CN101113131A - Method for preparing 2,3,5-trimethylbenzene quinone - Google Patents
Method for preparing 2,3,5-trimethylbenzene quinone Download PDFInfo
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- CN101113131A CN101113131A CNA2007100693185A CN200710069318A CN101113131A CN 101113131 A CN101113131 A CN 101113131A CN A2007100693185 A CNA2007100693185 A CN A2007100693185A CN 200710069318 A CN200710069318 A CN 200710069318A CN 101113131 A CN101113131 A CN 101113131A
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- trimethylbenzoquinone
- bmim
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Abstract
The invention relates to a preparation method of 2, 3, 5-trimethylquinone. The 2, 3, 5- trimethylquinone can be produced through taking ion liquor composed of imidazole, quaternary ammonium, pyridinium ion and acid group ion as mediator, copper halide as catalyst, and oxidating 2, 3, 6- trimethylphenol by pure oxygen or oxygen-enriched gas under the conditions of reaction temperature 20-120 DEG C, reaction pressure 0.1-2MPa. The method of the invention avoids the use of volatile solvent and has the advantages of gentle reaction, and high yield, which is the green technology of synthetizing 2, 3, 5- trimethylquinone.
Description
Technical field
The present invention relates to a kind of is catalyzer with the copper halide, uses pure oxygen or oxygen rich gas with 2,3 in ionic liquid, and the 6-pseudocuminol is oxidized to 2,3, the method for 5-trimethylbenzoquinone.
Background technology
2,3,5-trimethylbenzoquinone, English name 2,3,5-trimethylbenzoquinoe is the important intermediate of preparation vitamin-E, at present with 2,3,6 pseudocuminols (hereinafter to be referred as TMP) are oxidized to 2,3, and 5-trimethylbenzoquinone (hereinafter to be referred as TMBQ) has many known methods.TMBQ's is synthetic as follows:
TMBQ's is synthetic
In many synthetic methods of having reported, the water catalyst system of being made up of copper halide is paid close attention to by industry member especially, and the advantage of these methods is that post catalyst reaction and product are easy to separate, and can recycle.
EP0294584 has described in the two phase reaction medium, and with the effectively described reaction of catalysis of catalyzer that cupric chloride and lithium chloride constitute, this two phase reaction medium comprises water and the mixture that is made of aromatic hydrocarbon and the lower aliphatic with 1-4 carbon atom.
It is catalyzer that EP0475272 adopts the copper halide and the alkaline earth metal halide aqueous solution, and with 2,3, the oxidation of 6-pseudocuminol generates 2,3, the 5-trimethylbenzoquinone with molecular oxygen.It is solvent that this method adopts the fatty saturated family alcohol of 5-10 carbon atom or the mixture of aromatic hydrocarbons and 1-4 fat of carbon atom group composition.
CN1293182A adopts the catalyst system of being made up of copper halide and transition metal halide or thulium halogenide, can be with TMP oxidation generation TMBQ with oxygen or oxygen-containing gas in the two-phase liquid reaction medium.This method by water and have the aliphatics of 1-4 carbon atom and two phase reaction medium that the mixture of toluene or benzene is formed in carry out.
The shortcoming of aforesaid method is to be reflected to be higher than or a little less than carrying out under the temperature of solvent for use flash-point, and because reaction is to be oxygenant with the molecular oxygen, makes reaction have serious potential safety hazard.For this reason, EP0387820 is a solvent with the Fatty Alcohol(C12-C14 and C12-C18) of 12-18 carbon atom, and to adopt the copper halide and the alkaline earth metal halide aqueous solution be catalyzer, but Fatty Alcohol(C12-C14 and C12-C18) high melt point and boiling point make the TMP oxidation become more complicated.On this basis, CN1319582 adopts oxygen or oxygen-containing gas mixture, in the two-phase liquid reaction medium of forming by water and 8-11 new carboxylic acid of carbon atom, obtain TMBQ with oxidation TMP such as copper halide and alkaline earth metal halide such as lithium chlorides, but space-time yield is low, and separates comparatively complexity of refined product.
