FR2658529A1 - COMPLEX METALLIC COMPOUNDS. - Google Patents

Abstract

The compounds of formula (I) indicated below are suitable as dyes for the dyeing of very diverse textile or non-textile materials, and in particular for the dyeing of leathers and skins. (CF DRAWING IN BOPI) The meanings of the various substituents are mentioned in the description.

Description

COMPLEX METALLIC COMPOUNDS

  The present invention relates to novel compounds

  metal plexes, a process for preparing them, and

  that their use for the dyeing of various materials

  textiles or non-textiles, and especially leather.

  An object of the invention is therefore constituted

  metal complex compounds which, in their free acid form, correspond to the formula

D 1-N == Z-K G

C Oq O x

(CO)()

  N = NR as well as mixtures of metal complexes which contain them In formula 1, D1 and D2 each represent, independently of one another, the remainder of a benzene or naphthalene diazotable component, which carries, in the ortho-position with respect to the azo group, a hydroxy or carboxy group and which is optionally further substituted, Z represents a nitrogen atom or a CH group, X represents an oxygen atom or a group -NR In which R 1 represents a hydrogen atom or a C 1 -C 4 alkyl group, K represents, in the case where Z represents a CH group,

  the remainder of an o-hydroxybenzaldehyde or o-hydroxy-

  naphthaldehyde, which may be further substituted, or, in the case where Z represents a nitrogen atom,

  remainder of a coupler of the series of benzene or naphtha-

  or heterocyclic series, which carries the group X in ortho or alpha position with respect to the azo group and which is optionally further substituted, but

  provided that -KX does not represent a group of

mule

OH

  C = O R R represents an alkyl, aryl, cycloalkyl or aralkyl group, Me represents a chromium, cobalt or iron atom, and p and q each represent independently one of

the other, the number O or 1.

  The remains of diazotizable components D1 and D2 derived from

  for example aminobenzene or 1 or 2

  naphthylamine, aromatic amines considered to be

  each of which is a hydroxyl or carboxy group ortho to the amino group and may be further substituted by one or more groups

identical or different.

  Suitable substituents on the phenyl or naphthyl groups D 1 and D 2 are for example the following:

  C 1 -C 4 alkyl which generally include, here and elsewhere

  methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl or tert-butyl; C 1 -C 4 alkoxy,

  that it must be understood as comprehensively

  or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secbutoxy or tert-butoxy; halogeno, which generally means for example fluoro, bromo, and in particular chloro; trifluoromethyl; alkylsulfonyl

  C 1 -C 4, in particular methylsulfonyl or ethyl-

  sulfonyl; sulfamoyl; N-mono- (C 1 -C 4 alkyl) -

  sulfamoyl or N, N-di- (C 1 -C 4 alkyl) sulfamoyl; carba

  moyle; N-mono- (C 1 -C 4 alkyl) carbamoyl, or N, N-di-

  (C 1 -C 4 alkyl) carbamoyl; sulfo; nitro; cyano;

  carboxy; phenoxy; C 1 -C 4 alkanoylamino, in particular

  bind acetylamino, propionylamino; benzoylamino; alkoxy-

  C 1 -C 4 carbonyl, for example methoxycarbonyl or ethoxycarbonyl; phenylazo unsubstituted or substituted on the phenyl residue by sulfo, nitro, chloro, methyl

or methoxy.

  The radicals D 1 and D 2 derive, for example, amines

  anthranilic acid, 4 or 5-chloroacidic acid,

  anthranilic, 4 or 5-sulfoanthranilic acid, acid

  2-amino-3-naphthoic acid, 2-amino-1-hydroxybenzene, 4-chloro

  and 4,6-dichloro-2-amino-1-hydroxybenzene, 4 or 5-nitro-

  2-amino-1-hydroxybenzene, 4-chloro, 4-methyl and 4-

  acetylamino-6-nitro-2-amino-1-hydroxybenzene, 6-acetyl-

  amino and 6-chloro-4-nitro-2-amino-1-hydroxybenzene, 4-

  cyano-2-amino-1-hydroxybenzene, 4-sulfamoyl-2-amino-1-

  hydroxybenzene, 1-hydroxy-2-aminobenzene-4-sulfo

  anthranilide, 4-methoxy-2-amino-1-hydroxybenzene, 4-

  methoxy-5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2-

  amino-1-hydroxybenzene, 4-chloro-5-nitro-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydroxybenzene,

