DE1644260C - Mono- and disazo dyes that are sparingly soluble in water and processes for their production and use - Google Patents

Description

OH

IO

A-N = N

CH ₂ -CH ₂ -Y

correspond in the

A is a phenyl or naphthyl radical or the radical of an aromatic five-membered or one-membered group N-containing, optionally condensed heterocycle, the one customary in azo dyes Substituents, including phenylazo groups, may contain, and

Y denotes the cyano group or a functional derivative of the carboxyl group and the Benzene ring B contains further substituents kar.ii.

2. Process for the preparation of sparingly water-soluble mono- and disazo dyes according to Claim 1, characterized in that the diazonium compound of an amine is the formula

A-NH ₂

wherein A has the meaning given in claim 1, with a coupling component the formula

OH

CH, -CH _{2 -Y}

The present invention relates to new, sparingly water-soluble mono- and disazo dyes which can be used as disperse dyes, processes for their production and processes for dyeing fiber material from linear high-molecular esters of aromatic polycarboxylic acids with polyhydric alcohols, such as polyglycol terephthalate fibers, from cellulose esters and fibers from synthetic polyamides of the new dyes.
It has been found to be valuable in water

sparingly soluble mono- and disazo dyes are obtained if the diazonium compound of an amine is used of formula I.

A-NH ₂

with a coupling component of the formula II

OH

CH ₂ -CH ₂ -Y

couples to an azo dye of the formula III,
OH

40

(III)

CH ₉ -CH ₂ -Y

and the components of the formulas I and II are chosen so that the azo dye of the formula III neither complex-forming groups or substituents which dissociate acidic in water and make them soluble in water having.

In these formulas means

wherein Y and B have the meanings given in claim 1, coupling and thereby the Components selected so that the azo dye neither complexing groups nor in Water dissociating water-dissociating substances Has substituents.

3. The method according to claim 2, characterized by the use of a coupling component of the formula given in claim 2. in which Y denotes the cyano group and the benzene nucleus B is not further substituted.

4. Process according to Claims 2 and 3, characterized by the use of a diazo component of the formula given in claim 2, in which A is in p-position to the amino group substituted by an acylamino group Phcnylrest means.

A is a phenyl or naphthyl radical or the radical of an aromatic 5- or 6-membered N-iialtigen, optionally condensed heterocycle, including the substituents customary in azo dyes Phenylazo groups, may contain, and

Y is the cyano group or a functional derivative of the carboxyl group, where the benzene ring B may contain further substituents.

As a water-solubilizing agent which dissociates acidically in water Substituents are in particular the sulfonic acid, carboxylic acid, phosphonic acid or the disulfimide group locked out.

A preferably denotes a substituted phenyl radical. Substitutes used in accordance with the invention and customary in azo dyes are primarily electron-repelling groups: unsubstituted or

substituted normal or branched lower alkyl groups, such as the methyl, ethyl, / I-hydroxyethyl, β-hydroxypropyl, cyanoethyl or trifluoromethyl group, or the cyclohexyl, a phenyl or a benzyl group; also unsubstituted or substituted lower alkoxy groups, such as methoxy. Ethoxy, fi-hydroxyethoxy, ^ -methoxyethoxy, methoxycarbonyhnethoxy or ethoxycarbonyimethoxy group; unsubstituted or lower alkyl or halogen substituted phenoxy groups; unsubstituted or substituted aralkoxy groups, such as the benzyloxy or lower alkyl benzyloxy groups, but preferably unsubstituted lower alkanoylamino or alkenoylamino groups such as the acetylamino. Propionylamino, butyrylamino, acryloylamino or methacryloylamino group, or sub siii i'-places lower. Chlorine-. Bromine or trichloro - .. imino group or the - / - chlorine or / i-bromine

"\ laminosruppe. also the methoxycarbonyk a-, w.urbonyl- and butoxyearbonylamino group. - ''j'iem unsubstituted or halogenated sub- - '.! e benzo} - or NaphthoyliminozrupperL z; .luch lower Aikansulfonamidogruppen- as ^i: h.ir.- or Afnansulfonamidogruppe oaez-j..' ■>u'.ior.arnidogruppen furthermore Ureidognippec the AUEI. : - ".'- e: r.en Formula i \

the nitro or hydroxyl group substituted »a can. In this case! A preferably denotes one Phenylreet unsubstituted or substituted by lower alkyl and / or lower alkoxy groups, the the arylazo group in 3 or preferably in 4 positions to the amino group in formula I or to the azo group in formula IH, and is particularly fine 4-phenylazopbenyl group.

