DE1943904C3 - Water-soluble monoazo dyes and processes for their preparation and their use for dyeing or printing leather, wool, silk and cellulose - Google Patents

Description

or -CH = CH,

--CH, -CH -, - Z

IUN-

(2)

(SC) ₁ H) ,,,

in which X, m and η have the meanings given in claim 1, diazotized and with azo components of the general formula (3)

H - A

(3)

wherein A has the meaning given in claim 1, couples and optionally the obtained Dyes with X equal

-CH ₂ -CH ₂ -OH

then according to methods known per se in dyes with X equal

- CH ₂ -CH ₂ -Z

where Z has the meaning given in claim 1.

3. Modification of the method according to claim 2, characterized in that one according to claim 2 obtained dyes of the formula (1) with X being the same

--CH ₂ CH ₂ -Z

with Z of the meaning given in claim 1 converted into dyes with X being --CH CH ₂ according to methods known per se.

4. Use of those mentioned in claim 1 or those produced according to claim 2 or 3 Dyes for dyeing otter printing on leather or fiber materials made of wool, silk. Polyamides and / or native or regenerated cellulose.

The present invention relates to new, water-soluble monoazo dyes in the form of the free Acids of the general formula I)

correspond, in which A is the remainder of an azo component the benzene, naphthalene, Aeetessigsaurearylamid-, pyrazolone or quinoline series, X the grouping

represents, in which Z represents a customary inorganic or organic radical which can be split off under alkaline conditions, and m and) i denote the numbers 1 or 2, the sum of (in + n) not being 4.

2. Process for the preparation of the dyes of the formula mentioned and defined in claim 1 (1), characterized in that naphthylamines of the general formula (2)

.15

40

5 ° A - N = N--

X /

- (SCJ ₂ -X) _n

correspond, in which A is the remainder of an azo component of the benzene, naphthalene, acetoacetic arylamide, Pyrazolone or cinoline group, X the grouping

CH, CU, OH, CH-CH,

-CH ₁ -CH, Z

where Z stands for a customary inorganic or organic radical which can be split off under alkaline conditions, and m and »ι denote the numbers 1 or 2, the sum of (/ 11 f η) not being 4, and a process for their preparation.

The 3rd, 4th, 5th and 8th dyes in Table 1 are preferred.

The usual inorganic or organic radicals Z which can be split off under alkaline conditions are:

A halogen atom, preferably a chlorine or bromine atom, an alkyl or arylsulfonyl acid ester group, an acvloxy group such as acetoxy group. furthermore a phenoxy group, a dialkyuimino group, such as a dimethyl or diethylamino group, also the thiosulfuric acid group, the phosphoric acid ester group, and in particular the sulfuric acid ester group.

The new monoazo dyes represented by the above general formula (1) can be prepared by adding naphthylamines of the general formula (2)

H ₂ N--

'Y)

vV

- (SO ₂ -X) _n
- (SCO ₃ H) ₁₁₁

(2)

m which X, m and η have the meanings given above, by customary methods, for example with sodium nitrite and mineral acid, diazotized with azo components of the general formula (3)

HA

(3)

in which A has the meaning given above, couples in an aqueous medium and, if appropriate, the resulting dyes of the formula (1) in which X represents the grouping CH ₂ - CH ₂ --OH, then according to methods known per se into such dyes of the formula (1) in which X represents the grouping -CH ₂ - CH ₂ - Z, in which Z has the abovementioned meaning, or this grouping

CH ₂ -CFU-Z

converted into the group -CH CH ₂ .

The transfer of dyes dor general Formula (1), ii · where X is for the grouping

CH ₂ CU; OH

stands in such dyes of the formula (I). in the; ■■ \ for grouping

CH ₂ CH ₂ OSO ₁ H

stands, takes place in a well-known way mi. Su! -Fatierungsmittein, such as, for example, conical sulfuric acid, chlorosulfonic acid, anidosulfuric acid or SO ₃ releasing agents.

For the conversion of dyes of the general formula (1), in which X represents the group

- (ΊΙ, -CIK OH

stands in such dyes of the formula (I). in which X Door the group

-CH ₂ - CII, ■ --QI ¹ OjH ₂

phosphorylating agents are used in a manner known per se, such as concentrated phosphoric acid, pyrophosphoric acid, metaphosphoric acid, Polyphosphoric acid. Polyphosphoric acid alkyl esters. Mixtures of phosphoric acid and phosphorus) V) oxide or phosphorus oxychloride.

