CN1986513A - Preparing process of 2,3,5-trimethyl benzoquinone - Google Patents
Preparing process of 2,3,5-trimethyl benzoquinone Download PDFInfo
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- CN1986513A CN1986513A CN 200610155429 CN200610155429A CN1986513A CN 1986513 A CN1986513 A CN 1986513A CN 200610155429 CN200610155429 CN 200610155429 CN 200610155429 A CN200610155429 A CN 200610155429A CN 1986513 A CN1986513 A CN 1986513A
- Authority
- CN
- China
- Prior art keywords
- hso
- ionic liquid
- bmim
- pseudocuminol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 5
- -1 aliphatic alcohols Chemical class 0.000 claims description 22
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 229960003280 cupric chloride Drugs 0.000 claims description 12
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 4
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910002056 binary alloy Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 abstract 2
- 150000002191 fatty alcohols Chemical class 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYQWRHUSMUEYST-UHFFFAOYSA-N [14]annulene Chemical compound C1=CC=CC=CC=CC=CC=CC=C1 RYQWRHUSMUEYST-UHFFFAOYSA-N 0.000 description 2
- 150000001538 azepines Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- IGWHDMPTQKSDTL-JXOAFFINSA-N TMP Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to 2, 3, 5-trimethyl benzoquinone. Inside lower fatty alcohol with ionic liquid and copper chloride as binary catalyst system, and at the reaction temperature of 20-120 deg.c, 2, 3, 6-trimethyl phenol is oxidized with molecular oxygen or oxygen-rich air to produce 2, 3, 5-trimethyl benzoquinone. The present invention has the advantages of mild reaction condition, high reaction yield and low catalyst consumption.
Description
Technical field
The present invention relates to a kind of is catalyzer with ionic liquid and cupric chloride, uses molecular oxygen or oxygen rich gas with 2,3 in lower aliphatic alcohols, 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 just 2,3,6-pseudocuminol (hereinafter to be referred as TMP) is oxidized to 2,3,5-trimethylbenzoquinone (hereinafter to be referred as TMQ)) many known methods are arranged.TMQ's is synthetic as follows:
Known catalyzer comprises: Schiff-cobalt complex (DE-A3302498, JP-A127937), four azepines [14] annulene heavy metal complexes (EP0659727), metallic molecular sieve (TW090100156), heteropolyacid (CN1234789), copper halide and halogenation (EP0127888), copper halide and transition metal halide or rare earth element halogenide (CN 1293182A), copper halide and alkaline earth metal halide (EP0475272), cupric chloride and lithium chloride (EP0294584), copper halide and nitrogenous compound (EP0475272) etc.
Wherein, Schiff-cobalt complex, four azepines [14] annulene heavy metal complex, metallic molecular sieve and heteropolyacid etc. are easy to decompose in reaction, easy inactivation, and reaction yield is low, makes it be not suitable for industrial application.Though the aqueous phase catalyst that copper halide and various metal halide are formed has higher transformation efficiency and yield, deficiency need to be stoichiometry, has increased production cost.The catalyzer that copper halide and nitrogenous compound are formed influences product yield because of nitrogen component decomposes under oxidizing condition, production cost is higher.
Bibliographical information use cupric chloride and [Bmim] Cl (
J.MOL.CATAL.A-CHEM, 2005,240,119-122) make catalyzer, shortcoming is that reaction needs to be forced under the 10bar to carry out inconvenient operation, practical application difficulty in autoclave.
Summary of the invention
The objective of the invention is the problem that catalyst levels is big, reaction efficiency is low, provide a kind of reaction conditions gentleness, the reaction yield height at the prior art existence, catalyst levels is low, by 2,3,6-pseudocuminol oxidation preparation 2,3, the novel method of 5-trimethylbenzoquinone.
Provided by the invention 2,3, the preparation method of 5-trimethylbenzoquinone is a catalyzer with ionic liquid and cupric chloride, uses molecular oxygen or oxygen rich gas with 2,3 in lower aliphatic alcohols, and the 6-pseudocuminol is oxidized to 2,3, the method for 5-trimethylbenzoquinone.
The present invention 2,3, and 5-trimethylbenzoquinone preparation method is characterized in that with the lower aliphatic alcohols being reaction medium, use ionic liquid and cupric chloride binary system to be catalyzer, use molecular oxygen or oxygen rich gas oxidation 2,3, the 6-pseudocuminol, generate 2,3, the 5-trimethylbenzoquinone.
Be suitable for ionic liquid of the present invention imidazoles, amine are arranged, the various ionic liquid that croak class, quaternary phosphonium class etc. form, these raw materials can be bought on market, perhaps can be by the synthetic (Green.Chem. of known method, 2004,6,75-77), more specifically, used ionic liquid is meant that under a kind of normal temperature that organic cation and organic or inorganic anion form be the solution of liquid.
Among the present invention, the mol ratio of its ionic liquid and cupric chloride is 1: 50-50: between 1, and preferably 1: 10-10: between 1.
