US2007032487A1PendingUtilityA1

Inhibitors of phosphatidylinositol 3-kinase

Assignee: BRUCE IANPriority: May 2, 2003Filed: Apr 30, 2004Published: Feb 8, 2007
Est. expiryMay 2, 2023(expired)· nominal 20-yr term from priority
A61P 37/08A61P 3/04A61P 43/00A61P 9/10A61P 9/00A61P 37/06A61P 29/00A61P 31/04A61P 35/00A61P 3/10A61P 19/10A61P 17/06A61P 1/04A61P 19/02A61P 11/06A61P 11/00A61K 31/5377C07D 417/14A61K 45/06A61K 31/497C07D 417/04A61P 1/00
51
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Claims

Abstract

Compounds of formula I in free or salt form, 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 mediated by phosphatidylinositol 3-kinase. 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 free or salt form, wherein R 1  is C 1 -C 8 -alkylcarbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)aminocarbonyl, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5-or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, 
 or R 1  is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or R 1  is aminocarbonyl optionally substituted by a C 3 -C 15 -carbocycle or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is —CO—NR x R y , where R x  and R y  together with the nitrogen to which they are attached form a 5- to 12-membered N-heterocyclic ring optionally including one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is C 1 -C 8 -alkylaminocarbonyl or C 3 -C 8 -cycloalkylaminocarbonyl in either case optionally substituted in the alkyl group by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl) amino-carbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy, or R 1 is C 1 -C 8 -alkylaminocarbonyl or C 3 -C 8 -cycloalkylaminocarbonyl in either case optionally substituted by aminocarbonyl optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is hydrogen or C 1 -C 8 -alkyl;  
 R 2  is C 1 -C 3 -alkyl;  
 Y is carbon or nitrogen; and  
 when R 1  is unsubstituted C 1 -C 8 -alkylcarbonyl and Y is carbon then  
 R 3  is halo, hydroxy, cyano, amino, carboxy, -SO 2 NH 2 , C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl) aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkoxy, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy or di(C 1 -C 8 -alkyl)amino,  
 and R 4  is hydrogen, halo, hydroxy, cyano, amino, carboxy, —SO 2 NH 2  C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl) amino, di(C 1 -C 8 -alkyl)aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl) amino-C 1 -C 8 -alkoxy, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy or di(C 1 -C 8 -alkyl)amino,  
 otherwise R 3  and R 4  are each independently hydrogen, halo, hydroxy, cyano, amino, carboxy,  
 C 1 -C 8 -alkylsulfanyl, C 1 -C 8 -alkylsulfinyl, C 1 -C 8 -alkylsulfonyl, —SO 2 NH 2 , C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl)aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkoxy, C 1 -C 8 -acylamino, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, C 1 -C 8 -alkylamino or di(C 1 -C 8 -alkyl) amino each being optionally substituted by amino, hydroxy, di(C 1 -C 8 -alkyl)amino or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkoxy optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur.  
 
   
   
       2 . A compound according to  claim 1  wherein 
 R 1  is C 1 -C 8 -alkylcarbonyl optionally substituted by di(C 1 -C 8 -alkyl)amino, C 1 -C 8 -alkylcarbonyl or C 1 -C 8 -alkoxycarbonyl,    or R 1  is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    or R 1  is —CO—-NR x R y , where R x  and R y  together with the nitrogen to which they are attached form a 5- to 12-membered N-heterocyclic ring optionally including one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or R 1  is C 1 -C 8 -alkylaminocarbonyl optionally substituted in the alkyl group by hydroxy, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)amino-carbonyl, C 1 -C 8 -alkoxycarbonyl, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy,    or R 1  is C 1 -C 8 -alkylaminocarbonyl optionally substituted by aminocarbonyl optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    or R 1  is hydrogen;    R 2  is C 1 -C 3 -alkyl;    Y is carbon or nitrogen; and    when R 1  is unsubstituted C 1 -C 8 -alkylcarbonyl and Y is carbon then    R 3  is halo, C 1 -C 8 -alkyl or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    and R 4  is hydrogen or C 1 -C 8 -alkyl,    otherwise R 3  and R 4  are each independently hydrogen, halo, cyano, C 1 -C 8 -alkylsulfanyl, C 1 -C 8 -alkylsulfinyl, C 1 -C 8 -alkylsulfonyl, C 1 -C 8 -alkyl, C 1 -C 8 -acylamino, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, C 1 -C 8 -alkylamino or di(C 1 -C 8 -alkyl)amino each being optionally substituted by amino, hydroxy, di(C 1 -C 8 -alkyl)amino or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkoxy optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur.    
   
