DE1544561A1 - Reactive dyes and processes for their preparation - Google Patents

Description

Reactive dyes and processes for their preparation

The present invention relates to valuable new reactive dyes the general composition

-N OC-

In this formula, P is the radical of an organic dye, m is a number from 0.5 to 4, X is a removable sulfonyl radical, Y is a halogen substituent, preferably Cl or Br, and Z is hydrogen or a substituent.

Λ I

In the dyes of general formula I the N-OC group is on the Amidst ickstoff linked directly to the dye radical F or bonded to the dye radical via a further bridge member, such as an alkylene or arylene radical.

Examples of possible substituents R are: lower ones
Alkyl (preferably
Aryl groups; the amide group is preferably not further in the
substituted Fora -NH- before.

to C ^), aralkyl, cycloalkyl or

ΪΛ A 9912

009815/0698

BATH

As further possible bridging links between the carbonamide nitrogen -N (R) - and the remainder F, the following groups can be mentioned, for example, which are linked to the carbonamide nitrogen -N (R) - on the right-hand side of the following groups: -OC-arylene- ; -OC-alkylene-; -OC-aralkylene; -OC-alkarylene-; -OgS-arylene-; -OgS-alkylene-; -OgS-aralkylene-; -O ₂ S-alkarylene-j - (R) N-alkylene-; - (R) N-aralkylene-; - (R) N-alkarylene-; - (R) NA rylene-; - (R) N0 ₂ S-alkylene-; - (R) N0 ₂ S-aralkylene-; - (R) N0 ₂ S-alkarylene-; - (RjNOgS-arylene-; - (R) N-OC-alkylene-; - (R) N-OC-aralkylene-; - (R) N-OC-alkarylene-; - (R) N-OC-arylene- ; -NN-aralkylene-; -N = N-arylene-.

As reactive sulfonyl substituents X come in the pyrimidine ring lower alkyl sulfone radicals with preferably 1-5 carbon atoms, such as methylsulfonyl, ethylsulfonyl or propylsulfonyl radicals, arylsulfonyl radicals, such as phenylsulfonyl, p-toluenesulfonyl, p-chlorophenylsulfonyl radicals, Aralkylsulfonyl residues, such as benzylsulfonyl and p-toluylmethylsulfonyl residues, and also heterosulfonyl residues, such as 2-benzothiazolesulfonyl, in question.

Among the halogen substituents Y, Cl and Br are of preferred interest. Examples of substituents Z include: halogen, such as -Cl, -Br, alkyl, such as -CH ,, - C ₂ H ^, substituted alkyl radicals, such as -CHgCl, -CHCl ₂ , -CCl ^, -CH ₃ Br, -CH ₂ OCH ₅ ,, -CH ₂ OC ₂ H ₅ , -CH ₂ COOW (W = alkyl or aryl),

Le A9912

009815/0698

-CN, -SO, H, alkenyl groups such as vinyl, allyl, mono- and dichlorovinyl, mono- and dichloroallyl groups, aryl such as phenyl and substituted phenyl groups, alkoxy such as methoxy and ethoxy, aryloxy, alkylthio and arylthio groups * such as methylthio , Ethylthio and phenylthio groups, sulfonyl groups such as -SOgCH ,, -SOgCg-Hc, -SOgCgHc, primary, secondary and tertiary amino and quaternary ammonium groups such as -NHg, ₅ , -N (CH ^) ₂ , -NHC ₂ H ₅ , -N (C ₂ H ₅ J ₂ and -NHC ₆ H ₅ , as well as

Suitable pyrimidine radicals that are reactive in the 2-position Sulfonyl substituents, a halogen substituent in the 4-position and contain a CO group in the 5-position, include, for example: 2-Carbethoxymethylsulfonyl-4-chloro-5-pyrimidine-carbonyl-, 2-methylsulfonyl-6-raethyl-4-chloro or -] f_ brora-5-pyrimidine-carbonyl, 2-phenylsulfonyl-6-methyl-4-chloro-5-pyrimidine-carbonyl-, S-phenylsulfonyl-o-methyl - ^ - chlorine or "4". bromo ^ -pyriraidine-carbonyl-, 2,6-bis-methylsulfonyl-4-chloro-5-pyrimidine-carbonyl-, 2-methylsulfonyl-4-chloro or bromo-5-pyrimidine-carbonyl-, 2-phenylsulfonyl-4-chloro-5-pyrimidine carbonyl, 2-methylsulfonyl-6-chloro-methyl-4-chloro-5-pyΓimidine carbonyl, 2-CaΓbäthoxy-methylsulfonyl-6-methyl-4-chloΓ-5-pyrimidine-carbonyl, 2- (4-nitrophenyl) sulfonyl-4-chloro-5-pyrimidine carbonyl, 2-phenylsulfonyl-6-methoxy-4-chloro-5-pyrimidine-carbonyl, 2-methylsulfonyl-e-phenoxy ^ -chloro-S-pyrimidine-carbonyl.

Le A 9912 0 0 9 815/0698 BAD

The sulfonyl substituents in the pyrimidine ring can be in the aryl, Alkyl or hetero radicals by ionogenic or non-ionogenic Be further substituted groups, e.g. by carboxy- (for example in the form of carboxymethyl-), sulfo-. Hydroxy, nitro or halogen (C1, Br) radicals, such as those in carboxymethylsulfonyl, chloromethylsulfonyl, chloroethylsulfonyl, Hydroxyethylsulfonyl, nitrophenylsulfonyl, sulfophenylsulfonyl groups are present.

The new dyes can belong to the most varied of classes, e.g. the series of metal-free or metal-containing mono- or polyazo dyes, metal-free or metal-containing azaporphine dyes, such as copper or nickel phthalocyanine dyes, the athraquinone, oxazine, dioxazine, triphenylmethane «, nitro, Azomethine, benzanthrone and dibenzanthrone dyes, as well as the polycyclic condensation compounds of anthraquinone, Benzanthrone and Dibenzanthronverbindungen..In the context of these dye classes are among other dyes of the following general compositions particularly valuable.

009815/0698 "

1. Azo dyes

(IH)

m ¹

in which B and represent aromatic, carbocyclic or heterocyclic radicals, in particular B the radical of a carbocyclic diazo component of the benzene or naphthalene series, and D the radical of an enolic or phenolic coupling component, e.g. a 5-pyrazolone, an acetoacetic arylaride, an oxynaphthalene or an aminonaphthalene *, B and D can also have any substituents customary in azo dyes, including further azo groups; ^{R 1 represents} a substituent or preferably a hydrogen atom, m 1 represents an integer from 1 to 2, and

X-, Y and Z have the meanings already given.

Particularly valuable dyes of this series are those that are water-soluble, and especially those that sulfonic acid and / or have carboxylic acid groups. The azo dyes can be both metal-free and metal-containing, with among the metal complexes the copper, chromium and cobalt complexes are of preferred interest.

ο
σ>
co
α>

Important azo dyes are, for example, those of the benzo-azo-naphthalene series, the benzene-azo-l-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azonaphthalene series, of the naphthalene-azo-1-phenylpyrazolone-5 series and the stilbene-azo-benzene series, here too the ones containing sulfonic acid groups Dyes are preferred. In the case of metal complex azo dyes are the metal complex-bound ones Groups preferably in the o-positions to the azo

group, e.g. in the form of 0,0'-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino and o-hydroxy-y'-anuno-azo groups.

2. Anthraquinone dyes

NH,

NH

OC

(IV)

Here L denotes hydrogen or substituents, among these in particular the sulfonic acid group, ρ denotes the number 1 or 3 # R _{1 denotes} a substituent or preferably hydrogen, X, Y and Z have the meanings already given.

Also in the field of these dyes are the water-soluble products because of their excellent suitability for dyeing and Printing of cellulose-containing fibers is preferred, the dyes substituted by sulfonic acid groups proving to be particularly suitable.

3. Azaporphine dyes

Pc

SO ₂ NH J /

-N

OC

(V)

I I

in this formula Pc stands for the remainder of a phthalocyanine, in particular a copper or nickel phthalocyanine or a tetraphenyl copper or nickel phthalocyanine, L for

009815/0698

Le A9912

bath

Hydrogen or a substituent, the sulfonic acid group being preferred as the substituent, r for the number 1 or 2, q for the number 0, 1 or 2, H ₁ for a substitute or preferably hydrogen, X * Y and Z for those already specified meaning, m ^H FTIR a number of 0.5 ~ 4 · The phthalocyanine Pc may of course have weiter® Substitu "ducks, in particular sulfonic acids and Sulfona, miugruppen as -SOjjNHo" -SO ^ NH-alkyl, -SO "N ( alkyl) "" and S0 ₂ NH (aryl) groups? * * ^Ä .

Water-soluble phthalocyanine dyes of the formula V, which are used for Application to cellulose-containing materials are preferred, in particular those which contain sulfonic acid groups in the Pe radical and optionally additionally as substituents L wear.

The previous compilation of a selection suitable azo, anthraquinone and asapozphln dyes are not a restriction on the general formulas represent, namely neither with regard to the preparative possibilities for the preparation of such dyes in the context of the general formula I, nor with regard to the valuable application properties of these products. The new dyes can otherwise have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, alkylamino, aralkylamines), arylamines, acylamino, nitro, cyano, halogen, hydroxy, Alkoxy, thioether, azo groups and the like. The dyes can also contain other fixable groups, such as mono- or dihalotriazinylamino, mono-, di- or trihalopyrimidinylamino, 2,3-dihaloquinoxaline-6-eaΓbonyl- or-6-sulfonylamino-,!, ^ «dihalophthalazine-ö-carbonyl- or -6-sulfonylamino-» 2-halobenzothiazole-5-carbonyl- or -5-sulfonylamino, esterified

Sulfonic acid oxalkyl arid and oxalkyl sulfone groups, sulfofluoride,

009815/0698.

Le A 9912 ^BAD SOiHAl

Haloalkylamino, acryloylamino, haloacyiamino groups and the like.

The new dyes of the formula I are obtained by adding dyes or dye precursors to

Y processes knew at least one group -NOC-γ- ^ ίί (VI),

wherein R is hydrogen or a substituent, X is a removable Sulphonyl radical, Y is a halogen substituent, preferably Cl or Br, and Z is hydrogen or a substituent. If dye precursors are used, these are converted into the desired final dyes. The introduction Group (VI) in dyes or dye precursors can be realized by various preparative methods. So you can use dyes or dyes containing amino or amide groups Precursors that have a reactive hydrogen atom on the amine or amide nitrogen, with connection of the general formula

(VI a)

wherein "halogen" stands for a halogen atom, preferably Cl or Br, X is a removable sulfonyl radical, Y is a halogen substituent, preferably Cl or Br, and Z Hydrogen or a substituent,

implement and in the case of the use of dye precursors convert these in a suitable manner into the desired final dyes.

009815/0698 _{3AD OB! GINAL}

Le A9912

Suitable compounds of the general formula (VIa) are, for example: 2-carboethoxymethylsulfonyl-4-chloro-pyrimidine-5-carboxylic acid chloride, 2-methylsulfonyl-o-methyl ^ -chlor- or ^ - Bromopyrimidine-5-carboxylic acid chloride, 2-phenylsulphonyl-4-ehloro-methyl-pyriraidin ^ -carboxylic acid chloride, 2-ethylsulphonyl-4-bromo-chloro-pyrimidine-S-carboxylic acid chloride, 2-phenylsulphonyl-4,6-dichloro-pyrimidine -5-carbonic acid chloride, 2-methylsulfonyl-6-phenylamino ^ -chloropyriraidin ^ -earboxylic acid chloride, 2-methylsulfonyl-o-carboxymethylmercapto ^ -chloropyrimidine ^ -carboxylic acid chloride, 2,6-bls-methylsulfonyl-4-chloro-pyrimidine -5-caΓbonβ acid chloride, 2-methylsulfonyl-4-chloro-6-phenylsulfonyl-pyrimidine-5-carboxylic acid chloride, S-Nethylsulfonyl ^ -chlor-o-dimethylaminopyriraidln-5-oarboxylic acid chloride, 2-methyleulfonyl-4-chloro-or-4- bromopyriniidin-5-carbone acid chloride, 2-phenylsulfonyl-4-chloro or-4-bromopyrimidine-5-carbone acid chloride, 2-methyleulfonyl-6-chloromiethyl - ^ - chloropyrimidine-S-carboxylic acid chloride, 2-methylaulfonyl-4- chloro-6-phenylmercapto-pyrimidine-5-carboxylic acid chloride, 2-methylsulfonyl ^ -bromo-e-chloromethynyl-pyrimidine-S-carboxylic acid chloride, 2- (4 '-Nitrophenyl) -sulfonyl ^ -chloropyrimidine ^ -carboxylic acid chloride, 2-phenyl · sulfonyl-4-chloro-6-methoxy-or-6-phenoxy-pyriιnidin-5-carboxylic acid chloride, and the corresponding carboxylic acid bromides.

