DE2349752A1 - AZO CONNECTIONS, THEIR PRODUCTION AND USE - Google Patents

Description

Azo compounds, their manufacture and use

The invention relates to azo compounds which are the remainder of one Jj-Sulfomethylrpyrazolons- (5), especially of the formula

SO H

(D

contain, wherein R is a hydrogen atom, an alkyl or Means aryl radical or a heterocyclic radical. The remainder of the formula (1) is connected to the remainder via an azo bridge a diazo component bound. The diazo radical is a heterocyclic or aromatic radical, which itself is a Can contain azo group or which is derived from a compound of the anthraquinone, nitroaryl, phthalocyanine, stilbene series or the like. In particular, the diazo radical is a radical from the benzene or naphthalene series.

40981 5 / 11U

- ■ . -. O "37 Q7 ^r * 5

The azo compounds of the invention can exist in several tautomeric forms. To simplify the description the compounds in the formulas are only shown in one of these tautomeric forms. However, it is explicit emphasizes that the description, here as well as in the following, in particular in the claims, is always based Relates to compounds in any of these tautomeric forms.

In particular, the term pyrazolone should also include the relevant compounds substituted by a hydrogen atom in the 1-position of the pyrazolone ring, as well as the corresponding tautomeric 5-hydroxypyrazole. ^;

The inventive azo compounds can also Sulfomethyl group free of other water-soluble properties Groups such as sulfonic acid, carboxyl, or quaternized amino groups; but they can in particular also contain such groups. In particular, the compounds in the molecule can be one or more than one reactive Radical, such as a halotriazine radical. In addition to water-solubilizing groups, the azo compounds, namely both in the remainder of the diazo component and in the remainder of R, as usual by other atoms or Atqmgruppen be substituted, e.g. by halogen atoms,

Hydroxy, amino, alkyl, aryl, alkoxy, aryloxy, acylamino, cyano, acyl, carboalkoxy, acyloxy, nitro groups

409815/1144

Usvi .. contains the rest of the diazo component in the ortho-position to the azo bridge a complex-forming group such as a hydroxy, amino or carboxy group or an alkoxy group such as a methoxy group _s so the compounds in question, optionally prior to the introduction of reactive radicals, or after , are converted into their heavy metal complexes.

For example, iron, manganese, nickel, copper, cobalt and chromium can be considered as complex-forming metals. the Heavy metal complexes can have one or two molecules of azo compounds with the remainder of the formula (I) attached to a metal atom contain bound (1: 1 or 1: '2 complexes). In 1: 2 complexes, however, one of the two ligand molecules can also be an azo compound that does not contain the rest of the Has formula (I) as coupling component, for example a compound of the azobenzene type, the corresponding Contains complex forming groups.

Reactive radicals can 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 represents in particular a low molecular weight substituted by a removable atom or a removable group Alkanoyl or alkylsulfonyl radical, a low molecular weight ^ possibly by a splittable atom or a splittable

4 0 9 8 15/1144

-M-

bare group substituted alkenoyl or alkenesulfonyl radical, one through a carbonyl or suIfony group a leaving atom or a leaving group substituted carbo- or heterocyclic, 4-, 5- or 6-rings containing radical or one bonded directly via "a carbon atom, by a removable atom or a removable atom Group substituted triazine or pyrimidine radical or contains such. The reactive radical is preferred a six-membered heterocyclic radical containing halogen atoms and bonded via an —NH group with two or three ring nitrogen atoms, in particular a chlorine-1,3,5-triazine radical.

The invention particularly relates to compounds of the formula

D — N = N-

s 7 ^f '

0 ^ y

wherein R is a hydrogen atom, an alkyl radical with at most

or an aryl radical |

4 carbon atoms / and in which D is the residue of a diazo component of the benzene or naphthalene series. she
also relates in particular to compounds which have reactive radicals, especially cyclic reactive radicals, such as, for example, triasin, pyrimidine or cyclobutane radicals, and water-soluble ones
Have groups, it being possible for the reactive radicals also to be contained in the R substituent.

L 0 9 8 1 5/1 U k

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

N
ΐ —Cr ^ C-NH-D · —N = Ih-I r — CH _o S0 ^ H

where D ^! a sulfobenzene radical, one Y a halogen atom and the other Y a halogen atom or the radical of an amine, to which a fiber-reactive radical can be bonded, of an alcohol, phenol or mercaptan. In addition to one or two sulfonic acid groups, the benzene radical can, as already mentioned, carry further substituents.

Another group of interesting compounds are those of the formula

D-N = N

where D is the remainder of a diazo component of the benzene or naphthalene series, in particular one that makes water solubilizing Substituents, R 'contains a hydrogen atom

409815/1144

or a low molecular weight alkyl radical, and Z a reactive radical, in particular a dihalotriazine radical or a monohalotriazine radical, which is the radical of ammonia, an amine, alcohol, phenol or bond bonded to a carbon atom Contains mercaptans is.

In this case, low molecular weight alkyl radicals are to be understood as meaning alkyl radicals having 1 to 4 carbon atoms, e.g. the methyl, ethyl, propyl, isopropyl, butyl or ß-'hydroxyethyl radical.

Also of importance are compounds which each have a reactive radical in the diazo and coupling components, such as, for example, compounds of the formula (4) which, in addition to the reactive radical Z ".

contain another reactive radical in the diazo component D.

'■ The preparation of the azo compounds according to the invention can be made by coupling and optionally metallization or by acylation in order to introduce a reactive residue.

The preparation by coupling is characterized in that a diazo component, in particular a those of the benzene series, with a 3-sulfomethyl-pyrazolone- (5), in particular of the formula:

CH ₂ -SO H

409815/1144

wherein R is the one given in the explanation of the formula (I) Has meaning, is coupled, and that optionally the azo compound obtained by reaction with a heavy metal donor Agent in a heavy metal complex

v on / 'is performed. It is preferable to start / diazo components which contain a reactive radical and a water-soluble group. '

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 pyrazolone is also carried out by methods known per se in a weakly acidic to alkaline medium.

The reaction with the heavy metal-releasing agent takes place by customary methods, depending on the solubility the components in various solvents, such as water, ethanol, formamide, glycol ether, pyridine, etc., optionally at elevated temperature, in a weakly acidic to alkaline medium.

409815/1144

As a diazo component ^ for the production of the

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

. Aminobenzenes. "· '.

• ·

l-amino-4-chlorobenzene,. · ·. · ■.

l-amino-4-bromobenzene., · '', ·

l-amino-4-methylbenzene ·, · '. .. l-amino-2-nitrobenzene, · '".'. ·"

- 1-Amino - ^ - nitrobenzene ^ .. '. "' .-

• l-Amino - ^ - cyanobenzene,: - ". ··.

l-Amino-2 _> 5 ~ dicyanobenzene _/ .- ··. ·

. l-Amino-4-ynethylsulfcinylbenzene ,,. ·

■ l-Amino - ^ - carbalkoxybenzolj - "" .- ** '.. Araino-2,4-dichlorobenzene ,, '·'. '. '".. · *

l-Amino ^ -methyl - ^ - chlorobenzene ^ 1-Amino -2 -trifluoroniethyl -h -chlorobenzene, '

. l-Amino-2-cyano - ^ - ehlorberizol,. '.' ■. ' "'.«. ■ -. *. "·

I-Aniino72-carbomethoxy- ¹ t-chlorobenzene _J ■ - ·

l-Amino-S-carbomethoxy - ^ - nitrobenzene, * 1- Amino-2-chloro- ⁱ T-cyanobenzene>. ". '_;'l ~ Amino ~ 2-ehlor ~ 4-nitrobenzene, · ·. 1-Amino-2-bromo -h -nitr © benzene,. l-Amino ^ -chlor- ^ - carbethoxybenzolj l-Amino-2-chloro- ty-ynethylsulfonylbenzene,

. "·. -40981 5./11 44

ORlGlNALiNSPECTED

CLBA-GEIGY AG

1-amino-2-methylsulfonyl-4-chlorobenzene, 1-amino-2-methylsulfonyl-4-nitrobenzene, l-amino-4-methylsulfonyl-2-nitrobenzene, 1-amino-2,4-dicyanobenzene, 1-Amino-2-cyano-4-methylsulfony! Benzene, l-amino-2,6-dichloro-4-cyanobenzene, l-amino-2,6-dichloro-4-nitrobenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoic acid e-cyclohexyl ester, l-aminobenzene-2-, -3- or -4-sulfonic acid amides, such as that N-methyl or Ν, Ν-dimethyl or diethylamide, 2-aminonaphthalene-6-sulfonic acid-N, Y-isopropyloxypropylamide, 1-aminobenzene-2-, -3- or -4-sulfonic acid-N, γ-isopropyloxypropylamide ,

l-aminobenzene-2-, -3- or -4-sulfonic acid-N-isopropylamide, l-aminobenzene-2-, -3- or -4-sulfonic acid-N, γ-methoxypropylamide,

l-aminobenzene-2-, -3- or -4-sulfonic acid-N, N-bis- (ß-hydroxyä thy1) -amid,

l-amino-4-chlorobenzene-2-sulfonic acid amide, and the N-substituted derivatives,

409815/1144

CLBA-GEIQY AG

- 10 -

2-aminothiazole, 2-amino-5-methylsulfonyl-thiazole, 3-AmInO-S-chlorobenzisothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4- (4'-chloro) -phenylthiazole, 3-aminopyridine, 3-aminoquinoline, 3-aminopyrazole, 3-amino-l-phenylpyrazole, 3-aminoindazole, 3-amino-1,2,4-triazole, 5- (methyl-, ethyl-, phenyl- or benzyl) -1,2,4-triazole, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzothiazole, 2-amino-1,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole, 2-amino-4-phenyl- or -4-methyl-1,3,5-thiadiazole,

409815/1144

- Ii -

ty-aminoazobenzene,. > ·.

