EP0000315A1 - Process for preparing optically active citronellal - Google Patents

Process for preparing optically active citronellal Download PDF

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Publication number
EP0000315A1
EP0000315A1 EP78420001A EP78420001A EP0000315A1 EP 0000315 A1 EP0000315 A1 EP 0000315A1 EP 78420001 A EP78420001 A EP 78420001A EP 78420001 A EP78420001 A EP 78420001A EP 0000315 A1 EP0000315 A1 EP 0000315A1
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Prior art keywords
rhodium
chiral
radicals
carbon atoms
radical
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German (de)
French (fr)
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EP0000315B1 (en
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Paul Aviron-Violet
Tuan-Phat Dang
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Rhone Poulenc Recherches SA
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Rhone Poulenc Industries SA
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    • 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 octadienes or geranial (Z-dimethyl-3,7 octadiene-2,6 al) isomers achirau constitutive of citral.
  • the chiral citronellal is a suitable intermediary in organic synthesis; in particular d-citronellal is used for the preparation of (-) (lS) menthol designated below 1-menthol, by a process which implements the cyclization of d-citronclial into (-) (lS) -isopulégol under the influence of a proton or para catalyst. thermally, then the hydrogenation of isopulegol to (l) -menthol (cf. J.C. LEFFINGWELL and R.E.SHACKELFORD, Cosmetics and Perfumery 89 70-78 / 1974 /).
  • D-citronellal used for synthesis obtained from various natural essences containing d-citronellal and in particular from petrol
  • the use of chiral citronellal of natural origin is not satisfactory to the extent that due to fluctuation natural products, it periodically happens that the price of is higher than that of natural menthol. It is therefore important for the industry to have a source of chiral citronellal having relatively stable price and leading to a synthetic 1-menthol the cost price is lower than that of natural menthol.
  • the synthetic achiral citronellal obtained by hydrogenation of 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 does not have any process allowing synthetic chiral citronellals to be obtained.
  • 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 is meant 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.
  • the chiral diphosphine is tetramenthyidiphosphine bis (diphenylphosphinomethyl) -1,2 cyclobutane, bis (diphenylphosphino-methyl) -4,5 dimethyl-2 , 2 dioxolane, bis (diphenylphosphinomethyl) -1,2 acenaphthene, bis (diphenylphosphino) - !, 4 2,3-dimethoxy butane, bis [(N, N '-diphenylphosphinol] bis [N, N' - ( 1-phenylethyl)] 1,4-diaza butane.
  • phosphines mentioned above use is preferably made of bis (diarylphosphinomethyl) -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 complexes derived from Rh 4 (CO) 12 or Rh 6 (CO) 16 and bis (diarylphosphinomethyl) -1,2 cyclobutanes are particularly suitable for the asymmetric hydrogenation of the mineral and the geranial to enantiomers of citronellal because they provide both a high rate of hydrogenation, good selectivity for citronellal and good optical purity.
  • 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 x 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 neral or geranial is preferably conducted in an inert solvent for the aldehyde and the catal y- sor.
  • solvents that may be mentioned include hydrocarbons (hexane, heptane, cyclohexane, benzene, toluene), alcohols (methanol, ethanol), nitriles (acetonitrile, benzonitrile).
  • optical purity PO denotes the ratio of the rotary power ( ⁇ 1 ) D of the product obtained by the process to the rotary power (a) 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 esc stopped and the reaction mass is subjected to a gas chromatographic analysis: the rate of transformation of the geranial is 100% and the yield of citronellal of 99%.
  • the rotary power of pure 1-citronellal measured on a solution at 6 g / 100 cm 3 in cyclohexane is -15.6 °. With reference to this value, the P.0 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 geranium to the number of gram atoms of rhodium (G / Rh) is equal to 123 and 125 P / Rh to 4.
  • the (-) - DPCB has an optical purity of 95.5%.
  • a 35 cm3 glass ampoule containing 10 cm3 of toluene, 18.3 mg of (-) - DPCB, 91.9 mg is introduced into a 125 cm3 stainless steel autoclave equipped with a shaking system. RhH (CO) (P0) 3 and 1.91 g of geranial.
  • the autoclave is closed and hydrogen is introduced to a pressure of 25 bars. Maintained for 17 hours under these conditions, then the autoclave is degassed and the contents of the ampoule are treated and analyzed as in Example 1.

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Procédé de préparation de citronellal optiquement actif caractérisé en ce que l'on hydrogène le néral ou le géranial en présence d'un catalyseur constitué par un complexe soluble dans le milieu réactionnel, formé à partir d'un dérivé du rhodium et d'une phosphine chirale. Ce procédé permet d'accéder au d-citronellal intermédiaire de la synthése de (-) (1S) menthol.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 rhodium derivative and a phosphine chiral. This process gives access to the intermediate d-citronellal of the synthesis of (-) (1S) menthol.

Description

La présente invention a pour objet un procédé de préparation de citronellal optiquement actif, encore dénommé citronellal chiral, par hydrogénation asymétrique du néral (E-diméthyl-3,7 octadiènes

Figure imgb0001
ou du géranial (Z-diméthyl-3,7 octadiëne-2,6 al) isomères achirau constitutifs du citral.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 octadienes
Figure imgb0001
or geranial (Z-dimethyl-3,7 octadiene-2,6 al) isomers achirau constitutive of citral.

