US2012309774A1PendingUtilityA1

Selective antagonists of a2a adenosine receptors

53
Assignee: BEAUGLEHOLE ANTHONYPriority: Jul 17, 2006Filed: Aug 16, 2012Published: Dec 6, 2012
Est. expiryJul 17, 2026(~0 yrs left)· nominal 20-yr term from priority
A61P 35/00A61P 43/00A61P 25/08A61P 25/14A61P 25/00A61P 25/30A61P 25/16A61P 25/32A61P 25/34A61P 19/00A61P 21/00C07D 473/34
53
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Claims

Abstract

The present invention provides compounds of formulae Ia and Ib: wherein R 1-5 , Q, X, Y, Z, p, q, and r are as defined herein. The compounds are potent and selective antagonists of A 2A adenosine receptors (ARs). The invention further includes pharmaceutical compositions containing these compounds and methods of using the same.

Claims

exact text as granted — not AI-modified
1 - 17 . (canceled) 
     
     
         18 . A therapeutic method for preventing or treating a pathological condition or symptom in a mammal, wherein the activity of adenosine A2A receptors is implicated and antagonisim of its action is desired comprising administering to the mammal an effective amount of a compound of formula Ia or Ib or stereoisomer or a pharmaceutically acceptable salt thereof: 
       
         
           
           
               
               
           
         
         wherein: 
         the (CH 2 ) portions of (CH 2 ) n  and (CH 2 ) q  are independently substituted with 0-2 groups selected from OH, ═O, C 1-4  alkyl, C 3-6  cycloalkyl, and benzyl; 
         Q is O or S; 
         X is CH or N; 
         Y is selected from the group consisting of O, NY 1 , OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 , NY 1 CH 2 CH 2 OCH 2 , NY 1 CH 2 CH 2 OCH 2 CH 2 OCH 2 , and NY 1 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 ; 
         alternatively, Y is a bond; 
         Y 1  is selected from the group consisting of H, C 1-4  alkyl, benzyl, C 3-6  cycloalkyl, and (C 3-6  cycloalkyl)C 1-4  alkylene; 
         Z is selected from the group consisting of aryl and heteroaryl, wherein Z is attached via a carbon atom and is substituted with 1-4 Z 1  groups; 
         Z 1  is independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R a  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —; 
         R 1  is independently selected from the group consisting of II, C 1 - 8  alkyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, (aryl)(aryl)-C 1 - 8  alkylene, (heteroaryl)(heteroaryl)-C 1 - 8  alkylene, and (aryl)(heteroaryl)C 1-8  alkylene, wherein the alkyl and cycloalkyl optionally may be interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —, and the groups of R 1  are substituted with 0-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R 2  is selected from the group consisting of H, C 1-6  alkyl, OR a , N(R a ) 2 , C 3-8  cycloalkyl, aryl, heterocycle, and heteroaryl, wherein the alkyl, cycloalkyl, aryl, heterocycle, and heteroaryl optionally are substituted with 1-2 groups independently selected from the group consisting of F, Cl, I, Br, CH 3 , CF 3 , and CH 3 O; 
         R 3  is a bond or is C 1-8  alkylene, wherein the alkylene group optionally is interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—; 
         R 3  is unsubstituted or is substituted with 1-2 groups selected from the group consisting of F, Cl, Br, I, —OR d , —SR d , —N(R d ) 2 , C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, aryl, (aryl)C 1 - 4  alkylene, heteroaryl, and (heteroaryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —; and —NR c —; 
         R 4  is selected from the group consisting of C 1-8  alkyl, C 2-8  alkenyl, C 2-8  alkynyl, C 3 - 12  cycloalkyl, (C 3-12  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, CF 3 , —CO 2 R b , R b C(O)—, (R b ) 2 NC(O)—, R b OC(S)—, R b C(S)—, and R b S(═O)—, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—, and the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl are unsubstituted or are substituted with 1-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , OCF 3 , and —OS(O 2 )R a ; 
         alternatively, when R 3  is present, R 4  is additionally selected from the group consisting of H, F, Cl, Br, I, N(R b ) 2 , OR b , SR b , —CN, NO 2 , CF 3 O, R b C(O)O—, —OCO 2 R b , (R b ) 2 NC(O)O—, R b OC(O)NR b —, R b C(O)NR b —, (R b ) 2 NC(O)NR b —, and (R b ) 2 NC(S)NR b —; 
         provided that when R 2  is H and R 3  is a bond, then R 4  is other than 
       
