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Ep 1831144 B1 (19) & (11) EP 1 831 144 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 37/50 (2006.01) C07C 39/17 (2006.01) 17.08.2011 Bulletin 2011/33 C07C 39/26 (2006.01) (21) Application number: 05816593.7 (86) International application number: PCT/HU2005/000128 (22) Date of filing: 07.12.2005 (87) International publication number: WO 2006/061666 (15.06.2006 Gazette 2006/24) (54) A NEW PROCESS FOR THE PREPARATION OF PHENOLIC HYDROXY-SUBSTITUTED COMPOUNDS NEUES VERFAHREN ZUR HERSTELLUNG PHENOLISCHER HYDROXY SUBSTITUIERTER VERBINDUNGEN PROCEDE D’ELABORATION DE COMPOSES PHENOLIQUES A SUBSTITUTION HYDROXY (84) Designated Contracting States: • BORBÉLY, László AT BE BG CH CY CZ DE DK EE ES FI FR GB GR H-2510 Dorog (HU) HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI • HAÁSZ, Ferenc SK TR H-2500 Esztergom (HU) Designated Extension States: • JEKKEL, Péter AL BA HR MK YU H-2509 Esztergom-Kertváros (HU) (30) Priority: 08.12.2004 HU 0402530 (74) Representative: HOFFMANN EITLE 11.11.2005 HU 0501044 Patent- und Rechtsanwälte Arabellastraße 4 (43) Date of publication of application: 81925 München (DE) 12.09.2007 Bulletin 2007/37 (56) References cited: (73) Proprietor: Richter Gedeon Nyrt. US-A- 4 339 614 1103 Budapest (HU) • MANABU NODE ET.AL.: "Hard acid and soft (72) Inventors: nucleophile system. 2. Demethylation of methyl • VASS, András ethers of alcohol and phenol with an aluminium H-8200 Veszprém (HU) halide-thiolsystem" J. ORG. CHEM., vol. 45, 1980, • DUDÁS, József pages 4275-4277, XP002379759 cited in the H-8200 Veszprém (HU) application Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 831 144 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 831 144 B1 Description [0001] The invention relates to a process for the preparation of a phenolic hydroxy- substituted compound of the general formula (I) by desalkylation of an alkyl aryl ether of the general formula (II) by treatment with a thiourea/ aluminium chloride 5 reagent pair. 10 15 20 25 30 35 40 1 2 3 4 5 6 - in said general formulae R stands for straight chain or branched C1-6 alkyl group; R , R , R , R , and R have the same or different meanings and stand for hydrogen or halogen atom, hydroxy, carboxy, nitro, oxo, C1-6 alkylcarbonyl, straight chain or branched alkyl or - alkoxy, or aryl group, or R2 and R3 together may stand for a 5-7 membered ring or a fused ring system; said 5-7 membered ring may be a partially saturated ring optionally substituted with an oxo group or can be an unsaturated ring; or said fused ring system may constitute with the first ring a steroid, preferably 45 an estratriene derivative optionally substituted with an oxo or C1-6 alkylcarbonyloxy group in the 17 position-. [0002] Since the phenolic hydroxy is susceptible both to oxidation and to nucleophilic reactions, it is usually brought into temporalily protected form in the course of the synthesis. Various protective groups are known of which those protecting the hydroxy in the form of an ether, e. g. in the form of alkoxy, particularly methoxy are preferred, since these are easy-to-prepare and the protection is broad in scope. The drawback of this method, however, is that protective group 50 can only be removed under drastic reaction conditions. [0003] For demethylation of the alkyl aryl ethers various reactions and reagents are known of which - without the aim of completeness - those used most frequently are listed below: [0004] Demethylation of methoxybenzene by aluminium chloride (AlCl 3) was described in 1944. The drawback of this method is that during the reaction poisonous methyl chloride gas developed; what is more, depending on the molar ratio 55 of the starting material and the AlCl3, the aromatic ring became methylated to different extent (Baddeley, G.: J. Chem. Soc., p. 330, 1944). [0005] Acidic cleavage of the ether bond by hydrogen iodide (HI) (Coombs, M. M. and Roderick, H. R.: Steroids, Vol. 6, p. 841, 1965) or by boron tribromide (BBr 3) (Bhatt, M. V. and Kulkarni, S. U.: Synthesis, p. 249, 1983) is also known. 2 EP 1 831 144 B1 However, corrosive properties and high prices of these reagents are against the industrial application of both processes. [0006] The regioselective demethylation of polymethoxy benzaldehide by aluminium chloride was studied in benzene. The use of benzene, however, makes difficult the industrial application (Paul, E. G. and Wang, P. S.