P
USRE37686EExpiredUtilityPatentIndex 63

Azahydroxybenzotriazoles and derivatives thereof for peptide coupling reactions

Assignee: RES CORP TECHNOLOGIES INCPriority: Sep 28, 1992Filed: Dec 3, 1998Granted: Apr 30, 2002
Est. expirySep 28, 2012(expired)· nominal 20-yr term from priority
Inventors:CARPINO LOUIS A
C07K 1/082C07K 1/084C07K 1/10C07F 9/6561C07D 513/04C07D 495/04C07D 491/04C07D 471/04
63
PatentIndex Score
3
Cited by
36
References
136
Claims

Abstract

This invention relates to a process for forming an amide or an ester from a reaction between an amine or an alcohol, respectively and an acylating derivative of a carboxylic acid, in the presence of an effective amount of a compound having the formula: and N-oxides thereof and salts thereof.

Claims

exact text as granted — not AI-modified
What is claimed:  
     
       1. A compound of the formula:                    
       or N-oxides thereof or salts thereof wherein 
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15  or N;  
       G is CR 18  or N;  
       provided that one and only one of A, E, D or G is N; 
       R 15 , R 16 , R 17  and R 18  are independently hydrogen, lower alkyl or an electron donating group;  
       X is CR 7  or N;  
       Y is N or CR 5 ;  
       R 7  and R 5  are independently hydrogen or lower alkyl;  
       R 3  is SO 2 R 14 , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group of the formula P⊕ ( NR   12   R   13 ) 3 , or AA 1 -BLK 1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms;   
       R 14  is lower alkyl, aryl or aryl lower alkyl; BLK 1  is an amino acid protecting group; and AA 1  is an amino acid or peptide less a hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       2. The compound according to  claim 1  wherein A or G is N. 
     
     
       3. The compound according to  claim 1  wherein Y is CH or N and X is CH or N. 
     
     
       4. The compound according to  claim 1  wherein the electron donating group is amino, lower alkylamino, diloweralkylamino, hydroxy, lower alkoxy, lower aralkoxy, halo, aryl, mercapto, or lower alkylthio. 
     
     
       5. The compound according to  claim 4  wherein the electron donating group is lower dialkylamino or lower alkoxy. 
     
     
       6. The compound according to  claim 1  having the formula                    
       in which Y is N or CH and 
       X is N or CH.  
     
     
       7. The compound according to  claim 6  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkylcarbonyl, aryl carbonyl, or aryl lower alkyl carbonyl. 
     
     
       8. The compound according to  claim 6  wherein R 3  is AA 1 -BLK 1 . 
     
     
       9. The compound according to  claim 6  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       10. The compound according to claim  9   6 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10  and R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached from a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or  R 12  and R 13  taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       11. The compound according to  claim 10  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl, hydrogen or lower alkoxy lower alkyl. 
     
     
       12. The compound according to  claim 11  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl. 
     
     
       13. The compound according to  claim 12  wherein R 10 , R 11 ,  R 12  and R 13  are methyl. 
     
     
       14. The compound according to  claim 10  wherein R 3  is                    
       and m is 0 or 1. 
     
     
       15. The compound according to  claim 14  wherein R 11  and R 12  are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or CH 2 —CH 2 O—CH 2 —CH 3 . 
     
     
       16. The compound according to  claim 6  wherein R 3  is                    
       wherein U is N-ALK, CH 2  or O, and ALK is lower alkyl or hydrogen. 
     
     
       17. The compound according to  claim 16  wherein U is CH 2 . 
     
     
       18. The compound according to  claim 6  wherein the compound has the formula:                    
     
     
       19. The compound according to  claim 18  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkylcarbonyl, aryl carbonyl, or aryl lower alkyl carbonyl. 
     
     
       20. The compound according to  claim 18  wherein R 3  is AA 1 -BLK 1 . 
     
     
       21. The compound according to  claim 18  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       22. The compound according to claim  21   18 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10 , R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or  R 12  and R 13  taken together with the nitrogen atoms  to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       23. The compound according to  claim 22  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl, hydrogen or lower alkoxy lower alkyl. 
     
