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WO 2014/009767 Al 16 January 2014 (16.01.2014) P O PCT

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WO 2014/009767 Al 16 January 2014 (16.01.2014) P O PCT (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2014/009767 Al 16 January 2014 (16.01.2014) P O PCT (51) International Patent Classification: Pramod Kumar [IN/IN]; Micro Labs Limited, API Divi C07D 307/33 (2006.01) C07C 235/40 (2006.01) sion, Plot No. 43-45, K.I .A.D.B., Jigani-Bommasandra C07C 231/10 (2006.01) C07C 237/24 (2006.01) Link Road, Anekal Taluk, Bangalore-560 105, Karnataka C07C 233/58 (2006.01) (IN). (21) International Application Number: (74) Agents: NAIR, Manoj Vasudevan et al; M/s Lex Orbis PCT/IB20 12/00 1765 (Intellectual Property Practice), 709/710, Tolstoy House, 15-17 Tolstoy Marg, New Delhi - 110 001 (IN). (22) International Filing Date 12 September 2012 (12.09.2012) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, English (25) Filing Language: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (26) Publication Language: English BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (30) Priority Data: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 2752/CHE/2012 7 July 2012 (07.07.2012) IN KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (71) Applicant (for all designated States except US): MICRO ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, LABS LIMITED [IN/IN]; No.27, Race Course Road, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, Bangalore 560 001 (IN). RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, (72) Inventors; and ZM, ZW. (75) Inventors/Applicants (for US only): GADDAM, Venugo- pal Reddy [IN/IN]; Micro Labs Limited, API Division, (84) Designated States (unless otherwise indicated, for every Plot No. 43-45, K.I .A.D.B., Jigani-Bommasandra Link kind of regional protection available): ARIPO (BW, GH, Road, Anekal Taluk, Bangalore-560 105, Karnataka (IN). GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, VARADA, Jayakrishna [IN/IN]; Micro Labs Limited, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, API Division, Plot No. 43-45, K.I .A.D.B., Jigani-Bom TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, masandra Link Road, Anekal Taluk, Bangalore-560 105, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, Karnataka (IN). CHELUVARAJU [IN/IN]; Micro Labs MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Limited, API Division, Plot No. 43-45, K.I .A.D.B., Jigani- TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, Bommasandra Link Road, Anekal Taluk, Bangalore-560 ML, MR, NE, SN, TD, TG). 105, Karnataka (IN). GAJULA, Madhusudana Rao Published: [IN/IN]; Micro Labs Limited, API Division, Plot No. 43- 45, K.I .A.D.B., Jigani-Bommasandra Link Road, Anekal — with international search report (Art. 21(3)) Taluk, Bangalore-560 105, Karnataka (IN). RASTOGI, (54) Title: AN IMPROVED PROCESS FOR THE PREPARATION OF 1-ARYL 2-AMINOMETHYL CYCLOPROPANE CARBOXYAMIDE (Z) DERIVATIVES, THEIR ISOMERS AND SALTS o© (57) Abstract: The present invention relates to an improved and one-pot process for the preparation of 1-Aryl 2-aminomethyl cyclo - propane carboxyamide (z) derivatives, their isomers of formula (I) or its pharmaceutically acceptable salt thereof wherein R and R 2 are represents independently selected from the group consisting of hydrogen, lower alkyl, lower aryl, and lower-alkylaryl, which aryl or alkylaryl group is optionally substituted by a halogen atom. AN IMPROVED PROCESS FOR THE PREPARATION OF 1-ARYL 2- AMINOMETHYL CYCLOPROPANE CARBOXY AMIDE (Z) DERIVATIVES, THEIR ISOMERS AND SALTS The following specification particularly describes the invention and the manner in which it is to be performed. FIELD OF THE INVENTION: The present invention relates to an improved process for the preparation of Milnacipran, its stereo specific isomers and its derivatives or a pharmaceutically acceptable salts, hydrate, or solvate thereof. More particularly, the present invention relates to the process for preparation of Milnacipran by in-situ and also using with single solvent to give the high urity and good yield. BACKGROUND OF THE INVENTION: Milnacipran, is chemically known as cyclopropanecarboxamide, 2- (Aminomethyl)-N,N-diethyl-l -phenyl-, cis-(±)-; (±)-[lR(S) ', 2S(R)]-2-(Aminomethyl)- N,N-diethyl-l-phenylcyclopropanecarboxamide in the form of a base or of a pharmaceutically acceptable salt, and in particular the hydrochloride thereof. Milnacipran is an antidepressant inhibiting recapture of serotonin- noradrenaline recommended in the treatment of depression. It was first approved in France in December 1996. Milnacipran hydrochloride is currently marketed in the form of tablets in Europe, it is available under the brand name Ixel®. It is also available in Japan under the brand name Toledomin® and Mexico under the brand name Dalcipran® for depression. While In January 2009 the U.S. Food and Drug Administration (FDA) approved Milnacipran under the brand name Savella® only for the treatment of fibromyalgia, making it the third medication approved for this purpose in the United States. Milnacipran hydrochloride is a racemic mixture of two of the four possible stereoisomers; specifically, a 1:1 mixture of the two Z (cis) isomers and chemical structurally represented as followin : ( 1 S . 