CN103232384A - 3,6-diiodo-9-perfluoro butyl ethyl carbazole and preparation method thereof - Google Patents
3,6-diiodo-9-perfluoro butyl ethyl carbazole and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic small molecular materials, and particularly relates to 3,6-diiodo-9-perfluoro butyl ethyl carbazole and a preparation method thereof. The structural formula is shown in the specification. According to the preparation method provided by the invention, carbazole is used as a raw material, 3,6-diiodocarbazole is obtained through iodination, and an alkylation reaction is performed between the 3,6-diiodocarbazole and the perfluoro butyl ethyl iodide to obtain the 3,6-diiodo-9-perfluoro butyl ethyl carbazole. The preparation method of 3,6-diiodo-9-perfluoro butyl ethyl carbazole, provided by the invention, is simple, and the raw material is easily available. By use of the specificity of the fluorine atom, the prepared 3,6-diiodo-9-perfluoro butyl ethyl carbazole can obtain excellent water resistance and oil resistance, has a good application prospect, can be used for preparing a photoelectric material with good water resistance, and also can be used as a medical intermediate and the like.
Description
Technical field
The invention belongs to the organic small molecule material field, be specifically related to 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles and preparation method thereof.
Background technology
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.Along with development of science and technology, people are more and more higher to the performance requriements of material, and the material of single performance can not satisfy people's demand far away.
Though carbazole and derivative thereof are used comparatively extensive at aspects such as electroluminescent, photoluminescence and nonlinear optical materials at present, but organic molecule or water tolerance, the oil-proofness of polymer luminescent material by their preparations are all relatively poor, therefore, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles and preparation method thereof are provided.
The technical solution used in the present invention is as follows:
Of the present invention 3,6-two iodo-9-perfluoro butyl ethyl carbazoles is characterized in that chemical structural formula is:
Of the present invention 3, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles, its synthetic route is:
May further comprise the steps:
The first step iodate: in reaction flask, add carbazole, Glacial acetic acid and KI successively, stir, be heated to constant temperature after, add KIO again
3, back isothermal reaction under uniform temp, stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol;
The second step alkylation: in reaction flask, add toluene, 3 successively, 6-diiodocarbazol, perfluoro butyl iodoethane, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, the reaction solution that obtains dilutes and washing with ethyl acetate, the organic phase drying, vacuum concentration, the recrystallization that obtain get 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles.
Described 3, in preparation method's the first step of 6-two iodo-9-perfluoro butyl ethyl carbazoles, carbazole, KI, KIO
3, Glacial acetic acid mol ratio be 1:1.0 ~ 1.5:1.0 ~ 1.5:52 ~ 87, thermostat temperature is 70 ~ 120 ℃, the isothermal reaction time is 6 ~ 24h.
Described 3, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles is in second step, 3, the mol ratio of 6-diiodocarbazol, perfluoro butyl iodoethane, triethylamine, toluene is 1:1.0 ~ 1.5:0.7 ~ 1.0:15 ~ 29, the isothermal reaction temperature is 80 ~ 120 ℃, the isothermal reaction time is 18 ~ 72h, and the consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume.
Preparation principle of the present invention: be raw material with the carbazole, earlier by iodate, obtain 3,6-diiodocarbazol, again with perfluoro butyl iodoethane generation alkylated reaction, obtain of the present invention 3,6-two iodo-9-perfluoro butyl ethyl carbazoles.
The present invention utilizes the singularity of fluorine atom, and namely 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.
The present invention has the following advantages: (1) the present invention has utilized the singularity of fluorine atom, makes the present invention make 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles and can have more excellent water tolerance, oil-proofness; (2) of the present invention 3, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles is simple, and raw material is easy to get; (3) product of the present invention has a good application prospect, and not only can make the good photoelectric material of water tolerance, can also be as medicine intermediate etc.
Specific embodiment
Below in conjunction with embodiment the present invention is described in further detail.
