WO2018108606A1 - Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci - Google Patents

Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci Download PDF

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WO2018108606A1
WO2018108606A1 PCT/EP2017/081396 EP2017081396W WO2018108606A1 WO 2018108606 A1 WO2018108606 A1 WO 2018108606A1 EP 2017081396 W EP2017081396 W EP 2017081396W WO 2018108606 A1 WO2018108606 A1 WO 2018108606A1
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catalyst
trimethyl
dodec
hydrogen
range
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PCT/EP2017/081396
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English (en)
Inventor
Raphael Beumer
Werner Bonrath
Jonathan Alan Medlock
Thomas Mueller
Peter Hans RIEBEL
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Dsm Ip Assets B.V.
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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds

Definitions

  • the catalyst comprises a metal selected from the group consisting of palladium, platinum, rhodium, iridium and nickel and mixtures thereof. More preferably the catalyst comprises a metal selected from the group consisting of palladium, platinum and mixtures thereof. Even more preferably the catalyst is a metal selected from the group consisting of palladium, platinum and mixtures thereof. Most preferably the catalyst is palladium.
  • the 6, 10-dimethylundecan-2-one obtained according to the process of the present invention may be used as starting material for isophytol and a- tocopherol (acetate) via 3,7, 1 1 -trimethyl-dodec-1 -en-3-ol ("tetrahydro- nerolidol"; THNL), 6, 10, 14-trimethylpentadec-5-en-2-one ("(5E/5Z)-5,6- dehydro-C18-ketone") and 6, 10, 14-pentadecane-2-one or alternatively via 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol, 6, 10, 14-trimethylpentadec-4,5-dien-2-one ("C18-allene-ketone") and 6, 10, 14-pentadecane-2-one ("C18-ketone”).
  • the present invention is also directed to such processes which comprise the step of hydrogenating (5Z)-nerylacetone according to the process of the present invention.
  • the present invention is directed to a process for the manufacture of 6, 10-dimethylundecan-2-one comprising the step of hydrogenating (5Z)-nerylacetone with hydrogen in the presence of a catalyst, whereby the catalyst is capable of preferentially hydrogenating carbon-carbon double bonds over carbon-oxygen double bonds (see Fig. 1 ).
  • This process corresponds to the first step (step a)) in the process for the manufacture of 3,7, 1 1 -trimethyl-dodec-1 -en-3-ol ("tetrahydronerolidol"; THNL), 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol, 6, 10, 14-trimethylpentadec-4,5- dien-2-one ("C18-allene-ketone”), 6, 10, 14-trimethylpentadec-5-en-2-one, 6, 10, 14-pentadecane-2-one ("C18-ketone”), isophytol and a-tocopherol or its acetate.
  • the (5Z)-nerylacetone used as starting material may come from natural sources or any other source or obtained by fermentation or may be synthesized synthetically and, if needed, separated from (5E)- geranylacetone by any method known to the person skilled in the art.
  • Nerylacetone may for example be synthesized starting from linalool (see Fig. 9) in a Carroll reaction as described in CN-A 102 1 1 5 437, WO 2010/046199, DE 198 40 746 and JP-A 2002 121 165 or by reaction with isopropenyl alkyl ethers as described in DE 196 49 564 or by reaction with the dimethylacetal of acetone as described by P. Baeckstroem and L.
  • the hydrogenation of (5Z)-nerylacetone is performed in the presence of (5E)-geranylacetone of below 10 mol-%, preferably below 5 mol-%, more preferably below 2 mol-%, based on the total amount of (5E)- geranylacetone and (5Z)-nerylacetone.
  • 5E)-geranylacetone of below 10 mol-%, preferably below 5 mol-%, more preferably below 2 mol-%, based on the total amount of (5E)- geranylacetone and (5Z)-nerylacetone.
  • a mixture of (5E)- geranylacetone and (5Z)-nerylacetone where the amount of (5E)- geranylacetone is up to 10 mol-%, based on the total amount of the mixture, may also be used successfully.