The implementation of dyes containing amino or amide groups or Dye precursors with heterocyclic compounds of the formula (VIa) are depending on the nature of the starting compounds used in organic «organic-aqueous or aqueous medium at temperatures from -10 ° to 80 ° C, preferably in the presence

Le A 99X2

009815/0698

6AD ORSGiNAL

alkaline condensing agents such as pyridine, aqueous alkali carbonate or alkali hydroxide solutions.

When using dye intermediate products, the condensation products obtained are in a conventional manner in. converted to the desired final dyes. This method has a preferred interest in the preparation of azo dyes, for example by using a diazo and / or Coupling component, which has a reactive amino or anide group, initially with the reactive component VIa condensed and the intermediate product obtained then by diazotization and / or coupling and / or condensation In an azo dye. In this · can subsequently further transformation reactions are carried out, as described in Azo dyes are common, e.g. acylation, condensation · Reduction and metallization reactions. Also in the representation of other dyes, in particular those of the phthalocyanine and anthraquinone series, the condensation of a Reactive component VIa first takes place with an intermediate product, e.g. with m-phenylenediamine or an m-phenylenediaainsulfonic acid, and then the reaction product obtained with e.g. bromamic acid (l-amino ^ -broe-anthraquinone ^ -sulfonic acid) to a reactive anthraquinone dye or with Copper or nickel phthalocyanine sulfonic acid halide are further condensed to form a reactive phthalocyanine dye.

The dyes obtainable by the various processes described can, as already in some cases,

00 9 815/0898 8ad original

a 9912

imagines to be subjected to further reactions customary for dyes, for example by metalizable dyes with metal-releasing agents, in this case in particular treated with chromium, cobalt, copper or nickel salts, dyes that have reducible groups, in particular nitro groups, reduced, dyes that have acylatable groups Have groups, in particular acylatable amino groups, acylated, or by subsequently treating dyes with sulfonating agents, such as chlorosulfonic acid, Thionyl chloride, oleum or SO, in chlorinated hydrocarbons to introduce further sulfonic acid groups into the products. The last-mentioned procedure is sometimes peculiar Significance in the series of anthraquinone and phthalocyanine dyes.

Depending on the number of for the conversion reaction into consideration coming reactive -HNR- groups in the Dye residue or in the dye precursors, can incorporate one or more - up to 4 - groupings of the formula (VI) into the dyes.

SAD OBQl ^ AL Le A9912 00901570698

Purely the reaction of dyes containing amino groups with reactive components of the formula (VIa) are, for example, and in many cases preferred, aminoazo dyes of the formula

N D

NH

R ₁

(VIII)

wherein B, D, R, and m ^{1 have} the meaning already given.

or aminoanthraquinone dyes of the formula

(IX)

where L, R, and ρ have the meaning given,

or amino group-containing phthalocyanine dyes of the formula

Pc

SO ₂ NH- <7 ¹ V

-NH I R ₁

(X)

t I

Le A9912

where Pc, L, Fi, q, r and m '' have the meaning already given,

0098 15/0698 - - -, ~

8AD

a. The condensation products obtained correspond to general formula (I) for the new dyes. You can . be subjected to further conversion reactions, in particular subsequent sulfation in the series of anthraquinone and phthalocyanine dyes is often of interest. Instead of using the preformed amino group-containing dyes of the formulas (VIII), (IX), (X) themselves, it is also possible to use Use pre-products containing araino group for the preparation of such dyes, initially with the reactive component (VI a) condense and then further process in a conventional manner to give the final dyes. Such a procedure The dye intermediates are of great interest in the preparation of azo dyes and anthraquinone and phthalocyanines. In the case of azo dyes, this is done by adding a diazo component or a coupling component which has a reactive amino group, condensed with the reactive component of the formula (VI a) and then builds up the desired azo dye by coupling. This can then be re-metallized or diazotized and modified to a disazo or polyazo dye. In the case of anthraquinone dyes, for example, one can be Diaminoaryl compound of which one amino group, e.g. as an acylamino compound, is protected on the second amino group with condense a reactive component (VI a), then convert the first protected amino group into the free amino group, for example by saponification, and the compound obtained, e.g.

^LeA " ¹² 009815/0698 .___., -—,

3AD OPJGlNAL

condense. For the representation of phthalocyanine dyes, similar to what has been done for anthraquinone dyes, initially a monocondensed with the reactive component (VI a) Produce a dlaminoaryl compound and then condense it with, for example, copper or nickel phthalocyanine sulfonic acid halides, simultaneously or subsequently other amino compounds such as ammonia, aliphatic © amino compounds and / or aromatic amino compounds are also used In this way, phthalocyaninesulfonamide dyes are obtained which contain a certain proportion of sulfonarylamide groups which carry the reactive groups and in addition, a certain proportion of non-reactive sulfonamide groups and / or free sulfonic acid groups.

The new dyes are extremely valuable products that suitable for a wide variety of purposes. As water-soluble compounds, they are of preferred interest for dyeing textile materials containing hydroxyl groups and nitrogen, in particular textile materials made from native and regenerated Cellulose, also made from wool, silk, synthetic polyamide and polyunethane fibers. Thanks to the reactive sulfonyl substituent (s) in the pyrimidine ring, the products are particularly suitable as reactive dyes for dyeing cellulose materials according to the Techniques that have recently become known for this purpose. The fastness properties obtained, especially wet fastness properties, are excellent «O draws.

^ To dye cellulose, the dyes are preferably used in

^ an aqueous solution used «the old alkaline reacting

ο substances «such as alkali hydroxide or alkali carbonate, or with in

° Le A 9912 '- -' ^v

iS ■■■■ · ■■ BAD OFIiGlNAL

compounds with alkaline reacting substances »such as Alkali carbonate, can be added. Further auxiliaries can be added to the solution, however, with the dyes should not react in an undesirable way. Such additives are, for example, surface-active substances such as Alkyl sulfates or the migration of the dye prevented substances or dyeing auxiliaries such as urea (to improve the solubility and fixation of the dyes), or indifferent thickeners, such as oil-water emulsions, Tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are on the material to be dyed, for example by padding in the padding (short liquor) or applied by printing, and then some -time at an elevated temperature, preferably 40 to 150 ⁰ C, heated. The heating can be carried out in the hot flue, in the steamer, on heated rollers or by placing in heated concentrated salt baths, either on its own or in any order one after the other.

When using a padding or dye liquor without alkali, the dry goods pass through an alkaline one Solution to which common salt or Glauber's salt is added. The addition of salt reduces the migration of the dye from the fiber,

The material to be colored can also be pretreated with one of the aforementioned acid-inhibiting agents, then with ■■ · ■■ *. » ■ · "

treat the solution or paste of the dye and finally,

0098 15/0698 .- -— ·

Le A 9912; BATH ORIGINAL ■

Mi® indicated * fix at elevated temperature.

Färfo®n sag) long liquor is placed in an aqueous solution of the dye (Flotterwerältnis Is5 to 1 | 4O) at room temperature Gin and dyed for 40 to 90 minutes, behind partial addition of SsIz ₁ , iB sodium sulfate., And then alkali, for example BJat ^ iumptaosphateiii, sodium carbonate., MaOJi or KOH. This is where the chemical reaction occurs between the dye and the fiber. After chemical fixation of the dyed material is rinsed hot and finally soaped, which remains unfixed dye are removed "This gives excellent real, especially NAS and light-fast staining.

In the so-called cold padding process, subsequent heating of the padding fabric can be saved by storing the fabric for some time, for example 20 to 40 hours, at room temperature. In this process, the same alkali or a stronger alkali than in the dyeing process described above from a long liquor is used.

For printing on materials containing hydroxyl groups a printing paste made from the dye solution, a thickener such as sodium alginate and an alkaline compound or a compound that splits off alkali when heated, such as sodium carbonate, Sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium carbonate are used and the printed material is rinsed and soaped.

009815/0698

- 17 »- 1

Contain the dye® isiet & llkoniplexbllfäcl® grouping & cgenp go. The dyeings and prints can often be post- treated with metal-releasing agents _s wi © copper algae «. '"are" chromium, cobalt and Nlefcelsalzen as Chrocoacetat,' Kobaltsulfa-t or nickel sulfate, 'in their fastness improved g> B reulf © f _{s "e} Kwpf'.:

Textile material containing amide groups! © »* like. Wool, silk, synthetic polyamide and polyurethane fibers, are generally used according to the usual dyeing methods in acidic to colored neutral area, sometimes a final increase in the pH of the dye tape, e.g. to pH 6.5 to pH 8.5 is beneficial.

The dyes are applied, for example, to synthetic polyamide fabric as solutions or preferably in dispersed form and then, optionally together with (preferably smaller amounts) acid-binding agents, such as sodium carbonate, post-treated. Particularly favorable results are achieved with those dyes that are difficult or impossible to use Are soluble in water. These are customary in themselves Techniques and processed into a dye dispersion with the addition of the known auxiliaries and as such in the dyeing and / or block tape or applied in a printing paste. the Suitable auxiliaries for this application include compounds that prevent the migration of the dye on the fiber, such as cellulose ethers, alkali metal chlorides and sulfates, wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulfonated fatty alcohols, solvents such as thiodlglylcol, also thickeners such as starch, tragacanth,

009815/0698 \. v.

Le A 9912 BADORfGINAt

around.

The Ha © hbehaE ^ liaBg a @ r dyed on polysside fiber fabric

iKiprSgnlerungen and! Draek © preferably takes place at temperature of 50 to 110 ° C and "lit for a period of 5 to 60 Miputesio Aiseh herein may © di dyes for the case in which di @ vei'wenäeten dyes raetallkosiplexbildende groups © ^ nth lteug with Rsetallabgebendera Mittsln as Copper salts, for example copper sulphates or chromium, Kotelt and nickel salts, such as Chromaoet & t, cobalt sulphate or nickel sulphates, are sometimes improved in their fastness properties. .

Draw the colors available with the new dyes lip is generally characterized by good to very good fastness properties, in particular through excellent sewing fastness.

The dyes show a considerably higher reaction rate with the fiber as corresponding halogen compounds. Reactive dyes, which instead of in the pyrimidine ring of reactive sulfonyl groups have halogen substituents.

^LeA9912 .

009815/0698

45

In the following examples, file _ΰ, unless otherwise stated, is ₅ for Gewi -eht stell® ₀ "...

Example 1 ' - .....

