CS197332B2 - Process for preparing monoazodyes - Google Patents

Abstract

1,179,760. Reactive monoazo dyestuffs. CIBA Ltd. 1 Dec., 1967 [1 Dec., 1966], No. 54863/67. Heading C4P. The invention comprises fibre reactive (i.e. form a covalent bond with the fibre) monoazo dyestuffs of general formula wherein X is a fibre-reactive acylamino group, R 1 is a benzene residue containing a sulphonic acid group, R 2 is an amino or substituted amino group, Z is a sulphonic acid or sulphonic acid amide group and n is 1 or 2. The preferred values of X include α,#-dichloro- or α,#-dibromo-propionyl, α-chloro or α-bromo-acrylamino, and halo-pyridazines, pyrimidines and triazines. The dyes are prepared by (i) diazotization and coupling, (ii) splitting off hydrogen halide from dyestuffs where X is a propionylamino group containing at least one halogen atom by reaction with an alkaline agent or (iii) acylating dyestuffs where X is -NH 2 to introduce the reactive acyl group. The dyes dye nitrogenous materials, e.g. wool, silk, leather, polyamides and polyurethanes in red, blue and violet shades.

Description

The invention relates to novel valuable monoazo dyes of the formula I

where it means

X a heterocyclic fiber-reactive substituent, such as a 2,4-dichlorotriazine group, or an aliphatic halogenated acylamino group selected from the group consisting of α, β-dichloropropionylamino, α, β-di-bromoproplonylamino, α-chloroacrylamino and α-bromoacrylamino,

R1 is a benzene radical containing a sulphonic acid group, optionally substituted by a halogen atom with an acylamino group having 2 to carbon atoms in the acyl moiety or a methyl group,

R2 is amino, C1 -C4 alkylamino, alkyl or phenylamino, n a positive integer of not more than 2.

In particular, the invention relates to dyes which correspond to the general formula Ia

Y

wherein X is a heterocyclic fiber-reactive substituent, preferably an aliphatic, halogenated-acylamino group of at most. 13 carbon atoms in the acyl moiety such as α, β-dichloro-carbon in the acyl moiety such as α, β-dichloro- or aj -dimpropionylamino or α-chloro- or α-bromoacrylamino, n is as in formula I, Y is a halogen atom, an acylamino group having up to 13 carbon atoms in the acyl component, in particular a methyl group or a hydrogen atom, and R3 is a phenyl radical, an alkyl radical having 1 to 4 carbon atoms, or a hydrogen atom.

The novel mono-dyes can be prepared by the coupling components of formula II

in response. with diazo compounds from amines of formula III

V ^with a. (UD wherein R2 to 'R are as defined above, and X is an acylamino group having not more than 13 carbon atoms in the acyl component while ago. Coupling or Mon coupling, acylating the corresponding amine group introduced instead of the group X to fiber-reactive acylamine group X.

The amines used as starting materials of formula III can conveniently be obtained by reacting 1,4-diaminobenzene with an acid anhydride releasing a reactive acyl residue.

As such reactive acyl radicals releasing chlorides or anhydrides are mentioned: Compounds with unsaturated bonds such as derived from chloroformalic acid, propiolic acid, acrylic acid. acids, bromoacrylic acid, chloroacrylic acid or chlorocrotonic acid, furthermore compounds with transferable halogen atoms, for example derived from chloroacetic acid, sulfochloroacetic acid, .alpha.-bromopropionic acid, .beta., .beta.-dichloropropionic acid or .alpha. 3,5-dithro-4-chlorobenzoyl chloride, 3,5-diitro-4-chlorobenzenesulfonic acid chloride; acid chlorides of some acid-containing heterocyclic compounds having a labile halogen atom on the heterocyclic ring, i.e. heterocyclic compounds with at least two halogen atoms, such as tetrahalogeipyridazines, for example 2,4,5,6-Ceerachloropyridazine, halopyrimidines, for example 2 , 4,6-tri- or 2,4,5D-Ceerachlorpyrimidine, 5-bromo-2,4,6-trlchloropyrimidine, 5-acetyl-2,4,6-richlorpyrimidine, 2,4-dichloropyrimidine-5 acid

