CN109232383B - Method for synthesizing 4-bromocarbazole - Google Patents
Method for synthesizing 4-bromocarbazole Download PDFInfo
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- CN109232383B CN109232383B CN201811470191.2A CN201811470191A CN109232383B CN 109232383 B CN109232383 B CN 109232383B CN 201811470191 A CN201811470191 A CN 201811470191A CN 109232383 B CN109232383 B CN 109232383B
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- bromocarbazole
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- dinitrobiphenyl
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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 synthesis method of 4-bromocarbazole, belonging to the field of organic synthesis. The method comprises the steps of taking o-chloronitrobenzene as an initial raw material, synthesizing 2, 2' -dinitrobiphenyl through a high-temperature coupling reaction under the catalysis of copper powder, then obtaining 4-nitrocarbazole through ring closure of triethyl phosphite, obtaining diazonium salt through reduction and diazotization of zinc powder under the acidic condition of the 4-nitrocarbazole, and further reacting with cuprous bromide to synthesize a product, namely 4-bromocarbazole. The method has the advantages of easily available raw materials, low production cost, high yield of more than 70 percent, and easy industrial production, and provides a foundation for industrialization of 4-bromocarbazole and subsequent derivatives thereof.
Description
Technical Field
The invention relates to a production method of carbazole compounds, in particular to a synthesis method of 4-bromocarbazole, belonging to the field of organic synthesis.
Background
The organic electroluminescent thin film is an electric energy conversion film that converts applied electric energy into light energy. The organic electroluminescent film has the outstanding advantages of low power consumption, easy bending, fast response speed, wide visual angle, large-area display, uniform luminous color and the like, is a luminous device with various existing standards and compatible technologies and low cost, and therefore, has strong vitality in the aspect of realizing color flat panel display. At present, the organic electroluminescent device has been developed toward practical and commercial use, but further improvement in the luminance, efficiency and lifetime of the device is still required. Aiming at the current situation that most of the existing charge transport compounds have low mobility and poor stability, the development of organic macromolecules with strong electron-withdrawing groups and continuous pi conjugated systems, the assembly of molecules of various functional groups in the same molecule and the transport by utilizing hole charges become a new research direction. Carbazole and its derivatives belong to electron-rich systems, and have not only a large pi-conjugated system but also a strong intramolecular electron transfer characteristic. Structurally, the electrophilic N atom of carbazole attracts electrons of pi conjugated system through induction effect, and the lone pair of N atom of P-pi conjugated effect supplies electrons to pi conjugated system to enrich pi conjugated system, so that carbazole compound has strong hole transmission capacity. The positions of substituents on the carbazole ring are different, the electronic effects are completely different, and further the hole transport capabilities are greatly different. Polymers containing carbazole moieties have received increasing attention in the field of optoelectronic devices in recent years.
At present, 3-bromocarbazole and 3, 6-dibromocarbazole are synthesized by direct bromination of carbazole, and 4-bromocarbazole has relatively high synthesis difficulty due to the special structure thereof. Two existing methods for synthesizing 4-bromocarbazole are as follows:
1. o-bromonitrobenzene is used as a starting material, lithium halide exchange and boronization of butyl lithium are carried out at low temperature to prepare o-nitrobenzeneboronic acid, then the o-nitrobenzeneboronic acid is coupled with o-bromoiodobenzene, and 4-bromocarbazole is synthesized by cyclization of triethyl phosphite.
2. O-bromonitrobenzene is taken as a raw material, o-nitrobenzeneboronic acid pinacol ester is synthesized through Miyaura boronization, then the o-bromoiodobenzene is coupled, and finally 4-bromocarbazole is synthesized through cyclization of triethyl phosphite.
The two synthesis methods both need to use boronization reaction and Suzuki coupling reaction, and the used raw materials are expensive and the synthesis conditions are harsh, so that the cost is high and mass production cannot be realized.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing 4-bromocarbazole, which has the advantages of easily obtained raw materials and low production cost and can be applied to industrialization.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the method comprises the steps of taking o-chloronitrobenzene as an initial raw material, carrying out high-temperature coupling reaction under catalysis of copper powder to synthesize 2, 2' -dinitrobiphenyl, then carrying out ring closure through triethyl phosphite to obtain 4-nitrocarbazole, carrying out reduction and diazotization reaction through zinc powder under the acidic condition of the 4-nitrocarbazole to obtain diazonium salt, and further reacting with cuprous bromide to synthesize the product 4-bromocarbazole.
