CN102234220B - Method for preparing 4-bromo-1,2-xylene - Google Patents
Method for preparing 4-bromo-1,2-xylene Download PDFInfo
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- CN102234220B CN102234220B CN 201010161510 CN201010161510A CN102234220B CN 102234220 B CN102234220 B CN 102234220B CN 201010161510 CN201010161510 CN 201010161510 CN 201010161510 A CN201010161510 A CN 201010161510A CN 102234220 B CN102234220 B CN 102234220B
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Abstract
The invention relates to a method for preparing 4-bromo-1,2-xylene; the method adopts o-xylene as a raw material, and comprises the following steps: adding bromine dropwisely at -60 DEG C to -20 DEG C in the presence of a dichloromethane solution and catalysts with a molar ratio of o-xylene and bromine being 1:1, after the dropwise addition, performing thermal insulation and reaction, slowly heating to 10-20 DEG C, removing the dissolved hydrogen bromide in the reaction solution, adding a saturated aqueous sodium sulfite solution, stirring for 30 min, performing layered recovery of the dichloromethane-containing product, washing with a 5% dilute alkali solution to obtain a PH of 8-9, washing with water to become neutral so as to obtain a colorless or light yellow crude product of 4-bromo-1,2-xylene, recovering the solvent of dichloromethane by distillation under normal pressure, and performing reduced pressure distillation to obtain a product of 4-bromo-1,2-xylene. The invention adopts catalysts of ferric chloride and quaternary ammonium salts such as tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrapropyl ammonium bromide, trioctyl methyl ammonium chloride, and benzyl triethyl ammonium chloride, and the mass ratio of the ferric chloride and the quaternary ammonium salts is 4-5:1; therefore the selectivity of bromination is increased; the content of 4-bromo-1,2-xylene is increased to 85-93%; the content of by-products is decreased; and the product yield is increased.
Description
Technical field
The invention belongs to the chemical industry technical field, relate to a kind of preparation 4-bromo-1,2-YLENE has another name called 3, the method for 4-dimethyl bromobenzene.
Background technology
4-bromo-1,2-YLENE has another name called 3, the 4-dimethyl bromobenzene; Molecular formula: C
8H
9Br, molecular weight: 185.06, CAS NO:583-71-1; Fusing point :-0.2 ℃; Boiling point: 215 ℃.4-bromo-1,2-YLENE are used for the important monomer bibenzene tetracarboxylic dianhydride of synthetic super heat-proof polyimide mainly as the raw material of organic synthesis, also are the main raw materials of synthetic 5-bromobenzene and furanone.4-bromo-1 in the market, 2-YLENE product adopts following technology to produce.
1,3,4-xylidine diazotization method
This law is by 3, and the 4-xylidine after diazotization reaction makes diazonium salt, adds copper powder again and is heated to 60-100 ℃ of decomposition and makes 4-bromo-1,2-YLENE bullion in 48% Hydrogen bromide, a certain amount of Sodium Nitrite.Bullion makes 4-bromo-1,2-YLENE through rectifying.The 4-bromo-1 that this technology makes, the 2-xylene content is up to 98%, but yield is lower, and the three wastes are very many, and raw materials cost is high.Be unfavorable for suitability for industrialized production.
2, o-Xylol bromination method
In the present production technique both domestic and external, use I mostly
2, FeBr
3, FeCl
3, catalyzer such as iron powder, because o-Xylol particular chemical structure, the substitution reaction meeting of bromine generates 4-bromo-1,2-YLENE, 3-bromo-1,2-YLENE, and the dibromide of three isomeries.The product content that makes best about 75%.Improve content if desired, the mol ratio that will improve bromine and o-Xylol is to 1.3-1.5: 1 and with sulfurous gas as solvent, cause product yield low and produce a large amount of three wastes, suitable suitability for industrialized production.
side reaction
side reaction
Summary of the invention
The purpose of this invention is to provide a kind of preparation 4-bromo-1, the method for 2-YLENE, this method are raw material with the o-Xylol; In the presence of dichloromethane solvent and catalyzer, in-60 ℃ to-20 ℃ temperature dripping bromine, the mol ratio of o-Xylol and bromine is 1: 1; After dripping end, insulation is reacted, and slowly is warming up to 10-20 ℃ then; Remove dissolved hydrogen bromide in the reaction solution, add saturated sodium sulfite aqueous solution, stirred 30 minutes; The product that contains methylene dichloride is reclaimed in layering, washs to PH=8-9 with 5% dilute alkaline soln again, is washed with water to neutrality at last; Obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion, distillating recovering solvent methylene dichloride under condition of normal pressure; Rectification under vacuum obtains 4-bromo-1 then, and 2-YLENE product, said catalyzer are iron trichloride and quaternary ammonium mixture; This quaternary ammonium salt for example is: tetrabutylammonium chloride, Tetrabutyl amonium bromide, 4-propyl bromide, methyl trioctylphosphine ammonium chloride, benzyltriethylammoinium chloride, the mass ratio of iron trichloride and quaternary ammonium salt is 4-5: 1.Resulting 4-bromo-1, the content of 2-YLENE is brought up to 85-93%, has reduced by-products content simultaneously, has improved product yield, reaches 95%.
