CN100999446B - Production method of m-bromophonol and production device thereof - Google Patents
Production method of m-bromophonol and production device thereof Download PDFInfo
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- CN100999446B CN100999446B CN200710066702A CN200710066702A CN100999446B CN 100999446 B CN100999446 B CN 100999446B CN 200710066702 A CN200710066702 A CN 200710066702A CN 200710066702 A CN200710066702 A CN 200710066702A CN 100999446 B CN100999446 B CN 100999446B
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Abstract
This invention relates to a production methods of inter-Br-phenol. It includes diazotization reaction, also includes the following steps: 1. hydrolysis reaction: put the aqueous solution of inter-hypotyl heavy nitrogen sulfate that generate from diazotization in pipe reactor for hydrolysis; 2. Extraction: put the liquid generated form hydrolysis reaction into continuous extraction apparatus for extraction, until the water layer clarification; make the separation of the organic layer through vacuum distillation to obtain inter-Br-phenol. The invention also opens the device for the realization of the production: Liquid Storage Tank flow through the pump, then connect with temperature control device's pipeline reactor, outlet of pipeline reactor and continuous extraction unit Linked; Liquid Storage Tank with insulation kits.
Description
Technical field
The present invention relates to the production method and the production equipment thereof of a kind of bromophenol.
Background technology
Between bromophenol be a kind of organic synthesis intermediate, be the raw material of a kind of agricultural chemicals and medicine, can be used to synthetic Meta Bromo Anisole; It also is the many main intermediate of synthetic anticancer sedation-analgesia medicine song, and can be used in other medicine, the dye well organic synthesis.The synthetic method of industrial bromophenol generally is to be raw material with the meta-aminophenol, in the presence of the vitriol oil, carries out diazotization reaction with Sodium Nitrite under 5 ℃, generates diazonium salt, reacts with cuprous bromide in Hydrogen bromide then and gets.That is:
The defective that existing preparation method exists is: employing be that diazonium salt is by the halogen method of replacement, used concentrated hydrobromic acid and cuprous bromide to react, not only operation easier is big, to the equipment requirements height, also to discharge a large amount of waste water, and use tank reactor that side reaction easily takes place, product yield is low, long reaction time.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of throughput height, production cost is low, aftertreatment is simple, waste water is few, the preparation method and the production equipment thereof of suitable industrial bromophenol.
In order to solve the problems of the technologies described above, the invention provides the production method of a kind of bromophenol, comprise diazotization reaction, further comprising the steps of:
1), hydrolysis reaction: the aqueous solution of the m-bromoaniline diazonium vitriol of diazotization reaction gained is hydrolyzed in pipeline reactor, 60～120 ℃ of hydrolysis temperatures, 3～15 minutes time, the concentration of the aqueous solution of m-bromoaniline diazonium vitriol is 0.055～0.060mol/300ml;
2), extraction: the reaction solution of hydrolysis reaction gained is extracted in continuous extraction apparatus, and up to the water layer clarification, used extraction agent is water-soluble low solvent; With the organic layer of telling carry out rectification under vacuum promptly get between bromophenol; Water-soluble low solvent is alkane, aromatic hydrocarbons, ether or halides.
Improvement as production method of the present invention: the aqueous solution of m-bromoaniline diazonium vitriol enters pipeline reactor with the flow of 60～160ml/hr under the control of flow pump.
Further improvement as production method of the present invention: the consumption of water-soluble low solvent and the volume ratio of reaction solution are 0.3: 1～0.8: 1.Alkane is normal hexane or hexanaphthene, and aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and ether is ether, and halides is methylene dichloride or ethylene dichloride.
The present invention also provides the production equipment that is used to realize aforesaid method, the receiver of the aqueous solution of depositing m-bromoaniline diazonium vitriol links to each other with the pipeline reactor that has temperature control unit after by flow pump, and the outlet of pipeline reactor links to each other with continuous extraction apparatus; Receiver is provided with muff.
Improvement as production equipment of the present invention: this continuous extraction apparatus comprises cooling tube I, the pipe connecting that has venting port and the cooling tube II that links to each other successively, and cooling tube I links to each other with the outlet of pipeline reactor; Y-tube is connected with thrust-augmenting nozzle, cooling tube II and extension pipe simultaneously, and the other end of extension pipe is connected with the reaction solution container, and sleeve pipe one end that is enclosed within the extension pipe outside is connected with the reaction solution container, the other end is connected with return line; The other end of thrust-augmenting nozzle and the other end of return line are connected with the extraction liquid container respectively.