Solution tone 34 »7 parts. sulfonic acids ^ sodium and 7 parts of sodium anitrite ia 306 for water are added. Ice cooling 28 loliistGil © kosas @ äts hydrochloric acid and stir the mixture 1/2 Stiaade feel © ~ 1Q ^C After excess nitrous acids have been removed, 10.7 "parts of 3-Aüinotoliiölρ dissolved Ia 10 concentrated - hydrochloric acid and. 150 ropes of water _{9 are} added - nai the clutch by blunting of the mixture leads AAF pH 3 ■ -. 5.ZU end the resulting Aainoaaofarlsstoff w salted ± TAE, suction filtered, washed uad öaaa - ?? ieier In 70Ö parts of water and sodium hydroxide solution yon he ± pH 7 dissolved .! the aqueous .Lösung is then with 26 .Teilen 2-ifiethy sulfonylö-chloT-pyriinidin-S-carbonsäureehlorid T@rse.tzt and stirred vigorously "" the temperature of the Heaktiomsgemiseiies is held h® ± ea "■ 35 ° C; one dulls the released Salasäiaar © with soda solution until the reaction has ended = the dye of the probable formula

SO ^ Well

is salted out with 80 parts of sodium chloride, pressed ₉ washed and dried at about 30 ° C in a vacuum, jär is a yellow powder that is soluble in water with a yellow color.

When printing cellulose fabric with a printing paste, those in the kilogram 15 grams of the dye, 100 g Urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate per kg thickening), 2 g sodium hydroxide and

Le A9912

. . 009815/0698 sad

10g sodium carbonate and was filled up with water to 1 kg, dry, 8 minutes, "damps at 105 ⁰ C, rinsed with hot water and soaped boiling, one obtains a strong reddish yellow print of good wash and light fastness.

Example 2

0.1 mol of the copper complex compound of the formula

NaO ₃ S

SO ₃ Na

NaO ₃ S

(prepared according to the information in German Patent 1,117,235) by coupling diazotized 1-amino-8- (benzenesulfonyloxy) -naphthalene-disulfonic acid- (3,6j in an alkaline soda medium with the equivalent amount of 2-acetylamino-5-hydroxynaphthalenedisulfonic acid- (4.8), conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysis of the acetyl and the benzenesulfonyl group) are dissolved in 25OO parts by volume of water at 35 - 40 ⁰ C at pH 6 - 6.5 and at this temperature with 0, 12 mol of 2-methylsulfonyl-6-chloro-5-pyrimidinecarboxylic acid chloride are added.

During the condensation, sodium carbonate solution is added a pH of 6 - 6.5 is maintained. After the reaction has ended, the dye is salted out and isolated. When dried, the dye is a dark powder that dissolves in water with a blue color.

Le A 2 ^ 1

009815/0698

bath

100 parts by weight of a cotton fabric are fouladed at room temperature with an aqueous solution containing 2% of the dye 15 g / l sodium hydrogen carbonate and 150 g / l urea, dried in between, heated to HO ⁰ _{C for} 10 minutes, then rinsed and soaped at the boil. Bas fabric is dyed wetfast in very clear blue tones.

Example 3

46 parts of the method similar to that in Example 1 by coupling diazotized 2-aminonaphthalene-4,8-di3ulfonsäure 3-methylamino-toluene obtained monoazo dyes are dissolved in 400 parts of water, 30 to 35 ⁰ C at pH 6 - 7 and in the presence of dissolved of excess sodium acetate or calcium carbonate partially mixed with a total of 26 parts of 2-methylsulfony1-e-chloro-pyrimidine-S-carboxylic acid chloride and stirred at this temperature until a sample no longer changes color when acidified. The resulting dye of the likely formula

S0, well

.N = N- ^

is salted out, filtered off with suction, washed and dried.

Impregnating cotton fabric with a solution of 20-25 ⁰ C, the g per liter of liquor 20 of the above dyestuff and 0.5 g of niehtionogenen wetting agent contains (e.g., a polyoxäthylierten oleyl alcohol.) And 150 g of urea and 15 g Natriumblcarbonat. The fabric between two rubber rollers to a moisture content of about 100 i "is squeezed. After intermediate drying at 50 -

Le A9912

0 0 QS 1 ^{5/0 6 9 8 BAD 0RiGlislÄL}

60 C is ^{heated to HO 0} C for 10 minutes and the dye obtained in this way is rinsed thoroughly with white water and treated at the boil for 20 minutes with a solution which contains b g of Maraeiller soap and 2 g of soda per liter. After rinsing and drying, a strong reddish yellow coloration of good wet, rub and lightfastness is obtained.

The following table shows the mazo components, Coupling components and those with the amino group linkable reactive components listed, from which dyestuffs are built up analogously to the information in the examples 1-3 whose color tones - obtained using one of the application methods described - are also shown in the table are recorded.

Abbreviations for

the reactive components: A = 2-methylsulfonyl-6-chloro

pyrimidine-5-carboxylic acid

chloride

B · - 2-Ethylsuii'onyl-tj-chloropyrimidine-5-carboxylic acid chloride

Example reactive

No. Diazo component, coupling component, composite color

'nente

4 2-aminonaphthalene-1-amino-2-methoxy-A yellow 4,8-disulfonic acid 5-methylbenzene

5 μ «β Μ

6 1-aminonaphthalene-1-amino-3-methyl-A " 3 »6-diaulfonic acid benzene

j η ti g «

8 2-aminonaphthalene-i-amino-3-methyl-A ⁿ 5,7-disulfonic acid benzene

q n ■. η B "

2-aminonaphthalene-1-amino-3-a »thy1-A ^w 6,8-disulfonic acid benzene

w «B"

Le A9912. . BATH ORIGINAL '

-00-98-15 / 0698

Example reactive

No. Diazo component, coupling component, composite color

■ - ·. . -. . nent

12 4-Aminoazobenzene-i-amino-3-methyl-A brown-3,4'-di-sulfonbenzene yellow acid

13 i-aminobenzene-4-i-amino-3-methyl-B ^M sulfonic acid * ■ benzene

1-aminonaphthalene-6-sulfonic acid

14 2- (3 ¹ -Sulfö-4 ^l - i-Amino-3-methyl-A yellow aminophenylj-6-benzene
methyl-benzthiazole-

7-sulfonic acid

15 2-aminonaphthalene- i-methylamino-3-B * 418-disulfonic acid metkoxybenzene

16 "i-Amino-3-acetyl-A"

aminobenzene

17 '- ". Aniline A"

Example 18

In the solution of 36.5 parts of the sodium salt of i-amino-e-hydroxynaphthalene-? Ι6-disulfonic acid in 100 Teilet water with thorough stirring at 30-4O ⁰ C 26 parts of 2-methyleulfonyl-6-chloro-pyrimidine-S -carboxylic acid chloride entered and stirred with constant blunting of the released hydrochloric acid to pH 6-7 until no free. Amino group more, is detectable. The dye intermediate product thus obtained is, after dilution with 600 parts Wasservund addition of 12 parts sodium carbonate for 5 - 10 ⁰ C with I7 _f 5 parts of diazotized 2-aminobenzene sulfonic acid, solved in 200 parts of water coupled. The dye of the formula which is formed at a final pH of approx. 7

Le A9912

0OÖ81 S / 0898 - - ■ - - -.

BATH ORIGINAL

is salted out with 100 parts sodium chloride, filtered off with suction, washed and dried at 30 - 40 ⁰ C in vacuo. The dye forms red needles with a metallic sheen, which easily dissolve in water with a red color.

Is made of cotton or regenerated cellulose dyed or printed with this dye by one of the processes described in Examples 1-3, is obtained clear bluish red dyeing and prints of good wet, rub and lightfastness.

Equally good results can be obtained using the following procedure:

50 grams of cotton hank are dyed in 1 liter of a dye liquor containing 1.5 g of the above dye by increasing the temperature from 20 ^° C. to approx. 80 ^° C. within 30 minutes, a total of 50 g of table salt in several portions is added, then 20 g of soda are added and treated for 60 minutes at this temperature. After rinsing, boiling soaps and drying, a bluish red dyeing of good wet, rub and lightfastness is obtained.

The following table shows the other colors Dyestuffs listed, those from the also listed diazo components, coupling components and with the amino group in the latter linkable reactive components analogously to the information in Example 18 - or by conversion the corresponding aminoazo dyes with the reactive components

009815/0698

nents - to be built and according to one of the above Processes that can be dyed or printed on cellulosic materials:

Abbreviations for the reactive components as in the table for example 3

at
game
No. Diazo component Coupling component Reactive-
kompo- shade
nent 19th 1-aminobenzene-2-
sulfonic acid 1-amino-8-hyd roxy-
naphthalene-3 »6-di-
sulfonic acid Bread 20th Aminobenzene 1- (3'-aminobenzoyl-
amino) -8-hydroxy-
naphthalene-3,6-di-
sulfonic acid A ^w 21 η - H B " 22nd 1-amino-2-carb oxy-
benzo1-4 sulfone
acid 1-Amlno-8-hydroxy-
naphthalene-3 »6-d i-
sulfonic acid A ⁿ 23 1-amino-4-methyl-
benzene-2-sulfone
acid M. A ^w 24 1-amino-3-acetyl-
amina-benzene-6-
sulfonic acid Il B ^Λ 25th I-Amino-SU ¹ - ^? "-
sulfοphenyIamino7-
4 ^f -chiortriazine- Il A ⁿ aminobenzene-6-sul-
fonic acid 26th 1-aminobenzene-2-
s-sulfonic acid 2-amino-5-hydroxy
naphthalene-7-sul- A orange

26 a

1-amino-3- (2 · - ^ 4
sulfοphenylamino / -4'-methylaminotriazine-1 ¹ , 3 », 5 * -
yl-6 ¹ ) -aminobenzene-6-sulfonic acid

fonic acid

2-amino-5-hydroxynaphthalene-7-sul-

fonic acid

Le A9912

009 815/0698

BATH ORIGINAL

15A4561

Example diazo component no.

Reactive-

Coupling component composite color

nent

28 29

1-aminobenzene-2-sulfonic acid

1-Amino-4-acetyl 1-amino-6-sulfonic acid

2-methylamino-5-hydroxy-naphthalene-7 sulfonic acid

2-Amino-5-hydroxynaphthalene-7-sulfone

acid

orange

Scarlet fever

Example 30

In the solution of 21 parts of the sodium salt of 1, i-diaminobenzene-e-sulfonic acid in 100 parts of water with thorough stirring, 26.0 parts of 2-methylsulfonyl-6-chloropyrimidine-5-carboxylic acid chloride entered and at 35 - 40 C with constant blunting of the hydrochloric acid released pH 7 - 8 stirred until a sample is diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid a clear, yellowish red color. The resulting intermediate dye is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid after adding ice and then with a submitted solution of 47 parts of the sodium salt of i-benzoylamino-8-hydroxynaphthaiin-3f6-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye formula

SO ₃ Na

HO NH-OC-C ₆ H ₅

NaO ₇ S

, N

Le A9912

009815/0698

takes place, which is salted out, vacuumed, washed and at 30 - 40 ° C is dried in a vacuum. The dye dissolves easily in water with red color and delivers after one of the Process described above clear bluish red dyeings and prints on cellulose materials.

The following table shows the colors and the pH value of the coupling medium of dyes listed, analogous to the information in Example 30 from a diazo component, which contains a further, preferably acylatable amino group, from a coupling component and from one with the Diazo component linkable reactive component are produced. For dyeing and printing cellulose materials the methods mentioned above can be used with the dyes in the table.

