CN106458820A - Process for the production of 2,6-dimethylbenzoquinone - Google Patents
Process for the production of 2,6-dimethylbenzoquinone Download PDFInfo
- Publication number
- CN106458820A CN106458820A CN201580023802.7A CN201580023802A CN106458820A CN 106458820 A CN106458820 A CN 106458820A CN 201580023802 A CN201580023802 A CN 201580023802A CN 106458820 A CN106458820 A CN 106458820A
- Authority
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- China
- Prior art keywords
- iii
- mantoquita
- gas
- aforementioned
- solvent
- 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
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- SENUUPBBLQWHMF-UHFFFAOYSA-N 2,6-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=C(C)C1=O SENUUPBBLQWHMF-UHFFFAOYSA-N 0.000 title abstract 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 8
- -1 alkylene carbonates Chemical class 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000011877 solvent mixture Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- MLHQPPYBHZSBCX-UHFFFAOYSA-N 1-(2-hydroxyethoxy)propan-2-ol Chemical compound CC(O)COCCO MLHQPPYBHZSBCX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- KLIDCXVFHGNTTM-UHFFFAOYSA-N syringol Natural products COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 4
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-DiMepyz Natural products CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect 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
- 238000002955 isolation Methods 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an improved process for the production of 2,6-dimethylbenzoquinone (2,6-DMQ) by oxidation of 2,6-dimethylphenol with oxygen in the presence of a copper salt.
Description
The present invention relates to for the improved method for producing 2,6- phlorone (2,6-DMQ).
2,6- phlorones (2,6-DMQ) are the compound of formula (A),
Which is compound that is important and being widely used in organic synthesiss.2,6-DMQ is used for the conjunction of such as vitamin E
Become.
Multiple methods for producing 2,6-DMQ known in the art.But a lot of methods therein are implicitly present in 2,6 ,-
The yield of DMQ and selective problem.This problem of by-product is formed during being especially in the presence of reaction (forming dimer).
In JP 2006-249036, the method for producing TMHQ is disclosed.Reaction as the method
Step, in the presence of Cu (I) or Cu (II) compound, uses O2Oxidation 2,6- xylenol.The amount of Cu compound is 0.01
To between 0.02 molar equivalent (mol-eq).This method still produces substantial amounts of by-product.
It is therefore an object of the present invention to the method for finding a kind of 2,6-DMQ of production, wherein achieves excellent yield and choosing
Selecting property.
Surprisingly, it has been found that 2, the 6- xylenol (2,6-DMP) as compound (B)
Can be with more preferable selectivity by O in the presence of a large amount of mantoquitas (as catalyst)2Oxidation.
, it is surprising that the increase of the amount of catalyst has active influence to selectivity.
Therefore, the present invention relates to being used for producing the method (I) of 2,6- phlorone, wherein at least 0.4mol-eq (base
Mol in 2,6- xylenol) at least one mantoquita in the presence of pass through O2Oxidation 2,6- xylenol.
The amount (compared with Japanese patent application 2006-249036) of the increase of at least one mantoquita is generated with 2,6- bis-
The excellent yield of methylbenzoquinone and selective method.This means that the amount of by-product (dimer of formation) unexpectedly shows
Write and reduce.
Mantoquita is preferably at least a kind of Cu (I) salt and/or at least one Cu (II) salt, more preferably at least a kind of Cu (II)
Salt.Most preferably CuCl2(salt generally has water of crystallization=CuCl2×2H2O, therefore term CuCl2It is also covered by this shape
Formula).
Therefore, the invention further relates to method (II), it is Cu (I) salt and/or Cu which is wherein described at least one mantoquita
(II) method (I) of salt.
Therefore, the invention further relates to method (II'), its be wherein described at least one mantoquita be Cu (II) salt method
(I).
Therefore, the invention further relates to method (II "), it is CuCl which is wherein described mantoquita2Method (I).
At least one mantoquita (preferably Cu (II) salt, the more preferably CuCl2) usage amount be based on 2,6- dimethyl benzene
At least 0.4mol-eq of the mol of phenol.
The method of at least one mantoquita of 1.8mol-eq is more preferably up to using 0.4-2mol-eq preferably wherein.
Therefore, the invention further relates to method (III), its be the usage amount of wherein described at least one mantoquita be based on 2,6-
The mol of the xylenol at least method of 0.4mol-eq (I), (II), (II ') or (II ").
