DE2347756A1 - Basic azo dyes contg. (substd.) amino-isoquinoline gps. - as yellow-orange dyes for natural and synthetic materials, and pigments for paper - Google Patents

Abstract

The novel basic azo dyes of formula (I) (where D (+) is the residue of an aromatic or heterocyclic diazo component contg. a quaternary N atom; R1 is halogen, OH or primary, secondary or tertiary amino gp; R2 is primary, secondary or tertiary amino gp. or an ether gp. X(-) is an anion. (I) are used to dye or print tanned cellulose silk, leather, acetate, polyamides, acid modified polyamides and polyesters and esp. polyacrylonitrile and polyvinylidene cyanide fast yellow- orange shades from aqs. medium or organic solvent baths. (I) form fast pigments for paper printing when treated with anionic precipitants e.g. alumina.

Description

Basic azo dyes, process for their preparation and their use

The present invention relates to new basic azo dyes, Process for their manufacture and their use.

The new dyes, which are free from sulfonic acid groups, correspond to the general Fox'mel I.

©
DN

(D

wherein D is the residue of an aromatic or heterocyclic diazo component which contains a quaternary nitrogen atom, R is a halogen atom, a hydro?: y group or a primary, secondary or tertiary aromatic group _; R "denotes a primary, secondary or tertiary amino group or an ether group and X denotes an anion.

509817/0912

—Si-

The new dyes can be obtained in such a way that

a) the diazonium compound of a quaternary amine of the formula II

D ^e _- NH ₂

(ID

wherein D and X * ^{7 have} the meanings given above, with an azo component of the formula III

(HD

wherein R- and R_ have the meanings given above, clutch, or that one

b) an azo dye of the formula IV

D - N - N -

(IV)

where D is the radical of an aromatic or heterocyclic diazo component and R ₁ and R_ have the meanings given above, treated with alkylating agents.

The quaternary amines used for procedure (a) Formula II can be prepared by treating suitable aromatic or heterocyclic amines with alkylating agents, for example Alkyl halides, aralkyl halides, haloacetamides, ß-halopropionitriles, halohydrins, alkylene oxides,

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ORIGINAL INSPECTED

Acrylic acid amide, alkyl esters of sulfuric acid or organic Sulfonic acids.

Suitable quaternary amines of the formula II are, for example those of the formula V. .

I ■

IL-NC CC) -C- NH ₉ X ^e (V)

^R 4 ^R 5

where R “is an optionally substituted alkyl or aralkyl radical, Y is a divalent atom or a divalent group required to complete a 5- or 6-membered ring, R. and Rj are hydrogen atoms, alkyl radicals or substituents which form a fused aromatic ring add, η is the number 0 or 1 and X is an anion. Such quaternary compounds can be derived from amines of the pyridine, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, oxdiazole, thiadiazole, pyrimidine or triazine series, and also of the quinoline, indazole -, benzimidazole, benzisothiazole, arylguanazole, naphthimidazole, benzoxazole, naphthoxazole _f benzthiazole or naphthothiazole series.

Quaternary amines of the formulas VI and VII are also suitable

(VII)

wherein R- is an optionally substituted alkyl or aralkyl radical, A is a 5- or 6-membered heterocyclic ring, for example a pyx-idinium, triazolium, pyrazolium

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V / bö

or thiazolium radical and X is an Aiii.r.n and the ... benzene radical a further substituents, such as halogen atoms, alkoxy, Aryloxy, alkyl, trifluoromethyl, nitro, alkylsulfone, Contain arylsulfone, cyano or acyl groups, may.

Finally, quaternary amines of formulas VIII and IX are suitable R.

(VIII)

N-AIk- (B)

NILE.

