WO2011030350A1 - Procédé respectueux de l'environnement permettant l'oxydation catalytique par l'air de l'aloé-émodine en rheinal - Google Patents

Procédé respectueux de l'environnement permettant l'oxydation catalytique par l'air de l'aloé-émodine en rheinal Download PDF

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Publication number
WO2011030350A1
WO2011030350A1 PCT/IN2010/000562 IN2010000562W WO2011030350A1 WO 2011030350 A1 WO2011030350 A1 WO 2011030350A1 IN 2010000562 W IN2010000562 W IN 2010000562W WO 2011030350 A1 WO2011030350 A1 WO 2011030350A1
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dihydroxy
compound
oxidation
catalyst
anthraquinone
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PCT/IN2010/000562
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English (en)
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Bhairab Nath Roy
Girij Pal Singh
Piyush Suresh Lathi
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Lupin Limited
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Publication of WO2011030350A1 publication Critical patent/WO2011030350A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/66—Preparation of oxygen-containing organic compounds containing the quinoid structure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
    • C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen

Definitions

  • the present invention describes an environment friendly process for the synthesis of 4,5-dihydroxy-9, 10-dioxo-9, 10-dihydro-anthracene-2-carbaldehyde (rheinal) from 1 ,8-dihydroxy-3-hydroxymethyl-anthraquinone (aloe emodin) via aerial oxidation in presence of organometallic catalysts.
  • organometallic catalysts are selected from oxovanadium (IV), copper (II) and, enzyme containing copper (II).
  • 4,5-Dihydroxy-9,10-dioxo-9,10-dihydro-anthracene-2-carbaldehyde has a diversified synthetic utility in synthesis of various pharmacologically active anthraquinone derivatives.
  • e.gr.US5,480,873 describes various anthraquinone derivatives useful for modifying cell functions and are indicated for use in the treatment of skeletal diseases, diabetis and related complications. Most of these anthraquinone derivatives are routed through compound of formula I.
  • compound of formula I would have a potential utility in synthesis of diacerhein (compound II, described in French patent No. 2508798), an important therapeutic candidate useful in treatment of degenerative diseases of joints, such as osteoarthritis and connective tissue matrix diseases, such as osteoporosis and rheumatoid arthritis.
  • a key intermediate of diacerhein viz. 4,5-Dihydroxy-9, 10-dioxo-9,10-dihydro- anthracene-2-carboxylic acid (compound III) can be prepared from compound of formula T through well documented oxidation reactions employing heptavalent Mn such as potassium permanganate (CN 101 104583) , sodium hypochlorite (J. Org. Chem. 71 (2006) 9291-9296), sodium perborate (Tetrahedron 45 (1989) 3299- 3306).
  • heptavalent Mn such as potassium permanganate (CN 101 104583) , sodium hypochlorite (J. Org. Chem. 71 (2006) 9291-9296), sodium perborate (Tetrahedron 45 (1989) 3299- 3306).
  • the stated approach would be an environmentally benign approach when compared to the one reported in WO A-98 56750, involving chromium based catalyst.
  • US 5,480,873 describes a process for preparation of T through modified Swern oxidation of 1 ,8-Dihydroxy-3-hydroxymethyl-anthraquinone also known as aloe emodin (Compound IV) by employing sulphur trioxide-pyridine complex in dry dimethyl sulphoxide.
  • the by-products of above reaction are dimethyl sulfide, carbon monoxide, carbon dioxide and when alkyl amine is used as base gives alkylammonium chloride as byproduct.
  • Byproducts generated during the Swern oxidation are dimethyl sulfide and carbon monoxide both toxic and volatile. Further, dimethyl sulfide is a highly volatile liquid with an unpleasant odour.
  • CN 101 104583 describes a process for preparation of T by oxidation of compound IV via well documented literature methods such as chromium trioxide-pyridine complex, pyridine chlorochromate, pyridine dichromate, Dess-Martin catalyst etc. It is to be noted that any oxidation with Cr (IV) would produce Cr (III) salts which are not environmentally benign and require special effluent treatment.
  • Oxidation of alcohol to corresponding aldehyde in presence of metal catalyst with molecular oxygen is well documented in Tetrahedron 62 (2006) 8227-8241. It is advantageous because oxygen is inexpensive, readily available, and ultimately produces benign byproducts such as water.
  • metals such as cobalt, copper, gold, iron, palladium ruthenium and vanadium as organometallic complex are known for oxidizing alcohol to the respective aldehyde.