Therefore the invention further relates to method (III '), its be the usage amount of wherein at least one mantoquita be based on 2,6- diformazan
The method (I) of the 0.4-2mol-% of the mol of base phenol, (II), (II ') or (II ").
Therefore, the invention further relates to method (III "), its be the usage amount of wherein at least one salt compound be based on 2,
The method (I) for making 0.4-1.8mol-eq of the mol of 6- xylenol, (II), (II ') or (II ").
Mantoquita (catalyst) is reusable.
The method according to the invention generally at 50 DEG C -95 DEG C, preferably 60 DEG C -85 DEG C, more preferably 70-85 DEG C, most preferably 70-
Carry out at a temperature of 80 DEG C.
Therefore, the invention further relates to method (IV), which is the method that wherein the method is carried out at a temperature of 50 DEG C -95 DEG C
(I), (II), (II '), (II "), (III), (III ') or (III ").
Therefore, the invention further relates to method (IV'), which is the method that wherein the method is carried out at a temperature of 60 DEG C -85 DEG C
(I), (II), (II '), (II "), (III), (III ') or (III ").
Therefore, the invention further relates to method (IV "), which is the method that wherein the method is carried out at a temperature of 70-85 DEG C
(I), (II), (II '), (II "), (III), (III ') or (III ").
Therefore, the invention further relates to method (IV " '), which is the method that wherein the method is carried out at a temperature of 70-80 DEG C
(I), (II), (II '), (II "), (III), (III ') or (III ").
The method according to the invention is generally carried out in atent solvent (or solvent mixture), and the solvent can be nonpolar
Or polarity.The solvent (or solvent mixture) must be under the reaction condition (temperature, pressure) of the method according to the invention
Liquid.Suitably solvent is alkylene carbonates and glycol ethers.
Preferred solvent is ethylene carbonate and methyl diethylene glycol ether (methyl diethylene glycol)
(MDG).
Therefore the invention further relates to method (V), which is that wherein the method is carried out in atent solvent (or solvent mixture)
Method (I), (II), (II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV ") or (IV " ').
Therefore, the invention further relates to method (V '), which is the method that wherein the method is carried out at least one solvent
(I), (II), (II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV ") or (IV " '), the solvent choosing
From alkylene carbonates and glycol ethers.
Therefore, the invention further relates to method (V "), which is the method that wherein the method is carried out at least one solvent
(I), (II), (II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV ") or (IV " '), the solvent choosing
From ethylene carbonate and methyl diethylene glycol ether (MDG).
Method for oxidation according to the present invention can use pure O2Gas and contain O2The admixture of gas (such as air) of gas
Carry out.It is preferred that pure O2Gas.
Therefore, the invention further relates to method (VI), which is wherein the method with containing O2The admixture of gas of gas is carried out
Method (I), (II), (II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV "), (IV " '), (V),
(V ') or (V ").
Therefore, the invention further relates to method (VI '), which is method (VI) of the wherein described gas for air.
Therefore, the invention further relates to method (VI "), which is the wherein pure O of the method2The method (I) that carries out, (II),
(II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV "), (V), (V ') or (V ").
In a preferred embodiment, O2Or air is introduced directly in liquid reaction mixture.
The flow velocity of oxygen can be different.Flow velocity is depending on the size of reaction unit.
Therefore, the invention further relates to method (VII), which is wherein to contain O2Gas is introduced directly in liquid reaction mixture
Method (I), (II), (II '), (II "), (III), (III '), (III "), (IV), (IV '), (IV "), (IV " '), (V),
(V '), (V "), (VI), (VI ') or (VI ").
So obtained 2,6-DMQ can be separated using known method, or which can be without isolation is used for into one
Step reaction.
2,6-DMQ can be used as the starting material in organic synthesiss.For example, 2,6-DMQ can be used to form 2,3,5- trimethyls
Hydroquinone (TMHQ), is then made which be reacted with (totally disappeared rotation)-isophytol, obtains (totally disappeared rotation)-alpha-tocopherol.
Following examples are used for the present invention to be described.Temperature is degree Celsius to be given.
Embodiment
Embodiment 1
By the 4.10g CuCl in 8.4ml methyl diethylene glycol ether (MDG)2×2H2O solution is added in flask.By solution plus
Heat to 75 DEG C, and by O2It is introduced in (30ml/min) solution, and agitating solution.
