FR2508472A1 - MIXTURES OF METALLIC COMPLEXES, THEIR PREPARATION AND THEIR APPLICATION AS COLORANTS - Google Patents

Abstract

THE INVENTION RELATES TO MIXTURES OF COBALTIFER COMPLEXES 1: 2 SYMMETRICAL AND ASYMMETRIC OF AZOIC COMPOUNDS OF FORMULAS: (CF DRAWING IN BOPI) IN WHICH R MEANS HYDROGEN OR AN ALKYL GROUP, MEANS HYDROGEN OR A HALOGEN GROUP, ALKYL, ALCOXY OR CYANO, R MEANS HYDROGEN, A HALOGEN OR AN ALKYL OR ALCOXY GROUP AND X REPRESENTS AN OH OR NH GROUP. THESE MIXTURES OF COMPLEXES MAY BE USED AS COLORS FOR DYING OR PRINTING SUBSTRATES LIKELY TO BE DYED BY ANIONIC COLORANTS.

Description

The subject of the present invention is mixtures of metalliferous complexes

azoles, their preparation and

  their application as anionic dyes.

  The invention more particularly relates to a mixture of symmetrical and asymmetric 1: 2 cobaltiferic complexes of azole compounds of formulas I and II

OH X R OH X R

2 F

SO N CH 3 CH 3

1 2 # 02

N ((I) N-R l (II)

156 COOH

  in which the symbols R 1 each signify, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl group, the symbols R 2 each signify, independently of one another, a hydrogen or halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy or cyano group, the R 3 symbols each signify, independently of one another, an atom of hydrogen or halogen or a C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, and the symbols X each signify, independently of one another, an OH or NH 2 group, these complexes are in the form of a free acid or in the form of a salt, both for the cation which neutralises the negative charge of the anion, for the complex of each cobaltifer complex 1: 2, and for the carboxy group

of the compound of formula II.

  Preferably, the complex mixture contains the compounds of formulas I and II in a molar ratio of from 20 to 20:80, more preferably from 70:30 to 30:70, in particular from 60:40 to 40:60. , the

  ratio 1: 1 being most preferred.

  When R 1, R 2 and / or R 3 denote an alkyl group, this may be linear or branched and preferably means a methyl or ethyl group, the group

  methyl being most preferred.

  When R 2 and / or R 3 are alkoxy, it is preferably methoxy or ethoxy, the

  methoxy group being particularly preferred.

  Halogen means fluorine, chlorine or

  bromine, preferably chlorine.

  Each R 1 preferably denotes R, that is to say, independently of one another, a hydrogen atom or a methyl group.

  each symbol R 1 signifies hydrogen.

  Each R 2 symbol preferably means R, that is to say, independently of one another, a hydrogen or chlorine atom or a methyl, methoxy, ethoxy or cyano group. More preferably, R 2 means RI

  that is to say, independently of one another, an atom of hy-

  or chlorine or a methyl or methoxy group more parti-

  specifically, each symbol R 9 signifies hydrogen.

  Each R 3 symbol preferably means R, that is to say, independently of one another, a hydrogen or chlorine atom or a methyl, methoxy or

  More preferably, each R 3, inde-

  one of the other, means R ', R having one of the meanings of R 2 More particularly, each symbol

R 3 is hydrogen.

  The phenyl group of the copulation component

is preferably unsubstituted.

  When the phenyl nucleus containing the

  R 2 / R 3 is monosubstituted, each substituent preferably means chlorine or a methyl, methoxy, ethoxy or cyano group. When the phenyl ring is

  disubstituted, the substituents are preferably in

  2,4 2,4 2,6 or 3,4, more preferably in position 2,5 or 2,6, the symbols R 2 and R 3 may be identical or different and preferably meaning chlorine or a methyl group or methoxy.

  The symbols X in the copula components

  Monoazole compounds of formulas I and II

  preferably both leave an OH group or all

  both an NH 2 group, especially an OH group.

  The carboxy group of the monoazole compound of

  Formula II is preferably located in position 2.

