USRE49826EActiveUtility

Method for the preparation of (4S)-4-(4-cyano-2-methoxyphenyl)-5-ethoxy-2,8-dimethyl-1,4-dihydro-1-6-naphthyridine-3-carboxamide and the purification thereof for use as an active pharmaceutical ingredient

Assignee: Bayer Pharma AGPriority: Aug 21, 2015Filed: Aug 18, 2016Granted: Feb 6, 2024
Est. expiryAug 21, 2035(~9.1 yrs left)· nominal 20-yr term from priority
C07D 471/04C07B 2200/07A61P 11/00A61P 13/02A61P 13/12A61P 17/00A61P 19/02A61P 25/00A61P 25/04A61P 25/06A61P 25/16A61P 25/22A61P 25/24A61P 25/28A61P 27/02A61P 27/16A61P 29/00A61P 3/00A61P 3/04A61P 3/12A61P 3/14A61P 35/00A61P 37/02A61P 5/42A61P 7/10A61P 9/00A61P 9/04A61P 9/08A61P 9/10A61P 9/14A61P 3/10A61K 31/4375
75
PatentIndex Score
1
Cited by
42
References
30
Claims

Abstract

The present invention related to a novel and improved process for preparing (4S)-4-(4-cyano-2-methoxyphenyl)-5-ethoxy-2,8-dimethyl-1,4-dihydro-1,6-naphthyridine-3-carboxamide of the formula (I)

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising separating a racemic compound of the formula (XIII) into its enantiomers, wherein the compound of the formula (XIII) 
       
       
         
           
           
               
               
           
         
         is prepared by reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         with an orthoester (XX) 
       
       
         
           
           
               
               
           
         
         where R may be H or methyl, wherein 
         the compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         is prepared by reacting compounds of the formula (XVI a,b) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (IX) 
       
       
         
           
           
               
               
           
         
         and wherein 
         the compound of the formula (XVI a,b) is prepared by reacting a compound of the formula (VI) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (XVII) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       2. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising separating a racemic compound of the formula (XIII) into its enantiomers, where the compound of the formula (XIII) 
       
       
         
           
           
               
               
           
         
         is prepared by reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         with an orthoester (XX) 
       
       
         
           
           
               
               
           
         
         where R may be H or methyl, and wherein 
         the compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         is prepared by reacting compounds of the formula (XVI a,b) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (IX) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       3. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising separating a racemic compound of the formula (XIII) into its enantiomers, where the compound of the formula (XIII) 
       
       
         
           
           
               
               
           
         
         is prepared by reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         with an orthoester (XX) 
       
       
         
           
           
               
               
           
         
         where R may be H or methyl. 
       
     
     
       4. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising using the compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       5. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising using the compounds of the formula (XVI a,b) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       6. A process for preparing a compound of the formula (I) 
       
         
           
           
               
               
           
         
         comprising using a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
       
       and
 compounds of the formula (XVI a,b) 
 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       7. A compound of the formula (XVIII) 
       
         
           
           
               
               
           
         
         and the salts, solvates and solvates of the salts thereof. 
       
     
     
       8. A compound of the formula (XVI a,b) as an E/Z mixture 
       
         
           
           
               
               
           
         
         and the salts, solvates and solvates of the salts thereof. 
       
     
     
       9. A process for preparing a compound of the formula (XVIII) 
       
         
           
           
               
               
           
         
         comprising reacting compounds of the formula (XVI a,b) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (IX) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       10. A process for preparing compounds of the formula (XVI a,b) 
       
         
           
           
               
               
           
         
         comprising reacting a compound of the formula (VI) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (XVII) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       11. A process for preparing a compound of the formula (XIII) 
       
         
           
           
               
               
           
         
         comprising reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         with an orthoester (XX) 
       
       
         
           
           
               
               
           
         
         where R may be H or methyl. 
       
     
     
       12. A process for preparing a compound of the formula (XIII) 
       
         
           
           
               
               
           
         
         comprising reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
         with an orthoester (XX) 
       
       
         
           
           
               
               
           
         
         where R may be H or methyl, and wherein 
         the compound of the formula (XVIII) is prepared by reacting compounds of the formula (XVI a,b) 
       
       
         
           
           
               
               
           
         
         with a compound of the formula (IX) 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       13. A process for preparing a compound of the formula (I) in crystalline polymorph I 
       
         
           
           
               
               
           
         
         comprising preparing a compound of the formula (I) 
       
       
         
           
           
               
               
           
         
         according to  claim 1  and then stirring the compound of the formula (I), present in one or more polymorphs or as a solvate in an inert solvent, at a temperature of 20° C.-120° C. and isolating the compound of the formula (I) in crystalline polymorph I. 
       
