EP0000315B1 - Verfahren zur Herstellung von optisch aktiven Citronellal - Google Patents

Verfahren zur Herstellung von optisch aktiven Citronellal Download PDF

Info

Publication number
EP0000315B1
EP0000315B1 EP78420001A EP78420001A EP0000315B1 EP 0000315 B1 EP0000315 B1 EP 0000315B1 EP 78420001 A EP78420001 A EP 78420001A EP 78420001 A EP78420001 A EP 78420001A EP 0000315 B1 EP0000315 B1 EP 0000315B1
Authority
EP
European Patent Office
Prior art keywords
rhodium
process according
chiral
bis
carbon atoms
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.)
Expired
Application number
EP78420001A
Other languages
English (en)
French (fr)
Other versions
EP0000315A1 (de
Inventor
Paul Aviron-Violet
Tuan-Phat Dang
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.)
Rhone Poulenc Recherches SA
Original Assignee
Rhone Poulenc Industries SA
Rhone Poulenc Recherches SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Industries SA, Rhone Poulenc Recherches SA filed Critical Rhone Poulenc Industries SA
Publication of EP0000315A1 publication Critical patent/EP0000315A1/de
Application granted granted Critical
Publication of EP0000315B1 publication Critical patent/EP0000315B1/de
Expired legal-status Critical Current

Links

Classifications

    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
    • 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
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • B01J2531/822—Rhodium
    • 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
    • B01J31/20—Carbonyls

