EP4077301A1 - Formation d'alpha-tocophérol à partir de 2,3,6-triméthylphénol - Google Patents

Formation d'alpha-tocophérol à partir de 2,3,6-triméthylphénol

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Publication number
EP4077301A1
EP4077301A1 EP20821237.3A EP20821237A EP4077301A1 EP 4077301 A1 EP4077301 A1 EP 4077301A1 EP 20821237 A EP20821237 A EP 20821237A EP 4077301 A1 EP4077301 A1 EP 4077301A1
Authority
EP
European Patent Office
Prior art keywords
formula
solvent
process according
compound
carbon
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
Application number
EP20821237.3A
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German (de)
English (en)
Inventor
Werner Bonrath
Thomas Netscher
Michael Schneider
Jonathan Alan Medlock
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
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Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of EP4077301A1 publication Critical patent/EP4077301A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate

Definitions

  • the present invention relates to the field of the synthesis of a-tocopherol.
  • a-Tocopherol is an important substance and is part of vitamin E.
  • the major reaction pathway in its chemical synthesis uses a condensation of (iso)phytol with 2,3,5-trimethylhydroquinone (TMHQ) as disclosed for example in Ullmann's Encyclopedia of Industrial Chemistry, Release 2010, 7 th Edition, “Vitamins”, page 44 -46.
  • TMHQ 2,3,5-trimethylhydroquinone
  • TMQ 2,3,5-trimethylquinone
  • TMP 2,3,6-trimethylphenol
  • EP 0694541 A1 discloses that alkylene carbonates are very suitable for the condensation process of TMHQ and isophytol.
  • Cyclic alkyl carbonates are, somehow, still unusual solvents for chemical reactions, the more and more, however, these solvents are used due to excellent ecotoxicity and positive fire and working hazard properties.
  • alkylene carbonates have a flashpoint of more than 120°C. In contrast to this, this is not the case for non-cyclic carbonates (such as dimethyl carbonate or diethylcarbonate (flashpoint: 14°C resp. 25°C)).
  • flashpoint such as dimethyl carbonate or diethylcarbonate (flashpoint: 14°C resp. 25°C)).
  • alkylene carbonates are attractive in view of cost.
  • alkylene carbonates which is well-known to those skilled in the art, are prone to hydrolysis.
  • the hydrolysis leads to formation of CO2 and the respective alkanediol.
  • phenol and alkylene carbonates form different alkanediol ethers of the phenols.
  • the problem to be solved by the present invention is to offer a process for the manufacturing of a-tocopherol from TMP via TMQ, which uses for all reaction steps the same solvent.
  • a “C x-y -alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms.
  • the alkyl group can be linear or branched.
  • -CFI(CFl3)-CFl2-CFl3 is considered as a C4-alkyl group.
  • butyl can be "n-butyl” or “/so-butyl” or "sec-butyl” or "tert- butyl”.
  • a “C x -y-alkane” accordingly corresponds to a linear or branched alkane comprising x to y carbon atoms.
  • the term “independently from each other” in this document means, in the context of substituents, moieties, or groups, that designated substituents, moieties, or groups can occur simultaneously with a different meaning in the same molecule.
  • substituents, moieties, or groups that designated substituents, moieties, or groups can occur simultaneously with a different meaning in the same molecule.
  • the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.
  • the solvent of the formula (X) used in the three steps a) and b) and c) is the same molecule (i.e. the groups Y 1 and Y 2 have the same meaning for the steps a) and b) and c).
  • inert means that under the conditions of the reaction said material does not undergo any chemical reaction.
  • the process comprises a step a) a) oxidation of a compound of the formula (II) to yield a compound of the formula (III).
  • the oxidation is performed by a suitable oxidizing agent (Ox).
  • oxidizing agent is O2 or peroxides, particularly in the form of H2O2, hydroperoxides, peroxy acids and esters of peroxy acids, in the presence of a catalyst.
  • the oxidation in step a) is performed using an oxidizing agent which is either oxygen or hydrogen peroxide, more preferred oxygen, in the presence of a catalyst.
  • the oxidation is performed in the presence of catalyst being a salt or complex of a transition metal which is selected from the group consisting of Ce, Mn, Fe, Cu and Zn, particularly is selected from the group consisting of Mn, Fe, Cu and Zn, more preferably of Mn(ll), Mn(IV), Fe(ll), Fe(lll), Cu(l), Cu(ll) or Zn(ll).
  • catalyst being a salt or complex of a transition metal which is selected from the group consisting of Ce, Mn, Fe, Cu and Zn, particularly is selected from the group consisting of Mn, Fe, Cu and Zn, more preferably of Mn(ll), Mn(IV), Fe(ll), Fe(lll), Cu(l), Cu(ll) or Zn(ll).
  • the oxidation is preferably performed in the presence of at least one Cu(l) salt and/or at least one Cu(ll) salt, more preferred at least one Cu(ll) salt.
  • the Cu(ll) salts are particularly copper halides. Most preferred is
  • Step a) is usually carried out at a temperature of from 40°C to 95°C, particularly between 50°C and 85°C, preferably between 55°C and 80°C.
  • the above process is preferably carried out in the presence of an organic acid.
  • the organic acid is selected from the group consisting of acetic acid, adipic acid, lactic acid, oxalic acid, citric acid, particularly acetic acid.
  • the amount of organic acid added is in an amount that the pH of the reaction mixture is in the range of 4.8 -6.8, particularly 5 - 6.8, preferably 5.5 - 6.2.
