New stable, organic solvent-soluble cationic dyes with cyanoborate, fluoroalkyl phosphate, fluoroalkyl borate or imidate anion, useful e.g. for dyeing plastics, synthetic fibers or flexographic printing inks

摘要

New cationic dyes (I) consist of a cyanoborate, fluoroalkyl phosphate, fluoroalkyl borate or imidate anion and an azine, xanthene, polymethine, styryl, azo, tetrazolium, pyrylium, benzopyrylium, thiopyrylium, benzothiopyrylium, thiazine, oxazine, triarylmethane, diarylmethane, acridine, quinoline, isoquinoline or quaternized azafluorenone dye cation. Cationic dyes of formula CAT + . Y - (I) and their salts are new. Y -cyanoborate anion of formula (B(CN) yF 4 - y - x(R 0) x) - (II-1), fluoroalkyl phosphate anion of formula (P(C pF 2 p + 1 - xH x) yF 6 - y) - (II-2), fluoroalkyl borate anion of formula (B(C pF 2 p + 1 - xH x) yF 4 - y) - (II-3) or imidate anion of formula ((C rF 2 r + 1 - sH sXO z)N(C qF 2 q + 1 - kH kXO z)) - (II-4); y : 1-4; x : 0-3; R 0alkyl, fluorinated alkyl, aryl, fluorinated aryl, cycloalkyl or alkaryl; or may also be H if y = 3 or 4; p : 1-20; X : C or S; r, q : 0-20; s : 0 to (2 r + 1), provided that s = 0 if r = 0; q : 0 to (2 k + 1), provided that q = 0 if k = 0; CAT +cation of an azine, xanthene polymethine, styryl, azo, tetrazolium, pyrylium, benzopyrylium, thiopyrylium, benzothiopyrylium, thiazine, oxazine, triarylmethane, diarylmethane, acridine, quinoline, isoquinoline or quaternized azafluorenone dye; provided that: (1) z = 2 if X = S; (2) z = 1 and r or q = 1 or more if X = C; (3) the C-atoms of alkyl chains in (II-4) are optionally linked by single bonds, the resulting alkylene chains being optionally substituted by one or more F; and (4) the compound 3,3'-diethoxyethyl-2,2'-thiadicarbocyanine trifluoromethyltrifluoroborate is excluded. Independent claims are included for: (a) the preparation of (I); (b) new cyclic imine salt intermediates of formula (XXIV) and new diazonium salt intermediates of formula R'-N 2 + . Y - (XXIX); and (c) the preparation of (XXIV) and (XXIX). [Image] n : 0-4; G : H, alkyl, alkenyl, aryl, heteroaryl, N=C(R) 2, CONH-aryl, CO-aryl or CONH-alkyl; R : alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; R 1H, Cl, Br, I, optionally mono- or polychlorinated alkyl, alkenyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, mono- or dialkylamino, CHO, alkanoyl, aroyl, CN, -N=N-aryl, P(aryl) 2, NHCO-alkyl or NHCO-alkyl; ring system of (XXIV) : N-containing, 5-13 membered, mono-, bi- or tricyclic heterocycle, optionally additionally containing 1-3 N and/or 1 or 2 O or S and optionally substituted by one or more Z; Z : H, alkyl, NO 2, halo, OH, COOH, alkoxy, SCN, SCF 3, alkoxycarbonyl, alkoxycarbonylmethyl, NH 2 or mono- or dialkylamino; R' : aryl or heteroaryl.