CN101260030A - Method for preparing 2,3,5-trimethylbenzoquinone by using ionic liquid carrying catalyst - Google Patents
Method for preparing 2,3,5-trimethylbenzoquinone by using ionic liquid carrying catalyst Download PDFInfo
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- CN101260030A CN101260030A CNA2008100606016A CN200810060601A CN101260030A CN 101260030 A CN101260030 A CN 101260030A CN A2008100606016 A CNA2008100606016 A CN A2008100606016A CN 200810060601 A CN200810060601 A CN 200810060601A CN 101260030 A CN101260030 A CN 101260030A
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Abstract
The invention relates to a method of preparing 2, 3, 5-trimethyl benzoquinone through ionic liquid-supported catalyst, which uses 2, 3, 6-trimethylphenol raw material, uses ionic liquid-supported acetylacetone metal as catalyst and uses alcohol solvent containing three to ten carbon atoms. At the reaction temperature from -30 DEG C to 150 DEG C, molecular oxygen or oxygen-enriched gas is used to oxidize 2, 3, 6-trimethylphenol to form 2, 3, 5-trimethyl benzoquinone. The catalyst has the following general formula of [ace-Cnmim][X]-M, wherein ace represents the category of acetylacetone; mim represents the category of imidazole; X represents the category of anion; M represents metal. The catalyst used in the invention has very good thermal stability, good solubility, little corrosion, simple recycling and repeated utilization capability.
Description
Technical field
The present invention relates to a kind of is catalyzer with ion liquid supported cetylacetone metallic, by 2,3, and 6-pseudocuminol (TMP) oxidation preparation 2,3, the method for 5-trimethylbenzoquinone (TMBQ).
Background technology
2,3, the 5-trimethylbenzoquinone is the important intermediate that is used to prepare vitamin-E.
For a long time, pseudocuminol is oxidized to 2,3, the 5-trimethylbenzoquinone has many known methods.
In US3956346, described and used natural manganese dioxide to be oxygenant, in the presence of sulfuric acid, carry out the oxidation of pseudocuminol.This method can produce a large amount of corresponding reducing metal mud shape refuses, and also has spent acid to generate, and causes great environmental problem, and refuse is regenerated or handled the cost that must cost a lot of money.
In EP0659727, use four azepines [14] annulene manganese or cadmium complex as catalyzer, but this catalyst complex in oxidizing reaction with destroyed, thereby produced metal waste and production cost increased.This reaction simultaneously must be carried out in organic solvent, uses a large amount of organic solvents also can cause inevitable environmental problem.
In US2002/0143198, announced that a kind of transition metal salt with silicoaluminate is the oxidation scheme of catalyzer, but its productive rate do not wait from 1%～80%, generally be lower than known method, be unfavorable for industrialization.And use the bigger organic solvents of toxicity such as acetonitrile in the reaction, will work the mischief environment.
In CN1436877, publicity one step of a kind of paired electrolysis pseudocuminol prepare the method for Trimethylhydroquinone, the defective of this method is that gained Trimethylhydroquinone concentration is too low, must a large amount of electrolytic solution of use, spatiotemporal efficiency is low, and the processing of electrolysis waste solution need spend high cost.
In US3796732, to have described and used the oxidation scheme of cupric chloride as catalyzer, it carries out in homogeneous phase in the presence of inert solvent such as DMF, and this method is disadvantageous reclaiming on the catalyzer, and this method does not have competitive edge yet on yield.
In EP0127888, announced (CuCl at Li
3) there is the method that down pseudocuminol is oxidized to trimethylbenzoquinone, though this method has higher yield, must use excessive greatly lithium chloride, in known method, the price of lithium chloride is very expensive, this is very unfavorable to industrial application.
In DE19949795, the method for oxidation in the binary catalyst system of copper halide and transition metal halide composition has been described, though this scheme has higher yield, must use a large amount of organic solvents in order to reduce by product, make space-time yield descend.And used alcoholic solvent with this understanding also can be oxidized, causes difficulty to recycling.