Abbreviations for the reactive components as in the table to example 3

At- reactive- pH of the dye-

game diazo component coupling component compo- coupling No. nente mentation

inediums

31 1,3-diaminobes
zol-4-sulfone
acid 2-aminonaphthalene
5,7-disulfonic acid A. 4-5 orange 32 η 2-aminonaphthalene
3,6-disulfonic acid A. 4-5 η 33 ti 2-aminonaphthalene
6-sulfonic acid B. 4-5 η 34 t
η 2-N-methylamino-8-
hyd roxynaphthaiin-
6-sulfonic acid A. 4-5 η 35 1,3-diaminobes
zol-4-sulfone
acid 2 -thiazole-4'-carbon-
amide ο) -8-hydroxv- A. 7-8 Red

yy naphthalene-3 »6-disulfonic acid

1_ (2 ", 4'-Dihydroxy-B triazine-1 *, 3 ', 5 ^f , -yl-6 * -amino ) -8-hydroxynaphthalene-3,6-disulfonic acid

009815/0698

7-8

^{BAD 0} ^ gial

Le A9912

E.g. Diazo component, coupling component, reactive pH of color no. compo- coupling

ment medium

37 1,3-diaminobes
zol-4-sulfone
acid 1- (3 ', S'-dichloro-T,
2'-thiazole-4'-car-
bonamid ο ) -8-hydroxy
naphthalene- 3,6-di-
sulfonic acid A. 7-8 Red 38 Il 2-Hydroxynaphthalene-
3,6-disulfonic acid A. 8th sharp
laugh 39 It i-acetylamino-8-hy-
droxy naphthalene
3,6-di aulfonic acid B. 7-8 Red 40 Il 1- (3'-sulfophenyl-
3-methyl-pyrazolone-5 A. 6th yellow 41 N 1- (2, 5'-dichloro-4'-
sulfοphenyl) -3-methy1-
pyrazolone-5 A. 6th yellow 42 Il 1- (5 ^f , 7'-DiSuIfO-
naphthyl-2 '-) - 3-
methyl-pyrazolone-5 A. 6th yellow 43 η 1_ (3i_sulfophenyl) -
3-methyl-5-amino
pyrazole B. 6th yellow 44 1,4-diaminobes
zol-3-sulfone
acid 2-amino-8-hydroxy
naphthaiin-6-sulfone
acid A. 4-4.5 Red 45 1,4-diaminobes
zol-3-sulfone
acid 2-acetylamino-5-hy-
droxy naphthalene
7-sulfonic acid A. 6-7 sharp
laugh 46 Il 1-acetylamino-5-hy- B. 6-7 Red

d roxy-na phthalin-7-sulfonic acid

Example 47

51.6 parts of that obtained by diazotizing 1-hydroxy-2-aminobenzene-4-sulfonic acid and coupling on 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a Kupi'erabgebenden Means obtained dye of the formula

009815/0698

Le A9912

bath

SO, well

are dissolved in 1500 parts of water at pH 7. With thorough stirring contributes 35-40 ⁰ C 26.0 parts of 2-MethyIsulfonyle-chloro-pyrimidin-S-carboxylic acid chloride and blunts the hydrochloric acid liberated with sodium carbonate solution resulting in a pH 6 - 8 from. When free amino groups can no longer be detected, the reactive dye formed is of the formula

Cu - 0

SO ₂ CH ₅

Cl

salted, pressed, and dried in vacuo at 30 ⁰ C 40 dried. Fabrics made of cellulosic materials can be dyed or printed with this dye by one of the above-mentioned processes in wet, rub and lightfast ruby tones.

The following table shows the heavy metal complexes of other aminoazo dyes and those with the amino group linked reactive components as well as the color tones of these dyes on cellulose materials. the Production of the aminoazo dyes, their metal complexes and their conversion with the reactive components can be carried out analogously to the Details are given in Example 47.

Le A9912

009815/0698

BAD OPJGlNAL

example

Sr. Aminoazo Dye Complexed θ heavy metal

Reactive component

hue

• χ *
ο
σ »

48.

49 50

51 52

53

54 55 56

57 58

1-Hydroxy-2-aminobenzene-4,6-disulfonic acid > 2-Amino-5-hydroxynaphthalene-7-sulfonic acid

1-Hydroxy-2-aminobenzene-4-sulfonic acid

2-Ethylamino-5-hydΓoxynaphthalene-7-sulfonic acid

i-Amino ^ -hydroxy-e-nitronaphthalene ^ -sulfonic acid - + 2-amino-5-hydroxynaphthalene-7-sulfonic acid

1-Amino-2-hydΓoxy-6-nitronaphthalene-4-sulfonic acid »I-Amino-8-hydroxynaphthalene-4-sulfonic acid

1-Amino-2-hydroxy-5-methylsulfonyl-benzene

► i-Amino-ehdhlJei

sulfonic acid

ι-ΑΓιίί o-k'-riethylhenzene-4-sulfonic acid —— ♦

1-Air.iiic-i-hydroxy-5-methy! Benzene *

1 -Aiuir.o-8-h> droxy naphthalene-4 ₁ 6-disulfon-3 acid Cu Cu

. Cu

Cr Co

Cu

Co Cr Cu

Co Cr

rub in

rub in

rub in

greenish VjI
O A. reddish s I.
Gray B. violet black A. Gray A. greenish A. blue a chwars B. Gray B. greenish A. black: cn
.O...,.

cn

example
No.

Aminoazo dye

complex-bound heavy metal

Reactive component

hue

O CD (O OO

59

60 61

62

63

(1-Amino.-2-chlorobenzene-4-8ulfonic acid +

1-hydroxy-2-acetylaminobenzene) _f saponified

»I-Amino-e-hydroxynaphthalene-Sfo-disulfonic acid

i-Amino-e-hydroxynaphthalene-A-sulfonic acid <1-Hydroxy-2, o-diaminobenzene- ^ sulfonic acid ■ 1,3-dihydroxybenzene

1-Amino-e-hydroxynaphthalene-S> 6-di sulfone

acid » 1-hydroxy-2,6-diaminobenzene-4-

sulfonic acid > 2-hydroxynaphthalene

i-Amino-S-hydroxynaphthalene ^ -sulfonic acid ♦ -— 1-Hydroxy-2,6-diaminobenzene-4-sulforic acid 1 3-methylpyrazolone- (5j

Cu

Co Co

Co Co

A A

navy blue

grey black

cn CT)

- .32 -

Example 64

96 parts (based on 100 # stock) α it in usual Way by exposure to chlorosulfonic acid and thionyl chloride copper phthalocyanine tetrasulfochloride freshly prepared on copper phthalocyanine or of the isomeric from 1-sulfobenzene-3 »4-d! carboxylic acid via the corresponding Copper phthalocyanine tetrasulfonic acid built up copper phthalocyanine tetrasulfochloride are in the form of the moist,

· I ^un - ^d 500 Te ilen ι

The well-washed suction cake was suspended in 500 parts of water, the solution of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonic acid in 500 parts of water was added and the pH was adjusted to 8.5 with soda. The suspension is stirred for 24 hours at room temperature and the pH is always kept at 8.5 by continuously adding soda. The condensation product formed is precipitated at pH 1-2 by adding sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral. In the blue solution, 75 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride are added with vigorous stirring and under constant blunting with sodium carbonate solution to pH 7 - stirred 40 ⁰ C until no more free amino groups - 8 as long as at 35 are detectable. The reactive dye of the formula obtained in this way

(SO ₃ KaJ _n

Cu phthalocyanine

O ₂ CH ₃

4 - η η r ^ 2

is salted out, washed and dried at 30 - 40 C in a vacuum. It is a dark blue powder that is soluble in water with a blue color and dyes cotton and regenerated

Le A9912

009815/0698

bath

15U561

cellulose by one of the above-mentioned dyeing or printing processes in clear blue tones of good wet, rub and light fastness.

Instead of the 96 parts of copper phthalocyanine tetrasulfochloride can - with otherwise the same working method as in example 64 - also 87 parts (based on 100% goods; of the copper or nickel phthalocyanine trisulfochloride obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine can be used in the form of the moist absorbent cake washed well with ice water; you get then also clear blue coloring reactive dyes

Even if you work as indicated in Example 64, but start from 87 parts of copper phthalocyanine ^ t risulfochlorid and instead of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonyl acid 90 parts of the sodium salt of 4,4 ^l -diamino-diphenyl -2.2 ^l -disulfonic acid or 90 parts of the sodium salt of 4,4'- ^{diaminostiloen-2,2 1} -diaulfonic acid are used, reactive dyes are obtained which, by one of the processes mentioned above, give clear, wet, rub-fast and light-fast cellulose materials color blue tones.

Assuming 4 ^l _> 4 ^M , 4 ⁿⁱ , 4 "" - tetrapheny1-Cu-phthalocyanine, sulfochlorination and conversion with 1,3-phenylenediamine-4-3ulfonic acid and acylation with 2-methyl-sulfonyl-6 are obtained -amino-pyrimidine-4-carboxylic acid chloride a reactive dye which dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.

Le A9912

BAD ORJGiNAL

009815/0698

15U561

Example 65

Dissolve 71 parts of by conversion of 1-amino-4-bromoanthraquinone-2-sulfoneäure with excess 4.4 * -Diaminodiphenyl-2,2'-disulfonic acid obtained Aminoanthrachinonfarbstoffe in 700 parts of water, contributes 35 - 40 ⁰ C under good Stir in 26 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride and maintain a pH of 6-6.5 by continuously adding soda solution. When no more amino groups can be detected, the resulting dye is of the formula

SO ₂ CH,

salted out, filtered off with suction, washed and dried at 30 - 40 ⁰ C in vacuo. It dyes cotton and regenerated cellulose according to one of the processes listed above in wet, rub and lightfast blue tones.

If one proceeds as indicated in Example 65, but instead of 71 parts of the starting dye used there, equivalent amounts of one of the following derivatives of 1-amino-4- (aminoarylamino) -anthraquinone-2-sulfonic acid are used, similar dyes are obtained, whose also blue Dyeings have fastness properties similar to those of the dye obtained above: 1-amino-4- (4'-amino-2 ^l -8ulfopheny! AminoJ-anthraquinone-2-sulfonic acid, 1-amino-4- (4 ¹ -aminophenylamino) anthraquinone -2,6-disulfonic acid, mixture of isomers of 1-amino-4- (4 ¹ -aminophenylaminoi-anthraetiinOn-

^{16 A} " ¹² 009815/0698

-2,5- and -2 _t 8-disulfonic acids mixture of t-amino-4-.4 * -amino-2 ^l -sulfophenylamino) -anthraquinone-2 , 5- and -2 * 8-disulfonic acid, mixture of isomers of 1- amino-4- (3 ^t -aminophenylamino) anthraquinone-2 "-2 and 5-» 8-disulphonic acids, 1-amino-4- (3'-aminophenylamino) -anthraquinone-2 "6-disulfonic» 1-amino-4 -C3 * -amino-4 * -sulfophenylamino) -an thraquinone-2-8ulfonic acid. With t-amino-4- (4 ^t - /? ^L * -amino-2 ^lt -sulfophenyl7-aminophenyl) -anthraquinone-2,6-di-sulfonic acid, reactive dyes with a bluish gray color are obtained.

Example 66

If one proceeds as indicated in Example 47, but instead of the copper-containing amino monoazo dye used there, the equivalent amount of the chromium complex of the i-aminoe-hydroxy ^ -chlorobenzene-5-sulfonic acid obtained by coupling with 1- ^ ^l - (3 "- -Aininophenylj _i 7-sulfonylimido-sulfonyl-phenyl-3-n »ethyl-pyrazolone- (5) obtained aminoaeo dyestuff» thus one obtains a reactive dyestuff t which cellulose materials by one of the processes given above in good wet, rub- and lightfast yellow-brown Tones colors.

Example 67

0.1 mol of the copper complex compound of the formula . HO-S

HO, S O-Cu-O

are dissolved in 3000 parts by volume of water at pH 6 and with stirring at a temperature of about 4O ⁰ C with 26 weight

0 0-9815 / 0698- - -— »

^{A 9912 p} - "0 ORIGINAL

15U561

(0.1 mol of 2-methylsulfonyl-6-chloro-pyrimidine - ^ - carboxylic acid chloride combined. The mixture is stirred until
the condensation has ended and the dye is added
deposited and isolated from a little sodium chloride. Of the
The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained which dissolves in water with a green color and dyes cotton in green shades according to the procedures given in Examples 1-3.

Cotton fabric is impregnated with a solution at 20-25 ° C. which contains 25 g of the above dye and 5 g of a nonionic wetting agent per liter of liquor (e.g. a
polyethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate. The fabric is then placed between two rubber rollers to a moisture content of
about 100 i » squeezed off. After intermediate drying at 50 60 ⁰ C for 10 minutes at 140 ⁰ C is heated and purged the coloration thus obtained thoroughly with hot water and for 20 minutes boiling with a solution containing per ^ iter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and
Drying gives a green color of good wet,
Rub and light fastness.

