FR2594128A1 - ASYMMETRIC CHROMIUM 1: 2 COMPLEX DYES, THEIR PREPARATION AND THEIR USE - Google Patents

Abstract

The new chromium complex dyes, of formula: (CF DRAWING IN BOPI) in which: Z represents a nitrogen atom or a CH group; A represents a residue from the benzene or naphthalene series; B represents, when Z is a nitrogen atom, the residue of a coupling component, or when Z represents the CH group, the residue of an o-hydroxy-aldehyde; X represents an oxygen atom or also, when Z is a nitrogen atom, a group of formula -NH- or -N (C1-4 alkyl) -; Y ** 1 represents a chlorine atom or a sulfo, C1-4 alkyl, SO2- (C1-4 alkyl), -SO2NH2, -SO2NH (C1-4 alkyl) or -SO2N (C1- alkyl) group 4) 2; Y ** 2 represents a hydrogen or chlorine atom or a sulfo or C1-4 alkyl group; R ** 1 represents a hydrogen atom or a group of the formula -SO2-Q or of the formula -CO (O) nQ, in which n is zero or 1 and Q is a C1-5 alkyl or phenyl radical, this last optionally substituted; P is 0 or 1; and Ka ** (anion) is a cation, are suitable for dyeing wool, polyamide and especially leather.

Description

Chromium complex dyes 1: 2 asymmetric, their preparation

and their use.

  The present invention relates to asymmetric 1: 2 chromium complex dyes of the formula ## STR1 ## wherein:

(CO) / I

A - N = Z -B

  wherein Z represents a nitrogen atom or a CH group; A represents a residue of the benzene or naphthalene series,

  which has a hydroxyl or carboxyl group in the ortho position with respect to

  azo group or azomethine group; B represents, when Z is a nitrogen atom, the remainder of a coupling component, the coupling component containing the X group in the ortho or ¿position with respect to the azo moiety, where Z represents the CH group; remainder of an ohydroxy-aldehyde; X represents an oxygen atom or also, when Z is a nitrogen atom, a group of formula -NR-, wherein R represents a hydrogen atom or a C14 alkyl group; Atomic acid atom 1-4; Y 1 represents a chlorine atom or a sulfo group, C 1, 2 R 2 alkyl, OR 3 SO 2 -R 2, R 2 being a C 1-4 alkyl radical, or -SO 2 NRR 3, R and R being each, independently, one of the other, a hydrogen atom or a C1-4 alkyl radical; y represents a hydrogen or chlorine atom or a sulfo or C14 alkyl group; R represents a hydrogen atom or a group of formula -SO 2 -Q or of formula -CO- (O) n -Q, in which n is zero or 1 and Q is a C 15 alkyl or phenyl radical; the phenyl radical may be substituted by a halogen atom or a nitro group, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; p is 0 or 1; and

KaP represents a cation.

  In the case of the dyes according to the invention, these are asymmetric chromium 1: 2 complexes. When X is an oxygen atom, Z an atom

  nitrogen and p is zero, the diazo component A and the copula component

  B must not be identical to the component at the same time

  diazo and the copulation component of the other azo dye.

  In chromium complex dyestuffs of formula (1) above

  according to the invention, the remainder A may still bear one or more other substitutions

  for example a halogen such as chlorine or bromine, or a lower alkyl or lower alkoxy, nitro, cyano, sulfo, carboxyl, phosphono, alkylsulfonyl, such as for example methylsulfonyl, sulfamido, such as for example sulfamido or N-methylsulfamido , acylamino,

  phenylazo, sulfophenylazo or methoxyphenylazo. By "lower alkyl groups"

  In the context of the present application, it is generally understood that those having from 1 to 6, preferably 1 or 2 atoms,

  carbon, and the term "acylamino" denotes lower alkanoylamino residues

  lower alkylsulfonylamino and lower alkoxycarbonylamino

  as well as aroylamino, aryloxycarbonylamino and arylsulfonylamino residues.

  The residue A derives, for example, from the following amines: pentanilic acid, 4- or 5-chloro-anthranilic acid, 4- or -sulfofuranilic 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-

  ene, 4-chloro-, 4-methyl- and 4-acetylamino-6-nitro-2-amino-

  1-Hydroxybenzene, 4-chloro, 4-methyl- and 4-acetylamino-6-nitro-2-amino-

-3-

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

  benzene, 4-cyano-2-amino-1-hydroxybenzene, 4-sulfonamido-2-amino-1-

  hydroxybezizene, 1-hydroxy-2-aninobenzene-4-sulpho-anthranilide, 4methoxy-

  2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene, 4-chloro and 4-methyl-5-nitro-2-yl amino

  1-hydroxybenzene, 3,4,6-trichloro-2-amino-11-hydroxybenzene ,. 6acétylamino-

  4-Cliloro-2-aminto-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene,

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

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

  benzenesulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid,

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

  6-nitronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-chloroacetate

  Naphtalene-4-sulfonic acid, 1-amino-2-hydroxynaphthalic acid-4,6-

  disulfonic acid, 2-amino-1-hydroxybenzene-4,6-disulfonic acid.