3,2 '-Dimethyl - ^l \ -aminoazobenzene, · 2-methy1-5-methoxy- k -aminoazobenzene, ty ~ Aminc>-2-nitroazobenzene.,' R. 2,5-Eimethoxy -ty-aminoazobeiizole,

• ·

h ^x -Methoxy - ^ - aminoazobenzolj 2-methyl- ^J i '-methoxy - ^ - aminoazobenzene ^ ~ 5>& Λ ^% -Trimethoxy -k -arninoazobenzene, * ^ ¹ -Chlor - ^ - aminoazobenzene,' ..

.2'- or 3 ¹ -chloro- ¹ } -aminoazobenzene,. ■ 3- ^{Nitro- J} i - araIno-2 ^! , Λ '--dichlorazobenzene, h -arrainoazobenzene -k ^r -sul f onsaiireamld,. 1- or 2-aminonaphthalenes * '- ...

6-acetylamino- ¹ J - chlor-2-aminophenols 'o-nitro - ^ - chloro ^ -aminophenol, 6-nitro- ¹ J - methyl-2-aininophenol,' - /: --- v

. ·. ·; · "■ ·"; ^ "Ainino- ¹ ! - -hydroxy-acetophenone, ··" ■

6-Nitro- k -acetylamino-2-aminophenols. 5-Nitro-3-amino - ^ - hydroxy-acetophenone, • 2-aminophenol-4-carboxamide, ^ "-"

4,6-dichloro-2-aminophenols · '-. ": '3, ^ , 6-triehlor-2-aminophenol,

4 0.9 81 5 / V1? I "4

ORSGJWAL INSPECTED

- or 6-chloro-2-aminophynol - ^ - sulfonic acid amide 4-nitro-2-aminophenol-5- or -6-sulfonic acid amide 2-aminophenol-5-methylsulfone, -. ·. ■ ■ 2-aminophenol,

4- or 5 ~ nitro-2-aminophenol / ./ 4- or 5-chloro-2-aminophenols "" *. · "■. * ^, 5 ~ Di chi or-2 -aminophenol.,
Jr-chloro ^ -nitro ^ -aminophenol,. . *

2-aminophenol- ^J J- or -5 ~ sulfonic acid,

^ -Chlor ^ -arainophenol-S-sulfonic acid, "· -"

e-chloro ^ -arainophenol - ^ - sulfonic acid, "" '-.

4-nitro-2-aminophenol-β-sulfonic acids _. '. ".

• ·

6-Hitro-2-aminophenol-4-sulfonic acid, - '.: "·

2-Afflinophenol-4 ^ 6-disulfonic acid,,

4j6-Dinitro-27amiriophenol _i '*. "Ν." . ". ·

6 ~ Ethylamino-2-aminophenol-4-sulfonic acid, ^ -Acetyljamino ^ -arninophenol-o-sulfonic acid,

4-methyl-2-aminophenol; '* ·; . - *. . "-" ■ "".

. 4-methoxy-2-aminophenol, ·; .. ■ · .. · * '- . ■'. . '· S-aminophenol - ^ - sulfonamide, ·'. · _; · .;

. 2 ~ aminophenol - ^ - sulfone-N-ß-hydroxyethylamide,

ä-aminophenol - ^ - sulfonamide, ■ · ·

4-chloro-2-aminophenol-5- or -β-sulfonamide, ' · .. ... · '. -. 40 9 3.1 5 / -1 1 4 4. - ...

ORIGINAL INSFECTED

2-aminophenol- ^J t-sulfone-N, N-dimethyl amide,

. _: 2-aminophenol - ^ - methylsulfone, '. "-

• ·

2-aminophenol - ^ - ethyl sulfone, * ..; "

6-acetylamino-H-nitro-2-aminophenols 2-aminobphenol- ³ ^ ß-hydroxyethyisulfone, anthranilic acid,. · '. . "'

2-Araino-3-naphthoic acid ^. : ·

.h- or 5- chloroanthranilic acid,

4- or 5-nitroanthranilic acid, h- or 5-acetylaniinoanthranilic acid, h ~ or 5-sulfoanthranilic acid,. . "· Anthranilic acid ~ K -sulfonamides. '·". * · ** - * * "·

Anthranilic acid -Λ- or -5> ß-hydroxyethyl sulfone,

Anthranilic -JF ~ or ~ 5 "äthylsulfon, · '■ -'. · -. * '- ^ ^ chloro -anjinophenol -5-sulfonic acid -N -methylamido h ~ or 5-Benzoylarainoanthranilsäure ,, · _." 2 Anisidine,. ·. "· .. '' .. · ■■. \ ■ '' / ■■ /

4 ~ or 5-chloro-2-anisidine _> ■:. · ".. ·· -. ·

H- or 5-nitro-2-anisidine,. ■ .- ■ :.

S-anisidine- ^ r- or -5-sulfonic acid, '. · " S-kethoxy-ip-methylaniline., · '- · ..' · ... "■ '..-':

2-anisidine - ^ - or - 5-ß-hydroxyethylsulfone ^

■. * ■. · 2-Amino-1-naphthol -k ', 8-disulfonic acid, · -

l-Amino-2-naphthol- ^ - sulfonic acids. . . · '·· ". - '. * · · \" ■. : 40.9815 / 1Ί-Λ4- '".'

]? iÄL INSPECTED

1-amino -2-naphthol -H -sulfonainid,

6 ~ Nitro - 1-amino-2-naphthol-V-sulfonic acid, 6-acetylamino-1-amino-2-naphthol -h -sulfonic acid , ^ - (2 *, 5'-disulfophenylazo) ~ 2-methoxy- 5-fi <ethylaniline-j 4 ~ (2 ', 5' -disulfophenylazo) -2., 5-diniethoxyaniline, ty- (2 ^l , 5 '-disulfophenylazo) ^ -methoxy-1-naphthylarr.ino-S-

sulfonic acid, *. -.

^ - (1 '>5' -Disulfonaphth-2 '-ylazo) -2, 5-diinethoxyaniline, h- (2 *, 3 * - or V-sulfophenylazo) -2-methoxyaniline _/

Dianisidine,. '. - ·:

Benzidine-3i3'-dicarboxylic acids

Jl- (2 '~, 3 ^f - or h * -Sulfophenylazo) ^ -methoxy - ^ -. T.ethyl h- {2 ^x ~, ~ y - or h ' -Sulfophenylazo) -2,5-dimethoxyaniline, ^ - (S'j ^ ¹ - or 3 ', 5'-disulfophenylazo) -2-methoxyaniline,

^ - (3 ^t i5 ^l -öisulfophenylazo) -2-niethoxy-5-jriethylaniline, ^ - (3 ^f j 5'-disulfophenylazo) -2, 5-dimethoxyaniline, '4- (2'-carboxy - ^' - or -5 ¹ -sulfophenylazo) -2-methoxyaniline ^ 4- (2'-carboxy- ^ - or -5'-sulfophenylazo) -2,5-dimethoxyaniline, 4- (2 ^! -Carboxy- ^ ¹ -or ~ 5 ' -sulfophenylazo) -2-niethoxy-5-raethyl-

4- (6 *> 8 '-Disulfonaphth-2 ¹ -ylazo) -2-methoxyaniline., ^ - (6 *, 8' -Disulfonaphth-2 '-ylazo) -2-methoxyaniline,

ή · ~ (β ', 8' -Disulfonaphth-2 '-ylazo) -2-methoxy-5-.wethoxyaniline ,, ·

4- (6 ', 8' -r-disulfonaphth-2 ¹ -ylazo) -2,5-dyne; ethoxyaniline,

^ -Phenylazo-2-aminophenol. ^: ". '..

*. '".' .. · '-4Ό.9 8 1-5 / 1-UA'. ·; ■.

ORlGiiJAL IMSFECTED

CLBA-CELGY AG

- 15 -

Metanilic acid,

SuIfanilic acid,

Or thanilic acid,

l-amino-4-methylbenzene-2-sulfonic acid, Aniline-2,5 ~ disulfonic acid, 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-4,6,8- or -3,6,8-trisulfonic acid, l-amino-4- (ß-sulfatoethyl-sulfonyl) -benzene, l-Amino-3- (ß-sulfatoethyl-sulfonyl) -benzene, 1-Amino-2-methoxy-4- (ß-sulfatoethylsulfonyl) -5-methyl-benzene, l-amino-4- (ß-sulfatoäthylsulfonamido) -benzene, l-amino-4- (ß-hydroxyethylsulfonyl) benzene, l-amino-4- (ß-sulfatoethylsulfonylmethylamido) benzene, 2-amino-4- or -S-acetylaminobenzene sulfonic acid, 2-Amino-4- or -5-dibromopropionylamiiiobeBZolsialfonsaure, 2-amino-4- or -S-oc-bromoacroylaminobenzenesulfonic acid, 2-amino-4- or -S-chloroacetylaminobenzenesulfonic acid.

