WO2004096791A2 - Process for the manufacture of tocyl and tocopheryl acylates - Google Patents
Process for the manufacture of tocyl and tocopheryl acylates Download PDFInfo
- Publication number
- WO2004096791A2 WO2004096791A2 PCT/EP2004/004443 EP2004004443W WO2004096791A2 WO 2004096791 A2 WO2004096791 A2 WO 2004096791A2 EP 2004004443 W EP2004004443 W EP 2004004443W WO 2004096791 A2 WO2004096791 A2 WO 2004096791A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- acid
- tocopherol
- brόnsted
- featuring
- Prior art date
Links
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
Definitions
- the present invention is concerned with a novel process for the manufacture of acylates of tocol and of tocopherol.
- tocopherol as used herein is to be understood to refer to any compound derived from the basic structure of tocol [2-methyl-2-(4,8 J 12-trimethyltridecyl)-6- chromanol] and having vitamin E character, viz. any tocopherol having the saturated side chain 4,8,12-trimefhyltridecyl, such as -, ⁇ -, ⁇ -, ⁇ 2 - or ⁇ -tocopherol, and also any tocotrienol having three double bonds in the side chain [4,8,12-trimethyltridec-3,7,ll- trienyl], such as ⁇ - or ⁇ tocopherol.
- vitamin E is of primary interest, being the most active and industrially most important member of the vitamin E group.
- the present invention is preferably concerned with a novel process for the manufacture of acylates of tocopherols (tocopheryl acylates), more particularly tocopheryl acetates.
- the main commercial form of vitamin E being (all-rac)- ⁇ - tocopheryl acetate
- the invention in a more preferred aspect, is concerned with a process for the manufacture of (all-rac)- -tocopheryl acetate.
- tocol itself and the other tocopherols such as those mentioned above can be readily acylated by the process of the present invention.
- tocol and each of the tocopherols can be acylated in the form of an all-racemic mixture of its diastereoisomers (diasereoisomeric pairs of enantiomers) or of any individual stereoisomer.
- novel process according to the present invention provides excellent yields, avoids corrosion problems and can be carried in the absence of an additional solvent, thus avoiding the need to recycle solvents, and can be carried out in a continuous or batchwise mode.
- a process for the manufacture of an acylate of tocol or a tocopherol which comprises reacting tocol or a tocopherol with an acylating agent in the presence of a solid heterogeneous Br ⁇ nsted acid catalyst, said catalyst being an inorganic Br ⁇ nsted (protonic) acid on a solid carrier material which comprises silicon dioxide, titanium dioxide or both silicon dioxide and titanium dioxide, or being an organofunctional polysiloxane featuring sulpho (-SO 3 H) groups, the solid heterogeneous Br ⁇ nsted acid catalyst further featuring a BET surface area from about 10 m 2 /g to about 800 m 2 /g and a pore volume from about 0.1 ml/g to about 2.0 ml/g.
- a solid heterogeneous Br ⁇ nsted acid catalyst said catalyst being an inorganic Br ⁇ nsted (protonic) acid on a solid carrier material which comprises silicon dioxide, titanium dioxide or both silicon dioxide and titanium dioxide, or being an organofunctional polysiloxane featuring sulpho
- the inorganic Br ⁇ nsted acid is suitably sulphuric acid or orthophosphoric acid (also commonly known as phosphoric acid; H 3 PO 4 ), and such an acid is carried or supported on the solid carrier material, which itself comprises silicon dioxide, titanium dioxide or both silicon dioxide and titanium dioxide, particularly by adsorption thereon, the whole constituting the solid heterogeneous Br ⁇ nsted acid catalyst.
- the solid carrier material which itself comprises silicon dioxide, titanium dioxide or both silicon dioxide and titanium dioxide, particularly by adsorption thereon, the whole constituting the solid heterogeneous Br ⁇ nsted acid catalyst.
- Such solid heterogeneous Br ⁇ nsted acid catalysts are known from and/or can be produced by the skilled artisan by following the teachings in inter alia the European Patent Publications Nos. 0 452 619 Bl, 0 807 615 Bl, 0 916 402 Al and 0 997 193 Al and the further references cited therein.
