DE1644125C3 - Water-insoluble monoazo dyes of the dispersion series - Google Patents

Description

The invention relates to water-insoluble monoazo dyes of the dispersion series of the general formula

A-N = N-B

R,

or

Il "ί"

HO-C N

wherein Ri is hydrogen, methyl, alkanoylamino with up to 3 carbon atoms, phenoxy, phenylmercapto, phenyl, halogen or trifluoromethyl, R _{2 is} hydrogen, methyl, methoxy, ethoxy, R ₃ and R _{4 is} hydrogen or optionally by cyano, hydroxy, alkanoyloxy with 2 or 3 carbon atoms, methoxy, cyanoethoxy, carbomethoxy or carbamide substituted Ci-C ₃ -alkyl, R _{5 are} hydrogen, methyl, phenyl, chlorophenyl or dichlorophenyl and Rt, acetyl, carbomethoxy, carboethoxy or methyl .

2. Dyestuffs according to Claim 1, characterized in that A is from an aniline general formula

wherein A is a benzene radical of the, in addition to at least one nitro, cyano, carbomethoxy, carboxamides Methylsulfonyl or trifluoromethyl group in o- and / or p-position to the azo group (preferably a nitro group also a phenyloxy, chlorophenoxy, methylphenoxy, phenylmethoxy, Phenylmethyl mercapto, phenyl mercapto or phenyl methyl group and optionally a methyl or Contains methoxy group, and B is a radical of the coupling components 8-oxyquinoline or barbituric acid or a radical which is free of water-solubilizing groups of the general formulas

or

HO-C N

NH ₇

derives, in which X is nitro, cyano, carbomethoxy, carboxamide, methylsulfonyl or trifluor methyl, a Y is phenoxy, phenylmethoxy, phenylmercapto. Phenylmethylmercapto, phenylmethyl and the other Y are hydrogen, methyl, methoxy, phenylmethoxy, phenylmercapto, phenylmethylmercapto, phenylmethyl, the Y in "o-position also being the meaning given for X,

wherein Ri is hydrogen, methyl, alkanoylamino with up to 3 carbon atoms, phenoxy, phenylmercapto, phenyl, halogen or trifluoromethyl, R2 is hydrogen, methyl, methoxy, ethoxy, R ₃ and R _{4 is} hydrogen or optionally by cyano, hydroxy, alkanoyloxy with 2 or 3 Carbon atoms, methoxy, cyanoethoxy, carbomethoxy or carbamide substituted Ci-C ₃ - alkyl, R _{5 are} hydrogen, methyl, phenyl, chlorophenyl or dichlorophenyl and Rt, acetyl, carbomethoxy, carboethoxy or methyl.

The valuable azo color according to the invention

() <i substances can be obtained by using the diazonium compound of an aminobenzene of the general formula A-NH2, in which A has the same meaning as in formula above, with one of the water-soluble

Azo components free from photochemical groups 8-oxyquinoline or barbituric acid or one of these of the general formulas

or pyrazolones of the type mentioned in the claims into consideration. The aminobenzenes correspond to general formula

CH-c-a.

HO-C N

I.

R ₅

wherein Ri, R2, R3, R * and R5 have the same meaning as in have the above formulas for the corresponding radicals, couples

Diazo components of the general formula are of particular interest

35

40

45

-NH,

wherein X is nitro, cyano, carbomethoxy, carboxamide, methylsulfonyl or trifluoromethyl, a Y is phenoxy, Phenmethoxy, Phenylmercapto, Phenmethylniercapto, Phenylmethyl and the other Y hydrogen, methyl, Are methoxy, phenmethoxy, phenylmercapto, phenylmethylmercapto, phenylmethyl, where the Y is in The o-position can also have the meaning given for X and only one radical Y is phenoxy or phenmethoxy may be.

The following amines corresponding to the formula A-NH ₂ may be mentioned as examples:

1 - Amino-2-phenoxy-4-nitrobenzene

1-amino ^ -phenoxy ^ -cyanbenzene

1-amino-2-phenoxy-4-carbomethoxybenzene

) -Amino-2-p-chlorophenoxy-4-nitrobenzene

1-amino-2-o-methylphenoxy-4-nitrobenzene 1-amino-2-benzyloxy-4-nitrobenzene

l-amino-2-phenylmercapto-4-nitrobenzene

1-amino-2-benzylmercapto-4-nitrobenzene

1 - Amino-2-phenyI-4-nitrobenzo!

