CN102702208A - Bromine-containing indole [3,2-b] carbazole derivative and preparation method thereof - Google Patents
Bromine-containing indole [3,2-b] carbazole derivative and preparation method thereof Download PDFInfo
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- CN102702208A CN102702208A CN201210206543XA CN201210206543A CN102702208A CN 102702208 A CN102702208 A CN 102702208A CN 201210206543X A CN201210206543X A CN 201210206543XA CN 201210206543 A CN201210206543 A CN 201210206543A CN 102702208 A CN102702208 A CN 102702208A
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Abstract
The invention provides a bromine-containing indole [3,2-b] carbazole derivative, which is 4,10-dialkyl-7-bromo-1-indole [3,2-b] carbazole aldehyde. A preparation method comprises the following steps of: sequentially preparing cyclohexylamine-1,4-diketone-bi(4-bromobenzene) hydrazone, 2,8-dibromoindole [3,2-b] carbazole and 2,8-dibromo-5,11-dialkyl indole [3,2-b] carbazole; dissolving the 2,8-dibromo-5,11-dialkyl indole [3,2-b] carbazole in a tetrahydrofuran solvent; adding n-butyl lithium at 78 DEG C below zero and reacting at the temperature; adding N,N-dimethyl formamide for reacting again; and after the reaction solution is restored to room temperature, performing acidification, suction filtration, washing and separation to obtain the 4,10-dialkyl-7-bromoindole [3,2-b] carbazole aldehyde. The type of derivative has the advantages of high thermal stability, high environment suitability, easiness for processing and optimization and the like, and can be used as an intermediate for synthesis of an organic electroluminescent material.
Description
One, technical field
The present invention relates to the heterogeneous ring compound of carbon containing, hydrogen, oxygen, nitrogen, specifically belong to a kind of bromine-containing indole [3,2-b] carbazole derivative and preparation method thereof.
Two, background technology
Get into after 21 century, along with informationalized develop rapidly, can write down, store, the novel optical material of transmission and processes and displays large vol information will progressively lead the material market of becoming increasingly prosperous, organic photoelectric functional material causes people's research interest day by day.When the design functionality organic cpds, select suitable electron donor-acceptor (EDA) and conjugated bridge and carry out various molecules that to assemble the character of optimizing molecule be efficient ways.Current and after in the long-term time, become the research focus from the start with luminescent material of synthesizing new of the design of compound molecule.
Indoles [3; 2-b] carbazole and verivate thereof have big π-electron conjugated system; The characteristic of good rigidity conjugate planes and stronger intramolecularly transfer transport, so indoles [3,2-b] carbazole and verivate thereof have good photoelectric property; Have broad application prospects at aspects such as organic electroluminescent light, electroluminescent, nonlinear optical material and LB films, be widely used as good optical material.
With indoles [3,2-b] carbazole is parent, and design and synthetic indoles [3,2-b] carbazoles verivate with photoelectric functional are the photoelectric functional material hot research fields always.
Three, summary of the invention
The objective of the invention is to synthetic a kind of bromine-containing indole [3,2-b] carbazole derivative and preparation method thereof.This analog derivative has Heat stability is good, and is strong to environmental compatibility, is easy to advantages such as processing and optimization.The preparation method of this analog derivative is simple.
A kind of bromine-containing indole provided by the invention [3,2-b] carbazole derivative is 4,10-dialkyl group-7-bromo-1-indoles [3,2-b] carbazole aldehyde, and its molecular structure is:
In the formula: R=CH
3, CH
2CH
3, C
3H
7, C
4H
9, C
5H
11, C
6H
13Or C
6H
5
The invention provides the preparation method of a kind of bromine-containing indole [3,2-b] carbazole derivative, comprise the steps:
(R=CH
3,CH
2CH
3,C
3H
7,C
4H
9,C
5H
11,C
6H
13,C
8H
17,C
6H
5)
(1) 1:2 gets 1 in molar ratio, 4-cyclohexanedione and 4-bromophenyl-hydrazine hydrochloride; To be dissolved in 1 of absolute ethyl alcohol, 4-hexamethylene two
Ketone dropwise joins in the 4-bromophenyl-hydrazine hydrochloride that is dissolved in absolute ethyl alcohol; In the time of 60 ℃, reacted 2 hours; Through suction filtration, after the washing, obtain hexahydroaniline-1,4-diketone-two (4-bromobenzene) hydrazone;
(2) with hexahydroaniline-1,4-diketone-two (4-bromobenzene) hydrazone solid, under condition of ice bath, slowly joining Glacial acetic acid min. 99.5 and vitriol oil volume ratio is in the mixed solution of 4:1; Heat up subsequently, reaction is 10 hours in the time of 80 ℃; Reaction solution is poured in the frozen water, had a large amount of solids to separate out immediately, fully stir the back suction filtration, obtain thick product; Through washing with after ethanol washes, obtain the yellow-green colour solid, be 2,8-two bromo indoles [3,2-b] carbazole;
(3) 1:3:3 gets 2 in molar ratio, 8-two bromo indoles [3,2-b] carbazole, NaH and bromoalkane; With 2,8-two bromo indoles [3,2-b] carbazole is dissolved in the tetrahydrofuran solvent, in the time of 0 ℃, adds NaH; Reacted 1 hour, then elevated temperature; In the time of 60 ℃, reacted 10 hours; Be cooled to room temperature then, add bromoalkane; At room temperature, reaction is 24 hours; Remove and desolvate, use water washing, obtain 2,8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole;
(4) 1:0.8-0.9:1-1.5 gets 2 in molar ratio, 8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole, n-Butyl Lithium and N, dinethylformamide (DMF); With 2,8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole is dissolved in the tetrahydrofuran solvent, in the time of-78 ℃, adds n-Butyl Lithium, under this temperature, reacts 0.5-1.5 hour (preferred 1 hour); Then, add N, dinethylformamide (DMF) reacts 0.5-1.5 hour (preferred 1 hour) again; After question response liquid returns to room temperature, reaction solution is poured in the frozen water, is acidified to acidity with Hydrogen chloride, through suction filtration, the washing and separate, obtain 4,10--dialkyl group-7-bromo indole [3,2-b] carbazole aldehyde.
