WO2008003742A1 - Procédé et nouveaux produits intermédiaires permettant la production de 3,3'-dihydroxyisoréniératine - Google Patents

Procédé et nouveaux produits intermédiaires permettant la production de 3,3'-dihydroxyisoréniératine Download PDF

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Publication number
WO2008003742A1
WO2008003742A1 PCT/EP2007/056801 EP2007056801W WO2008003742A1 WO 2008003742 A1 WO2008003742 A1 WO 2008003742A1 EP 2007056801 W EP2007056801 W EP 2007056801W WO 2008003742 A1 WO2008003742 A1 WO 2008003742A1
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formula
cis
reaction
ketone
alcohol
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PCT/EP2007/056801
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German (de)
English (en)
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Hansgeorg Ernst
Klaus Henrich
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
    • C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/24—Halogenated derivatives
    • C07C39/373—Halogenated derivatives with all hydroxy groups on non-condensed rings and with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • C07C49/245—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
    • C07C49/248—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5456—Arylalkanephosphonium compounds

Definitions

  • the present invention relates to an improved process for the preparation of 3,3'-Dihydroxyisorenieratin in the formula I, hereinafter referred to ⁇ , ⁇ -carotene-3,3'-diol, as well as novel intermediates of this method.
  • 3,3'-Dihydroxyisorenieratin ( ⁇ , ⁇ -carotene-3,3'-diol) of the formula I is used as a feed additive (broiler skin pigmentation: Riv Zootec Vet 1974, 1, 31-44, egg yolk pigmentation: Z Allg. Microbiol. (1970), 10 (4), 237-244) are of great interest.
  • DE 1593440 describes the synthesis of ⁇ , ⁇ -carotene-3,3'-diol of the formula I.
  • crocetine dialdehyde 1 is reacted with two equivalents of the phosphonium salt 2 in a double Wittig olefination according to the synthesis strategy C10 + C20 + C10 to form ⁇ , ⁇ -carotene-3,3'-diol of the formula I.
  • R tetrahydropyranyl protecting group
  • the phosphonium salt of the formula 2 required for this synthesis is prepared in a four-step sequence from 2,3,6-trimethyl-4-hydroxybenzaldehyde of the formula II.
  • Example 1 obtained from 14.6 g (89.02 mmol) of aldehyde of the formula II, only 6.4 g (11, 13 mmol) of the phosphonium salt of formula 2. This yield is not satisfactory.
  • R tetrahydropyranyl protecting group
  • EP 882 709 describes the synthesis of zeaxanthin, the synthetic strategy
  • M 1 is Li, Na, K, MgCl, MgBr, MgI or Mgi / 2 , c) reacting the cis-alcohol of the formula VI with a strong organic or inorganic acid HX, wherein X represents the anion of the acid HX, to form a Ci5-building block of the formula VII,
  • steps c) and d) are preferably carried out.
  • step a) of the process according to the invention the cio-aldehyde of the formula II is reacted with a compound which is the equivalent of a building block of the formula MIa to give the C 13 -ketone of the formula IV, using as compounds the equivalent of a building block of the formula IIIa
  • acetone, (2-oxopropyl) phosphonic di-Ci-Cio-alkyl esters, such as (2-oxopropyl) phosphonic acid diethyl ester or a 1- (triarylphosphorane-ylidene) -2-propane, such as 1- (triphenylphosphorane -ylidene) -2-propane can be used.
  • the building block of the formula IMa replaces the carbonyl oxygen atom in the cio-aldehyde of the formula II.
  • the cio-aldehyde of the formula II is preferably reacted without the introduction of a protective group for the phenolic HO group to form the C 13 -ketone of the formula IV.
  • Step a) which thus represents a C3 extension, can in principle be carried out according to known rules, for example by a base-catalyzed condensation with acetone as the equivalent of a building block of the formula IIIa.
  • acetone is advantageously used in excess as the solvent.
  • Suitable basic catalysts are, for example, alkali metal hydroxides and alkaline earth metal hydroxides, especially alkali metal hydroxides, such as sodium or potassium hydroxide.
  • the Cio-aldehyde of formula II can be converted into the Ci3-ketone of formula IV by adding the Cio-aldehyde with about 10-20 times the molar amount of acetone and the solution after addition of about twice the equimolar amount NaOH powder based on the aldehyde heated to boiling under reflux.