1-Amino-2-benzyl-4-nitrobenzene 1-Amino-2,5-di (phenylmercapto) -4-nitrobenzene

l-amino-3-phenoxy-4-nitro-benzene

l-Amino-S-phenylmercapto ^ -nitro-benzoI

1-Amino-3-phenoxy-4-nitro-6-methyl-benzene

1 -Amino ^ -methoxy ^ -nitro-S-phenoxy-benzene o, _s

The azo components are primarily the aminobenzenes coupling in the p-position to the amino group

wherein Ri is hydrogen, methyl, alkanoylamino with up to 3 carbon atoms, phenoxy, phenylmercapto, phenyl, halogen or trifluoromethyl, R _{2 is} hydrogen, methyl, methoxy, ethoxy, R ₃ and R _{4 is} hydrogen or optionally by cyano, hydroxy, alkanoyloxy with 2 or 3 carbon atoms, methoxy, cyanoethoxy, carbomethoxy or carbamic) substituted Ct- Cj- alkyl, especially ethyl.
Examples are:
aniline

3-methylaniline
3-methyl-6-methoxyaniline
3-phenoxyaniline
2-methoxy-5-phenoxyaniline
N-methylaniline
N-Ethylaiiilin
N-cyanoethylaniline
N-cyanoethoxyethylaniline
N-cyanoethoxyethyl-5-acetylaminoaniline N-cyanoethoxyethyl ^ -methoxy-S-acetylaminoaniline N, N-diethylaniline
N, N-diethyl-3-methyl-aniline
N, N-Diethyl-2-methoxy-5-methyl-aniline N, N-Diethyl-5-acetylamino-aniline
N, N-diethyl-2-methoxy-5-acetylamino-aniline N, N-diethyl-2-methoxy-5-phenoxy-aniline, N-ethyl-N-tyanethyl-aniline
N-ethyl-N-cyanoethyl-3-methyl-aniline N-ethyl-N-cyanoethyl-2-methoxy-5-methyl-aniline N-ethyl-N-cyanoethyl-S-acetylamino-aniline N-ethyl-N-cyanoethyl -2-methoxy-5-acetylamino-aniline N-ethyl-N-cyanoethyl-3-phenoxy-aniline N-ethyl-N-cyanoethyl-2-methoxy-5-phenoxy-ajiiline N-ethyl-N-cyanoethyl-methoxy -S-phenyl mercaptoaniline

N-ethyl-N-acetoxyethyl-aniline
N-ethyl-N-acetoxyethyl-3-methylaniline N-ethyl-N-acetoxyethyl-3-propionylamino-aniline N-ethyl-N-acetoxyethyl-3-phenoxy-aniline N-ethyl-N-acetoxyethyl-2-methoxy-5 -phenoxy-aniline N-hydroxyethyl-N-cyanoethyl-aniline N-hydroxyethyl-N-cyanoethyl-3-methyl-aniline N-hydroxyethyl-N-cyanoethyl-3-acetylamino-aniline N, N-bis-hydroxyethyl-3-methyl -aniline N, N-bis-cyanoethyl-aniline
N, N-bis-cyanoethyl-3-methylaniline
N, N-bis-cyanoethyl-2-ethoxy-5-phenoxy-eniline N, N-bis-acetoxyethyl-aniline
N, N-Bis-acetoxyäthyl-3-methyl-aniline N, N-Bis-acetoxyäthyl-2-methoxy-5-methyl-aniline N ₁ N -Bis-acetoxyäthyl-S-acelylamino-a niline N, N-Bis- acetoxyethyl-2-methoxy-5-acetylamino-aniline N, N-bis-acetoxyethyl-3-phenoxy-aniline N, N-bis-acetoxyethyl-2-methoxy-5-phenoxyaniline

The pyrazolones are those of the general formula

V- Π? * - t \ -tt

I "Il

O = C

wherein R5 is hydrogen, methyl, phenyl, chlorophenyl or Dichlorophenyl and Re acetyl, carbomethoxy, carboethoxy or methyl.

Examples of pyrazolones that can be used as azo components are:
3-acetyl-pyrazolone-5
3-carbomethoxy-pyrazolone-5
3-carboethoxy-pyrazolone-5
1-phenyl-S-methyl-pyrazolone-S
lp-Chlorophenyl-S-methyl-pyrazolone-S l- (2 ', 5'-dichlorophenyl-3-methyl-pyrazolone-5.

