Reactive Dyestuffs

Beginning of the patent period: January 15, 1969.

The invention relates to a process for the preparation of valuable new reactive dyes of the general formula:

<img file="AT274983B_D0001.tif" />

where D is the radical of an organic dye or dye precursor from the series of the azo, aza5 porphine, anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone or dibenzanthrone dyes or for polycyclic condensation compounds of anthraquinone, Benzanthrone and dibenzanthrone compounds, R is a hydrogen atom or a lower alkyl group, R_x represents a hydrogen atom, halogen atom, an alkyl or alkenyl radical optionally substituted by halogen atoms, for the NO₂, CN, carboxylic acid, carboxylic acid ester or optionally N-substituted carboxamide or sulfonamide group, furthermore for the sulfonic acid and sulfonic acid ester group, for the alkylsulfonyl, aralkylsulfonyl or arylsulfonyl radical, R₂represents a hydrogen atom, a halogen atom, or an optionally halogen-substituted one

Alkyl or alkenyl radical, for the aralkyl or aryl radical, further for the carboxylic acid ester, optionally N-substituted carboxamide, optionally halogen-substituted alkylsulfone or Aryl15 sulfongruppe and F is a fluoro substituent, n is an integer from 1 to 3 wherein the -N group is directly or through another bridge member such as -SO₂ or CO- or via an alkylene group, an alkylene-CO group, an arylene, arylene-SO_z-, Arylene-CO- or optionally substituted by halogen, amino or alkoxy-substituted triazine or diazine ring or an Arylenamidosulfonylgruppe may be bonded to an aromatic ring of the dye D.

According to the invention, the new dyes of the general formula are obtained by reacting amino or amide-containing, preferably sulfonic acid and / or carboxylic acid group-containing, dyes or dye precursors which have a reactive hydrogen atom on the amine or amide nitrogen with compounds of the general formula:

Nr.274983

<img file="AT274983B_D0002.tif" />

X

F (H) in which R, R and F have the above meaning and X is a reactive with the -NH group

2 i

Rest, preferably for a halogen atom, is reacted, and converted in the case of the use of dye precursors by azo coupling or condensation in the desired final dyes and these optionally metallized, sulfonated or acylated.

In the dyes of the general formula I, the -N (R) group is linked directly to a carbon atom of the pyrimidine ring in the 2- or 4-position.

As substituents R_x in the 5-position of the pyrimidine ring, for example: for halogen, CI, Br and F, for alkyl radicals -CH ^ and -C ^, substituted alkyl radicals, such as mono-, di- or trichloro or tribromomethyl, trifluoromethyl, for alkenyl , Vinyl, halovinyl and allyl radicals.

Suitable substituents in the 6-position of the pyrimidine ring are, for example: halogen, CI, Br and F, alkyl, methyl and ethyl radicals, alkenyl, vinyl, halovinyl and allyl radicals, and substituted alkyl radicals, such as mono- , Di- or trichloro- or bromomethyl- or trifluoromethyl radicals, as carboxylic ester, dimethyl and ethyl ester, as alkylsulfonyl and arylsulfone radicals, CH, SO₂-, C₂I ^ SO₂-, C₆H-SO_zor p-Cl-C₆H₄SO₂-.

Dyes in which and hydrogen, halogen and / or alkyl radicals, belong to a preferred group of the compounds according to the invention, as well as those in which the number n is 1 or 2.

Suitable pyrimidine rings:

<img file="AT274983B_D0003.tif" />

F (m) which have at least one removable (reactive) fluorine substituent are, for example, 2-fluoro-4-pyrimidinyl,

2, 6-difluoro-4-pyrimidinyl,

2, 6-difluoro-5-chloro-4-pyrimidinyl,

2-fluoro-5,6-dichloro-4-pyrimidinyl,

2, 6-difluoro-5-methyl-4-pyrimidinyl,

2, 5-difluoro-6-methyl-4-pyrimidinyl,

2-fluoro-5-methyl-6-chloro-4-pyrimidinyl,

2-fluoro-5-nitro-6-chloro-4-pyrimidinyl,

- bromo-2-fluoro-4-pyrimidinyl,

2-fluoro-5-cyano-4-pyrimidinyl,

2-fluoro-5-methyl-4-pyrimidinyl,

2, 5, 6-trifluoro-4-pyrimidinyl,

5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl,

2, 6-difluoro-5-bromo-4-pyrimidinyl,

2-fluoro-5-bromo-6-methyl-4-pyrimidinyl,

2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl,

2, 6'-difluoro-5-chloromethyl-4-pyrimidinyl,

2, 6-difluoro-5-nitro-4-pyrimidinyl,

2-fluoro-6-methyl-4-pyrimidinyl,

2-fluoro-5-chloro-6-methyl-4-pyrimidinyl,

2-fluoro-5-chloro-4-pyrimidinyl,

2-fluoro-6-chloro-4-pyrimidinyl,

6- trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl,

Nr.274983

6-trifluoromethyl-2-fluoro-4-pyrimidinyl,

2-fluoro-5-nitro-4-pyrimidinyl,

2-fluoro-5-trifluoromethyl-4-pyrimidinyl,

2-fluoro-5-methylsulfony 1-4-pyrimidine iny 1,

2-fluoro-5-phenyl-4-pyrimidinyl,

2-fluoro-5-carbonamido-4-pyrimidinyl,

2-fluoro-5-carbomethoxy-4-pyrimidinyl,

2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl,

2-fluoro-6-carbonamido-4-pyrimidinyl,

2-fluoro-6-carbomethoxy-4-pyrimidinyl,

2-fluoro-6-phenyl-4-pyrimidinyl,

2-fluoro-6-cyano-4-pyrimidinyl,

2, 6-difluoro-5-methylsulfonyl-4-pyrimidinyl,

2-fluoro-5-sulfonamido-4-pyrimidinyl,

2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl,

2, 6-Difluoro-5-trifluoromethyl-4-pyrimidinyl.

Among the variety of binding possibilities of the rest

<img file="AT274983B_D0004.tif" />

on D, direct attachment of the -N (R) groups to a carbon atom of a carbocyclic ring of D is preferred. Suitable bridge members of this and other types, including the -N (R) group, are for example (A is the radical of the formula HI):

-NH-A, -NfCHp-A, -N (C₂^) - A, -N (C₃Hp "Α, -CONH-A, -SO₂NH-A,

-CON (CH,) -A, -SO_GN (CKp-A and the corresponding N-ethyl and N-propylamides,

-HN-CO-NH-A, -HN-C 1-8 -CO-NH-A, -NCC-, J-CF 1 -CONH-A,

- HN-CH, -CK ^ -NH-A, -NH-SO₂- (CH₂)₁_₃-NH-A, -NH-CO-CCH ^ -NH-A,

-CHj-NH-CO-iCH ^ -NH-A,

-HNOC- \ / /

NH-A,

-NH-NH-A

-NH- //

\.

-NH- ./

-NH-A, (SOjHJj _{Q (}j_{he 2}

NH-A -HNOC- / NH-A,

T

-HNOC-

<img file="AT274983B_D0005.tif" />

NH-A

No. 274983

-HNί \ = 7 \ (so₃H)_x or 2 "SO, NH- / ² \ _ /

NH-A

NH-A &lt;^S° 3^H\ or 2

-SO, NH- / NH-A, \ = /

S ° 2^HN- \ __/ ^ nh-a stupid 2 / \ == / -HN-SO - / -, \ = / \

-HN-SO, '\ = /

K 'NH-A and the corresponding N-alkyl (1-5 C) amides or amines -HN-

CI ^ (G ^ V ^ NH-A

CONH-A

SCH or ι

NH-A

HN

SQNH-A / \ =: / and the corresponding N-alkyl (L-3 CJamide or amines of the compounds mentioned.

The new dyes may belong to a wide variety of classes, eg. B. the series of metal-free or metal-containing mono- or polyazo dyes, metal-free or metal-containing Azaporphin10 dyes such as copper or Nickelphthalocyaninfarhstoffe, the anthraquinone, oxazine, Dioxazin-,

Triphenylmethane, nitro, azomethine, benzanthrone and Dihenzanthronfarbstoffe and the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds. Dyes of the following general compositions are particularly valuable among these classes of dyes:

1. azo dyes:

<img file="AT274983B_D0006.tif" />

wherein B and E are aromatic, carbocyclic or heterocyclic radicals, in particular B is the radical of a carbocyclic diazo component of the benzene or naphthalene series, and E is the radical of an enolic or phenolic coupling component, for. B. a 5-pyrazolone, an acetoacetic acid-2-olylamide, an oxynaphthalene or an aminonaphthalene; Incidentally, B and E may have any other substituents customary in azo dyes, including further aza groups; R 'represents a -CHg group or preferably a hydrogen atom, and R ^ and E ^' independently represent hydrogen or halogen groups.

Particularly valuable dyes of this series are those which are water-soluble, and in particular those which have sulfonic acid and / or carbohydrates. The azo dyes can be both me5

No. 274983, as well as being metal-free, of which the copper, chromium and cobalt complexes are of particular interest among the metal complexes.

Important azo dyes are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone, the benzene-azo-aminonaphthalinreihe, the naphthalene-azo-naphtha5 linreihe, the naphthalene-azo-l-phenylpyrazolon-5 And the stilbene-azo-benzene series, wherein also here the sulfonic acid-containing dyes are preferred. In the case of metal complex azo dyes, the metal-complex-bonded groups are preferably in the ortho-positions to the azo group, for example in the form of o, o'-dihydroxy, o-hydroxy-o * -carboxy, o-carboxy-o * - amino and o-hydroxy-o'-amino-azo groups. Particularly excellent types of monoazo dyes of the kind obtainable according to the invention are illustrated by the following formulas:

(S0₃hv / \ x / • N = NGC-CHI, (or COOH)

HO-C N. \ X, / (V) (or HjN^-) N

N (R ') A

H; Cl; CHj- | - - ^ - (δΟ, Η) ,.

H; Cl; CH₃ (H0₃sv!

H; OCE ^; NH-acyl I OH

k. I • - (- N = N4

N (R *) - A (VI)

<img file="AT274983B_D0007.tif" />

Me = Cu; Cr; Co (^sW-₂

O-Cu-O \₌i / t

<img file="AT274983B_D0008.tif" />

NE (, (or NH-acyl) (^SO3^H\ -3 (vm)

NH-A

Nr.274983

A ~ NH / C \.

J (sqHVx

-N = N *

NH /⁼\

YL / (^SO3^H) L-3

NH₂ (or NH-alkyl) (IX)

A-NH

/. -N = N ™ / Λ (IXa)

SO H0so₃H

OH (o)

A-HN - N = N \ =) Y (so₃hv₁ (NH-acyl)_{0 or χ} &lt;^SO3^H&gt; l-3 (X)} (o) represents the o-position of each indicated radical in the aryl nucleus, and A represents the radical of the general formula:

Λ '&gt; N / - • N ^ where Rj¹ and R ^ 'have the meaning already given; Acyl is an acyl radical; the cores drawn in dashed lines indicate that they may be present or absent.

Second anthraquinone:

° ^ 2

<img file="AT274983B_D0009.tif" />

(XI) herein L and L 'are sulfonic acid groups and alkyl groups or alkoxy groups, p is an integer of 0 to 2, R is a methyl or ethyl group or hydrogen, R / and R / are independently hydrogen or halogen groups.

Nr.274983

Third phthalocyanine:

Pc-SO₂NH \

<img file="AT274983B_D0010.tif" />

(L ')_r Wr "

R '

<img file="AT274983B_D0011.tif" />

F (ΧΠ) in this formula Pc is the radical of a nickel or copper phthalocyanine, L and L 'are sulfonic acid groups, and also alkyl radicals or alkoxy groups, r is an integer from 0 to 2, q is the number 0 or 1, R' for a mefliyl group or preferably hydrogen, R / and R₂ independently of one another hydrogen or halogen radicals. The phthalocyanine Pc preferably carries as further substituents 1 to 2 sulfonic acid and / or 1 to 2 sulfonic acid amide groups, such as -SC ^ NH ^ -SO₂NH-alkyl, -SO₂N (alkyl)₂and so₂NH (aryl) groups, where alkyl is alkyl radicals having 1 to 3 carbon atoms.

The foregoing compilation of a selection of suitable azo, anthraquinone and azaporphine dyes as well as fluoro-substituted pyrimidine rings is not a limitation of the general formulas. neither with regard to the preparative possibilities for the preparation of such dyes in the context of general formula I nor with regard to the valuable performance properties of these products. The novel dyes may, moreover, have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, sulfonamide and carboxamide groups which may be further substituted on the amide nitrogen atom, sulfonic acid ester and carboxylic acid ester groups, allyl, aralkyl and aryl radicals, alkylamino, aralkylamino -, arylamino, acylamino, nitro, cyano, halogen, such as Cl, Br and F, hydroxy, alkoxy, thioether, azo groupings u. like. The dyes may also contain other fixable groups such as mono- or dihalo-triazinylamino, mono-, di- or trihalo-pyrimidinylamino, 2,3-dihaloquinoxaline-6-carbonyl or -6-sulfonylamino, 1,4-dihalo-phthalazine-6 carbonyl or -6-sulfonylamino, 2-halo or 2-alkylsulfonyl or 2-arylsulfonylbenzothiazole-5-carbonyl or -5-sulfonylamino, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfoxylic acid oxalkylamide and oxalkylsulfone groups, sulfofluoride - Haloalkylamino, acryloylamino, Halogenacylaminogruppen or other reactive groups.

The reactive substituent X (Formula H) reacting with the amino or amide group of the dye or dye precursor has the fluorine substituent of particular interest. Further anionic cleavable radicals which are suitable from case to case are, for example, quaternary ammonium groups, such as + +

-NiCH,), and -N (^.

For the implementation of suitable heterocyclic pyrimidine compounds of the general formulas are, for example

2.4- difluoropyrimidine,

2,4-difluoro-6-methylpyrimidine,

2, 6-difluoro-4-methyl-5-chloropyrimidine,

2,4,6-trifluoropyrimidine,

2.4- difluoropyrimidine-5-ethylsulfone,

2, 6-difluoro-4-chloropyrimidine,

2,4,5,6-tetrafluoropyrimidine,

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

2, 6-difluoro-4-methyl-5-bromopyrimidine,

2,4-difluoro-5,6-dichloro- or -dibromopyrimidine,

4,6-difluoro-2, 5-dichloro- or -dibromopyrimidine,

2, 6-difluoro-4-bromopyrimidine,

2,4,6-trifluoro-5-bromopyrimidine,

2,4,6-trifluoro-5-chloromethylpyrimidine,

2,4,6-trifluoro-5-nitropyrimidine,

2,4,6-trifluoro-5-cyanopyrimidine,

2,4,6-trifluoropyrimidine-5-carboxylic acid methyl or ethyl ester or 5-carboxylic acid amide,

2, 6-difluoro-5-methyl-4-chloropyrimidine,

Nr.274983

2, 6-difluoro-5-chloropyrimidine,

2,4,6-trifluoro-5-methylpyrimidine,

2,4,5-trifluoro-6-methylpyrimidine,

2,4-difluoro-5-nitro-6-chloropyrimidine,

2,4-difluoro-5-cyanopyrimidine,

2,4-difluoro-5-methylpyrimidine,

6-trifluoromethyl-5-chloro-2,4-difluoropyrimidine,

6-phenyl-2,4-difluoropyrimidine,

6-trifluoromethyl-2,4-difluoropyrimidine,

5-trifluoromethyl-2,4,6-trifluoropyrimidine,. , 5-trifluoromethyl-2,4-difluoropyrimidine,

2,4-difluoro-5-nitropyrimidine,

2,4-difluoro-5-trifluoromethylpyrimidine,

2,4-difluoro-5-methylsulfonylpyrimidine,

2,4-difluoro-5-phenylpyrimidine,

2,4- difluoro-5-carboxamidopyrimidine, 2,4-difluoro-5-carbomethoxypyrimidine, 2,4-difluoro-6-trifluoromethylpyrimidine,

2.4- difluoro-5-bromo-6-trifluoromethylpyrimidine,. 2,4-difluoro-6-carbonamidopyrimidin,

2,4- difluoro - 6-carbomethoxypyrimidine,

2.4- difluoro-6-phenylpyrimidine, ..

2.4- difluoro-6-cyanopyrimidine,.

2,4,6-trifluoro-5-methylsulfonylpyrimidine,

2,4-difluoro-5-chloro-6-carbomethoxypyrimidin,

2.4- difluoro-5-sulfonamidopyrimidine.

In the condensation reaction with the amino or amide group-containing dyes or dye precursors, these pyrimidine derivatives react with elimination of the radical X, probably in the 4-position. In the general formulas I and IV to ΧΠ and in the rest:

<img file="AT274983B_D0012.tif" />

Therefore, the pyrimidine ring is likely, and preferably linked via the 4-position to the rest of the N (R) -, N (R ') - group-containing dye.

The above and other fluoropyrimidine compounds which can be used according to the invention can generally be readily obtained by reacting the corresponding chlorine or bromine compounds with

Alkali fluorides, eg with potassium fluoride, NaHF₂, KSO₂F, SOF₃, AgF₂, or by reacting corresponding OH compounds with SF₄, COF₂, COC1F or cyanuric fluoride, or by heating corresponding diazonium tetrafluoroborates. Particularly preferred for the reaction according to the invention are those reactive components which have the general formula:

'^ N (Ha) ,, / ^ N⁵ where R * and R₂'independently hydrogen or Haiogenreste (CI, Br or F) be interpreted and Y in particular represents a fluorine substituent.