The time of dripping bromine: 3-4 hour
The insulation reaction time: 2 hours
Alkali cleaning temperature: room temperature
Embodiment
Below with by way of example technical scheme of the present invention is described, the content of these embodiment does not limit protection scope of the present invention.
Embodiment 1:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 318g o-Xylol (3mol), 200ml methylene dichloride and catalyzer iron trichloride 2 gram and 0.4g tetrabutylammonium chlorides respectively, under the cryogenic liquid cooling; Temperature of reaction is controlled between-25 to-30 ℃; The control mixing speed is about 450 rev/mins, and dripping bromine 480g (3mol) slowly in 3-4 hour is after dropwising; Insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then; Add saturated sodium bisulfite solution 80ml subsequently, stir half a hour after, the gas producing formation that contains methylene dichloride is reclaimed in layering; Wash to PH=8-9 with 5% dilute alkaline soln again; Be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 740g.Methylene chloride is reclaimed in air distillation, and rectification under vacuum obtains 4-bromo-1 then, 2-YLENE product 535.6g, and the content of this product is 88.8%.Yield is 96.5%.
Embodiment 2:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 318g o-Xylol (3mol), 200ml methylene dichloride and catalyzer iron trichloride 2 gram and 0.5g methyl trioctylphosphine ammonium chlorides respectively, under the cryogenic liquid cooling; Temperature of reaction is controlled between-25 to-30 ℃; The control mixing speed is about 450 rev/mins, and dripping bromine 480g (3mol) slowly in 3-4 hour is after dropwising; Insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then; Add saturated sodium bisulfite solution 80ml subsequently, stir half a hour after, the gas producing formation that contains methylene dichloride is reclaimed in layering; Wash to PH=8-9 with 5% dilute alkaline soln again; Be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 735g.Methylene chloride is reclaimed in air distillation, and rectification under vacuum obtains 4-bromo-1 then, 2-YLENE product 533g, and the content of this product is 88.3%.Yield is 96.0%.
Embodiment 3:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 265g o-Xylol (2.5mol), 450ml methylene dichloride and catalyzer iron trichloride 2 gram and 0.5g methyl trioctylphosphine ammonium chlorides respectively, under the cryogenic liquid cooling; Temperature of reaction is controlled between-55 to-60 ℃; The control mixing speed is about 450 rev/mins, and dripping bromine 400g (2.5mol) slowly in 3-4 hour is after dropwising; Continued insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then; Add saturated sodium bisulfite solution 80ml subsequently, stir half a hour after, the gas producing formation that contains methylene dichloride is reclaimed in layering; Wash to PH=8-9 with 5% dilute alkaline soln again; Be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 924g.Methylene chloride is reclaimed in air distillation, and rectification under vacuum gets 4-bromo-1 then, 2-YLENE product 443g, and the content of this product is 91.8%.Yield is 95.8%.
Embodiment 4:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 318g o-Xylol (3mol) and catalyzer iron trichloride 2 gram and 0.4g Tetrabutyl amonium bromides respectively, under the cryogenic liquid cooling; Temperature of reaction is at-20 ℃; The control mixing speed is about 450 rev/mins, and dripping bromine 480g (3mol) slowly in 3-4 hour is after dropwising; Insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then, add saturated sodium bisulfite solution 80ml subsequently, stir half a hour after; Gas producing formation is reclaimed in layering, washs to PH=8-9 with 5% dilute alkaline soln again, is washed till neutrality with less water at last; Obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 540g.Rectification under vacuum obtains 4-bromo-1,2-YLENE product 537.2g, and the content of this product is 85.7%.Yield is 96.8%.
Following Comparative Examples is identical with the raw material that the foregoing description adopts, and difference is to use respectively iron powder, iodine, and anhydrous iron bromides etc. are as catalyzer and use sulfurous gas to make solvent.
Comparative Examples 1:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 318g o-Xylol (3mol), 200ml methylene dichloride, 8.9g iron bromide (0.03mol) respectively, under the cryogenic liquid cooling; Temperature of reaction is at-20 ℃; The control mixing speed is about 400 rev/mins, and dripping bromine 456g (2.85mol) slowly between 3-4 hour is after dropwising; Insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then; Add saturated sodium bisulfite solution 80ml subsequently, stir half a hour after, the gas producing formation that contains methylene dichloride is reclaimed in layering; Wash PH8-9 with 5% dilute alkaline soln again; Be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 720g.Methylene chloride is reclaimed in air distillation, and rectification under vacuum obtains 4-bromo-1 then, 2-YLENE product 502g, and this product content is 75.2%.Yield is 90.5%.