Dyes of the general formula (1) in which Z represents an alkyl or aryl sulfonic acid ester group or an acyloxy group can be selected from those dyes of the formula (1) in which Z is a hydroxyl group can be obtained, for example, by using these with alkyl or aryl sulfonic acid chlorides, such as methanesulfonic acid chloride or p-toluene sulfonic acid chloride, or with carboxylic acid chlorides, such as acetyl chloride or 3-sulfobenzoyl chloride, implemented in a known manner.

Dyes of the general formula (1) in which X stands for the group —CH = - CFl ₂ are made from dyes of the formula (1) in which X stands for the group —CH ₂ - CH ₂ - Z per se known manner by treatment with alkalis, such as sodium carbonate or sodium hydroxide, prepared.

Dyes of the general formula (1). in which Z stands for a thiosulfuric acid ester group or a dialkylamino group, dyes of the formula (1) in which X stands for the group - CH - (H _{2) are made} in a manner known per se by reaction with salts of thiosulfuric acid, such as sodium thiosulfate , or by reaction with dialkylamines such as diethylamine.

The following compounds, for example, come into consideration as azo components H - A: acetoacetic acid amides, Pyrazolones, especially 5-pyrazolones. which couple in the 4-position such as 3-methyl-5-pyrazolone. 1 - phenyl - 3 - methyl - 5 - pyrazolone. 1 - (2'-. 3 '- or 4 '- sulfophenyl) - 3 - methyl - 5 - pyrazolone, 1 - phenyl-5-pyrazolone-3 carboxylic acid, 5-pyrazolone-3-carboxylic acid esters and amides, i- (6'-chloro-2'-methyl-4'-sulfophenyl) -3-diethyl-5-pyrazolone. fine phenols and hydroxyquinolines, such as 8-hydroxychmolines, such as X-flydroxyquinoline sulfonic acids, Salicylic acid. \ - or / f-naphthols, a- or / (- naphthylamines, especially but naphtholsulphonic acids, aminonaphtholsulphonic acids, Acylamino-naphthol-sulfilonic acids. which are also reactive groups, for example an i-sulfaioethylsulfonyl radical, an acryloylamino, 2,6-dichloro-triazinylamino- or a 2-chloro-6-amino-s-iria / inylaminiiresi. may contain, also 2,3-Oxynaphlhoe \ iture and 2,3-O. \ ynaphthoesäurearylide.

The / ui production of the new monoazo dyes serving naphthylamines of the general formula (2). in which X stands for the group -CH ₂ CIi ₂ -OH, can for example be liergeslellt by • '^ eetaminonaphtlialinsuHinsüuren with Älhylenoxid or, / - chloroethanol in Aeetamino - (/ i-hydroxyäthylsullon \!) - converting naphlhaline and this sulhcri and enlacelylierl. The order of the two lel / th steps depends on the respective circumstances. As examples of naphthylamines of the I-formula (2) produced in this way. in which X represents the group ClI, CH ₂ Ol 1, may be mentioned.

l-Ammo-5 - (,; - hydroxyäthylsulfonylnapht ha I in-V-su! funic acid,

l-Amino-7 - (,; - hydroxyethylsulfonyl) -naphllialin-4-sulfonic acid,

2-Amino-6- ( _/ ; -hydroxyäthylsulfonyD-naphihalin-S-sulfonic acid,

2-Amino-iS- ( _! , ¹ -liydroxyät'nylsull'onyi) -napluhalin-6-sulfonic acid,

2-Amino-6,8-his - (, i-hydroxyethylsulfonyl) -n: iphlhalin-3-sulfonic acid and 2-amino-5 - (/) '- hydroxyethylsulfonyl) naphthalene-1,7-disulfonic acid.

Naphthylamines of the general formula (2). in. X stands for the group - CH ₂ CH ₂ OH, can be converted by processes known per se into those naphthylamines of the general formula (2) in which X either stands for the groups CH ₂ --CH ₂ Z. in which Z can be split off under alkaline conditions means inorganic or organic radical, or for the group

CiF-CH ₂ , and which can also serve as starting materials for the production of the new monoazo dyes, can be converted.