  • a further possibility, known per se, of converting the cio-aldehyde of the formula II into the C13-ketone of the formula IV consists in the reaction of the aldehyde of the formula II with (2-oxopropyl) -phosphonic acid diethyl ester as the equivalent of Building blocks of the formula IMa.
  • Particularly suitable bases here are C 1 -C 6 -alcohols, in particular C 1 -C 4 -alkali-metal alcoholates, such as, for example, sodium methoxide or sodium ethoxide.
  • the compound which is the equivalent of a building block of the formula IIIa is preferably 1- (triphenylphosphoranylidene) -2-propane.
  • Cio-aldehyde of the formula II in the Ci3-ketone of the formula IV is thus that the Cio-aldehyde with 1- (TYi-phenylphosphoran-ylidene) -2-propane (C3-ylidene) as Equivalent of a building block of the formula IIIa, in particular that the C10-aldehyde is reacted with an excess of 1- (triphenylphosphoranylidene) -2-propane (C3-ylidene) O
  • the C 13 -ketone of the formula IV can be isolated in good yield and high purity.
  • step b) of the process according to the invention the C 13 -ketone of the formula IV is converted to the C 15 -alcohol of the formula VI by reacting the ketone with either a vinyl compound of the formula Va
  • M 1 is Li, Na, K, MgCl, MgBr, MgI or Mgi / 2, in particular Li, Na, MgCl or MgBr.
  • Ci3-ketone of formula IV in the not yet described cis-alcohol of formula VI by reacting the Ci3-ketone of formula IV with an ethynyl compound of the formula Vb can be carried out according to the principle known.
  • the C13 ketone of formula IV can be prepared by 1,2-addition of lithium or sodium acetylide to the cis alcohol of formula VIa,
  • Ci3 ketone of formula IV is converted in one step by 1, 2-addition of vinyl lithium or vinyl Grignard reagents in the cis-alcohol of formula VI.
  • Preferred solvents for the ethynylation are liquid ammonia or open-chain or cyclic ethers
  • preferred solvents for the vinylation are open-chain or cyclic ethers.
  • the C 13 -ketone of the formula IV is preferably reacted with vinyl magnesium chloride.
  • the Grignard reagent is employed in an excess of 2-5 mol equivalents, preferably 3-4 mol equivalents, based on the ketone of the formula IV. Details on the vinylation of ketones are given, for example, in Bull. Soc. Chem. Japan 37, (1964), 207.
  • step c) of the process according to the invention the cis-alcohol of the formula VI is reacted with a strong organic or inorganic acid HX, where X represents the anion of the acid HX, to give a cis-building block of the formula VII
  • triarylphosphine-HX adduct of the formula P (aryl) 3 * HX which is present in isolated form or as a mixture of a strong organic or inorganic acid HX and triarylphosphine P (aryl) 3 can be converted directly to a cis-phosphonium salt of the formula VIII.
  • Strong organic or inorganic acids are understood as meaning those acids whose pK a values are less than 3, preferably less than 1.
  • Examples of strong organic or inorganic acids are hydrohalic acids, such as hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfonic acids, such as methanesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid, or trihaloacetic acids, such as trifluoroacetic acid or trichloroacetic acid.
  • strong acids such as hydrohalic acids, sulfonic acids or trifluoroacetic acid
  • X is then halide, sulfonate or trifluoroacetate
  • a triarylphosphane in particular Convert triphenylphosphane into a C 15-phosphonium salt of the formula VIII.
  • step c) hydrobromic acid or hydrochloric acid as the strong acid HX to convert the C15-alcohol of formula VI to the cis-building block of formula VII.
  • the aryl radicals represent both substituted and unsubstituted C ⁇ -cis, preferably C ⁇ -Cio-aryl radicals, in particular phenyl.
  • the substituents on the aryl radical can be, for example, halogens and / or C 1 -C 12, in particular C 1 -C 4 -alkyl radicals.
  • process step c) according to the first variant of the C15 alcohol of formula VI with hydrobromic acid to the cis-bromide of the formula VII, wherein in formula VII X is Br, and then reacted with triphenylphosphine to C15 phosphonium salt of formula VIII, wherein aryl is phenyl and X is Br.