  • the hydrogenation of (5Z)-nerylacetone is performed using (5Z)-nerylacetone as cis/trans isomeric pure (5Z)- nerylacetone.
  • cis/trans isomeric pure refers to the purity in respect to the amount of the isomers having different cis/trans (or E/Z) configuration at the carbon-carbon double bond as sole difference.
  • a compound considered as " cis/trans isomeric pure " has more than 99-mol % of the compound with the indicated configuration.
  • cis/trans isomeric pure (5Z)-nerylacetone is a mixture of as more than 99 mol-% (5Z)-nerylacetone and less than 1 mol-% of (5E)- geranylacetone.
  • the catalyst comprises a metal selected from the group consisting of palladium, platinum, rhodium, iridium and nickel and mixtures thereof. More preferably the catalyst comprises a metal selected from the group consisting of palladium, platinum and mixtures thereof.
  • the catalyst is a metal selected from the group consisting of palladium, platinum and mixtures thereof. Most preferably the catalyst is palladium.
  • a support/carrier being selected from the group consisting of carbon, graphite, inorganic oxides, inorganic carbonates, inorganic sulfates, as well as mixtures thereof where the active component (i.e. the metal) is deposited on.
  • Preferred support/carrier materials are carbon, silicon dioxide, aluminum oxide and calcium carbonate, as well as mixtures thereof.
  • An example for such mixtures are silica-alumina-mixtures.
  • the active metal catalyst content is preferably in the range of from 0.5 to 20 weight%, more preferably in the range of from 2 to 5 weight%, most preferably in the range of approximately 5 weight%, based on the total mass of active metal catalyst and support.
  • the amount of the active component of the catalyst (being preferably a metal selected from the group consisting of palladium, platinum, rhodium, iridium and nickel and mixtures thereof) is preferably in the range of from 0.0001 to 1 weight%, more preferably in the range of from 0.001 to 0.5 weight%, most preferably in the range of from 0.01 to 0.1 weight%, based on the weight of the starting material, the (5Z)-nerylacetone.
  • the hydrogenation reaction is preferably carried out at a temperature in the range of from 10 to 150° C, more preferably at a temperature in the range of from 20 to 100° C, most preferably at a temperature in the range of from 50 to 90 ° C.
  • the hydrogenation reaction is preferably carried out at a hydrogen pressure in the range of from 1 to 25 bar hydrogen absolute, more preferably at a hydrogen pressure in the range of from 2 to 10 bar hydrogen absolute, even more preferably at a hydrogen pressure in the range of from 2 to 6 bar hydrogen absolute, further more preferably at a hydrogen pressure in the range of from 2.5 to 4 bar hydrogen absolute most preferably at a hydrogen pressure of around 3 bar hydrogen absolute.
  • the hydrogenation reaction can be carried out without solvent or in the presence of an organic solvent.
  • the reaction is carried out in an organic solvent.
  • the organic solvent is preferably selected from the group consisting of hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, amides, nitriles and ketones and mixtures thereof. More preferred are C 4 -Cio
  • Ci -C 4 linear alkyl groups or C 3 -C 4 branched alkyl groups or halogens Ci -C 4 linear alcohols or C 3 -C 4 branched alcohols
  • acyclic and cyclic C 4 -Cio ethers Ci -Cio esters, C 3 -Cio ketones and mixtures thereof.
  • Especially preferred organic solvents are selected from the group consisting of hexane, heptane, toluene, methanol, ethanol, n-propanol, 2-propanol, n- butanol, tetrahydrofuran, 2-methyl-tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, acetone, and mixtures thereof.
  • the most preferred organic solvents are heptane and ethanol.
  • the 6, 10-dimethylundecan-2-one obtained according to the process of the present invention is ethynylated according to any process known to the person skilled in the art to yield 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol (see Fig.
  • the ethynylation may either be performed with acetylene, ammonia and a base, for example potassium hydroxide, or with an ethynyl Grignard.
