US10385035B2ActiveUtilityA1

Dinaphthothiophene compounds

Assignee: UNIV SAINT LOUISPriority: Jun 20, 2017Filed: Jun 20, 2018Granted: Aug 20, 2019
Est. expiryJun 20, 2037(~10.9 yrs left)· nominal 20-yr term from priority
C07D 333/74C07D 333/50
45
PatentIndex Score
0
Cited by
45
References
22
Claims

Abstract

The present invention generally relates to various dinaphthothiophene compounds and processes for preparing these compounds.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A dinaphthothiophene compound of Formula III: 
       
         
           
           
               
               
           
         
       
       wherein R 3  is hydroxy, substituted C 1 -C 20  alkyl, or substituted or unsubstituted aryl; R 4  is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20  alkyl, or substituted or unsubstituted aryl; and n is 1 or 2. 
     
     
       2. The compound of  claim 1  wherein R 3  is hydroxy, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       3. The compound of  claim 1  wherein R 3  is hydroxy, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl, C 1 -C 10  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       4. The compound of  claim 1  wherein R 3  is hydroxy, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl. 
     
     
       5. The compound of  claim 1  wherein R 4  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       6. The compound of  claim 1  wherein R 4  is hydrogen, hydroxy, C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl, C 1 -C 10  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       7. The compound of  claim 1  wherein R 4  is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl. 
     
     
       8. A dinaphthothiophene compound of Formula III: 
       
         
           
           
               
               
           
         
       
       wherein R 3  is hydroxy, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl; R 4  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl; and n is 1 or 2. 
     
     
       9. The compound of  claim 8  wherein R 3  is hydroxy, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl and R 4  is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl. 
     
     
       10. A dinaphthothiophene compound of Formula III: 
       
         
           
           
               
               
           
         
       
       wherein R 3  is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20  alkyl, or substituted or unsubstituted aryl; R 4  is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20  alkyl, or substituted or unsubstituted aryl; and n is 1 or 2, and wherein R 3  and R 4  are different. 
     
     
       11. The compound of  claim 10  wherein R 3  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       12. The compound of  claim 10  wherein R 3  is hydrogen, hydroxy, C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl, C 1 -C 10  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       13. The compound of  claim 10  wherein R 3  is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl. 
     
     
       14. The compound of  claim 10  wherein R 4  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       15. The compound of  claim 10  wherein R 4  is hydrogen, hydroxy, C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl, C 1 -C 10  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl. 
     
     
       16. The compound of  claim 10  wherein R 4  is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl. 
     
     
       17. The compound of  claim 10  wherein R 3  is methoxy, ethoxy, propoxy, or trifluoromethyl and R 4  is hydrogen, methyl, ethyl, propyl, butyl, or trifluoromethyl. 
     
     
       18. A dinaphthothiophene compound of Formula III: 
       
         
           
           
               
               
           
         
       
       wherein R 3  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl; R 4  is hydrogen, hydroxy, C 1 -C 20  alkyl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkyl, C 1 -C 20  haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl; and n is 1 or 2, and wherein R 3  and R 4  are different. 
     
     
       19. A process for preparing the dinaphthothiophene compound of  claim 1 , comprising oxidizing a dinaphthothiophene compound of Formula III-A: 
       
         
           
           
               
               
           
         
       
       to form the dinaphthothiophene compound of Formula III, wherein R 3  and R 4  are as defined for Formula III. 
     
     
       20. The process of  claim 19  further comprising:
 formylating 3,4-dibromothiophene to form 4-bromothiophene-3-carbaldehyde; 
 reacting, in the presence of a catalyst comprising palladium, a base, and organic solvent, 4-bromothiophene-3-carbaldehyde with a phenylethenyl boronic compound of Formula C-1: 
 
       
         
           
           
               
               
           
         
       
       to form a 3-formyl-4-styrylthiophene compound of Formula C-2: 
       
         
           
           
               
               
           
         
         reacting, in the presence of sodium hydride, the 3-formyl-4-styrylthiophene compound of Formula C-2 with a 4-substituted phosphonic acid diethyl ester compound of Formula C-3: 
       
       
         
           
           
               
               
           
         
       
       to form a compound of Formula C-4: 
       
         
           
           
               
               
           
         
         irradiating the compound of Formula C-4 with UV light in the presence of iodine and propylene oxide to form the dinaphthothiophene compound of Formula III-A: 
       
       
         
           
           
               
               
           
         
       
       wherein R 3  and R 4  are as defined for Formula III. 
     
     
       21. A process for preparing the dinaphthothiophene compound of  claim 10 , comprising oxidizing a dinaphthothiophene compound of Formula III-A: 
       
         
           
           
               
               
           
         
       
       to form the dinaphthothiophene compound of Formula III, wherein R 3  and R 4  are as defined for Formula III. 
     
     
       22. The process of  claim 21  further comprising:
 formylating 3,4-dibromothiophene to form 4-bromothiophene-3-carbaldehyde; 
 reacting, in the presence of a catalyst comprising palladium, a base, and organic solvent, 4-bromothiophene-3-carbaldehyde with a phenylethenyl boronic compound of Formula C-1: 
 
       
         
           
           
               
               
           
         
       
       to form a 3-formyl-4-styrylthiophene compound of Formula C-2: 
       
         
           
           
               
               
           
         
         reacting, in the presence of sodium hydride, the 3-formyl-4-styrylthiophene compound of Formula C-2 with a 4-substituted phosphonic acid diethyl ester compound of Formula C-3: 
       
       
         
           
           
               
               
           
         
       
       to form a compound of Formula C-4: 
       
         
           
           
               
               
           
         
         irradiating the compound of Formula C-4 with UV light in the presence of iodine and propylene oxide to form the dinaphthothiophene compound of Formula III-A: 
       
       
         
           
           
               
               
           
         
       
       wherein R 3  and R 4  are as defined for Formula III.

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