     
       24. The compound according to  claim 23  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl. 
     
     
       25. The compound according to  claim 24  wherein R 10 , R 11 ,  R 12  and R 13  are methyl. 
     
     
       26. The compound according to  claim 22  wherein R 3  is                    
       and m is 0 or 1. 
     
     
       27. The compound according to  claim 26  wherein R 11  and R 12  are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or CH 2 —CH 2 O—CH 2 —CH 3 . 
     
     
       28. The compound according to  claim 18  wherein R 3  is                    
       wherein U is N-ALK, CH 2  or O, and ALK is lower alkyl or hydrogen. 
     
     
       29. The compound according to  claim 28  wherein U is CH 2 . 
     
     
       30. A compound of the formula:                    
       or N-oxides thereof or salts thereof wherein 
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15  or N;  
       G is CR 18  or N;  
       and at least two of A, E, D and G are N; 
       R 15 , R 16 , R 17  and R 18  are independently hydrogen, lower alkyl or an electron donating group;  
       R 3  is hydrogen lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, SO 2 R 14 , a positively charged electron withdrawing group of the formula P⊕ ( NR   12   R   13 ) 3 , or AA 1 -BLK 1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms,   
       R 14  is lower alkyl, aryl, or aryl lower alkyl;  
       BLK 1  is an amino acid protecting group,  ; and  
       AA 1  is an amino acid or peptide less a hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       31. The compound of  claim 30  wherein two of A, D, E and G are N. 
     
     
       32. The compound of  claim 30  wherein the electron donating group is amino, lower alkylamino, diloweralkylamino, hydroxy, lower alkoxy, lower aralkoxy, halo, aryl, mercapto, or lower alkylthio. 
     
     
       33. The compound of  claim 32  wherein the electron donating group is lower dialkylamino or lower alkoxy. 
     
     
       34. The compound of  claim 30  wherein R 3  is hydrogen. 
     
     
       35. The compound of  claim 30  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkylcarbonyl, aryl carbonyl, or aryl lower alkyl carbonyl. 
     
     
       36. The compound of  claim 30  wherein R 3  is BLK 1 -AA 1 . 
     
     
       37. The compound of  claim 30  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       38. The compound of claim  37   30 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10  and R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or  R 12  and R 13  taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       39. The compound according to  claim 38  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl, hydrogen or lower alkoxy lower alkyl. 
     
     
       40. The compound of  claim 38  wherein R 3  is                    
       and m is 0 or 1. 
     
     
       41. The compound according to  claim 30  wherein R 3  is                    
       wherein U is N-ALK, CH 2  or O, and ALK is lower alkyl or hydrogen. 
     
     
       42. A compound of the formula:                    
       or N-oxides thereof or salts thereof; wherein 
       X is CR 7  or N;  
       Y is CR 5  or N; with the proviso that X and Y cannot both represent N simultaneously;  
       R 5  and R 7  are independently hydrogen or lower alkyl;  
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15  or N;  
       G is CR 18  or N;  
       with the further proviso that one and only one of A, E, D and G is N; 
       R 15 , R 16 , R 17  and R 18  are independently hydrogen, lower alkyl or an electron donating group;  
       R 3  is hydrogen, SO 2 R 14 , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group of the formula P ⊕  ( NR   12   R   13 ) 3 , or AA 1 -BLK 1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms;   
       R 14  is lower alkyl, aryl or aryl lower alkyl;  
       BLK 1  is an amino acid protecting group; and  
       AA 1  is an amino acid or peptide less an hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       43. The compound according to  claim 42  wherein R 3  is hydrogen. 
     