  The preferred mixtures are those in which

  poses of formulas I and II, (1) the symbols R 1, independently of one another, signify Ri; (2) the symbols R 2 and R 3, independently of each other, signify R 2 and R; (3) the symbols R 2 and R 3, independently of each other, signify R and R "

2 3 '

  (4) those of (1) to (3) o, in the compounds of formulas I and II, the symbols X signify both OH; (5) more preferably complex mixtures whose non-metallized components correspond to the formulas Ia and I Ia HOH 2 N an OH

N = N R N N:

SO 2 CH 3 CH 3

  NR (Ia) NR (I Ia) COOH in which the symbols Ri, R 2 and RI are independent of each other and the symbols Ru and R ', when they have a meaning other than hydrogen, are located in position 2.5 or 2, 6; the component of formula I Ia is preferably in salt form; (6) those of (5) o, in the component of formula Ia, the symbols Ri R 2 and RI have meanings identical to those of the component of formula I Ia; (7) those of (5) or (6) o R 2 and R 1 'signify hydrogen, (8) those of (1) to (7) where R 1 signifies hydrogen; (9) those of (1) to (8) where the compounds of formulas I (Ia) and II (I Ia) are in a molar ratio of 5: 4

  at 4: 6, especially in a molar ratio of 1: 1.

  The invention also relates to a process for the preparation of a mixture of symmetrical and asymmetric 1: 2 cobaltiferic complexes of the compounds of formulas I and II,

  a method of reacting a mixture of the compounds

  formulas I and II with a donor compound of

  cobalt Metallization of the mixture of monoazol compounds

  The molar ratio of the mixture of compounds of formulas I and II to the cobalt donor compound is preferably 2: 1. Suitable metal donor compounds are sulfate, acetate, formate and cobalt (II) chloride Compounds of formulas I

  and they are involved preferably in a molar ratio

re 1: 1.

  The mixture of cobalt-1: 2 complexes obtained can be isolated by known methods; for example, the product may be salted out with an alkali metal salt or a weak acid, filtered, washed with a solution of an alkali metal salt and dried. The product obtained contains the asymmetric and asymmetric complexes in a proportion which depends on the compound ratio of

  formula I to that of the compound of formula II used.

  According to the reaction and isolation conditions, the mixture of cobalt-enriched complexes 1: 2 obtained can be in free acid form or, preferably, in the form of a salt, both as regards the cation which compensates for the negative charge of the anion complex of each cobaltifer 1: 2 complex, that the carboxy group in a compound of formula II The nature of the complex anion neutralizing cation does not have an essential character and it can be any of the non-chromophoric cations commonly Examples of such cations include alkali metal cations and ammonium cations comprising unsubstituted and substituted ammonium cations, such as, for example, lithium, sodium, potassium,

  ammonium, mono-, di-, tri- and tetramethylammonium, triethyl-

  ammonium, mono-, di and triethanolammonium, mono-, di and triisopropanolammonium. The preferred cations are the alkali metal cations and the ammonium cation, the sodium being all

particularly preferred.

  Likewise, the carboxy group is preferably in salt form; when the carboxy group is in the salt form, the cation may be any of those indicated above for the anion-neutralizing cation

  complex and may be identical or different to the latter.

  Preferably, the cation of the carboxylic group and the cation neutralizing the complex anion are identical;

  more preferably, they both mean sodium.

  The monoazo compounds of formulas I and II are known or can be prepared analogously

  to known methods from known starting materials.

  Preferably, the mixture of compounds of formulas I and II is prepared directly by diazotising a mixture of amines of formulas III and IV (formulas III and IV see next page)

OH OH

cil) 2 NH 2 s 2 (III) S o (IV)

N-RR N-R 1

  in the desired ratio and by coupling the resulting mixture of diazonium salts with a compound of formula V

X R

H V)

H R 3

  CH 3 or a mixture of these compounds, under conditions

alkaline to slightly acidic.

  The product obtained can be metallized directly

  is lying. The mixtures of complexescobaltifèresl: 2 according

  The present invention is very soluble in water and can

  may be used as dyes for dyeing or printing nitrogen-containing organic substrates which may be dyed by anionic dyes. They are particularly useful for dyeing or printing textiles made wholly or in part of natural or synthetic polyamides such as wool, silk and nylon; they can also be used

  for dyeing in the mass of synthetic polyamides.

  complex mixtures can be used advantageously

  for the printing of destapis, specially destined in polyamido synthetic They are also useful for

dyeing of crossed bobbins.

  The dyes according to the invention can likewise be used for dyeing polyurethanes, polyolefins modified with basic groups,

  leather and metals such as anodized aluminum.

  Dyeing and printing can be

  performed according to known methods.

