DE2049810C3 - Disazo dyes and their use for dyeing fiber materials made from synthetic polyamides - Google Patents

Description

The present invention relates to new, valuable disazo dyes which are in the form of the free acid the general formula

R ₁ O- N R ₁ -N = N X N
ι R ₁ R ₄ I.
R ₅ X ₊ / SO ₁ H

as well as their use for coloring

Fiber materials made from synthetic polyamides.
In the general formula (I) stand

Ri for hydrogen, Ci - C4-alkyl or optionally phenyl substituted by chlorine, nitro or Q -Q-alkoxy,

R2 and Rif for hydrogen, halogen, Q-Q-alkyl. Q - Q-A! Koxy, formylamino, Ci-Q-Alkvlcarbonylamino, Phenylcarbonylaminino, Q-Q-Alkylsulfonylamino or Phenylsulfonylamino,

for Q-Q-alkyl, phenyl, 2-naphthyl or biphenylyl,

for hydrogen or optionally substituted by cyano, carbonamide or carboxyl Q -Q-alkyl,

for C ₁ -Q-alkyl, C, -C ₆ -AlkOXy, halogen, nitro or cyano and
for O,! or 2.

Preferred dyes are those of the general formula

R ₁ O

; -V-N-N-

'Ϊ

SO., H

where R | to R _{5 have} the meaning given for formula (I), in particular those of the formula

Ri

R ₁ O

SO ₃ H

N = N

(III)

wherein

R ₁ 'represents alkyl having 1-4 carbon atoms,

R ₂ 'denotes hydrogen or alkoxy with 1-4 carbon atoms,

R ₃ 'represents hydrogen or alkyl having 1-4 carbon atoms,

R ₄ 'represents alkyl having 1-4 carbon atoms or phenyl,

Rs' hydrogen or an optionally by one Denotes a nitrile, carbonamide or carboxyl group substituted alkyl group with 1-4 carbon atoms.

The new dyes are obtained by coupling anilinesulfonic acids of the general formula. ^{You can build up the} dyes according to the invention '5 also SO' ^{that you have a Miueltomponente}

ι ²

H ₂ N- <ζ J ^ R,

- acyl (VIII)

H ₂ N

- NO ₂

(IX)

R ₁ O <^> NH ₂ (IV)

M- where R ₂ and Rj have the meaning given above

SO ₁ H and acyl is an acyl radical, for example an acetyl,

Represents oxalyl or benzoyl radical, diazotized and in

wherein Ri has the meaning given in formula (1), to alkaline medium with phenol-2- or -3-sulfonic acid

diazotized and with coupling components of the general π dyes of the formula
my formula

Y _n
f>

HO

<f

> N

(V) N = N- <f> -

SO ₁ H

respectively.

in which R ₂ and R 3 have the meaning given in formula (I) and Z is H or the remainder of a cleavable group which facilitates the coupling, for example a sulfoalkylene group or a sulfonic acid group, and the monoazo dyes of the formula thus obtained are combined

R ₁

R ₂

NH-acyl

N - ~ N

SO ₁ H

R-,

I.
R,

Il

(Vl)

after or with elimination of the radical Z further diazotized and an indole of the formula

(R _h ) "

(VIl)

wherein R4, R ^, Rb and η have the meaning given in formula (I),

HO

- N = N <> NO ₂ (Xl)

-K

SO ₁ HR ₁

couples, the hydroxyl group optionally then alkylated, the acyl radical is split off from the dyes (X) or the nitro group in the dyes (XI) reduced to the amino group and then the aminoazo dye of the formula

N = N " ^{% <} NH, (XII) R ₁

R O

SO ₁ H

diazotized and as described above with an indole Formula (VII) couples.

Suitable anilinesulfonic acids (IV) are, for example: 4-methoxy-aniline-sulfonic acid- (3), 4-methoxy-aniline-sulfonic acid- (2), 4-ethoxy-aniline-sulfonic acid- (3). 4-ethoxy-anilinesulfonic acid- (2),

4-propoxy-aniline-sulfonic acid- (3), 4-isopropoxy-aniline-sulfonic acid- (2), 4-butoxy-aniline-sulfonic acid- (3),

4-isobutoxy-aniline-sulfonic acid- {2),

4-tert-butoxyaniline-sulfonic acid- (3), 5

4-hydroxy-aniline-sulfonic acid- (3),

4-phenoxy-aniline-sulfonic acid- (3). As coupling components of the general formula (V) are for example:

Aniline-w-methanesulfonic acid or ι ο

Aniline-N-sulfonic acid, 2-amino-toluene, polyamides 2-Amino-ethylbenzene, 3-Amino-ethylbenzene, 3-Chloraniiin, 3-Bromanilm, 2-Amino-anisole, 3-AminoanisoI, 2-Amino-ethoxybenzene,

3-amino-ethoxybenzene, ι =,

1-amino- ^ S-dimethylbenzene,

1 - amino-23-dimethyl-benzene,

1 - amino-3,5-dimethylbenzene,

3-amino-4-methoxy-toluene,

2-amino-4-methoxytoluene, 2u

2-amino-1,4-dimeihoxy-benzene,

2-amino-4-ethoxy-toluene,

2-amino-1,4-diethoxybenzene, 3-acetylamino-aniline, 3-propionyl-amino-aniline.

