3-hydroxy-6H-benzo [c] chromene-6-one derivative and manufacturing method thereof

1. A method of manufacturing comprising reacting a compound or a salt thereof expressed by formula (I) below

wherein R 1 , R 2 , or R 3 represents a hydrogen atom, a lower alkyl group, a hydroxy group, or a lower alkoxy group,

and a compound or a salt thereof expressed by formula (II) below

wherein R 4 represents a hydrogen atom, a lower alkyl group, a nitro group, an amino group, or a lower alkylamino group, R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a hydrogen atom, a halogen atom, a lower alkyl group, a carboxyl group, a nitro group, or —NR a R b , wherein R a and R b are the same or different and each represents a hydrogen atom, a formyl group, a lower alkyl carbonyl group, a lower alkenyl carbonyl group, a lower cycloalkyl carbonyl group, an aryl carbonyl group, a carboxyl group, a lower alkoxy carbonyl group, a lower alkenyloxycarbonyl group, a lower cycloalkyloxycarbonyl group, an aryloxy carbonyl group, or an arylalkyloxycarbonyl group, and X represents a halogen atom, a lower alkylsulfonyloxy group, or an aryl sulfonyloxy group,

to produce,

a compound or a salt thereof expressed by formula (III) below

wherein R 1 , R 2 , R 3 , R 4 , R 5 , or R 6 have the same definitions as in formula (I) and formula (II) above,

wherein the compound or the salt thereof expressed by formula (I) above and the compound or the salt thereof expressed by formula (II) above are reacted in the presence of carbonate and copper salt or in presence of hydroxide salt, carbonate, and copper salt.

2. A method of manufacturing comprising reacting a compound or a salt thereof expressed with a formula (Ia) below

and a compound or a salt thereof expressed by formula (II a) below

wherein R 7 represents a hydrogen atom, a lower alkyl group, a nitro group, an amino group, or a lower alkylamino group, R 8 represents a hydrogen atom or a lower alkyl group, R 9 represents a hydrogen atom or a lower alkyl group, R 10 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, an aryl group, a hydroxy group, a lower alkoxy group, a lower alkenyloxy group, a lower cycloalkyloxy group, an aryloxy group, or an arylalkyloxy group, and X representing a halogen atom, a lower alkylsulfonyloxy group, or an aryl sulfonyloxy group,

to produce,

a compound or a salt thereof expressed by formula (IIIa) below

wherein R 7 , R 8 , R 9 , or R 10 have the same definitions as in formula (IIa),

wherein the reaction is conducted in the presence of carbonate and copper salt or in the presence of hydroxide salt, carbonate, and copper salt.

3. The method according to claim 2 , wherein

in formula (IIIa), R 7 , R 8 , and R 9 each represent a hydrogen atom and R 10 represents a lower alkyl group, an aryl group, a lower alkoxy group, or an arylalkyloxy group.

4. The method according to claim 2 , wherein

in formula (IIIa), R 7 , R 8 , and R 9 each represent a hydrogen atom and R 10 represents a methyl group, a phenyl group, a tert-butoxy group, or a benzyloxy group.

5. The method according to claim 2 , wherein

the compound or the salt thereof expressed by formula (IIIa) is a compound or a salt thereof selected from the group consisting of

8-acetamide-3-hydroxy-6H-benzo [c] chromene-6-one,

8-benzyloxycarbonylamino-3-hydroxy-6H-benzo [c] chromene-6-one,

8-benzoylamino-3-hydroxy-6H-benzo [c] chromene-6-one, and

8-(tert-butoxycarbonylamino)-3-hydroxy-6H-benzo [c] chromene-6-one.

