DE2123061A1 - Azo compounds, their manufacture and use - Google Patents

Description

DR. BERQ DIPL.-INQ. STAPF

PATENT LAWYERS 8 MUNICH BO, MAUERKIRCHERSTR. ^ b 2123061

CIBA-GEIGY AG, Basel (Switzerland)

( Case 1-7041 / 1 + P / E

Germany ) \ Q,

OlIcU, **

Azo compounds, their manufacture and use.

The present invention relates to azo compounds which are a radical of the formula. ·

(U

R.
contain, in which R is an alkyl radical and R ^{1 is} an alkyl or aryl radical. The remainder of the formula (I) is linked to the remainder of a diazo component via an azo bridge. The diazo radical is a heterocyclic or aromatic radical which can itself contain an azo group or which is derived from a compound of the anthraquinone, nitroaryl, phthalocyanine, stilbene series or the like. In particular, the di-

109848/1771

a'zorest a residue of the benzene or naphthalene series.

The azo compounds according to the invention can be free from groups which make them soluble in water, such as, for example, sulfonic acid, carboxyl or quaternized amino groups; in particular, however, they can also contain such groups. Above all, the compounds in the molecule can have one or more than one reactive radical, such as, for example, a halotriazine radical. contain. In addition to water-solubilizing groups, the azo compounds, both in the remainder of the diazo component and in the residues R and R ¹ , can, as usual, also be substituted by other atoms or groups of atoms, for example by halogen atoms, hydroxy, amino, alkyl, Aryl-j alkoxy, aryloxy, acylamino, cyano, acyl, carboalkoxy, acyloxy, nitro groups etc. Contains

the rest of the diazo component in the ortho position to the azo bridge a complexing group such as a hydroxy, amino or carboxy group or an alkoxy group such as a Methoxy group, the compounds in question can optionally before the introduction of reactive residues or afterwards, are converted into their heavy metal complex compounds.

For example, iron, manganese, nickel, copper, cobalt and chromium can be considered as complex-forming metals. The heavy metal complexes can contain one or two molecules of azo compounds with the remainder of the formula (I) bonded to a metal atom (1: 1 or 1: 2 complexes). In 1: 2 complexes, however, one of the two ligand molecules can also be an azo compound,

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which does not use the remainder of the formula (I) as a coupling component has, e.g. a compound of the azobenzene type, which contains the corresponding complex-forming groups.

Reactive residues react with the

Hydroxyl groups of cellulose or the amino groups of polyamides groupings capable of forming a covalent chemical bond into consideration. Such a grouping provides in particular a low molecular weight alkanoyl substituted by a removable atom or a removable group or an alkylsulfonyl radical, a low molecular weight, optionally by a removable atom or a removable group substituted alkenoyl or alkenesulfonyl radical, one above.

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a carbonyl or sulfonyl group, by a cleavable one. Atom or a removable group substituted carba- or heterocyclic, 4-, 5- or 6-ring containing radical or one bonded directly through a carbon atom, through a A removable atom or a removable group is or contains a substituted triazine or pyrimidine radical. A preferred reactive radical is a via an -NH group

bonded six-membered heterocyclic ones containing halogen atoms A radical with two or three ring nitrogen atoms, in particular a chlorine-1,3,5 ^ triazine radical.

In particular, the radical of a 1,4-dialkyl-6-hydroxypyrid-2-one is used as the coupling component in formula (2) into consideration. ·

The invention particularly relates to compounds of the formula

(2)

in which H and R ^{1 are} alkyl radicals having at most 4 carbon atoms, and in which D is the radical of a diazo component of the benzene series. It also relates in particular to compounds which have reactive radicals, especially cyclic reactive radicals, such as triazines, pyrimidine or cyclobutane radicals, and water-solubilizing groups, it being possible for the reactive radicals to be contained in the substituents R and R ¹ .

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- K _

A special group of the compounds according to the invention are those of the formula

R '

1 Il I! I (3)

wherein D ^{1 is} a sulfobenzene radical, X is a halogen atom and Y is a halogen atom or the radical of an amine, alcohol, phenol or mercaptan. In addition to one or two sulfonic acid groups, as already mentioned, the benzene radical can carry further substituents »

Particularly valuable compounds are those of the formula (3) * in which D ^! a monosulfobenzene radical, in particular -a. those which contain no further substituents apart from a sulfonic acid group, X a halogen atom, Y the remainder of an aminobenzene (or naphthalene) disulfonic acid and R and R ^! is each a methyl or ethyl radical.

Another group of interesting compounds are those of the formula ri \.

(CHJ-NH-Z
ⁿ

where D is the remainder of a diazo component of the benzene or naphtha lin series, especially one * the water-solubilizing agent

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Contains substituents, R * an alkyl or aryl radical, Z a Reactive radical, in particular a dihalotriazine radical or a monohalotriazine radical, which is attached to a carbon atom contains bound remainder of ammonia, an amine, alcohol, phenol or mercaptan, and η is a whole positive number, is preferably between 1 and 4. Valuable connections of this type are "those of the formula

R ¹

(5)

I Y

where X is a halogen atom, in particular a chlorine or bromine atom, Y is the radical of an aminobenzene (or naphthalene) sulfonic acid, R ^{1 is} a low molecular weight alkyl radical, in particular a methyl radical, and m is 1 or 2.

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The azo compounds according to the invention can be prepared by coupling and, if appropriate, metallization or take place by acylation for the purpose of introducing a reactive radical.

The production by coupling is characterized by, that a diazo component, in particular one of the benzene series, with a compound of the formula

R ¹

wherein R and R 'are those given in the explanation of the formula (1) Have meanings, or in particular represent alkyl radicals having 1 to 4 carbon atoms, is coupled, and that optionally the azo compound obtained by reaction

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is converted into a heavy metal complex with a heavy metal releasing agent. Preferably one goes from Diazo components that contain a reactive radical and a water-solubilizing group. As coupling components of the formula (4) are in particular 1,4-dialkyl-6-hydroxypyrid-2-ones into consideration.

The diazotization takes place according to methods known per se, e.g. with the help of hydrochloric acid and sodium nitrite,

The coupling with the pyridone is also weak in itself /

known methods in acidic to / alkaline medium.

The reaction with the heavy metal releasing agent is carried out by customary methods, depending on the solubility of the Components in various solvents, such as water, ethanol, formamide, glycol ether, pyridine, etc., if necessary at elevated temperature, in a weakly acidic to alkaline medium.

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As a diazo component !!, which is used for the production of the

with the remainder / compounds according to the invention / the formula (1) or the corresponding heavy metal complexes can be used, the diazo compounds of the following amines may be mentioned:

Aminobenzenes.

1-amino-4-chlorobenzene, l-amino-4-bromobenzene,

1-amino-4-methylbenzene, ^

l-amino-4-nitrobenzene,.

