WO2005103025A1 - Procede de synthese d'isoflavene et catalyseur - Google Patents

Procede de synthese d'isoflavene et catalyseur Download PDF

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Publication number
WO2005103025A1
WO2005103025A1 PCT/AU2005/000556 AU2005000556W WO2005103025A1 WO 2005103025 A1 WO2005103025 A1 WO 2005103025A1 AU 2005000556 W AU2005000556 W AU 2005000556W WO 2005103025 A1 WO2005103025 A1 WO 2005103025A1
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Prior art keywords
hydroxy
substituted
catalyst
basified
isoflavan
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PCT/AU2005/000556
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English (en)
Inventor
Andrew Heaton
George Jeoffreys
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Novogen Research Pty Ltd
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Filing date
Publication date
Priority claimed from AU2004902130A external-priority patent/AU2004902130A0/en
Application filed by Novogen Research Pty Ltd filed Critical Novogen Research Pty Ltd
Publication of WO2005103025A1 publication Critical patent/WO2005103025A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
    • C07D311/38—2,3-Dihydro derivatives, e.g. isoflavanones
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing

Definitions

  • the present invention relates to an improved process for the synthesis of isoflavene compounds.
  • the invention relates to the selective hydrogenation of hydroxy- substituted or phenolic starting isoflavones to afford correspondingly substituted isoflav-3- ene product compounds.
  • the present invention further relates to a novel hydrogenation catalyst for effecting the methods of the present invention.
  • the invention still further relates to products made by said processes of the invention.
  • dehydroequol (4',7-dihydroxyisoflav-3-ene) and related compounds which show important and broad biological activity.
  • Dehydroequol was first recognised as having health benefits in animals including humans in 1997 with patent application No. WO 98/08503 entitled "Therapeutic methods and compositions involving isoflavones".
  • the patent specification teaches that dehydroequol belongs to a family of compounds based on a primary isoflavonoid ring structure, some members of which variously display estrogenic, anti-cancer, cardiovascular and anti-inflammatory health benefits in animals. More recent publications have expanded on the important biological activities of various isoflav-3-enes, including dehydroequol.
  • the synthesis of simple, unsubstituted isoflavene from isoflavone is relatively straightforward involving careful hydrogenation of the eneone system to stop at the secondary alcohol, followed by dehydration to isoflavene as depicted in Scheme 1.
  • the successful synthesis does have its drawbacks including the need to first protect any phenolic hydroxy groups prior to the hydrogenation step.
  • the starting isoflavone, daidzein must first have its free phenolic hydroxy moieties protected, typically as acetoxy groups.
  • the secondary alcohol product is isolated from the hydrogenation reaction mixture as an intermediate prior to dehydration, followed by a fourth step being removal of the acetoxy protecting groups to afford dehydroequol.
  • the reaction whilst being a marked improvement on what has gone before in the synthesis of dehydroequol, is time consuming, ungainly, expensive, requires many steps and can at times be unreliable.
  • a method for the preparation of a hydroxy-substituted isoflavan-4-ol comprising the step of hydrogenating a hydroxy-substituted isoflavone in the presence of a basified hydrogenation catalyst.
  • a method for preparing a hydroxy-substituted isoflavene comprising the further step of dehydrating a hydroxy-substituted isoflavan-4-ol prepared according to the above method.
  • the isoflavan-4-ol is not isolated before being subjected to the dehydration step.
  • a method for preparing a hydroxy- substituted isoflav-3-ene comprising the steps of hydrogenating a hydroxy-substituted isoflavone in the presence of a basified catalyst to prepare a hydroxy-substituted isoflavan- 4-ol, and dehydrating the hydroxy-substituted isoflavan-4-ol to prepare the hydroxy- substituted isoflav-3-ene.
  • isoflavan-4-ols and hydroxy-substituted isoflavenes obtainable by the methods above.
  • a basified hydrogenation catalyst comprising a hydrogenation catalyst in admixture with a base.