Synthetic bromine-containing indole of the present invention [3,2-b] carbazole derivative is one type of electroluminescent organic material synthetic midbody with wide application prospect.
Advantage of the present invention:
1. synthetic bromo indole of the present invention [3,2-b] carbazole derivative has Heat stability is good, and is strong to environmental compatibility, is easy to advantages such as processing and optimization.
2. the compound method of bromo indole provided by the invention [3,2-b] carbazole derivative, product productive rate and purity are high, and operation is simple.
Four, description of drawings
Fig. 1: 4, the infrared absorpting light spectra of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 2: 4, the hydrogen nuclear magnetic resonance spectrogram of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 3: 4, the carbon-13 nmr spectra figure of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 4: 4, the mass spectrum of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 5: 4, the thermogravimetric analysis figure of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 6: 4, the uv absorption spectrum of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Fig. 7: 4, the fluorescence spectrum figure of 10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Five, embodiment
Embodiment 1, get hexyl with R, preparation process is following:
(1) hexahydroaniline-1,4-diketone-two (4-bromobenzene) hydrazone synthetic
At room temperature; Get 1 of 5.62g (50mmol); The 4-cyclohexanedione is dissolved in the 100ml absolute ethyl alcohol; Be made into 1,4-cyclohexanedione ethanolic soln slowly is added drop-wise to above-mentioned solution with constant pressure funnel in the 200ml ethanol solution that is dissolved with 22.4g (100mmol) 4-bromophenyl-hydrazine hydrochloride and 8.2g (100mmol) sodium acetate, anhydrous under fully stirring.After dropwising, be warming up to 50 ℃ rapidly, reacted 2 hours.Reaction solution is cooled to 0 ℃, washes and drying, obtain the 15.7g faint yellow solid through suction filtration, washing, ethanol.Productive rate is 76%.
Synthesizing of (2) 2,8-two bromo indoles [3,2-b] carbazole
With 10g (22mmol) hexahydroaniline-1,4-diketone-two (4-bromobenzene) hydrazone solid slowly joins in 0 ℃ of mixing solutions of the 130mL Glacial acetic acid min. 99.5 and the 32mL vitriol oil.Stirring reaction 1 hour is warming up to 30 ℃ of reactions 1 hour subsequently, is warming up to 60-70 ℃ of reaction 2 hours again.Reaction solution is cooled to room temperature, pours in the frozen water, separate out solid.Wash and drying through suction filtration, washing, ethanol, obtain 4.62g yellow-green colour compound.Productive rate is 50%.
(3) 2,8-two bromo-5,11-di-n-hexyl indoles [3,2-b] carbazole synthetic
Under nitrogen protection, with 4.14g (10mmol) exsiccant 2,8-two bromo indoles [3,2-b] carbazole is dissolved in the tetrahydrofuran solvent of 100ml.Under nitrogen protection, add 0.72g (30mmol) NaH, at room temperature, reacted 2 hours.Slowly be warming up to 50 ℃, under this temperature, reacted 4 hours.Reaction solution is cooled to room temperature, adds the 1-bromine normal hexane of 4.09g (30mmol).Room temperature reaction 1 hour, and then be warming up to 50 ℃, under this temperature, reacted 24 hours.Reaction after finishing steams solvent, with water washing 2-3 time, obtains the 4.64g yellow compound to the solid that obtains with washing with acetone at last.Productive rate is 80%.
Synthesizing of (4) 4,10-di-n-hexyl-7-bromo-1-indoles [3,2-b] carbazole aldehyde
Under nitrogen protection, with 4.83g (8.32mmol) exsiccant 2,8-two bromo-5,11-di-n-hexyl indoles [3,2-b] carbazole is dissolved in the tetrahydrofuran solvent of 80ml.Under-78 ℃, add 3.03ml, concentration is the n-butyllithium solution of 2.5mol/L.Under this temperature, reacted 1 hour, add the N of 2.35ml then, dinethylformamide (DMF).Return to room temperature continued reaction 1 hour Deng reacting liquid temperature.Reaction solution is poured in the frozen water, dripped massfraction and be 5% Hydrogen chloride to solution and be neutral.Wash through suction filtration, washing and ether, obtain thick product, thick product obtains the 2.40g product after separating.Product is a yellow powder, and productive rate is 60%.