The reaction of the amino or amide group-containing dyes or Farbstoffvorpordukte with heterocyclic compounds of the formula Π is, depending on the nature of the starting compounds used in organic, organic-aqueous or aqueous medium at temperatures of -10 to 100 ° C,

No. 274983, preferably 0 to 50 ° C, preferably in the presence of alkaline condensing agents, such as aqueous

Alkalicarbonate or alkali metal hydroxide solutions, carried out.

When dye intermediates are used, the condensation products obtained are converted in a conventional manner to the desired final dyes. This process is of particular interest for the preparation of azo dyes by, for example, first comprising a diazo and / or coupling component which has a reactive amino or amide group with the reactive component (H) or (Ila) condensed and the resulting intermediate then converted by diazotization and / or coupling and / or condensing in an azo dye. In this subsequent subsequent conversion reactions can be carried out, as they are lent in azo dyes Ub10, for example, acylation, condensation, reduction and metallization reactions.

Also in the preparation of other dyes, in particular those of the phthalocyanine and anthraquinone series, the condensation of the reactive component (II) or (Ila) can be carried out first with an intermediate product, for. B. with m-phenylenediamine or m-phenylenediamine sulfonic acid, and then the resulting reaction product is further condensed with an anthraquinone sulfonic acid halide or with a copper or nickel phthalocyanine sulfonic acid halide to give a reactive phthalocycline dye.

The dyes obtainable by the differently described processes can, as already mentioned for some cases, be subjected to further customary reactions for dyes, for example by adding metallizable dyes with metal-donating agents, especially with chromium, cobalt, copper or nickel salts , dyes which have reducible groups, in particular nitro groups, reduced, dyes, the acylatable groups, in particular acylatable amino groups, have, acylated, or by subsequently treating dyes with sulfonating agents, such as with chlorosulfonic acid, oleum or SO_s in chlorinated hydrocarbons to introduce (further) sulfonic acid groups into the products. The latter method is sometimes of particular importance in the anthraquinone and phthalocyanine dye series. Sulfonic acid and / or carboxylic acid group-containing dyes of the formula (I) are preferred in the context of this invention.

If the dyes prepared according to the method contain metal complex-forming groups, these can be converted into their metal complex compounds by the action of metal-donating agents, for example of copper, nickel, chromium or cobalt salts. Likewise, they may be subjected to other convenient conversion reactions, such as diazotization, coupling, acylation, and

Condensation reactions.

In the reaction of amino group-containing dyes with reactive components of the formula II or Ha to obtain groups of particularly preferred dyes, if one uses the dyes of formulas IV to XII underlying amino-containing starting dyes, which therefore instead of the ^Rr 'I

<img file="AT274983B_D0013.tif" />

or the -N (R ') -A group have the grouping -N (R') - H or -N (R) -H.

In the preparation of phthalocyanine dyes, a diaminaryl compound monocondensed with the reactive component II or Ha can first be prepared and then condensed with preferably copper or nickel phthalocyanine sulfonic acid halides, whereby simultaneously or subsequently other amino compounds, such as ammonia, aliphatic amino compounds and / or aromatic amino compounds can be used , Obtained in this way phthalocyanine, preferably copper or nickel phthalocyanine sulfonamide dyes containing a certain part of sulfonarylamide, which carry the reactive group, and in addition a certain proportion of non-reactive sulfonamide and / or free sulfonic acid groups. Likewise you can

Copper or nickel phthalocyanine-sulfonic acid (aminoaryl) amides, which may additionally be added

N-substituted sulfonamide groups of other types and having free sulfonic acid groups, at the

Amino group of Aminoarylrestes with reactive components Π or Ha to the new dyes I condense.

Nr.274983

The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds, they find particular interest in dyeing hydroxyl-containing and nitrogen-containing textile materials, in particular textile materials of native and regenerated cellulose, furthermore wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive fluorine substituent (s) in the pyrimidine ring, the products are particularly useful as reactive dyes for dyeing cellulosic materials according to the techniques recently disclosed therein. The fastness properties, in particular wet fastness properties, are excellent.

The new products of the formula I have essential performance advantages over constitutionally nearest comparable known chlorine-containing or bromopyrimidinylamino-containing reactive dyes, as described, for example, in Belgian Pat. Nos. 5,729,773, 5,732,999 and 5,787,428. Thus, the new dyes containing a 2,6-difluoro-5-chloropyrimidinylamino or a 2-fluoro-5,6-dichloropyrimidinylamino radical surprisingly provide a better color yield compared to the closest comparable trichloropyrimidinylamino dyes on cotton and regenerated fibers and are superior in color strength when dyeing from long liquor. In contrast to the known chloropyrimidine reactive dyes, the novel fluoropyrimidine reactive dyes are also well suited for the so-called cold-pad residence process for cotton and regenerated fibers. In the printing process, the new dyes for rapid fixation can be used. The bond between fiber and dye is much stronger in the alkaline medium than in the known dyes.

The new fluoropyrimidine reactive dyes are also distinguished from the known chloropyrimidine dyes in that they give wool valuable dyeings with good washing, wetting and potting fastness. Also on silk and synthetic superpolyamide and polyurethane fibers wet-strength dyeings can be obtained.

In the following examples, parts, unless otherwise indicated, are parts by weight.

Example 1: To dissolve 34.7 parts of 2-aminonaphthalene-4, 8-disulfonsaurem sodium and 7 parts of sodium nitrite in 300 parts of water are added under ice cooling 28 parts by volume of conc. Hydrochloric acid and the mixture is stirred for 1/2 h at 0 to 10 C. After excess nitrous acid has been removed, are added 10, 7 parts of 3-aminotoluene, dissolved in 10 parts by volume of conc. Hydrochloric acid and 150 parts of water, and the coupling terminates by blunting the mixture to pjj 3 to 5 to an end. The resulting aminoazo dye is salted out, filtered off, washed and then redissolved in 1400 parts of water and 300 parts of acetone with the addition of sodium hydroxide solution at pjj 7. 19.2 parts of 2,4,6-trifluoro-5-chloro-pyrimidine are added dropwise to this solution at 20 to 30 ° C. and a pu of 5.5 to 6 is maintained with 2N soda solution. After completion of the reaction, the resulting dye of the probable formula:

N35. N = N- ^ NH-?

CH "

Cl like that₃Stained with 210 parts of saturated sodium chloride solution and the product crystallized in yellow needles and filtered off with suction and washed with 2% NaCl solution and dried in vacuo at 50 ° C.

If you print cellulosic tissue with a printing paste containing in kilograms 15 g of the dye, 100 g of urea, 300 ml of water, 500 g alginate thickening (60 g of sodium alginate per kg of thickening), 40 20 g of soda and was filled with water to 1 kg, Dried, steamed for 1 min at 105 ° C, rinsed with hot water and boiling soap, so you get a strong, reddish yellow pressure of good

Wash and light fastness.

Nr.274983

Example 2: 0.1 mol of the copper complex compound of the formula:

NaOgS // ~ \ \ _ / / ~ \

NaO₃SO

<img file="AT274983B_D0014.tif" />

^NH2

Cu-O

SOgNa (prepared according to the specifications of German Patent No. 1117 235) by coupling of diazotized

1-amino-8- (benzenesulfonyloxy) -naphthalenedisulfonic acid (3, 6) in soda alkaline medium with the equivalent amount of 2-acetylamino-5-hydroxynaphthalenedisulfonic acid (4,8), conversion of the monoazo compound into the copper complex by oxadative Coppering and hydrolysis of the acetyl and the

Benzenesulfonyl) are dissolved in 2500 parts by volume of water from 60 to 65 ° C at pjj 6 to 6.5 and treated at 20 to 30 C with 0.12 mol of 2,4, 6-trifluoro-5-chloropyrimidine.

During the condensation, a pjj of 6 to 6.5 is maintained by the addition of sodium carbonate solution. After completion of the reaction, the dye is salted out and isolated. The dye is dried a dark powder, which dissolves in water with blue color.

100 Parts by weight of a cotton fabric are padded at room temperature with an aqueous solution containing 2% of the dye, 15 g / 1 sodium bicarbonate and 150 g / 1 urea, inter-dried, heated to 140 ° C for 2 minutes, then rinsed and soaped by boiling , The fabric is dyed wet in very clear blue tones.

Example 3: 46 parts of the analogous to the information in Example 1 by coupling diazotized

2-Aminonaphthalene-4,8-disulfonic acid on 3-Methylyaminotoluol monoazo dye are dissolved in 400 parts of water, 100 parts of acetone at 20 to 30 ° C, 20 parts of 2,4, added 6-trifluoro-5-chloropyrimidine and thereby a pn maintained from 6 to 7 by means of 2N soda solution; Condensation continues until a sample no longer shows a hue change on acidification. The resulting dye has the probable formula:

HO_sS

NSO.H

N = N - \ =. / X

Chg

\.

/ '

Cl /

w

N ./. And is salted out, filtered off, washed and dried at 30 ° C in a vacuum.

Cotton fabric is impregnated with a solution of 20 to 25 C, which contains 20 g of the above dye per liter of liquor and 0.5 g of a nonionic wetting agent (eg a polyoxäthylierten oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate. Subsequently, the fabric is squeezed between two rubber rollers to a moisture content of approximately 100%. After intermediate drying at 50 to 60 ° C is heated for 2 min at 140 ° C and rinsed the dyeing thoroughly with hot water and 20 min boiling treated with a solution containing per liter 5 g Marseiller 30 soap and 2 g of soda. After rinsing and drying to obtain a strong reddish yellow color of good wet, rub and light fastness.

The following table lists the diazo components, coupling components and the reactive components which can be linked to the amino group, from which it is possible to synthesize, analogously to the details in Examples 1 to 3, dyes whose color shades - obtained by one of the described application methods - are also listed in the table are.

Abbreviations for the reactive components:

A = 2,4,6-trifluoro-5-chloropyrimidine

B - 2,4,6-trifluoropyrimidine.

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Reactive- component</td><td>hue</td>

<td>4</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>1-amino-2-methoxy-5-methylbenzene</td><td>A</td><td>yellow</td>

<td>5</td><td>2-Aminonaphihalin-4,8-disulfonic</td><td>1-amino-2-methoxy-5-methylbenzene</td><td>B</td><td>yellow</td>

<td>6</td><td>1-aminonaphthalene-3,6-disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>yellow</td>

<td>7</td><td>1-aminonaphthalene-3,6-disulfonic acid</td><td>1-amino-3-methylbenzene</td><td>B</td><td>yellow</td>

<td>8th</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>1-amino-3-methylbenzene</td><td>A</td><td>yellow</td>

<td>9</td><td>2-aminonaphthalene-5,7-disulfonic</td><td>1 - amino - 3-methylbenzene</td><td>B</td><td>yellow</td>

<td>10</td><td>2-aminonaphthalene-6,8-disulfonic</td><td>1-amino-3-methylbenzene</td><td>A</td><td>yellow</td>

<td>11</td><td>2-aminonaphthalene-6,8-disulfonic</td><td>1-amino-3-methylbenzene</td><td>B</td><td>yellow</td>

<td>12</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>brown yellow</td>

<td>13</td><td>1-aminobenzene-4-sulfonic acid -&gt; 1-aminonaphthalene-6-sulfonic acid</td><td>1-amino-3-methylbenzene</td><td>B</td><td>brown yellow</td>

<td>14</td><td>2- (3'-sulfo-4'-aminophenyl) -6-methylbenzothiazole-7-sulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>yellow</td>

<td>15</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-methylamino -3-methoxybenzene</td><td>B</td><td>yellow</td>

<td>16</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>1-amino-3-acetylaminobenzene</td><td>A</td><td>yellow</td>

<td>17</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>aniline</td><td>A</td><td>yellow</td>

EXAMPLE 18 20 parts of 2,4,6-trifluoro-5 are added to the solution of 36.5 parts of the sodium salt of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 200 parts of water at 8 to 10 ° C. Dropped chloropyrimidine and maintaining a constant dulling of the liberated hydrogen fluoride pnvon 5 5.5 to 6 maintained. The reaction is monitored by chromatography. The resulting solution of dye intermediate is added to 900 parts of water and coupled at a pg of 7 to 8 at 0 to 5 ° C with 17.5 parts of diazotized 2-aminobenzenesulfonic acid, dissolved in 200 parts of water. At a final p ^ of 6.5 is salted with 80 parts of sodium chloride, filtered off with suction and washed with 10% sodium chloride solution. It is dried in vacuo at 30 to 40 ° C, the dye

No. 274983 ^ _N = NN-, 1

OH NH-.

II r \

CI

HO₃S '' SO_sH makes red little things.

If cotton or regenerated cellulose fabric is dyed or printed with this dyestuff according to one of the procedures described in Examples 1 to 3, clear blue dyeings and prints of good wetfastness, rubfastness and lightfastness are obtained.

Equally good results are obtained in the following way:

Cotton cord are dyed in 1 1 dye liquor containing 1.5 g of the dye above, by adding 50 g of common salt in several portions within 30 min at 20 to 30 ° C, then 20 g of soda added and treated for 60 min at this temperature , After rinsing, boiling soaps and drying gives a bluish red color of good wet, rub and light fastness.

The following table lists the color shades of further dyes which are synthesized from the likewise cited diazo components, coupling components and reactive components which can be linked to the amino group in the latter analogously to the details in Example 18 or else by reaction of the corresponding aminoazo dyes with the reactive components can be dyed or printed on cellulosic materials by one of the methods described above:

Abbreviations for the reactive components as in table to Example 3:

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Reactive- component</td><td>hue</td>

<td>19</td><td>1-aminobenzene -2-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>B</td><td>red</td>

<td>20</td><td>aminobenzene</td><td>1- (3'-Aminobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>red</td>

<td>21</td><td>aminobenzene</td><td>1- (3'-aminobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid</td><td>B</td><td>red</td>

<td>22</td><td>l-amino-2-carboxy- benzene-4-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>red</td>

<td>23</td><td>l-amino-4-methyl- benzene-2-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>red</td>

<td>24</td><td>1-amino-3-acetylaminobenzene-6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>B</td><td>red</td>

<td>25</td><td>l-Amino-3- [2^.- (4 "-sulfophenylamino) -4 * -chlorotriazine-1 ', 3', 5 '¹ -yl-6 '] -aminobenzene -6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>red</td>

<td>26</td><td>1-aminobenzene -2-sulfonic acid</td><td>2-amino-5-hydroxynaphtha- lin-7-sulfonic acid</td><td>A</td><td>orange</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Reactive- component</td><td>hue</td>

<td>26a</td><td>l-Amino-3- [2 '- (4^,,-sulfophenylamino) -4'-methylaminotriazine-1¹3¹, 5¹ yl-6¹] -aminobenzene-6-sulfonic acid</td><td>2-amino-5-hydroxynaphtha lin-7-sulfonic acid</td><td>A</td><td>orange</td>

<td>27</td><td>1-aminobenzene -2-sulfonic acid</td><td>2-methylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>A</td><td>orange</td>

<td>28</td><td>1-amino-4-acetylamino-6-sulfonic acid</td><td>2-methylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>A</td><td>scarlet</td>

<td>29</td><td>1-amino-4-acetylamino-6-sulfonic acid</td><td>2-amino-5-hydroxynaphtha lin-7-sulfonic acid</td><td>A</td><td>scarlet</td>

Example 30: In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 700 parts of water are added dropwise with good stirring, 20.0 parts of 2,4, 6-trifluoro-5-chloropyrimidine and at 20 to 30 ° C. with continuous dulling of the hydrofluoric acid released on pn 6 to 7 5 until a sample on diazotization and coupling onto 1-hydroxynaphthalene-4-sulfonic acid gives a clear, yellowish-red coloration. The resulting dye intermediate product is added directly after addition of ice with 7 parts of sodium nitrite and 28 parts. Diazotized hydrochloric acid and then combined with a solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3, 6-disulfonic acid and 12 parts of soda in 200 parts of water, with coupling to the

Dye of the formula:

N ff \

N HN \ = /

Cl

SO, Na HO _ / ³ I \ N = N- ⁷ / ^ NaO₃S

NH-OC-C ^

SO₃Na takes place, which is salted out, filtered off, washed and dried at 30 to 40 ° C in a vacuum. The dye readily dissolves in water with red color and provides clear bluish red dyeings and prints on cellulosic materials by one of the methods described above.

The following table lists the color shades and the p.sub.i value of the coupling medium of dyes which, analogously to the information in Example 30, consist of a diazo component which contains a further, preferably acylatable, amino group, from a coupling component and from a reactive component which can be linked to the diazo component getting produced. For dyeing and printing cellulosic materials with the dyes of the table, the above-mentioned methods can be used.

Abbreviations for the reactive components as in the table for Example 3.

