SE334203B

Reactive Dyestuffs

Abstract

This record has no abstract on file.

SE334203B, drawing sheet 1 — Sheet 1 of 96

Term

No projected expiry on record.

14 claims: 2 independent, 12 dependent

1
Patentkrav claim 1 · New reactive dyes with the general formula. 1 · Nya reaktivfärgämnen med den al] mä.nna formeln . där D betecknar en rest av ett organiskt färgämne, R betecknar väte eller en lägre alkylgrupp, R^ betecknar väte eller en substituent, where D represents a residue of an organic dye, R represents hydrogen or a lower alkyl group, R 2 represents hydrogen or a substituent, R2 betecknar väte, halogen, eventuellt substituerade alkyloch arylrester eller karhonsyraxester-, karbonsyraamid-, alkylsulfonoch arylsulfongrupper och F betecknar en fluorsubstituent. R2 represents hydrogen, halogen, optionally substituted alkyloch aryl residues or carboxylic acid ester, carboxylic acid amide, alkylsulfonos and arylsulfone groups and F represents a fluorine substituent.
6
7. Reaktivfärgämnen enligt krav 1-6, kännetecknade av att resten respektive resten betecknar en 2,6-difluor-5-klorpyrimidinyl-U-rest. 7th Reactive dyes according to claims 1-6, characterized in that the residue and the residue respectively denote a 2,6-difluoro-5-chloropyrimidinyl-U residue.

Independent claims2

888 paragraphs in 24 sections, as filed

SWEDEN

PATENTS AND REGISTRATION OFFICE

<td colspan="2">PUBLISHING WRITING No. 334 203</td>

<td>Patent Application. No. 12517/67</td><td>Received on 11 IX 1967</td>

<td>Validity Day on</td><td>11 ix 1967</td>

<td>Ans. widely available on</td><td>1 VII 1968</td>

<td>Ans. laid out and laid out script published on</td><td>19 iv 1971</td>

<td colspan="2">Priority requested from 10 IX 1966 and on</td>

III 1967 (Federal Republic of Germany DT, F 50 181, F 51 942)

FARBENFABRIKEN BAYER AG, LEVERKUSEN, FEDERAL REPUBLIC OF GERMANY DT

Inventors HS Bien and E Klauke

Ombre PU Brain

Reactive dyes containing a fluorine-substituted pyrimidine residue and methods in their preparation

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

in which Formula D represents the balance of an organic dye, R represents hydrogen or a lower alkyl group, R 2 represents hydrogen or a substituent, R2 represents hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl and aryl residues, or

In the carboxylic acid ester, carboxylic acid amide, alkylsulfone and arylsulfone groups and F denotes a fluorine substituent.

In dyes of general formula (1), the -N (R) group is directly coupled to a carbon atom of the 2-or 4-position pyrimidine ring. On the other hand, the -NCR) group is attached to an aromatic ring of the dye D - either directly or over an additional bridge joint. such as -6 (+ - or -CO-, as in the case of amide groups, or over an alkylene group, an alkylene-CO-, an arylene, arylene-SO-, arylene or CO- or a triazine or diazine ring or a arylenamidosulfonylgrupp. Such additional bridge links contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl residues. these may also have additional reactive atoms or groups, such as halogen atoms or other large numbers of known substituents.

For example, of substituents R 1 at the 5-position of the pyrimidine ring can be mentioned halogen, such as Cl. Br and F, alkyl residues such as -CH 2 and -Cg Hg, substituted alkyl residues such as mono-, di- or trichloro- or tribromomethyl-, trifluoromethyl-, alkenyl-, such as vinyl, halogenvinyl and allyl residues, -NO 2, - CN, carboxylic, carboxylic ester and optionally N-substituted carboxylic or sulfonic acid amide groups, sulfonic acid and sulfonic acid ester groups, alkylsulfonyl, aralkylsulfonyl or arylsulfonyl residues.

