EP0000315B1 - Procédé de préparation de citronellal optiquement actif - Google Patents

Procédé de préparation de citronellal optiquement actif Download PDF

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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
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Prior art keywords
rhodium
process according
chiral
bis
carbon atoms
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EP78420001A
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German (de)
English (en)
French (fr)
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EP0000315A1 (fr
Inventor
Paul Aviron-Violet
Tuan-Phat Dang
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Rhone Poulenc Recherches SA
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Rhone Poulenc Industries SA
Rhone Poulenc Recherches 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 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.

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  • 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)
EP78420001A 1977-07-04 1978-06-14 Procédé de préparation de citronellal optiquement actif Expired EP0000315B1 (fr)

Applications Claiming Priority (2)

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

Publications (2)

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EP0000315A1 EP0000315A1 (fr) 1979-01-10
EP0000315B1 true EP0000315B1 (fr) 1980-09-17

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

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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
EP3452488A1 (de) * 2016-05-06 2019-03-13 Basf Se P-chirale phosphinliganden und deren verwendung zur asymmetrischen synthese
CN112638854B (zh) 2018-09-05 2023-10-27 巴斯夫欧洲公司 通过不对称氢化连续制备光学活性羰基化合物
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
US12202792B2 (en) 2019-12-09 2025-01-21 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
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
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

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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

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

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