초록 ▼

Compounds of the formula I Ar is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1and R2are C1-C20alkyl, OR11, CF3or halogen; R3, R4and R5are hydrogen, C1-C20alkyl, OR11or halogen; R6is unsubstitu

Compounds of the formula I Ar is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1and R2are C1-C20alkyl, OR11, CF3or halogen; R3, R4and R5are hydrogen, C1-C20alkyl, OR11or halogen; R6is unsubstituted or substituted C1-C24alkyl, C2-C24alkyl, which is interrupted by O, S or NR14and is unsubstituted or substituted; C2-C24alkenyl, uninterrupted or interrupted by O, S or NR14and unsubstituted or substituted; unsubstituted or substituted C7-C24arylalkyl; C4-C24cycloalkyl, uninterrupted or interrupted by O, S and/or NR14; or C8-C24arylcycloalkyl; R11is C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O or S and unsubstituted or substituted; R12and R13are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O atoms and unsubstituted or substituted; or R12and R13together are C3-C5alkylene, uninterrupted or interrupted by O, S or NR14; R14is hydrogen, phenyl, C1-C12alkyl or C2-C12alkyl, interrupted by O or S and unsubstituted or substituted; and M is hydrogen, Li, Na or K; are valuable intermediates for the preparation of unsymmetrical bisacylphosphine oxides and monoacylphosphine oxides.

대표청구항 ▼

Compounds of the formula I Ar is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1and R2are C1-C20alkyl, OR11, CF3or halogen; R3, R4and R5are hydrogen, C1-C20alkyl, OR11or halogen; R6is unsubstitu

Compounds of the formula I Ar is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1and R2are C1-C20alkyl, OR11, CF3or halogen; R3, R4and R5are hydrogen, C1-C20alkyl, OR11or halogen; R6is unsubstituted or substituted C1-C24alkyl, C2-C24alkyl, which is interrupted by O, S or NR14and is unsubstituted or substituted; C2-C24alkenyl, uninterrupted or interrupted by O, S or NR14and unsubstituted or substituted; unsubstituted or substituted C7-C24arylalkyl; C4-C24cycloalkyl, uninterrupted or interrupted by O, S and/or NR14; or C8-C24arylcycloalkyl; R11is C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O or S and unsubstituted or substituted; R12and R13are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O atoms and unsubstituted or substituted; or R12and R13together are C3-C5alkylene, uninterrupted or interrupted by O, S or NR14; R14is hydrogen, phenyl, C1-C12alkyl or C2-C12alkyl, interrupted by O or S and unsubstituted or substituted; and M is hydrogen, Li, Na or K; are valuable intermediates for the preparation of unsymmetrical bisacylphosphine oxides and monoacylphosphine oxides. n the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).7. The process as claimed in claim 5, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).8. The process as claimed in claim 1, wherein the reaction of the ortho-alkylnitrobenzene represented by formula (1) with the vinyl compound represented by formula (2) in the first step is conducted in the presence of at least one selected from the group consisting of a solvent capable of dissolving at least part of the base and a catalyst capable of solubilizing the base.9. The process as claimed in claim 8, wherein the solvent capable of dissolving at least part of the base is a cyclic urea derivative.10. The process as claimed in claim 4, wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).11. The process as claimed in claim 3, wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).12. The process as claimed in claim 2, wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).13. The process as claimed in claim 1, wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).14. The process as claimed in claim 9, wherein in the third step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).15. The process as claimed in claim 8, wherein in the step, a hydroxylamine derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) or an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) in the presence of hydrogen peroxide, to provide an oxime represented by formula (6):wherein R 1to R4and R6to are as defined in formulas (1) and (2), which is then converted by aromatization into a 5-nitro-1-aminonaphthalene derivative represented by formula (7):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced into the 1,5-diaminonaphthalene derivative represented by formula (5).16. The process as claimed in claim 4, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).17. (Previously added) The process as claimed in claim 3, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).18. The process as claimed in claim 2, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).19. The process as claimed in claim 1, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).20. The process as claimed in claim 9, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diamninonaphthalene derivative represented by formula (5).21. The process as claimed in claim 8, wherein in the third step, an ammonia derivative as the amine is reacted with the 5-nitro-1-tetralone derivative represented by formula (4) to provide an imine represented by formula (8):wherein R 1to R4and R6to R7are as defined in formulas (1) and (2), which is then reduced and aromatized to provide the 1,5-diaminonaphthalene derivative represented by formula (5).