US2016137608A1PendingUtilityA1

Substituted benzoazepines as toll-like receptor modulators

46
Assignee: HOWBERT JAMES JEFFRYPriority: Aug 18, 2009Filed: Oct 13, 2015Published: May 19, 2016
Est. expiryAug 18, 2029(~3.1 yrs left)· nominal 20-yr term from priority
A61P 9/00A61P 37/06A61P 37/02A61P 37/00A61P 37/08A61P 43/00A61P 31/00A61P 31/04A61P 35/00A61P 29/00C07D 403/04C07D 401/12C07D 403/06C07D 403/10A61P 11/06A61K 31/4025A61K 31/55C07D 223/16C07D 401/04C07D 403/14C07D 401/14
46
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Claims

Abstract

Provided are compositions and methods useful for modulation of signaling through the Toll-like receptors TLR7 and/or TLR8. The compositions and methods have use in treating or preventing disease, including cancer, autoimmune disease, infectious disease, inflammatory disorder, graft rejection, and graft-verses-host disease.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A compound having the formula I: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein: 
       Y is substituted aryl or substituted heteroaryl, wherein said substituted aryl or substituted heteroaryl is substituted with one or more groups independently selected from CN, OH, —C(═O)R 9 , halogen, and —CH═CHC(═O)R 9 ;
 R 9  is selected from alkyl, OR 15 , and NR 10 R 11 ; 
 R 15  is selected from H, alkyl, and —CH 2 O(alkyl), 
 R 10  and R 11  are each independently alkyl, wherein said alkyl is optionally substituted with —OH or R 10  and R 11  together with the nitrogen atom to which they are attached form a heterocyclic ring, wherein said heterocyclic ring is optionally substituted with one or more —OH; 
 R 2  is selected from OR 14  and NR 6 R 7 ; 
 R 6  and R 7  are each independently selected from H, alkyl, cycloalkyl, heterocycle or benzyl, wherein said alkyl, cycloalkyl, or benzyl is optionally substituted with one or more groups independently selected from —F, —OR 8 , —NR 12 SO 2 R 13 , —C(═O)NR 12 R 13  or R 6  and R 7  together with the nitrogen atom to which they are attached form a heterocyclic ring, further wherein said heterocyclic ring is optionally substituted with one or more —OH; 
 R 8  is selected from hydrogen and alkyl, and 
 R 12 , R 13  and R 14  are each independently selected from H and alkyl, wherein said alkyl is optionally substituted with —OH; 
 provided that 
 a) when Y is aryl substituted with 
 
       
         
           
           
               
               
           
         
       
       or 
       
         
           
           
               
               
           
         
       
       then R 2  is not —OCH 2 CH 3 ,
 or 
 b) when Y is aryl substituted with —C(═O)R 9  wherein R 9  is NR 10 R 11  and R 10  and R 11  together with the nitrogen atom to which they are attached form an unsubstituted pyrrolidine ring, then R 2  is not —OCH 2 CH 3  or —N(propyl) 2 . 
 
     
     
         2 . The compound of  claim 1 , having the formula II: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein W is H or —OH; Z is H or —OH; and n is 1 or 2. 
     
     
         3 . The compound of  claim 1 , having the formula V: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein U is N or CZ, and Z is halogen. 
     
     
         4 . The compound of  claim 1 , having the formula VI: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein
 J is independently selected from halogen, —C(═O)R 9  and —CH═CHC(═O)R 9 ; and 
 p is selected from 1, 2, and 3. 
 
     
     
         5 . A compound of  claim 1  having the formula VII: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein:
 Y is substituted aryl or substituted heteroaryl, wherein said aryl or heteroaryl is substituted with one or more groups independently selected from —C(═O)R 9 , halogen, and —CH═CHC(═O)R 9 ; 
 R 9  is selected from alkyl, OR 15 , and NR 10 R 11 ; 
 R 15  is selected from H, alkyl, and —CH 2 O(alkyl); 
 R 10  and R 11  are each independently alkyl, wherein said alkyl is optionally substituted with —OH or R 10  and R 11  together with the nitrogen atom to which they are attached form a heterocyclic ring, wherein said heterocyclic ring is optionally substituted with one or more —OH; and 
 R 6  and R 7  are each independently selected from H, alkyl or alkenyl, wherein said alkyl or alkenyl is optionally substituted with one or more groups independently selected from —F or —OH; 
 provided that when Y is aryl substituted with —C(═O)R 9 , R 9  is NR 10 R 11 , and R 10  and R 11  together with the nitrogen atom to which they are attached form an unsubstituted pyrrolidine ring, then R 6  and R 7  are not both propyl. 
 