  In place of the hydroxyl-containing amines mentioned above, the corresponding methoxy compounds or corresponding compounds, including the radical, are also taken into account for A.

  hydroxyl has been tosylated, such as anisidine, 4- or 5-chloro

  anisidine, 4- or 5-nitroanisidine, anisidine-4- or -sulfonic acid, or tosylated 1-hydroxy-2-aminobenzene, the methoxy or O-tosyl radical being converted to the 011 radical before metallation or during this one. Mostly, compounds containing these radicals are used when

  the corresponding 1-hydroxy-2-amino compounds poorly copulate.

  In preferred dyes of formula (1), A represents the residue of a 1-hydroxy-2-aminobenzene which is optionally substituted by a halogen atom or a nitro, sulfo, lower alkyl or lower alkoxy group, or the remainder of 1-amino-2-hydroxy-4-sulfonaphthalene which is optionally substituted in the 6-position by a halogen such as

  bromine or in particular chlorine, or a nitro or sulfo group.

  Dyestuffs of the formula (1) in which A represents the residue of a 1-hydroxy-2-aminophenol which is substituted are particularly preferred.

  by a nitro group and optionally by a sulfo group.

  The remainder B preferably derives from groups of

  following copula: phenols copulating in the ortho position, possibly

  substituted by alkyl or lower alkoxy groups, dialkyl-

  Amino or acylamino, "acylamino" means C1-C4 alkanoylemino, C14-alkylsulfonylamino, C14-alkoxycarbonylamino, aroylamino or arylsulfonylamino radicals; naphthols that are eventually. substituted with chlorine atoms or C1-4alkyl or C1-4alkoxy, amino, acylamino or sulfo, "acylamino" groups having the same meaning as given above; 5-pyrazolones or 5aminopyrazoles, preferably those having in the 1-position a phenyl or naphthyl radical optionally substituted by chlorine atoms or nitro, C 1-4 alkyl or C 1-4 alkoxy groups or with sulpho groups, and which have position 3 is a C 1-4 alkyl or carboxyl radical, in particular a methyl radical; naphthylamines which are optionally substituted with sulpho groups,

  sulfonamido or sulfonyls; acetylacetamides, especially acetyl-

  acetanilide, and benzoylacetanilides, which may be optionally substituted in the anilide ring by chlorine, bromine, nitro, C1-4alkyl or C1-4alkoxy, or by sutfo groups; 6-hydroxy-3-cyano- or 6-hydroxy-3-carbamyl-4-alkyl-2-pyridones

  which are substituted in position 1 by a C 14 alkyl group

  Substituted, for example, a methyl, isopropyl, (-hydroxy),

  ethyl, β-aminoethyl or β-isopropoxypropyl, or with a phenyl group,

  and which can carry a C 14 alkyl group in position 4, in particular

  a methyl group; or hydroxyquinolines.

  Examples of such copulation components are:

  2-naphthol, 1-naphthol, 1-acetylamino-7-naphthol, 1-propionyl-

  amino-7-naphthol, 1-carboxymethoxy-amino-7-naphthol, 1-carbo-ethoxy-

  amino-7-naphthol, 1-carbopropoxy-amino-7-naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7 - or -8-sulphonic acid

  1-naphthol-3-, -4- or -5-sulfonic acid, 1-naphthol-3,6- or -4,8-

  distulfonic acid, 2-naphthyl-6,8-disulfonic acid, 4-methyl-1-Naphthalene,

  4-methoxy-1-naphthol, 4-acetyl-1-naphthol, 5,8-dichloro-1-naphthol,

  5-chloro-1-naphthol, 2-naphthylamine, 2-naphthylamine-1-acid

  sulphonic acid, 1-naphthylamine-4- or -5-sulphonic acid, 2-amino-

  naphthalene-6-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid,

  6-methylsulfonyl-2-aminonaphthalene, 1-phenyl-3-methyl-pyrazol

  -One, 1-phenyl-5-pyrazolone-3-carboxylic acid amide, 1 (2'-, 3'- or 4'-methylphenyl) -3-methylpyrazol-5-one, the 1- (2'-,

