CN101148402A - Process for preparing 2-bromofluorenone - Google Patents
Process for preparing 2-bromofluorenone Download PDFInfo
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- CN101148402A CN101148402A CNA2007101396383A CN200710139638A CN101148402A CN 101148402 A CN101148402 A CN 101148402A CN A2007101396383 A CNA2007101396383 A CN A2007101396383A CN 200710139638 A CN200710139638 A CN 200710139638A CN 101148402 A CN101148402 A CN 101148402A
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Abstract
The process of preparing 2-bromofluorenone with fluorenone includes the following steps: adding fluorenone in certain amount and water into a reactor, heating to 75 deg.c and dropping bromine to react at 75-90 deg.c for 3-6 hr, cooling, absorbing excessive bromine with saturated sodium bisulfite solution, suction filtering, washing with water to obtain coarse product, re-crystallizing in alcohol and drying to obtain product. The process has yield of 93.6-95.1 % and product purity over 99 %, and possesses the advantages of simple operation, easy product separation and purification, high yield, low cost and less environmental pollution.
Description
Technical field
The present invention relates to a kind of aromatic organic compounds, specifically is a kind of method that is prepared 2-bromine Fluorenone by Fluorenone.
Background technology
2-bromine Fluorenone is widely used in the synthetic and preparation of medicine, agricultural chemicals, dye well functional high molecule material etc. as important fine chemicals intermediate.The preparation method of relevant both at home and abroad report 2-bromine Fluorenone mainly contains the following aspects:
(1) is raw material with 2-methyl-4 '-bromo biphenyl, obtains 2-bromine Fluorenone (J.Am.Chem.Soc., 1958,80 (9): 2283-2287) by prepared in reaction such as oxidation, acylations.This preparation method's complicated operation, the cost height is difficult for realizing industrialization.
(2) be raw material with the fluorenes, in organic solvents such as chloroform, obtain 2-bromine fluorenes, prepare 2-bromine Fluorenone (United States Patent (USP): 20060186797 by oxidation again with bromine or NBS reaction; J.Am.Chem.Soc., 1935,57 (11): 2163-2166; J.Am.Chem.Soc., 1958,80 (16): 4327-4330; J.Org.Chem., 1972,37 (3): 510-511; J.Org.Chem., 2002,67 (14): 4924-4936).Obviously, above-mentioned with the preparation method of fluorenes as raw material in because fluorenes itself is outstanding to the orientation effect of 2-position, direct bromo can generate more by product, exist problems such as productive rate is low, complicated operation, reactants separate difficulty, make that the production cost of 2-bromine fluorenes is higher; And oxidising process is with CrO
3Deng being that catalyzer carry out oxidation with highly basic such as KOH for oxygenant in DMSO or pyridine, some method is also used n-Bu
4Phase-transfer catalysts such as NOH, the cost height of product not only, and be unfavorable for environment protection.
(3) be raw material with the Fluorenone, in methylsulfonic acid, obtain 2-bromine Fluorenone (United States Patent (USP): 20050256290) with the NBS prepared in reaction.Therefore the used brominated reagent NBS of this method activity is higher, and to 2, the selectivity of 7-position is not high, generates more by product 2, and 7-dibromo fluorenone, productive rate only are 71%, and NBS and solvent methylsulfonic acid price are higher, and production cost is higher.
(4) 2003 years, the people such as Hachiya Tetsuo of Japan were raw material with the Fluorenone, and hierarchy of control temperature is 50 ℃, with bromine reaction 12h, prepares 2-bromine Fluorenone in water, and productive rate is brought up to 92% (United States Patent (USP): 20030065226).But this method has used tensio-active agent and sulfuric acid to carry out catalysis in building-up process, has used a large amount of toluene to carry out purifying in the last handling process, and technology is very complicated, the production cost height, nor be beneficial to environment protection.Obviously, in above-mentioned preparation method, exist that productive rate is low, cost is high, problem such as reactants separate purification difficult and environmental pollution.
Summary of the invention
In order to overcome above-mentioned preparation method's shortcoming, the object of the invention is to provide that a kind of productive rate height, cost are low, the preparation method of the simple 2-bromine of technology Fluorenone.
The preparation method of a kind of 2-bromine Fluorenone provided by the invention comprises the steps:
(1) with Fluorenone and water by weight 1: 3-6 joins in the reactor, stirs, and heating begins dripping bromine when temperature rises to 75 ℃, and the add-on of bromine is calculated in molar ratio as Fluorenone: bromine=1: 1.10-1.25, hierarchy of control temperature is 75-90 ℃, reaction 3-6h;
(2) after above-mentioned reaction finishes, cooling, excessive bromine absorbs with saturated sodium sulfite solution, and suction filtration washes with water, and drying gets the yellow solid crude product, and the crude product ethyl alcohol recrystallization gets pure product after the drying.Productive rate 93.6-95.1%, purity is greater than 99%; In reaction process, do not relate to any organic solvent, need not to add any catalyzer; Purge process is simple to operate, and involved unique organic solvent ethanol environmental pollution is little, and can recycle.
Step (1) preferred reaction conditions: the add-on of Fluorenone and water is 1 by weight: 3-4; The add-on of Fluorenone and bromine is calculated in molar ratio as 1: 1.15-1.20; Hierarchy of control temperature is 75-83 ℃; Reaction times is 3-4h.