Examples of substituents R 2 at the 6-position of the pyrimidine ring are as follows: Halogen, such as Cl, Br and F, alkyl, such as methyl and ethyl residues, alkenyl, such as vinyl, halogen vinyl and allyl residues, and substituted alkyl residues such as mono -, di- or trichloro- or bromomethyl or trifluoromethyl residues, carbonic acid ester, such as -methyl and ethyl ester, carbonicamide groups including N-substitution products, alkylsulfonyl and arylsulfonyl residues such as CH6hrsgSE2- and p-Cl-CgH 2 SOg residues.

Dyes in which R 1 and R 5 represent hydrogen, halogen and / or alkyl residues. is counted as a preferred group of the compounds of the invention.

The new dyes may in the molecule exhibit one or more times the residue (II)

Dyes with 1-2 such reactive residues are preferred for economic reasons. Suitable pyrimidine rings

which have at least one cleavable (reactive) fluorine substituent, 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, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-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, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethyl-4 -pyrimidinylIN 2-fluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-phenyl-4-pyrimidinyl, 2-fluoro-5-carbonamido4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro 5-bromo-6-trifluoromethyl4-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-carboxylic acid difluoro-5-trifluoromethyl "4-PYrpyrimidinyl.

Of the variety of bonding details for residue (II) at D, direct bonding of the -N (R) groups to a carbon atom of a carboxylic ring of D. is preferred. including the -N (R) group are, for example (A represents the residue of Formula III): -NH-Α, -N (CH 2> - A. -N (C2hrs5) -A, -NCC1-1A, -CONH-A, -SOgNH-A, -CON (CHg) -A, -SOgNiCHgl-A -HN-Cl 2 -CO-NH-A, -NiCH 2

-NH-A, -NH-CO- (C13-NH-A, -CH 2 NH-CO-1CH 2

-SO2NH-f ') -NB-A.

ellei 2· NH-A

-SO2hn

and the corresponding N-alkyl (I-5 C) araids and amines, respectively

-HN 'CH2(CVö7CTNH-A'

sO2NH-A

-ΗΝ. ^ 0 eHerF, H-A and the corresponding N-alkyl (1-3 C) amides and amines respectively of said compounds.

The new dyes can belong to different 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, anthraquinone, oxazine *, diojcazine, triphenylmethane, nitro, azomethane and benzanthrone , benzantrone and dibenzantrone compounds. Within the context of these dye classes, among other dyes having the following general compositions are particularly valuable:

1st Azo dyes

-N - = N-

CIV) where B and E represent aromatic, carbocyclic or heterocyclic residues, in particular B the residue of a carbocyclic diazocomponent in the benzene or naphthalene series, and E the residue of an enolic or phenolic coupling component, e.g. Moreover, of a 5-pyrazolone, acetacetic acid arylamide, oxynaphthalene or an aminonaphthalene, B and E may also have any substituents common in azo dyes, including additional azo groups. R 'represents a -CH 2 group or preferably a hydrogen atom and R'j and R'2 denote independently of each other hydrogen or halogen groups.

Particularly valuable dyes in this series are those which are cotton

- (, soluble, and especially those which have sulfonic acid and / or carboxylic acid groups. The axol dyes can be both metal-free and metal-containing, whereby the metal, copper, chromium and cobalt complexes are of particular interest.

