CN104030907B - A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone - Google Patents
A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone Download PDFInfo
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- CN104030907B CN104030907B CN201410228663.9A CN201410228663A CN104030907B CN 104030907 B CN104030907 B CN 104030907B CN 201410228663 A CN201410228663 A CN 201410228663A CN 104030907 B CN104030907 B CN 104030907B
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- bromine
- fluorenes
- fluorenone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
The invention belongs to field of fine chemical, be specifically related to a kind of method that liquid phase oxidation prepares 2 bromine Fluorenones.Specifically, 2 bromine fluorenes are dissolved in N, N dimethylformamide, are subsequently adding catalyst, at 30 40 DEG C, atmospheric agitation, air oxidation, react 24 hours, distillation, filter, washing, it is dried, prepares 2 bromine Fluorenones, productivity 96%, purity 99 99.5%；Wherein, 2 bromine fluorenes and N, the charged material weight ratio of N dimethylformamide is 1:3.5 5；2 bromine fluorenes are 1:0.03 0.5 with the molar ratio of catalyst.Reaction condition of the present invention is gentle, and easy and simple to handle, solvent load is relatively fewer, and productivity is high, low cost, and environmental pollution is little, and need not be further processed after solvent use i.e. can be recycled, and the response time is shorter, is especially suitable for large-scale industrial production.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of liquid phase oxidation and prepare 2-bromine
The method of Fluorenone.
Background technology
2-bromine Fluorenone is a kind of important fine Organic Chemicals, and this compound is not only and is produced
The important source material of light-guide material, silver system sensitive material is also its another important applied field.
The method of 2-bromine Fluorenone is prepared as liquid phase with 2-bromine fluorenes for raw material disclosed in prior art
Air oxidation process, current liquid phase prepared in 2-bromine Fluorenone method, and the solvent of selection is dimethyl
Sulfoxide and oxolane, dimethyl sulfoxide boiling point is high, and recycling needs evaporated under reduced pressure, diformazan
Have decomposition when base sulfoxide heating-up temperature is more than 90 DEG C, and react and require heat to 50
-100℃；Simultaneously in the oxidizing process in above solvent, apply phase transfer catalyst,
And the metallic catalyst of great number, and productivity is the highest, it is clear that can increase the cost of product.
Summary of the invention
For the shortcoming that product cost is high, yield is low overcoming existing preparation method to exist, this
The method that a kind of liquid phase oxidation of bright offer prepares 2-bromine Fluorenone.
For achieving the above object, the technical solution used in the present invention is:
A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone, and reaction equation is as follows,
It is characterized in that: 2-bromine fluorenes is dissolved in DMF, is subsequently adding
Catalyst, at 30-40 DEG C, atmospheric agitation, air oxidation, react 2-4 hour, distillation,
Filter, washing, be dried, prepare 2-bromine Fluorenone；Wherein, 2-bromine fluorenes and N, N-dimethyl methyl
The charged material weight ratio of amide is 1:2-5；2-bromine fluorenes is 1 with the molar ratio of catalyst:
0.04-0.06.Described catalyst is potassium hydroxide, sodium hydroxide, quaternary amine alkali or sodium alkoxide class
Compound.Described quaternary amine alkali is 4 bromide, tetramethyl ammonium chloride or benzyl tetraethyl chlorination
Ammonium；Described sodium alkoxide compounds is Feldalat NM or Sodium ethylate.
Further, described 2-bromine fluorenes is the heaviest with feeding intake of DMF
Amount ratio is 1:3.5-5, and optimum is 1:3.5；2-bromine fluorenes and the preferred molar ratio that feeds intake of potassium hydroxide
Being 1:0.03-0.5, optimum is 1:0.05, and reaction temperature is at 35-40 DEG C.