409815/1144

CIBA-GEIGY AG

The following are mentioned as coupling components:

3-sulfomethyl-pyrazolone- (5),
1-methyl-3-sulfomethyl-pyrazolone- (5), 1-ethyl-3-sulfomethyl-pyrazolone- (5), 1-propyl-3-sulfomethyl-pyrazolone- (5) * 1-phenyl-3-sulfomethyl -pyrazolon- (5), 1- (2'-chlorophenyl) -3-sulfomethyl-pyrazolone (5), 1- (2'-sulfophenyl) -3-sulfomethyl-pyrazolone (5) »1- (3 ¹ -Sulfophenyl) -3-sulfomethyl-pyrazolone- (5), I- (4 ^S -sulfophenyl) -3-suIfomethyl-pyrazolone- (5) * .1- (4'-nitrophenyl) -3-sulfomethyl-pyrazolone- ( 5) » 1_ (2'-Methy! Phenyl) -3-sulfomethyl-pyrazolone- (5), 1- (4'-methylphenyl) -3-sulfomethyl-pyrazolone- (5) , -1- (4 ^{1 -methoxyphenyl} ) -3-sulfomethyl-pyrasolone- (5},. 1- (2 ', 5'-dimethylphenyl) -3-sulfomethyl-pyrazolone- (3) ,; 1- benzyl-3-sulfomethyl-pyrazolone- (5; * l-Cyclohe3cyl-3-sulfomethyl-pyrazolone- (5) ₃ 1 "(4 ^! -Pluorophenyl) -3-sulfomethyl-pyrazolone- (5 / <

1- (4 ' ₅ 8 ^! -Disalfonaplith-2 ^: -yl) -3-suIfomethyl-p7raaolon- (5) ₃ 1-f2 ¹ , 3 ^: -Disshlorphenyl} -5-sulfomethyl-pyrasolon-'),

I- (4'-Bro ^ phenyI} -3 ~ sul? Oüiethyl-pyr ^s ar3clcn- ^; 'f

CLBA-GEIGY AG

- 17 -

1- (2 '-Chlor-6' -methyl-4 '- sulfophenyl) -3- sulf omethylpyrazolon- (5),

1- (2'-hydroxyethyl) -3- sulfomethyl-pyrazolone- (5), 1- (2'-methoxyphenyl) -3-sulfomethyl-pyrazolone- (5), 1- (3'-acetaminophenyl) -3-sulfomethyl-pyrazolone- (5).

The coupling components are manufactured by Reaction of a haloacetoacetic acid ester, e.g. Chloroacetoacetic acid ester, with a sulfite, e.g. sodium sulfite, and condensation of the sulfoacetoacetic acid ester formed with hydrazine, the desired 3-sulfomethyl-pyrazolone- (5) being formed under water. The implementation or condensation takes place in aqueous, acidic or alkaline solution at ordinary or elevated Temperature.

Azo compounds with the remainder of the formula (1) or the corresponding heavy metal complexes that contain one or contain several 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 add reactive groups subsequently to introduce into the azo compounds. The introduction can after the

409815/1144

•. - 18 - ■

Coupling or done after metallization. from

• - · with the grate / Such compounds / of the formula are of particular interest

(1) . - "- · the one about

an A.'nino group bonded six-membered heterocyclic

. · ".." ■. "- '; contain reactive residue.' · The reactive radical is preferably introduced

· Amino /

"by acylation of corresponding / azo compounds or

Coupling components which contain an acylatable amino group, or corresponding diazo components which, in addition to the araino group to be diazotized, have a further aylatable amino groups or a group which, for example. can be converted into an acylatable amino group by reduction or saponification, such as, for example, the nitro group or the acetylamino group. ; · - ^: ■ . ". _" · '* · ·· - - ·

As a corresponding diazo component ^. "

- the, as described above, for the

Introduction of a reactive radical are suitable, e.g. called: ''' . - ·. . "· - · ·" - ·

acid, '·.!, ^ - Diarninobenzene ^ -sulfonic acid,. -

1,4-diaminobenzene ~ 2 _J 5 ~ or -2,6-disulfonic acid,

l-Amino - ^ '- nitrobenzene,' ''. "· '

■ ■.

l-amino-2-chloro - ^ - nitrobenzene,

² benzene-6-sulfonic acid, ·. 0-9 8 1 5./1 1 A4 .; \ "·

"ORiG.'NAL

_ ₁₉ . . '23V9752

(> -Ace ty! Amino- ⁷ ! -Chlor ~ 2-aminopher> ol, 6-nitro- ^ - methyl-2-an} inophenol,. ·

ty-nitro-S-aminophenol-ö-sulfonic acid.,. · ö-acetylamino-l-amino - ^ - naphthol - ^ - sulfonic acid and others e.g. already in the list of possible diazo components called connections. * '

As Aminoazoverbjndungen., / Those after the coupling the reactive radicals can be introduced, e.g. the coupling products of the above-mentioned diazo components. .with pyrazolones of Eorrael (5) into consideration ";, · ·

For the preparation of compounds of formula (4)

one goes from _- I- (aminophenyl) -5-sulfomethyl-pyrazolonen- (5) or from l- (nitrophenyl) -3-sulfomethyl-pyrazoionen- (5) from ₃ in which. the nitro group to the amino group. reduces vs ± vd ₃ and acylates this before or after the coupling with acylating agents which contain a fiber reacti-vrest. '.. ".' *, ·

4 0 9 8 15 / "'" · ί ι

ORiGaNAL! NSPSCTCD

- As aeylating agent, which -

£ ■ ■ contain a reactive fiber radical, the halides or anhydrides of organic acids, which contain easily exchangeable atoms or groups of atoms, are particularly suitable.

Acylating agents containing a resctive residue for example the following are mentioned:

. Chloro- or bromoacetyl chloride, ·. ·

. Ss-chlorine or β-bromopropionyl chloride,

α, β-dichloro- or a ^ ß-dibromopropionyl chloride, '· "Chloromaleic anhydride, * ·.

Carbyl sulfate,. · "/*..'· '- · Acrylic chloride,. ...:"·'. · ...- ·.; ..-

β-chloro- or ß-bromoacrylic chloride> '. . .

α-chloro- or a-bromoacrylic chloride, ■

α, β-dichloro- or dibromoacrylic chloride, ■ Trichloroacrylic chloride, ". · *. '*

Chlorocrotonyl chloride, - '. ·'

Propiolic acid chloride, '■. "· * ·· 3i5 ~ Dinitro-'i ~ chlorobenzene-sulfone, acid ~ or -carboxylic acid-

• · *

chloride, * ·. ·, ... ' ; · "■ - ' 3-nitro- ^ i-chlorobenzene sulfonic acid or carboxylic acid chloride, 2,2,3i3 ~ tetrafluorocyclobutane-1-carboxylic acid chloride,

obutyl-acrylf
9 8 1.5 / 1 1.4 A

p-Chloräthylsulfonyl-endoraethylcn-cyclohcxeincarbonsäurechlorid ^ Acrylsulfonyl-endoraethylen-cyclohexanecharbonsäurechlorid, and above all heterocyclic acid halides and their. .Derivatives, such as the
2M? Hlorbenzoxazolccirboxylic acid chloride, "·· ·

2-Chlorbenzthiazolcarbon-Oder'-sulfonic acid chlorides and. -. ';

• ·

especially the following, at least 2 nitrogen atoms

as heteroatoms of a β-membered keterocycle •. .

Links: . ■ ■ - ''. - · \

^, 5 "Diehlor" l-phenylpyridazoncarbon- or sulfonic acid chloride, ^, 5 ~ I5ichiorpyridazonpropionäurechlorid,. '.' ··

Ijty-Dichlorphthalazijicarbon- or -sulfonsäurechlorid, "2,5 ~ ^i> i ^c ^ l ° ^rc ^^ ^noxa Ü ^ncarbon "'or -sulfonsäurechlorid, S ^^ - Dichlorquinazolinecar- or -sulfonsäurechlorid ^ - S-Methanesulfonyl - ^ - chlor -ö-methylpyriniidin,. ._... ·

Sj ^ -Bis-methanesulfonyl-ö-rfiethylpyrimidin., 2, ^, 6-TrO, - or 2,4,5,6-tetrachloropyrimidine,. . ■ 2,4,6-tri- or 2, ¹ l _i 5,6-tetrabromopyrimidine _jr "'2 ~ methanesulfony.l-ty, 5-dichloro-6-methylpyrimidine / 2 _< , 4-dichloropyrimidine-5 ~ 5ulfonic acid, · '

• · ■ *

• 5 ~ nitro or 5 ~ Cya_n-2, ⁱ l-, o-trichloropyriniidin _i> 2,6-bis-methanesulfonylpyridine - ^ - carboxylic acid chloride, '

2,4 ~ Biehlor-5-chloroniethyl-6-methyl-pyriinidine _i

8-15 / 1144 -.

* * ORIGINAL IMSFECTED

2, ty-dichloro-5-chloriacthylpyriniii.lia, '■

2 j 5,6 -Trichlor-ty-rac thy3. pyrimidine 2 _< , 6 "dichloro- ³ S-trichlorniebhylpyrifiiidin or in particular 2, ^ -3ismnethylsuif onyl ~ 5-chloro-6-methylpyrimidine, '

2 jh -Di chloropyrirnidine ,

^, ö-Dichlorpyridazine ^ -carboxylic acid chloride, ·· "2,6-DichloF ~ or 2,6 ~ Dibrcra ~ ^l r ~ earboäthoxypyriri] idin ,,

2 _/ ⁱ -dichloropyriinidine-6-carboxylic acid chloride _i . .;

2, 6-Dichlor ™ or Sj-S-Dibroiripyririiidin -} · - or acid or sulfonic acid amides bsw. ~ h- or ~ 5 ~ ^su li'oi ¹ acid chloride ^ -. _ ■ '·' ·. '.'. · "2 ^ ^J l, 5jO-Tetrachloropyridazine _J * _; '■

5 ~ acetyl-2, ⁱ f., 6-triehlorpyrir £ iid5.nj _I

2-chlorobenzthiazole-6-carboxylic acid chloride / 2 ~ chlorobenzothiazole-6-sulfonic acid chloride _i 5-nitro-6-ntsthyl-2, h -dichlorpyriniidin, 2, ⁱ o6-trichloro-5 ** bro "iiipyririiidiii _i -

, 6-di fluorine ~ 5-chloropyr iniidin,

hlorpyriroidin ^ 4098 1 5 / 1U4 ·.