-sulfonic,. 5-nitro- or 5-cyano-2,4,6-trichloropyrimidine, 5-nitro-6-methyl-2,4-dichloropyrimidine, 2-chlorobenzthiazole-6-carbonic acid chloride, 2-chlorobenzthiazole-6- sulfonic acid, 2,6-dichloropyrimidine-4-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 2,4-dichloropyrimidine-5-sulfonic acid chloride and the corresponding bromopyrimidines in particular. but di- a. trihalogentriazines such as cyanuric chloride,. 2-methyl-, 2-ethyl- or 2-phenyl-4,6-dichlorotriazine, and in particular triazines of formula V.

wherein A represents a hydroxyl or mercapto radical bound via an oxygen or sulfur atom, or in particular an NH2 group or an amino radical bound through a nitrogen atom, the amino compound, if any. aromatic, preferably has a strongly acidic group which induces water solubility.

The condensation with acid halides or anhydrides or heterocyclic halogenated compounds is conveniently carried out in the presence of acid-binding agents such as sodium carbonate. Of course, all these reactions are carried out in such a way that an unsaturated bond, or a halogen atom, is capable of exchange in the finished product.

Useful coupling components of Formula 4 include:

2-aminooaffalene-5-, -6- or -7- (4) -phonic acid;

2-N-methylaminonaphthalene-6-sulfonic acid,

2-N-β-laminonaphthalene-6-sulfonic acid, 2-amino-8-oxynaphthalene-6-sulfonic acid, 2-N-phenylamino-8-oxynaphthalene-6-sulfonic acid, as well as the corresponding compounds having unsubstituted or substituted sulfonamide group at position 6 such as the například-methyl-, -ethyl-, -isobutyl-, -β-oxyethyl-, -3'-methoxypropyl-, amide group. -cyclohexyl-, -furfuryl-, -dimethyl-, -diethyl-, -N-methyl-N-6-ethylethyl-, -phenyl-, -N-methyl-N-phenyl-, -N-ethyl-N-phenylsulfonic and phenylsulfonamides corresponding to the latter three phenylsulfonamides, which, for example, have a chlorine atom or a methyl atom as a substrate substituent.

Diazotization of amines of formula III used in this invention. way. as starting materials, can be carried out in a manner known per se, e.g. using a mineral acid, especially hydrochloric acid, and sodium nitrite, or using other methods. customary for difficult to diazotizable compounds, for example with the aid of nitrosylsulfonic acid. In the latter case it is often. it is expedient for the diazo compounds to be filtered off, for example by diluting the diazotizing mixture with water, and so on. copulated. Kopulace se. It is carried out in an acidic medium, for example, in a weakly acidic medium to a conglomerate up to an acidified medium with acetic acid. It is often useful and recommended that the effect of the free mineral acid resulting from the coupling reaction be blunted, for example, with sodium acetate. .

The dyes are isolated from the coupling mass in such a way that the reaction-capable residue of the isolated products remains intact.

The novel dyes of the formula (I) can also be prepared by a variation of said process, which is characterized in that they are:. condenses 1 mole of a monoazo dye of formula (I) wherein R 1, R 2, Z and n are as defined herein and X is an acylating amino group with chloride. acid. or an anhydride, for example above. of the type releasing a reactive acyl residue. The aminoazo dyes used as starting materials can be prepared. known about themselves. ways. . by coupling 1 of the coupling components described above,. in an acidic medium with diazo compounds which are present in addition to the diazo group and the sulfone group. k. her. in ortho position,. . have. in the para position a free amino group,. or. substituent. capable of being converted to such a group, for example, a nitrosubstituted or acetylamino substituent which, upon completion of the coupling, can be appropriately converted by reduction or saponification.

