CN102491937A - Preparation method of high-purity 3-bromine-N-phenylcarbazole - Google Patents
Preparation method of high-purity 3-bromine-N-phenylcarbazole Download PDFInfo
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- CN102491937A CN102491937A CN2011103821389A CN201110382138A CN102491937A CN 102491937 A CN102491937 A CN 102491937A CN 2011103821389 A CN2011103821389 A CN 2011103821389A CN 201110382138 A CN201110382138 A CN 201110382138A CN 102491937 A CN102491937 A CN 102491937A
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- YSXJVQUJYMWJAI-UHFFFAOYSA-N Nc(cc1)ccc1-[n]1c(ccc(N(c2ccccc2)c2ccccc2)c2)c2c2cc(C(c3ccccc3)c3ccccc3)ccc12 Chemical compound Nc(cc1)ccc1-[n]1c(ccc(N(c2ccccc2)c2ccccc2)c2)c2c2cc(C(c3ccccc3)c3ccccc3)ccc12 YSXJVQUJYMWJAI-UHFFFAOYSA-N 0.000 description 1
- YANFTNKUUXOXRY-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2N(c1ccccc1)c1ccccc1 Chemical compound c(cc1)ccc1N(c1ccccc1)c(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2N(c1ccccc1)c1ccccc1 YANFTNKUUXOXRY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of high-purity 3-bromine-N-phenylcarbazole. The invention relates to a preparation method of a carbazole compound. With existing technologies for preparing 3-bromine-N-phenylcarbazole, the purity is low, and separation is difficult. The method provided by the invention comprises steps that: 1, under a condition of a low temperature, a reaction product is prepared with a separated material addition manner; 2, the reaction product is sequentially processed by using a washing separation method, an anhydrous magnesium sulfate drying method and a rotary evaporation drying method, such that a crude product is obtained; 3, the crude product is sequentially processed by using a high-vacuum rectification method and a recrystallization method, such that the high-purity 3-bromine-N-phenylcarbazole is obtained. The method is advantaged in that: 1, the mass percentage of 3-bromine-N-phenylcarbazole in the crude product is 90-95%; 2, the mass percentage of 3-bromine-N-phenylcarbazole in the high-purity 3-bromine-N-phenylcarbazole is greater than 99.5%; 3, the separation method is simple, such that the preparation cost is reduced. The method provided by the invention is mainly used for preparing high-purity 3-bromine-N-phenylcarbazole.
Description
Technical field
The present invention relates to a kind of preparation method of carbazole compound.
Background technology
Because in extensive applications such as electroluminescent organic material, thin film transistor, actinic material, tree-shaped polymkeric substance, non-linear optical polymer and complex metal, carbazole compound has attracted more and more investigators' concern.Especially in field of organic electroluminescent materials, carbazoles fluorine-triphenylamine structure material has excellent hole transport performance, and therefore good thermostability becomes one type of important hole material, and in organic electroluminescence device, obtained practical application.Typical case's carbazoles hole material structure is as follows:
3-bromo-N-phenyl carbazole is the important intermediate of synthesizing carbazole electroluminescent organic material, prepares corresponding boric acid by it, can synthesize the carbazoles material with different performance through Suzuki coupling, Buchwald-Harwig linked reaction.Because 3,6 of carbazole are all more active, so often contain raw material, single bromo-derivative and two bromo-derivative in its brominated product, the three is difficult to separate.For example with N-phenyl carbazole raw material; When adopting NBS, bromine etc. be bromide reagent, when DMF, benzene, methylene dichloride etc. are solvent in the brominated product N-phenyl carbazole content be 7%, 3-bromo-N-phenyl carbazole content is 85%; 3,6-two bromo-N-phenyl carbazole content are 8%; If when improving feed stock conversion, dibrominated thing content increases, separation difficulty.Therefore prior art for preparing 3-bromo-N-phenyl carbazole exists purity low, and the problem of separation difficulty.
Summary of the invention
The present invention will solve prior art for preparing 3-bromo-N-phenyl carbazole and exist purity low, and the problem of separation difficulty, and a kind of preparation method of high purity 3-bromo-N-phenyl carbazole is provided.
