CN101062892A - Synthesis of 2-(4-Bromomethylphenyl) ethylformic acid - Google Patents
Synthesis of 2-(4-Bromomethylphenyl) ethylformic acid Download PDFInfo
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- CN101062892A CN101062892A CN 200610039935 CN200610039935A CN101062892A CN 101062892 A CN101062892 A CN 101062892A CN 200610039935 CN200610039935 CN 200610039935 CN 200610039935 A CN200610039935 A CN 200610039935A CN 101062892 A CN101062892 A CN 101062892A
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Abstract
The invention discloses a 2- (4- methyl bromide phenyl group) propanoic acid synthesis, which comprises the following steps: choosing benzyl chloride or bromide of benzyl as start raw material; proceeding esterification reaction with sodium acetate; generating benzyl acetate; proceeding acylated reaction with 2-chloride propionyl chloride; generating 2- chloride -1-(4-benzyl acetate group)-1-acetone; proceeding condensation reaction with octyl pentadiol; proceeding molecule rearrangement reaction; generating 2- (4- methyl bromide phenyl group) propanoic acid.
Description
The invention relates to the synthetic of 2-(4-2-bromomethylphenyl) propionic acid: with Benzyl Chloride or cylite is starting raw material, with sodium acetate generation esterification, generates jasmal; Jasmal and 2-chlorpromazine chloride generation acylation reaction generate 2-chloro-1-(4-jasmal base)-1-acetone; 2-chloro-1-(4-jasmal base)-1-acetone and hot pentanediol again through molecular rearrangement reaction, generate 2-(4-jasmal base phenyl) propionic acid through condensation reaction; At last, 2-(4-jasmal base phenyl) propionic acid through hydrolysis and bromo-reaction, generates 2-(4-2-bromomethylphenyl) propionic acid.
About the synthetic method of 2-(4-2-bromomethylphenyl) propionic acid, appear in the newspapers both at home and abroad.
Chinese Journal of New Drugs (2000,
9 (11)) report, be raw material with toluene, Synthetic 2-(4-2-bromomethylphenyl) propionic acid.Through alkylation, hydrolysis and decarboxylic reaction, synthesize loxoprofen sodium again.Total yield is more than 40%.
(2004 (8), 191-191) report is a starting raw material with toluene to the Heilungkiang scientific and technical information, through acidylate, ketal, rearrangement, hydrolysis and bromo-reaction, Synthetic 2-(4-2-bromomethylphenyl) propionic acid.Be used for Synthetic 2-(4-2-bromomethylphenyl) ethyl propionate.
The open CN1294115 of Chinese patent introduces, with the 2-chlorpromazine chloride is starting raw material, react through Friedel-Crafts, get 2-chloro-1-(4-aminomethyl phenyl)-1-ketone, again with neopentyl glycol under Catalyzed by p-Toluenesulfonic Acid, methylbenzene azeotropic dehydration obtains ketal, under the catalysis of zinc oxide, cupric oxide, obtain 2-(4-aminomethyl phenyl) propionic acid after hydrolysis, the acidifying, get 2-(4-2-bromomethylphenyl) propionic acid after the bromination.
The present invention is to be starting raw material with Benzyl Chloride or cylite, through esterification, generates jasmal; Through acylation reaction, generate 2-chloro-1-(4-jasmal base)-1-acetone; Through condensation reaction,, generate 2-(4-jasmal base phenyl) propionic acid again through molecular rearrangement reaction; At last, in the presence of Hydrogen bromide,, generate 2-(4-2-bromomethylphenyl) propionic acid through hydrolysis and bromo-reaction.
Esterification is carried out under normal pressure and reflux temperature, makes water as solvent, and sodium hydroxide or potassium hydroxide are catalyzer.Benzyl Chloride or cylite and sodium acetate generation esterification generate the acetate benzyl ester.Esterification is carried out under reflux state, keeps 10～25 hours, and the optimum time is 10～15 hours.The long reaction times helps the complete of esterification.The mol ratio of material is a water: halogenation benzyl: sodium acetate: catalyzer=20.00～100.00: 1.00: 1.00～1.10: 0.001～0.03.
