CN103204762B - The preparation method of 4-bromo-4-iodine biphenyl - Google Patents
The preparation method of 4-bromo-4-iodine biphenyl Download PDFInfo
- Publication number
- CN103204762B CN103204762B CN201310139730.5A CN201310139730A CN103204762B CN 103204762 B CN103204762 B CN 103204762B CN 201310139730 A CN201310139730 A CN 201310139730A CN 103204762 B CN103204762 B CN 103204762B
- Authority
- CN
- China
- Prior art keywords
- bromo
- biphenyl
- iodine
- preparation
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical field.Be specifically related to the preparation method of 4-bromo-4-iodine biphenyl.Technical problem to be solved by this invention is that prior synthesizing method productive rate is low, aftertreatment is loaded down with trivial details, pollution is large and cost is high.The technical scheme that the present invention solves the problems of the technologies described above is to provide the preparation method of a kind of 4-bromo-4-iodine biphenyl, is with iodo-hydrogen peroxide system iodate 4-bromo biphenyl synthesis 4-bromo-4-iodine biphenyl.The present invention is the novel method that suitability for industrialized production 4-bromo-4-iodine biphenyl provides a kind of high yield, low stain and low cost.
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 of organic electronics, constantly impels the maturation of Organic Light Emitting Diode technology, uses in the personal electric consumer's goods in a large number at present, such as mobile phone and digital camera.Estimate in 2015, big area high definition organic light emission pipe TV will be popularized in the market.Current Organic Light Emitting Diode lighting engineering also obtains very large development and improvement, estimates at the year two thousand twenty, universal use.Domestic and international market, to the demand of organic light-emitting diode material, every year all rising at double, expects 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 other intermediates a lot, Ullmann, Buchward and Sonogshira reaction forms conjugated molecule and tri-arylamine group compound, conjugated molecule is important luminescent material, and triaryl amine is important hole mobile material.Therefore, develop a low-cost industrial route synthesis 4-bromo-4-iodine biphenyl to be extremely important for the business-like Organic Light Emitting Diode material of exploitation.
Use acid iodide as iodinating agent in the patent (US201195269h and US201265432) of E.I.Du Pont Company, its reaction formula is as follows:
Aforesaid method temperature of reaction is high, inconvenient operation, needs to use expensive acid iodide, also will process a large amount of waste liquid containing acetic acid, and productive rate is low, only has 70 ~ 80%, and production cost is high.
Summary of the invention
Technical problem to be solved by this invention is that existing preparation method's cost is high, aftertreatment is loaded down with trivial details, pollution is large.
The technical scheme that the present invention solves the problems of the technologies described above is to provide the preparation method of a kind of 4-bromo-4-iodine biphenyl, and the method is with iodo-hydrogen peroxide system iodate 4-bromo biphenyl synthesis 4-bromo-4-iodine biphenyl.
Preferably, the iodination reaction temperature described in preparation method of above-mentioned 4-bromo-4-iodine biphenyl is 50 ~ 60 DEG C.
Preferred further, the preparation method of above-mentioned 4-bromo-4-iodine biphenyl comprises the following steps:
Under a, 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 DEG C, stirring reaction 3 ~ 5 hours;
B, use organic solvent recrystallization refined product, obtain 4-bromo-4-iodine biphenyl.
Wherein, in the preparation method of above-mentioned 4-bromo-4-iodine biphenyl, the mass concentration of the hydrogen peroxide described in step a is 25 ~ 30%.
Wherein, in aforesaid method, temperature during dropping hydrogen peroxide described in step a is 40 ~ 50 DEG C.
Wherein, in aforesaid method, the mol ratio of 4-bromo biphenyl, iodine and hydrogen peroxide described in step a is 1.0 ︰ 0.51 ~ 0.55 ︰ 2.0 ~ 3.0.
Wherein, in aforesaid method, the volume of acetic acid described in step a is 3 ~ 4 times of 4-bromo biphenyl volume.
Wherein, in aforesaid method, after the reaction described in step a terminates, acetic acid can be reclaimed.
Wherein, in aforesaid method, the organic solvent described in step b is at least one in methyl alcohol, ethanol or acetone.
Reaction formula of the present invention is as follows:
Provided by the invention by the method for iodo-hydrogen peroxide system as iodinating agent iodate 4-bromo biphenyl synthesis 4-bromo-4-iodine biphenyl, security is high, react at low temperatures, reaction conditions is gentle, and speed of response is fast, easy to operate, the purity of the 4-prepared bromo-4-iodine biphenyl is 99.8%, and productive rate is up to 95 ~ 97%.Solvent used also easily reclaims and repeats to apply mechanically, and the acetic acid after recovery can directly use in overlapping investment, greatly reduces the waste liquid containing acetic acid, environmentally friendly, more greatly reduces the cost of synthesis 4-bromo-4-iodine biphenyl.