1-amino-4-cyanobenzene, 1-amino-2,5-dicyanobenzene, 1-amino-4-methylsulfonylbenzene, 1-amino-4-carbalkoxybenzene, 1-amino-2,4-dichlorobenzene, 1-amino-2 , 4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino -2 -carborne thoxy- 4-chi orbenzene , l-amino ^ -carbomethoxy ^ -nitrobenzene, l-amino ~ 2-chloro-4-cyanobenzene, j ■

• - ■

1-amino-2-chloro-4-nitrobenzene, l-amino ^ -bromo ^ -nitrobenzene, l ~ amino-2-chloro-4-carbethoxybenzene, l-amino-2-chloro-4-methylsulfonylbenzene,

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'L-amino-2-methylsulfonyl-4-chlorobenzene, · 1-amino-2,4-dinitro-6-methylsulfonylbenzol, l-amino-2 _J 4-dinitro-6- (2 ^l -hydroxyathylsulfonyl) benzene, l -Amino-2,4-dinitro-6- (2'-chloroethylsulfonyl) -benzene, l-amino-2 ~ methylsulfonyl-4-nitrobenzene, l-amino ^ -methylsulfonyl ^ -nitrobenzene, l-amino-2,4- dinitrobenzene,

l-Amino-2,4-dicyanobenzene, ^ l-Amino ^ -cyan ^ -methylsulfonylbenzene,

1-Amino-2,6-dichloro-4-cyanobenzene, 1-Amino-2,6-dichloro-4-nitrobenzene, 1-Amino-2,4-dicyano-6-chlorobenzene, '' ■ ^ -aminobenzoic acid- cyclohexyl ester, l-amino-2,4-dinitro-6-chlorobenzene and especially l-amino-2-cyano-4-nitrobenzene, l-aminobenzene-2-, -3- or -4-sulfonic acid amides, such as

N-methyl or Ν, Ν-dimethyl or diethylamide, "2-aminonaphthalene-β-sulfonic acid-N, 7-isopropyloxy'propylamide, l-aminobenzene-2-, -3- or ^ -sulfonic acid-N ^ -isopropyloxy-

propylamide, -

l-aminobenzene-2-, -3- or -4-sulfonic acid-N-isopropylamide, l-aminobenzene-2-, '-3- or - ^ - sulfonic acid-NjT-methoxypropylamide, l-aminobenzene-2-, -3- or -4-sulfonic acid-N, N-bis- (ß-hydroxyethyl) -amide,

l-Amino ^ -chlorobenzene ^ -sulphonic acid amide,

'109848/1771. · |

and the N-substituted derivatives, 4-aminoazobenzene, 3,2'-dimethyl-4-aminoazobenzene,

2-methyl ~ 5 ~ methoxy ~ 4-aminoazobenzene, 4-amino ~ 2-nitroazobenzene, 2,5-dimethoxy-4-aminoazobenzo !, 4 ¹ -methoxy-4-aminoazobenzene, 2-methyl-4'-methoxy- ^ -aminoazobenzene, 3,6,4'-trimethoxy-4-aminoazobenzene, "4'-chloro-4-aminoazobenzene, 2'- or 3'-chloro-4-aminoazobenzene, 3-nitro-4-amino-2 ', 4'-dichlorazobenzene, 4-aminoazobenzene-4'-sulfonic acid amide, 1- or 2-aminonaphthalene, 4 - ^^ ethoxy-5-chloro-2-aminophenol, o-acetylamino ^ -ohlor ^ -aminophenol, e-nitro ^ - ehlor ^ -aminophenol, 6 -nitro -4 -methyl -2 -aminophenol, 3 ~ amino-4-hydroxy-acetophenone, e-nitro ^ -acetylamino ^ -aminophenol,

2-aminophenol-4-carboxamide, 4,6-Diehlor-2-aminophenol, 3,4,6-Trichlor-2-aminophenol, 4-nitro-6-chloro-2-aminophenol,

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6-nitro or 6-chloro-2-aminophenol-4-sulfonic acid amide, 4-nitro-2-aminophenol-5 ~ or -6-sulfonic acid amide, 2-aminophenol-5-methylsulfone, 2-aminophenols

4- or 5 * "nitro ~ 2-aminophenol / 4- or 5-chloro-2-aminophenol, 4,5-dichloro-2-aminophenol,

- ^ - or -5-sulfonic acid,

3 * ^ * 6-trichloraminophenols 4-chloro-2-aminophenol-6-sulfonic acid, 6-chloro-2-aminophenol-4-sulfonic acid, 4-nitro-2-aminophenol-6-sulfonic acid, 6-nitrο-2-aminophenol-4-sulfonic acid, 2-aminophenol-4,6-disulfonic acid,

6-Acetylamino-2-aminophenol-4-sulfonic acid, 4-Acetylamino-2-aminophenol-6-sulfonic acid, 4-Kethyl-2-aminophenol, 4-methoxy-2-aminophenol , 2-aminophenol-4-sulfonamide, 2- Aminophenol-4-sulfone-N-β-hydroxyethylamide, 2-aminophenol-4-sulfone-N-methylamide, 2-aminophenol-5-sulfonamide, 4-chloro ~ 2-aminophenol-5- or -6-sulfonamide,

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2-aminophenol-4-sulfone-N, N ~ dimethylamide, 2-aminophenol-4-methylsulfone, '. ■ 2-aminophenol-4-ethyl sulfone, 6-acetylamino-4-nitro-2-aminophenols 2-aminophenols, β-hy droxyäthyl sul f on, Anthranilic acid,

2-amino ~ 3-naphthoic acid, 4- or 5 ~ chloranthranilic acid,.

4- or 5-nitroanthranilic acid, 4- or 5-ethylaminoanthranilic acid, 4- or 5-sulfoanthranilic acid, Anthranilic acid-4-sulfonamides Anthranilic acid-4- or -5, ß-hydroxyethyl sulfone, Anthranilic acid 4- or -5-ethyl sulfone, 4-chloro-2-aminophenol ~ 5-sulfonic acid-N-methylamide, 4- or 5-benzoylaininoanthranilic acid, 2-anisidine,

4- or 5-chloro-2-anisidine, 4- or 5-nitro-2-anisidine, 2-anisidine-4- or -5- sulfonic acid, 2-methoxy.-5-methylaniline, 2,5- thoxyaniline ,

2-anisidine-4- or -5-ß-hydroxyethyl sulfone, 2-amino-1-naphthol-4,8-disulfonic acid, 1-amino-2-naphthol-4-sulfonic acid,

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* 1-Amino-2-naphthol ~ 4-sulfonamide, '.

6-nitro ~ l-amino-2-naphthol-4-sulfonic acid, ^o

6-acetylamino-1-amino ^ -naphthol-4-sulfonic acid, 4- (2 ', 5' -disulfophenylazo) -2-methoxy-5-methyl aniline ;, 4- (2 ', 5'-disulfophenylazo) -2.5 "dimethoxyaniline, 4 - (. 2 ', 5' -Disulfophenylazo) ^ -methoxy-1-naphthylamino-sulfonic acid, ·

4- (l ' _J 5'-disulfonaphth-2' -ylazo) -2,5-dimethoxyaniline, 4- (2 ^f , 3 '"or 4'-sulfophenylazo) -2-methoxyaniline, dianisidine,

Benzidine ~ 3i3'-dicarboxylic acid,

4- (2'-, 3'- or 4'-sulfophenylazo) -2 ~ methoxy-5-methylaniline, 4- (2'-, 3'- or 4'-sulfophenylazo) -2,5-dimethoxyaniline, 4- (2 ', 5' ~ or 3 '* 5'-disulfophenylazo) -2-methoxyaniline, 4- (3'ί5' .- disulfophenylazo) -2-methoxy-5-methylaniline, 4- (3 ', 5'- Disulfophenylazo) -2,5-dimethoxyaniline, 4- (2'-carboxy-4'- or -5 ¹ -sulfophenylazo) -2-methoxyaniline, P 4- (2'-carboxy-4- or -5'-sulfophenylazo ) -2,5-dirnethoxyaniline, 4- (2'-carboxy-4'- or -5'-sulfophenylazo) -2-methoxy-5-methylaniline, '

4- (6 '>8'-disulphonaphth-2'-ylazo) -2-methoxyaniline, 4- (6', 8'-Disulfonäphth-2 ^J -ylazo) -2-methoxyaniline, 4- ^(6!, 8 '-Disulfonaphth-2'-ylazo) -2-methoxy-5-methoxyaniline, 4- (6 ', 8' ^ disulfonaphth-2 ¹ -ylazo) -2,5-dimethoxyaniline, ^ -phenylazQ ^ -aminophenol.

