US2002019406A1PendingUtilityA1

9H-pyrimido[4,5-b]indole derivatives: CRF1 specific ligands

Assignee: NEUROGEN CORPPriority: Apr 30, 1999Filed: Aug 15, 2001Published: Feb 14, 2002
Est. expiryApr 30, 2019(expired)· nominal 20-yr term from priority
A61P 9/00A61P 25/24A61P 25/22G01N 2333/5751A61P 25/00A61P 3/04A61P 25/30C07D 487/04G01N 2333/726A61P 25/04A61P 25/18
47
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Claims

Abstract

Disclosed are compounds of the formula: wherein Ar, R 1 , R 2 , R 3 , R 4 and R 5 are defined herein, which compounds are selective antagonists at CRF1 receptors and are therefore useful in the diagnosis and treatment of stress related disorders such as post traumatic stress disorder (PTSD) as well as depression, headache, anxiety, cardiovascular disorders, and eating disorders. Methods of treatment of such disorders and well as packaged pharmaceutical compositions are also disclosed.

Claims

exact text as granted — not AI-modified
What is claimed is:  
     
         1 . A compound of the formula:  
       
         
           
           
               
               
           
         
       
       or pharmaceutically acceptable salts thereof wherein 
 Ar is phenyl, 1- or 2-naphthyl, 2-, 3-, or 4-pyridyl, 2-, 4- or 5-pyrimidinyl, each of which is mono-, di-, or trisubstituted with halogen, trifluoromethyl, hydroxy, amino, cyano, carboxamide, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, C 3 -C 7  cycloalkyl, or amino(C 1 -C 6 )alkyl with the proviso that at least one of the ortho or para positions of Ar is substituted;  
 R 1  is hydrogen, halogen, trifluoromethyl, carboxamide, carboxylate, C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, or (C 1 -C 6  alkyl)—G 1 —R 6  wherein G 1  is nitrogen, oxygen or sulfur and R 6  is hydrogen, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl;  
 R 2  and R 3  together represent —(C 0 -C 2 )—G 2 -(C 2 -C 4 )— wherein G 2  is methylene, oxygen, sulfur or NR 7 , wherein R 7  is hydrogen, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl; or  
 R 2  and R 3  taken together represent —CH═A—CH═CH— wherein 
 A is N or CR 8 ;  
 R 8  is —(C 0 -C 6  alkyl)—Z;  
 Z is —CR 9 R 9′ , NR 9 R 9′ , OR 9  or SR 9 ; and  
 R 9  and R 9′  independently represent hydrogen or (C 1 -C 6 )alkyl;  
 
 R 4  and R 5  are the same or different and represent hydrogen, hydroxy, C 1 -C 6  alkoxy(C 1 -C 6 )alkyl, hydroxy(C 1 -C 6 )alkyl, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl; or  
  phenyl, 2-, 3-, or 4-pyridyl, 2- or 3-thienyl, or 2-, 4-, or 5-pyrimidinyl, each of which is optionally mono- or disubstituted with halogen, trifluoromethyl, hydroxy, C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkoxy; or  
 R 4  and R 5  together represent —(C 2 -C 3 )—G 3 —(C 1 -C 3 )— where 
 G 3  is methylene, 1,2 phenylene, oxygen, sulfur or NR 10 ; and  
 R 10  is C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, phenyl, 2-, 3-, or 4-pyridyl, 2- or 3-thienyl, or 2-, 4- or 5-pyrimidyl.  
 
 
     
     
         2 . A compound according to  claim 1 , wherein R 2  and R 3  together represent —CH═CR 8 —CH═CH—.  
     
     
         3 . A compound according to  claim 2 , wherein R 8  is hydrogen or C 1 -C 6  alkyl.  
     
     
         4 . A compound according to  claim 1 , wherein Ar is phenyl mono-, di-, or trisubstituted with halogen, trifluoromethyl, hydroxy, amino, cyano, carboxamide, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, C 3 -C 7  cycloalkyl, or amino(C 1 -C 6 )alkyl with the proviso that at least one of the ortho positions of Ar is substituted.  
     