  • the present invention is directed to a process for the manufacture of 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol comprising the following steps: a) hydrogenating (5Z)-nerylacetone with hydrogen in the presence of a catalyst to obtain 6, 10-dimethylundecan-2-one according to the process of the present invention;
  • step b1 ethynylating 6, 10-dimethylundecan-2-one obtained in step a) to obtain 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol.
  • the 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol is then hydrogenated in presence of a Lindlar catalyst to THNL.
  • 6, 10-dimethylundecan-2-one may be reacted with vinyl Grignard according to a process known by the person skilled in the art to THNL (see Fig. 2).
  • the present invention is directed to a process for the manufacture of 3,7, 1 1 -trimethyl-dodec-1 -en-3-ol comprising the following steps: a) hydrogenating (5Z)-nerylacetone with hydrogen in the presence of a catalyst to obtain 6,10-dimethylundecan-2-one according to the process of the present invention;
  • a further object of the present invention is also a process for the
  • step b2) in the process for the manufacture of 3,7,11-trimethyl- dodec-1-en-3-ol a step b2) can be performed instead of performing step b1) and c1 ) to obtain 3,7, 11 -trimethyl-dodec-1 -en-3-ol.
  • 6,10,14-trimethylpentadec-5-en-2-one can be obtained by C3 elongation of tetrahydronerolidol ("THNL") (see Fig.3).
  • THNL tetrahydronerolidol
  • An example is the reaction of THNL with isopropenyl methyl ether or with isopropenyl ethyl ether in the presence of a catalyst to the mixture of (5E)-6,10,14-trimethylpentadec-5- en-2-one and (5Z)-6,10,14-trimethylpentadec-5-en-2-one.
  • catalyst either an acid or an ammonium salt can be used.
  • the catalyst is an acid, preferably wherein the catalyst is selected from the group consisting of phosphoric acid, sulfuric acid, p- toluenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and mixtures thereof, is further described in WO 2009/019132 whose content is hereby incorporated by reference.
  • the catalyst is an ammonium salt, preferably wherein the catalyst is selected from the group consisting of ammonium bromide, ammonium chloride or di-ammonium phosphate, is further described in WO 2010/046199 whose content is hereby incorporated by reference.
  • the C3 elongation of THNL may also be carried out according to the process as described in JP-A 2002-121 165.
  • C3 elongation of THNL may also be carried out with one of the following reagents according to processes known to the person skilled in the art.
  • Process for the manufacture of 6, 10, 14-trimethylpentadec-4,5-dien-2-one 6, 10, 14-trimethylpentadec-4,5-dien-2-one can be obtained by C3 elongation of 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol as obtained according to the process of the present invention.
  • the C3 elongation is preferably carried out by reacting 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol with isopropenyl methyl ether or with isopropenyl ethyl ether in the presence of a catalyst, to obtain 6, 10, 14- trimethylpentadec-4,5-dien-2-one (see Fig. 7).
  • catalyst either an acid or an ammonium salt can be used.
  • the catalyst is an acid, preferably wherein the catalyst is selected from the group consisting of phosphoric acid, sulfuric acid, p- toluenesulfonic acid, methanesulfonic acid and mixtures thereof, is further described in WO 2008/092655 whose content is hereby incorporated by reference.
  • the present invention is also directed to a process for the manufacture of
  • step b1 ethynylating 6, 10-dimethylundecan-2-one obtained in step a) to obtain 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol (see Fig. 6);
  • step b1 hydrogenating 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol obtained in step b1 ) to obtain 3,7, 1 1 -trimethyl-dodec-1 -en-3-ol (tetrahydronerolidol);
  • steps b1 ) and c1 the following step can also be performed:
  • step b2) vinylating 6, 10-dimethylundecan-2-one obtained in step a) by addition of a vinyl Grignard reagent to yield 3,7, 1 1 -trimethyl-dodec-1 -en-3-ol (see Fig. 2).
