US2007060563A1PendingUtilityA1

Quinuclidine derivatives binding to mucarinic m3 receptors

Assignee: COLLINGWOOD STEPHEN PPriority: May 2, 2003Filed: Apr 30, 2004Published: Mar 15, 2007
Est. expiryMay 2, 2023(expired)· nominal 20-yr term from priority
A61P 37/08A61P 43/00A61P 29/00A61P 11/00A61P 17/06A61P 11/02A61P 11/08A61P 11/06C07D 453/02
45
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Claims

Abstract

Compounds of formula I in salt or zwitterionic form wherein, wherein R 1 , R 2 , R 3 , and R 4 have the meanings as indicated in the specification, are useful for treating conditions that are mediated by the muscarinic M3 receptor. Pharmaceutical compositions that contain the compounds and a process for preparing the compounds are also described.

Claims

exact text as granted — not AI-modified
1 . A compound of formula I  
     
       
         
         
             
             
         
       
     
     in salt or zwitterionic form wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or —CR 1 R 2 R 3  together form a group of formula  
                     
 where R is a bond, —O—, —S—, —CH 2 —, —CH═CH—, —CH 2 —CH 2 —, amino or —N(CH 3 )—;  
 R 2  is hydrogen, halo, hydroxy, C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl optionally substituted by hydroxy;  
 R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —OR 11 , —O—CO—NHR 12 , —O—CO—R 13  or —CO—O—R 14 , 
 or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 5  is hydrogen or C 1 -C 8 -alkyl;  
 R 6  is C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 10 -alkynyl or C 1 -C 8 -alkoxy in each case optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 6  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 7  is a C 3 -C 15 -carbocyclic group;  
 R 8  is a C 3 -C 15 -carbocyclic group;  
 R 9  is hydrogen or C 1 -C 8 -alkyl;  
 R 10  is hydrogen, C 1 -C 8 -alkyl optionally substituted by cyano, amino, nitro, carboxy, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group, or by a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 10  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 11  is hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkyl-C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl-O—R 15 ;  
 R 12  is a C 3 -C 15 -carbocyclic group;  
 R 13  is C 1 -C 8 -alkyl or a C 3 -C 15 -carbocyclic group;  
 R 14  is hydrogen, a C 3 -C 15 -carbocyclic group, C 1 -C 8 -alkenyl, or C 1 -C 8 -alkyl optionally substituted by a C 3 -C 15 -carbocyclic group; and  
 R 15  is a C 3 -C 15 -carbocyclic group.  
 
 
   
   
       2 . A compound according to  claim 1 , wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—NH—R 2 , —O—CO—R 13  or —CO—O—R 4 ,    or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen or C 1 -C 8 -alkyl;    R 6  is C 1 -C 8 -alkyl, C 2 -C 10 -alkynyl or C 1 -C 8 -alkoxy in each case optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 6  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 15 -carbocyclic group;    R 8  is a C 3 -C 15 -carbocyclic group;    R 9  is hydrogen or C 1 -C 8 -alkyl;    R 10  is C 1 -C 8 -alkyl optionally substituted by cyano, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group or by a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 15 -carbocyclic group;    R 13  is C 1 -C 8 -alkyl; and    R 14  is hydrogen, a C 3 -C 15 -carbocyclic group, C 1 -C 8 -alkenyl, or C 1 -C 8 -alkyl optionally substituted by a C 3 -C 15 -carbocyclic group.    
   
   
       3 . A compound according to  claim 2 , wherein 
 R 1  and R 3  are each independently a C 6 -C 10 -carbocyclic aromatic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—NH—R 2 , —O—CO—R 13  or —CO—O—R 4 ,    or R 4  is C 3 -C 8 -alkynyl optionally substituted by a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen or C 1 -C 4 -alkyl;    R 6  is C 1 -C 4 -alkyl, C 2 -C 8 -alkynyl or C 1 -C 4 -alkoxy in each case optionally substituted by a C 3 -C 10 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 6  is a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 10 -carbocyclic group;    R 8  is a C 3 -C 10 -carbocyclic group;    R 9  is hydrogen or C 1 -C 4 -alkyl;    R 10  is C 1 -C 4 -alkyl optionally substituted by cyano, C 1 -C 4 -alkoxy, a C 3 -C 10 -carbocyclic group or by a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 10 -carbocyclic group;    R 13  is C 1 -C 4 -alkyl; and    R 14  is hydrogen, a C 3 -C 10 -carbocyclic group, C 1 -C 4 -alkenyl, or C 1 -C 4 -alkyl optionally substituted by a C 3 -C 10 -carbocyclic group.    
   
