CN104211634A - Synthetic method of 2-bromocarbazole - Google Patents
Synthetic method of 2-bromocarbazole Download PDFInfo
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- CN104211634A CN104211634A CN201410364546.5A CN201410364546A CN104211634A CN 104211634 A CN104211634 A CN 104211634A CN 201410364546 A CN201410364546 A CN 201410364546A CN 104211634 A CN104211634 A CN 104211634A
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- concentration
- ethyl acetate
- synthetic method
- bromo
- sodium sulfate
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- 0 *c(cc1)ccc1Br Chemical compound *c(cc1)ccc1Br 0.000 description 1
- MOIVJBOCTHTHON-UHFFFAOYSA-N C=[Br]c(cc1)ccc1-c1ccccc1[N+]([O-])=O Chemical compound C=[Br]c(cc1)ccc1-c1ccccc1[N+]([O-])=O MOIVJBOCTHTHON-UHFFFAOYSA-N 0.000 description 1
- PWJYOTPKLOICJK-UHFFFAOYSA-N Cc1ccc(c2ccccc2[nH]2)c2c1 Chemical compound Cc1ccc(c2ccccc2[nH]2)c2c1 PWJYOTPKLOICJK-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N Clc1ccccc1Cl Chemical compound Clc1ccccc1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N [O-][N+](c1ccccc1I)=O Chemical compound [O-][N+](c1ccccc1I)=O JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
Abstract
The invention discloses a synthetic method of 2-bromocarbazole. The synthetic method includes following steps: adding o-iodonitrobenzene, 4-bromophenylboronic acid and potassium carbonate to a DME/water solution with degasification; adding Pd(PPh3)4 with protection of nitrogen for carrying out a reaction; performing reflux; decrease the temperature to room temperature; performing phase separation to obtain an organic phase; drying the organic phase with anhydrous sodium sulfate and performing vacuum distillation to obtain a yellow oily substance; quickly passing the yellow oily substance through a silica column with ethyl acetate/hexane for separating 4-bromo-2-nitrylbiphenyl; heating and stirring the 4-bromo-2-nitrylbiphenyl, triethyl phosphate and o-dichlorobenzene with protection of nitrogen; performing pressure-reducing desolvation until no liquid is evaporated out; adding ethyl acetate and water for carrying out washing and extraction; performing a drying process with anhydrous sodium sulfate; performing a filtering process; performing a rotating-distillation process in vacuum to the filtrate; and quickly passing a crude product through silica gel to obtain the gray-white solid 2-bromocarbazole. In the invention, the 4-bromo-2-nitrylbiphenyl is firstly separated out and then the 2-bromocarbazole is synthesized. The synthetic method is easy and available, and is free of problems of high energy consumption, low yield and generation of waste gas, waste liquid and waste solid.
Description
Technical field
The invention belongs to organic chemical synthesis field, relate to a kind of synthetic method of bromine carbazole, be specifically related to a kind of synthetic method of 2-bromine carbazole.
Background technology
Carbazole (having another name called dibenzopyrrole) is a kind of nitrogen-containing heterocycle compound, is naturally present in coal-tar heavy oil, is one of composition that in coal tar, economic worth is the highest.The numerous areas such as dyestuff, pigment, plastics, agricultural chemicals can be widely used in, especially be used to manufacture para-dye and high-grade pigment dyestuff, there is advantage that is high temperature resistant, ultraviolet resistance.Recent domestic to the investigation and application of carbazole and derivative thereof further deeply, also swashs sharp increase to the demand of carbazole and derivative thereof and adds.
Up to the present, domestic and international Jin Youjijia enterprise can produce carbazole, and its method is all be separated to obtain from tar cuts.Although carbazole is present in coal tar, shared content is not very little yet, but along with dyestuff, pigment, plastics industry etc. added the sharp sharp increase of carbazole demand in recent years, this ancient production method because its process for refining is complicated, consume energy that carbazole purity that is high, that produce is low, three-waste pollution is serious, and tar stock is limited, be difficult to meet the demand of growing domestic and international market to carbazole, thus low cost chemosynthesis carbazole and derivative thereof are imperative, and more valuable and future.
