CN101851148A - Preparation method of 4,4'-dibromobiphenyl - Google Patents
Preparation method of 4,4'-dibromobiphenyl Download PDFInfo
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- CN101851148A CN101851148A CN201010179508A CN201010179508A CN101851148A CN 101851148 A CN101851148 A CN 101851148A CN 201010179508 A CN201010179508 A CN 201010179508A CN 201010179508 A CN201010179508 A CN 201010179508A CN 101851148 A CN101851148 A CN 101851148A
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- dibromobiphenyl
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Abstract
The invention discloses a preparation method of 4,4'-dibromobiphenyl, which comprises the following steps of: with water and glacial acetic acid as solvents, reacting biphenyl with bromine to generate the 4,4'-dibromobiphenyl under the heating condition in the presence of oxidant and aulixilary oxidant, then leaching through methanol and drying to obtain a finished product. The preparation method of the 4,4'-dibromobiphenyl not only has high product purity and yield and short reaction time, but also has simple operation and is easy for industrialized production.
Description
Technical field
The present invention relates to the organic chemical industry field, be specifically related to a kind of 4, the preparation method of 4 '-'-dibromobiphenyl.
Background technology
4,4 '-'-dibromobiphenyl is a kind of important organic synthesis intermediate, because of its hydrolysis preparation 4, the succeeding in developing of 4 '-dihydroxybiphenyl method makes this product at rubber, dyestuff, petroleum product additive and make and all be widely used aspect good engineering plastics and the matrix material.Especially the raw material as liquid crystalline polymers has reached the industrialization practical stage.This base polymer has multifrequency nature, and is of many uses, can weave and make high strength fibre, is used for fibre-optic enhancing, makes matrix material and rope etc., and the application prospect that very induces one is arranged.
Learn by retrieval, Lee now surely waits " 4, synthesizing of 4 '-'-dibromobiphenyl " (" University Of Qingdao's journal " the 24th volume, 2003.9) literary composition has disclosed in the laboratory with compound haloalkane is solvent, and make catalyzer with binary metal, synthetic method at normal temperatures obtains product purity 99.7%, yield 84.6%.But the author does not provide the concrete title of employed catalyzer, and does not see that this method is applied to the report of large-scale industrial production.
U.S. Pat 4935562 (" METHOD FOR PRODUCING 4,4 '-DIBROMOBIPHENYL ") disclose a kind of 4, the preparation method of 4 '-'-dibromobiphenyl: biphenyl and bromine are dissolved in the organic solvent, react as catalyzer with Lewis acid, preparation 4,4 '-'-dibromobiphenyl, the purity 92.1% of the product that obtains, yield about 90%.Mainly there are following these shortcomings in this preparation technology:
1. need in the reaction system to add Lewis acid, the subsequent product purifying is brought difficulty as catalyzer;
2. degree of purity of production is lower, can not satisfy present need of industrial production;
3. this arts demand adds a large amount of bromines, has increased production cost, and the bromine contaminate environment;
With an organic solvent equipment is had certain corrosive nature, shortened the work-ing life of equipment.
More than these drawbacks limit the large-scale application of this technology in actual production.
Summary of the invention
For overcoming deficiency of the prior art, the object of the present invention is to provide a kind ofly 4, the preparation method of 4 '-'-dibromobiphenyl, this method have solved that existing production technique moderate purity is low, and the purifying difficulty is big, problems such as the high and contaminate environment of cost.
For solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of 4, the preparation method of 4 '-'-dibromobiphenyl, it comprises the steps:
1) add solvent and oxygenant successively in reaction system, wherein, described solvent is mixed and made into by water and Glacial acetic acid;
2) temperature of reaction system is remained on 0-20 ℃ scope, in reaction system, slowly drip pro-oxidant then, after dropwising, stirred 15 minutes;
3) temperature of reaction system is remained on 0-20 ℃ scope, in reaction system, add biphenyl then;
4) temperature of reaction system is remained on 15-25 ℃ scope, in reaction system, slowly drip bromine then;
5) temperature of reaction system is warming up to 30-40 ℃ scope, stirred 2 hours, reaction system is warming up to 90 ℃ then, react and obtain containing 4 after 4 hours, the mixture of 4 '-'-dibromobiphenyl, its reaction equation is as follows:
6) with reaction system cooling, filter solid crude product;
7) wash described solid crude product with water until neutrality, again with methyl alcohol drip washing;
8) dry finished product.