  The mixtures according to the present invention can be used for dyeing as such or can be formulated into liquid or solid dye preparations. Stable liquid preparations, for example concentrated aqueous preparations, are obtained.

  or solid preparations using the same methods as

known.

  For liquid preparations which are in the form of stable concentrated stock solutions, organic solvents which are soluble in water are preferably used, optionally in admixture with water; the usual auxiliaries, such as dissolving agents such as, for example, urea, can be added to these solutions. The stock solutions can be diluted with water. Such preparations can be obtained, for example, according to the process described in US Pat. British Patent Nos. 1,112,032 and 1,301723. Concentrated stable aqueous preparations can also be used.

  which contain common additives.

  Solid preparations can be used under

  form of powder or granules, the size of which

  These solid preparations can be prepared, for example, according to the process described in British Pat. No. 1,370,845. Solid preparations are highly soluble.

in water.

  Moreover, complex mixtures of

  may be in the form of

  to disperse in cold water. Such dispersions

  It can be prepared, for example, by grinding the dye mixture in a dry or wet state in an aqueous dispersion medium in the presence of one or more usual anionic dispersing agents and optionally in the presence of other conventional additives. possibly

  with subsequent spray drying.

  The thus obtained parations give fine dispersions in water. The dyes obtained with the mixtures of

  dyes of the invention have remarkable solids

  light fastness, good wet fastness (washing, water, seawater, acid and alkaline perspiration and crushing), iron fastness, solvent resistance, wet rubbing and Dry, Chlorine, Carbonization and Decaturation Dyes are not adversely affected by electrolytes

or limestone.

  The complex mixtures of the invention are exhausted

  in neutral bath and rise well on the polyamide fibers.

  They generally have a good climbing power and mount identically on natural and synthetic polyamides when dyeing is carried out in the same bath. They are also suitable for dyeing in combination with other 1: 2 symmetrical or asymmetric metalliferous complexes. dyes obtained with such combinations have remarkable solidities

in the light.

  The following examples illustrate the present invention without in any way limiting its scope. The parts are indicated by weight and the temperatures in degrees Celsius.

Example 1

  It is dissolved at 650 in 700 parts of water and at 30% by addition of a 30% solution of sodium hydroxide.

  39.6 parts of N-phenylamide of 2-amino-1-hydroxy-acid

  benzene-4-sulfonic acid and 46.2 parts of N-2-carboxyphenyl

  2-amino-1-hydroxybenzene-4-sulfonic acid amide and mixed with 20.7 parts of sodium nitrite. After cooling the solution to 0-5 a, it is added dropwise, at 0.degree. 1 hour, 115 parts of 30% hydrochloric acid and 80 parts of ice, the temperature being maintained between 0 and 5 by adding additional ice.

  52.2 parts of 3-methyl-1-phenyl-5-

  pyrazolone in 200 parts of water and 33 parts of 30% sodium hydroxide solution, so as to obtain a fine suspension to this suspension is added, within one hour, the suspension of the salt of diazonium obtained above, while maintaining the pH between 9.0 and 9.5 by addition of a 30% sodium hydroxide solution. After 3 hours, the copulation is complete.

  isolates the monozoic dye mixture by filtration.

  For the metallization, the paste of monoazo dyes is stirred in 1800 parts of water and

  adjusts the pH to 10 by the addition of a hydroxyl

  30% sodium is then added dropwise, within 30 minutes and at a temperature of between 600 and 600, a solution of 42.2 parts of cobalt (II) sulfate in 120 parts of water. p H being maintained

  to 10 by addition of additional sodium hydroxide.

  After completion of the metallization, the mixture of complexcomposite 1: 2 is salted with sodium chloride, isolated by filtration, dried and ground. The resulting dye mixture, in the form of the sodium salt, contains the two monoazolous dyestuffs. compounds Ib and I Ib of general formula (formula see 'next page) in which H OH NH R 4 means H for Ib and N = N a / | R 4 means COO Na for 1 Ib N CH 3 so 2 3 δ 2 NH QOR in a molar ratio of 1: 1 The mixture contains two symmetrical 1: 2 cobaltiferic complexes (a 1: 2 complex of Ib / Ib and a complex 1 : 2 of I Ib / I Ib) and a complex

  1: 2 asymmetric cobaltifer of compounds Ib and Ib.

  The dye mixture is very soluble in

  water and dyes the fibers of natural polyamides and

  ticks in: - yellowish red nuances The dyes present

  good wet strength and remarkable

fastness to light.