A kind of preparation method of high purity 3-bromo-N-phenyl carbazole; Specifically accomplish according to the following steps: one, that N-phenyl carbazole and solvent is even; The thing that is uniformly mixed is-40 ℃～0 ℃ in temperature then and the N-bromo-succinimide is divided into 20～40 times joins in the uniform mixture, and adds afterreaction 20min～60min at every turn; It is-40 ℃～0 ℃ continuation reaction 20h～40h down in temperature that the N-bromo-succinimide all adds the back, promptly obtains reaction product; Two, the reaction product that at first step 1 is obtained adopts washing partition method washing 1～3 time, and the organic phase that then separation is obtained adopts anhydrous magnesium sulfate drying earlier, adopts rotary evaporation method drying treatment promptly to obtain the product bullion at last; Three, at first adopt the high vacuum rectification method that the product bullion that step 2 obtains is purified, obtain the preliminary purification product, adopt recrystallization method that the preliminary purification product is purified once more then, promptly obtain high purity 3-bromo-N-phenyl carbazole; The mass ratio of N-phenyl carbazole described in the step 1 and solvent is 1: (5～20); The mass ratio of the N-bromo-succinimide total mass of N-phenyl carbazole described in the step 1 and adding is 1: (0.65～0.8).
Advantage of the present invention: the massfraction of 3-bromo-N-phenyl carbazole is 90%～95% in the product bullion that, obtains in the step 2 of the present invention; Two, in the high purity 3-bromo-N-phenyl carbazole that obtains of the present invention the massfraction of 3-bromo-N-phenyl carbazole greater than more than 99.5%; Three, separation method of the present invention is simple, has reduced preparation cost.
Description of drawings
Fig. 1 is a liquid chromatogram of testing the product bullion that obtains in the step 2; Fig. 2 is the liquid chromatogram of the preliminary purification product that employing high vacuum rectification method obtains in test one step 3; Fig. 3 is the high purity 3-bromo-N-phenyl carbazole liquid chromatogram that obtains in test one step 3; Fig. 4 tests the nucleus magnetic hydrogen spectrum figure of the high purity 3-bromo-N-phenyl carbazole that obtains in the step 3.
Embodiment
Embodiment one: this embodiment is a kind of preparation method of high purity 3-bromo-N-phenyl carbazole, specifically accomplishes according to the following steps:
One, N-phenyl carbazole and solvent is even; Thing is uniformly mixed; Being-40 ℃～0 ℃ in temperature then is divided into 20～40 times with the N-bromo-succinimide and joins in the uniform mixture; And add afterreaction 20min～60min, it is-40 ℃～0 ℃ continuation reaction 20h～40h down in temperature that the N-bromo-succinimide all adds the back, promptly obtains reaction product at every turn; Two, the reaction product that at first step 1 is obtained adopts washing partition method washing 1～3 time, and the organic phase that then separation is obtained adopts anhydrous magnesium sulfate drying earlier, adopts rotary evaporation method drying treatment promptly to obtain the product bullion at last; Three, at first adopt the high vacuum rectification method that the product bullion that step 2 obtains is purified, obtain the preliminary purification product, adopt recrystallization method that the preliminary purification product is purified once more then, promptly obtain high purity 3-bromo-N-phenyl carbazole.
The mass ratio of N-phenyl carbazole described in this embodiment step 1 and solvent is 1: (5～20); The mass ratio of the N-bromo-succinimide total mass of N-phenyl carbazole described in this embodiment step 1 and adding is 1: (0.65～0.8).
