EP3140273A1 - Process for the production of 2,6-dimethylbenzoquinone - Google Patents
Process for the production of 2,6-dimethylbenzoquinoneInfo
- Publication number
- EP3140273A1 EP3140273A1 EP15721227.5A EP15721227A EP3140273A1 EP 3140273 A1 EP3140273 A1 EP 3140273A1 EP 15721227 A EP15721227 A EP 15721227A EP 3140273 A1 EP3140273 A1 EP 3140273A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iii
- process according
- mol
- present
- copper salt
- 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.)
- Withdrawn
Links
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
Definitions
- the present invention relates to an improved process for the production of 2,6- dimethylbenzoquinone (2,6-DMQ).
- 2,6-DMQ is used for example in the synthesis of Vitamin E.
- JP 2006-249036 a method for the manufacture of 2,3,5-trimehtlyhydroquinone is disclosed.
- 2,6-dimethylphenol is oxidised with 0 2 in the presence of a Cu(l) or Cu(ll) compound.
- the amount of the Cu compound is between 0.01 to 0.02 mol-equivalent (mol-eq). This process still produces significant amounts of side-products.
- the present invention relates to a process (I) for the production of 2,6- dimethylbenzoquinone, wherein 2,6-dimethylphenol is oxidised by O2 in the presence of at least 0.4 mol-eq, based on the mol of 2,6-dimethylphenol, of at least one copper salt.
- the increased amount of at least one copper salt leads to a process with an excellent yield and selectivity of 2,6-dimethylbenzoquinone. That means that the amount of side products (dimer formation) is surprisingly decreased dramatically.
- the present invention also relates to a process ( ⁇ ), which is process (I), wherein the at least one copper salt is a Cu(ll) salt. Therefore the present invention also relates to a process (II"), which is process (I), wherein the copper salt is CuC .
- the at least one copper salt (preferably Cu(ll) salt, more preferably CuCI 2 ) is used in amount of at least 0.4 mol-eq, based on the mol of 2,6-dimethylphenol.
- Preferred is a process, wherein 0.4 to 2 mol-eq, more preferably up to 1 .8 mol-eq, of at least one copper salt is used.
- the present invention also relates to a process (III), which is process (I), (II), (II') or (II"), wherein the at least one copper salt is used in an amount of at least 0.4 mol-eq, based on the mol of 2,6-dimethylphenol.
- the present invention also relates to a process (I II'), which is process (I), (II), ( ⁇ ) or (II"), wherein the at least one copper salt is used in an amount of 0.4 to 2 mol-%, based on the mol of 2,6-dimethylphenol.
- the present invention also relates to a process (III"), which is process (I), (II), ( ⁇ ) or (II"), wherein the at least one salt compound is used in amount of 0.4 to 1 .8 mol-eq, based on the mol of 2,6-dimethylphenol.
- the copper salt (catalyst) can be reused.
- the process according to the present invention is usually carried out at a temperature of from 50°C to 95°C, preferably from 60°C to 85°C, more preferably from 70 to 85°C, most preferably from 70 to 80°C.
- the present invention also relates to a process (IV), which is process (I), (II), ( ⁇ ), (II"), (III), (III * ) or (III"), wherein the process is carried out at a temperature of from 50°C to 95°C.
- the present invention also relates to a process (IV), which is process (I), (II), ( ⁇ '), (II"), (III), (III') or (III"), wherein the process is carried out at a temperature of from 60°C to 85°C. Therefore the present invention also relates to a process (IV"), which is process (I), (II), ( ⁇ ), (II"), (III), (III') or (III"), wherein the process is carried out at a temperature of from 70 to 85°C.
- the present invention also relates to a process (IV"), which is process (I), (II), ( ⁇ '), (II"), (III), (III') or (III"), wherein the process is carried out at a temperature of from 70 to 80°C.
- the process according to the present invention is usually carried out in an inert sol- vent (or mixture of solvents), the solvent can be non-polar or polar.