  • the amounts of organic acid added is 0.15 - 3.5 mol- equivalent, preferably 1.5 -2.5 mol-equivalent, based on the amount of compound of formula (II). It is important to stress that the optional organic acid is used in small amounts only. This is very advantageous as in view of handling, particularly in view of flammability.
  • the state-of-the-art technology uses large amounts of highly volatile organic substances, such as solvents or organic acids, in the presence of oxygen or oxygen-containing gas mixtures.
  • the oxidation takes place at a pH of 5 - 7.8, particularly of 5.5 - 6.8.
  • molecular oxygen (O2) can be used as oxidizing agent.
  • a mixture comprising oxygen and an inert gas is used as oxidizing agent. It is preferred that the amount of oxygen in such a mixture comprising oxygen and an inert gas is at least 15 % by volume, particularly at least 20 % by volume.
  • Such a mixture may, for example, be a binary mixture such as a mixture oxygen/nitrogen or oxygen/argon or alike.
  • Said mixture can consist of or comprise two or more inert gases. It is particularly preferred to use air as such a mixture comprising oxygen and an inert gas.
  • the oxidizing agent is O2 in the form of air or pure oxygen. Most preferred the oxidizing agent is O2 in the form of pure oxygen.
  • the process comprises a step b) which follows the step a) b) reduction of the compound of the formula (III) to yield the compound of the formula (I).
  • the compound of the formula (III) is reduced in the above process to the compound of the formula (I) by a reducing agent ⁇ Red).
  • the reducing agent is molecular hydrogen.
  • the compound of the formula (III) is hydrogenated by molecular hydrogen in the presence of a metal catalyst.
  • the metal of the metal catalyst is preferably selected from the group consisting of Ni, Ir, Pd, Pt, Rh and Ru, particularly Pd or Pt, particularly a heterogeneous metal catalyst on a carrier or a support material.
  • the metal catalyst can be a catalyst comprising more than one of the mentioned metals.
  • the metal of the metal catalyst is palladium.
  • the metal catalyst is preferably a heterogeneous metal catalyst on a carrier or a support material.
  • Such carrier material is particularly a solid material having a high surface area, to which the metal is affixed.
  • the support may be inert or participate in the catalytic reactions.
  • Typical supports/carrier material include various kinds of carbon or an oxide of Si, Al, Ce, Ti or Zr, particularly of Al or Si, such as alumina or silica.
  • the preferred support/carrier material is carbon. ln case the support is Cer, the preferred oxide is CeCte.
  • the oxide of Al is AI 2 O 3 and AIO(OH). Particularly preferred is Boehmite.
  • the surface area of the carrier is preferably in the range of 800 to 1500 m 2 /g, particularly of 1000 to 1200 m 2 /g.
  • the heterogeneous metal catalyst may also be affixed or immobilized on a surface of a larger object typically in form of a structured packing element which might be a part of the reactor in which the reduction takes place or an element which is inserted into said reactor.
  • the support material is, hence, preferably a structured packing element.
  • This structured packing element may be a dumped packing, a knit, an open-celled foam structure, preferably made of plastic, for example polyurethane or melamine resin, or ceramic, or a structured packing element, as already known in principle, i.e. by its geometric shape, from distillation and extraction technology.
  • structured packings in principle have a substantially smaller hydraulic diameter, frequently by a factor of from 2 to 10, than comparable internals in the field of distillation and extraction technology.
  • Useful structured packing elements are in particular metal fabric packings and wire fabric packings, for example of the design Montz A3, Sulzer BX, DX and EX. Instead of metal fabric packings, it is also possible to use structured packings made of other woven, knitted or felted materials.
  • structured packings are of flat or corrugated sheets, preferably without perforation, or other relatively large orifices, for example corresponding to the designs Montz Bl or Sulzer Mellapak.
  • the structured packings made of expanded metal are also advantageous, for example structured packings of the type Montz BSH.
  • the metal catalyst is a palladium catalyst, particularly a palladium on carbon catalyst (Pd/C).
  • the catalytic metal loading (weight ratio metal/catalyst, i.e. the weight metal / weight (metal+carrier)) is typically between 1 to 20%, preferably between 4 and 11 %, more preferably between 4 and 6% by weight.
  • the reducing agent is a transfer hydrogenation agent.
  • the compound of the formula (III) is transfer hydrogenated by a transfer hydrogenation agent to yield the compound of the formula (I).
  • Said transfer hydrogenation agent is preferably formic acid and/or a formic acid salt.
  • the reducing agent is a dithionite salt.
  • the reduction can be achieved with sodium dithionite in water according to the method as disclosed by K. Sato, Y. Fujima, A. Yamada Bull. Chem. Soc. Jap. 1968, 41, 442-444, the entire content of which is hereby incorporated by reference.
  • the reducing agent is either molecular hydrogen or a transfer hydrogenation agent or a dithionite salt.
  • Q represents a halide
  • Q represents Cl.
  • the acyloxy is preferably a group of the formula wherein R 10 represents either an C-i- 6 -alkyl or an aryl group, which is optionally substituted, particularly by at least one Ci- 6 -alkyl group.
  • R 10 represents either an Ci- 6 -alkyl or to a phenyl group.
  • R 10 represents either a methyl or a phenyl group, most preferably a methyl group.