- phosphoric acid is mentioned as a Br ⁇ nsted acid which may be carried or supported on the solid carrier material, and this applies analogously also for sulphuric acid as the carried or supported Br ⁇ nsted acid.
- the solid carrier material may if desired contain in addition to silicon dioxide and/or titanium dioxide further metal oxide such as zinc oxide, but such an additional metal oxide is generally present to a much lesser extent than the silicon dioxide and/or the titanium dioxide, preferably constituting up to about 5 weight percent (wt. %) of the total mixed metal oxide carrier.
- silicon dioxide (SiO 2 ) and titanium dioxide (TiO 2 ) are both present in the carrier material, the relative weight ratio SiO 2 : TiO 2 is suitably from about 80 : 20 to about 95 : 5.
- the amount of carried/supported Br ⁇ nsted acid is suitably from about 0.01 to about 70 wt. %, preferably from about 0.1 to about 20 wt. %, and most preferably from about 1 to about 5 wt. %, relative to the weight of the solid heterogeneous Br ⁇ nsted acid catalyst as a whole (acid and solid carrier material together).
- solid carrier material examples include the various grades of formed pyrogenic silica or titania commercially available under the trademark Aerolyst ® , such as those with the reference numbers 3038-3046, 350 and 355 (pyrogenic silica) and 7706 and 7708-7711 (pyrogenic titania), in tablet, extrudate, ring or other form from suppliers, particularly from Degussa AG, Postfach 302043, 40402 D ⁇ sseldorf, Germany, or local outlets of this company in other countries.
- solid heterogeneous Br ⁇ nsted acid catalysts of this type themselves are a solid comprising about 80-95 wt. % of silicon dioxide and about 10 wt. % of titanium dioxide as the carrier material and up to about 15 wt.
- % (relative to the weight of the aforementioned carrier material) of sulphuric acid as the inorganic Br ⁇ nsted acid; a solid comprising about 80-95 wt. % of silicon dioxide, up to about 5 wt. % of zinc oxide and up to about 15 wt. % of sulphuric acid (these weights being relative to the total weight of the carrier substances and the acid); a solid consisting practically entirely of titanium dioxide and about 1 wt. % (relative to the weight of this carrier material) of sulphuric acid; and a solid comprising about 30-70 wt. % of silicon dioxide, up to about 5 wt. % of titanium dioxide and about 30-70 wt. % of orthophosphoric acid (these weights being relative to the total weight of the carrier substances and the acid).
- the organofunctional polysiloxanes featuring sulpho groups are polysiloxanes bearing sulphohydrocarbyl groups.
- they have a basic polymeric silicate structure with repeating -Si-O- units in the matrix and in which are present, chemically integrated and attached to some of the silicon atoms, acid-functional groups of the formula -R-SO 3 H wherein R is a divalent hydrocarbyl group.
- organofunctional polysiloxanes featuring sulpho groups are producible in known manner by polycondensation of difunctional organosilicon compounds of the appropriate general formula (HO) 3 Si-R-SO 3 H, optionally together with tetrahydroxysilane ["orthosilicic acid", Si(OH) 4 ].
- difunctional organosilicon compounds are terminally trihydroxysilyl substituted .iralkanesulphonic acids, e.g.
- trihydroxysilyl-l-propanesulphonic acid trihydroxysilyl- Cs-g- cycloalkanesulphonic acids, (trihydroxysilyl-C ⁇ -6 -alkyl)-cyclohexanesulphonic acids, trihydroxysilyl-cyclohexyl-C 1-6 -alkanesulphonic acids and (trihydroxysilyl-C 1-6 -alkyl)- cyclohexyl-C 1-6 -alkanesulphonic acids; and trihydroxysilyl-benzenesulphonic acid, (trihydroxysilyl-C 1-6 -alkyl)-benzenesulphonic acids, trihydroxysilyl-phenyl-C 1-6 - alkanesulphonic acids and (trihydroxysilyl-Ci.e-alky -phenyl-C i.g-alkanesulphonic acids, e.g.
- [p-(trihydroxysilylmethyl)-phenyl]methanesulphonic acid may feature methyl substitution on said moiety.
- the . 12 -alkane, C 1-6 -alkane and C 1-6 -alkyl moieties when containing 2 or more carbon atoms may in each case be straight or branched chain.
