DE1057706B - Process for the production of water-soluble colored salts - Google Patents

Description

C O 94 »'

FEDERAL REPUBLIC OF GERMANY

kl. 22a l

INTERNAT. KL.

PATENT OFFICE

C O 9 B 2 9 / ο 3 3 ~

EXPLAINING EDITORIAL 1057 706

G18577IVb / 22a

TO M E LDETAGi DECEMBER 14, 1955

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL: MAY 21, 19S9

The invention relates to the production of water-soluble dye salts which contain an azo dye as a cation contain.

It has been found that stable, water-soluble Color salts are obtained which contain the azo dye as a cation, if one dissociates from acidic, salt-forming groups free azo dye, which the atomic grouping of the general formula I

C-N = N-C "'

(I)

where A is an alkylene radical which is connected to two »5 adjacent carbon atoms linked by a double bond with the S atom and the N atom is connected and which can still be further substituted, and wherein the connected to the azo group unsaturated carbon atom forms part of any azo component at elevated temperature Reacts with suitable alkylating agents.

In azo dyes used according to the invention, A denotes, for example, an ethene radical, a propene radical, a Zl ₁ or Zl ₂ butene radical, an _{I 3} hexene radical or a phenyl, cycloalkyl, halogen, alkoxy, nitro or acylaminoalkene radical. In other words, thiazole rings are bonded to the azo group, which do not contain any fused aromatic-isocyclic rings, but otherwise can be further substituted in the 4- and S-positions of the thiazole ring within the scope of the definition.

The unsaturated carbon atom bonded to the azo group can be part of an aliphatic, cycloaliphatic, isocyclic-aromatic or heterocyclic-aromatic group, for example an acyloacctyl group, a dihydroresorcinol ring, a phenyl or naphthalene ring, a pyrrole or a pyrazole ring, which in connection with other radicals, for example with amido, hydroxyl, amino, acylamino, Alkyl, aralkyl, aryl groups or with fused rings form the azo component. The unsaturated one C atom can therefore, for example, be the component of an acetoacetylphenylamide, an oxyphenyl or oxynaphthyl radical, an aminophenyl or naphthyl radical, an acylaminophenyl or an acylaminonaphthyl radical, a 3-Indolyirestes, a 5-Oxy- or 5-Aminopyrazolrcstes form. The term »azo component. <· Should thus not only be limited to the actual azo components, but include other classes of compounds, as they arise, for example, in the acylation of p-aminoazo dyes. Also comes this one Term no restrictive effect in the sense that only dyes produced by azo coupling ver process for the production of water-soluble colored salts

Applicant:
JR Geigy A.-G., Basel (Switzerland)

Representative: Dr. K. Griesing, patent attorney, Hönebach-Bebra, Bahnhofstr. 9

Claimed priority: Switzerland of December 15, 1954

Dr. Werner Bossard, Riehen, Dr. Jacques Voltz and Dr. Francois Favre, Basel

(Switzerland),
have been named as inventors

should be reversible. Rather, the dyes which can be used according to the invention can be prepared by any desired method be prepared, for example by alkaline condensation of p-nitrosophenols or of p-nitrosoamine phenyl compounds with 2-aminothi azo compounds by methods known per se, or technically more advantageous by coupling diazotized 2-ammothiazoles with azo components that are not substituted within the scope of the definition, the azo dyes formed optionally further changed before or during use, for example acetylated or alkylated can be.

The azo components are primarily isocyclic-aromatic, amino and hydroxyl compounds into consideration, preferably those coupling in the p-position to these groups, the isocyclic-aromatic Ring may also contain fused-on hetero rings, as in the 4-aminobenzotriazole, 4-aniinobenzimidazole or the 4-aminoindazole compounds. In the preferred p-aminoarylazo dyes, the amino group can be primary, secondary or tertiary. The substituent of the amino group can be aliphatic, araliphatic, alicyclic, aromatic or heterocyclic be. They can be further substituted, as in the oxyalkyl, fluoroalkyl, cyanoalkyl, alkoxy and phenoxyalkyl, the alkylphenyl, alkoxyphynyl, halophenyl and the alkylbenzyl, halobenzyl and alkoxybenzyl compounds. Aliphatic substitutions of the amino group can also be used among themselves or together with a Ether atom or form hydrogenated hetero rings with the aromatic radical bearing the amino group, as in

909 527/358

the piperidine, the morpholine, the 1,2,3,4-tetrahydroquinoline, the lilolidine, the julolidine, the perimidine compounds. The preferred p-aminophenyl radical according to the invention Usable azo dyes can be further substituted within the scope of the definition, for example with halogen, alkyl, alkoxy, nitro, acylamino, alkylsulfonyl groups. Monoazo dyes are preferable to polyazo dyes.