  • the present invention is also directed to an alternative process for the manufacture of 6, 10, 14-trimethylpentadecan-2-one comprising the followin steps:
  • step b1 ethynylating 6, 10-dimethylundecan-2-one obtained in step a) to obtain 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol; C3 elonging 3,7, 1 1 -trimethyl-dodec-1 -yn-3-ol as obtained in step b1 ), preferably by reacting it with isopropenyl methyl ether or with isopropenyl ethyl ether in the presence of a catalyst, to obtain 6, 10, 14- trimethylpentadec-4,5-dien-2-one (see Fig. 7); hydrogenating the thus obtained 6, 10, 14-trimethylpentadec-4,5-dien-2- one with hydrogen in the presence of a catalyst to obtain 6, 10, 14- trimethylpentadecan-2-one (see Fig. 8).
  • the present invention is directed to a process for the manufacture of isophytol comprising the following steps:
  • the steps b1 ), c1 ), d), e), f 1 ) and g1 ) may be carried out according to methods known to the person skilled in the art.
  • the ethynylation (steps b1 ) and f1)) e.g. may either be performed with acetylene, ammonia and potassium hydroxide or with ethynyl Grignard.
  • step b-c2 may be performed as follows:
  • step f-g2 vinylating 6,10-dimethylundecan-2-one by addition of a vinyl Grignard reagent to yield 3,7,11-trimethyl-dodec-1-en-3-ol.
  • steps f 1 ) and g1 ) a step f-g2) may be performed as follows:
  • isophytol may be manufactured by a process comprising the steps as follows which is also an embodiment of the present invention:
  • step b1 ethynylating 6, 10-dimethylundecan-2-one obtained in step a) to obtain 3,7, 11 -trimethyl-dodec-1 -yn-3-ol;
  • step b2 C3 elonging 3,7, 11 -trimethyl-dodec-1 -yn-3-ol obtained in step b1 ), preferably with isopropenyl methyl ether or with isopropenyl ethyl ether, in the presence of a catalyst to obtain 6, 10,14- trimethylpentadec-4,5-dien-2-one;
  • step d2) hydrogenating 6,10, 1 -trimethylpentadec-4,5-dien-2-one obtained in step d2) with hydrogen in the presence of a catalyst to obtain 6, 10, 14-trimethylpentadecan-2-one;
  • a further object of the present invention is a process for the manufacture of a-tocopherol and its acetate, respectively, comprising the following steps: i) manufacturing isophytol as described above;
  • Step ii) may also be performed according to any method known in the prior art.
  • the invention is now further illustrated in the following non-limiting examples.
  • a mixture of the substrate nerylacetone/geranylacetone (20 g) (either cis/trans isomeric pure (5Z)-nerylacetone or a mixture of (5E)-geranyl- acetone and (5Z)-nerylacetone) and solvent (20 g) is added to a 125 ml steel autoclave.
  • the catalyst is added and the reactor is sealed.
  • the mixture is purged three times with nitrogen (pressurise to 5 bar, then release) and three times with hydrogen (pressurise to 5 bar, then release).
  • the reactor is heated to the desired temperature and then pressurised with hydrogen to the desired pressure. Stirring is started at 1000 rpm and the hydrogen uptake is recorded. After a total experiment time of 18 hours the reaction mixture is cooled to room temperature, the pressure is released and a sample taken for quantitative GC analysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de 6,10-diméthylundecan-2-one comprenant l'étape d'hydrogénation du (5Z)-nerylacétone avec de l'hydrogène en présence d'un catalyseur, le catalyseur étant capable d'hydrogéner de manière préférentielle les liaisons doubles carbone-carbone par rapport aux liaisons doubles carbone-oxygène. Le catalyseur comprend de préférence un métal choisi dans le groupe constitué par le palladium, le platine, le rhodium, l'iridium et le nickel, et des mélanges de ceux-ci. Le 6,10-diméthylundécan-2-one obtenu selon le procédé de la présente invention peut être utilisé en tant que matière de départ pour l'isophytol et l'alpha-tocophérol (acétate) par l'intermédiaire de 3,7,11-triméthyl-dodéc-1-en-3-ol ("tétrahydronérolidol" ; THNL), 6,10,14-triméthylpentadéc-5-en-2-one ("(5E/5Z)-5,6-déhydro-C18-cétone") et de 6,10,14-pentadécane-2-one ("C18-cétone") ou en variante par l'intermédiaire de 3,7,11-triméthyl-dodéc-1-yn-3-ol, 6,10,14-triméthylpentadéc-4,5-dièn-2-one ("C18-allène-cétone") et de 6,10,14-pentadécane-2-one ("C18-cétone"). La présente invention concerne également de tels procédés qui comprennent l'étape d'hydrogénation de (5Z)-nerylacétone selon le procédé de la présente invention.