  3 '- or 4'-sulfophenyl) -3-methylpyrazol-5-one, 1- (2'-chiloro-5'-PulfO)

  phenyl) -3-methylpyrazol-5-one, 1- (2'- or 4'-methoxyphenyl) -3-methyl-

  pyrazol-5-one, 1- (2'-, 3'- or 4'-chlorophenyl) -3-methyl-pyrazol-5-one,

  1- (2'-, 3'- or 4'-nitrophenyl) -3-methylpyrazol-5-one, 1- (2 ', 5'-

  or 3 ', 4'-dichlorophenyl) -3-methylpyrazol-5-one, 1- (2', 5'-dichlorobenzene)

  4'-sulfophenyl) -3-methylpyrazol-5-one, 1- (2'-, 3'- or 4'-sulfophenyl) -

  3-methyl-5-aminopyrazole, 1-phenyl-3-methyl-5-aminopyrazole,

  1- (2'-chloro-5'-sulfophenyl) -3-methyl-5-aminopyrazole, acetoacetate

  acetanilide, acetoacetanilide-4-sulfonic acid, acetoacetate

  anisidide, acetoacet-o-toluidide, acetoacetate-o-chleranilide,

  aceto-acetyl-xylidide, tetralol, 4-methylphenol, 3-dialkyl-

  aminophenols, in particular 3-dimethylamino- and 3-diethylamino-

  phenol, a 4-butylphenol, preferably 4-tert.-butylphenol,

  4-amylphenol, in particular 4-tert.-amylphenol, 2-isopropyl-

  4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxy-

  carbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylplenol and 3,4-dimethylphenol, 1-methyl-3-cyano-4-ethyl-6-hydroxypyridone,

  1-methyl-3-cyano-4-methyl-6-hydroxypyridone, 1-phenyl-3-carbamoyl

  4-methyl-6-hydroxypyridone, 1-ethyl-4-hydroxy-2-quinolone,

  2,4-Diphydroxyquinoline or 3-methylpyrazol-5-one.

  The copulatory component giving the remainder B is preferably a 1-

  or 2-naphthol optionally substituted by an amino group and / or a sulfo group, a 1- or 2-naphthylamine optionally substituted with

  a sulfo group, a p-alkyl (Cl 16) -phenol, a 1-phenyl-3-methyl-5-

  pyrazolone or an acetylacetanilide, the phenyl radical in the two compounds mentioned last which may be substituted by a chlorine atom

  or C 1-4 alkyl, C 1-4 alkoxy, nitro or sulfo.

  When Z is CH, B is the residue of an o-hydroxy

  aldehyde, preferably an o-hydroxybenzaldehyde or ohydroxynaphthaldehyde,

  which may be substituted by a halogen atom or a lower alkyl group

  sulfon, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo.

  Suitable aldehydes are, for example: 2-hydroxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxybenzaldehyde, 3-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl -2-hydroxybenzaldehyde, 5-butyl-2-hydroxybenzaldehyde,

  5-chloro or 5-bromo-2-hydroxybenzaldehyde, 3-chloro

  2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo

  2-hydroxybenzaldehyde, 3-methyl-5-chloro-2-hydroxybenzaldehyde,

  5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-sulfophenyl)

  azo) -2-hydroxybenzaldehyde, 5- (6'-sulfonaphthyl-1'-azo) -2-hydroxy-

  benzaldehyde or 5- (4 "-sulfo-4'-phenylazo) -phenylazo-2-hydroxy-

  benzaldehyde. KP represents a cation, for example an alkaline cation such as lithium, potassium or preferably sodium. K can in

  in addition to being an ammonium cation or the ammonium salt of an organic amine.

  Suitable radicals R 1 in the dyes of formula (1) are

for example:

  a hydrogen atom, an acetyl, propionyl, butyryl, isopropyl,

  butyryl, valeryl, isovaleryl, pivaloyl, capronyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-pentoxycarbonyl, methylsulfonyl,

  ethylsulfonyl, butylsulfonyl, phenylsulfonyl, benzoyl or phenoxy

  carbonyl, the phenyl radicals in the last three compounds which may be substituted, for example, by a halogen such as bromine or in particular chlorine, a nitro group, a C 1 -C 4 alkyl group or a C 1 -C alkoxy group R preferably represents an atom of hydrogen or a radical

  acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenyl

  sulfonyl, and in particular a hydrogen atom or a methoxy radical

carbonyl or acetyl.

  The preferred radicals y 1 are a chlorine atom, a sulpho, methyl, sulphonamido, N-methylsulphonamido and methylsulphonyl group, the group

  sulfo being particularly preferred.

  The preferred radicals y 2 are a hydrogen or chlorine atom,

  or a sulfo or methyl radical, in particular a hydrogen atom.

