CN103232383A - N-perfluoro-butylethylcarbazole and preparation method thereof - Google Patents
N-perfluoro-butylethylcarbazole and preparation method thereof Download PDFInfo
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- CN103232383A CN103232383A CN2013101412748A CN201310141274A CN103232383A CN 103232383 A CN103232383 A CN 103232383A CN 2013101412748 A CN2013101412748 A CN 2013101412748A CN 201310141274 A CN201310141274 A CN 201310141274A CN 103232383 A CN103232383 A CN 103232383A
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Abstract
The invention belongs to the field of organic micromolecule materials, and particularly relates to N-perfluoro-butylethylcarbazole of which the structural formula is disclosed in the specification. According to the invention, carbazole and perfluoroalkyl iodine used as raw materials are subjected to alkylation reaction under the catalytic action of triethylamine to obtain the N-perfluoro-butylethylcarbazole. The invention has the advantages of simple preparation method and accessible raw materials. Meanwhile, by utilizing the speciality of the fluorine atoms, the prepared N-perfluoro-butylethylcarbazole has favorable application prospects, and can be prepared into photoelectric materials and the like with favorable water resistance with organic micromolecules, polymers and the like.
Description
Technical field
The invention belongs to the organic small molecule material field, be specifically related to N-perfluoro butyl ethyl carbazole and preparation method thereof.
Background technology
Along with the develop rapidly of science and technology, people are more and more higher to the performance requriements of material, particularly high performance photoelectric material.
Fluorine atom is the element of electronegativity maximum, has lower polarizability, because fluorine atom is stronger to the constraint ability of its extranuclear electron, the C-F bond polarization is low, therefore has special surface property, is embodied in excellent water tolerance, oil-proofness etc.
Carbazole and derivative thereof so have good optical performance and thermal property, are a kind of superior hole mobile material because have bigger πDian Zi conjugated system and rigid planar structure and stronger intramolecularly transfer transport characteristic.At present, though carbazole and derivative thereof have potential application prospect at aspects such as electroluminescent, photoluminescence and nonlinear optical materials, all very poor by organic molecule or water tolerance, the oil-proofness of polymer luminescent material of their preparations.
In sum, how to overcome the deficiencies in the prior art, preparing the carbazole compound with good water resistance energy is the technical problem that the organic small molecule material field needs to be resolved hurrily.
Summary of the invention
Purpose of the present invention is exactly in order to solve deficiency of the prior art, and N-perfluoro butyl ethyl carbazole and preparation method thereof is provided, and this compounds does not have report as yet at present.
The technical solution used in the present invention is as follows:
N-perfluoro butyl ethyl carbazole of the present invention is characterized in that chemical structural formula is:
The preparation method of N-perfluoro butyl ethyl carbazole of the present invention, its synthetic route is:
May further comprise the steps:
The first step reaction: add toluene, carbazole, perfluoro butyl iodoethane successively in reaction flask, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains with organic phase drying, vacuum concentration, recrystallization wherein, gets N-Polyfluoroalkyl carbazole with ethyl acetate dilution and washing.
In preparation method's the first step of described N-perfluoro butyl ethyl carbazole, the mol ratio of carbazole, perfluoro butyl iodoethane, triethylamine, toluene is 1:1.0 ~ 1.5:0.7 ~ 1.0:15 ~ 29, and the isothermal reaction temperature is 80 ~ 120 ℃, and the isothermal reaction time is 18 ~ 72h.
The preparation method of described N-perfluoro butyl ethyl carbazole is in second step, and the consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume.
Preparation principle of the present invention: be raw material with carbazole and Polyfluoroalkyl iodine, under the catalysis of triethylamine, by alkylated reaction, obtain N-perfluoro butyl ethyl carbazole.
The present invention has the following advantages: (1) the present invention has utilized the singularity of fluorine atom, makes the present invention make N-perfluoro butyl ethyl carbazole and has a good application prospect, and can make the good photoelectric material of water tolerance with resin, polymkeric substance etc.; (2) preparation method of N-perfluoro butyl ethyl carbazole of the present invention is simple, and raw material is easy to get; (3) application range of products of the present invention is comparatively extensive, not only can be for the synthesis of photoelectric material, and can also be as medicine intermediate etc.
Specific embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The preparation method of the N-perfluoro butyl ethyl carbazole that the present invention proposes may further comprise the steps:
The first step reaction: add toluene, carbazole, perfluoro butyl iodoethane successively in reaction flask, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains with organic phase drying, vacuum concentration, recrystallization wherein, gets N-Polyfluoroalkyl carbazole with ethyl acetate dilution and washing.
Preparation method's of the present invention further preferred bill is: the mol ratio of carbazole, perfluoro butyl iodoethane, triethylamine, toluene is 1:1.0 ~ 1.5:0.7 ~ 1.0:15 ~ 29 in the first step, the isothermal reaction temperature is 80 ~ 120 ℃, and the isothermal reaction time is 18 ~ 72h; The consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume in second step.
Embodiment 1
The first step reaction: add 10 mL toluene, 5 mmol carbazoles, 5 mmol perfluoro butyl iodoethanes successively in reaction flask, stir, add 3.5 mmol triethylamines again in reaction flask, the back is cooled to room temperature in 80 ℃ of reaction 24h, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains is with the dilution of 20 mL ethyl acetate and wash (3 * 20 mL), and the organic phase that obtains is through anhydrous Na SO
4Drying, vacuum concentration, recrystallization (ethyl acetate/normal hexane=1/20) get N-perfluoro butyl ethyl carbazole, and white powder, yield are 45%;
1H NMR (500 MHz, Acetone-d
6 ), δ: 2.98 ~ 3.06 (m, 2H), 4.63 (t, 2H, J=5 Hz), 7.23 ~ 8.10 (m, 8H).