The diazotization of the diazo components can be carried out by methods known per se, for example with the aid of Mineral acid, especially hydrochloric acid and sodium nitrite or z. B. with a solution of nitrosylsulfuric acid in concentrated sulfuric acid.

The coupling can also be carried out in a manner known per se, for. B. in weakly alkaline neutral to acidic medium, optionally in the presence of sodium acetate or the like, the coupling speed influencing buffer substances or catalysts such as. B. pyridine, respectively. its salts, be made.

After the coupling reaction has taken place, the dyes formed from the coupling mixture can easily, for. B. separated by filtration since they are practically insoluble in water.

The new dyes are suitable, for example, as pigments, but especially for dyeing and printing of structures, in particular fibers and fabrics, for example made of cellulose acetate and polyamides, but especially from aromatic polyesters. Strong colorations of excellent color are then obtained Fastness properties, in particular light fastness, sublimation fastness and rub fastness.

For dyeing, the new dyes are expediently used in finely divided form and under-dyeing Addition of dispersants, such as soap, sulphite cellulose waste liquor or synthetic detergents, or one Combination of different wetting and dispersing agents. As a rule, it is useful to add the dyes before Dyeing in a dye preparation that has a dispersant and finely divided dye in such Form contains that when the dye preparations are diluted with water, a fine dispersion is formed. Such dye preparations can in a known manner, for. B. by reprecipitation of the dye from sulfuric acid and grinding the slurry thus obtained with sulphite waste liquor, optionally also by grinding the Dye in highly effective grinding devices in dry or wet form with or without the addition of Dispersants are obtained during the milling process. To achieve stronger dyeings on polyethylene terephthalate fibers it proves to be expedient to add a swelling agent to the dyebath, or in particular the dyeing process under pressure at temperatures above

100 °, for example at i20 °. When Swelling agents are aromatic carboxylic acids, for example benzoic acid or salicylic acid, phenols, such as o- or p-oxydiphenyl, aromatic Halogen compounds, such as, for example, chlorobenzene, o-dichlorobenzene or tri-chlorobenzene, phenyl-, phenylmethylcarbinol or diphenyl. When dyeing under pressure, it is advantageous to use the dyebath to be weakly acidic, for example by adding a weak acid, e.g. B. acetic acid.

Thanks to their alkali fastness, the new dyes are also suitable for dyeing according to the so-called Thermosetting process, after which the fabric to be dyed with an aqueous dispersion of the dye, which suitably contains 1 to 50% urea and a thickener, especially sodium aligate, is preferably impregnated at temperatures of at most 60 ° and squeezed off as usual. Appropriate one squeezes off in such a way that the impregnated goods contain 50 to 100% of their initial weight in dyeing liquid holding back.

To fix the dye, the fabric impregnated in this way is expediently dried after prior drying, z. B. in a warm air stream, to temperatures of over 100 °, for example between 180 to Heated to 220 °.

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 dyes according to the invention, dyes suitable for dyeing cotton, in particular Vat dyes or reactive dyes, d. H. Dyes that form a cellulose fiber chemical bond are fixable, so for example dyes containing a chlorotriazine or chlordiazine radical. In the latter case, it proves to be expedient to add an acid-binding solution to the padding solution Agents, for example an alkali carbonate or alkali phosphate, alkali borate or perborate or their Add mixtures. When using vat dyes a treatment of the padded Fabric after heat treatment with an aqueous alkaline solution of a common in vat dyeing Reducing agent necessary.

Thanks to their good reserve of wool, the dyes according to the invention are also excellent for da: dyeing blended fabrics made from polyester fibers and wool.

The dyeings obtained are expediently subjected to an aftertreatment, for example by Heating with an aqueous solution of an ion-free detergent.

Instead of being impregnated, the dyes can also be applied by printing. To this Purpose one uses z. B. a printing ink, which in addition to the usual aids in printing, such as network and thickeners, the finely dispersed dye, optionally in admixture with one of the abovementioned Cotton dyes, optionally in the presence of urea and / or a:; acid-binding agent, contains.

Compared to the dyes of the azobenzene series described in US-PS 22 41 247 are those according to the invention Dyes are more lightfast and have better drawability; also compared to those in the US-PS 18 21 255 mentioned pyrazolone dyes they are significantly more lightfast.