The monoazo dyes obtainable by the process described are isolated by Salting out, for example with sodium or potassium chloride or by spray drying the preparation mixture.

The monoazo dyes obtainable by the process described are very suitable Dyeing and printing various materials such as wool. Silk, leather and polyamide fiber materials. in particular, however, native or regenerated cellulose fiber materials, such as Cotton, rayon and linen. You can preferably use those that are generally used technically Dyeing and printing processes for reactive dyes are used and result, for example strong dyeings and prints on cellulose fiber materials in the presence of alkaline agents good to very good light and wet fastness properties and good alkali resistance.

The closest comparable dyes known from German patents 9 65 902 and 9 60 534 are the monoazo dyes obtainable according to the process in terms of solubility and stability alkaline printing pastes and dyestuff, those in the Belgian patent 6 97 952 and in the German patent applications P 175.1. P 17 93 301.6. P! 7 94 064.6 and P 18 OX 587.5, the next comparable ivionoazo dyes Overlap in the color build-up after the dyeing and printing process.

The dyes according to the invention are distinguished from the known dyes of the formulas

SO., H OH

SO ₁ CII, ί'Η, OSO., H

N-N

Γ ν

CH ₁

SO ₃ H OH

- ■ - '■ Y ν ν - N- ^!

T "CH ₅

SO ₃ H

• SO, C ^- H ₂ - CM ₂ - OSO ₁ H

SO, H

CO - CH.,

OCH.,

- N N-C

-CH - CO NH - <f V "SO ₂ -CH ₂ -CH ₂ -OSO ₃ H

CH,

by a superior color strength when dyeing cotton by the exhaust process, and compared to the known dye of the formula

SO ₂ - CH ₂

SO ₃ H

HO ₁ S

by a significantly better water fastness and by significantly better acetic acid and sulfuric acid Fastness to over-dyeing when dyeing cotton fabrics out. It must be considered surprising that the dyes according to the invention by the The content of the specified diazo component is so similar to that of the known dyes The structure is characterized by such pronounced, superior coloring properties.

example 1

33.1 parts by weight of l-amino-5 - (/ i-hydroxyäthylsu fonyl!) -Naphthalene-7-sulfonic acid are added to 60 parts by weight of concentrated sulfuric acid at 10 to 2O ^U C and stirred overnight at room temperature. The resulting clear solution is then stirred into about 750 parts by weight of ice water, so that the temperature does not exceed 10 ⁰ C. The precipitated sulfuric acid ester is filtered off and dissolved in 300 parts by weight of water with the addition of geHO NHCO — NH

/ A

SO ₃ H

saturated sodium carbonate solution until neutral [reaction to. After adding 20 parts by volume 5 N sodium nitrite solution, this solution is stirred into a mixture of 150 parts by weight of ice and 35.5 parts by weight of 37% hydrochloric acid so that the temperature does not exceed 15 ° C. One stirs half an hour later, then destroys any excess of nitrous oxide that may still be present Acid with amidosulfonic acid, gives a solution of 40 parts by weight of 2-acetamino-5-naphthol-7-sulfonic acid (70.6%) in 200 parts by weight of water and adjusts to pH 6 with saturated soda solution. at this pH value, optionally with further addition of soda solution, until the end of the Clutch stirred. The resulting dye is then salted out with potassium chloride, filtered off and dried.

5.S 78 parts by weight of salt-containing dye are obtained, which dissolves easily in water with a red color and in the form of the free acid of the formula

SO ₃ H

HO ₃ S -O-CH ₂ -CH, - SO

—CO-CH ₃

is equivalent to.

The dye gives in the presence of alkaline compounds such as sodium hydrogen carbonate. Sodium carbonate or caustic soda, brilliant red dyeings and prints on cotton fabric, the opposite Wash basins and exposure to light are very stable.

Dyes with similar coloring properties are obtained if the example above

table

Naphthylamine of formula (2)

instead of l-amino-5 - (/> '- hydroxyethylsulfonyl) -naphthalene-7-sulfonic acid equivalent amounts of the naphthylamines of the formula (2) listed in the table below and instead of 2-acetumino-5-naphthol-7-sulfonic acid equivalent amounts of the azo components also listed in the table below begins.