Application number is that to disclose a kind of be catalyzer with ionic liquid and cupric chloride for 200610155429.3 Chinese patent, in lower aliphatic alcohols, use molecular oxygen or oxygen rich gas with 2,3, the 6-pseudocuminol is oxidized to 2,3, the method of 5-trimethylbenzoquinone, owing to being solvent with volatile lower aliphatic alcohols, there are shortcomings such as solvent is easily oxidized, reaction safety is poor, environmental pollution is big in the space-time yield height.
Summary of the invention
The objective of the invention is provides a kind of safety and reliability at problems such as the volatile solvent of employing, poor stability, the environmental pollution that exist in the existing technology are big, gentle efficient, the simple new synthetic method of technology.
Preparation 2 provided by the invention, 3, the method for 5-trimethylbenzoquinone, the ionic liquid that constitutes with imidazoles, quaternary amine and pyridylium and acid ion is a reaction medium, with copper halide as catalyzer, use pure oxygen or oxygen rich gas oxidation 2,3, the 6-pseudocuminol generates 2,3, the 5-trimethylbenzoquinone, temperature of reaction is between 20 ℃～120 ℃, and reaction pressure is between 0.1～2MPa.
Being suitable for ionic liquid of the present invention has various ionic liquids such as imidazoles, quaternary amine and pyridines, and these raw materials can be bought on market, perhaps can synthesize by known method (Green.Chem., 2004,6,75-77).Being fit to ionic liquid of the present invention is [Emim] [Cl], [Emim] [Br], [Emim] [BF
4], [Emim] [NO
3], [Bmim] [HSO
4], [Bmim] [Br], [Bmim] [Cl], [Bmim] [BF
4], [Bmim] [NO
3], [Bmim] [PF
6], [Hmim] [BF
4], [Et
3NH] [HSO
4], [EtNH
3] [HSO
4], [EtNH
3] [NO
3], [Me
3NH] [H
2PO
4], [EtNH
3] [BF
4], [Bu
3NH] [BF
4], [BuPy] [BF
4], [BuPy] [Cl], [BuPy] [Br] [BuPy] [HSO
4] in a kind of.
The mol ratio of ionic liquid of the present invention and TMP can be in the variation range of a broad, usually between 1000: 1 to 1: 1, and preferably between 10: 1 to 1: 1.
Copper halide catalyzer of the present invention is a kind of of cupric chloride, cupric bromide and cupric iodide.
The mol ratio of TMP of the present invention and copper halide is between 1000: 1 to 1: 5, and preferably between 5: 1 to 1: 2.
Employed in the present invention oxygenant can be pure oxygen, be rich in the gas or the air of oxygen, and in 1 kilogram of TMP, oxygen-supply quantity hourly is 50～1000L normally, and preferably at 100～500L.For other oxygen-containing gass, its air flow can be converted accordingly according to oxygen level.Especially, under the situation of using pure oxygen, can react under the condition of pressurization, oxygen pressure can be controlled in 0.1～2Mpa, and preferably at 0.1～1Mpa.
Be suitable for temperature of reaction of the present invention between 20 ℃～120 ℃, and preferably between 40 ℃～60 ℃.
After the present invention reacted end, underpressure distillation obtained product, and remaining mixing solutions is used for reaction after adding catalyzer once more.
The present invention compared with prior art, avoided the use of volatile solvent, ionic liquid can recycle repeatedly, reduced the consumption of catalyzer, thereby reduced the generation of " three wastes ", being a kind of synthesis technique of green, having advantages such as reaction yield height, security be good, low in the pollution of the environment, is a kind of green technology of synthetic trimethylbenzoquinone.
Embodiment
Following embodiment will more comprehensively describe the present invention.
Embodiment 1
With 11.2g (0.05mol) [Bmim] BF
4, 1.7gCuCl
22H
2O (0.01mol) and 1.4g (0.01mol) TMP are added in the three-necked flask of 250ml, be heated to 60 ℃, by the grass tube aerating oxygen, vigorous stirring (1000rpm) is reacted oxygen pressure may command 1.0Mpa under the condition of pressurization simultaneously, reacted 4 hours, after reaction finished, underpressure distillation obtained product, and the TMBQ productive rate is 85.6%.
