CN101412691A - Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof - Google Patents
Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof Download PDFInfo
- Publication number
- CN101412691A CN101412691A CNA2008100798459A CN200810079845A CN101412691A CN 101412691 A CN101412691 A CN 101412691A CN A2008100798459 A CNA2008100798459 A CN A2008100798459A CN 200810079845 A CN200810079845 A CN 200810079845A CN 101412691 A CN101412691 A CN 101412691A
- Authority
- CN
- China
- Prior art keywords
- carbazole
- alkyl
- phenyl
- hours
- diacetyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Indole Compounds (AREA)
Abstract
The invention provides a carbazyl dual-alpha, beta-unsaturated ketone compound, namely N-alkyl-3, 6-di(3'-phenyl-2'-propylene-1'-keto) carbazole. A method for preparing the compound comprises the following steps: reacting carbazole and NaOH with halohydrocarbon to obtain N-alkyl carbazole; reacting the N-alkyl carbazole and acetyl chloride with anhydrous AlCl3 to obtain 3, 6-diacetyl-N-alkyl carbazole; and reacting the 3, 6-diacetyl-N-alkyl carbazole with benzaldehyde to obtain the N-alkyl-3, 6-di(3'-phenyl-2'-propylene-1'-keto) carbazole. The preparation method has the advantages of simple and feasible operation, high product yield and high purity. The prepared compound has good thermal stability and long fluorescence emission wavelength so that the compound can be used as photoluminescence and electroluminescence organic luminescent material for emitting blue light.
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 carbazole derivative, the two alpha, beta-unsaturated ketone compounds of a kind of carbazyl and preparation method thereof of more specifically saying so.
Two, background technology
Enter 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 compound, selecting suitable electron donor-acceptor (EDA) and conjugated bridge and carry out various molecules and assemble the character of optimizing molecule, is efficient ways.Current or even from now on for a long time in, start with from the design of compound molecule, the luminescent material of synthesizing new becomes numerous investigators' research focus.
Carbazole and derivative thereof are the raw materials of synthesizing new photoelectric material, have caused people's attention.Since the IBM Corporation of the U.S. in 1970 used the carbazoles derivative as organic light-guide material at first in duplicating machine, the scientific research personage of countries in the world had produced keen interest to carbazole and derivative thereof.Because the carbazole molecule has rigidity conjugate planes well, the characteristic that has bigger π-electron conjugated system and stronger intramolecularly transfer transport in carbazole and the derivative molecular thereof, therefore carbazole and derivative thereof have good photoelectric property, carbazole and derivative thereof have broad application prospects at aspects such as organic electroluminescent light, electroluminescent, nonlinear optical material and LB films, are widely used as good optical material.With the carbazole is that parent carries out molecular designing, and design, synthetic carbazole derivative with photoelectric functional are one of the research focuses in photoelectric functional material field always, and many carbazole derivative with good photoelectric properties are furtherd investigate and Application and Development.Common molecular designing is the carbazole nitrogen-atoms to be linked to each other with conjugated bridge form D-π-A type molecule.At present, document Guan Bai etc., Dyes and Pigments, 75 (2007), 93-98 has reported that N-alkyl carbazole carries out the synthetic carbazyl list alpha, beta-unsaturated ketone compound of molecular modification.This compound conjugated degree is little, and the fluorescent emission wavelength is short.
Three, summary of the invention
The purpose of this invention is to provide the two alpha, beta-unsaturated ketone compounds of a kind of carbazyl, this compounds Heat stability is good, the fluorescent emission wavelength is long, and photic, the electricity that can be used as blue light-emitting cause luminous organic material; Its preparation method row simple to operate, easy, product yield and purity height.
The two alpha, beta-unsaturated ketone compounds of a kind of carbazyl provided by the invention are N-alkyl-3,6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole, its molecular structural formula is:
In the formula: R is methyl, ethyl, propyl group, normal-butyl or phenyl.