If A denotes a naphthyl radical, it can be either an unsubstituted or a substituted 1- or 2'naphthyl radical. Sub · are substituents in this case never <L ^H and alkyl re Alkoxygrupprn, further halogen, such as fluorine, chlorine or bromine, benzoylamino groups, sulfamoyl 'or carbamoyl groups of the formula V, phenoxysulfonyl' groups, AlkyUulfonyl "or Phenylwlfip» i »lower yl groups.

Does A denote the pea a ·. hViUia iiv.hcn ^ t -. ^ ri ^ .iini, fall-, -.uiritituicrten '- <Azr (> - /', taiημβη ii-h-alttjir.it Hetero / ,. ScIu * .. '>. <> har ^ kli t-. * .uh v> r all ^ rn urn ¹ Uu f ^J > rayjj! -. Thia //> l-. <>isAt> ./ j, \ - ihiznth // A- I 2.4 - ί η az / jl- or Pyndinffp. '<Λκϊ in the I

O 1

in d;
sturgeon. iT

i A> -z Ίί'Λ'ίΐζ / Αίλ'ί-.ί. '- .:

Λ '. ^! Ci uu ^ Ak'. '-. i '-. Vi'ji

N - C - N -

rjiryiti * κ \ \ sj. .. '.'. «S

"svkTi- AIi) I-. sxösr

subi ". '." _'- i ~ i

uti '.. «η, ίτ-ιπίιίπ:'» ν »-κ ι; π

ΓΤΟ "^ ¹ - 5 ¹ ^ -_JT"> iiU-

or HxogiS'.r

but r.üörr; ~.,: t. ~ A "'v ^ r>. ~ G: f

j> xL ·. wn 3; ! »Iszi-

or? ■ _: .—. 'C ^ -Srnryiir ^ T

".! Tr τ '-..- 7KTt iU« · .- vii'.r iifeofi -.Its. ·? J-gr

mroi ar: ^T o ~ rrc V

The coupling components of the formula II which can be used according to the invention are obtained, for example by reacting 1-hydroxybenzene compounds unsubstituted in the p-position with acrylonitrile, in the presence of suitable catalysts, such as aluminum chloride.

The p-cyanoethylphenols thus obtained can optionally be used converted into a functional derivative of the carboxyl group, e.g. by saponification the cyano group with 80% sulfuric acid to the corresponding carboxylic acids and esterification of the carboxylic acids with alcohols to dea corresponding Carboxylic acid esters and, if appropriate, subsequent reaction of these esters with ammonia, primary or secondary amines to the corresponding carboxamides.

Examples of coupling components are:

1 - Hy droxy-4- / i-cyanoethylbenzene;

l-hydroxy-2-chloro-, -2-bromo-, -2-methyl-,
-2-tert-butyl- or -2-meth xy-4- / i-cyano-

ethylbenzene;

> - [1-Hydroxyphenyl- (4)] - propionic acid methyl 1-,
propyl or isobutyl ester;

methyl y- [1-hydroxy-2-tert-butyl-phenyl- (4)] -propionate;

/ - [l-Hydroxy ^ -chlor-, -2-methyl- and
-2-tert-butyl-phenyl- (4)] propionic acid ether;

- / - [1-Hydroxyphenyl- (4)] - propionic acid amide

and -propionic acid-N-phenyl-, -N- (4'-chlorophenyl} -, -N- (3'-methylphenyl) -, -N-benzyl-,
-N-cyclohexyl-, -Ν, Ν-dimethyl-, -N-methyl-N-phenyl-, -N-methyl-N-acetoxyethyl- and
-N-ethy! -:! - / ^ - hydroxy- or - / f-ethoxyethylamide.

The coupling of the diizonium compound one Amüs of the formula I with the coupling component of the formula II takes place according to the usual methods, preferably in an alkaline aqueous medium. The isolation of the formed, sparingly soluble in water Dyes are made, for example, by filtration.

It is useful to grind the dyes according to the invention with surface-active dispersants to bring into a finely divided form. Anionic dispersants are suitable for this, for example Alkylarylsulfonates, alkali salts of the condensation products of formaldehyde with naphthalenesulfonic acids, Lignosulfonates or non-ionic, such as fatty alcohol or higher alkylphenol polyglycol ethers. The grinding of dyes according to the invention with such dispersants is preferably carried out with the addition of water in the presence of grinding media, such as. 3. Glass beads. The one with it resulting aqueous dye pastes which contain the dyes in finely divided form either used directly for dyeing or by gentle drying according to known methods be processed into non-dusting powder.