Summary of the invention
The present invention is directed to the operational requirement condition existed in the production method of traditional carbazole and derivative thereof high, complex manufacturing technology, consume energy high, the problem such as yield is low and three-waste pollution is serious, provides a kind of synthetic method of 2-bromine carbazole.The method first isolates the bromo-2 nitro biphenyl of 4-, resynthesis 2-bromine carbazole, synthesis technique simple possible, avoids the problems such as power consumption carbazole purity that is high, that produce in traditional method is low, three-waste pollution is serious.
For achieving the above object, the synthetic route of 2-bromine carbazole of the present invention is:
The 2-bromine carbazole that the present invention relates to building-up process comprise the following steps:
(1) take 9.42g concentration 37.84mmol/L o-iodonitrobenzene respectively, 7.6g concentration 37.84mmol/L 4-bromobenzeneboronic acid, 21g concentration is 151.36mmol/L salt of wormwood, together joins 190mLDME/ water
(2) by 437mg concentration be 0.38mmol/L Pd (PPh under nitrogen protection
3)
4add in reaction flask, and reflux 6 hours;
(3) 20-25 DEG C is cooled to, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 65-70 DEG C;
(4) use 5% ethyl acetate/hexane quickly through silicagel column the yellow oil obtained, finally isolate the bromo-2 nitro biphenyl of 4-that 9.8g concentration is 35.4mmol/L;
(5) in reaction flask, add the bromo-2 nitro biphenyl of 4-, 30mL triethyl-phosphite and 120ml orthodichlorobenzene that 9.8 concentration are g, 35.4mmol/L, be heated to 150-160 DEG C under nitrogen protection, and stirring reaction 15-25 hour;
(6) reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting;
(7) the organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained, quickly through silicagel column, obtains 4.1g pale solid, and yield is 47.3%.
According to claim 1, a synthetic method for 2-bromine carbazole, is characterized in that: the ratio of the volume of the DME/ aqueous solution used is 3: 2.
The described moving phase crossing silicagel column is that 15% ~ 30% ethyl acetate/hexane forms by mass content.
Gordian technique of the present invention is first to take o-iodonitrobenzene, 4-bromobenzeneboronic acid, salt of wormwood to add in the DME/ aqueous solution and degassed, add Pd (PPh3) 4 under nitrogen protection to react, reflux, be down to room temperature, phase-splitting obtains organic phase anhydrous sodium sulfate drying and vacuum distilling, and gained yellow oil uses ethyl acetate/hexane quickly through silicagel column, isolates the bromo-2 nitro biphenyl of 4-; By bromo-for 4-2 nitro biphenyl, triethyl-phosphite and orthodichlorobenzene; heat under nitrogen protection, stir; decompression precipitation steams to absence of liquid, adds ethyl acetate and water carries out washing, extracting, and with anhydrous sodium sulfate drying; filter; filtrate revolves steaming under vacuo, and the crude product obtained, quickly through silica gel, obtains pale solid 2-bromine carbazole; avoid the complexity extracted from coal tar and the large problem of operation easier, and three-waste pollution environment can not be caused.
Beneficial effect of the present invention is:
(1) the present invention avoids tradition by problems such as equipment manufacture used in the method for Doak Tar Oil and synthesis technique complexity.
(2) result that power consumption is high, yield is low using coal tar to cause is avoided, more environment-friendly high-efficiency.
Embodiment:
First taking respectively 9.42g concentration is 37.84mmol/L o-iodonitrobenzene, 7.6g concentration 37.84mmol/L 4-bromobenzeneboronic acid, 21g concentration 151.36mmol/L salt of wormwood, together adds in 190mL DME/ water (3: 2) solution, and degassed 15-30 minute; Be 0.38mmol/L Pd (PPh under nitrogen protection by 437mg concentration
3)
4add in reaction flask, and reflux 6 hours; Be cooled to 20-25 DEG C, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 65-70 DEG C; The yellow oil obtained uses 15% ~ 30% ethyl acetate/hexane quickly through silicagel column, finally isolates the colorless oil that 9.8g concentration is the bromo-2 nitro biphenyl of 4-of 35.4mmol/L; In reaction flask, add the bromo-2 nitro biphenyl of 4-, 30mL triethyl-phosphite and 120ml orthodichlorobenzene that 9.8g concentration is 35.4mmol/L, be heated to 150-160 DEG C under nitrogen protection, and stir 15-25 hour; Reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting; The organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained, quickly through silica gel (15% ~ 30% ethyl acetate/hexane), obtains 4.1g pale solid, finally checks yield.
