CN102311328A - Method for preparing acetophenone - Google Patents
Method for preparing acetophenone Download PDFInfo
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- CN102311328A CN102311328A CN2010102231445A CN201010223144A CN102311328A CN 102311328 A CN102311328 A CN 102311328A CN 2010102231445 A CN2010102231445 A CN 2010102231445A CN 201010223144 A CN201010223144 A CN 201010223144A CN 102311328 A CN102311328 A CN 102311328A
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- ethylbenzene
- dawson
- methyl phenyl
- phenyl ketone
- vanadium
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Abstract
The invention discloses a method for preparing acetophenone. Dawson phosphorus-molybdenum-vanadium multi-metal oxometallate taking cobalt and pyridine as counter ions and bromide are taken as catalysts; in the catalysts, a molar ratio of the cobalt to Dawson phosphorus-molybdenum-vanadium heteropolyacid is (1-5):1, a molar ratio of the pyridine Cpyr=(C15H32C5H4N)+ to the Dawson phosphorus-molybdenum-vanadium heteropolyacid is (1-10):1, and a molar ratio of the bromide to the main catalyst is (0.1-1):1; and ethylbenzene and an oxygen source taken as reactants, each 100ml of ethylbenzene is added with 3 to 8g of catalysts, the reaction temperature is 45-95DEG C and the reaction time is 4 to 11 hours.
Description
Technical field
The present invention relates to prepare the method for methyl phenyl ketone.
Background technology
At present, adopt benzene and Acetyl Chloride 98Min. under aluminum chloride, during synthetic methyl phenyl ketone, to react generation strong acid afterwards in the industry, be prone to cause the corrosion of production unit and the pollution of environment; When adopting ethylbenzene air direct oxidation method to prepare methyl phenyl ketone, this catalystsystem transformation efficiency is not high, and by product is many.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of methyl phenyl ketone.
The present invention is the preparation method of methyl phenyl ketone; It is characterized in that adopting cobalt and pyridine is catalyzer as the Dawson type phosphorus molybdenum-vanadium multi-metal oxygen hydrochlorate and the bromide of gegenion; In this catalyzer, the mol ratio of cobalt and Dawson type phosphorus molybdenum vanadium heteropolyacid is 1～5: 1, pyridine Cpyr=(C
16H
32C
5H
4N)
+Mol ratio 1～10: 1 with Dawson type phosphorus molybdenum vanadium heteropolyacid; Bromide and aforementioned Primary Catalysts mol ratio 0.1～2: 1; As reactant, the catalyst levels that adds in every 100ml ethylbenzene is 3～8g with ethylbenzene and oxygen source, and temperature of reaction is 45～95 ℃, and the reaction times is 4～11 hours.
The present invention compares with traditional cobalt salt catalytic oxidation, has following several advantage: one step of (1) reaction accomplishes, and process is simple; (2) temperature of reaction 45-95 ℃, mild condition; (3) conversion of ethylbenzene is high; (4) methyl phenyl ketone selectivity high; (5) oxygenant is a ydrogen peroxide 50, ydrogen peroxide 50, tertbutyl peroxide, air, oxygen, relative low price, environmentally safe; (6) catalyzer can with solution separating, renewable repeated use.Thereby be a kind of economy, eco-friendly compound method.
Description of drawings
Fig. 1 is (Cpyr)
4Co
2.5P
2Mo
15V
3O
62XRD spectra, Fig. 2 is (Cpyr)
4Co
2.5P
2Mo
15V
3O
62 31P NMR spectrogram.