Le citronellal chiral est un intermédiaire apprécié en synthèse organique ; en particulier le d-citronellal est utilisé pour la préparation du (-) (lS) menthol désigné ci-après 1-menthol, par un procédé qui met en oeuvre la cyclisation du d-citronclial en (-) (lS)-isopulégol sous l'influence d'un catalyseur protonique ou par. voie thermique, puis l'hydrogénation de l'isopulégol en (l)-menthol (cf. J.C.LEFFINGWELL et R.E.SHACKELFORD, Cosmetics and Perfumery 89 70-78 /1974/).The chiral citronellal is a suitable intermediary in organic synthesis; in particular d-citronellal is used for the preparation of (-) (lS) menthol designated below 1-menthol, by a process which implements the cyclization of d-citronclial into (-) (lS) -isopulégol under the influence of a proton or para catalyst. thermally, then the hydrogenation of isopulegol to (l) -menthol (cf. J.C. LEFFINGWELL and R.E.SHACKELFORD, Cosmetics and Perfumery 89 70-78 / 1974 /).

Le d-citronellal utilisé pour la synthèse

Figure imgb0002
obtenu à partir de diverses essences naturelles contenant
Figure imgb0003
Figure imgb0004
du d-citronellal et en particulier à partir de l'essence
Figure imgb0005
L'emploi de citronellal chiral d'origine naturelle n'est pas
Figure imgb0006
satisfaisant dans la mesure où, en raison de la fluctuation
Figure imgb0007
produits naturels, il arrive périodiquement que le prix du
Figure imgb0008
soit plus élevé que celui du menthol naturel. Il importe donc à l'industrie de disposer d'une source de citronellal chiral ayant
Figure imgb0009
prix relativement stable et conduisant à un 1-menthol synthétique
Figure imgb0010
le prix de revient soit inférieur à celui du menthol naturel.D-citronellal used for synthesis
Figure imgb0002
obtained from various natural essences containing
Figure imgb0003
Figure imgb0004
d-citronellal and in particular from petrol
Figure imgb0005
The use of chiral citronellal of natural origin is not
Figure imgb0006
satisfactory to the extent that due to fluctuation
Figure imgb0007
natural products, it periodically happens that the price of
Figure imgb0008
is higher than that of natural menthol. It is therefore important for the industry to have a source of chiral citronellal having
Figure imgb0009
relatively stable price and leading to a synthetic 1-menthol
Figure imgb0010
the cost price is lower than that of natural menthol.

Le citronellal synthétique achiral obtenu par hydrogénation du citral (mélange de néral et de géranial) pourrait constituer une source intéressante de citronellal chiral et notamment de d-citronellal, toutefois il n'existe pas de procédé industriel de dédoublement du citronellal racémique en ses énantiomères, de sorte que l'industrie.ne dispose d'aucun procédé permettant d'obtenir des citronellals chiraux par voie synthétique. La présente invention se propose précisément de résoudre un tel problème.'The synthetic achiral citronellal obtained by hydrogenation of citral (mixture of neral and geranial) 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 does not have any process allowing synthetic chiral citronellals to be obtained. The present invention aims precisely to solve such a problem. '

Plus particulièrement la présente invention a pour objet un procédé de préparation de citronellal optiquement actif caractérisé en ce que l'on hydrogène le néral ou le géranial en présence d'un catalyseur constitué par un complexe soluble dans le milieu réactionnel formé à partir d'un dérivé du rhodium et d'une phosphine chirale.More particularly, 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.

Par phosphine chirale on désigne une phosphine ou diphosphine dont l'un au moins des restes organiques liés à l'àtome de phosphore comporte au moins un atome de carbone chiral, et/ou dont un au moins des atomes de phosphore est chiral.By chiral phosphine is meant 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.

Le complexe soluble du dérivé du rhodium et de la phosphine chirale peut être préparé extemporanément ou être formé "in situ" dans les conditions de la réaction par mise en oeuvre des constituants du complexe. Cette dernière façon de faire qui a l'avantage de la simplicité est généralement préférée.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.

Comme dérivés du rhodium convenance la mise en oeuvre du procédé selon l'invention on utilise des dérivés du rhodium comportant des restes de nature diverses. Il peut s'agir de sels de rhodium d'acides minéraux ou organiques ou de complexes du rhodium dont les ligands peuvent être remplacés par la phosphine chirale. On peut par exemple faire appel à des halogénures de rhodium tel que le trichlorure de rhodium hydraté ; à des complexes du rhodium avec les oléfines de formule générale : - -

Figure imgb0011
dans laquelle X représente un atome d'halogène : chlore ou brome par

  • - un radical alcoylène linéaire ou ramifié ayant de 1 à 10 atomes de carbone, un radical cycloalcoylène ayant de 3 à 7 atomes de carbone cycliques éventuellement substitués par 1 à 3 radicaux alcoyles ayanc de 1 à 4 atomes de carbone, un radical arylène, un radical polycyclique divalent, lesdits radicaux pouvant être substitués par un ou plusieurs groupesalcoxy ayant de 1 à 4 atomes de carbone.
  • - un groupe hétérocyclique divalent ayant 1 ou 2 hétéroatomes du groupe de l'oxygène et de l'azote.
  • - un enchaînement de 1 ou plusieurs radicaux alcoylènes et/ou cycloalcoylènes et/ou hétérocycliques et/ou polycycliques divalents tels que ceux définis précédemment.
  • - un enchaînement de groupes alcoylènes tels que ceux définis précédamment et de groupes amino tertiaires qui peuvent être liés directement aux atomes de phosphore par l'intermédiaire de l'atome d'azote.
As derivatives of rhodium suitability for implementing the method according to the invention, derivatives of rhodium are used comprising residues of various nature. They can be rhodium salts of mineral or organic acids or rhodium complexes whose ligands can be replaced by chiral phosphine. It is possible, for example, to use rhodium halides such as hydrated rhodium trichloride; to rhodium complexes with olefins of general formula: - -
Figure imgb0011
 in which X represents a halogen atom: chlorine or bromine by
  • a linear or branched alkylene radical having from 1 to 10 carbon atoms, a cycloalkylene radical having from 3 to 7 cyclic carbon atoms optionally substituted by 1 to 3 alkyl radicals having 1 to 4 carbon atoms, an arylene radical, a divalent polycyclic radical, said radicals being able to be substituted by one or more alkoxy groups having from 1 to 4 carbon atoms.
  • - a divalent heterocyclic group having 1 or 2 heteroatoms from the oxygen and nitrogen group.
  • - A sequence of 1 or more alkylene and / or cycloalkylene and / or heterocyclic and / or polycyclic divalent radicals such as those defined above.
  • - A chain of alkylene groups such as those defined above and tertiary amino groups which can be linked directly to the phosphorus atoms via the nitrogen atom.