Even after another dyeing or printing process described in Examples 1-3 »18 and 30 it is obtained
cellulose materials have clear green tones with good fastness properties.

Le A9912

009815/0698 ^bathroom

.37-154456t

Example 68

0.1 mol of the paste of the aminoazo compound of the formula SO ₅ H

which is obtained by coupling the diazonium compound from 6-acetamino-2-amino-naphthalene-4,8-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex are in 2000 parts by volume of water at pH 6.5 dissolved and combined with 28 parts by weight of 2-Xthylsulfonyl-6-chloropyrimidine-5-carboxylic acid chloride. The Reaktionsgemiach is at 35 - 40 ⁰ C stirred, until the condensation completed, the pH of the reaction solution is maintained at 6-6.5 by addition of soda. When the reaction has ended, the dyestuff is salted out, isolated and dried in vacuo.

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

Example 69

27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-aulfonsaures sodium are dissolved in 1 50 parts of water, mixed with 28 parts of S-ethylsulfonyl-o-chloro-pyrimidin-S-carboxylic acid chloride and at 35-40 ^u C Stirred with a total of 30 parts by volume of 16% soda solution to pH 5-6 while constantly blunting the acid released. After a short time, the acylation is over, the pH is 5 and no longer changes

Le a 9912 009815/0698

BATH ORIGINAL

- J58 -

Jüan are then to 30 parts of sodium bicarbonate and allowed at 2O ⁰ C within 15 minutes from the Diazosuapension part 34 end of the disodium salt of 2-aminonaphthalene-1, 7-disulfonic acid in 200 parts of water are added dropwise. The orange reactive dye of the formula which was formed immediately

S0, well

SO ₂ CH ₂ CH ₃

01

is completely deposited by stirring for one hour by adding 80 parts of sodium chloride, filtered, washed with dilute sodium chloride solution and dried at 35 ⁰ C in vacuo. It dyes cellulose materials in reddish orange tones with very good wet fastness properties and good chlorine resistance using the above-mentioned processes.

In this example, 2-ethylsulfonyl-6-chloro-pyrimidine-5-carbon chloride is used instead of 28 parts by weight equivalent amounts of 2-methylsulfonyl-6-chloropyrimidine-5-carboxylic acid chloride, in this way an orange reactive dye and its coloring behavior are obtained corresponds to the reaction product of the ethylsulfonyl derivative, speaks.

In an analogous manner, acylation of the in Column 3 of the table below listed aminonaphthenol sulfonic acids with 2-methylsulfonyl-6-chloro-pyrimidine-4-carbon ~ acid chloride and coupling of the acylamino-naphtholsulfonic acids formed with the diazo components mentioned in column 2, orange to red reactive dyes.

009815/0698

Example,

No. diazo component

Shade on aminonaphthol sulfonic acid cotton

70 2-aminonaphthalene-2-ethylamino ~ 5-hydroxy-orange 1,7-disulfonic acid naphthalene-7-sulfonic acid

71 ^M 2- (ß-Kydroxyäthylamino) ~ "

S-hydroxynaphthaliri -? - sulfonic acid

72 "2-amino-5-hydroxynaphtha- ^M

lin-7-sulfonic acid

73 "2-Amino-5-hydroxynaphtha-"

lin-1,7-disulfonic acid

74 "2-amino-8-hydroxynaphtha-scarlet fever

lin-6-sulfonic acid

75 "2-Amino-8-hydroxynaphtha-" ·

lin-3 »6-di sulfonic acid

76 2-aminonaphthalene-2-methylamino-5-hydroxy-orange 1 _t 5-disulfonic acid naphthaline-7-sulfonic acid

77 "2-Ethylamino-5-hyäΓOxy-"

naphthalene-7-sulfonic acid

78 "2- (ß-Hydroxyäthylamino) -"

5-hydroxynaphthalene-7-sulf ons acid '

79 ⁿ 2-amino-5-hydroxynaphtha- "

lin-7-sulfonic acid

80 ⁿ 2-amino-5-hydΓoxynaphtha- "

lin-1,7-disulfonic acid

81 2-aminonaphthalene-2-amino-8-hydroxynaphtha-scarlet fever

1,5-disulfonic acid lin-6-sulfonic acid

82 ^w . 2-amino-8-hydroxynaphtha- "

lin-3,6-disulfonic acid

83, 2-aminonaphthalene-2-amino-5-hydΓoxynaphtha- orange

1.5 »7-trisulfon-lin-7-sulfonic acid
acid

84 "2-Methylamino-5-HydroIy-"

naphthalene-7-sulfonic acid

85 ⁿ 2-amino-8-hydroxynaphtha-scarlet fever

lin-6-sulfonic acid

Le A9912

009815/0698

Ex.
No. Diazo component 86 2-aminobenzene
sulfonic acid 87 η 88 η 89 ti 90 H 91 2-aminonaphthalene
1-sulfonic acid 92 93 2-aminonaphthalene
1,5-disulfonic acid 94 η 95 ti 96 2-aminonaphthalene
1,7-disulfonic acid 97 ti 98 N 99 2-aminonaphthalene
115 »7-trisulfone
acid 100 1-amino-4-chloro
benzene-2-sulfone
acid

Shade on aminonaphthol sulfonic acid cotton

2 ~ methylamino-5-hydroxy-orange naphthalene-7-sulfonic acid

2- (ß-Hydroxyethylamino) - "5-hydroxynaphthalene-7-sulfonic acid

2-amino-8-hydroxynaphtha-scarlet fever lin-6-sulfonic acid

2-amino-8-hydroxynaphtha- " lin-3,6-disulfonic acid

2-amino-5-hydroxynaphtha- orange lin-1,7-disulfonic acid

101 1-Amino-2-methoxybenzene-5-sulfonic acid

102 i-Amino-benzene-2-carboxylic acid-4-sulfones acid 1-amino-8-hydroxynaphthalene-316-d isulfonic acid

1-Amino-8-hydroxynaphthalene-4t6-disulfonic acid

i-Amino-8-hydroxynaphthalene-3 »6-disulfonic acid

1-amino-8-hydroxynaphthalene-4,6-disulfonic acid

1-amino-8-hydroxynaphthalene-6-sulfonic acid

1-Amino-8-hydroxynaphthalene-3 1 6-d isulfonic acid

1-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

1-amino-8-hydroxynaphthalene-6-sulfonic acid

1-amino-8-hydroxynaphthalene-6-sulfonic acid

1-Amino-8-hydroxynaphthalene-3 f 6-d isulfonic acid

1-Amino-8-hydroxynaphthalene-3 »6-disulfonic acid

1-Amino-8- hydroxynaphtha lin- 3 f 6-diaulfone acid

bluish red

Le A9912

009815/0698 ^bath

Example color shade aif no · Diazo component aminonaphtholaulphonic acid cotton

103 i-Amino-4-acetyl-i-Amino-8-hyaroxynaphtha violet aminobenzene-2-lin-3 »6-disulfonic acid sulfonic acid

104- "i-amino-8-hydroxynaphtha- bluish tinge-

lin-4,6-diaulfonic acid gea red

Le A 9912 009815/0698

15U-561

Example 105

56.8 parts of the diaminoaz of dye obtained by coupling diazotized 1-amino-3-acetylamino-benzene-6-8ulfonic acid to 2-aminonaphtha-lin-5f7-disulfonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are obtained in pH 7 dissolved in 450 parts of water. After addition of 26.0 parts of 2-methylsulfonylo-chloro-pyrimidine-5-carboxylic acid chloride, the acidic solution is constantly blunted and the mixture is ^{stirred at 40 °} C. for about one hour with soda solution to pH 6-7. When the acylation has ended, the reactive dye formed becomes the formula

NH,

NaO ₃ S

salted out, filtered off, dissolved nor male in 4000 parts water at 30 ⁰ C, filtered, and precipitated from the filtrate by addition of 400 parts of sodium chloride in completely pure form. Like it), the dye is ^{dried at 35 °} C. in a vacuum. It dyes cellulose materials in real yellowish orange tones according to one of the processes mentioned above.

Example 106

26 parts of 2-methylsulfonyl-6-chloro are added to a neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 3-acetylamino-aniline in an acetic acid medium in 500 parts of water -pyrimidine-5-carboxylic acid chloride and stirred for one hour at 35 ⁰ C, with constant

^LeA9912 00981 B / 069B ^{Bf 'D}

15AA561

- 43 -

Addition of sodium hydroxide solution a pH value of 6-7 is maintained. The partially precipitated acylation product is completely separated out and filtered off at pH 7 by adding 100 parts of sodium chloride. For purification, the reactive dye obtained in this way can be dissolved again in 2500 parts of water at 30 ^° C., clarified and separated out again by salting out the filtrate with 350 parts of common salt. The dye has the formula

Il NH-C-

, ~ NH-uuCH, ^C1

NaO ₅ S SO ₅ Ai a 3

and provides after filtration, drying at 35 ⁰ C and grinding a yellow powder is that readily dissolves in water with geloer color and dyes cellulose fibers by one of the above dyeing method in the presence of acid-binding agents in a very real reddish yellow tones. Real yellow dyeings are also obtained on wool and polyamide fibers.

Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4'-amino-2 ¹ -acetylaminophenyl- (1 ') -azonaphthalene- (2) -3,6,8-trisulfonic acid sodium corresponding amounts aminoazo dyes obtained from the amino compounds indicated in column 2 and the coupling components indicated in column 3 in the usual manner by diazotization and coupling in an acetic acid medium and acylated with Z-methylsulfonyl-G-chloropyrimidine-S-carboxylic acid chloride.

Le A9912

009815/0698 "bad original

15U561

Beiap.
No. Diazo component Clutch component Hue on
cotton 107 2-aminona phthalene-
1,5-disulfonic acid 1-amino-3-methy1-6-meth-
oxybenzene strong red
prickly
yellow 108 Il 1-amino-3-methoxybenzene yellow 109 Il 1-aminonaphthalene-6-
sulfonic acid reddish
yellow 110 Il 1-amino-3-acetylamino
benzene Il 111 H 3-aminophenylurea Il 112 Il 1-amino-3-hydroxyacety1-
aminobenzene Il 113 2-aminonaphthalene
5,7-disulfonic acid 1-amino-3-methyl-6-meth-
oxybenzene strong red
prickly
yellow 1H H 1-aminonaphthalene-7-
sulfonic acid reddish
yellow 115 Il 1-amino-3-acetylamino
benzene M. 116 Il 3-aminophenyl urea M. 117 η 1-amino-3-hydroxyacety1-
amino-benzene Il 118 1-aminonaphthalene
3,7-disulfonic acid 1-amino-3-methyl-6-meth-
oxybenzene strong red
prickly
yellow 119 Il 1-amino-3-methylbenzene reddish
yellow 120 1-aminonaphthalene
3,7-disulfonic acid 1-aminonaphthalene-6-
sulfonic acid H 121 2-aminonaphthalene
3,6-disulfonic acid 1-amino-3-methylbenzene η 122 η 1 -Amino ^ -methvl-e-meth- strong red