Important azo dyes are, for example, those belonging to the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalic series, the naphthalene-azo-naphthalene series, the naphthalene-azo-1-phenyl the series and stilbene-azo benzene series, in which case also sulfonic acid group-containing dyes are preferred. In metal complexazo dyes, the metal complexed groups are preferably present in o-positions to the azo group, e.g. in the form of ο-ο'-dihydroxy, o-hydroxy-o'carboxy, o-carboxy-o'-amino and o-hydroxy-o'-amino-azo groups. Particularly prominent types of monoazo dyes of the type obtained according to the invention can be illustrated by the following formulas:

(SOQHRS)no (V)

H, C1, or CH "

HjOCHgjNH acyl (H03stake-R

= N ·

(R ') - A <S°3HRS)l-3 (VI) (H03S)W

Me - Oh

N (R ') - A; C1; NO

Me = Cu; C (VII); Co

0-2 (SO 2 H)

NH ^ (or NH-acyl) il il-A3h> i_3 (VIII)

N = N = N

«Μ 1-3 (IX)

A HM

(S03®0-L

NH 2, (or NH-alkyl) / w

HO -

(IXa) = N ·

(NH-acyl) o or j (s °3h) i_3 (X)

A represents a residue of the formula r R

J. (o) means the o-position of the residues indicated at each point in the aaryl nucleus and μ », 'ώ334203 where R'j and R'2 have already given meanings. Acyl denotes an acyl residue and the cores shown with dashed lines indicate that these may be present or not.

2nd anthraquinone

In this formula, L and L 'represent substituents, including especially sulfonic acid groups, p denotes an integer from 0 to 2, R represents a methyl or ethyl group or hydrogen, R'j and R'2 denotes independently hydrogen or halogen residues.

3rd phthalocyanine

In this formula, Pc represents the residue of a nickel or copper phthalocyanine, L and L 'represent substituents, especially sulfonic acid groups, r represents an integer from 0 to 2, q represents the number 0 or 1, R' represents a methyl group or preferably hydrogen, R 'j and R'2 denote independently hydrogen or halogen residues. The phthalocyanine residue Pc preferably exhibits as additional substituents 1-2 sulfonic acid and / or 1-2 sulfonic acid amide groups such as -SOgNR2, -SOgNH-alkyl, -SO2N (alkyl)2- and -SO2NH (aryl) groups, wherein alkyl represents alkyl radicals having 1-3 carbon atoms.

The above compilation of a selection of suitable azo, anthraquinone and azaporphine dyes and fluorine-substituted pyrimidine rings does not limit the general formulas either with regard to the preparative possibilities of producing such dyes within the scope of the general formula (I) or with respect to the general formula (I). valuable utility properties of these products. The new dyes may also contain any substituents commonly used in dyes, such as sulfonic acid, carboxylic acid, sulfonamide and carbonamide groups, which may be further substituted by the amide nitrogen, sulfonic acid ester and carboxylic acid ester groups, alkyl, aralkyl and aryl residues, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, such as chlorine, bromine and fluorine, hydroxy, alkoxy, thioether, azo groups and the like. The dyes may also exhibit additional fixable groups, such as mono- or dihalogen triazinylamino-, mono-, di- or triheelogenpyrimidinylamino-, 2,3-dihaloquinoxaline-6-carbonyl- or -6sulfonylamino-, 1,4-dihalo-phthalazine - or -6-sulfonylamino, 2-halo or 2-alkylsulfonyl or 2-arylsulfonyl-benzthiazole-5-carbonyl or -5-sulfonylamino, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfonic acid oxalkylamide, oxoalkyl amide and oxo haloalkylamino, acryloylamino, haloacylamino groups or additional reactive groups.

The novel dyes of formula (I) are obtained by introducing into dyes or dye ex-products in a manner known per se, at least one fluorine-substituted pyrimidine ring

over an amino group -N (R) -. Where dye precursors are used, these are converted in a manner known per se, especially by diazotizing and / or coupling and / or condensation reaction to desired final dyes. In the formula (III), R 1 represents hydrogen or a substituent and R 8 is hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl or aryl residues, carboxylic acid ester, carboxylic acid amide, alkylsulfon or arylsulfone groups and F represents a fluorine atom.