The preparation method of the two alpha, beta-unsaturated ketone compounds of a kind of carbazyl provided by the invention comprises the steps:
(1), carbazole, NaOH and halohydrocarbon are got in 1:4～6:1.1～1.5 in molar ratio, earlier carbazole and NaOH are refluxed in acetone 2～6 hours, halohydrocarbon are added to continue in the acetone to reflux 10～24 hours again, separate, and obtain N-alkyl carbazole;
(2), N-alkyl carbazole, Acetyl Chloride 98Min. and anhydrous AlCl are got in 1:2～4:2～4 in molar ratio
3, at ClCH
2CH
2Cl or CH
2Cl
2Reacted 16～24 hours under the middle room temperature, separate, obtain 3,6-diacetyl-N-alkyl carbazole;
(3), with obtain in the step (2) 3,6-diacetyl-N-alkyl carbazole and dehydrated alcohol be with the mixed of 1mol:2.5～3.5L, stirs; Under ice-water bath, in mixed solution, drip the sodium ethylate-ethanolic soln (1mol sodium is dissolved in the refining dehydrated alcohol of 200ml and makes) of new system, mix; Then drip the new phenyl aldehyde that steams, stir, the control rate of addition makes temperature of reaction below 5 ℃; dropwised insulation reaction 6～8 hours; at room temperature reacted again 12～24 hours, and stopped to stir, reaction solution is poured in the frozen water; fully stir the back suction filtration; promptly get N-alkyl-3,6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole, wherein; 3, the mol ratio of 6-diacetyl-N-alkyl carbazole, sodium ethylate and phenyl aldehyde is 1:2～2.6:2～2.4.Reaction formula following (R is example with the ethyl):
Advantage of the present invention:
1, the present invention has synthesized the two alpha, beta-unsaturated ketone compound N-alkyl-3 of a kind of new carbazyl from having the active carbazole of photoelectric functional, 6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole; This material Heat stability is good, the fluorescent emission wavelength is long, can be used as organic photic, the electroluminescent material of blue light-emitting.
2, the invention provides the synthetic method of the two alpha, beta-unsaturated ketone compounds of carbazyl, this method productive rate and purity height, simple to operate, easy row.
Four, description of drawings
Fig. 1 is a synthetic N-ethyl-3 of the present invention, 6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) infrared absorpting light spectra of carbazole;
Fig. 2 is a synthetic N-ethyl-3 of the present invention, 6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) the hydrogen nuclear magnetic resonance spectrogram of carbazole;
Fig. 3 is a synthetic N-ethyl-3 of the present invention, 6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) uv absorption spectra of carbazole;
Fig. 4 is a synthetic N-ethyl-3 of the present invention, 6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) the photoluminescence collection of illustrative plates of carbazole.
Five, embodiment
(1), synthetic N-ethyl carbazole
16.700g (0.1mol) carbazole, 24.000g (0.6mol) NaOH are put into the 250ml round-bottomed flask, add 150ml acetone, stir also heating, make that reaction mixture refluxes in the bottle; Refluxing stops heating after 6 hours, question response liquid recovers to add 11.2ml (0.15mol) monobromethane after the room temperature, continuation reflux stopped reaction after 24 hours; Acetone is steamed as far as possible, then surplus materials is poured in the mixture of ice and water, vigorous stirring has a large amount of yellow solids to separate out; Be stirred to ice cube and melt entirely, mixed solution is put in the refrigerator refrigerates to behind the water; Suction filtration gets yellow thick product 17.358g afterwards; Use the dehydrated alcohol recrystallization, obtain white products 16.846g, yield is 86.4%, and m.p. is 68～70 ℃.
(2), synthesize 3,6-diacetyl-N-ethyl carbazole
Add the anhydrous AlCl of 26.700g (0.2mol) to being furnished with stirrer and being connected with in the 500ml round-bottomed flask of nitrogen
3With 225ml ClCH
2CH
2Cl starts stirring and makes AlCl
3Dissolving with the ice-water bath cooling, drips 14.2ml (0.2mol) Acetyl Chloride 98Min. with constant pressure funnel then, continues to be stirred to AlCl after dripping off
3Dissolving fully becomes transparent and homogeneous solution; Be furnished with stirrer and be connected with in the 250ml round-bottomed flask of nitrogen at another and add 9.750g (0.05mol) N-ethyl carbazole, use 75ml ClCH
2CH
2Cl dissolves it, cooling; Again with the ClCH of N-ethyl carbazole
2CH
2Cl transfers in the constant pressure funnel, dropwise splashes in the previous reaction flask, cools off with ice-water bath during dropping, dropwises in 1 hour, and insulation reaction is 6 hours afterwards, returns to room temperature reaction again 24 hours; Reaction is poured reaction solution in the mixture of ice (100g), water (100ml) and 30ml concentrated hydrochloric acid into after finishing, and vigorous stirring has a large amount of solids to separate out; After treating ice-out, add ClCH
2CH
2Cl all dissolves solid, separatory, uses ClCH
2CH
2The Cl extraction merges organic phase, adds anhydrous MgSO
4Dried overnight, suction filtration steams ClCH
2CH
2Cl drains after residuum washes with water, obtains yellow solid, gets faint yellow solid 12.134g with the dehydrated alcohol recrystallization, and yield is 87.0%, and m.p. is 180～182 ℃.
