US2004210051A1PendingUtilityA1

N-alkanoylphenylalanine derivatives

49
Priority: Aug 22, 1997Filed: Apr 21, 2004Published: Oct 21, 2004
Est. expiryAug 22, 2017(expired)· nominal 20-yr term from priority
C07C 255/57C07D 257/04C07D 217/26C07C 323/60C07C 275/60C07D 487/04C07C 237/24C07C 271/22C07C 2601/14C07D 261/18C07C 335/08C07D 213/89C07C 235/64C07C 317/44C07D 295/088C07D 401/06C07C 275/18C07C 275/24C07C 255/41C07D 277/14C07C 2601/08C07D 317/68C07D 233/32C07D 211/64C07D 317/30C07D 249/06C07C 233/87C07D 231/14C07C 275/30C07D 213/81C07C 235/40C07C 235/82
49
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Claims

Abstract

Compounds of the formula: are disclosed which have activity as inhibitors of binding between VCAM-1 and cells expressing VLA-4. Such compounds are useful for treating diseases whose symptoms and/or damage are related to the binding of VCAM-1 to cells expressing VLA-4.

Claims

exact text as granted — not AI-modified
1 . A compound of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 one of X and X′ is hydrogen, halogen, or lower alkyl, and the other is a group of the formula:  
                     
 wherein  
                     
 is a 5- or 6-membered heteroaromatic ring containing 1, 2 or 3 heteroatoms selected from N, O, and S; or  
                     
 is a 9- or 10-membered bicyclic heteroaromatic ring containing 1, 2, 3 or 4 heteroatoms selected from O, S, and N,  
 a is 0 or 1,  
 R 1  is hydrogen or lower alkyl,  
 R 15  is hydrogen, halogen, nitro, lower alkyl sulfonyl, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, carboxy, lower alkyl aminosulfonyl, perfluorolower alkyl, lower alkylthio, hydroxy lower alkyl, alkoxy lower alkyl, alkylthio lower alkyl, alkylsulfinyl lower alkyl, alkylsufonyl lower alkyl, lower alkylsulfinyl, lower alkanoyl, aroyl, aryl, aryloxy or a group of the formula R 17 —C≡C—,  
 and R 16  is hydrogen, halogen, nitro, cyano, lower alkyl, OH, perfluorolower alkyl, or lower alkylthio, and  
 R 30  is hydrogen or lower alkyl, or is absent; and  
 Y is a group of the formula:  
                     
 wherein:  
 R 22  and R 23  are independently aryl, heteroaryl or lower alkyl which is unsubstituted or substituted by one or more chloro, bromo, nitro, hydroxy, lower alkoxy, aryl, lower alkanoyl, aroyl or cyano,  
 R 24  is aryl, cyano, alkylsulfonyl or lower alkyl or alkenyl unsubstituted or substituted by an aryl or heteroaryl ring, and when R 22  is aryl and R 23  is aryl or lower alkyl, hydrogen, and the total number of carbon atoms in R 22 , R 23  and R 24  is from 6 to 14; or  
 Y is a 3-7 membered ring of the formula:  
                     
 wherein:  
 R 25  is lower alkyl, unsubstituted or fluorine substituted lower alkenyl, or a group of formula R 26 —(CH 2 ) e —,  
 R 26  is aryl, heteroaryl, azido, cyano, hydroxy, lower alkoxy, lower alkoxycarbonyl, lower alkanoyl, lower alkylthio , lower alkyl sulfonyl, lower alkyl sulfinyl, perfluoro lower alkanoyl, nitro, or R 26  is a group of formula —NR 28 R 29 , wherein:  
 R 28  is hydrogen or lower alkyl,  
 R 29  is hydrogen, lower alkyl, lower alkoxycarbonyl, lower alkoxycarbonylaminocarbonyl, lower alkanoyl, aroyl, heteroaroyl, perfluoro lower alkanoyl, lower alkyl sulfonyl, lower alkylaminocarbonyl, arylaminocarbonyl, heterocycloalkyl carbonyl, lower alkylaminothiocarbonyl, or  
 R 28  and R 29  taken together with the nitrogen atom to which they are attached form a 4, 5 or 6-membered saturated heterocyclic ring containing one or two heteroatoms with the second heteroatom being O, S, or N—R 27 ;  
 Q is —(CH 2 ) f O—, —(CH 2 ) f S—, —(CH 2 ) f —, or when f=0, a bond,  
 R 27  is hydrogen, lower alkyl, aryl, lower alkanoyl, aroyl, or lower alkoxycarbonyl;  
 the carbon atoms in said ring are unsubstituted or substituted by lower alkyl or halogen,  
 e is an integer from 0 to 4, and  
 f is an integer from 0 to 3; and  
 Z is hydrogen or lower alkyl;  
 and the pharmaceutically acceptable salts and esters thereof.  
 