   
       4 . A compound of formula I  
     
       
         
         
             
             
         
       
     
     in salt or zwitterionic form wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or —CR 1 R 2 R 3  together form a group of formula  
                     
 where R is a bond, —O—, —S—, —CH 2 —, —CH═CH—, —CH 2 —CH 2 —, amino or —N(CH 3 )—;  
 R 2  is hydrogen, halo, hydroxy, C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl optionally substituted by hydroxy;  
 R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —OR 11 , —O—CO—NHR 12 , —O—CO—R 13  or —CO—O—R 4 ,  
 or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 5  is hydrogen or C 1 -C 8 -alkyl;  
 R 6  is C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 10 -alkynyl or C 1 -C 8 -alkoxy in each case optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 6  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 7  is a C 3 -C 15 -carbocyclic group;  
 R 8  is a C 3 -C 15 -carbocyclic group;  
 R 9  is hydrogen or C 1 -C 8 -alkyl;  
 R 10  is hydrogen, C 1 -C 8 -alkyl optionally substituted by cyano, amino, nitro, carboxy, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group, or by a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 10  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 11  is hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkyl-C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl-O—R 15 ;  
 R 12  is a C 3 -C 15 -carbocyclic group;  
 R 13  is C 1 -C 8 -alkyl or a C 3 -C 15 -carbocyclic group;  
 R 14  is hydrogen, a C 3 -C 15 -carbocyclic group, or C 1 -C 8 -alkyl optionally substituted by a C 3 -C 15 -carbocyclic group; and  
 R 15  is a C 3 -C 15 -carbocyclic group.  
 
   
   
       5 . A compound according to  claim 4 , wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—NH—R 2 , —O—CO—R 13  or —CO—O—R 4 ,    or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen or C 1 -C 8 -alkyl;    R 6  is C 1 -C 8 -alkyl, C 2 -C 10 -alkynyl or C 1 -C 8 -alkoxy in each case optionally substituted by a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 6  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 15 -carbocyclic group;    R 8  is a C 3 -C 15 -carbocyclic group;    R 9  is hydrogen or C 1 -C 8 -alkyl;    R 10  is C 1 -C 8 -alkyl optionally substituted by cyano, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group or by a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 15 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 15 -carbocyclic group;    R 13  is C 1 -C 8 -alkyl; and    R 14  is hydrogen, a C 3 -C 15 -carbocyclic group or C 1 -C 8 -alkyl optionally substituted by a C 3 -C 15 -carbocyclic group.    
   
   
       6 . A compound according to  claim 5 , wherein 
 R 1  and R 3  are each independently a C 6 -C 10 -carbocyclic aromatic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—N H—R 12 , —O—CO—R 13  or —CO—O—R 14 ,    or R 4  is C 3 -C 8 -alkynyl optionally substituted by a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen or C 1 -C 4 -alkyl;    R 6  is C 1 -C 4 -alkyl, C 2 -C 8 -alkynyl or C 1 -C 4 -alkoxy in each case optionally substituted by a C 3 -C 10 -carbocyclic group or a 4- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 6  is a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 10 -carbocyclic group;    R 8  is a C 3 -C 10 -carbocyclic group;    R 9  is hydrogen or C 1 -C 4 -alkyl;    R 10  is C 1 -C 4 -alkyl optionally substituted by cyano, C 1 -C 4 -alkoxy, a C 3 -C 10 -carbocyclic group or by a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 10 -carbocyclic group or a 4- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 10 -carbocyclic group;    R 13  is C 1 -C 4 -alkyl; and    R 14  is hydrogen, a C 3 -C 10 -carbocyclic group or C 1 -C 4 -alkyl optionally substituted by a C 3 -C 10 -carbocyclic group.    
   