Alkylating agents suitable for the preparation of color salts according to the invention are the esters of strong mineral acids and organic sulfonic acids of preferably lower alcohols. Alkyl chlorides, alkyl bromides, aralkyl halides, Dialkyl sulfates and alkyl p-methylbenzene sulfates come first and foremost. The implementation of the monoazo dyes which can be used according to the invention with the suitable alkylating agents is expediently carried out in an inert organic solution, the Can separate color salts. Examples of inert organic solvents are benzene hydrocarbons, Halogen and nitrobenzenes are suitable. You can also in cycloaliphatic hydrocarbons or in excess alkylating agent work. The implementation is exothermic. Heating the components is but necessary in the presence of diluents. In some favorable cases, sab formation succeeds but also in aqueous or alcoholic solution or suspension, the color salts going into solution and can be isolated by salting out. If you work in the presence of inert organic solvents, so can this thanks to the great stability of the invention Color salts are removed, for example, by steam distillation, whereupon the color salts are salted out will. However, the color salts according to the invention can also be added by extraction with water Salt out or win by distilling off the organic solvents. The alkylating agent will expediently used in excess, with primary and secondary amino groups also optionally can be post-alkylated. But the cycloammonium salt formation appears to be clearly preferred. If necessary, he can find imgs according to obtained Color salts can also be changed further, for example acj'liert.

The color salts according to the invention correspond accordingly of the general formula II.

R ₁

A ^V C - N = N - B

s'

(II)

R ₁ denotes an optionally further substituted alkyl group, for example a methyl, ethyl, propyl, butyl, oxethyl, benzyl group, A an optionally further substituted alkene radical, B the radical of an azo component in the broadest sense of the word, including that optionally after Coupling still changed azo components, and Χ ^Θ the anion equivalent to the) colored cation.

As already emphasized, the colored cation advantageously does not contain any acidic dissociating groups. The anion is mostly, of a strong inorganic or organic Be derived acid, for example from the hydrohalic acids, sulfuric acid and the aromatic sulfonic acids. Chlorine ion, bromine ion, metho- and ethosulfate ion, sulfate ion, bisulfate ion and p-toluene sulfonate ion will be the most common anions. Since the strongly basic cations, however, also with weaker ■ Acids form stable salts, residues of other organic acids are also possible; for example Salts of formic acid, acetic acid, oxalic acid and lactic acid come into consideration, furthermore the color bases themselves Anion equivalent to the Katton is therefore also understood to include the hydroxyl group. Often with advantage Double salts made with inorganic salts and

ίο be used, especially the zinc chloride double salts.

The color salts according to the invention are to be referred to as basic dyes according to their character. she are particularly soluble in water in the form of salts of strong inorganic and organic acids. Less readily soluble compounds can be brought into aqueous solution by adding acids. the Dyes according to the invention dye, for example, cotton stained with tartar and tannin in mostly

so very pure tones. The with the invention The colorations produced by dyes are often distinguished by their lightfastness.

The following examples serve to illustrate the invention. The parts are in it, as far as nothing otherwise noted, understood as weight units and the temperatures given in degrees Celsius. Parts by weight relate to parts of volume like kilograms to liters.

example 1
30th

10 parts of 2-aminothiazole are more concentrated in 20 parts Dissolved sulfuric acid and mixed with 34 parts of nitrosylsulfuric acid, which corresponds to 6.9 parts of sodium nitrite, diazotized at -5 °. A solution of is added to the diazo solution diluted with 600 parts of ice at 0 ° 14.3 parts of 1-aminonaphthalene in 200 parts more concentrated Acetic acid flow. The mineral acid is blunted by the dropwise addition of a concentrated aqueous solution of sodium acetate up to the bisulfate stage, then sucks off the monoazo dye peat, washes it with water and Sodium carbonate solution well and dry it at 80 ° in a vacuum.