Summary of the invention
The purpose of this invention is to provide a kind of preparation 2,3, the novel method of 5-trimethylbenzoquinone, use ion liquid supported cetylacetone metallic mixture to be catalyzer, by 2,3, the oxidation of 6-pseudocuminol generates 2,3, the 5-trimethylbenzoquinone, the present invention also provides a kind of method that finishes the back reuse of catalyst in reaction.
Provided by the invention with ion liquid supported catalysts preparation 2,3, the method for 5-trimethylbenzoquinone, with 2,3, the 6-pseudocuminol is a raw material, with ion liquid supported cetylacetone metallic is catalyzer, uses the alcoholic solvent that contains three to ten carbon atoms, under-30 ℃～150 ℃ temperature of reaction, use molecular oxygen or oxygen rich gas oxidation 2,3, the 6-pseudocuminol, generate 2,3, the 5-trimethylbenzoquinone, described catalyzer has following general formula: [ace-C
nMim] [X]-M, wherein ace represents the kind of methyl ethyl diketone, and mim represents the kind of imidazoles, and X represents anionic kind, and M represents metal.
The structural formula of ion liquid supported cetylacetone metallic catalyzer used in the present invention is as follows:
Or
N=1～6 wherein; M1 is the trivalent transition-metal Fe
3+, Cr
3+, V
3+A kind of; M2 is divalent transition metal Ti
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+A kind of; R
1, R
2, R
3For H, have general formula C
mH
2m+1, the straight chain hydrocarbon of m=1 in the formula～6 or branched-chain hydrocarbon; X
-Be BF
4 -, PF
6 -, SbF
6 -, H
2PO
4 -, F
-, Cl
-, Br
-, HSO
4 -, NO
3 -Anionic a kind of.
The present invention 2,3, and the mol ratio of 6-pseudocuminol and ion liquid supported cetylacetone metallic catalyzer can be in the variation range of a broad, and is general common between 10000: 1 to 1: 1, and preferably between 5000: 1 to 5: 1.
Temperature of reaction of the present invention is between-30 ℃～150 ℃, and preferably between 0 ℃～120 ℃.
Of the present invention 2,3, the mass ratio of 6-pseudocuminol and alcohol is between 100: 1 to 1: 100.And preferably between 20: 1 to 1: 20.
Oxygenant used in the present invention is in 1 kilogram of pseudocuminol, and 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 0.2～2Mpa, and preferably at 0.5～1Mpa.
Ion liquid supported cetylacetone metallic catalyzer used in the present invention, adopt the isolating method of washing to reclaim, after reaction finishes, three washings of moisture organic phase with 0.1～5 times of organic solvent quality, merge water, 50 ℃～80 ℃ following underpressure distillation waters are to constant weight, and the residual solid thing is the catalyzer for reclaiming just.
Compare with traditional method, the used catalyzer of the present invention is very novel, and this ion liquid supported methyl ethyl diketone catalyzer has following characteristic: 1) good thermostability; 2) in water, has solvability preferably; 3) than the synthetic method more environmental protection of tradition with cupric chloride, and less to the corrosion of container; 4) catalyzer can repeatedly be recycled.
Embodiment
Following embodiment will more comprehensively describe the present invention.
Among the embodiment 2,3, the productive rate of 6-pseudocuminol is to demarcate and get with gas-chromatography, and timing signal use ethyl benzoate is interior mark.
Embodiment 1
With 13.62g TMP (0.1mol) and ion liquid supported acetylacetone copper [ace-Cmim] [the Cl]-Cu (0.01mol) of 4.93g N-Methylimidazole, water 13.9g, n-hexyl alcohol 60ml joins in the three-necked flask of 250ml, four neck flasks place water-bath, are heated to 70 ℃ under slowly stirring.By the grass tube aerating oxygen, while vigorous stirring (1000rpm).Stopped reaction after 20 hours, washing organic phase three times, standing demix is collected organic phase 14.25g, and liquid phase is demarcated TMBQ productive rate 53.4%.Collect isolated water, at 80 ℃ of backspin evaporate to dryness water, the methyl ethyl diketone copper catalyst that the N-Methylimidazole that obtains reclaiming is ion liquid supported.