  The dyes according to the invention which are particularly preferred correspond to

lay in the formula

L 924 1 2 8U22 2

-7-

0O3 30 (

  ## EQU1 ## represents a ## STR1 ## where ## STR2 ## is a solubility of a tom'd, 1HR halogen or a nitro group, su (2), ## EQU1 ## / ol

1_ N = Z -

in which

  R2 represents a hydrogen atom or an acetyl, methoxy-

  carbonyl, phenylsulfonyl or methylphenylsulfonyl; Z represents a nitrogen atom or a CH group;

  A1 represents the residue of a 1-hydroxy-2-aminobenzene which is optionally

  is substituted by a halogen atom or a nitro, sulpho group,

  lower alkyl or lower alkoxy, or the remainder of a 1-amino

  2-hydroxy-4-sulfonaphthalene which is optionally substituted in

  6 with a halogen such as bromine or in particular chlorine, or a nitro or sulfo group;

  B1, when Z is a nitrogen atom, represents the residue of a 1-or 2-naphtholoven-

  optionally substituted with an amino group and / or a sulfo group, a (C 6) -phenol-4-alkyl-phenyl, a 1-phenyl-3-methyl-5-pyrazolone or naphthyl-2-acetylacetanilide, the radical phenyl in the last two compounds which may be substituted by a chlorine atom or a C 1-4 alkyl, C 1-4 alkoxy nitro or sulfo group; or when Z is the CH group, the remainder of an o-hydroxybenzaldehyde or

  o-hydroxynaphthaldehyde which may be substituted by a halogen atom

  gene or a lower alkyl, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo group; and

Ka represents a cation.

  Among these dyes, those in which R 2 represents a hydrogen atom or a methoxycarbonyl or acetyl group are particularly preferred; A 'represents the residue of 4-nitro-2-amino-1-hydroxybenzene,

  4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid or 1-amino-

  2-hydroxy-4-sulfo-6-nitronaphthalene; B, when Z represents a nitrogen atom, represents the residue of a 2-naphthol, acetylacetanilide or 1-phenyl-3-methyl-5-pyrazolone, optionally substituted by an amino or acetylamino group, the phenyl radical in the two compounds cited last, which can be substituted by a chlorine atom or a group

  sulfo, or when Z is the CH group, the remainder of an o-hydroxy-

  benzaldehyde which is unsubstituted or substituted in position

  para phenylazo, sulfophenylazo, naphthylazo or sulfo

  naphthylazo; and Ka represents a cation.

  The dyestuffs of the formula (1) according to the invention can be prepared by methods known per se, for example by preparing the chromium 1: 1 complex of the azo dye of the formula Y 2 YH * -N = N 2. ## STR3 ## then reacting it with the dye of formula ## STR2 ##

A - N = Z - B

I I

(CO) XH

(Op

OH (4)

  or with a mixture of the formula amine

A - NH2

(CO)

i p

OH (5)

and formula aldehyde

HO B-CHO (6)

  to result in the chromium 1: 2 complex, or by preparing the chromium 1: 1 complex of a dye of formula (4) and then reacting

  this one with the dye of formula (3).

  A, B, Z, X, Y, Y2 R1 and bridge the meanings given for the

Formula 1).

  The dyes of formulas (3) and (4) are known or are prepared

in a manner known in principle.

-9

  The new chromium complex dyes of formula (1), which are

  by the above process, are isolated in the form of their salts, in particular alkaline salts, especially sodium, potassium or lithium salts, or also in the form of ammonium salts or organic amine salts with an atom of positively charged nitrogen, and they are suitable for

  dyeing and printing of various materials, possibly in pre-

  of a unison agent, but especially for dyeing and printing.

  of nitrogen-containing materials, such as silk, wool, as well as synthetic polyamide or polyurethane fibers, and

especially for leather.

  We get olive, brown, gray or black, very strong,

  especially in light and wet.

  The preferred use of the dyes according to the invention lies in the dyeing of wool, polyamide and, in particular, leathers or skins, all types of leather being suitable, for example chrome-tanned leather, retanned leather. or velvet kid leather,

  beef, mutton or pork. The dyes according to the invention are especially suitable

  for the dyeing of leather with dye mixtures, in parti-

  mixed with one or more metal complex dyes

1: 2 appropriate.

  The present invention is illustrated by the descriptive and nonlimiting examples hereinafter. Parts represent parts by weight and percentages by weight. Temperatures are

data in degrees Celsius.

-10-

Example 1

-o3 40

II I I I I I

/ 13 03SX -.

