USRE38761EExpiredUtility

Styryl compounds which inhibit EGF receptor protein tyrosine kinase

51
Assignee: YISSUM RES DEV COPriority: Dec 24, 1987Filed: Oct 14, 1994Granted: Jul 19, 2005
Est. expiryDec 24, 2007(expired)· nominal 20-yr term from priority
A61K 31/19A61K 31/165C07D 317/62C07C 255/00A61K 31/36A61K 31/275
51
PatentIndex Score
13
Cited by
16
References
32
Claims

Abstract

A method of inhibiting cell proliferation in a patient suffering from such disorder comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, which is a substituted styrene compound which can also be a naphthalene, an indane or a benzoxazine; including nitrile and molononitrile compounds, and pharmaceutical compositions comprising, in admixture with a pharmaceutically acceptable carrier, a pharmaceutically-effective amount of such compound.

Claims

exact text as granted — not AI-modified
1. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis and restenosis comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, selected from the group consisting of
 (A) a substituted styrene compound having the formula 
                 
 
  wherein:  
 one of R 1  and R 2  is alkyl, —H, —CN, —OH, —CONRR or —CSNRR;  
 the other of R 1  and R 2  is alkyl, —H, —CN, —OH, —CONRR, —CSNRR, —CONHR 9 , —CONHCH 2 CN, —CH═C(CN) 2 , —C(NH 2 )═C(CN) 2  or —NHCHO  
 wherein R 1  and R 2  are not both alkyl, —H, —CN or —OH;  
 R is alkyl or —H;  
 R 3  is alkyl, —H, —CN, —OH, —CONRR, —CSNRR, —CH 2 CN or —CH═C(CN)COHN 2 ;  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H, —CN, halo, —NO 2  or —NHCOCH 3 ;  
 R 3  and R 7  together may be —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —or, starting from R 3 , —CONH—;  
 R 9  is, —CONH 2 , 
                 
 
  R 10  is alkyl, halo or —NO 2 ;  
 R 11  is alkyl, —CN, halo, —NO 2  or —NHCOCH 3 ;  
 R 12  is alkyl, —H, halo,;  
 n is 0 to about 6; and  
 m is 2 to about 10,  
 provided that when one of R 1  and R 2  is —CH═C(CN) 2 , at least one of R 3 , R 4 , R 5 , R 6 , R 7  and R 8  is not —H;  
 (B) an α-substituted benzylidene malononitrile compound having the formula 
                 
 
  wherein:  
 R 3  is alkyl, —CN, —OH, —CONRR, —CSNRR, —CH 2  CN or —CH═C(CN)CONH 2 ;  
 R is alkyl or —H; and  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H, —CN, halo, —NO 2  or —NHCOCH 3 ;  
 (C) an α-unsubstituted benzylidene malononitrile compound having the formula 
                 
 
  wherein:  
 at least one of R 4 , R 5 , R 6 , R 7  and R 8  is C 2  to about C 6  alkyl or —CN;  
 the remainder of R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H, —CN, halo, —NO 2  or —NHCOCH 3 ; and  
 R is alkyl or —H; and  
 (D) a bicyclic benzylidene malononitrile compound having the formula 
                 
 
  wherein:  
 R 3  and R 7  together are —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —or, starting from R 3 , —CONH—; and  
 R 4 , R 5 R 6  and R 8  are each independently alkyl, —H, —CN, halo, —NO 2  or —NHCOCH 3 .  
 
     
     
       2. A method according to  claim 1  wherein said compound has the formula 
                 
 R 1  is —CN, —CONRR or —CSNRR;  
 R 2  is —H, —CN, —CONRR, —CSNRR or —CONHR 9 ;  
 wherein R 1  and R 2 are not both —CN;  
 R is alkyl or —H;  
 R 3  is —H;  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H, or halo;  
 R 3  and R 7  together may be —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —or, starting from R 3 , —CONH—;  
 R 9  is —CONH 2 , 
                 
 
 R 10  is alkyl, halo or —NO 2 ;  
 R 11  is alkyl or halo;  
 R 12  is alkyl or —H;  
 n is 0 to about 4; and  
 m is 2 to about 6.  
 
     
     
       3. A method according to  claim 1  wherein said compound has the formula 
                 
 
       wherein:
 at least one of R 4 , R 5 , R 6 , R 7  and R 8  is C 2  to C 6  alkyl; and  
 the remainder of R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H or halo.  
 
     
     
       4. A method according to  claim 1  wherein said compound has the formula 
                 
 
       wherein:
 R 3  and R 7  together are —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —or, starting from R 3 , —CONH—; and  
 R 4 , R 5 , R 6  and R 8  are each independently alkyl, —H or halo.  
 