N-bromo-succinimide bromo-reaction mechanism generally has two kinds of explanations: one, the N-bromo-succinimide bromination for vinyl carbon is a radical mechanism, and the following fact can prove: the existence of initiators such as (1) Lucidol, azo-bis-isobutyl cyanide can promote reaction to carry out; (2) reaction can be by Resorcinol, dinitrobenzene, to terminations such as tetrabromo-quinone and iodine; (3) position or para-orientation are consistent with this course to the influence of Benzyl Side-Chain Chloride between; (4) for acenaphthene and 1, the 2-diphenylethane adopts N-bromo-succinimide bromination then to show stereospecificity, has proved two step courses of side chain bromination, has confirmed the radical mechanism of vinyl charcoal bromination simultaneously effectively; Two, another course of N-bromo-succinimide bromination is the radical ion course of N-Br heterolytic fission, has carried out deep discovering through the N-bromo-succinimide bromination to aromatic hydrocarbons and allyl group charcoal, and this type reaction can be by AlCl
3, ZnCl
2And FeCl
3Deng Louis acid catalysis, this has also confirmed the radical ion course of N-bromo-succinimide bromination.The N-bromo-succinimide carries out bromination reaction with which kind of course, and this is decided by the solvent system that adopted to a great extent.When adopting the polar solvent system, like water, alcohol, Glacial acetic acid min. 99.5 etc., then N-Br key generation heterolytic fission forms Br
+Intermediate state meets the electrophilic substitution reaction course.And temperature of reaction has very big influence to product selectivity: the temperature of reaction height helps the heterolytic fission of N-bromo-succinimide, makes the Br in the reaction system
+Concentration is high, has accelerated speed of response, has reduced reaction preference, impels 3, the generation of 6-dibrominated product; On the other hand, after introducing a bromine atoms on the carbazole ring, because the electrophilic inductive effect of bromine; Cause the phenyl ring cloud density to reduce, reactive behavior is reduced, need higher activation energy; Therefore temperature is high, for further bromination accelerating effect is arranged, and impels 3; The generation of 6-dibrominated product, thus the selectivity of single bromination product reduced.Therefore, the temperature of reaction of this embodiment selection is-40 ℃-0 ℃.
Feed way also has very big influence for selectivity: with the disposable adding of N-bromo-succinimide, Br in the reaction system
+Concentration is high, helps the dibrominated product and generates, and has reduced the selectivity of single bromination product; If earlier the N-bromo-succinimide is dissolved in methylene dichloride, adopt the mode that drips to add then and carry out bromination, guarantee Br in the reaction system
+Concentration is kept lower level, but speed of response reduces greatly; Therefore this embodiment adopts the N-bromo-succinimide is divided into 20～40 addings, has both guaranteed Br in the reaction system
+Concentration is kept lower level, helps the selectivity of single bromination product, guarantees again Br in the reaction system can not occur
+Concentration is crossed low and is had influence on speed of response.
The massfraction of 3-bromo-N-phenyl carbazole is greater than more than 99.5% in the high purity 3-bromo-N-phenyl carbazole that this embodiment obtains.
The separation method of this embodiment is simple, has reduced preparation cost.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of high purity 3-bromo-N-phenyl carbazole, specifically accomplish according to the following steps:
One, N-phenyl carbazole and solvent is even; Thing is uniformly mixed; The N-bromo-succinimide is divided into 30 times joins in the uniform mixture for-10 ℃ in temperature then; And add afterreaction 40min, the N-bromo-succinimide all adds the back and continues reaction 30h in temperature down for-10 ℃, promptly obtains reaction product at every turn; Two, the reaction product that at first step 1 is obtained adopts washing partition method washing 2 times, and the organic phase that then separation is obtained adopts anhydrous magnesium sulfate drying earlier, adopts rotary evaporation method drying treatment promptly to obtain the product bullion at last; Three, at first adopt the high vacuum rectification method that the product bullion that step 2 obtains is carried out preliminary purification, obtain the preliminary purification product, adopt recrystallization method that the preliminary purification product is purified once more then, promptly obtain high purity 3-bromo-N-phenyl carbazole.
The mass ratio of N-phenyl carbazole described in this testing sequence one and solvent is 1: 15; The mass ratio of the N-bromo-succinimide total mass of N-phenyl carbazole described in this testing sequence one and adding is 1: 0.73.
Solvent described in this testing sequence one is a methylene dichloride.
High vacuum rectification method concrete operations step described in this testing sequence three is following: the product bullion that at first step 2 is obtained is to be melted up to molten state under 120 ℃ in temperature; Add in the rectifying tower then; Vacuum tightness is to carry out preliminary purification under 30 the condition for-0.098Mpa, theoretical plate number in tower still temperature is 280 ℃, tower, promptly obtains the preliminary purification product.
Recrystallization method concrete operations step described in this testing sequence three is following: at first adopting sherwood oil is dissolving fully under 60 ℃ with the preliminary purification product in temperature; Be-10 ℃ of following crystallizations in temperature then; Carry out recrystallization altogether 2 times, promptly obtain high purity 3-bromo-N-phenyl carbazole.