  • the cis-alcohol of the formula VI is prepared by methods which are known in principle (see, for example, J. Org. Chem. 47 (1982), 47 and 2130), directly with a corresponding triarylphosphine-HX adduct of the formula P (aryl) 3 * HX implemented.
  • This reaction is carried out at temperatures of - 10 ° C to + 40 ° C.
  • the solvents used are preferably polar, aprotic solvents such. As methylene chloride or dimethylformamide use.
  • triarylphosphine-HX adduct of the formula P (aryl) 3 * HX it is possible to use preferably triphenylphosphine hydrohalides or triphenylphosphane hydrogensulfate, in particular triphenylphosphine hydrobromide or hydrochloride.
  • the solvent is distilled off and the from another suitable solvent, such as acetonitrile crystallize.
  • step d) of the process according to the invention the cis-phosphonium salt of the formula VIII is reacted with 2,7-dimethyl-octa-2,4,6-trienedially to give the compound of the formula I.
  • Preferred bases for the production of the ylid are alkali metal or alkaline earth metal C 1 -C 6 -alcoholate, preferably as a solution in the corresponding C 1 -C 6 - ⁇
  • solvent chlorinated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 2-dichloropropane or open-chain or cyclic ethers can be used.
  • ethereal solvents for example tetrahydrofuran, dioxane or ethers of ethylene glycol can be used
  • Ethers such as 1-methoxy-2-propanol or 2-methoxy-2-propanol (1) can also be used, and the C 1 -C 6 -alcohol corresponding to the alcoholate is also alone or in combination on with one of the above-mentioned solvents - suitable for this reaction.
  • Another preferred embodiment is the generation of the ylide by oxiranes as "latent bases" (Chem. Ber 107, 2050 et seq., (1974)), for example by heating the cis-phosphonium salt of formula VIII for several hours in the presence of the dialdehyde
  • This reaction can be carried out in pure oxirane or in mixtures of the oxirane with one of the abovementioned solvents
  • the end product of the formula I can be isolated here by filtration of the reaction mixture without additional work-up steps become.
  • the method according to the invention thus solves the problem posed at the beginning by a synthesis strategy according to:
  • Another object of the present invention is the Ci3-ketone of the formula IV.
  • X represents the anion of a strong organic or inorganic acid HX, another object of the present invention.
  • X is preferably equal to Cl or Br.
  • Aryl is an aryl radical, preferably phenyl, and X represents the anion of a strong organic or inorganic acid HX, preferably equal to Cl or Br.
  • HX a strong organic or inorganic acid
  • the product fractions containing valuable product were combined and concentrated on a rotary evaporator at + 50 ° C to 20 mbar.
  • the evaporation residue was dissolved in the heat in acetonitrile; the hot solution was clear filtered through a pleated filter and cooled to 0 ° C. The resulting suspension was stirred for 1 hour at 0 ° C and filtered. The filter was washed with a little cold acetonitrile and dried at + 50 ° C / 20 mbar.
  • the crude product was processed further without purification.
  • the filtrate was concentrated on a rotary evaporator and taken up with 120 ml of methylene chloride.
  • the solvent was distilled off under atmospheric pressure with simultaneous feed of 230 ml of acetonitrile to a transition temperature of + 80 ° C.
  • the mixture was refluxed for 20 hours, cooled to 0 ° C and stirred for one hour at 0 ° C.
  • the crystals were filtered off, washed with a little cold acetonitrile and dried at + 50 ° C / 20 mbar.
  • the product was suspended in 700 ml of tetrahydrofuran. The suspension was refluxed for 30 minutes and clear filtered in the heat. 600 ml of solvent were distilled off from the filtrate through a distillation bridge under atmospheric pressure; 350 ml of acetonitrile were added dropwise to the bottom in the course of 15 minutes. The resulting crystal suspension was refluxed for 15 minutes. cooled to 0 ° C and stirred at 0 ° C for one hour. The crystals were filtered off and dried to + 50 ° C / 20 mbar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un procédé amélioré permettant la produciton de 3,3'-dihydroxyisoréniératine de formule (I), et de nouveaux produits intermédiaires obtenus à partir dudit procédé.
PCT/EP2007/056801 2006-07-07 2007-07-05 Procédé et nouveaux produits intermédiaires permettant la production de 3,3'-dihydroxyisoréniératine WO2008003742A1 (fr)

