US2003083319A1PendingUtilityA1

1,3-Dihydroxy-20,20-dialkyl-vitamin D3 analogs

Assignee: HOFFMANN LA ROCHEPriority: Sep 8, 1997Filed: Jul 25, 2002Published: May 1, 2003
Est. expirySep 8, 2017(expired)· nominal 20-yr term from priority
A61P 43/00A61P 35/00C07C 401/00A61P 19/10A61K 31/593
51
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Claims

Abstract

This invention relates to 1,3-dihydroxy-20,20-dialkyl-vitamin D3 analogs of Formula (I): compositions comprising the analogs, methods of preparing the analogs and methods of treatment of osteoporosis, secondary hyperparathyroidism, cancer and autoimmune diseases using such analogs.

Claims

exact text as granted — not AI-modified
We claim:  
     
         1 . A compound selected from the group of compounds represented by Formula (I)  
       
         
           
           
               
               
           
         
       
       wherein 
 X is hydrogen or ═CH 2 ;  
 R 1  and R 2  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl, or R 1  and R 2  together form ═CH 2 ;  
 R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 3  and R 4  together with C25 form a (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cyclofluoroalkyl;  
 A is a single or a double bond; and  
 B is a single, double or triple bond;  
 and prodrugs thereof, provided that:  
 (i) when R 1  and R 2  are (C 1 -C 4 )alkyl or R 1  and R 2  together with C20 form a cyclopropyl group or ═CH 2 , R 3  and R 4  are (C 1 -C 4 )alkyl, trifluoromethyl or R 3  and R 4  together with C25 form (C 3 -C 6 )cycloalkyl and A is a single bond, then B is not a trans double bond;  
 (ii) when B is a single bond, then R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl group; and  
 (iii) when R 1  and R 2  are (C 1 -C 4 )alkyl, R 3  and R 4  are (C 1 -C 4 )alkyl, X═CH 2  and A is a single bond, then B is not a double bond.  
 
     
     
         2 . The compound of  claim 1 , wherein: 
 B is a triple bond.    
     
     
         3 . The compound of  claim 2 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl;    X is ═CH 2 ; and    A is a single bond.    
     
     
         4 . The compound of  claim 3 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         5 . The compound of  claim 4 , wherein R 3  and R 4  are methyl namely, 1,25-dihydroxy-23-yne-20,21,28-cyclopropyl-cholecalciferol.  
     
     
         6 . The compound of  claim 4 , wherein R 3  and R 4  are trifluoromethyl, namely 1,25-dihydroxy-23-yne-26,27-hexafluoro-20,21,28-cyclopropyl-cholecalciferol.  
     
     
         7 . The compound of  claim 2 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl;    X is hydrogen; and    A is a single bond.    
     
     
         8 . The compound of  claim 7 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         9 . The compound of  claim 8 , wherein R 3  and R 4  are methyl, namely 1,25-dihydroxy-23-yne-20,21,28-cyclopropyl-19-nor-cholecalciferol.  
     
     
         10 . The compound of  claim 8 , wherein R 3  and R 4  are trifluoromethyl, namely 1,25-dihydroxy-23-yne-26,27-hexafluoro-20,21,28-cyclopropyl-19-nor-cholecalciferol.  
     
     
         11 . The compound of  claim 2 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl;    X is ═CH 2 ; and    A is a double bond.    
     
     
         12 . The compound of  claim 11 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 44  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         13 . The compound of  claim 2 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl;    X is H 2 ; and    A is a double bond.    
     
     
         14 . The compound of  claim 13 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         15 . The compound of  claim 1 , wherein: 
 A is a double bond; and    B is a double bond.    
     
     
         16 . The compound of  claim 15 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl; and    X is ═CH 2 .    
     
     
         17 . The compound of  claim 16 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         18 . The compound of  claim 15 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl; and    X is H 2 .    
     
     
         19 . The compound of  claim 18 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         20 . The compound of  claim 1 , wherein: 
 A is a single bond; and    B is a cis double bond.    
     
     
         21 . The compound of  claim 20 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl; and    X is ═CH 2 .    
     
     
         22 . The compound of  claim 21 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         23 . The compound of  claim 22 , wherein R 3  and R 4  are trifluoromethyl namely, 1,25-dihydroxy-23-(Z)-ene-26,27-hexafluoro-20,21,28-cyclopropyl-cholecalciferol.  
     
     
         24 . The compound of  claim 20 , wherein: 
 R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl;    R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or a (C 1 -C 4 )fluoroalkyl; and    X is H 2 .    
     
     
         25 . The compound of  claim 24 , wherein: 
 R 1  and R 2  together with C20 form a cyclopropyl group; and    R 3  and R 4  are, independently of each other, methyl, ethyl, trifluoromethyl, 1,1-difluoroethyl or 2,2,2-trifluoroethyl.    
     
     
         26 . The compound of  claim 25 , wherein R 3  and R 4  are trifluoromethyl namely, 1,25-dihydroxy-23-(Z)-ene-26,27-hexafluoro-20,21,28-cyclopropyl-19-nor-cholecalciferol.  
     
     
         27 . A method of treating osteoporosis via administration of a therapeutically effective amount of a compound of Formula (I)  
       
         
           
           
               
               
           
         
         wherein: 
 X is hydrogen or ═CH 2 ;  
 R 1  and R 2  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl, or R 1  and R 2  together form ═CH 2 ;  
 R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 3  and R 4  together with C25 form a (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cyclofluoroalkyl;  
 A is a single or a double bond; and  
 B is a single, double or triple bond;  
 and prodrugs thereof.  
 
       
     
     
         28 . A method of treating cancer via administration of a therapeutically effective amount of a compound of Formula (I)  
       
         
           
           
               
               
           
         
       
       wherein: 
 X is hydrogen or ═CH 2 ;  
 R 1  and R 2  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl, or R 1  and R 2  together form ═CH 2 ;  
 R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 3  and R 4  together with C25 form a (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cyclofluoroalkyl;  
 A is a single or a double bond; and  
 B is a single, double or triple bond;  
 and prodrugs thereof, provided that:  
 (i) when R 1  and R 2  are (C 1 -C 4 )alkyl or R 1  and R 2  together with C20 form a cyclopropyl group or ═CH 2 , R 3  and R 4  are (C 1 -C 4 )alkyl, trifluoromethyl or R 3  and R 4  together with C25 form (C 3 -C 6 )cycloalkyl and A is a single bond, then B is not a trans double bond;  
 (ii) when B is a single bond, then R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl group; and  
 (iii) when R 1  and R 2  are (C 1 -C 4 )alkyl, R 3  and R 4  are (C 1 -C 4 )alkyl, X═CH 2  and A is a single bond, then B is not a double bond.  
 
     
     
         29 . A method of treating secondary hyperparathyroidism via administration of a therapeutically effective amount of a compound of Formula (I)  
       
         
           
           
               
               
           
         
         wherein: 
 X is hydrogen or ═CH 2 ;  
 R 1  and R 2  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 1  and R 2  together with C20 form a (C 3 -C 6 )cycloalkyl or (C 3 -C 6 )cyclofluoroalkyl, or R 1  and R 2  together form ═CH 2 ;  
 R 3  and R 4  are, independently of each other, a (C 1 -C 4 )alkyl or (C 1 -C 4 )fluoroalkyl, or R 3  and R 4  together with C25, form a (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cyclofluoroalkyl;  
 A is a single or a double bond; and  
 B is a single, double or triple bond;  
 and prodrugs thereof.  
 
       
     
     
         30 . A pharmaceutical composition comprising an effective amount of a compound of  claim 1.

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