  • Particular examples for compounds of formula (IV-A) are isophytol, isophytyl chloride, isophytyl bromide, isophytyl iodide, isophytyl acetate, isophytyl methanesulfonate, isophytyl ethanesulfonate, isophytyl benzenesulfonate, and isophytyl toluenesulfonate.
  • Particular examples for compounds of formula (IV-B) are phytol, phytyl chloride, phytyl bromide, phytyl iodide, phytyl acetate, phytyl methanesulfonate, phytyl ethanesulfonate, phytyl benzenesulfonate, and phytyl toluenesulfonate.
  • the compound of formula (IV-B) can be used as E/Z-mixture as well as in pure E- or pure Z-form. Preferred is their use as E/Z-mixtures.
  • Q represents preferably OH or Cl.
  • preferred as compound of formula (IV-A) or (IV-B) are phytol, isophytol, phytyl chloride or isophytyl chloride, more preferred phytol or isophytol. Most preferred is isophytol.
  • the use of compounds of formula (IV-A) are preferred over compounds of formula (IV-B).
  • step c) the condensation reaction of step c) can be performed as described for example in Ullmann's Encyclopedia of Industrial Chemistry, Release 2010, 7 th Edition, “Vitamins”, page 44 - 46.
  • This condensation reaction (step c)) is preferably performed using a Lewis or a Bnzsnsted acid.
  • Said Lewis or a Bnzsnsted acid are particularly those as mentioned in
  • a key element of the present invention is the solvent of formula (X).
  • All reaction steps a) and b) and c) are performed in at least one solvent of the formula (X) wherein Y 1 and Y 2 represent independently from each other either H or a methyl or ethyl group; or in a two-phase solvent mixture comprising at least one solvent (A) being of a solvent of the formula (X) and at least one solvent (B) which is not miscible with solvent of the formula (X) at room temperature in a volume ratio of (A)/(B) of between 1/50 and 50/1 .
  • the substituent Y 1 is preferably H.
  • ethylene carbonate is a preferred solvent of the formula (X).
  • propylene carbonate is another preferred solvent of the formula (X).
  • butylene carbonate is another preferred solvent of the formula (X).
  • Ethylene carbonate and propylene carbonate are the most preferred solvents of the formula (X).
  • all three reaction steps a) and b) and c) are performed in at least two solvents of the formula (X), particularly a binary or ternary mixture of ethylene carbonate and/or propylene carbonate and/or butylene carbonate, most preferably a binary mixture of ethylene carbonate and propylene carbonate. It is preferred that the ratio of ethylene carbonate to propylene carbonate is between 20:80 to 80:20, particularly 25:75 to 75:25.
  • the solvent of the formula is a carbonate solvent as commer cialized by Huntsman under the trademark Jeffsol®, particularly the blends of ethylene carbonate with propylene carbonate Jeffsol® EC-75, Jeffsol® EC-50 and Jeffsol® EC-25.
  • Jeffsol® a carbonate solvent as commer cialized by Huntsman under the trademark Jeffsol®, particularly the blends of ethylene carbonate with propylene carbonate Jeffsol® EC-75, Jeffsol® EC-50 and Jeffsol® EC-25.
  • reaction steps a) and/or b) and/or c) are performed in a two-phase solvent mixture comprising at least one solvent (A) being of a solvent of the formula (X) and at least one solvent (B) which is not miscible with solvent of the formula (X) at room temperature in a volume ratio of (A)/(B) of between 1/50 and 50/1.
  • the solvent (B) which is not miscible with the solvent (A) of the formula (X) is preferably a hydrocarbon, more preferably an alkane, particularly a C5-16- alkane, most particularly a C 6-8 -alkane. Most preferably the solvent (B) is either hexane or heptane.
  • the a-tocopherol of formula (V) is accumulated in the solvent (B) which is not miscible with the solvent (A).
  • the good solubility also allows that the process can be performed at low temperatures, particularly at temperatures below 70 °C, more preferably at temperatures between the melting point of the solvent of the formula (X) and 60°C.
  • the solvent of formula (X) has an excellent stability against the oxidizing agent, particularly against molecular oxygen as well against the reducing agent. And the yield for both reaction step is high.
  • the catalyst can be easily removed from the reaction mixture.
  • Particularly useful for this separation are either filtration or extraction.
  • Alkylene carbonates are very attractive solvents due to their excellent ecotoxicity and positive fire and working hazard properties as well as in view of cost.
  • Figure 1 shows an overview of the complete reaction scheme for the manufacturing of a-tocopherol from TMP via TMQ via TMHQ in the alkylene carbonate of formula (X).
  • the invention relates to the use of ethylene carbonate and/or propylene carbonate and/or butylene carbonate as a solvent for the reduction of 2,3,5-trimethyM ,4-benzoquinone to 2,3,5-trimethyl- hydroquinone.
  • TMQ 2,3,5-trimethylquinone
  • TMHQ 2,3,5-trimethylhydro- quinone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne la formation d'α-tocophérol à partir de 2,3,6-triméthylphénol comprenant les étapes a) d'oxydation de 2,3,6-triméthylphénol en 2,3,5-triméthylquinone, b) de réduction de 2,3,5-triméthylquinone en 2,3,5-triméthylhydroquinone, c) de condensation de 2,3,5-triméthylhydroquinone et d'isophytol ou d'un dérivé de phytol de telle sorte que toutes les étapes de réaction a), b) et c) sont effectuées dans un solvant carbonate d'alkylène cyclique.
EP20821237.3A 2019-12-19 2020-12-14 Formation d'alpha-tocophérol à partir de 2,3,6-triméthylphénol Pending EP4077301A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19217787 2019-12-19
PCT/EP2020/085943 WO2021122439A1 (fr) 2019-12-19 2020-12-14 Formation d'alpha-tocophérol à partir de 2,3,6-triméthylphénol