14°) Procédé selon la revendication 13, caractérisé en ce que l'on utilise une diphosphine de formule (III) dans laquelle R1 et R2 représente un radical aryle et A est un groupe chiral.14 °) Process according to claim 13, characterized in that a diphosphine of formula (III) is used in which R 1 and R 2 represents an aryl radical and A is a chiral group.

15°) Procédé selon l'une quelconque des revendications 11 à 14, caractérisé en ce que la diphosphine chirale est la tétramenthyidiphosphine le bis(diphénylphosphinométhyl)-1,2 cyclobutane, le bis(diphénylphosphino- méthyl)-4,5 diméthyl-2,2 dioxolane, le bis(diphénylphosphinométhyl)-1,2 acénaphtène, le bis(diphénylphosphino)-!,4 diméthoxy-2,3 butane, le bis[(N,N' -diphénylphosphinol] bis[N,N' -(phényl-1 éthyl)] diaza-1,4 butane.15 °) A method according to any one of claims 11 to 14, characterized in that the chiral diphosphine is tetramenthyidiphosphine bis (diphenylphosphinomethyl) -1,2 cyclobutane, bis (diphenylphosphino-methyl) -4,5 dimethyl-2 , 2 dioxolane, bis (diphenylphosphinomethyl) -1,2 acenaphthene, bis (diphenylphosphino) - !, 4 2,3-dimethoxy butane, bis [(N, N '-diphenylphosphinol] bis [N, N' - ( 1-phenylethyl)] 1,4-diaza butane.

16°) Procédé selon l'une quelconque des revendications 1 à 15, caractérisé en ce que la quantité de complexe du rhodium exprimée en nombre d'atomes-grammes de rhodium par mole d'aldéhyde diénique est comprise entre 1 x 10-4 et 1 x 10-1.16 °) A method according to any one of claims 1 to 15, characterized in that the amount of rhodium complex expressed in number of gram atoms of rhodium per mole of diene aldehyde is between 1 x 10- 4 and 1 x 10-1.

17°) Procédé selon l'une quelconque des revendications

Figure imgb0012
caractérisé en ce que la quantité de phosphine exprima par le
Figure imgb0013
nombre d'atomes-grammes de phosphore au nombre d'atomes-grammes de rhodium est telle que ce rapport est compris entre 1 et 6.17 °) Method according to any one of claims
Figure imgb0012
characterized in that the amount of phosphine expressed by the
Figure imgb0013
number of gram atoms of phosphorus to the number of gram atoms of rhodium is such that this ratio is between 1 and 6.

18°) Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que l'hydrogénation est conduite à une température comprise entre 0 et 150°C et sous une pression d'hydrogène comprise entre 0,1 et 100 bars.18 °) A method according to any one of claims 1 to 17, characterized in that the hydrogenation is carried out at a temperature between 0 and 150 ° C and under a hydrogen pressure between 0.1 and 100 bar.

Figure imgb0014
Figure imgb0014
Figure imgb0015
Figure imgb0015
Figure imgb0016
Figure imgb0016
Figure imgb0017
Figure imgb0017

Parmi les diphosphines chirales qui peuvent être utilisées dans le procédé selon l'invention on peut citer à titre non limitatif :

  • le bis(diphénylphosphinométhyl)-1,2 cyclobutane (DPCB), le bis(diméthyl- phophinométhyl)-1,2 cyclobutane, le bis(di-n-butylphosphinométhyl)-1,2 cyclobutane, le bis(dioctylphosphinométhyl-)-1,2 cyclobutane, le bis(dito- lylphosphinométhyl)-1,2 cyclobutane, le bis(dinaphtylphosphinométhyl)-1,2 cyclobutane, le bis(éthyl,hexylphosphinométhyl)-1,2 cyclobutane, le bis-(diphénylphosphinométhyl)-1,2 cyclopentane ; le bis(diphénylphosphino- méthy)-1,2 cyclohexane ; le bis-(diméthylphosphinométhyl)-4,5 diméthyl-2,2 dioxolane-1,3, le bis-(diphénylphosphinométhyl)-4,5 diméthyl-2,2 dioxolane-1,3, (DIOP), le bis(ditolylphosphinométhyl)-4,5 dinéthyl-2,2 dioxolane-1,3 le bis(diméthylphosphinométhyl)-1,2 acénaphtène, le bis-(dibutylphosphinométhyl)-1,2 acénaphtène, le bis-(diphénylphosphinomërhyl)-1,2 acénaphtène (DPA), le bis(ditolylphosphinomëthyl)-1,2 acénaphtène, le bis(diphénylphosphino)-1,4 diméthoxy-2,3 butane (DDB), la tétramenthyl- diphosphine ; le bis (N,N'-diphénylphosphino)bis(N,N' (phényl-1 éthyl))-diaza-1,4 butane.
Among the chiral diphosphines which can be used in the process according to the invention, non-limiting examples that may be mentioned:
  • 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 (dinaphtylphosphinomethyl) -1,2 cyclobutane, bis (ethyl, hexylphosphinomethyl) -1,2 cyclobutane, bis- (diphenylphosphinomethyl) -1, 2 cyclopentane; bis (diphenylphosphino-methy) -1,2 cyclohexane; bis- (dimethylphosphinomethyl) -4.5 2,2-dimethyl-1,3-dioxolane, bis- (diphenylphosphinomethyl) -4,5 2,2-dimethyl-1,3-dioxolane (DIOP), bis (ditolylphosphinomethyl ) -4.5 dinethyl-2,2 dioxolane-1,3 bis (dimethylphosphinomethyl) -1,2 acenaphthene, bis- (dibutylphosphinomethyl) -1,2 acenaphthene, bis- (diphenylphosphinomethyl) -1,2 acenaphthene ( DPA), bis (ditolylphosphinomethyl) -1,2 acenaphthene, bis (diphenylphosphino) -1,4 2,3-dimethoxy-butane (DDB), tetramenthyl diphosphine; bis (N, N'-diphenylphosphino) bis (N, N '(1-phenylethyl)) - 1,4-diaza butane.