     
     
       5. A method according to  claim 2  wherein R 1  is —CN. 
     
     
       6. A method according to  claim 2  wherein said compound has the formula 
                 
 
     
     
       7. A method according to  claim 1  wherein said compound has the formula 
                 
 
     
     
       8. A method according to  claim 2  wherein said compound has the formula 
                 
 
     
     
       9. A method according to  claim 5  wherein
 R 2  is —H, CN, —CONRR, —CSNRR or —CONHR 9 ;  
 wherein R 1  and R 2  are not both —CN;  
 R is alkyl or —H;  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently lower alkyl, —H or halo;  
 R 9  is —CONH 2 , 
                 
 
  R 10  is lower alkyl;  
 R 11  is lower alkyl or halo; and  
 m is 2 to about 10.  
 
     
     
       10. A method according to  claim 6  wherein
 R 1  is —CN, —CONRR or —CSNRR;  
 R is alkyl or —H;  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently lower alkyl, —H or halo; and  
 R 10  is lower alkyl.  
 
     
     
       11. A method according to  claim 7  wherein
 R 1  is —CN, —CONRR or —CSNRR;  
 R 2  is —H, —CN, —CONRR, —CSNRR, —CONHR 9 ;  
 R is alkyl or —H;  
 R 4 , R 5 , R 6  and R 8  are each independently lower alkyl, —H or halo; and  
 R 10  is lower alkyl.  
 
     
     
       12. A method according to  claim 8  wherein
 R 1  is —CN, —CONRR or —CSNRR;  
 R is alkyl or —H;  
 R 4 , R 5 , R 6  and R 8  are each independently lower alkyl, —H or halo;  
 R 11  is lower alkyl or halo; and  
 m is 2 to about 6.  
 
     
     
       13. A method according to  claim 1  wherein said compound is α-cyano-β-(3,5-di-tert butylphenyl)propenethioamide. 
     
     
       14. A method according to  claim 1  wherein said cell proliferation condition comprises psoriasis. 
     
     
       15. A method according to  claim 1  wherein said cell proliferation condition comprises atherosclerosis. 
     
     
       16. A method according to  claim 14  wherein said compound is α-cyano-β-(3,5-di-tert-butylphenyl)propenethioamide. 
     
     
       17. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis and restenosis comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, selected from the group consisting of
 (A) a substituted styrene compound having the formula 
                 
 
  wherein:  
 R 1  and R 2  are each independently —CN or —CONH 2  or one of R 1  and R 2  may be —CSNH 2  or , when R 1  is CN, R 2  can also be the group —C(NH 2 )═C(CN) 2 , with the proviso that R 1  and R 2  are not both CN;  
 R 3  is —H, —CN 3  or —OH;  
 R 4 , R 5 , R 6  and R 7  are each independently alkyl of 1-5 carbons, —H, halo, or —NO 2 ; and  
 R 8  is H;  
 (B) an α-substituted benzylidene malononitrile compound having the formula 
                 
 
  wherein:  
 R 3  is —CH 3  or —OH;  
 R 4 , R 5 , R 6  and R 7  are each independently alkyl of 1-5 carbons, —H, halo, or —NO 2 ; and  
 R 8  is —H; or  
 (C) an α-unsubstituted benzylidene malononitrile compound having the formula 
                 
 
  wherein:  
 at least one of R 4 , R 5 , R 6  and R 7  is alkyl or 2-5 carbons;  
 the remainder of R 4 , R 5 , R 6  and R 7  are each independently alkyl of 1-5 carbons, H, halo or —NO 2 ; and  
 R 8  is —H;  
 or a pharmaceutically acceptable salt thereof.  
 
     
     
       18. A method according to  claim 17  wherein said disorder comprises psoriasis. 
     
     
       19. A method according to  claim 17  wherein said disorder comprises psoriasis and said compound comprises α-cyano-β-(3,5-di-tert-butylphenyl)propenethioamide. 
     
     
       20. A method according to  claim 1  wherein said compound has the formula 
                 
 
       wherein:
 R is alkyl or —H;  
 R 1  is —H, —CN, —OH or —CONRR;  
 R 3  is alkyl, —H, —CN or —OH;  
 R 4 , R 5 , R 6 , R 7  and R 8  are each independently alkyl, —H, —CN or halo.  
 
     
     
       21. A method according to  claim 17  wherein said compound has the formula 
                 
 
       wherein:
 R 1  is —CN or —CONH 2 ;  
 R 3  is —H, —CH 3  or —OH;  
 R 4 , R 5 , R 6  and R 7  are each independently alkyl of 2≧4 carbons, —H, halo or —NO 2 ; and  
 R 8  is —H.  
 
