Phenylazole compound, production process therefor and antioxidant

A production process of a compound represented by formula (1):

• (wherein,
• R1 represents a hydrogen atom or a C1-6 alkyl group which may be substituted,
• A represents an imidazolyl group or a pyrazolyl group represented by the following formulae:
• (wherein
• R2 and R3 represent a hydrogen atom or a C1-6 alkyl group which may be substituted by G1,
• R4 represents a hydrogen atom or a C1-6 alkyl group which may be substituted by G1, a C1-6 alkylcarbonyl group which may be substituted by G1, or a benzoyl group which may be substituted by G1,
• n represents 0 or an integer of 1 to 3,
• p represents 0 or an integer of 1 or 2, and
• R2 and R3 may be identical to each other, or different from each other, when n and p are 2 or more),
• B represents a group represented by the following formula:
• (wherein
• R5 and R6 each independently represents a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C2-6 alkenyloxy group, a C2-6 alkynloxy group, a C1-6 acyloxy group, or a C3-6 cycloalkyl group, or a phenyl group which may have a substituent,
• k represents 0 or an integer of 1 to 15, and
• R5 and R6 may be identical to each other, or different from each other, when k is 2 or more),
• Z represents a chroman-2-yl group which is substituted by G2, a 2,3-dihydrobenzofuran-2-yl group which is substituted by G2, a thiochroman-2-yl group which is substituted by G2, a 2,3-dihydrobenzothiophene-2-yl group which is substituted by G2, or a 1,3-benzoxathiol-2-yl group which is substituted by G2,
• G1 represents a cyano group, a formyl group, a hydroxyl group, an amino group, a dimethylamino group, or a halogen atom, and
• G2 is represented by the following formula:
• NHR (wherein R represents a hydrogen atom, a C1-6 alkylcarbonyl group, or a benzoyl group which may have a substituent), comprising:
• a step 1 in which a compound represented by the following formula (1′)
• (wherein
• R1 represents a hydrogen atom or a C1-6 alkyl group which may be substituted,
• A represents an imidazolyl group or a pyrazolyl group represented by the following formulae:
• (wherein
• R2 and R3 represent a hydrogen atom or a C1-6 alkyl group which may be substituted by G1,
• R4 represents a hydrogen atom or a C1-6 alkyl group which may be substituted by G1, a C1-6 alkylcarbonyl group which may be substituted by G1, or a benzoyl group which may be substituted by G1,
• n represents 0 or an integer of 1 to 3,
• p represents 0 or an integer of 1 or 2, and
• R2 and R3 may be identical to each other, or different from each other, when n and p are 2 or more)),
• B represents a group represented by the following formula:
• (wherein
• R5 and R6 each independently represents a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C2-6 alkenyloxy group, a C2-6 alkynloxy group, a C1-6 acyloxy group, or a C3-6 cycloalkyl group, or a phenyl group which may have a substituent,
• k represents 0 or an integer of 1 to 15, and
• R5 and R6 may be identical to each other, or different from each other, when k is 2 or more), and
• Z′ is represented by the following formula (A)′, (B)′, or (C)′:
• (wherein
• * represents an asymmetric carbon atom,
• X1 represents an oxygen atom or a sulfur atom,
• R7 to R17 each independently represents a hydrogen atom or a C1-6 alkyl group, and
• G2 is represented by the following formula:
• NHR
• (wherein R represents a hydrogen atom, a C1-6 alkylcarbonyl group, or a benzoyl group which may have a substituent))
• is produced by reacting an amine compound represented by formula (2):
• (wherein
• R1 represents a hydrogen atom or a C1-6 alkyl group which may be substituted, and
• A represents an imidazolyl group or a pyrazolyl group represented by the following formulae:
• (wherein
• R2 and R3 represent a hydrogen atom or a C1-6 alkyl group which may be substituted by G1,
• R4 represents a hydrogen atom or a C1-6 alkyl group which may be substituted by G1, a C1-6 alkylcarbonyl group which may be substituted by G1, or a benzoyl group which may be substituted by G1,
• n represents 0 or an integer of 1 to 3,
• p represents 0 or an integer of 1 or 2, and
• R2 and R3 may be identical to each other, or different from each other, when n and p are 2 or more))
• with a compound represented by the following formula (3):
• YOC-B-Z′ (3)
• (wherein
• Y represents a hydroxyl group or a halogen atom,
• B represents a group represented by the following formula:
• (wherein
• R5 and R6 each independently represents a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C2-6 alkenyloxy group, a C2-6 alkynloxy group, a C1-6 acyloxy group, or a C3-6 cycloalkyl group, or a phenyl group which may have a substituent,
• k represents 0 or an integer of 1 to 15, and
• R5 and R6 may be identical to each other, or different from each other, when k is 2 or more) and
• Z′ is represented by the following formula (A)′, (B)′, or (C)′:
• (wherein
• * represents an asymmetric carbon atom,
• X1 represents an oxygen atom or a sulfur atom,
• R7 to R17 each independently represents a hydrogen atom or a C1-6 alkyl group, and
• G2 is represented by the following formula:
• NHR
• (wherein R represents a hydrogen atom, a C1-6 alkylcarbonyl group, or a benzoyl group which may have a substituent));
• and
• a step 2 in which the nitro compound produced in the step 1 is converted to an amino group using a reducing agent.

An antioxidant comprising as its active ingredient at least one compound represented by formula (1):

• (wherein
• R1 represents a hydrogen atom or a C1-6 alkyl group which may be substituted,
• A represents an imidazolyl group or a pyrazolyl group represented by the following formulae:
• (wherein
• R2 and R3 represent a hydrogen atom or a C1-6 alkyl group which may be substituted by G1,
• R4 represents a hydrogen atom or a C1-6 alkyl group which may be substituted by G1, a C1-6 alkylcarbonyl group which may be substituted by G1, or a benzoyl group which may be substituted by G1,
• n represents 0 or an integer of 1 to 3,
• p represents 0 or an integer of 1 or 2, and
• R2 and R3 may be identical to each other, or different from each other, when n and p are 2 or more)),
• B represents a group represented by the following formula:
• (wherein
• R5 and R6 each independently represents a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C2-6 alkenyloxy group, a C2-6 alkynloxy group, a C1-6 acyloxy group, or a C3-6 cycloalkyl group, or a phenyl group which may have a substituent,
• k represents 0 or an integer of 1 to 15, and
• R5 and R6 may be identical to each other, or different from each other, when k is 2 or more),
• Z represents a chroman-2-yl group which is substituted by G2, a 2,3-dihydrobenzofuran-2-yl group which is substituted by G2, a thiochroman-2-yl group which is substituted by G2, a 2,3-dihydrobenzothiophene-2-yl group which is substituted by G2, or a 1,3-benzoxathiol-2-yl group which is substituted by G2,
• G1 represents a cyano group, a formyl group, a hydroxyl group, an amino group, a dimethylamino group, or a halogen atom, and
• G2 is represented by the following formula:
• NHR (wherein R represents a hydrogen atom, a C1-6 alkylcarbonyl group, or a benzoyl group which may have a substituent) or a pharmaceutically acceptable salt thereof.