Definitions

  • the subject of the present invention is a process for the preparation of optically active citronellal, also called chiral citronellal, by asymmetric hydrogenation of the mineral (E-dimethyl-3,7 octadiene-2,6 al) or geranial (Z-dimethyl-3.7 octadiene -2.6 al) achiral isomers constituting the citral.
  • the chiral citronellal is a suitable intermediary in organic synthesis; in particular d-citronellal is used for the preparation of (-) (1S) menthol designated below 1-menthol, by a process which implements the cyclization of d-citronellal in (-) (1 S) -isopulégol under the influence of a proton catalyst or thermally, then the hydrogenation of isopulegol to (D-menthoi (cf. JC LEFFINGWELL and RE SHACKELFORD, Cosmetics and Perfumery 89 70-78 / 1974 /).
  • the d-citronellal used for the synthesis of 1-menthol is obtained from various natural essences containing mainly d-citronellal and in particular from the essence of citronella.
  • the use of chiral citronellal of natural origin is not entirely satisfactory insofar as, due to the fluctuation of the prices of natural products, it happens periodically that the price of d-citronellal is higher than that of natural menthol . It is therefore important for the industry to have a source of chiral citronellal having a relatively stable prices and leading to a synthetic 1-menthol which D rices of returns is less than that of natural menthol.
  • 3,849,480 a process for the hydrogenation of ethylenically unsaturated compounds such as ⁇ -phenylacrylic acid, 3-methyl-2-cyclohexene one and methyl acid -2 butene-2 oic, but none of these compounds has a double ethylenic unsaturation linked to two asymmetric carbon atoms so that in these cases there is no risk of isomer formation.
  • the prior art has taught various types of catalysts which may be suitable for carrying out asymmetric syntheses.
  • 2,161,200 describes rhodium complexes with optically active ligands particular from the group of diphosphines, diarsines or distibines and teaches their use in synthesis. asymmetric, in particular for the hydrogenation of ⁇ -acetylaminocinnamic acid to acetylalanine.
  • hitherto it has never been proposed to prepare the chiral citronellal by asymmetric hydrogenation of the citral.
  • the achiral synthetic citronellal obtained by hydrogenation of the citral could constitute an interesting source of chiral citronellal and in particular of d-citronellal, however there is no industrial process for splitting the racemic citronellal into its enantiomers, so that the industry has no process for obtaining chiral citronellals synthetically.
  • the present invention aims precisely to solve such a problem.
  • the subject of the present invention is a process for the preparation of optically active citronellal, characterized in that the neral or geranial is hydrogenated in the presence of a catalyst consisting of a complex soluble in the reaction medium formed from a derived from rhodium and a chiral phosphine.
  • chiral phosphine denotes a phosphine or diphosphine in which at least one of the organic residues linked to the phosphorus atom comprises at least one chiral carbon atom, and / or in which at least one of the phosphorus atoms is chiral.
  • the soluble complex of the rhodium derivative and of the chiral phosphine can be prepared extemporaneously or be formed "in situ" under the conditions of the reaction by using the constituents of the complex. This latter method which has the advantage of simplicity is generally preferred.
  • rhodium derivatives suitable for carrying out the process according to the invention comprising residues of various kinds. They can be rhodium salts of mineral or organic acids or rhodium complexes whose ligands can be replaced by chiral phosphine.
  • rhodium halides such as hydrated rhodium trichloride
  • olefins of general formula: in which X represents a halogen atom: chlorine or bromine for example, x is an integer from 1 to 4 and L an aliphatic or cycloaliphatic olefin or diolefin such as ethylene, propylene, butene, isobutene , butadiene, 1,5-hexadiene, 1,4-heptadiene, 1,5-octadiene, isoprene, cyclohexadiene-1,3, cyclooctadiene-1,5; as examples of such complexes may be cited the ⁇ , ⁇ 'dichloro bis- (cyclohexadiene-1,3-rhodium), the ⁇ , ⁇ '-dichloro bis- (cydooctadiene-1
  • L 1 is triphenylphosphine.
  • rhodium derivatives use is preferably made of the various rhodiumcarbonyls and in particular tetrarhodium dodecacarbonyl and hexarhodiumhexadecacarbonyl. Rhodium complexes taken in cationic form can also be used.
