DE1644104C3 - See monoazo dyes - Google Patents

Description

wherein A is a mononitrophenyl radical, which optionally contains chlorine, cyano, carbomethoxy, phenoxy or methoxy as further substituents, Ri is hydrogen or methoxy, R _{2 is} hydrogen, methyl, acetylamino or chlorine, alkali methylene or ethylene, alk ₂ ethylene, X methoxy, Ethoxy ^ phenoxy, phenylmercapto, acetyl, acetoxy, ethoxycarbonyl, carbonamido, Ν, Ν-dimethylcarbonamido, benzoyl,

Cyano or cyanethoxy and K the over the ^ ^ j ___

Nitrogen atom bound pyridinio, methylpyridinio, dimethylpyridinio, piperidino, morpholino or pyrrolidino, the piperidino, morpholino and pyrrolidino also being quaternized can be and then an alkyl radical with 1 to 4 carbon atoms on their ring nitrogen atom or contain the benzyl radical bound and the anion in the quaternized dyes the radical a strong inorganic acid, a sulfuric acid half ester or an organic acid.

2. Dyes according to claim 1, wherein K is a pyridinium radical

The dyes according to the invention are obtained by

a) a diazonium compound of _{the general formula} AN 2} * with a coupling component of the general formula

! —X

couples, wherein A, Ri, R ₂ . alki, alki X and K have the meaning given above, or if one b) an azo dye of the general formula

alk, -X

alk ₂ - K ₁

wherein A, Ri, R ₂ , alki, alk ₂ and X have the meaning given above and Ki is a removable atom or a removable group, in particular a halogen or sulfato group, with pyridine, a methyl or dimethylpyridine, piperidine, or morpholine Pyrrolidine or a piperidine, morpholine or pyrrolidine substituted on the nitrogen by Ci-Q-alkyl or benzyl, or c) an azo dye of the general formula

R.

The invention relates to basic monoazo dyes of the general formula

40 A-N = N

alk, -X

alk, - K,

A-N = N

alk, -X

alk, —K

45

(D

wherein A is a mononitrophenyl radical, which optionally contains chlorine, cyano, carbomethoxy, phenoxy or methoxy as further substituents, Ri is hydrogen or methoxy, R _{2 is} hydrogen, methyl, acetylamino or chlorine, alkali methylene or ethylene, alk ₂ ethylene, X methoxy, ethoxy, Phenoxy, phenylmercapto, acetyl, acetoxy, ethoxycarbonyl, carbonamido, Ν, Ν-dimethylcarbonamido, benzoyl, cyano or cyanoethoxy and K is the pvridinio, methylpyridinio, dimethylpyridinio, piperidino, morpholino or pyrrole radical Piperidino, morpholino and pyrrolidino radicals can also be quaternized and then contain an alkyl radical with 1-4 carbon atoms or the benzyl radical bonded to their ring nitrogen atom and the anion in the quaternized dyes is the radical of a strong inorganic acid, a sulfuric acid half ester or an organic acid .

where A, Ri, R ₂ , alki, alk ₂ and X have the meaning given above and K _{2 is} a piperidine, morpholine or pyrrolidine radical which is bonded via its nitrogen atom and is reacted with Ct-Q-alkylating or benzylating agents

In the coupling components to be used according to embodiment (a) of the process mentioned is the amino group on the one hand by the above-mentioned group -alk, -X, z. B. by

0-cyanoethyl, 0-methoxyethyl,

jJ-Cyanäthoxyäthyl / i-Acetoxyäthyl,

ß-Phenoxyäthyl.Phenylmercaptoäthyl

or by a group

-CH ₂ -CO-CH ₃ , -CH ₂ -CO-C ₆ H ₅ , -CH ₂ CH ₂ -CO-NH ₂ or -CH ₂ CH ₂ -CO-OC ₂ H ₅

substituted On the other hand, it must _{carry the aminoalkylene radical —alk 2} —K, the nitrogen atom of which belongs to a pyridine, piperidine, morpholine or pyrrolidine ring.