       
         
           
           
               
               
           
         
       
       wherein:
  (a) “*” is the point of attachment; 
  (b) R z  is —CH 2 OR, —CO 2 R, —OC(O)R, —CH 2 OC(O)R, —CH 2 SR, —C(S)OR, —CH 2 OC(S)R, —CH 2 NRR, —C(S)NRR, and, —C(O)NRR; and, 
  (c) R is H or a substituent; 
 R b  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH— and wherein the alkyl, cycloalkyl, aryl, and heteroaryl are substituted with 0-4 substituents selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
 R c  is independently selected from the group consisting of H, C 1 - 6  alkyl, and benzyl; 
 R d  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, phenyl, and benzyl; 
 R 5  is independently selected from the group consisting of H, F, Cl, Br, I, —OR c , —N(R c ) 2 , C 1 - 6  alkyl, C 3-6  cycloalkyl, aryl, and (aryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —, and —NR—; 
 R 6  is selected from the group consisting of CH 2 CH 2 , CH═CH, and C≡C; 
 a is independently selected from the group consisting of 0, 1, and 2; 
 n is independently selected from the group consisting of 0, 1, and 2; 
 p is independently selected from the group consisting of 0, 1, and 2; 
 q is independently selected from the group consisting of 0, 1, and 2; and, 
 r is independently selected from the group consisting of 0, 1, and 2. 
 
     
     
         19 . A method for treating a movement disorder comprising administering to a subject suffering from a movement disorder with unwanted or excessive activity of the adenosine A2A receptor, a therapeutically effective amount of a compound of formula Ia or Ib or stereoisomer or a pharmaceutically acceptable salt thereof: 
       
         
           
           
               
               
           
         
         wherein: 
         the (CH 2 ) portions of (CH 2 ) n  and (CH 2 ) q  are independently substituted with 0-2 groups selected from OH, ═O, C 1-4  alkyl, C 3-6  cycloalkyl, and benzyl; 
         Q is O or S; 
         X is CH or N; 
         Y is selected from the group consisting of O, NY 1 , OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 , NY  I CH 2 CH 2 OCH 2 , NY 1 CH 2 CH 2 OCH 2 CH 2 OCH 2 , and NY 1 CH 2 C H 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2  ; 
         alternatively, Y is a bond; 
         Y 1  is selected from the group consisting of H, C 1-4  alkyl, benzyl, C 3-6  cycloalkyl, and (C 3-6  cycloalkyl)C 1-4  alkylene; 
         Z is selected from the group consisting of aryl and heteroaryl, wherein Z is attached via a carbon atom and is substituted with 1-4 Z 1  groups; 
         Z 1  is independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R a  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —; 
         R 1  is independently selected from the group consisting of H, C 1 - 8  alkyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, (aryl)(aryl)-C 1 - 8  alkylene, (heteroaryl)(heteroaryl)-C 1 - 8  alkylene, and (aryl)(heteroaryl)C 1-8  alkylene, wherein the alkyl and cycloalkyl optionally may be interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —, and the groups of R 1  are substituted with 0-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R 2  is selected from the group consisting of H, C 1-6  alkyl, OR a , N(R a ) 2 , C 3-8  cycloalkyl, aryl, heterocycle, and heteroaryl, wherein the alkyl, cycloalkyl, aryl, heterocycle, and heteroaryl optionally are substituted with 1-2 groups independently selected from the group consisting of F, Cl, I, Br, CH 3 , CF 3 , and CH 3 O; 
         R 3  is a bond or is C 1-8  alkylene, wherein the alkylene group optionally is interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—; 
         R 3  is unsubstituted or is substituted with 1-2 groups selected from the group consisting of F, Cl, Br, I, —OR d , —SR d , —N(R d ) 2 , C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, aryl, (aryl)C 1 - 4  alkylene, heteroaryl, and (heteroaryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —, and —NR c —; 
         R 4  is selected from the group consisting of C 1-8  alkyl, C 2-8  alkenyl, C 2-8  alkynyl, C 3 - 12  cycloalkyl, (C 3-12  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, CF 3 , —CO 2 R b , R b C(O)—, (R b ) 2 NC(O)—, R b OC(S)—, R b C(S)—, and R b S(═O)—, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—, and the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl are usubstituted or are substituted with 1-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , OCF 3 , and —OS(O 2 )R a ; 
         alternatively, when R 3  is present, R 4  is additionally selected from the group consisting of H, F, Cl, Br, I, N(R b ) 2 , OR b , SR b , —CN, NO 2 , CF 3 O, R b C(O)O—, —OCO 2 R b , (R b ) 2 NC(O)O—, R b OC(O)NR b —, R b C(O)NR b —, (R b ) 2 NC(O)NR 6 —, and (R b ) 2 NC(S)NR b —; 
         provided that when R 2  is H and R 3  is a bond, then R 4  is other than 
       
