US2011306794A1PendingUtilityA1

Process for preparing cinacalcet hydrochloride

Assignee: CATOZZI NICOLAPriority: Feb 19, 2009Filed: Feb 16, 2010Published: Dec 15, 2011
Est. expiryFeb 19, 2029(~2.6 yrs left)· nominal 20-yr term from priority
C07C 305/12C07C 221/00C07C 211/30C07C 209/70C07C 211/28C07C 303/28
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Claims

Abstract

A process for preparing N-[(1R)-1-(1-naphthyl)ethyl]-3-[3-(trifluoromethyl)-phenyl]propan-1-amine hydrochloride salt of formula (I) i.e. Cinacalcet hydrochloride and its intermediates of formulae (VII) and (VIII) wherein Z is chloride or another pharmaceutically acceptable anionic counterion.

Claims

exact text as granted — not AI-modified
1 . A method for preparing Cinacalcet hydrochloride of formula (I) 
       
         
           
           
               
               
           
         
         which comprises the steps of: 
       
       e) reducing a compound of formula (VII) 
       
         
           
           
               
               
           
         
         wherein Z is chloride or another pharmaceutically acceptable anionic counterion, to obtain a compound of formula (Ia) 
       
       
         
           
           
               
               
           
         
         wherein Z is as defined above and, when in a compound of formula (Ia) Z is a pharmaceutically acceptable anionic counterion different from chloride, 
       
       f) converting said compound of formula (Ia) to Cinacalcet hydrochloride of formula (I). 
     
     
         2 . A method according to  claim 1 , wherein the pharmaceutically acceptable anionic counterion different from chloride is selected from bromide, bisulfate, methanesulfonate, p-toluenesulfonate, phosphate, hydrogenphosphate, oxalate, formate, acetate, citrate, tartrate, succinate, maleate and malonate. 
     
     
         3 . A method according to  claim 1 , wherein when in the compound of formula (VII) Z is chloride, the compound has formula (VIIa) 
       
         
           
           
               
               
           
         
       
     
     
         4 . A method according to  claim 3 , which further comprises obtaining the compound of formula (VIIa), with a process which comprises the step of:
 g) converting a compound of formula (VII)   
       
         
           
           
               
               
           
         
         
           wherein Z is a pharmaceutically acceptable anionic counterion different from chloride. 
         
       
     
     
         5 . A method according to  claim 1 , wherein in a compound of formula (VII), Z is different from chloride. 
     
     
         6 . A method according to  claim 4 , wherein in the compound of formula (VII) Z is bisulfate, namely it is a compound of formula (VIIb) 
       
         
           
           
               
               
           
         
       
     
     
         7 . A method according to  claim 4 , which further comprises obtaining a compound of formula (VII) wherein Z is a pharmaceutically acceptable anionic counterion different from chloride, with a process which comprises the step of:
 j) eliminating sulfuric acid from the compound of formula (VIII)   
       
         
           
           
               
               
           
         
         
           wherein the wavy line represents a bond connected to carbon having R or S configuration, with a strong acid, neutralizing and acidifying with an acid HZ, wherein Z is a pharmaceutically acceptable anionic counterion different from chloride. 
         
       
     
     
         8 . A method according to  claim 7 , wherein the strong acid is sulfuric or phosphoric acid. 
     
     
         9 . A method according to  claim 7 , wherein the acid HZ is H 2 SO 4 . 
     
     
         10 . A method according to  claim 7 , which further comprises obtaining the compound of formula (VIII), with a process which comprises the steps of
 k) reducing the compound of formula (V)   
       
         
           
           
               
               
           
         
         
           to the corresponding benzylic alcohol of formula (Va) 
         
       
       
         
           
           
               
               
           
         
         
           wherein [ ] means that the compound of formula (Va) can be isolated or not from the reaction mixture, in the presence of a reducing agent or by mean of a catalytic hydrogenation process, and 
         
         l) converting the compound of formula (Va) into the sulfate ester of formula (VIII). 
       
     
     
         11 . A method according to  claim 10 , which further comprises obtaining the compound of formula (V), with a process which comprises the steps of:
 a) reacting 3-(trifluoromethyl)acetophenone of formula (II)   
       
         
           
           
               
               
           
         
         
           with (R)-(1-naphthyl)ethylamine of formula (III) optionally in the hydrochloride form, 
         
       
       
         
           
           
               
               
           
         
         in the presence of formaldehyde and hydrochloric acid. 
       