Embodiment 2
With 11.4g (0.05mol) [Bmim] HSO
4, 2.6gCuBr
22H
2O (0.01mol) and 1.4g (0.01mol) TMP are added in the three-necked flask of 250ml, be heated to 80 ℃, by the grass tube aerating oxygen, vigorous stirring (1000rpm) is reacted under the condition of pressurization simultaneously, oxygen pressure may command 1.0Mpa, reacted 2 hours, after reaction finished, underpressure distillation obtained product, underpressure distillation obtains product, and the TMBQ productive rate is 80.6%.
Embodiment 3
With 9.6g (0.05mol) [Bmim] Cl, 3.7gCuI
22H
2O (0.01mol) and 1.4g (0.01mol) TMP are added in the three-necked flask of 250ml, be heated to 100 ℃, by the grass tube aerating oxygen, vigorous stirring (1000rpm) is reacted oxygen pressure may command 1.0Mpa under the condition of pressurization simultaneously, reacted 1 hour, after reaction finished, underpressure distillation obtained product, and the TMBQ productive rate is 82.5%.
Embodiment 4-10
Be similar to embodiment 1, adopt different ionic liquid, temperature of reaction, reaction pressure gets following result after reaction finishes
(table one):
| Embodiment | Ionic liquid | Temperature of reaction (℃) | Reaction pressure (MPa) | TMBQ yield (%) |
| 4 | [Bmim][PF 6] | 80 | 1.0 | 84.2 |
| 5 | [Bmim][NO 3] | 80 | 1.0 | 82.2 |
| 6 | [Bmim][Br] | 80 | 0.5 | 85.7 |
| 7 | [Bmim][BF 4] | 60 | 0.1 | 83.5 |
| 8 | [Bmim][BF 4] | 100 | 1.0 | 80.2 |
| 10 | [EtNH 2][NO 3] | 60 | 1.0 | 74.9 |
Embodiment 11-15
Be similar to embodiment 1, adopt different TMP and the ion liquid mole mol ratio of TMP and cupric chloride when.
| Embodiment | The ionic liquid kind | TMP/CuCl 2·2H 2O/ ionic liquid (mol ratio) | TMBQ yield (%) |
| 11 | [Bmim][HSO 4] | 1∶0.6∶5 | 78.0％ |
| 12 | [Bmim][NO 3] | 1∶0.4∶5 | 83.6％ |
| 13 | [Bmim][Br] | 1∶0.25∶5 | 79.5％ |
| 14 | [Bmim][BF 4] | 1∶1∶8 | 86.0％ |
| 15 | [Bmim][BF 4] | 1∶1∶10 | 84.6％ |
Embodiment 16
Repeat reaction according to embodiment 1, after reaction finished, underpressure distillation obtained product, and remaining mixing solutions is used for reaction after adding catalyzer once more, repeats this process several times.
| Ionic liquid | Multiplicity | TMBQ yield (%) |
| [Bmim][BF 4] | 1 | 85.6％ |
| [Bmim][BF 4] | 2 | 83.6％ |
| [Bmim][BF 4] | 3 | 84.5％ |
| [Bmim][BF 4] | 4 | 80.0％ |
Claims (10)
1. one kind prepares 2,3, the method for 5-trimethylbenzoquinone is characterized in that the ionic liquid that constitutes with imidazoles, quaternary amine and pyridylium and acid ion is a reaction medium, with copper halide as catalyzer, use pure oxygen or oxygen rich gas oxidation 2,3, the 6-pseudocuminol generates 2,3, the 5-trimethylbenzoquinone, temperature of reaction is between 20 ℃～120 ℃, and reaction pressure is between 0.1～2MPa.
2. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone is characterized in that described ionic liquid is [Emim] [Cl], [Emim] [Br], [Emim] [BF
4], [Emim] [NO
3], [Bmim] [HSO
4], [Bmim] [Br], [Bmim] [Cl], [Bmim] [BF
4], [Bmim] [NO
3], [Bmim] [PF
6], [Hmim] [BF
4], [Et
3NH] [HSO
4], [EtNH
3] [HSO
4], [EtNH
3] [NO
3], [Me
3NH] [H
2PO
4], [EtNH
3] [BF
4], [Bu
3NH] [BF
4], [BuPy] [BF
4], [BuPy] [Cl], [BuPy] [Br], [BuPy] [HSO
4] a kind of.
3. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone is characterized in that the copper halide catalyzer that reacts used is a kind of of cupric chloride, cupric bromide and cupric iodide.
4. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone is characterized in that ionic liquid and 2,3, and the mol ratio of 6-pseudocuminol is between 1000: 1 to 1: 1.
5. according to the described preparation 2,3 of claim 4, the method for 5-trimethylbenzoquinone is characterized in that ionic liquid and 2,3, and the mol ratio of 6-pseudocuminol is between 10: 1 to 1: 1.
6. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone is characterized in that 2,3, and the mol ratio of 6-pseudocuminol and copper halide is between 1000: 1 to 1: 5.
7. according to the described preparation 2,3 of claim 6, the method for 5-trimethylbenzoquinone is characterized in that 2,3, and the mol ratio of 6-pseudocuminol and copper halide is between 5: 1 to 1: 2.
8. according to the described preparation 2 of claim 1,3, the method of 5-trimethylbenzoquinone, it is characterized in that under the situation of using pure oxygen or oxygen rich gas, with 1 kilogram 2,3,6-pseudocuminol meter, oxygen-supply quantity hourly is 50～1000L, reacts under the condition of pressurization, and oxygen pressure is controlled at 0.1～1Mpa.
9. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone is characterized in that temperature of reaction is between 40 ℃～60 ℃.
10. according to the described preparation 2,3 of claim 1, the method for 5-trimethylbenzoquinone, it is characterized in that reaction finishes after, underpressure distillation obtains product, remaining mixing solutions is used for reaction after adding catalyzer once more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100693185A CN101113131A (en) | 2007-06-15 | 2007-06-15 | Method for preparing 2,3,5-trimethylbenzene quinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100693185A CN101113131A (en) | 2007-06-15 | 2007-06-15 | Method for preparing 2,3,5-trimethylbenzene quinone |
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| Publication Number | Publication Date |
|---|---|
| CN101113131A true CN101113131A (en) | 2008-01-30 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260030B (en) * | 2008-04-10 | 2010-12-01 | 浙江大学 | Method for preparing 2,3,5-trimethylbenzoquinone by using ionic liquid carrying catalyst |
| CN102633614A (en) * | 2012-04-01 | 2012-08-15 | 河南大学 | Preparation method of 2, 3, 5-trimethyl benzoquinone (TMBQ) |
| CN101665422B (en) * | 2009-08-25 | 2013-05-22 | 浙江大学 | Method for preparing trimethylbenzoquinone with resin-supported catalyst |
| CN103172508A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,4-benzoquinone by directly oxidizing benzene |
| CN109809966A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of method of alkane C-H partial oxidation in ionic liquid |
-
2007
- 2007-06-15 CN CNA2007100693185A patent/CN101113131A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260030B (en) * | 2008-04-10 | 2010-12-01 | 浙江大学 | Method for preparing 2,3,5-trimethylbenzoquinone by using ionic liquid carrying catalyst |
| CN101665422B (en) * | 2009-08-25 | 2013-05-22 | 浙江大学 | Method for preparing trimethylbenzoquinone with resin-supported catalyst |
| CN103172508A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,4-benzoquinone by directly oxidizing benzene |
| CN102633614A (en) * | 2012-04-01 | 2012-08-15 | 河南大学 | Preparation method of 2, 3, 5-trimethyl benzoquinone (TMBQ) |
| CN109809966A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of method of alkane C-H partial oxidation in ionic liquid |
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