     
     
       14. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         wherein the x-ray diffractogram of the compound exhibits peak maxima of the 2 theta angle at 8.5, 14.1, and 19.0.  
       
     
     
       15. The compound of formula (I) in crystalline form of polymorph I according to claim 14, wherein the x-ray diffractogram of the compound further exhibits peak maxima of the 2 theta angle at 17.2, 20.5, 25.6, and 26.5.  
     
     
       16. The compound of the formula (I) in crystalline form of polymorph I according to claim 14, wherein the IR spectrum of the compound exhibits band maxima at 3475, 2230, 1681, 1658, 1606, 1572, 1485, 1255, 1136 and 1031 cm −1 .  
     
     
       17. The compound of the formula (I) in crystalline form of polymorph I according to claim 14, wherein the Raman spectrum of the compound exhibits band maxima at 3074, 2920, 2231, 1601, 1577, 1443, 1327, 1267, 827 and 155 cm −1 .  
     
     
       18. The compound of the formula (I) in crystalline form of polymorph I according to claim 14, wherein the compound has a melting point of 252° C.  
     
     
       19. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         wherein the IR spectrum of the compound exhibits band maxima at 3475, 2230, 1681, 1658, 1606, 1572, 1485, 1255, 1136 and 1031 cm −1 .  
       
     
     
       20. The compound of the formula (I) in crystalline form of polymorph I according to claim 19, wherein the x-ray diffractogram of the compound exhibits peak maxima of the 2 theta angle at 8.5, 14.1, 17.2, 19.0, 20.5, 25.6, and 26.5.  
     
     
       21. The compound of the formula (I) in crystalline form of polymorph I according to claim 19, wherein the Raman spectrum of the compound exhibits band maxima at 3074, 2920, 2231, 1601, 1577, 1443, 1327, 1267, 827 and 155 cm −1 .  
     
     
       22. The compound of the formula (I) in crystalline form of polymorph I according to claim 19, wherein the compound has a melting point of 252° C.  
     
     
       23. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         wherein the Raman spectrum of the compound exhibits band maxima at 3074, 2920, 2231, 1601, 1577, 1443, 1327, 1267, 827 and 155 cm −1 .  
       
     
     
       24. The compound of the formula (I) in crystalline form of polymorph I according to claim 23, wherein the x-ray diffractogram of the compound exhibits peak maxima of the 2 theta angle at 8.5, 14.1, 17.2, 19.0, 20.5, 25.6, and 26.5.  
     
     
       25. The compound of the formula (I) in crystalline form of polymorph I according to claim 23, wherein the IR spectrum of the compound exhibits band maxima at 3475, 2230, 1681, 1658, 1606, 1572, 1485, 1255, 1136 and 1031 cm −1 .  
     
     
       26. The compound of the formula (I) in crystalline form of polymorph I according to claim 23, wherein the compound has a melting point of 252° C.  
     
     
       27. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         prepared by a process comprising obtaining the compound of formula XIII 
       
       
         
           
           
               
               
           
         
         separating the compound of formula XIII by chiral separation to obtain the compound of formula I, 
         dissolving the compound of formula I in an inert solvent, 
         stirring at a temperature of 20° C.-120° C. and 
         isolating the compound of the formula (I) in crystalline form of polymorph I.  
       
     
     
       28. The compound of the formula (I) in crystalline form of polymorph I according to claim 27, where the compound of the formula (XIII) 
       
         
           
           
               
               
           
         
         is prepared by reacting a compound of the formula (XVIII) 
       
       
         
           
           
               
               
           
         
       
       with an orthoester (XX) 
       
         
           
           
               
               
           
         
         where R may be H or methyl.  
       
     
     
       29. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         wherein the compound is isolated in crystalline form by a process comprising: 
         filtering a solution of the compound of the formula (XIII) 
       
       
         
           
           
               
               
           
         
         in a mixture of acetonitrile and methanol or a mixture of acetonitrile and ethanol; 
         performing a solvent exchange with ethanol; 
         concentrating the solution until the compound crystallizes; 
         cooling the solution to 0° C.; and 
         isolating the compound in crystalline form.  
       
     
     
       30. A compound of the formula (I) in crystalline form of polymorph I 
       
         
           
           
               
               
           
         
         wherein the compound is crystallized from a solvent selected from the group consisting of methanol, ethanol, tetrahydrofuran, acetonitrile, and mixtures thereof with water.

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