DE1300618B - Process for the production of water-soluble color salts of azo dyes - Google Patents

Description

Here, Ri means hydrogen or an organic one Rest, d. H. primarily a lower alkyl group and preferably a methyl group, in properties, especially light and deca fastness, 20 secondly a phenyl group that contains azo color, if acidic substances which make water soluble contain the usual non-ionic substituents the groups free azo dyes of the general can; R2 is hydrogen or an organic residue,

Formula I.

RN = NC CR ₁

Il Il

H ₂ N - CN

(D

R ₂

that by coupling carbocyclic-aromatic diazonium compounds with one in the 4-position coupling 5-aminopyrazole can be obtained with alkylating agents of the general formula II

R ₃ -X

(H)

in this case preferably a phenyl group which can be further substituted nonionogenically, or a lower optionally substituted alkyl, an aralkyl, especially the benzyl, or a cycloalkyl, especially a cyclohexyl group.

Nucleophiles are preferred as nonionic substituents of phenyl radicals of the coupling component, for example the lower alkyl groups, the low molecular weight alkyl ether or phenyl ether groups, the acylamino groups such as the acetylamino group.

Ra in formula II means a lower alkyl radical or a substituted lower alkyl radical, then especially an aralkyl radical. The methyl, ethyl, n-propyl or n-butyl radicals come as alkyl radicals Aralkyl radical especially the benzyl radical into consideration. Reactive esters which can be used according to the invention

treated.

In these formulas, R denotes a carbocyclic aromatic radical, especially a radical of the benzene-optionally substituted lower alkanols with or naphthalene series, the optionally further strong acids of the formula II are z. B. the methyl, may be substituted, Ri and Ro a hydrogen, ethyl, propyl, butyl or benzyl ester of the chlorine atom or an organic residue, R3 a lower hydrogen, hydrogen bromide, hydrogen iodide, Alkyl radical or a substituted lower alkyl, the methyl or ethyl ester of sulfuric acid, the radical, then especially an aralkyl radical, X the radical 45 benzenesulfonic acid, p-toluenesulfonic acid or the a strong acid. 2,4-dinitrobenzene-1-sulfonic acid.

The diazo components should, according to the definition, The implementation of the azo dyes of the formula I.

no acidic dissociating residues in water, as is the case with the reactive ester of the formula II

Sulphonic or carboxylic acid groups contain. Your expedient by fusing the two together

carbocyclic radicals can incidentally any 50 starting materials at elevated temperature or through

be substituted, for example by hydrocarbons whose heating in an inert organic solvent

substance groups, such as methyl, ethyl, iso-propyl, solvents carried out. As an inert solvent

t-Butyl, cyclohexyl, phenyl, benzyl groups, for example optionally halogenated ones

Ether groups, such as methoxy, ethoxy, hydroxy or nitrated aromatic hydrocarbons, such as

ethoxy, phenoxy, cresoxy, phenylthio groups, 55 z. B. halogen or nitrobenzenes, or optionally

by acylamino groups, such as acetylamino, chloro-halogenated aliphatic hydrocarbons, such as acetylamino, methylsulfonylamino, benzoylamino groups, by tertiary amino groups, such as dimethylamino, diethylamino, biscyanethylamino, phenylalkylamino groups, but in particular by electroless 60
trophilic substituents, such as the nitro, the trifluoro

Trichlorethylene or tetrachloroethane, in question.

The color salts which can be prepared according to the invention correspond to the general formula IV

methyl, the cyano groups, the halogens fluorine, chlorine and bromine, the keto, the sulfonyl, like Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, toluylsulfonyl groups, through sulfonic acid amide groups, such as the sulfonic acid dimethylamide, diethylamide, cyclohexylamide, phenylalkylamide, piperidide and -mofpholide groups. Arylazo groups can also

RN = NC CR ₁

H ₂ NC NR ₃

\ _N /

R,

X © (IV)

In this formula IV, R denotes a carbocyclic-aromatic radical, especially a radical of the benzene series or a radical of the naphthalene series, preferably a phenyl radical which is electrophilically substituted in the o- and / or p-position with respect to the azo bond; Ri and R2 are each hydrogen or a monovalent organic radical, Ri especially a lower alkyl group and preferably the methyl group; R2 especially a phenyl group which is optionally further substituted nonionogenically, an aralkyl group, then preferably the benzyl group, or a cycloalkyl group, then preferably the cyclohexyl group; R _{3 is} an optionally substituted, lower alkyl radical, such as methyl, ethyl, butyl, benzyl. In the cation, sulfonic acid and carboxyl groups should be excluded as substituents of organic radicals. X means the anion of an acid.