The ester that esterification generated is the liquid heavier than water.After dividing water, can use the saturated common salt water washing 2～3 times, wash with water again 2 times.Behind anhydrous sodium sulphate or anhydrous magnesium sulfate drying, promptly obtain jasmal, can be used as the raw material of next step reaction.The product yield is no less than 95%, and content is more than 98%.The chemical equation of esterification is as follows:
Acylation reaction is to use 1, and the 2-ethylene dichloride is as solvent, and aluminum trichloride (anhydrous) is a catalyzer; under-5 ℃～10 ℃ temperature; optimum temperature is 0 ℃～5 ℃, and jasmal and 2-chlorpromazine chloride generation acylation reaction generate 2-chloro-1-(4-jasmal base)-1-acetone.Reaction times is 5～15 hours, and the optimum time is 10～12 hours.The molar ratio of material is: jasmal: aluminum chloride: the 2-chlorpromazine chloride: 1, and 2-ethylene dichloride=1.00: 1.00～2.50: 1.00～1.20: 10.00～20.00.
After the acylation reaction, pour into to ice in the frozen water and separate, used frozen water amount is 5～20 times of material, and temperature is no more than 50 ℃.By separatory, water layer is with 1, and the 2-ethylene dichloride extracts twice.Merge organic layer, wash secondary, the washing secondary with saturated common salt.Decompression and solvent recovery, raffinate are poured in 2～4 times the sherwood oil, cool off-5 ℃～2 ℃, and crystallization was filtered more than 2 hours, white solid be 2-chloro-1-(4-jasmal base)-1-acetone.Productive rate can reach more than 85%, and content is more than 98%.The chemical equation of acidylate is as follows:
The employed solvent of condensation reaction is 1, and 2-ethylene dichloride, p-methyl benzenesulfonic acid are catalyzer, under reflux state, keeps reaction 20～30 hours, and optimum return time is 20～25 hours, and the longer reaction times helps condensation reaction.Jasmal base-2-chloro-1-acetone and hot pentanediol generation condensation reaction generate a kind of excessive intermediate.This excessive intermediate need not separate, and can under the Zinc oxide catalytic effect molecular rearrangement reaction take place, and generates 2-(4-jasmal base phenyl) propionic acid.The temperature of rearrangement reaction is 100 ℃～190 ℃, and the time is 2～12 hours.The molar ratio of material is: jasmal base-2-chloro-1-acetone: hot pentanediol: p-methyl benzenesulfonic acid: zinc oxide=1.00: 1.10～2.50: 0.01～0.10: 0.50～1.50.Chemical equation is as follows:
After condensation reaction finished, room temperature was reduced in cooling, adds 1.0～1.5 times water, mixed the back and divided water.Water layer is with 1, and the 2-ethylene dichloride extracts.Merge organic layer, wash secondary with saturated common salt, the washing secondary after the dehydration, reclaims most of solvent, adds zinc oxide as the configuration conversion catalyst, 100 ℃～190 ℃ rearrangement reactions of carrying out molecule.The rearrangement time is 2～12 hours.After reset finishing, be cooled to below 70 ℃, add 0.5 times 1, the 2-ethylene dichloride drips 30% sodium hydroxide solution, its usage quantity is counted 1.1～1.5 times of 2-(4-benzylalcohol base) propionic acid by mole.After dropwising, reflux 3～6 hours.Be cooled to below 60 ℃, the water of quality such as adding and solvent after fully stirring, leaves standstill branch water, and organic layer washes with water.Combining water layer with 48% Hydrogen bromide acidifying, is transferred HP=1～2, separates out oily matter, is the crude product of 2-(4-benzylalcohol base) propionic acid.This oily matter of underpressure distillation obtains can be used as 2-(the 4-benzylalcohol base) propionic acid of next step bromo-reaction raw material.The product yield is more than 90%, and content is more than 96%.The chemical equation of condensation and rearrangement is as follows:
Bromo-reaction is the Hydrogen bromide of 2-(4-benzylalcohol base) propionic acid and 48%, sulfuric acid arranged or do not having under the sulfuric acid condition, and reflux 3～10 hours, crystallisation by cooling obtains 2-(4-2-bromomethylphenyl) propionic acid crude product.The molar ratio of material is: 2-(4-benzylalcohol base) propionic acid: Hydrogen bromide: sulfuric acid=1.00: 1.00～5.50: 0.00～5.00.The chemical equation of hydrolysis and bromo is as follows:
Crude product 2-(4-2-bromomethylphenyl) propionic acid can use the mixed solution of sherwood oil and ethyl acetate (weight ratio 4: 1), and is refining through recrystallization method.The product yield is more than 85%, and content is more than 99%.