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Methanilic acid,

• sulfanilic acid,

Orthanilic acid,

1-Amino - ^ - methylbenzene-2-sulfonic acid, aniline-2,5-disulfonic acid, 2-naphthylarain-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine- ^ j 8-disulfonic acid, 2- Naphthylamine-4,6 _J 8- or ~ J> ₃ & _} 8-trisulfonic acid, l-amino-4- (ß-sulfatoäthy1-sulfonyl) -benzene, l-amino -> - (ß-sulfatoethyl-sulfonyl) - benzene, l-anlino-2-methoxy-4- (ß-sulfatoethylsulfonyl) -5-methyl-benzene, l-amino-4- (ß-sulfatoethylsulfonamido) -benzene, l-amino-4- (ß-hydroxyäthylsulfonyl )-benzene.

1Ö9848 / 1771

. · 2123Ü61

* '■ The following are mentioned as coupling components:

1-ethyl-4-methyl-6-hydroxypyridone (2), 1- (β-hydroxyethyl) -4-methyl-6-hydroxypyridone (2), 1-methyl-4-phenyl-6-hydroxypyrldone (2), l-butyl-4-methyl-6-hydroxypyridone (2) _J l-ethyl-4-hexyl-6-hydroxypyridone (2), l-isopropyl-4-methyl-6-hydroxy- pyridoii (2), 1-ethyl- ² ! -phenyl-6-hydroxypyridone (2), 1,4-methyl-6-hydroxypyridone (2),

"1-Cβ-methoxyethyl) -4-raethyl-6-hydroxy-pyridone (2),

l-propyl - ^ - metliyl-e-hydroxy-pyridon (2) j 1- (β-Aminoethyl) -4-methyl-6-hydroxypyridone (2).

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Azo compounds with the remainder of the formula (I) or the corresponding heavy metal complexes, the one or contain more reactive groups, can be prepared in such a way that one diazo or coupling components used that already contain reactive groups. In many cases, however, it is also possible to have reactive groups subsequently to be introduced into the azo compounds. The introduction can after the

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Coupling or done after metallization. from

with the remainder / of particular interest are such compounds / of the formula

(1). ■ the one about

an amino group bonded six-membered heterocyclic

- "· Contains reactive residue.

The reactive radical is preferably introduced

Amino / by acylation of corresponding / azo compounds or

k coupling components containing an acylatable amino group contain, or corresponding diazo components which, in addition to the amino group to be diazotized, also contain a further, acylatable Amino group, or a group which, for example, can be converted into an acylatable amino group by reduction or saponification contains, e.g. the nitro group or the acetylamino group.

As a corresponding diazo component ^

■ φ

■■: the, as described above, for the

Introduction of a reactive radical are suitable, for example:.

l, 3-diaminobenzene-4-sulfonic acid, l.,> - diaminobenzene-4,6-disulfone-

acid, 1,4-diaminobenzene-2-sulfonic acid,. -.

l _> 4-diaminobenzene-2,5 ~ or -2,6-disulfonic acid, l-amino-4'-nitrobenzene,

l-amino-2-chloro-4-nitrobenzene, {

1 , 3-DIamino-4-methylbenzene-6-sulfonic acid,

103848/1771 · · ■;

6 ~ acetylamino - ^ - chloro ~ 2-aminophenol,
ö-nitro - ^ - methyl-S-aminophenol,
^ -Nitro-S-aminophenol-δ-sulfonic acid,.
6-Acetylaniino-1-amino-2-naphthol - ^ - sulfonic acid et al
eg compounds already mentioned in the list of possible diazo components. *

Aminoazo compounds which can be introduced into the reactive radicals after the coupling include e.g. the coupling products of the abovementioned diazo components with corresponding pyridones are possible.

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Acylating agents which, in addition to the acylating site, also contain a reactive radical, come in particular the halides or anhydrides of organic acids into consideration., which contain easily interchangeable atoms or groups of atoms.

The following are mentioned as examples of acylating agents containing a reactive radical: chlorine or bromoacetyl chloride,
ß-chlorine or ß-bromopropionyl chloride,

α, β-dichloro- or α, β-dibromopropionyl chloride, '

Chloromaleic anhydride,

Carbyl sulfate, ■ _ ■ ·.

Acrylic chloride,. · ...
ß-chloro- or β-bromoacrylic chloride>'
α-chloro- or α-bromoacrylic chloride,. Α, β-dichloro- or dibromoacrylic chloride, trichloroacrylic chloride,
Chlorocrotonyl chloride,

Propiolic acid chloride, "

3,5-1) 1111 ^ 0 - ^ - chlorobenzene sulfonic acid or carboxylic acid chloride, '.
3-nitro-4-chlorobenzene sulfonic acid or carboxylic acid chloride,

2,2,3,3 ~ tetrafluorocyclobutane-1-carboxylic acid chloride, 2,2,3,3-tetrafluorocyclobutyl-acrylic acid chloride,

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ß-chloroethylsulfonyl-endomethylene-cyclohexanecarboxylic acid chloride, Acrylsulfonyl-endomethylene-cyclohexanecarboxylic acid chloride, and especially heterocyclic acid halides and their derivatives, such as

2-chlorobenzoxazole carboxylic acid chlorides, 2-chlorobenzothiazole carbon or sulfonic acid chlorides and especially the following., at least 2 nitrogen atoms as heteroatoms of a 6-membered heterocycle having compounds:

• *

4,5-dichloro-1-phenylpyridazonecarbon or sulfonic acid chloride, 4,5-dichloropyridazonopropionic acid chloride,!, Jr-dichlorophthalazine carbon or sulfonic acid chloride, 2,3-dichloroquinoxaline carbon or sulfonic acid chloride, 2, ^ - dichloroquinazoline carbonic or sulfonic acid chloride, 2-methanesulfonyl- ^! i - chloro-6-methylpyrimidine, tetrachloropyridazine, ■.