Publications (1)

Publication Number Publication Date
EP4077301A1 true EP4077301A1 (fr) 2022-10-26

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EP20821237.3A Pending EP4077301A1 (fr) 2019-12-19 2020-12-14 Formation d'alpha-tocophérol à partir de 2,3,6-triméthylphénol

Country Status (3)

Country Link
EP (1) EP4077301A1 (fr)
CN (1) CN114901650A (fr)
WO (1) WO2021122439A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114829328A (zh) * 2019-12-19 2022-07-29 帝斯曼知识产权资产管理有限公司 由2,3,6-三甲基苯酚形成2,3,5-三甲基氢醌
CN114829327A (zh) * 2019-12-19 2022-07-29 帝斯曼知识产权资产管理有限公司 氢醌的制备方法
CN115785051A (zh) * 2022-11-28 2023-03-14 大丰海嘉诺药业有限公司 一种维生素e生产工艺

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5663376A (en) * 1994-07-27 1997-09-02 Eisai Co., Ltd. Process for the preparation of α-tocopherol
US6020505A (en) * 1994-07-27 2000-02-01 Eisai Co., Ltd. Process for the preparation of α-tocopherol
EP0949255B1 (fr) 1998-04-06 2006-05-24 DSM IP Assets B.V. Procédé de préparation de d,l-alpha-tocophérol utilisant comme solvant un carbonate et comme catalyseur un acide contenant du soufre
US20030060383A1 (en) 2001-09-17 2003-03-27 Huntsman Petrochemical Corporation Methods for stabilizing aqueous alkylene carbonate solutions
AU2003210291A1 (en) * 2002-02-25 2003-09-09 Dsm Ip Assets B.V. MANUFACTURE OF (ALL-RAC)-Alpha-TOCOPHEROL
DE10393642B4 (de) * 2002-11-21 2017-03-30 Dsm Ip Assets B.V. Herstellung von α-Tocopherol
CN106117017A (zh) * 2016-06-21 2016-11-16 南通柏盛化工有限公司 仿生催化还原制备2,3,5‑三甲基氢醌的方法

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WO2021122439A1 (fr) 2021-06-24
CN114901650A (zh) 2022-08-12

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