The insertion of residue (III) over an amino group -N (R) - in dyes or

10 dye preparations can be made by various preparative methods. Thus, amino or amide group-containing dyes or dye ex-products which have a reactive hydrogen atom at the amine and amide nitrogen can be reacted with compounds of the general formula

where R and R have the above meanings (F represents a fluorine substituent) and X 2 represents an anionically decomposable residue, where in case dye exchanger products are used, these are appropriately converted to desired final dyes. Among the splice reactive substituents X anionic residues, the fluorine substituent is of particular interest. Further case-by-case suitable anionically cleavable ++ residues are, for example, quaternary ammonium groups, such as -N (CHg) g and -NiCgHglg.

Suitable for the reaction heterocyclic pyrimidine compounds of formula (XIII) 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-trifluoropyrimidine75-carboxylic acid methyl or ethyl ester or -5-carboxylic acid amide, 2,6-difluoro-5-methyl-4-chloropyrimidine, 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-chloro2,4-difluoropyrimidine, 6-phenyl-2,4-difluoropyrimidine, 6-trifluoromethyl-2,4-difluoropyrimidine din, 5-trifluoromethyl-2,4,6-trifluoropyrimidine, 5-trifluoromethyl-2,4-difluoropyrimidine, 2,4-difluoro-5-nitropyrimidine, 2,4-difluoro-5-trifluoromethyl-pyrimidine, 2,4 -difluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-phenyl-pyrimidine, 2,4-difluoro-5-carbonamido-pyrimidine, 2,4-difluoro-5-carbomethoxypyrimidine, 2,4-difluoro-6-trifluoromethyl-pyrimidine, 2,4-difluoro-5-bromo-o-trifluoromethyl-pyrimidine, 2,4-difluoro-6-carbonamidopyrimidine, 2,4-difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6-phenylpyrimidine, 2,4-di-fluoro-6-cyanopyrimidine, 2,4,6-trifluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-chloro-6-carbomethoxy -pyrimidine, 2,4-difluoro-5-sulfonamido-pyrimidine.

In the condensation reaction with the amino and amide group containing dyes and dye products, these pyrimidine derivatives react during cleavage of the residue X, probably always in the 4-position. Therefore, in general formulas (I), (II) and (IV) η (XII), the pyrimidine ring is probable and preferably in the 4-position bonded to the residue of / N (R) -, N (R ') - group-containing dye .

The fluoropyrimidine compounds mentioned and further useful according to the invention can generally be readily obtained by reacting the corresponding chlorine or bromine compounds with alkali fluorides, e.g. with potassium fluoride, NallF ,,, KSOgF, SOFg, AgF2, or by reacting the corresponding OH compounds with SF SF, COF2, COC1F or cyanurfluoride or by heating the corresponding diazonium tetrafluoborates.

Particularly preferred for the reaction of the invention are reactive components which correspond to the general formula

where R'j and R '2 independently of one another denote hydrogen or halogen residues (chlorine, bromine or fluorine) and Y represents an anionically precipitated residue, especially a fluorine substituent.

The reaction of the amino and amide group-containing dyes or dye precursors with hetero-cyclic compounds of formula (XIII) is carried out depending on the type of starting compounds used in organic, organic-aqueous or aqueous media at temperatures of from -10 ° C to 100 ° C, preferably between 0 and 50 ° C, in the presence of alkaline condensing agents, such as aqueous alkali carbonate or alkali hydroxide solutions.

When using dye intermediates, the condensation products obtained are converted per se usually to the desired final dyes. This process is of particular interest in the preparation of azo dyes by, e.g. initially a diazo and / or coupling component exhibiting a reactive amino or amide group condenses with the reactive components (XIII) and (XIV, respectively) and then converts the resulting intermediate by diazotization and / or coupling and / or condensation to an azo dye. With this, further conversion reactions can then be undertaken, as is common with azo dyes, e.g. acylation, condensation, reduction and metallization reactions.