The synthetic route of the invention is as follows:
the specific reaction steps are as follows:
(1) adding o-chloronitrobenzene and copper powder catalyst into a reaction bottle, keeping the system temperature at 200-.
(2) Under the protection of inert gas, adding 2, 2' -dinitrobiphenyl into another reaction bottle, heating to 140-160 ℃, dropwise adding a ring-closing reagent triethyl phosphite into the reaction bottle through a dropping funnel while stirring, continuously keeping the temperature, stirring for reaction, adding alkali to neutralize the aqueous solution after the reaction is finished, separating an organic layer, cooling and filtering to obtain brown powder 4-nitrocarbazole, and recrystallizing to obtain a pure 4-nitrocarbazole product.
(3) Under the protection of inert gas, adding zinc powder into 4-nitro carbazole to reduce under an acidic condition to obtain 4-aminocarbazole, then adding hydrobromic acid, gradually dropwise adding a sodium nitrite aqueous solution under an ice-water bath condition to prepare diazonium salt, then dropwise adding a cuprous bromide aqueous solution, after complete reaction, adding sodium bisulfite to remove redundant bromine, washing with water to obtain a crude product, and then recrystallizing to obtain a white-like 4-bromo carbazole product.
In the step (1), the molar ratio of the copper powder catalyst to the o-chloronitrobenzene is 1: 1.1-1.3; in the step (2), the molar ratio of the 2, 2' -dinitrobiphenyl to the triethyl phosphite is 1: 4-5; in the step (3), the molar ratio of 4-nitrocarbazole to the zinc powder reducing agent is 1: 3-5.
The novel method for synthesizing 4-bromocarbazole has the innovation points and advantages that: the raw materials are easy to obtain, the production cost is low, the yield reaches more than 70 percent, the method is easy to be applied to industrial production, and a foundation is provided for industrialization of 4-bromocarbazole and subsequent derivatives thereof.
Detailed Description
To better illustrate the invention, the following examples are given:
example one
1) A500 mL three-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 44.1g (0.28mol) of o-chloronitrobenzene and 19.7g (0.31mol) of copper powder. The mixture was heated to 200 ℃ and incubated for 12 h.
And (3) stopping the reaction after the content of the raw material o-chloronitrobenzene is lower than 2 percent through chromatographic tracking detection, cooling to room temperature, and adding 150mL of dichloromethane into the reaction system for extraction. The reaction solution was washed with 450mL x 3 times of water, stirred to give a viscous solid, and then recrystallized from 200mL of methanol. 52.6g of 2, 2-dinitrobiphenyl was obtained as a pale yellow solid in a yield of 77%.
2) Under the protection of inert gas, 48.8g (0.20mol) of light yellow 2, 2-dinitrobiphenyl is put into a 500mL three-mouth reaction bottle with a mechanical stirrer and a thermometer, the temperature is raised to 160 ℃, 150g of triethyl phosphite is slowly dripped, the temperature is kept for 2h after the dripping is completed, the heating is stopped, sodium hydroxide aqueous solution is added for neutralization, the solution is cooled, the temperature is reduced and the filtration is carried out to obtain a crude product of 4-nitrocarbazole, and methanol is recrystallized to obtain a pure product of 4-nitrocarbazole, wherein the yield is 71 percent.
3) Under the protection of inert gas, 30g of zinc powder, 100mL of ethanol, 100mL of water, 10mL of glacial acetic acid and 22.6g (0.1mol) of 4-nitrocarbazole are put into a 500mL reaction bottle and heated and kept at 40 ℃. Keeping the temperature for 2 hours, stopping the reaction when the reaction solution is grey, adding a small amount of sodium hydroxide, adjusting the pH value of the system to 8-9, after the reaction system is cooled, adding 150mL of dichloromethane to extract an organic layer, extracting the organic layer, evaporating the dichloromethane, adding 150mL of hydrobromic acid with the mass percentage content of 40% when the product is about to be separated out, adding 150mL of water, and cooling in an ice water bath for 30 minutes. 50mL of aqueous sodium nitrite solution (13.7 g of sodium nitrite, 0.2mol) was added dropwise, and after completion of the addition, the temperature was maintained for 30min, and then 200mL of aqueous cuprous bromide solution (21.5 g of cuprous bromide, 0.15mol) was added dropwise. After reacting for 2h, adding 10g of sodium bisulfite to remove redundant bromine, adding 150mL of dichloromethane into the water phase for extraction, evaporating to remove dichloromethane, then adding 150mL of methanol for recrystallization, and filtering to obtain light yellow solid 4-bromocarbazole 17.7g with the content of 99% +, and the yield of 72%. MS (FAB) M/z 246(M +). 1H NMR (DMSO). delta. [ ppm ]11.66(s, 1H, NH), 8.57-8.59(d, 1H, Ar), 7.47-7.58(m, 2H, Ar), 7.24-7.39 (m, 4H, Ar).