The practical implementation method
Embodiment 1:
Catalyzer: with cetyl pyridinium pyridylium is provided, with Dawson type phosphorus molybdenum vanadium heteropolyacid as raw material, wherein cetyl pyridinium and H
9P
2Mo
15V
3O
62Mol ratio be 4: 1, synthesis step is following: with H
9P
2Mo
15V
3O
62Be dissolved in respectively in the hot water of 60 ℃ and PH=2 with the bromohexadecane yl pyridines,, be added drop-wise to H lentamente by tap funnel having under the magnetic agitation with bromohexadecane yl pyridines solution
7P
2Mo
17VO
62In the aqueous solution, in the dropping process, have a large amount of yolk yellow depositions and generate, drip and finish; Ageing reaction mixture 2～3h; Suction filtration is used boiling water, absolute ethyl alcohol, ether washing precipitation then respectively successively, places stink cupboard to spend the night then; Treat that ether volatilization back is dry in 80 ℃ vacuum drying oven, promptly get preliminary product (Cpyr)
4H
5P
2Mo
15V
3O
62
Adopt cobaltous dihydroxycarbonate (2CoCO
33Co (OH)
2XH
2O) the cobalt source is provided, with preliminary product (Cpyr)
4H
5P
2Mo
15V
3O
62As raw material, (2CoCO wherein
33Co (OH)
2XH
2O) with (Cpyr)
4H
5P
2Mo
15V
3O
62Mol ratio be 0.5: 1.In the 100ml there-necked flask of prolong, TM is housed, add 0.025mol ethylbenzene, 10mL glacial acetic acid and a certain amount of catalyzer, under induction stirring; Be heated under the certain temperature, dropwise add a certain amount of tertbutyl peroxide, the dropping time is about 50 minutes; Question response is poured reaction solution in the separating funnel into after finishing, and standing demix extracts filtrating and carries out product analysis; Form through the gas chromatographic detection oxidation products, and analyze with inner mark method ration.Conversion of ethylbenzene is 81.55%, and the selectivity of methyl phenyl ketone reaches 92.49%.
Embodiment 2～9:
According to method and the step of embodiment 1, change cetyl pyridinium and H
9P
2Mo
15V
3O
62Proportioning, its mol ratio was respectively 1: 1,2: 1,3: 1,5: 1,6: 1,7: 1,8: 1,9: 1, changed its preliminary product and cobaltous dihydroxycarbonate (2CoCO then
33Co (OH)
2XH
2O) proportioning, what its mol ratio was corresponding is respectively: 0.8: 1,0.7: 1,0.6: 1,0.4: 1,0.3: 1,0.2: 1,0.1: 1, the result all be conversion of ethylbenzene less than 81.55%, the selectivity of methyl phenyl ketone is less than 92.49%.
According to method and the step of embodiment 1, change the wherein content of vanadium of Dawson type phosphorus molybdenum vanadium heteropolyacid, change into H respectively
7P
2Mo
17VO
62, H
8P
2Mo
16V
2O
62, H
10P
2Mo
14V
4O
62, the result is respectively conversion of ethylbenzene 63.24%, and the selectivity of methyl phenyl ketone is less than 73.24%; Conversion of ethylbenzene 80.85%, the selectivity 94.12% of methyl phenyl ketone; Conversion of ethylbenzene is 54.85%, and the selectivity of methyl phenyl ketone is 80.16%.
Embodiment 13～15:
According to method and the step of embodiment 1, change the kind of oxygen source, change into ydrogen peroxide 50, air, oxygen result respectively and be respectively conversion of ethylbenzene 63.24%, the selectivity 84.26% of methyl phenyl ketone; Conversion of ethylbenzene 80.85%, the selectivity 91.53% of methyl phenyl ketone; Conversion of ethylbenzene is the selectivity 88.28% of 85.99% methyl phenyl ketone.
Fig. 1 is (Cpyr)
4Co
2.5P
2Mo
15V
3O
62XRD spectra, (Cpyr)
4Co
2.5P
2Mo
15V
3O
62Diffraction peak mainly concentrate on 2 θ=7 °～9 °, 14 °～20 °, 26 °～30 °, in 37 °～39 ° these 4 intervals; Wherein the diffraction peak intensity of 2 θ=7 °～9 ° is the strongest, and the diffraction peak intensity of 2 θ=26 °～30 ° takes second place, the diffraction peak intensity of 2 θ=37 °～39 ° a little less than; This and document (Liu Xia, Zhao Jun, Feng Changgen etc.; Synthetic and the spectral investigation of the substituted Dawson type of three vanadium phosphorus molybdenum vanadium glycocoll heteropoly compound, spectroscopy and spectroscopic analysis, 2006; The chemical shift of the Dawson structure phosphorus molybdenum vanadium heteropolyacid salt that 26 (12), p2226～2228) is provided is consistent, and institute's synthetic phosphorus molybdenum vanadium cobalt salt (Cpyr) is described
4Co
2.5P
2Mo
15V
3O
62Has the Dawson structure.Fig. 2 is (Cpyr)
4Co
2.5P
2Mo
15V
3O
62 31P NMR spectrogram, the Dawson structure phosphorus molybdenum vanadium heteropolyacid salt that this and document (Yu Jianfeng, Liu Yan, Yang Yu, Wu have friendly relations etc., the character [J] of Dawson type phosphorus molybdenum vanadium heteropoly compound, Jilin University's natural science journal, 1996,2 (1), p89～93.) are provided
31The PNMR chemical shift is consistent, and institute's synthetic phosphorus molybdenum vanadium cobalt salt (Cpyr) is described once more
4Co
2.5P
2Mo
15V
3O
62Has the Dawson structure.