  • alkylene radicals mention may be made of methylene, ethylene, propylene and 2-ethylpropylene radicals;
  • A can also represent a cyclobutylene radical; 1,4-cyclohexylene; 2-methyl-1,4-cyclohexylene; an ortho- or p-phenylene radical; a 2,3-dimethoxy-1,4-butylene radical.
  • divalent chiral radicals A formed by a chain of alkylene and cycloalkylene or heterocyclic or polycyclic or amino radicals mention may be made of those of formulas:
  • chiral diphosphines which can be used in the process according to the invention, there may be mentioned, without implying any limitation: bis (diphenylphosphinomethyl) -1,2-cyclobutane (DPCB), bis (dimethylphophinomethyl) -1,2 cyclobutane , bis (di-n-butylphosphinomethyl) -1,2 cyclobutane, bis (dioctylphosphinomethyl -) - 1,2 cyclobutane, bis (ditolylphosphinomethyl-1,2 cyclobutane, bis (dinaphthylphosphinomethyl) -1,2 cyclobutane bis (ethyl, hexylphosphinomethyl) -1.2 cyclobutane, bisldiphenylphosphinomethyl) -1.2 cyclopentane; bis (diphenylphosphinomethyl) -1.2 cyclohex
  • DDB 2,3-dimethoxy butane
  • tetramenthyldiphosphine bis (N, N'-diphenylphosphino) bis (N, N '(1-phenylethyl)) diaza-1,4 butane.
  • phosphines mentioned above use is preferably made of bis (diarylphosphino-methyl) -1,2 cyclobutanes described in French patent No. 73/18 319.
  • phosphines with chiral phosphorus atoms mention may be made of methyl cyclohexyl orthomethoxyphenyl phosphine; methylcyclohexylphenylphosphine; benzylphenylmethylphosphine.
  • the amount of rhodium derivative used in the process of the invention expressed in gram atoms of metal per mole of diene aldehyde to be hydrogenated can vary within wide limits. Whether it is the preformed complex or the derivative capable of generating this complex under the conditions of the reaction, the quantity can be chosen so that the number of gram atoms of rhodium per mole of aldehyde is between 1 ⁇ 10 - 4 and 1 ⁇ 10 -1 .
  • the amount of phosphine involved in the process depends on the nature of the phosphine and that of the rhodium derivative. This quantity, expressed by the number of gram atoms of phophore per gram atom of rhodium is such that this ratio can vary between 0.5 and 10; preferably the P / Rh ratio is between 1 and 6. However, P / Rh ratios greater than 10 could be used without departing from the scope of the present invention, but this would not provide any particular advantage.
  • the temperature at which the hydrogenation is carried out is not critical and can vary within wide limits. In general it is between 0 and 150 ° C and preferably between 10 and 100 ° C. It is the same for the hydrogen pressure which can vary between 0.1 and 100 bars and preferably between 0.5 and 50 bars.
  • the asymmetric hydrogenation of the mineral or geranial is preferably carried out in an inert solvent of the aldehyde and the catalyst.
  • solvents that may be mentioned include hydrocarbons (hexane, heptane, cyclohexane, benzene, toluene), alcohols (methanol, ethanol), nitriles (acetonitrile, benzonitrile).
  • optical purity P.0 will denote the ratio of the rotary power ( ⁇ 1 ) D of the product obtained by the process to the rotary power ( ⁇ ) D of the product measured under the same conditions, multiplied by 100, ie
  • optical yield is meant the value of the optical purity of the product which would be obtained by using an optically pure phosphine.
  • the apparatus is purged with hydrogen and then the contents of the flask are kept under 1 bar of hydrogen for 4 hours at 25 ° C.
  • the reaction is stopped and the reaction mass is subjected to a gas chromatographic analysis: the geranial transformation rate is 100% and the citronellal yield 99%.
  • the rotary power of pure 1-citronellal ( ⁇ ) 25 D measured on a solution at 6 g / 100 cm 3 in cyclohexane is -15.6 °.
  • the PO of the product obtained is 56%.
  • the reaction time is 10 hours
  • Example 2 The procedure is as in Example 1, replacing the (+) - DPCB with the (+) - DIOP.
  • the geranial / Rh ratio is 120 and a P / Rh ratio of 4 and 6 is used successively.
  • the procedure is as in Example 1, replacing the (+) - DPCB with the (-) - DPCB.
  • the ratio of the number of moles of geranial (G) to the number of gram atoms of rhodium (G / Rh) is equal to 123 and the ratio P / Rh to 4.
  • the (-) - DPCB has an optical purity of 95 , 5%.
  • the reaction time is 18 hours, the geranial transformation rate of 99%, the RT into citronellal of 99%.
  • the mineral used contained 7% geranial.

