WO2005061426A1 - Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone - Google Patents

Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone Download PDF

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Publication number
WO2005061426A1
WO2005061426A1 PCT/IB2004/003978 IB2004003978W WO2005061426A1 WO 2005061426 A1 WO2005061426 A1 WO 2005061426A1 IB 2004003978 W IB2004003978 W IB 2004003978W WO 2005061426 A1 WO2005061426 A1 WO 2005061426A1
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Prior art keywords
formula
process according
diene
acid
catalyst
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Ceased
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PCT/IB2004/003978
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English (en)
French (fr)
Inventor
Denis Jacoby
Bessaa Neffah
Christian Chapuis
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Firmenich SA
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Firmenich SA
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Priority to ES04799031T priority Critical patent/ES2393105T3/es
Priority to JP2006544571A priority patent/JP4696077B2/ja
Priority to EP04799031A priority patent/EP1697290B1/en
Publication of WO2005061426A1 publication Critical patent/WO2005061426A1/en
Priority to US11/438,756 priority patent/US7250536B2/en
Priority to IL175984A priority patent/IL175984A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C07C49/543—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings to a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C07C49/557—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings having unsaturation outside the rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • 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 the field of organic synthesis. More particularly it provides a process for the isomerisation of a 2-alkyl-cyclohex-3-enyl alkyl or alkenyl ketone into a mixture comprising the corresponding 2-alkyl-cyclohex-2-enyl ketones and the corresponding 2-alkylene-cyclohexyl ketones, using as catalyst a complex obtainable by the reaction of an appropriate ruthenium organometallic precursor and an acid.
  • the present invention provides a process for the isomerisation of a substrate of formula
  • each R 1 represents, simultaneously or independently, a hydrogen atom or a methyl group and R 2 represents a hydrogen atom linear or branched C 1-4 alkyl or a C 2 . 5 1-alkenyl group; into a mixture comprising at least one compound of formula (U) and at least one compound of formula (II')
  • R 1 and R 2 have the same meaning as indicated above; said process being carried but in a non-coordinating or weakly coordinating medium, under an inert atmosphere and in the presence of a catalyst obtainable by the reaction of a) a ruthenium precursor of the formula [Ru(diene)(allyl) ], [Ru(dienyl) 2 ], [Ru(tetraene)(ene)] or [Ru(diene)(triene)]; and b) a protic acid of formula HX, wherein X is a weakly- or non-coordinating anion; or a Lewis acid of formula B(R ) 3 , wherein R represents a fluoride or a phenyl group optionally substituted by one to five groups such as halide atoms or methyl or CF 3 groups, or a Lewis acid of formula FeX , FeX 2 , AgX, A1Y 3 , FeY 3 , FeY , SnY , SnY 4 , AgY, Ag,
  • R 1 and R 2 have the same meaning as indicated in formula (I).
  • Said compound (113) is an optional constituent of the mixture obtained at the end of the isomerisation.
  • the applicant has observed that the formation of said compound (III) depends on the specific experimental conditions, in particular on ratio Ru/acid, on the temperature and the duration of the reaction, or on the catalyst used and its concentration.
  • the compound (TIT) accounts for less than 2% of the weight of the final mixture.
  • the final mixture is devoid of said compound of formula (131).
  • the substrate is a compound of formula
  • R 1 and R 2 have the same meaning as indicated for formula (IV).
  • the optional ingredient, mentioned above, of the mixture would be of the formula
