US2020108059A1PendingUtilityA1

Processes for Preparing Quinoline Compounds and Pharmaceutical Compositions Containing Such Compounds

75
Assignee: EXELIXIS INCPriority: Feb 10, 2011Filed: Dec 6, 2019Published: Apr 9, 2020
Est. expiryFeb 10, 2031(~4.6 yrs left)· nominal 20-yr term from priority
C07D 215/233A61K 31/47A61P 35/00C07D 215/22
75
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Claims

Abstract

The present invention is directed to processes for making and compositions containing quinolines such as formula I or pharmaceutically acceptable salts thereof wherein: X1 is H, Br, Cl, or X2 is H, Br, Cl, or n1 is 1-2; and n2 is 1-2.

Claims

exact text as granted — not AI-modified
1 . A process for preparing a compound of formula I: 
       
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt thereof, wherein:
 X 1  is H, Br, Cl, or F; 
 X 2  is H, Br, Cl, or F; 
 n1 is 1-2; and 
 n2 is 1-2; 
 
         the process comprising: 
         contacting the compound of formula g(1) with reactant z(1) to yield the compound of formula I: 
       
       
         
           
           
               
               
           
         
       
     
     
         2 . The process according to  claim 1 , wherein the compound of formula g(1) is made by reacting a compound of formula f(1) with reactant y(1) to yield the compound of formula g(1): 
       
         
           
           
               
               
           
         
         wherein LG represents a leaving group, and each X 2  and n2 are as defined in  claim 1 . 
       
     
     
         3 . The process according to  claim 2 , wherein the compound of formula f(1) is made by converting compound e(1) to the compound of formula (f1): 
       
         
           
           
               
               
           
         
         wherein LG represents a leaving group. 
       
     
     
         4 . The process according to  claim 1 , wherein reactant z(1) is made by reacting reactant z(1a) with a chlorinating agent to yield reactant z(1): 
       
         
           
           
               
               
           
         
         wherein X 1  is Br, Cl, or F; and n1 is 1-2. 
       
     
     
         5 . The process according to  claim 1 , wherein the compound of formula I is compound IA-1: 
       
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt thereof, wherein:
 X 1  is H, Cl, Br, or F; and 
 X 2  is H, CI, Br, or F. 
 
       
     
     
         6 . The process according to  claim 5 , wherein the compound of formula f(1) is compound f(2): 
       
         
           
           
               
               
           
         
         reactant y(1) is reactant (y)(2): 
       
       
         
           
           
               
               
           
         
         wherein X 2  is hydrogen or fluoro; and 
       
       the compound of formula g(1) is of formula g(2): 
       
         
           
           
               
               
           
         
       
     
     
         7 . The process according to  claim 6 , wherein the reaction employs a non-nucleophilic base. 
     
     
         8 . The process according to  claim 7 , wherein the non-nucleophilic base is an alkali metal alkoxide; and the reaction is carried out in a polar solvent. 
     
     
         9 . The process according to  claim 8 , wherein the alkali metal alkoxide is sodium tert-butoxide, and the polar solvent is DMA. 
     
     
         10 . The process according to  claim 8 , wherein the alkali metal alkoxide is sodium tert-pentoxide, and the polar solvent is DMA. 
     
     
         11 . The process according to  claim 1 , wherein the compound of formula g(1) is of compound g(3): 
       
         
           
           
               
               
           
         
         reactant z(1) is reactant (z)(2): 
       
       
         
           
           
               
               
           
         
       
       and
 the compound of formula I is compound IA: 
 
       
         
           
           
               
               
           
         
       
     
     
         12 . The process according to  claim 11 , wherein the reaction is carried out in the presence of an inorganic base. 
     
     
         13 . The process according to  claim 12 , wherein the inorganic base is K 2 CO 3 , and the solvent employed in this reaction is a combination of THF and H 2 O. 
     
     
         14 . A process for preparing compound IB: 
       
         
           
           
               
               
           
         
         from compound IA: 
       
       
         
           
           
               
               
           
         
         comprising:
 (a) heating and agitating a mixture comprising compound IA and L-malic acid, methylethyl ketone, and water; 
 (b) cooling the mixture; 
 (c) vacuum distilling the mixture successively; and 
 (d) isolating the compound of IB by filtration. 
 
       
     
     
         15 . A process for preparing compound IB: 
       
         
           
           
               
               
           
         
         from compound IA: 
       
       
         
           
           
               
               
           
         
         comprising:
 (a) heating and agitating a mixture comprising compound IA and L-malic acid, methylethyl ketone, and water, 
 (b) cooling the mixture; 
 (c) seeding the mixture with the compound of IB; 
 (d) vacuum distilling the mixture; and 
 (e) isolating the compound of IB by filtration. 
 
       
     
     
         16 . Compound IA or IB admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         17 . Compound IB admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         18 . Compound 1B in the N-1 form admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         19 . Compound IB in the N-2 form admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         20 . Compound IB as a mixture of the N-1 form and N-2 form admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         21 . A pharmaceutical composition according to Table 1. 
       
         
           
                 
                 
                 
               
                   TABLE 1 
                 
                     
                 
                     
                   Ingredient 
                   % w/w 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound I 
                   31.68 
                 
                     
                   Microcrystalline Cellulose 
                   38.85 
                 
                     
                   (Avicel PH102) 
                     
                 
                     
                   Lactose anhydrous 60M 
                   19.42 
                 
                     
                   Hydroxypropyl Cellulose, EXF 
                   3.00 
                 
                     
                   Croscarmellose Sodium 
                   3.00 
                 
                     
                   Total Infra-granular 
                   95.95 
                 
                     
                   Silicon dioxide, Colloidal PWD 
                   0.30 
                 
                     
                   Croscarmellose Sodium 
                   3.00 
                 
                     
                   Magnesium Stearate 
                   0.75 
                 
                     
                   Total 
                   100.00 
                 
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         22 . A pharmaceutical composition according to Table 2. 
       