     
         5 . A compound according to  claim 4 , wherein Ar is phenyl substituted in the 2 and 4 positions with methyl, fluoro or chloro.  
     
     
         6 . A compound according to  claim 3 , wherein Ar is 2,4,6-trimethylphenyl.  
     
     
         7 . A compound according to  claim 6 , wherein R 4  and R 5  independently represent hydrogen, C 1 -C 6  alkoxy(C 1 -C 6 ) alkyl, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl.  
     
     
         8 . A compound according to  claim 2 , wherein R 8  is —NR 9 R 9′ .  
     
     
         9 . A compound according to  claim 2 , wherein R 8  is —(C 1 -C 6  alkyl)—NR 9 R 9′ .  
     
     
         11 . A compound according to  claim 8 , wherein Ar is 2,4,6-trimethylphenyl.  
     
     
         10 . A compound according to  claim 8 , wherein R 4  and R 5  independently represent hydrogen, C 1 -C 6  alkoxy(C 1 -C 6 ) alkyl, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl.  
     
     
         12 . A compound according to  claim 1 , wherein R 2  and R 3  together represent —(C 0 -C 2 )CH 2 (C 2 -C 4 )—.  
     
     
         13 . A compound according to  claim 12 , wherein Ar is 2,4,6-trimethylphenyl.  
     
     
         14 . A compound according to  claim 13 , wherein R 4  and R 5  independently represent hydrogen, C 1 -C 6  alkoxy(C 1 -C 6 ) alkyl, C 3 -C 7  cycloalkyl, or C 1 -C 6  alkyl.  
     
     
         15 . A compound according to  claim 1  which is 4-(N-Cyclopropylmethyl-N-propyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         16 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         17 . A compound according to  claim 1  which is 4-(N-Propyl-N-methyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         18 . A compound according to  claim 1  which is 4-(N-Cyclopropylmethyl-N-propyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         19 . A compound according to  claim 1  which 4-(N,N-Dipropyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         20 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-6-ethylamino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         21 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-6-diethylamino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         22 . A compound according to  claim 1  which is 4-Bis(2-methoxyethyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         23 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(4-bromo-2,6-dimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         24 . A compound according to  claim 1  which is 4-Bis(2-methoxyethyl)amino-2-methyl-9-(4-bromo-2,6-dimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         25 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(4-chloro-2-methylphenyl)-9H-pyrimidino [4,5-b]l indole.  
     
     
         26 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(4-cyano-2,6-dimethylphenyl)-9H-pyrimidino [4,5-b]indole.  
     
     
         27 . A compound according to  claim 1  which is 4-Bis(2-methoxyethyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         28 . A compound according to  claim 1  which is 4-(N-Cyclopropylmethyl-N-propyl)amino-6-ethylamino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         29 . A compound according to  claim 1  which is 4-(N-(2-Hydroxyethyl)-N-Cyclopropylmethyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         30 . A compound according to  claim 1  which is 4-(N-(2-Hydroxyethyl)-N-Cyclopropyl)amino-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         31 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-(2,4,6-trimethylphenyl)-5,6,7-trihydrocyclopenta[2,1-d]-8H-pyrimidino[4,5-b]indole  
     
     
         32 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(2,6-dimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         33 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(4-aminomethyl-2,6-dimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         34 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-methyl-9-(2,6-dimethyl-4-(methylaminomethyl)phenyl)-9H-pyrimidino [4,5-b]indole.  
     
     
         35 . A compound according to  claim 1  which is 4-(N-Cyclopropylmethyl-N-propyl)amino-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         36 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         37 . A compound according to  claim 1  which is 4-(N-Butyl-N-methyl)amino-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         38 . A compound according to  claim 1  which is 4-(N-Propyl)amino-8-(2,4,6-trimethylphenyl)-5,6,7-trihydrocyclopenta[2,1-d]-8H-pyrimidino[4,5-b]indole.  
     
     
         39 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-8-(2,4,6-trimethylphenyl)-5,6,7-trihydrocyclopenta[2,1-d]-8H-pyrimidino[4,5-b]indole.  
     
     
         40 . A compound according to  claim 1  which is Ethyl 4-(dipropylamino)-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydropyrimidino[4,5-b]indole-2-carboxylate.  
     