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Reactive- composted component</td><td>Pjj of the coupling medium</td><td>hue</td>

<td>31</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>A</td><td>4-5</td><td>orange</td>

<td>32</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>A</td><td>4 - 5</td><td>orange</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Reactive- composted component</td><td>Pjj of the coupling medium</td><td>hue</td>

<td>33</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>2-aminonaphthalene -6-sulfonic acid</td><td>B</td><td>4 - 5</td><td>orange</td>

<td>34</td><td>1,3-diaminobenzene-4-sulfonic acid</td><td>2-N-methylamino-8-hydroxynaphthalene-6-sulfonic acid</td><td>A</td><td>4 - 5</td><td>orange</td>

<td>35</td><td>1,3-diaminobenzene-4-sulfonic acid</td><td>1- (3 ', 5'-dichloro-1', 2'-thiazole-4¹carbonamido) - 8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>7 - 8</td><td>red</td>

<td>36</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>1- (2¹'4'-Dihydroxytriazine-Γ, 3', 5'-yl-6'-amino) -8-hydroxy-naphthalene-3, 6-disulfonic acid</td><td>B</td><td>7 - 8</td><td>red</td>

<td>37</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>1- (3 ', 5'-dichloro-1', 2'-thiazole-4'-carbonamido) -8-hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>7 - 8</td><td>red</td>

<td>38</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>2-Hydroxynaphthalene-3,6-disulfonic acid</td><td>A</td><td>8th</td><td>scarlet</td>

<td>39</td><td>1, 3-diaminobenzene-4-suifonic acid</td><td>1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>B</td><td>7 - 8</td><td>red</td>

<td>40</td><td>1,3-diaminobenzene-4-sulfonic acid</td><td>1- (3'-sulfophenyl) -3-methylpyrazolone-5</td><td>A</td><td>6</td><td>yellow</td>

<td>41</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methylpyrazolone-5</td><td>A</td><td>6</td><td>yellow</td>

<td>42</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>l- (5¹, 7-disulfo naphthyl-2 ') - 3-methylpyrazolone-5</td><td>A</td><td>6</td><td>yellow</td>

<td>43</td><td>1, 3-diaminobenzene-4-sulfonic acid</td><td>1- (3'-sulfophenyl) - -3-methyl-5-amino- pyrazole</td><td>B</td><td>6</td><td>yellow</td>

<td>44</td><td>1,4-diaminobenzene-3-sulphonic acid</td><td>2-Amino-8-hydroxy-naphthalene-6-sulfonic acid</td><td>A</td><td>4-4,5</td><td>red</td>

<td>45</td><td>1,4-diaminobenzene-3-sulphonic acid</td><td>2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>A</td><td>6 - 7</td><td>scarlet 1</td>

<td>46</td><td>1,4-diaminobenzene-3-sulphonic acid</td><td>1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>B</td><td>6 - 7</td><td>red</td>

Nr.274983

Example 47: 51.6 parts of by diazotizing 1-hydroxy-2-aminobenzene-4-sulfonic acid and coupling to 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper releasing agent obtained dye of the formula:

Cu-O

<img file="AT274983B_D0015.tif" />

| NaOgS SO, Na u

<img file="AT274983B_D0016.tif" />

NI ^ are dissolved in 1500 parts of water at p ^ 7. With good stirring is added dropwise at 20 to 30 ° C 20.0 parts of 2,4, 6-trifluoro-5-chloropyrimidine and dulled the fieswerdende hydrofluoric acid with sodium carbonate solution continuously to a pjj from 6 to 7 from. When no more free amino group is detectable, the formed reactive dye of formula ''

O-Cu - O

N = N-

N / A

NaO₃S '

Salted out, pressed off, washed and dried in vacuo at 30 to 40 ° C. Fabrics made of cellulosic materials can be dyed or printed with this dyestuff according to one of the abovementioned processes in wet, rubfast and lightfast ruby ​​tones.

The following table lists the heavy metal complexes of other aminoazo dyes and the reactive components associated with the amino group, as well as the hues of these dyes on cellulose materials. The preparation of the aminoazo dyes, their metal complexes and their conversion with the reactive components can be carried out analogously to the details in Example 47.

Abbreviations for the reactive components as in the table for Example 3.

<td>example No,</td><td>aminoazo</td><td>^: Complex bound ... heavy metal</td><td>Reactive- component</td><td>hue</td>

<td>48</td><td>1-hydroxy-2-aminobenzene-4,6-disulphonic acid -&gt; 2-amino-5-hydroxynapbthalene-7-sulfonic acid</td><td>Cu</td><td>A</td><td>ruby</td>

<td>49</td><td>1-hydroxy-2-aminobenzene -4-sulfonic acid -&gt; 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>Cu</td><td>A</td><td>ruby</td>

<td>50</td><td>1-amino-2-hydroxy-6-nitro naphthalene-4-sulfonic acid -&gt; 2-amino-5-hydroxynaphthalene-7-sulfonic acid</td><td>Cu</td><td>A</td><td>ruby</td>

<td>51</td><td>1 - amino - 2-hydroxy-6-nitronaphthalene-4-sulfonic acid -&gt; 2-amino-5-hydroxynaphthalene-7-sulfonic acid</td><td>Cr</td><td>A</td><td>greenish Gray</td>

-17 - No.274983

<td>example No.</td><td>aminoazo</td><td>complex bound heavy metal</td><td>Reactive- component</td><td>hue</td>

<td>52</td><td>1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-4-sulfonic acid</td><td>Co</td><td>B</td><td>reddish black</td>

<td>53</td><td>1-amino-2-hydroxy-5-methylsulfonylbenzene -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>Cu</td><td>A</td><td>violet</td>

<td>54</td><td>1-amino-2-hydroxy-5-methyl isulfonylbenzene -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>Co</td><td>A</td><td>Gray</td>

<td>55</td><td>1-amino-2-hydroxy-5-methylsulfonylbenzene -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>Cr</td><td>A</td><td>greenish black</td>

<td>56</td><td>1-Amino-2-methylbenzene-4-sulfonic acid - 1-amino-2-hydroxy-5-methylbenzene -&gt; 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>Cu</td><td>B</td><td>blue</td>

<td>57</td><td>1 - amino - 2-methylbenzene-4-sulfonic acid -&gt; l-amino-2-hydroxy- -5-methylbenzene -&gt; 1 - amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>Co</td><td>B</td><td>Gray</td>

<td>58</td><td>1 - amino - 2-methylbenzene-4-sulfonic acid -&gt; 1-amino-2-hydroxy-5-methylbenzene -&gt; 1-amino-8-hydroxy droxynaphthalene-4,6-disulfonic acid</td><td>Cr</td><td>A</td><td>greenish black</td>

<td>59</td><td>(1-amino-2-chlorobenzene-4-sulfonic acid -&gt; 1-hydroxy-2-acetylaminobenzene), saponified, -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>Cu</td><td>A</td><td>navy</td>

<td>60</td><td>(1-Amino-2-chlorobenzene-4-sulfonic acid -&gt; 1-hydroxy-2-acetylaminobenzene), saponified, -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid</td><td>Co</td><td>A</td><td>Gray</td>

Nr.274983

<td>example No.</td><td>aminoazo</td><td>complex bound heavy metal</td><td>Reactive- component</td><td>hue</td>

<td>61</td><td>l-Amino-8-hydroxynaphthalene-4-sulfonic acid &lt;- l-hydroxy-2,6-diaminobenzene-4-sulfonic acid -&gt; 1, 3-dihydroxybenzene</td><td>Co</td><td>A</td><td>black</td>

<td>62</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid &lt;- 1-hydroxy-2,6-diaminobenzene -4-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>Co</td><td>A</td><td>black</td>

<td>63</td><td>1 - Amino - 8-hydroxynaphthalene -4-sulfonic acid &lt;- l-hydroxy-2, 6-diaminobenzene-4-sulfonic acid -&gt; 3-methylpyrazolone (5)</td><td>Co</td><td>A</td><td>black</td>

Example 64: 96 Parts (based on 100% goods) of the prepared in the usual way by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine Kupferphthalocyanin tetrasulfochlorids or the isomeric, from l-sulfobenzene-3,4-dicarboxylic acid over the corresponding 5 Kupferphthalocyanintetrasulfonsäure constructed Kupferphthalocyanintetrasulfochlorids be in the form of moist, well-washed absorbent cake suspended in 500 parts of water and 500 parts of ice, the solution of 50 parts of 1,3-diaminobenzene in 500 parts of water was added and the pjj value was adjusted to 8.5 with soda. The suspension is stirred at room temperature for 24 h, keeping the pg value always at 8.5 by adding soda continuously. The resulting condensation product is precipitated at ρπ 1 to 2 10 by addition of sodium chloride, filtered off, washed and then redissolved in 1000 parts of water neutral. In the blue solution, 57 parts of 2,4, 6-trifluoro-5-chloropyrimidin are added with vigorous stirring and stirred under constant blunting with sodium carbonate solution to 6 at 20 to 30 ° C until no more free amino groups are detectable. The reactive dye of the

Formula:

Cu phthalocyanine (SO₃N / A)_n

- (SO-HN- / \ ² \ - /

<img file="AT274983B_D0017.tif" />

4-n is salted out, washed and dried at 30 to 40 ° C in a vacuum. It is a dark blue, blue-soluble in water color powder and dyes cotton and regenerated cellulose according to one of the above-mentioned dyeing or printing process in clear shades of blue of good wet, rub and light fastness.

Instead of the 96 parts Kupferphthalocyanintetrasulfochlorid - with otherwise the same procedure as in Example 64 - and 87 parts (based on 100% goods) of the obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine copper or Nickelphthalocyanintrisulfochlorids in the form of moist, good with Ice water washed absorbent cake are used; You then also receives clear blue dyeing reactive dyes.

Even if one operates as indicated in Example 64, but starting from 87 parts of copper phthalocyanine trisulfonyl chloride and instead of the 50 parts of the sodium salt of 1, 3-diaminobenzene-4-sulfone 19

No.274983 acid 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2, 2'-disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulfonic acid used, to obtain reactive dyes, which

Dyeing cellulosic materials according to one of the above methods in wet, rubfast and lightfast, clear blue tones.

If one starts from the 4 ', 4, 4 ™, 4 "-Trapraphenyl-Cu-phthalocyanine, so obtained after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with 2,4, 6-trifluoro-5-chloropyrimidine a reactive dye which dyes cellulosic materials in the presence of acid-binding agents in clear, wet and lightfast shades of green.

Example 65: 63 parts of 1-amino-4- (4'-aminophenyl) -aminoanthraquinone-2,5,8-trisulfonic acid are dissolved in 630 parts of water, adjusted to py 6 with sodium hydroxide solution, then added dropwise at 0 to 5 ° C 18 parts 2,4, 6-trifluoro-5-chloropyriraidin and holds with soda solution a pg of 6 to 6, 5 a. After the reaction is followed by salting with 7 parts of potassium chloride, filtered off with suction and washed with 3% potassium chloride solution. The obtained in blue-green Nädelchen dye is dried in vacuo at 30 to 40 ° C. He probably has the following formula:

ho₃s

O NH.

SO₃H ho₃s

Cl \ = / \ and dyes cotton in greenish blue tones.

Example 66: If the procedure is as in Example 47, but instead of the copper-containing Aminomonoazofarbstoff used there of the equivalent amount of the chromium complex by coupling diazotized l-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid with l- [ 3^.- (3-Ami20 nophenyl)] -sulfonylimido-sulfonylphenyl-3-methylpyrazolone- (5) from the aminoazo dye obtained, we obtain a reactive dye which dyes cellulose materials by one of the above-mentioned methods in good wet, rubfast and lightfast yellow-brown shades ,

Be ispie 1 67: 0.1 mol of the copper complex compound of the formula:

h °₃s_x

Z \ ₌/ V - OH

SO_sNa ho₃s \

J

I oN = N- =

Cu · • O ^ _N = NSO Na / V \ _ / ^CH3

-NH are dissolved in 3000 parts by volume of water at pjj 6 and with stirring at a temperature of 20 to 30 ° C with 16, 8 parts by weight (0.1 mol) of 2,4, 6-trifluoro-5- Chlorpyrimidine combined and with a 2n-potassium carbonate solution adhered to a pjj of 6. The mixture is stirred until the condensation is complete, the dye is deposited by addition of a little sodium chloride and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which dissolves in water with green color and dyes cotton according to the procedures given in Examples 1 to 3 in green shades.

Cotton fabric is impregnated with a solution of 20 to 25 ° C containing per liter of liquor 25 g of the above dye and 0.5 g of a nonionic wetting agent (eg a polyoxäthylierten oleyl alcohol), 150 g of urea and 20 g of sodium carbonate. Subsequently, the fabric is squeezed between two rubber rollers to a moisture content of approximately 100%. After intermediate drying at 50 to 60 ° C is heated for 2 min at 140 ° C and rinsed the dyeing thoroughly with hot water and 20 min boiling treated with a solution containing per liter 5 g of Marseille soap and 2 g

No. 274983

Contains soda. After rinsing and drying, a green color of good wet, frictional and

Lightfastness.

Also according to one of the other, described in Examples 1 to 3, 18 and 30 dyeing or

Printing process obtained on materials made of cellulose clear greens of good fastness properties.

Example 68: 0.1 mol of the paste of the aminoazo compound of the formula:

S °₃^H

Hqs' / ^ \ o-Cu-q / ^ so₃h obtained by coupling the diazonium compound of 6-acetamido-2-aminonaphthalene-4, 8-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound in the copper complex are in 2000 parts by volume Dissolved water at pjj 6.5 and combined with 20 wt. 10 parts of 2,4,6-trifluoro-5-chloropyrimidine. The reaction mixture is stirred at 20 to 30 ° C until the condensation is completed, wherein the pfj value of the reaction solution by addition of sodium carbonate solution is kept at 6 to 7. After completion of the reaction, the dye is salted out, isolated and dried in vacuo.

The dried dye is a dark powder that dissolves in water of violet color and cotton in the presence of alkali in bluish purple tones.

Example 69: The aqueous solution of 0.1 mol of the copper complex of the formula:

HO₃S O-Cu-O

<img file="AT274983B_D0018.tif" />

prepared according to the specifications of 1061460 or no. 1085 988, 2,4,6-trifluoro-5-chloropyrimidines is in the usual manner with 22 parts by weight. The pjj value is kept at 6 to 7 by addition of soda and the dye is isolated by salting out after the reaction has ended. When dried, it is a dark powder that dissolves in water of violet color. Cotton fabric is dyed in light and wetfast violet tones.

Example 70: 27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid are dissolved in 150 parts of water, mixed with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine and at 30 ° C and the blunt continuous blunting of the resul ting hydrogen fluoride with a total of 34 vol. parts of 16% sodium carbonate solution stirred on pu 6 to 7. After a short time, the acylation is complete, the pH is 6 and does not change.

Are then added to 30 parts of sodium bicarbonate and allowed at 20 ° C within 15 min, the diazo suspension of 34 parts of the disodium salt of 2-aminonaphthalene-l, 7-disulfonic acid in 200 parts

Add water. The immediately resulting orange reactive dye of the formula:

NaO "S

SO₃N / A

OH

7-N = N-,

NNaO₃S. \ = /^CHs / \ Cl F

No. 274983 is completely separated after one hour of stirring by addition of 80 parts of sodium chloride, filtered, washed with dilute sodium chloride solution and dried at 35 ° C in a vacuum. It dyes cellulosic materials according to the abovementioned processes in reddish orange shades of very good wet fastness and good chlorine resistance.

In an analogous manner obtained by acylation of the listed in column 3 of the table below Aminonaphtholsulfonsäuren with 2,4, 6-trifluoro-5-chloropyrimidine and coupling the Acylaminonaphtholsulfonsäuren formed with the diazo components mentioned in column 2 orange to red reactive dyes.