The color salts which can be prepared according to the invention fall as salts of the acids of the of the formula II corresponding esters, that is to say as salts of inorganic or organic acids at. It is primarily chlorides, bromides, iodides, methosulphates, ethosulphates, bisulphates, Benzenesulfonates or p-toluenesulfonates. If so desired salts of other acids can also be prepared by double conversion, for example Oxalates by adding oxalic acid. Double salts can also be represented, for example with the dye halides and the corresponding • zinc or cadmium salts.

The basic color salts obtainable according to the invention are generally readily soluble in water. she draw from aqueous, neutral or, more advantageously, from weakly acidic solution, optionally in the presence dispersing wetting agents (e.g. in the presence of condensation products of alkylene oxides with higher alkanols) on fiber material made of polymeric or copolymeric acrylonitrile open heating or in a closed dyebath under pressure largely to completely up and result in pure and real, yellow to orange colors.

Compared to the cationic azo dyes described in French patent 1 238 392, that by alkylation of the coupling product of diazotized aniline with l-phenyl-S-methyl-S-pyrazolone is produced, the basic 5 - aminopyrazole azo dyes according to the invention are distinguished due to their better steam, decatur and pleated fastness as well as their better stability.

The following examples illustrate the invention. In it mean, unless otherwise noted is, the parts are parts by weight. The temperatures are given in degrees Celsius. Parts by weight are in the same proportion to parts by volume as kilograms to liters.

example 1

18.3 parts of l-amino-2,4-dinitrobenzene are, as usual, in 30 parts of concentrated sulfuric acid at 15 ° with nitrosylsulfuric acid, corresponding to 6.9 parts of sodium nitrite, diazotized for 10 hours. The diazonium salt solution thus obtained is added dropwise to a cooled solution of 16.1 parts of 1-phenyl-3-methyl-5-aminopyrazole in 300 parts of glacial acetic acid and 500 parts of water, buffers the reaction mass after one hour by introducing sodium acetate to a pH of 4 to 4.5, the precipitated dye is filtered off, washed neutral and dries him.

3.7 parts of this dye are combined with 10 parts of dimethyl sulfate while stirring Heated to 120 ° for 5 minutes. The reaction mass is then 500 parts of 60 ° warm water poured. After adding a little sodium acetate and charcoal, the yellow dye solution is clarified and the color salt is precipitated as zinc chloride double salt with the help of zinc chloride and sodium chloride.

It dyes polyacrylonitrile fibers from acetic acid bath with extensive exhaustion of the same in Bright reddish yellow shades with excellent general fastness properties.

Dyes with similar properties are obtained if instead of as coupling components of 16.1 parts of 1-phenyl-3-methyl-5-aminopyrazole, the corresponding amounts of those in Table I below mentioned 5-aminopyrazole derivatives are used and the above procedure is followed.

Table I.

No. Diazo component Coupling component Hue on
Polyacrylonitrile fiber 1
2
3
4th
5
6th
7th
8th
9
10
11 l-amino-2,4-dinitrobenzene
the same
the same
the same
the same
the same
the same
the same
the same
the same
the same 1- (4'-methylphenyl) -3-methyl-5-aminopyrazole
1, S-diphenyl-S-aminopyrazole
l- (4'-acetylaminophenyl) -3-methyl-5-amino-
pyrazole
l- (3'-methoxyphenyl) -3-methyl-5-amino-
pyrazole
1-Isopropyl-S-methyl-S-aminopyrazole
1, S-dimethyl-S-aminopyrazole
H / S-cyanoethyl I-S-methyl-S-aminopyrazole
1-Cyclohexyl-S-methyl-S-aminopyrazole
3-methyl-5-aminopyrazole
1-methyl-S-phenyl-S-aminopyrazole
1-ethyl-S-methyl-S-aminopyrazole reddish yellow
reddish yellow
reddish yellow
reddish yellow
yellow
yellow
yellow
yellow
yellow
yellow
yellow

Example!

20.7 parts of l-amino- ^ o-dichloro- ^ nitrobenzene become in 40 parts of concentrated sulfuric acid with nitrosylsulfuric acid corresponding to 6.9 parts of sodium nitrite and within 1.5 hours at 20 to 25 ° diazotized. The diazonium salt solution is poured into a cooled solution of 16.1 parts l-Phenyl-3-methyl-5-aminopyrazole in dilute hydrochloric acid, blunted by adding sodium acetate the coupling solution to a pH of 4 to 4.5 and filtered after the coupling has ended the red dye off.