Parmi les phosphines citées précédemment on utilise de préférence les bis(diarylphosphinométhyl)-1,2 cyclobutanes décrits dans le brevet français n° 73/18 319.Among the phosphines mentioned above, use is preferably made of bis (diarylphosphinomethyl) -1.2 cyclobutanes described in French patent No. 73/18 319.

Comme exemples de phosphines à atomes de phosphore chiral on peut citer la méthyl cyclohexyl orthométhoxyphényl phosphine ; la méthylcyclohexylphénylphosphine ; la benzylphénylméthylphosphine.As examples of phosphines with chiral phosphorus atoms, mention may be made of methyl cyclohexyl orthomethoxyphenyl phosphine; methylcyclohexylphenylphosphine; benzylphenylmethylphosphine.

Les complexes dérivés de Rh4 (CO)12 ou de Rh6 (CO)16 et des bis(diarylphosphinométhyl)-1,2 cyclobutanes conviennent tout particulièrement bien à l'hydrogénation asymétrique du néral et du géranial en énantiomères du citronellal car ils procurent à la fois une vitesse élevée d'hydrogénation, une bonne sélectivité en citronellal et une bonne pureté optique.The complexes derived from Rh 4 (CO) 12 or Rh 6 (CO) 16 and bis (diarylphosphinomethyl) -1,2 cyclobutanes are particularly suitable for the asymmetric hydrogenation of the mineral and the geranial to enantiomers of citronellal because they provide both a high rate of hydrogenation, good selectivity for citronellal and good optical purity.

La quantité de dérivé du rhodium mise en oeuvre dans le procédé de l'invention, exprimée en atomes-grammes de métal par mole d'aldéhyde diénique à hydrogéner peut varier dans de larges limites. Qu'il s'agisse du complexe préformé ou du dérivé apte à engendrer ce complexe dans les conditions de la réaction la quantité peut être choisie pour que le nombre d'atomes-grammes de rhodium par mole d'aldéhyde soit compris entre 1 x 10-4 et 1 x 10-1.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 x 10-1.

Lorsque le complexe dérivé du rhodium/phosphine chirale est préparé "in situ", la quantité de phosphine engagée dans le processus dépend de la nature de la phosphine et de celle du dérivé du rhodium. Cette quantité, exprimée par le nombre d'atomes-grammes de phophore par atome-gramme de rhodium est telle que ce rapport peut varier entre 0,5 et 10 ; de préférence le rapport P/Rh est compris entre 1 et 6. On pourrait cependant mettre en oeuvre des rapports P/Rh supérieurs à 10 sans sortir du cadre de la présente invention, mais celà ne procurerait aucun avantage particulier.When the rhodium / chiral phosphine complex is prepared "in situ", 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.

La température à laquelle on conduit l'hydrogénation n'est pas critique et peut varier dans de larges limites. En général elle est comprise entre 0 et 150°C et de préférence entre 10 et 100°C. Il en est de même de la pression d'hydrogène qui peut varier entre 0,1 et 100 bars et de préférence entre 0,5 et 50 bars.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.

Bien qu'il soit préférable de soumettre à l'hydrogénation asymétrique un aldéhyde diénique aussi pur que possible, c'est-à-dire pratiquement exempt de son isomère, on peut mettre en oeuvre du néral contenant jusqu'à 15 % de géranial et vice versa.Although it is preferable to subject to asymmetric hydrogenation a diene aldehyde as pure as possible, that is to say practically free of its isomer, it is possible to use mineral containing up to 15% of geranial and vice versa.

De la même façon il est préférable d'utiliser une phosphine chirale ne contenant pas son énantiomère bien que l'on puisse opérer avec une phosphine chirale contenant moins de 15 % de son énantiomère.In the same way it is preferable to use a chiral phosphine not containing its enantiomer although one can operate with a chiral phosphine containing less than 15% of its enantiomer.

L'hydrogénation asymétrique du néral ou du géranial est de préférence conduite dans un solvant inerte de l'aldéhyde et du cataly- seur. Comme exemple de solvants, on peut citer des hydrocarbures (hexane, heptane, cyclohexane, benzène, toluène), des alcools (méthanol, éthanol), des nitriles (acétonitrile, benzonitrile).The asymmetric hydrogenation of neral or geranial is preferably conducted in an inert solvent for the aldehyde and the catal y- sor. Examples of solvents that may be mentioned include hydrocarbons (hexane, heptane, cyclohexane, benzene, toluene), alcohols (methanol, ethanol), nitriles (acetonitrile, benzonitrile).