Also, in the preparation of other dyes, especially those belonging to the phthalocyanine and anthraquinone series, the concen- tration of a reactive component (XIII) and (XIV), respectively, may initially be effected with an intermediate, e.g. with m-phenylenediamine or an m-phenylenediamine sulfonic acid, after which the resulting reaction product is further condensed with an anthraquinone sulfonic acid halide or with a copper nickel phthalocyanine sulfonic acid halide to one. reactive phthalocyanine dye.

A further variant for the preparation of the new dyes with former! (I), which is useful in some cases, consists in the presence of dyes or especially dye intermediates which have at least one group of the general formula. '

POOR QUALITY

Where R, H | and it, having the meanings specified and Z denotes an anionically cleavable residue except for a fluorine substituent »exchanges Z in per se known. way. against a fluorine substituent and when using dye ex-products then transfer them to desired final dyes. The yield of one or more anionically cleavable substituents Z, e.g. Cl or Br atoms, against, fluorine substituents can be carried out, for example, in the manner already stated.

The dyes obtainable according to the various described processes can, as already mentioned for some cases, be subjected to further reactions which are common to dyes, for example by treating all metallisable dyes with intermediates, especially with chromium, cobalt, copper or nickel salts, dyes. , which exhibit reducible groups, especially, nitro groups, reduced, dyes, which exhibit acylable groups, especially acylable amino groups, acylated or by subsequently treating dyes with sulfating agents such as chlorosulfonic acid. oleum or SO 2 in chlorinated hydrocarbons, for the purpose of introducing (additional) sulfuric acid groups into the products. The latter process is sometimes of particular importance for the anthraquinone and phthalocyanine dye series. Sulfonic acid and / or carboxylic acid group-containing dyes of formula (1) are preferred within the scope of this invention.

Depending on the number of reactive -HMR groups in question for the reaction reaction in the dye residue or in the dye ex-products, one or more groups of the general formula (11) can be incorporated into the dyes. In most cases, the number m = 4 is not exceeded, however, dyes, especially those with high molecular structure, can be more than 1, e.g. up to 11 groups of formula (11) are synthesized.

If the dyes prepared in accordance with the process of the invention contain metal complexing groups, these can be transferred to their metal complex compounds by the action of metal leaching agents, for example copper, nickel, chromium or cobalt salts. Likewise, they may be subjected to other common conversion reactions, such as diazotizing, coupling, acylation and condensation reactions.

In the reaction of amino group dyes with reactive components of formula (XIII) or (XIV), groups of especially preferred dyes are obtained if the amino group-containing starting dyes which form the dyes of the formulas (TV) to (XII) are substituted, instead of

and -N (R ') - A group, respectively, have the group -X (H') - H or -N (R) -H.

In the preparation of phthalocyanine dyes one can add. first producing one with the reactive components (XIII) or (XIV) monocondensed diamine ring compound and then condensing it with preferably copper or nickel phthalocyanine sulfonic acid halides, while simultaneously or subsequently, other amino compounds such as ammonia, aliphatic amine or amine compounds, In this way, phthalocyanine, preferably copper or nickel phthalocyanine sulfonamide dyes containing a certain content of sulfonarylamide groups bearing the reactive group, and in addition a certain content of non-reactive sulfonamide groups and / or free sulfonic acid groups are obtained. Likewise, one may condense copper or non-alkaline alocyanine sulfonic acid (aminoaryl) amides, which may also exhibit additional optionally X-substituted sulfonamide groups of other type and free sulfonic acid groups, at the aminoaryl residue's amino group with reactive components (XIII) or (XTV). to the new dyes of formula (I).

The new dyes are extremely valuable products, which are suitable for different uses. As water-soluble compounds, they find particular interest in dyeing hydroxyl group-containing and nitrogen-containing textile materials, especially textile materials of native and regenerated cellulose, in addition of wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive fluorine substituent (s) in the pyrimidine ring, the products are particularly well suited as reactive dyes for dyeing cellulose materials in accordance with the recent art. The results obtained, especially the wet-tinted lichen, are excellent.

