CN110229069A - The recoverying and utilizing method of trimethylphenyl tribromide ammonium in preparation method and the naproxen production of trimethylphenyl tribromide ammonium - Google Patents
The recoverying and utilizing method of trimethylphenyl tribromide ammonium in preparation method and the naproxen production of trimethylphenyl tribromide ammonium Download PDFInfo
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- CN110229069A CN110229069A CN201910639973.2A CN201910639973A CN110229069A CN 110229069 A CN110229069 A CN 110229069A CN 201910639973 A CN201910639973 A CN 201910639973A CN 110229069 A CN110229069 A CN 110229069A
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- ammonium
- trimethylphenyl
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- trimethylphenyl tribromide
- bromine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The present invention provides a kind of preparation methods of trimethylphenyl tribromide ammonium, using dimethylaniline as starting material, it is first reacted with dimethyl suflfate and generates phenyl trimethicone sulfate methyl ammonium, phenyl trimethicone sulfate methyl ammonium is dissolved in hydrobromic acid solution again, bromine reaction is added dropwise, filtering, water washing obtain crude product, and crude product is by being recrystallized to give product.The invention also discloses the recoverying and utilizing methods of trimethylphenyl tribromide ammonium in a kind of production of naproxen, it is characterized by: hydrobromic acid solution is added in the aqueous solution that trimethylphenyl tribromide ammonium bromo-reaction obtains into naproxen production, then bromine is added dropwise, rear room temperature is dripped off to be stirred to react, filtering after having reacted, water washing is dried to obtain product.High income, it is at low cost, it is easy to operate.
Description
Technical field
The present invention relates to trimethylphenyls three in a kind of preparation method of trimethylphenyl tribromide ammonium and naproxen production
The recoverying and utilizing method of ammonium bromide, belongs to organic synthesis field.
Background technique
Important drugs of the naproxen as antiphlogistic antibacterial field play an important role, at present in anti-inflammatory, antipyretic, analgesia field
It is mainly used for treating rheumatic arthritis, rheumatoid arthritis, osteoarthritis, ankylosing spondylitis, various types of rheumatism
Property myotenositis, periarthritis of shoulderjoint etc..
Naproxen is as large tonnage product, and cost is most important under fierce market competition.Trimethylphenyl tribromide ammonium
Abbreviation PTT is good selective bromination reagent, is the good raw material of selective bromo in Synthesis of Dl-naproxen.PTT bromine
The reaction equation of metaplasia production naproxen are as follows:
The operation of bromination reaction are as follows:
1.5 kilograms of dimethylbenzene are put into 5L three-necked flask, 600 grams of phenyltrimethylammonium bromide, 40 DEG C of stirring and dissolvings half are small
When, it then cools to 18 DEG C, is added 320 grams of naphthalene of 6- methoxyl group -2- propionyl, after the reaction was continued 8 hours at a temperature of this, to
The stirring liquid separation of 1.5 kg of water is added in system.Upper organic phase is directly entered in reaction in next step without purifying.
Trimethylphenyl tribromide ammonium is the important source material in naproxen production, however 2000 yuan or so of kilogram market
Price allows the industrialization cost of naproxen to sharply increase, and loses market competition.
Therefore, in order to reduce cost, trimethylphenyl used in PTT and recycling naproxen production process oneself is synthesized
Tribromide ammonium becomes the emphasis that we study.‘
Summary of the invention
In order to solve the above-mentioned technical problem, the first object of the present invention is to provide a kind of trimethylphenyl tribromide ammonium
Preparation method, high income is at low cost.Second is designed to provide time of trimethylphenyl tribromide ammonium in naproxen production
The method of utilizing is received, the rate of recovery is high, and cost recovery is low.
In order to realize above-mentioned purpose of the invention, the present invention provides a kind of preparation sides of trimethylphenyl tribromide ammonium
Method, it is characterised in that: using dimethylaniline as starting material, first reacted with dimethyl suflfate and generate phenyl trimethicone Methylsulfate
Ammonium, then phenyl trimethicone sulfate methyl ammonium is dissolved in hydrobromic acid solution, bromine reaction is added dropwise, filtering, water washing obtain slightly
Product, crude product is by being recrystallized to give product.
Reaction equation is
This method obtains product by two-step reaction, and reaction carries out under 35-45 DEG C of low temperature, or carries out at room temperature,
Low energy consumption, easy to operate, and total recovery can reach 76%-87%.
In above scheme: the molar ratio of the dimethyl suflfate and dimethylaniline is 1-1.2:1, the bromine and phenyl
The molar ratio of trimethyl sulfate methyl ammonium is 1.1-1.5:1.Guarantee that reaction is gone on smoothly, improves yield.