Another method for the preparation of blowing agents which have an acrylaminosubstituted or halogenated substituent X as substituent X. Acrylamino is based on the dyes of formula (1) wherein R 1, R 2, Z and n are as defined therein, while X is, for example, a halogen- or dihalopropionylamino group, and starting materials thereof. dyes are obtained by cleavage of the hydrogen halide to the dyes of. invention. Said starting dyes. can be produced by a process corresponding to the above-mentioned production variants, i.e. by coupling or condensation. In order to achieve the cleavage of the hydrogen halide according to the invention, these are treated. dyes, especially those having β-chloro- or β-bromopropionylamine. or an α, β-dichloro- or α, β-dibromopropionium group, suitably an alkali metal or alkaline earth metal hydroxide or carbonate. at low or slightly elevated temperatures. The dyes obtained by the process according to the invention and according to variations of this process are novel. They are suitable for dyeing and printing a wide variety of substances, in particular substances of animal origin, such as leather, silk and in particular wool, as well as for dyeing and printing various synthetic fibers, for example animalized rayon, polyamides or. The dyes according to the invention which have a sulfonic acid group in the coupling component are particularly suitable for application from an acid bath or optionally a sulfuric acid bath, on the other hand. dyes are. a sulfonamide group is suitable. to .ze application. a weakly acidic neutral bath. The dyeing and prints obtained with. new. Neutral or acid bath dyes. characterized by valuable color. shades, high light fastness, color uniformity and good. washing stability. and in the washboard and also in the case of chlorinated wool, in particular in acid wool. areas. Against known dyes. by. French patent number. 139,039, which have no sulfone group in the remainder of R 1, is. are characterized by the colorants obtained according to. . invention as. closest comparable to higher solubility and above all better stability at. and especially improved behavior in the presence of leveling agents, especially in the wetting agent. the presence of polyglycol ether derivatives which, on average, contain at least 10 groups —CH2 —CH2 —O— and. are derived. from primary monoamines containing an aliphatic hydrocarbon. residue. with at least 20 carbon atoms.

In other examples. are. parts and percentages, unless otherwise indicated, are by weight. and the temperature is in degrees Celsius. .

Example.l

A neutral solution of 228 parts of 5- (α, β-dibromopropionylamino) -2-amino-4'-methyl-1,1'-diphenylsulfone-3'-sulfonic acid in 2000 parts of water is mixed with 125 parts of 30% acid at 10 to 15 ° diazotization with 125 parts by volume of a 4N sodium nitrite solution and a small excess of nitrite decompose A solution of 120 parts of 2-amino-8-hydroxynaphthalene is added dropwise to the obtained nitrous acid-free diazo compound. Of 6-sulfonic acid in 500 parts by volume of 1 N sodium hydroxide solution are added dropwise with stirring dropwise 200 parts of 4 N sodium acetate solution at 20 to 25 ° until the coupling is complete, the coupling mixture is cooled at 10-15 ° is then mixed. with ..250 vol. parts of 10 N sodium hydroxide. sodium and. stirred for approximately 15 missed at 10 to 15 °, with α, ^β-ι dibrompropio nylov.á group converted to The α-bromoacrylic group is then neutralized with the dye suspension treated. 30% hydrochloric acid, except for a weakly alkaline reaction (pH about 8), filtered the dye. Wash thoroughly with 15% sodium chloride solution. and dries. under vacuum. at 80. to 90 °. Gets. is a red powder which dissolves in the upper water and stains. wool or fibers of superpolyamides in red-violet hues. standing in the wet. When, instead of 228 parts of 5- (α, β-dibromo-propionylamino) -2-amino-4'-methyl-1,1'-diphenylsulfone-3'-sulfonic acid, 180 parts of acid were used. · 5- (and-broinakrylamino) -2-amino-4'-methylll, r ^{difenyIsulfon-3'-i} with alfonové and omitting the solution. sodium hydroxide, the same dye is obtained.

