Production methods of 5-phthalancarbonitrile compound and an intermediate therefor

Abstract

The present invention provides a production method of a 5-phthalancarbonitrile compound, which comprises the use of a novel compound of the formula [I] wherein X is chlorine atom, bromine atom or iodine atom, as a key intermediate. The method of the present invention imposes small environmental burden (without use of a reagent imposing great burden on the environment, such as heavy metal, metal cyanide, thionyl chloride and the like) and is safe. The inventive method is based on a completely new strategy which is different from conventional production methods of 5-phthalancarbonitrile compound.

What is claimed is  
     
         1 . A compound of the formula [I] 
       
         
           
           
               
               
           
         
       
       wherein X is chlorine atom, bromine atom or iodine atom.  
     
     
         2 . A compound of the formula [II] 
       
         
           
           
               
               
           
         
       
       wherein R 1  is alkanoyl having 2 to 5 carbon atoms, alkyl having 1 to 5 carbon atoms, tetrahydropyran-2-yl, alkoxymethyl wherein an alkoxyl moiety has 1 to 5 carbon atoms, 1-alkoxyethyl wherein an alkoxyl moiety has 1 or 3 to 10 carbon atoms, or trialkylsilyl wherein each alkyl moiety has 1 to 5 carbon atoms, and X is chlorine atom, bromine atom or iodine atom.  
     
     
         3 . The compound of  claim 2  wherein R 1  is acetyl and X is bromine atom.  
     
     
         4 . A compound of the formula [III] 
       
         
           
           
               
               
           
         
       
     
     
         5 . A compound of the formula [IV] 
       
         
           
           
               
               
           
         
       
     
     
         6 . An oxime compound of the formula [V] 
       
         
           
           
               
               
           
         
       
     
     
         7 . A production method of a compound of the formula [I] 
       
         
           
           
               
               
           
         
       
       wherein X is chlorine atom, bromine atom or iodine atom, which comprises subjecting a compound of the formula [A] 
       
         
           
           
               
               
           
         
       
       wherein R 2  is alkanoyl having 2 to 5 carbon atoms, to chlorination, bromination or iodination and then to elimination of the alkanoyl group.  
     
     
         8 . A production method of a compound of the formula [III] 
       
         
           
           
               
               
           
         
       
       which comprises the steps of 
 (1) converting a compound of the formula [II-b] 
                     
  wherein R 1b  is alkyl having 1 to 5 carbon atoms, tetrahydropyran-2-yl, alkoxymethyl wherein an alkoxyl moiety has 1 to 5 carbon atoms, 1-alkoxyethyl wherein an alkoxyl moiety has 1 to 10 carbon atoms, or trialkylsilyl wherein each alkyl moiety has 1 to 5 carbon atoms, and X is chlorine atom, bromine atom or iodine atom, to a Grignard reagent or lithium compound,  
 (2) coupling same with p-fluorobenzaldehyde, and  
 (3) subjecting the obtained coupling compound to deprotection of R 1b  and cyclization.  
 
     
     
         9 . A production method of the formula [IV] 
       
         
           
           
               
               
           
         
       
       which comprises oxidizing a compound of the formula [III] 
       
         
           
           
               
               
           
         
       
     
     
         10 . A production method of an oxime compound of the formula [V] 
       
         
           
           
               
               
           
         
       
       which comprises reacting a compound of the formula [IV] 
       
         
           
           
               
               
           
         
       
       with hydroxylamine or a mineral acid salt thereof.  
     
     
         11 . A production method of a 5-phthalancarbonitrile compound of the formula [VI] 
       
         
           
           
               
               
           
         
       
       which comprises dehydrating an oxime compound of the formula [V] 
       
         
           
           
               
               
           
         
       
     
     
         12 . A production method of 5-phthalancarbonitrile compound of the formula [VI] 
       
         
           
           
               
               
           
         
       
       which comprises reacting a compound of the formula [IV] 
       
         
           
           
               
               
           
         
       
       with hydroxylamine or a mineral acid salt thereof and dehydrating the resulting compound.  
     
     
         13 . A production method of a compound of the formula [II′] 
       
         
           
           
               
               
           
         
       
       wherein R 1′  is alkanoyl having 2 to 5 carbon atoms, alkyl having 1 to 5 carbon atoms, tetrahydropyran-2-yl, alkoxymethyl wherein an alkoxyl moiety has 1 to 5 carbon atoms, 1-alkoxyethyl wherein an alkoxyl moiety has 1 to 10 carbon atoms, or trialkylsilyl wherein each alkyl moiety has 1 to 5 carbon atoms, and X is chlorine atom, bromine atom or iodine atom, which comprises 
 (1) converting the hydroxyl group of a compound of the formula [I] 
                     
 wherein X is chlorine atom, bromine atom or iodine atom, to alkoxy having 1 to 5 carbon atoms, tetrahydropyran-2-yloxy, alkoxymethoxy wherein an alkoxyl moiety has 1 to 5 carbon atoms, 1-alkoxyethoxy wherein an alkoxyl moiety has 1 to 10 carbon atoms, or trialkylsilyloxy wherein each alkyl moiety has 1 to 5 carbon atoms, or  
 (2) subjecting a compound of the formula [A] 
                     
 wherein R 2  is alkanoyl having 2 to 5 carbon atoms, to chlorination, bromination or iodination.