Azokomponcnlc

Color ion

l-Amino-5 - (/ i-hydroxyethylsulfonyl) -naphthalene-7-sulfonic acid l-Amino-7- (ß-hydroxyäthyIsulfonyl) -naphlhalin-4-sulfonic acid the same

2-Amino-8 - (/ Miydroxyäthylsulfonyl) -naphthalin-6-sulfonic acid the same

like. like. like. like. like. like.

like. like. like. like. like. like.

the same

like. like. like. like. like. like.

l-benzoylamino-8-naphthol- bluish red 3,6-disulfonic acid the same Red-violet 1 -Benzoylamino-8-naphthol- bluish red 4,6-disulfonic acid the same bluish red 1-benzoylamino-8-naphthol- bluish red 3,6-disulfonic acid 1-acetylamino- S -naphthol- bluish red 3,6-disulfonic acid 2-acetylamino-8-naphthol- yellowish red 6-sulfonic acid 2-acetylamino-5-naphthol- reddish orange 7-sulfonic acid 2-acctylamino-5-naphthol- reddish orange 1.7-disulfonic acid l-acryloylamino-8-naphlhol- bluish red 4,6-disulfonic acid 1 - (2'.4'-dichlorotriazinyl- bluish red (6) -amino) -8-naphthol-3,6-disulfonic acid c 1 -acetylamino-5-naphthol- Red 7-sulfonic acid l-aminonaphthalene-4-sulfonic acid Red 2-aminonaphthalene-5,7-disulfonic acid c reddish orange l-amino-8-naphlhol-2,4-disulfonic acid c violet 1-naphthol-4-sulfonic acid c yellowish RoI l-naphthol-5-sulfonic acid c Red · l-naphthol-3,6-disuironic acid c Red 2-hydroxy-naphthalene-3-carbonsallrc- Red (2'-methoxy-phenyl-1 ') -amide Z-Hydroxy-naphthalene-S-carboxylic acid bluish red (2 ', 4'-dim.cthoxy-.V-chloro-phcnyl-1') - amide l- (4 ^/ -Sulfophenyl) -3-mclhyl- yellow 5-pyrazolone l- (4'-sulfophenyl) -3-carboxy- red-cast GcIb 5-pyra / olone l- (2: 5'-dichloro-4'-siilfophenyl) - yellow 3-methyl-5-pyra / olone 1- (4; 8'-disulfonaphthyl-2 ') - GcIb 3-methyl-5-pyra / olone l-Acctoaeelylamino-3-mclhyl- griinslidiigc »yellow (vmethoxybcn / .ol-4-sulfonic acid c l- (4'-sulf (iphcnyl-3-carbälhoxy- reddish yellow 5-pyra / .olon I.K-Oihydroxynaphlhalin- Red 3.6-disulfonic acid

Fortset / unu

ίο

Naphlliylamine of the I-oriiiel (-1

2-Amino-6,8-bis (/ i-hydroxyethylsulfonyl) -naphthalene-3-sulfonic acid 2-Amino-5 - (/> '- hydroxyethyl sulfonyl) naphthalene-1,7-disulfonic acid c

Azokomponcnlo

l-Benzoylamino-8-naphthol-3,6-disulfonic acid c

the same

Farhlon

bluish red
bluish red

Example 2

33.1 parts by weight of I-amino-S-I / hydroxyethylsulphonyl) naphthalene-7-sulphonic acid graze in 5 (X) parts by weight of water with the addition of saturated Sodium carbonate solution dissolved until neutral reaction. 20 parts by volume are added to this solution 5 N sodium nitrite solution is added and it is then stirred into a mixture of 150 parts by weight of F.is and 35.5 parts by weight 37% hydrochloric acid so that the temperature does not exceed 15 ° C. Then leave a half Stirring for another hour destroys any excess of nitrous acid that may still be present Amidosulfonic acid, gives a solution of 3Ü.4 Geis weight of 1-naphthol-3,6-disulfonic acid in 200 parts by weight Add water and adjust to pH 6 with saturated soda solution. At this pH value, optionally with further addition of sodium carbonate solution, until the coupling is complete touched. The resulting dye is then salted out with potassium chloride, filtered off and dried. Hr is readily soluble in water and, in the form of the free acid, corresponds to the formula

S C), H

HO-CIL-CH ₁ -SO, <'

SO, H

Printed on cotton in the presence of alkaline agents and then thermofixed it delivers a washable and lightfast red print sample.

