CN106397304A - Production method of 1-bromocarbazole - Google Patents
Production method of 1-bromocarbazole Download PDFInfo
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- CN106397304A CN106397304A CN201610774744.8A CN201610774744A CN106397304A CN 106397304 A CN106397304 A CN 106397304A CN 201610774744 A CN201610774744 A CN 201610774744A CN 106397304 A CN106397304 A CN 106397304A
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- carbazole
- butyl
- bromine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
Abstract
The invention discloses a production method of 1-bromocarbazole, and belongs to the field of organic chemistry synthesis. The method comprises the following steps: 3,6-bis(tert-butyl)carbazole is used as an initial raw material, and a bromination reaction is carried out for synthesis of 1-bromine-3,6-bis(tert-butyl)carbazole; t butyl is removed in a condition with aluminium chloride and isopropanol; alkali treatment and purification are carried out for synthesizing 1-bromocarbazole. The method has the advantages of few side reactions in a reaction process, easy operation and high yield. 1-bromocarbazole can be used in the fields of organic photoelectric materials, medicine, and the like, and is an important intermediate of carbazoles photoelectric materials, medicines and pesticides.
Description
Technical field
The present invention relates to the preparation method of carbazole analog derivative, more particularly, to a kind of synthetic method of 1- bromine carbazole, genus has
Chemical machine synthesizes field.
Background technology
Organic electroluminescent technology has the advantages that prominent, such as low in energy consumption, flexible, response speed compared with other Display Techniques
Degree is fast, visual angle is wide, can large-area displays etc., the research of electroluminescent organic material causes many researchers both at home and abroad
Great interest.Carbazole and its derivative are heterocycle aromatics, have larger pi-electron conjugated system and stronger dividing
Electron transfer properties in son, from the point of view of structure, the electrophilic N atom of carbazole absorbs the electronics in double bond by inductive effect;Another
Aspect, the unshared electronics due to p- pi-conjugated effect N atom supplies double bond again, makes double bond electron rich.Therefore, carbazole derivates
Typically there is very strong cavity transmission ability, carbazole polymer or micromolecular compound can conducts in organic electroluminescence device
Hole transmission layer, which reduces the crystallization of small molecule material, improves device lifetime, increased the machine of electron-hole recombinations simultaneously
Meeting, improves the luminous efficiency of device.
On carbazole, substituting group position difference can affect its electronic effect, and then affects its cavity transmission ability.3- bromine at present
Carbazole analog derivative and its polymer, by wide coverages such as EP1972619, are applied to electroluminescent organic material and organic poly-
Hole mobile material in compound solar cell, luminescent material and novel agrochemical, medicine and other fields.The synthesis master of 3- bromine carbazole
If directly through carbazole bromination.1- bromine carbazole is also the class luminescent material intermediate that the rate of exchange are commonly used, the synthesis side of 1- bromine carbazole
Method report is less, and WO2011105161 reports one kind and uses bromophenyl hydrazine hydrochloride, and phthalic anhydride etc. is that initiation material synthesizes 1- bromine
The method of carbazole, the method step is more, and process is loaded down with trivial details in actual use, should not operate, and relatively costly, need to explore suitable
Close industrial new method.
Content of the invention
It is an object of the invention to provide a kind of course of reaction is simple, low cost and be suitable for industrialized production 1- bromine carbazole
Method.
For realizing the purpose of the present invention, the present invention, is synthesized through bromination reaction for initiation material with 3,6- di-t-butyl carbazole
1- bromo- 3,6- di-t-butyl carbazole, sloughs the tert-butyl group under the conditions of alchlor and isopropanol, through alkali process, purifies synthesis 1-
Bromine carbazole.
Concrete technical scheme is as follows:
The 4- bromine carbazole of present invention preparation has following structural:
Its synthetic route is as follows:
Concrete reactions steps are as follows:
Under noble gas protection, 3,6- di-t-butyl carbazole is dissolved in 1,2- dichloroethanes, adds hydrobromic acid, controlling reaction temperature
It is slowly added dropwise hydrogen peroxide, after dropping completely, overnight, reactant liquor aqueous solution of sodium bisulfite is washed, and separates organic for nature temperature reaction
Layer, is dried, and adds methyl alcohol dispersion, obtains 1- bromo- 3,6- di-t-butyl carbazole crude product;Then add 1- bromo- 3 in reaction bulb,
6- di-t-butyl carbazole and isopropanol solvent, controlling reaction temperature is slowly added to alchlor, and reaction adds water termination instead after terminating
Should, through extraction, organic layer sodium hydrate aqueous solution is washed, and is dried overnight, and is concentrated to give crude product, methylene chloride-methanol mixed solvent weight
Crystallization obtains product 1- bromine carbazole.