<td>example No.</td><td>diazo</td><td>aminonaphtholsulfonic</td><td>Coloring on cotton</td>

<td>71</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>72</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>2- (β-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>73</td><td>2-aminonaphthalene-1,7-disulfonic</td><td>2-amino-5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>74</td><td>2-aminonaphthalene-1,7-disulfonic</td><td>2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid</td><td>orange</td>

<td>75</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>2-amino-8-hydroxynaphthalene-6-sulfonic acid</td><td>scarlet</td>

<td>76</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>scarlet</td>

<td>77</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>2-methylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>78</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>79</td><td>2-aminonaphthalene-1, 5-disulfonic acid</td><td>2- (β-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>80</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>2-Amino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>orange</td>

<td>81</td><td>2-aminonaphthalene-1, 5-disulfonic acid</td><td>2-amino-5-hydroxy-naphthalene-1, 7-disulfonic acid</td><td>orange</td>

<td>82</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>2-amino-8-hydroxynaphthalene-6-sulfonic acid</td><td>scarlet</td>

<td>83</td><td>2-aminonaphthalene-1,5-disulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>scarlet</td>

<td>84</td><td>2-aminonaphthalene-1,5,7-trisulphonic acid</td><td>2-amino-5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>85</td><td>2-aminonaphthalene-1, 5, 7-trisulfonic acid</td><td>2-methylamino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>orange</td>

<td>86</td><td>2-aminonaphthalene-1, 5, 7-trisulfonic acid</td><td>2-amino-8-hydroxynaphthalene-6-sulfonic acid</td><td>scarlet</td>

<td>87</td><td>2-aminobenzene sulfonic acid</td><td>2-Methylamino-5-hydroxynaphthalene - 7-sulfonic acid</td><td>orange</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>aminonaphtholsulfonic</td><td>Coloring on cotton</td>

<td>88</td><td>2-aminobenzene sulfonic acid</td><td>2- (O-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>orange</td>

<td>89</td><td>2-aminobenzene sulfonic acid</td><td>2-amino-8-hydroxy naphthalene-6-sulfonic acid</td><td>scarlet</td>

<td>90</td><td>2-aminobenzene sulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>scarlet</td>

<td>91</td><td>2-aminobenzene sulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid</td><td>orange</td>

<td>92</td><td>2-aminonaphthalene -1-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>93</td><td>2-aminonaphthalene -1-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>bluish red</td>

<td>94</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>95</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>bluish red</td>

<td>96</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-8-hydroxynaphthalene-6-sulphonic acid</td><td>bluish red</td>

<td>97</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>98</td><td>2-aminonaphthalene-1, 7-disulfonic acid</td><td>1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>bluish red</td>

<td>99</td><td>2-aminonaphthalene-1,7-disulfonic</td><td>1-amino-8-hydroxynaphthalene-6-sulfonic acid</td><td>bluish red</td>

<td>100</td><td>2-aminonaphthalene-1, 5, 7-trisulfonic acid</td><td>1-amino-8-hydroxynaphthalene-6-sulfonic acid</td><td>bluish red</td>

<td>101</td><td>l-amino-4-chlorobenzene -2-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>102</td><td>1-amino-2-methoxybenzene-5-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>103</td><td>l-aminobenzene-2-carboxylic acid 4-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish red</td>

<td>104</td><td>1-amino-4-acetylaminobenzene-2-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>violet</td>

<td>105</td><td>l-amino-4-acetylamino- benzene-2-sulfonic acid</td><td>1-amino-8-hydroxy-naphthalene-4,6-disulfonic acid</td><td>bluish red</td>

EXAMPLE 10 6: 56.8 parts of the diaminoazo dye obtained by coupling diazotized 1-amino-3-acetylaminobenzene-6-sulfonic acid to 2-aminonaphthalene-5,7-disulfonic acid in acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are added at pjj 7 5 dissolved in 450 parts of water. After addition of 20 parts of 2,4,6-trifluoro-5-chloropyrimidine is stirred under constant blunting of the liberated hydrofluoric acid with sodium carbonate solution to pn 6 to 7 for about 1 h at 30 ° C. After completion of the acylation, the reactive dye formed is believed to be of the formula:

No.274983 / V \.

v / /

\ _

HN

yl

Y ./

SO Na NH, / 3 2 \

-N = N //

Y /

Y

Ύ ^ -SO_aN / A

NaOjS 'salted out, filtered off, redissolved in 4000 parts of water at 30 ° C, filtered and separated from the filtrate by addition of 400 parts of sodium chloride in completely pure form. The dye is dried as usual at 35 ° C in a vacuum. It dyes cellulosic materials according to one of the above

Process in true yellowish orange tones.

Example 107: To the neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8-trisulphonic acid with 3-acetylaminoaniline in acetic acid medium in 500 parts of water is added 20 parts 2,4, 6 Trifluoro-5-chloropyrimidine and stirred for 1 h at 30 ° C, whereby a p ^ value of 6 is maintained by constant addition of sodium hydroxide solution. The partially precipitated acylation product is completely separated off at pjj 7 by addition of 100 parts of sodium chloride and filtered off. For purification, the reactive dye thus obtained can again be dissolved in 2500 parts of water at 30 ° C., clarified and redeposited by salting out the filtrate with 350 parts of sodium chloride. The dye has the formula:

SO₃N / A

<img file="AT274983B_D0019.tif" />

Y_NH- ^ \ z / \

NH-COCE ^ Cl F and, after filtering off, drying at 35 ° C and grinding, is a yellow powder which readily dissolves in water with yellow color and cellulose fibers according to one of the above-mentioned dyeing methods in the presence of acid-binding agents in very true reddish yellow Tints colors. Also on wool and polyamide fibers, true yellow dyeings are obtained.

Similar dyes can be obtained by following the procedure above but replacing the 60 parts

4^.amino-2^.Acetylamino-phenyl (l ') - azo-naphthalene (2) -3, 6, 8-trisulfonsaurem corresponding amounts of the amino compounds given in column 2 and the coupling components indicated in column 3 in the usual manner by diazotization and coupling used in acetic acid medium Aminoazofarbstoffe and acylated with 2,4,6-trifluoro-5-chloropyrimidine.

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Hue up cotton</td>

<td>108</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-3-methyl-6-methoxy-phenol</td><td>strong reddish yellow</td>

<td>109</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>l-amino-3-methylbenzene</td><td>yellow</td>

<td>110</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-aminonaphthalene-6-sulfonic acid</td><td>reddish yellow</td>

<td>111</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-3-acetylaminobenzene</td><td>reddish yellow</td>

<td>112</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>3 -aminophenylurea</td><td>reddish Gete</td>

<td>113</td><td>2-aminonaphthalene-1,5-disulfonic</td><td>1-amino-3-hydroxyacetylaminobenzene</td><td>reddish yellow</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Coloring on cotton</td>

<td>114</td><td>2-aminonaphthalene-5,7-disulfonic</td><td>1-amino-3-methyl-6-methoxybenzene</td><td>strong reddish yellow</td>

<td>115</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>1-aminonaphthalene -7-sulfonic acid</td><td>reddish yellow</td>

<td>116</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>l-amino-3-acetylaminobenzene</td><td>reddish yellow</td>

<td>117</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>3-Aminophenylhamstoff</td><td>reddish yellow</td>

<td>118</td><td>2-aminonaphthalene-5,7-disulfonic acid</td><td>l-amino-3-hydroxyacetyl- aminobenzene</td><td>reddish yellow</td>

<td>119</td><td>1-aminonaphthalene-3,7-disulfonic acid</td><td>1-amino-3-methyl-6-methoxybenzene</td><td>strong reddish yellow</td>

<td>120</td><td>1-aminonaphthalene-3,7-disulfonic acid</td><td>1-amino-3-methylbenzene</td><td>reddish yellow</td>

<td>121</td><td>1-aminonaphthalene-3,7-disulfonic acid</td><td>1-aminonaphthalene -6-sulfonic acid</td><td>reddish yellow</td>

<td>122</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>reddish yellow</td>

<td>123</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1-amino-3-methyl-6-methoxybenzene</td><td>strong reddish yellow</td>

<td>124</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1-amino-3-acetylaminobenzene</td><td>reddish yellow</td>

<td>125</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>3-aminophenylurea</td><td>reddish yellow</td>

<td>126</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1-amino-3-hydroxyacetylaminobenzene</td><td>reddish yellow</td>

<td>127</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1-aminonaphthalene -6-sulfonic acid</td><td>reddish yellow</td>

<td>128.</td><td>2-aminonaphthalene-6,8-disulfonic acid</td><td>l-amino-3-acetylaminobenzene</td><td>reddish yellow</td>

<td>129</td><td>2-aminonaphthalene-6,8-disulfonic acid</td><td>l-amino-2-methoxynaphthalin- -6-sulfonic acid</td><td>strong reddish yellow</td>

<td>130</td><td>2-aminonaphthalene-6,8-disulfonic acid</td><td>1-aminonaphthalene -6-sulfonic acid</td><td>reddish yellow</td>

<td>131</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-aminonaphthalene -6-sulfonic acid</td><td>yellow</td>

<td>132</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-aminonaphthalene -7-sulfonic acid</td><td>yellow</td>

<td>133</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-amino-2-methoxynaphthalene-6-sulfonic acid</td><td>strong reddish yellow</td>

<td>134</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>l-methylamino-3-methylbenzene</td><td>yellow</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Coloring on cotton</td>

<td>135</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>l-ethylamino-3-methylbenzene</td><td>yellow</td>

<td>136</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>N-methylaniline</td><td>yellow</td>

<td>137</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>N-ethylaniline</td><td>yellow</td>

<td>138</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>N- (.beta.-hydroxyethyl) aniline</td><td>yellow</td>

<td>139</td><td>2-aminonaphthalene-4,8-disulfonic acid</td><td>N-butylaniline</td><td>yellow</td>

<td>140</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>aniline</td><td>reddish yellow</td>

<td>141</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1 - amino - 3-methylbenzene</td><td>reddish yellow</td>

<td>142</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>3-aminophenylurea</td><td>reddish yellow</td>

<td>143</td><td>2-aminonaphthalene-3,6,8-trisulphonic acid</td><td>1-amino-3-hydroxyacetylaminobenzene</td><td>reddish yellow</td>

<td>144</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1-amino-3-acetylamino-6-methoxybenzene</td><td>yellowish orange</td>

<td>145</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>l-amino-3-acetylamino- -6-methylbenzene</td><td>reddish yellow</td>

<td>146</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1 - amino - 3-methanesulfonylaminobenzene</td><td>reddish yellow</td>

<td>147</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>2,5-dimethoxyaniline</td><td>yellowish orange</td>

<td>148</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>3-methyl-6-methoxyaniline</td><td>yellowish orange</td>

<td>149</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>N-methylaniline</td><td>reddish yellow</td>

<td>150</td><td>2-aminonaphthalene-3,6,8-trisulphonic acid</td><td>N-ethylaniline</td><td>reddish yellow</td>

<td>151</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>N-butylaniline</td><td>reddish yellow</td>

<td>152</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>N- (.beta.-hydroxyethyl) aniline</td><td>reddish yellow</td>

<td>153</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>3 - (N-ethylamino) -toluene</td><td>reddish yellow</td>

<td>154</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>2-aminotoluene</td><td>reddish yellow</td>

<td>155</td><td>2-Am inonaphthalene-3, 6, 8-trisulfonic acid</td><td>l-amino-2,5-dimethylbenzene</td><td>strong reddish yellow 1</td>

No. 274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Coloring on cotton</td>

<td>156</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1-amino-2-methylbenzene</td><td>strong reddish yellow</td>

<td>157</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>l-amino-3-methoxybenzene</td><td>reddish yellow</td>

<td>158</td><td>2-aminonaphthalene -3, 6, 8-trisulfonic acid</td><td>1-ethylamino-3-methoxybenzene</td><td>reddish yellow</td>

<td>159</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1-aminonaphthalene-6-sulfonic acid</td><td>reddish yellow</td>

<td>160</td><td>2-aminonaphthalene-3, 6, 8-trisulfonic acid</td><td>1-aminonaphthalene -7-sulfonic acid</td><td>reddish yellow</td>

<td>161</td><td>2-aminonaphthalene-4,6,8-trisulphonic acid</td><td>1 - amino - 3-methylbenzene</td><td>reddish yellow</td>

<td>162</td><td>2-aminonaphthalene-4,6,8-trisulphonic acid</td><td>1 - amino - 3-acetylaminobenzene</td><td>reddish yellow</td>

<td>163</td><td>1-aminonaphthalene-2,4,4-trisulphonic acid</td><td>1-amino-3-methylbenzene</td><td>yellow</td>

<td>164</td><td>1-aminonaphthalene-2,4, 7-trisulfonic acid</td><td>1-aminonaphthalene-6-sulfonic acid</td><td>yellow</td>

<td>165</td><td>4-nitro-4'-aminostilbene-2, 2'-disulfonic acid</td><td>1-amino-3-acetylaminobenzene</td><td>reddish yellow</td>

<td>166</td><td>4-nitro-4¹ -aminostilbene-2, 2'-disulfonic acid</td><td>3 - Amino-phenylurea</td><td>reddish yellow</td>

<td>167</td><td>4-nitro-4'-aminostilbene-2, 2'-disulfonic acid</td><td>1 - amino - 3-hydroxyacetylaminobenzene</td><td>reddish yellow</td>

<td>168</td><td>4-nitro-4¹ -aminostilbene-2, 2'-disulfonic acid</td><td>N-methylaniline</td><td>reddish yellow</td>

<td>169</td><td>4-nitro-4'-aminostilbene-2,2'-disulfonic acid</td><td>N-ethylaniline</td><td>reddish yellow</td>

<td>170</td><td>4-N itro -4¹ - Amino-stilbene-2, 2 '-disulfonic acid</td><td>N - Butylanilaniline</td><td>reddish yellow</td>

<td>171</td><td>4-nitro-4'-aminostilbene-2,2'-disulfonic acid</td><td>N- (O -hydroxyethyl) -aniline</td><td>reddish yellow</td>

<td>172</td><td>4-nitro-4 '-am-inostilbene-2, 2'-disulfonic acid</td><td>l- (N-ethylamino) - -3-methyl benzene</td><td>reddish yellow</td>

<td>173</td><td>Aniline-2,5-disulfonic acid</td><td>1-aminonaphthalene -6-sulfonic acid</td><td>reddish yellow</td>

<td>174</td><td>Aniline-2,5-disulfonic acid</td><td>1-aminonaphthalene -7-sulfonic acid</td><td>reddish yellow</td>

<td>175</td><td>Aniline-2, 5-disulfonic acid</td><td>1-amino-3-methylbenzene</td><td>yellow</td>

<td>176</td><td>Aniline-2, 5-disulfonic acid</td><td>1-amino-3-acetylaminobenzene</td><td>yellow</td>

<td>177</td><td>Aniline-2, 5-disulfonic acid</td><td>l-amino-2-methoxy- -5-methylbenzene</td><td>reddish yellow</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Hue up cotton</td>

<td>178</td><td>Aniline-2,5-disulfonic acid</td><td>l-amino-2,5-dimethoxybenzene</td><td>reddish yellow</td>

<td>179</td><td>Aniline-2,4-disulfonic acid</td><td>1-amino-2-methoxy-5-methylbenzene</td><td>reddish yellow</td>

Example 18 0s 65 parts of the dye of the formula:

NaO₃S

Cu-O

<img file="AT274983B_D0020.tif" />

NaO₃S

SO₃Na (prepared by coupling diazotized 1-hydroxy-2-aminobenzene-4,6-disulfonic acid to 2-amino-5-8-hydroxynaphthalene-6-sulfonic acid and coppering the resulting azo dye) are dissolved in 700 parts

Water neutral dissolved. Are added 20 parts of 2,4,6-trifluoro-5-chloropyrimidine and stirred at 20 to 30 ° C with constant blunting of the liberated acid with sodium carbonate solution to pjj 6 to 7, until no more free amino group is detectable. The resulting reactive dye of the formula:

<img file="AT274983B_D0021.tif" />

SC ^ Na

NaO₃S is salted out, filtered off, washed and dried at 30 to 40 ° C. It dyes cellulosic materials in very real ruby ​​tones according to one of the methods given above.

Dyes of similar properties are obtained analogously to the procedure described above from the copper complexes of the azo dyes prepared from the diazo and azo components listed in the table below:

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Hue up cotton</td>

<td>181</td><td>1-hydroxy-2-aminobenzene-4-sulfonic acid</td><td>2-methylamino-5-hydroxynaphthalene-7-sulphonic acid</td><td>ruby</td>

<td>182</td><td>1-hydroxy-2-aminobenzene-4-sulfonic acid</td><td>2-ethylamino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>ruby</td>

<td>183</td><td>1-hydroxy-2-aminobenzene-4-sulfonic acid</td><td>2- (β-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>ruby</td>

<td>184</td><td>l-hydroxy-2-aminobenzene -4-sulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>ruby</td>

<td>185</td><td>l-hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid</td><td>ruby</td>

<td>186</td><td>1-hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>ruby</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>Hue up cotton</td>

<td>187</td><td>l-hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2-methylamino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>ruby</td>

<td>188</td><td>1-hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>ruby</td>

<td>189</td><td>1-Hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2- (β-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>ruby</td>

<td>190</td><td>1-hydroxy-2-amino-benzene-4,6-disulfonic acid</td><td>l-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>violet</td>

<td>191</td><td>1-Hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>l-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>violet</td>

<td>192</td><td>l-hydroxy-2-aminobenzene -5-suIfonsäure</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>violet</td>

<td>193</td><td>1-hydroxy-2-aminobenzene-5-sulfonic acid</td><td>l-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>violet</td>

<td>194</td><td>l-hydroxy-2-amino- -4-acetylaminobenzol- -6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>bluish violet</td>

<td>195</td><td>l-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid (4-acetylamino group</td><td>1-ethoxy-8-hydroxynaphthalene-3,6-disulfonic acid e saponified afterwards)</td><td>bluish violet</td>

<td>196</td><td>1-hydroxy-2-amino -4-acetylaminobenzol- -6-sulfonic acid (4-acetylamino group</td><td>1-amino-8-hydroxynaphthalene-2,4-disulfonic acid e saponified afterwards)</td><td>blue</td>

<td>197</td><td>1-hydroxy-2-amino -4-acetylaminobenzol- -6-sulfonic acid (4-acetylamino group</td><td>1 - Amino-8-hydroxynaphthaiin-2,4,6-trisulphonic acid e saponified afterwards)</td><td>blue</td>

<td>198</td><td>1-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid (6-acetylamino group</td><td>l-amino-8-hydroxynaphthalene-2,4-disulfonic acid saponified)</td><td>blue</td>

<td>199</td><td>1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid (active nitro group schi</td><td>1-amino-8-hydroxynaphthalene-2,4-disulfonic acid reduced to -NEy</td><td>blue</td>

<td>200</td><td>1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid (Compound nitro group schi</td><td>1 - amino - 8-hydroxynaphthalene -2,4,6-trisulphonic acid reduced to -Nl ^)</td><td>blue</td>

<td>201</td><td>1-hydroxy-2-amino -6-acetylaminobenzol- -4-sulfonic acid (6th acetylamino group:</td><td>1-amino-8-hydroxynaphthalene-2,4,6-trisulphonic acid 2 saponified)</td><td>blue</td>

No. 274983

Example 202: The procedure is as set forth in Example 30, but coupling the diazotized reactive group-containing intermediate in soda alkaline medium instead of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid with 40 parts of the sodium salt of 1-acetylamino 8-hydroxynaphthalene-3,6-disulfonic acid and isolating the resulting dye of the formula:

V^N

N

\.