In such preparations, the dyes according to the invention are more suitable for dyeing fiber material from aqueous dispersion, for example for dyeing cellulose acetate fibers such as Ccllulose-2 '/ ₂ -acetat- and cellulose triacetate fibers, but especially for dyeing textile fibers made from linear high molecular weight esters of aromatic polycarboxylic acids polyfunctional alcohols, for example from polyglycol terephthalate, polyglycol isophthalal or

35 poly (1,4-cyclohexanedimethylol terephthalate) fibers. But they can also be used to dye synthetic polyamide fibers such as nylon.

The dyeing of polyglycol terephthalate fibers with aqueous dispersions of dyes according to the invention is preferably carried out at temperatures above 100 ^° C. under pressure. But the coloring can also at the boiling point of the dye liquor in the presence of swelling agents, so-called "carriers," for example Alkaliphenylphenolaten, such as sodium o-phenylphenolate, Polychlorbenzolverbindungen or similar means may be performed, or after the pad process followed by heat setting at 180 to 220 ⁰ C. be made.

The dyes of the invention have a good affinity for Polyglykolterephthalat- and Cellulosetriacetatfasem and yield on these fibers g'eichmäßige, strongly colored, grünstichiggelbe, yellow and orange colorations, c ^': good wash, milling, sublimation, light, frictional, are sweat, solvent, dye, decatur, gas fading and exhaust gas resistant. They also reserve vegetable and animal fibers, especially cotton and wool, very well. You get with the new dyes on tightly twisted fabric or hard-twisted yarns, z. B. in the form of packages, good and even dyeing.

The dyes according to the invention are distinguished from known dyes of similar constitution of the formula III primarily due to an improved fastness to sublimation. Experience shows, that an improvement in the fastness to sublimation usually leads to a deterioration in the ability to draw and build up connected is. Surprisingly, however, remains with the new dyes the draw and Build-up capacity is retained or even improved in some cases despite very good sublimation fastness. Thanks to the extremely good fastness to sublimation and the high affinity for polyglycol terephthalate fibers the new dyes are very suitable for the so-called thermosol dyeing process. the In this application, too, dyes produce uniform greenish yellow, yellow and orange, which are fast to rubbing Colorations. The fluctuations in the fixing temperature that are usual in practice are minor Influence on color tone and depth of color of the colorations. Also are those made with the new dyes In many cases, dyeings are better lightfast.

Compared to the German Auslegeschrift 1,061,924 and the Belgian patent 632 992 known dyes, the dyes according to the invention show better drawability on polyester fibers, better lightfastness, better wool reserve and better fastness to sublimation.

The dyes according to the invention are also suitable for dyeing cellulose acetates and polyglycol terephthalates and polyamides in bulk. Thanks to their good solubility in organic Solvents, such as in acetone or chloroform, can also be used in paints and printing inks.

The following examples illustrate the invention. In which the temperatures are in degrees Celsius specified.

example 1

21.2 g of l-amino-4-benzoylamino-benzene are in a mixture of 550 ml of water and 35 ml of concentrated hydrochloric acid (36.5%) and finely dispersed

r H η e

by pouring in a solution of 6.9 g of sodium nitrile in 70 ml of water at 0 to 5 diazoticrt. the The diazonium salt solution obtained is added dropwise at 0 to 5 "to a solution of 14.7 g of l-hydroxy-4- / i-eyanethylbenzene in 450 ml of water and 20 ml of 30% aqueous sodium hydroxide solution. After finished Coupling, the separated yellow precipitate is filtered off and washed neutral with water and dried in vacuo at 70 to 75 '. The dye represents a yellow powder and corresponds to

formula

OH

CO-HN

N = N

No.

4th
5
6th
7th
8th
9
10

11
12th
13th
14th

1-amino-4- (4'-chlorobenzoyl-

amino) benzene
l-amino-4- (2'.5'-dichloro-

benzoylamino) -ber.zol
1-amino-4- (4'-methylbenzoyl-

amino) benzene
l-amino-3-benzoylamino-

benzene
I -amino-S-chloM-benzoyl-

amino-benzene
1 -amino-4-benzenesulfone-

amido-benzene
I-amino-4- (4'-methy] phenyl-

sulfamoyl) benzene

I -amino-3-methoxy-

4-benzoylamino-benzene I -amino-4-benzoylamino-

naphthalene

l-Amino-4-cyclohexyl-benzoI l-Amino-4-phenyI-benzene l-Amino-4-benzyl-benzene
1-amino ^ / i-hydroxyethoxybenzene

Shade on poly

glycol cphthalate

fiber

Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow

Yellow yellow yellow yellow

CH ₂ -CH ₂ CN

After grinding with the sodium salt of a condensation product of naphthalene-2-sulfonic acid and formaldehyde stains the dye thus obtained aqueous dispersion of polyglycol tercphthalate fibers, optionally in the presence of a swelling agent, like the sodium salt of o-phenylphenol, with extensive exhaustion of the dyebath in pure yellow tones. The colors are very washable, sublimation and lightfast.

