DE1226729B - Process for the production of metal-containing reactive dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 09 b

German KL: 22 a - 2

Number: 1226 729

File number: S 76236IV c / 22 a

Filing date: October 12, 1961

Opening day: October 13, 1966

The present invention relates to a process for the preparation of metal-containing reactive dyes, which in the metal-free form of the formula

HO

OH

NH-R

¹ IN = N

HO ₃ S

where X is hydrogen or - ■ SO ₃ H and R is the remainder of a compound which contains at least one substituent that enables chemical bonding to the substrate, and the core A can be further substituted, the entire dye molecule being at least two - SO ₃ H -Groups must contain. The process for the preparation of the new metal-containing reactive dyes consists in converting 1 mol of a diazo compound from an amine of the formula in any order

OH

NH ₅ ,

1 mol of a coupling component of the formula HO NH _a

HO, S

and reacting 1 mole of a compound which has an exchangeable hydrogen atom Body is condensable and also at least one chemical bond with the substrate Contains enabling substituents, during or after the build-up of the dye in substance is treated with a metal donor. You can proceed like this

that one mole of a monoazo dye, which is obtained by coupling 1 mole of a diazo compound from an amine of the formula (II) and 1 mole of a coupling component of the formula (III) and a process for the preparation of metal-containing
Reactive dyes

Applicant:

Sandoz A. G., Basel (Switzerland)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

Dr. Hanspeter Uehlinger, Basel (Switzerland)

Claimed priority:

Switzerland of October 14, 1960 (11562)

final metallization is obtained, with 1 mole of a compound which reacts with a body having an exchangeable hydrogen atom is condensable and also contains at least one substituent that enables chemical bonding with the substrate, or

that 1 mole of a coupling component of the formula (III) is reacted with 1 mole of a compound, which condensate with an exchangeable: hydrogen atom having body- (III) 35 and also at least one of the contains chemical bond with the substrate enabling substituents, and so the product obtained is reacted with 1 mol of a diazo compound from an amine of the formula (II) and then subject to metallization. The metal-containing ones obtainable by the process Reactive dyes are preferably the chromium or cobalt complex compounds of the reactive dyes of formula (I). The metal-free reactive dyes of the formula (I) can, however, also with advantage Treat with copper- or nickel-releasing compounds in the corresponding copper or Nickel complex compounds are transferred.

Possible substituents which the nucleus A can carry are: halogen atoms, low molecular weight Alkyl and / or alkoxy groups, nitro groups, acylamino groups or sulfonic acid groups.

609 670/365

3 4

The reactive substituent R is preferably the dimethylbenzene or acetone dissolved and this solution

Rest of at least one mobile halogen atom in the aqueous solution of the amino group carry-

or a body containing an adductible double bond, dropped in at a temperature of

the acid, such as B. chloroacetic acid, bromine 0 to 30 ⁰ C, preferably from about 2 to 5 ° C, at

acetic acid, jS-chloro and / S-bromopropionic acid, acrylic 5 presence of an acid-binding agent, preferably

acid, methacrylic acid, α-chloro and -bromo acrylic at a pH of 7 to 3.

acid, ß- or y-chloro- or -bromoerotonic acid, the implementation of the monoazo according to the invention

tx, ß- and / 3, JO-DiChIor- or -dibromoacrylic acid, or dyes or their metal complex compounds

the remainder of at least two mobile halogen atoms with the at least two mobile halogen atoms

atom-containing di- or triazine compound, such as io-containing di- or triazine compounds

z. B. the cyanuric chloride, cyanuric bromide, one also carried out in an aqueous medium. Here

primary condensation product of a cyanuric can be the halide as such in concentrated form

halides of the formula form or in an organic solvent

N can be applied in solution. As a solution

y / \ 15 medium are particularly suitable acetone, benzene,

• Hal — C C — Y chlorobenzene and toluene.

