US2010036130A1PendingUtilityA1

Processes for producing cycloalkylcarboxamido-pyridine benzoic acids

Assignee: VERTEX PHARMAPriority: Dec 7, 2007Filed: May 29, 2009Published: Feb 11, 2010
Est. expiryDec 7, 2027(~1.4 yrs left)· nominal 20-yr term from priority
C07D 317/60C07D 213/74C07D 213/73C07D 405/12
70
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Claims

Abstract

The present invention relates to a process of providing the 3-(6-(1-(2,2-difluorobenzo[d][1,3]dioxol-5-yl)cyclopropanecarboxamido)-3-methylpyridin-2-yl)benzoic acid in substantially free form (Compound 1).

Claims

exact text as granted — not AI-modified
1 - 70 . (canceled) 
     
     
         71 . A process for preparing a compound of formula 7a: 
       
         
           
           
               
               
           
         
       
       wherein,
 A is a fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring; 
 R 1  is independently selected from —R J , —OR J , —N(R J ) 2 , —NO 2 , halogen, —CN, —C 1-4 haloalkyl, —C 1-4 haloalkoxy, —C(O)N(R J ) 2 , —NR J C(O)R J , —SOR J , —SO 2 R J , —SO 2 N(R J ) 2 , —NR J SO 2 R J , —COR J , —CO 2 R J , —NR J SO 2 N(R J ) 2 , —COCOR J ; 
 R J  is hydrogen or C 1-6  aliphatic; 
 m is an integer from 0 to 3 inclusive; 
 n is an integer from 1 to 4 inclusive; and 
 X is a halide or OH; 
 comprising the steps of
 ic) reducing Compound 10a in a fourth organic solvent: 
 
 
       
         
           
           
               
               
           
         
         wherein, 
         A is a fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring; 
         R 1  is independently selected from —R J , —OR J , —N(R J ) 2 , —NO 2 , halogen, —CN, —C 1-4 haloalkyl, —C 1-4 haloalkoxy, —C(O)N(R J ) 2 , —NR J C(O)R J , —SOR J , —SO 2 R J , —SO 2 N(R J ) 2 , —NR J SO 2 R J , —COR J , —CO 2 R J , —NR J SO 2 N(R J ) 2 , —COCOR J ; 
         R J  is hydrogen or C 1-6  aliphatic; 
         R K  is C 1-6  aliphatic; and 
         m is an integer from 0 to 3 inclusive, 
         with a reducing agent to produce Compound 11a: 
       
       
         
           
           
               
               
           
         
         wherein, ring A, R 1 , and m are as defined in Compound 10a above;
 iic) reacting Compound 11a with a first halogenating agent in a fifth organic solvent to produce Compound 12a: 
 
       
       
         
           
           
               
               
           
         
         wherein, ring A, R 1 , and m are as defined in Compound 10a above, and Hal is a halide;
 iiic) reacting Compound 12a with a cyanide to produce Compound 13a: 
 
       
       
         
           
           
               
               
           
         
         wherein, ring A, R 1 , and m are as defined in Compound 10a above;
 ivc) reacting Compound 13a with a compound of formula 13aa in the presence of a third base: 
 
       
       
         
           
           
               
               
           
         
         wherein, 
         Hal is a halide; and 
         q is an integer from 0 to 3 inclusive; to produce a compound of formula 14a: 
       
       
         
           
           
               
               
           
         
         wherein, 
         r is an integer from 1 to 4 inclusive; and 
         ring A, R 1 , and m are as defined in Compound 10a above;
 vc) sequentially reacting Compound 14a with a hydroxide base and second acid to form Compound 15a, which is compound 7a when X═OH: 
 
       
       
         
           
           
               
               
           
         
         wherein, r, ring A, R 1 , and m are as defined in Compound 14a above; and
 vc) reacting Compound 15a with a second halogenating agent in a sixth organic solvent to form Compound 16a, which is compound 7a when X=halide: 
 
       
       
         
           
           
               
               
           
         
         wherein, 
         Hal is halide; and 
         r, ring A, R 1 , and m are as defined in Compound 14a above. 
       
     
     
         72 . The process of  claim 71 , wherein the fourth organic solvent is an aprotic solvent. 
     
     
         73 . The process of  claim 71 , wherein the fourth organic solvent is toluene. 
     
     
         74 . The process of  claim 71 , wherein the reducing agent is a hydride. 
     
     
         75 . The process of  claim 71 , wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride. 
     
     
         76 . The process of  claim 71 , wherein the reducing reaction is run at between 15° C. and 40° C. 
     
     
         77 . The process of  claim 71 , wherein the fifth organic solvent is an aprotic solvent. 
     
     
         78 . The process of  claim 71 , wherein the fifth organic solvent is methyl t-butyl ether. 
     
     
         79 . The process of  claim 71 , wherein the first halogenating agent is thionyl chloride. 
     
     
         80 . The process of  claim 71 , wherein the reaction of Compound 11a with a first halogenating reaction is run at between 15° C. and 30° C. 
     
     
         81 . The process of  claim 71 , wherein the cyanide is sodium cyanide. 
     
     
         82 . The process of  claim 71 , wherein the reaction of Compound 12a with a cyanide is run at between 30° C. and 40° C. 
     
     
         83 . The process of  claim 71 , wherein the third base is an inorganic base. 
     
     
         84 . The process of  claim 71 , wherein the third base is potassium hydroxide. 
     
     
         85 . The process of  claim 71 , wherein Compound 13aa is 1-bromo-2-chloroethane. 
     
     
         86 . The process of  claim 71 , wherein the reaction of Compound 13a with a compound of formula 13aa is run at between 50° C. and 90° C. 
     
     
         87 . The process of  claim 71 , wherein the hydroxide base is sodium hydroxide. 
     
     
         88 . The process of  claim 71 , wherein the second acid is an inorganic acid. 
     
     
         89 . The process of  claim 71 , wherein the second acid is hydrochloric acid. 
     
     
         90 . The process of  claim 71 , wherein the sequential reaction of Compound 14a with a hydroxide base and second acid is run at between 70° C. and 90° C. 
     
     
         91 . The process of  claim 71 , wherein the sixth organic solvent is an aprotic solvent. 
     
     
         92 . The process of  claim 71 , wherein the sixth organic solvent is toluene. 
     
     
         93 . The process of  claim 71 , wherein the second halogenating agent is thionyl chloride. 
     
     
         94 . The process of  claim 71 , wherein the reaction of Compound 15a with a second halogenating agent is run at between 40° C. and 80° C. 
     
     
         95 . (canceled) 
     
     
         96 . (canceled) 
     
     
         97 . The process of  claim 71 , wherein R K  is methyl. 
     
     
         98 - 106 . (canceled)

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