DE1795177A1 - Basic azo dyes and process for their preparation - Google Patents

Description

Basic Azo dyes and process for their preparation

The present invention relates to basic azo dyes, which are free from sulfonic acid groups and the general formula I

-AT

* Alk.O.CO.R _t

(D

possess, wherein R-. and R ^ optionally substituted alkyl or aralkyl radical β, R ^ a hydrogen atom, one optionally substituted alkyl, aralkyl or aryl group, R ^ one optionally substituted alkyl radical, Rc is an aliphatic, araliphatic, aromatic or heterocyclic radical, Y a hydrogen or halogen atom, an alkyl or Alkoaqrgruppe, A is a radical from the benzene or naphthalene series, Alk is an alkylene radical and X® is an anion and the benzene radical a may contain further substituents.

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- 2 ORiGfNAL INSPECTED

-Z-

1735177

The dyes can be obtained in such a way that one can a) the diazonium compound of a quaternary line of the general formula ZI

HH,

ill)

where R ^, Rg, H ,, X, I ^ and _§_ have the meaning given above, with an azo component of the general formula XIZ

AH

(III)

Alk. 0. CO.

wherein A, R ^, Rc and Alk have the meaning given above, clutch, or. '_.

b) the diazonium compound of a quaternary amine of the general formula II, wherein B ₁ ^ ^ ^ j ^. ^ ^ ^. have given meaning, with an Aao component of the formula IY

AT

(IV)

Alk - OH

wherein A, Rj, and Alk have the meaning given above, couples and then treated with acylating agents, or

c) an azo dye of the general formula V.

N-N-A-N (V)

, ^X Alk.O.CO.Rt- N - r />.

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wherein R ^ hydrogen, an optionally substituted alkyl or Ar alley Ire Bt, R ₂ , R ^, R ^, Y, A, Alk and a have the meaning given above, treated with alkylating agents, or

d) an azo dye of the general formula VI

(VI) AIk-OH

wherein R ₁ 'is hydrogen, an optionally substituted alkyl or aralkyl radical, R ₂ , R ₄ , Y, A, Alk and a. have the meaning given above, treated first with alkylating agents and then with aeylating agents.

The quaternary amines of the formula II used for procedure a) and b) can be obtained by treating amines of the Formula VII

(VII)

in which r /, R ₂ , Y and _a_ have the meaning given above, are obtained with quaternizing agents such as alkyl halides, aralkyl halides, haloacetamides, β-halopropionitriles, halohydrins, alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or organic sulfonic acids. 209853 / 11U

_ ₄ _ 1785177

Suitable amines of the formula III are 4 (7) -aminobenzimidazoles, the other nonionic substituents in the benzene radical ii in addition to the substituent T, for example halogen atoms, alkyl, Alkoxy, trifluoromethyl, nitro, aryloxy, acylamino or May contain cyano groups.

The amines of the formula IX are diazotized per se known methods, for example using hydrochloric acid and. Sodium nitrite.

of formulas III or IV

The coupling with the azo components aArird is known per se Catfish, for example in a neutral or acidic medium, optionally in the presence of buffer substances or the Coupling accelerating agents, such as pyridine, are made.

/ ■ '- ■■■■ · ■ ·

Suitable azo components of the formula III and XT are bent oil or naphthalene compounds which couple in the p-position to the tertiary amino group and which are free from sulfonic acid groups. The radical R ^ can be a lower alkyl radical, for example a methyl, ethyl, propyl or butyl radical, which may contain further substituents such as halogen atoms, hydroxy, alkoxy, aryloxy, phenyl, acyloxy, cyano, carbaayl -, dialkylamino, carboxyl or carbalkoxy groups. Rc can be a lower alkyl radical, for example a methyl, ethyl, propyl or butyl radical, an araliphatic radical, for example a Benejrlrest, an aromatic radical, for example a phenyl radical, which is replaced by halogen atoms, alkyl; Alkoxy or carbalkoxy groups can be substituted, or a heterocyclic ·! ¹ residue, for example a pyridine residue. The benzene or naphthalene radical A can contain further substituents, for example halogen atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl-1 carbamyl, sulfamyl, trifluoromethyl, acyl or acyl amino groups it is an optionally branched lower alkylene radical with preferably 2 to β carbon atoms.