PCT/EP2017/081396 2016-12-12 2017-12-04 Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci WO2018108606A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19649564A1 (de) 1996-11-29 1998-06-04 Basf Ag Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern
DE19840746A1 (de) 1998-09-07 2000-03-09 Basf Ag Verfahren zur Herstellung gamma,delta-ungesättigter Ketone durch Carroll-Reaktion
JP2002121165A (ja) 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
WO2006066863A1 (fr) * 2004-12-22 2006-06-29 Dsm Ip Assets B.V. Hydrogenation asymetrique d'alcenes au moyen de complexes chiraux d'iridium
WO2008092655A1 (fr) 2007-01-30 2008-08-07 Dsm Ip Assets B.V. Procédé d'élaboration de diènones
WO2009019132A1 (fr) 2007-08-08 2009-02-12 Dsm Ip Assets B.V. Procédé de préparation de (e, e)-farnésyl acétone
WO2010046199A2 (fr) 2008-10-21 2010-04-29 Dsm Ip Assets B.V. Fabrication de cétones gamma-delta-insaturées
CN102115437A (zh) 2010-04-12 2011-07-06 上海迪赛诺医药发展有限公司 制备γ,δ-不饱和酮的方法
WO2014096065A1 (fr) * 2012-12-18 2014-06-26 Dsm Ip Assets B.V. (6r,10r)-6,10,14-triméthylpentadécan-2-one préparée à partir de 6,10-diméthylundéc-5-én-2-one ou de 6,10-diméthylundéca-5,9-dién-2-one

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19649564A1 (de) 1996-11-29 1998-06-04 Basf Ag Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern
DE19840746A1 (de) 1998-09-07 2000-03-09 Basf Ag Verfahren zur Herstellung gamma,delta-ungesättigter Ketone durch Carroll-Reaktion
JP2002121165A (ja) 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
WO2006066863A1 (fr) * 2004-12-22 2006-06-29 Dsm Ip Assets B.V. Hydrogenation asymetrique d'alcenes au moyen de complexes chiraux d'iridium
WO2008092655A1 (fr) 2007-01-30 2008-08-07 Dsm Ip Assets B.V. Procédé d'élaboration de diènones
WO2009019132A1 (fr) 2007-08-08 2009-02-12 Dsm Ip Assets B.V. Procédé de préparation de (e, e)-farnésyl acétone
WO2010046199A2 (fr) 2008-10-21 2010-04-29 Dsm Ip Assets B.V. Fabrication de cétones gamma-delta-insaturées
CN102115437A (zh) 2010-04-12 2011-07-06 上海迪赛诺医药发展有限公司 制备γ,δ-不饱和酮的方法
WO2014096065A1 (fr) * 2012-12-18 2014-06-26 Dsm Ip Assets B.V. (6r,10r)-6,10,14-triméthylpentadécan-2-one préparée à partir de 6,10-diméthylundéc-5-én-2-one ou de 6,10-diméthylundéca-5,9-dién-2-one

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
P. BAECKSTROEM; L. LI, TETRAHEDRON, vol. 47, no. 32, 1991, pages 6521 - 6532
SATO, KIKUMASA; MIYAMOTO, OSAMU; INOUE, SEIICHI; KOBAYASHI, TORU; FURUSAWA, FUMIO, CHEMISTRY LETTERS, vol. 1981, pages 1711 - 14

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