Process for producing chromone compound

Abstract

A process for producing a dicarboxylic acid compound represented by the formula (4): wherein R 1 and R 2 are the same or different and each represents lower alkyl and the wavy line indicates that this compound is the E- or Z-isomer or a mixture of them, characterized by reacting a compound represented by the formula (2): wherein R 1 , R 2 and the wavy line have the same meanings as the above, and one of X 2 and X 3 represents hydrogen and the other represents halogen, with nitrophenol represented by the formula (3): in the presence of a base; a process for producing a nitrochromone compound represented by the formula (5): wherein R 1 has the same meaning as the above, characterized by reacting the dicarboxylic acid compound or carboxylic acid thereof with an acid; a process for producing an aminochromone compound which comprises reducing the nitrochromone compound; and a process for producing an amidochromone compound which comprises acylating the aminochromone compound are provided.

1 . A process for producing a dicarboxylic acid compound represented by the formula (4):  
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  and the wavy line are as defined below; which comprises reacting at least one compound selected from the group consisting of a dihalosuccinic acid compound represented by the formula (1):  
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are the same or different and independently represent a lower alkyl group and X 1  represents a halogen atom, and a compound represented by the formula (2):  
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are as defined above, one of X 2  and X 3  represents a hydrogen atom and the other represents a halogen atom, and the wavy line indicates that this compound is the E- or Z-isomer or a mixture of them, with a nitrophenol compound represented by the formula (3):  
     
       
         
         
             
             
         
       
     
     in the presence of a base.  
   
   
       2 . The process according to  claim 1 , wherein at least one compound selected from the group consisting of the dihalosuccinic acid compound represented by the formula (1) and the compound represented by the formula (2) is the dihalosuccinic acid compound represented by the formula (1).  
   
   
       3 . The process according to  claim 1 , wherein at least one compound selected from the group consisting of the dihalosuccinic acid compound represented by the formula (1) and the compound represented by the formula (2) is the compound represented by the formula (2).  
   
   
       4 . The process according to  claim 3 , wherein the compound represented by the formula (2) is a compound obtained by reaction of the dihalosuccinic acid compound represented by the formula (1) with a base.  
   
   
       5 . The process according to  claim 3 , wherein the compound represented by the formula (2) is a Z-isomer compound.  
   
   
       6 . The process according to  claim 1 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is higher than that of an erythro-dihalosuccinic acid compound.  
   
   
       7 . The process according to  claim 1 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       8 . The process according to  claim 1 , wherein the dihalosuccinic acid compound represented by the formula (1) is a threo-dihalosuccinic acid compound.  
   
   
       9 . The process according to  claim 6 , wherein the composition is a composition produced by adding a maleic acid compound represented by the formula (8):  
     
       
         
         
             
             
         
       
     
     wherein R 10  and R 20  are the same or different and independently represent a lower alkyl group, to a halogenating agent.  
   
   
       10 . The process according to  claim 1 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       11 . A dicarboxylic acid compound represented by the formula (4a):  
     
       
         
         
             
             
         
       
     
     wherein R 10  and R 20  are the same or different and independently represent a hydrogen atom or a lower alkyl group, and the wavy line indicates that this compound is the E- or Z-isomer or a mixture of them.  
   
   
       12 . A process for producing a dihalosuccinic acid compound in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher, which comprises adding a maleic acid compound to a halogenating agent.  
   
   
       13 . The process according to  claim 12 , wherein the maleic acid compound is a maleic acid compound represented by the formula (8):  
     
       
         
         
             
             
         
       
     
     wherein R 10  and R 20  are the same or different and independently represent a hydrogen atom or a lower alkyl group, the halogenating agent is X 1 -X 1  wherein X 1  is a halogen atom, and the threo-dihalosuccinic acid compound is a threo-dihalosuccinic acid compound having a relative configuration represented by the formula (9):  
     
       
         
         
             
             
         
       
     
     wherein R 10 , R 20  and X 1  are as defined above.  
   
   
       14 . The process according to  claim 13 , wherein R 10  and R 20  independently represent a lower alkyl group.  
   
   
       15 . The process according to  claim 13 , wherein at least one of R 10  and R 20  in the formulas (8) and (9) represents a hydrogen atom.  
   