3 of the present invention's proposition, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles may further comprise the steps:
The first step iodate: in reaction flask, add carbazole, Glacial acetic acid and KI successively, stir, be heated to constant temperature after, add KIO again
3, back isothermal reaction under uniform temp, stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol;
The second step alkylation: in reaction flask, add toluene, 3 successively, 6-diiodocarbazol, perfluoro butyl iodoethane, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, the reaction solution that obtains dilutes and washing with ethyl acetate, the organic phase drying, vacuum concentration, the recrystallization that obtain get 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles.
Preparation method's of the present invention further preferred bill is: carbazole, KI, KIO in the first step
3, Glacial acetic acid mol ratio be 1:1.0 ~ 1.5:1.0 ~ 1.5:52 ~ 87, thermostat temperature is 70 ~ 120 ℃, the isothermal reaction time is 6 ~ 24h; In second step, the mol ratio of 3,6-diiodocarbazol, 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 ℃, the isothermal reaction time is 18 ~ 72h, and the consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume.
Embodiment 1
The first step iodate: in reaction flask, add 5 mmol carbazoles, 20mL Glacial acetic acid and 6 mmol KI successively, stir, be heated to 70 ℃ after, add 6 mmol KIO again
3, the back is at 70 ℃ of following isothermal reaction 12h, and stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol, and white powder, yield are 90%;
The second step alkylation: in reaction flask, add 10 mL toluene, 5 mmol 3 successively, 6-diiodocarbazol, 5 mmol perfluoro butyl iodoethanes, stir, in reaction flask, add 3.5 mmol triethylamines again, the back is in 80 ℃ of reaction 24h, be cooled to room temperature, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles, and white powder, yield are 50%.
1H?NMR?(500?MHz，Acetone-d
6 )，δ：2.98~3.05?(m，2H)，4.61?(t，2H，J=5?Hz)，7.15?(m，2H)，7.55?(m，2H)?，8.02?(m，2H)。
19F?NMR(470?MHz，Acetone-d
6 )，δ：-80.5?(bs，3F)，-113.5?(bs，4F)，-124.2?(bs，2F)，-125.9?(bs，2F)。
Embodiment 2
The first step iodate: in reaction flask, add 5 mmol carbazoles, 18mL Glacial acetic acid and 5 mmol KI successively, stir, be heated to 80 ℃ after, add 7.5 mmol KIO again
3, the back is at 80 ℃ of following isothermal reaction 15h, and stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol, and white powder, yield are 92%;
The second step alkylation: in reaction flask, add 8 mL toluene, 5 mmol 3 successively, 6-diiodocarbazol, 7.5 mmol perfluoro butyl iodoethanes, stir, in reaction flask, add 5 mmol triethylamines again, the back is in 90 ℃ of reaction 72h, be cooled to room temperature, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles, and white powder, yield are 52%.
Embodiment 3
The first step iodate: in reaction flask, add 5 mmol carbazoles, 15mL Glacial acetic acid and 6 mmol KI successively, stir, be heated to 95 ℃ after, add 7 mmol KIO again
3, the back is at 95 ℃ of following isothermal reaction 20h, and stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol,, white powder, yield are 90%;
The second step alkylation: in reaction flask, add 12 mL toluene, 5 mmol 3 successively, 6-diiodocarbazol, 6 mmol perfluoro butyl iodoethanes, stir, in reaction flask, add 4 mmol triethylamines again, the back is in 100 ℃ of reaction 36h, be cooled to room temperature, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles, and white powder, yield are 49%.
Embodiment 4
The first step iodate: in reaction flask, add 5 mmol carbazoles, 25mL Glacial acetic acid and 7.5 mmol KI successively, stir, be heated to 110 ℃ after, add 6 mmol KIO again
3, the back is at 110 ℃ of following isothermal reaction 24h, and stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol, and white powder, yield are 91%;
The second step alkylation: in reaction flask, add 15 mL toluene, 5 mmol 3 successively, 6-diiodocarbazol, 6.5 mmol perfluoro butyl iodoethanes, stir, in reaction flask, add 4.5 mmol triethylamines again, the back is in 110 ℃ of reaction 18h, be cooled to room temperature, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles, and white powder, yield are 50%.