(3), synthetic N-ethyl-3,6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole
Add 2.790g (0.01mol) 3 in the round-bottomed flask of 100ml, 6-diacetyl-N-ethyl carbazole and 30.0ml make with extra care dehydrated alcohol, mix; In another 50ml round-bottomed flask, add the sodium piece that refining dehydrated alcohol of 5.2ml and 0.598g (0.026mol) newly cut, treat after the completely dissolve of sodium piece the solution cooling and be added drop-wise to 3, in 6-diacetyl-N-ethyl carbazole and the alcoholic acid mixed solution, use the ice-water bath control reaction temperature about 0 ℃; The mixing solutions that drips 2.4ml (0.024mol) phenyl aldehyde and 10.0ml dehydrated alcohol with constant pressure funnel is in above-mentioned round-bottomed flask, and temperature still remains in 5 ℃ in the dropping process; Dropwised insulation reaction 6 hours, room temperature reaction finishes reaction after 24 hours more afterwards; Reaction solution is poured in the 200ml frozen water, stirred hydrolysis, hydrolysis fully back suction filtration gets the glassy yellow solid, with draining after the washing with alcohol, gets yellow solid 3.772g, and yield is 82.9%.M.p. be 156～158 ℃.
1H?NMR(CDCl
3)δ：1.454(3H，-CH
3)，4.353(2H，-CH
2-)，7.412～8.848(16H，Ph)，7.849(2H，-COH＝)，8.213(2H，＝CH-Ph)。IR(KBr)cm
-1：1656(-CO-)。
Claims (2)
1, the two alpha, beta-unsaturated ketone compounds of a kind of carbazyl, feature is a N-alkyl-3,6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole, its molecular structural formula is:
In the formula: R is methyl, ethyl, propyl group, normal-butyl or phenyl.
2, the preparation method of the two alpha, beta-unsaturated ketone compounds of a kind of carbazyl as claimed in claim 1 is characterized in that, comprises the steps:
(1), 1: 4 in molar ratio～6: 1.1～1.5 get carbazole, NaOH and halohydrocarbon, earlier carbazole and NaOH were refluxed in acetone 2～6 hours, halohydrocarbon is added continue in the acetone to reflux 10～24 hours again, separation obtains N-alkyl carbazole;
(2), 1: 2 in molar ratio～4: 2～4 get N-alkyl carbazole, Acetyl Chloride 98Min. and anhydrous AlCl
3, at ClCH
2CH
2Cl or CH
2Cl
2Reacted 16～24 hours under the middle room temperature, separate, obtain 3,6-diacetyl-N-alkyl carbazole;
(3), with obtain in the step (2) 3,6-diacetyl-N-alkyl carbazole and dehydrated alcohol be with the mixed of 1mol:2.5～3.5L, stirs; Under ice-water bath, in mixed solution, drip the sodium ethylate-ethanolic soln of new system, mix; Then drip the new phenyl aldehyde that steams, stir, the control rate of addition makes temperature of reaction below 5 ℃; dropwised insulation reaction 6～8 hours; at room temperature reacted again 12～24 hours, and stopped to stir, reaction solution is poured in the frozen water; fully stir the back suction filtration; promptly get N-alkyl-3,6-two (3 '-phenyl-2 '-propylene-1 '-ketone group) carbazole, wherein; 3, the mol ratio of 6-diacetyl-N-alkyl carbazole, sodium ethylate and phenyl aldehyde is 1: 2～2.6: 2～2.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100798459A CN101412691A (en) | 2008-11-14 | 2008-11-14 | Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100798459A CN101412691A (en) | 2008-11-14 | 2008-11-14 | Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101412691A true CN101412691A (en) | 2009-04-22 |
Family
ID=40593460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100798459A Pending CN101412691A (en) | 2008-11-14 | 2008-11-14 | Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101412691A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106083694A (en) * | 2016-05-30 | 2016-11-09 | 山西大学 | A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof |
| CN109956935A (en) * | 2019-04-03 | 2019-07-02 | 北京化工大学 | A kind of one-component long wavelength light initiator and preparation method thereof |