- the solvent (or the mixture of solvents) has to be liquid at the reaction conditions (temperature, pressure) of the process according to the present invention.
- Suitable solvents are alkylene carbonates and glycol ethers.
- Preferred solvents are ethylene carbonates and methyl diethylene glycol (MDG).
- the present invention also relates to a process (V), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV") or (IV"), wherein the process is carried out in an inert solvent (or mixture of solvents). Therefore the present invention also relates to a process (V), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV”) or (IV"), wherein the process is carried out at in at least one solvent chosen from the group consisting of alkylene carbonates and glycol ethers.
- the present invention also relates to a process (V"), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV") or (IV"), wherein the process is carried out at in at least one solvent chosen from the group consisting of ethylene carbonates and methyl diethylene glycol (MDG).
- the oxidation process according to the present invention can be carried out with pure O2 gas as well as with a gas mixture containing O2 gas (such as air). Preferred is pure 0 2 gas.
- the present invention also relates to a process (VI), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV"), (IV"), (V), (V) or (V), wherein the process is carried with gas mixture containing O 2 gas. Therefore the present invention also relates to a process (VI'), which is process (VI), wherein the gas is air.
- the present invention also relates to a process (VI"), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV), (V), (V) or (V"), wherein the process is carried with pure O 2 .
- O 2 or air is induced directly into the liquid reaction mixture.
- the flow rate of the oxygen can vary. The flow rate is dependent on the size of the reaction apparatus.
- the present invention also relates to a process (VII), which is process (I), (II), ( ⁇ '), (II"), (III), (III'), (III"), (IV), (IV), (IV"), (IV"), (V), (V), (V) (VI), (VI') or (VI"), wherein (Vcontaining gas is induced directly into the liquid reaction mixture.
- the so obtained 2,6-DMQ can be isolated using commonly known methods or it can be used without isolation for further reactions.
- 2,6-DMQ can be used as starting material in organic synthesis.
- 2,6- DMQ can be used to form 2,3,5-trimethylhydroquinone (TMHQ), which is then reacted with (all-rac)-isophytol to obtain (all-rac)-a-tocopherol.
- TMHQ 2,3,5-trimethylhydroquinone
- Example 1 A solution of 4.10 g of CuC1 ⁇ 2 x 2H 2 0 in 8.4 ml of methyl diethyl glycol (MDG) was added into a flask. The solution was heated to 75°C and O2 was introduced (30 ml/min) into the solution and the solution was stirred.
- MDG methyl diethyl glycol
- the amount of CUCI2 x 2H 2 0 was 1 .2 mol-eq (in regard to the starting material). After the addition of the 2,6-DMP, the reaction mixture was stirred for another hour. Afterwards the obtained product (2,6-DMQ) was isolated.
- the yield was 81 % and the conversion was >99.9% and the selectivity was 81 %.
- Example 2 The procedure as described in Example 1 was repeated, but the O2 flow was in- creased to 60 ml/min.
- the yield was 84% and the conversion was >99.9 % and the selectivity was 84%.
- Example 3 Comparison Example The procedure as described in Example 1 was repeated, but the amount of CuC x 2H 2 0 was reduced to 0.68 g. which are 0.2 mol-eq.