       
         
           
           
               
               
           
         
       
       wherein:
  (a) “*” is the point of attachment; 
  (b) R z  is —CH 2 OR, —CO 2 R, —OC(O)R, —CH 2 OC(O)R, —CH 2 SR, —C(S)OR, —CH 2 OC(S)R, —CH 2 NRR, —C(S)NRR, and, —C(O)NRR; and, 
  (c) R is H or a substituent; 
 R b  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH— and wherein the alkyl, cycloalkyl, aryl, and heteroaryl are substituted with 0-4 substituents selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
 R c  is independently selected from the group consisting of H, C 1 - 6  alkyl, and benzyl; 
 R d  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, phenyl, and benzyl; 
 R 5  is independently selected from the group consisting of H, F, Cl, Br, I, —OR c , —N(R c ) 2 , C 1 - 6  alkyl, C 3-6  cycloalkyl, aryl, and (aryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —, and —NR b —; 
 R 6  is selected from the group consisting of CH 2 CH 2 , CH═CH, and C≡C; 
 a is independently selected from the group consisting of 0, 1, and 2; 
 n is independently selected from the group consisting of 0, 1, and 2; 
 p is independently selected from the group consisting of 0, 1, and 2; 
 q is independently selected from the group consisting of 0, 1, and 2; and, 
 r is independently selected from the group consisting of 0, 1, and 2. 
 
     
     
         20 . A method according to  claim 19 , wherein said movement disorder is selected from: Huntington's disease, catalepsy, Parkinson's disease, narcolepsy, progressive supernuclear palsy, multiple system atrophy, corticobasal degeneration, Wilson's disease, Hallervorden-Spatz disease, progressive pallidal atrophy, Dopa-responsive dystonia-Parkinsonism, and spasticity. 
     
     
         21 . A method of treating cancer and/or an addictive disorder (e.g., smoking, alcohol, drugs), comprising administering to a subject afflicted with cancer or an addictive disorder a therapeutically amount of a compound of formula Ia or Ib or stereoisomer or a pharmaceutically acceptable salt thereof: 
       
         
           
           
               
               
           