Les exemples suivants illustrent l'invention et montrent comment elle peut être mise en pratique. Dans ces exemples on désignera par pureté optique P.O le rapport du pouvoir rotatoire (α1)D du produit obtenu par le procédé au pouvoir rotatoire (a)D du produit mesuré dans les mêmes conditions, multiplié par 100, soit

Figure imgb0018
The following examples illustrate the invention and show how it can be practiced. In these examples, optical purity PO denotes the ratio of the rotary power (α 1 ) D of the product obtained by the process to the rotary power (a) D of the product measured under the same conditions, multiplied by 100, ie
Figure imgb0018

Par rendement optique on désigne la valeur de la pureté optique du produit que l'on obtiendrait par utilisation d'une phosphine optiquement pure.By optical yield is meant the value of the optical purity of the product which would be obtained by using an optically pure phosphine.

EXEMPLE IEXAMPLE I

Dans un ballon en verre de 50 cm3, équipé d'une arrivée de gaz par tube plongeant, d'un thermomètre, d'une agitation magnétique et d'un bouchon en verre permettant de procéder à des additions de réactifs ou des prélèvements de masse réactionnelle au moyen d'une seringue, on charge 18,2 mg de Rh6 (CO)16 (1,02 x 10-4 at-g de Rh), 67,5 mg (+)-(DPCB) soit 0,15 millimoie, puis on purge l'appareil à l'azote et injecte 20 cm3 de toluène. On agite le contenu du ballon pendant 1 heure sous atmosphère d'azote puis ajoute 1,79 g (soit 11,77 millimole) de géranial contenant 5 % de néral. On purge l'appareil à l'hydrogène puis maintient le contenu du ballon sous 1 bar d'hydrogène pendant 4 heures à 25°C. La réaction esc arrêtée et la masse réactionnelle est soumise à une analyse chromatogra- phique en phase gazeuse : le taux de transformation du géranial est de 100 % et le rendement en citronellal de 99 %. On évapore le solvant puis distille le résidu sous pression réduite. On recueille ainsi 1,28 g de 1-citronellal ayant un pouvoir rotatoire

Figure imgb0019
= -8,76° (mesuré sur une solution à 6 g pour 100 cm3 dans l'hexane) et
Figure imgb0020
= -9,1° mesuré en absence de solvant. Le pouvoir rotatoire du 1-citronellal pur
Figure imgb0021
mesuré sur une solution à 6 g/100 cm3 dans le cyclohexane est de -15,6°. Par référence à cette valeur, la P.0 du produit obtenu est de 56 %. Le pouvoir rotatoire du 1-citronellal pur (détermination sans solvant) est (α)25 D = -16° (cf. DONELL et al. Australian J. Chem. 19 525 [1966]).In a 50 cm 3 glass flask equipped with a gas inlet by dip tube, a thermometer, a magnetic stirrer and a glass stopper allowing reagents to be added or samples to be taken. reaction mass using a syringe, 18.2 mg of Rh 6 (CO) 16 (1.02 x 10 -4 at-g of Rh) are loaded, 67.5 mg (+) - (DPCB), ie 0 , 15 millimoie, then the apparatus is purged with nitrogen and injected 20 cm 3 of toluene. The contents of the flask are stirred for 1 hour under a nitrogen atmosphere and then 1.79 g (or 11.77 millimole) of geranial containing 5% mineral are added. 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 esc stopped and the reaction mass is subjected to a gas chromatographic analysis: the rate of transformation of the geranial is 100% and the yield of citronellal of 99%. The solvent is evaporated and then the residue is distilled under reduced pressure. 1.28 g of 1-citronellal having a rotary power are thus collected.
Figure imgb0019
 = -8.76 ° (measured on a 6 g solution per 100 cm 3 in hexane) and
Figure imgb0020
 = -9.1 ° measured in the absence of solvent. The rotary power of pure 1-citronellal
Figure imgb0021
 measured on a solution at 6 g / 100 cm 3 in cyclohexane is -15.6 °. With reference to this value, the P.0 of the product obtained is 56%. The rotary power of pure 1-citronellal (determination without solvent) is (α) 25 D = -16 ° (cf. DONELL et al. Australian J. Chem. 19 525 [1966]).

EXEMPLE 2EXAMPLE 2

On opère comme à l'exemple 1 sur les quantités suivantes :

Figure imgb0022
The procedure is as in Example 1 on the following quantities:
Figure imgb0022

La durée de réaction est de 10 heures

Figure imgb0023
The reaction time is 10 hours
Figure imgb0023

Après distillation on recueille 9,6 g de citronellal de (α)25 D = +10,15° (solution à 6 g/100 cm3 dans l'hexane) soit une pureté optique de 65 %.After distillation, 9.6 g of citronellal of (α) 25 D = + 10.15 ° are collected (solution at 6 g / 100 cm3 in hexane), ie an optical purity of 65%.

EXEMPLES 3 A 4EXAMPLES 3 TO 4

On opère comme à l'exemple 1 en remplaçant la (+)-DPCB par la (+)-DIOP. Le rapport géranial/Rh est de 120 et on utilise successivement un rapport P/Rh de 4 et de 6.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.

Dans ces conditions on a obtenu les résultats suivants :

Figure imgb0024
Under these conditions, the following results were obtained:
Figure imgb0024

EXEMPLE 5EXAMPLE 5

On opère comme à l'exemple 1 en remplaçant la (+)-DPCB par la (-)-DPCB. Le rapport du nombre de mole de géranium au nombre d'atomes-grammes de rhodium (G/Rh) est égal à 123 et 125 P/Rh à 4. La (-)-DPCB a une pureté optique de 95,5 %.The procedure is as in Example 1, replacing the (+) - DPCB with the (-) - DPCB. The ratio of the number of moles of geranium to the number of gram atoms of rhodium (G / Rh) is equal to 123 and 125 P / Rh to 4. The (-) - DPCB has an optical purity of 95.5%.

