DE2347849A1 - NEW POLYAZO DYES AND METHODS FOR THEIR PRODUCTION - Google Patents

Description

New polyazo and procedures for their Settin g Herste. ·

The present invention relates to new polyazo dyes and processes for their manufacture; it relates in particular to dyes, which are fibrous materials made from cotton, Silk, wool and similar fibers with hydroxyl and / or amide groups can stain, and processes for their manufacture.

Polyazo dyes, usually made from benzidine or its derivatives are known as dyes for "fibrous materials made from fibers with hydroxyl and / or amide groups. These dyes are excellent in color, coloring power, solubility in water and chemical resistance. Farther they ensure excellent dyeing property for silk, etc. Because of these advantages, the polyazo dyes has long been used for many different purposes. Recent research - however, has shown that benzidine and its derivatives medically attack the human body. It has actually revealed that these compounds were introduced upon introduction

4 09813/1110

May cause cancer, especially bladder cancer, in the body can. For this reason, it is extremely desirable to create dyes without any risk of causing cancer, which serve as a substitute for the benzidine type polyazo dyes can and the usual polyazo dyes with regard to dyeing power and are equivalent or superior to the other properties mentioned above. "" "" ""

The aim of the present invention is therefore to create new valuable dyes that meet the above requirements, as well as the creation of l / experienced to their manufacture.

The new polyazo dyes according to the invention are by the the following formula shown?

(I)

in which A stands for an optionally substituted aromatic ring, B for an aromatic ring with at least one Substituents from the group of amino, substituted amino and hydroxyl groups; X. For.

stands, where Q is SO ₉ or a heterocyclic ^ optionally substituted ring in the form of a 5- or 6-membered ring with at least one substituent of N, O and S as a heterocyclic atom; Y stands for a hydrogen atom, an alkali metal, the group -NH. or is an amine salt residue; η has a value of 1 or 2

1 2
Has; and R and R each represent a hydroxyl or amino group

409813/1 1 10

1 2

stand, where R stands for an amino group when R is a HydroxyL-

2 means group, or represents a hydroxyl group when R is a

Is amino group.

The novel compounds of the formula (i) according to the invention result excellent colorations and are in terms of coloring ability, solubility and water and chemical resistance almost as excellent uiie the usual polyazo dyes of the benzidine type, however, they have no carcinogenic properties and only extremely low toxicity.

Preferred polyazo dyes of the above formula (I) according to the invention are those in which A represents a phenyl group, naphthyl group or phenyl or naphthyl group with at least one substituent from the group consisting of halogen, lower alkyl, lower alkoxy, amino-carboxy, nitro and sulfonic acid groups; those in which

■ .- ■ · ■■ "ty B for. '. "■ · ■ ·. ·

is, lüobei m / denotes -NH ₂ , -NCR) or OH, uiobei R denotes lower alkyl, phenyl or alkylphenyl and M ¹ denotes hydrogen, a sulfonic acid group or lower alkyl; those in which R ^{1 is} a hydroxyl group, R is an amino group and Y. is hydrogen or sodium and η has a value of 1 or 2; those in which X is for

stands, where Q stands for-SO ₉ -,

'S. N . 0 '. S ■ JSC Η "- .H

A0981 3/1110

R is a hydrogen atom, an alkyl, aryl or U / -hydroxyalkyl group means. Such novel polyazo dyes according to the invention of the above formula (i), in which

A for

ι, -Q , hQ-no ₂ , - £> so ₃ h

stands ; those in which B for

NH,

-NH,

₄ -Q-HH ₂ V -Q-OH, -

CH

or

CH,

SO _x H

NH

-NH ₂ ,

NH

-SO, H or 5

HO

SO ₅ H

stands} those in which X stands for

or

stands, where Q -S0 _? or

Ν — Ν

■ n \ i

odsr

N-N

NO-

409813/1110

means, and FU has the above meaning.

The following table 1 gives typical examples of the invention new polyazo dyes of the formula (i). These connections

12th

are exemplified by A, R, R, Y, n, X and B in the following Formula,

shown.

A09813 / 1 110

No.
1

R ^2- T

ΟΗ NH ₂ - Na

-Χ

¹ ^ B

r-HH,

colour

bluish black

M It greenish black

HO, S
5

η η

it tt

ti · tt

bluish black

"6

dd dd

-Q-OH

bluish green

No.

