CN103204762A - Preparation method of 4-bromo-4-iodobiphenyl - Google Patents
Preparation method of 4-bromo-4-iodobiphenyl Download PDFInfo
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- CN103204762A CN103204762A CN2013101397305A CN201310139730A CN103204762A CN 103204762 A CN103204762 A CN 103204762A CN 2013101397305 A CN2013101397305 A CN 2013101397305A CN 201310139730 A CN201310139730 A CN 201310139730A CN 103204762 A CN103204762 A CN 103204762A
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Abstract
The invention belongs to the field of chemistry, in particular relates to a preparation method of 4-bromo-4-iodobiphenyl and aims to solve the technical problems that the convention synthesis method is low in yield, troublesome in aftertreatment, heavy in pollution and high in cost. The invention provides the preparation method of 4-bromo-4-iodobiphenyl to solve the technical problems. The preparation method comprises the step of: iodinating 4-bromobiphenyl by using an iodine-hydrogen peroxide system to synthesize 4-bromo-4-iodobiphenyl. The invention provides a novel method with high yield, low pollution and low cost for industrial production of 4-bromo-4-iodobiphenyl.
Description
Technical field
The invention belongs to chemical field.Be specifically related to the preparation method of 4-bromo-4-iodine biphenyl.
Background technology
The fast development that organic electronic is learned constantly impels the maturation of Organic Light Emitting Diode technology, uses in the personal electric consumer's goods in a large number at present, for example mobile phone and digital camera.Expectation was in 2015, and big area high definition organic light emission pipe TV will be popularized in market.The Organic Light Emitting Diode lighting engineering also obtains very big development and improvement at present, estimates at the year two thousand twenty, popularizes and uses.The domestic and international market is to the demand of Organic Light Emitting Diode luminescent material, and is annual all rising at double, expect the year two thousand twenty whole world to the demand of Organic Light Emitting Diode up to 80,000,000,000 dollars.
4-bromo-4-iodine biphenyl is a kind of intermediate of widespread use in luminous organic material, follow-uply can carry out Suzuki with a lot of other intermediates, Ullmann, Buchward and Sonogshira reaction form conjugated molecule and tri-arylamine group compound, conjugated molecule is important luminescent material, and three arylamine are important hole mobile materials.Therefore, the synthetic 4-bromo-4-iodine biphenyl of low-cost industrialized route of exploitation is extremely important for the business-like Organic Light Emitting Diode material of exploitation.
Use the iodo-acid iodide as iodinating agent in the patent of E.I.Du Pont Company (US201195269h and US201265432), its reaction formula is as follows:
Aforesaid method temperature of reaction height, inconvenient operation need to use expensive acid iodide, also will handle the waste liquid that contains acetic acid in a large number, and productive rate are low, have only 70～80%, and the production cost height.
Summary of the invention
Technical problem to be solved by this invention is existing preparation method's cost height, aftertreatment is loaded down with trivial details, pollution is big.
The technical scheme that the present invention solves the problems of the technologies described above provides a kind of preparation method of 4-bromo-4-iodine biphenyl, and this method is with the synthetic 4-bromo-4-iodine biphenyl of iodo-hydrogen peroxide system iodate 4-bromo biphenyl.
Preferably, the described iodination reaction temperature of preparation method of above-mentioned 4-bromo-4-iodine biphenyl is 50～60 ℃.
Further preferred, the preparation method of above-mentioned 4-bromo-4-iodine biphenyl may further comprise the steps:
Under a, the room temperature hydrogen peroxide is added drop-wise in the mixing solutions of 4-bromo biphenyl, iodine and acetic acid, stirs after 3～4 hours, at 50～60 ℃, stirring reaction 3～5 hours;
B, usefulness organic solvent recrystallization refined product obtain 4-bromo-4-iodine biphenyl.
Wherein, among the preparation method of above-mentioned 4-bromo-4-iodine biphenyl, the mass concentration of the described hydrogen peroxide of step a is 25～30%.
Wherein, in the aforesaid method, the temperature during the described dropping hydrogen peroxide of step a is 40～50 ℃.
Wherein, in the aforesaid method, the mol ratio of the described 4-bromo biphenyl of step a, iodine and hydrogen peroxide is 1.0 ︰, 0.51～0.55 ︰ 2.0～3.0.
Wherein, in the aforesaid method, the volume of the described acetic acid of step a is 3～4 times of 4-bromo biphenyl volume.
Wherein, in the aforesaid method, after the described reaction of step a finishes, can reclaim acetic acid.
Wherein, in the aforesaid method, the described organic solvent of step b is at least a in methyl alcohol, ethanol or the acetone.
Reaction formula of the present invention is as follows:
Provided by the invention with the method for iodo-hydrogen peroxide system as the synthetic 4-bromo-4-iodine biphenyl of iodinating agent iodate 4-bromo biphenyl, safe, reaction at low temperatures, the reaction conditions gentleness, and speed of response is fast, easy to operate, the purity of the 4-bromo-4-iodine biphenyl for preparing is 99.8%, and productive rate is up to 95～97%.Used solvent also reclaims easily and repeats to apply mechanically, and the acetic acid after the recovery directly overlapping investment uses, and has significantly reduced the waste liquid that contains acetic acid, and is environmentally friendly, has reduced the cost of synthetic 4-bromo-4-iodine biphenyl more widely.