In described bromination reaction, 3,6- di-t-butyl carbazole and hydrobromic acid consumption mol ratio are 1:0.85-0.95,3,
6- di-t-butyl carbazole and dioxygen water consumption mol ratio are 1: 0.9-1.1;- 20-0 DEG C of bromination reaction temperature.
Described de-t-butylation temperature 20-40 DEG C;Alchlor is with 3,6- di-t-butyl carbazole mol ratio bromo- with 1-
For 1: 0.1-0.3;
It is initiation material that the present invention adopts 3,6- di-t-butyl carbazole, has synthesized 1- bromine carbazole through bromination, the de- tert-butyl group.1- bromine click
The quality of azoles has vital impact for the combination property of supervention luminescent material thereafter, wherein, 1,8- dibromo carbazole content
It is the key of impact 1- bromine carbazole quality, the present invention uses hydrobromic acid method for oxidation bromination, the double bromine content of effective control, it is to avoid bromine
The waste in source and brominated accessory substance for the pollution of environment, 1,8- dibromo carbazole content in the method effective control 1- bromine carbazole
Less than 500ppm, meet the demand for high-purity 1- bromine carbazole market for the OLED industry development.Yield of the present invention is higher, total recovery
Reach more than 70%, product content reaches more than 99.9%, belong to regular industrial product, low production cost using raw material, and operate
Process is simple, is suitably applied industrialized production.
Specific embodiment
For preferably the present invention will be described, give an actual example as follows:Raw materials used it is commercially available product.
Example 1
Under argon gas protection, by 111.8 g in 2 L there-necked flasks(0.4 mol)3,6- di-t-butyl carbazole is dissolved in 400 mL1,
In 2- dichloroethanes, add 68.7 g(0.34 mol)Mass percent 40% hydrobromic acid aqueous solution, -20 DEG C of controlling reaction temperature
Under be slowly added dropwise 41.6 mL(0.44 mol)30% hydrogen peroxide, drips rear nature temperature reaction completely overnight, reactant liquor sulfurous
Sour hydrogen sodium water solution washing, separates organic layer, anhydrous magnesium sulfate is dried, and after filtration, filtrate adds 500 mL methyl alcohol dispersions, obtains
1- bromo- 3,6- di-t-butyl carbazole(Content 97.8%, 1, bromo- 3, the 6- di-t-butyl carbazole content 0.92% of 8- bis-), after drying
303.5 g;Bromo- for 1- 3,6- di-t-butyl carbazole is added in 2 L there-necked flasks, adds 1 L isopropanol solvent, then control 20
It is slowly added to alchlor 4.6 g at DEG C, after adding, continue reaction 48 h, after terminating plus 500 mL frozen water terminating reactions, 500
ML dichloromethane extracts, and organic layer sodium hydrate aqueous solution is washed, and anhydrous sodium sulfate drying overnight, is concentrated to give crude product, 500mL dichloro
Methane -350mL methanol mixed solvent recrystallization obtains product 1- bromine carbazole 70.68g, content 99.92% twice(Double bromines
475ppm), total recovery 71.8%.
Product fusing point:121.2-122.2℃;
1H NMR ( 400 MHz,CDCl3), δ/ppm: 8.179(s, 1H; N-H), 8.006-7.987(d, 2H;J=
7.6Hz; ArH), 7.582-7.563(d, 1H;J=7.6Hz;ArH), 7.467-7.404 (m, 2H; ArH),
7.284-7.197(m, 1H;ArH), 7.105-7.855 (t, 1H;J=7.6Hz; ArH).
13C NMR (100 MHz, CDCl3), δ/ppm: 139.1, 138.1, 127.9, 126.5, 124.6,
123.6, 120.8, 120.5, 120.1, 119.4, 111.0, 104.1..