     
       44. The compound according to  claim 42  having the formula:                    
     
     
       45. The compound according to  claim 44  wherein Y is CR 5  and X is N. 
     
     
       46. The compound according to  claim 45  wherein Y is CH. 
     
     
       47. The compound according to  claim 44  wherein X is CR 7  and Y is N. 
     
     
       48. The compound according to  claim 47  wherein X is CH. 
     
     
       49. The compound according to  claim 44  wherein X is CR 7  and Y is CR 5 . 
     
     
       50. The compound according to  claim 49  wherein X and Y are both CH. 
     
     
       51. A compound of the formula:                    
       wherein 
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15 ;  
       G is CR 18 ;  
       provided that one and only one of D and E is N; 
       R 15 , R 16 , R 17  and R 18  are independently hydrogen, lower alkyl or an electron donating group,  
       R 3  is hydrogen, SO 2 R 14 , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group of the formula P ⊕  ( NR   12   R   13 ) 3 , or AA 1 -BLK 1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms;   
       R 14  is lower alkyl, aryl or aryl lower alkyl;  
       BLK 1  is an amino acid protecting group; and 
       AA 1  is an amino acid or peptide less ana hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       52. The compound according to  claim 51  wherein D is N. 
     
     
       53. The compound according to  claim 51  wherein E is N. 
     
     
       54. The compound according to  claim 51  wherein D is N and A and G are CH. 
     
     
       55. The compound according to  claim 54  wherein R 3  is hydrogen. 
     
     
       56. The compound according to  claim 51  wherein E is N and A and G are CH. 
     
     
       57. The compound according to  claim 56  wherein R 3  is hydrogen. 
     
     
       58. A compound of the formula:                    
       or N-oxides thereof or salts thereof wherein 
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15  or N;  
       G is CR 18  or N;  
       provided that one and only one of D, E, A, and G is N; 
       at least one of R 15 , R 16 , R 17  and R 18  is an electron donating group, and the remainder is independently hydrogen, lower alkyl or an electron donating group;  
       X is CR 7  or N;  
       Y is N or CR 5 ;  
       R 7  and R 5  are independently hydrogen or lower alkyl;  
       R 3  is hydrogen, SO 2 R 14 , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group of the formula: P ⊕  ( NR   12   R   13 ) 3 , or AA 1 -BLK 1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms;   
       R 14  is lower alkyl, aryl or aryl lower alkyl;  
       BLK 1  is an amino acid protecting group and  
       AA 1  is an amino acid or peptide less a hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       59. The compund  compound according to  claim 58  wherein R 3  is hydrogen. 
     
     
       60. The compound according to  claim 58  wherein R 3  is AA 1 -BLK 1 . 
     
     
       61. The compound according to  claim 58  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       62. The compound according to  claim 58  wherein A or G is N. 
     
     
       63. The compound according to  claim 58  wherein Y is CH or N and X is CH or N. 
     
     
       64. The compound according to  claim 58  wherein the electron donating group is diloweralkylamino, lower alkoxy, lower aralkoxy, halo, aryl or lower alkylthio. 
     
     
       65. The compound according to  claim 64  wherein the electron donating group is lower dialkylamino or lower alkoxy. 
     
     
       66. The compound according to  claim 58  having the formula:                    
       wherein R 15  is lower alkyl or an electron donating group, and R 17  is lower alkyl, hydrogen or an electron donating group. 
     
     
       67. The compound according to  claim 66  wherein R 3  is hydrogen. 
     
     
       68. The compound according to  claim 66  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkyl carbonyl, aryl carbonyl or aryl lower alkyl carbonyl. 
     
     
       69. The compound according to  claim 66  wherein R 3  is AA 1 -BLK 1 . 
     
     
       70. The compound according to  claim 66  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       71. The compound according to claim  70   66 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10  and R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or  R 12  and R 13  taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       72. The compound according to  claim 71  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl, hydrogen or lower alkoxy lower alkyl. 
     