  • Oxidation of protected phenolic alcohol is very well reported with TEMPO (2,2,6,6- Tetramethylpiperidine-1-oxyl)/ Cu(ll) catalyzed system as well as organometallic catalysts obtained from Vanadium [Synthesis, (1996) 1 153-1 174; Tetrahedron Letters, 2006 (47) 922-926; J. Org. Chem. 72 (2007) 7030-7033; Org. Lett.
  • the object of the present invention is to provide cost effective, hazard-free and eco-friendly process for preparation of 4,5-Dihydroxy-9,10-dioxo-9,10-dihydro- anthracene-2-carbaldehyde, i.e. compound of formula I of high purity.
  • a further object of the present invention is to provide an improved and cost effective industrial process for the preparation of compound of formula I that produces minimum by-products.
  • the present invention provides a process for preparation of 4,5-Dihydroxy-9,10- dioxo-9,10-dihydro-anthracene-2-carbaldehyde T by employing aerial oxidation in presence of organometallic catalysts has been described.
  • the said metal catalysts are selected from Oxovanadium (IV)/DABCO (1 ,4-diazabicyclo[2.2.2]octane), Copper (ll)/TEMPO and enzyme containing Copper (ll) TEMPO.
  • mCPBA m- chloroperbenzoic acid
  • the invention embodies transition metal complex catalyzed oxidation of benzylic hydroxyl group of compound of formula IV to corresponding aldehyde of formula I, having purity of 98%.
  • oxidation of compound 'IV to corresponding aldehyde T was performed in presence of organometallic catalysts obtained from Oxovanadium (IV), Copper (II), Cobalt (II) and Iron (III); preferably with Oxovanadium (IV) and Copper (II). It was observed that rate of reaction and conversion is more with oxovanadium such as VO(acac)2 (Vanadyl acetylacetonate, compound of formula IX) as compared to other metal complexes such as copper, cobalt and iron.
  • organometallic catalysts obtained from Oxovanadium (IV), Copper (II), Cobalt (II) and Iron (III); preferably with Oxovanadium (IV) and Copper (II). It was observed that rate of reaction and conversion is more with oxovanadium such as VO(acac)2 (Vanadyl acetylacetonate, compound of formula IX) as compared to other metal complexes
  • TEMPO tetramethylpiperidinyloxyl radical
  • TEMPO with aqueous sodium hypochlorite (Adv. Synth. Catal. 346 (2004) 1051-1071); TEMPO with stoichimetric iodine (Organic Letters 5 (2003) 285-287); TEMPO with simple Cu (II) salts and Cu (II) complexes (Tetrahedron Letters, 2006 (47) 922-926) in presence of O 2 .
  • TEMPO with aqueous sodium hypochlorite Advanced sodium hypochlorite
  • TEMPO with stoichimetric iodine (Organic Letters 5 (2003) 285-287)
  • TEMPO with simple Cu (II) salts and Cu (II) complexes (Tetrahedron Letters, 2006 (47) 922-926) in presence of O 2 .
  • Laccases (EC 1.10.3.2, p-diphenol:dioxygen oxidoreductase, compound XI) belong to multinuclear copper-containing oxidases. They catalyse the monoelectronic oxidation of substrate at the expence of molecular oxygen (Trends in Biotechnology, 2006 (24) 219-226).
  • Copper in laccase enzyme has two N 2 ligands from two histidines and one oxygen ligand (Journal of Biological Chemistry, 2005). However, it is to be noted that there are, no report of oxidation of hydroxy antraquinone alcohol to the corresponding aldehyde.
  • oxoammonium ion The active from of TEMPO is the oxidized product; called oxoammonium ion, which is formed by laccaseox- Laccaseox is generated by oxidation of laccase through oxygen. Oxoammonium ion oxidizes the alcohol to aldehyde liberating back the inactive form of TEMPO (VI) that again gets oxidized.
  • Cu (II) salen H 4 complex is an efficient oxidizing catalyst in presence of oxygen/ air more as in presence of a peroxy acid such as m-chloroperbenzoic acid, peroxyacetic acid, peroxybenzoic acid, preferably m-chloroperbenzoic acid
  • a peroxy acid such as m-chloroperbenzoic acid, peroxyacetic acid, peroxybenzoic acid, preferably m-chloroperbenzoic acid
  • the Schiff base is obtained by reaction of an aromatic aldehyde with the diamine.
  • the aromatic aldehyde is selected from salicylaldehyde or substituted salicylaldehyde; preferably salicylaldehyde.
  • the diamine component in the Schiff base is aliphatic, substituted aliphatic or cyclic diamine such as ethylene diamine, 1 , 2-cyclohexane diamine; preferably ethylene diamine, 1 ,2-cyclohexyldiamine
  • Oxovanadium (IV) is in the organometallic complex such as, Oxovanadium (IV) acetylacetonate.
  • the acetylacetonate is simple acetylacetonate or substituted acetylacetonate.
  • VO(acac)2 is available from Sigma Aldrich co or could be prepared by literature method (Inorg. Synth. 1957; 5: 1 13— 1 16).
  • the so obtained compound of formula T could be further purified and un-reacted alcohol 'IV can be recycled to obtain compound T.
