CN102408321A - Preparation method of 2, 7-dibromofluorenone - Google Patents
Preparation method of 2, 7-dibromofluorenone Download PDFInfo
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- CN102408321A CN102408321A CN2011103375782A CN201110337578A CN102408321A CN 102408321 A CN102408321 A CN 102408321A CN 2011103375782 A CN2011103375782 A CN 2011103375782A CN 201110337578 A CN201110337578 A CN 201110337578A CN 102408321 A CN102408321 A CN 102408321A
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- Prior art keywords
- dibromo
- grams
- fluorenone
- preparation
- quaternary ammonium
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- FYEFHYMUEWRCRF-UHFFFAOYSA-N 2,7-dibromofluoren-1-one Chemical compound BrC1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 FYEFHYMUEWRCRF-UHFFFAOYSA-N 0.000 title claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 15
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000001555 benzenes Chemical class 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229940125782 compound 2 Drugs 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of production of aromatic compound 2, 7-dibromofluorenone, and particularly relates to a preparation method of 2, 7-dibromofluorenone, which is characterized by comprising the following steps: 1) taking industrial 2, 7-dibromofluorene, a benzene solvent, potassium hydroxide and quaternary ammonium salt, and adding the components into a four-mouth bottle; 2) heating to 80-90 ℃ for reaction, and introducing air for oxidation; 3) vacuum distilling, crystallizing the concentrate to obtain yellow 2, 7-dibromo fluorenone crystal; 4) washing with water once, and drying to obtain the 2, 7-dibromo fluorenone product. The benzene series solvent is toluene or xylene. Compared with the prior art, the invention has the beneficial effects that: 1) the reaction temperature is low, and the operation is simple and convenient. 2) Cheap potassium hydroxide is used as a catalyst, so that the cost is low. 3) The benzene solvent can be recycled by reduced pressure distillation, the washing water amount is small, the treatment is easy, and the environmental pollution is small. 4) The purity of the product gas chromatography is higher than 99.2%, the yield is higher than 85%, and the production requirement is met.
Description
Technical field
The present invention relates to aromatic compound 2, the production technical field of 7-dibromo fluorenone, particularly a kind of 2, the preparation method of 7-dibromo fluorenone.
Background technology
2, the 7-dibromo fluorenone is a kind of additive of light-guide material, simultaneously can also be as other important raw material that closes fine chemicals, be widely used in the synthetic and preparation of dyestuff, photoconductive material, material such as luminous.Therefore the research to its compound method has theory significance and application prospects.
Relevant both at home and abroad report 2, the preparation method of 7-dibromo fluorenone mainly contains the following aspects:
Human Fluorenone and bromine prepared in reaction 2 in water such as Borowitz of the U.S. in 1971,7-dibromo fluorenone, productive rate only have 51% [[J.Org.Chem., 36 (4), 553,1971];
Nineteen eighty-two Greece Gallos, human F3CCOZBr such as John as bromizating agent and Fluorenone reaction obtain productive rate be 73% 2,7-dibromo fluorenone [J.Chem.Res.; Synop.1982,6,150; (Eng)]; Though this method productive rate increases, bromizating agent F3CCOZBr price is higher, causes the cost up of product;
Nineteen eighty-two, the Asahi Glass Co. of Japan reacted generation 2 with fluorenes and nitrogen bromo fourth two phthalimides (NBS) in acetic acid and Hydrogen bromide, 7-dibromo fluorenes, and then with 2,7-dibromo fluorenes prepares 2 with the Cr03 oxidation in acetic acid; The 7-dibromo fluorenone (JP 58,177, and 955,1983; Appl.82,160,409; 13Apr.1982), this method prepares 2 through two-step reaction as raw material with fluorenes in organic solvent, the 7-dibromo fluorenone; But it is oxygenant that oxidising process adopts Cr03, and not only the cost of product is higher, and is unfavorable for environment protection.Obviously, in above-mentioned preparation method, exist problems such as productive rate is low, cost is high, reactants separate difficulty.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of 2, the preparation method of 7-dibromo fluorenone satisfies the requirement that reaction conditions is gentle, easy and simple to handle, productive rate is high, cost is low, environmental pollution is little in producing.