I I The reaction temperature is the reactivity

Adjust N ν of the individual starting products and

^ / varies between 0 and 100 ⁰ C, e.g. B. 0 to 20 ⁰ C for i

C 20 cyanuric chloride and cyanuric bromide, or 30 to 50 ° C

I. for those containing two mobile halogen atoms

Hai monocondensation products of cyanuric chloride or

-bromide with ammonia, a primary or secondary

wherein Hal is chlorine or bromine and Y is the gegebenen- dary amine, an alcohol, thioalcohol, phenol optionally further substituted residue of a primary or 25 or thiophenol, or 20 to 100 ⁰ C for the dichloro-, secondary aliphatic, alicyclic, aromatic · dibromo- , Trichloro-, tribromo-, tetrachloro- and tetra- or heterocyclic amine, an aliphatic, bromopyrimidine. If higher temperatures than alicyelic, aromatic or heterocyclic about 40 ⁰ C have to be used, it is hydroxy-. or thiol compound, but especially on the water vapor volatility of the halopyrimides radical of aniline, its alkyl and sulfonic acid dines indicated, to work in a vessel optionally equipped with one or carboxylic acid derivatives, from low mono reflux condenser,
and dialkylamines as well as the remainder of ammonia The reaction is reinterpreted in weakly alkaline; of the 2,4,6-trichloropyrimide and 2,4,6-tri-tral to weakly acidic medium, preferably bromopyrimide and their derivatives, which, however, in the pH range from 7 to 3, through-5-position, for example, the following substituents wear: 35 led. To neutralize the resulting methyl, ethyl, optionally hydrogen halide equivalent on the nitrogen atom, the reaction-substituted carboxylic acid or sulfonic acid amide solution is either initially an acid-binding agent, carboxylic acid methyl or ethyl ester, acyl, ζ. B. such as sodium acetate, added, or benzoyl, alkenyl, ζ. B. allyl, chlorovinyl, substitutes alkyl in small portions during the reaction, ζ. B. carboxymethyl, chlorine or sodium or potassium carbonate or bicarbonate in bromomethyl; des 2,4,5,6-tetrachloro- or tetra-. in solid, powdered form or as a concentrated bromopyrimidine, des 2,6-dichloro- or -dibromo-aqueous solution. Also suitable as neutralizing agents are ethyl pyrimidine-4-carboxylate, of 2,4,5-trichloro, but also aqueous solutions of napyrimidine, which may contain trium or potassium hydroxide on the nitrogen atom. The addition of small substituted 4- or 5-carboxamide or 45 amounts of a wetting or emulsifying agent to the reac sulfonic acid amide derivatives of the 2,6-dichloro or dionic mixture can accelerate the conversion reaction of 2,4-dichloro-5-pyrimidine -chloromethyl- nigen. The reaction is conducted in such a way that only one 6-methylpyrimidine, the 2,5,6-trichloro-4-methyl-halogen atom, reacts with an exchangeable hydrogen pyrimidine and the 2,6-dichloro-4-trichloromethyl atom.

pyrimidines. 50 The conversion of the monoazo dyes into their The coupling of the diazo compound from a chromium or cobalt complex compound is pre-amine of the formula (II) with an azo component which is partially in aqueous solution or in organic formula (ΠΙ) is advantageous in an alkaline medium, medium, for example in formamide, or in the aqueous solution of an alkali metal ^{which is preferably concentrated at temperatures from 0 to 10 ° C.} 55 salt of a low molecular weight aliphatic mono-The implementation of the resulting monoazo carboxylic acid carried out. It is advantageous here or their metal complex compounds with a monoazo dye per 2 molecules of a less than functional derivative of an acid containing at least one mobile number of metal atoms, but containing at least 1 atom of metal, will act before a metal-donating agent,
preferably with the acid chlorides of chloroacetic acid 60. Suitable compounds of chromium are z. B. or jS-chloropropionic acid made. Chromifluoride, chromium sulfate, chromiformate, chromium are used in an aqueous medium, preferably under good acetate, potassium chromium sulfate or ammonium chromium cooling and in the presence of acid-binding agents, sulfate. The chromates, e.g. B. sodium or sodium carbonate, sodium hydroxide, barium, potassium chromate or bichromate, are suitable in pre-, hydroxide, calcium hydroxide or sodium acetate. The carboxylic acid dyes used are used for the metallization of the monoazo-Acylation. It is advantageous to work in strong halide as such or in twice to five times: caustic alkaline medium, where optionally a reduced amount of benzene, chlorobenzene, methylbenzene can be added.