If, in the above example, instead of the 21.2 g of l-amino-4-benzoylamino-benzene, the equimolar amount of one of the diazo components given in column 2 of Table I is used and the rest of the procedure is as given in the example, dyes are obtained which on polyglycol terephthalate fibers give colorations of similarly good properties and their color tones are given in column 3

are.

Table I.

15th

16
17th
18th

19th 20th

21
22nd
23
24
25th
26th
27
28
29
30th
31

40 1 -amino-4- (methoxyethoxy) -

benzene

I-amino-4-ethyl-benzene
1-amino-4-isopropyl-benzene 1-amino-4 - (/ f-cyanoethyl) -

benzene

I-amino-4-bcnzyloxy-bcnzol 1-amino-4- (4'-methylbenzyl-

oxy) benzene

1-amino-4-acryloylamino-

bcnzol
1 -amino-4-methacryloy I-

amino-benzene
1-amino-4- (bromoacctyl-

amino) benzene
1-amino-4- (fluoroacetyl-

amino) benzene
1-amino-4- (3-chloropropionyl-

amino) -bcnzene
1 -amino ^ -chloM-bcnzoyl-

amino-bcnzol
l-amino-4- (4'-methoxy-

benzoylaminoj-bcnzol
l-amino-4-methoxycarbonyl-

benzene
1-amino-4-methanesulfone-

amido-benzene
l-amino-4-ethanesulfone

amido-benzene
I-amino-4- (4'-methylbenzene-

sulfonamido) benzene

Example 32

Shade on poly

glycol tercphthalate

lascrn

yellow

Yellow yellow yellow

Yellow yellow

Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow

15 g of l-amino-4-acetylamino-benzene are in a mixture of 320 ml of water and 35 ml of concentrated hydrochloric acid (36.5%) and finely dispersed by adding dropwise a solution of 6.9 g of sodium nitrite in 110 ml of water at a temperature of diazotized up to 3 °. The diazonium salt solution drips one at 0 to 5 'to a solution of 14.7 g of 1-hydroxy-4 - ^ - cyanoethyl-benzene in 400 ml of water and 20 ml of 30% aqueous sodium hydroxide solution. After the coupling has ended, the precipitated becomes yellow Filtered off precipitate. washed neutral with water and dried in vacuo at 70 to 75 ". The dye represents a yellow powder and corresponds to the formula

CH ₃ CO-HN

N = N

CH ₂ -CH ₇ -CN

With the sodium salt of a Kona? Nsation product of naphthalene-2-sulfonic acid and formaldehyde « grind, the preparation of the aqueous dispersion colors

10

sion fibers made of polyglycol tercphthalal, optionally in the presence of yuellmittcln. like the sodium salt of o-phenylphenol. in pure yellow tones. The colors are very easy to wash, sublimicr and lightfast.

In the example above, the 15 g I -Ami ~ o-4-acctylamino-benzene by the corresponding Amount of one of the following in column 2

Table II

Table II indicated diazo component !! and unites them under the bcschricbenci in the above example Conditions with one of the coupling components given in column 3, get times Dyes which are colored on polyglycol tercphthalate fibers of similar good properties and the hues of which are given in the last column of Table II.

