CN102295523A - Preparation method of 1, 6-dibromopyrene - Google Patents
Preparation method of 1, 6-dibromopyrene Download PDFInfo
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- CN102295523A CN102295523A CN201110207636XA CN201110207636A CN102295523A CN 102295523 A CN102295523 A CN 102295523A CN 201110207636X A CN201110207636X A CN 201110207636XA CN 201110207636 A CN201110207636 A CN 201110207636A CN 102295523 A CN102295523 A CN 102295523A
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- pyrene
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- dibromo
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- FOKTURHFJPODMT-UHFFFAOYSA-N C(C=C1)c2ccc3c4c2C1=CCc4ccc3 Chemical compound C(C=C1)c2ccc3c4c2C1=CCc4ccc3 FOKTURHFJPODMT-UHFFFAOYSA-N 0.000 description 1
- FEMQUQIIMLTPTR-UHFFFAOYSA-N CC(C)(C)c1cc(Oc2c(-c(c3c4c(C(O5)=O)cc(Oc6cc(C(C)(C)C)cc(C(C)(C)C)c6)c3-c3ccc6C(OC7=O)=O)ccc4C5=O)c3c6c7c2)cc(C(C)(C)C)c1 Chemical compound CC(C)(C)c1cc(Oc2c(-c(c3c4c(C(O5)=O)cc(Oc6cc(C(C)(C)C)cc(C(C)(C)C)c6)c3-c3ccc6C(OC7=O)=O)ccc4C5=O)c3c6c7c2)cc(C(C)(C)C)c1 FEMQUQIIMLTPTR-UHFFFAOYSA-N 0.000 description 1
- FOSTUVCZMYWPIG-UHFFFAOYSA-N CCCCCC#Cc1ccc2c3c1ccc(CC=C1C#CC)c3C1=CC2 Chemical compound CCCCCC#Cc1ccc2c3c1ccc(CC=C1C#CC)c3C1=CC2 FOSTUVCZMYWPIG-UHFFFAOYSA-N 0.000 description 1
- QTDJWTRVKLJWGA-UHFFFAOYSA-N C[BrH]c(c1ccc2CC=C3Br)ccc4c1c2C3=CC4 Chemical compound C[BrH]c(c1ccc2CC=C3Br)ccc4c1c2C3=CC4 QTDJWTRVKLJWGA-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a preparation method of 1, 6-dibromopyrene. The preparation method mainly employs pyrene as the raw material. Under the protection of nitrogen, bromine is added dropwisely into pyrene for a substitution reaction so as to synthesize 1, 6-dibromopyrene, which is then purified through recrystallization.
Description
Technical field
The present invention relates to the optical material preparation field, relate to 1 especially, the preparation method of 6-dibromo pyrene.
Background technology
Liquid crystal is that its state of aggregation both had been similar to crystal to a certain extent, and molecule is ordered arrangement, is similar to liquid again, and the organic compound of certain fluidity is arranged.Discotic liquid-crystalline molecules forms the super-molecule assembling body that column is piled up easily, because molecule has certain fluidity in liquid crystal state, make assembly have good textural defect self-repair function. the discotic liquid-crystalline molecules that therefore has specific aromatic conjugated structure can present higher conductive characteristic, effectively transmission charge has the potential using value of preparation photoelectric device.
The perylene diimides derivative is one of important discotic liquid-crystalline molecules of several classes.Though its application is subjected to the restriction of solubleness, this restriction can overcome by introducing the difference in functionality group, so it still has a good application prospect.1,6-dibromo pyrene is the important intermediate of He Cheng perylene diimides derivative host structure (PDI).Its synthetic route is as follows:
At present synthetic PDI adopts this route, so 1,6-dibromo pyrene is to have a good application prospect through intermediate.
Summary of the invention
Based on above-mentioned prior art, the purpose of this invention is to provide a kind of advantages of simplicity and high efficiency 1, the preparation method of 6-dibromo pyrene.The objective of the invention is to be achieved through the following technical solutions:
It is a kind of 1 that embodiment of the present invention provides, and the preparation method of 6-dibromo pyrene comprises:
A, in room temperature, nitrogen protection and keep under the stirring condition, the carbon tetrachloride solution of bromine is added drop-wise in the carbon tetrachloride solution of pyrene;
B, the mixed solution that makes among the step a is continued to stir 45～60h under the condition that keeps room temperature, filter then, obtain raw product with methanol wash again;
C, with organic solvent the raw product that makes among the step b is carried out recrystallization and obtain pure product 1,6-dibromo pyrene.
Wherein, the chemical equation that relates to is:
Wherein, the mol ratio of pyrene and bromine is 1: 2～1: 4 among the step a.