5 6

Serve as cobalt compounds ζ. B. cobalt on cellulose fibers have good light and wet formate, Cobaltoacetate and cobaltosulfate. If the authenticity, e.g. B. water, washing, sweat, rubbing, Metallization in the concentrated aqueous solution and alkali fastness, and are against crease resistance Alkali metal salt of a low molecular weight aluminum finish resistant.

phatic monocarboxylic acid, the dyeings on wool and synthetic polynes amide fibers also have water-insoluble metal compounds, especially if they are to be used afterwards find, for example, cobalt hydroxide or treatment under weakly alkaline conditions Cobalt carbonate. be subjected to good light, water, washing,

Metallization in fulling, welding, rubbing and dry cleaning is particularly advantageous.

aqueous or alkaline medium, io units and are resistant to weak acids such as vinegar

the metal compounds, in the presence of such acid and tartaric acid, persist.

Compounds are added, which the metals The new chromium complex dyes stand out

in a caustic alkaline medium in a complex bond compared to those from German patent 509 289

keep resolved, such as B. tartaric acid, citric acid and known, next comparable Clirom complex color

Lactic acid. 15 substances due to better solubility in the printing

The metal complex compounds obtained become pasty and their ease of washing out becomes easier

if necessary after pouring the organic prints onto cotton.

Metallization solutions in brine, from aqueous die with the new copper complex dyes

Medium separated by adding salt, the prints created here have a better washout

after filtered off, optionally washed and then 20 availability than that from the German patent

dried. 528166 known, next comparable copper

The new chromium or cobalt-containing reactive complex dyes produced prints on tree dyes are suitable for padding or printing on wool.

of wool, silk, leather, synthetic polyamide- In the following examples the mean

fibers and fibers from natural or regenerated 25 parts by weight, the percentages percentages by weight,

Cellulose in brown and purple tones. and the temperatures are in degrees Celsius

Give the obtained an alkaline aftertreatment.

Example 1, optionally subjected to an elevated temperature
and then soaped padding and prints

on cellulose fibers have good light, washing, 30 23.4 parts of 2-amino-4-nitro-1-hydroxybenzene-6-sul-

Water, perspiration, rubbing and alkali fastness properties and fonsäure are in 80 parts water and 15 parts

are resistant to anti-crease finishes. 30% hydrochloric acid and stirred at 0 to 5 ° with

The dyeings on wool and synthetic poly- a solution of 7 parts of sodium nitrite in 25 parts have amide fibers, especially if they diazotized a post-water. The by adding sodium treatment under weakly alkaline conditions 35 bicarbonate can be Congoneutral diazo solution be subjected to good light, washing, sweat, one at a temperature of 0 to 5 ° to a Water, fulling, rubbing and dry cleaning real solution of 23.9 parts of 2-amino-3-hydroxynaphunities and are against weak acids such as acetic thalin-6-sulfonic acid, 10.5 parts of 30% sodium acid or tartaric acid, persistent. add dropwise hydroxide solution in 200 parts of water,

The conversion of the monoazo dyes in their 40 with the pH value of the coupling mass through Copper or nickel complex compounds take place further addition of 28 parts of 30% sodium advantageously in weakly acidic aqueous solution. The hydroxide solution is kept between 8.5 and 9.0, allows 1 molecule of monoazo dye to be used. After stirring for 1 hour, the coupling is complete an amount of a metal terminated containing 1 atom of metal. By adding sodium chloride, the act the releasing agent. 45 dye completely precipitated, then filtered off and

Suitable compounds of copper are, for. B. washed with sodium chloride solution. The filter-

Cupric sulfate, cupriformate, cupric acetate or cupric cake is suspended in 160 parts of water at 70 °,

chloride. Within half an hour you leave with one

The nickel compounds used are, for. B. Nickel ormiat, temperature of 70 to 75 ° a solution of 15 parts Nickel acetate and nickel sulfate. Add dropwise the 50 cobalt sulfate obtained in 40 parts of water. By Copper or nickel complex compounds are made from simultaneous addition of a dilute sodium Their aqueous solutions by adding carbonate solution, the pH is between 5.0 and Salt deposited, then filtered off, optionally kept 6.0. After adding the cobalt sulfate solution washed and then dried. the complex solution is still for 30 minutes