. Similar dyes that dye wool in the shades shown in column II of the table that follows are obtained when the diazo compounds of the amines listed in column I are coupled with the azocomponents listed in column II of this example and when the obtained dihalogemopropionyllylamine dyes are converted by hydrogen halide cleavage. monohalogenacrylic dyes. However, dyes with dihalopropionyl amine groups can be used for dyeing without modification.

II III

1 5- (a, (S-Dibromopropionyl-amino) -2- <amino-4'-methyl-1,1'-diphenylsulfone-3'-sulfonic acid 2-Aminonaphthalene-6-sulfonic acid red 2 5- (α, β-Dibromopropionyl-amino) -2- <amino-4‘-methyl-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-Amino-naphthalene-5-sulfonic acid red 3 5- (α, β-Dibromopropionyl-amino) -2-amino-4‘-methyl-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-Aminonaphthalene-7-sulfonic acid red

5- (α, η-dibromopropionylamino) -2-amino-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-amino-8-hydroxy-naphthalene-6-isulfonic acid tnodravěčervený 5- (α, β-dibromopropionylamino) -2-amino-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-N-methylamino-8-hydroxynaphthalene-6-sulfonic acid red violet 5- (α, β-Dibromopropionylamino) -2-amino-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-aminonaphthalene-6-sulfonic acid red 5- (α, β-dichloropropionylamino) -2-amino-4‘-chloro-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-Amino-naphthalene-6-sulfonic acid red 5- (α, β-Dibromopropionylamino) -2-amino-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-aminonaphthalene • 5-sulfonic acid red 5- (α, β-dibromopropionylamino) -2-amino-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-Amino-naphthalene-7-sulfonoic acid red 5- (α, β-dibromoproplonylamino) -2-amino-4‘-methyl-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-methylaminonaphthalene-6-sulfonic acid bluish red 5- (α, β-Dibromopropionylamino} -2-amino-4‘-methyl-1,1‘-diphenylsulfone-3‘-sulfonic acid 2-Amino-naphthalene-8-sulfonic acid red

Example 2 parts of a secondary condensation product of one mole of cyanuric chloride, one mole of methoxyethylamine and one mole of 2,5-diamino-4'-methylthiylilir-diphenylsulfone-3'-sulfonic acid are suspended in a mixture of 500 parts of water. and 25 parts of 30% hydrochloric acid and the resulting suspension is diazotized at 10-15 ° using 25 parts by volume of a 4 N sodium nitrite solution. The yellowish-colored suspension obtained is mixed with sodium acetate until it shows only a weak reaction of acidic nature to the congerveft. Then, the suspension is poured into a suspension of 23 parts of 2-naphthalene-6-sulfonic acid in 150 &apos; 4 N sodium acetate solution. It is stirred at 20-25 ° until the coupling is complete, the separated dye is filtered off and dried under vacuum. A brownish-red powder is obtained which gives a red solution in hot water and dyes the wool from a neutral or · weakly acidic bath in very stable red shades-resistant to moisture and light.

Example 3

To a neutral solution of 54.4 parts dye of formula

20 parts of 2,4,6-trichloropyrimidine, dissolved in 200 parts of alcohol and 25 parts of sodium acetate, are added in 1000 parts of water. The mixture is heated at 60 ° C with stirring for 4 to 6 hours, the alcohol is distilled off and the dye is added after addition of the hydrogen halide. -salt salted, filtered and dried.

Dye from a bath slightly acidified with acetic acid to neutral in wet shades of red.

When replaced by 2,4,6-trichloropyrimidine with tetrachloropyrimidine, a dye-like property is obtained. x

Example 4 parts dye of formula

is dissolved in 1000 parts of water and neutralized with 2 N sodium hydroxide solution and mixed with 16.4 parts of anhydrous sodium acetate. With vigorous stirring from 0 to 5 ° over 30 minutes, a solution of 25 parts of N -bromomopropionyl chloride is added dropwise. - After a short time, the amino group is fully acylated. The dye thus obtained is separated in a conventional manner by the addition of sodium chloride, separated by filtration and dried. The dye thus obtained stains - wool from a neutral bath - to a bath acidified with acetic acid - in bluish-red shades that are stable in wet and light conditions.