Principle of the present invention is to generate m-bromoaniline diazonium vitriol by m-bromoaniline under the vitriol oil and Sodium Nitrite effect earlier, by pipeline reactor the hydrolysis of m-bromoaniline diazonium vitriol is made a bromophenol again.
Its reaction formula is:
Owing to produce a large amount of nitrogen during the diazonium salt hydrolysis, in the sliding reactor of pipeline, flow fast; Make that the residence time of reaction solution in reactor is very short, improved throughput greatly.
The present invention compared with prior art, its remarkable advantage is: 1. reselected operational path, avoided the use Hydrogen bromide as reaction reagent, the reaction conditions gentleness is easy to realize.2. adopt pipeline reactor to carry out the hydrolysis of diazonium salt, effectively avoided the generation of side reaction, improved the yield of product; Reaction times shortens greatly, and only need can be finished reaction in about 10 minutes, had improved throughput.Adopt continuous extraction apparatus further to improve the yield of product.Reach more than 90% through rectification process the finished product yield.3. reacted raffinate filters the back fresh sulfuric acid of interpolation part promptly can be reused for the next batch reaction, and this method had both reduced the discharging of waste water, had also reduced production cost, had improved product yield simultaneously.
Description of drawings
Fig. 1 is the structural representation of production equipment of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is described further.Fig. 1 has provided the production equipment of a kind of bromophenol, the receiver 1 that is used to deposit the aqueous solution of m-bromoaniline diazonium vitriol links to each other with pipeline reactor 4 by flow pump 3 backs, the outside surface of whole receiver 1 is surrounded by muff 2, and adding ice-water bath in muff 2 is below 5 ℃ with the temperature that keeps the m-bromoaniline diazonium sulfate solution in the receiver 1.The temperature control unit 5 of pipeline reactor 4 peripheral hardwares is an oil bath heater, and effect is the temperature that is used to regulate in the pipeline reactor 4.The principal dimension parameter of pipeline reactor 4 is as follows: internal diameter of the pipeline 4mm, long 20m, pipeline internal volume 0.2512L.
The outlet of pipeline reactor 4 links to each other with continuous extraction apparatus 6.This continuous extraction apparatus 6 comprises cooling tube I 61, the pipe connecting 62 that has venting port and the cooling tube II 63 that links to each other successively, and cooling tube I 61 links to each other with the outlet of pipeline reactor 4.Cooling tube I 61 is a kind of tyre cooling-water ducts, is used to cool off the pipeline of pipe temperature in it that flow direction of its water coolant is shown in arrow among Fig. 1; In like manner, cooling tube II63 also is a kind of tyre cooling-water duct, is used to cool off the pipeline of pipe temperature in it that flow direction of its water coolant is also shown in arrow among Fig. 1.
Y-tube 64 is connected the intracavity inter-connection of the other end of extension pipe 65 and reaction solution container 67 simultaneously with cooling tube II 63, thrust-augmenting nozzle 68 and extension pipe 65.An end that is enclosed within the sleeve pipe 66 of extension pipe 65 outsides is connected with the bottleneck of reaction solution container 67, the other end is connected with return line 69; The other end of the other end of thrust-augmenting nozzle 68 and return line 69 is connected with the bottleneck of extraction liquid container 70 respectively.That is to say that extension pipe 65 extend in the reaction solution container 67, therefore in height, the lower end of extension pipe 65 is lower than the lower end of sleeve pipe 66.
During real work, diazotization reaction belongs to a kind of prior art, can in tank reactor, make m-bromoaniline diazonium vitriol according to literature method, then m-bromoaniline diazonium sulfate solution is joined in the receiver 1, utilizing the ice-water bath in the muff 2 is below 5 ℃ to keep the temperature in the receiver 1.Flow pump 3 is used to control the flow of m-bromoaniline diazonium sulfate solution, and m-bromoaniline diazonium sulfate solution enters the reaction that is hydrolyzed in the pipeline reactor 4 through behind the flow pump 3.The reaction solution of hydrolysis reaction gained extracts in continuous extraction apparatus 6.
Embodiment 1: the production method of a kind of bromophenol, carry out following steps successively:
1), diazotization reaction: following (the Preparation of m-bromophenol of typical method, C.FrederickKoelsch, Journal of the American Chemical Society (1939), 61,969): the 10g m-bromoaniline is dissolved in ebullient 300ml water and the 50ml vitriolic solution, mixture is cooled to 10 ℃, and with 4.0g Sodium Nitrite diazotization.The aqueous solution 300ml of the m-bromoaniline diazonium vitriol of gained (containing m-bromoaniline diazonium vitriol 0.0578mol).