(IX)

wherein R_, R _ß and R optionally substituted lower alkyl groups, Alk a straight-chain or branched lower alkylene radical, B a -0-, -S-, -CO-, -SO ₃ -, -CONH-, -OCO- or -SO ₂ NH group, η 0 or 1 and X is an anion and the benzene radical a can contain further substituents, for example halogen atoms, alkoxy, aryloxy, alkyl, trifluoromethyl, nitro, alkylsulphone, arylsulphone, cyano or acyl groups .

The azo components used according to the invention can be prepared according to known methods Methods are obtained. For example, heating o-cyano-benzyl cyanide with 5% sodium hydroxide is obtained l-amino-3-hydroxy-iso-quinoline (cf. Chem.Ber. 27, 836 (1894).

By heating o-cyano-benzyl cyanide with methanolic ammonia to 140 ° C. for 24 hours, 1,3-diamino-iso-quinoline is obtained in good yield (see J. Chem. Soc. 1964 , 1423).

Amino-iso-quinolines are further characterized by reacting 1,3-Dichloriso-quinoline with amines available (see FIG. Chem.Ber. 102, 3677 (1969). At higher temperature (180 ⁰ C) of the training is carried out

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Exchange of both chlorine atoms for amino groups, at lower temperatures (approx. 60 - 100 ⁰ C) only the chlorine atom in the 1-position is replaced by amino or ' Alkoxy groups exchanged. In the case of high-boiling amines, the exchange can take place in the melt, in the case of low-boiling amines under pressure in an autoclave, if appropriate in the presence of solvents. Examples of suitable solvents are alcohols such as methanol, ethanol or isopropanol.

The diazotization of the amines of the formula II can be carried out by known methods, for example by means of alkyl nitrite and an inorganic Acid, for example hydrochloric acid, sulfuric acid or phosphoric acid, or by means of nitrosylsulfuric acid.

The coupling with the azo components of the formula III can likewise in a manner known per se, for example in a neutral to acidic medium, optionally in the presence of sodium acetate or other known ones influencing the coupling speed Buffer substances or catalysts, such as dimethylformamide, Pyridine or its salts.

The starting dyes used for procedure (b) of the formula IV can by coupling the diazotized amines of the formula D-NEL with the azo components or by condensation of the Amines can be obtained with the corresponding p-nitroso compounds of the compounds of the formula III.

Procedure (b) is particularly useful for amines of formula X.

1 ^Y >

N = (g - C) "= C - NH ₂ (X)

PP

^R 4 ^R 5

in which Y, R ₄ , R ₅ and η have the meaning given for formula V, suitable. Amines of the formula X are particularly those of the pyridine, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, oxdiazole, thiadiazole, pyrimidine or triazine series, and also the quinoline series , Indazole, benzimidazole, benzisothiazole,

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Arylguanazole, naphthimidazole, benzoxazole, benzthiazole. or naphthothiazole series into consideration.

Alkyl halides, aralkyl halides, Haloacetamides, ß-halopropionitriles, halohydrins, Alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids are suitable.

Suitable alkylating agents are, for example, methyl chloride, bromide or iodide, ethyl bromide or iodide, propyl bromide or iodide, benzyl chloride, chloroacetaraid, ß-chloropropionitrile, Ethylene chlorohydrin, dimethyl sulfate, benzenesulfonic acid methyl ester, p-Toluenesulfonic acid methyl, ethyl, propyl or butyl ester. The alkylation is expediently carried out in an inert organic solvent, for example in a hydrocarbon, chlorinated hydrocarbon, stifled or nitro hydrocarbon, such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride, such as dimethylformamide, N-methylacetamide or acetic anhydride, in dimethyl sulfoxide or in a ketone such as acetone or methyl 1-ethyl ketone. Instead of an organic solvent, it is also possible to use an excess of the alkylating agent.

Depending on the number of alkylatable nitrogen atoms in the starting dye one or more alkyl groups are introduced into the dye molecule. The alkylation is carried out at elevated temperature, optionally with the addition of acid-binding agents such as magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and, if necessary, under pressure. The most favorable conditions in each case can be determined by a Easily determine the preliminary test.