The following coupling components of the general formula 25 (VII) can be used, for example:

2-methylindole, 2-phenylindole, 2-phenylindole, l-methyl-2-phenylindole, 1,2-dimethylindole, 1 -j3-cyanoethyl-2-methylindol,

l-jS-cyanoethyl-2-phenyl-indole, 30

y- (2-Phenylindolyl-I) propionic acid amide, y- (2-methylindolyl-1) propionic acid amide, y- (2-methylindolyl-1) propionic acid, 2-j3-naphthyl-indole,

2-p-biphenylyl indole, 2,5-dimethylindole, y,

2,4-dimethyl-7-methoxyindole,

2-Pheynl-5-ethoxyindole,

2-methyl-5-ethoxyindole, 2-methyl-5-chloroindole, 2-methyl-6-chloroindole, 2-methyl-5-nitroindole,

2-methyl-5-cyanoindole, 2-methyl-7-chloroindole, 40

2 methyl-5-fluoroindole, 2-methyl-5-bromoindole, 2-methyl-5,7-dichloroindole and

1-cyanoethyl-2,6-dimethylindole.
The diazo components of the formula (IV) are used in a manner known per se, for example in an acidic, aqueous manner

H ₃ CO ^ f> --N = N-

Solution diazotized with sodium nitrite solution at 0-20 ⁰ C and combined with the coupling components of formula (V). The coupling can be carried out in a neutral to strongly acidic, but preferably in a weakly acidic pH range in an aqueous or organic-aqueous medium.

The Weiterdiazotierung the aminoazo (VI) or (XII), for example in acid, aqueous dispersion, carried out with sodium nitrite solution, can be the Diazotierungstemperaturen between 0 and 30 ⁰ C, aminoazo dyestuffs of the formula (XII) may further be diazotized indirectly by they are dissolved under alkaline conditions, sodium nitrite solution is added and the mixture is poured into aqueous hydrochloric acid or hydrochloric acid is added

The coupling of the diazotized aminoazo dyes (VI) or (XII) with the indoles (VII) to give the Disazo dyes (I) are likewise carried out in a manner known per se, for example in neutral, weakly or in a strongly acidic aqueous medium or in an aqueous-organic medium. The disazo dyes of Formula (I) are generally rather sparingly soluble in an acidic medium and can be easily obtained by Filter off and, if necessary, isolate after adding 2-10% common salt. If the dyes fall impure on, they can be prepared in a known manner from hot water, optionally with the addition of alkali, be unsolved. The poorly soluble, acid-isolated dyes (I) can therefore be readily soluble in water can be made that they can be mixed with salts of strong bases and weak acids, for example trisodium phosphate, Disodium hydrogen phosphate, sodium tetraborate, sodium metaphosphate, sodium metasilicate or sodium carbonate mixed.

The dyes according to the invention are suitable for dyeing fiber materials made from synthetic polyamides in even, extensive, yellowish orange, red and bluish red tones of very good Lightfastness. They absorb well on polyamide fibers in a neutral to weakly acidic dye bath. Fiber materials made from synthetic polyamides include those made from synthetic polyamides such as E-polycaprolactam or condensation products on adipic acid and hexamethylenediamine understood.

The dye of the formula according to the invention

OC ₂ H ₅

SO ₃ H

surprisingly shows improved wash fastness in mechanical washing at 60 compared to the dye known from DE-AS 11 06 287, Example 5.
The dye of the formula according to the invention

SOjH

shows a surprisingly improved dye compared to DE-AS 12 44 102. Example I Solubility in hard water.

20.3 g (= 0.1 mol) of 4-aminoanisole-sulfonic acid (2) are dissolved in 200 ml of water with sodium hydroxide solution at pH 7 dissolved, 6.9 g of sodium nitrite added, cooled with ice and 28 ml of concentrated hydrochloric acid added at 0-5 °. The diazotization is complete after 30 minutes. The solution of 10.7 g (0.1 Mol) 3-aminotoluene in 100 ml of water and 5 ml of concentrated hydrochloric acid. At 0-10 ° then becomes slowly butted with concentrated sodium hydroxide solution until the pH value is 6. The dye is 10% Salted out table salt and vacuumed off.

The aminoazo dye thus obtained is dissolved in 300 ml of water at pH 7. Then 6.9 g of sodium nitrite are added added, cooled and 28 ml of concentrated hydrochloric acid added at 0-5 ° C. After an hour

Diazotizing, the diazo suspension will flow into a solution of 19.3 g (0.1 mol) of 2-phenyl-indole in glacial acetic acid leave and blunt it a little with sodium acetate or caustic soda. After coupling, the dye! isolated as usual and dried at 90 °. The dye dyes polyamide from a weakly acidic or neutral bath in reddish orange with good lightfastness.

If you proceed as indicated above, but the diazo component in column I, as the middle component the compounds listed in column II and as the final component used in column III are obtained Also valuable water-soluble disazo dyes, the polyamide in orange to bluish red shades with dye with good lightfastness and neutral drawability.

St.

CH ₃ O

the same

-NH,

ΙΓ ~ 1 Ί

the same

the same

the same

the same

the same

NH,

the same

likewise H., CN
H

H ₃ CN
H

Continuation

Ni. I.

8 CH ₃ O

NH ₂

9 the same.

10 the same.

11 the same.

12 C ₂ H

13 the same.

14 the same

i 5 uesgi.

16 the same

17 the same.

SO ₁ H

SO ₁ H

• f, · "NH,

NH ₂

OCH ₃

/ ~ \ -NH ₂ CH ₃

the same

dcsgl.

the same

CH _{3 the} same.

the same

10

OY

C ₂ H ₄ CONH ₂

H ₃ CNH

X k "

H ₃ CNH

N H

CH ₃

Ii Il I

J) 1 y

H, C N H

N X / H

I.

N

■ ι ί- · ν ι

11th

continuation

No. I.

18 C ₂ H ₅ O - / '■ - NH ₂

SO ₁ H

19 the same.

20 the same

21 the same.

the same

23 the same

24 the same.

26 the same

27 the same.

SO ₃ H

Υ> ΝΗ ₂ OCH ₃

the same

OCH ₃

NH,

CH _{3 the} same.

the same

OCH.,

the same

> —NH,

the same

the same

12th

ι

\/ H

CH,

Γ "ΐ '

H, C N H

LH ^Ν

\ H

- Λ

CH ₂ CH ₂ CN

'λ J

N H

H ₃ CNH

CH ₃

13th

continuation

number 1

SO., H

29 the same.

30 the same.

> - NH,

NH,

CH ₃

the same

14th

Il Il

CH ₂ CH ₂ CN

H., C N H

N H

31 the same.

32 the same.

33 the same.

34 the same.

35 the same.

the same

the same

NH,

CH,

OCH ₃

the same

I CH ₃

H, C N

CH, CH, CN

H ₃ CNH

36 the same

the same

15th

Fortselzurm

No. I.

37

> - () - : ζ V-NH ₂

38 dcsul.

39 the like.

OCH.,

the same

OCH,

J '

C ₂ H ₅

Ii ii I ί ^N

\/ H

H ₃ CNH

N H

40 dcsul.

41 the like.

42 HC ₄ H ₁ , -O - / ^x > NH,

SO ₃ H

43 H ₃ CO- /

SO., H

44 the like.

45 dcsgl.

dcsgl.

dcsgl.

V- NH,

dcsgl.

dcsgl.

dcsul.

CH,

A λ

H ₃ CN

CH, CH, CN

/ V \

I I N \ / H

H ₃ CNH

H ₃ CN H

CH ₃

Cl

NO,

030 213/53

continuation

Ill

46 H ₁ C - () - ζ y- NH,

SO ₁ H

47 the same.

■> - NH,

NH,

Γ 1

H ₁ CN II

Cl

4S the same.

desel.

49 desal.

the same

the same

desul. H ₁ CN] H Br

Cl

N 1 Il C!

H ₁ CN CII ₁

CH, CH, CN

Example 51

0.1 moles of 4-acctylaminoaniline are used in more common Way diazoiated and combined in an alkaline medium with a solution of 0.1 mol of phenol-3-sulfonic acid. After the coupling has ended, the monoazo dye obtained is isolated and, as usual, with dimethyl sulfal methylated. The methoxy dye is saponified with 4% strength aqueous sodium hydroxide solution for about 1 hour. the obtained aminoazo compound is diazotized at room temperature and with the solution of 0.1 mol 2-phenylindole combined in F.isessig. Man isolated in the usual way and after drying and grinding it receives a dye, the polyamide from neutral or a weakly acidic bath stains in a reddish orange tone.

Claims (2)

Patent claims: 1. Disazo dyes in the form of the free acid of the general formula R ₂ N = SO ₃ H correspond to where Ri hydrogen. Ci-C ₄ -alkyl or phenyl optionally substituted by chlorine, nitro or Ci - Q-alkoxy, R ₂ and R _{3 are} hydrogen, halogen, Ci-Q-alkyl, Ci-Q-alkoxy, formylamino, QQ-alkylcarbonylamino, phenylcarbonylamino, Ci- Q-alkylsulfonylamino or phenylsulfonylamino, R ₄ Ci -C ₄ alkyl, phenyl, 2-naphthyl or Biphenylyl, Rs hydrogen or optionally through Cyan, carbonamide or carboxyl substituted Ci -Q-alkyl, Re Ci-Ce-alkyl, C | -C ₆ -alkoxy, halogen, Nitro or cyan and π are 0, 1 or 2. 2. Use of the dyestuffs according to Claim 1 for dyeing fiber materials made of synthetic polyamides.