19F?NMR(470?MHz，Acetone-d
6 )，δ：-80.6?(bs，3F)，-113.6?(bs，4F)，-124.1?(bs，2F)，-125.8?(bs，2F)。
Embodiment 2
The first step reaction: add 8 mL toluene, 5 mmol carbazoles, 7.5 mmol perfluoro butyl iodoethanes successively in reaction flask, stir, add 5 mmol triethylamines again in reaction flask, the back is cooled to room temperature in 90 ℃ of reaction 72h, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains is with the dilution of 24 mL ethyl acetate and wash (3 * 20 mL), and the organic phase that obtains is through anhydrous Na SO
4Drying, vacuum concentration, recrystallization (ethyl acetate/normal hexane=1/20) get N-perfluoro butyl ethyl carbazole, and white powder, yield are 47%.
Embodiment 3
The first step reaction: add 12 mL toluene, 5 mmol carbazoles, 6 mmol perfluoro butyl iodoethanes successively in reaction flask, stir, add 4 mmol triethylamines again in reaction flask, the back is cooled to room temperature in 100 ℃ of reaction 36h, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains is with the dilution of 30 mL ethyl acetate and wash (3 * 20 mL), and the organic phase that obtains is through anhydrous Na SO
4Drying, vacuum concentration, recrystallization (ethyl acetate/normal hexane=1/18) get N-perfluoro butyl ethyl carbazole, and white powder, yield are 47%.
Embodiment 4
The first step reaction: add 15 mL toluene, 5 mmol carbazoles, 6.5 mmol perfluoro butyl iodoethanes successively in reaction flask, stir, add 4.5 mmol triethylamines again in reaction flask, the back is cooled to room temperature in 110 ℃ of reaction 18h, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains is with the dilution of 35 mL ethyl acetate and wash (3 * 25 mL), and the organic phase that obtains is through anhydrous Na SO
4Drying, vacuum concentration, recrystallization (ethyl acetate/normal hexane=1/18) get N-perfluoro butyl ethyl carbazole, and white powder, yield are 46%.
Embodiment 5
The first step reaction: add 10 mL toluene, 5 mmol carbazoles, 7 mmol perfluoro butyl iodoethanes successively in reaction flask, stir, add 4 mmol triethylamines again in reaction flask, the back is cooled to room temperature in 120 ℃ of reaction 48h, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains is with the dilution of 25 mL ethyl acetate and wash (3 * 20 mL), and the organic phase that obtains is through anhydrous Na SO
4Drying, vacuum concentration, recrystallization (ethyl acetate/normal hexane=1/20) get N-perfluoro butyl ethyl carbazole, and white powder, yield are 44%.
Claims (4)
1. N-perfluoro butyl ethyl carbazole shown in formula I,
Formula I.
2. as the preparation method of formula I N-perfluoro butyl ethyl carbazole, it is characterized in that may further comprise the steps:
The first step reaction: add toluene, carbazole, perfluoro butyl iodoethane successively in reaction flask, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, obtains reaction solution;
The second step aftertreatment: the reaction solution that obtains with organic phase drying, vacuum concentration, recrystallization wherein, gets N-Polyfluoroalkyl carbazole with ethyl acetate dilution and washing.
3. the preparation method of N-perfluoro butyl ethyl carbazole according to claim 2, it is characterized in that: the mol ratio of carbazole, perfluoro butyl iodoethane, triethylamine, toluene is 1:1.0 ~ 1.5:0.7 ~ 1.0:15 ~ 29 in the first step, the isothermal reaction temperature is 80 ~ 120 ℃, and the isothermal reaction time is 18 ~ 72h.
4. the preparation method of N-perfluoro butyl ethyl carbazole according to claim 2 is characterized in that: the consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume in second step.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230788A (en) * | 2014-09-23 | 2014-12-24 | 苏州圣谱拉新材料科技有限公司 | N-perfluorinated octyl ethyl carbazole and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701111A (en) * | 2002-03-22 | 2005-11-23 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| CN101454695A (en) * | 2006-05-31 | 2009-06-10 | 光学转变公司 | Photochromic materials comprising haloalkyl groups |
| JP2011006560A (en) * | 2009-06-24 | 2011-01-13 | Fujifilm Corp | Pigment compound, photoelectric conversion element and pigment sensitized solar battery, using the same |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701111A (en) * | 2002-03-22 | 2005-11-23 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| CN101454695A (en) * | 2006-05-31 | 2009-06-10 | 光学转变公司 | Photochromic materials comprising haloalkyl groups |
| JP2011006560A (en) * | 2009-06-24 | 2011-01-13 | Fujifilm Corp | Pigment compound, photoelectric conversion element and pigment sensitized solar battery, using the same |
Non-Patent Citations (2)
| Title |
|---|
| DOMINIK K. KÖLMEL: "Rhodamine F: a novel class of fluorous ponytailed dyes for bioconjugation", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| 刘贵军等: "磷光配体3-[4-(2-吡啶基)苯基]-9-(4-氟苯基)-9H-咔唑的合成", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230788A (en) * | 2014-09-23 | 2014-12-24 | 苏州圣谱拉新材料科技有限公司 | N-perfluorinated octyl ethyl carbazole and preparation method thereof |
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Application publication date: 20130807 |