         
         wherein: 
         the (CH 2 ) portions of (CH 2 ) n  and (CH 2 ) q  are independently substituted with 0-2 groups selected from OH, ═O, C 1-4  alkyl, C 3-6  cycloalkyl, and benzyl; 
         Q is O or S; 
         X is CH or N; 
         Y is selected from the group consisting of O, NY 1 , OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 , OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 , NY  1 CH 2 CH 2 OCH 2 , NY 1 CH 2 CH 2 OCH 2 CH 2 OCH 2 , and NY 1 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 ; 
         alternatively, Y is a bond; 
         Y 1  is selected from the group consisting of H, C 1-4  alkyl, benzyl, C 3-6  cycloalkyl, and (C 3-6  cycloalkyl)C 1-4  alkylene; 
         Z is selected from the group consisting of aryl and heteroaryl, wherein Z is attached via a carbon atom and is substituted with 1-4 Z 1  groups; 
         Z 1  is independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R a  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —; 
         R 1  is independently selected from the group consisting of H, C 1 - 8  alkyl, C 3 - 8  cycloalkyl, (C 3 -8 cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, (aryl)(aryl)-C 1 - 8  alkylene, (heteroaryl)(heteroaryl)-C 1 - 8  alkylene, and (aryl)(heteroaryl)C 1-8  alkylene, wherein the alkyl and cycloalkyl optionally may be interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NR c —, and the groups of R 1  are substituted with 0-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
         R 2  is selected from the group consisting of H, C 1-6  alkyl, OR a , N(R a ) 2 , C 3-8  cycloalkyl, aryl, heterocycle, and heteroaryl, wherein the alkyl, cycloalkyl, aryl, heterocycle, and heteroaryl optionally are substituted with 1-2 groups independently selected from the group consisting of F, Cl, I, Br, CH 3 , CF 3 , and CH 3 O; 
         R 3  is a bond or is C 1-8  alkylene, wherein the alkylene group optionally is interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—; 
         R 3  is unsubstituted or is substituted with 1-2 groups selected from the group consisting of F, Cl, Br, I, —OR d , —SR d , —N(R d ) 2 , C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, aryl, (aryl)C 1 - 4  alkylene, heteroaryl, and (heteroaryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —, and —NR c —; 
         R 4  is selected from the group consisting of C 1-8  alkyl, C 2-8  alkenyl, C 2-8  alkynyl, C 3 - 12  cycloalkyl, (C 3-12  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, (heteroaryl)C 1 - 8  alkylene, CF 3 , —CO 2 R b , R b C(O)—, (R b ) 2 NC(O)—, R b OC(S)—, R b C(S)—, and R b S(═O)—, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH—, and the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heteroaryl are usubstituted or are substituted with 1-4 groups independently selected from the group consisting of F, Cl, Br, I, C 1 -6 alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , OCF 3 , and —OS(O 2 )R a ; 
         alternatively, when R 3  is present, R 4  is additionally selected from the group consisting of H, F, Cl, Br, I, N(R b ) 2 , OR b , SR b , —CN, NO 2 , CF 3 O, R b C(O)O—, —OCO 2 R b , (R b ) 2 NC(O)O—, R b OC(O)NR b —, R b C(O)NR b —, (R b ) 2 NC(O)NR b —, and (R b ) 2 NC(S)NR b —; 
         provided that when R 2  is H and R 3  is a bond, then R 4  is other than 
       
       
         
           
           
               
               
           
         
       
       wherein:
  (a) “*” is the point of attachment; 
  (b) R z  is —CH 2 OR, —CO 2 R, —OC(O)R, —CH 2 OC(O)R, —CH 2 SR, —C(S)OR, —CH 2 OC(S)R, —CH 2 NRR, —C(S)NRR, and, —C(O)NRR; and, 
  (c) R is H or a substituent; 
 R b  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3 - 8  cycloalkyl, (C 3 - 8  cycloalkyl)C 1 - 8  alkylene, aryl, (aryl)C 1 - 8  alkylene, heteroaryl, and (heteroaryl)C 1 - 8  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted with 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 — and —NH— and wherein the alkyl, cycloalkyl, aryl, and heteroaryl are substituted with 0-4 substituents selected from the group consisting of F, Cl, Br, I, C 1 - 6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, —(CH 2 ) a OR a , —(CH 2 ) a NR a R a , —(CH 2 ) a NHOH, —(CH 2 ) a NR a NR a R a , —(CH 2 ) a NO 2 , —(CH 2 ) a CN, —(CH 2 ) a CO 2 R a , —(CH 2 ) a C(O)R a , —(CH 2 ) a OC(O)R a , —(CH 2 ) a CONR a R a , CF 3 , and OCF 3 ; 
 R c  is independently selected from the group consisting of H, C 1 - 6  alkyl, and benzyl; 
 R d  is independently selected from the group consisting of H, C 1 - 6  alkyl, C 3-6  cycloalkyl, (C 3-6  cycloalkyl)C 1-4  alkylene, phenyl, and benzyl; 
 R 5  is independently selected from the group consisting of H, F, Cl, Br, I, —OR c , —N(R c ) 2 , C 1 - 6  alkyl, C 3-6  cycloalkyl, aryl, and (aryl)C 1 - 4  alkylene, wherein the alkyl and cycloalkyl optionally are interrupted by 1-2 heteroatoms selected from the group consisting of —O—, —S(O) 0-2 —, and —NR b —; 
 R 6  is selected from the group consisting of CH 2 CH 2 , CH═CH, and C≡C; 
 a is independently selected from the group consisting of 0, 1, and 2; 
 n is independently selected from the group consisting of 0, 1, and 2; 
 p is independently selected from the group consisting of 0, 1, and 2; 
 q is independently selected from the group consisting of 0, 1, and 2; and, 
 r is independently selected from the group consisting of 0, 1, and 2.

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