AR ¹ R ² Y

-X-

colour

OH NH

^9rUn

' 8th

10

SO ₂ Na

NH,

NH

OH

SO ₂ H

bluish
black

bluish
green

11 · HO ₅ S

1 »It

NH,

CO

OQ

approx

No.

Rl

-X-

colour

12th

O-"

OH NH ₂ ■ Na

,-so.

-NH,

reddish black

O ₂ N-

tt ti reddish black

NaO _x S-

dd Tt

dd dd

-NH,

CH.

bluish black

green

16

tt rt

NH,

bluish green

dd dd

black

-3

approx

No. A. .E ¹ R ² T -X- B '- color

18 O ^ S-4 V OH NH ₀ Na

O ■ i

to «

■ χ. ... N — N

Il 20 ^ ~ V ""

-21 OpN- ^ V """ ⁽ ^ ~ \ -"

HgN _s Ί
OH ₅ black I. -OH VO
t V bluish
green NHh CH ₅ , purple
black

OO

LQ

No.

22nd (25

P. 24

Q-

H ¹ "Έ ²

OH

11 It

Il Π

Ν — π

H ₂ N

colour

bluish black

green

25th

26th

HO _x S 7

11 ti

NH ₂ , OH Na

■ H

OH

S0, well

bluish black

No;

-X-

colour

27

28

O CD OO

29

Ν — Ν

Il Il

so

NaO, S.

■ Ρ:

ΝΗ ·

OH

OH,

NH,

SO ₃ Na

blue

bluish schujarz

schujarz

•O-

H ₂ N

NH ₂

No.

R ¹ R ² '"" Y

OH

-Ύ—

NH,

CH,

colour

black

32 Η0.8- / Λ-33

t »tl

-Q-OH

NH,

green

greenish black

ί! II

ti Il

■ oi

OH

-b- ^ 2

green

black

No,

. E.

B Farba

36

NH ₂ OH Na

N-N

V /

N = N

greenish
black

NHhQ

CH.

38

NH,

-OH

SO ₃ Na

NH,

SO-, well

black

39 greenish
black

No

-X-

colour

40

CD CO OO

Q-

OH

N / A

Ν — Ν '

-CXJO

CVJ

N-N

y ¹

NH

green

reddish schuiarz

42

N-N

CH

N-N

greenish black

" green

CH ₂ CH ₂ OH

Ύ-

—X—

colour

HH ₂ OH

It ι

■ CH _r

SO ^ Well

green

bluish
black

₂ N ₁

black

No,

-X-

colour

52

O-

NH "OH

It tt

dd dd

N / A

■ Ν — Ν

-Q ^ l

n /

N-N

H
—N

Ν — Ν

H ₂ N

Y _n

CH

bluish black

reddish green

bluish green

green

No. AR ¹ R ² T -X- '- ' -B color

co cc ξ ^ λ. 'ti it ti

55 ί \

58 Q-

11 dd

It It

⁵⁷ * -r, 1 = ^

NN ■ - H ₂ N

53 O ₉ N - / "V OH NHp Na. / ~ V \ € \ J / ^ im black

"Greenish

schu / arz

purple
schu / arz I. —Λ
. -J greenish
schu / arz 1 bluish
black ti 2347849

No.

59

AR ¹ 'R ² Y

£ 3 «OH. 'NH ₂ Na

-X-

N-N

colour

greenish protection

60

to 61

62

OH

N-N

CH-

N-N ίί

NH J '

N-N

CH.

purple black

bluish

green

CO

- <] OO

CO

No.

-X-

B '

colour

O CD CO

64

67

O ₂ HQ-

ο-

OH NH,

Na -Ql

! t »t

τι ti

ti tJ

Ν — Ν

H N-N

H ₃ N
• η / V

ν /

SO ₃ H

A-E

reddish schu / arz

bluish black

greenish black

68

-QH green

69

H ₂ N. bluish
black 234 -CH ₃ ¹ OO CQ

R ¹ E ² I.

—Χ— ■

B '

colour

Oh

Ν — Ν

b '

bluish black

Il tt

π ti

ti ti

Ν — Ν

CH.

bluish green

greenish black

ti ti

tt η NaO, S

7> -0H

SO ₅ Well

bluish black

23478Ag

The novel polyazo dyes of the formula (i) according to the invention contain neither benzidine nor SBine derivatives as basic components and are therefore not carcinogenic and of extremely low toxicity.