2,4-bis-nlethansulfonyl-6-methylpyriIllidin, 2,4,6-Tri-- or 2, ¹ -, 5,6-Tetrachloropyrimidine, 2,4,6-tri- or 2,4,5,6 -Tetrabromopyrimidine, 2-methanesulfony.1-4, S-dichloro-o-methylpyrimidine, 2,4-dichloropyrimidine-5-sulfonic acid _J

5-nitro- or 5-cyano-2,4,6-trichloropyrimidine, 2, β-bis-methanesulphonylpyridiral- ^{^} ^ -carboxylic acid chloride, 2,4-dichloro-5-ahromethyl-6-methyl-pyrimidine, · 2 , 4-dibromo-5-bromomethyl-6-methyl-pyrimidine,

1098A8 / 1771

'2, ty-dichloro 5-ehlormethylpyrimidine ₅ 2,4-dibromo-5-bromine fchylpyrimidine 2,5 ^ 0-trichloro- ^ - methylpyrimidine, 2 _i 6-dichloro-4-trichloromethylpyrimidine or especially 2 _J ⁱ i-' Bisraethylsulfonyl-5-chloro-6-methylpyrirnidine,

2 _J , 4-dichloropyrirrtidiri _j,.

3i6-dichloropyridazine ^

3,6-dichloropyridazine-5 ~ carbonsäurechiorid, 2,6-dichloro- or 2j, 6-dibromo - ^ - carboäthoxypyrimidinj, 2 h _{3 s} 5 "Trichlorpyriffiidin _{:) j} 2 _i ⁱ i-Dichlorpyrimiäin-6-carboxylic acid chloride _J, 2 _s h -Diehlorpyrimidin ~ 5 ~ carboxylic acid elilorid _f 2 ^ 6-dichloro- or S ^ ö -dibronipyriraidin- ^ · - or -5-carboxylic acid or -sulphonic acid amides or »-4- or -5-sulphonic acid chloride, '. ■

~ 2_, h _s 6-trichloropyrimidine,

5-nitro-6-methyl-2 _s 4-dichloropyrimidine>S-chlorobenzthia'zol-o-carboxylic acid chloride, 2'-chlorobenzothiazole-6-sulfonic acid chloride,

-4,6-Difluoro-5-chloropyrimidine, 2 _J 4,6-trifluoro-5-chloropyrimidine,

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2, *! ·, 5 ~ trifluoropyrimidine, ", ·

2, ^, 6-TrIcHlOr- (-tribromo- or -trifluoro) -1,3 * 5-triazine, as well as 4,6-Diehlor (dibromo- or difluoro) -1,3,5-triazine, which in 2-position are substituted by an aryl or alkyl radical, E.g. a phenyl, methyl or ethyl residue, or an aliphatic or aromatic residue due to the rust, via the sulfur ■ atom-bound mercapto or via the oxygen atom bonded hydroxyl compound or in particular by an NHp group or by the remainder of a via the nitrogen atom bound aliphatic, heterocyclic or aromatic amino compound. As such compounds, their remnants through Reaction with trihalotriazines in the 2-position on the triazine nucleus bonded, the following may be mentioned, for example: aliphatic or aromatic mercapto or hydroxy compounds, such as thio alcohols, thioglycolic acid, thiophenols, alkoxyalkanols, methyl, ethyl, isopropyl alcohol, glycolic acid, Phenol, chloro- or nitrophenols, phenolic carboxylic and sulphonic acids, naphthols, naphtholsulphonic acids, etc., in particular but compounds containing ammonia and acylatable amino groups, such as hydroxylamine, hydrazine, phenylhydrazine, Phenylhydrazine sulfonic acids, glycol monoalkyl ethers, methyl, Ethyl-, isopropyl-, methoxyethyl-, methoxypropyl-amine, Dimethyl, diethyl, methylphenyl, ethylene phenylamine, chloroethylamine * Ethanolamines, propanolamines, benzylamine; Cyclohexylamine, Morpholine, piperidine, piperazine, aminocarbonic acid

'ester, aminoacetic acid ethyl ester, aminoethahsulfonic acid,

10984 8/1771

N-methylaminoethanesulfonic acid, but above all aromatic amines such as aniline, N -Methyl aniline, toluidines, xylidines, chloroanilines, p- or m-aminoacetanilide, aminophenols, anisidine, phenetidine and especially acidic anilines, sulfanil, methanil -, Orthanilic acid, aniline disulphonic • acid, aminobenzylsulphonic acid, aniline-co-methanesulphonic acid, aminopbenzenedicarboxylic acids, naphthylamino mono-, di and tri. sulfonic acids, aminobenzoic acids, such as 2-hydroxy-5-amino) benzoic acid, and also colored compounds or compounds with a coloring agent character, e.g. 4-nitro-4'-aminostilbene disulfonic acid, 2-nitro-V -amino-diphenylamino-ty ^ '"stilbene-disulfonic acid, 2-nitro-4'-aminodiphenylamine-4, J5 ^! " disulfonic acid and in particular aminoazo dyes or aminoanthraquinones or phthalocyanines which still contain at least one reactive amino group.

The introduction of the substituent in the 2-position of the triazine radical can also after the condensation with the starting diamine or after the reaction according to the invention

with the rest /
to the azo compound / the formula (1) happen.

In addition to those which can be introduced by acylation, fiber-reactive radicals such as the vinylsulfone, the β-sulfato- or -Thiosulfatoäthylsulfon-, ß-Thiosulfatopropionylamid-, the ß-Thiosulfatoäthylsulfony'lamid- or the Sulfonic acid-Njß-sulfatoethylamide group, which in another way, e.g. introduced into the diazo component by ester or thioester formation *. 109848/1771

As compounds which contain a fiber reactive radical which cannot be introduced by acylation, in which the Fiber-reactive residue so preferably not over one Amino groups but is bound directly to the benzene residue, the sulfoesters of the following sulfones should be mentioned in particular: l-amino-2-methoxy-5 "(β" hydroxyethyl) phenyl sulfone, l ~ aminobenzene ~ 3 ~ or -4-ß-hydroxyethyl sulfone, l-amino-2-methyl-benzene-5-ß-hydroxyäthylsulfon-, l ~ Amino-4- (β-hydroxyethylsulfonylpropionylaminomethyl) benzene, 1 - ^ Amino-4- (β-hydroxyethylsulfonylamino) -benzene,

as well as via corresponding methy.lole according to unicorn available reactive compounds, e.g.

1-Amino-4-chloroacetylaminomethyl-benzene or -.

1-Amino-3-chloroacetylaminomethyl-benzene-6-sulfonic acid,

The condensation with the acid halides or anhydrides or with the heterocyclic halogen compounds is carried out in two ways in the presence of acid-binding agents such as sodium carbonate. With all of these reactions it goes without saying proceed in such a way that an unsaturated bond or an exchangeable halogen atom remains in the finished product remain.

The azo compounds and their heavy metal complexes obtainable by the present process and its variants

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are new; they are suitable for dyeing and printing check verschiedenster materials such as silk., leather _s wool, synthetic parsers are from Super polyamides, polyurethanes Super ,, polyester or polyacrylonitrile ,, polyhydroxylated materials ₃ such as cellulose-containing materials of fibrous structure, such as linen, wood pulp, regenerated cellulose , Cotton and the like.

The demetallized azo compounds according to the invention are of particular importance as dyes. The water-insoluble compounds are suitable as disperse dyes for dyeing semi-synthetic or fully synthetic fibers, especially for dyeing polyester material "

The acetone-soluble ones, those containing sulfonamide groups Compounds can be used to dye cellulose esters in the dope.