The concrete operations that the dimethylaniline is reacted with dimethyl suflfate are as follows: the dimethylaniline and dimethyl suflfate are anti-
The concrete operations answered are as follows: dimethylaniline and toluene, stirring and dissolving are added in the reaction vessel, is heated to 35-45 DEG C, stops adding
Heat is added dropwise dimethyl suflfate, first reacts at room temperature after adding, and then continues heating reaction in steam bath, cooling after having reacted,
Filtering, filter cake are washed with toluene, are dried to obtain product.The concrete operations that phenyl trimethicone sulfate methyl ammonium is reacted with bromine are as follows:
Phenyl trimethicone sulfate methyl ammonium and hydrobromic acid solution are added in the reaction vessel, bromine is added dropwise in stirring and dissolving, precipitating is generated,
Continue to be stirred to react at room temperature, until fully reacting, filtering, water washing dry to obtain crude product.
The method of recrystallization are as follows: crude product is first added in acetic acid and is recrystallized, filters, is dried to obtain product；It either will be thick
Product dissolve by heating in methanol, after to be dissolved, are cooled to room temperature, and ether is added, precipitates crystal, and filter, are dried to obtain production
Product.
In above scheme: the mass concentration of the hydrobromic acid solution is 45%-50%, hydrogen bromide and phenyl trimethicone sulphur
The molar ratio of sour ammonium methyl is 1.4-1.5:1.
The second object of the present invention is achieved in that returning for trimethylphenyl tribromide ammonium in a kind of production of naproxen
Receive the method for utilizing, it is characterised in that: in the aqueous solution that trimethylphenyl tribromide ammonium bromo-reaction obtains into naproxen production
Hydrobromic acid solution is added, bromine is then added dropwise, drips off rear room temperature and is stirred to react, filtering after having reacted, water washing is dried to obtain
Product.
PTT recycling is directly used in after brominated water layer stratification, water layer main component is single bromo after bromine
Quaternary ammonium salt, is added aqueous solution of hydrogen bromide into system, and product is precipitated after bromine is added dropwise, centrifugation, washing, dry Product recycling
Rate is up to 90% or more.
In above scheme: the bromine and the molar ratio for joining trimethylphenyl tribromide ammonium to be recycled are 1.1-1.5:
1。
In above scheme: the mass concentration of the hydrobromic acid solution is 45%-50%, hydrogen bromide and joins to be recycled three
The molar ratio of aminomethyl phenyl tribromide ammonium is 1.4-1.5:1.
The utility model has the advantages that the present invention with dimethyl suflfate first to react and generate phenyl front three using dimethylaniline as starting material
Base sulfate methyl ammonium, then react to obtain trimethylphenyl tribromide ammonium with bromine in hydrobromic acid solution, it is easy to operate, it is suitble to
Industrialized production, at low cost, high income.PTT in the production of recycling naproxen by means of the present invention, easy to operate, recycling
Rate reaches 90% or more, greatly reduces the production cost of naproxen.
Specific embodiment:
Below with reference to embodiment, invention is further described in detail.
Embodiment 1
The preparation of PTT, reaction equation are as follows:
In the conical flask for being equipped with thermometer and magnetic stirrer, 248 grams (260 milliliters, 2 moles) are added and newly steam diformazan
The solution of aniline and 1000 milliliters of toluene.Stirring and dissolving is heated to 35 DEG C under stiring.Stop heating, exists by dropping funel
The dimethyl suflfate that 190 milliliters (2 moles) newly distill is added in 20 minutes.After a few minutes, colourless Methylsulfate ammonium salt starts
Crystallization.During dropwise addition, temperature is slightly changed, and after dripping 1 hour, due to exothermic heat of reaction, temperature is raised slowly to 50 DEG C.
Then it reacts under room temperature (thermal response is not added) 1.5 hours, is then heated 1 hour in steam bath again.After cooling, by benzene
The filtering of base trimethyl sulfate methyl ammonium, is washed, thousand is dry under vacuum with 200 milliliters of dry toluenes.Obtain phenyl trimethicone sulfuric acid first
450 grams of ester ammonium, yield 91%.
In 1250 milliliters of conical flasks, 100 grams of (0.4 mole) phenyl trimethicone sulfate methyl ammoniums are dissolved in 100 milliliters
48% hydrobromic acid, and diluted with 300 milliliters of water.Under magnetic stirring, in about 20 minutes, by dropping funel to this solution
25 milliliters of bromines of middle addition, generate orange-yellow precipitating immediately, are stirred to react at room temperature 5 one 6 hours.By product phenyl trimethicone
The filtering of tribromide ammonium, with about 100 milliliters of water washings, dries to obtain about 150 grams of crude product in draught cupboard.