The new copper- or nickel-containing reactive 55 stirred at 70 °. The cobalt complex compound dyes are very little sensitive to salt and are precipitated by adding sodium chloride, own, especially if they are three water-soluble then filtered off and made with sodium chloride solution Groups have a very good solvent wash.

possibility in water, so that after the fixation of the dye paste is in 150 parts of water

non-chemically bound part easily washed out 60 80 ° dissolved, with 21.8 parts 2,4,5,6-tetrachloropyri-

can be. They are therefore well suited for padding with added and stirred for 4 hours at 80 °,

or printing on wool, silk, leather and syn- The pH of the solution is increased during this time

synthetic polyamide fibers, but in particular by adding a dilute sodium carbonate

Fibers made from natural or regenerated cellulose solution kept between 4 and 5, after finished

in red tones. 65 condensation is the dye by adding

The resulting, an alkaline aftertreatment, sodium chloride is precipitated at 80 ° and filtered off. Of the

Dried dye, possibly subjected to elevated temperature, is a dark powder that turns

and then dissolves soaped blocks and prints in water with a dark brown color.

¹⁰

Mercerized cotton sateen is printed with a printing paste of the following composition:
30 parts of the dye obtained as described above

100 parts urea '

372 parts of water, '

450 parts of a 3% sodium alginate thickener, 15 parts of l-nitrobenzene-3-sulfonic acid sodium,
33 teaspoons of sodium carbonate,

-
iuuu lene.

The dried textile material is steamed for 10 to 15 minutes at 102 to 104 ° and then Rinsed cold and warm. After soaking at the boil, followed by rinsing again and Drying gives a reddish brown print of good wet and light fastness.

β e ι s ρ ι e ι ζ

22.4 parts of 2-amino-6-chloro-1-hydroxybenzene-4-sulfonic acid are mixed in 80 Teüen water and 15 parts of 30% hydrochloric acid and at 0 to 5 ° with a Solution of 7 parts of sodium nitrite in 25 parts of water, diazotized. Made by adding sodium bicarbonate Congo-neutral diazo solution is allowed to form a solution of 23.9 parts at a temperature of 0 to 5 ° 2-Amino-3-hydroxynaphthalene-6-sulfonic acid and 10.5 parts of 30% sodium hydroxide solution in 200 parts Add water dropwise, the pH of the coupling compound by further addition of 28 parts 30% sodium hydroxide solution is kept between 8.5 and 9.0. After stirring for 3 hours the dye through. Addition of sodium chloride completely precipitated, then filtered off and washed with sodium chloride solution washed. ·

The feed cake is suspended in 160 parts of water at 70 ° and according to the instructions in Example 2 cobalted. The cobalt complex compound is precipitated by adding sodium chloride and then filtered off and washed with sodium chloride solution.

The paste is dissolved in 150 parts of water at 80 ° and mixed with 18.3 parts of 2,4,6-trichloropyrimidine stirred for 4 hours at 80 °. The pH of the solution is adjusted during this time by adding a diluted sodium carbonate solution kept between 4 and 5. When the condensation is complete, the dye becomes precipitated by adding sodium chloride at 80 ° and filtered off. The dried dye is a dark powder that dissolves in water with a dark brown color.

A print on cotton cretonne, produced according to the instructions in Example 1, has a reddish-tinged brown color Shade of good wet and light fastness.

A fabric made of mercerized cotton is treated with a solution containing 30 g / l calcined sodium carbonate, 20 g / l of the dye available above and 5 g / l of l-nitrobenzene-3-sulfonic acid Contains sodium, impregnated at 40 ° and 1.8 to 2 times its original dry weight squeezed. The material is then placed in a box at 90 to 95 ° for 4 to 6 hours conditioned with constant moisture content. Then rinse thoroughly in cold and hot water, soapy for 45 minutes at the boil with 5 g / l soap, rinses again and dries. A reddish-tinged brown color is obtained Coloring of good wet and light fastness properties.