55

60

The following are mentioned as coupling components of this type:

CH ₃

NC - CH ₂ CH ₂ - N - CH ₂ CH ₂ - N

CH ₃ - CO - CH ₂ - N - CH ₂ CH ₂ - N '

he

O - - CH ₂ CH ₂ - N - CH ₂ CH ₂ -] CH ₂ CH ₂ -CN

Br "

H ₃ C
NC - CH ₂ CH ₂ --N - CH ₂ CH ₂

Cl "

H ₃ C
CH ₃ CO-O-CH ₂ CH ₂ -N-CH ₂ Ch

Cl '

OC - CH ₂ CH ₂ - N - CH ₂ CH ₂ OC ₂ H ₅ / \ Cl

OC - CH ₂ CH ₂ - N - CH ₂ CH ₂ -

/ \
H ₃ C CH ₃

S - CH ₅ CH, - N - CH ₂ CH ₂ - N

Cl

also the N ^ - (N'-phenyl-N ', j3-cyanoethyl) -aminoethylpyridinium chloride or -broroid, N, 2- (N'-Phenyl-N ', 0-

acetoxyäthyO-aminoethylpyridinium chloride, N, 2- (N'-

Phenyl-N '^ - cyanoethoxyethyl) -aminoethylpyridini-. Umchlorid u. dgL These compounds can be obtained by reacting the corresponding N- (Halo-

genalkyfy-aniline with z. B. pyridine, morpholine, piperidine,

Pyrrolidine and the like
From the series of useful diazo components

of the nitrobenzene series are, for example, the following ib called:

1 - Amino-2-cyano-4-nitrobenzoL
1 - Amino ^ -carbomethoxy- ^ nitrobenzene,
1 - amino-2-chloro-4-nitrobenzene,
l-Amino-2-methoxy-4-nitrobenzoL

1 - Amino-2,6-dichloro-4-nitrobenzoL

The diazotization of the diazo components mentioned can be carried out by methods known per se, e.g. B. with help mineral acid, especially hydrochloric acid, and sodium nitrite.

The coupling can also be carried out in a manner known per se, for. B. in neutral to acidic medium if necessary in the presence of sodium acetate or the like.

the coupling speed influencing buffer substances or catalysts, such as. B. pyridine, respectively. its salts, are made.

According to embodiment b) of the abovementioned process, halogen- or sulfatoalkyl-containing groups are used Dyes with z. B. pyridine, picoline, lutidine, piperidine, morpholine, pyrrolidine reacted, appropriate by heating in an excess of the amine in the presence or absence of a solvent. the Dyes containing halogen or sulfatoalkyl groups are advantageously obtained by azotizing one of the dyes mentioned amines of the benzene series and coupling of the diazo compound with a sulfatoalkyl or haloalkylaniline, z. B. with N ^ -Methoxyäthyl- or N.jJ-Acetoxy-ethyl-NjJ'-chloroethylaniline, Nji-Cyanäthyl-N ^ '- chloroethylaniline, N ^ -Cyanäthyl-N ^ '- sulfatoethylaniline.

For embodiment c) of the above-mentioned process, of course only for the production of dyes with the quaternary heterocyclic amino radical comes into question, whose nitrogen atom is also not bound to a double bond, the starting materials are those corresponding to the end materials, however, azo dyes having a tertiary heterocyclic amino radical can be used. These will

so with Ci-Cralkylating or benzylating agents, expediently with alkyl or benzyl halides or alkyl or benzyl esters of sulfuric acid or of organic sulfonic acids. Examples of alkylating or benzylating agents are:

Methyl chloride, methyl bromide or iodide, benzyl chloride, Trimethyloxonium borofluoride, dimethyl sulfate, diethyl sulfate, Methyl benzenesulfonate, ethyl p-toluenesulfonate or butyl ester. The alkylation is expediently carried out by heating in an inert organic solvents, for example hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons, such as carbon tetrachloride, tetrachloroethane, chlorobenzene, o-dichlorobenzene or nitrohydrocarbons, such as nitromethane, nitrobenzene or nitronaphthalene. Also acid anhydrides, acid amides or nitriles, such as acetic anhydride, dimethylformamide or acetonitrile or even dimethyl sulfoxide can be used. Instead of an indifferent one

Solvent you can also use a large excess of alkylating agents. In this case it is However, care should be taken that the mixture is not excessively heated, since the reaction is strongly exothermic Nevertheless, in most cases, especially in the presence of organic solvents, it is necessary that To heat the reaction mixture from the outside in order to start the reaction. In special cases the alkylation also in an aqueous medium or using an alcohol, possibly in the presence small amounts of potassium iodide can be carried out.