Claims (2)
1. the preparation method of methyl phenyl ketone; It is characterized in that adopting cobalt and pyridine is catalyzer as the Dawson type phosphorus molybdenum-vanadium multi-metal oxygen hydrochlorate and the bromide of gegenion; In this catalyzer, the mol ratio of cobalt and Dawson type phosphorus molybdenum vanadium heteropolyacid is 1～5: 1, pyridine Cpyr=(C
16H
32C
5H
4N)
+Mol ratio 1～10: 1 with Dawson type phosphorus molybdenum vanadium heteropolyacid; Bromide and aforementioned Primary Catalysts mol ratio 0.1～2: 1; As reactant, the catalyst levels that adds in every 100ml ethylbenzene is 3～8g with ethylbenzene and oxygen source, and temperature of reaction is 45～95 ℃, and the reaction times is 4～11 hours.
2. according to the preparation method of the said methyl phenyl ketone of claim 1, it is characterized in that oxygen source is a ydrogen peroxide 50, perhaps is tertbutyl peroxide; Perhaps being air, perhaps is oxygen, calculates by every 100ml ethylbenzene; The add-on of ydrogen peroxide 50 is 50～150ml; The add-on of tertbutyl peroxide is 20～60ml, air 2-10L/h, oxygen 1-3L/h.
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|---|---|---|---|
| CN2010102231445A CN102311328A (en) | 2010-07-09 | 2010-07-09 | Method for preparing acetophenone |
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|---|---|---|---|
| CN2010102231445A CN102311328A (en) | 2010-07-09 | 2010-07-09 | Method for preparing acetophenone |
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|---|---|
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Family
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN105646220A (en) * | 2016-03-25 | 2016-06-08 | 董道青 | Synthesizing method of propiophenone compound |
| CN105669459A (en) * | 2016-03-25 | 2016-06-15 | 青岛农业大学 | Synthetic method of propiophenone compound |
| CN110317131A (en) * | 2019-07-15 | 2019-10-11 | 内蒙古民族大学 | A kind of method that second benzene-like compounds prepare ketone compounds |
-
2010
- 2010-07-09 CN CN2010102231445A patent/CN102311328A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 李家其 等: "乙苯催化氧化合成苯乙酮研究进展", 《精细化工中间体》 * |
| 李贵贤 等: "Keggin型磷钼钒杂多化合物催化氧化乙苯制苯乙酮", 《现代化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN105646223B (en) * | 2014-12-04 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method that levulic acid catalysis oxidation esterification prepares succinate |
| CN105646220A (en) * | 2016-03-25 | 2016-06-08 | 董道青 | Synthesizing method of propiophenone compound |
| CN105669459A (en) * | 2016-03-25 | 2016-06-15 | 青岛农业大学 | Synthetic method of propiophenone compound |
| CN105669459B (en) * | 2016-03-25 | 2017-09-01 | 青岛农业大学 | A kind of synthetic method of phenylpropyl alcohol ketone class compound |
| CN105646220B (en) * | 2016-03-25 | 2017-12-01 | 董道青 | Synthetic method of propiophenone compound |
| CN110317131A (en) * | 2019-07-15 | 2019-10-11 | 内蒙古民族大学 | A kind of method that second benzene-like compounds prepare ketone compounds |
| CN110317131B (en) * | 2019-07-15 | 2022-02-01 | 内蒙古民族大学 | Method for preparing ketone compound from ethylbenzene compound |
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Application publication date: 20120111 |