The fact that the aromatic starting _{diamines of the formula H 9} NX-NH ₉ (where X has the above meaning) do not have any carcinogenic properties can be seen from the following test.

Carcinogenic properties

4,4'-Diaminodiphenylsulfone was administered orally to 40-day old female rats once every three days. After 9 months of continuous administration, the animals were sacrificed. The internal organs were weighed and made into tissue samples for determination of ancerogenic properties. No carcinomas were found found at a dose 25 times the amount of benzidine, at which 50 % carcinomas were found.

The new polyazo dyes are as good as the usual ones, ■ dyes usually made from benzidine or its derivatives with regard to coloring power and chemical resistance and the known dyes in the achievement of excellent colors almost equivalent. The new dyes according to the invention are readily soluble in water and dye fibrous materials from hydroxyl and / or amide-containing fibers in an effective manner. The dyeings obtained not only show excellent, colors equivalent to the usual benzidine type polyazo dyes, but they also have good fastness to one another Light, washing, acids and alkalis.

409 8.1 3/1 1 1 0

The novel polyazo dyes according to the invention can be used according to the various processes shown below:

-V experience 1 / · ,,.,. \

; (any)

A tetrazotized product is used in the desired / sequence an aromatic diamine of the following formula:

H ₂ NX-NH ₂ (II)

in which X has the above meaning, with an aminonaphtholsulfonic acid the formula:

'(III)

(SOY)

» -J 11 ·.

in u / elcher R ₁ , R ^, η and Y 'have the above meaning, and with an aromatic compound of the formula:

B-H (IU)

in which B has the above meaning, coupled and the disazo dyes obtained with a diazotized product of an aromatic Amines of the formula:

A - NH ₂ (V)

in which A has the above meaning, coupled. Procedure 2

This is a tetrazotized product of an aromatic diamine of the formula (II) coupled with an aminonaphtholsulfonic acid of the formula (III), the product obtained with a diazotized one Product of an aromatic amine of the formula (U) coupled and the product obtained with an aromatic compound of Formula (IV) coupled.

409813/1110

Procedure 3

Here, an aminonaphtholsulfonic acid of the formula (III) is used a diazotized product of an aromatic amine of the formula. (V) for the preparation of a compound of the formula:

E ¹ E ²

A-H = N

1 7

in iuelcher A, R, R ", Y and η have the above meaning, coupled, the compound is coupled with a tetrazotized product of an aromatic diamine of the formula (II) and the obtained Product coupled with an aromatic compound of formula (IV).

The new dyes according to the invention can according to any of the

1 above method produced luerden. However, if R is in the through Formula (Hl) is OH, i.e.

OH Ν

then processes 1 and 2 are to be preferred, while if R ^{1 is} NH ₂ , ie. ^ 2 ^H

then the procedure 3 is timely.

The aromatic diamines of the formula (II) to be used as starting materials, ie H ₃ NX-NH, in which X has the above meaning, are, for example, 3,3 ¹ -diaminodiphenylsulphone, 4,4'-diaminodiphenylsulphone, 3,5-bis- (p-aminophenyl) -1,2,4-triazole, 3,5-bis- (m-aminophenyl) -1,2,4-triazole, 2,5-bis- (p-aminophenyl) -1,2, 4-. -

409813 / !; nO

ox'adiazole, 2,5-bis- (m-aminophenyl) -1,3,4-oxadiazole, 2,5-bis- (paminophenyl) -1,3,4-thiadiazole, 2,5-bis (m-aminophenyl) -1,3,4-thiadiazole, 2,5-bis- (p-aminophenyl) -furan, 2,5-bis- (m-aminophenyl) -furan, 2,5-bis- (p-aminophenyl) -pyrene, 2,5-bis- (jn-aminoph8nyl) -pyrene, 2,5-bis- (p-aminodiphenyl) -oxazole, 2,5-bisr- (maminodiphenyl) -oxazole, 2,5-bis- (p-aminodiphenyl) -thiazole, 2,5-bis- (m-aminodiphBnyl) -thiazole, 2,5-bis- (p-aminophenyl) -imidazo1, 2,5-bis- (m-aminophenyl) -imidazole, 2,5-bis- (p-aminophenyl) -thiophene, 2,5-bis- (m-arainophenyl) -thiophene, 2,7-diaminodiphenylsulfone, Diaminotetrazine, etc.