Further, the mass ratio of described water and Glacial acetic acid is 1: 3-3.5.
Further, described oxygenant can be sodium perchlorate, ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
Preferably, described pro-oxidant is the vitriol oil.
Further, the mass ratio of described oxygenant and described pro-oxidant is 1.5-5: 1.
Preferably, the mass ratio of described oxygenant and described pro-oxidant is 2.5: 1.
Further, the mass ratio of described solid crude product and described methyl alcohol is 1: 1.
Compared with prior art, the present invention has following advantage:
1. of the present invention 4, in the preparation method's of 4 '-'-dibromobiphenyl the process, under the effect of pro-oxidant, make the oxygenizement of oxygenant stronger, thereby accelerated bromine and biphenyl reaction generation 4,4 '-'-dibromobiphenyl, shortened the reaction times, improved reaction efficiency, reduced usage quantity, reduced the risk of contaminate environment bromine.
2. among the preparation method of the present invention, the growing amount of impurity such as 4-bromo biphenyl is few, uses the methyl alcohol drip washing of equivalent once can remove impurity, simplifies the operation, and has reduced the use to organic solvent.
3. of the present invention 4, the preparation method of 4 '-'-dibromobiphenyl has optimized reaction times and temperature of reaction, has simplified reaction process greatly, satisfies the demand of suitability for industrialized production.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
Implement 1:
In three mouthfuls of reactors of a 3L, add 300g water successively, 1000g Glacial acetic acid, 250g sodium perchlorate, slowly drip the vitriol oil then to 50g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 308g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine until 330g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 559.1g, purity 99.0%, yield 89.6%.
Embodiment 2:
In three mouthfuls of reactors of a 3L, add 300g water successively, 1000g Glacial acetic acid, 200g sodium perchlorate, slowly drip the vitriol oil then to 100g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 308g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine until 330g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 534.1g, purity 98.6%, yield 85.6%.
Embodiment 3:
In three mouthfuls of reactors of a 3L, add 300g water successively, 1000g Glacial acetic acid, 250g sodium perchlorate, slowly drip the vitriol oil then to 100g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 308g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 330g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 575.3g, purity 99.8%, yield 92.2%.
Embodiment 4:
In three mouthfuls of reactors of a 3L, add 300g water successively, 1000g Glacial acetic acid, 250g sodium perchlorate, slowly drip the vitriol oil then to 150g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 308g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 330g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 574.0g, purity 99.6%, yield 92.0%.
Embodiment 5:
In three mouthfuls of reactors of a 3L, add 300g water successively, 1000g Glacial acetic acid, 300g sodium perchlorate, slowly drip the vitriol oil then to 100g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 308g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 330g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 572.2g, purity 99.7%, yield 91.7%.
Embodiment 6:
In three mouthfuls of reactors of a 3L, add 150g water successively, 500g Glacial acetic acid, 190g ammonium persulphate, slowly drip the vitriol oil then to 100g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 154g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 190g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 265.1g, purity 99.4%, yield 84.9%.
Embodiment 7:
In three mouthfuls of reactors of a 3L, add 150g water successively, 500g Glacial acetic acid, 262g Sodium Persulfate, slowly drip the vitriol oil then to 100g, keep dripping 15 ℃ of process system temperature, dropwise, stirring 15 minutes below 15 ℃, add 154g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 180g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 269.8g, purity 99.2%, yield 85.6%.