ORiGJWL SUSPECTED

21'1,6-TrIcKlOi- (-Tribroin- or -Tririuor) -l _J 3 _J 5-triazine _J and ^, 6-dichloro (dibromo- odor -DIfluor) -1,3,5-tr! Azines, the are substituted in the 2 position by an aryl or alkyl radical, for example a phenyl, methyl or ethyl radical, or by the radical of an aliphatic or aromatic mercapto or oxygen atom bonded via the sulfur atom

• *

bonded hydroxyl compound or in particular through a KH _p group or through the remainder of an aliphatic, heterocyclic or aromatic Ämlnoverblindung bonded via the nitrogen atom. As such compounds, the radicals of which by reaction with trihalotriazines in 2-position on the Triazln-

can be bound to the core, e.g. the following mentioned:

aliphatic or aromatic mercapto or hydroxyl compounds, such as thloalcohols, thioglycolic acid, thiophenols, "-alkoxyalkanols, methyl, ethyl, isopropyl alcohol, glycolic acid, Phenol, chloro- or nitrophenols, phenol carbon and -sulphonic acids, naphthols, naphtholsulphonic acids, etc., especially

but special ones containing ammonia and aylable amino groups

Compounds such as hydroxylamine, "hydrazine, phenylhydrazine,

Phenylhydrazine sulfonic acids, glycol monoalkyl ethers, methyl, * Ethyl, isopropyl, methoxyethyl, kethoxypropyl-amine, Dimethyl, methyl, methyl phenyl, ethylene phenyl amine, chloroethyl amine., Ethanolamines, propanolamines, benzylamine, cyclo-

hexylamine, morpholine, 'piperidine, piperazine, aminocarbonic acid ester, Aralnoesslgsäureäthylester, aminoethane sulfonic acid,

40.9 8 1-5 / 1 144. . *. · ·.

■ ORIGIMAL INSPECTED

•. - ■ - 24 -

N-Kethylaniinoethanesulfonic acid, but above all aromatic Amines, such as aniline, N-mefchylaniline, toluidine, xylidine, Chloranilines, p- or m-aminoacetanilide, aminophenols',

• #

Anisidine, phenetidine and, in particular, anilines containing acidic groups, sulfanil, methanil, orthanilic acid, aniline disulfonic acid, aminobenzylsulfonic acid, aniline-iü-methanesulfonic acid, arrainobenzenedicarboxylic acids, naphthylamino-mono-oxy-, di- and tri-2-benzoic acids, such as sulfonic acids 5 ~ a ^ ino ~ .benzoic acid, also colored compounds, or "compounds with dye character, e.g. 4-Hitro7 ⁱ r '-aminostilbene disulfonic acid, 2-nitro- ^' -aniino-diphenylamino- ³ } ·, ^ ¹ · * Etilben-disulfonic acid, 2-Mitro- ² J * -aininodiphenylamin-Jl ·, ^ '"* disulfonic acid and in particular aminoazo dyes, or aminoanthraquinones or phthalocyanines, which still contain at least one reactive amino group,

The introduction of the 2-position des'Triazinrestes standing substituents can also after the condensation with.

the starting diamine or according to the implementation according to the invention

with the rest / . ·

2U done for azo compound / the formula (I). - .. '

In addition to those which can be introduced by acylation, fiber-reactive radicals should also be mentioned, e.g. the vinyl sulfone, the ß-sulfato or thiosulfatoethyl sulfone, ß-thiosulfator ■ propionylamide, the ß-Thiosulfätoäthylsulfonylamid- or the ·. Sulfonic acid-N ^ ß-sulfatoäthylamidgruppe, which "in a different way, e.g. by ester or thioester formation into the diazo component introduced v / earth. 4098 15/1144. . '·

• · * '· ORfGiNAL INSPECTED'

• ·

As compounds that don't get you through acylation. insertable fiber reactive residue, in which the Fiber reactlvres't therefore preferably not via a "' Amino group, but is bound directly to the benzoin residue, the sulfoesters of the following sulfones may be mentioned in particular: X ~ amino-2 ~ methoxy-5 ~ (ß-hydroxyethyl) phenyl sulfone, - ·

• 1-aminobenzene ~ 3 ~ 'or -4 ~ ß-hydroxyethyl sulfone,

I -amino -2-methylbenzene -5 -ß -hydr oxyä thylsul f on 1-Amino - ^ - {ß-hydroxyethylsulfonylpropionylaminoinethyl) benzene ,.

1-Amino -K - (β-hydroxyethylsulfonylamino) -benzene.,

• ° as well as via corresponding methy.lole according to Einhorn -available reactive "compounds, such as

• l-Amino - ^ - chloroacetylaminomethyl-benzene or · -. - ■

■ -l-Araino ^ -chloracetylarainome thyl -benzene -ö-sulfonic acid,

The condensation with acyl halides or dan .Anhydriden or heterocyclic halogen compounds. • is carried zweckmäss3.g 'in the presence of acid-binding agents, such as', for example, sodium carbonate, from. In all of these reactions, self-

• ·

understandable to proceed in such a way that there is still a . • unsaturated bond. Or one exchangeable halogen atom left over remain* . - '-. · *. *. '. · ■' ■ "·. 1" "- ■ '" *. * "■"

According to the present process and its variants, available azo compounds as well as their heavy metal complexes

•. 4 0-9 8 1 5 / M 144 · '. · '""

L-! WSPECTED

- 26 are new; sic are suitable for dyeing and printing various materials, such as silk, leather., wool, synthetic fibers made from super polyamides, super polyurethanes,

polyhydroxylated

Materials, such as cellulosic materials, more fibrous Structure such as linen, pulp, regenerated cellulose, cotton and the like. ■. "

The nientmetallized azo compounds according to the invention are of particular importance as dyes.

Most important, however, are those according to the invention

Azo compounds, which have a reactive radical and a water-soluble one Group, especially a sulfonic acid group contain. These dyes are preferably used for the

Dyeing of nitrogenous fibers, such as super polyamides, Super-polyurethanes, silk, leather and especially V / oll3,

0 3 8 1.5 / 1 144

ORiGIiMAL INSPECTED

ζ.B from weakly acidic, neutral or weakly alkaline Bath, if necessary with the addition of the usual aids, e.g. of ethylene oxide condensation products of high molecular weight Amines, and especially of cellulose materials, in particular Cotton, e.g. after the exhaust process from a long liquor, from alkaline, possibly highly salty, aqueous Bath and especially after the poulard 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 ground fixed under the influence of heat, used.

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

The dyeings and prints are interesting and valuable "yellow, very pure and brilliant shades

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. In particular on cotton, excellent hate fastness. Worth mentioning is also the high one. Degree of fixation and the good removability unfixed dye components. . -

■ ··. '· ■ ·' 409815/11 A4 ·. · .. "■

ORlGfMAl INSPECTED

■. : '' ··. '. 234B7.52

- 28. In order to improve the wet fastness properties, it is recommended to

the dyeings and prints obtained with thorough rinsing cold and hot water, optionally with the addition of a dispersing agent acting and the diffusion of the unfixed portions promoting agent to submit.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius. Between parts by weight and parts by volume there is the same relationship as between grams and cubic centimeters. '. - ". '- -' - ■

5/11 4-4

· ORfui ^ ÄL! MSPECTED

Example 1.

To a neutralized solution of 17.2 parts ! -Aminobenzenesulfonic acid in 100 parts of water and 100 Parts of ice are poured into a solution of 18.5 parts of cyanuric

Chloride in 50 parts of acetone and holds the ρ -, - value during

ix

the condensation by adding dropwise 2N sodium hydroxide solution 6 to 7 »After the condensation has taken place, a neutral one is given

18, 8 parts /

Solution of / T3-piamTnobenzene-4-sulfonic acid to, warmed up 20-25 ° and keeps the p "value of the solution at 6 to" 7

Add dropwise 2N sodium hydroxide solution. As soon as diaminobenzenesulfonic acid is no longer detectable in the mixture, 7 parts of sodium nitrate are added and, after dissolution, it is poured onto a mixture of 200 parts of ice and 25 parts of concentrated hydrochloric acid = the yellow suspension of the diazo compound is stirred in an ice bath for 1 hour, then added small excess of nitrous acid • destroyed by adding sulfamic acid. A solution of 27.6 parts of 1-phenyl-3-sulfomethyl-pyrazolone - (5) """- ■ '-''is now poured into this diazo suspension: in 100 parts of water. The p ^ -V value, which is 1.5 at the beginning, is increased to 6.5 by adding sodium hydroxide solution dropwise, a clear yellow solution being obtained. The mixture is stirred for 1 hour in an ice bath, then provides to p _H 7, and falls

the dye by adding sodium chloride. The thus obtained Dye dyes cotton in pure .. · yellow tones.

■ 409815/1 1 Uh

Further yellow dyes are obtained if, as in the example, the amines listed in column I of the table below are condensed with cyanuric chloride, the monocondensation products obtained are condensed with the diamines listed in column II, diazotized and with those in column IT. called coupling components.