The water-soluble basic compounds containing a quaternized or quaternized amino group are suitable for dyeing polyacrylonitrile or polyester fibers from aqueous solution

Most important, however, are those according to the invention a Azo compounds, which have a reactive radical and a water-solubilizing one Group, in particular a sulfonic acid group contain «, These dyes are preferably used for dyeing nitrogen-containing fibers, such as super poly-

Super-polyurethanes, silk, leather and especially wool, 10 9 8 4 8/1771

ζ.Β from weakly acidic, neutral or weakly alkaline Bath, if necessary with the addition of the usual auxiliaries, e.g. ethylene oxide condensation products of high molecular weight Amines, and especially of cellulose materials, especially cotton, e.g. after the exhaust process from long liquor, from an alkaline, possibly very salty, aqueous bath and in particular by the pad-dyeing process, after which the goods are impregnated with aqueous and possibly also salt-containing dye solutions, and the dyes after an alkali treatment or in the presence of alkali, optionally fixed under the action of heat, are used.

The water-soluble reactive dyes according to the invention show an excellent build-up capacity. They are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. wool, silk or blended fabrics containing wool.

The dyeings and prints are characterized by interesting and valuable greenish-yellow, very pure and brilliant nuances the end. The dyeings and prints show good acid and alkali resistance as well as good resistance to synthetic resin finishing agents, good lightfastness and, especially on cotton, excellent wetfastness. Worth mentioning is also the high degree of fixation and the good removability of unfixed dye components.

109848/1771

In order to improve the wet fastness properties, it is recommended the dyeings and prints obtained a thorough rinsing with cold and hot water, if necessary with the addition of a dis acting and diffusing the unfixed. Submit shares of promotional agent.

In the following examples, the parts Unless otherwise indicated, parts by weight, percentages percentages by weight, and temperatures are in Degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

109848/1771

Example 1.
To a neutral solution of 26.8 parts 1,3 ~ diamino-

benzene-4,6-disulfonic acid in 500 parts of water from 0 to

a solution of 18.5 parts of cyanuric chloride in 50 parts of acetone is added and the ρ ,, value is maintained between 6 and 7 during the condensation by adding dropwise 2N sodium hydroxide solution Way diazotized. A neutral solution of 15 * 3 parts of 1-ethyl-6-hydroxy-4-methyl-pyridone (2) is then added to the solution of the diazonium salt. _{The coupling mixture is adjusted to p TT} 7 in the course of about 1 hour by adding 2N sodium hydroxide solution

Solution of the dichlorotriazine dye is then treated with a neutral solution of 17 * 3 parts of 1-aminobenzene-3-sulfonic acid added and heated to 40 to 45, the p "value by Dropwise addition of 2N sodium hydroxide solution kept between 6 and 7 will. The resulting dye is isolated by sprinkling in common salt, filtered off and dried. The product dyes cotton in very pure, strongly greenish yellow tones.

The same dye is also obtained if the primary mono-condensation product of l, 3-diaminobenzene-4,6-disulfonic acid and cyanuric chloride is first condensed with l-aminobenzene-3-sulfonic acid and then converted to l-ethyl-6-hydroxy- ^z l-methyl-pyridone (2) is coupled.

The preparation of the coupling component 1-ethyl-6-hydroxy-4-methyl-pyridone- (2) takes place through several hours

1.09848 / 1771

Boiling of ethyl-6-hydroxy-4-methyl-pyridon- (2) -> - carbonamide with approx. Melting point 1; 54-Γ56 ^Ο precipitates in crystalline form.

1-Ethyl-6-hydroxy- ^2- methylpyridone (2) is obtained by heating 1-ethyl-1-cyano- 1-methyl-o-hydroxypyridone (2) in an aqueous 5 % acid solution at 130 to .to stop the development of carbon dioxide.

109848/1771

2123Q61

If, instead of l-aminobenzene-3-sulfonic acid, the amines indicated in the table below in the second column and in place of 1-ethyl-6-hydroxy-4-methylpyridone-2 that pyridones listed in the table in the third column, receives so one more yellow dyes with good fastness properties.

Amines Pyridone 1 ; 5-aminobenzoic acid l-methyl-4-phenyl ~ 6-hydroxypyridon-2 2 4-aminobenzoic acid 1-isopropy1-4-methy1-β-hydroxypyri-
don-2 l-aminobenzene-3-me-
thanesulfonic acid 1- (ß-acetylaminoethyl) -4-methyl-
6-hydroxypyridone-2 4th 2-amino-5-sulfo-
benzoic acid l-benzyl-4-methyl-6-hydroxy-.
pyridon-2 5 N-methylaniline-4-
sulfonic acid 1,4-diethyl-6-hydroxypyridone-2 6th Aniline-2,4-disulfone-
acid 1-butyl-4-ethyl-6-hydroxypyridone-2 7th Anthrani lsäxire-ω-
methanesulfonic acid 1-Ethy1-4-methyl-6-hydroxypyridon-2 8th Aminomethanesulfone
acid 1- (β-phenoxyethyl) -4-methyl-6-hy- j
droxypyridone-2 9 aniline 1-Methy1-4-butyl-6-hydroxypyridone-2 10 Dimethylamine 1-Cyclohexyl-4-methyl-6-hydroxypyri
don- 2 11 Diethanolamine 1-ethyl-4-methyl-6-hydroxypyridone-2 12th Methylamine 1-Methy1-4- (4 ^f -methoxyphenyl) -6-hy
droxy pyridon-2 13th Methyl taurine 1,4-dimethyl-6-hydroxypyridone-2 14th Morpholine 1-ethyl-4-methyl-6-hydroxypyridone-2

1098A8 / 1771

2123Q61

Amines 15th ammonia 16 1-aminofcenz o1-2-
sulfonic acid it 2-Aminot ο IuOl- ¹ J--
sulfonic acid 18th l-naphthylamine
5-sulfonic acid 19th l-naphthylamine-Λ, 6-
disulfonic acid 20th l-naphthylamine-3, 5 ₃ 7-
trisulfonic acid

■■■■ ι

Pyridone

1- Ae thy me thy 1- 6-hy dr oxy pyridone 2 1 ^{1 I-:}

1- (7-hydroxypropyl) -4-benz'yl-6- i hydroxypyridone-2 j

1, 4-diisopropyl-6-hydroxypyridone-2 \

1- (ß-chloroethyl) -4-ethyl-6-hydroxy- _: pyridon-2

1- (2 ¹ _J 3'-dihydroxypropyl) ^-1 l -methyl-6-hydroxypyridone-2

1,4-diethyl-6-hydroxypyridone-2

- 25 -

BeisDiel 2.