2R) ( 1 R, 2S) The structural formula for Milnacipran hydrochloride will signify for subsequently convenient as followin : Various methods for Milnacipran hydrochloride was specifically disclosed in the art, first United States Patent No. 4,478,836 (referred to as '836 patent hereinafter). The '836 patent discloses for the preparation of Milnaciprah and its hydrochloride salt form, which involves a hydrolysis of 1-phenyl- 1-ethoxy carbonyl-2-aminomethyl cyclopropane in ethanol as a solvent in the presence of sodium hydroxide as base to obtained an acid compound. The intermediate of acid compound was chlorinated by using thionyl chloride in organic solvent to obtained the acid chloride intermediate. The resulting acid chloride compound is condensed with diethyl amine at room temperature to get crude milnacipran hydrochloride. The desired Milnacipran hydrochloride is recrystallized from petroleum ether. The reaction is schematically represented by scheme 1. Scheme- 1: The process involves multi step and ether as solvent, which is not commercially feasible. The United States Patent No. 5,034,541 discloses a process for the preparation of phthalimide derivative, which involves the l-Phenyl-3-oxabicyclo [3,1,0] hexan-2- one reacted with diethyl amine in presence of lewis acid such as aluminum chloride in dichloroethane as a solvent to get the hydroxyl compound. The obtained intermediate of hydroxyl compound is chlorinated by using with thionyl chloride in dichloroethane as solvent and the resulting chloro compound was reacted with potassium phthalimide in dimethyl formamide to get a phthalimide derivative. The reaction is schematically represented.by scheme 2. Scheme-2: The United States Patent Application No.US2008/0051604 Al discloses process for preparing Milnacipran, which involves the hydrolysis of (Z)-l -phenyl- 1 diethylaniinocarbonyl-2-phthalimidomethylcyclopropane in the presence of aqueous methylamine solution having concentration of from 1 to 25% by weight to obtain (Z)- 1-phenyl- l-diethylaminocarbonyl-2-aminoethylcyclopropane. The reaction is schematically represented by scheme 3. Scheme-3: The process involves costly key starting material and uses methyl amine, which is irritating to eyes, nose and throat. The United States Patent Application No.US 2010/0145099 Al discloses a process for preparing Milnacipran, which involves the hydrolysis of (Z)- 1-Phenyl- 1- diethylaminocarbonyl-2-phthalimidomethylcyclopropane in presence of aqueous hydrazine hydrate in ethanol. The resulting Milnacipran hydrochloride was obtained in a mixture of IPA-HC1 and ethyl acetate. The reaction is schematically represented by scheme 4. Scheme-4: The process involves costly key starting material and uses hydrazine hydrate, which is highly explosive. The European Patent No. EP 0200638 Bl discloses a process for preparing Milnacipran hydrochloride, which comprises the reaction of potassium phthalimide with l-Phenyl-3-oxabicyclo [3,1,0] hexan-2-one in presence of high boiling solvent such as dimethyl sulfoxide at 150-200°C to get the intermediate of acid compound. The intermediate of acid compound was treated with thionyl chloride and followed by diethyl amine to resulting phthalimide compound, further it's hydrolyzed in presence of organic base in organic solvent to get the desired compound. The reaction is schematically represented by scheme 5. Scheme-5: SOCI2 The PCT Patent Application No. WO2010/086394 A l discloses a process for the preparation of Milnacipran hydrochloride, which comprises the reaction of phenylacetonitrile and (R)-epichlorohydrin in presence of alkaline metal base, followed by basic hydrolysis and acid treatment to obtain the lactone compound. The lactone compound is opened by using diethyl amine in presence of lewis acid such as aluminum chloride in toluene as a solvent and further chlorination with thionyl chloride in dichloroethane as solvent. The resulting chloro compound is reacted with potassium phthalimide in toluene to forms phthalimide intermediate. The resulting compound of phthalimide intermediate is hydrolyzed in ethanolamine as base in presence of toluene. The desired Milnacipran hydrochloride was isolated in mixture of isopropyl acetate and IPA-HC1. The reaction is schematically represented by scheme 6. Scheme-6: Ethanolamine 1PA -HC1 Moreover, various syntheses for the racemic Milnacipran have been described in the literature as EP 1 845 084; EP 1 757 597; EP 1 767 522; and Shuto S. et al., J.
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