   
       7 . A compound of formula I  
     
       
         
         
             
             
         
       
     
     in salt or zwitterionic form wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or —CR 1 R 2 R 3  together form a group of formula  
                     
 where R is a bond, —O—, —S—, —CH 2 —, —CH═CH—, —CH 2 —CH 2 —, amino or —N(CH 3 )—;  
 R 2  is hydrogen, halo, hydroxy, C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl optionally substituted by hydroxy;  
 R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —OR 11 , —O—CO—NHR 2 , —O—CO—R 13  or —CO—O—R 14 ,  
 or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 5  is hydrogen or C 1 -C 8 -alkyl;  
 R 6  is C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy in either case optionally substituted by a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 6  is a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 7  is a C 3 -C 15 -carbocyclic group;  
 R 8  is a C 3 -C 15 -carbocyclic group;  
 R 9  is hydrogen or C 1 -C 8 -alkyl;  
 R 10  is hydrogen, C 1 -C 8 -alkyl optionally substituted by cyano, amino, nitro, carboxy, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group, or by a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,  
 or R 10  is a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;  
 R 11  is hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkyl-C 1 -C 8 -alkoxy or C 1 -C 8 -alkyl-O—R 15 ;  
 R 12  is a C 3 -C 15 -carbocyclic group;  
 R 13  is C 1 -C 8 -alkyl or a C 3 -C 15 -carbocyclic group;  
 R 14  is hydrogen, C 1 -C 8 -alkyl or a C 3 -C 15 -carbocyclic group; and  
 R 15  is a C 3 -C 15 -carbocyclic group.  
 
   
   
       8 . A compound according to  claim 7 , wherein 
 R 1  and R 3  are each independently a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—NH—R 2 , —O—CO—R 13  or —CO—O—R 14 ,    or R 4  is C 3 -C 10 -alkynyl optionally substituted by a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen;    R 6  is C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy in either case optionally substituted by a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 6  is a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 15 -carbocyclic group;    R 8  is a C 3 -C 15 -carbocyclic group;    R 9  is hydrogen or C 1 -C 8 -alkyl;    R 10  is C 1 -C 8 -alkyl optionally substituted by cyano, C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocyclic group or by a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 15 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 15 -carbocyclic group;    R 13  is C 1 -C 8 -alkyl; and    R 14  is hydrogen, C 1 -C 8 -alkyl or a C 3 -C 15 -carbocyclic group.    
   
   
       9 . A compound according to  claim 8 , wherein 
 R 1  and R 3  are each independently a C 6 -C 10 -carbocyclic aromatic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 2  is halo or hydroxy;    R 4  is C 1 -C 8 -alkyl substituted by —NHR 5 , —NR 5 —CO—R 6 , —NR 5 —CO—NH—R 7 , —NR 5 —SO 2 —R 8 , —CO—NR 9 R 10 , —O—CO—NH—R 2 , —O—CO—R 13  or —CO—O—R 4 ,    or R 4  is C 3 -C 8 -alkynyl optionally substituted by a C 3 -C 10 -carbocyclic group or a 5- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 5  is hydrogen;    R 6  is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy in either case optionally substituted by a C 3 -C 10 -carbocyclic group or a 5- to 12-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 5  is a C 3 -C 10 -carbocyclic group or a 5- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 7  is a C 3 -C 10 -carbocyclic group;    R 8  is a C 3 -C 10 -carbocyclic group;    R 9  is hydrogen or C 1 -C 4 -alkyl;    R 10  is C 1 -C 4 -alkyl optionally substituted by cyano, C 1 -C 4 -alkoxy, a C 3 -C 10 -carbocyclic group or by a 5- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur,    or R 10  is a C 3 -C 10 -carbocyclic group or a 5- to 10-membered heterocyclic group having at least one ring heteroatom selected from nitrogen, oxygen and sulphur;    R 12  is a C 3 -C 10 -carbocyclic group;    R 13  is C 1 -C 4 -alkyl; and    R 14  is hydrogen, C 1 -C 4 -alkyl or a C 3 -C 10 -carbocyclic group.    
   