\ eN =. N- To 4Na /.H2 -Cro

/ ', _ N CH O

  In 500 parts of water, the chromium complex 1: 1

  contains 43.9 parts of the dye consisting of 2-amino acid

  Diazotized 1-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxy-acid

  naphthalene-6-sulphonic acid, as well as 5.2 parts of chromium, and is added

  , 4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the

  monoazoic acid consisting of 2-aminobenzene-sulfonic acid

  diazotized and salicylaldehyde. After that, the reaction mixture is heated

  At 80-85, it is adjusted to pH 7-7.5 with sodium hydroxide, and maintained at this temperature and constant pH until the starting materials are no longer detectable. After completion of the addition reaction, the dye is isolated by evaporation. We obtain

  a dark louse that dissolves in the water, giving a green hue

  olive and dyes the leather in strong olive nuances.

-11-

Example 2

/ O 3 403

  9 \ 9 XNH4 I l II o --- N = N-_ a 4 | Gold. 0 0I

/ '2

- CH I I I IlI

= I II

3

  48.9 parts of chromium complex compound of type 1 chromium atom are suspended in 500 parts of water: 1 molecule of dye,

  which contains 5.2 parts of chromium and 43.9 parts of the mono-

  azo compound consisting of diazotised 2-amino-1-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid, with

  , 4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of

  monoazoic acid consisting of 3-aminobenzene sulfonic acid and salicylaldehyde. After that, the reaction mixture was heated to 80 ° C, the pH was adjusted to 7-7.5 with 5N sodium hydroxide solution,

  and the reaction mixture is maintained at this temperature and at pH

  until the starting materials are no longer detectable.

  After completion of the addition reaction, the dye is isolated by spray drying. We get a dark powder that dissolves in the water giving an olive-green tint and dyeing the leather in strong shades

olive.

-12-

Example 3

  03 N i 4 o./'IÏN- 3s- / ''. 6 th day

I I II 2

3 / O Cr / Z --- O, / * x .. * - .. e * I II

II I

  The chromium 1: 1 complex is introduced into 600 parts of water

  contains 43.9 parts of the dye consisting of 2-amino acid

  Diazotized 1-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxy-acid

  naphthalene-6-sulphonic acid, as well as 5.2 parts of chromium, and is added

  , 4 parts of 4-nitro-2-amino-1-hydroxybenzene and 35.6 parts of the

  copulation product obtained from 1-aminonaphthalene-6-

  diazotized sulfonic acid and salicylaldehyde. After that, the reaction mixture is heated to 80-85, adjusted to pH 7-7.5 with sodium hydroxide and maintained at this temperature and constant pH until

  that the starting materials are no longer detectable. Once completed

  After the addition reaction, the dye is isolated by evaporation. After drying, we obtain a dark powder that dissolves in the water giving an olive green hue, and that dyes the leather in solid shades

olive green.

-13-

Example 4

- 50 O s

I II II I

_ 03

NI a / 5Na t / \ i. "2i / l 2

<0 I

  In 500 parts of water, the chromium 1: 1 complex is introduced.

  contains 43.9 parts of the dye consisting of 2-amino acid

  Diazotized 1-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene

  6-sulfonic acid and 5.2 parts of chromium, and 23.4 parts of 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid and 35.6 parts of

  Monoazoic dye obtained from 1-aminonaphthalene-6-

  diazotized sulfonic acid and salicylaldehyde. After that, you warm up the

The reaction mixture at 80-85 is adjusted to pH 6.5-7 with 5N sodium hydroxide solution and maintained at this temperature and at constant pH until departure have disappeared. The dye obtained is then isolated by evaporation. After drying, a dark powder is obtained which dissolves in the water giving a hue

  olive green and dyes the leather in very strong olive nuances.

Examples 5 to 42

  If one proceeds as described in Examples 1 to 4, but using

  the chromium 1: 1 complex of the azo dyestuff indicated in column 2 of the table below and reacting it with the azo or azomethine dye indicated in column 3, or with the amine and the aldehyde

  component of this dye, chromium 1: 2 complexes are obtained which

  feel the shade indicated in column 4 and dye the leather

in very solid shades.

- 14 -

Board

  No Azoic dye Azoic dye or azomethineNuance? H nH? IH? H

/ 0 // \, NH2 e e- -

  5./'x._ N = N _. '. /' X./H2 * -.N = N-_. '.

II I II II I I II brown

  HO S H * O HS # / purple $ o2% </-;.// 3H3il he NO2

?. ? H

  6 e / ee-N = CH-, olive oil id II I I II x.zx 'x. /; 3

o02 N - /.

YIOH YH? HI He to

/ '\ T_N = fO brown-

  ## EQU1 ## ## STR1 ## ## STR1 ## ## STR2 ##

? H? H H H OH

  8 l /. N = N- '/ H 2 e 3 ee-N = CH-, f olive $ o ^ 2 N = -til,

H-2CH 3.

? H? "? 1 9./H,

  H HO S TO C-N-- brown H 5! I \ N -'e / pulling MHO3S on the purple 2

- 15 -

  No Colo Colantant azoAzoic Colourant or Azcmethine Nuance

/ 0%. NOT.