     
       73. The compound according to  claim 72  wherein R 10 , R 11 ,  R 12  and R 13  are independently lower alkyl. 
     
     
       74. The compound according to  claim 73  wherein R 10 , R 11 ,  R 12  and R 13  are methyl. 
     
     
       75. The compound according to  claim 71  wherein R 3  is                    
       wherein m is 0 or 1. 
     
     
       76. The compound according to  claim 70  wherein R 3  is                    
       wherein U is N-ALK, CH 2  or O, and ALK is lower alkyl or hydrogen. 
     
     
       77. The compound according to  claim 66  wherein R 15  is an electron donating group and R 17  is hydrogen or an electron donating group. 
     
     
       78. The compound according to  claim 77  wherein the electron donating group is diloweralkylamino or lower alkoxy. 
     
     
       79. An N-oxide of a compound of the formula:                    
       or a salt thereof, wherein 
       D is CR 16  or N;  
       E is CR 17  or N;  
       A is CR 15  or N;  
       G is CR 18  or N;  
       provided that one and only one of A, E, D or G is N; 
       R 15 , R 16 , R 17  and R 18  are independently hydrogen, lower alkyl and  or electron donating group, ; 
       X is CR 7  or N;  
       Y is CR 5  or N;  
       R 7  and R 5  are independently hydrogen or lower alkyl;  
       R 3  is hydrogen, SO 2 R 14 , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group of the formula P ⊕  ( NR   12   R   13 ) 3 , or BLK 1 -AA 1 AA 1 - BLK   1 ;  
       R 12    and R   13    are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms;   
       R 14  is lower alkyl, aryl or aryl lower alkyl;  
       BLK 1  is an amino acid protecting group; and  
       AA 1  is an amino acid or peptide less a hydrogen on the N-terminus and an OH on the C-terminus.  
     
     
       80. The compound according to  claim 79  wherein R 3  is hydrogen. 
     
     
       81. The compound according to  claim 79  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkyl carbonyl, aryl carbonyl, or lower alkyl carbonyl. 
     
     
       82. The compound according to  claim 79  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       83. The compound according to claim  82   79 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently halogen,  hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10  and R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 1 R 12  and R 13  taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       84. The compound according to  claim 79  wherein A or G is N. 
     
     
       85. The compound according to  claim 79  wherein Y is CH or N and X is CH or N. 
     
     
       86. The compound according to  claim 79  having the formula:                    
     
     
       87. The compound according to  claim 86  wherein R 3  is hydrogen. 
     
     
       88. The compound according to  claim 86  wherein R 3  is OSO 2 R 14 SO 2   R   14 , lower alkyl carbonyl, aryl carbonyl, or lower alkyl carbonyl. 
     
     
       89. The compound according to  claim 86  wherein R 3  is a positively charged electron withdrawing group. 
     
     
       90. The compound according to claim  89   86 wherein R 3  is                    
       wherein R 10 , R 11 ,  R 12  and R 13  are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or 
       R 10  and R 11  taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or R 10  and R 12  taken together with the atoms to which they are attached form a heterocyclic ring containing up to 6 ring atoms and up to a total of 5 ring carbon atoms or  R 12  and R 13  taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring containing up to a total of 5 ring carbon atoms.  
     
     
       91. The compound according to  claim 1  of the formula:                    
       wherein R 3  is                    
       wherein U is CH 2 , O or N-ALK and ALK is H or lower alkyl. 
     
     
       92. The compound according to  claim 1  of the formula:                  
                   
       wherein U is CH 2 , O or N-ALK is H or lower alkyl.  Ar is aryl. 
     
     
       93. The compound according to  claim 91  wherein U is CH 2 . 
     
     
       94. A compound prepared from the reaction of R 3   L with                      
       
         under substitution reaction conditions wherein  
       
       
         D is CR 
         16  
         or N;  
       
       
         E is CR 
         17  
         or N;  
       
       
         A is CR 
         15  
         or N;  
       
       
         G is CR 
         18  
         or N;  
       
       
         provided that one and only one of A, E, D or G is N;  
       
       
         R 
         15 
         , R 
         16 
         , R 
         17  
         and R 
         18  
         are independently hydrogen, lower alkyl or an electron donating group;  
       