Example 1
Synthesizing of jasmal: in the 500ml there-necked flask, add water and the 18.1g sodium-acetate of 300ml.Heated and stirred, controlled temperature are no more than 75 ℃.After treating that sodium acetate is molten entirely, add 25.20g Benzyl Chloride and catalyzer 0.15g, reflux is after 12 hours, and stop stirs, and puts layering only.Divide and remove upper water, and with after lower floor's oil drying, as the raw material of next step reaction.The heavy 28.65g of oil reservoir, productive rate 95.53%.
2-chloro-1-(4-jasmal base)-1-acetone preparation method: in the 500ml there-necked flask, add 300ml 1,2-ethylene dichloride, 30.1g jasmal and 52.5g trichlorine aluminium mix and stir, and are cooled to 0 ℃, drip 27.5g 2-chlorpromazine chloride.Drip and finish again equality of temperature reaction 8 hours, pour into then to ice in the frozen water and separate.Separatory, water layer are with 1, and 2-ethylene dichloride (50 * 2) extracts.The merging organic layer is washed secondary with saturated common salt, the washing secondary, and decompression and solvent recovery, the raffinate cooling adds sherwood oil 80ml, cools off 0～-5 ℃ of crystallization 2 hours, filters, and gets white solid 41.73g, and productive rate 85.3% is surveyed content 98.6%.
The preparation of 2-(4-benzylalcohol base) propionic acid: in the 2000ml there-necked flask, add 250ml 1,2-ethylene dichloride, 36.0g2-chloro-jasmal base-1-acetone, 34.5g neopentyl glycol methyl alcohol and 1.80g p-methyl benzenesulfonic acid.Mix and stir, under reflux state, reacted about 20 hours, simultaneously that water is clean with the time-division.Cool to room temperature, add 1.1 times water, Hou Fenshui is mixed.Water layer is with 1, and 2-ethylene dichloride (60 * 2) extracts.Merge organic layer, with the saturated common salt washing once, the washing secondary after the dehydration, reclaims most of solvent, is adding 14.5g zinc oxide, stirs 2 hours down at 140 ℃.Reaction is finished, and adds 150ml 1, and the 2-ethylene dichloride drips 30% sodium hydroxide (500ml), and reflux was cooled to about 70 ℃ after 4 hours.Add entry 300ml, stirred 0.5 hour, separatory, organic layer water (200ml * 3) washing.Combining water layer is transferred PH=1～2 with 48%HBr solution, separates out oily matter.Tell organic layer, drying and underpressure distillation get 2-(4-benzylalcohol base) propionic acid 24.45g, yield 90.56%, and content 96.50% can be used as the raw material of next step reaction.
The preparation of 2-(4-2-bromomethylphenyl) propionic acid: in the 250ml there-necked flask, add above-mentioned oily matter 20.5g and 48% Hydrogen bromide 80g, reflux 6 hours.In mixture, add 100ml water, stir cooling, separate out crystallization 25.2g.Refining with sherwood oil and ethyl acetate (4: 1) mixed solution, get crystallization 24.1g, yield 87.06%, liquid chromatography is surveyed content 99.2%.
Example 2
Synthesizing of jasmal: in the 500ml there-necked flask, add water and the 20.50g sodium-acetate of 300ml.Heated and stirred, controlled temperature are no more than 65 ℃.After treating that sodium acetate is molten entirely, add 34.20g cylite and catalyzer 0.20g, reflux is put layering after 8 hours only.Divide and remove upper water, lower floor's oil reservoir weighs 29.35g, productive rate 97.83% after drying.
2-chloro-1-(4-jasmal base)-1-acetone preparation method: in the 500ml there-necked flask, add 250ml 1,2-ethylene dichloride, 30.1g jasmal and 50.2g trichlorine aluminium mix and stir, and are cooled to-3 ℃, drip 29.0g 2-chlorpromazine chloride.Drip and finish, pour into then to ice in the frozen water and separate-3 ℃～0 ℃ reaction 15 hours.Handle with above-mentioned method, get white solid 42.06g, productive rate 86.01% is surveyed content 98.5%.