47.4 parts of the aminoazo dye of the formula

PH ₂ CH

(prepared by coupling 21 parts of 1-amino-3-acetylaminobenzene-4,6-disulfonic acid. 15., 3 parts of 1-ethyl-6-hydroxy-4-methyl-pyridone- (2) and by subsequent saponification of the acetylaraino group with 2 ~ N hydrochloric acid) ■ dissolved in 500 parts of water until neutral and treated with a solution of 18.5 parts of cyanuric chloride in 50 parts of acetone. By adding dropwise 2N sodium hydroxide solution, the ^: p value is kept between 6 and 7 during the condensation. After the condensation has ended, the dichlorotriazine dye is salted out, filtered off and treated with a concentrated solution of 5 parts of disodium phosphate and 5 parts Fonosodium phosphate mixed and dried in vacuo at 40 to 50 °. ■. "· '■■■'" - ■ ■: '. The dye thus obtained dyes cotton in very pure, strongly greenish yellow shades. · ·. · .-

109848/17 pts

Similar yellow dyes are obtained if, instead of cyanuric chloride, equivalent amounts of α, β-dibromopropionyl chloride, chloroacetyl chloride, α-bromoacrylic chloride, 4,5-dichloropyridazonopropionyl chloride, 2,> - dichloroquinoxalinearboxylic acid chloride, 2,4,53 6-tetraehlorpyrimidine, 2 ₃ 4 ₃ 6-trifluoro-5-chloropyrimidine, 2, 4-Bismethylsülfonyl-5-chloro-6-methylpyrimidine _J> 2,4-dichloropyrimidine-5-carboxylic acid chloride, ^ j ^ py

/ 2,4-dichloro-6-phenoxy-1 _; , 3 ·. 5-triazine,

5-carboxylic acid chloride, 2 _J 4-Diehlor-6-methyl-l ^, 5-triazine, / ^ Cy a nur br or ~ ^: d /

W 2-amino-4,6-dichlorotriazine, / or 2-methoxy-4,6-dichloro-1,3i 5 triazine is used.

109848/1771

Example 3 .

To a neutral solution of 26.8 parts of 1,3- ■ diaminobenzene- ^ δ-disulfonic acid in 500 parts of water, 23 parts of 2-isopropoxy- ^ j6-dichloro-l ₃ 3j5-triazine are added and the reaction mixture is warmed up 40 to 45. By adding dropwise 1N sodium hydroxide solution, the p “-V / ert is kept between 6 and 7 during the condensation. After the condensation has ended, the compound thus obtained is diazotized in the usual way by adding 25 parts of 4N sodium nitrite solution and 25 parts of 30% hydrochloric acid. Then the pure yellow suspension of the diazonium salt is mixed with a neutral solution of 15 * 3 parts of 1-ethyl-o-hydroxy - ^ - methylpyridone- (2). The coupling mixture is neutralized by adding dropwise 2N sodium hydroxide solution. The resulting dye is then salted out with potassium chloride, filtered off and dried. The product dyes cotton in very pure, strongly greenish yellow shades.

If the corresponding amount of l-methyl-6-hydroxy-4-methylpyridone (2) is used as the coupling component, this gives a dye with very similar properties.

109848/1771

Example 4.

The procedure is as in Example 2, however, are on completion of condensation, a solution of 55 parts of the disodium salt of 1-amino ■ * ■ - (4'-aminophenylarnino) -anthrachinori-2 _J 3 '~ disulfonic water in 600 parts. , increases the temperature to 40 - 50 ° and maintains a pH value of 6-7 by adding sodium hydroxide solution until the condensation has ended. The resulting dye is precipitated by adding table salt. It dyes cotton in real, green shades.

■ Is used instead of the said aminoanthraehinone -a phthaloeyanine dye of the formula

- (SO ^ H) ₀

.. = Best -Ses Kupfe.rpht; hal: ooyanin.s) mm. Also a green dye.

Example 5

11 parts of 2-amino-5-sulfobenzoic acid are diazotized in the usual way. The Dlazolösung obtained is added dropwise to a solution of J, ater run in 6 parts of l-ethyl-4-methyl ~ 6-hydroxypyridone-2 in 500 parts V / 0 and 5 parts 3> 0 $ aqueous sodium hydroxide solution, whereby an immediate intense. yellow dye is produced, which is completely precipitated by adding table salt. He dyes wool from an acid bath in pure greenish yellow shades. Chromium plating gives a brownish yellow color.

If, instead of 2-amino-5-sulfobenzoic acid, those listed in the table below in column II are used Diazo components and instead of 1-ethyl-4-methyl-6-hydroxypyridone-2 as coupling components, the pyridones mentioned in column III, further dyes are obtained, the colorations of the result in the nuance listed in column IV.

109848/1771

No. Diazo component Coupling component
HO - ^ ϊΓ ^ Ο
I.
R. R ' Nuance on
Polyamide-
fiber
material 1 R. methyl 2 2-aminobenzenesulfone
acid methyl n-hexyl greenish]
yellow 5 2-Na ph thy la mi η-1-
sulfonic acid ß-hydroxy
ethyl methyl yellow
- i 4th 4-aminobenzene sulphate
fonic acid Isopropyl methyl greenish
yellow 5 4- (6 ', 8 ^f -Disulfonaph ~
th-2'-ylazo) -3-me-
thylaniline Benzyl Isopropyl orange 6th 6-acetylamino-2-amino-
phenol-4-sulfonic acid Aethy1 methyl yellow-brown
(Cu complex) 7th 2-aminopheno1-4,6-d i-
sulfonic acid Butyl methyl yellow-brown
(Co complex) 8th 4,4'-diaminodiphenyl
urea-3,3'-di-
sulfonic acid Aethy1 Phenyl reddish
yellow 9 4,4 ^f -dlaminostilbene-
2,2'-disulfonic acid n-propyl methyl yellow 2-aminobenz oil sulfone
acid Chloraceous
tyl-amino-
ethyl yellow

109848/1771

Example 6.

A solution of 25 ) 3 parts of aniline-2,5-disulfonic acid neutralized with sodium carbonate is added to a suspension of 19 parts of cyanuric chloride in 200 parts of ice water. The mixture is kept weakly Congo acidic with a dilute sodium hydroxide solution and stirred at a temperature of 8 ° until complete dissolution occurs. A neutral solution of 18.8 parts of 1.3-laminobenzene-4-sulfonic acid is then added. The mixture is heated to 30 times and slowly neutralized with a solution of sodium hydroxide * After condensation has taken place, diazotization is carried out in the usual way with hydrochloric acid and sodium nitrite. A weakly alkaline solution of 15-3 parts of 1-ethyl-6-hydroxy-4-methylpyridone- {2) is added to the diazo compound and the coupling mixture is kept weakly acidic to neutral by adding 2N sodium hydroxide solution. The dye is precipitated by adding sodium chloride, filtered off and dried. »It dyes cellulose fibers in very pure, strongly greenish yellow shades,

instead of the aniline - ^, 5 ~ disulfonic acid the

equal amount of aniline - ^^ - disulfonic acid or

/ or Gejtflis.che derselfaen / SuIf anti acid, metanilic acid or anthranilic acid /

old one yellow _dye-s having similar Eigensehaffren • the above-mentioned dye. Replacing the 1 ~ A
& as l, 4 ~ dimethyl ^ -hyäroxy * pyridon «- (iS) js © tiriiält a? aa

101848/1111

BAD ORlQiNAt ¹

a greenish yellow dye with good fastness properties.

Other yellow dyes are obtained according to Example 6 from the components listed in the following table.

109848/1771

BAD ORIQfNAt

- hi -

II

Acylating agent] ^

SO ₅ II

'·. ■ Diazo component ■!

HO "S

-C ^ Nj-Cl

v ι π

Cl

<y

Cl

^ C-Cl i!

HO S

HO S

Cl

NH-C 1 -C 4 -Cl ! ti

Cl

^wv C-Cl I!

Cl

SO _x H
5

C-Cl !!