Embodiment 1
First taking respectively 9.42g concentration is 37.84mmol/L o-iodonitrobenzene, 7.6g concentration is 37.84mmol/L4-bromobenzeneboronic acid, 21g concentration is 151.36mmol/L salt of wormwood, together adds in 190mL DME/ water (3: 2) solution, and degassed 15 minutes; Be 0.38mmol Pd (PPh under nitrogen protection by 437mg concentration
3)
4add in reaction flask, and reflux 6 hours; Be cooled to 20 DEG C, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 65 DEG C; The yellow oil obtained uses 5% ethyl acetate/hexane quickly through silicagel column, finally isolates 9.8g concentration to be, the colorless oil of the bromo-2 nitro biphenyl of 4-of 35.4mmol; In reaction flask, adding 9.8g concentration is, the bromo-2 nitro biphenyl of 4-of 35.4mmol, 30mL triethyl-phosphite and 120ml orthodichlorobenzene, be heated to 150 DEG C under nitrogen protection, and stir 15 hours; Reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting; The organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained is quickly through silica gel (15% ~ 30% ethyl acetate/hexane), obtain 4.0g (16.55mmol) pale solid, yield is 47.1%.
Embodiment 2
First taking respectively 9.42g concentration is 37.84mmol/L o-iodonitrobenzene, and 7.6g concentration is 37.84mmol 4-bromobenzeneboronic acid, and 21g concentration is 151.36mmol salt of wormwood, together adds in 190mL DME/ water (3: 2) solution, and degassed 30 minutes; Be 0.38mmol Pd (PPh under nitrogen protection by 437mg concentration
3)
4add in reaction flask, and reflux 6 hours; Be cooled to 23 DEG C, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 68 DEG C; The yellow oil obtained uses 5% ethyl acetate/hexane quickly through silicagel column, finally isolates the colorless oil that 9.85g concentration is the bromo-2 nitro biphenyl of 4-of 35.5mmol; In reaction flask, add the bromo-2 nitro biphenyl of 4-, 30mL triethyl-phosphite and 120ml orthodichlorobenzene that 9.85g concentration is 35.4mmol, be heated to 155 DEG C under nitrogen protection, and stir 20 hours; Reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting; The organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained is quickly through silica gel (15% ~ 30% ethyl acetate/hexane), obtain 4.05g (16.60mmol) pale solid, yield is 47.2%.
Embodiment 3
First taking respectively 9.42g concentration is 37.84mmol o-iodonitrobenzene, 7.6g concentration is 37.84mmol/L 4-bromobenzeneboronic acid, 21g concentration is 151.36mmol/L salt of wormwood, together adds in 190mL DME/ water (3: 2) solution, and degassed 45 minutes; Be 0.38mmol Pd (PPh under nitrogen protection by 437mg concentration
3)
4add in reaction flask, and reflux 6 hours; Be cooled to 25 DEG C, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 70 DEG C; The yellow oil obtained uses 5% ethyl acetate/hexane quickly through silicagel column, finally isolates the colorless oil that 9.9g concentration is the 4 '-bromo-2 nitro biphenyl of 35.6mmol; In reaction flask, add the bromo-2 nitro biphenyl of 4-, 30mL triethyl-phosphite and 120ml orthodichlorobenzene that 9.9g concentration is 35.4mmol, be heated to 160 DEG C under nitrogen protection, and stir 25 hours; Reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting; The organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained is quickly through silica gel (15% ~ 30% ethyl acetate/hexane), obtain 4.1g (16.66mmol) pale solid, yield is 47.3%.