No. Diazo component Coupling component Color at
tcrcphll 33 l-amino-4-propionylamino-benzene l-Hydroxy ^ -Zf-cyanathyl-bcnzol yellow 34 ! -Amino-4-butyrylamino-benzene the same yellow 35 l-amino-4-chloroacetylamino-benzene l-Hydroxy-Z-methyl ^ -Zi-cyanoethyl-
bcnzol yellow 36 l-amino-4-trichloroacctylamino-benzene the same yellow 37 N-BenzyI-N '- (4-aminophenyl) -
brain matter the same yellow 38 ILClI llolWll
N-methyl-N '- (4-aminophenyl) - the same yellow urinary stolT 39 N.N-Dimethyl-N '- (4-aminophenyl) - ; <- [l-Hydroxy-2-methylphenyl- (4)] - yellow urea propionic acid ethyl ester 40 N-Ethyl-N-Zf-hydroxyathyl- the same yellow N '- (4-aminophynyl) urea 41 N - / - methoxypropy! -N '- (4-amino- the same yellow phenylj-urea 42 N-phenyl-N '- (4-aminophenyi) - desgi. yellow urea 43 N-methyl-N-phenyl-N '- (4-amino- j- [l-Hydroxy-2-chlorophenyl- (4)] - yellow phenylj-urea ethyl propionate 44 N-phenyl-N'-methyl-N '- (4-amino- the same. ■ yellow phcnyl) urea 45 N-methyl-N- (4 "-methylphenyl) - the same yellow N '- (4-aminophenyl) urea 46 N-Cyclohexyl-N '- (4-aminophenyl) - ■ - [1-Hydroxy-2-chlorophynyl- (4)] - yellow urea ethyl propionate 47 I-amino-4-methylsulfamoyl-benzene the same yellow 48 I-amino-4-phenylsulfamoyl-benzene the same yellow 49 aniline I-Hydroxy ^ -chlor - ^ / f-cyano-ethyl-
benzene yellow 50 1-amino-4-methyl-benzene desgi. yellow 51 1-amino-4-methoxy-benzene the same yellow 52 1-amino-4-ethoxy-benzene the same yellow 53 1-Amino-4 - (/ f-hydroxyethyl) benzene the same yellow 54 4-aminophenoxy-acetic acid met ^ yl- l-hydroxy-2-methoxy-4- / ί-cyanoethyl yellow ester benzene 55 l-amino-4-phenoxy-benzene the same yellow 56 1-amino-4- (4'-chlorophenoxy) benzene the same yellow 57 1-amino-4- (2'-methyiphenoxy) benzene the same yellow 58 2-amino-5-methyl-sulfamic acid
nanhthalin l-hydroxy-4- / i-cyanoethyl benzene yellow 59 1 ICjI LJII LIlUlJI I
1 -amino-S-methoxy ^ acetylamino- dejgl. yellow benzene 60 1-amino-4-bromobenzene the same yellow 61 1-amino-2,4-dibromobenzene the same yellow 62 I-amino-4-fluorobenzoI 1-hydroxy-4 - ^ - cyanoethyl-benzene yellow 63 1-amino-4-cyano-benzene the same GeIo 64 ■ l-amino ^ -chlor ^ -benzoylamino- the same yellow benzene

Example 65
Line suspension of 13.8 g of l-amino-4-nilro-benzoi

12th

in 150 ml of water and 30 ml of concentrated hydrochloric acid (36%) is added by adding a solution of 6.9 g of sodium nitrite in 50 ml of water in the usual Way at 0 to 5 dia / .otieit. The diazonium salt

O, N

solution is left with stirring at 5 to 10 to one Solution of 14.7 g of l-hydroxy-4 - ^ - cyanoethyl-benzene flow in 450 ml of water and 20 ml of 30% strength aqueous sodium hydroxide solution. After the coupling is complete is the precipitated yellow-orange precipitate, its composition of the formula

CH ₂ -CH ₂ -CN, filtered off, washed neutral with plenty of water and dried in vacuo at 60 to 70 °.

After grinding with the sodium salt of a The dye obtained in this way dyes lignosulfonate from an aqueous dispersion of polyglyco-kerephthalate fiber, optionally in the presence of a source. like trichlorobenzene, with extensive exhaustion of the Dyebath in yellow-orange shades. The coloring are easy to wash and sublime.

Dyes with similar properties are obtained if, instead of the 13.8 g of I-amino

4-nitro-benzene is the equimolarc amount of one of the in the following Table III, column 1, indicated diazo components among those in this example specified conditions with the equimolar amount of one of those listed in column 3 Coupling components couple. In column 4 are the hues of the mis these dyes on fibers colorations obtained from polyglycol phthalate are given.

Diazo component Table III Hue on polyglycol
icrcprithalaifascrTi No. I-amino-3-nitro-benzene Coupling component Yellow orange 66 l-Hydroxy ^ -tcrt.-butyM - ^ - cyanoethyl- 1-amino-2-nitro-benzene benzene Yellow orange 67 I-amino-4-trifluoromethyl-benzene the same Gclorange 68 I-amino-4-acetyl-benzene the same Yellow orange 69 1-amino-4-benzpyl-benzene the same GfcrOrange 70 1-Amino-4-methyl-sulfonyl-benzene the same Yellow orange c 71 1-Amino-4-phenylsulfonyl-benzene the same Yellow orange 72 l-amino-4-phenoxysulfonyl-benzene the same Yellow orange 73 1-amino-4-methoxycarbon. 1-benzene l-Hydroxy ^ - ^ - cyanoethyl-benzene Yellow orange 74 1-amino-4-ethoxycarbonyl-benzene the same Yellow orange 75 } '- [l-Hydroxy-2-tert.-buty! -phenyl- (4)] - 1-amino-4-phenoxycarbonyl-benzene methyl propionate Yellow orange 76 1-amino-4-dimethylsulfamoyl-benzene the same Yellow red 77 I-amino-4-methylsulfamoyl-benzene the same Yellow orange 73 γ-Ι I -hydroxy-2-tert-butyl-phenyl- (4)] - 1-Amino-4-diethyl sulfamoyl benzene ethyl propionate yellow 79 1-amino-4- (N-ethyl-N-fi-hydroxy- the same yellow 80 ethylsulfamoyl) benzene dusgl. I-Ammo-4- (y-methoxypropyl- yellow 81 su llamoylj-benzene the same 1-Amino-4-phenylsulfamoyl-benzene yellow 82 I-amino-4- (N-methyI-N-phenyl- l-Hydroxy ^ / i-cyanoethyl-benzene yellow 83 sulfamoyl benzene the same l-amino-4-cyclohexylsulfamoyl- yellow 84 benzene the same 1-amino-4-methylcarbamoyl-benzene yellow 85 1 -amino ^ -dimethylcarbamoyl-
benzene the same yellow 86 l-Amino ^ -diethylcarbairoyl-benzene 1 -hydroxy- 2-bromo-4- / i-cyanoethyl-
benzene yellow 87 the same