| CN110003089A (en) * | 2019-03-04 | 2019-07-12 | 陕西科技大学 | A kind of 3- methylol -9- substituted carbazole and preparation method thereof |
-
2008
- 2008-11-14 CN CNA2008100798459A patent/CN101412691A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106083694A (en) * | 2016-05-30 | 2016-11-09 | 山西大学 | A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof |
| CN110003089A (en) * | 2019-03-04 | 2019-07-12 | 陕西科技大学 | A kind of 3- methylol -9- substituted carbazole and preparation method thereof |
| CN110003089B (en) * | 2019-03-04 | 2022-07-01 | 陕西科技大学 | 3-hydroxymethyl-9-substituted carbazole and preparation method thereof |
| CN109956935A (en) * | 2019-04-03 | 2019-07-02 | 北京化工大学 | A kind of one-component long wavelength light initiator and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104498025B (en) | Many phenyl benzene constructs cyano-containing light emitting molecule and its production and use | |
| CN102229623B (en) | Spirofluorene xanthene phosphine oxide electro-phosphorescent main materials and synthesis and application methods thereof | |
| CN106318380B (en) | A kind of tetraphenylethylene derivative ionic complex and preparation method | |
| CN104557856A (en) | Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide | |
| CN106588869A (en) | Dialkyl-substituted naphtho-dioxodibenzothiophene monomer and preparation method thereof and polymer containing dialkyl-substituted naphtho-dioxodibenzothiophene unit and application of polymer | |
| CN101412691A (en) | Carbazolyl bis(alpha, beta)-unsaturated ketones and preparation thereof | |
| CN101209988B (en) | Phenanthrene series derivatives and organic light-emitting diode containing the same | |
| CN102443004A (en) | Organic luminescent material 6,7,14,15-tetrahydro-5,13-disubstituted benzene [1,2-c:4,5-c']bis-acridine compound, its synthesis method and its application | |
| CN111620817A (en) | Novel blue thermal activity delayed fluorescent material and application thereof | |
| CN111825634A (en) | Novel compounds, process for their preparation and their use | |
| CN112876406A (en) | Deuterated carbazole compound, preparation method thereof, photoelectric material and medicine | |
| CN103539737B (en) | A kind of azepine phenanthro- fluorene kind derivative, preparation method and electroluminescent fluorescent luminescent device | |
| CN109879870B (en) | Synthesis and application of novel functional material based on benzothiadiazole | |
| CN100494144C (en) | Chemical synthesis process for hypericin and derivatives thereof | |
| CN102491936A (en) | Conjugated compound with yellow-green fluorescence and preparation method and use thereof | |
| CN111848676B (en) | Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof | |
| CN101481611B (en) | Novel organic luminescent material containing p-carbazole cinnamenyl structure, as well as synthesizing method and use thereof | |
| CN105505379A (en) | Long-wavelength BODIPY fluorescent dye derivative and preparation method thereof | |
| CN112851701A (en) | Anthracene-based mechanoluminescence organic material and preparation method and application thereof | |
| CN109776768A (en) | A kind of blue light conjugated polymer and the preparation method and application thereof based on triphenylamine and sulphur dibenzofuran unit | |
| CN116102492A (en) | Blue light organic luminescent molecule with ortho-steric hindrance induced torsion structure | |
| CN111087323B (en) | Tetracyanoanthraquinone-dimethane small molecule acceptor material, and preparation method and application thereof | |
| CN113024591A (en) | Aggregation-induced emission molecular compound, preparation method and application | |
| CN111574538A (en) | D-A type near-infrared organic luminescent material and preparation method and application thereof | |
| CN112538097B (en) | Metal organic complex, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090422 |