The preparation of 2-(4-benzylalcohol base) propionic acid: in the 2000ml there-necked flask, add 300ml 1,2-ethylene dichloride, 36.7g2-chloro-jasmal base-1-acetone, 32.5g neopentyl glycol and 1.50g p-methyl benzenesulfonic acid.Mix and stir, under reflux state, reacted about 30 hours.After above-mentioned method processing, adding 10.50g zinc oxide.60 ℃～70 ℃ of temperature kept 3 hours, constantly steamed solvent, and temperature raises gradually, after 4 hours, reached 150 ℃, continued 2 hours again.Reaction is finished, and adds 200ml 1, and the 2-ethylene dichloride drips 30% sodium hydroxide (500ml), and reflux was cooled to about 70 ℃ after 4 hours.Add entry 300ml, stirred 0.5 hour.Handle with above-mentioned method, get 2-(4-benzylalcohol base) propionic acid 24.77g, yield 91.74%, content 96.80%.
The preparation of 2-(4-2-bromomethylphenyl) propionic acid: in the 250ml there-necked flask, add above-mentioned oily matter 36.20g and 48% Hydrogen bromide 100g, vitriol oil 30g heats 70 ℃～80 ℃, continues 4 hours.In mixture, add 150ml water, stir cooling, separate out crystallization 44.24g.Refining with sherwood oil and ethyl acetate (4: 1) mixed solution, get crystallization 42.16g, yield 86.75%, liquid chromatography is surveyed content 99.3%.
Example 3
Synthesizing of jasmal: in the 1000ml there-necked flask, add water and the 49.5g sodium-acetate of 500ml.Heated and stirred adds 63.30g Benzyl Chloride and catalyzer 0.30g, and reflux is put layering after 10 hours only.Divide and remove upper water, after lower floor's oil drying, heavy 72.10g, productive rate 96.13%.
2-chloro-1-(4-jasmal base)-1-acetone preparation method: in the 1000ml there-necked flask, add 600ml 1,2-ethylene dichloride, 75.20g jasmal and 107.0g trichlorine aluminium mix and stir, and are cooled to 2 ℃, drip 70.6g 2-chlorpromazine chloride.Drip and finish, pour into then to ice in the frozen water and separate 0 ℃～8 ℃ reactions 10 hours.Handle with above-mentioned method, get white solid 108.2g, productive rate 88.51% is surveyed content 98.7%.
The preparation of 2-(4-benzylalcohol base) propionic acid: in the 3000ml there-necked flask, add 650ml 1,2-ethylene dichloride, 49.0g2-chloro-jasmal base-1-acetone, 41.2g neopentyl glycol methyl alcohol and 1.30g p-methyl benzenesulfonic acid.Mix and stir, under reflux state, reacted about 40 hours.After above-mentioned method processing, adding 24.4g zinc oxide.80 ℃～90 ℃ of temperature kept 10 hours.Reaction is finished, and drips 30% sodium hydroxide (1000ml), and reflux was cooled to about 60 ℃ after 5 hours.Add entry 400ml, stirred 0.5 hour.Handle with above-mentioned method, get 2-(4-benzylalcohol base) propionic acid 33.2g, yield 92.2%, content 97.10%.
The preparation of 2-(4-2-bromomethylphenyl) propionic acid: in the 500ml there-necked flask, add above-mentioned oily matter 90.5g and 48% Hydrogen bromide 200g, reflux 5 hours.In mixture, add 200ml water, stir cooling, separate out crystallization 110.6g.Refining with sherwood oil and ethyl acetate (4: 1) mixed solution, get crystallization 106.6g, yield 87.74%, liquid chromatography is surveyed content 99.4%.
Claims (6)
1, the method for a kind of Synthetic 2-(4-2-bromomethylphenyl) propionic acid is characterized in that with Benzyl Chloride or cylite be starting raw material, through esterification, generates jasmal; Through acylation reaction, generate 2-chloro-1-(4-jasmal base)-1-acetone; Through condensation reaction,, generate 2-(4-jasmal base phenyl) propionic acid again through molecular rearrangement reaction; At last, through hydrolysis and bromo-reaction, generate 2-(4-2-bromomethylphenyl) propionic acid.