Claims (3)
1. a bromine-containing indole [3,2-b] carbazole derivative is 4,10-dialkyl group-7-bromo-1-indoles [3,2-b] carbazole aldehyde, and its molecular structure is:
In the formula: R=CH
3, CH
2CH
3, C
3H
7, C
4H
9, C
5H
11, C
6H
13Or C
6H
5
2. the preparation method of a kind of bromine-containing indole as claimed in claim 1 [3,2-b] carbazole derivative is characterized in that, comprises the steps:
(1) preparation hexahydroaniline-1,4-diketone-two (4-bromobenzene) hydrazone;
(2) preparation 2,8-two bromo indoles [3,2-b] carbazole;
(3) preparation 2,8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole;
(4) preparation 4,10--dialkyl group-7-bromo indole [3,2-b] carbazole aldehyde: 1:0.8-0.9:1-1.5 gets 2 in molar ratio, 8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole, n-Butyl Lithium and N, dinethylformamide; With 2,8-two bromo-5,11-dialkyl group indoles [3,2-b] carbazole is dissolved in the tetrahydrofuran solvent, in the time of-78 ℃, adds n-Butyl Lithium, under this temperature, reacts 0.5-1.5 hour; Then, add N, dinethylformamide reacted 0.5-1.5 hour again; After question response liquid returns to room temperature, reaction solution is poured in the frozen water, is acidified to acidity with Hydrogen chloride, through suction filtration, the washing and separate, obtain 4,10--dialkyl group-7-bromo indole [3,2-b] carbazole aldehyde.
3. the preparation method of a kind of bromine-containing indole as claimed in claim 2 [3,2-b] carbazole derivative is characterized in that, and is described 2,8-two bromo-5, and 11-dialkyl group indoles [3,2-b] carbazole, n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1:08:15.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104430408A (en) * | 2014-12-31 | 2015-03-25 | 江阴苏利化学股份有限公司 | New application of pesticide composite containing carbazole and used for preventing and treating cabbage aphides |
| CN104447506A (en) * | 2014-12-03 | 2015-03-25 | 中国科学院青海盐湖研究所 | Preparation method of 2-acetyl-9-alkyl carbazole |
| CN104604893A (en) * | 2014-12-31 | 2015-05-13 | 江阴苏利化学股份有限公司 | Carbazole-containing pesticide composition for controlling brevicoryne brassicae |
| CN107474257A (en) * | 2017-07-13 | 2017-12-15 | 兰州大学 | A kind of indolocarbazole covalent organic frame material and its synthetic method |
| CN114516876A (en) * | 2022-03-22 | 2022-05-20 | 安徽科技学院 | Indole [3,2-b ] carbazole based blue fluorescent material and synthetic method thereof |
| CN115286562A (en) * | 2022-08-18 | 2022-11-04 | 青海大学 | Benzoylation method of aromatic heterocyclic or aromatic amine compound containing rich electrons |
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Cited By (9)
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|---|---|---|---|---|
| CN104447506A (en) * | 2014-12-03 | 2015-03-25 | 中国科学院青海盐湖研究所 | Preparation method of 2-acetyl-9-alkyl carbazole |
| CN104447506B (en) * | 2014-12-03 | 2017-10-24 | 中国科学院青海盐湖研究所 | The preparation method of the alkyl carbazole of 2 acetyl group 9 |
| CN104430408A (en) * | 2014-12-31 | 2015-03-25 | 江阴苏利化学股份有限公司 | New application of pesticide composite containing carbazole and used for preventing and treating cabbage aphides |
| CN104604893A (en) * | 2014-12-31 | 2015-05-13 | 江阴苏利化学股份有限公司 | Carbazole-containing pesticide composition for controlling brevicoryne brassicae |
| CN107474257A (en) * | 2017-07-13 | 2017-12-15 | 兰州大学 | A kind of indolocarbazole covalent organic frame material and its synthetic method |
| CN107474257B (en) * | 2017-07-13 | 2020-10-02 | 兰州大学 | Indolocarbazole covalent organic framework material and synthesis method thereof |
| CN114516876A (en) * | 2022-03-22 | 2022-05-20 | 安徽科技学院 | Indole [3,2-b ] carbazole based blue fluorescent material and synthetic method thereof |
| CN115286562A (en) * | 2022-08-18 | 2022-11-04 | 青海大学 | Benzoylation method of aromatic heterocyclic or aromatic amine compound containing rich electrons |
| CN115286562B (en) * | 2022-08-18 | 2024-02-23 | 青海大学 | Method for benzoylating aromatic heterocyclic or aromatic amine compound containing rich electron |
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Application publication date: 20121003 |