       
         X is CR 
         7  
         or N;  
       
         Y is N or CR   5 ;  
       
         R 
         7  
         and R 
         5  
         are independently hydrogen or lower alkyl;  
       
         R   3    is SO   2   R   14   , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group or AA   1 - BLK   1 ;  
       
         R 
         14  
         is lower alkyl, aryl or aryl lower alkyl;  
       
       
         L is a leaving group;  
       
       
         BLK 
         1  
         is an amino acid protecting group; and  
       
         AA   1    is an amino acid or peptide less a hydrogen on the N - terminus and an OH on the C - terminus.   
     
     
       95. The compound according to  claim 94  wherein A or G is N. 
     
     
       96. The compound according to  claim 94  wherein Y is CH or N and X is CH or N. 
     
     
       97. The compound according to  claim 94  wherein R 3    is a positively charged electron withdrawing group.   
     
     
       98. The compound according to  claim 97  wherein R 3    is                      
       
         wherein  
       
       
         R 
         10 
         , R 
         11 
         , R 
         12  
         and R 
         13  
         are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or  
       
         R   10    and R   11    taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms or R   10    and R   12    taken together with the atoms to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms, or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms.   
     
     
       99. The compound according to  claim 98  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl, hydrogen or lower alkoxy lower alkyl.   
     
     
       100. The compound according to  claim 99  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl.   
     
     
       101. The compound according to  claim 100  wherein R 10   , R   11   , R   12    and R   13    are methyl.   
     
     
       102. The compound according to  claim 98  wherein R 3    is                      
       
         and m is  0  or  1 . 
       
     
     
       103. The compound according to  claim 102  wherein R 11    and R   12    are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or CH   2   —CH   2   O—CH   2   CH   3 . 
     
     
       104. The compound according to  claim 94  wherein R 3    is                      
         wherein U is N - ALK, CH   2    or O and ALK is lower alkyl or hydrogen.   
     
     
       105. The compound according to  claim 104  wherein U is CH 2 . 
     
     
       106. The compound according to  claim 94  prepared from the reaction of R 3   L with                      
         
     
     
       107. The compound according to  claim 106  wherein A or G is N. 
     
     
       108. The compound according to  claim 106  wherein R 3    is a positively charged electron withdrawing group.   
     
     
       109. The compound according to  claim 108  wherein R 3    is                      
       
         wherein  
       
       
         R 
         10 
         , R 
         11 
         , R 
         12  
         and R 
         13  
         are independently hydrogen, lower alkyl or lower alkoxy lower alkyl or  
       
         R   10    and R   11    taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms or R   10    and R   12    taken together with the atoms to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms.   
     
     
       110. The compound according to  claim 109  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl, hydrogen or lower alkoxy lower alkyl.   
     
     
       111. The compound according to  claim 110  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl.   
     
     
       112. The compound according to  claim 111  wherein R 10   , R   11   , R   12    and R   13    are methyl.   
     
     
       113. The compound according to  claim 94  wherein R 3    is                      
       
         and m is  0  or  1 . 
       
     
     
       114. The compound according to  claim 113  wherein R 11    and R   12    are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, or CH   2   —CH   2   O—CH   2   CH   3 . 
     
     
       115. The compound according to  claim 107  wherein R 3    is                      
         wherein U is N - ALK, CH   2    or O and ALK is lower alkyl or hydrogen.   
     
     
       116. The compound according to  claim 115  wherein U is CH 2 . 
     
     
       117. The compound according to  claim 106  wherein                    
       
         is prepared by reacting  
         
           
           
               
               
           
         
       
       
         with hydrazine under conditions effective to form said compound wherein  
       
       
         R 
         1  
         is halogen, NH—NH 
         2  
         or OR 
         11  
         and  
       
       
         R 
         11  
         is lower alkyl. 
       