If necessary, the dye salts can be cleaned by dissolving them in water, Any unreacted starting dye can be filtered off as an insoluble residue. From the aqueous solution can by adding water-soluble salts, for example sodium chloride, the dye to be separated again

The dyes according to the invention contain, provided they have a quaternary amino group, as an anion preferably the remainder of a strong acid, for example sulfuric acid, or its half-ester, or an aryl sulfonic acid or a halogen ion. The mentioned, according to the method in the dye molecule Introduced anions can also be replaced by anions of other inorganic acids, for example the Phosphoric acid, sulfuric acid, or organic acids, such as. B. formic acid or acetic acid, the Chloroacetic acid, oxalic acid, lactic acid or tartaric acid are replaced; in certain cases you can the free bases can also be used. The dye salts can also be in the form of double salts, for example with halides of the elements of the second group of the periodic table, in particular Zinc or cadmium chloride, can be used.

The dyes according to the invention with the quaternized cyclic amino radical of the type defined in claim are suitable for dyeing and printing a wide variety of fully synthetic fibers, such as. B. of polyvinyl chloride, polyamide, polyurethane fibers, also of fibers made of polyesters of aromatic dicarboxylic acids, such as. B. of polyethylene terephthalate fibers, but in particular of polyacrylonitrile fibers or of polyvinylidene anide fibers. Polyacrylonitrile fibers are primarily understood to mean polymers which contain more than 80%, for example 80 to 95%, acrylonitrile ^1; They also contain 5 to 20% vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters.

These fibers, which can also be dyed in a mixture with one another, are obtained with the fibers according to the invention Dyes intensive and level dyeings with good lightfastness and good all-round fastness properties, especially good washing, sweat, sublimation, wrinkle-proof, decatur, ironing, rubbing, carbonizing, Fastness to water, seawater, dry cleaning, dyeing and solvents Dyes have inter alia. also good stability in a larger pH range, good affinity e.g. Am aqueous solutions of different pH values. In addition, they generally show a good reserve on wool and other natural or synthetic polyamide fibers as well as good touchfastness.

The quaternized water-soluble dyes are generally not very sensitive to electrolytes and show partly an extremely good solubility in water or organic solvents. The coloring with the In general, quaternized, water-soluble dyes are aqueous, neutral or acidic Medium, at boiling temperature under atmospheric pressure or in a closed vessel under elevated temperature and increased pressure. The commercially available leveling agents do not interfere, but are not required.

The specified dyes are particularly suitable for trichromatic coloring. Furthermore, they are due their hydrolysis resistance can be used with advantage for high temperature dyeing and for dyeing in Presence of wool. They can also be applied to the fibers by printing. to For this purpose, one uses, for example, a printing paste which contains the dye in addition to the Printing aids such as wetting and thickening agents, they are also suitable for Bulk coloring of acrylonitrile polymerization products, as well as other plastic ones, if necessary dissolved masses, in light and washfast nuances, also for the coloring of oil paints or Varnishes, or finally also for the dyeing of cotton, especially of stained cotton Cellulose, regenerated cellulose and paper.

The non-water-soluble dyes according to the invention which have a tertiary amino group are expediently in finely divided form and with the addition of dispersants such as soap or sulphite cellulose waste liquor or synthetic detergents, or a combination of different wetting and dispersing agents are used As a rule, it is expedient to convert these dyes into a dye preparation before dyeing Contains dispersant and finely divided dye in such a form that when diluting the Fai-K «toffpräparate a fine dispersion is formed with water. Such dye preparations can be used in a known manner, for. B. by reprecipitating the dye from sulfuric acid and grinding the resulting slurry with Sulphite waste liquor, optionally also by grinding the dye in highly effective grinding devices in dry or wet form can be obtained with or without the addition of dispersants during the milling process. They are also suitable for dyeing and printing a wide variety of fully synthetic fibers, such as z. B. polyacrylonitrile, polyvinyl chloride, polyamide or polyurethane fibers, but especially made of fibers Polyesters of aromatic dicarboxylic acids, such as. B. of polyethylene terephthalate fibers.

To achieve strong colors, e.g. Example, on polyethylene terephthalate fibers, it has proven advantageous to add to the dye bath a swelling agent, or else to carry out the dyeing under pressure at temperatures above 10O ⁰ C, for example at 120 ⁰ C. Suitable swelling agents are aromatic carboxylic acids, for example benzoic acid or salicylic acid, phenols, such as, for example, o- or p-oxydiphenyl, aromatic halogen compounds, such as, for example, chlorobenzene, o-dichlorobenzene or trichlorobenzene, phenylmethylcarbinol or diphenyl. When dyeing under pressure, it is advantageous to make the dyebath slightly acidic, for example by adding a weak acid, e.g. B. acetic acid.