  • a method for preparing a basified hydrogenation catalyst comprising the steps of treating a hydrogenation catalyst with an aqueous solution of a metal hydroxide, and filtering the resultant suspension to obtain the basified hydrogenation catalyst.
  • Fig. 1 shows the relative concentration of reactants and products over time for the hydrogenation of daidzein to cis- and tr ⁇ ns-tetrahydrodaidzein (47-dihydroxyisoflavan-4- ol) via the isoflavan-4-one intermediate according to the methods of the present invention.
  • Quantities of substantially pure, substituted isoflavenes are now reliably accessible directly from their corresponding isoflavones by hydrogenation with a modified catalyst for the first time.
  • the methodology is particularly suited to the synthesis of hydroxy-substituted or phenolic isoflavenes which are acidic in nature.
  • the basified catalyst and hydrogenation methods are applicable to the reduction of additional hydroxy-substituted and phenolic compounds.
  • Hydrogenation catalysts are basified by contacting the catalyst with a solution of base, such as an aqueous hydroxide solution.
  • a solution of base such as an aqueous hydroxide solution.
  • the resultant suspension of catalyst, such as palladium on alumina, and aqueous hydroxide is kept moving vigorously to ensure an even distribution of hydroxide through the catalyst particles. Simple filtration affords the basified catalyst as a clumping solid.
  • a hydrogenation reactor is then charged with the basified catalyst and the isoflavone added to the reaction pot, preferably as slurry in a lower alcohol or alkyl acetate. Reaction under a positive pressure of hydrogen is monitored until conversion of the isoflavone to the desired isoflavan-4-ol intermediate is observed.
  • reaction mixture is filtered to remove the spent catalyst.
  • the filtrate is then acidified to effect dehydration of the isoflavan-4-ol to isoflav-3-ene.
  • the end product is quickly recovered to avoid prolonged contact of the isoflavene with acid and possible decomposition of the product.
  • the dehydration stage uses p-toluenesulfonic acid in preference to phosphorus pentoxide, giving a cleaner product without the need to change solvents, and the workup entailed in doing so.
  • Isoflavones for use in the methods of the present invention are preferably compounds of formula I
  • Ri, R 2 , R 3 , I , R 5 , R 6 , R 7 and R 8 are independently hydrogen, hydroxy, OR 9 , OC(O)R 9 , OS(O)R 9 , alkyl, haloalkyl, aryl, arylalkyl, thio, alkylthio, amino, alkylamino, dialkylamino, nitro or halo, and R 9 is alkyl, haloalkyl, aryl, arylalkyl or alkylaryl.
  • Isoflavan-4-ol products of the present invention are preferably compounds of formula II wherein
  • Ri, R , R , Ri, R 5 , Re, R 7 , R 8 and R 9 are as defined above.
  • Isoflavene products of the present invention are preferably compounds of formula III
  • Ri, R 2 , R 3 , R 4 , R 5 , R ⁇ , R 7 , R 8 and R are as defined above.
  • the starting isoflavone of formula I, the isoflavan- 4-ol hydrogenation product of formula II and the isoflav-3-ene dehydration product of formula III preferably have the following substituents wherein
  • Ri, R 2 , R 3 , R 4 , R 5 , R , R 7 and R 8 are independently hydrogen, hydroxy, OR , OC(O)R 9 , OS(O)R 9 , alkyl, aryl, arylalkyl, thio, alkylthio, bromo, chloro or fluoro, and R is alkyl, fluoroalkyl or arylalkyl;
  • R 2 , R 3 , R 4 , R 5 , -5 and R 7 are independently hydrogen, hydroxy, OR 9 , OC(O)R 9 , alkyl, aryl or arylalkyl,
  • R 8 is hydrogen
  • R is methyl, ethyl, propyl, isopropyl or trifluoromethyl; and most preferably they have the following substituents wherein Ri is hydroxy,
  • R 2 , R 3 , R 4 , R 5 and R 7 are independently hydrogen, hydroxy, OR , OC(O)R 9 , alkyl, aryl or arylalkyl,
  • R 6 and R 8 are hydrogen, and R 9 is methyl.