Landscapes

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

Claims (18)

1. Verfahren zur Herstellung von optisch aktivem Citronellal, dadurch gekennzeichnet, daß man Neral oder Geranial in Gegenwart eines Katalysators hydriert, der aus einem in dem Reaktionsmilieu löslichen Komplex besteht, gebildet aus einem Rhodiumderivat und einem chiralen Phosphin.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Komplex des Rhodiums und des chiralen Phosphins frisch zubereitet wird.
3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Komplex des Rhodiums und des chiralen Phosphins "in situ" aus einem Derivat des Rhodiums und einem chiralen Phosphin gebildet wird.
4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß das Derivat des Rhodiums ein Salz einer Mineralsäure oder organischen Säure oder ein Komplex des Rhodiums mit einem achiralen Liganden ist.
5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß das Derivat des Rhodiums das Rhodiumtrichlorid ist.
6. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß der Komplex ders Rhodiums die allgemeine Formel
Figure imgb0021
hat, worin:
X ein Halogenatom bedeutet,
x eine ganze Zahl von 1 bis 4 ist,
L ein Mono- oder Diolefin bedeutet.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß der Komplex des Rhodiums das µ, µ'-Dichlor-bis-(cyclooctadien-1,5-rhodium) ist.
8. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß der Komplex des Rhodiums die allgemeine Formel
Figure imgb0022
hat, worin R einen achiralen Alkyl-, Cycloalkyl- oder Arylrest mit 1 bis 10 Kohlenstoffatomen bedeutet.
9. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, daß der Komplex des Rhodiums die Formel Rh H (CO)[P―(C6H5)3]3 hat.
10. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß der Komplex des Rhodiums ein Rhodiumcarbonyl ist, genommen aus der Gruppe von Tetrarhodiumdodecarbonyl und von Hexarhodiumhexadecacarbonyl.
11. Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das chirale Phosphin wenigstens ein chirales Kohlenstoffatom und/oder wenigstens ein chirales Phosphoratom aufweist.
12. Verfahren gemäß Anspruch 11, dadurch gekennzeichnet, daß das chirale Phosphin ein Diphosphin der allgemeinen Formel
Figure imgb0023
ist, worin:
R, und R2, welche identisch oder verschieden sind, Kohlenwasserstoffreste mit 1 bis 15 Kohlenstoffatomen bedeuten,
A eine Valenzbindung oder einen zweiwertigen organischen Rest bedeutet, der gegebenenfalls durch eine oder mehrere inerte funktionelle Gruppen substituiert ist, wobei wenigstens einer der Reste R1, R2 und A chiral ist.
13. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, daß man ein chirales Diphosphin der Formel (III) verwendet, worin R, und R2 Alkylreste mit 1 bis 10 Kohlenstoffatomen, Cycloalkylreste mit 4 bis 8 cyclischen Kohlenstoffatomen, Aryl- oder Alkylarylreste bedeuten und A darstellt:
a) einen linearen oder verzweigten Alkylenrest mit 1 bis 10 Kohlenstoffatomen, einen Cycloalkylenrest mit 3 bis 7 cyclischen Kohlenstoffatomen, die gegebenenfalls durch 1 bis 3 Alkylreste mit 1 bis 4 Kohlenstoffatomen substituiert ist, einen Arylenrest, einen zweiwertigen polycyclischen Rest, wobei diese Reste gegebenenfalls durch eine oder mehrere Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen substituiert sein können;
b) eine zweiwertige heterocyclische Gruppe mit 1 oder 2 Heteroatomen aus der Gruppe von Sauerstoff oder Stickstoff;
c) eine Verkettung von einem oder mehreren zweiwertigen Alkylenresten und/oder Cycloalkylenresten und/oder heterocyclischen und/oder polycyclischen Resten, wie diejenigen die oben unter a) und b) definiert sind;
d) eine Verkettung von Alkylengruppen wie diejenigen die oben unter a) definiert sind und von tertiären Aminogruppen, die an die Phosphoratome über das Stickstoffatom direkt gebunden sein können.
14. Verfahren gemäß Anspruch 13, dadurch gekennzeichnet, daß man ein Diphosphin der Formel (111) verwendet, worin R, und R2 einen Arylrest und A eine chirale Gruppe bedeuten.
15. Verfahren gemäß einem der Anspruch 11 bis 14, dadurch gekennzeichnet, daß das chirale Diphosphin das Tetramethyldiphosphin, das 1,2-Bis-(diphenylphosphinomethyl)-cyclobutan, das 4,5-Bis-(diphenylphosphinomethyl)-2,2-dimethyldioxolan, das 1,2-Bis-(diphenylphosphinomethyl)-acenaphthen, das 1,4-Bis-(diphenylphosphino)-2,3-dimethoxybutan, das 1,4-Bis-[N,N'-diphenyl- phosphino]-bis-[N,N'-(1-phenyläthyl)]-diaza-butan ist.
16. Verfahren gemäß einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß die Menge an Komplex des Rhodiums ausgedrückt in Anzahl Grammatome Rhodium je Mol dienischer Aldehyd zwischen 1 x 10-4 und 1 x 10-' beträgt.
17. Verfahren gemäß einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß die Menge an Phosphin ausgedrückt durch das Verhältnis der Anzahl Grammatome Phosphor zur Anzahl Grammatome Rhodium derart ist, daß dieses Verhältnis zwischen 1 und 6 beträgt.
18. Verfahren gemäß einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß die Hydrierung bei einer Temperatur zwischen 0 und 150°C und unter einem Wasserstoffdruck zwischen 0,1 und 100 bar durchgeführt wird.
EP78420001A 1977-07-04 1978-06-14 Verfahren zur Herstellung von optisch aktiven Citronellal Expired EP0000315B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7721377A FR2396735A1 (fr) 1977-07-04 1977-07-04 Procede de preparation de citronellal optiquement actif
FR7721377 1977-07-04