3.8 parts of this dye are suspended in 300 parts of hot tetrachloroethane. At 100 ' ^: this solution is mixed with 2.6 parts of dimethyl sulfate and then heated to 120 to 130 for one hour. After the reaction mass has cooled down, 300 parts of water are added and the mixture is subjected to steam distillation to remove the organic solvent. The yellow, aqueous dye solution obtained in this way is clarified while hot with a little charcoal and the dye salt is precipitated as a zinc chloride double salt by adding zinc chloride and sodium chloride. This dissolves in water with a yellow color and dyes fibers made of polyacrylonitrile from acetic acid bath, with extensive exhaustion of the same, in bright reddish-yellow shades with excellent general fastness properties.

ίο To one containing the same color cation Color salt can also be obtained by heating the abovementioned azo dyes with methyl iodide in the presence of methanol in a closed tube at 130 to 150 "for 2 hours.

In the above example, equimolar amounts are used in place of the 20.7 parts of l-amino-2,6-dichloro-4-nitrobenzene Amines of the amines listed in Table II below and otherwise adheres to the conditions given above, this gives dyes which are similar to polyacrylonitrile dyeings deliver good properties. ·

Table II

No. Diazo component Coupling component Hue on
Polyacrylonitrile fiber 1 l-amino-4-nitrobenzene 1-phenyl-3-methyl-5-aminopyrazole Reddish yellow 2 l-amino-3-nitrobenzene the same Reddish yellow 3 1 - amino-2-nitrobenzene the same Reddish yellow 4th l-amino-2-chloro-4-nitrobenzene the same Reddish yellow 5 1-amino-2-methoxy-4-nitrobenzene the same Reddish yellow 6th l-amino-2,5-dichloro-4-nitrobenzene the same Reddish yellow 7th l-amino-2-nitro-4-ethylsulfonylbenzene the same Reddish yellow 8th 1-amino-2,4-dicyanobenzene the same Reddish yellow 9 aniline the same yellow 10 2-aminonaphthalene the same orange 11 1-amino-2-methylbenzoI the same yellow 12th 1-amino-4-methylbenzene the same yellow 13th 1 - Amino-4-chlorobenzoI the same yellow 14th 1 - amino-4-methoxybenzene the same yellow 15th 1 - amino-2-methoxybenzene the same yellow

B e i s ρ i e 1 3

A suspension of 19.7 parts of 4-amino-1,1'-azobenzene in 125 parts of water and 25 parts of concentrated hydrochloric acid is at 15 with 6.9 parts of sodium nitrite diazotized in 100 parts of water as usual. The diazonium salt solution is added to a solution of 14.9 parts of l-iso-propyl-3-methyl-5-aminopyrazole in 300 parts of acetic acid and 500 parts of water flow. The pH of the coupling solution is brought to 4 to 4.5 by adding sodium acetate. To When the coupling is complete, the reaction product is filtered off with suction, washed with water and dried red dye in vacuo.

3.5 parts of the disazo dye thus obtained are mixed with 10 parts of ethyl p-toluenesulfonate and the mixture is heated to 130 ° for 10 minutes. The melt, which is still hot, is poured on 500 parts of warm water, clarifies the orange solution with a little charcoal and then drops the color salt by adding sodium chloride. Fibers can be extracted from acetic acid solution with this coloring salt Color polyacrylonitrile in reddish yellow tones. The coloring is characterized by excellent. Lightfastness the end.

Products with similar coloring properties are obtained by using the equimolar Amounts of 4-amino-3,2'-dimethyl-l, l'-azobenzene, 4-amino-2,5,2'-trimethyl-1,1'-azobenzene, 4-Amino-2-methyl-5-methoxy-l, r-azobenzene or 4-Amino-2,5-dimethoxy-1,1'-azobenzene, = instead of the 19.7 parts of 4-amino-1,1'-azobenzene in the above example.

Claims (2)

Patent claims: 1. Process for the preparation of water-soluble color salts of azo dyes ^ in which the azo dye forms the cation, characterized in that azo dyes are used the general formula RN = NC CR ₁ H, N -C in which R is a carbocyclic-aromatic radical, Ri and R2 are each a hydrogen atom or a mean organic radical by reaction with alkylating agents of the general formula Rj - X, where R3 is an optionally substituted one lower alkyl radical and X means the radical of a strong acid, converted into color salts and the components are chosen so that the dye does not dissociate acidic in water Contains groups. 2. The method according to claim 1, characterized in that monoazo dyes are used. 909 532/295