2), hydrolysis reaction: above-mentioned m-bromoaniline diazonium sulfate solution is through behind the flow pump 3, enters the reaction that is hydrolyzed in the pipeline reactor 4 with the flow of 100ml/hr.120 ℃ of hydrolysis temperatures, 10 minutes residence time.
3), extraction (this is as a kind of prior art): reaction solution is all by collecting behind the pipeline reactor 4, enters then in the continuous extraction apparatus 6 to extract, and is specific as follows:
The reaction solution of hydrolysis reaction gained at first enters cooling tube I 61 and cools off, and carries out the secondary cooling by entering cooling tube II 63 behind the pipe connecting 62 then; The nitrogen that hydrolysis reaction produces is drained from the venting port of pipe connecting 62.Continued to enter reaction solution container 67 from Y-tube 64, extension pipe 65 successively by the cooled liquid of secondary, accumulate in reaction solution container 67 inside.In extraction liquid container 70, be placed with 150ml toluene.Reaction solution in reaction solution container 67 is abundant, in the time of being back to return line 69 by sleeve pipe 66; Heating extraction liquid container 70 (also can need not above-mentioned condition, direct heating extraction liquid container 70).Toluene vapor enters reaction solution container 67 by Y-tube 64, extension pipe 65 after being condensed and becoming liquid state by thrust-augmenting nozzle 68, Y-tube 64 arrival cooling tube II 63 more successively, and the reaction solutions in the reaction solution container 67 are extracted.Liquid levels in the reaction solution container 67 increase with toluene and raise, and extraction liquid just constantly is back in the extraction liquid container 70 from sleeve pipe 66 and return line 69 successively; Be heated again then and become steam repetition above-mentioned steps.Extract after 1.5 hours, water is clarified substantially, and water intaking is carried out gas chromatographic analysis mutually and do not contained product substantially.Tell toluene and be used for rectifying mutually.
4), product purification: get the toluene phase rectification under vacuum that finishes of extraction, vacuum tightness 30mmHg, toluene distillates in the time of 32～34 ℃, collects 138～140 ℃ of cuts, through chromatogram detection purity 98.7%, infrared spectra is determined structure.Obtain bromophenol between 9.0g altogether.
Embodiment 2: the production method of a kind of bromophenol, carry out following steps successively:
1), diazotization reaction: with embodiment 1.
2), hydrolysis reaction: above-mentioned m-bromoaniline diazonium sulfate solution is through behind the flow pump 3, enters the reaction that is hydrolyzed in the pipeline reactor 4 with the flow of 60ml/hr.120 ℃ of hydrolysis temperatures, 15 minutes residence time.
3), extraction: be placed with the 150ml normal hexane in extraction liquid container 70, the extraction time is 2 hours; All the other are with embodiment 1.
4), product purification: get the organic phase rectification under vacuum that finishes of extraction, vacuum tightness 30mmHg, normal hexane distillates in the time of 22～24 ℃, collects 138～140 ℃ of cuts, through chromatogram detection purity 98.8%, obtains bromophenol between 8.7g.
Embodiment 3: the production method of a kind of bromophenol, carry out following steps successively:
1), diazotization reaction: with embodiment 1.
2), hydrolysis reaction: above-mentioned m-bromoaniline diazonium sulfate solution is through behind the flow pump 3, enters the reaction that is hydrolyzed in the pipeline reactor 4 with the flow of 160ml/hr.70 ℃ of hydrolysis temperatures, 3 minutes residence time.
3), extraction: be placed with the 150ml ether in extraction liquid container 70, the extraction time is 2.5 hours; All the other are with embodiment 1.
4), product purification: get the ether phase rectification under vacuum that extraction finishes, vacuum tightness 30mmHg collects 138～140 ℃ of cuts, detects purity 99% through chromatogram, obtains bromophenol between 8.5g.
Embodiment 4: the production method of a kind of bromophenol, carry out following steps successively:
1), diazotization reaction: with embodiment 1.
2), hydrolysis reaction: above-mentioned m-bromoaniline diazonium sulfate solution is through behind the flow pump 3, enters the reaction that is hydrolyzed in the pipeline reactor 4 with the flow of 100ml/hr.100 ℃ of hydrolysis temperatures, 10 minutes residence time.
3), extraction: be placed with the 150ml methylene dichloride in extraction liquid container 70, the extraction time is 2 hours; All the other are with embodiment 1.
4), product purification: get the organic phase rectification under vacuum that extraction finishes, vacuum tightness 30mmHg collects 138～140 ℃ of cuts, detects purity 98.5% through chromatogram, obtains bromophenol between 8.9g.
