Phenylurethane compounds and methods for producing same, asymmetric urea compounds and methods for producing same, barbituric acid derivative, and diazo thermal recording material containing the derivative

Abstract

Phenylurethane compounds of the following general formula (1); asymmetric urea compounds of the following general formula (10) obtained from the phenylurethane compounds; barbituric acid derivatives of general formula (18) produced from the asymmetric urea compounds, which have specific substituents and are useful in diazo thermal recording materials; and diazo thermal recording materials containing the barbituric acid derivative.

What is claimed is:  
     
         1 . A phenylurethane compound comprising a molecular structure corresponding to the following general formula (1):  
       
         
           
           
               
               
           
         
       
       wherein R 1  represents an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total; R 2  represents a hydrogen atom or an alkyl group; R 1  and R 2  may be bonded to each other to form a ring; and R 3 , R 4 , R 5 , R 6  and R 7  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.  
     
     
         2 . A phenylurethane compound comprising a molecular structure corresponding to the following general formula (2):  
       
         
           
           
               
               
           
         
       
       wherein R 11  represents an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group; R 12  represents a hydrogen atom or an alkyl group; R 11  and R 12  may be bonded to each other to form a ring; and R 13 , R 14 , R 15 , R 16  and R 17  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.  
     
     
         3 . A phenylurethane compound comprising a molecular structure corresponding to the following general formula (3):  
       
         
           
           
               
               
           
         
       
       wherein R 20  represents an alkyl group having from 6 to 30 carbon atoms in total or an aralkyl group having from 6 to 30 carbon atoms in total; R 21  represents a hydrogen atom, an alkyl group or an aralkyl group; R 22  represents a hydrogen atom or an alkyl group; and R 23 , R 24 , R 25 , R 26  and R 27  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.  
     
     
         4 . A method for producing a phenylurethane compound, the method comprising the steps of: 
 (a) adding a base to an aqueous solvent;    (b) adding to the aqueous solvent an amino compound of the following general formula (4):                           in which R 31  represents an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total, and R 32  represents a hydrogen atom or an alkyl group;    (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (5):                           in which R 33 , R 34 , R 35 , R 36  and R 37  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X 1  represents a halogen atom, an imidazolyl group or a tetrazolyl group; and    (d) allowing the amino compound and the phenoxycarbonyl derivative to react to form a phenylurethane compound of the following general formula (1):                           wherein R 1  represents an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total; R 2  represents a hydrogen atom or an alkyl group; R 1  and R 2  may be bonded to each other to form a ring; and R 3 , R 4 , R 5 , R 6  and R 7  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.    
     
     
         5 . A method for producing a phenylurethane compound, the method comprising the steps of: 
 (a) adding a base to an aqueous solvent;    (b) adding to the aqueous solvent an amino compound of the following general formula (6):                           wherein R 41  represents an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group, and R 9  represents a hydrogen atom or an alkyl group;    (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (7):                           wherein R 43 , R 44 , R 45 , R 46  and R 47  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X 2  represents a halogen atom, an imidazolyl group or a tetrazolyl group; and    (d) allowing the amino compound and the phenoxycarbonyl derivative to react to form a phenylurethane compound of the following general formula (2):                           wherein R 11  represents an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group; R 12  represents a hydrogen atom or an alkyl group; R 11  and R 12  may be bonded to each other to form a ring; and R 13 , R 14 , R 15 , R 16  and R 17  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.    
     
     
         6 . A method for producing a phenylurethane compound, the method comprising the steps of: 
 (a) adding a base to an aqueous solvent;    (b) adding to the aqueous solvent an amino compound of the following general formula (8):                           wherein R 50  represents an alkyl group having from 6 to 30 carbon atoms in total or an aralkyl group having from 6 to 30 carbon atoms in total, R 51  represents a hydrogen atom, an alkyl group or an aralkyl group, and R 52  represents a hydrogen atom or an alkyl group;    (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (9):                           wherein R 53 , R 54 , R 55 , R 56  and R 57  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X 3  represents a halogen atom, an imidazolyl group or a tetrazolyl group; and    (d) allowing the amino compound and the phenoxycarbonyl derivative to react to form a phenylurethane compound of the following general formula (3):                           wherein R 20  represents an alkyl group having from 6 to 30 carbon atoms in total or an aralkyl group having from 6 to 30 carbon atoms in total; R 21  represents a hydrogen atom, an alkyl group or an aralkyl group; R 22  represents a hydrogen atom or an alkyl group; and R 23 , R 24 , R 25 , R 26  and R 27  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.    
     