The present invention adopts following technical scheme to realize:
A kind of 2, the preparation method of 7-dibromo fluorenone may further comprise the steps:
1) gets industry 2; 7-dibromo fluorenes, benzene series solvent, Pottasium Hydroxide, quaternary ammonium salt join above-mentioned four kinds of components in the four-hole bottle, on four-hole bottle, install TM, stirring, reflux condensing tube; Pottasium Hydroxide is as catalyzer, and quaternary ammonium salt is as phase-transfer catalyst;
2) normal pressure begins to stir, and is heated to solid dissolving more than 80 ℃, and feeding flow down at 80～90 ℃ is that the air of 300-500ml/min carries out oxidation, after reaction is carried out 4～6 hours, and stopped reaction;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization, yellow 2,7-dibromo fluorenone crystal;
4) step 3) gained crystal washing is once removed alkali, after the drying, promptly get yellow 2,7-dibromo fluorenone crystal product.
Said benzene series solvent is toluene or YLENE.
When the benzene series solvent was toluene, the mass ratio of said four kinds of components was:
Industry 2,7-dibromo fluorenes 10 grams, toluene 80～90 grams, Pottasium Hydroxide 1.5～2 grams, quaternary ammonium salt 0.4～0.5 gram.
When the benzene series solvent was YLENE, the mass ratio of said four kinds of components was:
Industry 2,7-dibromo fluorenes 10 grams, YLENE 50～60 grams, Pottasium Hydroxide 1.5～2 grams, quaternary ammonium salt 0.4～0.5 gram.
Compared with prior art, the invention has the beneficial effects as follows: 1) temperature of reaction is low, and is easy and simple to handle, reaction conditions is gentle.2) Pottasium Hydroxide with cheapness is catalyzer, and cost is low.3) the benzene series solvent can be through the underpressure distillation recycling use, and leaching requirement is handled seldom easily, and environmental pollution is little.4) the product gas chromatographic purity is higher than 99.2%, and yield is higher than 85%, satisfies production requirement.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, YLENE 100g, quaternary ammonium salt 0.79g; Pottasium Hydroxide 3g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls, and the air that feeds flow and be 300ml/min carries out oxidation; Reaction was carried out 4 hours, stopped reaction, and after still liquid filtered, vacuum distillation recovered solvent recycled; The enriched material crystallization gets yellow solid, and a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, liquid chromatography purity 99.6%, yield 90%.
Embodiment 2
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, YLENE 109g, quaternary ammonium salt 0.9g; Pottasium Hydroxide 3.5g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls to feed flow be that the air of 300ml/min carries out oxidation, reaction was carried out 4 hours; Stopped reaction, after still liquid filtered, vacuum distillation recovered solvent recycled, the enriched material crystallization; Get yellow solid, a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, yield 88%, liquid chromatography purity 99.2%.
Embodiment 3
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, YLENE 117g, quaternary ammonium salt 0.84g; Pottasium Hydroxide 3.9g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls to feed flow be that the air of 300ml/min carries out oxidation, reaction was carried out 4 hours; Stopped reaction, after still liquid filtered, vacuum distillation recovered solvent recycled, the enriched material crystallization; Get yellow solid, a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, yield 87%, liquid chromatography purity 99.2%.
Embodiment 4
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, toluene 160g, quaternary ammonium salt 0.79g; Pottasium Hydroxide 3g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls to feed flow be that the air of 300ml/min carries out oxidation, reaction was carried out 4 hours; Stopped reaction, after still liquid filtered, vacuum distillation recovered solvent recycled, the enriched material crystallization; Get yellow solid, a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, yield 90%, liquid chromatography purity 99.5%.