NH ^XC1 z

// \ \ -_ / / ~

SO₃N / A

-N = N-,

NaOjS

OH NH-CO-CHg

SOjNa in the manner indicated in Example 30. The water-soluble dye dyes cellulosic materials by the pad / pad heat setting method (at 140 ° C) in white, wet, rub, and lightfast bluish red tones.

Example 203: The solution of 19.5 parts of the sodium salt of 1-aminobenzo-4-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is poured into a mixture of 100 parts of ice and 28 parts by volume of conc. Hydrochloric acid allowed to run in; then stirred for 1/2 h at 0 to 10 C, and then excess nitrous acid is removed. To the resulting diazo suspension is added at 0 to 10 ° C, the cooled and thus partially recrystallized solution of 26, 2 parts of the potassium salt of l-aminonaphthalene-8-sulfonic acid in 250 parts of hot water and blunts the strong acid coupling mixture at 10 to 20 ° C by careful addition of sodium hydroxide solution on pjj 4 from. The clutch is completed quickly; the aminoazo dye formed is completely salted out with 100 parts of sodium chloride, filtered off, washed and redissolved in 500 parts of water at 10 ° C and pjj θ to 7. The aqueous solution is added dropwise with 20 parts of 2,4, 6-trifluoro-5-chloropyrimidine and under constant dulling of the liberated acid with sodium carbonate solution to pjj 6 to 7 1 h at 20 to

30 ° C stirred. When no aminoazo dye is detectable, the partially-fumed reactive dye has the formula:

NaO, S- / N = N³ \ _ /

-NH \ -SO Na V ³

Salted out with 40 parts of common salt, filtered off and, for purification, again dissolved in 800 parts of warm water. After clarifying the solution, the pure dye is separated from the filtrate by adding 80 to 100 parts Koch25 salt. After filtering off, drying at 35 ° C. and grinding, a yellow powder is obtained which readily dissolves in water with yellow color and dyes the cellulose fibers in one of the abovementioned dyeing processes in the presence of acid-binding agents in very good wet, light and chlorine-resistant yellow shades. Even on wool and polyamide fibers true yellow colorations are obtained.

If one proceeds as indicated above, but instead of the 19.5 parts of the sodium salt of l-aminobenzene-4-sulfonic acid equivalent amounts of the diazo components listed in the following table coupling to the l-aminonaphthalene-8-sulfonic acid, obtained after acylation with 2 , 4,6-trifluoro-5-chloropyrimidine also valuable yellow to brown reactive dyes.

<td>diazo</td><td>Hue up cellulose fiber</td>

<td>1-Aminobenzene-2, 5-disulfonic acid</td><td>reddish yellow</td>

<td>2-aminonaphthalene-4,8-disulfonic</td><td>strong reddish yellow</td>

<td>2-aminonaphthalene-5,7-disulfonic</td><td>strong reddish yellow</td>

Nr.274983

<td colspan="2">diazo</td><td>Coloring on cellulose fiber</td>

<td colspan="2">2-aminonaphthalene-6,8-disulfonic acid</td><td>strong reddish yellow</td>

<td colspan="2">2-aminonaphthalene-3,6,8-trisulphonic acid</td><td>strong reddish yellow</td>

<td colspan="2">2-aminonaphthalene-4,6,8-trisulphonic acid</td><td>strong reddish yellow</td>

<td colspan="2">4-amino-azo-benzene-3,4¹ disulfonic</td><td>yellowish brown</td>

<td colspan="2">4-amino-2-acetylamino-azo-benzene-2 ​​', 5¹ disulfonic</td><td>orange Brown</td>

<td>SO Na</td><td></td><td></td>

<td></td><td rowspan="2">Vnh _ / 2</td><td></td>

<td>\ _ / - N = N _v</td><td>reddish brown</td>

<td>z /</td><td>\</td><td></td>

<td>SO_sN / A</td><td></td><td></td>

<td>/</td><td></td><td></td>

<td colspan="2">SOjNa</td><td></td>

<td colspan="2">(l-Aminobenzene-2, 5-disulfonic sour</td><td></td>

<td>on 1-aminonaphthalene</td><td>6-sulfonic acid coupled)</td><td></td>

<td>SO, Na</td><td></td><td></td>

<td>_ / ³</td><td></td><td></td>

<td></td><td>/ -¹¾</td><td>reddish brown</td>

<td>//</td><td>\</td><td></td>

<td>SO₃N / A</td><td>J</td><td></td>

<td>c</td><td>5O₃Na (6.7)</td><td></td>

<td colspan="2">(l-aminobenzene-2, 5-disulfonic acid acidic coupled to the technical mixture of 1-aminonaphthalene-6 and -7-sulfonic acid)</td><td></td>

<td>SO, Na</td><td></td><td></td>

<td>/ ³</td><td></td><td></td>

<td>/ \ _ /</td><td>= N- / NH,</td><td>violet-tipped brown</td>

<td>^{N / A}° '^s-O</td><td>/ \</td><td></td>

<td>\</td><td>/</td><td></td>

<td>SO₃N / A</td><td>SO₃N / A</td><td></td>

<td colspan="2">(l-aminonaphthalene-2, 5, 7-trisulfonic sour on 1-aminonaphthalene-6-sulfonic acid coupled)</td><td></td>

<td>SO, Na z ³</td><td></td><td></td>

<td>/ _N = \ /</td><td>= N-- NH₂</td><td>reddish brown</td>

<td>wQ</td><td>z ^ 3</td><td></td>

<td>\</td><td></td><td></td>

<td>SO₃N / A</td><td></td><td></td>

<td colspan="2">(l-aminonaphthalene-2,5,7-trisulfonic acid acidic on l-amino-2-methoxy-5-methylbenzene coupled)</td><td></td>

No. 274983

Example 204: When printing cellulosic fabric with a printing paste, the kilogram 30 g of the dye described in Example 18, 100 g of urea, 300 g of water, 500 g Alginatverdikkung (60 g sodium alginate per kilogram of thickening), 10 g of soda and 10 g of the sodium salt of the 3rd Contains nitrobenzenesulfonic acid and which was made up to 1 kg with water, then intermingled 5 net and then attenuated in a suitable buffer for 30 sec at 103 to 115 ° C, so you get after rinsing and boiling soaps a strong bluish red pressure of good wet, rub and light fastness.

Example 205: A mixture of the solutions of each 65.5 parts of the chromium-2 s l complex and the cobalt-2: 1 complex of the dye of the formula:

OH HO NHL

<img file="AT274983B_D0022.tif" />

in each 400 parts of water is stirred with 40 parts of 2,4,6-trifluoro-5-chloropyrimidine for about 2 h at 30 to 40 ° C while maintaining p ^ 6-7. If chromatographically no aminoazo dye (Co complex: blue, Cr complex: blue-green) is detectable, the formed mixture of the two reactive dyes is salted out with potassium chloride, filtered off and geirocknet.

The dye provides strong, very good wet and lightfast blacks on cellulosic materials after the pad dyeing process or under pressure in the presence of acid-binding agents.

If one proceeds accordingly but uses the mixture of the chromium 2: 1 and cobalt 2: 1 complex of the following aminoazo dyes, one also obtains valuable black dyes:

<td>diazo</td><td>coupling component</td><td>Clutch PJJ</td>

<td>l-hydroxy-2-amino- -4-nitrobenzene</td><td>1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid</td><td>9</td>

<td>1 -Hy droxy - 2 - amino - -4-nitronaphthalin- -7-sulfonic acid</td><td>l-hydroxy-8-aminonaphthalene-3,6-disulfonic acid</td><td>9</td>

Example 206: The neutral solution of 53.15 parts of the disodium salt of the diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with l- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone is added to the neutral solution. (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo in 300 parts of water, 20 parts of 2,4,6-trifluoro-5-chloropyrimidine and the mixture is stirred for 1 h at 30 ° C, wherein the liberated acid continuously with sodium carbonate solution to a p ^ value of 6, 0 from 25 dulls. The deposited dye of the formula:

SO "Na _ / ³

C-CH,

CI

CN HO^ZXN^Z

CI

NaO₃S 'is filtered off, dissolved in 3000 parts of water at pjj 6 to 7 warm and from the filtered solution by

Addition of sodium chloride precipitated again. After Abfiltiieren, drying and powders you get one

No. 2749S3 yellow, highly water-soluble powder, the cellulosic materials from long liquor at 30 ° C or after the

Klotz-Kaltverweil process with soda as an acid-binding agent in clear, wash, rub and lightfast yellows colors.

If one proceeds as indicated above, but instead of the Aminoazofarbstof5 fes used there are equivalent amounts of built up from the components listed in the following table

Aminoazofarbstoffe uses, you also get valuable new reactive dyes.

In the table, the term saponifies that an acylamino group contained in the aminoazo dye has been post-saponified, while the term reduced means that a nitro group contained in the diazo component is reduced to the amino group after coupling, where10 forms the desired aminoazo dye.

<td>example No.</td><td>diazo</td><td>azo</td><td>PH of the coupling medium</td><td>Color on cellulose</td>

<td>207</td><td>1-amino-4-nitrobenzene-2-sulfonic acid (4-nitro group ans</td><td>l- (4'-sulfophenyl) -3-methylpyrazolone- (5) reduced)</td><td>5 - 6</td><td>yellow</td>

<td>208</td><td>l-amino-4-nitrobenzene -2-sulfonic acid (4th nitro group ansc</td><td>l- (4-sulfophenyl) -3-carboxypyrazolone- (5) continuously reduced)</td><td>5 - 6</td><td>reddish yellow</td>

<td>209</td><td>l-amino-4-nitrobenzene -2-sulfonic acid (4th nitro group ansc:</td><td>1- (3-sulfophenyl) - -3-methyl-5-amino- pyrazole saponified)</td><td>6 - 7</td><td>yellow</td>

<td>210</td><td>1-amino-3-acetylaminobenzene-6-sulfonic acid (3-acetylamino group</td><td>1- (3-sulfophenyl) -3-methyl-5-amino-pyrazole then saponified)</td><td>6-7</td><td>yellow</td>

<td>211</td><td>1-amino-3-acetylaminobenzene-6-sulfonic acid (3-acetylamino group</td><td>l- (β-hydroxyethyl) -3-methylpyrazolone (5) ie saponified)</td><td>5 - 6</td><td>yellow</td>

<td>212</td><td>2 moles of 1-amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>1 mole of bis-pyrazolone 4,4'-bis-hydrazinodibenzyl-2, 2'-disulfonic acid and acetoacetic acid ester</td><td>5 - 6</td><td>yellow</td>

<td>213</td><td>1 mole of 1-amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>1- (4'-sulfophenyl) -3-carboxypyrazolone (5)</td><td>5 - 6</td><td>Yellow.</td>

<td>214</td><td>1-Amino-5-acetylaminonaphthalene-3,7-disulphonic acid (saponified)</td><td>1- (4'-sulfophenyl) -3-carboxypyrazolone- (5)</td><td>5-6</td><td>reddish yellow</td>

<td>215</td><td>1-amino-2-methylbenzene-4,6-disulfonic acid</td><td>2-acetylamino-5-naphthaol-7-sulfonic acid (saponified)</td><td>7 - 8</td><td>orange</td>

<td>216</td><td>1-amino-2-methylbenzene-4,6-disulfonic acid</td><td>2-Acetylamino-8-naphthol-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>azo</td><td>p_Hof clutch medium</td><td>Hue up cellulose</td>

<td>217</td><td>1-amino-2-methylbenzene-4,6-disulfonic acid</td><td>1-chloro-2-acetylamino-5-naphthol-7-sulfonic acid (saponified)</td><td>7 - 8</td><td>orange</td>

<td>218</td><td>1-aminobenzene -2-sulfonic acid</td><td>1-acetylamino-8-hydroxynaphthalene-4,6-disulphonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>219</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1-acetylamino-8-hydroxynaphthalene-4,6-disulphonic acid (saponified)</td><td>7 - 8</td><td>bluish red</td>

<td>220</td><td>2-aminonaphthalene-3,7-disulfonic</td><td>1-acetylamino-8-hydroxynaphthalene-4,6-disulphonic acid (saponified)</td><td>7 - 8</td><td>bluish red</td>

<td>221</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-Acetylamino-8-hydroxynaphthalene-4, 6-disulfonic acid (saponified)</td><td>7 - 8</td><td>bluish red</td>

<td>222</td><td>2-aminonaphthalene-3,6-disulfonic acid</td><td>1 - Acety lam ino - 8 -hy droxynaphthalene-3,6-disulphonic acid (saponified)</td><td>7 - 8</td><td>bluish red</td>

<td>223</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1-Acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid (saponified)</td><td>7 - 8</td><td>bluish red</td>

<td>224</td><td>1-amino-4-methoxybenzene-2-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid (saponified)</td><td>7 - 8</td><td>yellowish red</td>

<td>225</td><td>1 - Amino-4-methoxybenzene-2-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -8-hydroxy-naphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>226</td><td>1-aminobenzene - 2-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -8-hydroxy-naphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>227</td><td>1-aminobenzene -3-sulfonic acid</td><td>2- (N-Acety 1-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>228</td><td>1-aminobenzene -4-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>azo</td><td>Ppj of the coupling medium</td><td>Color on cellulose</td>

<td>229</td><td>l-amino-4-methyl benzene -2-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>230</td><td>l-amino-2,4-dimetbylbenzol-6-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) -8-hydroxynapbtbaline-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>231</td><td>1-amino-2,4-dimethylbenzene-6-sulfonic acid</td><td>2-Acetylamino-8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>232</td><td>1-amino-2,4-dimethylbenzene-6-sulfonic acid</td><td>2-Acetylamino-8-hydroxynaphthalene-3, 6-disulfonic acid (saponified)</td><td>7 - 8</td><td>red</td>

<td>233</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>l-amino-3-acetyl- aminobenzene</td><td>5 - 6</td><td>buff</td>

<td>234</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>l-amino-3-hydroxy- acetylaminobenzene</td><td>5 - 6</td><td>buff</td>

<td>235</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>1-aminonaphthalene-6-sulfonic acid</td><td>5 - 6</td><td>buff</td>

<td>236</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>1-aminonaphthalene-7-sulfonic acid</td><td>5 - 6</td><td>buff</td>

<td>237</td><td>4-aminoazobenzene-3,4'-disulfonic acid</td><td>1-Amino-2- (4'-amino-2'-sulfophenyl- (1 ') -azo) -8-hydroxynaphthalene-3,6-disulfonic acid</td><td>8th</td><td>black</td>

Example 238: 52.4 parts of the disodium salt of 4 - [(4-aminophenyl) amino] -2'-nitrodiphenylamine-3,4'-disulphonic acid are dissolved in 1000 parts of water and mixed with 20 parts of 2,4,6-trifluoro- 5-chloropyrimidine for 1 h at 20 to 30 ° C stirred. The liberated acid is continuously blunted with soda to a pjq value of 5.5 to 6. The formed reactive nitro dye of the formula:

/ P

NaOS - / NH- / NH- {NH- {\ "\ \" / \

NO, SO, Na Cl F

3 is salted out, filtered off, washed and dried. It dyes cellulosic fibers from long liquor or by one of the usual padding processes in the presence of soda as an acid-binding agent in wet and rubbed, deep violet brown tones.

Example 239: 52 parts of 1-amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2, 2'-disulphonic acid are dissolved in 550 parts of water and adjusted to pH 6 with sodium hydroxide solution. 18 parts of 2,4,6-trifluoro-5-chloropyrimidine are then added dropwise at room temperature and a ppj is added with 2N soda solution

No. 274983 of 6 upright. The reaction is monitored by chromatography. The crystallized in blue needles

Reaction product is filtered off with suction and washed the filter residue with 3% sodium chloride solution. On cotton gives clear blue dyeings of good wet fastness and good light fastness.

The resulting dye corresponds to the probable formula:

- === ¾

<img file="AT274983B_D0023.tif" />

NH.