The organic solvent of mentioning among the step c preferably uses the double solvents of toluene, chloroform, tetrahydrofuran (THF), tetracol phenixin, chlorinated benzene or above-mentioned solvent.
The technical scheme that provides by the invention described above embodiment as can be seen, embodiment of the present invention is by being raw material with bromine and pyrene, under room temperature, stirring and nitrogen protection condition, the carbon tetrachloride solution of bromine is added drop-wise in the carbon tetrachloride solution of pyrene.Above-mentioned mixed reaction solution is continued to stir at normal temperatures 45～60h, filter then, use methanol wash again, obtain raw product, carry out recrystallization with organic solvent and obtain pure product 1,6-dibromo pyrene.
The raw material that above-mentioned preparation method uses is cheap and easy to get, and the reaction conditions gentleness can be saved cost greatly, can well adapt to industrialized needs.Adopt this preparation method's productive rate higher, can reach 90%, and obtained 1, the purity of 6-dibromo pyrene is higher than market common product 96%-97%, purity surpasses 99%.
Specific embodiment
For ease of understanding, preparation method of the present invention is described further below by specific embodiment to embodiment of the present invention.
Example one:
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (6.32ml; 0.126mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 2.1) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 48h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with 260ml toluene thick product is carried out recrystallization and obtain the pure product 1 of 19.56g, 6-dibromo pyrene, productive rate are 90%, and purity is 99.0%.
Example two:
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (6.50ml; 0.13mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 2.17) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 50h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the 260ml chloroform thick product is carried out recrystallization and obtain the pure product 1 of 19.7g, 6-dibromo pyrene, productive rate are 90.6%, and purity is 99.1%.
Example three
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (7.00ml; 0.14mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 2.33) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 46h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the 260ml tetrahydrofuran (THF) thick product is carried out recrystallization and obtain the pure product 1 of 19.4g, 6-dibromo pyrene, productive rate are 89.2%, and purity is 99.0%.
Example four
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (7.5ml; 0.15mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 2.5) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 50h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml chloroform and toluene thick product is carried out recrystallization and obtain the pure product 1 of 19.7g, 6-dibromo pyrene, productive rate are 90.6%, and purity is 99.3%.
Example five
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (8.0ml; 0.16mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 2.67) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 52h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml chloroform and chlorinated benzene thick product is carried out recrystallization and obtain the pure product 1 of 19.75g, 6-dibromo pyrene, productive rate are 90.8%, and purity is 99.5%.
Example six
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (9.0ml; 0.18mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 3) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 55h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml tetracol phenixin and toluene thick product is carried out recrystallization and obtain 19.77 pure product 1,6-dibromo pyrene, productive rate are 90.9%, and purity is 99.5%.
Example seven
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (11.0ml; 0.22mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 3.67) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 57h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml chlorinated benzene and tetracol phenixin thick product is carried out recrystallization and obtain the pure product 1 of 19.77g, 6-dibromo pyrene, productive rate are 90.9%, and purity is 99.6%.
Example eight
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (11.5ml; 0.23mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 3.83) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 59h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml tetracol phenixin and tetrahydrofuran (THF) thick product is carried out recrystallization and obtain the pure product 1 of 19.77g, 6-dibromo pyrene, productive rate are 90.9%, and purity is 99.8%.
Example nine
1, with pyrene (12.2g; 60mmol) and the 300ml tetracol phenixin put in the there-necked flask that dropping funnel is housed; under room temperature, stirring and nitrogen protection condition; with bromine (12ml; 0.24mol) be dissolved in the 50ml tetracol phenixin, drips of solution is added to (mol ratio of pyrene and bromine is 1: 4) in the reactor then.
2, above-mentioned mixed reaction solution is continued to stir 60h at normal temperatures, filter then, divide with 100ml methyl alcohol and wash the raw product that obtains three times.
3, with the mixed solvent of 260ml chloroform and tetrahydrofuran (THF) thick product is carried out recrystallization and obtain the pure product 1 of 19.77g, 6-dibromo pyrene, productive rate are 90.9%, and purity is 99.6%.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the replacement that can expect easily or variation all should contain and cover within protection scope of the present invention.
Claims (6)
1. the preparation method of a 6-dibromo pyrene is characterized in that this preparation method may further comprise the steps:
A, the carbon tetrachloride solution of bromine is added drop-wise in the carbon tetrachloride solution of pyrene;
B, the mixed solution that makes among the step a is stirred for some time, filter then, obtain raw product with methanol wash again;
C, with organic solvent the raw product that makes among the step b is carried out recrystallization and obtain pure product 1,6-dibromo pyrene.
2. as claimed in claim 11, the synthetic route of 6-dibromo pyrene is characterized in that whole process of preparation is to carry out under protection of nitrogen gas.