-C.: J. Org. Chem., Vol. 44, p. 2307, 1979). No mention happens in this publication to demethylation of alkyl groups other than methyl, 5 neither to the demethylation of fused ring aromatic ethers or steroids. [0007] Demethylation by pyridine hydrochloride requires extreme reaction conditions (180-220 °C) (Groen, M. B. and Zeelen, F. J.: Tetrahedron Letters, Vol. 23, p. 3611, 1982). [0008] Regioselective cleavage of the ether bond by aluminium iodide (AlI3) in acetonitrile was described by Bhatt, M. V. and Babu, J. R. Tetrahedron Letters, Vol. 25, p. 3497, 1984, and the same effect was found by Node, M. et al 10 when they used aluminium chloride/sodium iodide reagent pair (Chem. Pharm. Bull., Vol. 31, p. 4178,1983). [0009] The effect of trimethylsilyl iodide reagent [(Me)3Sil] on several ethers was studied by Jung, M. E. and Lister, M. A. (J. Org. Chem., Vol. 42, p. 3761, 1977), while Winterfeldt, E. (Synthesis, p. 617, 1975) used diisobutylaluminium hydride reagent (DIBAH) in his experiments. [0010] Stein, R. P. et al used methylmagnesium iodide (MeMgI) for the demethylation of acid sensitive steroids (Tet- 15 rahedron, Vol. 26, p 1917 (1970)), while Wunderwaldt, M. et al demethylated 3- methoxyestra-1,3,5(10)-triene derivatives substituted on the D- ring by treatment with a potassium- tert-butoxide/ethanethiol (KOCMe 3/EtSH) reagent pair (Z. Chem., Vol. 21, p. 145, 1981). In the latter case hexamethylphoshorous triamide (HMPT) was used as solvent. [0011] An interesting reagent pair, i. e. a 2,3,11,12-dicyclohexano-1,4,7,10,13,15-hexaoxacyclooctadecane/potassi- um pair (or otherwise: dicyclohexano-18-crown-6/potassium) was used by Ohsawa, T. et al (Tetrahedron Letters, Vol. 20 33, p. 5555, 1992) to demethylate anisole-derivatives and the products were obtained with good yields. [0012] Andre, J. D. et al demethylated opiate derivatives by using a methanesulfonic acid (MeSO3H)/methionine (α- amino-γ-methyl-mercaptobutyric acid) reagent pair with success (Syn. Commun., Vol. 22. p. 2313, 1992). However, the high price of the methanesulfonic acid and that it was used in a 30-fold excess is against its industrial application. [0013] Of the processes listed above the best yields for the ether bond cleavage could be achieved when BBr3 in 25 dichloromethane, DIBAH in toluene, as well as when KOCMe3/EtSH or dicyclohexano-18-crown-6/potassium reagent pairs were used. [0014] The processes reviewed above are common in that their plant scale realisations are not without difficulties: the reagents are expensive and the reactions require extreme conditions and/or result in poor yields. [0015] The application of a "strong acid/weak nucleophil" reagent pair brought a break- through to the ether- desalkyla- 30 tion technique. In the so called Fujita-method a Lewis acid (a metal halogenide) and - as weak nucleophil - EtSH were used. [0016] Of the reagent pairs of this type the boron trifluoride diethyl etherate, the AlCl 3/EtSH and the aluminium bromide (AlBr3)/EtSH gave the most promising results (Node, M. et al: J. Org. Chem., Vol. 45, p. 4275, 1980). Considering the necessary reaction conditions, the safe application of the reagents and last but no least the price of the reagents, it is only the AlCl3/EtSH reagent pair used in the Fujita ether cleavage process which can be realised with proper yield and 35 at reasonable cost in plant scale. Besides the advantages, this process has several drawbacks: the AlCl 3/EtSH reagent pair should be used in 3-6 fold excess based on the amount of the ether to be demethylated; when the reaction is finished the excess EtSH (which is used also as a solvent for the reaction) and the ethyl methyl thioether (which presumably is formed in the reaction) should be eliminated by oxidation; the thio compounds used and formed in the reaction have low boiling points and have disagreeable odor also in low concentrations, causing additional costs to provide environmentally 40 acceptable operation and any fault of the operation may result in air pollution. [0017] To avoid problems arising from the penetrating odor, recently efforts have been made to improve the methods working with alkylthiol and arilthiol reagents to cleave the ether bond. According to Node’s version (Node, M. et al: Tetrahedron Letters, Vol. 42, p. 9207, 2001) the penetrating EtSH could be replaced by the odorless 1-dodecanethiol (lauryl mercaptan) among others in the Fujita-method. This publication mentions only the yield, which is excellent, but 45 no other details are given. [0018] At the first sight the use of the 1- dodecanethiol seems attractive, but when plant scale application is considered, several questions come up. The 1-dodecanethiol is sparingly soluble in water (0.01 g in 100 g water) but is readily soluble in organic solvents, causing that during the work up of the reaction mixture with an aqueous treatment, it is contained in the same phase as the product, i.
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