It is added to a solution of 2.5 parts of the dry, blue-violet dye in 100 parts of chlorobenzene 1.9 parts of dimethyl sulfate in 10 parts of chlorobenzene are added dropwise at the boiling point within one hour. Included the red-violet solution turns blue and the colored salt precipitates as a dark powder. The dye is filtered off after cooling and, for further purification, dissolved in 250 parts of hot water and removed from the with some animal charcoal clarified solution precipitated with sodium chloride, suctioned off and dried. He puts a dark blue, bronzing powder, which is yellow in concentrated sulfuric acid and blue in water Color dissolves. He dyes fibers of tannic cotton from acetic acid bath in bright blue-violet tones of good fastness properties. Dyes with similar properties are obtained by coupling the diazotized 2-aminothiazoles with 14.3 parts of 2-aroinonaphthalene, 17.3 parts of 1-amino-2-methoxynaphthalene, 21.9 parts 1- (N-Phenyl) aminonaphthalene, 17.1 parts of 1- (N, N-dimethylamino) naphthalene, 20.0 parts of 1,2,3,4-tetrahydro-3-oxy-7,8-benzquinoline or 18.3 parts of 1,2,3,4-tetrahydro-5,6-benzquinoline instead of 14.3 parts of 1-aminonaphthalene and by subsequent methylation of the monoazo dyes.

Example 2

11.4 parts of 2-ammo-4-methylthiazole are, as in Example 1 described, with Nitrosylschwcfclsänre,

speaking 6.9 parts of sodium nitrite, diazotized and the Diazo compound with 18.3 parts of diphenyl-N-methylamine coupled in the presence of 200 parts of concentrated acetic acid. 3.1 parts of the dry azo dye; are in 100 parts of chloroform with 3 parts of diethyl sulfate at the reflux temperature of the solvent ethylated for a few hours. After the reaction mass has cooled, the precipitated reaction product is filtered off and poured into 200 parts of hot water solved. The blue solution is filtered and the dye is precipitated with 1.5 parts of zinc chloride and sodium chloride and filtered off with suction and dried. It is obtained as a dark powder that is concentrated in water with dark blue in Sulfuric acid dissolves with a yellowish green color.

The dye dyes tannin cotton from acetic acid Bath in blue-violet tones with good fastness properties. To water-soluble dyes with similar Properties are obtained using equivalent amounts of 2-amino-4-methoxythiazole (13.0 parts), 2-amino-4-acetylthiazole (14.2 parts), 2-amino-4-n-butylthiazole (15.6 parts), 2-amino-4-phenylthiazole (17.6 parts), 2-Ammo-4,5-dimethylthiazole (12.8 parts), 2-Amino-4-methyl-5-ethyzole (14.2 parts), 2-Amino-4-ethyl-5-methylthiazole (14.2 parts), 2-amino-4-methyl-5 - (/? - oxethyl) -thiazole (15.8 parts) or 2-amino-4,5-diphenylthiazole (25.2 parts), 2-amino-4-carbethoxy-5-methylthiazole (18.6 parts) or 2-amino-4-bromo 5-phenylthiazole (25.4 parts) as a diazo component !! and the same azo component and by ethylation of the Monoazo dyes.

Example 3

10 parts of 2-aminothiazole are as in Example 1 described, diazotized and coupled in acetic acid medium with 9.4 parts of phenol.

The orange monoazo dyes obtained are carried out, as in Example 1, with dimethyl sulfate using from toluene as a solvent to the water-soluble dye. The colored salt is isolated and purified analogous to example 1 and it is always obtained as a red powder, which is red in water and concentrated in water Sulfuric acid dissolves with a yellow color. The dye dyes tannic cotton from an acetic acid bath in orange Tones with good properties. The same water-soluble dye can be obtained by handling the Azo dye with dimethyl sulfate in an aqueous alkaline solution. Instead of dimethyl sulfate you can also Ethyl iodide, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, Use ρ - toluenesulfonic acid - η - butyl ester and benzyl bromide as alkylating agents.

Example 4

As described in Example 1, 12.8 parts are diazotized 2-Amino-4,5-dimethylthiazole and then coupled with 10.8 parts of l-oxy-4-methylbenzene in 20 parts Acetic acid has been dissolved. The dried dye is methylated with methyl iodide in benzene under pressure at 130 ° for several hours and the reaction mixture, as described in Example 1, works up. Of the Dye dyes tannin cotton from acetic acid

ίο bathing brownish red. To a dye of similar properties is leached using 16.4 parts of 1-Oxv-4-amylbenzene as the azo component.