! ι

>; Amine "

1? L-aminobenzene-3- ϊ sulfonic acid ί

f υ

? Diamine

T in '~ j coupling component

f 1,3-phenylenediamine-p-sulfomethylpyrazolone

f 4-sulfonic acid-e "! (5)

1-methyl ~ 3-sulfomethyl pyrazolone- (5)

l-aminobenzene-2-sulfonic acid

l-aminobenzene-4-sulfonic acid

l- (2 ^f -chlorophenyl -) -> sulfomethylpyrazolone

- (5

1-aminobenzene -2, h disulfonic acid

1-aminobenzene-2,5 · disulfonic acid

1-aminobenzene ~ 3j5 ~ disulfonic acid

1,4-phenylendiarnine-2-sulfonic acid

1, 3-phenyl endifin

| l- (2 ^J -Sulfophenyl) -3-fsulfomethylpyrazolone- (5)

! l- (3 ^f -Sulfophenyl) -3-isulfomethylpyrazolon- (5)

l-ethyl-3-sulfomethylpyrazolone- (5)

l-propyl-3-sulfomethyl pyrazolone- (5)

l- (4'-nitrophenyl) -> sulfomethylpyrazolone- (5)

^ -Sulfomethyl-pyrazolone- (5)

40981 5/1 IU

II

III

11 '1-Naphthylamine sulfonic acid

j I ₃ 3-PhenylenediarnIn- i3-sulfomethyl-pyrazolone-4j6-disulfonic acid |)

1-naphthylamine-6-sulfonic acid

1-naphthylamine-7 sulfonic acid

e, _{7-1 3} 4-phenylenediamine · disulfonic acid 2 ₃ 5-disulfonic acid

4-aminobenzylsulfonic acid

2-anrino-5-sulfobenzoic acid

4-aminobenzoic acid

2-aminobenzoic acid

l-aminobenzene-3- and -4 - sul fön acid in a ratio of 1: 1

1-aminobenzene-4-ß-chloroethyl sulfone

1-amino-3-chloroacetyl aminoinethyl benzene-6-sulfonic acid

Anil in -li-cu-methanesulfonic acid

3-phenylenediamine sulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

3-phenylenediamine-4-sulfonic acid

L- (2'-methylphenyl) -

5-sulfomethylpyrazolone- (5th

L- (2'-cyanoethyl) -3-sulfomethylpyrazolone- (5)

I- (2'-methoxyethyl) -> sulfomethylpyrazolone- (5)

1- (4 ^! -Methoxyphenyl) -> sulfomethylpyrazolone- (5)

1- (2 '^ dimethylphenyl) - ^ · sulfomethylpyrazolone- (5)

3-sulfomethylpyrazolone- (5th

• 1-Benzyl-3-sulf omethylpyrazolone- (5)

l-Cyclohexyl-3-sulfomethylpyrazolone- (5)

1- (4'-fluoro phenyl) -> ; sulfomethylpyrazolone- (5);

815/1144

I. I. 1 _} 3 ~ P ^ ^en ylenediamine
4-sulfonic acid Il 23 3-amino-2,4-bis-
phenylamino-6- 2,6-diaraincnaphtha-
lin-4,8-disulfone
acid azin-3 "-sulfone
acid I! 24 3'-amino-2,4-bis-
phenylamino-6-
ehlor-l _J 3,5-tri-
asin-4 ', 3 "~ di-
sulfonic acid 4-sulfonic acid 25th l-aminoben2; ol-3-
sul-f onic acid it 26th 1-aminobenzol-2-
sulfonic acid It 27 An illn-N-to
methanesulfonic acid 28 aniline 29 l-aminobenzene-3-
sulfonic acid

III

3-sulfomethylpyrazolone- (5)

l- (2'-chloro-5 ^T -sulfophenyl) -3-sulfomethylpyrazolone- (5)

1_ (4 « _} S» ^ disulfonaphth-2'-yl) -3-sulfomethylpyrazolone- (5)

1- (4'-sulfophenyl) -3-sulfomethylpyrazolone- (5.

3-sulfomethylpyrazolone- (5)

k O 9 8 1 5/1 U 4

Example 2. · ·.

9.4 parts l, j5 ~ diaminobenzene-4-sulfonic acid are in 100 parts V / water suspended and by adding lye up to

dissolved to a p _H ~ = 7. To this solution are added at room temperature with good stirring IQ _-, 4 parts of 2-isopropoxy-4, 6-dichloro ~ ljj5,5-triazine and holding during the condensation by dropwise addition of 2N sodium hydroxide solution at _pH 6-7 ·

• After the condensation has ended, cool by adding ice to 0 °, IJ parts by volume of concentrated hydrochloric acid are added and diazotized by adding dropwise 50 parts of sodium nitrite solution. A solution of 8.9 parts of 5-sulfomethylpyrazolone- (5) - --._. "Is then poured into the diazo suspension obtained.

>_;; - I ^ ■ - · -. · I _n 40 parts of water and the coupling mixture is _{prepared by adding 5N sodium hydroxide solution dropwise to D 17} 7 within 1 hour. The dyestuff is isolated from the yellow dyestuff solution by adding potassium chloride. He dyes cotton in real yellow tones. . - "

If the diamine used in column II of the table below is used, and the acylating agent used is the "in column I." and the coupling component mentioned in column III. Link, this gives other yellow dyes with similar properties. ■ '■. . · '

4Ö98f5 / 1144

2,4-dichloro-6-methoxy-1,3i 5-triazine

J2-amino-4,6-di- | chloro-1,3,5-itriazine

J, 2- (2'-ethoxy) -iathoxy-4,6-di- ehlor-1,3,5-triazine

2,4,5,6-tetrachloropyrimidine

| 2,3-dibromopropi-I acid chloride

J2,4-dichloropyriimidine-5-earbonic acid chloride

2, h -Di chi or -6 phenyl-1,3,5-triazine

- 34 -

II

1,3-pheny

4-sulfonic acid

III

[2.4
[5'-jarnin

1,4-phenyl 3-sulfonic acid

2,4-diamino ~ 5-sulfo-benzoic acid

1,3-Diarninobenzene-4, β-disulfonic acid

1,3-phenylenediamine 4-sulfonic acid 3-sulfomethylpyrazolone {

l-methyl-3-sulf ome thylpyrazolone- (5)

l-ethyl ~ 3-sulfome thylpyrazolon- ^)

l-Cyclohexyl-3-sulfomethv py ra zol on— (5)

l-Senzyl-3-sulf otne thylpyrasolon- {5)

l-phenyl-3-sulf onset hylpyrazolon- {5)

jarnino) -l, 3 * 5-triazine-2 "-ylamino] -phenylamino-1,3j5-triazine-2'-sulfonic acid

Chloroacetyl chloride

α-bromoacrylic acid chloride

3,5-dinitro-4-chlorobenzenesulphonic acid chloride

2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid chloride

l, 3-Tue. ^air '3-benzene-4,6-disulfonic acid

409815 / 1U4 sulfomethyl pyrazolone (5)

- (2 · -L'ethylphenyl) -3 _T sulfoine tiiylpyraEolon- ί 5)

_ (31_sulfopheny1) -3-sulf O £ nethylpyrazolone- (5)

3-sulf ome thylpyrazolone (5)

3-sulf ometh3 ^r lpyrazol on (5)

1-C V -acetaminophenyl) 3-suIfome thylpyrazolon- (5)

Il

β-Chloräthylsulfonyl- J2 ₃ 4-Diarcinotoluol · endomethylene cyclo- \ 5-sulfonic acid hexanecarboxylic acid I chloride f

III

2-chlorobenzene carboxylic acid chloride

4 _Λ 5-Βί propionic acid chloride

2,3 dichloroethinoxa lin-6-sulfonic acid chloride

2-methanesulfonyl -k chi or -6 -rne thyl pyrimidine

2, k, 6-tribrojiipyriinidine

2-methanesulfonyl-4, 5-di chloro-6-methylpyrimidine

5-cyano-2 _i 4j6-trichloropyriinidine

2,6 -Bisine thanesulfonyl pyridine-4-carboxylic acid ■ ehlorid

2., 4-Dichloro-5-chloroethyl-6-methylpyrimidine

2 ₃ 4-bismethylsulfonyl 5-chloro-6 -rne thyl pyrimidine

2,4,6-trimethylsulfonyl-1,3 > 5-triazine

i 1,4 -Di am in o -5 chiorbeηζöl-2-sulfonic acid

] 1 ₃ 4-Diarninobenzene 12 _Λ 5 ~ isulfonic acid

^: Ij4-diaminobenzene · 2 ₃ 6-disulfonic acid

1.3 ~ Di arainobsnzol ■ 4-sulfonic acid

jl- (2 «-chlorophenyl) -3-sulfomethyIpyrazolon- {5)

- ( 4 * —Broispli enyl) 3 ~ su liornethylpyra- ζο1οη- (5)

3-sulfomethylpyrazolone ~ (5)

1,4-diarninobenzene "
2,6-disulfonic acid

815 / 11Λ4 Il

l-Kethyl-3-sulfο-me thy lpy ra 7, oil on- (5)

l-phenyl-3-sulfoffiethy pyrazolone- (5)

3-sulfomethylpyrazolone- (5)

! - (2 ¹ -Sulfophenyl) - 3-sulfome tiiyl pyra zolon- (5)

Il

I. j - II 25th 3,6-dichloropyri-
dazin-5-carbon-
acid chloride t
! 1,4-diaminobensol
2 ₃ 6-disulfonic acid 26th 2,4-dichloropyri-
midin-6-carbon-
acid chloride 1.3 ~ diaminobenzene
4,6-disulfonic acid 27 2,4,5,6-tetra
chloropyridazine Il 28 2,4,5,6-tetra
fluoropyrimidine. 1,3 ~ dis.minobenzene
4-sulfonic acid 29 2,4,6-trifluoro
5-chloropyrimidine 11 30th 2,4,6-trichior
Ij3i5-triazine Il 31 2, 4 -Di chi or -6 -
ine thy lmer capt o-
l, 3 * 5-triaziri Il 32 2,4-dichloro-6-
ethyl-1,3,5-
triazine 1,3-diaminobenzene
4,6-disulfonic acid 33 2,4-dichior-6-
isopropoxy
Ii3j5 ~ triazine Il 3 ^ 11 1, J) -T) ± zm ± no \ ienz, o \
4-sulfonic acid 35 !! 1,4-phenylenediami
3-sulfonic acid 36 2 -amino -4 , -6 -di -
chlorine-1,3,5-
triazine 1,3-oisminobenzene
4-sulfonic acid 37 2,4,6-Triehlor-
I, 3j5 ~ triazine 11