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The azo dyes of the formulas V and VI used for procedure c) and d) can be prepared in a manner known per se by coupling the diazotized amines of the formula VII with azo components of the formulas III and IV or by condensation of the amines of the formula VU with the corresponding p- Nltroso compounds of the tertiary aromatic amines +) are obtained. Suitable alkylating agents are alkyl halides, alkyl halides, haloacetamides, β-halopropionitriles, halohydrins, alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or allyl esters of organic sulfonic acids. Suitable alkylating agents are, for example, methyl chloride, bromide or iodide, ethyl bromide or iodide, propyl bromide or iodide, benzyl chloride, chloroacetamide, ß-chloropropionitrile, ^ ethylene chlorohydrin, dimethyl sulphate, diethyl sulphate, methyl benzene sulphonate, methyl benzene sulphonate, p-toluene acid methyl ester, propyl or butyl ester. The alkylation is expediently carried out in an inert organic solvent, for example in a hydrocarbon, chlorinated hydrocarbon 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 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 of the λ ™ 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 optionally under pressure. The most favorable conditions in each case can easily be determined through a preliminary test.

+) of the formulas III or IV

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The acylating agents are aliphatic «, araliphatic ^, aromatic and heterocyclic carboxylic acids and their functional derivatives, such as halides, anhydrides and esters, in Consideration. For example, acetic acid, propionic acid, isobutyric acid, cyanoacetic acid, chloroacetic acid, phenylacetic acid, benzoic acid, chlorobenzoic acids, toluylaic acids, anisic acids, phenoxyacetic acid and pyridinecarboxylic acids and theirs are suitable functional derivatives.

The dyes obtainable according to the invention ^{preferably contain, as anion X e,} the radical of a strong acid, for example sulfuric acid or its half-ester, an arylsulfonic acid or a hydrohalic acid. These anions introduced according to the method can also be replaced by anions of other acids, for example phosphoric acid, acetic acid, oxalic acid, lactic acid or tartaric acid. The dyes can be obtained in the form of their double salts with zinc or cadmium halides.

The new dyes are suitable for dyeing or printing tarmaced cellulose fibers, silk, leather or fully synthetic fibers such as acetate silk, polyamide fibers or acid-modified polyester fibers, but especially polyacrylonitrile or polyvinylidene-containing fibers. The dyeings obtainable on these fibers are usually very clear and strongly colored and generally have good light and wet fastness properties, for example good washing, fulling, over-dyeing, carbonisler, chlorine and perspiration properties, as well as good decatur, steaming and ironing properties -, rubbing and solvent fastness. The dyes are generally insensitive to a change in the pH of the dyebath and can therefore be used in both weakly acidic and strongly acidic baths. They are also stable at temperatures above 100 ^° C., as used in high-temperature dyeing. Wool is completely reserved by the dyes under normal dyeing conditions.

Compared to the next comparable dyes from the French Patent specification 1 4-20 692, which contain a non-esterified hydroxyalkyl group in the tertiary amino group of the azo component, the new dyes with an acyloxyalkyl group are distinguished by the better lightfastness of the polyacrylonitrile dyeings.

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example 1

A suspension of 181.5 parts by weight of 5-chloro-7-amino-methylbenzi "idazol and 50 parts by weight of magnesium oxide in 500 parts by volume of water is at 60 - 150 volume parts of dimethyl quaternized 7O ⁰ CMIT. The solution of the quaternary compound of the formula

N - CH ₅

is filtered, mixed with 4qO parts by volume of 30% hydrochloric acid and ^{diazotized at -5 to 0} ° C. with 205 parts by volume of 5N sodium nitrite solution. The diazo solution is allowed to run into a suspension of 217 parts by weight of N-ethyl-N-ß-acetoxyäthrlanilin in 300 parts by volume of water. At the same time, a 2N soda solution is run in to such an extent that a pH of 1-2 is established. After the coupling is filtered the precipitated in bluish red crystals dye off, washed with 5% brine and dried at 60-80 ⁰ C. This gives 400 parts by weight of the dye of the formula

H ₅ C - N

: CH-

N - CH

which dissolves very easily in water or dilute acetic acid with a yellowish-red color.