  • the particularly preferred compounds of formula I are 4',7-dihydroxyisoflavone (daidzein) and 7-hydroxy-4'-methoxyisoflavone;
  • the particularly preferred compounds of formula II are 4',7-dihydroxyisoflavan-4-ol (tetrahydrodaidzein) and 7-hydroxy-4 , -methoxyisoflavan-4-ol;
  • the particularly preferred compounds of formula III are 4 , ,7-dihydroxyisoflav-3-ene (dehydroequol) and 7-hydroxy-4'-methoxyisoflav-3-ene.
  • alkyl is taken to mean both straight chain and branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, tertiary butyl, and the like.
  • the alkyl group is a lower alkyl of 1 to 6 carbon atoms.
  • the alkyl group may optionally be substituted by one or more of fluorine, chlorine, bromine, iodine, carboxyl, C ⁇ -C 4 -alkoxycarbonyl, C ⁇ -C 4 -alkylamino-carbonyl, di-(C ⁇ -C 4 -alkyl)-amino-carbonyl, hydroxyl, C ⁇ -C 4 -alkoxy, formyloxy, C ⁇ -C 4 -alkyl-carbonyloxy, C ⁇ -C 4 -alkylthio, C 3 -C 6 - cylcoalkyl or phenyl.
  • aryl is taken to include phenyl and naphthyl and may be optionally substituted by one or more C ⁇ -C 4 -alkyl, hydroxy, C ⁇ -C 4 -alkoxy, carbonyl, C ⁇ -C 4 -alkoxycarbonyl , d- C -alkylcarbonyloxy or halo.
  • halo is taken to mean one or more halogen radicals selected from fluoro, chloro, bromo, iodo and mixtures thereof, preferably fluoro and chloro, more preferably fluoro.
  • Reference to for example "haloalkyl” includes monohalogenated, dihalogenated and up to perhalogenated alkyl groups. Preferred perhalogenated groups are trifluoromethyl and pentafluoroethyl.
  • the compounds of the invention include all salts, such as acid addition salts, anionic salts and zwitterionic salts, and in particular include pharmaceutically acceptable salts standard in the art.
  • the hydrogenation is ideally preformed with hydrogen in the presence of a reduction catalyst and a solvent.
  • the reaction is preferably conducted under hydrogen at a pressure of 1-20 atmospheres, more preferably 1-5 atmospheres.
  • the reaction may be performed from 10 to 60°C and is typically carried out at room temperature.
  • reaction time may range from 12 hours to 96 hours or more and is typically about 24 hours or more. Generally better yields and cleaner reactions are achieved with longer reaction times and monitoring of the reaction products. It will be appreciated that reaction conditions may be varied depending on the individual nature of the compounds and the progress of the hydrogenation reaction.
  • the reduction catalysts suitable for the methods of the present invention include Raney nickel, palladium black, palladium hydroxide on carbon, palladium on activated carbon, palladium on alumina powder, palladium on various barium salts, sodium borohydride reduced nickel, platinum metal, platinum black, platinum on alumina, platinum on activated carbon, platinum oxide, rhodium salts, ruthenium salts and their chiral salts and zinc oxide.
  • the catalyst is palladium on alumina (5% Pd or 10% Pd), more preferably about 10% palladium on alumina.
  • palladium on carbon typically having a content of 5% Pd or 10% Pd.
  • the solvents suitable for use in the present invention include but are not limited to C ⁇ -C 8 alcohols and polyols, alkyl acetates, tetrahydrofuran, ethers, dioxane and C ⁇ -C 3 acids.
  • the solvent is a C ⁇ -C 6 alcohol or C ⁇ -C 6 alkyl acetate, more preferably methanol, ethanol or ethyl actate, as well as propanol, isopropanol, butanol, isobutanol, secbutanol, tertiary butanol, methyl formate, ethyl formate and methly acetate.