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

2.3 parts of i-amino ^ -phenoxy ^ -nitrobenzene are dissolved in 45 parts of glacial acetic acid and at a temperature of 15-20 ⁰ C to a solution of 0.7 parts of NaNO ₂ in 10 parts of sulfuric acid which was added with 15 parts of glacial acetic acid was dripped. After the end of the diazotization, the excess nitrite is destroyed and the solution at a temperature of 0-10 ° C and a pH between 7 and 8 to a solution of 1.8 parts of 1-phenyl-3-methyl-pyrazoion-5 in 150 parts of alcohol dripped. To complete the coupling, the mixture is stirred for a while, then the dye is filtered off, washed with water and dried in vacuo. It dyes polyester fibers in yellow tones with excellent light and sublimation fastness.

Staining instructions

1 part of the dye obtained according to the preceding example is mixed with 2 parts of a 50% strength aqueous Wet-ground solution of the Na salt of 1,1'-dinaphthylmethane-2,2'-disulfonic acid and dry.

This dye preparation is mixed with 40 parts of a 10% aqueous solution of the Na salt

N-Benzyl-jU-heptadecyl-benzimidazole-disulfonic acid
stirred and 4 parts of a 40% acetic acid solution were added. A dyebath of 4000 parts is prepared from it by diluting it with water.

100 parts of a purified polyester fiber material are introduced into this bath at 50 °, and the amount is increased Temperature in half an hour to 120 to 130 ° unc colors an hour in a closed vessel with diesel Temperature. Then it is rinsed well. A strong yellow color of excellent light and color is obtained Fastness to sublimation.

Example 2

Is used in place of the in Example 1

1.8 parts of 1-phenyl-3-methyl-pyrazolone-5 described

ίο 1 part 3-methyl-pyrazolon-S, you get one Dye of the polyester fibers in yellow tones with excellent lightfastness and sublimation fastness.

Example 3

2.3 parts of 1-amino ^ -phenoxy ^ -nitrobenzene are dissolved in 45 parts of glacial acetic acid and at a temperature of 15-20 ° C. to a solution of 0.7 parts of NaNO ₂ in 1/3 parts of sulfuric acid, which is mixed with 15 parts of glacial acetic acid was dripped. When the diazotization is complete, the excess nitrite is destroyed and the solution is added dropwise at a temperature of 0-10 ° C. to a solution in front of 2 parts of NN-bis-jJ-cyanoethylaniline in 150 parts of 80% acetic acid. After stirring for six hours, the mixture is buffered with 30% NaOH, stirred for a while, the dye is filtered off, washed and dried in vacuo. He dyes polyester fibers in orange tones of excellent!

Fastness to light and sublimation.

Further dyes are shown in the table below listed, which are obtained when each given in column I diazo component with eini Coupling component of column II couples. The dyeing obtained on polyester fibers is in column III specified.

I. Il III 4th 1-amino-2-phenoxy-4-nitrobenzene N, N-bis-cyanoethyl-3-methyl-aniline orange 5 the same N-cyanoethyl-N-acetoxy-ethyl-aniline orange 6th the same N, N-bis-acetoxyethylaniline Scarlet fever 7th the same N, N-bis-acetoxyethyl-3-methyl-aniline Red 8th the same Ν, Ν-bis-acetoxypropylaniline Scarlet fever 9 the same Di-propionic acid ester of N-bis-oxyäthyl- Scarlet fever aniline 10 the same N-cyanoethyl-2-methoxy-5-phenoxy-aniIine Red 11th the same N, N-bis-acetoxyethyl-2-methoxy-5-phenoxy- Red aniline 12th 3-phenylmercapto-4-nitro-aniline 1-phenyl-3-methylpyrazolone yellow 13th 2-chloro-4-nitro-5-phenylmercaptoaniline 1-phenyl-3-methylpyrazolone yellow 14th 2-phenoxy-4-nitro-aniIine Barbituric acid yellow 15th 2-phenoxy-4-nitro-aniline 8-oxyquinoline Brown 16 2-methoxy-4-nitro-5-phenyl-aniline 1-phenyl-3-methylpyrazolone yellow 17th 2-methoxy-4-nitro-5-phenoxy-aniline N-bis-0-cyanoethylaniline orange 18th 3-phenoxy-4-nitroaniline N-bis-ß-cyanoethylaniline orange 19th 2-phenoxy-4-nitro-aniline aniline Scarlet fever

Dye No. 15 also shows good drawability for nickel-containing polypropylene fibers.