     
     
         2 . The compound of  claim 1  wherein X′ is hydrogen.  
     
     
         3 . The compound of  claim 2  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein Q′ is unsubstituted or lower alkyl substituted —(CH 2 ) f —, f is 1, 2 or 3, and X and R 25  are as in  claim 1 .  
     
     
         4 . The compound of  claim 3  wherein f is 2 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R m1 , R m2  and R m3  are independently hydrogen or lower alkyl, and R 25  is lower alkyl, lower alkenyl which is unsubstituted or substituted by fluorine, or a group of the formula R 26 —(CH 2 ) e — wherein R 26  and e are as in  claim 1 .  
     
     
         5 . The compound of  claim 4  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R m1 , R m2  and R m3  and R 25  are as in  claim 4 .  
     
     
         6 . The compound of  claim 4  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         7 . The compound of  claim 6  wherein a is 0.  
     
     
         8 . The compound of  claim 4  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R m1 , R m2  and R m3  and R 25  are as in  claim 4 .  
     
     
         9 . The compound of  claim 8  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         10 . The compound of  claim 9  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         11 . The compound of  claim 10  wherein a is 0.  
     
     
         12 . The compound of  claim 11  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         13 . The compound of  claim 8  wherein R m1 , R m2  and R m3  are all hydrogen, and R 25  is lower alkyl or lower alkenyl which is unsubstituted or substituted by fluorine.  
     
     
         14 . The compound of  claim 4  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein X, R 26  and e are as in  claim 1 .  
     
     
         15 . The compound of  claim 14  wherein e is 0 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         16 . The compound of  claim 15  wherein R 26  is cyano or aryl.  
     
     
         17 . The compound of  claim 16  wherein R 26  is cyano or phenyl which is unsubsituted or mono-substituted by halogen, lower alkyl or lower alkoxy.  
     
     
         18 . The compound of  claim 17  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         19 . The compound of  claim 18  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 1  and a are as in  claim 1 .  
     
     
         20 . The compound of  claim 19  wherein a is 0.  
     
     
         21 . The compound of  claim 20  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         22 . The compound of  claim 17  wherein R 26  is phenyl which is unsubsituted or mono-substituted by halogen, lower alkyl or lower alkoxy.  
     
     
         23 . The compound of  claim 22  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         24 . The compound of  claim 23  wherein a is 0.  
     
     
         25 . The compound of  claim 24  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         26 . The compound of  claim 24  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         27 . The compound of  claim 24  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         28 . The compound of  claim 24  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         29 . The compound of  claim 24  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         30 . The compound of  claim 22  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 1  and a are as in  claim 1 .  
     
     
         31 . The compound of  claim 30  wherein a is 0.  
     
     
         32 . The compound of  claim 31  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         33 . The compound of  claim 14  wherein e is 1 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         34 . The compound of  claim 33  wherein R 26  is lower alkoxy or aryl.  
     
     
         35 . The compound of  claim 34  wherein R 26  is methoxy, or is phenyl which is unsubsituted, mono-substituted by halogen, lower alkoxy, cyano or tetrazolyl which tetrazolyl is unsubstituted or monosubstituted by methyl, or disubstituted by lower alkoxy.  
     
     
         36 . The compound of  claim 35  wherein R 26  is methoxy.  
     
     
         37 . The compound of  claim 35  wherein R 26  is phenyl which is mono- or di-substituted by lower alkoxy.  
     
     
         38 . The compound of  claim 37  wherein R 26  is phenyl which is mono-substituted by lower alkoxy.  
     
     
         39 . The compound of  claim 38  wherein R 26  is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         40 . The compound of  claim 39  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         41 . The compound of  claim 40  wherein a is 0.  
     
     
         42 . The compound of  claim 41  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         43 . The compound of  claim 35  wherein R 26  is unsubstituted phenyl.  
     
     
         44 . The compound of  claim 43  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         45 . The compound of  claim 44  wherein a is 0.  
     
     
         46 . The compound of  claim 45  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         47 . The compound of  claim 37  wherein R 26  is phenyl which is di-substituted by lower alkoxy.  
     
     
         48 . The compound of  claim 47  wherein R 26  is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         49 . The compound of  claim 35  wherein R 26  is phenyl monosubstituted by chloro, tetrazolyl, which is unsubstituted or mono-subsituted by methyl, or cyano.  
     
     
         50 . The compound of  claim 49  wherein R 26  is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         51 . The compound of  claim 33  wherein R 26  is tetrazolyl or cyano.  
     
     
         52 . The compound of  claim 14  wherein e is 2 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         53 . The compound of  claim 52  wherein R 26  is —NR 28 R 29  where R 28  and R 29  are as in  claim 1 .  
     