Example two
1) 44.1g (0.28mol) of o-chloronitrobenzene and 22.8g (0.36mol) of copper powder were placed in a 500mL three-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser. First heated to 220 ℃ and then kept at temperature for reaction for 10 h. And (3) detecting by chromatography tracking, when the content of the raw material o-chloronitrobenzene is lower than 2%, cooling to stop the reaction, cooling the reaction solution to room temperature, and adding 150mL of dichloromethane into the reaction system for extraction. The reaction solution was washed with 450mL x 3 times of water, stirred to give a viscous solid, and then recrystallized from 200mL of methanol. 51.2g of 2, 2-dinitrobiphenyl were obtained as a pale yellow solid in a yield of 75%.
2) Under the protection of inert gas, 48.8g (0.20mol) of 2, 2-dinitrobiphenyl obtained in the previous step is put into a 500mL three-mouth reaction bottle with a mechanical stirrer and a thermometer, heated to 140 ℃, 133g (0.80mol) of triethyl phosphite is slowly dripped, heat preservation is carried out for 2 hours after dripping is finished, cooled to 80 ℃, added with sodium hydroxide aqueous solution for neutralization, cooled and filtered to obtain a crude product of 4-nitrocarbazole, and methanol is recrystallized to obtain a pure product of 4-nitrocarbazole, wherein the yield is 31.7g and 70%.
3) Under the protection of inert gas, 20g of zinc powder, 100mL of ethanol, 100mL of water, 10mL of glacial acetic acid and 22.6g (0.1mol) of 4-nitrocarbazole are put into a 500mL reaction bottle and heated and kept at 40 ℃. And (3) preserving the temperature for reaction for 2h, stopping the reaction when the reaction solution is grey, adding a sodium hydroxide aqueous solution to adjust the pH value of the system to 8-9, cooling the reaction system, adding 150mL of dichloromethane to extract an organic layer, extracting the organic layer, evaporating to remove the dichloromethane, adding 150mL of hydrobromic acid with the mass percentage content of 40% when a product is about to be separated out, adding 150mL of water, and cooling in an ice water bath for 30 min. 50mL of aqueous sodium nitrite solution (13.7 g of sodium nitrite, 0.2mol) was added dropwise, and after completion of the addition, the temperature was maintained for 30min, and then 200mL of aqueous cuprous bromide solution (21.5 g of cuprous bromide, 0.15mol) was added dropwise. After reacting for 2h, adding 10g of sodium bisulfite to remove redundant bromine, stopping the reaction, extracting the water phase by 150mL of dichloromethane, evaporating to remove the dichloromethane, then adding 150mL of methanol for recrystallization, and filtering to obtain light yellow solid 4-bromocarbazole 17.2g with the content of 99% +, and the yield of 70%.
Example three
1) A500 mL three-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 44.1g (0.28mol) of o-chloronitrobenzene and 19.7g (0.31mol) of copper powder. The mixture was heated to 200 ℃ and incubated for 10 h. And (3) stopping the reaction after the content of the raw material o-chloronitrobenzene is lower than 2 percent through chromatographic tracking detection, cooling to room temperature, and adding 150mL of dichloromethane into the reaction system for extraction. After hydrolysis, the reaction solution was washed with 450mL of 3 times of water, stirred to give a viscous solid, and then recrystallized from 200mL of methanol. 52.6g of 2, 2-dinitrobiphenyl was obtained as a pale yellow solid in a yield of 77%.
2) Under the protection of inert gas, 48.8g (0.20mol) of 2, 2-dinitrobiphenyl is put into a 500mL three-mouth reaction bottle with a mechanical stirrer and a thermometer, the temperature is raised to 150 ℃, 150g (0.9mol) of triethyl phosphite is slowly dripped, the temperature is kept for 2h after the dripping is completed, the temperature is reduced to 80 ℃, sodium hydroxide aqueous solution is slowly added to neutralize the reaction solution, the temperature is reduced to room temperature, the crude product of 4-nitrocarbazole is obtained by filtering, 100mL of methanol is used for recrystallization to obtain 32.7g of pure product of 4-nitrocarbazole, and the yield is 72%.