Example3

¹⁸ > ^{9 parts of} 2-amino-1-hydroxybenzene-4-sulfonic acid are stirred in 80 parts of water and 10 parts of 30% hydrochloric acid and ^{diazotized at 0 to 5 ° with a solution of} ^ parts of sodium nitrite in 25 parts of water. The neutral to Congo red by the addition of sodium bicarbonate gesteUte diazo solution is allowed at a temperature of 0 to 5 ° to a solution of 31.9 TEI * ^s 2-amino-3-hydroxynaphthalene-6,8-disulfonic acid _and 20% sodium carbonate solution in _50Teüen ioo Add small amounts of water dropwise, the pH of the coupling compound being kept between 8.5 and 9.0 by further addition of 20% sodium carbonate solution. After 8 hours of stirring, the coupling is complete. The dye is completely precipitated by adding sodium chloride, then filtered off and washed with sodium chloride solution.

_Dej . _{Filter cake becomes 150 parts of} water at 60 °

solved. A solution of 25 parts of copper sulfate in 50 parts of water is added dropwise at a temperature of 60 to 65 ° over the course of 2 hours. By simultaneously adding a dilute sodium acetate solution ird the pH between 4.0 and 4.5 _w maintained. After the copper sulfate solution has been added, the complex solution is stirred for a further 30 minutes at 60 °. The copper complex compound is precipitated by adding sodium chloride, then frozen off _and washed with sodium chloride solution.

The dye paste is dissolved in 200 parts of water at 80 °, and 21.8 parts of 2,4,5,6-tetrachloropyrimidine are added and stirred for 8 hours at 80 °. The pH of the solution will through during this time Adding a dilute sodium carbonate solution between 4 and 5 kept. After condensation has ended the dye is precipitated by adding sodium chloride at 80 ° and filtered off. The dried one Dye is a dark powder that dissolves in water with a red color. You get one on rayon red print of good wet and lightfastness.

Example 4

48.4 Part of that described in Example, Section I. Monoazo dye are mixed in 300 parts of water. The dye suspension is added at 80 ° 30 parts of crystallized sodium acetate and 30 parts of crystallized chromium potassium sulfate and heat the mixture reflux for 24 hours. The chromium complex compound is obtained by adding Sodium chloride precipitated, then filtered off and washed with sodium chloride solution.

The chromium complex compound is dissolved in 300 parts of water and at a temperature of 0 ° with 18.5 parts of cyanuric chloride are added. The pH of the reaction solution is diluted by adding dropwise Sodium carbonate solution kept between 3.0 and 4.0. After stirring for 4 hours at 0 ° is the Condensation ended.

The chromium complex solution is then heated to 45 ° and treated with 17.3 parts of 2-aminobenzene-1-sulfonic acid, which was dissolved in 100 parts of water at a pH of 6.0. The pH of the reaction solution is kept between 5.0 and 6.0 by adding a dilute sodium carbonate solution dropwise.

After stirring at 45 ° for 1 hour, the condensation has ended. By adding sodium chloride the dye is precipitated and then filtered off. Of the

ίο

Dye dried in a vacuum is a dark powder that dissolves in water with a purple color.

A violet print of good wet and light fastness is obtained on mercerized cotton sateen.

The following table contains further metal-containing reactive dyes, which according to the information in the examples 1 to 4 are available, and by the diazo component and azo component [columns (I)

and (JI)] the compound which is condensable with a body having an exchangeable hydrogen atom and also contains at least one substituent which enables chemical bonding with the substrate [column (HI)], the metal used for metal complex formation [column (IV)] and the The color of the dye on cotton [column (V)] are marked.