When 17 parts of α, β-dibromopropionyl chloride are used in place of the aforementioned 25 parts of α, β-dibromopropionyl chloride, a similar dye-blue-red is obtained.

Example 5 β

54.4 - parts of dye - formulas

Dissolve in 1000 parts of water and neutralize with a 2 N solution of sodium hydroxide and add 25.5 parts with thorough stirring ^. parts of fine powdered chloride- ₁ 2 3 ·· dichlσrchlnoxalin 6-ikaTboxylové -acid and at 30 ° - 40 ° for AZ- constant uvolňované- neutralization of hydrochloric acid - the reaction -se -směs- -solution was stirred with 2 N sodium carbonate -in pH 6 to 7 until the diazo group in the para-position is fully acylated. The dye thus obtained is separated in a customary manner by addition of sodium chloride, dried by filtration. The dye thus obtained dyes the wool from the bath neutral. - and acidified with acetic acid in red shades, stable in m-ocher and light.

Prescription- coloring

Dissolve 2 parts of the dye in 4000 parts of water, add 10 parts of crystalline sodium sulphate or 0.5 parts of ethylene oxide and oleylamine edition product and add 100 parts of well-wetted wool to the dye bath thus obtained. 40-50 °. Then 2 parts of 40% acetic acid are added, - the bath is brought to reflux for half an hour, and the bath is dyed for one hour. Finally, the wool is rinsed with cold water and dried. Wool - is dyed in red shades that are wash-resistant and light-fast.

Production of ethylene oxide addition product

100 parts of technical oleylamine are mixed with one part of finely divided sodium and heated to 140 °, then ethylene oxide is introduced at 135 to 140 °. Once the reaction was completed with ethylene oxide, the reaction temperature was lowered to 120-125 ° C and continued. with ethylene oxide feed until 113 parts are bound. The reaction product thus obtained is practically perfectly soluble in water.

OBJECT OF THE INVENTION

Claims (4)

OBJECT OF THE INVENTION A process for the preparation of monoazo dyes of the general formula I wherein is X a heterocyclic fiber-reactive substituent such as 2,4-dichlorotriazinyl or an aliphatic halogenated acylamino group selected from the group consisting of ‘α, β-dichloropropionylamino, α-dibromopropionylamino, α-chloroacrylamino and α-bromoacrylamino, R 1 is a benzene radical containing sulfonic acid groups optionally substituted by a halogen atom with a C 2 -C 4 acylamino group or a methyl group, R2 is amino, (C1 -C4) alkylamino or phenylamino,. n a positive integer not exceeding 2, characterized in that:. wherein the coupling components of formula II wherein R2 and n are as defined above are reacted with the diazo compounds of amines of formula III RfSO * (III) where. R 1 is as defined above, and X 1 is an acylamino group having up to 13 carbon atoms in the acylene component, wherein the acylamino group X is introduced instead of the group X 1 on the fiber before or after coupling by acylation of the corresponding amine group. 2. A process according to claim 1, wherein the diazo compounds are acylamine-reactive as a fiber. they contain an aliphatic acylamino group having 3 carbon atoms, and the radical R 1 is a benzene radical bearing sulfonic acid groups. , 3. Method according to points 1. and 2, characterized in that the diazocomponents of the amines of the formula IV are reacted with the coupling components of the formula V wherein X2 is an aliphatic halogenated acylamino group having 3 carbon atoms, Y is a chlorine atom, an acylamino group having a maximum of 13 carbon atoms and R3 is a phenyl or C1-C4 alkyl radical or a hydrogen atom; is a positive integer of no more than 2. 4. A process according to any one of claims 1 to 3, wherein the diazo compound of the amines of formula VI is reacted with a coupling component of formula VII wherein X2 is monohalo propionylamino; or methyl and an 'm are positive integers of not more than 2. Severografífi, n. P., Plant 7, Most