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US 6,271,418 B1Granted
Process for preparing (hetero) aromatic substituted benzene derivatives
AssigneeNippon Kayaku Kabushiki Kaisha
InventorsTetsuya Toya, Hidetoshi Shirakura, Junichi Kon
Life of this patent
Estimating the term…
Abstract
Three processes are described for preparing (hetero)aromatic substituted benzene derivatives which comprise aromatization of cyclohexenone derivatives via (chloro)cyclohexadiene derivatives.
Claims12
A process for preparing a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s);
- which comprises aromatizing a cyclohexenone derivative represented by the formula (II):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s).
4 more elements
A process for preparing a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s);
- which comprises halogenating a cyclohexenone derivative represented by the formula (II):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), to obtain a chlorocyclohexadiene derivative or a mixture of isomers represented by the formula (IIIA and/or IIIB):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- W represents a halogen atom;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), followed by dehydro-, dehalogenation.
8 more elements
A process for preparing a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s);
- which comprises halogenating a cyclohexenone derivative represented by the formula (II):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), to obtain a halocyclohexadiene derivative or a mixture of isomers represented by the formula (IIIA and/or IIIB):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- W represents a halogen atom;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), followed by dehydrogenation to a halobenzene derivative represented by the formula (IV):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- W represents a halogen atom;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), and reduction to a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s).
15 more elements
A process for preparing a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy c group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s);
- which comprises reducing a cyclohexenone derivative represented by the formula (II):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), to obtain a cyclohexenol derivative represented by the formula (V):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), followed by dehydration to a cyclohexadiene derivative or a mixture of isomers represented by the formula (VIIA add/or VIIB):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s), and dehydrogenation to a benzene derivative represented by the formula (I):
- wherein X represents a phenyl group, a naphthyl group or a heteroaromatic group which are optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s), halogen atom(s) or nitro group(s);
- Y represents a (C1-C4)alkoxycarbonyl group, a cyano group, a nitro group or a (C1-C4)alkoxysulfonyl group;
- R1, R2 and R3 each independently represent a hydrogen atom, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a phenyl group which is optionally substituted with (C1-C4)alkyl group(s), (C1-C4)alkoxy group(s) or halogen atom(s).
13 more elements
Dependencies are inferred from the claim text.