Example 2
Under argon gas protection, by 279.4 g in 5 L there-necked flasks(1 mol)3,6- di-t-butyl carbazole is dissolved in 2 L1,2- dichloros
In ethane, add 192.1 g(0.95 mol)Slow at mass percent 40% hydrobromic acid aqueous solution, 0 DEG C of controlling reaction temperature
Drip 84.9 mL(0.9 mol)30% hydrogen peroxide, overnight, reactant liquor sodium hydrogensulfite is water-soluble for the completely natural temperature reaction of dropping
Liquid washs, and separates organic layer, and anhydrous magnesium sulfate is dried, and after filtration, filtrate adds 1 L methyl alcohol dispersion, obtains bromo- 3, the 6- of 1- bis- uncle
Butyl carbazole(Content 98%, 1, bromo- 3, the 6- di-t-butyl carbazole content 0.85% of 8- bis-), 292.8 gs are dried;By bromo- for 1- 3,6-
Di-t-butyl carbazole adds in 5 L there-necked flasks, adds 3 L isopropanol solvents, is slowly added to alchlor at then controlling 40 DEG C
32.8 g, continue reaction 48 h after adding, be added to terminating reaction in 2 L frozen water, 2 L dichloromethane extractions, organic layer after terminating
Sodium hydrate aqueous solution is washed, and anhydrous sodium sulfate drying overnight, is concentrated to give crude product, and 800 mL dichloromethane -500 mL methyl alcohol mixes
Solvent recrystallization obtains product 1- bromine carbazole 183.1g, content 99.93% twice(Double bromine 420ppm), total recovery 74.4%.
Example 3
Under argon gas protection, by 279.4 g in 5 L there-necked flasks(1 mol)3,6- di-t-butyl carbazole is dissolved in 1.5 L1,2- bis-
In chloroethanes, add 182.1 g(0.9 mol)Slow at mass percent 40% hydrobromic acid aqueous solution, -10 DEG C of controlling reaction temperature
Slow dropping 94.3 mL(1 mol)Hydrogen peroxide, the completely natural temperature reaction of dropping overnight, wash by reactant liquor aqueous solution of sodium bisulfite
Wash, separate organic layer, anhydrous magnesium sulfate is dried, after filtration, filtrate adds 1 L methyl alcohol dispersion, obtains 1- bromo- 3,6- di-t-butyl
Carbazole(Content 98.1%, 1, bromo- 3, the 6- di-t-butyl carbazole content 0.97% of 8- bis-), 332.1 gs are dried;By bromo- for 1- 3,6- bis-
Tert-butyl carbazole adds in 5 L there-necked flasks, adds 2 L isopropanol solvents, then controls 30 DEG C and is slowly added to alchlor 23
G, continues reaction 48 h after adding, be added to terminating reaction in 2 L frozen water, 2 L dichloromethane extractions, organic layer hydroxide after terminating
Sodium water solution is washed, and anhydrous sodium sulfate drying overnight, is concentrated to give crude product, 800 mL dichloromethane -500 mL methanol mixed solvent weight
Crystallization obtains product 1- bromine carbazole 172.8 g, content 99.91% twice(Double bromine 437ppm), total recovery 70.2%.
Above-described 1- bromine carbazole content reaches more than 99.9%, is important fine-chemical intermediate, has expanded carbazole
Analog derivative application in organic photoelectrical material design synthesis as intermediate, also has extensively in the field such as medicine and agricultural chemicals
Application prospect.
Claims (5)
1. a kind of production method of 1- bromine carbazole is it is characterised in that synthesize as follows:Under noble gas protection, by 3,6- bis-
Tert-butyl carbazole is dissolved in 1,2- dichloroethanes, adds hydrobromic acid, controlling reaction temperature to be slowly added dropwise hydrogen peroxide, dropping is completely
Overnight, reactant liquor is washed, and separates organic layer for natural temperature reaction, is dried, and adds methyl alcohol dispersion, obtains the tertiary fourth of bromo- 3, the 6- of 1- bis-
Base carbazole;Then 1- bromo- 3,6- di-t-butyl carbazole and isopropanol solvent are added in reaction bulb, controlling reaction temperature slowly adds
Enter alchlor reaction, add water after terminating terminating reaction, through extraction, organic layer sodium hydrate aqueous solution is washed, and is dried overnight, concentrate
Obtain crude product, methylene chloride-methanol mixed solvent is recrystallized to give product 1- bromine carbazole.