  According to the process described in Example 1, it is possible to prepare other 1: 2 cobalt complex mixtures.

  which contain monoazo dyes with

  diazotising poses of compounds Ib and Ib Ib of Example 1 and both having the same component of coupling of formula V

X 2 '3'

x H il R <> f, 2 (V)

H_ 6 '5' R 3

CH 3

  in a molar ratio of 1: 1 The meanings of X, R 2 and R 3 and the positions of the substituents in the phenyl ring are given in the following table. The symbol I in the last column of the table indicates the shade of the dye on natural or synthetic polyamides, meaning reddish yellow and reddish yellow. The dyes obtained from good fastness to light

BOARD

  b meaning brown on polyamidespresent

and wet.

  Example X R 2 (position) R 3 (position) I Cl (2 ')

CI (3 ')

Cl (4 ')

CI (2 ')

  H Cl (2 ') Cl (3') Cl (4 ') Cl (2')

CN (3 ')

CH 3 (2 ')

C 2 H 5 (2 ')

OCH 3 (2 ')

OC 2 H 5 (4 ')

CH 3 (3 ')

CH 3 (4 ')

CH 3 (2 ')

OCH 3 (2 ')

CN (3 ')

CH 3 (2 ')

CH 3 (3 ')

  H (H) H (5 ') H H H H Cl (5') H H H H H H H H

CH 3 (5 ')

CH 3 (5 ')

  H H H a a b b b b b a a a a a b b b b OH do. do. do. NH 2 do. do. NH 2 do. OH do. do. do. do. do. do. do. do. NH 2 do. do. TABLE (continued) Example XR 2 (position) R 3 (position) I 23 do CH 3 (4 ') H b 24 OH CN (4') H a do C 1 (3 ') Cl (4') a 26 do CH 3 (2 ') Cl (6') to 27 NH 2 Br (4 ') H b 28 do CH 3 (2') C 1 (6 ') b 29 do C 1 (3') C 1 (4 ') b CH 3 (2 ') CH 3 (6') a similarly to the process described in

  Example 1, other blends of

  plexescobaltifers: 2 containing the two mono-dyes

  azoles of formulas Ib and Ib Ib of Examples 1 to 30 in

  30:70, 70:30, 40:60 and 60:40 reports.

  The resulting colorants are also soluble in water and dye the fibers of polyaminesnaturelsou

  synthetic in reddish yellow or reddish brown shades.

  The dyes have good fastness to light

and wet.

  Other mixtures of 1: 2 complexescobaltifers can be prepared analogously to the process described in Example 1, using monoazole compounds of

  formulas I and II which contain copula components

  different and / or different in the symbols

R 1 of the diazotization components.

  The complex mixtures of Example 1 and Examples 2 to 30 of the table which are in the form of

  may, depending on the reaction / isolation conditions,

  be obtained by known methods in the form of free acid or in the form of other salts, for example under

  form of salts as indicated previously in the

  scription. EXAMPLE 2 A 1 part of the mixture of cobaltifer 1: 2 complexes of Example 1 was dissolved in 3000 parts of water.

  2 parts of ammonium sulphate are added.

  then a pre-wetted substrate (50 parts of

  wool dine or 50 parts of nylon satin) in the bath which is heated to boiling temperature in the space of 30 minutes Dyeing is continued for another 30 minutes, while replacing the water which is The substrate is then rinsed and dried to give a reddish-yellow dye with outstanding fastness to light and wet. Dyestuff can be dyed with dye mixtures

examples 2 to 30.

  Example of Application B A polyamide fabric is printed with a paste containing: parts parts 250 parts 500 parts parts The fabric of the dye mixture of example 1, urea, a dissolving agent (for example thiodiethylene glycol), water, a thickening agent, for example based on locust bean meal, an acid generator, such as ammonium tartrate, and

thiourea.

  printed matter is then treated with saturated steam for 40 minutes at 1020, rinsed with

  cold water, washed for 5 minutes at 60 with a solution

  diluted with a conventional detergent and rinsed again with cold water. A reddish-yellow impression with good fastness to light is obtained.

wet.

  Similarly, printing pastes can be prepared using any of the

dyestuffs of Examples 2 to 30.