La durée de réaction est de 18 heures, le taux de transformation du géranial de 99 %, le RT en citronellal de 99 % L3 pureté optique du (d)-citronellal obtenu est de 49 % [

Figure imgb0025
= +7 7°. solution à 6 g/100 cm3 dans l'hexane]. Si l'on tient compte de la purete de la phosphine le rendement optique s'élève à 52 %.The reaction time is 18 hours, the geranial transformation rate of 99%, the RT into citronellal of 99% L3 optical purity of the (d) -citronellal obtained is 49% [
Figure imgb0025
 = +7 7 °. 6 g / 100 cm3 solution in hexane]. If the purity of the phosphine is taken into account, the optical efficiency is 52%.

EXEMPLE 6EXAMPLE 6

On opère comme à l'exemple 5 en remplaçant le géranial par le néral, les autres conditions étant par ailleurs identiques. On a obtenu les résultats suivants :

Figure imgb0026
The procedure is as in Example 5, replacing the geranial with the neral, the other conditions being otherwise identical. The following results were obtained:
Figure imgb0026

EXEMPLE 7EXAMPLE 7

On opère suivant le mode opératoire de l'exemple 1 et dans les mêmes conditions de pression et de température en remplaçant (Rh6(CO)16 par Rh4(CO)12. Le rapport P/Rh est de 3 et le rapport G/Rh de 120. Les résultats sont les suivants :

Figure imgb0027
The procedure is as in Example 1 and under the same pressure and temperature conditions, replacing (Rh 6 (CO) 16 by Rh 4 (CO) 12. The P / Rh ratio is 3 and the G ratio / Rh of 120. The results are as follows:
Figure imgb0027

EXEMPLE 8EXAMPLE 8

On opère comme à l'exemple 7 en remplaçant le géranis par le néral (le rapport N/Rh est de 140). On a obtenu les résultats suivants :

Figure imgb0028
The procedure is as in Example 7, replacing the geranis with the mineral (the N / Rh ratio is 140). The following results were obtained:
Figure imgb0028

EXEMPLE 9EXAMPLE 9

On opère comme à l'exemple 1 en portant le rapport N/Rh à 750 au lieu de 115 et le rapport P/Rh à 2. On a obtenu les résultats suivants :

Figure imgb0029
The procedure is as in Example 1, bringing the N / Rh ratio to 750 instead of 115 and the P / Rh ratio to 2. The following results have been obtained:
Figure imgb0029

EXEMPLES 10 à 18EXAMPLES 10 to 18

On opère selon le mode opératoire et les conditions de température et de pression de l'exemple 1, en faisant varier la nature de l'aldéhyde, de la phosphine chirale et du dérivé du rhodium. Les autres conditions et les résultats obtenus figurent dans le tableau suivant':

Figure imgb0030
The procedure is carried out according to the procedure and the temperature and pressure conditions of Example 1, by varying the nature of the aldehyde, chiral phosphine and the rhodium derivative. The other conditions and the results obtained are shown in the following table:
Figure imgb0030

EXEMPLE 19EXAMPLE 19

Dans un autoclave en acier inoxydable de 125 cm3 équipé d'un système d'agitation à secousses, on introduit une ampoule de verre de 35 cm3 contenant 10 cm3 de toluène, 18,3 mg de (-)-DPCB, 91,9 mg de RhH(CO)(P0)3 et 1,91 g de géranial. On ferme l'autoclave et introduit de l'hydrogène jusqu'à une pression de 25 bars. On maintient 17 heures dans ces conditions, puis l'autoclàve est dégazé et le contenu de l'ampoule est traité et analysé comme à l'exemple 1.A 35 cm3 glass ampoule containing 10 cm3 of toluene, 18.3 mg of (-) - DPCB, 91.9 mg is introduced into a 125 cm3 stainless steel autoclave equipped with a shaking system. RhH (CO) (P0) 3 and 1.91 g of geranial. The autoclave is closed and hydrogen is introduced to a pressure of 25 bars. Maintained for 17 hours under these conditions, then the autoclave is degassed and the contents of the ampoule are treated and analyzed as in Example 1.

Le taux de transformation du géranial s'élève à 69 % le rendement en citronellal par rapport au géranial transformé à 99 % et la pureté optique à 60 % (pouvoir rotatoire

Figure imgb0031
= +6,6° mesuré sur le produit pur).The geranial transformation rate is 69% the citronellal yield compared to the geranial transformed at 99% and the optical purity at 60% (rotational power
Figure imgb0031
 = + 6.6 ° measured on the pure product).

Claims (13)