YH 0H VH IOH

  HO S 0 _.- N-e / Àmarron 3l.e-N = N-_e.e // '2 3 \' / \ -N = N-C / I.l IlI I IlI I / pulling

AT_C = N AT

  ## EQU1 ## on the 31 H NO32 3 violet 1H? H n ci \ = N -. \\. xxx.Z2 il1l1N = - l t id id

/ 0 HO S / "/ \, /

03H 3

? H OH OH H

  ## STR1 ## wherein N is N, N, N, N, N, N, N, N, N

123e-N = N-C; **.

I I: I, I, 1.% Id \ / # H / <\. H3 eSN3H

H 3I3 3

  133% - N = N- /%. H id id% 0 // HO S / \ o / .0 03H 3

H H YH

14 he-N = N-1 OC 3 id id

/ HO S /./.

o03H 3

? H? H?

  ci \ aakH id id \ - 1 <-N = N- * I -; he OCHidd

\ 'HO S / / \

? H YH OH O H

1649/9 <ótHos - = -; Brown.

I III II _3

  16 -NN-1e eN = C i I I I '' '% zz' = NÀ

6HO 3 0 \ H

3HO

- 16 -

  No Azoic dye Azoic dye or azamethineNuance

? H? H? H? H

  At 17% .- N = N--, ee / -N CH-s and olive II I [[] l I I il

HOS 3 /

iO3H ho O3H

? H1? H

18 '/ -N CH-

  id -N = CH-. * olive id I I IlI N2 I [I *. /

? H? H?

19 '/' * -N = CH- ". \ - olive

II. I I II

id

* {

pulling on

/ * - N = CH- =

II I I II the mrron id \ 00H

I I

2 I I

? H?

olive

21 to / -N = CH -, // - I

id II I I o2 = N - // ". eIl \ / Cl

- 17 -

  N Azoric dye Azoic dye or azcmethine Nuance 22 * / ktNH? H * H2 HO? H olive * Colorant </ \. \ oliqe

H O S TO

S03H; 2 =

_ 033

3 2

  ## EQU1 ## ## EQU1 ## ## EQU1 ## H / 'tNO2 3 tviolet id 3 / N = N_ \

\

II IIII brown

  HONS purple He 1 I \ x \ hoz 26 id H3S id'N io2 ___ you il _, Ili, _ 1, 3 [w_ 1 w - \ .O 7 - O _. 0 = 0 U> -e / e-O o \\ // =

\ I

o 1 to% /; Im el-e

o -

  go o: c / 0 = e / \ / \ Ln e tn, uL, / o 0'- 'C.-o c ,, 0 = 0 He

O \ \\ /

/ I '', \ \ _

  t '. "-.t \ / M 0 = 0 = 0 f / e - O o \\ //

P = = 1

w He e-e

0 // \\ * -

* -o

\ //

0 = 0 / -

\\ //

  el-e 'e-e.1 \ P = \ / ot: w. * 0 t '0 = 0

/ \ * -

jól-e e -

  Ili3 0-e1 ll I II e - e "- // \\ * - O

* / \ ',. / =

0 = 0 * 0 =

v / \ -

  o \\ // P: w he óln z "/ o II \ I - e // \\

\\ //

  0 = 0 ee \\ ._ 0 = 0 / \ Cr .-- e e - oo \\ // = w oe Im: * I oi ca zC \ ól e //.- N / \\ // C0 - LI- <jo./ La., O 0 = 0

Cr .-- * \ * -

n-e '- O o \\ // =

= =

  w II cn \ z \ 2 * a 2 // \\ 0 = 0 / \ t \\, "eo ncJ o 0 = 0 Oe- I II I 0-eo / t \\ ./ I ooe -, tr / #### ################################################################################################################################################## O rc ce o tz

H.I. H.

S-p P-a. CD t L n. pv pz CD L CL

- 19 -

  N Azo dye Azo dye or azoméethine Nuance

? H? H? H? H

/ 32'-N = N-e i / e-N = N-e i

II I III II I I II gray

  * // HO S /./ \ ./ / OCH3 / d. / SO3H JI v black O3H 3 N _. '.' Y -Ie e H 33 id. / 't-N = N-.//'xi

I II I

  N-e-S0e! it is CO-NH-e on the brown N 2 e 8 N N-. brown id 1 I pulling i / N N - i id on the * aN purple% // 3 2NH2

? H YH /

id id 7 N 3 e

_ _ _ _ _ _ _ _ _ _ _ _ _ _ 2 2

  id 911 gCH 37 id'N - CH olive e _a \ CO-NH -.