I / °&gt;^H

IN-^Z

NH - ^ - CHjN /⁼\

SQH CI F

<td>example No.</td><td>water-soluble aminoanthraquinone derivative</td><td>hue</td>

<td>240</td><td>1 - amino -4- (4¹ -N-methylaminomethylanilino) anthraquinone-2,6,2'-trisulphonic acid</td><td>greenish blue</td>

<td>241</td><td>1-Amino-4- (4 '- N -methylaminomethylanilino) -anthraquinone-2,5,8-trisulphonic acid</td><td>greenish blue</td>

<td>242</td><td>l-amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,8-disulfonic acid</td><td>blue</td>

<td>243</td><td>1-Amino-4- (4'-aminoanilino) -antrhachinone-2,6-disulfonic acid</td><td>Blue green</td>

<td>244</td><td>l-amino-4- (4'-aminoanilino) anthraquinone-2,5-disulfonic acid</td><td>greenish blue</td>

<td>245</td><td>1-amino-4- (3'-aminoanilino) -anthraquinone-2, 6-disulfonic acid</td><td>blue</td>

<td>246</td><td>1-Amino-4- (3'-aminoanilino) anthraquinone-2, 5-disulfonic acid</td><td>blue</td>

<td>247</td><td>1 - Amino-4- (3 '- on inoanilino) - anthr achinone-2,4'-disulfonic acid</td><td>a little reddish blue</td>

<td>248</td><td>1 - Amino -4- (3 '- on inoanilino) - anthraquinone -2,4', 6'-trisulfonic acid</td><td>reddish blue</td>

<td>249</td><td>1 - Amino-4- (4'-aminocyclohexylamino) anthraquinone-2,5,8-trisulphonic acid</td><td>clear blue</td>

<td>250</td><td>1-amino-4- (4¹ N-methylaminomethylanilino) anthraquinone-2,3'-disulfonic acid</td><td>blue</td>

<td>251</td><td>1-Amino-4- [4 '- (4-aminobenzoylamino) -anilino] -anthraquinone-2,5,8-trisulfonic acid</td><td>Blue green</td>

<td>252</td><td>l-Amino-4- [4 '- (4-aminobenzenesulfamido) -anilino] -anthraquinone-2,5,8-trisulfonic acid</td><td>greenish blue</td>

<td>253</td><td>1-Amino-4- (4-aminostilbenamino) -anthraquinone-2,2 ', 2-trisulphonic acid</td><td>green</td>

Nr.274983

<td>example No.</td><td colspan="2">water-soluble aminoanthraquinone derivative</td><td>hue</td>

<td></td><td>1 1 /^S° 3^HI</td><td></td><td></td>

<td>254</td><td>UJUM ch₃ -</td><td></td><td>clear reddish</td>

<td></td><td>II O NH- so₂nh.so₂- / ^</td><td></td><td>nice blue</td>

Example 255: If the procedure of Example 18, but the resulting dye intermediate not with the diazo compound of 17.5 parts of 2-aminobenzenesulfonic acid but with the diazo compound of 20.8 parts of 3-chloroaniline-6-suifonsäure in the presence of

12 Parts of soda coupled at a final pjj of 7, we obtain a reactive dye of the formula:

Cl

SO₃N / A ₌z /

NaO₃S

HO

N- / NH- (\

I \ / /

Cl

SO₃Can be dyed or printed with the cellulosic materials from a long liquor at 40 ° C or by one of the usual reactive dyes for padding or printing process with soda as the acid-binding agent in wet fast, brilliant reds.

In an analogous manner obtained from the coupling components listed in the following TabeUe by acylation of their amino group with 2,4, 6-trifluoro-5-chloropyrimidine and coupling the resulting dye intermediates with the indicated diazo components valuable reactive dyes with which cellulose materials in the listed tones - preferably in Presence of soda - can be dyed or printed:

<td>example No.</td><td>diazo</td><td>coupling component</td><td>- Coupling PH</td><td>hue</td>

<td>256</td><td>1 - Amino-4-methoxybenzene-6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>7 - 8</td><td>violet</td>

<td>257</td><td>1-amino-4-methoxybenzene-6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>7 - 8</td><td>reddish violet</td>

<td>258</td><td>1-amino-4-methoxybenzene-6-sulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1,7-disulfonic acid</td><td>7</td><td>scarlet</td>

<td>259</td><td>1-amino-5-chlorobenzene-2-sulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1,7-disulfonic acid</td><td>7</td><td>orange</td>

Nr.274983

<td>example No.</td><td>diazo</td><td>coupling component</td><td>clutch ?H</td><td>hue</td>

<td>260</td><td>1-aminobenzene -3-sulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1,7-disulfonic acid</td><td>7</td><td>orange</td>

<td>261</td><td>1-aminobenzene -4-sulfonic acid</td><td>2-amino-5-hydroxynaphthalene-1,7-disulfonic acid</td><td>7</td><td>orange</td>

<td>262</td><td>1-aminobenzene -4-sulfonic acid</td><td>2-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>7 - 8</td><td>scarlet</td>

<td>263</td><td>4-aminobenzoic acid ~ (ß-sulfoethyl) -amide</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>7 - 8</td><td>red</td>

<td>264</td><td>l-amino-4-sulfo- acetylaminobenzol- -6-sulfonic acid</td><td>1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>7 - 8</td><td>violet</td>

<td>265</td><td>1-amino-3-sulfoacetylaminobenzol-6-sulfonic</td><td>2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid</td><td>7</td><td>orange</td>

<td>266</td><td>1-amino-4-sulfoacetylaminobenzene</td><td>2-amino-5-hydroxynaphthalene-1,7-disulfonic acid</td><td>7</td><td>scarlet</td>

<td>267</td><td>1-aminobenzene-2,4-disulfonic acid</td><td>1- (2'-methyl-3'-amino-5'-sulfophenyl) -3-methylpyrazolone (5)</td><td>6</td><td>yellow</td>

<td>268</td><td>2-aminonaphthalene-4,8-disulfonic</td><td>1- (2'-methyl-3'-amino-5'-sulfophenyl) -3-methylpyrazolone (5)</td><td>6</td><td>yellow</td>

Example 269s Following the procedure of Example 30, but the dye intermediate obtained from 1,3-diaminobenzene-6-sulfonic acid and 2,4,6-trifluoro-5-chloropyrimidine after diazotization at 10 ° C and pH 7.5 to 6, 5 coupled with the solution of 40.5 parts of disodium salt 5 of 2-sulfoacetylamino-5-hydroxynaphthalene-7-sulfonic acid, to obtain a reactive dye of the formula:

_z^S03^H

OH f

^f\ _n y

N^Z \ - NH \_Ä/ ^{7z / X}G1

Λ _ / -N = N-, · ^⁵'ho₃s

NH-CO-CHj, -SO₃H of the cellulosic materials according to the usual application method with soda as an acid-binding agent in true orange shades.

Example 270: If one proceeds as described in Example 206, but instead of the aminoazo dye used there 53.15 parts of the disodium salt of the diazotized by l-amino-4-nitrobenzene-2-sulfonic acid with l- (2'-chloro 5'-sulfophenyl) -3-methylpyrazülon- (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo with the

2,4, G-triluor-o-cliloropyrimidine acylated, we also obtain a valuable reactive dye,

No. 274983 with which cellulosic materials can be printed according to the usual dyeing and printing in real yellow shades.

Similar reactive dyes are obtained by acylating one of the aminoazo dyes composed of the components listed in the table below with 2,4,6-trifluoro-5-chloropyrimidine instead of the abovementioned aminoazo dye:

<td>example No.</td><td>diazo</td><td>azo</td><td>hue</td>

<td>271</td><td>1 - Amino-4-nitrobenzene-2-sulfonic acid (reduced)</td><td>1 - (2'-methyl-4¹ -sulfophenyl) - 3-methylpyrazolone- (5)</td><td>yellow</td>

<td>272</td><td>l-amino-4-nitrobenzene-2-sulfonic acid (reduced)</td><td>l- (2¹, 5'-disulfophenyl) -3-methylpyrazolone- (5)</td><td>yellow</td>

<td>273</td><td>1-Amino-4-nitrobenzene-2-sulfonic acid (reduced)</td><td>1- (2'-methyl-4'-sulfo-6'-chlorophenyl) -3-methylpyrazolone (5)</td><td>yellow</td>

<td>274</td><td>1-Amino-4-nitrobenzene-2-sulfonic acid (reduced)</td><td>1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methylpyrazolone - (5)</td><td>yellow</td>

<td>275</td><td>1-Amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>1 - (2'-methyl-4'-sulfophenyl) -3-methylpyrazolone (5)</td><td>greenish yellow</td>

<td>276</td><td>1-amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>1- (4'-sulfophenyl) -3-methylpyrazolone (5)</td><td>greenish yellow</td>

<td>277</td><td>1-Amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>1- (2'-methyl-4'-sulfophenyl) -3-carboxypyrazolone (5)</td><td>greenish yellow</td>

<td>278</td><td>1-Amino-3-acetylaminobenzene-6-sulfonic acid (saponified)</td><td>l- (2'-chloro-4¹ -sulfophenyl) - 3-carboxypyrazolone- (5)</td><td>greenish yellow</td>

Example 279: 58 parts of the dye of the formula:

O CuNH-CIL

N = N-

NaO₃S

Cl

NaO₃S (prepared by coupling diazotized 1-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid to 2-methoxyamino-8-hydroxynaphthalene-6-sulphonic acid and coppering the obtained azo dye) are prepared in

700 Dissolve water neutral. Is added dropwise 20.0 parts of 2,4, 6-trifluoro-5-chloropyrimidine and stirred at 20 to 30 ° C with constant blunting of the freed hydrofluoric acid with sodium carbonate solution to pjj 6.0 to 6.5, to no free amino group is more detectable. The formed reactive dye of the formula:

Nr.274983

Ο-Cu-0 F

Λ \ Λ ..

I ll I II I x

NaOgS ^^^ NaOgS ^^^^^ Cl F

Cl is salted out, filtered off, washed and dried at 30 to 40 ° C. It dyes cellulosic materials in very true violet tones according to one of the methods given above.

Dyes of similar properties are obtained analogously to the above-described procedure of 5 - obtained by simple, demethylating or oxidizing copper - copper complexes of the mono- and prepared from the diazo and azo components listed in the following table

Disazofarbstoffei

<td>example No.</td><td>diazo</td><td>azo</td><td>clutch PH</td><td>hue</td>

<td>280</td><td>1-hydroxy-2-amino -4-chlorobenzene -5-sulfonic acid</td><td>2-amino-8-hydroxy- naphthalene- -3,6-disulfonic acid</td><td>10</td><td>reddish violet</td>

<td>281</td><td>l-Hydtoxy-2-amino-4-chlorobenzene-5-sulfonic acid</td><td>l-amino-8-hydroxy- naphthalene- -3,6-disulfonic</td><td>10</td><td>bluish violet</td>

<td>282</td><td>2-aminonaphthalene-4,6,8-trisulfonic acid (oxidatively copper-plated)</td><td>2-hydroxy-6-acetylaminonaphthalene-4-sulfonic acid (saponified)</td><td>8 - 9</td><td>reddish blue</td>

<td>283</td><td>1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid (reduced)</td><td>l-hydroxy-8 - ethoxy - naphthalene- -3,6-disulfonic</td><td>10</td><td>blue</td>

<td>284</td><td>l-hydroxy-2-aminobenzene-4,6-disulfonic acid</td><td>2-hydroxy-3-amino- naphthalene- -5,7-disulfonic</td><td>10</td><td>red</td>

<td>285</td><td>2-aminonaphthalene-4,8-disulphonic acid (oxidatively coppered)</td><td>2-hydroxy-3-amino- naphthalene- -5,7-disulfonic</td><td>8 - 9</td><td>blue</td>

<td>286</td><td>2-aminonaphthalene-4, 6,8-trisulfonic acid (oxidatively coppered)</td><td>2-hydroxy-3-aminonaphthalene-7-sulfonic acid</td><td>8 - 9</td><td>blue</td>

<td>287</td><td>3-metiioxy-4-amino-6-methyl-azo-benzene-2 ​​', 4'-disulphonic acid (demethylated copper-clad)</td><td>2-Methylamino-5-hydroxynaphthalene-7-sulfonic acid</td><td>10</td><td>navy</td>

<td>288</td><td>3-methoxy-4-amino- 6-methyl-azo-benzene 2 ', 4'-disulfonic acid (demethylated copper-clad)</td><td>2-amino-8-hydroxy- naphthalene- -3,6-disulfonic acid</td><td>10</td><td>navy</td>

Nt.274983

<td>example No.</td><td>diazo</td><td>azo</td><td>Kuppkmgs- PH</td><td>hue</td>

<td>289</td><td>3-methoxy-4-amino- 6-methyl-azo-benzene - 2 ', 4¹ disulfonic acid (demethylated copper-clad)</td><td>2-Amino-5-hydroxy- naphthalene- -1,7-disulfonic</td><td>10</td><td>navy</td>

<td>290</td><td>3-Methoxy-4-amino-6-methyl-azo-benzene-2 ​​', 5'-disulfonic acid (demethylated copper-clad)</td><td>2-methylamino 5-hydroxynaphthalene -7-sulfonic acid</td><td>10</td><td>navy</td>

<td>291</td><td>3-methoxy-4-amino- 6-methyl-azo-benzene 2 ', 5'-disulfonic acid (demethylated copper-clad)</td><td>2-amino-8-hydroxy naphthalene- -3,6-disulfonic</td><td>10</td><td>navy</td>

<td>292</td><td>3-methoxy-4-amino- 6-methyl-azo-benzene 2 ', 5'-disulfonic acid (demethylated copper-clad)</td><td>2-Amino-5-hydroxy- naphthalene- -1,7-disulfonic</td><td>10</td><td>navy</td>

Example 293: 62.0 parts of the trisodium salt of the dye obtained by soda-alkaline coupling from diazotized 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 300 parts of water at 70 to 80 ° C and a pg of 8 to 9 with 5 54.2 parts of the 1: l chromium complex of the dye of 6-nitro-l-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene. After 10 minutes, a deep blue solution has formed.

The mixed complex is acylated in about 1 h at 30 to 40 ° C and a pn of 6.5 to 7.5 with 20 parts of 2,4, 6-trifluoro-5-chloropyrimidine. Hiebei the pjj value is kept constant by dropwise addition of sodium carbonate solution. The acylated dye is precipitated with 20% sodium chloride, filtered off with suction and dried at 30 ° C °₂\ __ // \ \ _ / os- / \³

N = N / X \ _ / / \

Λ //

Cr ° 3^S

N = N \, n- / // *

\.

/ \ = ¾¾. CI^XF

NH

N / A

CI ° 3^S

SO"

On cotton obtained according to the procedure given in Example 3, a blue-black

Printing of excellent light and washfastness.

Nr.274983

Example 294: 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid become neutral in

300 Dissolved water, heated to 60 to 65 ° C and 20 parts of 2,4, added 6-trifluoro-5-chloropyrimidine. In the course of 1 h, 40 parts of 15% sodium carbonate solution are added so that the pjj value is 6 to 6.5 The acylation product partially precipitates.

A freshly prepared diazonium salt solution of 13, 6 parts of p-aminobenzylsulfonic acid is added dropwise at 0 5 to 5 ° C in the staggered with 12.5 parts of soda suspension of the acylation product. After five hours of stirring at ice bath temperature is salted out with sodium chloride, filtered off with suction, washed with dilute sodium chloride solution and dried at 30 ° C in a vacuum oven. The dye obtained corresponds to the formula:

OH

<img file="AT274983B_D0024.tif" />

F

NaOjS

SO₃N / A

If one proceeds as above, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3, 6-disulfonic acid 30.4 parts of 2-amino-5-oxynaphthalene-l, 7-disulfonic acid with 2.4, Acylates 6-trifluoro-5-chloropyrimidine and couples the reactive group-containing coupling component with diazotized p-aminobenzylsulfonic acid, to obtain a readily soluble reactive dye, which dyes cellulosic fibers in brilliant reddish orange shades.

Cotton or cotton wool fabric is impregnated on a pad at 20 to 25 C with a solution containing per liter of liquor 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda, squeezed to a moisture content of about 100% off and rolls up the wet tissue again. After standing for 4 hours at room temperature, the fabric is rinsed, soaped and dried in a conventional manner. This gives a brilliant scarlet color of good wet and light fastness.

Cotton or cotton wool fabric is impregnated on a pad at 20 to 25 ° C with a solution containing per liter of liquor 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda, squeezed to a moisture content of about 100% off and steamed for 30 sec at 103 ° C. After rinsing, boiling soaps and drying also gives a brilliant scarlet color with good wet and light fastness.

Cotton fabric is impregnated with a solution of 20 to 25 C, the per liter liquor 20 g of the dye according to this example, paragraph 1, available and 0.5 g of a nonionic wetting agent (eg a polyoxäthylierten oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate contains. Then the fabric is squeezed between two rubber rollers to a moisture content of about 30 100%. After intermediate drying at 50 to 60 ° C is heated for 10 min at 140 ° C and rinsed the dyeing thoroughly with hot water and 10 min boiling treated with a solution containing per liter 5 g of Marseille soap and 2 g of soda. After rinsing and drying to obtain a strong scarlet color of good wet and light fastness.

When printing cellulosic fabric with a printing paste containing, in kilograms, 30 g of the dye described in this example, paragraph 1, 100 g urea, 300 g water, 500 g alginate thickening (60 g sodium alginate per kilogram thickening), 10 g soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was filled with water to 1 kg, then inter-dried and then attenuated in a suitable buffer for 30 sec at 103 to 115 ° C, So after washing and soapy soaps you get a strong scarlet color with good fastness properties.

100 Parts wool are introduced at 40 ° C in a bath containing in 5000 parts of water 1, 5 parts of the dye described in this example, paragraph 1, and 6 parts of 30% acetic acid and 0.5 parts of a polyoxäthylierten hydroxyl-containing stearylamine derivative , The dyebath is brought to the boil in 30 minutes, then it is stained for 1 h. After rinsing and drying gives a brilliant, good wash, walk and light scarlet color.

Example 295: 2S, 9 parts of 2-amino-1-methylbenzene-3, 5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The resulting monoazo dye is isolated and then or without

Isolation immediately diazotized in solution and with 25.3 parts of 2-methylamino-5-hydro .ynaphthalin-7-sul- 42

No. 274983 fonsäure alkaline coupled. The disazo dye obtained is salted out by addition of sodium chloride, filtered off with suction and the isolated product with about 50 parts of crystallized copper sulfate, 40 parts of diethanolamine, 50 parts of ammonia (D: 0, 88) metallized in 5 h at 95 to 100 ° C. From the coppering solution, the dye is isolated by salt addition and careful acidification.

The copper-doped amino disazo dye is then acylated in aqueous solution at pjj 6 to 7 at a temperature of 20 to 30 ° C with 20 parts of 2,4, 6-trifluoro-5-chloropyrimidine, the ppj value by soda addition in the specified range is held. After completion of Acylieru ng the dye is isolated with sodium chloride and dried at 35 ° C. The dye corresponds in the form of the free sulfonic acid of the formula:

ho₃sY _Z^CHs

Y.