Claims (18)

  1. A mixture of symmetrical and asymmetric 1: 2 cobaltiferic complexes of the azole compounds of formulas I and II X OH X OH X, f NRNN = N R 3 -N 3 N R 3 CH 3 so 2 CH 3 () N-RI) N-R 1 1   COOH in which the symbols R 1 each signify, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl group, the R 2 symbols each signify independently of each other , a hydrogen or halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy or cyano group, the R 3 symbols each signify, independently of one another, an atom of hydrogen or halogen or a C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, and the symbols X each signify, independently of one another, an OH or NH 2 group, these complexes in the form of a free acid or a salt form for both the neutralizing cation of the negative charge of the complex anion of each cobaltifer 1: 2 complex and the carboxy group of the compound of formula II.   2. A mixture according to claim 1,   characterized in that the mixture contains the compounds of formulas I and II in a molar ratio between : 20 and 20:80.   A mixture according to claim 2, which is   in that the molar ratio is between : 40 and 40:60.   4. A mixture according to claim 1,   in that the mixture contains the compounds of   Formulas I and II in a molar ratio of 1: 1.   A mixture according to any one of   Claims 1 to 4, characterized in that the symbols   R 1 signify each independently of one another a   hydrogen atom or a methyl group.   6. A mixture according to any one of   Claims 1 to 5, characterized in that the symbols   R 2, independently of one another, means a hydrogen or chlorine atom or a methyl group, methoxy or ethoxy.   7. A mixture according to any one of   Claims 1 to 6, characterized in that the symbols R 3   mean each, independently of one another, a hydrogen or chlorine atom or a methyl group, methoxy or ethoxy.   8. A mixture according to any of the   Vencidations 1-7, characterized in that the X symbols both signify an OH group or both an NH 2 group.   9. A mixture according to claim 8,   terized in that the symbols X signify both an OH group.   10. A mixture according to any of the   Claims 1 to 9, characterized in that the carboxy group   compound of formula II is in position 2.   11. A mixture of symmetrical and asymmetric 1: 2 cobaltiferic complexes of the compounds of formulas I and II (formulas I and II see next page) ## STR2 ## gt N R 3 SO CH 3 CH 3 N-R '(I) N-R' (II)   td COOH in which the symbols R 1 each signify, independently of one another, a hydrogen atom or a methyl group, the R symbols each signify, independently of one another, a hydrogen atom or chlorine or a methyl or methoxy group, and the R 'symbols each signify, independently of one another, a hydrogen or chlorine atom or a methyl or methoxy group,   the symbols R 2 and RI being in position 2.5 or 2.6 when   that they have a meaning other than hydrogen, these complexes being in the form of free acid or   salt form for both the neutral cation and   reading the negative charge of the complex anion of each 1: 2 cobalt complex, that the carboxy group of compound of formula II.   12. A mixture of 1: 2 symmetrical and asymmetric cobaltiferic complexes of azole compounds of formulas (formulas see next page) OH OH OH OH cii) N N CN CH 3 CH 3 S 21 3 and 2 NH NH 6 S COOH   said complexes being present in a molar ratio of 1: 1.   13. A mixture according to any of the   Claims 1 to 12, characterized in that the complexes are in the form of a sodium salt for both the complex anion neutralizing cation of each cobaltifer 1: 2 complex and the carboxy group of the formula II.   A process for the preparation of symmetrical and asymmetric 1: 2 cobalt complex mixtures of the azole compounds of formulas I and II, as defined in claim 1, characterized in that a mixture of the compounds of formulas I and II is reacted with a compound cobalt donor.   15. The use of complex mixtures   1: 2 cobalt-based compounds specified in any of the claims   cations 1 to 13 as dyes for dyeing or   pressure of substrates that can be dyed by anionic dyes.   16. The use of complex mixtures   1: 2 cobalt-based compounds specified in any of the claims   cations 1 to 13, for dyeing or printing   substrates consisting, in whole or in part, of poly-   natural or synthetic amides, polyurethanes or polyolefins modified by basic groups, and leather and anodized aluminum.   17. Substrates capable of being dyed by anionic dyes, characterized in that they have been dyed or printed with at least one of the specified 1: 2 cobalt complex mixtures to any one of Claims 1 to 13.   18. Substrates made wholly or in part of natural or synthetic polyamides, polyurethanes or polyolefins modified by basic groups, and leather and anodized aluminum, characterized in that they have been dyed or printed with at least one of the specified 1: 2 cobalt complex mixtures specified in   any one of claims 1 to 13 -