123

124 125

oxybenzene pricked

yellow

Ii

It

1-amino-3-acetylaminobenzene

3-aminophenylurea

1-Amino-3-hydroxyaeetylaminobenzene

1-aminonaphthalene-6-sulfonic acid

reddish yellow

Le A9912

009815/0698

Diazo component 1 Coupling component 544561 fieisp.
No. 2-aminonaphthalene
6,8-disulfonic acid 1-amino-3-acetylamino
benzene Hue on
cotton 127 η 1-amino-2-methoxy-
naphthalene-6-sulfone
acid reddish
yellow 128 Il 1-aminonaphthalene-6-sul-
fonic acid strong red
prickly
yellow 129 2-aminonaphthalene
4,8-diaulfonic acid 1-aminonaphthalene-6-sul-
fonaäure rotatichiges
yellow 130 η 1-aminonaphthalene-7-sul-
fonic acid yellow 131 1-amino-2-methoxy-
naphthalene-6-sulfone
acid H 132 It 1-methylamino-3-methyl-
benzene strong red
prickly
yellow 133 It 1-ethylamino-3-methyl-
benzene yellow 134 It N-methylaniline H 135 Il N-ethylaniline ti 136 ti N- (ß-hydroxyethyl) -
aniline Il 137 It N-butylaniline Il 138 2-aminonaphthalene
3> 6.8-t risulfon
acid aniline ti 139 It V-amino-3-methylbenzene reddish
yellow 140 It 3-aminophenylurea H 141 H i-Amiho-3-hydroxyacetyl-
aminobenzene Il 142 H 1-amino-3-acetylamino
6-methoxybenzene It 143 η 1-amino-3-acetylamino-6-
methylbenzene gelbstichi
full orange 144 N 1 -amino-3-ine than- sul-
fonyl-aminobenzene reddish
yellow 145 Il 2,5-dimethoxyaniline 146 It 3-methyl-6-methoxy
aniline gelbstichi
full orange 147 Il N-methylaniline It 148 Le ^{A9912 00981} 5/0698 reddish
yellow BATH ORIGINAL

15AA561

Ex. Diazo component η η η M. Coupling component Hue on No. 2-amin ona pht hai i n- H Il N-ethylaniline cotton 149 3,6,8-1ri sulfone Ί-Aminonapht hai in- 4-nitro-4-amino- rotatichigea acid ti 2.4 »7-tri sulfone atilDen-2,2'-disul- yellow Il acid fonic acid N-butylaniline 150 η N- (ß-hydroxyethyl) - H 151 aniline H 3- (N-ethylamino j-toluene 152 H 2-aminotoluene Il 153 η 1-amino-2,5-dime thy I- n 154 benzene strong red H atichigea Il 1-amino-2-methoxybenzene yellow 155 i-amino-3-methoxybenzene η 156 Il rotatichigea 1-ethylamino-3-methoxy
benzene yellow 157 2-aminonaphthalene 1-aminonaphthalene-6-aul- Il 158 4,6,8-trisulfone fonic acid Il acid 1-aminonaphthalene-7-Bul- 159 fonaäure Il i-amino-3-methylbenzene 160 It 1-amino-3-acetylamino 161 benzene η 1-amino-3-methylbenzene 162 yellow 1-aminonaphthalene-6-aul- 163 fonaäure H 1-amino-3-acetylamino 164 benzene reddish yellow 3-aminopheny! Urea 165 1-amino-3-hytiroxyacetyl- N 166 aminobenzene Il

Τ. «Α 9912

009815/0698

bath

Ex.

No. diazo component

Clutch component e

Color on .cotton

167 4-nitro-4'-amino-N-methylaniline atilDen-2,2'-disul-

fonic acid

168 "Im-A thy laniline

169 "K-butylanilaniline

170 "N- (ü-Hydroxyäthylj-

aniline

171 "'1- (N-ethylamino) -3-

methylbenzene

172 Aniline-2,5-disulfonic-1-aminonaphthalene-b-sulic acid fonic acid

173 "1-aminonapnthalin-7-aul-

fonic acid

174 "1-Amino-3-methyl" benzene

175 "i-amino-3-acetylamino-

benzene

176 * 1-amino-2-methoxy-5-

methylbenzene

177 ^w 1-amino-2,5-dimethoxy-

benzene

178 Aniline-2,4-disulfonic-1-amino-2-methoxy-5-acid methylbenzene

reddish yellow

yellow

reddish yellow

Τ. «Δ QQIg

009815/0698 BAD ORiGlNAJ

- 46 -

Example 179

65 parts of the dye of the formula

Cu

NaO, S 1 Ii-N.
3> ^^

NaO, 3
SO ₃ Na

(produced by coupling diazotized i-hydroxy-2-amino-benzo-4,6-disulphonic acid to 2-amino-δ-hydroxynaphthalene-6-sulphonic acid and coppering aes obtained azo dyes) are dissolved in 700 parts of water in a neutral manner. 25 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride are added and the mixture is stirred at 35-4O ⁰ C with constant blunting of the acid liberated with soda solution to pH 6-7 until no free amino group can be detected. I / he resulting reactive dye of the formula

SO ₃ Na

is salted out, filtered off, washed una at 30 - 4O ⁰ C dried. It dyes cellulose materials in very real ruby tones using one of the methods given above.

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

Le A Q912

00981 5/0698

Example, hue on

No. Diazo component Coupling component cotton

180 i-Hydroxy-2-amino-Z-methylamino- ^ - hydroxy-ruby benzene-4-sulfon-naphthalene-7-sulfonic acid acid

181 "2-ethyl-amino-b-hydroxy-"

naphthalene-7-sulfonic acid

182 "2- (fi-hydroxyethylamino) -"

5-hydroxynaphthalene-7-sulfonic acid

183 "2-Amino-8-hydroxynaphtha-"

lin-3,6-diaulfonaic acid

184 i-Hydroxy-2-amino-2-amino-5-hydroxynaphtha- " benzene-4,6-disulfon-lin-1,7-diaulfonaic acid

acid

185 ^M 2-amino-8-hydroxynaphtha- "

lin-3 »6-disulfonic acid

186 ^w 2-methylamino-5-hydroxy- "

naphthalene-7-sulfonic acid

187 "2-ethylamino-5-hydΓoxy-"

naphthalene-7-sulfonic acid

188 "2- (ß-hydroxyethylamino; - ⁿ

5-hydroxynaphthalene-7-sulfonic acid

189 i-Hydroxy-2-amino-i-amino-8-hydroxynaphtha violet benzene-4,6-disulfon-lin-3,6-diaulfonic acid

acid

190 "i-Amino-8-hydroxynaphtha- ^M

lin-4,6-diaulfonic acid

191 i-Hydroxy-2-amino- i-Amino-8-hydroxynaphtha- " benzene-5-sulfon-lin-3,6-disulfonic acid

acid

192 "i-Amino-8-hydroxynaphtha- ^M

lin-4,6-disulfonic acid

193 1-Hydroxy-2-amino-i-amino-8-hydroxynaphtha bluust. 4-acetylaminobenzolin-3,6-disulfonic acid violet 6-sulfonic acid

194 1-Hydroxy- 2- amino-4-i-ethoxy-8-hydroxynaphtha- ^M acetylaminobenzene-6-lin-3,6-disulfonic acid

eulfonic acid

(4-position acetylamino group then saponified)

Le A 9912 00 9815/0698 BATH

Beiap. Color shade on no. Diazo component, coupling component, cotton

1-Hydroxy-2-amino-4-i-Ajnino-8-hydroxynaphtha blue acetylaminobenzene-6-lin-2,4-disulfonic acid sulfonic acid

"i-Amir.o-8-hydroxy naphtha-"

iin-2,4, t-trisulfonic acid

i-Hydroxy-2-amino-t- i-Amino-8-hydroxynaphtha- " acetylaminobenzene-4-lin-2,4-disulfonic acid sulfonic acid

(6-position acetylamino group saponified;

i-amino-2-hydroxy-b- "" nitronaphthalene-4-sulfonic acid

(6-person Mtro group then reduced to -

i-Amino-2-hydroxy-e- i-Amino-8-hydroxynaphtha- " nitronaphthalene-4-lin-2,4,6-trisulfonic acid sulfonic acid

(6-8 position nitro group then reduced to -

1-hydroxy-2-amino-6- "" acetylaminobenzene-4-sulfonic acid

(6-position acetylamino group saponified)

^A 99 ¹² ■

00981B / 0698

Example 201

The solution of 19t5 parts of the sodium salt of i-aminobenzene-4-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is concentrated in a mixture of 100 parts of ice and 28 parts by volume. Let in hydrochloric acid; then a half hour at 0. - 10 ⁰ C stirred and then excess nitrous acid is removed. To the resulting diazo suspension is added at 0 - 10 ⁰ C, the cooled and thereby again partially crystallized solution of 26.2 parts of the potassium salt of i-amino-naphthalene-8-sulfonic acid in 250 parts of hot water and dulls at the strongly acidic coupling mixture 10 - 20 C by carefully adding sodium hydroxide solution to pH 4. The coupling is completed quickly; the aminoazo dyestuff formed is completely salted out with 100 parts of sodium Sale, suction filtered, washed and redissolved in 500 parts of water at 10 ⁰ C and pH. 6 25.0 parts of 2-methylsulfony1-6-chloro-pyrimidine-5-carboxylic acid chloride are added to the aqueous solution, and the acid liberated is blunted with it. For one hour at 35 7 - - 40 ⁰ C stirred solution of soda on pH. 6 If no more aminoazo dye can be detected, the partially precipitated reactive dye becomes of the formula

NaO

Salted out with 40 parts of sodium chloride, filtered off and redissolved in 800 parts of warm water for cleaning purposes. After the solution has been clarified, the pure dye is separated out from the filtrate by adding 80 to 100 parts of Kochealz. After filtering off, drying at 35 ^° C. and grinding, a yellow powder is obtained which turns slightly yellow in water

0098 1 B / 06 9 8 Le A 9912

Color dissolves and the cellulose fibers by one of the above-mentioned dyeing processes in the presence of acid-binding agents colors in very good wet, light and chlorine-fast yellow tones. True yellow colorations are also obtained on wool and polyamide fibers.

If you proceed as indicated above, but instead of 19.5 parts of the sodium salt of i-aminobenzene-4-sulfonic acid equivalent amounts of those in the table below listed diazo components to i-amino-naphthalene-8-sulfonic acid couplings, after acylation with 2-ethylsulfonyl.6-chloropyrimidine-5-carboxylic acid chloride, valuable yellow ones are obtained to brown reactive dyes.

Diazo component shade on * cellulose fiber

1-aminobenzene-2,5-disulfonic acid reddish yellow

2-Amino-naphthalene-4,8-disulfonic acid strongly reddish yellow 2-amino-naphthalene-5,7-disulfonic acid "

2-amino-naphthalene-6,8-sulphonic acid "

2-Amino-naphthalene-3 »6, B-trisulphonic acid" 2-Amino-naphthalene-4,6,8-trisulphonic acid ^M

4-amino-azobenzene-; 5,4'-disulfonic acid yellowish brown

4-Amino-2-acetylamino-azobenzene-2 ', 5'-orange-brown disulfonic acid

SO ₅ Well

reddish brown

SO ₅ Well

(1-aminobenzene-2,5-disulfonic acid acidic on i-amino-naphthalene-6-sulfonic acid coupled)

Le A 9912 009815/0698

Diazo component

Color on cellulose fiber

SO, well

reddish brown

SO ₃ Na

SO ₃ Na (6 * 7)

(i-aminobenzene-2,5-disulfonic acid acidic on the technical mixture of 1-aminonaphthalene-6- and -7-sulfonic acid coupled;

SO ₅ Well

N = N

purple-tinged brown

NaO ₃ S

(i-Amino-naphthalene-2,5 _f 7-trisulfonic acid acidic to-i-amino-naphthalene-b-sulfonic acid coupled )

NaO

reddish brown

SO-ha

(1-Amino-naphthalene-2 _f 5 , 7-trisulfonic acid acidic to 1-amino-2-methoxy-5-methy1-benzene coupled)

Le A9912

0098 15/06 9

^BATH

-54- 1 5 A A56

Example 202

If cellulose fabric is printed with a printing paste containing 30 g of the dye described in Example 18, 100 g of urea, 300 g of water, 500 g of alignate thickening (60 g of sodium alginate per kilogram of Veruickungj, 10 g of soda and 10 g of the sodium salt of the 3- Contains nitrobenzenesulphonic acid and which was made up to 1 kilogram with water, then dried in the meantime and then steamed in a suitable steamer for 30 seconds at 103 to 115 ^° C., a strong bluish red print of good size is obtained after rinsing and boiling soaps. , Rubbing and light fastness.