   
       3 . A compound according to  claim 2  wherein 
 R 1  is C 1 -C 4 -alkylcarbonyl optionally substituted by di(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxycarbonyl,    or R 1  is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    or R 1  is —CO—NR x R y , where R x  and R y  together with the nitrogen to which they are attached form a 5- to 9-membered N-heterocyclic ring optionally including one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    or R 1  is C 1 -C 4 -alkylaminocarbonyl optionally substituted in the alkyl group by hydroxy, C 1 -C 4 -alkoxy, hydroxy-substituted C 1 -C 4 -alkoxy, di(C 1 -C 4 -alkyl)amino, di(C 1 -C 4 -alkyl)amino-carbonyl, C 1 -C 4 -alkoxycarbonyl, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, C 1 -C 4 -alkylaminocarbonyl optionally substituted by hydroxy, or by C 1 -C 4 -alkoxy, or R 1  is C 1 -C 4 -alkylaminocarbonyl optionally substituted by aminocarbonyl optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    or R 1  is hydrogen;    R 2  is C 1 -C 3 -alkyl;    Y is carbon or nitrogen; and    when R 1  is unsubstituted C 1 -C 4 -alkylcarbonyl and Y is carbon then    R 3  is halo, C 1 -C 4 -alkyl or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    and R 4  is hydrogen or C 1 -C 4 -alkyl,    otherwise R 3  and R 4  are each independently hydrogen, halo, cyano, C 1 -C 4 -alkylsulfanyl, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkyl, C 1 -C 4 -acylamino, a C 3 -C 10 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, C 1 -C 4 -alkylamino or di(C 1 -C 4 -alkyl)amino each being optionally substituted by amino, hydroxy, di(C 1 -C 4 -alkyl)amino or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 4 -alkoxy optionally substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur.    
   
   
       4 . A compound of formula I  
     
       
         
         
             
             
         
       
     
     in free or salt form, wherein 
 R 1  is C 1 -C 8 -alkylcarbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl) aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is aminocarbonyl optionally substituted by a C 3 -C 15 -carbocycle or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,  
 or R 1  is C 1 -C 8 -alkylaminocarbonyl or C 3 -C 8 -cycloalkylaminocarbonyl in either case optionally substituted in the alkyl group by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)amino-carbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;  
 R 2  is C 1 -C 3 -alkyl;  
 Y is carbon or nitrogen; and  
 when R 1  is unsubstituted C 1 -C 8 -alkylcarbonyl and Y is carbon then  
 R 3  is halo, hydroxy, cyano, amino, carboxy, —SO 2 NH 2 , C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl) aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkoxy, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy,  
 and R 4  is hydrogen, halo, hydroxy, cyano, amino, carboxy, —SO 2 NH 2 , C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl) amino, di(C 1 -C 8 -alkyl)aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl) amino-C 1 -C 8 -alkoxy, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy,  
 otherwise R 3  and R 4  are each independently hydrogen, halo, hydroxy, cyano, amino, carboxy, —SO 2 NH 2 , C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, amino-C 1 -C 8 -alkyl, amino-C 1 -C 8 -alkoxy, C 1 -C 8 -alkylaminocarbonyl, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)aminocarbonyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkyl, di(C 1 -C 8 -alkyl)amino-C 1 -C 8 -alkoxy, aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, carboxy-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkoxy, a C 3 -C 15 -carbocycle, a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy.  
 
   
   
       5 . A compound according to  claim 4  wherein 
 R 1  is C 1 -C 8 -alkylcarbonyl or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or R 1  is C 1 -C 8 -alkylaminocarbonyl optionally substituted in the alkyl group by C 1 -C 8 -alkoxycarbonyl, di(C 1 -C 8 -alkyl)aminocarbonyl or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;    R 2  is C 1 -C 3 -alkyl;    Y is carbon or nitrogen; and    when R 1  is unsubstituted C 1 -C 8 -alkylcarbonyl and Y is carbon then    R 3  is halo, C 1 -C 8 -alkyl or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur,    and R 4  is hydrogen or C 1 -C 8 -alkyl,    otherwise R 3  and R 4  are each independently hydrogen, halo, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, a 5-or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylamino optionally substituted by hydroxy or di(C 1 -C 8 -alkyl)amino.    
   
   
       6 . A compound according to  claim 5 , in free or salt form, wherein 
 R 1  is C 1 -C 4 -alkylcarbonyl or a 5- or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or R 1  is C 1 -C 4 -alkylaminocarbonyl optionally substituted in the alkyl group by C 1 -C 4 -alkoxycarbonyl, di(C 1 -C 4 -alkyl)aminocarbonyl or by a 5- or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;    R 2  is C 1 -C 3 -alkyl;    Y is carbon or nitrogen; and    when R 1  is unsubstituted C 1 -C 4 -alkylcarbonyl and Y is carbon then    R 3  is halo, C 1 -C 4 -alkyl or a 5- or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, and R 4  is hydrogen or C 1 -C 4 -alkyl,    otherwise R 3  and R 4  are each independently hydrogen, halo, C 1 -C 4 -alkyl, C 3 -C 5 -cycloalkyl, a 5-or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 4 -alkylamino optionally substituted by hydroxy or di(C 1 -C 4 -alkyl)amino.    
   
   
       7 . A compound according to  claim 1 , which is also a compound of formula XXI  
     
       
         
         
             
             
         
       
     
     where R 1  , Y, R a  and R b  are as shown in the following table:  
     
       
         
               
               
               
               
             
                   
               
                   
               
                 R 1   
                 Y 
                 R a   
                 R b   
               
                   
               
                   
                   
                   
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 H 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 —CH 3   
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                   
               
           
              
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       8 . A compound according to  claim 1 , which is also a compound of formula XXI  
     
       
         
         
             
             
         
       
     
     where R 1  , Y, R a  and R b  are as shown in the following table:  
     
       
         
               
               
               
               
             
                   
               
                   
               
                 R 1   
                 Y 
                 R a   
                 R b   
               
                   
               
                   
                   
                   
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 C 
                 Cl 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 —CH 3   
                 —CH 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 N 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                   
               
           
              
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       9 . A compound according to claims  1  in combination with another drug substance which is an anti-inflammatory, a bronchodilator, an antihistamine, a decongestant or an anti-tussive drug substance.  
   
   
       10 . (canceled)  
   
   
       11 . A pharmaceutical composition comprising as active ingredient a compound according to claims  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.  
   
   
       12 - 13 . (canceled)  
   