Dyes with similar properties are obtained. if in the previous example instead of the 1 - Amino - 7 - (/ f - hydroxyethylsulfonyl) - naphlhalin-4-sulfonic acid equivalent amounts of the naphthylamines listed in the table on the Linde of Example 1 of the formula (2) is used.

Example 3

64.6 parts by weight of the dye prepared in Example 2 are concentrated in 1 × 5 parts by weight Entered sulfuric acid and stirred until everything is dissolved. The solution obtained is in a mixture .VS of 450 parts by weight of F.is and 50 parts by weight Water stirred in, and the resulting. Window dyes are treated with potassium chloride. Fr will then filtered off, submerged in 300 parts by weight of water Addition of sodium hydrogen carbonate up to pi I 5.5

4 «dissolved, and the resulting solution is evaporated to dryness.

The dye obtained shows very good solubility in water and is suitable for printing, but especially for dyeing. So one gets from salty

• is dye liquors in the cold or in the warm with the help of alkalis on native or regenerated cellulose fibers strong red colorations from good to very good good wet conditions and good lightfastness.

The dye corresponds in the form of the free acid

so the formula

| IO, S O CII, (H, SO, Oll

N N

Example 4

HO, S

SO ₁ II

72.6 Gcwichlsleilo of the i'cmäl.t example 3 produced The dye is dissolved in 500 parts by weight of water. 7.5 weight percentages are added at 20 to 25 ° C Diethylamine was added, then about 30 Gc slowly gave way to Isleile 33 ".. sodium hydroxide solution until the pll value of 12.0 until I 2.5 is reached. and then stirred for 16 hours at 20 to 25 C. Then put ilei pll-W en do: Heaktionsgemisches by adding voi <> s about 35 (parts by weight of 20 "strength hydrochloric acid to 7.S bi H, 3. The dye slips out by salting out with sodium chloride completely. lillrierl him off. jokes him in Nalnumchloridlöstiiii '. and dry it.

The dye produced in this way corresponds to the formula

ru SO ₃ H

N-CH ₂ -CH ₂ -SO ₂ <f \

OH

It is soluble in water with a red color and is suitable excellent for printing cotton fabrics, although it has an alkaline effect in the presence

HOjS

/ \ A SO., H

Provides medium strong red prints with excellent fastness properties. The resistance is adjusted to be alkaline Printing pastes of this dye are very good.

Example 5

36.3 parts by weight of the dye prepared in Example 3 are dissolved in 350 parts by weight of water. Is slowly about 30 parts by weight added to this solution at 25 to 30 C ¹ 33% IGCR sodium hydroxide added, until it reaches the pH from 12.0 to 12.5 and is maintained. The mixture is stirred for a short time, the solution is rendered neutral by adding hydrochloric acid and the dye is isolated by salting out with sodium chloride.

In the form of the free acid, the dye obtained corresponds to the formula

SO., H

OH

It is ideally suited for dyeing and printing cotton fabric on which it is in The presence of alkaline agents is red dyeings and prints with very good washfastness and good lightfastness supplies.

Compared to that from the German patent specification

HO ₁ S SO ₁ H

9 60 534, Example 4, known dye next comparable Constitution shows the dye unites better water solubility and a better resistance wedge alkaline printing tapes and dye liquors.

Example 6

31.4 parts by weight of the vinylsulfonyl dye prepared in Example 5 are in 300 parts by weight Water entered. The solution is heated to 70 to 75 ° C. and at this temperature 23.5 parts by weight of sodium thiosilicate containing crystalline water are added. The pll-We.t is made by adding 50%

NaO ₁ SS CII, CII, SO,

which dissolves easily in water with ml of paint and / around Dyeing and printing of cellulose textiles in <«> The presence of alkaline agents can serve. The dyeings and prints obtained are wash- and lightfast.

B e i s ρ i e I 7 << s

Fine solution of 41.1 Gewiehlslcilen 2-Ληπικι-H - (/ (- pliosplialoälhylsulf'onyl) -naphthalin-d-sulfon- Acetic acid adjusted to 5.7-6.2 and 3 hours held by adding more acid.