3. as claimed in claim 11, the synthetic route of 6-dibromo pyrene is characterized in that whole process of preparation is to carry out at ambient temperature.
4. as claimed in claim 11, the synthetic route of 6-dibromo pyrene, the mol ratio that it is characterized in that pyrene and bromine is 1: 2～1: 4.
5. as claimed in claim 11, the synthetic route of 6-dibromo pyrene, the churning time that it is characterized in that mixed solution among the step b is 45～60h.
6. as claimed in claim 11, the synthetic route of 6-dibromo pyrene is characterized in that the organic solvent described in the step c can be the double solvents of toluene, chloroform, tetrahydrofuran (THF), tetracol phenixin, chlorinated benzene or described solvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164392A (en) * | 2018-01-19 | 2018-06-15 | 李现伟 | A kind of biphenyl compound and its application in 1,6- dibromo pyrenes are prepared |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535089A (en) * | 2002-12-24 | 2004-10-06 | Lg������ʽ���� | Organic electro luminous device |
| WO2008032586A1 (en) * | 2006-09-12 | 2008-03-20 | Idemitsu Kosan Co., Ltd. | Process for production of halogen-substituted aromatic compound, halogen-substituted aromatic compound, non-halogenated aromatic compound, organic el light-emitting element |
| JP2008120695A (en) * | 2006-11-08 | 2008-05-29 | Nippon Oil Corp | Method for preparing pyrene-1,6-dicarboxylic acid |
| JP2009004351A (en) * | 2006-12-07 | 2009-01-08 | Mitsubishi Chemicals Corp | Organic phosphor, organic phosphor material, light-emitting device, and its light-emitting method |
| US20090179196A1 (en) * | 2006-03-20 | 2009-07-16 | Chihaya Adachi | Pyrene-Based Organic Compound, Transistor Material and Light-Emitting Transistor Device |
| CN101981086A (en) * | 2008-04-02 | 2011-02-23 | 三菱化学株式会社 | Polymer compound, reticulated polymer compound produced by crosslinking the polymer compound, composition for organic electroluminescent element, organic electroluminescent element, organic EL display, and organic el lighting |
-
2011
- 2011-07-25 CN CN201110207636XA patent/CN102295523A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535089A (en) * | 2002-12-24 | 2004-10-06 | Lg������ʽ���� | Organic electro luminous device |
| US20090179196A1 (en) * | 2006-03-20 | 2009-07-16 | Chihaya Adachi | Pyrene-Based Organic Compound, Transistor Material and Light-Emitting Transistor Device |
| WO2008032586A1 (en) * | 2006-09-12 | 2008-03-20 | Idemitsu Kosan Co., Ltd. | Process for production of halogen-substituted aromatic compound, halogen-substituted aromatic compound, non-halogenated aromatic compound, organic el light-emitting element |
| JP2008120695A (en) * | 2006-11-08 | 2008-05-29 | Nippon Oil Corp | Method for preparing pyrene-1,6-dicarboxylic acid |
| JP2009004351A (en) * | 2006-12-07 | 2009-01-08 | Mitsubishi Chemicals Corp | Organic phosphor, organic phosphor material, light-emitting device, and its light-emitting method |
| CN101981086A (en) * | 2008-04-02 | 2011-02-23 | 三菱化学株式会社 | Polymer compound, reticulated polymer compound produced by crosslinking the polymer compound, composition for organic electroluminescent element, organic electroluminescent element, organic EL display, and organic el lighting |
Non-Patent Citations (3)
| Title |
|---|
| CHANG-KEUN LIM ET AL.: "Cleavage-induced fluorescence change via hydrophilicity control: a new strategy for biological application", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY》, vol. 188, no. 23, 20 May 2007 (2007-05-20), pages 149 - 154 * |
| HIKARU SUENAGA, ET AL.: "Pyrenylboronic acids as a novel entry for photochemical DNA cleavage: diradical-forming pyrene-1,6-diyldiboronic acid mimics the cleavage mechanism of enediyne antitumor antibiotics", 《J. CHEM. SOC., PERKIN TRANS. 1》, no. 7, 1 January 1998 (1998-01-01), pages 1263 - 1267 * |
| JAMES GRIMSHAW ,J. TROCHA-GRIMSHAW: "Characterisation of 1,6- and 1,8-dibromopyrenes", 《J. CHEM. SOC., PERKIN TRANS. 1》, 1 January 1972 (1972-01-01), pages 1622 - 1623 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164392A (en) * | 2018-01-19 | 2018-06-15 | 李现伟 | A kind of biphenyl compound and its application in 1,6- dibromo pyrenes are prepared |
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