- the organofunctional polysiloxanes featuring sulpho groups used as the solid heterogeneous Br ⁇ nsted acid catalysts in the process of the present invention are preferably polysiloxanes bearing sulphoalkyl or sulphoaryl groups (so-called acid- functional groups) of the formula -(CH 2 ) x -SO 3 H or -arylene-SOsH, respectively, wherein x is an integer from 1 to 3, and arylene is a divalent aromatic group derived from benzene, e.g. 1,4-phenylene, or toluene, e.g. 2-methyl-l,4-phenylene.
- the acid-functional groups are most preferably 3-sulphopropyl, of the formula -(CH 2 ) 3 -SO 3 H.
- the polymerized matrix of the organofunctional polysiloxanes featuring sulpho groups may if desired also feature, as well as integral silicon atoms, titanium and/or aluminium atoms integrated in a like manner to the silicon atoms in the whole matrix.
- Such organofunctional polysiloxane featuring sulpho groups preferably features a molar ratio of silicon atoms to sulpho groups of at least 2 : 1.
- organofunctional polysiloxanes featuring sulpho groups for use as the alternative type of solid heterogeneous Br ⁇ nsted acid catalysts in the process of the present invention are also generally commercially available from suppliers, particularly from Degussa AG, Postfach 302043, 40402 D ⁇ sseldorf, Germany, or local outlets of this company in other countries. Some have been available from Degussa AG under the trademark Deloxan ® , e.g. Deloxan ® ASP 1/9.
- the acylation can be carried out in principle using any acylating agent conventionally used for the acylation of a phenolic hydroxyl group as is present in tocol and tocopherols.
- acylating agents are acid anhydrides and acyl halides.
- the acyl groups in such acylating agent may be derived from aliphatic carboxylic acids, e.g. from straight or branched chain alkanoic acids, in particular .
- alkanoic acids such as acetic acid, propionic acid, butyric acid and pivalic acid, or from higher alkanoic acids (fatty acids) with up to 20 carbon atoms such as palmitic acid; or from aromatic carboxylic acids, particularly benzoic acid, so that in each case the appropriate acylate, being an alkanoate, or e.g. the benzoate, respectively, of tocol or the tocopherol is produced in the acylation process.
- aliphatic acyl halides are straight or branched chain alkanoyl chlorides such as acetyl, propionyl and butyryl chloride, and an example of aromatic acyl halides is benzoyl chloride.
- the preferred acylating agent is acetic anhydride or acetyl chloride, most preferably acetic anhydride.
- the acylation in accordance with the present invention may by carried out in the presence or in the absence of an added solvent, but preferably one of the reactants, i.e. tocol or the tocopherol as the one reactant or the acylating agent as the other reactant, is used in excess and no added solvent used.
- the acylating agent is used in excess, preferably in a one- to about a sixfold molar amount, more preferably in a 1.5- to 2.5-fold molar amount, and most preferably in a 1.75- to 2.25-fold molar amount, relative to the molar amount of tocol or the tocopherol present in the initial reaction mixture.
- an additional solvent is suitably a polar or non-polar aprotic organic solvent, particularly an aliphatic, preferably C 4 to C 10 aliphatic, hydrocarbon, e.g. pentane, hexane, heptane or decane; an alicyclic, preferably C 5 to C 7 alicyclic, hydrocarbon, e.g. cyclohexane; or an aromatic, particularly C 6 to do aromatic, hydrocarbon, e.g. benzene, toluene, an xylene or naphthalene.
- a polar or non-polar aprotic organic solvent particularly an aliphatic, preferably C 4 to C 10 aliphatic, hydrocarbon, e.g. pentane, hexane, heptane or decane; an alicyclic, preferably C 5 to C 7 alicyclic, hydrocarbon, e.g. cyclohexane; or an aromatic, particularly C 6 to do aromatic
- the amount of the solid heterogeneous Br ⁇ nsted acid catalyst used is based on the amount of the reactant, i.e. tocol or the tocopherol or the acylating agent, usually the former, which is used in the lesser molar amount and is suitably in the range from about 0.0025 to about 0.025 grammes (g) per g of the reactant used in said lesser molar amount, when the process is effected in a batchwise operational mode.
