to claim 4 (4-2-bromomethylphenyl) propionic acid preparation method, is characterized in that: 2-(4-2-bromomethylphenyl) is in the propionic acid stage, and the dropping temperature of sulfuric acid is 40 DEG C.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753685A (en) * | 2016-03-30 | 2016-07-13 | 浙江丽水有邦新材料有限公司 | Method for preparing loxoprofen intermediate |
| CN106866404A (en) * | 2017-01-04 | 2017-06-20 | 昆山力田医化科技有限公司 | A kind of synthetic method of the different benzenpropanoic acid of 4 bromomethyl |
| CN107573230A (en) * | 2017-08-11 | 2018-01-12 | 重庆沃肯精细化工有限公司 | A kind of synthetic method to bromomethyl benzenpropanoic acid |
| CN105037139B (en) * | 2015-07-07 | 2018-04-17 | 浙江博聚新材料有限公司 | A kind of 2 phenylpropionic acid preparation methods |
| CN109180470A (en) * | 2018-09-10 | 2019-01-11 | 浙江大学 | Liquid phase circulation method prepares 2- (4- 2-bromomethylphenyl) propionic acid |
| CN109180464A (en) * | 2018-09-10 | 2019-01-11 | 浙江大学 | Gas circulation method prepares 2- (4- 2-bromomethylphenyl) propionic acid |
| CN109438285A (en) * | 2018-11-06 | 2019-03-08 | 浙江大学 | Benzene acetonitrile methylation method based on compression rectification technology |
| CN109485556A (en) * | 2018-10-19 | 2019-03-19 | 浙江大学 | The method of one pot process 2- phenylpropionic acid |
| CN109912399A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | The method of high-pressure synthesis 2- phenylpropionic acid |
| CN110872235A (en) * | 2018-08-30 | 2020-03-10 | 江苏瑞科医药科技有限公司 | Application of novel methyl carbonate methylation catalyst in preparation of α -methylphenylacetic acid |
| EP4151616A4 (en) * | 2021-04-26 | 2023-12-20 | Mitsubishi Gas Chemical Company, Inc. | Compound and method for producing same |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037139B (en) * | 2015-07-07 | 2018-04-17 | 浙江博聚新材料有限公司 | A kind of 2 phenylpropionic acid preparation methods |
| CN105753685A (en) * | 2016-03-30 | 2016-07-13 | 浙江丽水有邦新材料有限公司 | Method for preparing loxoprofen intermediate |
| CN106866404A (en) * | 2017-01-04 | 2017-06-20 | 昆山力田医化科技有限公司 | A kind of synthetic method of the different benzenpropanoic acid of 4 bromomethyl |
| CN107573230A (en) * | 2017-08-11 | 2018-01-12 | 重庆沃肯精细化工有限公司 | A kind of synthetic method to bromomethyl benzenpropanoic acid |
| CN107573230B (en) * | 2017-08-11 | 2021-09-14 | 重庆沃肯精细化工有限公司 | Synthetic method of p-bromomethyl phenylpropionic acid |
| CN110872235A (en) * | 2018-08-30 | 2020-03-10 | 江苏瑞科医药科技有限公司 | Application of novel methyl carbonate methylation catalyst in preparation of α -methylphenylacetic acid |
| CN109180464A (en) * | 2018-09-10 | 2019-01-11 | 浙江大学 | Gas circulation method prepares 2- (4- 2-bromomethylphenyl) propionic acid |
| CN109180470B (en) * | 2018-09-10 | 2021-02-02 | 浙江大学 | Preparation of 2- (4-bromomethylphenyl) propionic acid by liquid phase circulation method |
| CN109180470A (en) * | 2018-09-10 | 2019-01-11 | 浙江大学 | Liquid phase circulation method prepares 2- (4- 2-bromomethylphenyl) propionic acid |
| CN109485556A (en) * | 2018-10-19 | 2019-03-19 | 浙江大学 | The method of one pot process 2- phenylpropionic acid |
| CN109438285A (en) * | 2018-11-06 | 2019-03-08 | 浙江大学 | Benzene acetonitrile methylation method based on compression rectification technology |
| CN109912399A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | The method of high-pressure synthesis 2- phenylpropionic acid |
| EP4151616A4 (en) * | 2021-04-26 | 2023-12-20 | Mitsubishi Gas Chemical Company, Inc. | Compound and method for producing same |
| US11919833B2 (en) | 2021-04-26 | 2024-03-05 | Mitsubishi Gas Chemical Company, Inc. | Compound and method for producing same |
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