     
     
       118. The compound according to  claim 94  which is formed by reacting  1 - hydroxy -   7   - aza - benzotriazole with R   3   L, wherein R   3    is  1 , 1 , 3 , 3   - tetramethyluronium salt and L is a leaving group.   
     
     
       119. The compound according to  claim 118  wherein the leaving group is a halide. 
     
     
       120. A compound of the formula:                    
         or N - oxides thereof or salts thereof wherein    
       
         D is CR 
         16  
         or N;  
       
       
         E is CR 
         17  
         or N;  
       
       
         A is CR 
         15  
         or N;  
       
       
         G is CR 
         18  
         or N;  
       
       
         provided that one and only one of A, E, D or G is N;  
       
       
         R 
         15 
         , R 
         16 
         , R 
         17 
         , R 
         18  
         are independently hydrogen, lower alkyl or an electron donating group;  
       
       
         X is CR 
         7  
         or N;  
       
         Y is CR   5 ;  
       
         R 
         7  
         and R 
         5  
         are independently hydrogen or lower alkyl;  
       
         R   3    is SO   2   R   14   , lower alkyl carbonyl, aryl carbonyl, aryl lower alkyl carbonyl, a positively charged electron withdrawing group or AA   1 - BLK   1 ;  
         R   14    is lower alkyl, aryl or aryl lower alkyl; BLK   1    is an amino acid protecting group; and AA   1    is an amino acid or peptide less a hydrogen on the N - terminus and an OH on the C - terminus.   
     
     
       121. The compound according to  claim 120  wherein A or G is N. 
     
     
       122. The compound according to  claim 120  wherein Y is CH and X is CH or N. 
     
     
       123. The compound according to  claim 120  wherein the electron donating group is amino, lower alkylamino, diloweralkylamino, hydroxy, lower alkoxy, lower aralkoxy, halo, aryl, mercapto, or lower alkylthio. 
     
     
       124. The compound according to  claim 123  wherein the electron donating group is lower dialkylamino or lower alkoxy. 
     
     
       125. The compound according to  claim 120  having the formula:                    
       
         in which Y is CH and  
       
       
         X is N or CH. 
       
     
     
       126. The compound according to  claim 125  wherein R 3    is SO   2   R   14   , lower alkylcarbonyl, aryl carbonyl, or aryl lower alkyl carbonyl.   
     
     
       127. The compound according to  claim 125  wherein R 3    is AA   1 - BLK   1 . 
     
     
       128. The compound according to  claim 125  wherein R 3    is a positively charged electron withdrawing group.   
     
     
       129. The compound according to  claim 125  wherein R 3    is                      
       
         wherein R 
         10 
         , R 
         11 
         , R 
         12  
         and R 
         13  
         are independently hydrogen, lower alkyl or lower alkoxy lower alkyl; or  
       
         R   10    and R   11    taken together with the nitrogen atom to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms or R   10    and R   12    taken together with the atoms to which they are attached form a heterocyclic ring containing up to  6  ring atoms and up to a total of  5  ring carbon atoms or R   12    and R   13    taken together with the nitrogen atom to which they are attached form a  5   -  or  6   - membered heterocyclic ring containing up to a total of  5  ring carbon atoms.   
     
     
       130. The compound according to  claim 129  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl, hydrogen or lower alkoxy lower alkyl.   
     
     
       131. The compound according to  claim 130  wherein R 10   , R   11   , R   12    and R   13    are independently lower alkyl.   
     
     
       132. The compound according to  claim 130  wherein R 10   , R   11   , R   12    and R   13    are methyl.   
     
     
       133. The compound according to  claim 129  wherein R 3    is                      
       
         and m is  0  or  1 . 
       
     
     
       134. The compound according to  claim 133  wherein R 11    and R   12    are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, or CH   2   —CH   2   O—CH   2   —CH   3 . 
     
     
       135. The compound according to  claim 125  wherein R 3    is                      
         wherein U is N - ALK, CH   2    or O, and ALK is lower alkyl or hydrogen.   
     
     
       136. The compound according to  claim 16  wherein U is CH 2 .

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