Production of the diazo components

Regulation I
S-phenylmercapto ^ -nitro-aniline

17.25 parts of 3-chloro-4-nitro-aniline are dissolved in 150 parts by volume of dimethyl sulfoxide, then 10.4 Parts by volume of thiophenol added, heated to 70 ° and 20 Parts of 30% strength NaOH are added dropwise. The mixture is stirred at 85 ° to 90 ° overnight. Then it is set to approx. 30 ( Parts of ice discharged, then filtered off, washed neutral see and dried in vacuo at 80 °. Recrystallized from ethano, a product of the formula is obtained

O ₂ N

NH,

Analysis:

Calculated: C 58.52%, H 4.09%, S 13.02%;
found: C 58.2%, H 4.3%, S 13.2%.

Regulation Il

2-chloro-4-nitro-5-phenylmercapto-aniline

3-chloro-4-nitroaniline is substituted for 17.25 parts in regulation I 20.7 parts of 2,5-dichloro-4-nitro-aniline, a product of the formula ι ο is obtained

O, N

SQ ₁ H ₅

Regulation III
3-phenoxy-4-nitro-aniline

If instead of 10.4 parts by volume of thiophenol in Regulation I 12 parts of phenol, a product of the formula is obtained

NH,

O-C.H,

Regulation IV
2-phenoxy-4-nitro-aniline

a) 185.23 parts of 2-phenoxy-aniline are mixed with acetic anhydride acylierL

b) 113.5 parts of finely powdered 2-phenoxyacetylaniline are introduced into 224 parts by volume of 63% strength HNO _{3 at a temperature of 20 to 25 °. 64 parts by volume of 96% strength HNO 3 are then} added dropwise at a temperature of 15 to 20 °, the mixture is stirred for 15 minutes, 100 parts of ice water are added dropwise and the mixture is stirred for a further 2 1/2 hours. It is then filtered off, the residue with highly diluted ammonia

3 °

35

triturated, filtered again and finally the residue is washed neutral.

c) The moist product is deacetylated in aqueous sulfuric acid. A product of the formula

O -QH,

O, N- \ Y-NH,

Regulation V
2-methoxy-4-nitro-5-phenoxy-aniline

a) 21.5 parts of 2-methoxy-5-phenoxy-ani! in are acetylated with acetic anhydride.

b) 12.85 parts of 2-methoxy-5-phenoxy-acetylaniline are suspended in 100 parts by volume of glacial acetic acid. then it is cooled to 15 ° and 50 parts by volume of HNOi (d = 1.402) are added dropwise, the temperature being between 15 ° is held up to 20 °. The mixture is then stirred for a further 3 hours at the same temperature, then 100 parts of water are added dropwise, the mixture is stirred for a further 30 minutes and filtered off. The residue is with Triturated highly dilute ammonia, filtered off, washed neutral, dried and extracted from toluene recrystallized.

c) The product obtained under b) is deacetylated in ethanol with the addition of a little hydrochloric acid. After recrystallization from ethanol, a product of the formula is obtained

OCH ₃

NH ₂

40 OC _h H ₅

Analysis: Calculated: C 59.99%, H 4.65%, N 10.77%;
Found: C 59.9%, H 4.8%, N 10.9%.

Claims (1)

Patent claims: 1. Water-insoluble monoazo dyes of the dispersion series of the general formula A-N = N-B wherein A is a benzene radical which, in addition to at least one Nitro, cyano, carbomethoxy, carboxamides, methylsulfonyl or trifluoromethyl groups in o- and / or p-position to the Azognippe, also a phenyloxy, chlorophenoxy, methylphenoxy, Phenylmethoxy, phenylmethylmercapto, phenylmercapto or phenylmethyl group and optionally a methyl or methoxy group contains, and B a radical of the coupling components free of water-solubilizing groups 8-oxyquinoline or barbituric acid, or a residue of the general formulas and only one radical Y may be phenoxy or phenylmethoxy. 3. Dyestuffs according to Claims 1 to 2, characterized in that B is one of the in claim I. defined pyrazolone radicals. 4. Dyestuffs according to Claims 1 to 2, characterized in that B is one of the in claim 1 defined Ν, Ν-substituted aniline radicals