Publications (2)

Publication Number Publication Date
EP0000315A1 EP0000315A1 (de) 1979-01-10
EP0000315B1 true EP0000315B1 (de) 1980-09-17

Family

ID=9193250

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78420001A Expired EP0000315B1 (de) 1977-07-04 1978-06-14 Verfahren zur Herstellung von optisch aktiven Citronellal

Country Status (7)

Country Link
US (1) US4237072A (de)
EP (1) EP0000315B1 (de)
JP (1) JPS5414911A (de)
CA (1) CA1117981A (de)
DE (1) DE2860165D1 (de)
FR (1) FR2396735A1 (de)
IT (1) IT1096979B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013103563A1 (de) 2013-04-10 2014-10-16 Basf Se Verfahren zur Herstellung von Citronellal

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2934250A1 (de) * 1979-08-24 1981-03-19 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von olefinisch ungesaettigten carbonylverbindungen und alkoholen
FR2651152B1 (fr) * 1989-08-23 1991-11-29 Elf Aquitaine Perfectionnement a la preparation de catalyseurs chiraux a base de complexes du ruthenium et du phosphore.
ZM3391A1 (en) * 1990-08-06 1992-04-30 R & C Products Pty Ltd Insect repellent
JP3247277B2 (ja) * 1994-07-29 2002-01-15 高砂香料工業株式会社 液状ｌ−ｎ−メントール組成物及びその調製法
DE102004049631A1 (de) * 2004-10-11 2006-04-20 Basf Ag Verfahren zur Herstellung optisch aktiver Carbonylverbindungen
DE102005036340A1 (de) * 2005-07-29 2007-02-01 Basf Ag Verfahren zur Herstellung optisch aktiver Bis-Phosphinylalkane
EP1951884B1 (de) * 2005-11-17 2009-03-04 Basf Se Verfahren zur herstellung von citronellal
CN101415831B (zh) * 2005-11-17 2013-03-13 巴斯夫欧洲公司 用于产生香茅醛的方法
ES2636840T3 (es) 2007-04-25 2017-10-09 Basf Se Procedimiento para la preparación de compuestos carbonílicos ópticamente activos
CN101932543B (zh) 2007-11-30 2014-07-30 巴斯夫欧洲公司 生产光学活性、外消旋薄荷醇的方法
EP2353714A4 (de) 2008-11-27 2012-05-16 Takasago Perfumery Co Ltd Asymmetrischer hydrierungskatalysator
CN101747152B (zh) * 2008-12-18 2012-10-24 复旦大学 一种柠檬醛液相加氢合成不饱和醇的方法
WO2010140636A1 (ja) 2009-06-03 2010-12-09 高砂香料工業株式会社 不斉水素化触媒
EP2543437A4 (de) 2010-03-04 2014-09-03 Takasago Perfumery Co Ltd Homogener asymmetrischer hydrierungskatalysator
JP5560464B2 (ja) 2010-11-29 2014-07-30 高砂香料工業株式会社 不斉水素化触媒
EP2646150A4 (de) 2010-11-29 2014-10-08 Takasago Perfumery Co Ltd Katalysator für asymmetrische hydrierung und verfahren zur herstellung einer optisch aktiven carbonylverbindung damit