  • the solvent is methanol, ethanol or ethyl acetate. Particular mention is made of ethanol.
  • the base for synthesising the catalyst is preferably an alkali metal hydroxide such as sodium, potassium or lithium hydroxide. Particular mention is made of potassium hydroxide.
  • the present inventors have found that with a judicious choice of a basified catalyst and solvent in the presence of hydrogen that hydroxy-substituted isoflavones are reduced cleanly and in high yields to corresponding isoflavanols.
  • Dehydration is most preferably effected with />-toluenesulfonic acid. Dehydration may also be effected by treatment with other catalysts including acids such as trifluoroacetic acid, sulfuric acid, hydrochloric acid, polyphosphoric acid, thionyl chloride and the like. The results may vary depending on the solvent system employed and the substrates being reacted.
  • dehydroequol most conveniently begins with the corresponding starting isoflavone daidzein.
  • Daidzein is readily obtainable from commercial sources or alternatively it may be synthesised by established routes (see for example WO 98/08503).
  • access to other substituted isoflavone compounds including those disclosed above is obtainable by the methods of WO 98/08503.
  • the phenolic proton is acidic enough to dissociate from the isoflavone molecule and attack the isoflavan-4-ol intermediates generated during the hydrogenation reaction. This may have the effect of dehydrating the 4-hydroxy intermediates in situ to 3 -ene products, which are themselves rapidly hydrogenated to isoflavan compounds.
  • the inventors observed that in general simple addition of base to the reaction mixtures introduces further problems including the reaction not going to completion, decomposition and ring opening of the pyran ring.
  • the present invention allows for ready access to isoflavene products from the hydrogenation of isoflavones in their native phenolic form. There is no need to go to the expense and time of protecting and deprotecting the phenolic groups, such as their respective acetates. Moreover, the basified catalyst and methods of the invention allow direct access to isoflavenes by hydrogenation of the corresponding isoflavones in effectively what is a one-pot process, without the need to isolate any intermediates.
  • the isoflav-3-ene compounds produced by the methods of the present invention can be end products themselves or used as intermediates in the synthesis of further derivatives, such as 4-alkyl or aryl substituted isoflavans.
  • the methodology described herein may be extended to the reduction of substrates other than just isoflavones. It will be appreciated that the basified catalyst can be employed in the hydrogenation of a wide range and variety of compounds. The hydrogenation of further substrates and compounds with the basified catalyst is a further aspect of the invention.
  • Catalyst pre-treatment was effected by stirring 10% palladium on alumina in a 1:1 w/v solution of potassium hydroxide.
  • potassium hydroxide (10 g) was carefully dissolved in chilled, purified water (10 mL) in a flask standing in an ice- water bath. Once the basic solution returned to room temperature, 10% palladium on alumina catalyst (1 g) was added in a single portion and the suspension was stirred for 60 minutes. The suspension was filtered (Whatman Grade 114 paper) to give the basified catalyst as a damp clump. Once no more water was observed to be coming from the filter, the catalyst was immediately transferred to the hydrogenation vessel.
  • Additional catalysts are also prepared by substituting other alkali hydroxides including sodium hydroxide or catalysts including platinum on alumina.
  • Daidzein (3 g) was suspended in degassed ethanol (47.5 mL) and added to the hydrogenation vessel. Two further aliquots of degassed ethanol (47.5 mL each) were used to rinse the daidzein remnants out of the transfer vessel into the hydrogenation vessel.
  • the hydrogenation vessel was then purged with nitrogen by sequentially evacuating the air from the vessel to -100 Kpa, and recharging with nitrogen gas for a total of 5 cycles.
  • the vessel was charged with hydrogen by sequentially evacuating the nitrogen from the vessel to -100 Kpa, and recharging with hydrogen gas again for a total of 5 cycles.
  • FIG. 1 depicts the relative proportions of the reactants and products over time for the hydrogenation.
  • the reaction vessel was purged with nitrogen. This was carried out by evacuating the hydrogen from the vessel to - lOOKpa and recharging with nitrogen for a total of 5 cycles.