Embodiment
The preparation method of 4-provided by the invention bromo-4-iodine biphenyl, comprises the following steps:
Under a, room temperature by mass concentration be 25 ~ 30% hydrogen peroxide be added drop-wise in the mixing solutions of 4-bromo biphenyl, iodine and acetic acid, during dropping, control temperature is 40 ~ 50 DEG C; The described mol ratio adding 4-bromo biphenyl, iodine and hydrogen peroxide is 1.0 ︰ 0.51 ~ 0.55 ︰ 2.0 ~ 3.0; Stir after 3 ~ 4 hours, maintain temperature of reaction at 50 ~ 60 DEG C, stir 3 ~ 5 hours.
B, use organic solvent recrystallization refined product, obtain 4-bromo-4-iodine biphenyl.
Wherein, in aforesaid method, the volume of acetic acid described in step a is 3 ~ 4 times of 4-bromo biphenyl volume.
Wherein, in aforesaid method, the organic solvent described in step b is at least one in methyl alcohol, ethanol or acetone.
In step a, add in hydrogen peroxide process, the control for temperature is to prevent hydrogen peroxide from reacting too violent, causing danger.
In order to reduce costs further, after the iodination reaction of step a terminates, can Distillation recovery acetic acid, the acetic acid of recovery, can reuse, and avoids the waste liquid in a large number containing acetic acid to produce.
Occur danger in order to avoid reclaiming in acetic acid process, need to use starch potassium iodide paper to be detected oxide compound, described superoxide refers to hydrogen peroxide and/or Peracetic Acid.If starch potassium iodide paper does not have variable color, confirm there is no superoxide; If become blue, illustrate still containing superoxide, then add S-WAT and stir, check nondiscoloration to reaction solution starch potassium iodide paper.As long as be detected oxide compound whether to there is starch potassium iodide paper nondiscoloration and just can meet security requirement.
Below by way of specific embodiment, content of the present invention is further elaborated.
Embodiment 1
Under a, room temperature, 4-bromo biphenyl (2.33kg, 10mol), solid iodine (1.30kg, 5.10mol) and acetic acid (7L) are joined 10L there-necked flask, stir after one hour, drip hydrogen peroxide (0.68kg, 25%, 20mol), in controlling, temperature is lower than 50 DEG C, stirs 3.5 hours; Then holding temperature is at 50 DEG C, stirs 4 hours.
Without superoxide in starch potassium iodide paper test detection reaction liquid, acetic acid 6L is reclaimed in pressure distillation, obtains soup compound.
B, add 12L alcohol reflux, treat that soup compound is dissolved completely in the ethanolic soln of backflow, after solution to clarification, heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 1L washing with alcohol, 4-bromo-4-iodine biphenyl (3.41kg, the 9.5mol) productive rate that vacuum 40 DEG C of dryings obtain white powder for 5 hours is 95%, HPLC detection purity is 99.8%.
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 pillar model is C18 post, and column temperature is 25 DEG C, and column length is 25cm, and column internal diameter is 50mm.
Embodiment 2
Under a, room temperature, 4-bromo biphenyl (4.66kg, 20mol), solid iodine (1.378kg, 10.6mol) and acetic acid (16.3L) are joined 20L there-necked flask, stir after one hour, drip hydrogen peroxide (1.7kg, 25%, 40mol), in controlling, temperature is lower than 50 DEG C, stirs 4 hours; Then holding temperature is at 55 DEG C, stirs 4 hours.
Test without superoxide in detection reaction liquid with starch potassium iodide paper, acetic acid 15L is reclaimed in pressure distillation, obtains soup compound.
B, add 12L methanol eddy, treat that soup compound is dissolved completely in the methanol solution of backflow, after solution to clarification, heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 5L methanol wash, the 4-bromo-4-iodine biphenyl (6.89kg, 19.2mol) that vacuum 40 DEG C of dryings obtain white powder for 5 hours, yield is 95%, HPLC detection purity is that 99.8%(HPLC testing conditions is with embodiment 1).
Embodiment 3
Under a, room temperature, 4-bromo biphenyl (11.65kg, 50mol), solid iodine (3.575kg, 27.5mol) and acetic acid (46.6L) are joined 50L there-necked flask, stir after one hour, drip hydrogen peroxide (4.25kg, 30%, 150mol), in controlling, temperature is lower than 50 DEG C, stirs 3 hours; Then holding temperature is at 60 DEG C, stirs 5 hours.
Test with or without superoxide in detection reaction liquid with starch potassium iodide paper, acetic acid 45L is reclaimed in pressure distillation, obtains soup compound.
B, add 20L acetone reflux, treat that soup compound is dissolved completely in the acetone soln of backflow, after solution to clarification, heat filtering, filtrate crystallisation by cooling.Refilter and obtain white solid, solid 12L washing with acetone, the 4-bromo-4-iodine biphenyl (17.4kg, 48.5mol) that vacuum 40 DEG C of dryings obtain white powder for 5 hours, productive rate is 97%, HPLC detection purity is that 99.8%(HPLC testing conditions is with embodiment 1).
4-provided by the invention bromo-4-iodine biphenyl preparation method, easy and simple to handle, safety, yield is high, environmentally friendly, greatly reduces production cost.