The present invention is compared with prior art:
Present invention employs solvent N,N-dimethylformamide and instead of current liquid phase preparation process
The high boiling dimethyl sulfoxide of middle use, dimethyl sulfoxide recycling needs evaporated under reduced pressure
(when dimethyl sulfoxide heating-up temperature is more than 90 DEG C, having decomposition), and react and need heating
To 50-100 DEG C.When solving current benzene series as solvent simultaneously, should in oxidizing process
With phase transfer catalyst, and productivity is the highest, can increase the cost of product.Also use is solved
Your solvents tetrahydrofurane is in industrial difficulty.
Meanwhile, much less, greatly relative to the consumption of benzene series and oxolane for solvent load of the present invention
Reduce greatly the production efficiency in production.And the present invention uses air oxidation process, solve mesh
Used in the process of front production, oxidant is the danger that industrial oxygen brings.
It addition, reaction temperature of the present invention is at 30-40 DEG C, reaction condition is gentle, and 2-4 hour anti-
Should terminate, the time is short, is suitable for industrialization temperature conditions.Easy and simple to handle, productivity is high, and solvent is used
Measuring relatively fewer, power cost is significantly lower than the cost of current production technology, and environmental pollution is little,
And, the present invention prepares 2-bromine Fluorenone, productivity 96%, purity 99-99.5%, and solvent uses
After need not be further processed and i.e. can be recycled, not only reduce the cost of solvent, and
Decreasing the recovery loss of solvent, cost, well below the cost of market product, is especially suitable for big
Technical scale metaplasia is produced.
Detailed description of the invention
Following example are used for further describing and demonstrating the present invention, to be more fully understood that this
Bright, and it is not intended to limit the claim that the present invention is stated.Agents useful for same is commercially available.
The embodiment 1:2-bromine fluorenes oxidation preparation bromo-9-Fluorenone of 2-
Carry out by following reaction,
Operating procedure: equipped with reflux condensing tube and churned mechanically 250 milliliters of three-neck flasks
20 grams of 2-bromine fluorenes (0.082mol) of middle addition, 80 grams of DMFs, 1 gram
Potassium hydroxide (0.018mo1), opens stirring, and 35 DEG C are reacted 2 hours, by gas phase color
Analysis of spectrum is followed the tracks of, and when the content of raw material fluorenes is less than 0.1%, stops blowing air, and reaction terminates；
Reactant liquor filters after distillation, washing, is dried, i.e. obtains the bromo-9-of 2-that purity is 99.5%
Fluorenone, yield 96%.Solvent after being used after reaction retains, and lower batch continues cycling through and apply mechanically.
Embodiment 2:
Operating procedure: equipped with reflux condensing tube and churned mechanically 250 milliliters of three-neck flasks
20 grams of 2-bromine fluorenes (0.082mol) of middle addition, 80 grams of N,N-dimethylformamide (experiments 1
Reclaim), 1 gram of potassium hydroxide (0.018mo1), open stirring, 35 DEG C are reacted 2 hours,
Followed the tracks of by gas chromatographic analysis, when the content of raw material fluorenes is less than 0.1%, stop blowing air,
Reaction terminates；Reactant liquor filters after distillation, washing, is dried, and i.e. obtaining purity is 99.5
The bromo-9-Fluorenone of 2-of %, yield 96%.Solvent after being used after reaction retains, lower batch
Continue cycling through and apply mechanically.
Embodiment 3, the 2-bromine fluorenes oxidation preparation bromo-9-Fluorenone of 2-
Operating procedure: equipped with reflux condensing tube and churned mechanically 250 milliliters of three-neck flasks
20 grams of 2-bromine fluorenes (0.082mol) of middle addition, 70 grams of DMFs, 1 gram of hydrogen
Sodium oxide (0.025mo1), opens stirring, reacts 3 hours under room temperature.Reactant liquor is through steaming
Filter after evaporating, washing, be dried, i.e. obtain the bromo-9-Fluorenone of 2-that purity is 99.4%, receive
Rate 95.5%.