Ill

I l-ethyl-3-sulfomethyl-

- I T _.- fcN

l-Pher.yl-3-suifomethyl- ()

j 3 ~ sulf omethylp3 ^r razolon ~ (

1-methyl_3_sulfomethj'-1- j pyrazolone- (5) {

3-on- SulfotsethyIpyrazol * (5) I

1- (3 ¹ -Sulfophenyl) ~ 3- j sulxOir.ethylpyx'azolon-C 5) I

l- (2 '-Chlcr-5' -sulf opher. -3-sulfoGie tiiylpyrazolon-j (5)

l- (2'-chloro-6'-methyl-4 'sulfopher, yl) -3-s-alfo- | methy2pyrazolone- (5) \

3-sulfomethylpyrasolone- ( f

l ~ (4 ^f -Sulfophenyi) -3-sulf otnethylpyrazolon- (5) ί

A09815 / 1 1

I. II III 38 2,4-dichloro-6-
Isopropoxy
1,3 * 5-triazine 1,3-diaminobenzene
4-sulfonic acid l- (2'-Hydroxyethyl) -3-
• sulfomethylpyrazolone- (5) 39 2,4,6-trifluoro
5-chloropyrimidine Il 1-phenyl-3-sulfomethyl
pyrazolone- (5) 4ο 2,4,6-tribromo
Ii3i5 "triazine It 1- (2 ¹ -methoxyphenyl) -3-
sulfomethylpyrazolone- (5) ) 41 2-ethylamino
4,6-dichloro
triazine Il 3-sulfomethylpyrazolone- - |
(5) 42 2-morpholino
4,6-dlchlor-
triazine Il ', "
i 43 2-υΓβΐαο-4, β-
dichlorotriazine Il ! I 44 2-dimethylamino
sulfonylamino
4,6-dichloro
triazine. ■ Il It
ί

4 0 9 815 / 1U 4

Example 3 »

To a neutral aqueous solution containing 35. »8 Parts of the sodium salt of 2- (j5 '~ aminophenyl) amino-4,6-di- -ljjjj5-triazine-4'-sulfonic acid are 25 parts by volume of a

^ n-sodium nitrite solution; cools to 0 by adding ice and drops 25 parts by volume of concentrated hydrochloric acid at once. When the diazotization is complete, a small excess of nitrous acid is destroyed by adding sulfamic acid. In the suspension of the diazo compound is now 20 parts poured into an aqueous solution containing the sodium salt of 3-Sulfomethylpyrazolon- (5) £ -. ■ - ". '-' -__ ■ -. The diazo compound goes into solution and there is a clear Yellow dye solution The pH is adjusted and a neutral aqueous solution of 21 parts of the sodium salt of 1,3-phenylenediamine-4-sulfonic acid is then added when the condensation is complete, the mixture is cooled to 0 °, a solution of 18.5 parts of cyanuric chloride in 50 parts of acetone is added, and the mixture is condensed at 0-5 °, the pH being adjusted by adding dropwise sodium hydroxide solution at 6-7. When the condensation has ended, 25 parts by volume of a 20% aqueous ammonia solution are added and the mixture is stirred for 3 hours

at HO . By adding saline wird'der dye of the formula Cl · ■ -.

/ Level N

BJ - / ^HH ? CHNE- <_> -S0, H ·. ■.

LN-C C ~ NH- <> I "I CH ₀ SO ^ H

ν sy, ""S> - ^ NN \ T_ij_ yd 3 _.

^C1 ·: · η

■ - 39 -

salted out, then filtered off and dried. It dyes cellulose fibers in real .- .. .-- ■ »·" yellow tones.

Λ 0 1 9.8 5/1 ^1: 44

ORFGJNAL INSPECTED

example H.

It is diazotized and coupled as indicated in Example 3. To the neutral dye solution containing the dye of

Formula.

Cl ...

C-.

NN

Ii I ■ ......

0 C-NH- <~> -SO H { '

J- '

they are now a neutral aqueous solution of 53 ', 3 parts of 1-amino - ^ - (2'-aminophenylJ-aminoanthraquinone-S ^ h'. disulfonic acid is heated to 40 ^ 5 ° and condensed at this temperature, viobei is maintained by dropwise addition of sodium hydroxide solution the pH at 6-7. After the condensation is isolated aen dye by addition of sodium chloride. It dyes fabrics of Celliilosefasern in Rainen greens... '

405815/114

ORI6JNAL INSPECTED

If, instead of vonl-Amlno - ^ - C ^ ¹ -aminophenyl) -aminoanthraquinones, *} '- disulfonic acid, an equivalent amount of the phthalocyanine dye of the formula is used

CuPc

- (SO-H).

SO H

H,

or the amxnoformazan dye of the formula

^ ⁰ N

te

, Cu

S0 "H 3

in this way, dyes are also obtained that dye tissue made of cellulose fibers in real shades of green.

409 8 1571 UA

Example 5

17.5 parts of 2-aminobenzenesulfonic acid are dissolved in 100 parts of water with the addition of 5.5 parts of anhydrous sodium carbonate. The solution obtained is admixed with 25 vol. Parts by 4N sodium nitrite solution and poured into a mixture of 100 parts of ice and 25 parts by volume of concentrated hydrochloric acid. The suspension of the diazo compound is made by adding 10 # sodium carbonate solution to a pH value of 8.5. 90 parts by volume of an aqueous solution containing 20 parts of the sodium salt of 3-sulfomethylpyrazolone- (5) are now added and the pH of the reaction mixture is kept at 8 to 8.5 during the coupling Dye solution the dye is precipitated by adding sodium chloride. He dyes fabrics made of synthetic polyamide material in real yellow tones. _:

Other dyes that contain the fabric material indicated in column III of the table below in the indicated Coloring nuances is obtained according to the specifications of the For example, by diazotizing the diazo components listed in column I and coupling with those mentioned in column II Coupling components.

409815/1144

Aminobenzene

1-amino-4-chlorobenzene

1-amino-4-nitrobenzene

1-amino-4-methylsulfonylbenzene

1-amino-2-trifluoromethyl-4-chlorobenzene

1-amine ο-2-chloro-4-methylsulfonyl- benzene

1-amino-2,4-dicyanobenzene

4-aminobenzoic acid cyclohexyl ester

1-aminonaphthalenes, J-sulfomethylpyrazolone- (5)

1-phenyl-3-sulfomethylpyrazolone- (5)

1-methyl-> sulfomethyl-pyrazolone- (5)

1-Cyclohexy1-3-sulfomethy1-pyrazolone- (5)

1-ethyl-5-sulfomethylpyrazolone- (5)

5-sulfomethylpyrazolone- (5)

1- (2'-chlorophenyl) -5-sulfomethylpyrazolone- (5)

X- (5'-acetylaminophenyl) -3-sulfomethylpyrazolone- (5)

isopropyloxypropyl amide

1-aminobenzene-4 sulfonic acid-N-iso- propylamide

4-aminophenyl sulfarnate

2-aminothiazole 2-aminoquinoline

2-amino-6-methyl benzthiazole 5-sulfomethylpyrazolone- (5)

thiadiazol 1- (2 ^f -Methylphenyl) -> sulfomethylpyrazolon- (5)

3-sulfomethylpyrazolone- (5)

9815/1 U4

yellow on polyamide

orange on polyamide

3-aminobenzisothiazole

4-aminoazobenzene

4-aminoazobenzene 3'-sulfonic acid

4- (6 ', 8'-disulfonaphth-2'-ylazo) -3-methylaniline

SuIfanilic acid

2-naphthylamine · 1-sulfonic acid

l-Amino-4 ~ (ßsulfatoäthylsulfonyl) -benzene

l ~ Amino-4- (ßsulfatoäthylsulfonarfiido) benzene

II

1- (3'-sulfophenyl) -3-sulfomethylpyrazolone- (5)

3-sulfomethylpyrazolone- (5)

1- (4'-chlorophenyl) -3-sulfomethylpyrazolone- (5)

3-sulfomethylpyrazolone- (5)

1-Benzyl-3-sulfomethylpyrazolone- (5)

1-propyl-3-sulforaethylpyrazolone- (5)

3-sulfomethylpyrazolone- (5)

III

orange on polyamide

yellow on polyamide

yellow on cotton

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Example 6

15 * 4 parts of 5-nitro-2-amino-1-hydroxybenzene are used in 120 parts of water and 15 parts of 50% hydrochloric acid Heating dissolved. The solution obtained is cooled to 5 and at 5 to 10 ° by dropwise addition of 25 parts of 4N sodium nitrite solution diazotized.

5 parts of 1-phenyl-3-sulfiOmethyl-5-pyrazolone

are dissolved in 100 parts V / water of .20 with a neutral reaction and mixed with 50 parts of a 4N sodium acetate solution. After cooling to 5, the above diazo suspension is added with stirring and the orange-yellow coupling mixture is adjusted to a neutral to slightly alkaline reaction by adding dropwise 2N sodium carbonate solution. The coupling is complete after a few hours. The partially precipitated dye is through. Addition of sodium chloride separated out completely, filtered off and washed with dilute sodium chloride solution; it has the following ^structure: OH

58.7 parts of the dye obtained are in the form of the F. filter paste slurried with 600 parts of 50 water. After adding 25 parts of basic chromium sulfate, 50 parts of 2N sulfuric acid are added to the metallization mixture and then in the autoclave for 12 hours

4098 1-5 / 1144

Stirred at 120 - 125 °. After cooling to 60 °, the 111-chromium complex present in the form of green-bronzing crystals becomes filtered off, washed with dilute sodium chloride solution until neutral and dried. By means of ; Oil with a little sodium carbonate is easily soluble in water Dye obtained, the wool from a strong sulfuric acid bath in pure, blue-red shades of very good lightfastness colors.

