CN106397304B - A kind of production method of 1- bromines carbazole - Google Patents
A kind of production method of 1- bromines carbazole Download PDFInfo
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- CN106397304B CN106397304B CN201610774744.8A CN201610774744A CN106397304B CN 106397304 B CN106397304 B CN 106397304B CN 201610774744 A CN201610774744 A CN 201610774744A CN 106397304 B CN106397304 B CN 106397304B
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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
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Abstract
The invention discloses a kind of production methods of 1 bromine carbazole, belong to organic chemical synthesis field.It realizes by the following method：With 3,6 di-t-butyl carbazoles for starting material, 1 bromine, 3,6 di-t-butyl carbazole is synthesized by bromination reaction, tertiary butyl is sloughed under the conditions of alchlor and isopropanol, 1 bromine carbazole has been synthesized through alkali process, purifying.Reaction process side reaction is few, easy to operate and high income.1 bromine carbazole of synthesis can be used for organic photoelectrical material, medicine and other fields, be the important intermediate of carbazoles photoelectric material, medicine and pesticide.
Description
Technical field
The present invention relates to the preparation methods of carbazole analog derivative more particularly to a kind of synthetic method of 1- bromines carbazole, category to have
Chemical machine synthesizes field.
Background technology
Organic electroluminescent technology has the advantages that protrusion compared with other display technologies, such as low in energy consumption, flexible, response speed
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 aromatic compounds, have larger pi-electron conjugated system and stronger point
Electron transfer properties in son, from the point of view of structure, the electrophilic N atoms of carbazole absorb the electronics in double bond by inductive effect；It is another
Aspect makes double bond electron rich since the unshared electronics of the pi-conjugated effect N atoms of p- supplies double bond again.Therefore, carbazole derivates
Generally there is very strong cavity transmission ability, carbazole polymer or micromolecular compound can the conducts in organic electroluminescence device
Hole transmission layer, which reduce the crystallizations of small molecule material, improve device lifetime, while increasing the machine of electron-hole recombinations
Meeting improves the luminous efficiency of device.
Substituting group position difference can influence its electronic effect on carbazole, and then influence its cavity transmission ability.3- bromines at present
Carbazole analog derivative and its polymer are applied to electroluminescent organic material and organic poly- by wide coverages such as EP1972619
Hole mobile material, luminescent material and novel agrochemical, medicine and other fields in conjunction object solar cell.The synthesis master of 3- bromine carbazoles
If directly through carbazole bromination.1- bromine carbazoles are also the rate of exchange commonly a kind of luminescent material intermediate, the synthesis side of 1- bromine carbazoles
Method report is less, and WO2011105161 reports a kind of use bromophenyl hydrazine hydrochloride, and phthalic anhydride etc. is that starting material synthesizes 1- bromines
The method of carbazole, this method step is more, and process is cumbersome in actual use, should not operate, and cost is higher, need to explore suitable
Close industrial new method.
Invention content
The purpose of the present invention is to provide a kind of reaction process is simple, at low cost and suitable industrialized production 1- bromine carbazoles
Method.
To achieve the purpose of the present invention, the present invention is synthesized with 3,6- di-t-butyl carbazoles for starting material through bromination reaction
Bromo- 3, the 6- di-t-butyls carbazoles of 1-, tertiary butyl is sloughed under the conditions of alchlor and isopropanol, through alkali process, purifying synthesis 1-
Bromine carbazole.
Specific technical solution is as follows：
4- bromine carbazoles prepared by the present invention have following structural：
Its synthetic route is as follows：
Specific reaction step is as follows：
Under noble gas protection, 3,6- di-t-butyl carbazoles are dissolved in 1,2- dichloroethanes, hydrobromic acid, control reaction is added
Hydrogen peroxide is slowly added dropwise in temperature, and natural temperature reaction is overnight after being added dropwise completely, and reaction solution aqueous solution of sodium bisulfite is washed, and has been separated
Machine layer, it is dry, methanol dispersion is added, obtains bromo- 3, the 6- di-t-butyls carbazole crude products of 1-；Then it is bromo- that 1- is added in reaction bulb
3,6- di-t-butyl carbazoles and isopropanol solvent, controlling reaction temperature are slowly added to alchlor, and after reaction plus water terminates
Reaction, through extraction, organic layer sodium hydrate aqueous solution is washed, is dried overnight, and crude product, methylene chloride-methanol mixed solvent are concentrated to give
It is recrystallized to give product 1- bromine carbazoles.