     
     
         6 . The compound of  claim 5 , wherein Y is substituted aryl, wherein said aryl is substituted with —C(═O)R 9 . 
     
     
         7 . The compound of  claim 6 , wherein R 9  is NR 10 R 11 . 
     
     
         8 . The compound of  claim 5 , having the formula VIIa: 
       
         
           
           
               
               
           
         
       
       or a tautomer, enantiomer or salt thereof, wherein:
 v is 0, 1, or 2; 
 R 6  is selected from H, allyl, prop-1-enyl, and propyl, wherein said propyl is optionally substituted with one or more —OH; 
 R 7  is selected from allyl, prop-1-enyl, and propyl, wherein said propyl is optionally substituted with one or more —OH; 
 provided that when v is 0, then R 6  and R 7  are not both propyl. 
 
     
     
         9 . The compound of  claim 8 , wherein v is 1. 
     
     
         10 . The compound of  claim 1 , wherein Y is substituted is substituted with CN. 
     
     
         11 . The compound of  claim 10 , wherein Y is phenyl. 
     
     
         12 . The compound of  claim 1 , selected from the group consisting of: 
       
         
           
                 
                 
               
                     
                 
                   101 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   102 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   103 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   104 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   105 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   106 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   107 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   112 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   109 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   110 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   115 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   117 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   119 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   120 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   121 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   122 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   136 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   124 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   125 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   126 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   127 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   128 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   129 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   130 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   137 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   138 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   139 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   154 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   145 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   146 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   147 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   220 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   155 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   156 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   174 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   176 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   186 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   178 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   211 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   182 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   187 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   188 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   194 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   190 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   195 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   202 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   203 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   204 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   206 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   207 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   208 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   209 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   212 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   210 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   227 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   228 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   230 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   232 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   233 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   234 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   235 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   236 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   237 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   238 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   239 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
       and tautomers, enantiomers and salts thereof. 
     
     
         13 . The compound of  claim 12 , selected from the group consisting of: 
       
         
           
                 
                 
               
                     
                 
                   109 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   124 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   127 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   128 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   126 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   136 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   137 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   138 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   145 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   146 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   147 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   154 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   155 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   156 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   178 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
       and tautomers, enantiomers and salts thereof. 
     
     
         14 . The compound of  claim 13 , selected from the group consisting of: 
       
         
           
                 
                 
               
                     
                 
                   109 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   127 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   128 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
             
                
               
               
                
                
                
                
                
                
               
            
           
         
       
       and tautomers, enantiomers and salts thereof. 
     
     
         15 . The compound of  claim 5 , selected from the group consisting of: 
       
         
           
                 
                 
               
                     
                 
                   229 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   231 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
             
                
               
               
                
                
                
                
               
            
           
         
       
       and tautomers, enantiomers and salts thereof. 
     
     
         16 . The compound of  claim 1 , wherein the salt is a pharmaceutically acceptable salt. 
     
     
         17 . A pharmaceutical composition, which comprises a compound of  claim 1  or a tautomer, enantiomer or salt thereof together with a pharmaceutically acceptable diluent or carrier. 
     
     
         18 . A method of treating cancer, comprising administering to a patient in need thereof an effective amount of a compound of  claim 1  or a tautomer, enantiomer or salt thereof such that said cancer is treated, wherein said cancer is selected from biliary tract cancer, brain cancer, breast cancer, cervical cancer, choriocarcinoma, colon cancer, endometrial cancer, esophageal cancer, gastric cancer, intraepithelial neoplasms, leukemia, lymphoma, liver cancer, lung cancer, melanoma, neuroblastomas, oral cancer, ovarian cancer, pancreatic cancer, prostate cancer, rectal cancer, renal cancer, sarcomas, skin cancer, testicular cancer, thyroid cancer, other carcinomas and sarcomas. 
     
     
         19 . A method of treating allergy, comprising administering to a patient in need thereof an effective amount of a compound of  claim 1  or a tautomer, enantiomer or salt thereof such that said allergy is treated. 
     
     
         20 . The method of  claim 19 , wherein said allergy is acquired hypersensitivity to an allergen, eczema, allergic rhinitis or coryza, hay fever, asthma, urticaria (hives), food allergies, or other atopic conditions.

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