_ /

N = N - so₃H //

\. / '^CHs • Cu ·

Y- N = Nho₃s

NZ

N- ( ^XNI \ = / s I \

Cl F

CH "

It dyes cellulosic tissue according to the methods known for reactive dyes in wet and lightfast navy blue shades.

In a similar manner, further dyes according to the invention can be prepared by reacting the abovementioned monoazo dye of 2-amino-1-methylbenzene-3,5-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene with the amino-naphtholsulfonic acids listed in the table below and 2,4,6-trifluoro-5-chloropyrimidine are combined according to the procedure given above.

Coupling component:

2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid 2-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

The resulting dyes are blue in color.

Example 296: Ο, ΙΜοΙ 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid is diazotised and then coupled alkaline with 0.1 mole of 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid. The coupling solution is adjusted to a level of 2 moles per liter with caustic soda and then refluxed for 3 hours to saponify the ureido group. After cooling, it is neutralized with hydrochloric acid. By

Addition of 25 parts of copper sulfate and 100 parts of 2N sodium hydroxide solution, the dye is metallized at 45 ° C and a pjj value of 4 to 6 and after 30 min at pg 6 to 7 and temperatures of 20 to 30 ° C with 0.1 mol 2,4,6-trifluoro-5-chloropyrimidine acylated. The resulting dye of the formula:

Cu ·

NH ".z so₃H

N \

r. / ./ • HN

Cl like that₃h is salted out. On cotton you get a blue color.

Example 297: A neutral prepared from 600 g of 96% technical grade copper phthalocyanine

Paste of copper phthalocyanine 3, 3 ', 3-trisulfonyl chloride is stirred with a little water, adjusted to 4 l and at a from 3.5 to 6.0, with 216 g of N-methyl-N- (4'-amino-2' -sulfobenzyl) amine initially at 0 to 3 ° C, last 20 to 35 ° C, with the addition of 300 ml (= 295 g) of pyridine reacted and then the pyridine at ρπ θ, 0 with water vapor from the resulting solution of copper phthalocyanine 35th disulfonic acid-monosulfonic acid (3-sulfo-4'-methylaminomethylanilide) distilled off. In the on 20 to

No. 274983

30 ° C solution are added dropwise in portions 300 g of 2,4, 6-trifluoro-5-chloropyrimidine in the course of 1 to h and maintained by the addition of dilute sodium hydroxide a pjj 6-7. At the same time, if necessary, the reaction mixture is diluted with water so far that the dye always remains dissolved.

This gives 10 1 of dye solution, which is separated from the excess acylating agent, by addition of acetic acid to pjj 7.0 and by stirring 2.5 1 conc. Saline drops.

After aspirating and drying at 30 ° C to obtain a clear turquoise blue dye, which is fixed from sodaalkalischer solution at 40 to 60 ° C with very good yield and wash fastness to cotton.

If one uses the NiPc-3,3 ', 3-trisulfonsäurechlorid as starting material, one obtains only a little greener turquoise blue with equally valuable properties.

Example 298: 0.1 mole of the aminoazo dye of the formula:

SOH

I

SOH ι | Y - I ho₃s \₌/ I II I / \ UU

I

prepared according to the specifications of German Pat. No. 1115 865 by coupling the diazonium compound of 2-aminonaphthalene-4,8-disulphonic acid with 1-aminonaphthalene-6-sulphonic acid, further diazotizing the resulting aminoazo dye, coupling with the equivalent amount of 2,5- Diaminonaphthalene-4,8-disulfonic acid and conversion to the aminotriazole - are dissolved in 1000 vol. Dissolve water at pH 6 and add 21 parts of 2,4,6-trifluoro-5-chloropyrimidine while stirring at a temperature of 20 to 30 ° C. Blunt the slowly released hydrofluoric acid with soda solution until the reaction is complete. The dye is then separated by the addition of sodium chloride, isolated and dried at about 50 ° C in a vacuum. It represents a yellow powder soluble in water of yellow color.

Example 299: 38, 9 parts of the obtained by sodaalkalische coupling of 6-nitro-2-diazo-l-hydroxybenzene-4-sulfonic acid and 2-hydroxynaphthalene dye are dissolved in 200 parts of water at 25 ph θ at a temperature of 70 to 80 ° C touched. In this suspension is carried out 67, 9 parts of the containing on 1 molecule of dye 1 chromate chromium complex of the azo dye

4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3, 6-disulfonic acid, wherein the pn is maintained between 7 and 9 by dropwise addition of sodium carbonate solution. After 20 minutes at 70 to 80 ° C, a dark blue solution has formed. The paper chromatogram shows that a uniform mixed complex has been formed. The mixed complex is within 1 h at 40 ° C and pn 6.5 to

Acylated 7.5 with 22.0 parts of 2,4,6-trifluoro-5-chloropyrimidine, wherein the pH is maintained by dropwise addition of a So dalösung in the specified range. The acylated dye is salted out with 20% potassium chloride, filtered off and dried at 30 ° C. This gives a dark powder that dissolves in water with blue-gray color.

The dye corresponds as the pentasodium salt of the formula:

Nr.274983

SO.

N = No₂n /

\ _ / / \ "V _ // /

O ': cr;

° 3^S

N = N *

N- (NH-)^B Si

Λ, i \ i ci

N / A

I

Gl ° s^S so.

It dyes cotton according to the procedure given in Examples 1 to 3 in gray to black shades.

It is also possible to obtain valuable dyes from the starting components indicated in the following table in the manner indicated in this example. For the preparation of these dyes, the azo dye, which carries the reactive group in the 2: 1 mixed complex, was always used as a 1: 1 chromium complex.

<td>example No.</td><td>1: 1 chromium complex</td><td>metal-free dye</td><td>Hue up cotton</td>

<td>300</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid. - ~&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitritol - 2-amino-1-hydroxybenzene -&gt; , 2-hydroxynaphthalene</td><td>Black .</td>

<td>301</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>302</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>303</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydrotoxynaphthalene-6-sulforic acid</td><td>black</td>

<td>304</td><td>4-nitro - 2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene-6-sulfonic acid</td><td>black</td>

<td>305</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro - 2-amino-1-hydroxybenzene -&gt; 1-hydroxynaphthalene-4-sulfonic acid</td><td>navy</td>

Nr.274983

<td>example No.</td><td>1: 1 chromium complex</td><td>metal-free dye</td><td>Coloring on cotton</td>

<td>306</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid</td><td>6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>307</td><td>4-N itro - 2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 1 - acetylamino - 7-hydroxynaphthalene</td><td>black</td>

<td>308</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>309</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>4-nitro-2-amino-l-hydroxy- naphthalene - 6-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>310</td><td>4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene</td><td>blue Black</td>

<td>311</td><td>4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene</td><td>blue Black</td>

<td>312</td><td>4-chloro-2-amino-l-hydroxy- benzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene - 6-sulfonic acid</td><td>blue Black</td>

<td>313</td><td>4-chloro-2-amino-l-hydroxy- benzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-chloro-2-amino-1-hydroxybenzene - 2-hydroxynaphthalene</td><td>navy</td>

<td>314</td><td>4-Chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>blue</td>

<td>315</td><td>4-chloro-2-amino-l-hydroxy- benzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid</td><td>navy</td>

<td>316</td><td>4-Chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>6-nitro-l-amino-2-hydroxynaphthalene-4-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>blue Black</td>

<td>317</td><td>4-Chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid</td><td>2-aminobenzene-l-carboxylic acid -5-sulfonic acid -&gt; l-Phenyl-3-methyl-5-pyrazolone</td><td>gray Green</td>

Nr.274983

<td>example No.</td><td>1: 1 chromium complex</td><td>metal-free dye</td><td>Coloring on cotton</td>

<td>318</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>6-nitro-l-amino-2-hydroxynaphthalene-4-sulfonic acid -&gt; 2-hydroxynaphthalene</td><td>black</td>

<td>319</td><td>4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-Chloro-2-amino-1-hydroxybenzene -&gt; 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone</td><td>violet</td>

<td>320</td><td>4-Methyl-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-Chloro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene-6-sulfonic acid</td><td>reddish blue</td>

<td>321</td><td>4-N itro - 2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>5-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene-6-sulfonic acid</td><td>black</td>

<td>322</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 2-hydroxynaphthalene-8-sulfonic acid</td><td>black</td>

<td>323</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene -&gt; 1 - hydroxynaphthalene-5-sulfonic acid</td><td>black</td>

<td>324</td><td>4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid -&gt; 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>6 -Nitro -4-chloro-1-hydroxybenzene -&gt; 1 - hydroxynaphthalene-5-sulfonic acid</td><td>black</td>

Example 325: 8.2 parts of 1-amino-4- (3'-amino-anilino) -anthraquinone-2-sulfonic acid are dissolved in a mixture of 160 parts of water and 80 parts of dioxane with the addition of 1:05 parts of sodium carbonate. 3.8 parts of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise at 0 ° C. and a pjj of from 6 to 6.5 is obtained by adding 5% of 2N soda solution. After completion of the acylation, the dye is salted out at 20 C with 25 parts of sodium chloride and the crystalline product is filtered off, washed with 2% saline and dried in vacuo at 30 ° C.

The dye dyes wool in very wetfast blue tones.

<img file="AT274983B_D0025.tif" />

.^S03^H

Cl, F //

NH-N

No. 274983

Example 3 26: 8.3 parts of 1-amino-4- (4'-amino-cyclohexylamino) -anthraquinone-2-sulfonic acid are dissolved in 160 parts of water and 80 parts of dioxane with the addition of 1, 3 parts of 45% sodium hydroxide solution and at 0 to 5 ° C 3, 8 parts of 2,4, 6-trifluoro-5-chloropyrimidine zugetcopft. By addition of 2NSodalösung keeps a p ^ from 9 to 10. After completion of the acylation, the pjj by addition of 5 hydrochloric acid to 4.5. The crystalline product is filtered off with suction and washed with 2% saline solution until the colorless effluent. The dye obtained is dried in vacuo at 30 to 40 ° C, he dyed

Wool in clear washfast blue tones.

<img file="AT274983B_D0026.tif" />

V /

CI F \ _Z

NH- / H NH- / \ ^XF

Example 3 27: 15.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 150 parts of water and acylated at 20 ° C at a pH of 5.5 to 6 with 10.2 parts of dichlorodifluoropyrimidine. The liberated hydrogen fluoride is neutralized with '2N sodium hydroxide solution. For coupling, the batch is diluted with 450 parts of water, 10 parts of soda added and allowed at 0 ° C, a suspension containing 9.9 parts of diazotized 2-aminobenzenesulfonic acid, run. The pfj value is kept at 7 to 8. After completion of the reaction, place on pjj θ, salt with 100 parts of sodium chloride, filtered off with suction and washed with 20% saline. The red dye of the formula is obtained:

so₃H

OH NH

C1 CI \ _z _Z ^ -N = Nho₃That's how it is₃h which dyes cotton from long liquor at 20 to 40 ° C in wet red shades.

Example 3 28: 15.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 150 parts of water and acylated at 20 to 25 ° C with 8.3 parts of 2,4-difluoro-6-chloropyrimidine. The frei20 expectant hydrogen fluoride is neutralized with sodium hydroxide solution. The further procedure follows

Example 327. The red dye of the formula is obtained:

so₃h / ^ __ N = N-Z _z //

OH NH-fN

I ^NZ.

Cl

HO₃S 'like that₃h the cotton at about 30 to 50 ° C colors.

Example 329: 8.2 parts of 1-amino-4- (p-aminoanilino) anthraquinone-2-sulfonic acid are dissolved in a mixture of 160 parts of water and 80 parts of dioxane and 3.8 parts of trifluorochloropyrimidine at 0 ° C and a pn of 6 to 7 implemented. The pn value is maintained with 2N sodium hydroxide solution. After completion of the reaction is filtered off with suction at 20 ° C and washed with 2% saline.

It is dried at 60.degree. The dye of the formula:

Nr.274983

<img file="AT274983B_D0027.tif" />

NH

Cl Jffff

NH-NN = '\_r dyes wool in greenish shades with good wet fastness properties.

Example 33 0: 7.6 parts of 2-oxynaphthalene-6,8-disulfonic acid are passed through in 100 parts of water

Addition of soda dissolved. Then, a suspension of the diazonium salt of 1-amino-3- (2 ', 6 * -di5-fluoro-5^.-chlorpyrimidinyl-4^.) -aminobenzene-6-sulfonic acid (prepared from 4.7 parts of 1,3-diaminobenzene-4-sulfonic acid, according to Example 30) at 0 ° C and holds a pjj of 8. After the acidification is salted out with 20 parts of NaCl, the crystalline reaction product is filtered off with suction and washed with 20% NaCl solution. The dyestuff is dried at 60.degree. He dyes wool with good whiskering and potting fastness in clear orange tones.

Example 331: 9.5 parts of 1-amino-4- (p-aminophenylamino) -anthraquinone-2,6,2'-trisulfonic acid are dissolved in 95 parts of water and at 20 to 25 ° C. 5.0 parts of 2,4, Added dropwise 6-trifluoro-5-chloropyrimidine. The pjj value is kept between 6 and 7. After completion of the reaction, the precipitated reaction product of the formula:

HO_sS

<img file="AT274983B_D0028.tif" />

HO_sS '

Filtered with suction and washed with 5% saline solution. It is dried in vacuo at 60 ° C.

Example 33 2: 57 parts of l-amino-4- (p-aminophenylamino) -anthraquinone-2, 6,3 * -trisulfonic acid are dissolved in 600 parts of water and admixed with 18 parts of trifluorochloropyrimidine. With caustic soda, a p ^ of 6 to 7 is maintained. The work-up is carried out according to Example 331. The cyan dye of the formula:

<img file="AT274983B_D0029.tif" />

/

O HN like that₃H like that₃H

Cl F ff

NH-N

Nr.274983

Example 333: 15.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 150 parts of water and reacted at pjj 6 to 7 with 10 parts of 2,4-difluoro-5-chloropyrimidine. The liberated hydrogen fluoride is neutralized with 2N sodium hydroxide solution. The coupling and workup he follow Example 327. The dye of the formula:

.^s°₃H // ^ __{Ν = Ν}γ

HC ^ S

Cl \ ff

OH NH-fN ¹ I

SO, H stains the cotton at 60 ° C in alkaline medium in wet-fast bluish red tones.

Example 334: 15.9 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid are dissolved in 150 parts of water and acylated at pg 6 nis 7 with 6 parts of difluoropyrimidine. The coupling and workup are carried out according to Example 327. The dye of the formula:

.^SOs^H

OH ff

NH- / N

I ^N&lt;

-N * NX 'ho₃That's how it is₃h which provides red prints of good wet fastness on cotton.

Example 335: 15.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 150 parts of water and reacted with 9 parts of tetrafluoropyrimidine at a pjj of 5.5 to 6. The coupling and further work-up are carried out in accordance with Example 327. The dye of the formula:

/^{S0 # H} I ^ _N = N-X * //

OH NHNN

HO₃S '' S0₃h dyed in real red tones cotton from a long fleet.

Example 336: 12.2 parts of 1-amino-4- (p-aminophenylamino) -anthiachinone-2,2'-disulfone-6-carboxylic acid are dissolved in 360 parts of water and acylated at pH 6 with 3.7 parts of difluorodichloropyrimidine , The resulting dye of the formula:

HOOC

O NHL

<img file="AT274983B_D0030.tif" />

II I Ο HN

\.

Cl ho_ss

NH- .x /

'\

Cl

No. 274983 is salted out with 10 g of sodium chloride, filtered off with suction and washed with 10% sodium chloride solution. He dyed on wool a greenish blue of very good walk and Pottingechtheit.

Example 337: To a solution of 15.1 parts of acidic coupling product of l-amino-8-hydroxynaphthalene-3, 6-disulfonic acid and diazotized o-sulphanilic acid in 150 parts of water at pH 5 8 and 0 to 5 ° C, a suspension of Diazonium salt of l-amino-3- (2 ', 6'-difluoro-5'-chloropyrimidinyl-4') - aminobenzenesulfonic acid (prepared from 5.7 parts of 1,3-diaminobenzene-4-sulfonic acid according to Example 30) was added. During the coupling one holds a pjj of 8 and after completion of the reaction on pjj 6. The dye of the formula:

<img file="AT274983B_D0031.tif" />

N = NSO₃H

SO H

V ./% \ = / is salted out with 100 parts of sodium chloride, filtered off with suction and dried in vacuo at 60 ° C. On cotton you get when dyeing from long liquor a black.

Example 338: 10 parts of 1-amino-4- [3 '- (2 * 6-difluoro-5-chloropyrimidinylamino) -anilino] -anthraquinone-2-sulfonic acid are introduced into 70 parts of 13% oleum at 0 ° C. Towards the end of the reaction, the temperature is brought to 20 ° C and added after complete sulfation in a mixture 15 of 220 parts of ice water and 30 parts of potassium chloride. The very well crystallized product is filtered off with suction and washed neutral with saturated potassium chloride solution. The dye of the probable formula:

<img file="AT274983B_D0032.tif" />

SO.H / ³

HN

Cl F

NH- / \

N =

HO₃S '

SOAH dyes cotton and wool in reddish blue tones with good wet fastness properties,

Example 339: 10 parts of 1-amino-4- [3 ^ (2 ^ 6 '^.difluoro-5^H-chloro-pyrimidinyl) -anilino] -anthraquinone-2, 6-disulfonic acid are dissolved at 0 ° C in 65 parts of 13% oleum and added after completion of sulfation in a mixture of 220 parts of ice and 30 parts of potassium chloride. It is suctioned off, washed with saturated potassium chloride solution and dried at 60 ° C in vacuo. On cotton blue prints of good wet fastness.