3,6- di-t-butyls carbazole and hydrobromic acid dosage molar ratio are 1 in the bromination reaction:0.85-0.95,3,
6- di-t-butyls carbazole is 1 with dioxygen water consumption molar ratio: 0.9-1.1；- 20-0 DEG C of bromination reaction temperature.
20-40 DEG C of the de-t-butylation temperature；Alchlor with the bromo- 3,6- di-t-butyls carbazole molar ratios of 1-
It is 1: 0.1-0.3；
The present invention is starting material using 3,6- di-t-butyl carbazoles, and 1- bromine carbazoles have been synthesized through bromination, de- tertiary butyl.1-
The quality of bromine carbazole has vital influence for the comprehensive performance of supervention luminescent material thereafter, wherein 1,8- dibromo carbazole
Content is the key that influence 1- bromine carbazole qualities, and the present invention uses hydrobromic acid method for oxidation bromination, the effectively double bromine contents of control, keeps away
Exempt from the pollution of the waste and brominated by-product in bromine source for environment, this method effectively controls 1,8- dibromo carbazoles in 1- bromine carbazoles
Content is less than 500ppm, meets demand of the OLED industry developments for high-purity 1- bromines carbazole market.Yield of the present invention is higher, always
Yield reaches 70% or more, and product content reaches 99.9% or more, belongs to regular industrial product using raw material, and production cost is low, and
Operating process is simple, is suitably applied industrialized production.
Specific implementation mode
For preferably the present invention will be described, an example is as follows：Raw materials used 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 carbazoles are dissolved in 400
In mL1,2- dichloroethanes, 68.7 g are added（0.34 mol）40% hydrobromic acid aqueous solution of mass percent, controlling reaction temperature-
41.6 mL are slowly added dropwise at 20 DEG C（0.44 mol）30% hydrogen peroxide, natural temperature reaction is overnight after being added dropwise completely, reaction solution
Aqueous solution of sodium bisulfite washs, and separates organic layer, and anhydrous magnesium sulfate drying, the dispersion of 500 mL methanol is added in filtrate after filtering,
Obtain the bromo- 3,6- di-t-butyls carbazoles of 1-（Content 97.8%, 1, bis- bromo- 3,6- di-t-butyls carbazole contents 0.92% of 8-）, dry
303.5 g afterwards；Bromo- 3, the 6- di-t-butyls carbazoles of 1- are added in 2 L there-necked flasks, 1 L isopropanol solvents are added, then control 20
4.6 g of alchlor is slowly added at DEG C, the reaction was continued 48 h after adding, after plus 500 mL ice water terminate reaction, 500
ML dichloromethane extracts, and organic layer sodium hydrate aqueous solution is washed, and anhydrous sodium sulfate is dried overnight, and is concentrated to give crude product, 500mL dichloros
Methane -350mL methanol mixed solvents 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 carbazoles are dissolved in 2 L1,2-
In dichloroethanes, 192.1 g are added（0.95 mol）At 40% hydrobromic acid aqueous solution of mass percent, 0 DEG C of controlling reaction temperature
84.9 mL are slowly added dropwise（0.9 mol）30% hydrogen peroxide is added dropwise completely natural temperature reaction and stays overnight, reaction solution sodium hydrogensulfite
Aqueous solution washs, and separates organic layer, anhydrous magnesium sulfate drying, the dispersion of 1 L methanol is added in filtrate after filtering, obtains 1- bromo- 3,6-
Di-t-butyl carbazole（Content 98%, 1, bis- bromo- 3,6- di-t-butyls carbazole contents 0.85% of 8-）, dry 292.8 g；1- is bromo-
3,6- di-t-butyl carbazoles are added in 5 L there-necked flasks, and 3 L isopropanol solvents are added, and then control and are slowly added to trichlorine at 40 DEG C