Embodiment 2-8
Be similar to embodiment 1, use the ion liquid supported acetylacetone cobalt of N-Methylimidazole (II), manganese acetylacetonate (II), acetylacetonate nickel (II), acetylacetone copper (II) to make catalyzer respectively, and ion liquid supported acetylacetone copper (II) catalyzer of N-Methylimidazole gets following result (table one) after reaction finishes under different mol ratio, the temperature:
| Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Catalyzer | [ace-Cmim] [Cl]-Co (II) | [ace-Cmim] [Cl]-Mn (II) | [ace-Cmim] [BF 4]-Ni (II) | [ace-Cmim] [Cl]-Cu (II) | [ace-Cmim] [Cl]-Cu (II) | [ace-Cmim] [Cl]-Cu (II) | [ace-Cmim] [Cl]-Cu (II) |
| Mol ratio TMP: catalyzer | 100∶1 | 100∶1 | 100∶1 | 100∶1 | 10∶1 | 10∶1 | 10∶1 |
| Temperature | 80℃ | 80℃ | 80℃ | 80℃ | 90℃ | 80℃ | 70℃ |
| The TMBQ productive rate | 46.3％ | 46.9％ | 36.1％ | 46.3％ | 40.2％ | 49.8％ | 53.4％ |
Embodiment 9
Be similar to embodiment 1,13.62g TMP (0.1mol) and 4.79g imidazole ion liquid are propped up acetylacetone copper [ace-mim] [the Cl]-Cu (0.01mol) that carries join in the four neck flasks of 250ml, add entry 13.9g again, n-hexyl alcohol 60ml, 70 ℃ of following vigorous stirring, aerating oxygen simultaneously.Stopped reaction washing organic phase is three times after 6 hours, and standing demix is collected organic phase 14.22g, and liquid phase is demarcated TMBQ productive rate 55.4%.Collect isolated water, at 80 ℃ of backspin evaporate to dryness water, the imidazole ion liquid that obtains reclaiming props up the methyl ethyl diketone copper catalyst that carries.
Embodiment 10
Be similar to embodiment 1,3.40g TMP (0.025mol) and ion liquid supported manganese acetylacetonate [ace-Cmim] [the Cl]-Mn (0.0025mol) of 1.21g N-Methylimidazole are added in the 100ml four-hole boiling flask, add entry 3.50g again, n-hexyl alcohol 15ml, aerating oxygen, 70 ℃ of following vigorous stirring 8 hours.Washing organic phase three times, standing demix is collected organic phase 15.20g, and liquid phase is demarcated TMBQ productive rate 53.8%.Collect isolated water,, reclaim the ion liquid supported methyl ethyl diketone Mn catalyst of N-Methylimidazole at 80 ℃ of backspin evaporate to dryness water.
Embodiment 11
Be similar to embodiment 1, ion liquid supported acetylacetone copper [ace-Cmim] [the Cl]-Cu (0.01mol) of N-Methylimidazole that reclaims from embodiment 1 with 4.93g replaces the ion liquid supported acetylacetone copper of N-Methylimidazole of directly preparation to react, collect organic phase 15.15g, liquid phase is demarcated TMBQ productive rate 48.0%.Reclaim catalyzer once more.
Embodiment 12
Be similar to embodiment 1, ion liquid supported acetylacetone copper [ace-Cmim] [the Cl]-Cu (0.01mol) of N-Methylimidazole that reclaims from embodiment 11 with 4.93g replaces the ion liquid supported acetylacetone copper of N-Methylimidazole of directly preparation to react, collect organic phase 14.85g, liquid phase is demarcated TMBQ productive rate 60.8%.Reclaim catalyzer once more.
Claims (8)
1, a kind of with ion liquid supported catalysts preparation 2,3, the method for 5-trimethylbenzoquinone, it is characterized in that with 2,3 the 6-pseudocuminol is a raw material, with ion liquid supported cetylacetone metallic is catalyzer, uses the alcohols that contains three to ten carbon atoms to be solvent, under-30 ℃～150 ℃ temperature of reaction, use molecular oxygen or oxygen rich gas oxidation 2,3, the 6-pseudocuminol, generate 2,3, the 5-trimethylbenzoquinone, described catalyzer has following general formula: [ace-C
nMim] [X]-M, wherein ace represents the kind of methyl ethyl diketone, and mim represents the kind of imidazoles, and X represents anionic kind, and M represents metal.