The dyes according to the invention with a tertiary amino group prove to be particularly suitable for dyeing by the so-called heat setting process, according to which the fabric to be dyed with an aqueous dispersion of the dye, which advantageously contains 1 to 50% urea and a thickener, in particular sodium alginate, preferably at Impregnated temperatures of at most 6O ⁰ C and as usual

is squeezed. Expediently, one squeezes off so that the impregnated goods are 50 to 100% of theirs Retains initial weight of dye liquid.

To fix the dye, the fabric so impregnated, expediently after prior drying, for. B. in a warm air stream to temperatures of over 100 ⁰ C, for example between 180 to 220 ⁰ C, heated.

The heat setting process just mentioned is of particular interest for dyeing blended fabrics made of polyester fibers and cellulose fibers, especially cotton. In this case, the padding liquid contains in addition to the dye according to the invention, dyes suitable for dyeing cotton, for example Direct dyes or vat dyes, or in particular so-called reactive dyes, d. H. Dyes that can be fixed on the cellulose fiber with the formation of a chemical bond, for example dyes, containing a chlorotriazine or chlordiazine residue. In the latter case it proves to be useful to use the Padding solution contains an acid-binding agent, for example an alkali metal carbonate or alkali metal phosphate, alkali metal borate or perborate or mixtures thereof. When using vat dyes is one Treatment of the padded fabric after the heat treatment with an aqueous alkaline solution a reducing agent commonly used in vat dyeing is required.

The dyeings obtained on polyester fibers with the dyes according to the invention are useful subjected to an aftertreatment, for example by heating with an aqueous solution of a ion-free detergent.

The dyes according to the invention are also suitable for dyeing blended fabrics made from polyester fibers and wool, the wool portion remaining reserved and subsequently dyed with a wool dye can be.

The dyes according to the invention can also be applied by printing instead of by impregnation. For this purpose one uses z. B. a printing ink which, in addition to the auxiliaries customary in printing, such as wetting agents and thickeners, contains the finely dispersed dye, optionally mixed with one of the cotton dyes mentioned above, optionally in the presence of urea and / or an acid-binding agent

The dyes according to the invention give strong dyeings and prints with excellent fastness properties, in particular good light fastness. Sublimation, decatur, washing and chlorinated water fastnesses. Another advantage is the good wool and cotton reserves of the dyes to be used in accordance with the process.

FR-PS 14 21 912 describes dyes which differ from the S5 according to the invention in that they contain an alkanoyl, alkylsulf-myl or sulfonamido group in the 4-position of the diazo component and that the alkyl radical on the nitrogen atom of the coupling component (R;) The dyes according to the invention which carry a nitro group in the 4-position of the diazo component and whose nitrogen atom carries the substituted alkyl group. For example, cyanoethyl, methoxyethyl or ethoxyethyl, are distinguished from these previously known dyes by better lightfastness.

From FR-PS 14 03 396 dyes with 2 nitro groups in the diazo component and unsubstituted N-alkyl radical are known. Compared to these previously known dyes, too, compounds according to the invention are distinguished by better lightfastness.

The DT-PS 6 52 215 describes in Example 1 dyes with an N-butyl-N- (j3-pyridiniumethyl) aniline as a coupling component (Example 1) or N- (j9-hydroxyethyl) -N- (j? -hydroxy -)> - pyridiniurnäthyl) aniline (Example 3). These compounds are more difficult to access than those according to the invention.

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

34.4 parts of a 10% paste of 2-chloro-4-nitroaniline are concentrated with 6 parts. Hydrochloric acid and 20 parts Stirred ice and diazotized with 20 parts of n-nitrite solution. It is filtered from traces of an insoluble The residue and the diazo solution is poured into a solution of 5.8 parts of N- (2, N'-phenyl-N ', j3-cyanoethyl) -arr.inoäthylpvridiniumchlorid in 500 parts of ice water and adjusts the coupling mixture by adding sodium acetate Congo neutral. The precipitated dye is filtered off and dried. It is clearly soluble in water and colors polyacrylonitrile from an aqueous bath in very lightfast scarlet shades.

If, instead of 2-chloro-4-nitroaniline, the diazo components indicated in the table below in column II are used, further, true dyes are obtained which dye polyacrylonitrile fibers in the shade indicated in column III.

III

4-nitroaniline

2 2,6-dichloro-4-nitroaniline

3 2-cyano-4-nitroaniline

reddish
yellow

yellow-brown
Red

Staining instructions

I part of the dye is dissolved in 5000 parts of water with the addition of 2 parts of 40% strength acetic acid. In this Dyebath one goes at 60 ° with 100 parts of dried yarn made of polyacrylonitrile staple fibers, increases the Temperature to 100 ° within half an hour and colors one hour at boiling temperature. Then the Staining rinsed well and dried.