     
     
       22. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis, restenosis, and leukemia comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, comprising a substituted styrene compound having the formula 
                   
       
         wherein:  
         
           one of R 
           1  
           and R 
           2  
           is alkyl, —H, —CN, —OH, —COOR, —CONRR or —CSNRR;  
         
           the other of R   1    and R   2    is alkyl, —H, —CN, —OH, —COOR, —CONRR, —CSNRR, —CHO, —CONHR   9   , —CONHCH   2   CN, —CH═C ( CN ) 2   , —C ( NH   2 )═ C ( CN ) 2   , —NHCHO,                      
         
           wherein R 
           1  
           and R 
           2  
           are not both alkyl, —H, —CN or —OH;  
         
         
           R is alkyl or —H;  
         
           R   3    is alkyl, —H, —CN, —OH, —COOR, —CONRR, —CSNRR, —CH   2   CN or —CH═C ( CN ) CONH   2 ;  
           R   4   , R   5   , R   6   , R   7    and R   8    are each independently alkyl, —H, —CN, halo, —OR, —CHO, —COOH, —NRR, —NO   2   , —NHCOCH   3   , —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino;    
         
           R 
           3  
           and R 
           7  
           together may be —CH 
           2 
           CH 
           2 
           —, —CH 
           2 
           CH 
           2 
           CH 
           2 
           —or, starting R 
           3 
           , —CONH—;  
         
           R   9    is —NH   2   , —CONH   2 , 
                   
           R   10    is alkyl, halo, —OR, —COOR, or —NO   2 ;  
           R   11    is alkyl, —CN, halo, —OR, CHO, COOH, NRR, —NO   2   , —NHCOCH   3   , —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino;    
         
           R 
           12  
           is alkyl, —H, halo, —OR, or —COOR;  
         
         
           n is  0  or about  6 ; and  
         
         
           m is  2  to about  10 ;  
         
         
           provided that when each of R 
           4  
           and R 
           7  
           is OH, when each of R 
           3 
           , R 
           5 
           , R 
           6 
           , and R 
           8  
           is —H and when one of R 
           1  
           and R 
           2  
           is —CN, then other of R 
           1  
           and R 
           2  
           is not —CONH 
           2 
           ; and also  
         
           provided that when one of R   1    and R   2    is —CH═C ( CN ) 2   , at least one of R   3   , R   4   , R   5   , R   6   , R   7    and R   8    is not —H; and    
         
           provided that when said R 
           1  
           or R 
           2  
           is COOR or CONRR, the other of said R 
           1  
           or R 
           2  
           is not alkyl or cyano. 
         
       
     
     
       23. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis, restenosis, and leukemia comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, comprising a substituted benzylidene malononitrile compound having the formula 
                   
       
         wherein:  
           R   3    is alkyl, —CN, —OH, —COOR, —CONRR, —CSNRR, —CH   2   CN or —CH═C ( CN ) COHN   2 ;  
         
           R is alkyl or —H; and  
         
           R   4   , R   5   , R   6   , R   7    and R   8    are each independently alkyl, —H, —CN, halo, —OR, —CHO, —COOH, —NRR, —NO   2   , —NHCOCH   3   , —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino.   
       
     
     
       24. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis, restenosis, and leukemia comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, comprising unsubstituted benzylidene malononitrile compound having the formula 
                   
       
         wherein:  
           at least one of R   4   , R   5   , R   6   , R   7    and R   8    is C   2    to about C   6    alkyl, —CN, —CHO, —COOH, —NHR, —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino;    
           the remainder of R   4   , R   5   , R   6   , R   7    and R   8    are each independently alkyl, —H, —CN, halo, —OR, —CHO, —COOH, —NRR, —NO   2   , —NHCOCH   3   , —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino; and    
         
           R is alkyl or —H. 
         
       
     
     
       25. A method for inhibiting, in a patient, cell proliferation associated with a disorder selected from the group consisting of psoriasis, atherosclerosis, restenosis, and leukemia comprising administering to said patient an effective amount of a composition comprising, in admixture with a pharmaceutically acceptable carrier, a compound, or a pharmaceutically acceptable salt thereof, selected from the group consisting of a bicyclic benzylidene malononitrile compound having the formula 
                   
       
         wherein:  
         
           R 
           3  
           and R 
           7  
           together are —CH 
           2 
           CH 
           2 
           —, —CH 
           2 
           CH 
           2 
           CH 
           2 
           —or, starting from R 
           3 
           , —CONH—; and  
         
           R   4   , R   5   , R   6    and R   8    are each independently alkyl, —H, —CN, halo, —OR, —CHO, —COOH, —NRR, —NO   2   , —NHCOCH   3   , —SR, —CH═CHCOOH, —NHCO ( CH   2 ) 2   COOH or morpholino; and    
         
           R is alkyl or —H. 
         