Examples of aromatic amines of the formula (III) which can be used _{according to the invention, ie A-NH 9} , in which A has the above meaning, are aniline, methylaniline, ethylaniline, tert-butylaniline, cyclohexylaniline, dimethylaniline, methoxyaniline, ethoxyaniline, nitroaniline, dinitroaniline , Nitrochloroaniline, 2-aminodiphenyl ether, 4-aminodiphenyl ether, 2-amino-2'-methyldiphenyl ether, 4-amino-4'-methyldiphenyl ether, 2-amino-2'-chiordiphenyl ether, 4-amino-4'-chloro-diphenyl ether, propanilineaminoetyl, aceto-diphenyl ether , Oxalylaminoanilin, aminophenylurea, benzoylaminoanilin, 3-Chlorbenzoylaminoanilin, 4'-Chlorbenzoylaminoanilin, 3'-methyl · benzoylaminoanilin, 4'-Methylbenzoylaminoanilin, 3'-Nitrobenzoylaminoanilin, 4 -Nitrobenzoylaminoanilin ^1, 4-Benzoyläthylaminoanilin, 2-methyl-4-acetylaminoaniline, 2-methyl-5-acetylaminoaniline, 2-methyl-4-benzoylaminoaniline, 2-methyl-5-benzoylaminoaniline, 2-methyl-4-formylaminoaniline, 4-methyl-3-formylaminoaniline, 2-methyl-5-oxalylaminoaniline, 4- Methyl 1-3-oxalylamine oaniline, chloroaniline, methylchloraniline, methylmethoxyaniline,

409813 / H TO

Methoxychloraniline, dimethoxyaniline, methoxyacetylaniline, methoxyacetylaminoaniline, rethoxyoxalylaminoaniline, 4-methylaniline-2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 4-methylaniline-3-sulfonic acid, 4-methylaniline-3-sulfonic acid, 4-methylaniline-3-sulfonic acid, Aniline-2-sulfonic acid, 5-acetylaminoaniline-2-sulfonic acid, 4-chloro aniline-3-sulfonic acid, 4- acetylaminoaniline-2-sulfonic acid, 4-benzoylaminoaniline-2-sulfonic acid, 4-oxalylaminoaniline-3-sulfonic acid , Aniline-3-sulfonic acid, aniline-4-sulfonic acid, aminobenzoic acid, anisidines, naphthionic acid, etc. One of the above compounds are particularly preferred aniline, 4-nitroaniline, aniline-sulfonic acid 4 and IMaphthionsäure.

The compounds of the formula (IV) which can be used according to the invention, ie BH, in which B has the above meaning, include aromatic amines, phenols or naphthols, which are optionally substituted, such as, for example, toluenediamine, N, N-diethyl-N'-acetyl- r m-phenylenediamine, aminonaphthalene, aminonaphthalenesulfonic acid, aminonaphthalenedisulfonic acid, aminonaphtholsulfonic acid, aminonaphthol disulfonic acid, acetylaminonaphtholsulfonic acid, acetylaminonaphthol disulfonic acid, benzoylaminonaphthol disulfonic acid, benzoylaminonaphthol-3, 6-naphthol-8-naphthol, naphthol-3-naphthol-3-naphthol-3-naphthol-3-naphthol-3-naphthol-8-naphthol-3,6 -m-aminophenol, 3-acetylaminophenol, 3-hydoxy-4-methyldiphenylamine, aniline, 3-aminotoluene, 1,3-phenylenediamine, 3-ß-hydroxyethylaminoaniline, 2-methyl-1,3-phenylenediamine, 4-methyl-1 , 3-phenylenediamine, 3-acetylaminoaniline, 3-aminophenylhafnstoff, 3-aminophenylglycine, G- methyl-3-aminophenylglycine, 1,3-phenylenediamino-4-sulfonic acid,

4098 13/1110

4-chloro-1,3-phenylenediamine, 4-l \! Itro-1,3-phenylenediamine, 3-aminoanisole, 3-dimethylaminoaniline, 3-dxalylaminoaniline, 3-glyconyl " aminoaniline, 2,4-diaminoacetoanilide, naphthol, naphtholsulfonic acid, Naphtholtrisulfonic acid, phenol, cresol, chlorophenol, etc.