- the relative amount of catalyst will be adjusted to the size of the reactor and the flow of the reactants. In this case it will be appreciated that the determination of the appropriate relative amount based on the figures for the batchwise operational mode is within the normal skill of the production chemist.
- acylation process in accordance with the present invention is conveniently carried out in a temperature range from about 80°C to about 120°C, preferably from about 90°C to about 110°C.
- the process is conveniently carried out under an inert gas atmosphere, preferably under gaseous nitrogen or argon, especially the former.
- the progress of the reaction is suitably monitored by analytical means, such as gas chromatographical analysis of samples taken from the reaction mixture at various time intervals during the reaction.
- the produced tocyl or tocopheryl acylate can be isolated by cooling the mixture after acylation, neutralization by addition of a suitable base, e.g. sodium carbonate, filtration of the mixture, and distilling off from the filtrate, preferably under reduced pressure, the remaining (unreacted) tocol or tocopherol or acylating agent, whichever has been used in excess, and the secondary product formed in the acylation, e.g. acetic acid when acetic anhydride is used as the acylating agent, followed by further distillation, also preferably under reduced pressure, to collect as pure a fraction of the desired acylation product as required.
- a suitable base e.g. sodium carbonate
- an organopolysiloxane containing sulpho groups derived from 3-(trihydroxysilyl)-l-propanesulphonic acid and having a BET surface area in the range of about 400 to about 600 m 2 /g and a pore volume in the range of about 1.5 to about 2.0 ml/g) in a 50 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and argon gasification means.
- the mixture was stirred at 400 rpm and heated at 100°C (internal temperature) for 1.5 hours.
- acetic anhydride (0.55 1, 5.8 mol) of acetic anhydride was pumped through a reactor filled with 4.75 g of Deloxan® ASP 1/9 (see Example 1 for its specification) at a feed rate 0.4 ml/minute at 100°C for 12 days. During the reaction several samples were taken and worked up. During 2 hours a solution of 46.48 g of crude reaction product was collected. The excess acetic anhydride was distilled off and the crude product (23.83 g) was transferred to a flask and the 23.21 g therein purified by bulb-to-bulb distillation at 206°C [0.0054 mbar (0.15 Pa)].
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Seasonings (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Medicines Containing Plant Substances (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/554,885 US7321053B2 (en) | 2003-05-02 | 2004-04-27 | Process for the manufacture of tocyl and tocopheryl acylates |
CN2004800112783A CN1780827B (en) | 2003-05-02 | 2004-04-27 | Process for the manufacture of tocyl and tocopheryl acylates |
EP04729614A EP1622887B1 (en) | 2003-05-02 | 2004-04-27 | Process for the manufacture of tocyl and tocopheryl acylates |
JP2006505290A JP4740834B2 (en) | 2003-05-02 | 2004-04-27 | Process for producing tosyl acylate and tocopheryl acylate |
AT04729614T ATE475657T1 (en) | 2003-05-02 | 2004-04-27 | METHOD FOR PRODUCING TOCYL AND TOCOPHERYL ACYLATES |
KR1020057020815A KR101126811B1 (en) | 2003-05-02 | 2004-04-27 | Process for the manufacture of tocyl and tocopheryl acylates |
DE602004028357T DE602004028357D1 (en) | 2003-05-02 | 2004-04-27 | PROCESS FOR THE PREPARATION OF TOCYL AND TOCOPHERYL ACYLATES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03009985 | 2003-05-02 | ||
EP03009985.7 | 2003-05-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004096791A2 true WO2004096791A2 (en) | 2004-11-11 |
WO2004096791A3 WO2004096791A3 (en) | 2005-01-06 |
Family
ID=33395781
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/004443 WO2004096791A2 (en) | 2003-05-02 | 2004-04-27 | Process for the manufacture of tocyl and tocopheryl acylates |