Example 5

A diazo solution of 12.1 parts of Ν, Ν-dimethylaminobenzene in 50 parts of 60 ⁰ / |, acetic acid and the equivalent amount of mineral acid is added dropwise. The mixture is stirred for 2 hours, then 300 parts of water are added in portions and the mineral acid reaction is blunted by the dropwise addition of an aqueous solution of sodium acetate. Then the precipitated red-violet dye is suctioned off, washed and dried.

A solution of 2.3 parts of this dye in 100 parts of chlorobenzene is added at the boiling point 1.9 parts of dimethyl sulfate in 10 parts of chlorobenzene are added dropwise over the course of one hour. The color changes red solution turns blue, and the dye precipitates. After cooling, it is filtered off for further purification dissolved in 250 parts of hot water and precipitated from the solution clarified with a little animal charcoal with sodium chloride, filtered off and dried. The dye represents a dark powder that dissolves in concentrated sulfuric acid with yellow, dissolves in water with blue color. He

to dyes fibers from tannic cotton from acetic acid bath in bright blue-violet tones. The colorations are lightfast.

Instead of chlorobenzene, other solvents such as chloroform, benzene, toluene, xylene, decalin,

♦ 5 tetralin, o-dichlorobenzene, can be used. About dyes Similar properties are obtained if, in the above example, the azo components in the the following table listed compounds and used in the alkylation of the specified amounts of substance and otherwise proceed in the same way.

Azo component c

Parts Parts Allocation funds Solution book in H ₂ SO ₄ Coloring aiii Color Solution conc. taiuniertcr material middle 1.9 parts of dimethyl sulfate in H ₂ O yellow cotton 2.92 150 Reddish Reddish the same blue the same blue 2.62 130 the same the same the same the same 2.61 130 the same the same the same the same 3.22 170 2.8 parts of p-toluenesulfone the same the same the same 3.84 200 acid methyl ester blue the same 2.3 parts of diethyl sulfate the same 2.94 150 the same the same the same the same 2.74 140 Reddish the same 2.8 parts of p-toluenesulfone blue the same 2.77 140 acid methyl ester the same the same the same the same 2.60 130 the same the same

N, N-di (/ 3-oxethyl) aminobenzene. ...

N-methyl-N-zJ-oxäthylaminobenzol ..
N-methyl-N - ^ - cyanoethylaminobenzene

N-ethyl-N-benzyl-aminobenzene

N.N-dibenzylaminobenzene

N-methyldiphenylamine

N-phenylmorpholine

N, N-Dimethylamino-3-nitrobenzene.,
Ν, Ν-diethylaminobenzene

Azo component

Dear
dye

Parts solvent alkylating agent

Solution color

in H ₈ O

inH _a SO ₄
conc.

Coloring on tannin cotton

N, N-Dimethylamino-3-methylbenzene.,
N, N-dimethylamino-2,5-dimethyl-

benzene

N, N-dimethylarnino-2-methoxy-

S-methylbenzene

N ^ -Dimethylaraino ^ .S-diTnethoxybenzene

N ^ -Diethylammo-S-chlorobenzene

N ^ -Dimethylamino-S-methoxybenzene

N.N-Dimethylamino-S-carbethoxybenzene

l-Phenyl-3-methyl-S-aminopyrazole ...

Pyrrole

Indole

2.46
2.60
2.76

2.92
2.95
2.62

3.04

2.84
1.80
2.80

120 130 140

150 150 130

150

120 100 100 1.9 parts dimethyl sulfate
the same

2.8 parts of methyl p-toluenesulfonate

the same
2.6 parts of benzyl bromide

1.9 parts of dimethyl sulfate

3.8 parts of dimethyl sulfate

1.9 parts of dimethyl sulfate
1.9 parts of dimethyl sulfate
2.3 parts of diethyl sulfate

Red Blue
the same
the same

the same

Red Blue

the same

Reddish blue

Yellow-brown
blue
the same

the same
the same
the same

the same
yellow
the same

the same
the same
the same

Red-blue the same.

the same

Red Blue

the same

Reddish blue

Yellow-brown

blue

ruby

Example 6

10 parts of 2-aminothiazole are, as described in Example 5, diazotized and coupled with 15.3 parts of 2,5-dimethoxy-1-amtnobenzene in acetic acid as solvent. The monoazo dye is, as described there, isolated and dried. 2.64 parts of the dry dye are dissolved in 100 parts of chlorobenzene and, as described in Example 5, reacted with 1.9 parts of dimethyl sulfate, isolated and precipitated from aqueous solution with zinc chloride and dried. The dye presents a blue powder, which dissolves in water with a violet color and tannin-treated cotton in the presence of l ° / ₀ acetic stained in violet shades. The azo components listed in the following table can also be used in place of 2,5-dimethoxy-1-arninobenzene and colored salts with similar properties are obtained when the above alkylation conditions are used.