1°) Procédé de préparation de citronellal optiquement actif, caractérisé en ce que l'on hydrogène le néral ou le géranial en présence d'un catalyseur constitué par un complexe soluble dans le milieu réactionnel, formé à partir d'un dérivé du rhodium et d'une phosphine chirale.1 °) Process for the preparation of optically active citronellal, characterized in that the mineral or the geranial is hydrogenated in the presence of a catalyst consisting of a complex soluble in the reaction medium, formed from a rhodium derivative and of a chiral phosphine. 2°) Procédé selon la revendication 1, caractérisé en ce que le complexe du rhodium et de la phosphine chirale est préparé extemporanément.2 °) Method according to claim 1, characterized in that the complex of rhodium and chiral phosphine is prepared extemporaneously. 3°) Procédé selon la revendication 1, caractérisé en ce que le complexe du rhodium et de la phosphine chirale est formé "in situ" à partir d'un dérivé du rhodium et d'une phosphine chirale.3 °) Method according to claim 1, characterized in that the complex of rhodium and chiral phosphine is formed "in situ" from a derivative of rhodium and a chiral phosphine. 4°) Procédé selon la revendication 3, caractérisé en ce que le dérivé du rhodium est un sel d'acide minéral ou organique ou un complexe du rhodium avec un ligand achiral.4 °) Method according to claim 3, characterized in that the rhodium derivative is a mineral or organic acid salt or a rhodium complex with an achiral ligand. 5°) Procédé selon la revendication 4, caractérisé en ce que le dérivé du rhodium est le trichlorure de rhodium.5 °) Process according to claim 4, characterized in that the rhodium derivative is rhodium trichloride. 6°) Procédé selon la revendication 4, caractérisé en ce que le complexe du rhodium a pour formule générale :
Figure imgb0032
dans laquelle : - X représente un atome d'halogène - x est un nombre entier de 1 à 4 - L représente une mono- ou dioléfine. 6 °) Method according to claim 4, characterized in that the rhodium complex has the general formula:
Figure imgb0032
 in which : - X represents a halogen atom - x is an integer from 1 to 4 - L represents a mono- or diolefin. 7°) Procédé selon la revendication 6, caractérisé en ce que le complexe du rhodium est le µ,µ'-dichloro bis(cyclooctadiene-1,5 rhodium).7 °) Process according to claim 6, characterized in that the rhodium complex is µ, µ'-dichloro bis (cyclooctadiene-1,5 rhodium). 8°) Procédé selon la revendication 4, caractérisé en ce que le complexe du rhodium a la formule générale :
Figure imgb0033
dans laquelle R représente un radical alcoyle, cycloalcoyle ou aryle achiral ayant de 1 à 10 atomes de carbone.8 °) Method according to claim 4, characterized in that the rhodium complex has the general formula:
Figure imgb0033
 in which R represents an alkyl, cycloalkyl or achiral aryl radical having from 1 to 10 carbon atoms. 9°) Procédé selon la revendication 8, caractérisé en ce que le complexe du rhodium a la formule Rh H (CO[P-(C6H5)3]3.9 °) Process according to claim 8, characterized in that the rhodium complex has the formula Rh H (CO [P- (C 6 H 5 ) 3 ] 3 . 10°) Procédé selon la revendication 4, caractérisé en ce que le complexe du rhodium est un rhodium carbonyle pris dans le groupe du tétrarhodiumdodécarbonyle et de l'hexarhodiumhexadécacarbonyle.10 °) A method according to claim 4, characterized in that the rhodium complex is a rhodium carbonyl taken from the group of tetrarhodiumdodecarbonyl and hexarhodiumhexadécacarbonyle. 11°) Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la phosphine chirale comporte au moins un atome de carbone chiral et/ou au moins un atome de phosphore chiral.11 °) A method according to any one of claims 1 to 10, characterized in that the chiral phosphine comprises at least one chiral carbon atom and / or at least one chiral phosphorus atom. 12°) Procédé selon la revendication 11, caractérisé en ce que la phosphine chirale est une diphosphine de formule générale :
Figure imgb0034
dans laquelle : - RI et R2, identiques ou différents, représentent des radicaux hydrocarbonés ayant de 1 à 15 atomes de carbone, - A représente un lien valentiel ou un radical organique divalent éventuellement substitué par un ou plusieurs groupes fonctionnels inertes, l'un sa moins des radicaux R1, R2 et A étant chiral. 12 °) Method according to claim 11, characterized in that the chiral phosphine is a diphosphine of general formula:
Figure imgb0034
 in which : - R I and R 2 , identical or different, represent hydrocarbon radicals having from 1 to 15 carbon atoms, - A represents a valence bond or a divalent organic radical optionally substituted by one or more inert functional groups, one less of the radicals R 1 , R 2 and A being chiral. 13°) Procédé selon la revendication 12, caractérisé en ce que l'on utilise une diphosphine chirale de formule (III) dans laquelle R1 et R2 représentent des radicaux alcoyles ayant de 1 à 10 atomes de carbone, cycloalcoyles ayant de 4 à 8 atomes de carbone cycliques, aryles ou alcoylaryles et A symbolise :
Figure imgb0035
Figure imgb0036
dans laquelle L1 représente un ligand mono- ou polydentate et notamment une phophine achirale de formule générale :
Figure imgb0037
dans laquelle R représente un radical achiral alcoyle, cycloalcoyle aryle ayant de 1 à 10 atomes de carbone tel que les radicaux méthyle éthyle, propyle, butyles, pentyles, hexyles, octyles, cyclohexyle, phényle, toluyle. De préférence L1 est la triphénylphesphine. Parmi les dérivés du rhodium précités on fait appel de préférence aux divers rho- diumcarbonyle et notamment au tétrarhodium dodécacarbonyle et à l'hexa- rhodiumhexadécacarbonyle. Les complexes du rhodium pris sous forme cationique peuvent également être utilisés. Comme phosphine chirale convenant à la mise et oeuvre de l'invention on peut utiliser aussi bien des monophosphines que des diphosphines. Comme exemplesde monophosphines chirale on