\ // I II

e 2 02NH2 e /

  - J _ _ _ _ _ _ _ _ _ _ _ _ _ 2 2 ...._ _

- 20 -

  No Nuance N Azolate dye Azoic dye or azomethine Nuance

? H? H? H H '

  At N / A N / A / N / N / N / N / N / N / N / N / N / N / C / i

\ / HO S H

io H 3 0 H 3

3 3 _ _

? H? H?

  gray-id purple He I I-l / \ ho 2 a \. # ''

\ // /% /

id e- / N- oI, /, id o2 OI

? H? H?

402 id id I 2I I He

02N / À \ À I

He id id / i 41 re-N = N-_

[I I I II

HIN-e

0I II I

j 2 Izz '

2 3

NH2 COCH;

? H? H?

id 42 id a = II I I ICHCH COCH;

  -21- Dyeing method for leather pieces of velvet leather (dry weight) are streaked for 2 hours at 50 C in a solution of 1000 parts by volume of water and 2 parts of a solution of ammonia at 24% , then dyed for 1 hour at 60 ° C in a solution of 1000 parts by volume of water, 2 parts of a solution of ammonia 24% and 6 parts of the dye from Example 1. After that, we add a solution of 40 parts by volume of water and 4 parts of 85% formic acid, and dyed for a further minute. The leather is then thoroughly rinsed and possibly further treated for 30 minutes at 50 C with 2 parts of a condensation product

  of dicyandiamide and formaldehyde.

  It is possible to dye in the same way other velvet leathers,

as well as leather for gloves.

  The olive hues thus obtained stand out for their good

  and covering powers.

  Dyeing method for polyamide 100 parts of polyamide knitting yarn are introduced at 50 ° C. into a dyeing bath containing, for 4000 parts of water, 2 parts of the dye of Example 9 and 4 parts of sulphate. of ammonium and 2 parts of a unison agent. We bring the bath to the boil in the space of

  minutes, then hold it for another 45 minutes at

  boiling water. After that, remove the dyed item, rinse it thoroughly with cold water, and then dry it. A dyed purple-brown polyamide is obtained, with good characteristics

of solidity.

  Wool dyeing method 100 parts of yarn of wool are knitted into a 50 C dye bath containing, for 4000 parts of water, 2 parts of the dye of Example 9, 4 parts of acetic acid at 80% and 2 parts of a unison agent. The bath is boiled in minutes and then maintained for 45 minutes at the boiling point. After that, remove the dyed item, rinse thoroughly

in cold water, then dry.

  We obtain a wool dyed in brown drawing on the violet, with

  good strength characteristics.

-22-

Claims (15)