  • Compound 'IV with oxaammonium ion, in particular 2,2,6,6 - tetramethyl piperdin-1 oxyl (TEMPO) and in the presence Cu (II) containing enzymes such as laccase 'XI' (Trends in Biotechnology, 2006, 24, 219-226) gives the Compound T and compound ⁇ . Further purification of mixture of compound T and 'III' is achieved by column chromatography as per condition described in example 4.
  • Useful enzymes for oxidiation of alcohol compound to aldehyde and or carboxylic acid may thus include oxidative enzyme, including laccase.
  • oxidative enzyme including laccase.
  • laccase Such enzyme may be obtained from a variety of natural sources, including animal organs and microorganisms.
  • Particularly useful laccase include enzyme derived from the microorganism Trametes versicolor such as available from Sigma-Aldrich co.
  • the oxidation reaction for obtaining compound T with metal catalyst is carried out in solvent such as 1 ,4 dioxane, dimethyl formamide, dimethyl sulfoxide and N-methyl pyrrolidine; preferably reaction is performed in 1 ,4- dioxane.
  • the oxidation reaction for obtaining compound ⁇ with metal catalyst is carried out in mixture of solvent such as water and 1 ,4 dioxane (1 : 1 ).
  • the oxidation reaction for obtaining compound ⁇ with laccase enzyme is carried out in buffer having pH range 4-6; preferably at pH 5.
  • Reaction is generally employ VO(acac) 2 as catalyst, loading of catalyst is about 5% to 20 %; preferably VO(acac)2 loading of about 5% is used.
  • Reaction is generally employ Cu (II) salen-HU as catalyst, loading of catalyst is about 10% to 30%; preferably Cu (II) salen-H 4 loading of about 10% is used.
  • Reaction is generally employ laccase enzyme loading of about 10% to about 30%; preferably enzyme loading of about 10% is used
  • Organometallic catalyzed oxidation is carried out over a wide range of temperature.
  • the reaction may be carried out at temperature of about 75 °C to 100 °C, but typically carried out at 90 °C.
  • Enzymatic reaction is carried out at temperature of 25 to 50 °C, but typically carried out at 25 °C.
  • a par autoclave reactor was charged with 200 ml of 1 ,4 Dioxane to that aloe-emodin (85% purity) (3 g) , VO (acac) 2 (0.150 g), DABCO (0.200 g) were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 90 °C for 8 h. Reaction was monitored by TLC (1 : 1 , hexane/ethyl acetate). After complete disappearing of starting material (normally after 8hr), reaction mixture was cooled to RT and filtered to remove insoluble material.
  • a par autoclave reactor was charged with 100 ml of 1 ,4 Dioxane to that aloe-emodin (1 g) (85% purity), Cu(ll) Salen H 4 (0.150g), TEMPO (0.150g) were added and stirred at room temperature for 15 min.
  • Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor.
  • the resulting mixture was stirred at 95 °C for 8 h and then reaction mixture was cooled to RT and filtered to remove insoluble material. Filtrate was then poured in 1 L of ice cool water to obtain the product. After filtering and washing with water (200 ml), the collected brown solid was dried at 45° C. in vacuo.
  • a par autoclave reactor was charged with 100 ml of 1 ,4 Dioxane to that aloe-emodin (1.5 g) (85% purity), Cu(ll) Salen-H 4 (0.075g), TEMPO (0.075g), mCPBA (0.100 g) were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 95 °C for 8 h. Workup and purification of crude product was done as per given in example 4 Isolated yield: 0.74 (58%)
  • a par autoclave reactor was charged with 10 mmole sodium acetate buffer of pH 5 (100ml) to that aloe-emodin (3gm) (85% purity), laccase from T. versicolor (0.5gm), TEMPO (0.9 g) were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 25 °C for 96 h. Reaction was monitored by HPLC gives 34 % carboxylic acid and 48% aldehyde and 15 % un-reacted aloe emodin. Workup and purification of crude product was done as per given in example 4.
  • a par autoclave reactor was charged with 200ml of 1 ,4 Dioxane to that aloe-emodin (2gm) (85% purity), Cu(ll) (OAc) 2 (0.075gm), TEMPO (0.56g) were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 90 °C for 8 h. Reaction was monitored by TLC (1 : 1 , hexane/ethylacetate) and no oxidative product was observed.
  • a par autoclave reactor was charged with 200ml of 1 ,4 Dioxane to that aloe-emodin (3gm) (85% purity), Fe (III) salen (0.150gm), were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 90 °C for 8 h. Reaction was monitored by TLC (1 :1 , hexane/ethylacetate) and no oxidative product was observed.
  • a par autoclave reactor was charged with 200ml of 1 ,4 Dioxane to that aloe-emodin (2gm) (85% purity), Co (II) salen (0.120gm), were added and stirred at room temperature for 15 min. Reactor was purged with oxygen gas for 5 min and then 1 bar oxygen pressure was maintained in reactor. The resulting mixture was stirred at 90 °C for 8 h. Reaction was monitored by TLC (1 :1 , hexane/ethylacetate) and no oxidative product was observed.