SO H

Cl

SO H

NH

H ₀ N NH ₀
\ λ / 2

NH

Ill

ciC "

H0 ^{/ x} N

H0 ^/

CH.

N-

C ₂ H ₅

cm

^C 6 ^H 5

1098A8 / 1771

* 6

Acylating agents

N -NH-C C-Cl

SO H N N

Cl

-NH-C C-Cl

SO-H
3

Cl

COCl

Cl

Cl N

YV ¹

COCl II
Diazo component

SO ₇ H

-NH,

Cl

SO H

NHc

SO H

SO H

III

Coupling component!

HO

CH,

10984 8/177: 1

Example 7.

To the group consisting of 25.3 parts of aniline-2 _J 5-disulfonic acid Di.izoverbindung obtained are admixed with a weakly alkaline solution of 16.8 parts of l- (β-aminoethyl) -6-hydroxy ~ 4-methylpyridon- (2) (obtained by dissolving in water with addition of a sodium hydroxide solution) and makes the coupling mixture neutral with sodium carbonate. After coupling is complete, a solution of 32, 2 parts of 2-phenylamino-4 _J 6-dichlorotriazine-3'-sulfonic acid are added and condensed for 2 hours at 30 to 40, wherein by the dropwise addition of a 2N sodium hydroxide solution of p ..- value between 6 and 7 is held. Of the

The dye formed is then salted out, filtered off and dried. It dyes cotton in real green tones yellow tones.

The pyridone used as the coupling component is obtained by heating 1- (β-aminoethyl) -3-cyano-4-methyl-6-hydroxypyridone- (2) in aqueous 75% sulfuric acid until the evolution of COp has ended.

109848/1771

Similar yellow dyes are obtained if equivalents are used instead of aniline-2,5- <3isulphonic acid Amounts of the following diazo components used:

Diazo component ..... ₍
Shade on cotton 1 6-chloro-2-aminopheno1-4-sulfonic acid reddish yellow 2 5-sulfoanthranilic acid yellow 3 4- (6 ¹ , 8'-disulfonaphth-2'-ylazo) -
2 ₃ 5-dimethoxyaniline orange 4th 2-naphthylamine-1,5-disulfonic acid yellow 5 2-naphthylamine 6, 8-trisulfon-
acid yellow 6th 1-Amino-4- (ß-sulfatoethyl-sulfonyl) -
benzene. yellow 7th 1-Amino-4 (β-sulfate oäthy1sulfonamid) -
benzene yellow 8th 1-Amino-4- (ß-hydroxyethyl-sulfonyl) -
benzene yellow

109848/1771

Example 8.

58 parts of that obtained according to the information in Example 2 Dichlorotriazine dye are dissolved in 1000 parts of water at pH 7. A solution of five and a half parts is given 1,4-Phenylenediamine is added and condenses at 40-50, a pH of 6-7 being obtained by adding 2N sodium hydroxide solution maintains. After the condensation has ended, the bireactive Dye in which the two. Reactive groups are linked by a phenylenediamine bridge, by adding , Table salt precipitated. It dyes cotton or regenerated cellulose fibers in pure, strongly greenish yellow tones.

If, instead of 1,4-phenylenediamine, an equivalent amount of 1,3-phenylenediamines, 1,4-phenylenediamine-2-sulfonic acids, 4,4'- ^{diaminostilbene-2,2 f} -disulfonic acid, 4,4 ^f -diaminodiphenyl-2 is used as the bridging component ,, 2'-disulfonic acid or 4,4'-diaminodiphenylurea-j5j3 ^! -ciisulfonic acid, dyes with similar properties are obtained.

109848/1771

Example 9 «

17.3 parts of l-aminobenzene-3-sulfonic acid are used in Water dissolved neutrally by adding sodium hydroxide solution and mixed with 18.5 parts of cyanuric chloride in the usual V / eise 0-5 condensed. After the condensation has ended, an aqueous solution of 21 parts of the sodium salt of the 1,3-

in addition /

Phenylenediamine-4-sulfonic acid / and condensed at 25-30. The mixture is then cooled to 0, 18.5 parts of cyanuric chloride are added and 2N sodium hydroxide solution is added dropwise to condense at pH 4-6. A further 21 parts of the sodium salt of 1,3-phenylenediamine-4-sulfonic acid are then added, the temperature is increased to 30 and the mixture is condensed at pH 6-J. The resulting solution is cooled to 0 by adding ice, acidified with 25 parts by volume of 30% hydrochloric acid and diazotized by adding dropwise 4N sodium nitrite solution until it remains blue on iodine potassium starch paper.

A solution of 14 parts of 1-ethyl-4-methyl-6-hydroxypyridone-2 in 50 parts is added to the yellow diazo solution Water and 9.5 parts of 30% sodium hydroxide solution. After finished Coupling is neutralized to pH 7 by adding sodium bicarbonate and- the dye precipitates by sprinkling in potassium chloride. It dyes cotton in real green tones yellow nuances.

10-9848 / 1771

Example 10.

12.6 parts of δ-acetylamino ^ -aminophenol - ^ - sulfonic acid are suspended at 0 in a mixture of 100 parts of water and 15 parts of 30 ^ hydrochloric acid and added dropwise diazotized by 25 parts of 2N sodium nitrite solution. The diazo suspension obtained is added to a solution of

7.7 parts of 1-ethyl - ^ - methyl-6-hydroxypyridone-2 in 50 parts of water, 50 parts of ice and 5.5 parts of sodium hydroxide solution at 30 $ and slowly adjusts to pH f by the dropwise addition of sodium hydroxide solution. After the coupling has ended 30 parts of 36% hydrochloric acid are added and the mixture is refluxed for 1 hour to saponify the acetyl group. The dye which has crystallized out after cooling is filtered off, dissolved in 250 parts of V / water at pH 7, and a solution of 13 parts of cobalt acetate tetrahydrate is added. It is refluxed for 20 minutes, then allowed to cool and the cobalt complex is precipitated by adding sodium chloride. It is dissolved in 500 parts of water at 35- ^ 0 ° and treated with an aqueous solution of 16.1 parts of 2-phenylamino-4,6-dichlorotriazine-3 ^! - sulfonic acid added. The condensation is carried out at 35- ^ 0, a pH of 6-7 being maintained by adding 2N sodium hydroxide solution.

When the condensation has ended, the dye is precipitated by adding potassium chloride. It dyes cellulose fiber material in red-orange, real nuances.

If an equivalent is used instead of cobalt acetate

Amount of chromium acetate, a dye is obtained that dyes cellulose fiber in real, red-brown tones.

109848/1771

Dyeing regulation I.

2 parts of the dye from Example 1, 1st paragraph, are dissolved in 100 parts of water.

A cotton fabric is impregnated with this solution on the padder and the excess liquid is squeezed. kelt so that the fabric 75 $ of its weight in dye solution holding back.

The so impregnated goods are dried, then impregnated at P room temperature in a solution that per liter Contains 10 g sodium hydroxide and ^ 00 g sodium chloride Liquid absorption squeezed and for 60 seconds

damped at 100 to 101 °. It is then rinsed for a quarter of an hour in a 0.5% solution of an ion-free solution Detergent soaped, rinsed and dried at boiling temperature

The result is a boil-fast, fixed coloration. If you use a rayon fabric instead of a cotton fabric, so you get a similarly good result.