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EP06116816 2006-07-07
EP06116816.7 2006-07-07

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CN114105737A (zh) * 2021-11-24 2022-03-01 重庆华邦胜凯制药有限公司 一种阿维a的中间体的制备方法及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1593440B1 (de) * 1965-10-07 1971-11-25 Farmaceutici Italia Substituierte 1,18-Di-[2',3',6'-trimethylphenyl-(1')]-3,7,12,16-tetramethyl-1,3,5,7,9,11,13,15,17-octadecanonaene und Verfahren zu ihrer Herstellung
EP0882709A1 (fr) * 1997-06-04 1998-12-09 Basf Aktiengesellschaft Procédé pour la préparation de la zéaxanthine, intermédiaires pour ce procédé et procédé pour leur préparation
WO2007090095A2 (fr) * 2006-01-27 2007-08-09 Cardax Pharmaceuticals, Inc. Synthese d'analogues ou derives de carotenoides dotes de proprietes antioxydantes ameliorees

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1593440B1 (de) * 1965-10-07 1971-11-25 Farmaceutici Italia Substituierte 1,18-Di-[2',3',6'-trimethylphenyl-(1')]-3,7,12,16-tetramethyl-1,3,5,7,9,11,13,15,17-octadecanonaene und Verfahren zu ihrer Herstellung
EP0882709A1 (fr) * 1997-06-04 1998-12-09 Basf Aktiengesellschaft Procédé pour la préparation de la zéaxanthine, intermédiaires pour ce procédé et procédé pour leur préparation
WO2007090095A2 (fr) * 2006-01-27 2007-08-09 Cardax Pharmaceuticals, Inc. Synthese d'analogues ou derives de carotenoides dotes de proprietes antioxydantes ameliorees

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AGRICULTURAL AND BIOLOGICAL CHEMISTRY , 42(7), 1437-8 CODEN: ABCHA6; ISSN: 0002-1369, 1978 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ORITANI, TAKAYUKI ET AL: "Studies on abscisic acid. Part XII. Synthesis of aromatic analogs of abscisic acid", XP002454442, retrieved from STN Database accession no. 1978:563769 *
RUETTIMANN ET AL: "SYNTHESIS OF OPTICALLY ACTIVE NATURAL CAROTENOIDS AND STRUCTURALLY RELATED COMPOUNDS 5. SYNTHESIS OF 3 R 3' R ZEAXANTHIN 3 S 3' S ZEAXANTHIN AND 3 R 3' S MESO ZEAXANTHIN BY ASYMMETRIC HYDRO BORATIONA NEW APPROACH TO OPTICALLY ACTIVE CAROTENOID BUILDING UNITS - synthese von optisch aktiven, natuerlic", HELVETICA CHIMICA ACTA, vol. 63, no. 154, 1980, pages 1456 - 1462, XP002080806, ISSN: 0018-019X *

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