If appropriate, the alkylation can also be carried out in water.

The new Fai'stoffen can in modification of the above

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Process can also be obtained so that one Hydrazone or benzene sulfonyl hydrazone of the general formula XI

Y_

R ₃ -N-f C = C 1 -C JC = N-NII-B. (XI)

^R 4 ^R 5

in which Y, R ₃ , R ₄ , R ₅ and η have the meaning given for formula V and B is a hydrogen atom or a benzenesulfonyl radical, couples with an azo component of the formula III under the action of oxidizing agents.

The new dyes preferably contain X ^ * "'as the anion the remainder of a strong acid, for example sulfuric acid or their half-esters, an arylsulfonic acid or a hydrohalic acid. These were introduced in accordance with the procedure Anions can also be replaced by anions of other acids, for example phosphoric acid, acetic acid, oxalic acid, lactic acid or white acid can be replaced. The dyes can also be in the form of their double salts with zinc or cadmium halides be won.

They are suitable for dyeing or printing tannin cellulose fibers, Silk, leather or fully synthetic fibers such as acetate silk, polyamide fibers or acid modified polyamide or Polyester fibers, but especially of polyacrylonitrile or fibers containing polyvinylidenecyanide. The dyeings available on these fibers are usually very strong and generally have good light and wet fastness properties, for example good washing, fulling, over-dyeing, carbonizing, chlorine and Perspiration fastness, as well as good decatur, steam, ironing, rubbing and solvent fastness. The dyes are generally to a change in the pH of the dyebath, largely insensitive and can therefore be used in both weakly acidic as well as in a strongly acidic bath. You are further

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at temperatures above 100 C, as in high-temperature dyeing applied consistently. Wool is completely reserved by the dyes under normal dyeing conditions.

The dyeing is generally carried out in an aqueous medium at the boiling point or in closed vessels at temperatures above 100 ° C and under pressure. The dyes can also from organic solvents can be applied.

To prepare the aqueous dye baths and printing pastes, raan the dyes in the form of powders, the optionally adjusting agents, such as, for example, inorganic salts, dextrin and optionally contain other additives. However, it is more advantageous to use concentrated ones that are easier to handle aqueous solutions of the dyes, which contain about 20 to 60% dye, one or more lower aliphatic carboxylic acids, such as formic acid, acetic acid, propionic acid or lactic acid, and optionally other additives such as water-soluble polyvalent acids Alcohols, their ethers or esters, polyethers, aliphatic carboxamides, lactams, lactones, nitriles, dimethyl sulfoxide, Contain diacetone alcohol, dioxane, tetrahydrofuran or urea and water.

The dye baths which only contain organic solvents, for example chlorinated hydrocarbons, are used to prepare the dye baths advantageous concentrated solutions containing the dye as a free base or as a salt of a monobasic organic acid, chlorinated hydrocarbons, contain organic acids and polar organic solvents.

The new dyes form real ones with anionic precipitants such as clay, tannin or heteropoly acids Pigments that can be used in paper printing.

The following examples serve to illustrate the invention.

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example 1

29.7 parts by weight ^ amino-S-chlorophenyl-trimethyl-ammoniuminethylsulfat are diazotized in loo parts by weight of 2N hydrochloric acids at 0-5 ⁰ C with 21 parts by weight of 5N sodium nitrite solution. A solution of 16 parts by weight of 1-amino-3-hydroxy-isσ-quinoline in 100 parts by weight of 2N hydrochloric acid is added to the dxazoniura salt solution thus prepared and the mixture is stirred at room temperature until the coupling is complete. The dye formed is precipitated, sucked off and dried 60 ⁰ C by addition of 10% sodium chloride. 40.1 parts by weight of a yellow dye of the formula are obtained

< ^CH 3> 3 ^N

Cl

which gives real yellow colorations on polyacrylonitrile and acid modified polyester fibers. Table I below contains further diazo and azo components which can be used according to the invention and which can be used as described in Example 1, as well as the shades obtainable with these dyes on polyacrylic and acid-modified polyester fibers. * ,

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-Ιο-

Table I.