Example 2

36 ^ parts of the diazotized by domes! 4-nitroaniline on N ^ -Chloräthyl-N ^ '- methoxyäthylani-Hn available, water-insoluble monoazo dye are stirred with 20 parts of pyridine under reflux until a sample is water-soluble. The reaction mixture is now diluted with 200 parts of chlorobenzene and, after cooling, the dye salt is filtered off and dried. Orange is obtained on polyacrylitrile fibers Dyeings of very good lightfastness

Similar orange colorations are obtained if, instead of pyridine, N-Methylpiperidm, N-Methylpyrrolidin. Piperidine or morpholine used

Example 3

II parts of the diazotized) 2,6-dichloro-4-nitroanflin on the methanesulfonic acid-

709 810/61

ίο

ster des ^ '- Phenoxy ^^ hydroxy-N.N-diethyl-l ^ -tolui- The same procedure gives d

dins available dye are stirred with 10 parts of additional N-methylmorpholine indicated in the table below for 8 hours at 120 to 130 ° under and by means of the substituents A, R ₁ , R ₂ , X, K, π and reflux. It is then diluted with 400 parts of the general formula of water, 5 parts of glacial acetic acid are added, 5 parts are filtered off
some insoluble material and falls in the filtrate

Color by adding 20 parts of sodium bromide

out. The dye obtained dyes polyacrylonitrile fibers A N = N

in real brown nuances.

Similar brown dyes are obtained by using io
instead of N-methylmorpholine pyridine, piperidine,
Morpholine or N-methylpiperidine uses defined dyes.

(CH ₂ ) "X

(CH ₂ ) ", K

1 O, N -

2 the same.

3 O, N 4 the same.

CN

Cl

Cl

5 O ₂ N

6 the same.

7 the same.

8 O ₂ N

9 O ₂ N

Cl

R ₁ R ₂ X

H H —CN

-OCH ₃ CH ₃ -OCH ₃

H H —O

H CH _{3 the} same.

η m nuance

H H-S

HH -COCH ₃

HH -OCOCH ₃

CH ₃

CH ₂ -CH ₂

-N

CH, 2 2 red

CH ₂ -CH ₂

-O

the same

2 2 purple

2 2 red

CH ₂ CH ₂ -NO 2 2 red

CH ₂ -CH ₂ CH ₃

CH ₂ CH ₂

—N

2 2 yellow brown

CH ₂ -CH ₂ —Ν ^Ν > 1 2 yellow-brown

CH ₂ -CH ₂

CH ₂ -CH ₂

CH ₂ 2 2 yellow brown

OCH ₃ CH ₃ -OCH ₂ CH ₂ CN like.

-O- η η -co-o -u ^ y

10 O ₂ N - ^ V - H CH ₃ -OC ₂ H ₅

—Ν

CH ₂ -CH ₂

CN

CH ₂ -CH ₂

2 2 red

1 2 orange

2 2 on-board team

continuation

π »ι nuance

CH ₇ -CH ₂

11 O ₂ N

12 Ο, Ν

CN

CH, -OCH ₃

H -CONH ₂ CH ₂ 2 2 bordeaux

/
CH ₂ -CH ₂

-N
β

2 2 red

OCH,

Example 4

132 parts of the diazotized by coupling of! 2-chloro-4-nitroaniline on N, 2- (N'-phenyl-N ', 2'-cyanoethyl) aminoethylpiperidine available Monoazoiarerstoffes are dissolved in 200 parts of chlorobenzene and at 100 ° with a solution of 5.2 parts of dimethyl sulfate in 10 parts of chlorobenzene. The mixture is stirred at 110 bis 120 ° until the quaternary dye salt is deposited has, lets it cool, filters and dries. With this Dye is very effective on polyacrylonitrile fibers real scarlet tones.

Instead of dimethyl sulfate, equivalent amounts of diethyl sulfate, benzyl chloride, p-toluenesulfoiisäuremethyl-, ethyl or butyl ester are quaternized.

A dye with similar properties that

Polyacrylonitrile fibers in yellow-brown tones dyes, maintains you follow the same procedure if you have 2,6-dichloro-4-nitroaniline on N, 2- (N'-phenyl-N ', 2'-phenthioethyl) aminoethylpyrrolidine couples and quaternized the resulting azo dye as indicated.

Claims (1)

Patent claims: 1. Basic monoazo dyes of the general formula S- J »alk, -X A-N = N- /> - N X alk ₂ -K ^K ₂