Compared with prior art, the present invention has easy and simple to handle, the easily separated purifying of product, and the productive rate height, cost is low, the advantage that environmental pollution is little.
Embodiment
Embodiment 1
Reagent: Fluorenone, technical grade; Bromine, technical grade; Ethanol, chemical pure.
Operation steps:
In the 250mL four neck round-bottomed flasks that mechanical stirrer, reflux condensing tube, thermometer and constant pressure funnel are housed, add 9.00g (0.05mol) Fluorenone and 36mL water, open and stir, heating in water bath when treating that temperature rises to 80 ℃, drips 9.6g (0.06mol) Br gradually
2, about 1h drips, and constant temperature is reaction 3h down; Be cooled to room temperature, add the saturated sodium sulfite solution of 10mL (absorbing unreacted bromine); Suction filtration washes with water, and drying gets the yellow solid crude product, and the crude product ethyl alcohol recrystallization gets pure product 12.32g, productive rate 95.1%, purity 99.6% after the drying.
Embodiment 2
Reagent: with embodiment 1.
Operation steps:
In the 250mL four neck round-bottomed flasks that mechanical stirrer, reflux condensing tube, thermometer and constant pressure funnel are housed, add 9.00g (0.05mol) Fluorenone and 30mL water, open and stir, heating in water bath when treating that temperature rises to 80 ℃, drips 9.28g (0.058mol) Br gradually
2, about 1h drips, and constant temperature is cooled to room temperature after reacting 3h down, adds the saturated sodium sulfite solution of 10mL and absorbs unreacted bromine; Suction filtration washes with water, and drying gets the yellow solid crude product, and the crude product ethyl alcohol recrystallization gets pure product 12.24g, productive rate 94.5%, purity 99.4% after the drying.
Alcoholic acid is recycled: the used ethanol of recrystallization can reuse after distilling.
The physical constant of product and spectral data: product appearance: yellow solid; Fusing point: 146-148 ℃; IR (KBr) cm
-1: 3012.0,1716.9,1595.6,1454.7,1392.6,1266.1,1055.6,877.0,812.7,756.2,735.6,671.4;
1HNMR?δ
ppm：7.76(s，1H)，7.70-7.68(d，1H)，7.63-7.42(m，5H)。
13CNMR?δ
ppm：192.8，143.6，142.6，141.0，135.1，134.3，133.6，129.1，127.6，124.8，123.0，122.1，120.9。
EA：C，60.56；H，2.69；Br，30.24；O，6.51。
Claims (5)
1. the preparation method of a 2-bromine Fluorenone is characterized in that comprising the steps:
(1) with Fluorenone and water by weight 1: 3-6 joins in the reactor, stirs, and heating begins dripping bromine when temperature rises to 75 ℃, and the add-on of bromine is calculated in molar ratio as Fluorenone: bromine=1: 1.10-1.25, hierarchy of control temperature is 75-90 ℃, reaction 3-6h;
(2) after above-mentioned reaction finishes, cooling, excessive bromine absorbs with saturated sodium sulfite solution, and suction filtration washes with water, and drying gets the yellow solid crude product, and the crude product ethyl alcohol recrystallization gets pure product after the drying.
2. the preparation method of 2-bromine Fluorenone according to claim 1 is characterized in that the add-on of described Fluorenone and bromine is calculated in molar ratio as 1: 1.15-1.20.
3. the preparation method of 2-bromine Fluorenone according to claim 1, the add-on that it is characterized in that described Fluorenone and water is 1 by weight: 3-4.
4. the preparation method of 2-bromine Fluorenone according to claim 1 is characterized in that described hierarchy of control temperature is 75-83 ℃.
5. the preparation method of 2-bromine Fluorenone according to claim 1 is characterized in that the described reaction times is 3-4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101396383A CN101148402A (en) | 2007-10-26 | 2007-10-26 | Process for preparing 2-bromofluorenone |
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| CNA2007101396383A CN101148402A (en) | 2007-10-26 | 2007-10-26 | Process for preparing 2-bromofluorenone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774141A (en) * | 2015-05-13 | 2015-07-15 | 河南省商业科学研究所有限责任公司 | Synthetic method of 2-Bromo-9-fluorenone |
| CN110357768A (en) * | 2019-08-28 | 2019-10-22 | 郑州圣壹新材料科技有限公司 | A kind of preparation method of 2- bromine Fluorenone |
| CN114213229A (en) * | 2021-12-27 | 2022-03-22 | 苏州久显新材料有限公司 | Preparation method of 2-bromofluorenone |
-
2007
- 2007-10-26 CN CNA2007101396383A patent/CN101148402A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774141A (en) * | 2015-05-13 | 2015-07-15 | 河南省商业科学研究所有限责任公司 | Synthetic method of 2-Bromo-9-fluorenone |
| CN104774141B (en) * | 2015-05-13 | 2016-06-01 | 河南省商业科学研究所有限责任公司 | The synthetic method of the bromo-9-Fluorenone of a kind of 2- |
| CN110357768A (en) * | 2019-08-28 | 2019-10-22 | 郑州圣壹新材料科技有限公司 | A kind of preparation method of 2- bromine Fluorenone |
| CN114213229A (en) * | 2021-12-27 | 2022-03-22 | 苏州久显新材料有限公司 | Preparation method of 2-bromofluorenone |
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Open date: 20080326 |