Embodiment 8:
In three mouthfuls of reactors of a 3L, add 150g water successively, 500g Glacial acetic acid, 324g Potassium Persulphate, slowly drip the vitriol oil then to 100g, keeping dripping the process system temperature is 15 ℃, dropwises, and is stirring 15 minutes below 15 ℃, add 154g biphenyl then, finish, system is cooled to below 20 ℃, slowly drips bromine to 180g, keep dripping bromine process system temperature at 20 ℃, after bromine dropwised, system can be warming up to 35 ℃, and stirred 2 hours under this temperature, be warming up to 90 ℃ of degree reactions 4 hours then, reaction finishes postcooling, filters solid phase prod, and washes solid with water to neutral, again with the drip washing of equivalent methyl alcohol, dry at last finished product 270.2g, purity 99.5%, yield 86.5%.
The foregoing description just is to allow the one of ordinary skilled in the art can understand content of the present invention and enforcement according to this for technical conceive of the present invention and characteristics being described, its objective is, can not limit protection scope of the present invention with this.The variation or the modification of every equivalence that the essence of content has been done according to the present invention all should be encompassed in protection scope of the present invention.
Claims (7)
1. one kind 4, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, comprises the steps:
1) add solvent and oxygenant successively in reaction system, wherein, described solvent is mixed and made into by water and Glacial acetic acid;
2) temperature of reaction system is remained on 0-20 ℃ scope, in reaction system, slowly drip pro-oxidant then, after dropwising, stirred 15 minutes;
3) temperature of reaction system is remained on 0-20 ℃ scope, in reaction system, add biphenyl then;
4) temperature of reaction system is remained on 15-25 ℃ scope, in reaction system, slowly drip bromine then;
5) temperature of reaction system is warming up to 30-40 ℃ scope, stirred 2 hours, reaction system is warming up to 90 ℃ then, react and obtain containing 4 after 4 hours, the mixture of 4 '-'-dibromobiphenyl, its reaction equation is as follows:
6) with reaction system cooling, filter solid crude product;
7) wash described solid crude product with water until neutrality, again with methyl alcohol drip washing;
8) dry finished product.
2. according to claim 14, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, the mass ratio of described water and Glacial acetic acid is 1: 3-3.5.
3. according to claim 14, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, described oxygenant can be sodium perchlorate, ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
4. according to claim 14, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, described pro-oxidant is the vitriol oil.
5. according to claim 1 or 3 or 4 described 4, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, the mass ratio of described oxygenant and described pro-oxidant is 1.5-5: 1.
6. according to claim 1 or 3 or 4 described 4, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, the mass ratio of described oxygenant and described pro-oxidant is 2.5: 1.
7. according to claim 14, the preparation method of 4 '-'-dibromobiphenyl is characterized in that, the mass ratio of described solid crude product and described methyl alcohol is 1: 1.
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| CN201010179508A CN101851148A (en) | 2010-05-24 | 2010-05-24 | Preparation method of 4,4'-dibromobiphenyl |
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| CN201010179508A CN101851148A (en) | 2010-05-24 | 2010-05-24 | Preparation method of 4,4'-dibromobiphenyl |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950817A (en) * | 1988-03-19 | 1990-08-21 | Bayer Aktiengesellschaft | Process for the preparation of 4,4'-dihalobiphenyls |
| US4983781A (en) * | 1988-03-02 | 1991-01-08 | Rhone-Poulenc Chimie | Process for the preparation of 4,4'-dibromobiphenyl in a solvent medium and with a catalyst |
-
2010
- 2010-05-24 CN CN201010179508A patent/CN101851148A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983781A (en) * | 1988-03-02 | 1991-01-08 | Rhone-Poulenc Chimie | Process for the preparation of 4,4'-dibromobiphenyl in a solvent medium and with a catalyst |
| US4950817A (en) * | 1988-03-19 | 1990-08-21 | Bayer Aktiengesellschaft | Process for the preparation of 4,4'-dihalobiphenyls |
Non-Patent Citations (2)
| Title |
|---|
| ALICE M. CLARK ET AL.: "Preparation of biphenyl-2,2",3,3",5,5",6m6"-2Hg", 《JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS》 * |
| 杨果等: "p,p,p,p"-四氯联苯二膦的合成", 《化学研究与应用》 * |
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Application publication date: 20101006 |