The 'tetrazotization and diazotization in one of the above I / experiences according to the invention are carried out in the customary manner. For example, the aromatic starting diamine of the formula H ₇ NX-NH ₉ , in which X has the above meaning, is treated with a nitrite in the presence of a mineral acid such as sulfuric acid, hydrochloric acid, etc., at low temperature, preferably at 0-10 ° C. , reacted to form a tetrazotized product of the aromatic diamine. The diazotization of the aromatic amine of the formula A-NH "i, in which A has the above meaning, can also be carried out under the abovementioned conditions.

The coupling can also be carried out in the usual way, e.g. at a temperature below 25 ° C, preferably between 0-5 C, for 10 minutes to 24 hours. The pH of the reactant system can vary over a wide range and is expedient accordingly selected the type of reactants to be coupled. The reaction sequence and the pH of the reaction system in the l / experienced above is represented as follows, where AA represents the aromatic amine of formula (U)

1-ANS for the i-amino-8-naphtholsulfonic acid of the formula OH NH.

* ■ -

stands in which Y and η have the above meaning

409813/1110

8-ANS for the B-amino-1-naphtholsulfonic acid of the formula

NH ₀ OH ''

stands in which Y and η have the above meaning ADA is the aromatic diamine of the formula (II) and ' AC represents an aromatic compound of formula (IV).

Procedure 1

AA - r - l - ANS I - ADA ■ - - T - AC

alkalxsch sour sour or

alkaline.

AA —2—8 - ANS —r, - r ~. ü -ADA - * -. - ~ AC

acidic alkaline alkaline

or sour

AA τ-1-ANS - ADA

alkaline acid

τ- 1-ANS - ADA —_

alkaline acidic or acidic

alkaline

3 2 1

^Afl acidic ⁸ ~ ^ANS alkaline ^ADA alkaline ^AC

or sour

Procedure 2

^AA alkaline or ¹ ~ ^ANS acidic ^ADA alkaline ^AC neutral or acidic

2

^AA acid or ⁸ " ^ANS alkaline ^ADA alkaline ^AC neutral or acidic

A 0 9 8 1 3 / M .1 0

Procedure 3

■ 1? 3

alkaline acidic ^AUH acidic or ^HL

alkaline

AA.- - -: 8-ANS - _π - % -. r ADA TT ^ n PT " ^AC

acidic or alkaline alkaline

neutral or sour

The new polyazo dyes according to the invention are used for dyeing fibrous materials made from fibers with hydroxyl and / or amide groups used. Containing hydroxyl groups. Fibers are "e.g. cotton, hemp, cellulose, viscose rayon, artificial cuprammonrum silk, Vinylon (polyvinyl alcohol fibers), etc. Examples of amide groups Fibers are silk, dinghy, synthetic polyamide (nylon) fibers, synthetic polyurethane fibers, etc. Fibrous or fiber-containing materials from these fibers include various Products such as threads, woven "fabrics, knitted fabrics, Felts, non-woven fabrics, paper. Leather etc.

The fibrous materials made from the fibers containing hydroxyl and / or amide groups can be used with

Ir

the novel polyazo dyes according to the invention are dyed or printed in the same way as is the case with conventional polyazo dyes. For example, to color a fibrous material made of cotton, is suitably a dyebath having a pH of 8-10 and a content of dye of 1-8 wt .-> s and an inorganic salt of 5-40 wt -.%, each based on the fibrous material to be dyed. The material is added to the bath at a liquor ratio of 1:20 to 1:40, then the bath is gradually heated and used for dyeing