No. (D (ID (III) (IV) (V) 5 2-amino-4-nitro-l-hy- 2-amino-3-hydroxynaph- 2,4,6-trichloropyrimidine Cr violet droxybenzene-6-sulfone thalin-6-sulfonic acid acid 6th 2-amino-6-nitro-l-hy- the same 2,4-dichloro-6-amino- Co Reddish droxybenzene-4-sulfone 1,3,5-triazine Brown acid 7th the same the same 2,4,5,6-tetrabromopyri- Cr violet midin 8th 2-amino-4-chloro-l-hydro- the same ^ -Chloropropionic acid- Co Reddish xybenzene-6-sulfonic acid chloride Brown 9 the same the same Chloroacetic acid chloride Cr violet 10 2-amino-6-chloro-l-hydro- the same Cyanuric chloride Co Reddish xybenzene-4-sulfonic acid Brown 11 the same the same 2,4,5,6-tetrachloropyrimidine Cr violet 12th 2-amino-l-hydroxybenzene the same S-chloromethyl ^^ - dichloro- Co Reddish 4-sulfonic acid 6-methyl-pyrimidine Brown 13th the same the same 2,4,5,6-tetrachloro. Co Reddish pyrimidine Brown 14th 2-amino-4-nitro-l-hy- 2-amino-3-hydroxy 2,4,5,6-tetrachlor Co Reddish droxybenzene phthalene-6,8-disulfone- pyrimidine Brown acid 15th the same the same Cyanuric chloride Cr violet 16 2-amino-4-chloro-l-hy- the same 2,4,6-tribromopyrimidine Co Reddish droxybenzene Brown 17th the same the same 2,4-dichloro-6-amino- Cr violet 1,3,5-triazine 18th 2-amino-l-hydroxybenzene the same 2,4,6-trichloropyrimidine Co Reddish 4-sulfonic acid the same Brown 19th the same the same 2,4,5,6-tetrabromo Cr violet pyrimidine 20th 2-amino-l-hydroxy 2-amino-3-hydroxynaph- Cyanuric chloride Co Reddish benzene-4,6-disulfonic acid thalin-6-sulfonic acid Brown 21 the same the same 2,4,6-trichloropyrimidine Cr violet 22nd 2-amino-l-hydroxy 2-amino-3-hydroxynaph- Cyanuric bromide Ni Red benzene-4-sulfonic acid thalin-6,8-disulfonic acid 23 the same 2-amino-3-hydroxynaph- 2,4-dichloro-6-phenyl- Ni Red thalin-6-sulfonic acid amino-1,3,5-triazine 4'-suconic acid 24 the same the same 2,4-dichloro-6-amino- Cu Red 1,3,5-triazine 25th 2-amino-l-hydroxy-6-ace- the same 2,4-dichloro-6-methyl- Co Reddish tylaminobenzene-4-sul- amino-1,3,5-triazine Brown fonic acid 26th the same the same 2,4,5,6-tetrabromo Cr violet pyrimidine 27 2-amino-l-hydroxy 2-amino-3-hydroxy-naph- 2,4,6-trichloropyrimidine Co Reddish 4-bromobenzene thalin-6,8-disulfonic acid Brown 28 2-amino-l-hydroxy the same the same Co Reddish 4-methylbenzene Brown 29 2-amino-l-hydroxy the same Cyanuric chloride Co Reddish 4-methoxybenzene Brown 30th 2-amino-l-hydroxy 2-amino-3-hydroxynaph- 2,4,5,6-tetrachlor Cu Red benzene-4,6-disulfonic acid thalin-6-sulfonic acid pyrimidine

609 670/365

Claims (2)

Patent claims: 1. A process for the production of metal-containing reactive dyes, characterized in that that one mole of a diazo compound from an amine in any order formula OH NH ₂ (II) 1 mol of a coupling component of the formula HO NH ₂ (III) 20th HO ₃ S where X is hydrogen or - So ₃ H, and converts 1 mol of a compound which is condensable with a body having an exchangeable hydrogen atom and also contains at least one substituent which enables chemical bonding with the substrate, where- rend or after the build-up of the dye in substance with a metal donor is, with the formation of a metal-containing reactive dye, which in the metal-free Form of the formula HO OH NH-R ¹ IN = HO ₃ S where X is hydrogen or - SO ₃ H and R is the remainder of a compound which contains at least one substituent that enables chemical bonding with the substrate and the core A can be further substituted, the entire dye molecule at least two - SO ₃ H groups must contain. 2. The method according to claim 1, characterized in that one is used as the metal donating agent a chromium, cobalt, copper or nickel releasing agent is used. Considered publications:
German patent specifications No. 509 289, 528 166. When the application was announced, two coloring tables with explanations were laid out. 609 670/365 10.66 © Bundesdruckerei Berlin