2, preparation method according to claim 1 is characterized in that the structural formula of described ion liquid supported cetylacetone metallic catalyzer is as follows:
Or
N=1～6 wherein; M1 is the trivalent transition-metal Fe
3+, Cr
3+, V
3+A kind of; M2 is divalent transition metal Ti
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+A kind of; R
1, R
2, R
3For H, have general formula C
mH
2m+1, the straight chain hydrocarbon of m=1 in the formula～6 or branched-chain hydrocarbon; X
-Be BF
4 -, PF
6 -, SbF
6 -, H
2PO
4 -, F
-, Cl
-, Br
-, HSO
4 -, NO
3 -Anionic a kind of.
3, preparation method according to claim 1 is characterized in that 2,3, and the mol ratio of 6-pseudocuminol and ion liquid supported cetylacetone metallic catalyzer is between 10000: 1 to 1: 1.
4, preparation method according to claim 3 is characterized in that 2,3, and the mol ratio of 6-pseudocuminol and ion liquid supported cetylacetone metallic catalyzer is between 5000: 1 to 5: 1.
5, according to the described preparation method of claim 1, it is characterized in that 2,3, the mass ratio of 6-pseudocuminol and alcohol is between 100: 1 to 1: 100.
6, preparation method according to claim 5 is characterized in that 2,3, and the mass ratio of 6-pseudocuminol and alcohol is between 20: 1 to 1: 20.
7, preparation method according to claim 1 is characterized in that reacting under the condition of pressurization under the situation of using pure oxygen, and oxygen pressure is controlled at 0.2～2Mpa, and temperature of reaction is between 0 ℃～120 ℃.
8, preparation method according to claim 1, it is characterized in that ion liquid supported cetylacetone metallic catalyzer adopts the isolating method of washing to reclaim, after reaction finishes, three washings of moisture organic phase with 0.1～5 times of organic solvent quality, merge water, 50 ℃～80 ℃ following underpressure distillation waters are to constant weight, and the residual solid thing is the catalyzer for reclaiming just.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633614A (en) * | 2012-04-01 | 2012-08-15 | 河南大学 | Preparation method of 2, 3, 5-trimethyl benzoquinone (TMBQ) |
| CN104892515A (en) * | 2014-10-09 | 2015-09-09 | 广东工业大学 | Coordination polymer with copper spiral structure and method for preparing same |
| CN105693490A (en) * | 2016-03-11 | 2016-06-22 | 南京工业大学 | Method for oxidizing preparation of TMBQ (2,3,5-trimethylbenzoquinone) |
| CN109513461A (en) * | 2018-10-23 | 2019-03-26 | 南京工业大学 | A kind of copper catalyst of Polymer-supported and preparation and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986513A (en) * | 2006-12-25 | 2007-06-27 | 浙江大学 | Preparing process of 2,3,5-trimethyl benzoquinone |
| CN101113131A (en) * | 2007-06-15 | 2008-01-30 | 浙江大学 | Method for preparing 2,3,5-trimethylbenzene quinone |
-
2008
- 2008-04-10 CN CN2008100606016A patent/CN101260030B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633614A (en) * | 2012-04-01 | 2012-08-15 | 河南大学 | Preparation method of 2, 3, 5-trimethyl benzoquinone (TMBQ) |
| CN104892515A (en) * | 2014-10-09 | 2015-09-09 | 广东工业大学 | Coordination polymer with copper spiral structure and method for preparing same |
| CN105693490A (en) * | 2016-03-11 | 2016-06-22 | 南京工业大学 | Method for oxidizing preparation of TMBQ (2,3,5-trimethylbenzoquinone) |
| CN105693490B (en) * | 2016-03-11 | 2018-02-23 | 南京工业大学 | It is a kind of to aoxidize the method for preparing 2,3,5 trimethylbenzoquinones |
| CN109513461A (en) * | 2018-10-23 | 2019-03-26 | 南京工业大学 | A kind of copper catalyst of Polymer-supported and preparation and application |
| CN109513461B (en) * | 2018-10-23 | 2021-12-28 | 南京工业大学 | Polymer-supported copper catalyst, preparation and application thereof |
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