     
         54 . The compound of  claim 53  wherein R 28  and R 29  are independently hydrogen or lower alkyl.  
     
     
         55 . The compound of  claim 53  wherein R 28  is hydrogen and R 29  is lower alkoxycarbonyl, lower alkylsulfonyl, heterocycloalkyl, aroyl or heteroaroyl.  
     
     
         56 . The compound of  claim 53  wherein R 28  is lower alkyl and R 29  is lower akanoyl, lower alkoxycarbonyl or lower alkylaminocarbonyl.  
     
     
         57 . The compound of  claim 53  wherein R 28  and R 29  taken together with the nitrogen atom to which they are attached form a morpholinyl group.  
     
     
         58 . The compound of  claim 52  wherein R 26  is lower alkyl sulfonyl, lower alkyl thio, lower alkyl sulfinyl, lower alkylthio, azido, cyano, hydroxy, lower alkoxy, lower alkanoyl or lower alkanoylamino.  
     
     
         59 . The compound of  claim 14  wherein e is 3 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         60 . The compound of  claim 59  wherein R 26  is lower alkyl sulfonyl, lower alkyl sulfinyl, lower alkylthio, azido, cyano, hydroxy, lower alkoxy, lower alkanoyl or lower alkanoylamino.  
     
     
         61 . The compound of  claim 14  wherein e is 4 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         62 . The compound of  claim 61  wherein R 26  is lower alkyl sulfonyl, lower alkyl sulfinyl, lower alkylthio, azido, cyano, hydroxy, lower alkoxy, lower alkanoyl or lower alkanoylamino.  
     
     
         63 . The compound of  claim 62  wherein a is 0, R 1  is hydrogen and R 26  is lower alkyl sulfonyl.  
     
     
         64 . The compound of  claim 63  wherein Het is a 6-membered heteroaromatic ring of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         65 . The compound of  claim 64  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         66 . The compound of  claim 64  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         67 . The compound of  claim 64  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         68 . The compound of  claim 63  wherein Het is a 5-membered heteroaromatic ring of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         69 . The compound of  claim 68  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         70 . The compound of  claim 68  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         71 . The compound of  claim 68  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         72 . The compound of  claim 63  wherein Het is a 9-membered heteraromatic ring of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         73 . The compound of  claim 72  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         74 . The compound of  claim 3  wherein f is 1 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 25  is lower alkyl or a group of the formula R 26 —(CH 2 ) e — wherein R 26  and e are as in  claim 1 .  
     
     
         75 . The compound of  claim 74  wherein R 25  is a group of the formula R 26 —(CH 2 ) e —.  
     
     
         76 . The compound of  claim 75  wherein e is 1 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         77 . The compound of  claim 76  wherein R 26  is lower alkoxy or aryl.  
     
     
         78 . The compound of  claim 77  wherein R 26  is methoxy or phenyl which is unsubsituted, mono-substituted by halogen, lower alkoxy, cyano or tetrazolyl which tetrazolyl is unsubstituted or monosubstituted by methyl, or disubstituted by lower alkoxy.  
     
     
         79 . The compound of  claim 78  wherein R 26  is phenyl which is monosubstituted by tetrazolyl which terazolyl is monosubstituted by methyl.  
     
     
         80 . The compound of  claim 79  wherein R 26  is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         81 . The compound of  claim 3  wherein f is 3 and said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 25  and X are as in  claim 1 .  
     
     
         82 . The compound of  claim 81  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 25  and X are as in  claim 1 .  
     
     
         83 . The compound of  claim 82  wherein R 25  is lower alkyl.  
     
     
         84 . The compound of  claim 83  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         85 . The compound of  claim 84  wherein a is 0.  
     
     
         86 . The compound of  claim 85  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         87 . The compound of  claim 81  wherein said compound is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 25  and X are as in  claim 1 .  
     
     
         88 . The compound of  claim 87  wherein R 25  is lower alkyl.  
     
     
         89 . The compound of  claim 88  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         90 . The compound of  claim 89  wherein a is 0.  
     
     
         91 . The compound of  claim 90  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         92 . The compound of  claim 87  wherein R 25  is a group of the formula R 26 —(CH 2 ) e — wherein R 26  and e are as in  claim 1 .  
     
     
         93 . The compound of  claim 92  wherein e is 0 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         94 . The compound of  claim 93  wherein R 26  is lower alkoxy or aryl.  
     
     
         95 . The compound of  claim 94  wherein R 26  is methoxy, or is phenyl which is: 1) unsubstituted, 2) mono-substituted by halogen, lower alkoxy, cyano or tetrazolyl which tetrazolyl is unsubstituted or monosubstituted by methyl, or 3) disubstituted by lower alkoxy.  
     