  • reaction mix was then filtered (celite/Whatman grade 114 paper combination) and the solid rinsed with fresh ethanol.
  • the filtrate and rinsings were combined and then reduced in vacuo to one-third its original volume at 80°C.
  • Dehydroequol was isolated in very good to excellent yields and was of high purity based on 1H n.m.r. analysis. Dehydroequol was recrystallised from ethanol/water or methanol/benzene.
  • 1H NMR ⁇ 5.01 (s, 2H, H2), 6.24 (br s, 1H, H4), 6.33 (dd, 1H, J2, 8 Hz, H6), 6.72 (br s, 1H, H8), 6.76 (d, 2H, J 8 Hz, ArH), 6.93 (d, 2H, J 8 Hz, H5), 7.35 (d, 2H, J8 Hz, ArH), 9.5 (br s, OH).
  • the dehydration reaction is also effected with other acid catalysts including trifluoroacetic acid, sulfuric acid and thionyl chloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pyrane Compounds (AREA)

Abstract

L'invention concerne un procédé amélioré de synthèse de composés d'isoflavan-4-ol et d'isoflavène hydroxy substitués à partir d'isoflavones. L'invention concerne également un nouveau catalyseur d'hydrogénation incorporant une base et ses utilisations.
PCT/AU2005/000556 2004-04-21 2005-04-21 Procede de synthese d'isoflavene et catalyseur WO2005103025A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2004902130 2004-04-21
AU2004902130A AU2004902130A0 (en) 2004-04-21 Isoflavene synthetic method and catalyst

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7875735B2 (en) 2009-05-19 2011-01-25 Kaohsiung Medical University Processes for preparing isoflavonoids using 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran as a starting material
US7875736B2 (en) 2009-05-19 2011-01-25 Kaohsiung Medical University Intermediate compounds and processes for the preparation of 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran
CN103224481A (zh) * 2013-05-20 2013-07-31 黑龙江大学 一种去氢雌马酚的制备方法
CN110590727A (zh) * 2019-09-16 2019-12-20 西安联泽生物科技有限公司 一种雌马酚的制备方法

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Publication number Priority date Publication date Assignee Title
GB760737A (en) * 1954-03-23 1956-11-07 Laporte Chemical Improvements in or relating to catalytic hydrogenation
US3824193A (en) * 1972-03-30 1974-07-16 Eastman Kodak Co Alkaline reactivation of alumina supported palladium catalysts
US4264509A (en) * 1977-06-08 1981-04-28 Z-L Limited Partnership Isoflavones and related compounds, methods of preparing and using and antioxidant compositions containing same
EP0011439B1 (fr) * 1978-11-08 1982-05-05 Shin-Etsu Chemical Co., Ltd. Méthode de préparation sélective d'isomères cis de composés éthyléniquement insaturés
JPS5681305A (en) * 1979-12-06 1981-07-03 Nippon Zeon Co Ltd Hydrogenation of conjugated diene type polymer
JPS5738940A (en) * 1980-08-18 1982-03-03 Res Assoc Residual Oil Process<Rarop> Catalyst composition
JPS5756041A (en) * 1980-09-19 1982-04-03 Mitsui Mining & Smelting Co Ltd Palladium catalyst
JPS58180447A (ja) * 1982-04-19 1983-10-21 Sanko Kagaku Kk Ｏ−フエニルフエノ−ル類の製造方法
JPS59182890A (ja) * 1983-03-31 1984-10-17 Sumitomo Chem Co Ltd 選択的水素添加の方法
JPS61130249A (ja) * 1984-11-30 1986-06-18 Sumitomo Chem Co Ltd 芳香族アルコ−ルの製法
US4774221A (en) * 1985-10-26 1988-09-27 Bayer Aktiengesellschaft Supported hydrogenation catalysts
JPS6396146A (ja) * 1986-10-14 1988-04-27 Mitsubishi Kasei Corp メチルイソブチルケトンの製造方法
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