It is recrystallized in 25 milliliters of acetic acid, after filtering and drying, obtains 140 grams of products, yield 93% is orange crystal, melts
Point 114-115.5.
Embodiment 2
The preparation of PTT
In the conical flask for being equipped with thermometer and magnetic stirrer, 248 grams (260 milliliters, 2 moles) are added and newly steam diformazan
The solution of aniline and 1000 milliliters of toluene.Stirring and dissolving is heated to 45 DEG C under stiring.Stop heating, exists by dropping funel
The dimethyl suflfate that 228 milliliters (2.4 moles) newly distill is added in 20 minutes.After a few minutes, colourless Methylsulfate ammonium salt is opened
Begin to crystallize.During dropwise addition, temperature is slightly changed, and after dripping 1 hour, temperature is raised slowly to 55 DEG C.Then at room temperature
It reacts 1.5 hours, is then heated 1 hour in steam bath again.After cooling, phenyl trimethicone sulfate methyl ammonium is filtered, is used
200 milliliters of dry toluene washings, thousand is dry under vacuum.465 grams of phenyl trimethicone sulfate methyl ammonium are obtained, yield 94%.
In conical flask, 100 grams of (0.4 mole) phenyl trimethicone sulfate methyl ammoniums are dissolved in 97 milliliter of 50% hydrobromic acid,
And it is diluted with 300 milliliters of water.Under magnetic stirring, in about 20 minutes, 30.7 millis are added into this solution by dropping funel
Bromine is risen, orange-yellow precipitating is generated immediately, is stirred to react at room temperature 5 one 6 hours.By product phenyltrimethyl-ammonium tribromide mistake
Filter, with about 100 milliliters of water washings, dries to obtain about 149 grams of crude product in draught cupboard.
It being recrystallized in 250 milliliters of acetic acid, after filtering and drying, obtains 139g product, yield 92.3% is orange crystal,
Fusing point 114-115.5.
Embodiment 3
The preparation of PTT
In the conical flask for being equipped with thermometer and magnetic stirrer, 248 grams (260 milliliters, 2 moles) are added and newly steam diformazan
The solution of aniline and 1000 milliliters of toluene.Stirring and dissolving is heated to 40 DEG C under stiring.Stop heating, exists by dropping funel
The dimethyl suflfate that 209 milliliters (2.2 moles) newly distill is added in 20 minutes.After a few minutes, colourless Methylsulfate ammonium salt is opened
Begin to crystallize.During dropwise addition, temperature is slightly changed, and after dripping 1 hour, temperature is raised slowly to 45 DEG C.Then at room temperature
It reacts 1.5 hours, is then heated 1 hour in steam bath again.After cooling, phenyl trimethicone sulfate methyl ammonium is filtered, is used
200 milliliters of dry toluene washings, thousand is dry under vacuum.440 grams of phenyl trimethicone sulfate methyl ammonium are obtained, yield 89%.
In conical flask, 100 grams of (0.4 mole) phenyl trimethicone sulfate methyl ammoniums are dissolved in 100 milliliter of 45% hydrogen bromine
Acid, and diluted with 300 milliliters of water.Under magnetic stirring, it in about 20 minutes, is added by dropping funel into this solution
22.5 milliliters of bromines, generate orange-yellow precipitating immediately, are stirred to react at room temperature 5 one 6 hours.By product phenyl trimethicone tribromo
Change ammonium filtering, with about 100 milliliters of water washings, dries to obtain about 142 grams of crude product in draught cupboard.
Crude product is added in 200 ml methanols, is dissolved by heating, cold rear 200 milliliters of tertbutyl ether of methylate precipitates crystal,
It filters and wind is in rear, obtain 129g product, yield 86% is orange crystal, fusing point 114-115.5.
Embodiment 4
The operation of naproxen bromination reaction are as follows:
0.25 kilogram of dimethylbenzene, 100 grams of phenyltrimethyl-ammonium tribromide (0.265mol), 40 DEG C is put into three-necked flask
Then stirring and dissolving half an hour cools to 18 DEG C, be added 53 grams of naphthalene of 6- methoxyl group -2- propionyl, and the reaction was continued at a temperature of this
After 8 hours, the stirring liquid separation of 0.25 kg of water is added into system.Upper organic phase is directly entered anti-in next step without purifying
Ying Zhong.Water layer collects recycling.So it is repeated several times.
Embodiment 5
64.3 milliliter of 50% (mass concentration) hydrobromic acid is added in the aqueous solution of embodiment 4, under magnetic stirring, greatly
In about 20 minutes, 0.29mol bromine is added into this solution by dropping funel, generates orange-yellow precipitating immediately, stirs at room temperature
Mix reaction 5 one 6 hours.Product phenyltrimethyl-ammonium tribromide is filtered, with about 100 milliliters of water washings, is dried to obtain product
90g, yield 90%.