     
         96 . The compound of  claim 95  wherein R 26  is phenyl which is unsubsituted or mono-substituted by lower alkoxy.  
     
     
         97 . The compound of  claim 96  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         98 . The compound of  claim 97  wherein a is 0.  
     
     
         99 . The compound of  claim 98  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         100 . The compound of  claim 98  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         101 . The compound of  claim 92  wherein e is 1 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         102 . The compound of  claim 101  wherein R 26  is lower alkoxy or aryl.  
     
     
         103 . The compound of  claim 102  wherein R 26  is methoxy, or is phenyl which is: 1) unsubstituted, 2) mono-substituted by halogen, lower alkoxy, cyano or tetrazolyl which tetrazolyl is unsubstituted or monosubstituted by methyl, or 3) disubstituted by lower alkoxy.  
     
     
         104 . The compound of  claim 103  wherein R 26  is phenyl which is unsubsituted or mono-substituted by lower alkoxy.  
     
     
         105 . The compound of  claim 1  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein X, R 22 , R 23  and R 24  are as in  claim 1 .  
     
     
         106 . The compound of  claim 105  wherein R 22  and R 23  are independently unsubstituted phenyl or lower alkyl, and R 24  is hydrogen or unsubstituted lower alkyl or alkenyl.  
     
     
         107 . The compound of  claim 106  wherein R 22 , R 23  and R 24  are lower alkyl.  
     
     
         108 . The compound of  claim 107  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         109 . The compound of  claim 108  wherein a is 0.  
     
     
         110 . The compound of  claim 108  wherein R 22  is methyl, R 23  is ethyl and R 24  is n-butyl.  
     
     
         111 . The compound of  claim 110  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         112 . The compound of  claim 106  wherein R 22  is unsubstituted phenyl, R 23  is lower alkyl and R 24  is hydrogen.  
     
     
         113 . The compound of  claim 112  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         114 . The compound of  claim 113  wherein a is 0.  
     
     
         115 . The compound of  claim 114  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         116 . The compound of  claim 114  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         117 . The compound of  claim 106  wherein R 22  and R 23  are unsubstituted phenyl and R 24  is hydrogen.  
     
     
         118 . The compound of  claim 117  wherein X is a group of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         119 . The compound of  claim 118  wherein a is 0.  
     
     
         120 . The compound of  claim 119  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         121 . The compound of  claim 1  which is an ester of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 31 , is lower alkyl; or  
 R 31  a group of formula:  
                     
  wherein: 
 R 32  is hydrogen or lower alkyl,  
 R 33  is hydrogen, lower alkyl, or aryl,  
 R 34  is hydrogen or lower alkyl,  
 h is an integer from 0 to 2,  
 g is an integer from 0 to 2, and  
 the sum of h and g is 1 to 3; or  
 
 R 31  is a group of formula:  
                     
  wherein: 
 R 32 , g, and h are as above for P-1,  
 T is O, S, —(CH 2 ) j —, a group of the formula N—R 35 , or when j=0, a bond,  
 R 35  is hydrogen, lower alkyl, lower alkanoyl, or lower alkoxycarbonyl, and  
 j is 0, 1 or 2  
 and wherein X, X′ Y and Z are as in  claim 1 .  
 
 
     
     
         122 . The compound of  claim 121  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein Q″ is unsubstituted or lower alkyl substituted —(CH 2 ) f —, f is 1, 2 or 3, and X and R 25  are as in  claim 1 .  
     
     
         123 . The compound of  claim 122  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein X, R 26  and e are as in  claim 1 .  
     
     
         124 . The compound of  claim 123  wherein e is 4 whereby said compound is of the formula:  
       
         
           
           
               
               
           
         
       
     
     
         125 . The compound of  claim 124  wherein R 26  is lower alkyl sulfonyl, lower alkyl thio, lower alkyl sulfinyl, lower alkylthio, azido, cyano, hydroxy, lower alkoxy, lower alkanoyl or lower alkanoylamino.  
     
     
         126 . The compound of  claim 125  wherein a is 0, R 1  is hydrogen, R 26  is lower alkyl sulfonyl or lower alkoxy and Het is pyridyl.  
     
     
         127 . The compound of  claim 126  wherein R 31  is ethyl, 2-(N,N-diethylamino)ethyl or 2-(4-morpholinyl)ethyl.  
     
     
         128 . The compound of  claim 127  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         129 . The compound of  claim 127  having the formula:  
       
         
           
           
               
               
           
         
       
     
     
         130 . The compound of  claim 1  wherein Z is lower alkyl.  
     
     
         131 . The compound of  claim 130  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein Q′″ is unsubstituted or lower alkyl substituted —(CH 2 ) f —, f is 1, 2 or 3, and X and R 25  are as in  claim 1 .  
     
     
         132 . The compound of  claim 131  having the formula:

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