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- 47 Example 7

44.0 parts of the 1: 1 chromium complex of the azo dye from diazotized 5-nitro-2-amino-1-hydroxybenzene and 1-phenyl-3-sulfomethyl-5-pyrazolone, which can be obtained by a known process and contains 1 atom of chromium per molecule are stirred in 1000 parts of hot water together with 33.9 parts of the monoazo dye obtained by a known process from diazotized 5-nitro-2-amino-1-hydroxybenzene and 1-phenyl-3 * -methyl-5-pyrazolone. The suspension is concentrated by adding 20 parts by volume. Sodium hydroxide solution adjusted to p "7-8 and then stirred at 90-95 until both starting dyes can no longer be detected. The uniform chromium mixed complex in a clear solution is precipitated by adding sodium chloride, isolated by filtration and, after washing with sodium chloride solution, dried in vacuo. After grinding, the dyestuff is in the form of a red, readily water-soluble powder and dyes wool or polyamide fibers from a dyebath containing ammonium sulfate in full red shades with good fastness properties. He has the following constitution:

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Example 8

44.0 parts of the 1: 1 chromium complex of the azo dye, which is obtainable by a known process and contains 1 atom of chromium per molecule of monoazo dye, of diazotized 4-nitrc-2-ciinino-1-hycliOxybenzol and 1-phenyl-3-sulfomethyl-5 -pyrazolone are stirred in 1000 parts of hot water together with 32.2 parts of the monoazo dye, which is accessible according to known ure-ironing, from diazotized 1-aminobenzene-2-carboxylic acid and 1-phenyl-3-methyl-5-pyrazolone. The suspension wi_ * d crrch addition of 20 parts by volume of conc. Sodium hydroxide solution adjusted to p "7-8 and then stirred at 90-95 until both starting dyes Liichi iaeh" can be detected

4 0 3 8 15/1144

The uniform chromium complex in the solution is precipitated by adding sodium chloride Filtration isolated and, after washing with sodium chloride solution, dried in vacuo. The dye is lagging behind before grinding as a red, easily water-soluble powder and dyes wool or polyamide fibers made from ammonium sulfate Dyebath in full yellowish orange tones with good fastness properties. He has the following Constitution:

409815/1 144

- 50 Example 9

42.95 parts of the obtained by a known process, containing 1 atom of chromium for 1 molecule of monoazo dye 1: 1 chromium complex of the azo dye from diazotized 4-chloro-2-amino-1-hydroxybenzene and 1-phenyl-3-sulfomethyl-5-pyrazolone are together with 29.85 parts of the monoazo dye accessible by known processes from diazotized 4-chloro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene in 1000 parts of hot water stirred. The suspension is concentrated by adding 20 parts by volume. Sodium hydroxide solution adjusted to p "7-8 and then stirred at 90-95 ° until both starting dyes can no longer be detected. Of the A uniform chromium mixed complex in a clear solution is precipitated by adding sodium chloride, isolated by filtration and, after washing with sodium chloride solution, dried in vacuo. The dye lies after grinding as a dark red, easily water-soluble powder and dyes wool or polyamide fibers Dyebath containing ammonium sulfate in full brown tones with good fastness properties. He has the following constitution :

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Cl

2-Ia ^G

Example 10

45.4 parts of the obtained by a known method, containing 1 atom of chromium for 1 molecule of monoazo dye 1: 1 chromium complex of the Aad dye from diasotized 6-nitro-4-methyl-2-amino-1-hydroxybenzene and 1-Phenyl-3-sulfomethyl-5-pyrazolone are used together with 33.9 parts of the monoazo color accessible by a known method from diazotized! 4-nitro-2-amino-1-hydroxybenzene and 1-phenyl-3-methyl-5-pyrazolone stirred in 1000 parts of hot water. The suspension will by adding 20 parts by volume of conc. Sodium hydroxide solution adjusted to p "7-8 and then as long as Stirred at 90-95 until both starting dyes no longer exist

409815/1144

must be proven. The uniform chromium mixed complex, which is in a clear solution, is made by adding sodium chloride precipitated, isolated by filtration and, after washing with sodium chloride solution, dried in vacuo. After grinding, the dye is in the form of a dark red, easily water-soluble powder and dyes wool or Polyamide fibers from dyebath containing ammonium sulfate in full scarlet shades with good fastness properties. He has the following constitution:

40981 5/1 1 UU

- 53 Example 11

15.4 parts of 4-nitro-2-amino-l-hydroxybenzene were dissolved in 120 parts water and 15 parts hydrochloric acid 307 _o under .Erv7ä rms *. The resulting solution is cooled to 5 and diazotized at 5 to 10 by adding dropwise 25 parts of 4N sodium nitrite solution.

23.9 parts 1- (2'-methyl-phenyl) -3-sulfomethyl-5- " Pyrazolon are dissolved with a neutral reaction in 100 parts of water of 20 and with 50 parts of a 4N sodium acetate solution offset. After cooling to 5, the above diazo suspension is added with stirring and the orange-yellow one Coupling mixture by adding dropwise 2N sodium carbonate solution adjusted to a neutral to slightly alkaline reaction. The coupling is complete after a few hours. Of the Partly precipitated dye is completely separated off by the addition of sodium chloride, filtered off and washed with dilute sodium chloride solution; he has the following constitution:

-N = N-

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39.4 parts of the dye obtained v / earth with 600 parts of water of 70-80 slurried and by adding 20 parts of 30% sodium hydroxide solution in Solution brought. At the same temperature, the solution of 15 parts of crystallized cobalt (II) sulfate is used and 15 parts of tartaric acid in 200 parts of 70-80 water. Under color change from brown-red to The symmetrical 1: 2 cobalt complex is produced in a brownish yellow; it is made out of solution by adding sodium chloride precipitated, isolated by filtration, with dilute sodium chloride solution washed and then dried. The new dye obtained as a brownish powder after grinding dyes woolen fabrics from weakly acidic baths in the presence of suitable auxiliaries in full, genuine shades of brownish yellow .

If 39.4 parts of the above dye are metallized with 130 parts of an _{aqueous solution of sodium disalicylatochromate III containing 3.07% by volume of Cr 2} O ₃ in a weakly alkaline reaction by stirring for several hours under reflux, the symmetrical 1: 2-chromium complex obtained, which dyes wool yarn in full, yellow-tinged orange tones using the same dyeing process.

40981 5 / 11U

- 55 Example 12
26.7 parts of the dye of the formula

j! "I = J '* CCGH" ο 0 _r , H

Il il ² ^ HO-C, N

made by coupling 11.5 parts of 2-amino-4-acetylaminobenzenesulfonic acid with 16.7 parts of 1- (3'-sulfophenyl) -3-sulfomethyl-pyrazolone-5 and then Saponification in 47% sodium hydroxide solution is dissolved in 250 parts of water with the addition of sodium hydroxide solution at p "7. Man cools to 0 °, 9.25 parts of cyanuric chloride are added and the mixture is condensed at the specified temperature, the Keeping the reaction mixture neutral by gradually adding dropwise 2N sodium hydroxide solution. After condensation has ended a solution of 2.7 parts of 1,4-diaminobenzene is added, warms up to 30 ° and holds at this temperature for as long ρ 6.5 to 7 until condensation has ended. The yellow dye I'd solution obtained is dried to dryness in a vacuum evaporated. The dye powder obtained dyes cotton fabric after the exhaust process in real, yellow tones. Used instead of 1,4-diaminobenzene

409815/1 UA

equivalent amounts of 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, l ^ -diaminobenzene-S-sulfonic acid, 4,4'-diaminodiphenylurea, 4.4 ^! -Diaminostilbene disulphonic acid or 4,4'-diarainodiphenyl ether, one obtains more yellow dyes suitable for the exhaust process.

Example 13

6.37 parts of 2,6-diaminoiiaphthalene-4, 8-disulfonic acid are dissolved in 100 parts of water with the addition of sodium hydroxide solution at Po 7.3. The mixture is cooled to 0 by adding ice and a solution of 7.4 parts of cyanuric chloride in 25 parts of acetone is added. It is then condensed at 0 to 5 ° and a p “value of 6 to 6.5. When free amino groups can no longer be detected, 7.52 parts of 1,4-phenylenediamine-2-sulfonic acid, which have been dissolved neutrally in 50 parts of water, are added and the mixture is condensed at 30 and a p "value of 6 to 7 When the condensation has ended, 10 parts by volume of a 4N aqueous sodium nitrite solution are added and the resulting solution is poured onto a mixture of 10 parts of 32% strength hydrochloric acid and 150 parts of ice. After stirring for one hour, the tetrazotization has ended. A solution of 12.4 parts of the sodium salt of 1- (2'-chlorophenyl) -3-sulfomethylpyrazolone-5 in 100 parts of water is then added to the suspension of the tetrazonium compound

409815/1144

couplings at 0 to 5 ", keeping the p" value of the coupling mixture between 7 and 8. From the clear, reddish tint yellow solution of the tetrazo dye of the formula

H (L SCH ^ -C- ^ ^ Ii

SO-, Η

C-N = IT-A

Ii KJ 1

C-OH

-Cl

the dye is obtained by salting out with table salt. He dyes cotton fabrics in real, reddish yellow Tones.