  6-acetylamino-4-chloro-2-amino-1-hydroxybenzene, 4,6-di-

  nitro-2-amino-1-hydroxybenzene, 2-amino-1-hydroxy-acid

  benzene-4 or -5-sulfonic acid, 4-nitro-2-amino-1-acid

  hydroxybenzene-6-sulfonic acid, 6-nitro-2-amino-1-acid

  4-chloro-2-amino-1-hydroxybenzene-4-sulfonic acid

  hydroxybenzene-6-sulfonic acid, 1-amino-2-hydroxy-acid

  naphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-nitro-

  naphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-acid

  chloronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-acid

  naphthalene-4,6-disulfonic acid, 2-amino-1-hydroxy-acid

  benzene-4,6-disulfonic acid, 4-phenylazo-2-aminophenol.

  Instead of the amines mentioned above,

  both of the hydroxy groups can also be considered for D 1 and D 2 the corresponding methoxyl compounds or the corresponding compounds whose hydroxy groups have been tosylated, such as anisidine, 4-chloranisidine, 4-chloranisidine, 4-nitroanisidine, 5-nitroanisidine, anisidine-4-sulfonic acid, anisidine-5-sulfonic acid or 1-hydroxy-2-aminobenzene

  tosylated, the methoxy or o-tosyl groups being transformed

  in OH groups before or during metallation

  compounds with these groups are then used

  everything when the 1-hydroxy-2-amino compounds correspond to

people copulate badly.

  In the advantageous dyes of formula (1), each of D 1 and D 2 represents, independently of one another, the residue of a 1-hydroxy-2-aminobenzene optionally further substituted by chloro, nitro, sulpho, methyl or methoxy. , methylsulfonyl, carbamoyl, sulfamoyl and / or

  phenylazo, or the remainder of a 2-hydroxy-1-amino-

  naphthalene, unsubstituted or substituted by sulfo and / or

  nitro, or the rest of the anthranilic acid.

  Particularly preferred diazotizable components

  Res for D 1 and D 2 are the following: 4-nitro-2- acid

  amino-1-hydroxybenzene-6-sulfonic acid, 6-nitro-2- acid

  amino-1-hydroxybenzene-4-sulfonic acid, 4 or 5-nitro-2-

  aminophenol, 4-chloro-2-aminophenol, 4-sulfamoyl-2-aminophenol

  phenol, 1-amino-2-hydroxynaphthalene-4-sulfonic acid and

  1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid.

  Preferably, q and p represent each, independently

  one of the other, the number 0.

  When Z represents the group CH, K represents the residue of an ohydroxynaphthaldehyde or preferably of a

  o-hydroxybenzaldehyde, the aromatic aldehydes

  may be unsubstituted or further substituted, for example by C 1 -C 4 alkyl, halo, sulfo or phenylazo, itself unsubstituted or substituted in the phenyl part by sulfo, nitro, chloro,

methyl, carboxy and / or methoxy.

  K here preferably represents the remainder of a

  hydroxybenzaldehyde, which is unsubstituted or is

  substituted with phenylazo, sulfophenylazo or disulfo

phenylazo.

  Examples of particular o-hydroxybenzaldehydes

  The most preferred compounds from which the radical K is derived are: 2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, - (2 '-, 3' or 4'-sulfophenylazo) -2-hydroxybenzaldehyde,

  and 5- (2 ', 5'-disulfophenylazo) -2-hydroxybenzaldehyde.

  If Z represents a nitrogen atom, what is

  the coupler from which the rest is derived K is then

  phenol, which is unsubstituted or substituted, for example,

  C 1 -C 5 alkyl, C 1 -C 4 alkoxy, N, N-di- (lower alkyl)

  C 1 -C 4) amino, (C 1 -C 4) alkoxycarbonylamino or alkanoyl

  amino C 1 -C 4; 1-naphthol or 2-naphthol, not

  substituted or substituted for example by C 1 alkyl