         
           
                 
                 
                 
               
                   TABLE 2 
                 
                     
                 
                     
                   Ingredient 
                   (% w/w) 
                 
                     
                 
                     
                   Compound I 
                   25.0-33.3 
                 
                     
                   Microcrystalline Cellulose, NF 
                   q.s 
                 
                     
                   Hydroxypropyl Cellulose, NF 
                   3   
                 
                     
                   Poloxamer, NF 
                   0-3 
                 
                     
                   Croscarmellose Sodium, NF 
                   6.0 
                 
                     
                   Colloidal Silicon Dioxide, NF 
                   0.5 
                 
                     
                   Magnesium Stearate, NF 
                   0.5-1.0 
                 
                     
                   Total 
                   100    
                 
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         23 . A pharmaceutical composition according to Table 2A. 
       
         
           
                 
                 
                 
               
                   TABLE 2A 
                 
                     
                 
                     
                   Ingredient 
                   % w/w 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound IB (10% drug load as 
                   12.67 
                 
                     
                   Compound IA) 
                     
                 
                     
                   MCC 
                   51.52 
                 
                     
                   Lactose 
                   25.76 
                 
                     
                   Hydroxypropyl cellulose 
                   3.0 
                 
                     
                   Croscarmellose Sodium 
                   6.0 
                 
                     
                   Colloidal Silicon Dioxide 
                   0.3 
                 
                     
                   Magnesium Stearate 
                   0.75 
                 
                     
                   Total 
                   100 
                 
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         24 . A pharmaceutical composition according to Table 3. 
       
         
           
                 
                 
                 
               
                   TABLE 3 
                 
                     
                 
                     
                   Ingredient 
                   mg/unit dose 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound IB (10% drug 
                   25 
                 
                     
                   load as Compound IA) 
                     
                 
                     
                   Silicified Microcrystalline 
                   196.75 
                 
                     
                   Cellulose 
                     
                 
                     
                   Croscarmellose sodium 
                   12.5 
                 
                     
                   Sodium starch glycolate 
                   12.5 
                 
                     
                   Fumed Silica 
                   0.75 
                 
                     
                   Stearic acid 
                   2.5 
                 
                     
                   Total Fill Weight 
                   250 
                 
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         25 . A pharmaceutical composition according to Table 4. 
       
         
           
                 
                 
                 
               
                   TABLE 4 
                 
                     
                 
                     
                   Ingredient 
                   mg/unit dose 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound IB (50% drug 
                   100 
                 
                     
                   load as Compound IA) 
                     
                 
                     
                   Silicified Microcrystalline 
                   75.40 
                 
                     
                   Cellulose 
                     
                 
                     
                   Croscarmellose sodium 
                   10.00 
                 
                     
                   Sodium Starch Glycolate 
                   10.00 
                 
                     
                   Fumed silica 
                   0.6 
                 
                     
                   Stearic Acid 
                   4.0 
                 
                     
                   Total Fill Weight 
                   200 
                 
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         26 . A pharmaceutical composition according to Table 5. 
       
         
           
                 
                 
                 
               
                   TABLE 5 
                 
                     
                 
                     
                     
                   mg/unit dose 
                 
                     
                   Ingredient 
                   50 mg 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound IB (10% drug 
                   63.35 
                 
                     
                   load as Compound IA) 
                     
                 
                     
                   Microcrystalline Cellulose 
                   95.39 
                 
                     
                   Croscarmellose sodium 
                   9.05 
                 
                     
                   Sodium starch glycolate 
                   9.05 
                 
                     
                   Fumed Silica 
                   0.54 
                 
                     
                   Stearic acid 
                   3.62 
                 
                     
                   Total Fill Weight 
                   181.00 
                 
                     
                 
             
                
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         27 . A pharmaceutical composition according to Table 6. 
       
         
           
                 
                 
                 
               
                   TABLE 6 
                 
                     
                 
                     
                     
                   mg/unit dose 
                 
                     
                   Ingredient 
                   60 mg 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   Compound IB 
                   73.95 
                 
                     
                   Microcrystalline Cellulose 
                   114.36 
                 
                     
                   Croscarmellose sodium 
                   10.85 
                 
                     
                   Sodium starch glycolate 
                   10.85 
                 
                     
                   Fumed Silica 
                   0.65 
                 
                     
                   Stearic acid 
                   4.34 
                 
                     
                   Total Fill Weight 
                   217.00 
                 
                     
                 
             
                
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         28 . The pharmaceutical composition of  claims 20 - 27  admixed with 100 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         29 . The pharmaceutical composition of  claims 20 - 27  admixed with 50 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         30 . The pharmaceutical composition of  claims 20 - 27  admixed with 25 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         31 . The pharmaceutical composition of  claims 20 - 27  admixed with 15 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         32 . The pharmaceutical composition of  claims 20 - 27  admixed with 10 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         33 . The pharmaceutical composition of  claims 20 - 27  admixed with 5 ppm or less of 6,7-dimethoxy-quinoline-4-ol. 
     
     
         34 . The pharmaceutical composition of  claims 20 - 27  admixed with 2.5 ppm or less of 6,7-dimethoxy-quinoline-4-ol.

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