1 g of dye is mixed with 2.5 g of 50% acetic acid and dissolved in 6 l of water. The dye bath is still 1 g crystalline sodium acetate and 10 g calcined Glauber's salt were added. Then you start out with 100 g of prewashed yarn

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Polyacrylonitrile staple fiber in the 6O ⁰ C warm dyebath, increases the temperature slowly to 10O ⁰ C and dyes for one hour at the boiling temperature. It is then allowed to ^{cool slowly to about 60 °} C., rinsed and dried.

A clear scarlet dyeing with very good light and wet fastness properties is obtained.

Example 2

18.15 parts by weight of 5-chloro-7-amino-l-methylbenzimidazole in 300 parts by volume of water and 60 parts by volume of 5N hydrochloric acid at 0 - 5 ⁰ C diazotized in a conventional manner using 20.5 parts by volume of 5N sodium nitrite solution. The diazo solution is allowed to drop into a suspension of 28 parts by weight of R, N-bis (ß-acetoatyäthyl) -mtoluidine, 12 parts by weight of acetic acid and 200 parts by volume of water Hydrochloride of the dye of the following constitution

- OCO - CH ₅ ) ₂ · HCl

off, wash it off with water and squeeze it off well. The moist press cake is stirred in 500 parts by volume of toluene and, after adding 55 parts by volume of 2N soda solution, dehydrated azeotropically. The free dye base dissolves clearly in toluene; is filtered from the precipitated salt from, are to Färbstofflösung 1 part soda ash and leaves at 90 ⁰ C. 10 parts by volume of dimethyl sulfate shrink. The mixture is then stirred until quaternization is complete, and the quaternary dye of the following formula which has precipitated out in red crystals is sucked off

ν. ^Λ

H _x C - N 'CH ^
N - CH ₅ - N- Cl A-- ' C.

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off, washed with toluene until colorless outlet and dried at 60-80 ⁰ C. It is 47 parts by weight of β receives a red crystalline powder which dissolves with yellow-red color very well in warm water or dilute acetic acid.

20 g of dye are mixed with 50 g of ß.ß-Dioxydiethylsulfid, 30 g Cyclohexanol, 50 g of 30% acetic acid and 400 g of water were dissolved while hot and stirred into 450 g of crystal rubber thickening 1: 2. A fabric made of polyacrylonitrile staple fiber is printed with this printing ink.

The print obtained is dried, steamed for 30 minutes at 0.5 atm, at 50 ⁰ C with 1 a condensation product of oleic acid and methyl taurine g soaped and cured as usual in a liter of water. A well-set, scarlet print with very good light and wet fastness properties is obtained.

The table below contains further dyes obtainable according to the invention and the shades of those with the Dyes available on polyacrylonitrile fibers:

R ₂

AT

AlkOCOR

hue

Methyl hydrogen methyl substance

Methyl hydrogen methyl substance

Methyl hydrogen methyl substance

Methyl hydrogen methyl substance

Ethyl hydrogen methyl substance

Ethyl hydrogen

chlorine

chlorine

3-chloro-N, N-bis- (ß-acetoxyethyl) aniline

3-methyl-N-ethyl-N-ßac et oxy ät hy I-aniline

Chlorine N-methyl-N-ß-

CH ₃ SO ₄

Chlorine N, N-bis- (ß- CH, SO ₄ acetoxyethy]) · ■> aniline

Chlorine N-ethyl-N-ß-Cl acetoxyethylaniline

Chlorine N-ethyl-N-ß- ZnCl ₄

acetoxyethyl

aniline

Scarlet fever

self-piercing lot

Scarlet red-orange

Scarlet fever

yellowish dead

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- 10 -

R ₂ - 10 - «Λ χ« 1795177 ^ß l methyl Ϊ N-ethyl-N-ß-Cl
acetoxyethyl
aniline ¹ shade methyl Ityl methyl chlorine N-ethyl-H-ß-Cl
acetoxyethyl
aniline Scarlet fever methyl methyl chlorine Scarlet fever