After the reaction has ended, the dye is precipitated by adding sodium chloride (Illuminated and dried. 48 parts by weight are obtained of the saline dye of the formula

SO ₁ Well Oll

N N-

NaO ₁ S

SO, well

acid in 300 C iewichlsleilen water, which is neutralized by adding saturated sodium carbonate solution 5 n-Naliiumnitritelösiing with 20 parts by volume and then slowly in a mixture of 150 Gewielilsleilcii F sharp and 36 (iewichlsleilen 37% salt acid is stirred in so that the Tenipcralui 15 C not excess. One lüßl one Follow up for half an hour / then destroy a possibly still existing Ciberschul.i of salpelrigei Acid by adding sulfamic acid. wearing

13th

then add 64.2 parts by weight of 1-benzoylamino-8-naphthol-3,6-disulfonic acid (66%) and adjusts to pH 6 by adding about 50 parts by weight of saturated soda solution. After completing the coupling 14

ment, the dye solution obtained is evaporated Dry up.

The dye produced in this way has the following formula (in the form of its free acid):

H ₂ O ₃ PO - CH ₂ CH ₂ "SO ₂ HO Nil CO-;

Vn- Ν -'- '

HO., S

HOjS

\ ■

SO., H

It dissolves in water with a bluish-tinged red color. and results in the example described on cotton in the presence of alkaline, and result in tree-weavers Medium a strong, bluish red wool coloration and print, which is also good coloring of good lightfastness and resistance wedge to very good fastness properties excellent versus washing treatments. are.

The mono-

Naphthylamine of formula (2)

2-Amino-8 - (/ i-diethylaminoethylsulfonyl) -naphthalene-6-sulfonic acid c 2-Amino-8 - (/ Mhiosulfato-ethylsulfonyl) -naphthalene-6-sulfonic acid 2-Amino-8- (ß-chloroethyl-sulfonyl) -naphthalene-6-sulfonic acid c 2-Amino-8 - (// - acetoxy-ethylsulfonyl) -naphlhalin-6-sulfonic acid c 2-Amino-8 - (/ i-bromoethyl-sulfonyl) -naphthalene-6-sulfonic acid c 2-Amino-8- (ß-phenoxyethyl-sulfonyl) -naphthalene-6-sulfonic acid 2-Amino-8 - (// - hydroxyethylsulfonyl) -naphthalene-6-sulfonic acid c.

Met hy! Sulfonic acid ester 2-amino-8 - (/ i-hydroxyethylsulfonyl) -naphthalene-6-sulfonic acid, p-Toluenesulfonic acid ester l-Amino-5 - (/ i-sulfatoethylsulfonyl) -naphthalene-7-sulfonic acid c the same

the same

the same

the same

the same

the same

the same

Azokornponcnlc 2-Acctylamino-8-naphlhol-6-sulfonic acidc

l-naphthol-4-sulfonic acid

l-naphthol-S-sulfonic acid c

I-acetylamino-8-naphthol-3,6-disulfonic acid c

2-acelylaniino-5-naphthol-1,7-disulfonic acid c

I-Benzoylamino-8-naphthol-4,6-disulfonic acid 1- (4'-sulfophynyl) -3-methyl-5-pyrazolone

1- (4'-sulfophynyl) -3-carboxy-5-pyrazolone

3-amino-toliol

phenol

Salicylic acid

Resorcinol 3-methyl-N.N-diulhykinum

8-hydroxyquinoline

1- (2'-chloro-4 '- aminolria / ynyl - ((■>) - amino) -8-naphthol-disilphonic acid

1- (2: 4'-Dihydi oxy-tria / ynyl- (fi) -ainino) -K-naphthol-3.6-tlisuiroiisihiii;

hue

yellowish red yellowish red red

bluish red reddish orange bluish red reddish yellow

reddish yellow

reddish yellow

yellow

reddish yellow yellowish brown
orange

orange
bluish feces

bluish red

Claims (1)

Patent claims: 1. Water-soluble monoazo dyes found in Form of the free acid of the general formula (1) Λ-N- N- (SO ₂ X) ,, - IS U ₃ H) ₁₁ ,