Comparative Examples 2:
In the 1L four-hole boiling flask of TM, whisking appliance and tap funnel is housed, add 500g o-Xylol (4.72mol), 6g iron (0.1mol), 6g iodine (0.025mol) respectively, under the icy salt solution cooling; Temperature of reaction is at-5 ℃ to 0 ℃; The control mixing speed is about 400 rev/mins, and dripping bromine 661g (4.13mol) slowly in 3-4 hour is after dropwising; Insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then, add saturated sodium bisulfite solution 120ml subsequently, stir half a hour after, wash to PH=8-9 with 5% dilute alkaline soln again, be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 905g.Rectification under vacuum obtains 4-bromo-1,2-YLENE product 727g, and this product content is 75.3%.Yield is 95.2%.
Comparative Examples 3:
In the withstand voltage glass reaction container of the 1L that TM, constant pressure funnel are arranged, add 270g o-Xylol (2.55mol), 190g sulfurous gas respectively, under the icy salt solution cooling; Temperature of reaction is at-5 ℃ to 0 ℃, and pressure is about 0.15Mpa, and the control mixing speed is about 400 rev/mins; Dripping bromine 360g (2.55mol) slowly in 3-4 hour; After dropwising, insulation reaction 2 hours, sampling analysis.Naturally be warming up to 10-20 ℃ then, add saturated sodium bisulfite solution 100ml subsequently, stir half a hour after, wash to PH=8-9 with 5% dilute alkaline soln again, be washed till neutrality with less water at last, obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion 480g.Rectification under vacuum obtains 4-bromo-1, and 2-YLENE product 430, this product content are 84.2%.Yield is 91.2%.
Through the foregoing description and Comparative Examples, can find out that the present invention has used a kind of new catalyst, the selectivity that bromizates is improved; 4-bromo-1, the content of 2-YLENE is brought up to 85-93%, has reduced by-products content simultaneously; Improve product yield, reached 95%.
Claims (6)
1. one kind prepares 4-bromo-1, and the method for 2-YLENE, this method are raw material with the o-Xylol, in the presence of dichloromethane solvent and catalyzer; In-60 ℃ to-20 ℃ temperature dripping bromine, the mol ratio of o-Xylol and bromine is 1: 1, and after dropping finished, insulation was reacted; Slowly be warming up to 10-20 ℃ then, remove dissolved hydrogen bromide in the reaction solution, add saturated sodium sulfite aqueous solution, stirred 30 minutes; The product that contains methylene dichloride is reclaimed in layering, washs to pH=8-9 with 5% dilute alkaline soln again, is washed with water to neutrality at last; Obtain colourless or faint yellow 4-bromo-1,2-YLENE bullion, distillating recovering solvent methylene dichloride under condition of normal pressure; Rectification under vacuum obtains 4-bromo-1 then, and 2-YLENE product, said catalyzer are iron trichloride and quaternary ammonium mixture.
2. preparation 4-bromo-1 according to claim 1, the method for 2-YLENE is characterized in that: the time of dripping bromine is 3-4 hour.
3. preparation 4-bromo-1 according to claim 1 and 2, the method for 2-YLENE is characterized in that: the insulation reaction time is 2 hours.
4. preparation 4-bromo-1 according to claim 1 and 2, the method for 2-YLENE is characterized in that: the alkali cleaning temperature is a room temperature.
5. preparation 4-bromo-1 according to claim 1 and 2, the method for 2-YLENE is characterized in that: said quaternary ammonium salt is tetrabutylammonium chloride, Tetrabutyl amonium bromide, 4-propyl bromide, methyl trioctylphosphine ammonium chloride or benzyltriethylammoinium chloride.
6. preparation 4-bromo-1 according to claim 1 and 2, the method for 2-YLENE is characterized in that: the mass ratio of iron trichloride and quaternary ammonium salt is 4-5: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2803737C1 (en) * | 2022-12-21 | 2023-09-19 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Method for producing monohalo-o-xylenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2601752C1 (en) * | 2015-06-10 | 2016-11-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" | Method for bromination of xylenes into ring |
| CN106631839B (en) * | 2016-11-23 | 2019-03-12 | 盐城利民农化有限公司 | A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline |
| CN110357768A (en) * | 2019-08-28 | 2019-10-22 | 郑州圣壹新材料科技有限公司 | A kind of preparation method of 2- bromine Fluorenone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026932A (en) * | 1990-02-22 | 1991-06-25 | Amoco Corporation | Preparation of 4-bromo-o-xylene in liquid sulfur dioxide |
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2010
- 2010-05-04 CN CN 201010161510 patent/CN102234220B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026932A (en) * | 1990-02-22 | 1991-06-25 | Amoco Corporation | Preparation of 4-bromo-o-xylene in liquid sulfur dioxide |
Non-Patent Citations (1)
| Title |
|---|
| Daisuke Kikuchi,et al.An Alternative Method for the Selective Bromination of Alkylbenzenes Using NaBrO3/NaHSO3 Reagent.《J.Org.Chem.》.1998,第63卷(第17期),6023-6026. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2803737C1 (en) * | 2022-12-21 | 2023-09-19 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Method for producing monohalo-o-xylenes |
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