- 409813/1110

■ held at about boiling temperature for 2D-50 minutes for dyeing. To

rough . After dyeing, the fibrous material is removed / washed with water, pressed and dried. Fibrous materials made from fibers containing amide groups can furthermore be dyed in a wide pH range from acidic to alkaline; however, they are appropriately dyed in a neutral to acidic pH range, in particular at a pH of about 2-7. If a fiber-like material made of wool is to be dyed, a dyebath with a pH of 2-7 and a content of 3-10% by weight of dye and 1-5 % by weight of conc. Sulfuric acid or acetic acid, each based on the fiber-like material to be dyed, is used. The fibrous material is added to the bath at 60 ° C. with a liquor ratio of 1:30 to 1:40, then this is gradually heated to the boiling point and kept at this temperature for 30-90 minutes. After dyeing, the material is removed, roughly washed with water, pressed and dried. Fibrous material should be dyed silk, then suitably a dyebath having a pH of 7-10 and a content of 50-300 wt, - / o dye and 0.5-20 wt -.% Of an inorganic acid, in each case based on the weight of the material to be colored. The fibrous material is in the bath having a liquor ratio of 1:50 "to 1: optionally 150, then this is heated for 15-90 minutes at 70-100 ⁰ C.. After dyeing, the fibrous material is taken out and treated as above.

Various common additives, such as accelerators, Leveling agents, retarders, etc., added will. Accelerators are e.g. sodium chloride, sodium sulfate,

4098 13/1110

various surfactants, etc. j leveling and Retardants are e.g. higher alcohol detergents, Turkish red oil, Marseille * soap, monopoly. Soap, "silk scouring u / aste", Sodium carbonate, sodium pyrophosphate usui. That with the invention Dye-stained fibrous material can continue. subject to the usual aftercare .. To these Zuieck you can use acetic acid, formalin, polyethylene polyamines, cationic, surface-active agents, developers, metal salts, etc., use.

B -eis ρ ie 1 1

25 g (0.1 mol) of 3,5-bis (p-aminophenyl) -1,2,4-triazole (aromatic diamine) were concentrated in 60 g. Hydrochloric acid and 60 g of water were dissolved with heating, and the resulting solution was poured into a mixture of 100 g of water and 100 g of ice. Then, to the above solution at 0 ⁰ C. A solution of 14 g (0.2 mol) of sodium nitrite in 50 g of water was added to the tetrazotizing. An aqueous solution of 36.4 g (0.1 mol) of sodium 1-amino-8-naphthol-3,6-disulfonate was added to the tetrazotized solution and the mixture was ^{stirred at 0} ° C. for 3-6 hours.

Subsequently, an aqueous sodium carbonate solution was added to the resulting solution to make the former solution alkaline. Then a previously by dissolving 10 g (about 0.1 mol) of aniline (aromatic amine) in 30 g of conc. Hydrochloric acid and 100 g of water produced diazotized solution and also 7 g (0.1 mol) of sodium nitrite at 0 ^° C. were added. The mixture was stirred at 0 ° C. for 2 hours.

40981 3/1110

Hydrochloric acid was then added to the solution obtained above for the purpose of acidification added. Then there was a solution of 12 g (0.12 mole) of m-phenylenediamine (aromatic compound) was added in 200 g of water and the mixture was stirred overnight to terminate the reaction. That The product obtained was filtered off with suction, washed with water and then with ethyl alcohol and turned into a bluish-black Dye dried. (No. 65)

Example 2

25.0 g of 4.4 ^t -diaminodiphenylsulfone (aromatic diamine) were concentrated in 60 g. Hydrochloric acid and 60 g of water were dissolved with heating, then the resulting solution was poured into a mixture of 100 g of water and 100 g of ice. A solution of 14 g of sodium nitrite in 50 g of water at 0 ° C. was then added for the purpose of tetrazotization. An aqueous solution of 36.4 g of sodium 1-amino-8-naphthol-3,6-disulfonate was added to the tetrazotized solution and the mixture was ^{stirred at 0} ° C. for 3-6 hours.

The obtained solution was made by adding an aqueous sodium carbonate solution made alkaline. Then a diazotized solution was added, previously prepared by dissolving 10 g of aniline in 30 g conc. Hydrochloric acid and 100 g of water and the addition of 7 g of sodium nitrite at 0 C. / The resulting solution was then acidified with hydrochloric acid. A solution was found 12 g of m-phenylenediamine in 200 g of water were added and the mixture was stirred overnight to terminate the reaction. The product was filtered off with suction, washed with water and then with ethyl alcohol and given a bluish black dye

dried. (No. 1) / * The mixture was ^{stirred at 0} ° C. for 2 hours.