Embodiment, 4, the 2-bromine fluorenes oxidation preparation bromo-9-Fluorenones of 2-
Operating procedure: equipped with reflux condensing tube and churned mechanically 250 milliliters of three-neck flasks
20 grams of 2-bromine fluorenes (0.082mol) of middle addition, 90 grams of DMFs, 1 gram of first
Sodium alkoxide (0.02mo1), opens stirring, reacts 4 hours at 40 DEG C.Reactant liquor is after distillation
Filter, washing, be dried, i.e. obtain the bromo-9-Fluorenone of 2-that purity is 99.4%, yield
95%.
The physical constant of the bromo-9-Fluorenone of 2-is prepared in the 2-bromine fluorenes oxidation that the various embodiments described above obtain
And spectral data: the outward appearance of product: yellow solid；Fusing point: 83-85 DEG C；
The physical constant of 2-bromine Fluorenone and spectral data:
The outward appearance of product: yellow solid；Fusing point: 147-148 DEG C；
Target compound IR (KBr) (Impact400 that Nicolet company of the U.S. produces):
3068,3050,1738,1602,1510,1460,1412,1300,1010,
832,770,685,510；Target compound NMR is (with CHCl3=7.264ppm in CDCl3
For internal standard) (Mercury300 (UX) that Varian company of the U.S. produces): δ H, ppm (DMSO):
7.86 (s, 1H), 7.68-7.70 (d, 1H), 7.40-7.52 (m, 5H).
Claims (3)
1. the method that liquid phase oxidation prepares 2-bromine Fluorenone, reaction equation is as follows,
It is characterized in that: 2-bromine fluorenes is dissolved in DMF, is subsequently adding catalyst,
At 30-40 DEG C, atmospheric agitation, air oxidation, react 2-4 hour, distillation, filter, washing, dry
Dry, prepare 2-bromine Fluorenone；Wherein, 2-bromine fluorenes is 1 with the charged material weight ratio of DMF:
2-5；2-bromine fluorenes is 1:0.04-0.06 with the molar ratio of catalyst；
Described catalyst is potassium hydroxide, sodium hydroxide, quaternary amine alkali or sodium alkoxide compounds.
2. the method that liquid phase oxidation as described in claim 1 prepares 2-bromine Fluorenone, it is characterised in that: institute
Stating quaternary amine alkali is 4 bromide or tetramethyl ammonium chloride；Described sodium alkoxide compounds is Feldalat NM or second
Sodium alkoxide.
3. the method that liquid phase oxidation as described in claim 1 prepares 2-bromine Fluorenone, it is characterised in that: institute
The charged material weight ratio stating 2-bromine fluorenes and N,N-dimethylformamide is 1:3.5-5；Reaction temperature exists
35-40℃。
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| CN201410228663.9A CN104030907B (en) | 2014-05-28 | 2014-05-28 | A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone |
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| CN201410228663.9A CN104030907B (en) | 2014-05-28 | 2014-05-28 | A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone |
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| CN108276261B (en) * | 2018-02-08 | 2021-01-05 | 新乡市润宇新材料科技有限公司 | Method for preparing 2-bromofluorenone by catalyzing molecular oxygen oxidation in aqueous phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962597A (en) * | 2006-11-28 | 2007-05-16 | 山西大学 | Oxidation preparation method for 9- fluorenone compound from fluorine compound |
| CN102731281A (en) * | 2012-07-06 | 2012-10-17 | 兰州大学 | Method for preparing coarse fluorene and fluorenone by taking wash oil as raw material |
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- 2014-05-28 CN CN201410228663.9A patent/CN104030907B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962597A (en) * | 2006-11-28 | 2007-05-16 | 山西大学 | Oxidation preparation method for 9- fluorenone compound from fluorine compound |
| CN102731281A (en) * | 2012-07-06 | 2012-10-17 | 兰州大学 | Method for preparing coarse fluorene and fluorenone by taking wash oil as raw material |
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Effective date of registration: 20211201 Address after: 110021 no.8-12, East SHENLIAO Road, Tiexi District, Shenyang City, Liaoning Province Patentee after: Sinochem Safety Science Research (Shenyang) Co.,Ltd. Address before: 110021 No. 8 Shen Liaodong Road, Tiexi District, Liaoning, Shenyang Patentee before: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
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