     
         41 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-carboxyamido-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         42 . A compound according to  claim 1  which is 4-(N,N-Dipropyl)amino-2-aminomethyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         43 . A compound according to  claim 1  which is 4-(N-Cyclopropylmethylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         44 . 4-(N,N-Dibutylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         45 . 4-(N,N-Dibutylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         46 . A compound according to  claim 1  which is 4-(N-(2-(4-Chlorophenyl)ethyl)amino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         47 . A compound according to  claim 1  which is 4-(N-(2-(4-Chlorophenyl)ethyl)amino)-2-methyl-9-(2,4-dimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         48 . A compound according to  claim 1  which is 4-(N-(4-Chlorophenyl)methylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         49 . A compound according to  claim 1  which is 4-(N-(2-Methylphenyl)methylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         50 . A compound according to  claim 1  which is 4-(N-(3-Trifluromethylphenyl)methylamino)-2-methyl-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         51 . A compound according to  claim 1  which is (N,N-Dipropylamino)-2-methyl-6-dimethylamino-9-(2,4,6-trimethylphenyl)-9H-pyrimidino[4,5-b]indole.  
     
     
         52 . A compound according to  claim 1 , which is 4-(N-Butyl-N-methyl)amino-9-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-9H-pyrimidino[4,5-b]indole.  
     
     
         53 . A pharmaceutical composition comprising a compound according to  claim 1  and at least one pharmaceutically acceptable carrier or excipient.  
     
     
         54 . A process for preparing a compound according to  claim 1 .  
     
     
         55 . A packaged pharmaceutical composition comprising the pharmaceutical composition of  claim 53  in a container and instructions for using the composition to treat a patient in need thereof.  
     
     
         56 . The packaged pharmaceutical composition of  claim 55 , wherein said patient is suffering from stress, posttraumatic stress disorder, anxiety, depression, cardiovascular disease, headache, obesity or an eating disorder.  
     
     
         57 . A method for localizing CRF receptors in tissue section samples comprising: 
 contacting with a sample of tissue a detectably-labelled compound of  claim 1  under conditions that permit binding of the compound to the sample of tissue;    washing the tissue sample to remove unbound compound; and    detecting the bound compound.    
     
     
         58 . A method for the treatment or prevention of physiological disorders associated with excess of or insufficient amount of CRF, which method comprises administration to a patient in need thereof an effect amount of a compound according to  claim 1 .  
     
     
         59 . A method of inhibiting the binding of CRF to the CRF1 receptor, which method comprises contacting, in the presence of CRF, a solution comprising a compound of  claim 1 , with cells expressing the CRF1 receptor, wherein the compound is present in the solution at a concentration sufficient to reduce levels of CRF binding to IMR32 cells in vitro.  
     
     
         60 . A method for altering the signal-transducing activity of a cell surface CRF1 receptor, said method comprising contacting cells expressing such a receptor with a solution comprising a compound according to  claim 1 , wherein the compound is present in the solution at a concentration sufficient to reduce levels of CRF binding to IMR32 cells in vitro.  
     
     
         61 . A compound according to  claim 1  wherein in a standard assay of CRF binding the compound exhibits an IC 50  of 1 micromolar or less.  
     
     
         62 . A compound according to  claim 1  wherein in a standard assay of CRF binding the compound exhibits an IC 50  of 100 nanomolar or less.  
     
     
         63 . A compound according to  claim 1  wherein in a standard assay of CRF binding the compound exhibits an IC 50  of 10 nanomolar or less.  
     
     
         64 . A method for treating stress, posttraumatic stress disorder, anxiety or depression which comprises administering an effective amount of a compound according to  claim 1  to a patient in need thereof.  
     
     
         65 . A method for treating obesity or eating disorders which comprises administering an effective amount of a compound according to  claim 1  to a patient in need thereof.  
     
     
         66 . A method for treating cardiovascular disorders which comprises administering an effective amount of a compound according to  claim 1  to a patient in need thereof.  
     
     
         67 . A method for treating headache which comprises administering an effective amount of a compound according to  claim 1  to a patient in need thereof.

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