6. A method of manufacturing comprising reacting a compound or a salt thereof expressed by formula (I) below

wherein R 1 , R 2 , or R 3 represents a hydrogen atom, a lower alkyl group, a hydroxy group, or a lower alkoxy group,

and a compound or a salt thereof expressed by formula (II) below

wherein R 4 represents a hydrogen atom, a lower alkyl group, a nitro group, an amino group, or a lower alkylamino group, R 5 represents a hydrogen atom or a lower alkyl group, R 6 represents a hydrogen atom, a halogen atom, a lower alkyl group, a carboxyl group, a nitro group, or —NR a R b , wherein R a and R b are the same or different and each represents a hydrogen atom, a formyl group, a lower alkyl carbonyl group, a lower alkenyl carbonyl group, a lower cycloalkyl carbonyl group, an aryl carbonyl group, a carboxyl group, a lower alkoxy carbonyl group, a lower alkenyloxycarbonyl group, a lower cycloalkyloxycarbonyl group, an aryloxy carbonyl group, or an arylalkyloxycarbonyl group, and X represents a halogen atom, a lower alkylsulfonyloxy group, or an aryl sulfonyloxy group,

in presence of carbonate and copper salt or in presence of hydroxide salt, carbonate, and copper salt to produce,

a compound or a salt thereof expressed by formula (III) below

wherein R 1 , R 2 , R 3 , R 4 , R 5 , or R 6 have the same definitions as in formula (I) and formula (II),

and reacting the compound or the salt thereof expressed by formula (III) above to react with hydroxide salt for conversion to a compound or a salt thereof expressed by formula (IV) below

wherein R 1 , R 2 , R 3 , R 4 , R 5 , or R 6 have the same definitions as in formula (I) and formula (II),

and then reacting the compound or the salt thereof expressed by formula (IV) above with an acid.

7. A method of manufacturing comprising reacting, a compound or a salt thereof expressed by formula (Ia) below

and a compound or a salt thereof expressed by formula (IIa) below

wherein R 7 represents a hydrogen atom, a lower alkyl group, a nitro group, an amino group, or a lower alkylamino group, R 8 represents a hydrogen atom or a lower alkyl group, R 9 represents a hydrogen atom or a lower alkyl group, R 10 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, an aryl group, a hydroxy group, a lower alkoxy group, a lower alkenyloxy group, a lower cycloalkyloxy group, an aryloxy group, or an arylalkyloxy group, and X representing a halogen atom, a lower alkylsulfonyloxy group, or an aryl sulfonyloxy group,

in presence of carbonate and copper salt or in presence of hydroxide salt, carbonate, and copper salt to produce,

a compound or a salt thereof expressed by formula (IIIa) below

wherein R 7 , R 8 , R 9 , or R 10 have the same definitions as in formula (IIa),

and reacting the compound or the salt thereof expressed by formula (IIIa) above to react with hydroxide salt for conversion to a compound or a salt thereof expressed by formula (IVa) below

wherein R 7 , R 8 , R 9 , or R 10 have the same definitions as in formula (IIa),

and then reacting the compound or the salt thereof expressed with formula (IVa) above with an acid.

8. The method according to claim 7 , wherein

in formula (IIIa), R 7 , R 8 , and R 9 each represent a hydrogen atom and R 10 represents a lower alkyl group, an aryl group, a lower alkoxy group, or an arylalkyloxy group.

9. The method according to claim 7 , wherein

in formula (IIIa), R 7 , R 8 , and R 9 each represent a hydrogen atom and R 10 represents a methyl group, a phenyl group, a tert-butoxy group, or a benzyloxy group.

10. The method according to claim 7 , wherein

the compound or the salt thereof expressed with formula IIIa) is a compound or a salt thereof selected from the group consisting of

8-acetamide-3-hydroxy-6H-benzo [c] chromene-6-one,

8-benzyloxycarbonylamino-3-hydroxy-6H-benzo [c] chromene-6-one,

8-benzoylamino-3-hydroxy-6H-benzo [c] chromene-6-one, and

8-(tert-butoxycarbonylamino)-3-hydroxy-6H-benzo [c] chromene-6-one.