Claims (6)
- The preparation method of 1.4-bromo-4-iodine biphenyl, is characterized in that: comprise the following steps:Under a, 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 DEG C, stirring reaction 3 ~ 5 hours; The mol ratio of described 4-bromo biphenyl, iodine and hydrogen peroxide is 1.0 ︰ 0.51 ~ 0.55 ︰ 2.0 ~ 3.0;B, use organic solvent recrystallization refined product, obtain 4-bromo-4-iodine biphenyl.
- 2. the preparation method of 4-according to claim 1 bromo-4-iodine biphenyl, is characterized in that: the mass concentration of the hydrogen peroxide described in step a is 25 ~ 30%.
- 3. the preparation method of 4-according to claim 1 bromo-4-iodine biphenyl, is characterized in that: temperature during dropping hydrogen peroxide described in step a is 40 ~ 50 DEG C.
- 4. the preparation method of 4-according to claim 1 bromo-4-iodine biphenyl, is characterized in that: the volume of acetic acid described in step a is 3 ~ 4 times of 4-bromo biphenyl volume.
- 5. the preparation method of 4-according to claim 1 bromo-4-iodine biphenyl, is characterized in that: after the reaction described in step a terminates, and reclaims acetic acid.
- 6. the preparation method of 4-according to claim 1 bromo-4-iodine biphenyl, is characterized in that: the organic solvent described in step b is at least one in methyl alcohol, ethanol or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310139730.5A CN103204762B (en) | 2013-04-09 | 2013-04-22 | The preparation method of 4-bromo-4-iodine biphenyl |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310121608 | 2013-04-09 | ||
| CN201310121608.5 | 2013-04-09 | ||
| CN201310139730.5A CN103204762B (en) | 2013-04-09 | 2013-04-22 | The preparation method of 4-bromo-4-iodine biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103204762A CN103204762A (en) | 2013-07-17 |
| CN103204762B true CN103204762B (en) | 2016-02-10 |
Family
ID=48752199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310139730.5A Active CN103204762B (en) | 2013-04-09 | 2013-04-22 | The preparation method of 4-bromo-4-iodine biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103204762B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536489B (en) * | 2022-11-01 | 2024-08-13 | 济宁金汉斯环保材料股份有限公司 | Green preparation process of high-purity 4-bromodiphenyl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080206662A1 (en) * | 2007-02-28 | 2008-08-28 | Xerox Corporation | Asymmetric arylamine compounds and processes for making the same |
-
2013
- 2013-04-22 CN CN201310139730.5A patent/CN103204762B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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)
| Title |
|---|
| Eco-friendly Oxidative Iodination of Various Arenes with Sodium Percarbonate as the Oxidant;Agnieszka Zielinska and Lech Skulski;《Molecules》;20051031;第10卷;1308 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103204762A (en) | 2013-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104744303B (en) | Bromomethylbiphenyls of 2 R 4 ' and preparation method thereof | |
| CN101367760B (en) | Synthesis of 2-chlorine apellagrin | |
| CN111647011B (en) | Preparation method of monohalogenated phenylboronic acid | |
| CN105175691A (en) | Conjugated polymer semiconductor materials based on thienoarylindole unit and preparation method thereof, and application of conjugated polymer semiconductor materials in high-efficiency polymer solar cells. | |
| CN109320489A (en) | A kind of color alkyl compound and preparation method thereof | |
| CN108558949A (en) | A method of synthesizing benzo phosphene with Pd nano particle catalysis | |
| CN103204762B (en) | The preparation method of 4-bromo-4-iodine biphenyl | |
| CN113896678A (en) | Method for preparing 2-chloro-4-neopentyl pyridine | |
| CN106749020A (en) | A kind of synthetic method of 3 acyl group quinolines | |
| JP5578809B2 (en) | Method for producing 3-methyl-2-thiophenecarboxylic acid | |
| CN102675152A (en) | Preparation method of intermediate glycol of antidepressant citalopram | |
| CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
| CN106748966A (en) | A kind of synthetic method of Ramipril key intermediate | |
| CN103333204B (en) | One class 9, the synthetic method of 9 '-spirobifluorene derivative | |
| CN114181074B (en) | Preparation method of p-chlorobenzoyl fluoride | |
| CN101391982B (en) | Alkylation reaction method of benzimidazoles compounds | |
| CN1762989A (en) | Semicarbazone synthesis method | |
| CN100554235C (en) | Preparation method to alkoxyl mandelic acid | |
| CN106242934A (en) | Oxidation synthesis method for beta-position C-H bond acetyl of ketone | |
| CN105622334A (en) | Synthetic method of 3-bromo-9,9'-spirobifluorene | |
| CN104447293B (en) | A kind of method preparing 1-methylcyclopropyl groups formic acid | |
| CN112194612A (en) | Synthesis method of photoelectric material intermediate N- (7-bromo-9, 9-dimethylfluorene-2-yl) carbazole | |
| CN101245040B (en) | Process for producing 4-ethynyl benzene sulfonamide (I) | |
| CN104030906A (en) | Method for preparing 9-fluorenone by liquid-phase oxidation | |
| CN103483366A (en) | Preparation method of methoxy diethyl borane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
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. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
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 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |