US2004063727A1PendingUtilityA1

6-Substituted biaryl purine derivatives as potent cyclin/cdk inhibitors and antiproliferative agents

Priority: Mar 17, 1999Filed: Aug 13, 2003Published: Apr 1, 2004
Est. expiryMar 17, 2019(expired)· nominal 20-yr term from priority
A61P 35/00A61P 37/06A61P 3/10A61P 7/02A61P 43/00A61P 35/02A61P 25/00C07D 473/18C07D 473/16C07D 473/24A61P 19/06A61P 19/02C07D 401/12A61K 31/52C07D 213/06
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Claims

Abstract

The present invention is directed to compounds useful in inhibiting cellular proliferation. Processes of preparing such compounds are also disclosed.

Claims

exact text as granted — not AI-modified
What is claimed:  
     
         1 . A compound of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl; and  
 C 3 -C 4 -branched chain alkyl;  
 
 X=CH;  
 R 2 =phenyl; 
 substituted phenyl, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of R 1 , OR 1 , SR 1 , S(O)R 1 , S(O 2 )R 1 , NHR 1 , NO 2 , OC(O)CH 3 , NHC(O)CH 3 , F, Cl, Br, CF 3 , C(O)R 1 , C(O)NHR 1 , phenyl, and C(O)NHCHR 1 CH 2 OH;  
 1-naphthyl;  
 2-naphthyl;  
 heterocycles selected from the group consisting of: 
 2-pyridyl;  
 3-pyridyl;  
 4-pyridyl;  
 5-pyrimidyl;  
 thiophene-2-yl;  
 thiophene-3-yl;  
 2-furanyl;  
 3-furanyl;  
 2-benzofuranyl;  
 benzothiophene-2-yl;  
 2-pyrrolyl;  
 3-pyrrolyl;  
 2-quinolinyl;  
 3-quinolinyl;  
 4-quinolinyl;  
 1-isoquinolinyl;  
 3-isoquinolinyl; and  
 4-isoquinolinyl; or  
 
 substituted heterocycle, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of Br, Cl, F, R 1 , and C(O)CH 3 ;  
 
 R 3  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl;  
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; and  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ;  
 
 R 4 =H; 
 C 1 -C 4 -straight chain alkyl; or  
 C 3 -C 4 -branched chain alkyl;  
 
 R 3  and R 4  can be linked together by a carbon chain to form a 5-8-membered ring;  
 n=0-3;  
 Y=H; 
 OR 1 ;  
 NHR 1 ;  
 NHC(O)R 3 ;  
 NHSO 2 R 3 ;  
 NHC(O)NHR 3 ;  
 NHC(O)R 5 ; or  
 NHC(O)OR 6 ;  
 
 R 5 ═C 3 -C 7 -cycloalkyl;  
 R 6 =C 1 -C 4 -straight chain alkyl; 
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; or  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ; or a pharmaceutically acceptable salt thereof;  
 with the proviso that when R 1 =CH(CH 3 ) 2 , and R 2 =Ph, and X=CH, then R 3 ≠H, and n≠0, and R 4 ≠H, and Y≠OH.  
 
 
     
     
         2 . A compound according to  claim 1 , wherein 
 R 3  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl; and  
 C 3 -C 4 -branched chain alkyl;  
   Y=H; 
 OR 1 ;  
 NHR 1 ;  
 NHC(O)R 3 ;  
 NHSO 2 R 3 ; or  
 NHC(O)NHR 3 ; or a pharmaceutically acceptable salt thereof.  
   
     
     
         3 . A compound of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl; and  
 C 3 -C 4 -branched chain alkyl;  
 
 X=CH;  
 R 2 =phenyl; 
 substituted phenyl, wherein the substituents (1-2 in number) are in any position and independently selected from the group consisting of R 1 , OR 1 , SR 1 , S(O)R 1 , S(O 2 )R 1 , NHR 1 , NO 2 , OC(O)CH 3 , NHC(O)CH 3 , F, Cl, Br, CF 3 , C(O)R 1 , C(O)NHR 1 , phenyl, and C(O)NHCHR 1 CH 2 OH;  
 heterocycles selected from the group consisting of: 
 2-pyridyl;  
 3-pyridyl;  
 4-pyridyl;  
 5-pyrimidyl;  
 thiophene-2-yl;  
 thiophene-3-yl;  
 2-furanyl;  
 3-furanyl;  
 2-benzofuranyl;  
 benzothiophene-2-yl;  
 2-pyrrolyl;  
 3-pyrrolyl;  
 2-quinolinyl;  
 3-quinolinyl;  
 4-quinolinyl;  
 1-isoquinolinyl;  
 3-isoquinolinyl; and  
 4-isoquinolinyl; or  
 
 substituted heterocycle, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of Br, Cl, F, R 1 , and C(O)CH 3 ;  
 