Example 340: 79.7 Parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 500 parts of water and to this a suspension of the diazo salt of 1-amino-3- (2 ', e'-difluoro-S' -chloropyrimidinyl-4 ') - aminobenzene-6-sulfonic acid (from 47 parts of 1,3-diaminobenzenesulfonic prepared according to Example 30). It adjusts with sodium acetate solution a pjj of 4.5 and sucks after completion of the coupling, the crystalline reaction product and washed with 10% sodium chloride solution. The Farb30 fabric is dried at 60 ° C in a vacuum.

Example 341: 36.6 parts of monoazo dye from Example 340 are dissolved in 460 parts of water and

Dissolved 6.7 parts of soda and while maintaining a p ^ from 8 to 8.5, the diazonium solution of 4.7 parts of aniline at 0 to 5 ° C was added. It is allowed to stir for about 3 h, adjusted with hydrochloric acid a pjj of 5.5, filtered off with suction and washed with 5% saline. The dye of the formula:

Nr.274983

OH

NH, /% \ = /

-N = N- ^S^^H

N = N-7 ⁼\

SO_sH ^C\ _X NH- / \, /

X is dried at 60 ° C in a vacuum and provides at 8 to 10% coloration black on tree and rayon.

If, in this example, instead of aniline, the 5 diazo components given in the following table are used in an equivalent amount, valuable dyestuffs are likewise obtained:

<td>example No.</td><td>diazo</td><td>hue</td>

<td>342</td><td>2-aminobenzene-1-sulfonic acid</td><td>black</td>

<td>343</td><td>2-amino-5-chlorobenzene-l-sulfonic acid</td><td>black</td>

<td>344</td><td>2-amino-5-methylbenzene-1-sulfonic acid</td><td>black</td>

<td>345</td><td>2-amino-5-nitrobenzene-l-sulfonic acid</td><td>black</td>

<td>346</td><td>2-aminonaphthalene-l-sulfonic acid</td><td>black</td>

<td>347</td><td>Dehydro-p-toluidindisulfonsäure</td><td>black</td>

<td>348</td><td>2-aminonaphthalene-l, 5-disulfonic acid</td><td>black</td>

Example 349: Analogously to Example 340, the dye of the following formula is obtained from 1,4-diaminobenzene-2-sulphonic acid:

OH

I-N = N

SO, H \ __ /

Cl F \ _ /

-NH · /

\

N^:

N

J

X:

HO_sS '' SO_sH

Coupling this with the following diazo components, one also obtains black dyes:

<td>example No.</td><td>diazo</td><td>hue</td>

<td>350</td><td>2-aminobenzene-1-sulfonic acid</td><td>black</td>

<td>351</td><td>2-amino-5-nitrobenzene-1-sulfonic acid</td><td>black</td>

<td>352</td><td>2-amino-5-methylbenzene-1-sulfonic acid</td><td>black</td>

<td>353</td><td>2-aminonaphthalene-l, 6-disulfonic acid</td><td>black</td>

<td>354</td><td>2-aminonaphthalene-l, 7-disulfonic acid</td><td>black</td>

<td>355</td><td>p-'Toluidin</td><td>black</td>

Example 356: 9.4 parts of p-phenylenediamino-2-sulfonic acid are dissolved in 95 parts of water at pjj 7 and at 0 to 5 ° C with 9.3 parts of 5-chloro-2,4,6-trifluoropyrimidine while maintaining the pjj-Wer52 No. 274983 tes acylated by dropwise addition of 2N sodium hydroxide solution. It is diluted with 70 parts of water, giving 3.5 parts

Sodium nitrite and leaves the mixture with good stirring at 0 to 5 ° C in a mixture of 150 parts

Water and 13 parts conc. Hydrochloric acid. After 1 h, the excess nitrite is destroyed with sulfamic acid and the suspension of the diazonium salt at 0 to 5 C in a solution of 15.9 parts of 1-amino-8-oxynaphthalene-2,4-disulfonic acid in 100 parts of an 8% sodium carbonate solution , One holds the p_HValue of 8 until the coupling is complete, then adjust to pH 5.5 with hydrochloric acid and salt out the dye. The product is filtered off, washed with brine and dried at 60 ° C in a vacuum. Cotton or wool gives violet dyeings of good wet fastness.

If, in this example, the coupling components used are the compounds given in the table below, valuable reactive dyes are likewise obtained:

<td>example No.</td><td>coupling component</td><td>hue</td>

<td>357</td><td>2-methylamino-8-oxynaphthalene-6-sulfonic acid</td><td>bluish red</td>

<td>358</td><td>2-Oxyanaphthalin-6,8-disulfonic</td><td>orange</td>

<td>359</td><td>1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid</td><td>red</td>

Example 360: 15.9 parts of 1-amino-8-oxynaphthalene-4,6-disulfonic acid are dissolved in 100 parts of water and acylated at 0 ° C with 9.3 parts of trifluorochloropyrimidine. One holds a pjj value of

6.5 to 7. It is coupled with a solution of diazotised aniline at 0 ° C and a pjj of 7 to 8. After completion of the reaction, place on pjj 6, the reaction product is filtered off with suction and washed with

5% saline. The dye of the formula:

OH

Z

\.

N = NCI F \ _Z //%

NH-N

I ^{N =}\

I ho₃s

7 'is vacuum dried at 60 ° C and dyes cotton in wet red shades.

Example 3 61: 6 parts of 1-amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,6,2'-trisulfonic acid are dissolved in 160 parts of water and treated at 0 to 5 ° C. with 2 parts of 5-nitro- 2,4-difluoropyrimidine acylated. With sodium hydroxide solution to keep a pjj of 6.5 to 7. After the reaction is salted out with sodium chloride, filtered off with suction and dried in vacuo. On wool, the dye gives the formula:

/ ° 3^Η

HO.S

HN

NO.

ho₃s //

N = / blue shades.

9¾ \

Nr.274983

Example 362: 12.3 parts of the dye prepared by coupling 1- (5'-chloro-2^.6'-di-fluoropyrimidinylamino) -8-hydroxynaphthalene-3,6-disulfonic acid with diazotized aniline are dissolved in 160 parts of 10% oleum at 0 ° C and after completion of sulfation to a mixture of

500 Add ice / 120 parts of sodium chloride, filtered off and washed with saturated brine.

It is dried in vacuo at 80 ° C. Cotton is dyed in real red shades.

Example 363: 10.0 parts of 1-amino-4- (2 ', 6'-dimethylanilino-S'-sulfonamido-1-anairachinone-2-sulfonic acid are dissolved in 150 parts of Waster and adjusted to pjj 12. The product is acylated with 3, 7 Dissolve trifluorochloropyrimidine and, when the reaction is complete, adjust to pjj 5, salt with 25 parts of potassium chloride, suction and wash with ice-cold 15% potassium chloride solution.

kj

SO.H / '

Cl

O HN

\.

_z

SO, .NH-Y z ² is dried in vacuo at 60 ° C and dyes wool in clear blue tones.

Example 364: 26 parts of 1-amino-4- (4'-N-methylaminomethylanilino) -anthraquinone-2,2'-disulphonic acid are dissolved in 560 parts of water and acylated at 0 to 5 ° C with 10, 2 parts of difluorodichloropyrimidine. With 2N sodium hydroxide solution keeping a pjj of 6 to 6.5 upright By addition of 10 parts of conc. Hydrochloric acid to pn 1.5, sucks and washed with 5% saline. The dried at 60 ° C in vacuo dye of the formula:

O NH.

<img file="AT274983B_D0033.tif" />

O HN

\.

ho_8ths

CHs CHj.N -

Cl

J _ /

N = dyes cotton in real, clear blue tones.

Example 365: 13.3 parts of 1-amino-4- (4'-N-methylaminomethylanilino) anthraquinone 20-2,6,2 * -trisulfonic acid are dissolved in 360 parts of water and at 20 to 25 ° C with 6 parts of 2, 4, 6-trifluoropyrimidine acylated. The pjj value is maintained at 6 to 7 by addition of 2N sodium hydroxide solution. After completion of the reaction, salt is quickly salted out with 65 parts of sodium chloride and dried at 60 ° C. in vacuo. The resulting dye of the formula:

No.274983 ho₃s

<img file="AT274983B_D0034.tif" />

O NH

<img file="AT274983B_D0035.tif" />

HN

HO₃S 'gives a greenish blue color to wool.

In an analogous manner, valuable dyes can be obtained from the following components:

<td>example No.</td><td>dye</td><td>reactive component</td><td>hue</td>

<td>366</td><td>1 - Amino-4- (4 '- N -methylamino-methylanilino) -anthraquinone-2, 6, 2' -trisulfonic acid</td><td>2,4-difluoro-6-chloropyrimidine</td><td>greenish blue</td>

<td>367</td><td>1-Amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,7,2'-trisulphonic acid</td><td>2,4-difluoro-5-chloropyrimidine</td><td>blue</td>

<td>368</td><td>1-amino-4- (4'-aminoanilino) -anthraquinone-2,7-disulfonic acid</td><td>2,4-difluoro-6-difluoromethyl-5-chloropyrimidine</td><td>Blue green</td>

<td>369</td><td>1 - Amino -4- (4 * -N-methylamino-methylanilino) -anthraquinone-2,6, 2'-trisulphonic acid</td><td>2,4-difluoro-6-trifluoromethyl-5-chloropyrimidine</td><td>blue</td>

Example 37 0: To a solution of 15.6 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts of 3% sodium carbonate solution is allowed at 0 to 5 ° C, a suspension of the diazonium salt of 1-amino-5 - (2 ', 6'-difluoro-5^.-chloropyrimidinylamino-4 ') - benzene-2-sulfonic acid (prepared from 18, 8 parts of 1, 5-diaminobenzene-2-sulfonic acid according to Example 30) run in and holds by the addition of Na acetate a pn of 4 to 4.5. After completion of the coupling are added to 5, 7 parts of sodium carbonate solution and stirred 10 at a pn of 7.5 to 8 for 3 h after. The resulting dye is salted out with 100 parts of sodium chloride, filtered off and washed with 15% saline. It is dried at 60 ° C in a vacuum.

On cotton, the dye obtained gives a black color of very good wet fastness. Similar dyes are obtained when the following diazo components are used in this example;

<td>example No.</td><td>diazo</td>

<td>371</td><td>1-Amino-4- (2 ', 6'-difluoro-5'-chloropyrimidinylamino-4 *) - benzene-2-sulfonic acid</td>

<td>372</td><td>1-amino-3- (2'-fluoro-5¹'6'-dichloropyrimidinylamino-4') benzene-2-sulfonic acid</td>

<td>373</td><td>1-methyl-2- (2 ', 6'-difluoropyrimidinylamino-4') - 4-aminobenzene-5-sulfonic acid</td>

<td>374</td><td>1-Amino-4- (2'-fluoro-5'-chloropyrimidinylamino-4 ') - benzene-2-sulfonic acid</td>

Nr.274983

Example 375: 6.1 parts of 1-amino-4- (3'-aminomethyl-2 ', 6'-dimethylanilino) anthraquinone-2,6,5'-trisulfonic acid are dissolved in 65 parts of water and at pH 6 acylated with 2 parts of chlorotrifluoropyrimidine. The pg value is adjusted with 2N sodium hydroxide solution. The resulting dye is salted out with 10 parts of potassium chloride and washed with 20% potassium chloride solution. It is dried in vacuo at 60 °. The dye of the formula:

HC ^ S

NI ^ so_8thH

HN

Cl F \ _X

m.NH- (NXN = (^ sq, H colors wool in clear blue shades of good flex and perspiration fastness.

Example 376: 10.6 parts of 1-amino-4- (3'-aminomethyl-2 ', 6'-dimethylanilino) -anthraquinone-2,5'-disulphonic acid are dissolved in 110 parts of water. It is acylated with 4.4 parts of trifluorochloro-10-rimidine at 20 to 25 ° C and a pn of 6 to 6.5. The pg value is maintained with 2N sodium hydroxide solution. After completion of the reaction, the resulting dye of the formula:

_zso₃H

O HN

Cl F \ _x ^ CHj.NH-FN

N =

HjC / '

SO, H salted out with 20 parts of sodium chloride, filtered off with suction and washed with 10% saline solution. The dried at 60 ° C in vacuo dye gives wet or clear on reddish blue cotton or wool

Colorations.

Example 377: 7.8 parts of 1-amino-4- (3'-N-methylaminomethyl-2^., 6'-dimethylanilino) -anthraquinone-2, 6,5'-trisulfonic acid are dissolved in 85 parts of water at 20 to 25 ° C with 2.3 parts

2,4,6-Tiifluoro-5-chloropyrimidine acylated. During the reaction, a pn of 6 to 6.5 is maintained with 2N soda solution. Before the rapid addition of 20 parts of common salt is concentrated with 1 part. Salt20 acid adjusted a pjj of 3.5. Wash with saturated saline. The resulting dye of the formula:

ho₃s

O HN .X like that₃H ^GHsx I _ Cl F

7¾ \ _x

Λ · «- / \ ^N- \ "

H, C · + like that₃H

No. 274983 dyes wool or cotton in wet-fast clear blue tones.

Example 378: 7, 6 parts of 1-amino-4- (3'-N-methylaminomethyl-2 ', 6-dimethylanilino) anthraquinone-2,6-disulfonic acid are dissolved in 250 parts of water and treated with 3.1 parts of trifluorochloropyrimidine acylated under the following conditions: pjj 6 to 6.5, temperature 20 to 25 ° C. It maintains the pjj value by adding 2N sodium hydroxide solution. After completion of the reaction, the mixture is salted with 10 parts of sodium chloride and washed with 2% saline. On cotton or wool you get wet-fast clear blue shades.

By analogy with the procedures described in Examples 375 to 378, when using the components indicated in the following table, likewise valuable dyes are obtained

Dyeing cotton and wool in reddish to greenish blue clear shades:

<td>example No.</td><td>dye</td><td>reactive component</td>

<td>379</td><td>l-amino-4- (3¹ -N-methylaminomethyl-2 ', 6 * -dimethylanilino) -anthraquinone-2,7-disulfonic acid</td><td>2,4-difluoro-5,6-dichloropyrimidine</td>

<td>380</td><td>1-amino-4- (3¹ -N-methylaminomethyl-2^r, 6'-dimethylanilino) anthraquinone-2,7,5'-trisulphonic acid</td><td>2,4-difluoro-6-chloropyrimidine</td>

<td>381</td><td>1-Amino-4- (4'-N-methylaminomethyl-2 *, 6-dimethylanilino) -anthraquinone-2, 6,5 * -trisulfonic acid</td><td>2,4,6-trifluoropyrimidine</td>

<td>382</td><td>1-Amino-4- (3 * -N-methylaminomethyl-2 ', 6 * -dimethylanilino) -anthraquinone-2,6,4'-trisulfonic acid</td><td>2,4-difluoro-5,6-dichloropyrimidine</td>

<td>383</td><td>1-amino-4- (3'-aminomethyl-4¹ -methylanilino) -anthraquinone-2,6, 6'-trisulfonic acid</td><td>2,4,6-trifluoro-5-difluormethylpyrimidin</td>

<td>384</td><td>1-Amino-4- (3-aminomethyl-4'-methyl-amino) -anthraquinone-2,6'-disulfonic acid</td><td>2,4,6-trifluoro-5-trifluoromethylpyrimidine</td>

<td>385</td><td>1-Amino-4- (3'-aminomethyl-4-methylanilino) anthraquinone-2,7,6'-trisulphonic acid</td><td>2,4-difluoro-5-trifluoromethylpyrimidine</td>

<td>386</td><td>1-Amino-4- (3'-methylamino-4-methoxyanilino) anthraquinone-2,7,6'-trisulphonic acid</td><td>2,4-difluoro-5-carbonamidopyrimidin</td>

<td>387</td><td>1-Amino-4- (4-aminoanilino) anthraquinone-2,3 ', 6-trisulfonic acid</td><td>2,4-difluoro-5-chloro-6-phenylpyrimidine</td>

<td>388</td><td>1-amino-4- (3'-aminoanilino). anthraquinone-2, 6-disulfonic acid</td><td>2,4-difluoro-5-cyanopyrimidine</td>

<td>389</td><td>1-amino-4- (4-aminoanilino) -anthraquinone-2,6-disulfonic acid</td><td>2,4-difluoro-5-carbonäthylesterpyrimidin</td>

<td>390</td><td>1-amino-4- (4-aminoanilino) -anthraquinone-2,7-disulfonic acid</td><td>2,4-difluoro-5-methylsulfonylpyrimidine</td>

<td>391</td><td>1-Amino-4- (3'-aminoanilino) anthraquinone-2,7-disulfonic acid</td><td>2,4,6-trifluoro-5-bromopyrimidine</td>

<td>392</td><td>1-Amino-4- (2 ', 4 *, 6 * -trimethyl-3-aminoanilino) -anthraquinone-2,5'-disulfonic acid</td><td>2,4,6-trifluoro-5-chloropyrimidine</td>

Nr.274983