continuation

N :. Diazo component Coupling component Color ion on polyglycol
tcrcphthalate fiber 88 l-amino-4- (N-ethyl-N- / mydroxy- l-Hydroxy-2-bromo-4- / i-cyanoethy! - yellow ethylcarbamoyl) benzene bcnzol 39 1-amino-4- (j'-methoxypropyl- the same yellow carbamoyl) benzene 90 1-amino-4-n-butylcarbamoyl-benzene 1-hydroxy-2-chloro-4- / i-cyanoethyl
benzene yellow 91 1-amino-4-ph; nylcarbamoyl-benzene the same yellow 92 ! -Amino-4- (N-methyl-N-phcny 1- the same yellow carbamoyl) benzene 93 1 -Amino-4-cyclohexylcarbamoy 1- the same GcIb bcnzol 94 I -Ainino-4-benzoylamino-benzene y- [I -hydroxyphcnyl- (4)] -propion- GcIb acid N- (4'-chlorophynyl) amide 95 the same ) - [l-hydroxyphenyl- (4)] - propion- yellow acid N- (3'-methylphenyl) amide 96 the same ) - [l-hydroxyphenyl- (4)] - propion- yellow acid-N-benzylamide - 97 the same y- [l-hydroxyphenyl- (4)] -propion- GcIb acid-N-cyclohexylamide 98 the same y- [l-hydroxyphenyl- (4)] -propion- yellow Acid-N-ethyl-N - /? - ethoxyethylamide 99 the same ) '- [l-hydroxyphenyl- (4)] - propion- yellow acid propyl ester IIX ") desgi. / - [! - hydroxyphenyl (4)] propiors yellow acid isobutyl ester 101 ! -Amino-4-benzoylamino-benzene y- [l-hydroxyphenyl- (4)] -propion- yellow acidic-N-methyl-N-aceloxyethyl-
amide 102 1-Amino-4-butylsuironyl-benzene l-hydroxy ^ / f-cyanoethyl-benzene yellow 103 1 -Amino-4- {4'-ch loφhcnoxysu I fön y 1) - the same yellow benzene 104 1-Amino-3-butoxysulfonyl-benzene the same yellow 105 1-amino-4- (4'-methylphenoxy- the same yellow carbonyl) benzene 106 1-amine-isopropoxycarbonyl- the same yellow bcnzol 107 1-amino- ^ n-butoxycarbonyl-benzene the same yellow

Example 1 (λ;

A fine suspension of 19.7 g of 4-amino-l, l'azobenzoi in 700 ml of water and 30 ml of 36% hydrochloric acid is added by pouring in a solution of 6.9 g Sodium nitrite in 50 ml of water at 10 to 15 ° in the usual way

l-Hydroxy-l-methyW-Zi-cyaniithyl-benzene in 400 ml Water and 20 ml of 30% aqueous sodium hydride solution. To terminate the coupling, the reaction mixture is kept at 5 to ίθ ° for 10 hours

Way diazotized. The clarified diazonium salt solution ₅₅ stirred. The precipitated dye formed is added dropwise at 0 ° to 5 ° to a solution of 16.1 g of formula

OH

is filtered off, washed with water and dried in vacuo at 60 to 65 °. The dye sets egg-orange powder. 5 g of the

CH ₂ -CH ₂ -CN

The dyestuff retained are converted into a finely dispersible form by grinding with 12 g of lignosulfonate brought. This dye preparation is used to dye in

ι i

aqueous dispersion fibers made of polyglycol terephthalate, optionally in the presence of a swelling agent, like sodium o-phenylphenolate, in pure yellow-orange Shades. The bulges are rubbing, sublii.iier- and lightfast.