Ionic liquid of the present invention is [Bmim] [HSO
4], [Bmim] [Br], [Bmim] [BF
4], [Bmim] [H
2PO
4], [Bmim] [PF
6], [Emim] [HSO
4], [Emim] [H
2PO
4], [Hmim] [HSO
4], [Hmim] [H
2PO
4], [BuPy] [HSO
4], [BuPy] [BF
4], [BuPy] [Cl], [BuPy] [Br], [Me
2NH] [BF
4], [Me
3NH] [HSO
4], [Me
3NH] [H
2PO
4], [Me
3NH] [BF
4], [EtNH
2] [HSO
4], [EtNH
2] [NO
3], [Et
3NH] [HSO
4], [Et
3NH] [H
2PO
4] a kind of.
The present invention 2,3, and 6-pseudocuminol and ion liquid mol ratio can be in the variation ranges of a broad, usually between 10000: 1 to 5: 1, and preferably between 5000: 1 to 10: 1.
Being fit to lower aliphatic alcohols of the present invention has ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol a kind of.
The present invention 2,3, and the mass ratio of 6-pseudocuminol and lower aliphatic alcohols is between 50: 1 to 1: 50, and preferably between 10: 1 to 1: 10.
Employed in the present invention oxygenant can be pure oxygen, be rich in gas, the air of oxygen.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 0.2～2Mpa, and preferably at 0.5～1Mpa.
Be suitable for temperature of reaction of the present invention between 20 ℃～120 ℃, and preferably between 50 ℃～100 ℃.
Of the present invention 2,3, the method for 5-trimethylbenzoquinone uses common ionic liquid and cupric chloride as catalyzer, the reaction conditions gentleness, and the reaction yield height, and catalyst levels is low.
Embodiment
Following embodiment will more comprehensively describe the present invention.
Among the embodiment 2,3, the productive rate of 5-trimethylbenzoquinone is to demarcate and get with gas-chromatography, and timing signal use ethyl benzoate is interior mark.
Embodiment 1
With 1.1g (0.005mol) [bmim] BF
4, 0.8gCuCl
22H
2O (0.005mol) and 25.0ml n-hexyl alcohol are added in the four neck flasks of 250ml, and vigorous stirring (1000rpm) is heated to 80 ℃, simultaneously by the grass tube aerating oxygen.The n-hexyl alcohol solution that will contain 6.8g (0.05mo1) TMP then slowly joins in the flask, reacts under the condition of pressurization, and oxygen pressure may command 1.2Mpa continues reaction 5 hours, and after reaction finished, demarcating the TMQ molar yield with gas-chromatography was 90.6%.
Embodiment 2
With 0.6g (0.005mol) [Me
2N] BF
4, 0.8gCuCl
22H
2O (0.005mol) and 25.0ml n-hexyl alcohol are added in the four neck flasks of 250ml, and vigorous stirring (1000rpm) is heated to 80 ℃, simultaneously by the grass tube aerating oxygen.To contain 2,3 then, the n-hexyl alcohol solution of 6-pseudocuminol slowly joins in the flask, continues reaction 5 hours, and after reaction finished, demarcating the TMQ molar yield with gas-chromatography was 82.7%.
Embodiment 3
With 1.1g (0.005mol) [BuPy] BF
4, 0.8gCuCl
22H
2O (0.005mol) and 25.0ml n-hexyl alcohol are added in the four neck flasks of 250ml, and vigorous stirring (1000rpm) is heated to 80 ℃, simultaneously by the grass tube aerating oxygen.To contain 6.8g (0.05mol) 2,3 then, the n-hexyl alcohol solution of 6-pseudocuminol slowly joins in the flask, continues reaction 5 hours, and after reaction finished, demarcating the TMQ molar yield with gas-chromatography was 81.0%.