  • R 1 and R 2 have the same meaning as indicated for formula (V3). Furthermore, it is also important to mention, regardless of the specific embodiments, than compounds of formula (I), as well as the corcesponding compounds (H) or (IT), can be in an optically active form. In particular, compounds (I), (13) or (IT) can be of formula
  • compound (I) optically active are (2E)-l-[(lS,2R)-2,6,6- trimethyl-3-cyclohexen-l-yl]-2-buten-l-one, (2E)-l-[(lS,2S)-2,6,6-trimethyl-3- cyclohexen- 1 -yl]-2-buten- 1 -one, 1 -[( 1 S,2R)-2,6,6-trimethyl-3 -cyclohexen- 1 -yl] - 1 - ethanone or l-[(lS,2S)-2,6,6-trimethyl-3-cyclohexen-l-yl]-l-ethanone.
  • the catalyst is an essential element of the invention's process.
  • said catalyst is obtainable by the reaction of an organometalhc ruthenium precursor and a particular Lewis or protic acid in a non-coordinating or weakly coordinating medium and under an inert atmosphere.
  • dienyl stands for a C 4 -C 20 , preferably C 4 -C ⁇ 5 ,
  • ruthenium complexes are of formula [Ru(diene)(triene)], wherein "triene” stands for a C 7 -C 20 , preferably C -C ⁇ 2 , hydrocarbon group comprising three carbon-carbon double bonds, such as for example cycloocta-l,3,5-triene (COT), benzene or a substituted benzene such as a hexa-methyl-benzene.
  • COT cycloocta-l,3,5-triene
  • benzene or a substituted benzene such as a hexa-methyl-benzene.
  • the preferred trine is COT.
  • ruthenium complex is of formula [Ru(tetraene)(ene)], wherein "tetraene” stands for a C 8 -C 2 o, preferably C 8 -C 1 , hydrocarbon group comprising four carbon-carbon double bonds, such as for example cycloocta-l,3,5,7-tetraene, and "ene” stands for a C 2 -C ⁇ o, preferably C 4 -C 8 , hydrocarbon group comprising one carbon-carbon double bond, such as for example cyclooctene or cyclohexene.
  • Ru precursor the compound of formula [Ru(COD)(2-methallyl) 2 ], [Ru(COD)(COT)], [Ru(2,4-dimethylpentadienyl) ] (e.g. L. Stahl et al. or T.D. Newbound et al., references cited) or the [Ru(2,4-dimethyl-l-oxapentadienyl) 2 ] complexes (e.g. T. Schmidt et al, reference cited).
  • [Ru(COD)(2-methallyl) 2 ] the preparation of which was first reported by J. Powell et al., in J. Chem.
  • a weakly- or non- coordinating anion is an anion which does not coordinate at all the Ru center of the catalyst or which has a coordination stability constant inferior to that of the substrate of formula (I).
  • protic acids suitable for the preparation of the catalyst are acid of formula HX, wherein X is a ClO 4 " , R 4 SO 3 " , wherein R 4 is a chlorine of fluoride atom or a d-C 8 fluoroalkyl or fluoroaryl group, BF 4 PF 6 -, SbCl 6 -, AsCl 6 ", SbF 6 -, AsF 6 - or BPA, wherein R is a phenyl group optionally substituted by one to five groups such as halide atoms or methyl or CF groups.
  • the weakly- or non- coordinating anion is BF 4 -, PF 6% C 6 F 5 SO 3 " , CF SO 3 " or yet B[3,5-(CF 3 ) 2 C 6 H 4 -, even more preferably BF court-.
  • protic acids can be used in the form of the conesponding etherates (for example HBF 4 R 5 2 O, R 5 being a -Cs hydrocarbon group such as C 2 H 5 or C H 9 ).
  • These etherates are commercial products, or they can be prepared by reacting AgX with HCl in a solvent containing a dialkylether, for example a mixture of dichloromethane and diethylether. As the silver chloride precipitates, it provides the etherate solution of the acid, which can then be used according to the invention in the reaction with the ruthenium precursor.
  • a second type of suitable acid employed in the preparation of the catalyst is of the
  • Suitable examples of such acids are FeCl 3 , A1C1 3 , SbF 5 , AsF or PF 5 , AgF, Fe(CF 3 SO 3 ) 3 , AgBF 4 , SnCl 2 , BF 3 or BMe 3 .
  • Said acids can be in an anhydrous form or, for some of them, also in a hydrate form.
  • the boron or aluminum derivative, especially BF 3 could be in the form of anyone of its adduct with an ether or carboxylic acid, such as R 2 O or R COOH, wherein R 6 is a Ci-C 5 alkyl group and R 7 is a C ⁇ -C 20 alkyl group.