1 0 9 8 A 8/1 7 7 1

Printing regulations:

2 parts of the dye obtained in Example 2 are mixed with 20 parts of urea, dissolved in 28 parts of water and stirred into 10 parts of a 5% sodium alginate thickener. Then another 10 parts of a 10 ^ igen sodium carbonate solution are added. .

A cotton fabric is printed with this printing ink on a roller printing machine, dried and steamed the pressure obtained for 8 minutes at 105 · Then the printed Tissue in cold and hot water, rinsed and dried thoroughly.

109848/1771

Color regulation II

1 part of the dye according to Example 5 of the table on page J and 5 parts of 80% acetic acid are dissolved in 4000 parts of water. 100 parts of polyamide fabric are entered into this bath at 40, the temperature is increased to 96-98 ° within 50 minutes and dyeing is carried out for 60 minutes at the specified temperature. The dye is then rinsed well. A strong greenish yellow coloration is obtained.

109848/1771

Claims (1)

Claims. .1 · Azo compounds, which have an acidic water-solubilizing Substituents and a radical of the formula R ' (D contain, in which R is an alkyl radical and R 'is an alkyl or aryl radical. 2. Azo compounds according to claim 1 of the formula R ¹ D-N = N- | f \ .ηοΑ ,, Α (2) viorin R and R ^{1 are} alkyl radicals having 1 to 4 carbon atoms and D is the radical of a diazo component of the benzene series. j5. . Azo compounds according to claims 1 and 2, the one reactive residue contain. k. Azo compounds according to claim 3 * which contain a Re active radical in the substituents R. and / or R ^1. 5. Azo compounds according to claim 3, of the formula 109848/1771 R ¹ —UH— _D i—. _{Ν =} (3) wherein D 'is a sulfobenzene radical, X is a halogen atom and Y is Halogen atom or the remainder of an amine, alcohol, phenol or mercaptans, and where the benzene radical can contain further substituents, in particular complexing groups. . 6. Azo compounds according to claim 5 > formula (3) »where D ^{1 is} a monosulfobenzene radical, X is a halogenator, Y is the radical of an aminobenzene (or naphthalene) disulfonic acid and R and R 'are each a methyl or ethyl radical. 7. Azo compounds according to claim 6, wherein D ¹ contains no further substituents apart from a sulfonic acid group. 8. Azo compounds according to claim 4, of the formula R ¹ D-N = N- / S ηΛΑ <*> ■ (CH ₂ ) -NH-Z where D is the radical of a diazo component of the benzene or naphthalene series, R ^{1 is} an alkyl or aryl radical, Z is a reactive radical • 10984871771 and η is a positive integer. 9-azo compounds according to claim 8, wherein D is an acidic Contains water-solubilizing substituents. 10. Azo compounds according to claims 8 and 9 * wherein Z a dihalotriazine radical or a monohalotriazine radical, which is the radical of ammonia bonded to a carbon atom, contains an amine, alcohol, phenol or mercaptan. 11. Azo compounds according to Claims 8 to 10, in which η is a number from 1 to 4. 12. Azo compounds according to claim 8 of the formula (5) j NH-C where X is a halogen atom, Y is the radical of an aminobenzene (or naphthalene) sulfonic acid, R ^{1 is} a low molecular weight alkyl radical and m = 1 or 2. 13 · Azo compounds according to claim 12, wherein X is chlorine or Bromine atom is. l4. Azo compounds according to claims 12 and 13i in which R ^{1 is} a methyl radical. • 10 9 8 4 8/1771 15- heavy visual metal complexes of azo compounds according to claims 1 to β and 8 to 11. / an acidic water-solubilizing substituent and / 16. A process for the preparation of azo compounds. which / a Remainder of the formula R ¹ (1) HO I.
. R. contain, in which R is an alkyl radical and R ^{1 is} an alkyl or aryl radical, by coupling and optionally metallization or acylation. 17. The method according to claim l6, characterized in that that a diazo component of the benzene series with a compound of the formula (6) A ₀ > R where R and R 'represent alkyl radicals having 1 to K carbon atoms, is coupled, and that the azo compound obtained is optionally metallized and / or is optionally acylated after the coupling or after the metallization. 18. The method according to claims l6 and 17 *, characterized in that that the starting compounds used, in particular as diazo components, are those which have a reactive radical • 109848/1771; contain. 19. The method according to claim 18, characterized in that a compound of formula (6) is used as the coupling component, which in the substituents R and / or R ^! contain a reactive radical. 20. The method according to claims ΐβ to l8 for production of compounds of the formula R ' —D «—M = N Λ I ■ »Η JL ^ N Where D * is a sulfobenzene radical, X is a halogen atom and Y is a halogen atom or the radical of an amine, alcohol, phenol or mercaptan, and the benzene radical can contain further substituents, in particular complex-forming groups, by coupling and acylation with a halotriazine and, if necessary, replacement a halogen atom of the halotriazine by reaction with ammonia, an amine, alcohol, phenol or mercap tan in any order. 109848/1771 21. The method according to claim 20 for the preparation of compounds the formula (3). " wherein D 'is a monosulfobenzene radical, X is Halogen atom, Y the residue of an aminobenzene (or naphthalene) disulfonic acid and R and R 'are each a methyl or ethyl radical. 22. The method according to claim 21 for the preparation of compounds of the formula (3) , v / orin D ^1, apart from a sulfonic acid group, contains no further substituents. 23 · The method according to claim 19 for the production of Ver bonds of the formula where D is the radical of a diazo component of the benzene or naphthalene series, R ^{f is} an alkyl or aryl radical, Z is a reactive radical and η is an integer positive number. 24. The method according to claim 23 for the preparation of compounds of formula (4), wherein D contains an acidic water-solubilizing substituent. 25. The method according to claims 23 and 24 for production of compounds of the formula (4) in which Z is a dihalotriazine radical or a monohalotriazine radical which is attached to a carbon atom Bound remainder of the ammonia ^ an amine, alcohol, phenol or mercaptan contains is. 109848/1771 2.6. Process according to Claims 23 to 25 for the preparation of compounds of the formula (4), in which η is a number from 1 to 4. 27. The method according to claim 2j5 for the preparation of compounds the formula R ¹ -N = N- (CH_) _O- NH-C CX ²² II NN wherein X is a halogen atom, Y is the residue of an aminobenzene (or naphthalene) sulfonic acid, R 'is a low molecular weight alkyl radical and m = or 2. 28. The method according to claim 27 for the preparation of compounds of the formula (5) i in which X is a chlorine or bromine atom. 29. Process according to Claims 27 and 28 for the preparation of compounds of the formula (5) in which R ^{1 is} a methyl radical. Method according to claim 16, characterized in that that according to claims l8 to 21 and 23 to 29 obtained Azo compounds are treated with metal donors. 109848/1771 31 · The compounds obtained according to the examples 32. Procedure according to the examples given. 33 · The ones obtained according to claims ΐβ to 30 Links. Use of the compounds according to claims 1 to 15 or those obtained according to claims 16 to 30 ■ Compounds as dyes or pigments. 35. A method for dyeing and printing using the dyestuff according to claim 34. 36. The material dyed or printed according to claim 35, ™ especially the textile material. 109848/1771