3) Under the protection of inert gas, 30g of zinc powder, 100mL of ethanol, 100mL of water, 10mL of glacial acetic acid and 22.6g (0.1mol) of 4-nitrocarbazole are put into a 500mL reaction bottle, the reaction liquid is heated to 40 ℃ and kept for 2 hours, the reaction is stopped when the reaction liquid gradually changes from light yellow to grey, the pH value of the system is adjusted to 8-9 through a sodium hydroxide solution, the reaction liquid is fully cooled, 150mL of dichloromethane is added to extract an organic layer, the organic layer is combined, dichloromethane is evaporated under reduced pressure, 150mL of hydrobromic acid with the mass percentage content of 40% is added when a product is about to be separated out, 150mL of water is added, and the mixture is cooled for 30 minutes in an ice water bath. 50mL of an aqueous solution of sodium nitrite (13.7 g of sodium nitrite, 0.2mol) was slowly dropped into the reaction solution, and after completion of the dropping, the temperature was maintained for 30min, and then 200mL of an aqueous solution of cuprous bromide (21.5 g of cuprous bromide, 0.15mol) was continuously dropped. After reacting for 2h, adding 10g of sodium bisulfite to remove excessive bromine, stopping the reaction, extracting the aqueous phase by 150mL of dichloromethane, combining the organic phases, evaporating the dichloromethane under reduced pressure, recrystallizing by using 150mL of methanol, and filtering to obtain 17.7g of light yellow solid 4-bromocarbazole, wherein the content is 99% +, and the yield is 72%.
Claims (2)
1. A method for synthesizing 4-bromocarbazole is characterized by comprising the following steps:
(1) adding o-chloronitrobenzene and copper powder catalyst into a reaction bottle, keeping the system temperature at 200-;
(2) adding 2, 2' -dinitrobiphenyl into another reaction bottle, heating to 140-;
(3) under the acidic condition, reducing zinc powder of 4-nitro carbazole to obtain 4-aminocarbazole, then adding hydrobromic acid, gradually dropwise adding a sodium nitrite aqueous solution under the ice-water bath condition to prepare diazonium salt, then dropwise adding a cuprous bromide aqueous solution, after complete reaction, adding sodium bisulfite to remove redundant bromine, washing to obtain a crude product, and then recrystallizing to obtain a 4-bromocarbazole product.
2. The method of synthesizing 4-bromocarbazole according to claim 1, characterized in that: in the step (1), the molar ratio of the copper powder catalyst to the o-chloronitrobenzene is 1: 1.1-1.3; in the step (2), the molar ratio of the 2, 2' -dinitrobiphenyl to the triethyl phosphite is 1: 4-5; in the step (3), the molar ratio of 4-nitrocarbazole to the zinc powder reducing agent is 1: 3-5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1850800A (en) * | 2005-11-26 | 2006-10-25 | 山西大学 | N-bromo carbazole, and its preparing method |
| CN102060717A (en) * | 2011-01-07 | 2011-05-18 | 大连凯飞精细化工有限公司 | Method for synthesizing 3-amino-4-bromophenol |
| CN103936656A (en) * | 2014-04-11 | 2014-07-23 | 河南省科学院化学研究所有限公司 | Preparation method of 4-bromocarbazole |
| CN107108485A (en) * | 2014-10-24 | 2017-08-29 | 小野药品工业株式会社 | The channel activator of KCNQ2~5 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850800A (en) * | 2005-11-26 | 2006-10-25 | 山西大学 | N-bromo carbazole, and its preparing method |
| CN102060717A (en) * | 2011-01-07 | 2011-05-18 | 大连凯飞精细化工有限公司 | Method for synthesizing 3-amino-4-bromophenol |
| CN103936656A (en) * | 2014-04-11 | 2014-07-23 | 河南省科学院化学研究所有限公司 | Preparation method of 4-bromocarbazole |
| CN107108485A (en) * | 2014-10-24 | 2017-08-29 | 小野药品工业株式会社 | The channel activator of KCNQ2~5 |
Non-Patent Citations (1)
| Title |
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| Studies of Polyphenyls and polyphenylenes. I. Synthesis and infrared and electronic spectra of several sexiphenyls;Ibuki, Eiichi et al.;《Bulletin of the Chemical Society of Japan》;19751231;第48卷(第6期);1868-1874 * |
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