Embodiment 5
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, toluene 167g, quaternary ammonium salt 0.9g; Pottasium Hydroxide 3.5g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls to feed flow be that the air of 300ml/min carries out oxidation, reaction was carried out 4 hours; Stopped reaction, after still liquid filtered, vacuum distillation recovered solvent recycled, the enriched material crystallization; Get yellow solid, a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, yield 88%, liquid chromatography purity 99.2%.
Embodiment 6
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dibromo fluorenes 19.6g, toluene 175g, quaternary ammonium salt 0.84g; Pottasium Hydroxide 3.9g is heated to the dissolving of 80 ℃ of solids then, and 80～90 ℃ of temperature controls to feed flow be that the air of 300ml/min carries out oxidation, reaction was carried out 4 hours; Stopped reaction, after still liquid filtered, vacuum distillation recovered solvent recycled, the enriched material crystallization; Get yellow solid, a small amount of washing once is drying to obtain 2; 7-dibromo fluorenone product, yield 85%, liquid chromatography purity 99.3%.
Claims (4)
1. one kind 2, the preparation method of 7-dibromo fluorenone is characterized in that, may further comprise the steps:
1) gets industry 2; 7-dibromo fluorenes, benzene series solvent, Pottasium Hydroxide, quaternary ammonium salt join above-mentioned four kinds of components in the four-hole bottle, on four-hole bottle, install TM, stirring, reflux condensing tube; Pottasium Hydroxide is as catalyzer, and quaternary ammonium salt is as phase-transfer catalyst;
2) normal pressure begins to stir, and is heated to solid dissolving more than 80 ℃, and feeding flow down at 80～90 ℃ is that the air of 300-500ml/min carries out oxidation, after reaction is carried out 4～6 hours, and stopped reaction;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization, yellow 2,7-dibromo fluorenone crystal;
4) step 3) gained crystal washing is once removed alkali, after the drying, promptly get yellow 2,7-dibromo fluorenone crystal product.
2. according to claim 1 a kind of 2, the preparation method of 7-dibromo fluorenone is characterized in that, said benzene series solvent is toluene or YLENE.
3. according to claim 2 a kind of 2, the preparation method of 7-dibromo fluorenone is characterized in that, the mass ratio of said four kinds of components is:
Industry 2,7-dibromo fluorenes 10 grams, toluene 80～90 grams, Pottasium Hydroxide 1.5～2 grams, quaternary ammonium salt 0.4～0.5 gram.
4. according to claim 2 a kind of 2, the preparation method of 7-dibromo fluorenone is characterized in that, the mass ratio of said four kinds of components is:
Industry 2,7-dibromo fluorenes 10 grams, YLENE 50～60 grams, Pottasium Hydroxide 1.5～2 grams, quaternary ammonium salt 0.4～0.5 gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103375782A CN102408321A (en) | 2011-10-31 | 2011-10-31 | Preparation method of 2, 7-dibromofluorenone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103375782A CN102408321A (en) | 2011-10-31 | 2011-10-31 | Preparation method of 2, 7-dibromofluorenone |
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| CN102408321A true CN102408321A (en) | 2012-04-11 |
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| CN2011103375782A Pending CN102408321A (en) | 2011-10-31 | 2011-10-31 | Preparation method of 2, 7-dibromofluorenone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0782206A (en) * | 1993-09-14 | 1995-03-28 | Sumikin Chem Co Ltd | Production of fluorenone |
| US20040059160A1 (en) * | 2002-09-24 | 2004-03-25 | Jfe Chemical Corporation | Production process of 2,7-dibromofluorenone |
-
2011
- 2011-10-31 CN CN2011103375782A patent/CN102408321A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0782206A (en) * | 1993-09-14 | 1995-03-28 | Sumikin Chem Co Ltd | Production of fluorenone |
| US20040059160A1 (en) * | 2002-09-24 | 2004-03-25 | Jfe Chemical Corporation | Production process of 2,7-dibromofluorenone |
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Application publication date: 20120411 |