Preparation of quaterylene-bisimides, useful as fluorescent dyes, e.g. for natural or synthetic textiles or as markers for biomolecules, by base cyclization of a bis-perylene-dicarboxylic acid imide

摘要

Preparing quaterylene-bisimides (I) comprising treating the corresponding 9,9'-bis(perylene-3,4-dicarboxylic acid-3,4-imide) (II) with a tertiary alkoxide (particularly potassium tert-amylate or, best tert-butylate) in presence of an auxiliary base, especially DBU (1,5-diazabicyclo(4,3,0)non-5-ene, is new. Preparing quaterylene-bisimides of formula (I) comprises treating the corresponding 9,9'-bis(perylene-3,4-dicarboxylic acid-3,4-imide) of formula (II) with a tertiary alkoxide (particularly potassium tert-amylate or, best tert-butylate) in presence of an auxiliary base, especially DBU (1,5-diazabicyclo(4,3,0)non-5-ene. R1, R2 = H or 1-4 (preferably 1-3) groups such as isocyclic aromatic groups (especially mono- to tetracyclic, particularly mono- or bicyclic groups such as phenyl, diphenyl, naphthyl or anthryl), heterocyclic aromatic groups (preferably mono- to tricyclic groups, which may be pure heterocyclic groups or a heterocyclic ring and one or more fused benzene rings) or Z. The isocyclic as well as the heterocyclic aromatic groups may be substituted by Z which do not impart water solubility Z = halo e.g. Cl, Br, I or F, alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C, the alkyl groups may be substituted by groups which do not impart water solubility, OR9, CN, N(R10)(R11), COR12 , N(R13)COR14, N(R15)COOR16, N(R17)CON(R18)(R19), NHSO2R20, SO2R21, SOR22, SO2OR23, CON(R24)(R25), SO2N(R26)(R27), N=N-R28, OCOR29, OCONHR30; R9 = H, alkyl, aryl, e.g. naphthyl or especially unsubstituted phenyl, 3-24C cycloalkyl; R10 , R11, R13, R20, R21, R22, R23, R24, R25, R26, R27, R29 = alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C. The alkyl groups may be substituted by groups which do not impart water solubility; R12, R30 = halo; R15-R19 = alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C, the alkyl groups may be substituted by groups which do not impart water solubility, or OR9; R28 = is the residue of coupling component or phenyl (optionally substituted by halo, alkyl or -O-alkyl). The full definitions are given in the DEFINITIONS (Full Definitions) Field. An Independent claim is also included for a method for preparing (II) by reacting the corresponding perylene-3,4,9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide (III) in presence of copper powder and an auxiliary base.