Embodiment 5: the production method of a kind of bromophenol, carry out following steps successively:
The water (gained after the extraction step) that use to reclaim in diazotization reaction is as solvent preparation acid solution, and other conditions are with embodiment 1, bromophenol between final 9.1g.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (6)
1. the production method of bromophenol between a kind comprises diazotization reaction, it is characterized in that further comprising the steps of:
1), hydrolysis reaction: the aqueous solution of the m-bromoaniline diazonium vitriol of diazotization reaction gained is hydrolyzed in pipeline reactor (4), 60～120 ℃ of hydrolysis temperatures, 3～15 minutes time, the concentration of the aqueous solution of m-bromoaniline diazonium vitriol is 0.055～0.060mol/300ml;
2), extraction: the reaction solution of hydrolysis reaction gained is extracted in continuous extraction apparatus (6), and up to the water layer clarification, used extraction agent is water-soluble low solvent; With the organic layer of telling carry out rectification under vacuum promptly get between bromophenol; Described water-soluble low solvent is alkane, aromatic hydrocarbons, ether or halides.
2. the production method of a bromophenol according to claim 1 is characterized in that: the aqueous solution of described m-bromoaniline diazonium vitriol enters pipeline reactor (4) with the flow of 60～160ml/hr under the control of flow pump (3).
3. the production method of a bromophenol according to claim 1 and 2 is characterized in that: the consumption of described water-soluble low solvent and the volume ratio of reaction solution are 0.3: 1～0.8: 1.
4. the production method of a bromophenol according to claim 3 is characterized in that: described alkane is normal hexane or hexanaphthene, and described aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and described ether is ether, and described halides is methylene dichloride or ethylene dichloride.
5. production equipment that is used to realize claim 1,2,3 or 4 described methods, it is characterized in that: the receiver (1) of depositing the aqueous solution of m-bromoaniline diazonium vitriol links to each other the outlet of pipeline reactor (4) and continuous extraction apparatus 6 by flow pump (3) back with the pipeline reactor that has temperature control unit (5) (4)) link to each other; Described receiver (1) is provided with muff (2).
6. production equipment according to claim 5, it is characterized in that: described continuous extraction apparatus (6) comprises cooling tube I (61), the pipe connecting (62) that has venting port and the cooling tube II (63) that links to each other successively, and described cooling tube I (61) links to each other with the outlet of pipeline reactor (4); Y-tube (64) is connected with thrust-augmenting nozzle (68), cooling tube II (63) and extension pipe (65) simultaneously, the other end of extension pipe (65) is connected with reaction solution container (67), and sleeve pipe (66) one ends that are enclosed within extension pipe (65) outside are connected with reaction solution container (67), the other end is connected with return line (69); The other end of the other end of thrust-augmenting nozzle (68) and return line (69) is connected with extraction liquid container (70) respectively.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557480A (en) * | 2014-12-19 | 2015-04-29 | 上海生农生化制品有限公司 | Synthetic method of 3-tert-butylphenylethylether |
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| CN103160145B (en) * | 2013-03-12 | 2014-01-22 | 浙江迪邦化工有限公司 | Method and device for automatic-control continuous production of dye |
| CN108558607B (en) * | 2018-05-03 | 2021-05-18 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of o-fluorophenol |
| CN108774112B (en) * | 2018-05-14 | 2021-12-03 | 海门市新港医药科技有限公司 | Preparation method of m-bromophenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914325A (en) * | 1973-06-21 | 1975-10-21 | Olin Corp | Method for preparing phenol compounds using mixed acid system |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914325A (en) * | 1973-06-21 | 1975-10-21 | Olin Corp | Method for preparing phenol compounds using mixed acid system |
Non-Patent Citations (2)
| Title |
|---|
| 曹玉庆等.间溴苯甲醚的合成.中国医药工业杂志36 2.2005,36(2),73-74页. |
| 曹玉庆等.间溴苯甲醚的合成.中国医药工业杂志36 2.2005,36(2),73-74页. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557480A (en) * | 2014-12-19 | 2015-04-29 | 上海生农生化制品有限公司 | Synthetic method of 3-tert-butylphenylethylether |
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Address after: 332700 No. 1, Jishan Industrial Park, Pengze, Jiujiang, Jiangxi Co-patentee after: Zhejiang University Patentee after: Jiangxi Yang Fan New Material Co., Ltd. Address before: 332700 No. 1, Jishan Industrial Park, Pengze, Jiujiang, Jiangxi Co-patentee before: Zhejiang University Patentee before: Jiangxi Renming Pharmaceutical Chemical Industry Co., Ltd. |