2, according to the synthetic method of the described 2-of claim 1 (4-2-bromomethylphenyl) propionic acid, it is characterized in that preparing jasmal, employed material is sodium acetate and Benzyl Chloride or cylite, and solvent is a water, and catalyzer is a sodium hydroxide, or potassium hydroxide.Esterification kept 10～25 hours under reflux state.The mol ratio of material is: halogenation benzyl: sodium acetate: catalyzer=1.00: 1.00～1.10: 0.001～0.03.
3, according to the synthetic method of the described 2-of claim 1 (4-2-bromomethylphenyl) propionic acid; it is characterized in that preparing 2-chloro-1-(4-jasmal base)-1-acetone; employed solvent is 1; the 2-ethylene dichloride; aluminum trichloride (anhydrous) is a catalyzer; under-5 ℃～10 ℃ temperature, jasmal and 2-chlorpromazine chloride generation acylation reaction and generate.Reaction times is 5～15 hours.The molar ratio of material is: jasmal: aluminum chloride: 2-chlorpromazine chloride=1.00: 1.00～2.50: 1.00～1.20.
4, according to the synthetic method of the described 2-of claim 1 (4-2-bromomethylphenyl) propionic acid, it is characterized in that preparing 2-(4-jasmal base phenyl) propionic acid, employed solvent is 1, the 2-ethylene dichloride, p-methyl benzenesulfonic acid is a catalyzer, under reflux state, keep reaction 20～30 hours, 2-chloro-jasmal base-1-ketone and hot pentanediol generation condensation reaction generate a kind of excessive intermediate.Molecular rearrangement reaction under the Zinc oxide catalytic effect, takes place again in this excessive intermediate, generates 2-(4-jasmal base phenyl) propionic acid.The temperature of rearrangement reaction is 100 ℃～190 ℃, and the time is 2～12 hours.The molar ratio of material is: 2-chloro-jasmal base-1-acetone: hot pentanediol: p-methyl benzenesulfonic acid: zinc oxide=1.00: 1.10～2.50: 0.01～0.10: 0.50～1.50.
5, according to the synthetic method of the described 2-of claim 1 (4-2-bromomethylphenyl) propionic acid, it is characterized in that 2-(4-jasmal base phenyl) propionic acid and strong mineral alkali generation hydrolysis reaction, generate 2-(4-benzylalcohol base) propionic salt.Hydrolysis reaction uses excessive alkali, reflux 3～6 hours, and 2-(4-benzylalcohol base) propionic acid is separated out in acidifying then.
6, according to the synthetic method of the described 2-of claim 1 (4-2-bromomethylphenyl) propionic acid, the Hydrogen bromide that it is characterized in that 2-(4-benzylalcohol base) propionic acid and 48%, sulfuric acid is being arranged or do not having under the sulfuric acid condition, reflux 3～10 hours, 2-(4-2-bromomethylphenyl) propionic acid crude product is separated out in cooling.Crude product 2-(4-2-bromomethylphenyl) propionic acid can use the mixed solution of sherwood oil and ethyl acetate (weight ratio 4: 1), and is refining through recrystallization method.The molar ratio of material is: 2-(4-benzylalcohol base) propionic acid: Hydrogen bromide: sulfuric acid=1.00: 1.00～5.50: 0.00～5.00.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355988A (en) * | 2014-11-11 | 2015-02-18 | 山东国润精细化工有限公司 | Synthesis method of 2-(4-bromomethyl phenyl) propionic acid |
| CN107778129A (en) * | 2016-08-24 | 2018-03-09 | 李长荣化学工业股份有限公司 | The preparation system and preparation method of fragrance derivatives |
-
2006
- 2006-04-25 CN CN 200610039935 patent/CN101062892A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355988A (en) * | 2014-11-11 | 2015-02-18 | 山东国润精细化工有限公司 | Synthesis method of 2-(4-bromomethyl phenyl) propionic acid |
| CN104355988B (en) * | 2014-11-11 | 2016-01-13 | 山东国润精细化工有限公司 | A kind of 2-(4-2-bromomethylphenyl) propionic acid synthesize method |
| CN107778129A (en) * | 2016-08-24 | 2018-03-09 | 李长荣化学工业股份有限公司 | The preparation system and preparation method of fragrance derivatives |
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