- the yield was 49% and the conversion was >99.9 % and the selectivity was 49%. It can be seen that a low amount of CuCI 2 x 2H 2 O results in lower selectivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14167752 | 2014-05-09 | ||
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 |
---|---|
EP3140273A1 true EP3140273A1 (en) | 2017-03-15 |
Family
ID=53059106
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15721227.5A Withdrawn EP3140273A1 (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) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3781543B1 (en) | 2018-04-17 | 2023-09-27 | DSM IP Assets B.V. | Oxidation of alkylated p-hydroquinones in aqueous solutions by oxygen |
EP3781542B1 (en) | 2018-04-17 | 2022-05-18 | DSM IP Assets B.V. | Oxidation of alkylated p-hydroquinones in aqueous solutions by hydrogen peroxide |
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005063669A1 (en) * | 2003-12-18 | 2005-07-14 | General Electric Company | Processes for preparing benzoquinones and hydroquinones |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL39225A (en) * | 1971-05-17 | 1975-07-28 | Sparamedica Ag | Process for the manufacture of methyl substituted p-benzoquinones |
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 |
JPH0657669B2 (en) * | 1985-12-23 | 1994-08-03 | 三井東圧化学株式会社 | Method for producing quinones |
JPH0381249A (en) * | 1989-08-23 | 1991-04-05 | Agency Of Ind Science & Technol | Production of 2,6-dimethyl-p-benzoquinone |
US20050137380A1 (en) * | 2003-12-18 | 2005-06-23 | Mahalingam Rathinam J. | 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 |
CN102336643B (en) * | 2011-07-13 | 2014-06-25 | 北京博源恒升高科技有限公司 | Process for synthesizing benzoquinones by direct oxidation of phenols |
-
2015
- 2015-05-07 WO PCT/EP2015/060063 patent/WO2015169898A1/en active Application Filing
- 2015-05-07 EA EA201692246A patent/EA035035B1/en not_active IP Right Cessation
- 2015-05-07 EP EP15721227.5A patent/EP3140273A1/en not_active Withdrawn
- 2015-05-07 CN CN201580023802.7A patent/CN106458820A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005063669A1 (en) * | 2003-12-18 | 2005-07-14 | General Electric Company | Processes for preparing benzoquinones and hydroquinones |
Also Published As
Publication number | Publication date |
---|---|
EA201692246A1 (en) | 2017-04-28 |
EA035035B1 (en) | 2020-04-20 |
WO2015169898A1 (en) | 2015-11-12 |
CN106458820A (en) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2903797C (en) | Processes for the preparation of an apoptosis-inducing agent | |
CN102911079B (en) | The method of-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate is prepared by ketoxime ether | |
WO2018025722A1 (en) | Method for producing intermediate of biotin and method for producing biotin | |
EP3275886A1 (en) | Method for producing dialkylaminosilane | |
WO2018163517A1 (en) | Method for producing dialkylaminosilane | |
EP3140273A1 (en) | Process for the production of 2,6-dimethylbenzoquinone | |
WO2019057600A1 (en) | New intermediates for the vitamin a synthesis | |
CN111233617A (en) | Synthesis method of 1-iodoalkyne compound | |
KR20200041319A (en) | Production process of arylsulfonylpropennitrile by photocatalytic reaction | |
US20120053048A1 (en) | Diaryliodonium salt mixture and process for production thereof, and process for production of diaryliodonium compound | |
JP6682968B2 (en) | Method for producing epoxy compound | |
JP2011105762A (en) | Method for preparing 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane | |
KR102641324B1 (en) | Process for preparing dialkyl dicarbonates using tertiary amines as catalysts | |
EP3112334A1 (en) | Process for manufacturing 1-cyclopropyl-naphthalenes | |
WO2019170712A1 (en) | Process for the production of springene | |
JPWO2020004043A1 (en) | Method for producing α-azidaniline derivative or α, α'-diazide derivative | |
JP2018024643A (en) | Method for producing intermediate of biotin, and method for producing biotin | |
CN111132955A (en) | Novel process for the production of β -spring ene | |
JP7227711B2 (en) | Method for producing 2-(2-haloethyl)-1,3-dioxolane | |
JP5878842B2 (en) | Process for producing 2,3,6,7,10,11-hexahydroxytriphenylenes | |
JP7279702B2 (en) | Method for producing aromatic hydroxy compound | |
JP2018108979A (en) | Method for producing lactone compound and method for producing biotin using the lactone compound | |
CN112399968A (en) | Catalytic ethynylation | |
KR101574719B1 (en) | C5 sulfone compound, method for preparing the same, method for preparing crocetin dinitrile using the same, and use thereof | |
CN116715646A (en) | Method for preparing 3-organic selenium functionalized chromone compound by three components in series through silver catalysis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20161024 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20191122 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20201021 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20210302 |