   
       14 . A process for the preparation of a compound of formula I as defined in  claim 1 , in free or salt form which comprises the steps of: 
 (i) (A) reacting a compound of formula II                          wherein R 2 , R 3 , R 4  and Y are as hereinbefore defined and X is halogen, with a compound of formula III                          wherein R 1  is as hereinbefore defined;    (B) for the preparation of compounds of formula I where R 3 is a 5- or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, reacting a compound of formula I    wherein R 1  , R 2 , R 4  and Y are as hereinbefore defined and R 3 is chloro or bromo, with a compound of formula IV                          wherein R 5  and R 6  together form a 5- or 6-membered N-heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;    (C) for the preparation of compounds of formula I where R 3  is C 1 -C 8 -alkylamino optionally substituted by hydroxy or di(C 1 -C 8 -alkyl)amino, reacting a compound of formula I wherein R 1  , R 2 , R 4  and Y are as hereinbefore defined and R 3 is chloro or bromo, with a compound of formula V      R 7 −NH 2  V    wherein R 7  is C 1 -C 8 -alkyl optionally substituted by hydroxy or di(C 1 -C 8 -alkyl)amino;    (D) for the preparation of compounds of formula I where R 1  is C 1 -C 8 -alkylcarbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)-aminocarbonyl, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, reacting a compound of formula VI                          wherein R 2   3  R 3 , R 4  and Y are as hereinbefore defined, with a compound of formula VII                          or an amide-forming derivative thereof such as an acid halide or anhydride wherein R 1  is C 1 -C 8 -alkylcarbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)-aminocarbonyl, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;    (E) for the preparation of compounds of formula I where R 1  is C 1 -C 8 -alkylamino-carbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy, reacting a compound of formula VI wherein R 2 , R 3 , R 4  and Y are as hereinbefore defined, with a compound of formula VIII      O═C═N−R 8  VIII    wherein R 8  is C 1 -C 8 -alkyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl) amino, di(C 1 -C 8 -alkyl)aminocarbonyl, C 1 -C 8 -alkoxy-carbonyl, a C 3 -C 15 -carbocycle, a 5-or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy;    (F) for the preparation of compounds of formula I where R 1  is C 1 -C 8 -alkylamino-carbonyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl)amino, di(C 1 -C 8 -alkyl)aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy, reacting a compound of formula IX                          wherein R 2 , R 3 , R 4  and Y are as hereinbefore defined and T 1 is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, with a compound of formula X      R 9 −NH 2  X    wherein R 9  is C 1 -C 8 -alkyl optionally substituted by halo, hydroxy, cyano, amino, carboxy, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, hydroxy-substituted C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkylamino, di(C 1 -C 8 -alkyl) amino, di(C 1 -C 8 -alkyl)aminocarbonyl, C 1 -C 8 -alkoxycarbonyl, a C 3 -C 15 -carbocycle, or by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, or C 1 -C 8 -alkylaminocarbonyl optionally substituted by hydroxy;    (G) for the preparation of compounds of formula I where R 3  is C 1 -C 8 -alkylsulfinyl or C 1 -C 8 -alkylsulfonyl, oxidising the corresponding C 1 -C 8 -alkylsulfanyl or C 1 -C 8 -alkylsulfinyl respectively;    (H) for the preparation of compounds of formula I where R 3  is di(C 1 -C 8 -alkyl)amino optionally substituted by amino, hydroxy, di(C 1 -C 8 -alkyl)amino or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, reacting the corresponding compound where R 3  is C 1 -C 8 -alkylsulfinyl or C 1 -C 8 -alkylsulfonyl with a compound of formula Xa                          or a protected form thereof where R m  and R n  are independently C 1 -C 8 -alkyl optionally substituted by amino, hydroxy, di(C 1 -C 8 -alkyl)amino or a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur;    (I) for the preparation of compounds of formula I where R 3  is C 1 -C 8 -alkoxy, reacting the corresponding compound where R 3  is C 1 -C 8 -alkylsulfinyl with an alkali metal C 1 -C 8 -alkoxide;    (J) for the preparation of compounds of formula I where R 3  is C 1 -C 8 -alkoxy substituted by a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur, reacting the corresponding compound where R 3  is C 1 -C 8 -alkylsulfinyl with a compound of formula Xb      HO−V−T 2  Xb    where V is C 1 -C 8 -alkyl and T 2  is a 5- or 6-membered heterocyclic ring having one or more ring hetero atoms selected from the group consisting of oxygen, nitrogen and sulphur in the presence of a base; or    (K) for the preparation of compounds of formula I where R 3  is cyano, reducing the corresponding compound where R 3  is C 1 -C 8 -alkylsulfonyl with an alkali metal cyanide; and    (ii) removing any protecting groups and recovering the resultant compound of formula I in free or salt form.    
   
   
       15 . A pharmaceutical composition comprising as active ingredient a compound according to  claim 1 .  
   
   
       16 . A method of treating a disease mediated by phosphatidylinositol 3-kinase 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.  
   
   
       17 . 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.  
   
   
       18 . A method of treating cancer 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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