       
     
     
       26. A method according to  claim 22  wherein said compound has the formula 
                   
       
         wherein  
         
           R 
           1  
           is —CN, —COOR, —CONRR or —CSNRR;  
         
         
           R 
           2  
           is —H, —CN, —COOR, —CONRR, —CSNRR, —CONHR 
           9  
           or  
           
             
             
                 
                 
             
           
         
         
           wherein R 
           1  
           and R 
           2  
           are not both —CN;  
         
         
           R is alkyl or —H;  
         
         
           R 
           3  
           is —H;  
         
         
           R 
           4 
           , R 
           5 
           , R 
           6 
           , R 
           7  
           and R 
           8  
           are each independently alkyl, —H, halo or —OR;  
         
         
           R 
           3  
           and R 
           7  
           together may be —CH 
           2 
           CH 
           2 
           —, —CH 
           2 
           CH 
           2 
           CH 
           2 
           —or, starting from R 
           3 
           , —CONH—; and  
         
           R   9    is —NH   2   , —CONH   2 , 
                   
           R   10    is alkyl, halo, —OH, —COOR, or —NO   2 ;  
         
           R 
           11  
           is alkyl, halo or —OR;  
         
         
           R 
           12  
           is alkyl or —H;  
         
         
           n is  0  to about  4 ; and  
         
         
           m is  2  to about  10 . 
         
       
     
     
       27. A method according to  claim 22  wherein said compound has the formula 
                   
       
         wherein:  
         
           at least one of R 
           4 
           , R 
           5 
           , R 
           6 
           , R 
           7  
           and R 
           8  
           is C 
           2  
           to C 
           6  
           alkyl; and  
         
         
           the remainder of R 
           4 
           , R 
           5 
           , R 
           6 
           , R 
           7  
           and R 
           8  
           are each independently alkyl, —H, halo or —OR; and  
         
         
           R is alkyl or —H. 
         
       
     
     
       28. A method according to  claim 22  wherein said compound has the formula 
                   
       
         wherein:  
         
           R 
           3  
           and R 
           7  
           together are —CH 
           2 
           CH 
           2 
           —, —CH 
           2 
           CH 
           2 
           C—H 
           2 
           —or, starting from R 
           3 
           , —CONH—; and  
         
         
           R 
           4 
           , R 
           5 
           , R 
           6 
           , and R 
           8  
           are each independently alkyl, —H, halo or —OR; and  
         
         
           R is alkyl or —H. 
         
       
     
     
       29. A method according to  claim 5 , wherein
   R   2    is —H, CN, —COOR, —CONRR, —CSNRR, —CONHR   9    or                          wherein R   1    and R   2    are not both —CN;        R is alkyl or —H;        R   4   , R   5   , R   6   , R   7    and R   8    are each independently lower alkyl, —H, —OH, lower alkoxy or halo;        R   9    is NH   2   , CONH   3 , 
                       R   10    is lower alkyl or —COOR;        R   11    is lower alkyl, —OH, lower alkoxy or halo; and        m is  2  to about  10 .     
     
     
       30. A method according to  claim 6  wherein
   R 1  is —CN, —COOR, —CONRR or CSNRR;                          R is alkyl or —H;        R   4   , R   5   , R   6   , R 7  and R   8    are each independently lower alkyl, —H, —OH, lower alkoxy or halo; and        R   10    is lower alkyl or —COOR.     
     
     
       31. A method according to  claim 7  wherein
   R 1  is —CN, —COOR, —CONRR or CSNRR;        R   2    is —H, —CN, —COOR, —CONRR, —CSNRR, —CONHR   9 ;      R is alkyl or —H;        R   4   , R   5   , R   6   , R 7  and R   8    are each independently lower alkyl, —H, —OH, lower alkoxy or halo; and        R   10    is lower alkyl or —COOR.     
     
     
       32. A method according to  claim 8  wherein
   R 1  is —CN, —COOR, —CONRR or CSNRR;        R is alkyl or —H;        R   4   , R   5   , R   6   , R 7  and R   8    are each independently lower alkyl, —H, —OH, lower alkoxy or halo; and        R   11    is lower alkyl, —OH, lower alkoxy or halo; and        m is  2  to about  6 .

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