Embodiment 6
62.5 milliliter of 48% hydrobromic acid is added in the aqueous solution of embodiment 4, under magnetic stirring, in about 20 minutes,
0.318mol bromine is added into this solution by dropping funel, generates orange-yellow precipitating immediately, is stirred to react 5 one 6 at room temperature
Hour.Product phenyltrimethyl-ammonium tribromide is filtered, with about 100 milliliters of water washings, is dried to obtain product 92g, yield
92%.
Embodiment 7
69 milliliter of 45% hydrobromic acid is added in the aqueous solution of embodiment 4, under magnetic stirring, in about 20 minutes, warp
It crosses dropping funel and 0.398mol bromine is added into this solution, generate orange-yellow precipitating immediately, it is small to be stirred to react 5 one 6 at room temperature
When.Product phenyltrimethyl-ammonium tribromide is filtered, with about 100 milliliters of water washings, is dried to obtain product 92.5g, yield
92.5%.
Claims (9)
1. a kind of preparation method of trimethylphenyl tribromide ammonium, it is characterised in that: using dimethylaniline as starting material, elder generation and sulphur
Dimethyl phthalate reaction generates phenyl trimethicone sulfate methyl ammonium, then phenyl trimethicone sulfate methyl ammonium is dissolved in hydrobromic acid solution
In, bromine reaction is added dropwise, filtering, water washing obtain crude product, and crude product is by being recrystallized to give product.
2. the preparation method of trimethylphenyl tribromide ammonium according to claim 1, it is characterised in that: the dimethyl suflfate
Molar ratio with dimethylaniline is 1-1.2:1, and the molar ratio of the bromine and phenyl trimethicone sulfate methyl ammonium is 1.1-1.5:
1。
3. the preparation method of trimethylphenyl tribromide ammonium according to claim 2, which is characterized in that the dimethylaniline with
The concrete operations of dimethyl suflfate reaction are as follows: dimethylaniline is added in the reaction vessel and toluene, stirring and dissolving are heated to 35-
45 DEG C, stop heating, dimethyl suflfate is added dropwise, is first reacted at room temperature after adding, then continues heating reaction, reaction in steam bath
Cooling after complete, filtering, filter cake is washed with toluene, is dried to obtain product.
4. the preparation method of trimethylphenyl tribromide ammonium according to claim 3, which is characterized in that phenyl trimethicone sulfuric acid
The concrete operations that ammonium methyl is reacted with bromine are as follows: phenyl trimethicone sulfate methyl ammonium is added in the reaction vessel and hydrobromic acid is molten
Bromine is added dropwise in liquid, stirring and dissolving, generates precipitating, continues to be stirred to react at room temperature, until fully reacting, filtering, water washing are dried
Obtain crude product.
5. the preparation method of any one of -4 trimethylphenyl tribromide ammoniums according to claim 1, which is characterized in that recrystallization
Method are as follows: crude product is first added in acetic acid and is recrystallized, filter, be dried to obtain product；Either crude product is dissolved by heating in first
It in alcohol, after to be dissolved, is cooled to room temperature, ether is added, precipitates crystal, filter, be dried to obtain product.
6. the preparation method of trimethylphenyl tribromide ammonium according to claim 5, it is characterised in that: the hydrobromic acid solution
Mass concentration be 45%-50%, the molar ratio of hydrogen bromide and phenyl trimethicone sulfate methyl ammonium is 1.4-1.5:1.
7. the recoverying and utilizing method of trimethylphenyl tribromide ammonium in a kind of naproxen production, it is characterised in that: raw to naproxen
Hydrobromic acid solution is added in the aqueous solution that trimethylphenyl tribromide ammonium bromo-reaction obtains in production, bromine is then added dropwise, drips off
Room temperature is stirred to react afterwards, and filtering after having reacted, water washing is dried to obtain product.
8. according to claim 7 in naproxen production trimethylphenyl tribromide ammonium recoverying and utilizing method, feature exists
In: the bromine is 1.1-1.5:1 with the molar ratio for joining trimethylphenyl tribromide ammonium to be recycled.
9. according to claim 8 in naproxen production trimethylphenyl tribromide ammonium recoverying and utilizing method, feature exists
In: the mass concentration of the hydrobromic acid solution is 45%-50%, the hydrogen bromide trimethylphenyl tribromide ammonium to be recycled with ginseng
Molar ratio is 1.4-1.5:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805039A (en) * | 2022-04-13 | 2022-07-29 | 山东海王化工股份有限公司 | Production process of high-melting-point flame retardant methyl octabromoether |
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Application publication date: 20190913 |