Methods of making tris(N-aryl benzimidazoles)benzenes and their use in electronic devices

Abstract

Provided are methods for preparing a compound of Formula I: where the method comprises the steps of: contacting a compound of Formula II: with 1,3,5-benzene-tricarbonyl chloride in the presence of a polar aprotic solvent to form an amide adduct; and subsequently condensing the amide with a proximate anilino group present in the adduct in the presence of a condensing agent to form a compound of Formula I wherein R 1 , R 2 , Ar, m, p, and t are as defined in the specification.

1 . A compound of Formula I:  
     
       
         
         
             
             
         
       
     
     prepared by a method comprising the steps of:  
     contacting a compound of Formula II:  
     
       
         
         
             
             
         
       
     
     with 1,3,5-benzene-tricarbonyl chloride in the presence of a polar aprotic solvent to form an amide adduct; and subsequently condensing the amide with a proximate anilino group present in the adduct in the presence of a condensing agent to form a compound of Formula I wherein: 
 R 1  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O— (CH 2 ) t —O— or a fused aromatic ring;  
 R 2  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O— (CH 2 ) t —O— or a fused aromatic ring;  
 Ar is the same or different at each occurrence and is C 6 -C 20  aryl or C 4 -C 20  heteroaryl;  
 m, and p are the same or different at each occurrence and are each independently 0 or an integer from 1 to 3; and  
 t is the same or different at each occurrence and is an integer from 1 to 6.  
 
   
   
       2 . The compound of  claim 1  that is 2,2′,2″-(1,3,5-Phenylene)-tris[1-phenyl-1H-benzimidazole].  
   
   
       3 . A composition comprising a compound of Formula I:  
     
       
         
         
             
             
         
       
     
     prepared by a method comprising the steps of:  
     contacting a compound of Formula II:  
     
       
         
         
             
             
         
       
     
     with 1,3,5-benzene-tricarbonyl chloride in the presence of a polar aprotic solvent to form an amide adduct; and subsequently condensing the amide with a proximate anilino group present in the adduct in the presence of a condensing agent to form a compound of Formula I wherein: 
 R 1  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O—(CH 2 ) t —O— or a fused aromatic ring;  
 R 2  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 2 0 aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O— (CH 2 ) t —O— or a fused aromatic ring;  
 Ar is the same or different at each occurrence and is C 6 -C 20  aryl or C 4 -C 20  heteroaryl;  
 m, and p are the same or different at each occurrence and are each independently 0 or an integer from 1 to 3; and  
 t is the same or different at each occurrence and is an integer from 1 to 6.  
 
   
   
       4 . The composition of  claim 3  further comprising a solvent, a processing aid, a charge transporting material, a charge blocking material, or combinations thereof.  
   
   
       5 . The composition of  claim 3  wherein the compound of formula I is 2,2′,2″-(1,3,5-Phenylene)-tris[1-phenyl-1H-benzimidazole].  
   
   
       6 . The composition of  claim 4  wherein the compound of formula I is 2,2′,2″-(1,3,5-Phenylene)-tris[1-phenyl-1H-benzimidazole].  
   
   
       7 . An organic electronic device comprising at least one layer comprising at least one compound of Formula I:  
     
       
         
         
             
             
         
       
     
     prepared by a method comprising the steps of:  
     contacting a compound of Formula II:  
     
       
         
         
             
             
         
       
     
     with 1,3,5-benzene-tricarbonyl chloride in the presence of a polar aprotic solvent to form an amide adduct; and subsequently condensing the amide with a proximate anilino group present in the adduct in the presence of a condensing agent to form a compound of Formula I wherein: 
 R 1  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O—(CH 2 ) t —O— or a fused aromatic ring;  
 R 2  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O—(CH 2 ) t —O— or a fused aromatic ring;  
 Ar is the same or different at each occurrence and is C 6 -C 20  aryl or C 4 -C 20  heteroaryl;  
 m, and p are the same or different at each occurrence and are each independently 0 or an integer from 1 to 3; and  
 t is the same or different at each occurrence and is an integer from 1 to 6.  
 
   
   
       8 . The organic electronic device of  claim 7  wherein said layer is a charge transport layer.  
   
   
       9 . The organic electronic device of  claim 7  wherein the compound of Formula I is 2,2′,2″-(1,3,5-Phenylene)-tris[1-phenyl-1H-benzimidazole].  
   
   
       10 . An article useful in the manufacture of an organic electronic device, comprising at least one layer comprising at least one compound of Formula I:  
     
       
         
         
             
             
         
       
     
     prepared by a method comprising the steps of:  
     contacting a compound of Formula II:  
     
       
         
         
             
             
         
       
     
     with 1,3,5-benzene-tricarbonyl chloride in the presence of a polar aprotic solvent to form an amide adduct; and subsequently condensing the amide with a proximate anilino group present in the adduct in the presence of a condensing agent to form a compound of Formula I wherein: 
 R 1  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O— (CH 2 ) t —O— or a fused aromatic ring;  
 R 2  is the same or different at each occurrence and is hydrogen, C 1 -C 20  alkyl, halo, C 1 -C 20  fluoroalkyl, C 6 -C 20  aryl, C 4 -C 20  heteroaryl, C 1 -C 20  alkoxy, C 6 -C 20  aryloxy, C 1 -C 20  thioalkoxy, C 6 -C 20  thioaryloxy, amino, carboxyl, cyano, nitro, or two adjacent R groups together can be —O—. (CH 2 ) t —O— or a fused aromatic ring;  
 Ar is the same or different at each occurrence and is C 6 -C 20  aryl or C 4 -C 20  heteroaryl;  
 m, and p are the same or different at each occurrence and are each independently 0 or an integer from 1 to 3; and  
 t is the same or different at each occurrence and is an integer from 1 to 6.  
 
   
   
       11 . The article of  claim 10  wherein the compound of Formula I is 2,2′,2″-(1,3,5-Phenylene)-tris[1-phenyl-1H-benzimidazole].