EP3140273A1 - Process for the production of 2,6-dimethylbenzoquinone - Google Patents

Process for the production of 2,6-dimethylbenzoquinone

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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Withdrawn
Application number
EP15721227.5A
Other languages
German (de)
French (fr)
Inventor
Bettina WÜSTENBERG
Werner Bonrath
Thomas Netscher
Jan SCHÜTZ
Bruno Lohri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of EP3140273A1 publication Critical patent/EP3140273A1/en
Withdrawn legal-status Critical Current

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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

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

PROCESS FOR THE PRODUCTION OF 2,6-DIMETHYLBENZOQUINONE
The present invention relates to an improved process for the production of 2,6- dimethylbenzoquinone (2,6-DMQ).
2,6-dimethylbenzoquinone (2,6-DMQ), which is the compound of formula (A),
is an important and widely used compound in organic synthesis. 2,6-DMQ is used for example in the synthesis of Vitamin E.
Many processes for the production of 2,6-DMQ are known from the prior art. But many of them do have the issues with the yield and the selectivity of 2,6,-DMQ. Es- pecially the forming of side products during the reaction (i.e. dimer forming) is a problem.
In JP 2006-249036 a method for the manufacture of 2,3,5-trimehtlyhydroquinone is disclosed. As a reaction step in this process 2,6-dimethylphenol is oxidised with 02 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.
Therefore the goal of the present invention was to find a process for the production of 2,6-DMQ, wherein an excellent yield and selectivity is achieved. Surprisingly, it was found out that the 2,6-dimethylphenol (2,6-DMP), which is the compound (B)
can be oxidised with O2 in the presence of a high amount of a copper salt (as a catalyst) in better selectivity.
It is surprising that the increase of the amount of the catalyst has a positive impact on the selectivity.
Therefore, 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 (in comparison the Japanese patent application 2006-249036) 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 copper salt is preferably at least one Cu(l) salt and/or at least one Cu(ll) salt, more preferred at least one Cu(ll) salt. Most preferred is CuC^ (this salt usually has crystal water= CuCl2x2H20, so the this form is also covered by the term CuCI2 ). Therefore the present invention also relates to a process (II), which is a process (I), wherein the at least one copper salt is a Cu(l) salt and/or Cu(ll) salt.
Therefore the present invention also relates to a process (ΙΓ), 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 CuCI2) 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.
Therefore 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.
Therefore the present invention also relates to a process (I II'), which is process (I), (II), (ΙΓ) 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.
Therefore the present invention also relates to a process (III"), which is process (I), (II), (ΙΓ) 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.
Therefore the present invention also relates to a process (IV), which is process (I), (II), (ΙΓ), (II"), (III), (III*) or (III"), wherein the process is carried out at a temperature of from 50°C to 95°C.
Therefore the present invention also relates to a process (IV), which is process (I), (II), (ΙΙ'), (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), (ΙΓ), (II"), (III), (III') or (III"), wherein the process is carried out at a temperature of from 70 to 85°C. Therefore the present invention also relates to a process (IV"), which is process (I), (II), (ΙΙ'), (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).
Therefore the present invention also relates to a process (V), which is process (I), (II), (ΙΙ'), (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), (ΙΙ'), (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. Therefore the present invention also relates to a process (V"), which is process (I), (II), (ΙΙ'), (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 02 gas. Therefore the present invention also relates to a process (VI), which is process (I), (II), (ΙΙ'), (II"), (III), (III'), (III"), (IV), (IV), (IV"), (IV"), (V), (V) or (V), wherein the process is carried with gas mixture containing O2 gas. Therefore the present invention also relates to a process (VI'), which is process (VI), wherein the gas is air.
Therefore the present invention also relates to a process (VI"), which is process (I), (II), (ΙΙ'), (II"), (III), (III'), (III"), (IV), (IV), (IV), (V), (V) or (V"), wherein the process is carried with pure O2.
In a preferred embodiment O2 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.
Therefore the present invention also relates to a process (VII), which is process (I), (II), (ΙΙ'), (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. For example, 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.
The following examples serve to illustrate the invention. The temperature is given in degree Celsius. Examples
Example 1 A solution of 4.10 g of CuC½ x 2H20 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.
A solution of 2.49 g (20 mmol) of 2,6-DMP in 8.4 ml of MDG was added slowly to the catalyst solution. The addition time of the DMP was about 3 hours.
The amount of CUCI2 x 2H20 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 2H20 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 CuCI2 x 2H2O results in lower selectivity.

Claims

Claims
1. A process 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.
2. Process according to claim 1 , wherein the at least copper salt is a Cu(l) and/or Cu(ll) salt.
3. Process according to claim 1 , wherein the at least copper salt is a Cu(ll) salt.
4. Process according to claim 1 , wherein the copper salt is CuC .
5. Process according to any of the preceding claims, wherein the at least copper salt is used in an amount of 0.4 to 2 mol-eq.
6. Process according to any of the preceding claims, wherein the process is 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.
7. Process according to any of the preceding claims, wherein the process is carried out at in an inert solvent (or mixture of solvents).
8. Process according to claim 7, wherein the solvent (or mixtures of solvents) is chosen from the group consisting of alkylene carbonates and glycol ethers.
9. Process according to any of the preceding claims, wherein the process is carried with a gas containing O2 gas.
10. Process according to claim 7, wherein the gas is air.
11. Process according to any of the preceding claims 1 - 8, wherein the process is carried with pure O2. Process according to any of the preceding claims 1 - 8, wherein the pure 02 gas or the 02-containing gas is induced directly into the liquid reaction mixture.
EP15721227.5A 2014-05-09 2015-05-07 Process for the production of 2,6-dimethylbenzoquinone Withdrawn EP3140273A1 (en)

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

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EP15721227.5A Withdrawn EP3140273A1 (en) 2014-05-09 2015-05-07 Process for the production of 2,6-dimethylbenzoquinone

Country Status (4)

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EP (1) EP3140273A1 (en)
CN (1) CN106458820A (en)
EA (1) EA035035B1 (en)
WO (1) WO2015169898A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112041295B (en) 2018-04-17 2023-05-09 帝斯曼知识产权资产管理有限公司 Oxidation of alkylated hydroquinone compounds in aqueous solution 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
WO2021122437A1 (en) * 2019-12-19 2021-06-24 Dsm Ip Assets B.V. Formation of 2,3,5-trimethylhydroquinone from 2,3,6-trimethylphenol

Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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
EA035035B1 (en) 2020-04-20
WO2015169898A1 (en) 2015-11-12
CN106458820A (en) 2017-02-22
EA201692246A1 (en) 2017-04-28

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