If, in the above example, the equimolar amount is used instead of the 19.7 g of 4-amino-l, l'-azo-benzene one of the in column 2 of Table IV below

specified diazo components and combined them under the conditions specified in the above example with one of those specified in column 3 Coupling components, this gives dyes that dye on polyglycol terephthalate fibers result in similar good properties and the color shades of which are given in the last column of the table.

Table IV

Diazo component Coupling component Hue on polyglycol
terephthalate fibers 109 4 Amino-1'-chloro-1,1'-azo-benzene 1-Hydroxy- ^ / i-cyanoethyl-benzene Yellow orange HO 4-amino-3'-chloro-1,1'-azo-benzene the same Yellow orange 111 4-Amino-2'.4'-dichloro-1.l'-azo-benzene the same Yellow orange 112 4-Amino-4'-methoxy-1.1'-azo-benzene ; - [l-Hydro.xyphenyl- (4)] - propion- Yellow orange acid methyl ester 113 4-Amino-3'-nitro-1.1'-azo-beiizole the same Yellow orange 114 4-amino-4'-nitro-1.1'-azo-benzene the same Yellow orange 115 4-amino-2-methyl-1,1'-azo-benzene the same Yellow orange 116 4-amino-2.2'-dimethyl-1.1'-azo-benzene ; .- [l-hydroxyphenyl- (4)] -propion- Yellow orange ethyl acid ester 117 4-amino-4'-methylsulfonyl-1.1'-azo the same Yellow orange benzene 118 4-Amino-2-methyl-4'-nitro- 1 .1 '-azo- the same Yellow orange benzene ■ "* ■ 119 4-amino-2,5-dimethoxy-4'-nitro the same Yellow orange 1,1'-azo-benzene 120 4-amino-2-methyl-5-methoxy- the same Yellow orange 4'-nitro-1,1'-azo-benzene 121 4-amino-2,5-dimethyl-4'-nitro y- [l-hydroxyphenyl- (4)] -propion- Yellow orange l, l'-azo-benzene acid amide 122 4-amino-4'-nitro-2'-chloro-1.1'-azo ■ / - [1 -hydroxyphenyl- (4)] -propion- Yellow orange benzene acid amide 123 4-amino-4'-hydroxy-1,1'-azo-benzene the same Yellow orange 124 4-amino-4'-hydroxy-1,1'-azo-benzene } '- [l-hydroxyphenyl- (4)] - propion-
<5iiiirf * H impth vlamiH Yellow orange 125 4-amino-2'-hydroxy-5'-methyl- - / - [1-hydroxyphenyl- (4)] - propion- Yellow orange 1,1'-azo-benzene acid-N-ethyl-N-, 9-hydroxyethyl- amide 126 4-amino-2-methyl-5-methoxy- ;> - [1-hydroxyphenyl- (4)] - propion- Yellow orange 4 - (/ i-hydroxyethoxy) -1,1'-azo acid phenylamide benzene 127 4-amino-2-methyl-5-methoxy- > - [1 -hydroxyphenyl- (4)] - propion- Yellow orange 4'-hydroxy-1,1'-azo-benzene acid-N-methyl-N-phenylamide 128 4-amino-4'-bromo-1,1'-azo-benzene 1-Hydroxy ^ - ^ - cyanoethyl-benzene Yellow orange 129 4-amino-4'-nuoro-1,1'-azo-benzene the same Yellow orange 130 4-Amino-4'-isobutene vl-1.1'-azo-benzene the same Yellow orange

example

Finally, 18 g of 2-amino-6-methoxy-benzothiazole are washed with water. The 100 g of concentrated sulfuric acid formed are dissolved and diazolized at 5 'with the amount of nitrosyl sulfuric acid corresponding to 6.9 g of sodium nitrite for 3 hours. The resulting diazonium salt solution is added dropwise to a solution of 14.7 g of 1-hydroxy-4 -, - cyanathylbenzene in 100 ml of glacial acetic acid in the course of 1 hour, with good cooling. By adding in portions

Dyestuff is dried at 60 to 70 °. It is a yellow-brown powder that corresponds to the formula

OH

S-

C-N = N

of crystalline sodium acetate, the reaction solution is blunted to a pH of 4 to 4.5 away. The resulting orange precipitate is filtered off. neutral with dilute soda solution and

Corresponds to CH ₂ -CH _{2 -CN.} 5 g of the dye thus obtained

brought into a finely dispersible form by grinding with 15 g of a lignosulfonate Dyeing apparatus is obtained from an aqueous dispersion, optionally in the presence of a swelling agent such as of the sodium salt of o-phenylphenol, polyglycol teruphthalate fibers dyed in clear, yellow-brown shades. The dyeings have good lightfastness and sublimation fastness.