Country Status (9)
Country | Link |
---|---|
US (1) | US7321053B2 (en) |
EP (2) | EP2206708A1 (en) |
JP (2) | JP4740834B2 (en) |
KR (1) | KR101126811B1 (en) |
CN (2) | CN101899032B (en) |
AT (1) | ATE475657T1 (en) |
DE (1) | DE602004028357D1 (en) |
ES (1) | ES2347653T3 (en) |
WO (1) | WO2004096791A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007039245A1 (en) * | 2005-09-29 | 2007-04-12 | Dsm Ip Assets B.V. | Cleavage of alkynediols |
DE112007003075T5 (en) | 2006-12-27 | 2009-12-17 | Dsm Ip Assets B.V. | Process for the acylation of organic hydroxy compounds |
CN102276572A (en) * | 2011-09-14 | 2011-12-14 | 重庆大学 | Method for preparing vitamin E acetate acetic ester |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101787248B1 (en) | 2016-04-14 | 2017-10-18 | 라인 가부시키가이샤 | Method and system for keyword search using messaging service |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3459773A (en) * | 1966-12-27 | 1969-08-05 | Takasago Perfumery Co Ltd | Process for producing alpha-tocopherol and its esters |
EP0582811A1 (en) * | 1992-07-17 | 1994-02-16 | Degussa Aktiengesellschaft | Formed sulfonate groups containing polysiloxanes, process for their preparation and their application |
US5703272A (en) * | 1994-02-15 | 1997-12-30 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing a carboxylic acid ester |
WO1998025876A1 (en) * | 1996-12-12 | 1998-06-18 | Sasol Technology (Proprietary) Limited | Production of organic carboxylic acid esters |
US5922900A (en) * | 1996-09-04 | 1999-07-13 | Degussa Aktiengesellschaft | Process for producing carboxylic acid esters and catalysts therefor |
EP0997193A1 (en) * | 1998-09-24 | 2000-05-03 | Degussa-Hüls Aktiengesellschaft | Shaped body, consisting of pyrogenic mixed oxide, and use thereof |
WO2002042286A1 (en) * | 2000-11-22 | 2002-05-30 | Basf Aktiengesellschaft | Method for continuously acylating chromanol ester derivatives |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2723278A (en) | 1954-01-25 | 1955-11-08 | Hoffmann La Roche | Preparation of alpha-tocopherol |
JPS4955633A (en) | 1972-07-30 | 1974-05-30 | ||
DE3226093C2 (en) | 1982-07-13 | 1987-01-02 | Degussa Ag, 6000 Frankfurt | Organopolysiloxanes containing sulfonate groups, processes for their preparation and use |
DE4012479A1 (en) | 1990-04-19 | 1991-10-24 | Degussa | Titanium dioxide pellets, process for their preparation and their use |
JP3712008B2 (en) * | 1994-02-15 | 2005-11-02 | 三菱瓦斯化学株式会社 | Method for producing silica-titania catalyst for carboxylic acid ester production |
DE19619961A1 (en) | 1996-05-17 | 1997-11-20 | Degussa | Compacts based on pyrogenic silicon dioxide |
DE19750238A1 (en) | 1997-11-13 | 1999-05-27 | Degussa | Compacts based on pyrogenic silicon dioxide |
WO2004096790A1 (en) * | 2003-04-28 | 2004-11-11 | Dsm Ip Assets B.V. | Process for the manufacture of tocyl and tocopheryl acylates |
-
2004
- 2004-04-27 EP EP10157639A patent/EP2206708A1/en not_active Withdrawn
- 2004-04-27 JP JP2006505290A patent/JP4740834B2/en not_active Expired - Fee Related
- 2004-04-27 ES ES04729614T patent/ES2347653T3/en not_active Expired - Lifetime
- 2004-04-27 CN CN201010151061XA patent/CN101899032B/en not_active Expired - Lifetime
- 2004-04-27 EP EP04729614A patent/EP1622887B1/en not_active Expired - Lifetime
- 2004-04-27 CN CN2004800112783A patent/CN1780827B/en not_active Expired - Lifetime
- 2004-04-27 AT AT04729614T patent/ATE475657T1/en not_active IP Right Cessation
- 2004-04-27 KR KR1020057020815A patent/KR101126811B1/en active IP Right Grant
- 2004-04-27 DE DE602004028357T patent/DE602004028357D1/en not_active Expired - Lifetime
- 2004-04-27 WO PCT/EP2004/004443 patent/WO2004096791A2/en active Search and Examination
- 2004-04-27 US US10/554,885 patent/US7321053B2/en not_active Expired - Lifetime
-
2011
- 2011-01-26 JP JP2011014518A patent/JP5300883B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3459773A (en) * | 1966-12-27 | 1969-08-05 | Takasago Perfumery Co Ltd | Process for producing alpha-tocopherol and its esters |