Adopt the product bullion of liquid-phase chromatographic analysis to obtaining in this testing sequence two, as shown in Figure 1, can calculate through the peak area normalization method that 3-bromo-N-phenyl carbazole massfraction is 94.39% in the product bullion that obtains in this testing sequence two.
Adopt the preliminary purification product of liquid-phase chromatographic analysis to adopting the high vacuum rectification method to obtain in this testing sequence three; As shown in Figure 2, can calculate through the peak area normalization method that 3-bromo-N-phenyl carbazole massfraction is 98.13% in the product bullion that obtains in this testing sequence two.
Adopt the high purity 3-bromo-N-phenyl carbazole of liquid-phase chromatographic analysis to obtaining in this testing sequence three; As shown in Figure 3, can calculate through the peak area normalization method that 3-bromo-N-phenyl carbazole massfraction is 99.78% in the product bullion that obtains in this testing sequence two.
Adopt proton nmr spectra to characterize to the high purity 3-bromo-N-phenyl carbazole that obtains in this testing sequence three, as shown in Figure 4, can confirm that through Fig. 4 the high purity 3-bromo-N-phenyl carbazole that obtains is a 3-bromo-N-phenyl carbazole.
Embodiment two: this embodiment with the difference of embodiment one is: the solvent described in the step 1 is selected from N, methylene dichloride, 1,2-ethylene dichloride and propylene carbonate.Other is identical with embodiment one.
Embodiment three: this embodiment with one of embodiment one or two difference is: in the step 1 that N-phenyl carbazole and solvent is even; Thing is uniformly mixed; Being-30 ℃～-5 ℃ in temperature then is divided into 25～35 times with the N-bromo-succinimide and joins in the uniform mixture; And add afterreaction 30min～50min, it is-30 ℃～-5 ℃ continuation reaction 25h～35h down in temperature that the N-bromo-succinimide all adds the back, promptly obtains reaction product at every turn.Other is identical with embodiment one or two.
Embodiment four: this embodiment with one of embodiment one to three difference is: the high vacuum rectification method concrete operations step described in the step 3 is following: the product bullion that at first step 2 is obtained is to be melted up to molten state under 110 ℃～130 ℃ in temperature; Add in the rectifying tower then; In tower still temperature is 260 ℃～320 ℃, tower vacuum tightness for-0.090Mpa～-0.098Mpa, theoretical plate number carry out preliminary purification under 30 the condition, promptly obtain the preliminary purification product.Other is identical with embodiment one to three.
Embodiment five: this embodiment with one of embodiment one to four difference is: the recrystallization method concrete operations step described in the step 3 is following: at first adopting recrystallization solvent is dissolving fully under 55 ℃～65 ℃ with the preliminary purification product in temperature; Be-15 ℃～0 ℃ following crystallization in temperature then; Carry out recrystallization altogether 1～3 time, promptly obtain high purity 3-bromo-N-phenyl carbazole; Described recrystallization solvent is sherwood oil, hexanaphthene, normal hexane, benzene, toluene, ethanol, methyl alcohol, methylene dichloride, chloroform or 1, the 2-ethylene dichloride.Other is identical with embodiment one to four.
Claims (5)
1. the preparation method of a high purity 3-bromo-N-phenyl carbazole is characterized in that high purity 3-bromo-N-phenyl carbazole accomplishes according to the following steps:
One, N-phenyl carbazole and solvent is even; Thing is uniformly mixed; Being-40 ℃～0 ℃ in temperature then is divided into 20～40 times with the N-bromo-succinimide and joins in the uniform mixture; And add afterreaction 20min～60min, it is-40 ℃～0 ℃ continuation reaction 20h～40h down in temperature that the N-bromo-succinimide all adds the back, promptly obtains reaction product at every turn; Two, the reaction product that at first step 1 is obtained adopts washing partition method washing 1～3 time, and the organic phase that then separation is obtained adopts anhydrous magnesium sulfate drying earlier, adopts rotary evaporation method drying treatment promptly to obtain the product bullion at last; Three, at first adopt the high vacuum rectification method that the product bullion that step 2 obtains is purified, obtain the preliminary purification product, adopt recrystallization method that the preliminary purification product is purified once more then, promptly obtain high purity 3-bromo-N-phenyl carbazole; The mass ratio of N-phenyl carbazole described in the step 1 and solvent is 1: (5～20); The mass ratio of the N-bromo-succinimide total mass of N-phenyl carbazole described in the step 1 and adding is 1: (0.65～0.8).