Claims (3)
1. a synthetic method for 2-bromine carbazole, is characterized in that:
(1) take 9.42g concentration 37.84mmol/L o-iodonitrobenzene respectively, 7.6g concentration 37.84mmol/L 4-bromobenzeneboronic acid, 21g concentration is 151.36mmol/L salt of wormwood, together joins in the 190mL DME/ aqueous solution;
(2) by 437mg concentration be 0.38mmol/L Pd (PPh under nitrogen protection
3)
4add in reaction flask, and reflux 6 hours;
(3) 20-25 DEG C is cooled to, phase-splitting, the upper organic phase salt water washing separated 1 time, then with anhydrous sodium sulfate drying and vacuum distilling at 65-70 DEG C;
(4) use 5% ethyl acetate/hexane quickly through silicagel column the yellow oil obtained, finally isolate the bromo-2 nitro biphenyl of 4-that 9.8g concentration is 35.4mmol/L;
(5) in reaction flask, add the bromo-2 nitro biphenyl of 4-, 30mL triethyl-phosphite and 120ml orthodichlorobenzene that 9.8 concentration are g, 35.4mmol/L, be heated to 150-160 DEG C under nitrogen protection, and stirring reaction 15-25 hour;
(6) reaction solution is carried out at 100 DEG C decompression precipitation to steam to absence of liquid, add ethyl acetate and water carries out washing, extracting;
(7) the organic phase anhydrous sodium sulfate drying obtained, filter, filtrate revolves steaming under vacuo, and the crude product obtained, quickly through silicagel column, obtains 4.1g pale solid, and yield is 47.3%.
2. the synthetic method of a kind of 2-bromine carbazole according to claim 1, is characterized in that: the ratio of the volume of the DME/ aqueous solution used is 3: 2.
3. the synthetic method of a kind of 2-bromine carbazole according to claim 1, is characterized in that: the described moving phase crossing silicagel column is that 15% ~ 30% ethyl acetate/hexane forms by mass content.
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| CN201410364546.5A CN104211634A (en) | 2014-07-23 | 2014-07-23 | Synthetic method of 2-bromocarbazole |
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| CN201410364546.5A CN104211634A (en) | 2014-07-23 | 2014-07-23 | Synthetic method of 2-bromocarbazole |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061296A (en) * | 2015-08-10 | 2015-11-18 | 张家港江苏科技大学产业技术研究院 | Preparation method for 2-substituted carbazole compounds |
| CN106117113A (en) * | 2016-07-02 | 2016-11-16 | 湘潭大学 | Polysubstituted carbazole, derivant and synthetic method thereof |
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| CN102924520A (en) * | 2012-10-31 | 2013-02-13 | 陕西科技大学 | Preparation method of blue phosphorescent host material having bipolar carrier transport performance |
| US20130168656A1 (en) * | 2012-01-03 | 2013-07-04 | Universal Display Corporation | Cyclometallated tetradentate platinum complexes |
| CN103703003A (en) * | 2011-06-09 | 2014-04-02 | 罗门哈斯电子材料韩国有限公司 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| WO2014109814A2 (en) * | 2012-10-26 | 2014-07-17 | Arizona Board Of Regents Acting For And On Behalf Of Arizona State University | Metal complexes, methods, and uses thereof |
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2014
- 2014-07-23 CN CN201410364546.5A patent/CN104211634A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103703003A (en) * | 2011-06-09 | 2014-04-02 | 罗门哈斯电子材料韩国有限公司 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| US20130168656A1 (en) * | 2012-01-03 | 2013-07-04 | Universal Display Corporation | Cyclometallated tetradentate platinum complexes |
| WO2014109814A2 (en) * | 2012-10-26 | 2014-07-17 | Arizona Board Of Regents Acting For And On Behalf Of Arizona State University | Metal complexes, methods, and uses thereof |
| CN102924520A (en) * | 2012-10-31 | 2013-02-13 | 陕西科技大学 | Preparation method of blue phosphorescent host material having bipolar carrier transport performance |
Non-Patent Citations (2)
| Title |
|---|
| DRAHOMÍR VÝPRACHTICKÝ等: "New two-step synthesis of N-(2-ethylhexyl)-2,7-diiodocarbazole as a monomer for conjugated", 《DESIGNED MONOMERS AND POLYMERS》 * |
| MARTIN SONNTAG等: "Novel 2,7-Linked Carbazole Trimersas Model Compounds for Conjugated Carbazole Polymers", 《CHEM.MATER.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061296A (en) * | 2015-08-10 | 2015-11-18 | 张家港江苏科技大学产业技术研究院 | Preparation method for 2-substituted carbazole compounds |
| CN106117113A (en) * | 2016-07-02 | 2016-11-16 | 湘潭大学 | Polysubstituted carbazole, derivant and synthetic method thereof |
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Application publication date: 20141217 |