 Y=OR 1 ; 
 NHR 1 ;  
 NHC(O)R 1 ;  
 NHSO 2 R 1 ;  
 NHC(O)NHR 1 ; or  
 NHC(O)OR 1 ;  
 
 R 6 =C 1 -C 4 -straight chain alkyl; 
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain; or  
 or a pharmaceutically acceptable salt thereof.  
 
 
     
     
         4 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         5 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         6 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         7 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         8 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         9 . A compound according to  claim 3 , wherein the compound has the following formula:  
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof.  
     
     
         10 . A pharmaceutical composition of matter comprising the compound of  claim 1  and one or more pharmaceutical excipients.  
     
     
         11 . A pharmaceutical composition of matter comprising the compound of  claim 3  and one or more pharmaceutical excipients.  
     
     
         12 . A process for preparation of a purine derivative compound of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl; and  
 C 3 -C 4 -branched chain alkyl;  
 
 X=CH;  
 R 2 =phenyl; 
 substituted phenyl, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of R 1 , OR 1 , SR 1 , S(O)R 1 , S(O 2 )R 1 , NHR 1 , NO 2 , OC(O)CH 3 , NHC(O)CH 3 , F, Cl, Br, CF 3 , C(O)R 1 , C(O)NHR 1 , phenyl, and C(O)NHCHR 1 CH 2 OH;  
 1-naphthyl;  
 2-naphthyl;  
 heterocycles selected from the group consisting of: 
 2-pyridyl;  
 3-pyridyl;  
 4-pyridyl;  
 5-pyrimidyl;  
 thiophene-2-yl;  
 thiophene-3-yl;  
 2-furanyl;  
 3-furanyl;  
 2-benzofuranyl;  
 benzothiophene-2-yl;  
 2-pyrrolyl;  
 3-pyrrolyl;  
 2-quinolinyl;  
 3-quinolinyl;  
 4-quinolinyl;  
 1-isoquinolinyl;  
 3-isoquinolinyl; and  
 4-isoquinolinyl; or  
 
 substituted heterocycle, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of Br, Cl, F, R 1 , and C(O)CH 3 ;  
 
 R 3  are the same or different and independently selected from the group consisting of 
 H;  
 C 1 -C 4 -straight chain alkyl;  
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; and  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ;  
 
 R 4 =H; 
 C 1 -C 4 -straight chain alkyl; or  
 C 3 -C 4 -branched chain alkyl;  
 
 R 3  and R 4  can be linked together by a carbon chain to form a 5-8-membered ring;  
 n=0-3;  
 Y=H; 
 OR 1 ;  
 NHR 1 ;  
 NHC(O)R 3 ;  
 NHSO 2 R 3 ;  
 NHC(O)NHR 3 ;  
 NHC(O)R 5 ; or  
 NHC(O)OR 6 ;  
 
 R 5 =C 3 -C 7 -cycloalkyl;  
 R 6 =C 1 -C 4 -straight chain alkyl; 
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; or  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ; or a pharmaceutically acceptable salt thereof;  
 with the proviso that when R 1 =CH(CH 3 ) 2 , and R 2 =Ph, and X=CH, then R 3 ≠H, and n=0, and R 4 ≠H, and Y≠OH, said process comprising:  
 
 reacting a first intermediate compound of the formula:  
                     
  where 
 Z=Br or I  
 with a compound of the formula: R 2 —B(OH) 2 , R 2 —Sn(n-Bu) 3 , R 2 —Sn(Me) 3 , or mixtures thereof, under conditions effective to form the purine derivative compound.  
 
 
     
     
         13 . A process according to  claim 12  further comprising: 
 reacting a second intermediate compound of the formula:  
                     
  with a second compound of the formula:  
                     
  under conditions effective to form the first intermediate compound.  
 
     
     
         14 . A process according to  claim 13 , wherein if Y in the second compound is NH 2 , said process further comprises: 
 reacting the purine derivative compound with R 3 C(O)Cl or R 3 SO 2 Cl or R 3 NCO or R 3 OC(O)Cl under conditions effective to form a final product having the same formula as the purine derivative compound except that Y is NHC(O)R 3  or NHSO 2 R 3  or NHC(O)NHR 3  or NHC(O)OR 6 .    
     
