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

A phenylurethane compound comprising a molecular structure corresponding to the following general formula (2):

• 53
• wherein R11 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;
• R12 represents a hydrogen atom or an alkyl group;
• R11 and R12 may be bonded to each other to form a ring;
• and R13, R14, R15, R16 and R17 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.

A phenylurethane compound comprising a molecular structure corresponding to the following general formula (3):

• 54
• wherein R20 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;
• R21 represents a hydrogen atom, an alkyl group or an aralkyl group;
• R22 represents a hydrogen atom or an alkyl group;
• and R23, R24, R25, R26 and R27 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.

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):
• 55
• in which R31 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 R32 represents a hydrogen atom or an alkyl group;
• (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (5):
• 56
• in which R33, R34, R35, R36 and R37 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X1 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):
• 57
• wherein R1 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;
• R2 represents a hydrogen atom or an alkyl group;
• R1 and R2 may be bonded to each other to form a ring;
• and R3, R4, R5, R6 and R7 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.

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):
• 58
• wherein R41 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 R42 represents a hydrogen atom or an alkyl group;
• (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (7):
• 59
• wherein R43, R44, R45, R46 and R47 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X2 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):
• 60
• wherein R11 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;
• R12 represents a hydrogen atom or an alkyl group;
• R11 and R12 may be bonded to each other to form a ring;
• and R13, R14, R15, R16 and R17 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.

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):
• 61
• wherein R50 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, R51 represents a hydrogen atom, an alkyl group or an aralkyl group, and R52 represents a hydrogen atom or an alkyl group;
• (c) adding to the aqueous solvent a phenoxycarbonyl derivative of the following general formula (9):
• 62
• wherein R53, R54, R55, R56 and R57 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group, and X3 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):
• 63
• wherein R20 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;
• R21 represents a hydrogen atom, an alkyl group or an aralkyl group;
• R22 represents a hydrogen atom or an alkyl group;
• and R23, R24, R25, R26 and R27 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a carbonyl derivative group, or a nitro group.

An asymmetric urea compound comprising a molecular structure corresponding to the following general formula (10):

• 64
• wherein R1 and R3 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;
• R2 and R4 each independently represent a hydrogen atom or an alkyl group;
• and the combination of substituents R1 and R2 differs from the combination of substituents R3 and R4.

An asymmetric urea compound comprising a molecular structure corresponding to the following general formula (11):

• 65
• wherein R11 and R13 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;
• R12 and R14 each independently represent a hydrogen atom or an alkyl group;
• and the combination of substituents R11 and R12 differs from the combination of substituents R13 and R14.

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):
• 66
• wherein R21 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, R22 represents a hydrogen atom or an alkyl group, R23, R24, R25, R26 and R27 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 R21 and R22 differs from the combination of substituents R28 and R29 of the following general formula (13);
• (c) adding to the organic solvent an amino compound of the following general formula (13):
• 67
• wherein R28 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, R29 represents a hydrogen atom or an alkyl group, and the combination of substituents R28 and R29 differs from the combination of substituents R21 and R22 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):
• 68
• wherein R1 and R3 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;
• R2 and R4 each independently represent a hydrogen atom or an alkyl group;
• and the combination of substituents R1 and R2 differs from the combination of substituents R3 and R4.

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):
• 69
• wherein R31 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, R32 represents a hydrogen atom or an alkyl group, R33, R34, R35, R36 and R37 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 R31 and R32 differs from the combination of substituents R38 and R39 of the following general formula (15);
• (c) adding to the organic solvent an amino compound of the following general formula (15):
• 70
• wherein R38 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, R39 represents a hydrogen atom or an alkyl group, and the combination of substituents R38 and R39 differs from the combination of substituents R31 and R32 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):
• 71
• wherein R11 and R13 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;
• R12 and R14 each independently represent a hydrogen atom or an alkyl group;
• and the combination of substituents R11 and R12 differs from the combination of substituents R13 and R14.

A barbituric acid derivative comprising a molecular structure corresponding to the following general formula (18):

• 72
• wherein R1 and R2 each represent an optionally-substituted alkyl group or an optionally-substituted aralkyl group;
• R1 and R2 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.

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):

• 75
• wherein R1 and R2 each represent an optionally-substituted alkyl group or an optionally-substituted aralkyl group;
• R1 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.