Example 203

A mixture of the solutions of 65.5 parts each of the chromium 2: 1 complex and the cobalt 2: 1 complex of the dye the formula

OH

SO ₃ Na

SO ₅ Well

in each 400 parts of water is about 2 hours at 40 with 60 parts of finely powdered methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride 2 - stirred for 7 - 50 ⁰ C while maintaining pH. 6 When the aminoazo dye (Co complex blue; Cr X complex: blue-green) is no longer detectable by chromatography _? the mixture formed of the two reactive dyes is salted out with potassium chloride, filtered off and dried.

009815/0698 Bad _On , ■

Le A9912

15U561

The dye replenishes on jellulosic materials the pad dyeing process or in pressure in the presence of acid-binding agents Smock strong, very good wet and lightfast black tones.

If one proceeds accordingly, however, the mixture of the chromium-2: 1 and cobalt-2: 1 complexes of the following aminoazo dyes is used, you also get valuable black dyes:

Coupling diazo component Coupling component p_H

1-Hydroxy-2-amino-4-1-hydroxy-8-amino-9 nitrobenzene naphtha1in-3 »6-disul-

fonic acid

nitronaphthalene-7-sulfonic acid

Example 204

To the neutral solution of 53.15 parts of the disodium salt obtained by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5 ¹ -sulfophenylj-3-methyl-pyrazolone- (5 } and subsequent reduction of Kitrogruppe obtained with sodium sulfide aminoazo dyestuff in 300 parts of water 28.0 parts of S-ethylsulfonyl-o-chloropyrimidine-5-carboxylic acid chloride and the mixture is stirred for one hour at 35-40 ⁰ C to give the acid liberated continuously with sodium carbonate solution blunted to a pH of 6.5-7 The deposited dye of the formula

0098 15/0698 EAD

Le A9912

SO, well

NaO ₃ S '

is filtered off, dissolved in 3000 parts of warm water at pH 6-7 and precipitated again from the filtered solution by adding sodium chloride. After filtering off, drying and powders obtained a yellow highly water-soluble powder, the cellulosic materials from a long liquor at 40 ⁰ C, or after the cold pad-batch process with sodium carbonate as acid-binding agent in clear, washing, rubbing and light-fast yellow shades .

If one proceeds as indicated above, but instead of the aminoazo dye used there, equivalent amounts from the components listed in the table below built-up aminoazo dye uses, you also get valuable new iteaktivfarbstof fe.

In the table, the term "saponified" means that an acylamino group contained in the aminoazo dye is subsequently added has been saponified, while the term "reduced" means that a nitro group contained in the liazo component after the coupling is reduced to the amino group, whereby forms the desired aminoazo dye.

^{Le A qql2} 0 0 9 8 1 B / 0 6 9 8 ^Bad

15U561

Beiap.

No. Diazo component Azo component

pH of the coupling medium

Shade on cellulose

205

206

207

208

209

210

211
212

213
214
215

1-amino-4-nitrobenzene-2-sulfonic acid

1- (4 "-Sulfo-

phenyl) -3-

methyl pyrazo

lon- (5)

5-6

yellow

(4-position nitro group then reduced)

"1- (4'-sulfo- 5-6 reddish

phenyl) -3-carb- yellow

oxy-pyrazolone

1- (3'-SuIfO-

phenyl) -3-

methyl-5-amino pyrazole

1-Amino-3-ace ty 1 aminobenzene-6-sulfonic acid 6-7

6-7

yellow

(3-position acetylamino group then saponified)

1- (ß-Hydroxy- 5-6 »ethy1) -3-methy1-pyrazolone- (5)

2 moles of 1-amino-3-acetyl-aminobenzene-6-sulfonic acid (saponified)

1 mole of 1-amino-3-acetyl-aminobenzene-6-sulfonic acid (saponified)

1-Amino-5-acetylamino-naphthalene-317-d i sulfonic acid (saponified)

1-Amino-2-methyl-benzene-4 »6-disulfonic acid

1 mole of bis-pyrazo-5-6 ion from 4,4'-bishydrazinodibenzyl-2,2'-d isulfonic acid and ethyl acetoacetate

1- (4'-sulfophenyl) -5 - ( 3-carboxy-pyrazo-

lon- (5) 1- (4'-SuIfO-phenyl) -3-carboxy-pyrazolone- (5)

5-6

1-Amino-2-methyl 1-benzene-4,6-disulfone aur β

2-acetylamino-5- 7-8 naphthol-7-sulfonic acid (saponified)

2-acetylamino-8-7-8 naphthol-6-sulfonic acid (saponified)

i-chloro-2-acetyl- 7-8 amino- 5-naphthol- 7-sulfonic acid (saponified)

reddish yellow

orange

Red

orange

Le A9912

009815/0698 BAD OR ^F CV *>! Ät

Diazo component 58 - pH des
Coupling
mediums 7 - 8th 15U561 Ex.
No. 1-aminobenzene-2-
sulfonic acid Azo component 7 - 7 - 8th Hue on
Cellulose 216 2-aminonaphthalene
3,6-disulfonic acid 1-acetylamino
8-hydroxynaph-
thalin-4,6-di-
sulfonic acid
(saponified) -I _ 7 - 8th Red 217 2-aminonaphthalene
3 »7-disulfonic acid H 7 - 7 - 8th bluish p3
Red 218 2-aminonaphthalene
4,8-disulfonic acid η 7 - 7 - 8th η 219 2-aminonaphthalene
3,6-disulfonic acid η 1-acetylamino- 7 -
8-hydroxynaph-
thalin-3,6-disul-
fonsäure (ver
soaps) 7 - 8th Il 220 2-aminonaphthalene
4 1 8-disulfonic acid Il 7 - 8th η 221 i-amino-4-methoxy-
benzene-2-sulfone
acid 2- (N-acetyl-N-
methylamino) -5-
hydroxynaphtha-
lin-7-sulfone-
acid (saponified) 8th Il 222 2- (N-acetyl-N-
methylamino) -8-
hyd roxynaphtha-
lin-6-eulfon-
acid (saponified) 8th yellow.
Red 223 1-aminobenzene-2-
8ulfonic acid Il 8th Red 224 1-aminobenzene-3-
eulfonic acid H 8th η 225 1-aminobenzene-4-
8ulfonic acid N 8th η 226 1-Amino-4-me thy I-
benzene-2-sulfone
acid η N 227 N

228 1-Amino-2,4-dimethylbenzene-6-sulfonic acid

7-8

Le A9912

009815/0698

J Of

15U561

Ex.

No.

Diazo component

Azo component

pH des

Couplings,

meditzma

Shade on cellulose

229 1-Amino-2,4-dimethylbenzene-6-sulfonic acid

230 1-Amino-2,4-dimethylbenzene-6-sulfonic acid

231 4th
3 -Aminoazobenzene-
, 4 '-d i sulfonic acid 232 M. 233 ti

2-acetylamino-7-8 8-hydroxynaphthalene-fc-sulfonic acid (saponified)

2-acetylamino-7-8 8-hydroxynaphthalene-3,6-disulfonic acid
(saponified)

i-Amino-3-ace- t- (> tyl-aminobenzol

1-amino-3-hy-5-6 hydroxyacetylaminobenzene

1-amino-naphtha- 5 - b lin-6-sulfonic acid

1-amino-naphthalene-7-sulfonic acid

-2- (4 ¹ -amino-2'-sulfophenyl- (1'j-azo) -8-hydroxynaphthalene-3,6-disulfonic acid

5-6

Red

yellow-brown

black

Example 236

30.4 parts of 2-amino-8-oxynaphthalene-3 »6-disulfonic acid are dissolved neutrally in 300 parts of water, heated to 30-45 ° C and 26 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride added. In "an hour will be 40 parts of 15 $ soda solution added so that the pH is between 6-7. The acylation product partially precipitates.

Le A9912

009815/06 9 BAD

- 6ο -

Its freshly prepared diazonium salt solution from 13.6 parts of p-aminobenzylsulfonic acid is added dropwise at 0-5 ° C. to the suspension of the acylation product to which 12.5 parts of soda have been added. After five hours of stirring at ice bath is salted out with sodium chloride, suction filtered, washed with dilute sodium chloride solution and dried at 3O ⁰ C in Vakmuntrockenschrank. The dye obtained corresponds to the formula

ff
NaO, S-CH ₉ -Z ^ N = N ^ J ^ - ^ NH-C - / \ - S0 _o CH,

^^^ SO ₃ Well

If you proceed as indicated above, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid 30.4 parts of 2-amino-5-oxynaphthalene-1,7-disulfonic acid with 2-liter / ethylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride acylated and the coupling component containing reactive groups couples with diazotized p-aminobenzylsulfonic acid, is obtained one is a readily soluble reactive dye, the cellulose fiber-containing fabric in brilliant reddish orange tones colors.

Cotton or cellulose fabric is impregnated on a padder at 20-25 ^° C. with a solution which contains 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezes to a moisture content of about 100 fi and roll up the moist tissue again. After standing for 24 hours at room temperature, the fabric is rinsed, soaped at the boil in the usual way and dried. A brilliant scarlet dyeing of good wet and light fastness is obtained.

Le A9912

0098 15/0698

- 6i -

Cotton or rayon fabric is impregnated A padder at 20 - 25 C with a solution containing 30 g of the one described in the example, paragraph 1, per liter of liquor Dye, 100 g urea and 20 g soda contains, squeezes to a moisture content of about 100 # and steams 30 seconds at 103 ° C. After "rinsing, boiling soaps and drying, a brilliant scarlet dyeing with good wet and light fastness is also obtained.

Cotton fabric is impregnated with a solution of 20 - 25 ° C, the per liter of liquor 20 g of the according to this example, Paragraph 1, available dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated Oleyl alcohol) as well as 150 g urea and 15 g sodium bicarbonate contains. The fabric is then placed between two rubber rollers to a moisture content of about $ 100 squeezed. After intermediate drying at 50-60 ° C., the mixture is heated to 140 ° C. for 10 minutes and the dyeing obtained in this way rinsed thoroughly with hot water and treated boiling for 10 minutes with a solution containing 5 g of Marseilles per liter Contains soap and 2 g of soda. After rinsing and drying, a strong, sharp color of good color is obtained Wet and light fastness.

When printing oil-based fabrics with a printing paste, those in the kilogram 30 g of the one described in this example, paragraph 1 Dye, 100 g urea, 300 g water, 500 g alginate thickener (60 g sodium alginate per kilogram thickener), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was filled with water to 1 kilogram, then zwischentrocüiet and then in steams in a suitable steamer for 30 seconds at 103 - 115 ° C, in this way, after rinsing and boiling soaps, a strong charcoal-colored dyeing with good fastness properties is obtained.

Le A Q912 009815/0698 ^BAD

15 A 4 56 1

- ö2 -

100 parts of wool are introduced at 40 ⁰ C in a bath containing in 5000 parts of water 1.5 parts of this .Example, paragraph 1. The dye described and 6 parts of 5% acetic acid and 0.5 part of a polyoxyethylene derivative containing hydroxyl groups and containing btearylamine- ^ erivates. The dyebath is brought to a boil in 30 minutes, then it is dyed at the boil for one hour. After rinsing and drying, a brilliant scarlet dyeing that is washable, millfast and lightfast is obtained.

Example 237

28.9 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 monoazo dye obtained is isolated and then or immediately diazotized in solution without isolation and alkaline coupled with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid, the disazo dye obtained is salted out by adding 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) in 5 hours at 95-10O ⁰ C metallized. The dye is isolated from the coppering solution by adding salt and carefully acidifying it.

The coppered amino-disazo dye is then acylated in aqueous solution at pH 7-8 at a temperature of 30-45 ° C. with 28.0 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride, the pH being adjusted by adding soda is kept in the specified range. After the acylation is complete the dye is isolated with sodium chloride and dried at 35 ⁰ C. In the form of the free sulfonic acid, the dye corresponds to the formula:

009815/0698 A 9912

-63 - 1 5 A Λ 5 6

He dyes cellulose fabric according to the methods known for reactive dyes Process in wet and lightfast navy blue tones.