     
         15 . A process according to  claim 13  further comprising: 
 reacting a third intermediate compound of the formula:  
                     
 with a compound of the formula R 1 -Z under conditions effective to form the second intermediate compound.  
 
     
     
         16 . A process according to  claim 15  further comprising: 
 reacting a first starting compound of the formula:  
                     
  with a second starting compound of the formula  
                     
  under conditions effective to form the third intermediate compound.  
 
     
     
         17 . A process according to  claim 12 , wherein the purine derivative compound has the formula:  
       
         
           
           
               
               
           
         
       
     
     
         18 . A process for preparation of a purine derivative compound of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  are the same or different and independently selected from the group consisting of: 
 H;  
 C 1 -C 4 -straight chain alkyl; and  
 C 3 -C 4 -branched chain alkyl;  
 
 X=CH;  
 R 2 =phenyl; 
 substituted phenyl, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of R 1 , OR 1 , SR 1 , S(O)R 1 , S(O 2 )R 1 , NHR 1 , NO 2 , OC(O)CH 3 , NHC(O)CH 3 , F, Cl, Br, CF 3 , C(O)R 1 , C(O)NHR 1 , phenyl, and C(O)NHCHR 1 CH 2 OH;  
 1-naphthyl;  
 2-naphthyl;  
 heterocycles selected from the group consisting of: 
 2-pyridyl;  
 3-pyridyl;  
 4-pyridyl;  
 5-pyrimidyl;  
 thiophene-2-yl;  
 thiophene-3-yl;  
 2-furanyl;  
 3-furanyl;  
 2-benzofuranyl;  
 benzothiophene-2-yl;  
 2-pyrrolyl;  
 3-pyrrolyl;  
 2-quinolinyl;  
 3-quinolinyl;  
 4-quinolinyl;  
 1-isoquinolinyl;  
 3-isoquinolinyl; and  
 4-isoquinolinyl; or  
 
 substituted heterocycle, wherein the substituents (1-2 in number) are in any position and are independently selected from the group consisting of Br, Cl, F, R 1 , and C(O)CH 3 ;  
 
 R 3  are the same or different and independently selected from the group consisting of 
 H;  
 C 1 -C 4 -straight chain alkyl;  
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; and  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ;  
 
 R 4 =H; 
 C 1 -C 4 -straight chain alkyl; or  
 C 3 -C 4 -branched chain alkyl;  
 
 R 3  and R 4  can be linked together by a carbon chain to form a 5-8-membered ring;  
 n-=0-3;  
 Y=H; 
 OR 1 ;  
 NHR 1 ;  
 NHC(O)R 3 ;  
 NHSO 2 R 3 ;  
 NHC(O)NHR 3 ;  
 NHC(O)R 5 ; or  
 NHC(O)OR 6 ;  
 
 R 5 =C 3 -C 7 -cycloalkyl;  
 R 6 =C 1 -C 4 -straight chain alkyl; 
 C 3 -C 4 -branched chain alkyl;  
 C 2 -C 4 -alkenyl chain;  
 (CH 2 ) n Ph; or  
 (CH 2 ) n -substituted phenyl, wherein the phenyl substituents are as defined above in R 2 ; or a pharmaceutically acceptable salt thereof;  
 with the proviso that when R 1 =CH(CH 3 ) 2 , and R 2 =Ph, and X=CH, then R 3 ≠H, and n≠0, and R 4 ≠H, and Y≠OH, said process comprising:  
 
 reacting a first intermediate compound of the formula:  
                     
  with a second compound of the formula:  
                     
  under conditions effective to form the purine derivative compound.  
 
     
     
         19 . A process according to  claim 18 , wherein if Y in the second compound is NH 2 , said process further comprises: 
 reacting the purine derivative compound with R 3 C(O)Cl or R 3 SO 2 Cl or R 3 NCO or R 3 OC(O)Cl under conditions effective to form a final product having the same formula as the purine derivative compound except that Y is NHC(O)R 3  or NHSO 2 R 3  or NHC(O)NHR 3  or NHC(O)OR 6 .    
     
     
         20 . A process according to  claim 18  further comprising: 
 reacting a third intermediate compound of the formula:  
                     
  with a compound of the formula R 1 -Z under conditions effective to form the first intermediate compound.  
 
     
     
         21 . A process according to  claim 20  further comprising: 
 reacting a first starting compound of the formula:  
                     
  with a second starting compound of the formula  
                     
  under conditions effective to form the third intermediate compound.

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