  1. Asymmetric 1: 2 chromium complex dyes, A: characterized in that they correspond to the formula y1 2-02 os 03il / 2 Ka 'a' -N = N-e 'a (() (O) / i A-N = Z-B   wherein Z represents a nitrogen atom or a CH group; A represents a residue of the benzene or naphthalene series,   which has a hydroxyl or carboxyl group in the ortho position with respect to   azo group or azomethine group; B represents, when Z is a nitrogen atom, the remainder of a coupling component, the coupling component containing the group X in the ortho or a position with respect to the azo group, or when Z represents the group CH, the remainder an ohydroxy-aldehyde; X is an oxygen atom or Z is a nitrogen atom, a group of the formula -NR-, wherein R is a hydrogen atom or a C1-4 alkyl group; Y1 represents a chlorine atom or a sulfo group, C1-alkyl S 2- 22 3 3   S02-R2, wherein R is C1-C4alkyl, or -SO2NRR3, wherein R and R are each, independently of each other, a hydrogen atom or a C1-C4alkyl radical; y2 represents a hydrogen or chlorine atom or a sulfo or C1-4 alkyl group; R1 represents a hydrogen atom or a group of formula -SO2-Q or of formula -CO- (O) -Q, wherein n is zero or 1 and Q is a C1-5 alkyl or phenyl radical; the phenyl radical may be substituted by a halogen atom or a nitro group, C1-5 alkyl or C1-5 alkoxy; P is 0 or 1; and KaJ represents a cation.   2. Dyes according to claim 1, characterized by the fact   in formula (1), A represents the residue of a 1-hydroxy-2-amino-   benzene which is optionally substituted by a halogen atom or a nitro, sulfo, lower alkyl or lower alkoxy group, or the remainder of a 1-amino-2-hydroxy-4-sulfonaphthalene which is optionally   substituted in position 6 by a halogen such as bromine or in particular   bind chlorine, or a nitro or sulfo group.   3. Dyes according to claim 2, characterized in that in the formula (1), A is the residue of a 1-hydroxy-2-aminophenol which is substituted with a nitro group and, optionally, with a sulfo group.   4. Dyes according to any one of claims 1 to 3,   characterized by the fact that in formula (1), B repreents the remainder of a   or 2-naphthol optionally substituted by an amino group and / or a sulfo group, a-or 2-naphthylamine optionally substituted by a sulpho group a p-alkyl (C1 6) -phenol, a-3-phenyl-3-phenyl 5-methyl-5-pyrazolone or acetylacetanilide, the phenyl radical in the two last-mentioned compounds which may be substituted by a chlorine atom or a group   C1-4alkyl, C1-4alkoxy, nitro or sulfo, and Z is a nitrogen atom.   5. Dyes according to any one of claims 1 to 3,   characterized by B being the remainder of an o-hydroxy   benzaldehyde or o-hydroxynaphthaldehyde, which may be substituted by a   halogen atom or a lower alkyl group, sulfo, phenylazo, sulfo   phenylazo, naphthylazo or sulfonaphthylazo, and Z is the group -CH.   6. Dyes according to any one of claims 1 to 5, characterized   characterized by the fact that in formula (1), R1 represents an atom   hydrogen, acetyl, methoxycarbonyl, benzoyl, phenyl   sulfonyl or methylphenylsulfonyl.   7. Dyes according to claim 6, characterized in that R1 represents a hydrogen atom or a methoxycarbonyl group or acetyl.   8. Dyes according to any one of claims 1 to 7, characterized   characterized in that in formula (1), Y1 represents a 24-chlorine atom or a sulfo, methyl, sulfonamide, N-methylsulfonamide group; or methylsulfonyl.   9. Dyes according to claim 8, characterized by the fact Y1 represents the sulfo group.   10. Dyes according to any one of claims 1 to 9, characterized   characterized by the fact that in formula (1), Y represents an atom   hydrogen or chlorine, or a sulfo or methyl group.   11. Dyes according to claim 10, characterized by the fact that Y is a hydrogen atom.   12. Dyestuffs according to claim 1, of the formula: ## STR2 ## wherein: ## STR2 ## -N = z - B in which   R2 represents a hydrogen atom or an acetyl, methoxy-   carbonyl, phenylsulfonyl or methylphenylsulfonyl; Z represents a nitrogen atom or a CH group;   A1 represents the residue of a 1-hydroxy-2-aminobenzene which is optionally   is substituted by a halogen atom or a nitro, sulpho group,   lower alkyl or lower alkoxy, or the remainder of a 1-amino   2-hydroxy-4-sulfonaphthalene which is optionally substituted in   6 with a halogen such as bromine or in particular chlorine, or a nitro or sulfo group;   B 1, when Z is a nitrogen atom, represents the remainder of a 1-or 2-naphthol optionally   optionally substituted with an amino group and / or a sulfo group, a (C1 6) -phenol alkyl, a 1-phenyl-3-methyl-5-pyrazolone or a acetylacetanilide, the phenyl radical in the two compounds cited lastly, which may be substituted by a chlorine atom or a C 1-4 alkyl, C 1-4 alkoxy, nitro or sulfo group; or when Z is the CH group, the remainder of an o-hydroxybenzaldehyde or   o-hydroxynaphthaldehyde, which may be substituted by a halogen atom   gene or a lower alkyl group, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and Ka represents a cation.   13. Dyes according to claim 12, characterized in that in formula (2), R2 represents a hydrogen atom or a group   methoxycarbonyl or acetyl; A1 represents the remainder of 4-nitro-2-amino-   1-hydroxybenzene, 4-nitro-2-amino-1-hydroxybenzene-6-acid   sulfonic acid or 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene; B1, when Z represents a nitrogen atom, represents the residue of a 2-naphthol,   acetylacetanilide or 1-phenyl-3-methyl-5-pyrazolone, possibly   optionally substituted with an amino or acetylamino group, the phenyl radical in the last two compounds which may be substituted by a chlorine atom or a sulfo group, or when Z is the CH group, the residue of an o-hydroxy -benzaldehyde which is not substituted   or which is substituted in the para position by a phenylazo, sulpho   phenylazo, naphthylazo or sulfonaphthylazo; and K represents a cation.   14. Process for the preparation of the dyestuffs of formula (1), characterized in that the 1: 1 chromium complex of the azo dye of formula 2 is prepared and subsequently reacted. with the formula dye A - N = Z - B   (CO) p XH (4) OH or with a mixture of the amine of formula A - NH2   iop OH (5) and the aldehyde of formula HO - B -CHO (6)   to result in the chromium 1: 2 complex, or that the chromium 1: 1 complex of a dye of formula (4) is prepared and then reacted with the dye of formula (3), A, B, Z, X, Y1, y2,   R1 and p having the meanings given for formula (1).   15. Use of the dyes of formula (1) for the dyeing of   wool, polyamide, and in particular hides and skins.