Embodiment 5
The first step iodate: in reaction flask, add 5 mmol carbazoles, 25mL Glacial acetic acid and 7 mmol KI successively, stir, be heated to 120 ℃ after, add 7 mmol KIO again
3, the back is at 120 ℃ of following isothermal reaction 6h, and stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol, and white powder, yield are 92%;
The second step alkylation: in reaction flask, add 10 mL toluene, 5 mmol 3 successively, 6-diiodocarbazol, 7 mmol perfluoro butyl iodoethanes, stir, in reaction flask, add 4 mmol triethylamines again, the back is in 120 ℃ of reaction 48h, be cooled to room temperature, 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 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles, and white powder, yield are 51%.
Claims (4)
1. shown in formula I 3,6-two iodo-9-perfluoro butyl ethyl carbazoles,
Formula I.
2. shown in formula I 3, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles is characterized in that may further comprise the steps:
The first step iodate: in reaction flask, add carbazole, Glacial acetic acid and KI successively, stir, be heated to constant temperature after, add KIO again
3, back isothermal reaction under uniform temp, stopped reaction is poured reaction solution in the frozen water into, has solid to separate out, and suction filtration is used saturated NaHSO
3Washing, drying obtains 3,6-diiodocarbazol;
The second step alkylation: in reaction flask, add toluene, 3 successively, 6-diiodocarbazol, perfluoro butyl iodoethane, stir, add triethylamine again in reaction flask, back isothermal reaction is cooled to room temperature, the reaction solution that obtains dilutes and washing with ethyl acetate, the organic phase drying, vacuum concentration, the recrystallization that obtain get 3,6-, two iodo-9-perfluoro butyl ethyl carbazoles.
3. according to claim 23, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles is characterized in that: carbazole, KI, KIO in the first step
3, Glacial acetic acid mol ratio be 1:1.0 ~ 1.5:1.0 ~ 1.5:52 ~ 87, thermostat temperature is 70 ~ 120 ℃, the isothermal reaction time is 6 ~ 24h.
4. according to claim 23, the preparation method of 6-two iodo-9-perfluoro butyl ethyl carbazoles, it is characterized in that: second the step in 3, the mol ratio of 6-diiodocarbazol, perfluoro butyl iodoethane, triethylamine, toluene is 1:1.0 ~ 1.5:0.7 ~ 1.0:15 ~ 29, the isothermal reaction temperature is 80 ~ 120 ℃, the isothermal reaction time is 18 ~ 72h, and the consumption of ethyl acetate is 2 ~ 3 times of reaction solution volume.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230789A (en) * | 2014-09-18 | 2014-12-24 | 苏州圣谱拉新材料科技有限公司 | 3, 6-diiodo-9-perfluorooctyl ethyl carbazole and preparation method thereof |
| 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
- 2013-04-23 CN CN2013101412786A patent/CN103232384A/en not_active Withdrawn
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 |
|---|
| BONESI, SERGIO M. 等: "Synthesis and Isolation of Iodocarbazoles. Direct Iodination of Carbazoles by N-Iodosuccinimide and N-Iodosuccinimide-silica Gel System", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》, vol. 38, no. 1, 28 February 2001 (2001-02-28) * |
| 李笃信等: "3,6-双(二苯胺基)-9-乙基咔唑的合成", 《精细化工》, vol. 18, no. 05, 15 May 2001 (2001-05-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230789A (en) * | 2014-09-18 | 2014-12-24 | 苏州圣谱拉新材料科技有限公司 | 3, 6-diiodo-9-perfluorooctyl ethyl carbazole and preparation method thereof |
| 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 |