4098 13/1110

- 32 B β is ρ ie 1 3

13.0 g of a hydrochloric acid salt of aniline was dissolved in a mixture of 23 g of hydrochloric acid and 50 g of water; ^{the solution obtained was diazotized at 0} ° C. with 69 g of sodium nitrite. A neutral aqueous solution of 31.9 g of 1-amino-8-naphthol-3,6-disulfonic acid was added to the diazotized product and the mixture was stirred overnight to complete the coupling. In the product obtained, Ma CO was dissolved in order to adjust the pH to 7. Then 25.2 g of 2,5-bis (p ~ aminophenyl) -1,3,4-oxadiazole. in a mixture of 100 g of water and 56 g of 30% HCl at 0 ° C. Tetrazotized with 13.8 g of sodium nitrite. The product coupled first was treated with 20 g of Na CCu, then 2,5-bis- (p-aminophenyl) -1,3,4-oxadiazole, which had previously been neutralized with an aqueous sodium acetate solution, was added to the tetrazotized product. The mixture was stirred to complete the coupling. A solution of 100 g of water, 17 g of Na ₂ CO ₃ and 9.4 g of phenol was added to the solution obtained, and the mixture was stirred for 12 hours. Then the obtained dye was salted out with common salt, filtered and dried. The dye obtained stained silk green. (Dye No. 68).

In the above description, "alkyl" (also in connection with "alkoxy", "alkyl ^ phenyl, etc.) stands in particular for lower alkyl. This BS preferably stands for alkyl radicals with 1-6, in particular 1.4, carbon atoms, such as methyl, ethyl, propyl, isopropyl, Butyl, pentyl, hexyl.

409813/1110

Example 4

The components listed in Table 2 below were identified as aromatic diamines (HpN-X-NHp)> aromatic amines or aromatic compounds according to Example 1 used in order to make various Obtaining dyes by the method of Example 1. The dyes and colorations are also listed in Table 2.

A 0 9 8 1 3/1 1 1 0

Tabel

Aromatic
E.g. amine

Aromatic diamine

Aromatic compound dye no. coloring

A p-nitroaniline

B. aniline O
CO
CO C. aniline CJ
1 D. p-nitroaniline ι
O E. aniline F. p-nitroaniline

aniline

H aniline

p-nitroaniline

3,5 -Bis- (p-aminophenyl) -1,2,4-triazole

3, 5-bis (p-aminophenyl) -1 ■ ethoxy-1,2,4-triazole

3,5-bis (m-aminophenyl) ■ 1,2,4-triazole

3,5-bis-? (M-aminophenyl) 1,2,4-triazole

2,5-bis (p-aminophenyl) -1,3 »4-oxadiazole

2,5-bis (m-aminophenyl) ■ 1,3,4-oxadiazole

2,5-bis (p-aminophenyl) furan

2,5-bis (p-aminophenyl) ■ 1,3,4-thiadiazole

2,5-bis (p-aminophenyl) ■ 1,3,4-thiadiazole

reddish

m-phenylenediamine m-tolylenediamine

m-phenylenediamine m-tolylenediamine m-tolylenediamine m-tolylenediamine m-phenylenediamine m-phenylenediamine m-tolylenediamine

64
63 black
bluish
black . 61 greenish
black 66 I.
greenish ^
black -f *
I. 67 greenish
black 69 greenish
black 55 purple
black ^ CO 20th purple ^ j
black oo • 31 CD
purple
black.

Aromatic
Amine

Table 2, continued Aromatic Amine Aromatic Compound

Dye no. coloring

J p-nitroaniline

'K OO aniline \ aniline Zl ¹ N p-nitroaniline aniline

O p-nitroaniline

P aniline

aniline

aniline

3,5-bis (p-aminophenyl) ■
1,2,4-triazole

3,5-bis (p-aminophenyl) -1-ethoxy-1,2,4-triazole

3,5-bis (m-aminophenyl) ■
1,2,4-triazole

3,5-bis (m-aminophenyl) -1,3,4-oxadiazole

2,5-bis (p-aminophenyl) -1 i 3,4-oxadiazole

2,5-bis (m-aminophenyl) ■
1,3,4-oxadiazole

m-phenylenediamine m-tolylenediamine m-phenylenediamine m-tolylenediamine m-tolylenediamine m-tolylenediamine

2,5-bis- (p-aminophenyl) -m-phenylenediamine furan

2,5-bis (p-aminophenyl)
1,3,4-thiadiazole

m-phenylenediamine

2,5-bis- (p-aminophenyl) -m-tolylenediamine oxazole

64 reddish
black 234 ' VJl
I. 63 bluish
black 7849 49 reddish
black. 73 greenish
black 67 greenish
black 69 greenish
black 55 purple
black 20th purple
black 22nd bluish
black

Claims (12)

Claims 1, - New polyazo dyes of the formula: E ¹ E ² ■ ■. · - [: A - N = K - J ^ s K - N = N - X - H = N - B in which A stands for an optionally substituted, aromatic ring, B for an aromatic ring with at least one substituent from the group of amino, substituted
Amino and hydroxyl groups; X for. or stands, where Q is a -50 "group or an optionally substituted one Ring from the group of 5- or 6-membered rings with at least one N, 0 or S as heterocyclic atom; Y represents a hydrogen atom, an alkali metal, an -NH. Group or an amine salt residue; η has a value of 1 or 2; 1 2 R and R each stand for a hydroxyl or amino group, 1 7 u / obei R is an amino group when R is a hydroxyl group, or a hydroxyl group when R is
represents an amino group. 2. Dye according to Claim 1, characterized in that X is for stands. 3. Dye according to claim 1, characterized in that X is for stands. -. 4 0 9 8 1 3/1110 4. Dye according to claim 3, characterized in that Q is for ■ ο stands, where R is hydrogen, an alkyl group, aryl group or (^ / - hydroxyalkyl group. 5. Dye according to claim 1, characterized in that A represents a phenyl group, naphthyl group or a phenyl or naphthyl group stands, which is at least by a halogen atom or lower alkyl, lower alkoxy, amino, carboxy, nitro or Sulfonic acid group is substituted. 6. Dye according to claim 5, characterized in that A for f / X · ■ JX - - / - ^ ^or ■ < V ³⁰ * ^H stands. 7, - dye according to claim 1, characterized in that B for or ₆ M β where M is -NH_, -N (R) or OH, where R is a lower alkyl, a phenyl or alkylphenyl group and M ^{1 is} hydrogen, a sulfonic acid group or lower alkyl. O 9 8 1 3/1 1 1 8, - dye according to claim 1, characterized in that B for NH NH OH NH, SO ₃ H NH. or H0- < SCLH 7 stands. 9, - Process for the production of new polyazo dyes of the formula R ¹ R ² , -N = N-X-N = N-B A-N »N- characterized in that a tetrazotized product of an aromatic diamine of the formula: NH ₂ -X-NH ₂
in which X has the above meaning, with a naphtholsulfone- acid of the formula: Xl 1 2
in which R, R, η and Y have the above meaning, and with an aromatic compound of the form: BRA 40981 3/1 1 1 Ο ¹ in which B has the above meaning, couples and the disazo dye obtained with a diazotized product of an aromatic Amines of the formula: A-NH ₂ in which A has the above meaning, couples. 10, - Process for the production of new polyazo dyes of the formula: A-N = Ν-, characterized in that a tetrazotized product of an aromatic diamine of the formula: H ₂ NX-NH ₂ in which X has the above meaning with a naphtholsulfonic acid the formula: 1 2
in which R, R, η and Y have the above meaning, couples, the product obtained with the diazotized product of an aromatic amine of the formula A-NH ", in which A has the above meaning, couples, and the product obtained with an aromatic compound of the formula BH, in which B has the above meaning, couples. 11.- Process for the production of new polyazo dyes of the formula: -A-N = N -t ^ V ^ -N = N-X-N = N-B 409813/1110 characterized in that a naphtholsulfonic acid is used
Formula: in which R, R, η and Y have the above meaning, with a diazotized product of an aromatic amine of the formula A-NH ₉ , in which A has the above meaning, for the preparation of a compound of the formula: A- H «H (SO ₅ Y) _1- 1 2 in which A, R, R, η and Y have the above meaning, couples, the compound obtained with a tetrazotized product of an aromatic diamine of the formula: in which X has the above meaning, couples and the product obtained with an aromatic compound of the formula BH, in
which B has the above meaning, couples. 12.- A process for dyeing hydroxyl and / or amide-containing fibers, characterized in that a dye is used
according to claim 1 to 8 used. The patent attorney: ^ 09813/1110 "