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Abstract

La présente invention concerne un procédé de préparation du 4,5-dihydroxy-9,10-dioxo-9,10-dihydro-anthracène-2-carbaldéhyde à partir de la 1,8-dihydroxy-3-hydroxyméthyl-anthraquinone, comprenant l'oxydation par l'air de la 1,8-dihydroxy-3-hydroxyméthyl-anthraquinone sous une pression d'oxygène d'environ 1 bar à 2 bar en présence d'un complexe de métal de transition, d'un co-catalyseur et éventuellement d'un agent oxydant dans un solvant organique, tel que le 1,4-dioxanne, l'eau ou leurs mélanges, à une température située dans la plage allant de 25 °C à 100 °C, l'isolement par un procédé approprié et éventuellement la purification du produit.
PCT/IN2010/000562 2009-09-08 2010-08-26 Procédé respectueux de l'environnement permettant l'oxydation catalytique par l'air de l'aloé-émodine en rheinal WO2011030350A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557503A (zh) * 2013-10-22 2015-04-29 成都中医药大学 一种大黄素配合物及其制备方法和用途

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2508798A1 (fr) 1976-03-16 1983-01-07 Proter Spa Derives anthraquinoniques pour le traitement des arthrites
EP0570091A1 (fr) * 1992-02-28 1993-11-18 Lilly Industries Limited Dérivés d'anthraquinone, procédés pour leur préparation et leur utilisation comme médicaments
EP0636602A1 (fr) 1993-07-30 1995-02-01 Laboratoire Medidom S.A. Procédé de préparation de la diacérein
WO1998056750A1 (fr) 1997-06-11 1998-12-17 Synteco S.R.L. Procede pour la preparation de diacereine
WO2000068179A1 (fr) 1999-05-07 2000-11-16 Synteco S.P.A. Purification de diacereine
WO2001096276A1 (fr) 2000-06-13 2001-12-20 Synteco S.P.A. Procede de purification de diacereine
WO2004050601A2 (fr) 2002-11-29 2004-06-17 Synteco S.P.A. Procede de purification de diacereine
EP1666446A1 (fr) 2004-11-12 2006-06-07 Laboratoire Medidom S.A. Procédé pour préparation du rhéine et diacerhéine
CN101104583A (zh) 2006-07-13 2008-01-16 上海汇瑞生物科技有限公司 两步氧化法制备双醋瑞因的新工艺

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* Cited by examiner, † Cited by third party
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FR2508798A1 (fr) 1976-03-16 1983-01-07 Proter Spa Derives anthraquinoniques pour le traitement des arthrites
EP0570091A1 (fr) * 1992-02-28 1993-11-18 Lilly Industries Limited Dérivés d'anthraquinone, procédés pour leur préparation et leur utilisation comme médicaments
US5480873A (en) 1992-02-28 1996-01-02 Lilly Industries Limited Pharmaceutical compounds
EP0636602A1 (fr) 1993-07-30 1995-02-01 Laboratoire Medidom S.A. Procédé de préparation de la diacérein
WO1998056750A1 (fr) 1997-06-11 1998-12-17 Synteco S.R.L. Procede pour la preparation de diacereine
WO2000068179A1 (fr) 1999-05-07 2000-11-16 Synteco S.P.A. Purification de diacereine
WO2001096276A1 (fr) 2000-06-13 2001-12-20 Synteco S.P.A. Procede de purification de diacereine
WO2004050601A2 (fr) 2002-11-29 2004-06-17 Synteco S.P.A. Procede de purification de diacereine
EP1666446A1 (fr) 2004-11-12 2006-06-07 Laboratoire Medidom S.A. Procédé pour préparation du rhéine et diacerhéine
CN101104583A (zh) 2006-07-13 2008-01-16 上海汇瑞生物科技有限公司 两步氧化法制备双醋瑞因的新工艺

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557503A (zh) * 2013-10-22 2015-04-29 成都中医药大学 一种大黄素配合物及其制备方法和用途

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