CN103384657B (zh) 2011-02-22 2015-08-05 弗门尼舍有限公司 在不含一氧化碳的气氛下使用铑络合物对二烯醛的氢化
EP3489213B1 (de) 2014-12-19 2021-04-28 Basf Se Zusammensetzung zur verwendung in einem verfahren zur herstellung optisch aktiver carbonylverbindungen
CN105218335B (zh) * 2015-10-20 2017-06-16 万华化学集团股份有限公司 一种由柠檬醛不对称催化氢化制备手性香茅醛的方法
CN105254474B (zh) * 2015-10-20 2017-07-21 万华化学集团股份有限公司 一种由柠檬醛不对称催化氢化制备手性香茅醇的方法
CN105330515B (zh) * 2015-10-20 2017-07-21 万华化学集团股份有限公司 一种光学纯香茅醇的制备方法
US10919921B2 (en) 2016-05-06 2021-02-16 Basf Se P-chiral phosphine ligands and use thereof for asymmetric synthesis
JP7439055B2 (ja) 2018-09-05 2024-02-27 ビーエーエスエフ ソシエタス・ヨーロピア 不斉水素化による光学活性カルボニル化合物の連続的調製
CN109851486B (zh) * 2018-12-20 2022-03-11 万华化学集团股份有限公司 一种钌络合物选择性氢化二烯酮的方法
CN111056932A (zh) * 2019-12-09 2020-04-24 万华化学集团股份有限公司 一种制备光学活性香茅醛的方法
US20230043867A1 (en) 2019-12-09 2023-02-09 Wanhua Chemical Group Co., Ltd. Preparation method for optically active citronellal
CN110872217A (zh) * 2019-12-09 2020-03-10 万华化学集团股份有限公司 一种光学活性的香茅醛的制备方法
CN111004102B (zh) * 2019-12-23 2022-11-04 万华化学集团股份有限公司 一种制备光学活性香茅醛的方法及用于该方法的催化剂
CN111056933B (zh) * 2019-12-24 2022-11-08 万华化学集团股份有限公司 一种制备光学活性香茅醛的方法及用于该方法的催化剂体系

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3489786A (en) * 1964-12-10 1970-01-13 Shell Oil Co Hydrogenation process
US3849480A (en) * 1968-09-09 1974-11-19 Monsanto Co Catalytic asymmetric hydrogenation
US3860657A (en) * 1970-03-25 1975-01-14 Givaudan Corp Process for the preparation of citronellal
FR2116905A5 (fr) * 1970-12-10 1972-07-21 Inst Francais Du Petrole Nouveaux coordinats bidentes,leur fabrication et leurs applications
CA1022187A (en) * 1971-12-23 1977-12-06 Peter S. Gradeff Process for the semihydrogenation of citral to citronellal
US3939188A (en) * 1972-03-24 1976-02-17 Exxon Research And Engineering Company Preparation of zerovalent phosphine substituted rhodium compounds and their use in the selective carbonylation of olefins
FR2314911A1 (fr) * 1975-06-18 1977-01-14 Rhone Poulenc Ind Procede de semi-hydrogenation du citral et de ses homologues en citronnellal et homologues du citronnellal
US4029709A (en) * 1976-02-17 1977-06-14 Rhodia, Inc. Process for the hydrogenation of citral to citronellal and of citronellal to citronellol using chromium-promoted Raney nickel catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013103563A1 (de) 2013-04-10 2014-10-16 Basf Se Verfahren zur Herstellung von Citronellal