EP0582811A1 (en) * | 1992-07-17 | 1994-02-16 | Degussa Aktiengesellschaft | Formed sulfonate groups containing polysiloxanes, process for their preparation and their application |
US5703272A (en) * | 1994-02-15 | 1997-12-30 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing a carboxylic acid ester |
US5922900A (en) * | 1996-09-04 | 1999-07-13 | Degussa Aktiengesellschaft | Process for producing carboxylic acid esters and catalysts therefor |
WO1998025876A1 (en) * | 1996-12-12 | 1998-06-18 | Sasol Technology (Proprietary) Limited | Production of organic carboxylic acid esters |
EP0997193A1 (en) * | 1998-09-24 | 2000-05-03 | Degussa-Hüls Aktiengesellschaft | Shaped body, consisting of pyrogenic mixed oxide, and use thereof |
WO2002042286A1 (en) * | 2000-11-22 | 2002-05-30 | Basf Aktiengesellschaft | Method for continuously acylating chromanol ester derivatives |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 1975 Derwent Publications Ltd., London, GB; AN 1975-02567W XP002292233 & JP 49 055633 A (TEIJIN LTD) 30 May 1974 (1974-05-30) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007039245A1 (en) * | 2005-09-29 | 2007-04-12 | Dsm Ip Assets B.V. | Cleavage of alkynediols |
DE112007003075T5 (en) | 2006-12-27 | 2009-12-17 | Dsm Ip Assets B.V. | Process for the acylation of organic hydroxy compounds |
CN102276572A (en) * | 2011-09-14 | 2011-12-14 | 重庆大学 | Method for preparing vitamin E acetate acetic ester |
CN102276572B (en) * | 2011-09-14 | 2013-03-27 | 重庆大学 | Method for preparing vitamin E acetate acetic ester |
Also Published As
Publication number | Publication date |
---|---|
CN101899032B (en) | 2012-05-30 |
KR20060011983A (en) | 2006-02-06 |
JP4740834B2 (en) | 2011-08-03 |
US20060293529A1 (en) | 2006-12-28 |
EP1622887B1 (en) | 2010-07-28 |
ES2347653T3 (en) | 2010-11-03 |
WO2004096791A3 (en) | 2005-01-06 |
JP5300883B2 (en) | 2013-09-25 |
CN1780827B (en) | 2010-06-16 |
DE602004028357D1 (en) | 2010-09-09 |
ATE475657T1 (en) | 2010-08-15 |
KR101126811B1 (en) | 2012-03-23 |
US7321053B2 (en) | 2008-01-22 |
EP1622887A2 (en) | 2006-02-08 |
EP2206708A1 (en) | 2010-07-14 |
JP2011105746A (en) | 2011-06-02 |
JP2006525263A (en) | 2006-11-09 |
CN1780827A (en) | 2006-05-31 |
CN101899032A (en) | 2010-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8431727B2 (en) | Process for the manufacture of chroman derivatives, especially α-tocopherol and alka-noates thereof | |
JP2002519416A (en) | Manufacture of tocopherol | |
JP2011178801A (en) | Process for producing ester | |
JP5300883B2 (en) | Process for producing tosyl acylate and tocopheryl acylate | |
EP1583753B1 (en) | Process for the manufacture of alpha-tocopheryl acetate | |
EP1740567B1 (en) | Process for the manufacture of tocopheryl acylates | |
KR101078957B1 (en) | Manufacture of tocopheryl acetate | |
WO2008077543A1 (en) | Process for the acylation of organic hydroxy compounds | |
KR100341556B1 (en) | Method for preparing allylquinone derivatives and intermediates thereof | |
EP1641772A1 (en) | Manufacture of tocopherols using a bismuth catalyst | |
JP2714400B2 (en) | Chromane derivative and method for producing the same | |
US20060235234A1 (en) | New route to alpha-tocopherol, alpha-tocopheryl alkanoates and precursors thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004729614 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20048112783 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006293529 Country of ref document: US Ref document number: 10554885 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020057020815 Country of ref document: KR Ref document number: 2006505290 Country of ref document: JP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057020815 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2004729614 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10554885 Country of ref document: US |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) |