Dyes with similarly good properties are obtained if the equimolar amount of one of the in column 2 of the following Table V listed diazo components with corresponding amounts of one of the coupling components specified in Column. 3 in compliance with the above example The specified conditions couple the color shades of the colorations achieved with the dyes obtained on polyglycol terephthalate fibers are indicated in the last column of the table.

Table V

Diazo component Coupling component Hue on polyglycol No. 2-aminothiazole I-hydroxy-4 - ^ - cyanoethyI-benzene terephthalate fibers 132 2-aminobenzothiazoI the same Yellow down 133 5-amino-1,2,4-triazole the same Yellow-brown 134 2-amino-1,3,4-thiadiazole the same Yellow-brown 135 3-amino pyridine the same Yellow-brown 136 3-amino-indazole 1 -hydroxy- 2-methyl-4 - ^ - cyanoethyl- Yellow-brown 137 benzene Yellow-brown 4-amino-quinoline the same 138 1-phenyl-3-methyl-5-aminopyrazole the same Yellow / aun 139 2-amino-5-nitrothiazole the same Yellow-brown 140 4-amino-benzotriazole the same Yellow-brown Ml 2-amino-6-chloro-benzoi.hiazole the same Yellow-brown 142 2-amino-6-methyl-benzothiazole l-Hydroxy ^ -tert.-butyM - ^ - cyano- Yellow-brown 143 ethyl benzene Yellow-brown 2-amino-6-acetyl] amino-benzothiazole the same 144 2-amino-6-methylsulfonyl-benzo- l-Hydroxy-2-tert.-butyl-4 - ^ - cyano- Yellow-brown 145 thiazole ethyl benzene Yellow-brown 1-methyl-3-amino-1,2,4-triazole 1-hydroxy ^ -cyanoethyl-benzene 146 2-amino-1,3,4-oxadiazole the same yellow 147 2-amino-6-bromo-benzothiazole the same yellow 148 2-Amino-4-methylthiazoI the same yellow 149 2-amino-4-phenylthiazole the same yellow 150 2-amino-5-chloropyridine the same yellow 15! 1-phenyl-3-carbamoyl-5-aminopyrazole the same yellow 152 l- (3'-chlorophenyl) -3-methyl-5-amino- the same yellow 153 pyrazole yellow 2-amino-4-methylquinoline the same 154 2-amino-4-chloroquinoline the same yellow 155 2-amino-4-bromoquinoline the same yellow 156 Ge! B

Example 157

In a printing dyeing machine, 2 g of the dye obtained according to Example 33 are dissolved in 2000 g of water, which contains 4 g of oleyl polyglycol ether, finely suspended. The pH of the dyebath is adjusted with acetic acid set to 5 to 5.5.

100 g of polyglycol terephthalate fabric are now used at 50 °, heats the bath to 140 ° within 30 minutes and colors it for 50 minutes Temperature. The dye is then rinsed with water, soaped and dried. You get if these conditions are observed, a wash, perspiration, light and sublimation fast, pure yellow coloration.

The dyes described in the other examples This process results in colorations of equal quality.

Example 158

2 g of the dye obtained according to Example 5 are dispersed in 4000 g of water. About this dispersion 12 g of sodium o-phenylphenolate are added as the swelling agent and 12 g of diammonium phosphate and dyed 100 g of polyglycol terephthalate yarn for 1 hour and a half long at 95 to 98 °. The dye is rinsed and washed with dilute sodium hydroxide solution and a dispersant post-treated.

This gives a wash-, light- and sublimation-fast, pure yellow coloration.

In the example above, if the 100 g polyglycol terephthalate yarn is replaced through 100 g cellulose triacetate fabric, dyed under the specified conditions and then rinsed with water, the result is a yellow, very washable and sublime-fast dye.

example

Polyglycol terephthalate fabric is made on a padder at 40 ° with a liquor of the following composition impregnated:

20 parts by weight of the according to Example 34

obtained dye finely dispersed in 7.5 parts by weight of sodium alginate, 20 parts by weight of triethanolamine, 20 parts by weight of octylphenol polyglycol ether and
Parts by weight of water.

The fabric, which has been squeezed off to a content of about 100% impregnation liquor, is dried at 100 ° and the dye is then fixed for 30 seconds at a temperature of 210 °. the Dyed goods are rinsed with water, soaped and dried. These are obtained under these conditions a wash, rub, light and sublimated yellow coloration.

The dyes described in the other examples give colorations by this process equal quality

Claims (1)

Patent claims: 1. Mono- and disazo dyes used by complexing groups and by in Waiser acidic dissociating, water-solubilizing substituents are free and of the formula 5. Process for dyeing fiber material based on polyesters, cellulose acetate or synthetic polyamides, characterized by the use of the dyes according to claim 1.