Figure imgb0038
diphanylmenthylphosphine, la phényldimenthylphosphine
Figure imgb0039
phosphine. On préfére toutefois faire appel
Figure imgb0040
de formule générale :
Figure imgb0041
dans laquelle : - R1 et R2, identiques ou différents, représentent des radicaux
Figure imgb0042
carbonés ayant de 1 à 15 atomes de carbone, - A représente un lien valentiel ou un radical organique divaient éventuellement substitué par un ou plusieurs groupes fonctionnels inertes,
l'un au moins des radicaux R1, R2 et A étant chiral. Plus spécifiquement R1 et R2, qui sont de préférence identiques, représentent des radicaux alcoyles ayant de 1 à 10 atomes de carbone (méthyle, éthyle, isobutyle, sec-butyle, sec-pentyle, éthyl-2 hexyle), cycloalcoyle ayant de 4 à 8 atomes de carbone cycliques (cyclobutyle, méthyle-1 cyclobutyle, cyclohexyle, méthyle-1 cyclohexyle, méthyle-2 cyclohexyle), aryles ou alcoylaryles (phényle, naphtyle, toluyle). A représente : - un radical alcoylène linéaire ou ramifié ayant de 1 à 10 atomes de carbone, un radical cycloalcoylène ayant de 3 à 7 atomes de carbone cycliques, éventuellement susbstitué par 1 à 3 groupes alcoyles ayant de 1 à 4 atomes de carbone, un radical arylène, un radical polycyclique divalent, ces radicaux étant éventuellement substitués par 1 ou plusieurs groupes fonctionnels inertes et notamment 1 à 3 groupes alcoxy ayant de 1 à 4 atomes de carbone. - un groupe hétérocyclique divalent (pyridylène, dioxa-1,3 cyclopenty- lène-4,5) ayant 1 ou 2 hétéroatomes tels que l'oxygène et/ou l'azote. - un enchaînement de 1 ou plusieurs radicaux alcoylène et/ou cycloalcoylènes et/ou hétérocycliques et/ou polycycliques divalents tel que ceux définis précédemment. - un enchaînement de groupes alcoylènes tels que ceux définis précédemment et de groupes amino tertiaire qui peuvent éventuellement être liés directement aux atomes de phosphore par l'intermédiaire de l'atome d'azote. Comme exemple de radicaux alcoylènes ont peut citer les radicaux méthylène, éthylène, propylène, éthyl-2 propylène A peut encore représenter un radical cyclobutylène ; cyclohexylène-1, 4 ; méthyl-2 cyclohexylène-1,4 ; un radical ortho- ou p-phénylène ; un radical diméthoxy-2,3 butylène-1,4. Comme exemple de radicaux A chiraux divalents formés par un enchaînement de radicaux alcoylènes et cycloalcoylènes ou hétérocycliques ou polycycliques ou amino on peut citer ceux de formules : 13 °) Process according to claim 12, characterized in that a chiral diphosphine of formula (III) is used in which R 1 and R 2 represent alkyl radicals having from 1 to 10 carbon atoms, cycloalkyls having from 4 to 8 cyclic, aryl or alkylaryl carbon atoms and A symbolizes:
Figure imgb0035
Figure imgb0036
 in which L 1 represents a mono- or polydentate ligand and in particular an achiral phophine of general formula:
Figure imgb0037
 in which R represents an achiral alkyl, cycloalkyl aryl radical having from 1 to 10 carbon atoms such as the methyl ethyl, propyl, butyl, pentyles, hexyls, octyls, cyclohexyl, phenyl, toluyl radicals. Preferably L 1 is triphenylphesphine. Among the aforementioned rhodium derivatives, use is preferably made of the various rhodiumcarbonyls and in particular tetrarhodium dodecacarbonyl and hexa- rhodiumhexadecacarbonyl. Rhodium complexes taken in cationic form can also be used. As chiral phosphine suitable for carrying out the invention, both monophosphines and diphosphines can be used. As examples of chiral monophosphines we
Figure imgb0038
diphanylmenthylphosphine, phenyldimenthylphosphine
Figure imgb0039
phosphine. However, we prefer to appeal
Figure imgb0040
of general formula:
Figure imgb0041
in which : - R 1 and R 2 , identical or different, represent radicals
Figure imgb0042
carbon having 1 to 15 carbon atoms, - A represents a valential bond or an organic radical divide optionally substituted by one or more inert functional groups,
at least one of the radicals R 1 , R 2 and A being chiral. More specifically, R 1 and R 2 , which are preferably identical, represent alkyl radicals having from 1 to 10 carbon atoms (methyl, ethyl, isobutyl, sec-butyl, sec-pentyl, 2-ethylhexyl), cycloalkyl having 4 to 8 cyclic carbon atoms (cyclobutyl, methyl-1 cyclobutyl, cyclohexyl, methyl-1 cyclohexyl, methyl-2 cyclohexyl), aryls or alkylaryl (phenyl, naphthyl, toluyl). A represents: a linear or branched alkylene radical having from 1 to 10 carbon atoms, a cycloalkylene radical having from 3 to 7 cyclic carbon atoms, optionally substituted by 1 to 3 alkyl groups having from 1 to 4 carbon atoms, an arylene radical, a divalent polycyclic radical, these radicals being optionally substituted by 1 or more inert functional groups and in particular 1 to 3 alkoxy groups having from 1 to 4 carbon atoms. - a divalent heterocyclic group (pyridylene, 1,3-dioxa-4,5-cyclopentylene-4,5) having 1 or 2 heteroatoms such as oxygen and / or nitrogen. - A sequence of 1 or more alkylene and / or cycloalkylene and / or heterocyclic and / or polycyclic divalent radicals such as those defined above. - A chain of alkylene groups such as those defined above and tertiary amino groups which may optionally be linked directly to the phosphorus atoms via the nitrogen atom. As an example of alkylene radicals, there may be mentioned the methylene, ethylene, propylene, 2-ethylpropylene radicals A may also represent a cyclobutylene radical; cyclohexylene-1, 4; 2-methyl-1,4-cyclohexylene; an ortho- or p-phenylene radical; a 2,3-dimethoxy-1,4-butylene radical. As an example of 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:
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JP2009515541A (en) * 2005-11-17 2009-04-16 ビーエーエスエフ ソシエタス・ヨーロピア Citronellal production method
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US7534921B2 (en) 2004-10-11 2009-05-19 Basf Aktiengesellschaft Method for the production of optically active carbonyl
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