   
       16 . The process according to  claim 15 , which further comprises a step of reacting the resulting threo-dihalosuccinic acid compound represented by the formula (9) with lower alkyl alcohol in the presence of an acid catalyst to obtain a threo-dihalosuccinic acid compound represented by the formula (9) wherein R 10  and R 20  independently represent a lower alkyl group.  
   
   
       17 . A process for producing a nitrochromone compound represented by the formula (5):  
     
       
         
         
             
             
         
       
     
     wherein R 10  is as defined below; which comprises reacting a dicarboxylic acid compound represented by formula (4′):  
     
       
         
         
             
             
         
       
     
     wherein R 10  and R 20  are the same or different and independently represent a hydrogen atom or a lower alkyl group and the wavy line indicates that this compound is the E- or Z-isomer or a mixture of them, with an acid.  
   
   
       18 . The process according to  claim 17 , wherein R 10  and R 20  represent a hydrogen atom.  
   
   
       19 . The process according to  claim 18 , wherein the dicarboxylic acid compound represented by the formula (4′) wherein R 10  and R 20  represent a hydrogen atom is a dicarboxylic acid compound obtained by hydrolyzing the dicarboxylic acid compound represented by the formula (4):  
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  independently represent a lower alkyl group and the wavy line is as defined above.  
   
   
       20 . The process according to  claim 17 , wherein R 10  and R 20  independently represent a lower alkyl group.  
   
   
       21 . The process according to  claim 17 , wherein the acid is fuming sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid or a mixture of them.  
   
   
       22 . The process according to  claim 17 , wherein the reaction product nitrochromone compound represented by the formula (5) is nitrochromone carboxylic acid represented by the formula (5) wherein R 10  represents a hydrogen atom or a mixture of said carboxylic acid and a nitrochromone compound represented by the formula (5) wherein R 10  represents a lower alkyl group, and which further comprises a step of esterifying the nitrochromone carboxylic acid represented by the formula (5) in the resulting reaction product by a reaction of said product with an alkylating agent having a lower alkyl group in the presence of a base to obtain the nitrochromone compound represented by the formula (5) wherein R 10  represents a lower alkyl group.  
   
   
       23 - 28 . (canceled)  
   
   
       29 . The process according to  claim 2 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is higher than that of an erythro-dihalosuccinic acid compound.  
   
   
       30 . The process according to  claim 3 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is higher than that of an erythro-dihalosuccinic acid compound.  
   
   
       31 . The process according to  claim 4 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is higher than that of an erythro-dihalosuccinic acid compound.  
   
   
       32 . The process according to  claim 5 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is higher than that of an erythro-dihalosuccinic acid compound.  
   
   
       33 . The process according to  claim 2 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       34 . The process according to  claim 3 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       35 . The process according to  claim 4 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       36 . The process according to  claim 5 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       37 . The process according to  claim 6 , wherein the dihalosuccinic acid compound represented by the formula (1) is a composition in which the proportion of a threo-dihalosuccinic acid compound is 70% or higher.  
   
   
       38 . The process according to  claim 2 , wherein the dihalosuccinic acid compound represented by the formula (1) is a threo-dihalosuccinic acid compound.  
   
   
       39 . The process according to  claim 3 , wherein the dihalosuccinic acid compound represented by the formula (1) is a threo-dihalosuccinic acid compound.  
   
   
       40 . The process according to  claim 4 , wherein the dihalosuccinic acid compound represented by the formula (1) is a threo-dihalosuccinic acid compound.  
   
   
       41 . The process according to  claim 5 , wherein the dihalosuccinic acid compound represented by the formula (1) is a threo-dihalosuccinic acid compound.  
   
   
       42 . The process according to  claim 7 , wherein the composition is a composition produced by adding a maleic acid compound represented by the formula (8):  
     
       
         
         
             
             
         
       
     
     wherein R 10  and R 20  are the same or different and independently represent a lower alkyl group, to a halogenating agent.  
   
   
       43 . The process according to  claim 2 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       44 . The process according to  claim 3 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       45 . The process according to  claim 4 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       46 . The process according to  claim 5 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       47 . The process according to  claim 6 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       48 . The process according to  claim 7 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       49 . The process according to  claim 8 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.  
   
   
       50 . The process according to  claim 9 , wherein the nitrophenol represented by the formula (3) is 2-nitrophenol.