     
         7 . The method for producing a phenylurethane compound according to  claim 4 , wherein, during the step of allowing the amino compound and the phenoxycarbonyl derivative to react, a reaction temperature is from 0 to 100° C.; wherein the step of adding the amino compound comprises adding the amino compound to the aqueous solvent in a reaction concentration of from 0.5 to 4.0 mols/liter; and wherein the step of adding the phenoxycarbonyl derivative comprises adding the phenoxycarbonyl derivative in an amount of from 0.8 to 2.0 equivalents per equivalent of the amino compound.  
     
     
         8 . The method for producing a phenylurethane compound according to  claim 5 , wherein, during the step of allowing the amino compound and the phenoxycarbonyl derivative to react, a reaction temperature is from 0 to 100° C.; wherein the step of adding the amino compound comprises adding the amino compound to the aqueous solvent in a reaction concentration of from 0.5 to 4.0 mols/liter; and wherein the step of adding the phenoxycarbonyl derivative comprises adding the phenoxycarbonyl derivative in an amount of from 0.8 to 2.0 equivalents per equivalent of the amino compound.  
     
     
         9 . The method for producing a phenylurethane compound according to  claim 6 , wherein, during the step of allowing the amino compound and the phenoxycarbonyl derivative to react, a reaction temperature is from 0 to 100° C.; wherein the step of adding the amino compound comprises adding the amino compound to the aqueous solvent in a reaction concentration of from 0.5 to 4.0 mols/liter; and wherein the step of adding the phenoxycarbonyl derivative comprises adding the phenoxycarbonyl derivative in an amount of from 0.8 to 2.0 equivalents per equivalent of the amino compound.  
     
     
         10 . An asymmetric urea compound comprising a molecular structure corresponding to the following general formula (10):  
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 3  each independently represent an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total; R 2  and R 4  each independently represent a hydrogen atom or an alkyl group; and the combination of substituents R 1  and R 2  differs from the combination of substituents R 3  and R 4 .  
     
     
         11 . An asymmetric urea compound comprising a molecular structure corresponding to the following general formula (11):  
       
         
           
           
               
               
           
         
       
       wherein R 11  and R 13  each independently represent an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group; R 12  and R 14  each independently represent a hydrogen atom or an alkyl group; and the combination of substituents R 11  and R 12  differs from the combination of substituents R 13  and R 14 .  
     
     
         12 . A method for producing an asymmetric urea compound, the method comprising the steps of: 
 (a) adding a base to an organic solvent;    (b) adding to the organic solvent a phenylurethane compound of the following general formula (12):                           wherein R 21  represents an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total, R 22  represents a hydrogen atom or an alkyl group, R 23 , R 24 , R 25 , R 26  and R 27  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and the combination of substituents R 21  and R 22  differs from the combination of substituents R 28  and R 29  of the following general formula (13);    (c) adding to the organic solvent an amino compound of the following general formula (13):                           wherein R 28  represents an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total, R 29  represents a hydrogen atom or an alkyl group, and the combination of substituents R 28  and R 29  differs from the combination of substituents R 21  and R 22  of the general formula (12); and    (d) allowing the phenylurethane compound and the amino compound to react to form an asymmetric urea compound of the following general formula (10):                           wherein R 1  and R 3  each independently represent an alkyl group having from 8 to 30 carbon atoms in total or an aralkyl group having from 8 to 30 carbon atoms in total; R 2  and R 4  each independently represent a hydrogen atom or an alkyl group; and the combination of substituents R 1  and R 2  differs from the combination of substituents R 3  and R 4 .    
     
     
         13 . A method for producing an asymmetric urea compound, the method comprising the steps of: 
 (a) adding a base to an organic solvent;    (b) adding to the organic solvent a phenylurethane compound of the following general formula (14):                           wherein R 31  represents an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group, R 32  represents a hydrogen atom or an alkyl group, R 33 , R 34 , R 35 , R 36  and R 37  each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and the combination of substituents R 31  and R 32  differs from the combination of substituents R 38  and R 39  of the following general formula (15);    (c) adding to the organic solvent an amino compound of the following general formula (15):                           wherein R 38  represents an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group, R 39  represents a hydrogen atom or an alkyl group, and the combination of substituents R 38  and R 39  differs from the combination of substituents R 31  and R 32  of the general formula (14); and    (d) allowing the phenylurethane compound and the amino compound to react to form an asymmetric urea compound of the following general formula (11):                           wherein R 11  and R 13  each independently represent an unsubstituted alkyl group having from 8 to 30 carbon atoms in total, an unsubstituted aralkyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylmethyl group having from 8 to 30 carbon atoms in total, an alkoxycarbonylethyl group having from 8 to 30 carbon atoms in total, an aryloxycarbonylethyl group having from 8 to 30 carbon atoms in total, or a carbamoylmethyl group; R 12  and R 14  each independently represent a hydrogen atom or an alkyl group; and the combination of substituents R 11  and R 12  differs from the combination of substituents R 13  and R 14 .    
     