  • prefened Lewis acid is BF 3 or a BF adduct with Et 2 O, Bu 2 O or AcOH.
  • the acid and the Ru precursor are reacted in a molar ratio comprised between 0.3 and 3.1.
  • said ratio is comprised between approximately 0.5 and 2.
  • the catalyst should also be prepared in a non-coordinating or weakly coordinating solvent and under an inert atmosphere.
  • non-coordinating or weakly coordinating solvent we mean here a solvent which does not deactivate significantly the catalyst and allows the substrate to interact with the catalyst, such a notion is well understood by a person skilled in the art of the catalysis.
  • a weakly- or non-coordinating solvent is a solvent which does not coordinate at all the Ru center of the catalyst or which has a coordination stability constant inferior to that of the substrate of formula (I).
  • any solvent which is inert under the experimental conditions and is able to solubilize the substrate and catalyst is particularly appreciated.
  • such a solvent is a chlorinated hydrocarbon, saturated or unsaturated hydrocarbon, an ether, an ester, a carboxylic acid, a weakly coordinating ketone (sterically hindered ketone) or a substrate of formula (I) or a mixture thereof.
  • Specific examples of such solvents are CH 2 C1 2 , heptane, octane, dibutylether, butylacetate, acetic acid, teramyl methylether, diisopropylketone or yet a compound of formula (TV) as defined above.
  • inert atmosphere we mean here an atmosphere which is not reactive towards the catalyst, and in particular an atmosphere whose oxygen content is lower than 200 ppm, and preferably not above 100 ppm.
  • the catalysts obtained according to a process described above and wherein the acid is a Lewis acid, as defined above are new compounds. Said catalysts are also an object of the present invention.
  • Prefened Lewis acid are BF 3 , BF 3 'Et 2 O, BF 3 'Bu 2 O or BF 3 '(AcOH) 2 .
  • Prefened ruthenium precursor are the complexes [Ru(COD)(2-methallyl) 2 ], [Ru(COD)(COT)], [Ru(2,4-dimethylpentadienyl) 2 ] or [Ru(2,4-dimethyl-l-oxapentadienyl) 2 ], and in particular [Ru(COD)(2-methallyl) 2 ].
  • 3he invention's process should also be carried out in a non-coordinating or weakly coordinating solvent and under an inert atmosphere. Said solvent and atmosphere are defined as above for the formation of the catalyst.
  • the amount in which the catalyst may be employed in the invention's process is typically comprised between 0.01 and 2 molar %, relative to the substrate.
  • the catalyst is used in a concentration comprised between about 0.05 and 1 molar %. More preferably, the amount of the catalyst can be comprised between approximately 0.1 and 0.4 molar %. The use of high amounts of catalyst may lend to the presence of the compound of formula (HI) in the obtained mixture.
  • the temperature at which the process of the invention can be carried out is comprised between 60°C and the refluxing temperature of the solvent or of the substrate. Preferably, the temperature is in the range of between 60°C and 180°C, more preferably between 110°C and 165°C, and even more preferably between 110° and 150°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/IB2004/003978 2003-12-16 2004-11-30 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone Ceased WO2005061426A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES04799031T ES2393105T3 (es) 2003-12-16 2004-11-30 Procedimiento de isomerización de un ciclohexenil alquilo o una alquenil cetona
JP2006544571A JP4696077B2 (ja) 2003-12-16 2004-11-30 シクロヘキセニルアルキルまたはアルケニルケトンの異性化法
EP04799031A EP1697290B1 (en) 2003-12-16 2004-11-30 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone
US11/438,756 US7250536B2 (en) 2003-12-16 2006-05-22 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone
IL175984A IL175984A (en) 2003-12-16 2006-05-29 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IB0306118 2003-12-16
IBPCT/IB03/06118 2003-12-16
EP03029166 2003-12-18
EP03029166.0 2003-12-18