2.49g (20mmol) 2,6-DMP solution in 8.4ml MDG is slowly added in catalyst solution.DMP adds
It is for about 3 hours between the added-time.
CuCl2×2H2The amount of O is 1.2mol-eq (with respect to starting material).
After adding 2,6-DMP, reactant mixture is stirred for 1 hour.
It is then peeled off products therefrom (2,6-DMQ).
Yield is 81%, and conversion ratio is>99.9%, selectivity is 81%
Embodiment 2
Repeat the operation described in embodiment 1, simply by O2Stream increases to 60ml/min.
Yield is 84%, and conversion ratio is>99.9%, selectivity is 84%.
Embodiment 3 (comparative example)
Repeat the operation described in embodiment 1, simply by CuCl2×2H2O amount is decreased to 0.68g, i.e. 0.2mol-eq.
Yield is 49%, and conversion ratio is>99.9%, selectivity is 49%.
As can be seen that a small amount of CuCl2×2H2O causes relatively low selectivity.
Claims (12)
1. one kind is used for the method for producing 2,6- phlorone, wherein in the mol based on 2,6- xylenol at least
Pass through O in the presence of at least one mantoquita of 0.4mol-eq2Oxidation 2,6- xylenol.
2. method according to claim 1, wherein at least one mantoquita is Cu (I) and/or Cu (II) salt.
3. method according to claim 1, wherein at least one mantoquita is Cu (II) salt.
4. method according to claim 1, the wherein mantoquita is CuCl2.
5. the method according to aforementioned any one of claim, the wherein usage amount of at least one mantoquita are 0.4-
2mol-eq.
6. the method according to aforementioned any one of claim, wherein methods described at 50 DEG C -95 DEG C, preferably 60 DEG C -85 DEG C,
More preferably 70-85 DEG C, carry out at a temperature of most preferably 70-80 DEG C.
7. the method according to aforementioned any one of claim, wherein methods described is in atent solvent (or solvent mixture)
Carry out.
8. method according to claim 7, wherein described solvent (or solvent mixture) selected from alkylene carbonates and
The group of glycol ethers composition.
9. the method according to aforementioned any one of claim, wherein methods described are with containing O2The gas of gas is carried out.
10. method according to claim 7, the wherein gas are air.
11. methods according to aforementioned any one of claim 1-8, the wherein pure O of methods described2Carry out.
12. methods according to aforementioned any one of claim 1-8, wherein pure O2Gas or contain O2Gas directly drawn
Enter in liquid reaction mixture.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14167752 | 2014-05-09 | ||
| EP14167752.6 | 2014-05-09 | ||
| EP14198910.3 | 2014-12-18 | ||
| EP14198910 | 2014-12-18 | ||
| PCT/EP2015/060063 WO2015169898A1 (en) | 2014-05-09 | 2015-05-07 | Process for the production of 2,6-dimethylbenzoquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106458820A true CN106458820A (en) | 2017-02-22 |
Family
ID=53059106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580023802.7A Pending CN106458820A (en) | 2014-05-09 | 2015-05-07 | Process for the production of 2,6-dimethylbenzoquinone |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP3140273A1 (en) |
| CN (1) | CN106458820A (en) |
| EA (1) | EA035035B1 (en) |
| WO (1) | WO2015169898A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114829328A (en) * | 2019-12-19 | 2022-07-29 | 帝斯曼知识产权资产管理有限公司 | Formation of 2,3,5-trimethylhydroquinone from 2,3,6-trimethylphenol |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3781542B1 (en) | 2018-04-17 | 2022-05-18 | DSM IP Assets B.V. | Oxidation of alkylated p-hydroquinones in aqueous solutions by hydrogen peroxide |