Embodiment
The preparation method of 4-bromo-4-iodine biphenyl provided by the invention may further comprise the steps:
Under a, the room temperature be that 25～30% hydrogen peroxide is added drop-wise in the mixing solutions of 4-bromo biphenyl, iodine and acetic acid with mass concentration, the control temperature is 40～50 ℃ during dropping; The mol ratio of described adding 4-bromo biphenyl, iodine and hydrogen peroxide is 1.0 ︰, 0.51～0.55 ︰ 2.0～3.0; Stir after 3～4 hours, keep temperature of reaction at 50～60 ℃, stirred 3～5 hours.
B, usefulness organic solvent recrystallization refined product obtain 4-bromo-4-iodine biphenyl.
Wherein, in the aforesaid method, the volume of the described acetic acid of step a is 3～4 times of 4-bromo biphenyl volume.
Wherein, in the aforesaid method, the described organic solvent of step b is at least a in methyl alcohol, ethanol or the acetone.
In step a, add in the hydrogen peroxide process, be too violent in order to prevent the hydrogen peroxide reaction for temperature controlling, cause danger.
In order further to reduce cost, after the iodination reaction of step a finishes, can distill recovery acetic acid, the acetic acid of recovery can be reused, and the waste liquid of avoiding containing acetic acid in a large number produces.
Occur danger in the acetic acid process for fear of reclaiming, need to use starch potassium iodide paper to detect superoxide, described superoxide refers to hydrogen peroxide and/or Peracetic Acid.If having variable color, starch potassium iodide paper do not confirm there is not superoxide; If become blueness, illustrate and still contain superoxide, then add S-WAT and stir, to reaction solution starch potassium iodide paper inspection nondiscoloration.Detect whether superoxide exists as long as the starch potassium iodide paper nondiscoloration just can be satisfied security requirement.
Below by specific embodiment content of the present invention is further elaborated.
Embodiment 1
Under a, the room temperature with the 4-bromo biphenyl (2.33kg, 10mol), solid iodine (1.30kg, 5.10mol) and acetic acid (7L) join the 10L there-necked flask, stir after one hour, drip hydrogen peroxide (0.68kg, 25%, 20mol), temperature is lower than 50 ℃ in the control, stirs 3.5 hours; Holding temperature stirred 4 hours at 50 ℃ then.
Do not have superoxide in the starch potassium iodide paper test detection reaction liquid, acetic acid 6L is reclaimed in pressure distillation, obtains soup compound.
B, adding 12L alcohol reflux treat that soup compound is dissolved in the ethanolic soln of backflow fully, after solution is extremely clarified, and heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 1L washing with alcohol, 40 ℃ of dryings of vacuum obtained the 4-bromo-4-iodine biphenyl of white powder in 5 hours (3.41kg, 9.5mol) productive rate are that to detect purity be 99.8% to 95%, HPLC.
The HPLC testing conditions: moving phase is Yi Jing ︰ (water-0.1% trifluoroacetic acid-0.1% triethylamine)=9 ︰ 1, and flow velocity is 1.0min/L, and the pillar model is the C18 post, and column temperature is 25 ℃, and column length is 25cm, and column internal diameter is 50mm.
Embodiment 2
Under a, the room temperature with the 4-bromo biphenyl (4.66kg, 20mol), solid iodine (1.378kg, 10.6mol) and acetic acid (16.3L) join the 20L there-necked flask, stir after one hour, drip hydrogen peroxide (1.7kg, 25%, 40mol), temperature is lower than 50 ℃ in the control, stirs 4 hours; Holding temperature stirred 4 hours at 55 ℃ then.
With not having superoxide in the starch potassium iodide paper test detection reaction liquid, acetic acid 15L is reclaimed in pressure distillation, obtains soup compound.
B, adding 12L methanol eddy treat that soup compound is dissolved in the methanol solution of backflow fully, after solution is extremely clarified, and heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 5L methanol wash, 40 ℃ of dryings of vacuum obtained the 4-bromo-4-iodine biphenyl (6.89kg, 19.2mol), yield is that 95%, HPLC detection purity is that the 99.8%(HPLC testing conditions is with embodiment 1) of white powder in 5 hours.
Embodiment 3
Under a, the room temperature with the 4-bromo biphenyl (11.65kg, 50mol), solid iodine (3.575kg, 27.5mol) and acetic acid (46.6L) join the 50L there-necked flask, stir after one hour, drip hydrogen peroxide (4.25kg, 30%, 150mol), temperature is lower than 50 ℃ in the control, stirs 3 hours; Holding temperature stirred 5 hours at 60 ℃ then.