Also Published As

Publication number Publication date
IT7825303A0 (it) 1978-07-04
DE2860165D1 (en) 1980-12-18
JPS5414911A (en) 1979-02-03
JPS6123775B2 (de) 1986-06-07
FR2396735A1 (fr) 1979-02-02
EP0000315A1 (de) 1979-01-10
IT1096979B (it) 1985-08-26
CA1117981A (fr) 1982-02-09
US4237072A (en) 1980-12-02
FR2396735B1 (de) 1980-02-01

Similar Documents

Publication Publication Date Title
EP0000315B1 (de) Verfahren zur Herstellung von optisch aktiven Citronellal
EP0136210A1 (de) Chirale Posphor-Liganden, Verfahren zu ihrer Herstellung und ihre Anwendung für die Katalyse von enantioselektiven Synthese-Reaktionen
EP2939743A1 (de) Neue verbindungskomplexe auf nickelbasis, und ihre verwendung in einem transformationsverfahren von olefinen
EP0648201B1 (de) Verfahren zur enantioselektiven hydrierung der carbonylgruppe unter verwendung von ruthenium komplexen mit biphosphineliganden
EP0243281A2 (de) Verfahren zur Dimerisierung eines niedrigen Alkylacrylates und katalytische Zusammensetzung
EP0319406B1 (de) Herstellungsverfahren von ungesättigten Alkoholen
EP0912467B1 (de) Verfahren zur asymmetrischen hydrierung von ketonverbindungen und ihren derivaten
CA1313196C (fr) Procede de preparation d'alcools insatures
EP0564568B1 (de) Verfahren zur hydrierung von olefinischen ungesättigten verbindungen ud ruthenium-katalysatoren zu ihrer durchführung
EP0441708B1 (de) Verfahren zur Herstellung von Terpenketonen
CN111718250B (zh) 一种制备r-香茅醛的方法
EP0489071A1 (de) Verbesserung bei der herstellung von chiralen katalysatoren auf basis von ruthenium- und phosphorkomplexen.
FR2477533A1 (fr) Procede de production d'aldehydes ayant un groupe perfluorocarbone
EP0009429B1 (de) Funktionalisierte Undecadienverbindungen, die einen Substituenten des Methylen-Typs enthalten und Verfahren zu ihrer Herstellung
EP0118354A1 (de) Chemisches Verfahren zur Reiningung einer Isoprentrimerenmischung
FR2588197A1 (fr) Catalyseur et procede d'hydrogenation des liaisons ethyleniques ou acetyleniques
EP0927152B1 (de) Verfahren zur herstellung von optisch aktiven alpha-substituierten benzylalkoholen
EP0152324B1 (de) Tetraen, seine Herstellung und seine Anwendung
EP0362037A2 (de) Verfahren zur Herstellung von gesättigten Aldehyden durch Hydrogenation von alfa-beta-ungesättigten Aldehyden
EP0949241B1 (de) Stereospezifische Isomerisierung von Allylaminen unter Verwendung von Chiralen Phospho-Liganden
WO2023166004A1 (en) Process for preparing gamma,delta-unsaturated aldehydes derivatives
Bulic Palladium and copper-catalysed (CC)-bond formation
FR2619564A1 (fr) Perfectionnement au procede de dimerisation catalytique d'un acrylate d'alkyle
FR2721926A1 (fr) Procede de preparation stereoselective de composes cycliques terpeniques carbonyles par cyclocarbonylation catalytique, et applications de ces composes comme desinfectants ou produits odoriferants
JPS5850207B2 (ja) 水素添加方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE GB NL

REF Corresponds to:

Ref document number: 2860165

Country of ref document: DE

Date of ref document: 19801218

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: RHONE-POULENC RECHERCHES

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910531

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910628

Year of fee payment: 14

Ref country code: BE

Payment date: 19910628

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910630

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910701

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19920614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19920630

Ref country code: BE

Effective date: 19920630

BERE Be: lapsed

Owner name: RHONE-POULENC INDUSTRIES

Effective date: 19920630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920614

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930302

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT