DE2333423A1 - AZO DYES CONTAINING SULPHONIC ACID GROUPS, THEIR PRODUCTION AND USE - Google Patents

Description

Patent attorney

Dipl.-f.ig. P. Wirth

Dr. V. SchmkJ-Kcwarzik

Dipl. Frsg. G. Dannenberg

Df. P. Weinheld, Di-. D. Gudcl

'6 Frankfurt; M., Gr. Eschenheimer Str.

SANDOZ AQ BASEL CSchwefzD

Case 150-3595

Azo dyes containing sulfonic acid groups, their preparation and use

The invention relates to new azo dyes of the formula containing sulfonic acid groups

R-N = N

N = N-R,

(D,

wherein R is the remainder of a coupling component,

R _{1 is} the remainder of a coupling component different from R and
η mean 1 to 8

and the aromatic rings A and / or B can be further substituted by substituents customary in azo chemistry

can.

309884/1355

The invention accordingly relates to asymmetric dis- and polyazo dyes which have at least one sulfonic acid group, it being possible for the -SO, H groups to occur in the aromatic rings A and / or B and / or in the R or R radicals. The azo compounds of the formula (Ι) preferably contain jd sulfonic acid groups, where jd * " ^{stands for 1} ^ ² * 5 or 4 and the -SO, H group or groups can mainly occur in the radicals R and / or R. Dyes , in which the aromatic rings A and B carry no further substituents, are to be emphasized in particular. The invention includes in particular azo compounds of the formula

R-N = N

BV-N = NR ₁ - (SO ₃ H) (II)

wherein q is 1, 2 or 5 or azo compounds of the formulas

_q -RN = N _N

BV-Ji = NR ₁ (III),

(HO ₃ S) -RN = N (IV),

30988A / 13BB

Case I5O-3395

wherein r is 1 or 2 or

HO, S-R-N = N

(V)

The invention also includes azo compounds of the formulas

R ₅ -OR ₂ -N = N

/ a \ - / b \ —N = N-

(VI)

R ₁ -N = N

--(SO

N = NR ₂ -OR

3 ^H) P

(VII),

wherein R _{2 is} an optionally substituted arylene

rest and

R, denotes an optionally substituted hydrocarbon radical or acyl radical and £ —SO, H groups can occur in the aromatic rings A and / or B and / or in the radicals R or R _p .
Preferred compounds correspond to the formula

30988Ä / 13BB

Cace 150-5595

ROR ₂ -N = N

H) (VIII),

5 'q

/ A \ / B \ N = N-R ^ -O-

₂ -OR (IX)

(HO S) _t -R-O-R ₂ -N = N.

(X)

or

(SO ₅ H) ₁₁ -R ₁ -N = N

Q- ^ y ^ -i

(χι),

wherein t is zero or 1.

Equally good azo compounds correspond to the formula / \

R ₅ -OR ₂ -N = N.

(XII),

wherein R 'denotes an optionally substituted arylene radical different _{from R p, and}

3Q9884 / 135E

Case 150-5595

r-SCUH groups in the aromatic rings A and / or B and / or in the radicals Rp or R 'or R, can occur

or azo compounds of the formula

N = N-Rj-OR ₃

, (XIII).

The aromatic rings R ~ and / or R 'in the compounds of the formulas (XII) and (XIII) can be substituted by carboxylic acid groups and / or sulfonic acid amide groups.
Similar good azo compounds correspond to the formula

R-N = N

N = NR ₁

-X-Y

(XV)

where X is the direct bond or a bivalent or trivalent bridge member,
Y is a fiber-reactive radical and ν is 2, 3 or 4
and v-SO, H groups in the aromatic rings A and / or

09884/1355

ORtGlNAL INSPECTED

Case 150-5395

B and / or in the radicals R or R can occur. The compounds of the formula (XV) preferably contain 3 or 4 sulfonic acid groups.

This class of new azo compounds includes those of the formulas

Y-X-R-N = N

- (- SO ^ H)
^v 3 'v

(XVI),

R-N = N

/ A \ / βΛ N = NR ₁ -XY

(XVII)

or in particular the formulas

YXRN = N (SO _x H).

N = NR ₁ - (SO

(XVIII),

N = NR ₁ -XY

I ¹

(XIX),

30988A / 1

_o ", ■ _q - 7 - Case 130-5595

2 ο i ο 4 Z ο

Y-X-R-N = N

N = NR ₁ -CSO ^ H)

or

N = NR ₁ -XY (XXI),

(SOH) _t

wherein w is 2 or 5.

The invention also includes those azo compounds of the formula (i) in which R and / or R _{1 are} radicals of metal-containing compounds, ie the new azo compounds of the formula (I) can also be used for the preparation of metal-containing compounds of the formula (I) if compounds of the formula (I) in which the aromatic rings A and / or B and / or the radicals R and / or R contain groups capable of forming metal complexes which are advantageously in the ortho position to the azo groups, in substance or on the fiber is treated with metal-releasing compounds.

According to their structure, the dyes of the formula (I) belong to the class of the so-called anionic or acidic Dyes which have water-solubilizing groups, such as sulfonic acid and / or carboxylic acid and / or sulfonic acid amide groups contain. But they can also be metal complex dyes, such as 1: 1- and / or 1: 2-

ORIGINAL INSPECTED

- 8 - Case 1.50-5395

Metal complex dyes. You can therefore use a metal atom, such as an iron, cobalt, copper, nickel, manganese, aluminum, chromium or zinc atom in a complex bond contain.

The compounds of the formula (i) can also carry reactive fiber groups, for example stand for the radical Y as in the compounds of the formula (I), can also carry reactive groups, for example stand for the radical Y as disclosed in the compounds of the formula (XV) is, for example, the residue of di- or trihalo-1,35-triazines, of di-, tri- or tetrahalopyrimidines, alkylsulfomylhalopyrimidines, or acyl radicals which carry a substituent which can be split off as an anion and / or a -CC- multiple bond capable of addition. Such compounds are described for example in British Patent Specifications I'l44'477 and 1,145 ^f 385 are met. Suitable reactive groups are, for example, chloroacetyl; / 3-chloro-propionyl; α-chloroacryloyl; 2,3-dichloroquinoxalyl-6-carbonyl; j3- (4,5-dichloropyridazonyl-1) propionyl; 4,6-dichloro-1,3,5-triazinyl-2; 2,6-dichloro-pyrimidyl-4; 2,5,6-trichloropyrimidyl-4; 4-chloro- 6- amino-1,3-5-triazinyl-2; 4-chloro-6- (4'-sulfophenylamino) -1,3,5-triazinyl-2; 5-chloro-2,6-difluoropyrimidyl-4; / 3-sulfatoethylsulfonyl or a compound of the formula

I ²

₅ ) H ₂ NC CN (CH ₅ ) ₂

° ^the ° ^ΐΘ

30933A / 1355

Gases I5O-3595

Suitable azo compounds correspond to the formula

N = N>

3 'ρ

. (XXII)

R'-N = N

SO, H),

3 'P

(XXIII),

wherein R ^, a low molecular weight, optionally substituted Alkyl radical, in particular the methyl or ethyl radical or the phenylsulfonyl radical the formula

(XXIV)

and R ¹ denotes the remainder of a coupling component of the benzene, pyrazolone-5, amino-pyrazole or naphthalene or heterocyclic series or the remainder of an acetoacetylamino compound

and the aromatic rings Z ₁ and / or Z _p can be further substituted.
These include the compounds of the formulas

309884/1355

Case 15C-5395

R ₄ -O

N = N _n

(T) (T) N = NR ^r - (SO ₅ H) _q

^ O ^^ (XXV),

(S0, H) -R ^f -N = N

N = N

(XXVI),

N = Mn

, r (XXVII)

(SO ₅ H) ₁₁ -R'-N = N

A> (B) N = N

(XXVIII)

or in particular the formulas

(XXIX),

309884/1355

Oasis I5O-3595

OH

N = N

(XXX),

N = N

N = N. NH

(XXXI),

A ) <B) N = N

NH,

-N = N.

(SO ₅ H) _q

(XXXII),

0-R

N = N. (XXXIII), OH

/ aS / b \ N = N

OH NH,

N = N.

A) (B) N = N

* 0

(XXXIV),

0-R ₁ ,

309 8 8 / * / 1355

Case 150-5595

OH A ) (B) N = N (>

(XXXVI)

or the formula

N = N.

CO-CH

N = N-CH i SO H) CO-NH-R ₅

(XXXVII),

wherein PU is one, by q -SO-, Η groups, preferably substituted by 1 or 2 sulfonic acid groups and optionally further substituted Alkyl or aryl radical, such as phenyl or naphthyl radical,

or azo compounds of the formula

CO-CH

N = N

0-R,

(XXXVIII),

30988W 1 35 [deg.]

Case 150-5595

or azo compounds of the formula

N = N

l ^ ßy

Ν-

= N-C-

-CR ₁

■ 8

(XXXIX),

wherein Rg -OH, -0-SO ₂ -Rq or a radical of the formula

-NH or -NH-SO ₂ -R ₉ ,

R _{7 is} hydrogen or an optionally substituted acyl radical or hydrocarbon radical, such as, for example, an optionally substituted alkyl, phenyl or naphthyl radical,

Ro is a low molecular weight, optionally substituted alkyl or alkoxy radical, acetyl, Carboxyl or carboxamide residue,

R _{Q is} an optionally substituted hydrocarbon residue,

R ₁₀ denotes hydrogen or an optionally substituted hydrocarbon radical, or azo compounds of the formula

- (SO, H)

N = N

309884/1355

Case

Likewise suitable new azo compounds correspond to the formula

N = N.

N = N-C C-R

^ -C
⁶ \ /

Il

R,

(XLI)

wherein the aromatic ring Z, is substituted by a substituent which enables coupling, means, for example through a hydroxyl or amino group, for example a primary, secondary or tertiary amino group;

or azo compounds of the formula

Ro-C C-N = N

Il

N = N

--fso.

(XLII),

or the formula

N = N

-N - C C-R

^ -C

N I

(XLIII),

30988-4 / 13BS

2 150-3395

or the formula

N = N.

(XLIV),

N = N-C C-Rn

Il Il ⁸

v ^c _x /.

or the formula

Z,) N = N,

- C CR ₀

I! β ⁸

\ -Κγ /

■ SO K

(XLV),

or the formula

or the formula N = N

C CR ₀

i i ^8th

R ^ -C N

V

(XLVI),

30988A / 13 5 B

Case 150-5595

--(so.

N = N <Z

(XLVII),

wherein the aromatic ring Z ₁ . is substituted by a substituent enabling coupling, means, for example by a hydroxyl or amino group, for example by a primary, secondary or tertiary amino group,

or the formula

N = N

(XLVIII),

wherein the aromatic rings Ζ ~ and Zg by a die Coupling permitting substituents are substituted, for example by a hydroxyl or amino group, for example through a primary, secondary or tertiary amino group, or the formula

R ₈ -OCN = H C-Rg

309884/135

Case 150-5595

or the formula

CO-CH, I 5

CH - N = N, I

CO-NH-R, -,. 5 ( A

CO-CH ₇ . I 5

N = N-CH

CO-NH-R,

- (SO _x H)

or the formula

Z _1. ) N = N

<A) - / B> N = N c a _h

or the formula

(SO _x H).

N = N.

(LII),

or the formula

.Z _x ) N = N.

SO H

(LIII),

30988A / 135B

Cas

or the formula

HO S

Z) N = N

(* Η ^ ^β =

N (Z

(LIV),

or the formula

N = N,

A} (B) N = N

; ^(S0 5 ^H) q

(LV),

or the formula

N = N _n

A) <B> N = N

(LVI),

or the formula

(HO _x S)

5 τ

N = N.

A> (B) N = N

(LVII),

-SO H

309884/1355

Cit.se- IJO-

or the formula HO, S

N = N ΥΖ

(LVIII),

or the formula

Ro-C C-N = N

⁸ 'I' I Vs r- x

B V-N = -N-C

-NSO ₅ H) _q

(LIX),

or the formula

Ro-C C-NH-N

O Il H

/ A) ( B) N = NC ^ C-Rq

\ - Cyy II ⁸ (LX),

. ^X o ^{X R} 6- \ /

or the formula

30 388 U / 1355

Case 15O-3J95

R ₀ -C (MM =

⁰ Il Il

B> -N == N-C C-R

^ N
^ 7

SO H (LXI),

or the formula

SO H

-N = N

Il Κ

(LXII),

or the formula

Z ^ N = N

B ) N = N

(LXIII),

or the formula

-N-N.

B) N-N μ Z

(LXIV),

3 0 9 8 8 Λ / 1355

or the formula

(SO-H),

or the formula (HO ₅ S)

2 Y N = N

(LXVI)

or the formula

(LXVII)

or the formula

3 09884/13

Case 1ί5Ο-37> 95

N = N

B Htf = N -. (

C-R

\ χ I. I

^{0 B} 6 " ^C \ / ^N (LXVIII)

N I

Similar suitable azo compounds correspond to the formula

R'-N = N '''/ A} / B VN = N

wherein R ^{1 is} the radical of a coupling component of the benzene, pyrazolone-5-, aminopyrazole or naphthalene or heterocyclic series or the radical of an acetoacetylamino compound, X _{1 is} a divalent bridge member, such as an optionally substituted alkylene or arylene radical, -0- or -N-,

Io

Y is the remainder of a fiber-reactive compound and

ν means 2, 5 or 4

and the aromatic ring Z "through a coupling enabling substituents is substituted, means and may optionally be further substituted, or the formula

309884 / 135B

Ca.se: · .30-

Y-X

"ii

(LXX)

Suitable reactive groups are, for example, the radicals given above or, in particular, 4,6-dichloro, 3,5-triazinyl-2; 2,6-dichloro- or 2,6-difluoropyrimidyl-4, etc.
These include, in particular, compounds of the formula

N = R

/ α Λ / B \ —N = N-R '

O (LXXI),

wherein one or two X "hydrogen or each chlorine,

Denotes bromine or fluorine, or compounds of the formula

N = N.

wherein X, hydrogen, chlorine, bromine or fluorine

Mean chlorine, bromine or fluorine, 3 0988A / 13BB

Case 150-5195

or in particular the formula

Y-HN

OH

(SCLH).

(LXXIII).

Analogously, all of the listed compounds of the formulas (LXX) to (LXXIII) with regard to their asymmetrical structure and the position of the -SCLH groups have the same structure in the molecule as the compounds of the formulas (II) to (VI) or (XVI) to (XXI).

The dyes listed below can be metalized by known methods of the corresponding metal-free dyes are obtained in substance or on the fiber as metal complex dyes; she correspond to the formula

RN = N _n

: ^ - Me — X ^ 5 \ ι ο

θ '

(LXXIV),

or the formula

I! I.

R ₁ -NiN-R '-N-IL

/ A \ / B \ -NNR

309884/1355

¹ SO _x H)

(LXXV),

Case-150-3395

wherein R 'and R' each represent the remainder of a coupling component the benzene, pyrazolone-5, or aminopyrazole or naphthalene series or from the Acetoacetylamino series,

X ₁ - and X ^ each -NH-R ₁ -, - 0- or -COO- and ρ D IU

Me means a metal atom such as copper, nickel, iron, cobalt, manganese or chromium and "

Xp. and X ^ are each available in an adjacent position -N = N group,

or the formula

^L 6 ~ ^M f T5

d γ

I ⁶ II ⁵

Ri ^ -N ^ N-R ^ -N = N

χ Me — X

I Γ

• n = n-r _'10 -n = n-r'_{i; l}

(LXXVI)

or of the formula R-N = N.

-Me-X,

N = N-R

10

(LXXVII)

or the formula

Me-X.

09884/136

(LXVIII)

BAD ORfGIMAt

Case 150-5 ^ 95

Examples of R ,, are aminobenzenesulfonic acids, aminonaphthalenesulfonic acids, etc.

The new azo compounds of the formula (I) can be obtained by adding a tetrazo compound in any order from a diamine of the formula

B 5

iNilp

(Ia)

with a coupling component of the formula.

R-H

(Ib)

and with a coupling component of the formula

R ₁ -H

(Ic)

coupling, and n, or ρ or q or r or t or ν
or w —SO, H groups in the aromatic rings A and / or B and / or in the coupling components R and / or R, occur.

Leave the azo compounds of formulas (II) and (III)
can be produced if, in any order, a tetrazo compound of a diamine of the formula (Ia) with a coupling component of the formula

HR ₁ -

(Ha)

and with a coupling: .rnponente der For; - (Ib), or,

309884/1 3 5 B.

SAD ORK3INAL

Ca ^ e ^ 50-5395

or in particular the formula

N L,.

/ A \ / B \ —N = N

(LXXIX),

wherein the aromatic rings Zg and / or Z ~ and / or Z, _Q can be further substituted.

All listed compounds of the formulas (LXXIV) to LXXIX) can analogously with regard to their asymmetrical Structure and position of the -SO-, Η groups have the same structure in the molecule as the compounds of the formulas (II) to (XIV) or (XVl) to (LXXIII).

Polyazo compounds mainly correspond to the formula

R ₁₂ -N = N.

NH ₂ OH

B> -N = N

(LXXX),

SO, H (SO, H).

wherein R, p is the remainder of a coupling component of the benzene, pyrazolone-5- or aminopyrazole or naphthalene series,
R ₁ , the remainder of a diazo or coupling component

of the benzene or naphthalene series and t is zero or 1.

Examples of R, ₂ are hydroxy or dihydroxy, amino or diaminobenzenes;

309884/13

Case 3 50-5595

with a coupling component of the formula

H-R- (SOH)

and with a coupling component of the formula (Ic) coupling the azo compounds of formulas ¹ (IV) and (V) can be prepared by reacting in any order a tetrazo compound of a diamine of the formula (la) with a Kupplungskompontene of formula

HR- (SO H) _r

(IVa)

and with a coupling component of the formula (ic), or with a coupling component of the formula

HR ₁ -

(Va)

and with a coupling component of the formula (Ib) kup ^:

pelt.

The azo compounds of the formulas (VI) or (VII) can you get when you have a compound of the formula

/ V

HO-R ₃ -N = N

/ a \ \ ^ß \ —N = N-

-f-f SO ^ H)

5 'P

(Via)

309884 / 135B

Ci-.se 130-5 ^ 95

or a compound of the formula

R ₁ -N = N

/ A \ (βΛ-N = NR ₂ -OH

(VIIa)

etherified or acylated, for example tosylated, it being possible for the p-S0, H groups to occur in the aromatic rings A and / or B and / or in the radicals R or R _p . The azo compounds of the formula (XII) can be obtained by using a compound of the formula

HO-R ₂ -N = N,

A) ( B> -N = NR ₂ -OH

(XIIa)

etherified or acylated, e.g. tosylated, where r -SO-, Η groups in the aromatic rings A and / or B and / or in the radicals R "or R".

The azo compounds of the formula (XV) can be obtained if the diazo compound is obtained from an aminoazo compound the formula

9884/1355

Case

B) N = N-R

L-X-Y

(XVa),

where y 'denotes r, t, ν or w with a coupling component of the formula

(HO S), -R -H

clutch and

the final dye contains 2 to 4 sulfonic acid groups. The azo compounds of the formula (XV) can also be obtained by using a compound of the formula

R-N = N

X-H

(XVb)

reacts with a reactive compound.

It is also possible to use compounds of the formula (Ia) which are substituted by the SO, H group, e.g. the diamine of the formula

NH

etc.

309884/1355

Such compounds are known or can be prepared by known methods, e.g., the 3,8-diaminodibenzofuran-7-sulfonic acid compound by sulfonating 3,8-diaminodibenzofuran in 30% oleum at 30-40 ° C can be obtained in a conventional manner.

Suitable coupling components, for example R, R ^, R ₃ , R ^, R ', R', ^R iii ^R ip ' ^R i3 ^are those of the aromatic series, for example those of the benzene or naphthalene series, which carry a substituent which enables coupling; these belong, for example, to the aminobenzene, hydroxybenzene, aminonaphthalenes or hydroxynaphthalene series. It is also possible to use coupling components of the heterocyclic series, such as those of the pyrazole series, for example those of the pyrazolone-5 or aminopyrazole series, also of the quinoline, hydroxyquinoline, barbaric acid, indole or carbazole series; Coupling components with a couplable methylene group are also suitable; These include, for example, acylacetylamino compounds, such as acylacetylamino-alkyl or -aryl compounds.

Examples of suitable coupling components are:

Alkylphenols 1,3-dihydroxybenzene, 2-hydroxynaphthalene, 1-hydroxy-4-alkoxynaphthalene,

2-hydroxy-8-acetylamino-6-methylsulphonylaminonaphthalene,

l-hydroxy-6-and-7-aminonaphthalene, l-hydroxy-6-and-7-methylaminonaphthalene, l-hydroxy-6-and-T-phenylaminonaphthalene,

30988A / 1355

A? 3
^l ^ -52- Case

1-hydroxy- (4'-methoxyphenylamino) -naphthalenes,

l-hydroxy- (2 ', 4', 6'-trimethylphenylamino) -naphthalene, etc.

Aromatic coupling component with a primary or secondary amino group, such as aminobenzene and its'

Derivatives,

1,5-diaminobenzene,

1-aminonaphthalene,

2-aminonaphthalene,

2-phenylaminonaphthalene,

2-methylamino-5- _{hydroxynaphthalene J} 2-hydroxynaphthalene sulphonic acids, such as, for example, 2-hydroxynaphthalene-4-, 5-, 6-, 7- or 8-sulphonic acid, 2-hydroxynaphthalene-disulphonic acid, such as, for example, 2-hydroxynaphthalene 4,6 -, 4,7-, 4,8-, 5,8- and 6,8-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-3,6 -disulfonic acid, 1-hydroxynaphthalenetrisulfonic acid, such as, for example, 1-hydroxynaphthalene-trisulfonic acid.

Heterocyclic coupling components are e.g. 1-phenyl-

3-methylpyrazolone-5,

1- (SuIfophenyl) -3-methyl-pyrazolon-5, l- (chlorophenyl) -3-methyl-pyrazolon-5, l- (cyanophenyl) -5-methyl-pyrazolon-5 »

1- (5'-halophenyl) -3-methylpyrazolon-5,
1- (5'-cyanophenyl) -3-methylpyrazolon-5,
1- (alkylphenyl) -3-methyl-pyrazolon-5,
1- (di- or trialkylphenyl) -> methyl-pyrazolon-5,
Aliphatic coupling components with an active methylene group are for example
1-acetoacetylarylamides such as
1-acetoacetylaminobenzene, etc.

309884/1355

l-acetoacetylamino-2-ethylhexane, l-acetoacetylamino-buta.n, etc.

The coupling components and all radicals of aromatic character can be substituted by substituents customary in dye chemistry, for example by halogen atoms, nitro, amino, such as primary, secondary or tertiary amines, cyano, rhodium, hydroxyl, alkyl, alkoxy -, trifluoroalkyl, trichloroalkyl, mercapto, alkyl or pheny! Mercapto, phenyl, cycloalkyl, phenyloxy, alkylamino, dialkylamino, phenylamine, acyl, acyloxy, -COOH, -SO ~ H , Acylamino, such as acetylamino, benzoylamino, alkylsulfonyl, arylsulfonyi, sulfonic acid amide,. Sulphonic acid alkylamide, sulphonic acid dialkylamide, sulphonic acid arylamide groups, arylazo groups, for example phenylazo, diphenylazo, etc. Preferred acyl groups correspond to the formula Rj ^ · "^!" or R ' u -Z-, in which R, j, denotes an optionally substituted Kohi @ iiwass © ret off radical which can carry the abovementioned substituents and / or may contain heteroatoms, preferably an optionally substituted alkyl or phenyl radical, Y, a Rest; of the formula -O-CO-, -SO "- or -0-SOp-, R * ^ a hydrogen at em or R- * h *

Z is a radical of the formula -CO-, -NR ^ CO- or -NR% S0 ₂ - and R% is a hydrogen atom or R ₁₂ . Halogen stands for bromine, fluorine or iodine, but in particular for chlorine. * '· ■

Hydrocarbon radicals mainly represent alkyl, aryl or cycloalkyl radicals. Alkyl radicals can be 1 to 18, but also 1 to 12, but advantageously 1 to 6 carbon atoms contain, preferably they stand for low molecular weight alkyl radicals having 1, 2, 3 or 4 carbon atoms. Aryl or arylene radicals mainly represent phenyl

30S8S4 / 13SS

or naphthyl radicals, or phenylene or naphthylene radicals, which the above. Can carry substituents. Cycloalkyl radicals are advantageously 5- or 6-membered saturated or partially saturated ring systems, but preferably cyclohexyl radicals which, if appropriate can be substituted by alkyl, alkoxy or halogen.

Alkoxy radicals usually contain 1, 2, 3 or -4 carbon atoms in the alkyl radical. Divalent bridge members are e.g. optionally substituted alkylene or alkeny

len -, arylene radicals, -0- ,, -S- or AlO where the first three groups mentioned can be interrupted by heteroatoms or heteroatom groups, for example by -IJI-, -0-, -S-, -NH-CO-, - . ^R 10

-CO-NH-, etc. or optionally substituted arylene radicals »Preferred substituents in the aromatic rings Z ^ to Z ₁₀ are, for example, halogen, alkyl or alkoxy. These rings Z, to Z, _Q can also have a group -CH = CH-CH = CH- condensed.

The couplings can be carried out by methods known per se; the first coupling in water is advantageous for one. pH-value of 6 to 8, and temperatures from -10 ° to +20 ⁰ C, preferably at 5 ° to 10 ° and most in the presence of coupling accelerators such as Pyridln, urea, etc; and the coupling of the diazo compound from the Amlnoazofarbstoff with the second coupling component is usually in water, at pH values of 9 to 12, preferably between 10 to 11 and at temperatures from -10 ° to +20 ⁰ C, preferably at 10 ° to 20 ° C carried out «The usual coupling accelerators can also be used in this coupling reaction.

-309884/1355

The acylation or tosylation is also in water 'at pH values of 8-10, preferably around 9 and at temperatures of 50 ° to 80 ° C, for example 50 ⁰ C; it is advantageous to work in the presence of sodium carbonate or disodium phosphate; you can also add an inert solvent such as dichlorobenzene.

The etherification, for example with dimethyl or diethyl sulfate, takes place mainly in water at a pH of 8 to 10 and temperatures of 30 to 80 ° C, preferably hO ° - 60 ° C and in the presence of, for example, sodium or potassium carbonate or -bicarbonate. The introduction of a reactive component, ie the reaction of the hydrogen atom of a free -OH or free -amino group with the halogen atom or a sulfato group of a reactive component, can also be carried out in water / water at a pH of 5 to 7 and at temperatures of 20 ° to 40 ° C, mainly in the presence of sodium acetate or sodium bicarbonate.

Metallization is generally carried out in water at a pH of 9 to 12 and at temperatures from 40 ° C to boiling temperature, preferably at 5O-8O ⁰ and in the presence of sodium hydroxide.

The metallization is advantageous with metal-releasing agents, e.g. with chrome, iron, cobalt, copper, manganese or nickel releasing agents carried out.

Copper-releasing compounds are, for example, copper acetate, chloride and formate; Nickel releasing compounds are e.g. nickel formate, acetate, sulfate; as chrome

30 9 88 4/13 55

releasing compounds are to be named; Chromium trioxide, Chromifluoride, Chromisulfat, Chromiformiat, Chromiacetat, Chromiamraoniumsulfat; also sodium chromate or bichromate can be used. Examples of compounds that donate manganese, cobalt or iron are. For example Manganese, cobalt or iron formate, acetate or sulfate.

The compounds can be used for various purposes. They are mainly used for dyeing or printing from natural and synthetic polyamides such as wool, silk and nylon, from cotton, tannic Cotton, cellulose fibers or fibers made from regenerated cellulose or from basic modified ones Polypropylene fibers; of synthetic polyamides or synthetic polyesters modified by acidic groups as well as of paper and leather; the polyazo compounds are particularly suitable for dyeing or printing on leather.

The anionic dyes as well as the metal complex dyes have good light and wet fastness properties on the aforementioned substrates, such as good washing, fulling and washing Potting, water, sweat, rubbing and sea water fastness; the substrates are evenly colored in brilliant shades and migrate well; they have a good neutral draw power and build-up ability and cover streaky coloring Nylon fabric. You have good substantivity on cotton and paper. They also have good fastness to solvents and are alkali and acid resistant.

The natural and colored with reactive dyes

30988A / 13BB

57 - Case 150-3Γ> 95

synthetic polyamides, as well as cellulose fibers ^ own good light fastness and good wet fastness, such as water, sea water, milled and perspiration fastness; the fixing power is also good.

A significant group of dyes, so-called benzidine dyes, i.e. those that differ from benzidine derive are due. Health hazard · withdrawn or considered, these dyes can no longer be manufactured.

There is therefore a real need for this group of valuable colorants to be replaced by others, in type and shade to replace similar dyes, intermediate compounds being used for the production of these dyes which are not, like benzidine, carcinogenic.

The new compounds of the present invention have this advantage because all of the bridging members of the formula

contain.

In the following examples, parts are parts by weight, percentages are percentages by weight; the temperatures are given in degrees Celsius.

4/1355

example

19.8 parts of J5> 8-diaminodibenzofuran are used in 150 Parts of water and 25 parts of hydrochloric acid suspended at O -2. Then a solution is made from 1 ^ parts of sodium nitrite in 60 parts of V / water is added dropwise to the suspension, the temperature is kept between 0 -5. After 30 minutes a solution consisting of 22.4 parts of 2-hydroxynaphthalene-8-sulfonic acid, 8 parts of sodium carbonate and 200 parts of water Tetrazo solution was added dropwise. The coupling compound is stirred at 0-5 ° for 2 hours. Afterward gives the coupling mass a solution consisting of 25.4 parts of l- (4'-sulfo) -phenyl-> methyl-5-pyrazolone, JJO parts of a $ 30 aqueous sodium hydroxide solution and 100 parts of water. The coupling mixture is stirred for 4 hours, during which the temperature can be allowed to rise to room temperature. The pH of the suspension is increased to 7 placed, the precipitated dye is then filtered off with an aqueous sodium chloride solution washed and dried at 100 °. The dye colors natural and synthetic polyamide neutral to slightly acidic bath in a pure orange shade with good wet and light fastness properties. The dye the formula

3 09 8 8 h I 1 3 E.

Cas2

= N-C C-CJL

HO

C-N-N

SO _V H

also dyes cotton. Paper and leather with good fastness properties.

Example

The tetrazotized 3 * 8-diaminodibenzofuran is coupled first on l- (4'-sulfo) -phenyl-3-methyl-5-pyrazolone then on 2-hydroxynaphthalene-8-sulfonic acid according to the reaction conditions described in Example 1,

in this way the isomeric dye of the formula N = N is obtained.

The dye stains natural and synthetic 30988W1355

Polyamide from a neutral to weakly acidic bath in pure Sharia tone with the. same good wet and Light fastness as the dye of Example 1.

The structure of other dyes is given in Table (I) below. You can after are prepared as in Example 1 and correspond to the formula.

Ca),

- (V- N = NR ₁

in which in the columns for R, R and X ¹ the starting compounds or radicals for the preparation of the dye (a) are indicated. In a further column (i) the shade of the coloring on synthetic polyamide (nylon), cellulose and leather is given.

30988W 1 3 B B

Case:> 50-3395

Table I.

No, Coupling com X ¹ Coupling com do. I. - orange component component R. ^R l. 3 2-hydroxy-naph- H 1-Pheny1-3-me- orange thalin-8-sul- ethyl-5-pyrazo- fonic acid lon 4th do. do. 1- (4- ¹ chIOr) - pheny1-3-me- orange ethyl ~ 5-pyrazo- lon 5 1- (2.5- ¹ DiChIOr- do 2-hydroxynaph - 4 ^J -sulfo) phenyl- thalin-8-sul- Scarlet fever 3-methyl-5-py-. fonic acid razolone 6th 2-hydroxynaph do. 2-hydroxynaph Scarlet fever thalin-6,8-di- thalin ν sulfonic acid Red 7th do. do. 1-hydroxynaph- thalin δ 1-hydroxynaph- do. thalin-3,6-di- sulfonic acid

309884/1355

Case 150-5 ^ 95

No, Coupling com X ¹ Coupling com I. component component R. ' ^R i 9 1-hydroxynaph- H 1-Pheny1-3-me orange thalin-2,6-di- ethyl 5-pyrazo sulfonic acid lon 10 2-amino-8-hy- do. 1-hydroxynaph- Red droxynaphtha- thalin-4-sul- lin-6-sulfone fonic acid acid (sour coupled) 11 1-aminonaph- do. do. orange thalin-4-sul- fonic acid 12th l-phenyl-3-me- do. l-amino-8-hy- Red ethyl-5-amino- droxynaphtha- pyrazole lin-3,6-disul- fonsäure (al Kalisch coupled) 13th do. do. l-amino-8-hydro- Red xynaphthalene 4,6-disulfonic acid - re (alkaline coupled) -

'309884 / 135-5

e 150-5595

No. Coupling com X ' Coupling com do. I. Red component component R. H ^R l 14th N-ethyl-N-ben- 2-hydroxynaph 1-4'Sulfo-phe- Red zylaniline-3- thalin-6-sul- nyl-5-methyl-5- Red sulfonic acid H fonic acid pyrazolone
I. 15th N-diethylaniline H 'do. Red 16 N-methylaniline 1-hydroxynaph- Red H fonic acid 17th N-phenyianiline H do. 18th N-ethyl-N-ben- ortho-hydroxy Red zylaniline-5 ^! - benzoic acid Red sulfonic acid S0, H 19th do. ' do. do. 20 · 1-hydroxynaph- 1-Pheny1-5-me- Red thalin-5,6-di- ethyl-5-pyrazo- sulfonic acid do. lon 21 2-hydroxynaph Red thalin-6-sul- r
fonic acid H 22nd 2-hydroxynaph thalin-8-sul- fonic acid

309884/1355

No. Coupling com
component
R. X ' Clutch compo-
component
^R l I. Red 2? 2-hydroxynaph
thalin-8-sul-
fonic acid SO H 2-hydroxynaph
thalin Red 24 1-4'-SuIfo-phe-
nyl-3-methyl-
5-pyrazolone do. 2-hydroxynaph
thalin-8-sul-
fonic acid Red 25th N-ethyl-N.-ben-
cylaniline do. 2-hydroxynaph
thalin Red 26th do. do. 1-hydroxynaph-
thalin Red 27 do. do. 2-hydroxynaph
thalin-8- sulf on-
acid Red 28 N-ethyl-N-ben-
zylaniline-5'-
sulfonic acid do. 1-hydroxynaph-
thalin orange 29 1-acetoacetyl
amino-2,5-di
methoxy benzene do. 2-hydroxynaph
thalin-8-sul- ■
fonic acid orange 30th Acetoacetyl
aminobenzene do. do.

3 09884/1355

Case

No Coupling com
component
R. X ¹ Coupling com
component
^R l T 51 Acetoacetic acid
o-anisidide SO H 2-hydroxynaph
thalin-8-sul-
fonic acid orange 52 1-acetoacetyl
amino-2-ethyl-
hexane do. do. orange 55 l- (4'-sulfo) -
phenyl-5-me-
thyl-5-pyrazoloj do. Acetoacetylarai-
nobenzol yellow 54 N-ethyl-N-ben-
cylaniline do. 1-hydroxynaph-
thalin-5-sul-
fonic acid bluish tint
Red 55 1-hydroxynaph-
thalin-5,6,8-
trisulfonic acid H I-phenyl-5 ~ never-
ethyl-5-pyrazo ~
lon orange 56 2-hydroxynaph
thalin-5,6,8-
tri sulfonic acid H do. orange. 57 2-amino-8-hy-
droxynaphtha-
lin-6-sulfone-
acid (acid
Coupling) H ortho-hydroxy
benzoic acid Red

30988Λ / 1355

Case lpO-3395

No. - Coupling com * X ¹ Coupling com do. I. component component 41 R. l- (4'-sulfo) phe- H orange 58 l-phenyl-J-me- nyl-3-methyl-5- 2-hydroxybene 2-amino-8-hydro- ethyl-5-pyrazo- aminopyrazole zol-1 carbon xynaphthalene-6- 42 lon-4 ^! -sulfone- acid sulfonic acid acid H Brown 39 2,4,2'-trihydro 1-hydroxynaphtha- xyazobenzene-5 ¹ - lin-3,6,8-tri- sulfonic acid H sulfonic acid blue-schv-ia 40 1-amino-8-hydro- 2-hydroxynaph xynaphthalene thalin-3,6,8- 3,6-disulfonic acid trisulfonic acid re H l- (4'-sulfo) me- orange l-phenyl-3-me- ethyl-3-methyl- thyl-5-pyrazolone ;. py ^ra zolon H orange do. H yellow

3 0988 U / 1355

Case

No. Coupling com
component
R. X ' Clutch skom-
component
^R l I. 44 N-ethyl-ben-
zylaniline-5'-
sulfonic acid H l- (4'-sulfo) me-
ethyl-5-methyl-
5-pyrazolone yellow 45 2-hydroxyna? Ph-
thalin-8-sul
fonic acid H 1- (2J5'-dichloro-
4'-sulfo) phenyl-
3-methyl-5-py-
razolone orange 46 2-hydroxyn ^ ph-
. thaiin H do. orange 47 db. H 2-hydroxynaph
thalin-6,8-di-
sulfonic acid Scarlet fever 48 l-phenyl-3-me-
ethyl-5-pyrazo-
lon H do. yellow 49 do. H 2-hydroxynaph
thalin-8-sul
fonic acid yellow
• 50 do. SO, H do. yellow 51 do. do. 1-hydroxynaph-
thalin-5-sul
fonic acid Scarlet fever'

098ΒΛ / 135Β

ORIGINAL tNSPECTED

Case 150-5595

No. Coupling com do. X ' Coupling com - I. component component R. SO, H ^R l yellow , 52 l-phenyl-5-me- 2-hydroxynaph ethyl-5-pyrazo- thalin-6-sul- lon H fonic acid bluish cast 55 do. l-amino-8-hy- Red droxynaphtha- lin-5,6-disul- fonsäure (al kalisch gekup H pelt) do. 54 2-hydroxynaph 1-acetylamino thalin-8-sul- 8-hydroxynaph- fonic acid thalln-5.6-dl- 2-hydroxybene sulfonic acid zol- 1- carbon- ■ (alkaline ge acid H coupling) Scarlet fever 54a N-ethyl-N-ethyl phenyl.-5-sulfon- H acid do. 54b l-phenyl-5-me- ethyl pyrazolone 5- (4-sulfone acid re)

309884/1355

- 49 - Ca? E 150-2393

Example 55

51 parts of 2-hydroxynaphthalene-6,8-disulfonic acid are used in 500 parts by volume of water with the addition of 15 parts of sodium carbonate solved. This solution is added dropwise to the tetrazo solution prepared according to Example 1. After five hours Stirring at 0 ° -5 °, the coupling compound is given a solution consisting of 9.5 parts of phenol and 25 parts of sodium carbonate and 200 parts of water. The coupling mixture is stirred for 4 hours, the temperature may rise to room temperature. The disazo dye is after an intermediate isolation in 800 parts Stirred water with the addition of 30 parts of sodium carbonate, heated to 50 ° and added at this temperature benzenesulfonyl chloride with stirring, in portions. If no more starting material can be determined in the thin-layer chromatogram, the suspension will increase cooled, filtered, washed with a 2 # aqueous sodium chloride solution and dried at 100 °. The dye dyes natural and synthetic polyamide in a pure scarlet shade with good wet, Alkali-Γ light and boiled fastness. The dye of formula

N = N- \ / - 0-SOg- / \

309884/1355

Gas «lfsC-5295

also dyes cotton, paper and leather with good fastnesses.

Example 56

The free hydroxyl group obtained in Example 55 Disazo dye can also be used with diethyl sulfate instead of benzenesulfochloride under the same conditions implemented. The dye of the formula is obtained

N = N

OC ₂ H ₅ ,

which dyes natural and synthetic polyamide in scarlet shades with good fastness properties. Table II shows the structure of other dyes which can be prepared according to the information in Example 55.
They correspond to the formula

R ₁ -N = N

N = NR ₂ -OR

Cb),

309884/1355

- 51 - Case 1 ^ 0-5395

in which in the columns for R ¹ and X 1 the starting compounds or the radicals for the preparation of the dye (b) are indicated. The radicals R _p and R are listed in further columns and the shade of the dyeing on nylon, cellulose and leather is given in a further column (I).

309884/1355

Case lbO-J>7> 95

Table II

No. Coupling com X ' Remainder R Remainder R, I. ponent ^R l 57 2-hydroxynaph
thalin-6,8-di-
sulfonic acid H O- Scarlet fever 58 do. H do. -CH ₅ do. 59 do. H dP " do. do. 60 do. H do. -O ₂ H ₅ do. 61 do. H do. -SO ₂ -O-OH ₅ do. 62 1-hydroxynaph-
thalin-3,6-di-
sulfonic acid H do. do. do. 6 ^ do. H O- do. do. 64 do. H do. -C ₂ H ₅ do. 65 do. H do. -CH ₅ do. 66 1-hydroxynaph-
thalin- ^ sul-
fonic acid H do. -SO ₂ O-CH ₅ do. 67 do. SO H do. do. do. 68 do. do. do. -C ₂ H ₅ do.

09884/1355

~ 55 -

Case 150-5395

No. Coupling com X ¹ Radical R ₂ Remainder R, I. ponent ^R l 69 2-hydroxynaph
thalin-8-sul-
fonic acid SO H -O- -SO ₂ -Q-CH ₅ Scarlet fever 70 do. do. do. "C ₂ H ₃ do. 71 do. H do. -SO ₂ -Q-CH ₅ do. 72 l- (4'-sulfo) -
phenyl-5-me-
ethyl-5-pyra-
zolon H do. do. yellow 75 1- (2i 5-! Disul-
fo) -phenyl-5-
methyl-5-pyra-
zolon H do. do. do. 74 do. H do. -C ₂ H ₅ do. 75 do. H do. -CH, do. 76 do. H -8th" -SO ₂ OCH ₅ orange 77 l-phenyl-5-me-
ethyl-5-pyrazo-
ion 5'-sulfone
acid SO H do. yellow 78 l-phenyl-5-me-
ethyl-5-amino-
pyrazole-4 ¹ -sul-
fonic acid do. do. do. do.

309884/1355

So yes

No. Coupling com
ponent
^R l Χ ' Radical R ₂ Remainder R I. 79 N-ethyl-ben
zyl aniline-5 ¹ -
sulfonic acid O f \ TJ O -rO-, yellow 80 do. do. do. - ° a ^H 5 do. 81 2-amino-8-hy-
droxynaphtha-
lin-6-sulfone- do. do. -SO ₂ O-CH ₃ Red acid 82 2-acetoacetyl
amino-naphtha-
lin-5,7-disul-
fonic acid H do. do. yellow 85 2-aminonaph-
thalin-5,6-di-
sulfonic acid H do. do. orange .84 do. H do. -C ₂ H ₅ do. 85 do. H do. " ⁸⁰ SO do. 86 1-hydroxy
naphthalene-
5,6,8-trisul-
fonic acid H do. -SO ₂ -Q-OH ₅ Red 87 do. H do. -C ₂ H ₅ do. 88 2-hydroxynaph
thalin-5,6,8-
trisulfonic acid H do. do. Scarlet fever 89 do. H do. -SO ₂ -Q-CH ₅ do. 90 do. H do. - ^S0 2 "O do.

3098 8 A / 1355

Casu

No. Coupling com
ponent
^R l X ¹ Radical R ₂ Remainder R I. 91 2-hydroxynaph
thalin-3,6,8-
trisulfonic acid H O- -CH, Sharia 92 1-hydroxynaph-
thalin-3,6,8-
trisulfonic acid H do. -, Ο do. 92a 1-hydroxynaph-
thalin-3,6-di-
sulfonic acid H ■ 8 " "™ ^ ** ^ tV J V *» Xi - » do.

309884/1355

Cas3 150-5595

Example 95

The tetrazotized 5j8-diaminodibenzofuran is coupled first on phenol and then on 2-hydroxynaphthalene-6,8-disulfonic acid according to those described in Example 55 Reaction conditions are obtained after the reaction of the hydroxyazo dye obtained with p-Toluolsulfonsäurechlorld a dye of the formula

SO ₂ -O

N = N,

The dye dyes natural and synthetic polyamide in scarlet, pure shades with good fastness properties.

In. the structural design is more similar to Table III Listed dyes which can be prepared according to the information in Example 95. They correspond to the formula

R ₃ -OR ₂ -N = N.

X '- / \ - <^ N— N = N-

(c)

309884/1355

OF.se

Table III

No. Coupling com
ponent
^R l X ' Radical R ₂ Remainder R, I. 94 2-hydroxynaph
thalin-6,8-di-
sulfonic acid H O -VO Scarlet fever 95 do. H do. -CH, do. 96 do. H -P-
CH, do. do. 97 do. H do. -C ₂ H ₅ do. 98 do. H do. ™ "OW / ~ ί ^ \ / vll-f do. 99 1-hydroxynaph-
thalin-Jjö-di-
sulfonic acid H do. do. do. 100 do. H -O- do. do. 101 do. H do. -C ₂ H ₅ do. 102 do. H do. -OH ₃ do. 103 1-hydroxynaph-
thalin-3-sul-
fonic acid H do. -SO ₂ O-CH ₃ do. 104 do. SO _} H do. do. do. 105 do. do. ok -C ₂ H ₅ do. 106 2-hydroxynaph
thalin-8-sul-
fonic acid do. do. -SO ₂ -O-CH ₃ do. 107 do. do. do. "C ₂ H ₅ . do.

309884/1355

Case 1 ^ 0-5595

No. Coupling com
ponent
^R l X ' Remainder R _n
d Remainder R I. io8 2-hydroxynaph
thalin-8-sul-
fonic acid H -0- -SO ₂ -Q-CH ₅ Sharlaoh 109 l- (4'-sulfo) -
phenyl-3-me-
ethyl-5-pyra-
zolon H do.. do. yellow 110 l- (2] 5'-disul-
fo) -phenyl-3-
methy1-5-pyra-
zolon H do. do. do. 111 do. H do. -C ₂ H ₅ do. 112 do. H do. -CH ₅ do. 113 do. H -SO ₂ -OCH ₅ orange 114 l-phenyl-3-me-
ethyl-5-pyrazo-
ion 3'-sulfone
acid SO ₅ H O do. yellow 115 l-phenyl-3-me-
ethyl-5-amino-
pyrazole-4 ¹ -sul-
fonic acid do. do. do. do. 116 N-ethyl-ben-
zyl-aniline-3 ^! -
sulfonic acid do. do. do. do. 117 do. do. do. -C ₂ H ₅ do. 118 2-amino-8-hy-
droxynaphtha-
lin-6-sulfone- do. do. -SO ₂ Q) -CH ₅ Red acid

309884/1355

150-5595

No. Coupling com
ponent
^R l X ¹ Remainder Rp Remainder R I. 119 2-acetoacetyl
amino-naphtha-
lin-5,7-disul-
fonic acid H Ό- - ^S0 2 <> ^CH 5 orange

10988 W1355

- 60 - Case 150-519?

Example 120

19.8 parts of 3,8-diaminodibenzofuran v / earth in 150 parts Suspended water and 25 parts of hydrochloric acid at 0-2 °. Afterward a solution consisting of 14 parts of sodium nitrite in 60 parts of water is added dropwise to the suspension, keeping the temperature between 0 ° -5 °.

After 50 minutes a solution consisting of 13j7 Parts of para-cresidin, 100 parts of acetone and 20 parts of water were added dropwise to the tetrazo solution. After 3 hours Stirring at 0 ° -5 °> the pH of the suspension is adjusted to 5 by adding 10 parts of sodium acetate. After a further hour, the coupling compound is given a solution consisting of 58.4 parts of 1-hydroxynaphthalene-5,6,8-trisulfonic acid, 40 parts of a 50% aqueous sodium hydroxide solution and 100 parts of water. The coupling mixture is stirred for 4 hours, the temperature being allowed to rise to room temperature allowed. The pH of the suspension is adjusted to 7, the dyestuff which has precipitated out is then filtered off with suction and washed with an aqueous sodium chloride solution.

18.4 parts of cyanuric chloride are suspended in 200 parts of water and 200 parts of ice. While stirring vigorously leaving a neutral solution of the amino disazo dye obtained Flow in 600 parts V / water at 0 °. Blows! the pH of the reaction medium is maintained Addition of a 15% aqueous sodium carbonate solution always between 5 and 4. The condensation product

Ί098ΒΑ / 1355

- 6i -

Case 150-3595

it is precipitated with sodium chloride, filtered off and purified with an aqueous sodium chloride solution. The dye is dried in vacuo at 40 ° -5O °. He is a brown powder when ground, which dissolves in water with a scarlet color. The dye the formula

Cl

OCH,

CH,

OH SP ₃ H

no s

dyes cellulose fibers in light, wash, water, and sweat-proof tones and wool, silk and synthetic polyamide in light, wash, water, smoldering, milled and dry-cleaning scarlet tones.

In the following Table IV the structural structure of further dyes is given, according to the information in Example 120 can be made. They correspond to the formula

X '

N = N-R,

20th

in which in the columns the symbols Rp ₀ , Hp ₃ , X ¹ and Rp, the starting compounds or radicals used for the preparation of the azo compounds of the formula (d)

309884/1355

- 62 - Case χ? 0-5; · 95

are led. In a further column (1) the nuance is found indicated by the coloring on cellulose and polyamide.

309884/1355

Case

Table IV

No. ^R 20 X ' ^R 21 ^R 22 Nuance of
Coloring on
Polyamide (I) 121 1-hydroxynaph-
thalin-3,6-di-
sulfonic acid H O Cyanuric chloride Scarlet fever 122 do. H do. do. 123 2-hydroxynaph
thalin-6,8-di-
sulfonic acid H do. do. do" 124 do. H do. Tetrachloropy
rimidin do. 125 do. - H do. Trifluorochlorine
pyrimidine do. 126 do. H do. do. CH ₅ 127 do. H -Q-
CH, Cyanuric chloride do. 128 2-hydroxynaph
thalin-3,6,8-
trisulfonic acid H do. do. do. 129 l-phenyl-3-me-
ethyl-5 ~ pyrazo-
lon-2 ', 5'-di-
sulfonic acid H do. do. golden yellow 2-IIydro>: ynaph-
thalin-6,8-di-
sulfonic acid H SO, H do. Red

3Q988W135B

Case I5C-5395

No. ^R 20 X ' ^R 21 ^R 22 Nuance of
Coloring on
Polyamide (I) 151
152 2-hydroxynaph
thalin-6,8-di-
sulforic acid
1-hydroxynaph-
thalin-4-sul-
fonic acid H
-SO H SO H
do. Cyanuric chlorine d
do. golden yellow
Red 155 2 - hydroxynaph
thalin-8-sul-
fonic acid do. do. do. do. 154 do. H ft », do. do. 155 do. H \ ~ y 5
OH do. bluish tint
Red 156 do. H OH do. Red 157 N-ethyl-N-ben-
zylaniline-5 ¹ -
sulfonic acid H SO H
OCH
CH Trichlorofluoro-
pyrimidine violet 158 2-hydroxynaph
thalln-6,8-di-
sulfonic acid H do. do. Red 159 do. H do. Cyanuric chloride Red 140 do. H do. 2-anilino- > \, G-
dichloro-S · vri-.
azin Red 141 do. H do. 2-anilino · ■ ■ :. 6-
diehlor-S-U'i-
azin-4'-aulfon-
acid Red

:.? 0 9 8 IU / 1 3 5 K

BADOHKaINAt

- 65 - OtLhe 3 5C-3595

Example l42

19.8 parts of 3,8-diaminodibenzofuran are in 150 parts Suspended water and 25 parts of hydrochloric acid at 0 ° -2 °. Then a solution consisting of 14 parts Sodium nitrite in 60 parts of water in the suspension, added dropwise, keeping the temperature between 0 ° -5 °. ■

After 50 minutes, a solution consisting of 30.4 parts of 1-hydroxynaphthalene - ^ / δ-disulfonic acid, 8 parts of sodium carbonate and 200 parts of water is added dropwise to the tetrazo solution. The coupling compound is stirred at 0-5 ° for 2 hours. The coupling compound is then poured into a template consisting of 13.7 parts of p-cresidin, 100 parts of acetone, 70 parts of water and 25 parts of an aqueous hydrochloric acid solution. The coupling mixture is stirred for a further 1 hour, the pH being below 1. The pH of the suspension is gradually adjusted to 4.5 by adding a 25% strength aqueous sodium acetate solution dropwise over a period of J hours.

The pH of the suspension is adjusted to 7 with sodium hydroxide solution, and the dyestuff which has precipitated out is then filtered off with suction, washed with an aqueous sodium chloride solution and dried at 100 °. The amino disazo dye is reacted with cyanuric chloride as described in Example 120.
The dye of the formula

3 0 9 8 8 4/1355

- 66 - Case 150-559.

dyes cellulose fibers in light, wash, water and Sweat-proof tones and wool, silk and nylon in light, wash, water, sweat, milled and dry cleaning-proof scarlet tones,

Example 145

52 parts of 5-acetylamino-8-aminodibenzofuran-7-sulfonic acid (obtained by acetylating 5,8-diaminodibenzofuran-7-sulfonic acid with acetic anhydride in an aqueous medium at room temperature) are dissolved in 100 parts of water and 10 parts of 50% aqueous sodium hydroxide solution dissolved at room temperature. 5 * 5 parts of sodium nitrite are added to this solution and the mixture is stirred for 15 minutes. The solution is then dripped into 50 parts of concentrated hydrochloric acid and 150 parts of water at 0 ° -5 ° over the course of 50 minutes, while stirring, and the resulting slide suspension is allowed to stir for a further half an hour. A solution consisting of 50.4 parts of 1-hydroxynaphthalene-5,6-disulfonic acid, 20 parts of a 50% aqueous sodium hydroxide solution and 200 parts of water is added dropwise to the diazo suspension. The coupling mass is used during 2
Stirred at 0-5 ° for hours. The paraffin suspension is then heated to 90 ° and, after adding

309884 / 13SS

- 67 - Case 150-3395

50 parts of a 30 $ aqueous hydrochloric acid solution boiled for 3 hours at 90 °. The precipitated aminoazo dye is filtered at 60 ° and washed with a 10% strength hydrochloric acid solution, stirred in 200 parts of water and dissolved with 20 parts of 30% aqueous sodium hydroxide solution. 3 parts of sodium nitrite are added to this solution and the nitrite-containing solution is then added dropwise with stirring in 25 parts of hydrochloric acid and 150 parts of water at 0-5 °. The resulting diazo suspension is stirred for a further half an hour.

Then a solution consisting of 12 parts of p-Kre'sidin, Ί00 parts of acetone and 70 parts of water / water Diazo suspension added. By adding dropwise for 3 hours a 25 $ -lgen aqueous sodium acetate solution is the The pH of the suspension was gradually adjusted to 4.5. The coupling mixture is stirred for 4 hours, with one allow the temperature to rise to room temperature. The pH of the suspension is adjusted to 7, the precipitated dye is then filtered off with suction and washed with an aqueous sodium chloride solution. The implementation of the amino disazo dye obtained with cyanuric chloride is carried out as described in Example 120. The dye is dried in vacuo at 40-50 °. When ground it is a brown powder that dissolves in water with a scarlet color. The dye the formula

10988 A / 135R

Case IpC-3395

egg

= N- / N-NH- / ^V N
OCH, Cl

dyes cellulose fibers in light, wash, water, and Sweat-proof tones and fulls, silk and synthetic Polyamide in light, wash, water, sulphurous, walked and dry-cleaning scarlet tones.

In the following table V the structural structure of further dyes is given, according to the information in example l4j. They correspond to the formula

R ₂₅ -N = _NV

in which in the columns the _{symbols R p} ,, RphJ X 'and R ₂ ^ the starting compounds or radicals used for the preparation of the azo compounds of the formula (e) are listed. In a further column (I) the shade of the color on cellulose and polyamide is given.

BAD OBtGlNAL

0 98RA / 1 3 5 5

Oasis 150-5. ^ 95

Table V

No. R ₂₅ do. X ^{1 R} 24 do. SOjH ^R 25 I. 144 1-hydroxynaph-
thalin-5,6-di-
sulfonic acid H O do. Cyanuric chloride Scarlet fever 145 do. H "8th" do. do. 146 2-hydroxynaph
thalin-6,8-di-
sulfonic acid H do. SO H do. do, 147 do; H do. T et raehlorpy-
riinidin do. 148 do. H do. : Trifluorochlorine
pyrijrildin do. 149 do. H ^ 0CH ₅ do. do. 150 do. H ~ o ~ Cyanuric chloride do. CH, 151 2-hydroxynaph
thalin-3,6,8-
trisulfonic acid e H do. do, 152 l-phenyl-3-me-
ethyl-5-pyrazo-
lon-2, '5 -! - di sul
fonic acid H do. golden yellow 153 2-hydroxynaph
thalin-6,8-di-
sulfonic acid H do. Red I. 154 H do. do.

309884/1

- • 70 -

■ Weeding -3 5C-5595

No. R ₂₅ X ¹ ) - (' OCH _x ^R 25 I. Red 155 1-hydroxynaph- -so. \ / O- Cyanuric chloride thalin-4-sul- SOH V- / fonic acid do. CH-, do? do. 156 2-hydroxynaph do do. thalin-8-sul- (Vs 0-, H fonic acid OH
■ ttx do. do. 157 do. H SO H SO H do. do. bluish tint
Red 158 do. H OH do. Sun ₅ H Red 159 do. H do. do. violet Ι6θ N-ethyl-N-ben- H ; Trichlorofluid zylaniline-3 ¹ - -0- orpyrimidiri sulfonic acid Red 161 2-hydroxynaph H do. thalin ~ 6,8-di- sulfonic acid Red 162 do. H Cyanuric chloride Red Χ6 ₅ do. H 2-anilino-4,6- dichloro-S-tri- azin Red 164 do. H 2-aniline-4,6- dichloro-S-tri- fonic acid Red 164σ 1-hydroxynaph- SO I Prifluorochlorine thalin ^, 6-di- pyrimidine sulfonic acid

ORIGINAL INSPECTED

4/13 pp

Case 150-3,595

No. R ₂₅ X ^{1 R} 24 ^R 25 I. l64b l ~ phenyl-3i-
methyl pyra
zolon-5- (2j5'-
disulfonic acid H SO H Cyanuric chloride orange

fNSPECTEO

'J 0 9 8 8 / * / 1 3 5B

Gases 150 5595

Example I65

75/6 parts of the dye from Example 100 are dissolved in 1000 parts of water at 60 °, and JO parts of sodium acetate and 115 parts of a 1 molar copper sulfate solution are added. Within 5 hours, added dropwise to a 4o $ Wassersfcoffperoxydlösung strength at a temperature of 6O-65 ⁰ 29 portions, the pH * 5 is held by the dropwise addition of a 30 ^ ammonia solution at 5 * 0-5. The copper complex is precipitated by adding sodium chloride, filtered off and washed with a dilute aqueous sodium chloride solution. The dye of the formula

dyes natural and synthetic polyamides and. Cellulose in real brown tones.

In Table VI is the structure of other dyes listed, which can be prepared according to the information in Example 165.

J 0 9 8 R A / 1 3 5 R

3 example no.

166

167

168

169

Starting dye from example no.

101

95

99

111

Complex dye

H "C _o 0 - Ο - N = N.

O Cu O

H-C-O

U on,% ΐ c

N = N SO H

0 - Cu 0.

SO H

r-Cu 0

SO, H SO ₇ H

N = N-

0-Cu-0

HO S

-CK-

-N

Brown

Brown

dark

Brown

Brown

Kf CD

ro

CO -ΡΙΟ

-J

example

No.

CD CD CO

ω cn cn

170

171

172

175

Starting dye from example no.

57

Complex dye

SO.H 3

SO H SO ^ H

N = N- <o;

Brown

OC ₂ H ₅

red brown j

red-brown

red-brown

V ;.

Case 150-3593

Example 174

If one uses p-cresol instead of phenol is used as the second coupling component, the disazo dye can no longer tosylate. But it is possible to treat the disazo dye obtained under the same conditions as in Example 165, however with twice the amount of sodium acetate, copper sulfate and hydrogen peroxide. The obtained dye of the formula

dyes polyamide and cellulose fibers in navy blue shades.

In a manner similar to that stated in Example I65, the following examples can be produced.

Example 175

navy blue

BAD OFBQiNAL

098fU / 13BR

Case 150-3395

Example 176

navy blue

Example 177

navy blue

Example 178

O-

N = N navy blue

-CH

, Ο N "I S O Ji

HO S

3Q988W135S

Case 150-5395

Example 179

GOOH OH

Color regulations

The dyeing with the metal-containing dyes can, according to the information in French patent 1,570 * 521 *, the dyeing with the anionic dyes according to the information in the Belgian patent 752 * 845, the dyeing of leather
the information in the Belgian patent 745'82I and dyeing are performed with the reactive dyes according to the information in French Patent 1'42O ^1687.

309884/1 355

Claims (1)

Claims 1. Azo dyes containing sulfonic acid groups of the formula R-N = N (D, wherein R is the remainder of a coupling component, R is the remainder of a coupling component different from R and
η mean 1 to 8 and the aromatic rings A and / or B by in. the azo chemistry Usual substituents can be further substituted. 2. Azo dyes containing sulfonic acid groups of the formula (i) according to claim 1, characterized in that the -SO Η groups can be present in the aromatic radicals R or R, and contain ρ sulfonic acid groups,
where ρ is 1, 2, J or 4. ^. Azo dyes containing sulfonic acid groups according to claim 1 according to the formula R-N = N CMD- 309884/1355 Case 150-3393 wherein q is 1, 2 or J. 4. Azo dyes containing sulfonic acid groups according to claim 1 according to the formula ; -Ν / -ν / A \ / B \ —N = NR ₁ (III) 5, sulfonic acid group-containing azo dyes according to claim 1 according to the formula (HO ₅ S) _r -RN = (IV) ,. / AN f ΒΛ — N = N - R ₁ - O ^ SO, H viorin r means 1 or 2. · 6. Azo dyes containing sulfonic acid groups according to claim 1 according to the formula HO ₅ SRN = N (V) B VN = NR ₁ - (SO ₅ H) ₂ 7. Azo dyes containing sulfonic acid groups according to claim 1 according to the formulas 8AD ORKaINAL 309884/1355 - 8ο - Case- 150-2295 R ₅ -OR ₂ -N = N. B> —N = N-R, (VI) or R ₁ -N = N, N = NR ₂ -OR (VlI), wherein R _{p is} an optionally substituted arylene rest and R denotes an optionally substituted hydrocarbon radical or acyl radical and 2 —SO, H groups can occur in the aromatic rings A and / or B and / or in the radicals R. or R. 8. Azo dyes containing sulfonic acid groups according to the patent claim 1 according to the formula R-N = N (XV) -X-Y where X is the direct bond or a bivalent or trivalent bridge member,
Y is a fiber-reactive radical and ν is 2, 2 or H. .Ί 09884/135 5 Case 15O-> 595 and v-SQ, H - groups in, the aromatic rings Λ and / or B and / or in the radicals R or. R-. can occur. 9. Azo dyes containing sulfonic acid groups according to claim 1 according to the formulas Y-X-R-N = N / ~ Ä ~ \ / b \ N = NR ₁ (XVI), R-N = N N = NR ₁ -XY (XVII) where v is 2, 3 or 4. 10. Azo dyes containing sulfonic acid groups according to claim 1 according to the formula R-N = N Me— , 5 N, -n = n-r _'10 -n = n-r' _{i: l} (LXXIV), 8AD ORiGiNAL 3098 8 4/1355 Case or the formula X Me-X ^ ⁶ f I ⁵ N = N-R (LXXV), wherein RVq and R 'are each the remainder of a coupling component of the benzene, pyrazolone-5, or aminopyrazole or naphthalene series, or from the series of the acetoacetylamine series, and Xg each -NH-R ₁₀ JO- or -CQO- and a metal atom, such as Mean copper, nickel, iron, cobalt, manganese or chromium and j. and Χ. each in a position adjacent to -N = N- Group stand and R, "Uassei'stoff or an optionally Substituted hydrocarbon residue means. X, - Me 11. Azo dyes containing sulfonic acid groups according to claim 1 corresponding to the formula Me — X ₁ . I ⁶ ί Ι; ι ⁵ ι Γ BV-N = N-R _'10 -N = N-R' ₁₁ 5 Q. (LXXVI) 309884/13 55 Cass 130-159? 12. Azo dyes containing sulfonic acid groups according to claim 1 according to the formula R-N = R -Me-X, --(so. NiN-R '. (LXXVII) or the formula Me-X, - -N = N-Rl 10 / SO ₃ H) (LXVIIIX Polyazo dyes containing sulfonic acid groups according to claim 1 corresponding to the formula NH ₂ OH (LXXX), wherein R, p is the remainder of a coupling component of the benzene, pyrazolone-5 ™ or aminopyrazole or naphthalene series,
R ₁ ^. the remainder of a diazo or coupling component the benzene or naphthalene ihe and t mean zero or 1. BATH ORIGINAL 1098 8 4/1355 14. Process for the preparation of sulfonic acid group-containing azo dyes of the Poi-mel (I) according to claim 1, characterized in that in any order a tetrazo compound from a diamine of the formula NH (Ia) with a coupling component of ^{the 1 B formula} R-H (Ib) and with a coupling component of the formula R ₁ -H (Ic) clutch, and n, or ρ or q or r or t or ν or w -SO-H groups in the aromatic rings A and / or B and / or in the coupling components R and / or R occurrence. 15. Process for the preparation of azo dyes of the formulas (VI) or (VIl) according to claim 7, characterized in that a compound of the formula HO-R-N = N N = N-R, SO _x H) 5 ^y (Via) 3O988 / 4 / I355 Case 130-i595 or a compound of the formula (Vila) Yerätnert or acyliert ,, where the p-SO, Η groups in the aromatic rings A and / or B and / or in the radicals R ₁ or R _{0 can} occur. 16. Process for the preparation of azo dyes of the formula ~~ fso. where R ' _{denotes an optionally substituted arylene radical different from R 2} , and r-SQ, H groups can occur in the aromatic rings A and / or B and / or in the radicals R _p or R' or R, characterized in that one connects the formula HO-R ₂ -N = N N = NR ₂ -OH (XIIa) 309884/1355 ~ 86 - So yes etherified or acylated, it being possible for r ~ SCuH groups to occur in the aromatic rings A and / or B and / or in the radicals R ₂ or R '. 17. Process for the preparation of azo dyes of the formula (XV) according to claim 8, characterized in that that one can convert the diazo compound from an aminoazo compound the formula B V-N = N-R -X-Y (XVa), where y ' denotes v, t, ν or w with a coupling component of the formula (HO ₅ S) _yl -R ₁ -H clutch and- the final dye contains 2 to 4 sulfonic acid groups. 18. A process for the preparation of azo dyes of the formula (XV) according to claim 8, characterized in that that you can get a compound of the formula R-N = N - (S0 ₅ H) _v XH (XVb) 309884/1355 reacts with a reactive compound. 19. Process for the production of metal-containing azo dyes of the formula (I) according to claim 1, characterized in that compounds of the formula (I), in which the aromatic rings A and / or B and / or the radicals R and / or R enabled metal complex formation Contain groups, treated in substance or on the fiber with metal donating compounds. 20. Process for dyeing, padding and printing natural and synthetic polyamides, of cotton, tannin cotton, of cellulose fibers or of fibers from regenerated cellulose or from basic modified polypropylene fibers, from leather and from paper, characterized in that azo dyes are used for this purpose of the formula (l) according to claim 1 is used. 21. The padded colored according to claim 20 and printed materials. _/ Ζ The patent attorney 988 4/1355