| EP3781543B1 (en) | 2018-04-17 | 2023-09-27 | DSM IP Assets B.V. | Oxidation of alkylated p-hydroquinones in aqueous solutions by oxygen |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3796732A (en) * | 1971-05-17 | 1974-03-12 | Hoffmann La Roche | Process for oxidizing phenols to quinones |
| JPS5093931A (en) * | 1973-12-22 | 1975-07-26 | ||
| US3987068A (en) * | 1975-07-28 | 1976-10-19 | E. I. Du Pont De Nemours And Company | Oxidation of monohydroxy aryl compounds to 1,4-quinones |
| JPS62148446A (en) * | 1985-12-23 | 1987-07-02 | Mitsui Toatsu Chem Inc | Production of quinone compound |
| JP2006249036A (en) * | 2005-03-14 | 2006-09-21 | Honshu Chem Ind Co Ltd | Method for producing 2, 3, 5-trimethylhydroquinone |
| CN1918101A (en) * | 2003-12-18 | 2007-02-21 | 通用电气公司 | Processes for preparing benzoquinones and hydroquinones |
| CN102336643A (en) * | 2011-07-13 | 2012-02-01 | 北京博源恒升高科技有限公司 | Process for synthesizing benzoquinones by direct oxidation of phenols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0381249A (en) * | 1989-08-23 | 1991-04-05 | Agency Of Ind Science & Technol | Production of 2,6-dimethyl-p-benzoquinone |
| US20050137409A1 (en) * | 2003-12-18 | 2005-06-23 | Sunil Ashtekar | Processes for preparing benzoquinones and hydroquinones |
-
2015
- 2015-05-07 EA EA201692246A patent/EA035035B1/en not_active IP Right Cessation
- 2015-05-07 WO PCT/EP2015/060063 patent/WO2015169898A1/en active Application Filing
- 2015-05-07 CN CN201580023802.7A patent/CN106458820A/en active Pending
- 2015-05-07 EP EP15721227.5A patent/EP3140273A1/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3796732A (en) * | 1971-05-17 | 1974-03-12 | Hoffmann La Roche | Process for oxidizing phenols to quinones |
| JPS5093931A (en) * | 1973-12-22 | 1975-07-26 | ||
| US3987068A (en) * | 1975-07-28 | 1976-10-19 | E. I. Du Pont De Nemours And Company | Oxidation of monohydroxy aryl compounds to 1,4-quinones |
| JPS62148446A (en) * | 1985-12-23 | 1987-07-02 | Mitsui Toatsu Chem Inc | Production of quinone compound |
| CN1918101A (en) * | 2003-12-18 | 2007-02-21 | 通用电气公司 | Processes for preparing benzoquinones and hydroquinones |
| JP2006249036A (en) * | 2005-03-14 | 2006-09-21 | Honshu Chem Ind Co Ltd | Method for producing 2, 3, 5-trimethylhydroquinone |
| CN102336643A (en) * | 2011-07-13 | 2012-02-01 | 北京博源恒升高科技有限公司 | Process for synthesizing benzoquinones by direct oxidation of phenols |
Non-Patent Citations (5)
| Title |
|---|
| GO HIRAI等: "synthetic study of zoanthamine alkaloids:the C-RING MODEL POSSESSING THREE CONSECUTIVE QUATERNARY CARBONS", 《CHEMISTRY LETTERS》 * |
| KEN TAKAKI等: "Selective Oxidation of Phenols to Hydroxybenzaldehydes and Benzoquinones with Dioxygen Catalyzed by Polymer-Supported Copper", 《BULL.CHEM.SOC.JPN》 * |
| MASAO SHIMIZU等: "synthesis of alkyl substituted p-benzoquinones from the corresponding phenols using molecular oxygen catalyzed by copper(II)chloride-amine hydrochloride systems", 《BULL.CHEM.SOC.JPN》 * |
| TAKEHIRA等: "Novel Oxidation of Phenols by a Copper(I1) Complex Catalyst /02 System", 《STUDIES IN SURFACE SCIENCE AND CATALYSIS》 * |
| TAKIZAWA,Y.ETAL.: "Novel Oxidative Coupling of Monophenols in the System of Cupric Chloride-Oxygen-Alcohol", 《J.ORG.CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114829328A (en) * | 2019-12-19 | 2022-07-29 | 帝斯曼知识产权资产管理有限公司 | Formation of 2,3,5-trimethylhydroquinone from 2,3,6-trimethylphenol |
| CN114829328B (en) * | 2019-12-19 | 2025-01-10 | 帝斯曼知识产权资产管理有限公司 | Formation of 2,3,5-trimethylhydroquinone from 2,3,6-trimethylphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| EA201692246A1 (en) | 2017-04-28 |
| WO2015169898A1 (en) | 2015-11-12 |
| EP3140273A1 (en) | 2017-03-15 |
| EA035035B1 (en) | 2020-04-20 |
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