Embodiment 4-10
Be similar to embodiment 1, adopt different ionic liquid, lower aliphatic alcohols, temperature of reaction, reaction pressure, get following result (table one) after reaction finishes:
Table one
| Embodiment | The ionic liquid kind | The lower aliphatic alcohols kind | Temperature of reaction (℃) | Reaction pressure (atm) | TMQ yield (%) |
| 4 | [bmim][HSO 4] | N-propyl alcohol | 120 | 1.5 | 80.2 |
| 5 | [bmim][NO 3] | Ethanol | 80 | 1.5 | 82.2 |
| 6 | [bmim][Br] | Propyl carbinol | 80 | 1.0 | 85.7 |
| 7 | [bmim][BF 4] | N-Heptyl alcohol | 50 | 1.0 | 95.2 |
| 8 | [bmim][BF 4] | N-Heptyl alcohol | 100 | 1.0 | 91.0 |
| 9 | [EtNH 2][HSO 4] | N-Octanol | 80 | 2.0 | 75.5 |
| 10 | [EtNH 2][NO 3] | N-Octanol | 20 | 1.0 | 74.9 |
Embodiment 11-15
Be similar to embodiment 1, adopt the mol ratio of different ionic liquid and cupric chloride, TMP and ion liquid mole be the mass ratio of TMP and lower aliphatic alcohols when, must following result (table two):
Table two
| Embodiment | The ionic liquid kind | The lower aliphatic alcohols kind | TMP/ ionic liquid/CuCl 22H 2O (mol ratio) | TMP/ lower aliphatic alcohols (mass ratio) | TMQ yield (%) |
| 11 | [bmim][HSO 4] | N-propyl alcohol | 1∶0.1∶0.5 | 1∶30 | 82.0％ |
| 12 | [bmim][NO 3] | Ethanol | 1∶0.1∶1.0 | 1∶30 | 83.6％ |
| 13 | [bmim][Br] | Propyl carbinol | 1∶0.25∶1 | 1∶25 | 88.9％ |
| 14 | [bmim][BF 4] | N-Heptyl alcohol | 1∶0.25∶1 | 1∶25 | 90.0％ |
| 15 | [bmim][BF 4] | N-Octanol | 1∶0.5∶0.5 | 1∶30 | 87.8％ |
Claims (10)
1, a kind of preparation 2,3,5-trimethylbenzoquinone method is characterized in that with the lower aliphatic alcohols being reaction medium, use ionic liquid that imidazoles is arranged, amine, the croak class, a kind of ionic liquid liquid and the cupric chloride binary system of quaternary phosphonium class are catalyzer, use molecular oxygen or oxygen rich gas, oxidation 2,3, the 6-pseudocuminol generates 2,3, the 5-trimethylbenzoquinone, described 2,3,6-pseudocuminol and ion liquid mol ratio are 10000: 1-5: between 1, described 2,3, the mass ratio of 6-pseudocuminol and lower aliphatic alcohols is 50: 1-1: between 50, described temperature of reaction is between 20 ℃～120 ℃.
2, according to the described preparation method of claim 1, it is characterized in that described ionic liquid and cupric chloride binary system catalyzer, the mol ratio of its ionic liquid and cupric chloride is 1: 50-50: between 1.
3, according to the described preparation method of claim 2, the mol ratio that it is characterized in that described ionic liquid and cupric chloride is 1: 10-10: between 1.
4,, it is characterized in that described ionic liquid is [Bmim] [HSO according to claim 1 or 2 described preparation methods
4], [Bmim] [Br], [Bmim] [BF
4], [Bmim] [H
2PO
4], [Bmim] [PF
6], [Emim] [HSO
4], [Emim] [H
2PO
4], [Hmim] [HSO
4], [Hmim] [H
2PO
4], [BuPy] [HSO
4], [BuPy] [BF
4], [BuPy] [Cl], [BuPy] [Br], [Me
2NH] [BF
4], [Me
3NH] [HSO
4], [Me
3NH] [H
2PO
4], [Me
3NH] [BF
4], [EtNH
2] [HSO
4], [EtNH
2] [NO
3], [Et
3NH] [HSO
4], [Et
3NH] [H
2PO
4] a kind of.
5, according to the described preparation method of claim 1, it is characterized in that describedly 2,3,6-pseudocuminol and ion liquid mol ratio are between 5000: 1 to 10: 1.
6,, it is characterized in that lower aliphatic alcohols is an ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol a kind of according to the described preparation method of claim 1.
7, according to the described preparation method of claim 1, it is characterized in that 2,3, the mass ratio of 6-pseudocuminol and lower aliphatic alcohols is between 10: 1 to 1: 10.
8,, it is characterized in that reaction pressure is between 0.1～2Mpa under the situation of using pure oxygen according to the described preparation method of claim 1.
9, described according to Claim 8 preparation method is characterized in that reaction pressure is between 0.5～1Mpa under the situation of using pure oxygen.
10,, it is characterized in that temperature of reaction is between 50 ℃～100 ℃ according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610155429 CN1986513A (en) | 2006-12-25 | 2006-12-25 | Preparing process of 2,3,5-trimethyl benzoquinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610155429 CN1986513A (en) | 2006-12-25 | 2006-12-25 | Preparing process of 2,3,5-trimethyl benzoquinone |
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| Publication Number | Publication Date |
|---|---|
| CN1986513A true CN1986513A (en) | 2007-06-27 |
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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 |
| JP2016526549A (en) * | 2013-07-02 | 2016-09-05 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing 2,3,5-trimethylbenzoquinone by oxidation of 2,3,6-trimethylphenol |
| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
-
2006
- 2006-12-25 CN CN 200610155429 patent/CN1986513A/en active Pending
Cited By (6)
| 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 |
| CN102633614A (en) * | 2012-04-01 | 2012-08-15 | 河南大学 | Preparation method of 2, 3, 5-trimethyl benzoquinone (TMBQ) |
| JP2016526549A (en) * | 2013-07-02 | 2016-09-05 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing 2,3,5-trimethylbenzoquinone by oxidation of 2,3,6-trimethylphenol |
| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
| CN107413386B (en) * | 2017-08-21 | 2020-11-24 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing methylal by methanol liquid-phase one-step oxidation, and preparation method and use method thereof |
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