methyl

methyl

methyl

methyl

Benzyl Methyl Chlorine N-Ethyl - »- ß ~ Cl

acetoxyethylaniline

Oxy-methyl chloromethyl

α-oxyethyl

Methyl chlorine

Methoxy-chloro-methyl-methyl

Methyl η-butyl methyl chlorine N-ethyl-N-f-Ql

acetoxyethyl

aniline

N-Ethyl-H-ß-Cl ac et oxyäthyI-aniline

N-ethyl-N-A-Cl

acetoxyethyl

aniline

N-ethyl-H-B-Cl ac et oxy ethy 1-aniline

Methyl Waseer- methyl methyl N-ithyl-H-ß-Cl substance acetoxyethyl

aniline

Meth-N-ethyl-H-ß-Cl oxy acetoxyethylaniline

methyl water
material methyl methyl water
material methyl methyl water
material methyl methyl water
material methyl methyl water
material methyl

chlorine

chlorine N-ethyl-N-β-CH, SO ₄ isobutyryl- ⁷ oxyethyl aniline

N-ethyl-N-ß-

phenylacetate

oxyethylaniline

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Yellow orange

orange

Scarlet fever

Scarlet fever

Chlorine N-ethyl-NB- CH ₃₅ SO ₄ scarlet benzoyloxy- ° , ethylaniline

Chlorine N-Ethyl-N-ß- CH ₃₅ SO ₄ cyanacetoxy- ^
ethylaniline

Scarlet fever

- 11 -

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R _n R ₀ R, Y AN X ^ö hue

AIkOGOR ₅

Methyl water- methyl chlorine N-ethyl-N-ß- CH, SO ₄ scarlet fabric acetoxypropyl- ^

aniline

Methyl water- methyl chlorine N-ß-cyano- CH _x SOn scarlet

substance ethyl-N-ß-acet- ^ ^

oxyethylaniline

- 12 209853 / 11U

Claims (2)

- 12 fat entrances 1) Basic azo dyes that are free from sulfonic acid groups are and the general formula N-A-N Alk.O.CO.Rc R _x -N N- R ₁ in which R ₁ and R, optionally substituted alkyl or aralkyl radicals, R2 a hydrogen atom, an optionally substituted alkyl, aralkyl or aryl group, R ^ an optionally substituted alkyl radical, Rc an aliphatic, araliphatic, aromatic or heterocyclic radical, Y a Hydrogen or halogen atom, an alkyl or alkoxy group, A a radical from the benzene or naphthalene series, Alk an alkylene radical and X ^ an anion and the benzene radical .a can contain further substituents. 2) Process for preparing basic azo dyestuffs, characterized in that _r a) the diazonium compound of a quaternary amine of the general formula R, - (II) where R ^ and R, optionally substituted alkyl or aralkyl radicals,]? 2 denote a hydrogen atom, an optionally substituted alkyl, aralkyl or aryl group, Y denote a hydrogen or halogen atom, an alkyl or alkoacy group, X ^ denote an anion and the Benzene radical bl further substituents - 13 - 209853 / 11U can hold, with an azo component of the general formula A - where A is a residue of the benzene or naphthalene series, R ^, an optionally substituted alkyl radical, R, - a aliphatic, araliphatic, aromatic or heterocyclic radical and Alk is an alkylene radical, couples or b) the diazonium compound of a quaternary amine of the general formula II, in which R ₁ , R ₂ , R ,, Y, Xnind a_ have the meaning given above, with an azo component of the formula AT ^ AIk - OH wherein A, R ^, and Alk have the meaning given above, couples and then treated with acylating agents, or c) an azo dye of the general formula (V) Alk.0.GO.R _c wherein R- / hydrogen, an optionally substituted alkyl or aralkyl radical, R ₂ , R ^, Rr, Y, A, Alk and j ^ have the meaning given above, treated with alkylating agents, or 0 9 8 5 3/1 IU d) an azo dye of the general formula ' N-N-A-N (VI) AIk-OH N NR- / / 1 wherein R · / hydrogen, an optionally substituted one Alkyl or aralkyl radical, ί? 2, R ^., Y, A, Alk and _a_ the above Have given meaning, first with alkylating Agents and then treated with acylating agents, with azo dyes that are free of sulfonic acid groups and the general formula N-N-A-N K * Alk, O.CO.R _E where R ,, R ^, R *, ^ ₄ , «.c, have the meaning given above, are obtained. R ₄ , R ₅ , Y, A, Alk, 209853/1 1 U