   
       10 . A compound according to  claim 1 , which is also a compound of formula XIV  
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , R 3 , and R 4  are as shown in the following table:  
     
       
         
               
               
               
             
                   
               
                   
               
                 R 1  and R 3   
                 R 4   
                 R 2   
               
                   
               
                   
                   
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
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
         
       
     
   
   
       11 . A compound according to  claim 1 , which is also a compound of formula XIV  
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , R 3 , and R 4  are as shown in the following table:  
     
       
         
               
               
               
             
                   
               
                   
               
                 R 1  and R 3   
                 R 4   
                 R 2   
               
                   
               
                   
                   
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                   
                     
                     
                         
                         
                     
                   
                 
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       12 . A compound according to  claim 1 , which is also a compound of formula XIV  
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , R 3 , and R 4  are as shown in the following table:  
     
       
         
               
               
               
             
                   
               
                   
               
                 R 1  and R 3   
                 R 4   
                 R 2   
               
                   
               
                   
                   
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                   
               
           
              
              
              
              
             
             
              
              
              
              
              
              
             
          
         
       
     
   
   
       13 . A compound according to  claim 1  in combination with another drug substance which is an anti-inflammatory, a bronchodilator, an antihistamine, a decongestant or an anti-tussive drug substance.  
   
   
       14 . (canceled)  
   
   
       15 . A pharmaceutical composition comprising as active ingredient a compound according to  claim 1  in combination with another drug substance which is an anti-inflammatory, a bronchodilator, an antihistamine, a decongestant or an anti-tussive drug substance, optionally together with a pharmaceutically acceptable diluent or carrier.  
   
   
       16 - 17 . (canceled)  
   
   
       18 . A process for the preparation of a compound of formula I as claimed in  claim 1  which comprises 
 (i) (A) reacting a compound of compound of formula II                          or a protected form thereof where R 1 , R 2  and R 3  are as defined in  claim 1 , with a compound of formula III      R 4 —X  III    where R 4  is as hereinbefore defined and X is chloro, bromo or iodo;    (B) for the preparation of compounds of formula I where R 4  is C 1 -C 8 -alkyl substituted by —NR 5 —CO—R 6  where R 5  and R 6  are as defined in  claim 1 , reacting a compound of formula IV                          or a protected form thereof where R 1 , R 2 , R 3  and R 5  are as defined in  claim 1 , optionally in the presence of a coupling agent, and T denotes C 1 -C 8 -alkylene, with a compound of formula V                          where R 6  is as defined in  claim 1  or an amide-forming derivative thereof such as an acid halide;    (C) for the preparation of compounds of formula I where R 4  is C 1 -C 8 -alkyl substituted by —NR 5 —CO—NH—R 7  where R 5  and R 7  are as defined in  claim 1 , reacting a compound of formula IV or a protected form thereof where R 1 , R 2 , R 3  and R 5  are as defined in  claim 1  and T denotes C 1 -C 8 -alkylene, with a compound of formula VI      O═C═N—R 7   VI    where R 7  is as defined in  claim 1;     (D) for the preparation of compounds of formula I where R 4  is C 1 -C 8 -alkyl substituted by —NR 5 —SO 2 —R 8  where R 5  and R 8  are as defined in  claim 1 , reacting a compound of formula IV or a protected form thereof where R 1 , R 2 , and R 3  are as defined in  claim 1  and T denotes C 1 -C 8 -alkylene, with a compound of formula VII                          where R 8  is as defined in  claim 1  and X is halo; or    (E) for the preparation of compounds of formula I where R 4  is C 1 -C 8 -alkyl substituted by —CO—NR 9 R 10  where R 9  and R 10  are as defined in  claim 1 , reacting a compound of formula VIII                          or a protected form thereof where R 1 , R 2 , and R 3  are as defined in  claim 1  and T denotes C 1 -C 8 -alkylene, optionally in the presence of a coupling agent, or an amide-forming derivative thereof such as an acid halide, with a compound of formula IX                          where R 9  and R 10  are as defined in  claim 1;  and    (ii) recovering the product in salt or zwitterionic form.    
   
   
       19 . A pharmaceutical composition comprising as active ingredient a compound according to  claim 1 .  
   
   
       20 . A method of treating a condition mediated by the muscarinic M3 receptor in a subject in need of such treatment, which comprises administering to said subject an effective amount of a compound of formula I as defined in  claim 1  in free form or in the form of a pharmaceutically acceptable salt.  
   
   
       21 . A method of treating an inflammatory or obstructive airways disease in a subject in need of such treatment, which comprises administering to said subject an effective amount of a compound of formula I as defined in  claim 1  in free form or in the form of a pharmaceutically acceptable salt.

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