Diazo component

Azo component hue

Cl

^NH 2

/ c 1-amino-3-hydroxyiso-quinoline

Yellow

(CHg) ₃ N-CH ₂ -CO -

l-araino-3-hydroxy yellow iso-quinoline

/ Λ- l-amino-3-hydroxyiso-quinoline

Yellow

_t : 1-amino-3-hydroxy-yellow iso-quinoline

CH

CH0SO4 l ~ amino-3-hydroxy-

iso-quinoline

Cl golden yellow

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Diazo component

Azo component

hue

l-amino-3-hydroxy-yellow iso-quinoline

NH ₂

ZnCl,

1-amino-3-hydroxy-golddiso-quinoline yellow

Example 2

8.4 parts by weight of 3-amino-l, 2,4-triazole are dissolved in 40 parts by volume of 60% sulfuric acid and 0-3 at ⁰ C with
17 parts by volume of 42% nitrosylsulfuric acid are diazotized.
The diazonium salt solution thus obtained is added with stirring to a solution of 15.9 parts by weight of 1,3-diamino-iso-quinoline in 50 parts by volume of 30% strength sulfuric acid.

The precipitated dye is filtered off with suction in aqueous bicarbonate solution stirred, filtered off with suction, washed with water and dried at 60.degree. 21.2 parts by weight of a yellow dye are obtained the formula

N-

H ₉ NN = N- / V-NH ₂

NH

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I6k I / bö

12.7 parts by weight of the dye thus obtained become fine powdered, in 100 parts by weight of water with 7 parts by weight Suspended magnesium oxide and alkylated at 20 ° C with 20 parts by weight of dimethyl sulfate. After the reaction has ended, give Add 30 parts of the face to glacial acetic acid, heat to the boil, clarify with activated charcoal and allow to cool. After adding zinc chloride the dye is precipitated, filtered off with suction and dried at 60.degree.

A dye of the formula is obtained

ZnCl ₄ ^v

-a

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the polyacrylonitrile and acid modified polyester fibers results in very real golden yellow colorations.

Example 3

22.8 parts by weight of 4 • -Aminophenacyltrimethylaramoniumehlorid are concentrated in 100 parts by weight of water and 35 parts by weight. Dissolved hydrochloric acid and diazotized with 20 parts by weight of 5N sodium nitrite solution at 0-5 ° C. When the diazotization is complete, 15.9 parts by weight of 1,3-diaminoisoquinoline, dissolved in 100 parts by weight of 2N hydrochloric acid, are added to the diazo solution and the mixture is stirred until the coupling has ended. The dye obtained is precipitated with 10% sodium chloride, filtered off with suction and dried at 60.degree.

34.2 parts by weight of a dye of the formula are obtained

the polyacrylonitrile and acid modified polyester fibers gives strong orange, real colorations. Table II below contains further diazo and azo components which can be used according to the invention and which, according to the Information in Examples 2 and 3 can be used, and the shades available with these dyes on polyacrylonitrile and acid-modified polyester fibers.

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Table II

Diazo component azo component

hue

Cl 1,3-diamino-iso-quinoline orange

1,3-diamino-iso-quinoline orange

1,3-diamino-iso-quinoline orange

Cl

1,3-diamino-iso-quinoline orange

(® ^> - ^NH 2 1,3-diamino-iso-quinoline yellow-

prickly

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D iazokoüipoiiente azo component

hue

NH ₂ Cl '