Further according to the invention can be created in a similar manner Dyes can be produced by using the above-mentioned monoazo dye from 2-amino-1-methylbenzene-3f5-disulfonic acid and 1 ~ amino-2-methoxy-5-methylbenzene with those in the the following table listed aminonaphtholsulfonic acids and Z-MethylBulfonyl-B-chloro-pyrimidine-S-carboxylic acid chloride combined according to the regulation given above.

Clutch component e

Z-amino-S-hydroxynaphthalene-1,7-disulfonic acid

2-amino-8-hydroxynaphthalene-3f6-diaulfonic acid

The dyes obtained are blue in color. Example 238

38.9 parts of 2-DIABO-1-hydroxybenzene-4-sulfonic acid 6-Nitro-by sodaalkalische clutch and 2-hydroxynaphthalene dye obtained are dissolved in 200 parts of water at pH 8 at a temperature of 70 - 80 ⁰ O touched. 67.9 parts of the per molecule are carried into this suspension

009815/0698

15U561

Dye 1 chromium complex compound of the azo dyes containing chromium atoms from ^ chloro ^ -diazo-i-hydroxybenzene-o-sulfonic acid and 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid, the pH being adjusted to between 7 and 9 by the dropwise addition of soda solution is held. After 20 minutes at 70-80 ^° C., a dark blue solution has formed. The paper chromatography shows that a uniform mixed complex has arisen. Ler mixed complex is acyllert within one hour at 45 C and pH 6-7 with 28.0 parts of 2-methylsulfonyl-6-chloΓ-pyΓimidin-5-caΓbonsäurechlorid, the pH being kept in the specified range by adding a soda solution dropwise. The acylated dyestuff is salted out * potassium chloride 20 i, filtered and dried at 30 C. A dark powder is obtained which dissolves in water with a blue-gray color.

The dye corresponds to ale pentasodium salt

formula

C ^r C Ϊ O ^ ^ ₀ NH-C N = N

. 5 Well

It dyes cotton according to the method given in Examples 1-3 Process in gray to black tones.

Le A9912

0098 1 B / 0698

bath

From the starting components specified in the following table valuable dyes can also be obtained in the manner indicated in this example. For the production of these dyes was always the azo dye, the in the 2: 1 mixed complex carries the reactive group, used as a 1: 1 chromium complex.

Le A 9912 -

BATH

0098 15/0698

: 1-chrome complex metal-free dye

) \; o i

σ
ο
co

239

240 241 242

243 244

245 246 247 248

249

250 251

252

4-nitro-2-araino-1-hydroxybenzene-6-sul-

fonsäure * i-Ainino-8-hydroxynaphtha-

lin-3,6-disulfona acid

4-NitΓO-2-amino-1-hydΓoxybenzene-6-3Ulfonsäure »1-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

4-chloro-2-amino-1-hydroxybenzene-6-sul-

fonsäure * 1-amino-8-hydroxynaphtha-

lin-3,6-diaulfonaic acid

η η 4-nitro-2-amino-1-hydroxybenzene-2-hydroxynaphthalene

black

H
Π

4-nitro-2-amino-1-hydroxybenzene - 2-hydroxynaphthalene-6-sulfonic acid

4-nitro-2-amino-1-hydroxybenzene *

1-hydroxynaphthalene-4-sulfonic acid

6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid ——► 2-hydroxynaphthalene

4-nitro-2-amino-1-hydroxybenzene *

1-acetylamino-7-hydroxynaphthalene

e-Nitro-i-amino ^ -hydroxynaphthalene-4-sulfonic acid ——> 2-hydroxynaphthalene

4-nitro-2-amino-1-hydroxynaphthalene-6-sulfonic acid * 2-hydroxynaphthalene

4-nitro-2-amino-1-hydroxybenzol y

2- hydroxynaphthalene

4-nitro-2-amino-1-hydroxybenzene - 2-hydroxynaphthalene-6-sulfonic acid

4-chloro-2-amino-1-hydroxybenzene - ■ 2-hydroxynaphthalene

navy blue

a black

a black

blue-black

Il

navy blue

1: 1 chromium complex metal-free particle material

Shade on cotton

CD CXJ

253 254

255 256

257 258 259 260

261

262 263

4-chloro-2-amino-i-hydroxy benzene-6-sul-

fonsäure y i-AminO-8-hydroxynaphtha-

lin-3,6-disulfonic acid

4-ϊ ^ itro-2-amino-1-hydrΌxybenzene-6-sulfonic acid - > - f i-amino-8-hydroxynaphthalene-2,6-disulfanoic acid

4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid ——> 1-amino-8-hydroxynaphthalene-3s6-disulfonic acid

4-Methy 1-2 - amino-1-hyd ro Xy benzo 1-6 ^ -aulfonic acid - > r i-amino-8-hydroxynaphthalene-3,6-disulfonic acid

4-nitro-2-amino-1-'hydroxybenzene-6-sul-

f onic acid -> i-amino-8-hydroxynaphtha-

lin-3,6-disulfonic acid 4-nitro-2-amino-1-hydroxybenzene i-acetylamino-8-hydroxynaphthalene 3,6-disulfonic acid

4-nitro-2-amino-1-hydroxybenzene 1-amino-8-hydroxynaphthalene-2,4-sulfonic acid

o-Nitro-i-amino - ^ - hydroxynaphthalene-4-8ulfonic acid - -r 2-hydroxynaphthalene

2-aminobenzene-1-carboxylic acid-5-8ulfonic acid > 1-phenyl-3-methyl-5-pyrazo-

6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid ——-> 2-hydroxynaphthalene

4-chloro-2-amino-1-hydroxybenzene --— * 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone

4-chloro-2-amino-1-hydroxybenzene> ·

2-hydroxynaphthalene-6-sulfonic acid

5-nitro-2-amino-1-hydroxybenzene ->

2-hydroxynaphthalene-6-sulphonic acid

4-Kitro-2-amino-1-hydroxybenzol y

2-hydroxynaphthalene-8-sulfonic acid

4-nitro-2-amino-1-hydroxybenzene *

1-hydroxynaphthalene-5-sulfonic acid

6-nitro-4-chloro-1-hydroxybenzene »1-hydroxynaphthalene-5-sulfonic acid

blue navy blue

blue-black gray-green

black purple

red-tinged blai black

62.0 parts of the trisodium salt of the aurch soda-alkaline coupling of diazotized 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid and 1-amino-e-hydroxynaphthalene ^, 6-disulfonic acid are obtained in 300 parts of water at 70 - 8O ⁰ C and a pH of 8-9 NIIT 54.2 parts of the 1: I chromium complex of the dye of 6-nitro-1-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene were added. After 10 minutes a deep blue solution has formed.

The mixed complex takes about an hour at 40 - 50 C and a pH of 6.5-7.5 with 28 parts of 2-methylsulfonyl-6-chloro-pyrimidine-5-carboxylic acid chloride acylated. The pH value is kept constant by adding soda solution. The acylated dye is deposited with 20 # sodium chloride, suctioned off and dried at 30 °.

5 Na®

The procedure given in Example 3 is obtained on cotton Procedure a blue-black liruck of excellent Fastness to light and washing.

Le A9912

0098 1 6/06 98

15 4 A56 I.

Example 264

79.9 parts of the aminoazo compound of the formula prepared according to Belgian patent specification No. 599 581

0 - Ou -

HO_S

are dissolved in 500 parts of water at 30.degree.-35.degree. C. and 25 parts of 2-methylsulfonyl-o-chloro-pyrimidine-S-carboxylic acid chloride are added at this temperature with stirring. The slowly released hydrochloric acid is blunted with soda solution, keeping a pH between 5 and 6. After condensation is complete, the dye is salted out by addition of 150 parts of potassium chloride, isolated and dried at about 50 ⁰ C in vacuo. A dark powder is obtained which dissolves in water in a blue color and dyes cotton in reddish-tinged blue shades of excellent lightfastness and whiteness.

Le A9912

0098 15/0698 ^ßAD

Example 265

0.1 mol dea according to the specifications of Example 2 produced reactive agents in 2000 parts by volume of water at 40 - 50 ^ C at cH o - o, 5 yellow, with t. 1 mole of aminobenzene-5-suifonsäure added and slowly aui 50 - ou ^J C heated. The pH value of 6-6.5 is maintained during the condensation by adding sodium carbonate solution. After the reaction has ended, the reaction product is seeded out and isolated. The likely formula dye

NaO

—Cu-0 SO ₃ Na

When dried, it is a dark powder that dissolves in water with a blue color.

If the aminobenzene-3-sulfonic acid is replaced by equivalent amounts of aminobenzene-4-sulfonic acid, ethanolamine, aminobenzene-3,5-disulfonic acid, 3- or 4-aminobenzoic acid or by ammonia, reactive dyes are also obtained, the cotton in clear blue Color tones .

Le A9912

00 9 815/0698

Claims (1)

Patent claims: 1 «Process for the production of reactive dyes ^ thereby * characterized in that one in dyes or dye precursors at least one grouping of the formula according to processes known per se -NO where R is hydrogen or a substituent, X is a removable sulfonyl group, Y is a halogen substituent, preferably Cl or Br, and Z is hydrogen or a substituent. and in the case of the use of dye precursors converts these in a suitable manner into the desired final dyes. 2. Process for the preparation of reactive dyes, thereby characterized in that one dyes containing amino or amide groups or dye precursors which are reactive Have hydrogen atom on the amine or amide nitrogen, with compound of the general formula Le A 9912 ■; ... ■ 0098 Tb / 06 98 & AD ORIGINAL * 15U561 halogen-OC, wherein "halogen" stands for a halogen atom, preferably Cl or Br, X is a removable sulfonyl radical, Y is a halogen substituent, preferably Cl or Br, and Z is hydrogen or a substituent, mean, implemented and in the case of the use of dye precursors converts these in a suitable manner into the desired final dyes. J>. Process according to Claims 1 and 2, characterized in that, after the condensation, the dyes obtained are subjected to customary conversion reactions, in particular metallization, acylation, reduction and / or sulfation reactions. 4. The method according to claim 2, characterized in that there is a diazo or coupling component which is a reactive Has amino or amide group, with a compound of the formula halogen OC wherein "halogen", X * Y and Z are those given in claim 2 Have meaning condensed and the intermediates thus obtained through Converts diazotization and / or coupling into azo dyes. Le A 9912 00 98 15/06 98 5. Process according to Claims 1 to 4, characterized in that such dyes are built up or starting components used which have one or more sulfonic acid groups. 6. The method according to claims 1 to 5, characterized in that the reactive sulfonyl substituents in the starting or. End products are methylsulfonyl groups. 7. reactive dyes of the formula F- wherein F is the residue of an organic dye, m is a Number from 0.5 to 4, X is a removable sulfonyl radical, Y is a halogen substituent, preferably Cl or Br, Z is hydrogen or a substituent and R is hydrogen or a substituent. 8. Reactive dyes of the formula of Claim 7, wherein F is a or has more than one sulfonic acid group. 9. Dyes of claims 7 and 8, wherein the reactive Sulfonyl groups are methylsulfonyl groups. 10. Process for dyeing and printing hydroxyl groups Materials, especially textile materials made from native or regenerated cellulose, characterized in that one is on 0098 15/0698 BATH ORIGINAL Le A9912 one or more of these materials in any order Dyes of claim 7 and an acid-binding agent applies and optionally subjecting the material treated in this way to the action of elevated temperature. 11. Process for dyeing N-containing materials, preferred of wool, silk »synthetic super polyamide and polyurethane fibers j, characterized by the fact that one can use these materials colors with one or more dyes of claim 7 from acidic to neutral liquor and optionally then the pH range of the dyebath is increased, preferably to pH 6.5 to 8.5. Le A9912 009815/0698 ^6a ® 0η _Θ ,