2. the production method of 1- bromine carbazole as claimed in claim 1 is it is characterised in that described 3,6- di-t-butyl carbazole and hydrogen
Bromic acid consumption mol ratio is 1: 0.85-0.95;3,6- di-t-butyl carbazole and dioxygen water consumption mol ratio are 1: 0.9-
1.1.
3. the production method of 1- bromine carbazole as claimed in claim 1 is it is characterised in that described bromination reaction temperature is -20-0
℃.
4. the production method of 1- bromine carbazole as claimed in claim 1 is it is characterised in that described alchlor consumption is that 1- is bromo-
0.1-0.3 times of 3,6- di-t-butyl carbazole mole.
5. the production method of 1- bromine carbazole as claimed in claim 1 is it is characterised in that described de-t-butylation temperature is
20-40℃.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107325037A (en) * | 2017-05-24 | 2017-11-07 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of 1 bromine carbazole |
CN113372261A (en) * | 2021-07-14 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Method for preparing 1-bromine/chlorocarbazole and derivatives thereof |
CN114349683A (en) * | 2022-01-19 | 2022-04-15 | 西安欧得光电材料有限公司 | Amido protection and deprotection method of carbazole and carbazole similar derivatives |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101550104A (en) * | 2009-05-11 | 2009-10-07 | 深圳大学 | Benzene-naphthalene diimide derivative, preparation method and its application |
CN103641856A (en) * | 2013-12-26 | 2014-03-19 | 黑龙江大学 | Multifunctional modified tert-butyl carbazole phosphine oxide main material and synthesis method and application thereof |
KR20150098062A (en) * | 2014-02-19 | 2015-08-27 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
JP2016020322A (en) * | 2014-07-16 | 2016-02-04 | 大学共同利用機関法人自然科学研究機構 | 1,1'9,9'-bicarbazole, 1,1'-bicarbazole salt, and production method thereof |
-
2016
- 2016-08-31 CN CN201610774744.8A patent/CN106397304B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101550104A (en) * | 2009-05-11 | 2009-10-07 | 深圳大学 | Benzene-naphthalene diimide derivative, preparation method and its application |
CN103641856A (en) * | 2013-12-26 | 2014-03-19 | 黑龙江大学 | Multifunctional modified tert-butyl carbazole phosphine oxide main material and synthesis method and application thereof |
KR20150098062A (en) * | 2014-02-19 | 2015-08-27 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
JP2016020322A (en) * | 2014-07-16 | 2016-02-04 | 大学共同利用機関法人自然科学研究機構 | 1,1'9,9'-bicarbazole, 1,1'-bicarbazole salt, and production method thereof |
Non-Patent Citations (4)
Title |
---|
D. BOGDAL,等: "Halogenation of carbazole and other aromatic compounds with hydrohalic acids and hydrogen peroxide under microwave irradiation", 《GREEN CHEMISTRY》 * |
JOHN MUMBO,等: "Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling", 《ENVIRON SCI POLLUT RES》 * |
MARIA C. TERRON,等: "CHEMICAL BROMINATION OF PHENOL RED BY HYDROGEN PEROXIDE IS POSSIBLE IN THE ABSENCE OF HALOPEROXIDASES", 《CHEMOSPHER》 * |
姜辉,等: "3-溴咔唑的绿色合成新工艺研究", 《广州化学》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107325037A (en) * | 2017-05-24 | 2017-11-07 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of 1 bromine carbazole |
CN107325037B (en) * | 2017-05-24 | 2020-03-13 | 北京八亿时空液晶科技股份有限公司 | Preparation method of 1-bromocarbazole |
CN113372261A (en) * | 2021-07-14 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Method for preparing 1-bromine/chlorocarbazole and derivatives thereof |
CN113372261B (en) * | 2021-07-14 | 2023-06-27 | 中国科学院兰州化学物理研究所 | Method for preparing 1-bromo/chloro carbazole and derivatives thereof |
CN114349683A (en) * | 2022-01-19 | 2022-04-15 | 西安欧得光电材料有限公司 | Amido protection and deprotection method of carbazole and carbazole similar derivatives |
CN114349683B (en) * | 2022-01-19 | 2023-12-22 | 西安欧得光电材料有限公司 | Amino protection and deprotection method for carbazole and carbazole-like derivatives |
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