Related Child Applications (1)

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US11/438,756 Continuation US7250536B2 (en) 2003-12-16 2006-05-22 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone

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WO2005061426A1 true WO2005061426A1 (en) 2005-07-07

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PCT/IB2004/003978 Ceased WO2005061426A1 (en) 2003-12-16 2004-11-30 Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone

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US (1) US7250536B2 (https=)
EP (1) EP1697290B1 (https=)
JP (1) JP4696077B2 (https=)
CN (1) CN100404487C (https=)
ES (1) ES2393105T3 (https=)
IL (1) IL175984A (https=)
WO (1) WO2005061426A1 (https=)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009015360A3 (en) * 2007-07-26 2009-03-26 Univ San Diego State Res Found Catalysts for alkene isomerization and conjugating double bonds in polyunsaturated fats and oils
WO2014114615A1 (en) * 2013-01-23 2014-07-31 Firmenich Sa Process for the preparation of 4-methylpent-3-en-1-ol derivatives
WO2025125532A1 (en) * 2023-12-15 2025-06-19 Givaudan Sa Perfume ingredients and compositions containing them
WO2026017530A1 (en) 2024-07-18 2026-01-22 Firmenich Sa Ruthenium-catalyzed isomerization of cyclohexenyl aldehydes, esters, or ketones
WO2026017532A1 (en) 2024-07-18 2026-01-22 Firmenich Sa Ruthenium-catalyzed isomerization of alkenes

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GB0624814D0 (en) * 2006-12-13 2007-01-24 Givaudan Sa Organic compounds
GB0624818D0 (en) * 2006-12-13 2007-01-24 Givaudan Sa Organic compounds
CN101125805B (zh) * 2007-09-14 2010-05-26 杭州格林香料化学有限公司 1-(2,6,6-三甲基环己-3-烯基)丁-2-烯-1-酮的制备方法
CN108101760B (zh) * 2017-12-19 2020-11-24 万华化学集团股份有限公司 一种α-环柠檬醛的合成方法
CN116867762A (zh) * 2021-02-19 2023-10-10 株式会社Api 环己烯酮化合物的制造方法
WO2025120108A1 (en) * 2023-12-08 2025-06-12 Firmenich Sa Isomerization process

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CH537352A (fr) * 1969-08-08 1973-05-31 Firmenich & Cie Procédé pour la préparation de cétones insaturées
EP1162190A2 (en) 2000-06-07 2001-12-12 Takasago International Corporation Production process of cyclohexenyl methyl ketones

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DE69820205T2 (de) * 1997-05-20 2004-09-30 Firmenich S.A. Ruthenium-katalysatoren und ihre verwendung zur asymmetrischen hydrierung von substraten mit schwacher koordination
US6214763B1 (en) * 1997-05-20 2001-04-10 Firmenich Sa Ruthenium catalysts and their use in the asymmetric hydrogenation of weakly coordinating substrates
US6175047B1 (en) * 1997-12-26 2001-01-16 Takasago International Corporation Ruthenium metathesis catalyst and method for producing olefin reaction product by metathesis reaction using the same
JP2003160529A (ja) * 2001-11-29 2003-06-03 Takasago Internatl Corp ２，２，６−トリメチルシクロヘキセニルメチルケトンの二重結合異性体組成物およびその製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH537352A (fr) * 1969-08-08 1973-05-31 Firmenich & Cie Procédé pour la préparation de cétones insaturées
EP1162190A2 (en) 2000-06-07 2001-12-12 Takasago International Corporation Production process of cyclohexenyl methyl ketones

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009015360A3 (en) * 2007-07-26 2009-03-26 Univ San Diego State Res Found Catalysts for alkene isomerization and conjugating double bonds in polyunsaturated fats and oils
WO2014114615A1 (en) * 2013-01-23 2014-07-31 Firmenich Sa Process for the preparation of 4-methylpent-3-en-1-ol derivatives
US9381507B2 (en) 2013-01-23 2016-07-05 Firmenich Sa Process for the preparation of 4-methylpent-3-en-1-ol derivatives
WO2025125532A1 (en) * 2023-12-15 2025-06-19 Givaudan Sa Perfume ingredients and compositions containing them
WO2026017530A1 (en) 2024-07-18 2026-01-22 Firmenich Sa Ruthenium-catalyzed isomerization of cyclohexenyl aldehydes, esters, or ketones
WO2026017532A1 (en) 2024-07-18 2026-01-22 Firmenich Sa Ruthenium-catalyzed isomerization of alkenes

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CN1890204A (zh) 2007-01-03
US20060211889A1 (en) 2006-09-21
IL175984A0 (en) 2006-10-05
EP1697290A1 (en) 2006-09-06
JP2007515421A (ja) 2007-06-14
EP1697290B1 (en) 2012-09-12
ES2393105T3 (es) 2012-12-18
IL175984A (en) 2010-12-30
US7250536B2 (en) 2007-07-31
JP4696077B2 (ja) 2011-06-08
CN100404487C (zh) 2008-07-23

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