2. the preparation method of a kind of high purity 3-bromo-N-phenyl carbazole according to claim 1 is characterized in that the solvent described in the step 1 is selected from N, methylene dichloride, 1,2-ethylene dichloride and propylene carbonate.
3. the preparation method of a kind of high purity 3-bromo-N-phenyl carbazole according to claim 2; It is characterized in that in the step 1 N-phenyl carbazole and solvent is even; Thing is uniformly mixed; Being-30 ℃～-5 ℃ in temperature then is divided into 25～35 times with the N-bromo-succinimide and joins in the uniform mixture; And add afterreaction 30min～50min, it is-30 ℃～-5 ℃ continuation reaction 25h～35h down in temperature that the N-bromo-succinimide all adds the back, promptly obtains reaction product at every turn.
4. according to the preparation method of claim 1,2 or 3 described a kind of high purity 3-bromo-N-phenyl carbazoles; It is characterized in that the high vacuum rectification method concrete operations step described in the step 3 is following: the product bullion that at first step 2 is obtained is to be melted up to molten state under 110 ℃～130 ℃ in temperature; Add in the rectifying tower then; In tower still temperature is 260 ℃～320 ℃, tower vacuum tightness for-0.090Mpa～-0.098Mpa, theoretical plate number carry out preliminary purification under 30 the condition, promptly obtain the preliminary purification product.
5. the preparation method of a kind of high purity 3-bromo-N-phenyl carbazole according to claim 4; It is characterized in that the recrystallization method concrete operations step described in the step 3 is following: at first adopting recrystallization solvent is dissolving fully under 55 ℃～65 ℃ with the preliminary purification product in temperature; Be-15 ℃～0 ℃ following crystallization in temperature then; Carry out recrystallization altogether 1～3 time, promptly obtain high purity 3-bromo-N-phenyl carbazole; Described recrystallization solvent is sherwood oil, hexanaphthene, normal hexane, benzene, toluene, ethanol, methyl alcohol, methylene dichloride, chloroform or 1, the 2-ethylene dichloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445886A (en) * | 2017-05-24 | 2017-12-08 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of the phenyl carbazole of 3 bromine of high-purity 9 |
| CN112209869A (en) * | 2020-10-22 | 2021-01-12 | 中钢集团南京新材料研究院有限公司 | Method for synthesizing high-purity 3-bromo-N-phenylcarbazole |
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| JP2007119354A (en) * | 2005-10-25 | 2007-05-17 | Gunma Univ | New carbazole derivative having silyl substituent |
| WO2010043691A1 (en) * | 2008-10-16 | 2010-04-22 | Solvay Sa | N-phenyl carbazole-based host material for light-emitting diodes |
| CN102030699A (en) * | 2009-09-28 | 2011-04-27 | 莱阳市盛华科技有限公司 | Method for synthesizing 3-iodine-phenylcarbazole |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119354A (en) * | 2005-10-25 | 2007-05-17 | Gunma Univ | New carbazole derivative having silyl substituent |
| WO2010043691A1 (en) * | 2008-10-16 | 2010-04-22 | Solvay Sa | N-phenyl carbazole-based host material for light-emitting diodes |
| CN102030699A (en) * | 2009-09-28 | 2011-04-27 | 莱阳市盛华科技有限公司 | Method for synthesizing 3-iodine-phenylcarbazole |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445886A (en) * | 2017-05-24 | 2017-12-08 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of the phenyl carbazole of 3 bromine of high-purity 9 |
| CN107445886B (en) * | 2017-05-24 | 2020-02-21 | 北京八亿时空液晶科技股份有限公司 | Preparation method of high-purity 3-bromo-9-phenylcarbazole |
| CN112209869A (en) * | 2020-10-22 | 2021-01-12 | 中钢集团南京新材料研究院有限公司 | Method for synthesizing high-purity 3-bromo-N-phenylcarbazole |
| CN112209869B (en) * | 2020-10-22 | 2022-04-29 | 中钢集团南京新材料研究院有限公司 | Method for synthesizing high-purity 3-bromo-N-phenylcarbazole |
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