     
     
         12 . A method according to  claim 10 , which further comprises obtaining the compound of formula (V), with a process which comprises the steps of:
 b) reacting the compound of formula (II)   
       
         
           
           
               
               
           
         
         
           (i) with a compound of formula
   HNR 1 R 2 , 
 wherein R 1  and R 2  represent, independently, hydrogen or C 1 -C 5  alkyl, provided that when one of R 1  and R 2  is hydrogen, the other is not hydrogen; or 
 wherein R 1  and R 2  together form a C 4 -C 7  alkyl bridge, so that with the inclusion of the nitrogen atom to which they are linked a heterocycle is formed, wherein one —CH 2 — group of the C 4 -C 7  alkyl bridge, can be replaced by —O—, in the presence of formaldehyde; or 
 
           (ii) with a N-methyl-N-methylenemethanaminium halide of formula 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein Hal is a halogen atom, 
           
           to obtain the compound of formula (IV) 
         
       
       
         
           
           
               
               
           
         
         
           wherein R 1  and R 2  are as defined above; 
         
         c) alkylating the compound of formula (IV) with an alkylating agent selected from the group of compounds of formula:
 R 3 —X, CO(OR 3 ) 2 , SO 2 (OR 3 ) 2 , PO(OR 3 ) 3 , CH 3 PO(OR 3 ) 2  and (4-NO 2 C 6 H 4 O)PO(OR 3 ) 2 , wherein R 3  is C 1 -C 4  alkyl and X is I, Br, OSO 2 CF 3  or OSO 2 F, to obtain a compound of formula (IVa) 
 
       
       
         
           
           
               
               
           
         
         
           wherein Y═X as defined above, R 3 OCO 2 , R 3 OSO 3 , (R 3 O) 2 PO 2 , CH 3 PO 2 OR 3 , or (4-NO 2 —C 6 H 4 O)PO 2 OR 3 ; and 
         
         d) coupling a compound of formula (IVa) with (R)-(1-naphthyl)ethylamine of formula (III) 
       
       
         
           
           
               
               
           
         
       
     
     
         13 . A method for preparing Cinacalcet intermediate of formula (VIII) 
       
         
           
           
               
               
           
         
       
       wherein the wavy line represents a bond connected to carbon having R or S configuration, which comprises the steps of:
 k) reducing the compound of formula (V) 
 
       
         
           
           
               
               
           
         
       
       to the corresponding benzylic alcohol of formula (Va) 
       
         
           
           
               
               
           
         
         
           wherein [ ] means that the compound of formula (Va) can be isolated or not from the reaction mixture, in the presence of a reducing agent or by mean of a catalytic hydrogenation process, and 
         
         l) converting the compound of formula (Va) in the sulfate ester of formula (VIII). 
       
     
     
         14 . A method for preparing Cinacalcet hydrochloride of formula (I) 
       
         
           
           
               
               
           
         
         which comprises the steps of 
         k) reducing the compound of formula (V) 
       
       
         
           
           
               
               
           
         
         to the corresponding benzylic alcohol of formula (Va) 
       
       
         
           
           
               
               
           
         
         
           wherein [ ] means that the compound of formula (Va) can be isolated or not from the reaction mixture, in the presence of a reducing agent or by mean of a catalytic hydrogenation process, 
         
         l) converting the compound of formula (Va) into the sulfate ester of formula (VIII) 
       
       
         
           
           
               
               
           
         
         
           wherein the wavy line represents a bond connected to carbon having R or S configuration, 
         
         j) eliminating sulfuric acid from the compound of formula (VIII) with a strong acid, neutralizing and acidifying with the H 2 SO 4  to give the compound of formula (VIIb) 
       
       
         
           
           
               
               
           
         
         g) converting the compound (VIIb) into the compound (VIIa) and 
       
       
         
           
           
               
               
           
         
         e) reducing the compound (VIIa) to Cinacalcet hydrochloride of formula (I). 
       
     
     
         15 . Cinacalcet intermediate having the following formula (VII) 
       
         
           
           
               
               
           
         
       
       wherein Z is chloride or another pharmaceutically acceptable anionic counterion. 
     
     
         16 . Cinacalcet intermediate according to  claim 15 , wherein the pharmaceutically acceptable anionic counterion is selected from chloride, bromide, bisulfate, methanesulfonate, p-toluenesulfonate, phosphate, hydrogenphosphate, oxalate, formate, acetate, citrate, tartrate, succinate, maleate and malonate. 
     
     
         17 . Cinacalcet intermediate having the following formula (VIIa) 
       
         
           
           
               
               
           
         
       
     
     
         18 . Cinacalcet intermediate having the following formula (VIIb) 
       
         
           
           
               
               
           
         
       
     
     
         19 . Cinacalcet intermediate having the following formula (VIIc) 
       
         
           
           
               
               
           
         
       
     
     
         20 . Cinacalcet intermediate having the following formula (VIId) 
       
         
           
           
               
               
           
         
       
     
     
         21 . Cinacalcet intermediate having the following formula (VIIe) 
       
         
           
           
               
               
           
         
       
     
     
         22 . Cinacalcet intermediate having the following formula (VIII) 
       
         
           
           
               
               
           
         
       
       wherein the wavy line represents a bond connected to carbon having R or S configuration.

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