With having or not superoxide in the starch potassium iodide paper test detection reaction liquid, acetic acid 45L is reclaimed in pressure distillation, obtains soup compound.
B, adding 20L acetone reflux, and treat that soup compound is dissolved in the acetone soln of backflow fully, after solution is extremely clarified, and heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 12L washing with acetone, 40 ℃ of dryings of vacuum obtained in 5 hours white powder 4-bromo-4-iodine biphenyl (17.4kg, 48.5mol), productive rate is that 97%, HPLC detection purity is that the 99.8%(HPLC testing conditions is with embodiment 1).
4-bromo-4-iodine biphenyl preparation method provided by the invention, easy and simple to handle, safety, the yield height, environmentally friendly, greatly reduce production cost.
Claims (9)
1.4-the preparation method of bromo-4-iodine biphenyl is characterized in that: with the synthetic 4-bromo-4-iodine biphenyl of iodo-hydrogen peroxide system iodate 4-bromo biphenyl.
2. the preparation method of 4-bromo-4-iodine biphenyl according to claim 1, it is characterized in that: described iodination reaction temperature is 50～60 ℃.
3. according to the preparation method of claim 1 or 2 each described 4-bromo-4-iodine biphenyl, it is characterized in that: may further comprise the steps:
Under a, the room temperature hydrogen peroxide is added drop-wise in the mixing solutions of 4-bromo biphenyl, iodine and acetic acid, stirs after 3～4 hours, at 50～60 ℃, stirring reaction 3～5 hours;
B, usefulness organic solvent recrystallization refined product obtain 4-bromo-4-iodine biphenyl.
4. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3, it is characterized in that: the mass concentration of the described hydrogen peroxide of step a is 25～30%.
5. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3 is characterized in that: the temperature during the described dropping hydrogen peroxide of step a is 40～50 ℃.
6. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3, it is characterized in that: the mol ratio of the described 4-bromo biphenyl of step a, iodine and hydrogen peroxide is 1.0 ︰, 0.51～0.55 ︰ 2.0～3.0.
7. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3, it is characterized in that: the volume of the described acetic acid of step a is 3～4 times of 4-bromo biphenyl volume.
8. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3 is characterized in that: after the described reaction of step a finishes, reclaim acetic acid.
9. the preparation method of 4-bromo-4-iodine biphenyl according to claim 3 is characterized in that: the described organic solvent of step b is at least a in methyl alcohol, ethanol or the acetone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536489A (en) * | 2022-11-01 | 2022-12-30 | 济宁金汉斯环保材料股份有限公司 | Green preparation process of high-purity 4-bromobiphenyl |
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| US20080206662A1 (en) * | 2007-02-28 | 2008-08-28 | Xerox Corporation | Asymmetric arylamine compounds and processes for making the same |
| WO2008143175A1 (en) * | 2007-05-21 | 2008-11-27 | Idemitsu Kosan Co., Ltd. | Method for producing aromatic triamine compound |
| CN102574790A (en) * | 2009-10-02 | 2012-07-11 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element |
| CN102633606A (en) * | 2012-03-26 | 2012-08-15 | 南京邮电大学 | 3,3'-dimethoxy-5,5'-dibromo-6,6'-diiodobiphenyl and synthesis method thereof |
| CN102643203A (en) * | 2005-01-05 | 2012-08-22 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element using same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102643203A (en) * | 2005-01-05 | 2012-08-22 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element using same |
| US20080206662A1 (en) * | 2007-02-28 | 2008-08-28 | Xerox Corporation | Asymmetric arylamine compounds and processes for making the same |
| WO2008143175A1 (en) * | 2007-05-21 | 2008-11-27 | Idemitsu Kosan Co., Ltd. | Method for producing aromatic triamine compound |
| CN102574790A (en) * | 2009-10-02 | 2012-07-11 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element |
| CN102633606A (en) * | 2012-03-26 | 2012-08-15 | 南京邮电大学 | 3,3'-dimethoxy-5,5'-dibromo-6,6'-diiodobiphenyl and synthesis method thereof |
Non-Patent Citations (1)
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| AGNIESZKA ZIELINSKA AND LECH SKULSKI: "Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant", 《MOLECULES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115536489A (en) * | 2022-11-01 | 2022-12-30 | 济宁金汉斯环保材料股份有限公司 | Green preparation process of high-purity 4-bromobiphenyl |
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Address after: Wenjiang District 610000 of Sichuan city of Chengdu province Chengdu Strait science and Technology Industry Development Park No. 488 West Ke Lin Lu Patentee after: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Address before: Ke Lin Lu Xi Duan cross-strait science and Technology Industrial Development Park in Wenjiang District of Chengdu City, Sichuan Province, No. 488 611137 Patentee before: ASTATECH (CHENGDU) PHARM. CO., LTD. |
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Denomination of invention: Preparation method of 4-bromo-4-iodobiphenyl Effective date of registration: 20170822 Granted publication date: 20160210 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Registration number: 2017510000052 |
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Date of cancellation: 20180801 Granted publication date: 20160210 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Registration number: 2017510000052 |