Azo component

Parts Parts Color Solution material middle 2.32 150 2.48 130 2.18 120 2.91 110 2.385 110 2.32 160 2.94 120 2.80 110 2.46 150 2.665 140

Alkylating agents

Solution color c

in H ₈ O

inH _a SO ₄
conc.

Coloring on tannicrtcr cotton

Amino-2,5-dimethylbenzene

Amino-2-methoxy-5-methylbenzene ..
Amino-3-methylbenzene

Amino ^ -methoxy-S-acetaininobenzene

Amino-3-chlorobenzene

N-ethylaminobenzene

N-benzylaminobenzene

N-phenylarainobenzoJ

N-ethylamio-3-methylbenzene

N-ethylamino-3-chlorobenzene

1.9 parts of dimethyl sulfate

the same

2.8 parts of methyl p-toluenesulfonate

the same

the same
2.6 parts of benzyl bromide

the same

the same
2.3 parts of diethyl sulfate

the same

violet
the same
the same

the same
Red Blue
violet

the same

the same

the same

the same

yellow

the same
the same

the same
the same
the same
the same
the same
the same
the same

Violet the same.

same red-blue violet

the same

the same

the same

the same

Example 7

In a manner analogous to Example 1, the dye is prepared from 2-aminothiazole and N.N-dimethylamino ^ .S-dimethylbenzene represent.

A solution of 2.6 parts of this dye in absolute alcohol is mixed with 4.35 parts of ethyl bromide heated under pressure to 120 ° for 2 hours. The reaction mixture is largely evaporated in vacuo a. The further work-up is carried out as described in Example 1.

The dye is yellow in concentrated sulfuric acid, soluble in water with a blue color. He dyes tannic cotton from acetic acid bath blue.

Dyes with similar properties are obtained by acylation with methyl iodide, methyl bromide, methyl chloride or butyl iodide in compliance with the above conditions.

Examples

12.8 parts of 2-amino-4,5-dimethylthiazole are as in Example 1 diazotized and with N-diethylamiiiobenzol in coupled to a weakly acidic medium.

Then 2.88 parts of the dry azo dye in 100 parts of chlorobenzene with 3 parts of diethyl sulfate ethylated at the reflux temperature of the solvent. After cooling, the dye is filtered off, dissolved in 180 parts of hot water, clarified and 1.5 Parts of zinc chloride and common salt are precipitated. The dye dissolves in water with a blue color, in more concentrated Sulfuric acid with a yellowish green color. He dyes tannic cotton from acetic acid bath in blue-violet Shades of very good fastness properties. Dyes from

Similar properties are obtained by using the equivalent amounts of 2-amino-4,5-diethylthiazole (15.6 parts) or 2-amino-5-methylthiazole (11.4 parts).

Claims (3)

Patent claims: 1. Process for the preparation of water-soluble color salts of azo dyes, in which the azo dye the cation forms, characterized in that there are free of acidic dissociating groups Monoazo dyes which have the atom grouping of the general formula I / V / A C-N-N-C (I) contain, wherein A is an alkene radical which ao at two carbon atoms linked by a double bond with the N and the S atom is connected and which can optionally be further substituted, and in which that with the azo group connected, unsaturated carbon atom denotes the bas forms part of any azo component. converted into color salts by the action of suitable alkylating agents. 2. The method according to claim 1, characterized in that one monoazo dyes which the Atom grouping of the general formula II C-N = N-Y-Z (H) contain, in which A has the meaning given, Y is a p-arylene radical and Z is a hydroxyl or a Amino group, where the amino group can also form part of a ring, is used. 3. The method according to claim 2, characterized in that one monoazo dyes with the atomic grouping of the general formula II, where A has the meaning given, Y is an optionally further substituted p-phenylene radical and Z is a primary, secondary or tertiary amino group, which optionally also denotes Can form part of a hydrocycle, used. Considered publications:
British Patent No. 313 293. A coloring table was displayed when the application was announced. ® 909 527/352 5.59