CH ₃ 1,3-diamino-isoquinoline

bluish red

Cl

-NH ₂ Cl ⁽ 1- (3-methoxypropylamino) -3-chloro-isoquinoline

yellow

Cl

-NH ₂ Cl ¹ yppy araxno) -3-chloro-isoquinoline

l-diethylamino-3-chloro-iso-quinoline

yellow

Golden yellow

^C ? 3

CH ₃

'»3

ZnCl 1-diethylamino-3-chloro-iso-quinoline

l-morpholino-3-chloro-iso-quinoline

Golden yellow

yellowish red

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-κτ-

Diazo component

Azo component

hue

Cl 1,3-bis-phenylamino ~ red iso-quinoline

ZnCl 1,3-bis-phenylaminoiso-quinoline orange

Cl 1,3-bis- (2-hydroxy-orange ethy! Amino) -isoquinoline

^{: Ή} 3

Cl

^NH 2

ZnCl

ΘΘ

1,3-bis (2-hydroxyathy! Amino) isoquinoline

l-diethylamino-3
methoxy-isoquinoline

l-diethylamino-3 ■
methoxy-isoquinoline

orange

orange

orange

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Diazo component

Azokoiuponente

hue

Cl

l-diethylamino-3 raethoxy-isoquinoline

Red

V-NH ₉ Cl l-Morpholino-3- f * ethoxy-iso ~

quinoline

orange

0 ^ -NH ₂ CH ₃ SO ₄

l-morpholino-3-ethoxy-isoquinoline

bluish red

Cl

JE, SO ₄ 1,3-diamine ο-iso-

■ * * quinoline

Red

Claims (6)

HOE 73 / F 296 -Vi- PATENT CLAIMS 1) Basic azo dyes that are free from sulfonic acid groups and of the general formula where D is the radical of an aromatic or heterocyclic diazo component containing a quaternary nitrogen atom, R _{1 is} a halogen atom, a hydroxyl group or a primary, secondary or tertiary amino group, R "is a primary, secondary or tertiary amino group or an ether group and X ^ a Mean anion. 2. Process for the preparation of basic azo dyes, the are free of sulfonic acid groups and have the general formula N- X-) correspond, in which D is the radical of an aromatic or heterocyclic diazo component containing a quaternary nitrogen atom, R- a halogen atom, a hydroxyl group or a primary, secondary or tertiary amino group, R ₁ , a primary, secondary or tertiary amino group or an ether 509817/0912 group and X ^K ~ ' mean an anion, characterized in that one a) the diazonium compound of a quaternary amine of the formula - NK ₂ wherein D ^ ' and X ^ have the meanings given above, with an azo component of the formula wherein R ^ and R _{2 have} the meanings given above, or that one b) an azo dye of the formula D-N = N wherein D is the radical of an aromatic or heterocyclic diazo component and R ₁ and R _{2 have} the meanings given above, treated with alkylating agents. 3. Process for the preparation of basic azo dyes General formula mentioned in claim 1, characterized in that a hydrazone or benzsvilfonylhydrazone is used general formula 509 817/0912 ff E ₃ ~ N -f- C - C -) - _n CN-KH-B ^R 5 where R _{3 is} an optionally substituted alkyl or aralkyl radical, Y is a divalent atom or a divalent group required to complete a 5- or 6-membered ring, R ₄ and R_ are hydrogen atoms, alkyl radicals or substituents that complete a fused aromatic ring, η the number 0 or 1 and X is an anion and B is a hydrogen atom or a benzenesulfonyl radical, under the action of oxidizing agents with an azo component of the formula where R ₁ denotes a halogen atom, a hydroxyl group or a primary, secondary or tertiary amino group, R "denotes a primary, secondary or tertiary amino group or an ether group. 4. Use of the dyes described in claim 1 for dyeing or printing textile materials made of natural or synthetic fibers 5. Use of the dyes described in claim 1 for dyeing or printing textile material composed of acidic groups containing synthetic fibers. 6. Powdery or liquid dye preparation for dyeing or printing of textile material made of natural or synthetic fibers containing one or more dyes of the claim 1 mentioned general formula. 509817/0912