Change 32.8 g of aluminium, the reaction was continued 48 h after adding, after be added in 2 L ice water and terminate reaction, the extraction of 2 L dichloromethane has
Machine layer sodium hydrate aqueous solution is washed, and anhydrous sodium sulfate is dried overnight, and is concentrated to give crude product, -500 mL methanol of 800 mL dichloromethane
Mixed 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 carbazoles are dissolved in 1.5 L1,
In 2- dichloroethanes, 182.1 g are added（0.9 mol）40% hydrobromic acid aqueous solution of mass percent, -10 DEG C of controlling reaction temperature
Under 94.3 mL are slowly added dropwise（1 mol）Hydrogen peroxide is added dropwise completely natural temperature reaction and stays overnight, and reaction solution sodium hydrogensulfite is water-soluble
Liquid washs, and separates organic layer, anhydrous magnesium sulfate drying, the dispersion of 1 L methanol is added in filtrate after filtering, obtains bromo- 3,6-, bis- uncles of 1-
Butyl carbazole（Content 98.1%, 1, bis- bromo- 3,6- di-t-butyls carbazole contents 0.97% of 8-）, dry 332.1 g；By 1- bromo- 3,
6- di-t-butyl carbazoles are added in 5 L there-necked flasks, and 2 L isopropanol solvents are added, and then controlling 30 DEG C is slowly added to alchlor
23 g, the reaction was continued 48 h after adding, after be added in 2 L ice water and terminate reaction, the extraction of 2 L dichloromethane, organic layer hydrogen
Aqueous solution of sodium oxide is washed, and anhydrous sodium sulfate is dried overnight, and is concentrated to give crude product, and the mixing of -500 mL methanol of 800 mL dichloromethane is molten
Agent recrystallization obtains 172.8 g of product 1- bromines carbazole, content 99.91% twice（Double bromine 437ppm）, total recovery 70.2%.
Above-described 1- bromines carbazole content reaches 99.9% or more, is important fine-chemical intermediate, has expanded carbazole
Application of the analog derivative as intermediate in organic photoelectrical material design synthesis, also has extensive in the fields such as medicine and pesticide
Application prospect.
Claims (1)
1. a kind of production method of 1- bromines carbazole, which is characterized in that synthesize as follows：Under noble gas protection, by 3,6- bis-
Tert-butyl carbazole is dissolved in 1,2- dichloroethanes, and hydrogen peroxide is slowly added dropwise in addition hydrobromic acid, controlling reaction temperature, is added dropwise complete
Natural temperature reaction is stayed overnight, and reaction solution washing separates organic layer, dry, and methanol dispersion is added, obtains bromo- 3,6-, the bis- tertiary fourths of 1-
Base carbazole；Then bromo- 3, the 6- di-t-butyls carbazoles of 1- are added in reaction bulb and isopropanol solvent, controlling reaction temperature slowly add
Enter alchlor reaction, after plus water terminate reaction, through extraction, organic layer sodium hydrate aqueous solution washes, is dried overnight, and concentrates
Crude product is obtained, methylene chloride-methanol mixed solvent is recrystallized to give product 1- bromine carbazoles；
The 3,6- di-t-butyls carbazole is 1 with hydrobromic acid dosage molar ratio: 0.85-0.95；3,6- di-t-butyls carbazole with
Dioxygen water consumption molar ratio is 1: 0.9-1.1；
The bromination reaction temperature is -20-0 DEG C；
The alchlor dosage is 0.1-0.3 times of the bromo- 3,6- di-t-butyls carbazole moles of 1-；
The de-t-butylation temperature is 20-40 DEG C.
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| 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 |
| 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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