40981 5/1 UA

23,975

Example 14

First, as described in Example 1, 17.3 parts of 1-aminobenzene-3-sulfonic acid are condensed with 18.5 parts of cyanuric chloride, the monocondensate is reacted with 18.8 parts of 1,3-phenylenediamine-4-sulfonic acid and diazotized The resulting diazosuspenson is admixed with a solution of 29.1 parts of the sodium salt of 1- (4'-aminophenyl) -3-sulfomethyl-pyrazolone-5. The coupling mixture is brought to ό 8 by the dropwise addition of sodium hydroxide solution and the mixture is stirred from 0 to 5 to to end the

rl
Reaction. Phosgene is now passed through the yellow dye solution at 30 to 40 until no more free amino groups can be detected. A p “value of 7 to 8 is maintained during the phosgenation. The dye is precipitated by adding sodium chloride. He dyes cotton in real yellow shades.

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Example 15

75.3 parts of the aminopyrazolone dye of the formula obtainable according to the details of the example

- im— Λ

SCLH IN = IJ C C-CH ₉ SCLH

? oi " ^{! i J}

are dissolved in Xiasser at p _TJ 7. 16.5 parts are added

rl

2-Amino-4,6-dichloro-1,3,5-triazine to and condensed at 30 to 40, whereby 2N sodium carbonate solution is added dropwise keep the p "value at 6 to 7. After finished Condensation, the bireactive dye is precipitated by adding sodium chloride and dried in vacuo. Man receives the dye as an orange dye powder, the Cotton dyes in real, reddish yellow tones.

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- 60 Example 16

41.7 parts of the reactive dye of the formula

C-CH, .. SCH

in the usual way in aqueous hydrochloric acid solution by adding dropwise 25 parts by volume of 2N-Na.trium nitrite solution diazotized. On the other hand, 16.1 parts of 2- (3'-sulfophenylamino) -4,6-dichloro-1,3,5-triazine are grounded condensed with 13.5 parts of 1- (4'-aminophenyl) -3-sulfomethylpyrazolone-5. The solution of the diazotized dye is combined with the solution of the coupling component and put through Addition of sodium bicarbonate to ρ 6. After completion Coupling turns the bi-reactive disazo dye through Sprinkle with potassium chloride precipitated, suctioned off and dried. He stains tissue made of cellulosic material in real yellow tones.

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- 61 production regulations for 3-sulfomethylpyrazolones

I. 1-Phenyl-3- sulfoniethylpyrazolone- (5)

To a solution of 30 parts of anhydrous sodium sulfite in 200 VoI - Share V / ater are added 7-Chloracetess3gester at 50 33 parts and stirred at the same temperature, until all has passed into solution. 21.2 parts of phenylhydrazine are now added. and stir for 1 hour at 80 - 85 · After. Cooling to room temperature is made strongly Congo acidic with 40 parts by volume of concentrated hydrochloric acid; the precipitated product is filtered off with suction and dried.

II. 3-sulfomethylpyrazolone- (5)

Sodium sulfite in 500 dividers. To a solution of 150 parts / water is added "

164.5 parts of 7-chloroacetoacetic ester run in rapidly. By the exothermic reaction rises the temperature to 60 and a clear solution is formed. You now give 53 parts at once Hydrazine hydrate, with 150 parts by volume, is 30 percent more Sodium hydroxide solution strongly alkaline and heated to 90 for 1 hour. After cooling down, hydrochloric acid is added dropwise the pH of the solution is adjusted to 5. The received Solution of 3-sulfomethylpyrazolone, the content of which by Titration determined with 4-nitrobenzenediazonium chloride solution can be used directly for the production of azo dyes use.

If the hydrazine hydrate used is replaced by

equivalent Kengen methylhydrazine, ethylhydrazine, 2-chloro

409815/11 A4

phenylhydrazine, 2-methylphenylhydrazine ,, Pheny! hydrazin-2., 5- or ^ 4-sulfonic acid, one also obtains the corresponding one in the 3-position of the pyrazolone ring by a Suli'o- "methy! group substituted pyrazolones.

A0981 5/1144

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

A Baunivjollgevicbe on the foulard is impregnated with this solution and the excess liquid is squeezed off in such a way that the fabric retains 75% of its weight in dye solution. \ - '

The "so impregnated goods are dried, then at Room temperature impregnated in a solution that per liter Contains 10 g of Katrrurahj'öroxyd and 300 g of sodium chloride / £ liquid uptake and squeezed for βθ seconds

damped at 100 to 101 °. ' Then it is rinsed during a Quarter of an hour in a 0, ^ igen solution of an ion-free • Detergent roped, rinsed and dried at high temperature

"The result is a boil-proof, fixed color." If you use a rayon fabric instead of a cotton fabric, you get a similarly good result »

09 8 1-5 / 1 14 4.

ORIGINAL INSPECTED

2 parts of the dye obtained in Example 2 are mixed with 20 parts. Urea mixed in 28 parts of water, dissolved and in ^; 10 parts of a 5 / ^ strength sodium walginate thickener stirred in. Then add 10 parts of the above sodium carbonate solution.

A building is printed with this printing ink ;;, v / oil »' fabric on a roller printing machine., dries and steams the pressure obtained for 8 minutes at 10 ^ °. Then the printed Fabrics rinsed thoroughly in cold and hot water and dried. . · ·

ORIGINAL INSPECTED

Dyeing regulations II

4 parts of the chromium coraplex dye obtained in Example 7 are dissolved in 4000 parts of water and left at 40 to 50 ° with 100 parts of well-moistened wool flannel into the dye bath. 3 parts of 40% acetic acid are then added to the bath and heated within half an hour to the boil and keeps it at the boiling point for 3/4 hours. Then you rinse them dyed goods with cold water and dry them. The red wool dye obtained is very light and light wetfast.

If you use a dye liquor that contains formic acid instead of acetic acid, wool dyeings are also used similarly good fastness properties are obtained.

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Claims (15)

Pa tonta n sayings
1. Azo compounds of the formula _Γ / (2) ΐ R where R is hydrogen, an alkyl or aryl radical and D is the radical of a diazo component. 2. Azo compounds according to claim 1, the one Contain reactive radical and a water-solubilizing group. 3. Azo compounds according to claim 2 of the formula C-KH-D '-N = IT- - ■ -j _H (3) where D 'is a sulfobenzene radical, R is hydrogen, an AJLk) ⁷ I or aryl radical, one Y is halogen and the other Y is halogen or an amino, alkoxy, phenoxy, alkyl mercapto or aryl mercapto group, and the benzene radical is further substituents, in particular may contain complex-forming groups. 409815/1144 4. Azo compounds according to claim 1 of the formula JH., SO., H (4) where D is the radical of a diazo component of the benzene or naptithalin series, R ^{1 is} hydrogen or a low molecular weight alkyl radical and Z is a reactive radical. 5. Heavy metal complexes of azo compounds according to claims 1 to 4. 6. Process for the preparation of azo compounds of the formula DN = I 1 π CH "SO _V H wherein R is hydrogen, an alkyl or aryl radical and D is the radical of a diazo component, characterized in that the diazo compound of an amine of the formula D-NH ₉ with a coupling component of the formula 15/1144 is coupled, and that the azo compound obtained, optionally with metal donating agents and / or is reacted with acylating agents. 7. The method according to claim 6, characterized in that the starting compounds, in particular as diazo components are used that have a Contain reactive residue and a water-solubilizing group. 8 «Method according to claim 6 or 7 for production of compounds of the formula Y-C 1 ^N 1 C-WH-D '-H = IT-ι π CH ₀ SO ₇ H lfcN I < ³⁾ .τι / wherein D ^{1 is} a sulfobenzene radical, R is hydrogen, an alkyl or aryl radical, one Y is halogen and the other Y is halogen or an amino, alkoxy, phenoxy, alky, mercapto or arylme capto group, and the benzene radical is further 409815/11 ^ 4 Substituentsj in particular complex-forming groups may contain, * characterized in that the diazo compound of an amine of the formula Y — C ^ ^Wx C — NH-D '- is coupled with a coupling component of the formula (5), or that the diazo compound is a diaminobenzene sulfonic acid of the formula EUN-D'-Nl ^ is coupled with a coupling component of the formula (5), and that the obtained azo compound with a halo-s-triazine of Formula '^ -F \ Y-C ^ ^- ^ C-Y wherein a Y is halogen or an amino, alkoxy, phenoxy, alkyl mercapto or aryl mercapto group and the two other Y are halogen, is acylated. 9. Continuation of the method according to claim 8, characterized in that the azo compound of the formula (3) obtained according to claim 8, provided that both Y Are halogen, for the purpose of replacing a halogen with an amino, alkoxy, phenoxy, alkyl mercapto or aryl mercapto group, rait ammonia, an amine, alcohol, or phenol 4 0 9 8 1 5/1 1 4 U Mercaptan is implemented. 10. The method according to claim 6 for the preparation of compounds of the formula ρ— _{1Ϊ = Κ,,} CH ₀ 80.,. H wherein D is the radical of a diazo component of the benzene or naphthalene series, R 'is hydrogen or a low molecular Alkylrestj ursd Z is a reactive radical ± _st} characterized in that the diazo compound of an Asiins of formula D-HK ₉ with a coupling component of the Forme! F, τ / is coupled, or that the diazo compound is a
Amine of the formula D-NH ^ with a coupling component of the formula 0 9 8 15/11 UU -CH ₂ S0,, H R ^f is coupled, and that the azo compound obtained with an acylating agent introducing the reactive radical Z is reacted. 11. The compounds obtained according to the examples. 12. Procedure according to the examples given. 13. Use of the compounds according to claims 1 to 5 or those obtained according to claims 6 to 10 Compounds as dyes or pigments. 14. Method of dyeing and printing using the dyes according to claim 13. 15. The according to claim 14 colored or printed Material, especially the textile material. 15/1144