     
         14 . The method for producing an asymmetric urea compound according to  claim 12 , wherein, during the step of allowing the amino compound and the phenylurethane compound to react, a reaction temperature is from 50 to 110° C.; wherein the step of adding the phenylurethane compound comprises adding the phenylurethane compound to the organic solvent in a reaction concentration of from 0.2 to 5.0 mols/liter; and wherein the step of adding the amino compound comprises adding the amino compound in an amount of from 0.8 to 5.0 equivalents per equivalent of the phenylurethane compound.  
     
     
         15 . The method for producing an asymmetric urea compound according to  claim 13 , wherein, during the step of allowing the amino compound and the phenylurethane compound to react, a reaction temperature is from 50 to 110° C.; wherein the step of adding the phenylurethane compound comprises adding the phenylurethane compound to the organic solvent in a reaction concentration of from 0.2 to 5.0 mols/liter; and wherein the step of adding the amino compound comprises adding the amino compound in an amount of from 0.8 to 5.0 equivalents per equivalent of the phenylurethane compound.  
     
     
         16 . A barbituric acid derivative comprising a molecular structure corresponding to the following general formula (18):  
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  each represent an optionally-substituted alkyl group or an optionally-substituted aralkyl group; R 1  and R 2  are different from each other; and L represents a hydrogen atom, or a substituent capable of leaving the barbituric acid derivative when the barbituric acid derivative is coupled with a diazo compound.  
     
     
         17 . The barbituric acid derivative according to  claim 16 , comprising a molecular structure corresponding to the following general formula (19):  
       
         
           
           
               
               
           
         
       
       wherein R 3  represents a hydrogen atom, an optionally-substituted alkyl group, or an optionally-substituted aralkyl group; R 4  represents an optionally-substituted alkyl group or an optionally-substituted aralkyl group; and R 3  is independent of R 4 .  
     
     
         18 . The barbituric acid derivative according to  claim 17 , comprising a molecular structure corresponding to the following general formula (20):  
       
         
           
           
               
               
           
         
       
       wherein R 5  represents a hydrogen atom, an optionally-substituted alkyl group, or an optionally-substituted aralkyl group; R 6  represents an optionally-substituted alkyl group or an optionally-substituted aralkyl group; and R 5  is independent of R 6 .  
     
     
         19 . A diazo thermal recording material comprising a support and a thermal recording layer disposed on the support, the recording layer including a diazo compound, a coupling component and an organic base, the coupling component including at least one barbituric acid derivative comprising a molecular structure corresponding to the following general formula (18):  
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  each represent an optionally-substituted alkyl group or an optionally-substituted aralkyl group; R 1  and R 2  are different from each other; and L represents a hydrogen atom, or a substituent capable of leaving the barbituric acid derivative when the barbituric acid derivative is coupled with a diazo compound.  
     
     
         20 . The diazo thermal recording material according to  claim 19 , wherein the coupling component includes at least one barbituric acid derivative comprising a molecular structure corresponding to the following general formula (19):  
       
         
           
           
               
               
           
         
       
       wherein R 3  represents a hydrogen atom, an optionally-substituted alkyl group, or an optionally-substituted aralkyl group; R 4  represents an optionally-substituted alkyl group or an optionally-substituted aralkyl group; and R 3  is independent of R 4 .  
     
     
         21 . The diazo thermal recording material according to  claim 19 , wherein the coupling component includes at least one barbituric acid derivative comprising a molecular structure corresponding to the following general formula (20):  
       
         
           
           
               
               
           
         
       
       wherein R 5  represents a hydrogen atom, an optionally-substituted alkyl group, or an optionally-substituted aralkyl group; R 6  represents an optionally-substituted alkyl group or an optionally-substituted aralkyl group; and R 5  is independent of R 6 .  
     
     
         22 . The diazo thermal recording material according to  claim 19 , wherein the diazo compound includes at least one compound comprising a molecular structure corresponding to the following general formula (21):  
       
         
           
           
               
               
           
         
       
       wherein R 7 , R 8  and R 9  each independently represent an optionally-substituted alkyl group or an optionally-substituted aryl group; and X −  represents an anion.  
     
     
         23 . The diazo thermal recording material according to  claim 19 , wherein the diazo compound is encapsulated in microcapsules.