For staining cellulose, the dyes are preferably inserted into an aqueous solution which can be added with alkaline reacting substances such as alkali hydroxide or alkali carbonate or with compounds passing into alkaline reacting substances such as alkali hydrogen carbonate and C The solution can be added with additional aids, which, however, are not allowed to react with the dye in the desired manner. Such additives are, for example, surfactants, such as alkyl sulfates, or substances which prevent the dye migration, or coloring, auxiliary products, such as urea, or inert thickening agents, such as oil-wetted enemulsions, trays, starches, alginates or methylcells.

The solutions or pastes thus prepared are applied to the material to be transported, for example, by means of lumpy nuggets in foulard (short bathing solution) or by applying pressure, and then heated for a period of time to higher temperature, preferably 10 ° to 15 ° C. The heating may be effected by exhaust heat, in steam apparatus, on heated rollers, or by introduction into heated concentrated salt baths, either by one of these devices or in any order in succession.

When using a scrubbing or dye nuisance bath without alkali, a passage of the dry material is connected through an alkaline reacting solution, which is added with saline or yeluber salt. Sa It.ti In this case the removal of dye from the fibers in this way decreases.

It is also possible to pre-treat the material, which is to be dyed, with electricity in the abovementioned acid-binding agents, then treat it with the solution or paste of the dye and finally, in the specified manner, effect a fixation at elevated temperature.

When dyeing from a long bath solution, an aqueous solution of the dye (bath solution ratio 1: 5 - 1:40) is used at room temperature and colors for 40-90 minutes, possibly while raising the temperature to 20-9()C, preferably 30-50 ° C, during batch addition of salts, e.g. sodium sulfate, and then alkali, for example, sodium phosphates, sodium carbonate, VaOIJ or KOH. In this case, the chemical reaction between dye and fiber occurs. After subsequent chemical fixation, the dyed material is rinsed, hot and then saponified, whereby non-fixed residues of the dye are removed. +An obtains excellent genuine, special, hydrogen and lb light-resistant colors.

In some so-called "cold storage" seals, one can disregard the post-heating of the scribbled tissue by storing the tissue for a period of time, e.g. 2-20 hours, at room temperature. In this process stronger alkaline is added than in the above-described staining process from long bathing solution.

When printing hydroxyl groups containing materials, a printing paste from the dye solution is used, a thickener such as sodium alginate, and an alkaline reacting or alkaline decomposing compound such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium hydrogen the material is flushed and saponified.

If the dyes contain metal complexing groups, the dyes and prints can often obtain better authenticity by finishing with meta 1 leaching agents, such as copper salts, e.g. copper sulphate., chromium, cobalt and nickel salts such as chromium acetate, cobalt sulphate or nickel sulphate.

Amide groups containing textile materials, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally stained according to common staining methods in the acid to neutral range, sometimes a final increase in the pH of the dye bath, e.g. to 6.5-8.5, is advantageous.

The dyes are applied, for example, to synthetic polyamide tissue as solutions or preferably in dispersed form and then treated, possibly together with (preferably small amounts) of acid binding agents such as sodium carbonate.

Particularly favorable results are obtained with such dyes, which are not soluble ('These are processed?

or only slightly soluble in water. In accordance with conventional techniques and under the addition of known auxiliaries to a dye dispersion and used as such in a dyeing and / or scrubbing bath or in a printing paste. Aids suitable for this use include: compounds which prevent the dye migration on the fibers such as cellulose ethers, alkali metal chlorides and sulphates, wetting agents such as ethylene oxide and fatty alcohol condensation products and phenols, sulphonated fatty alcohols, solvents such as thiodiglycol,

The post-treatment of the dyes, impregnations and prints obtained on polyamide fiber fabrics is preferably carried out at a temperature of from 50 to 110 ° C, and for a period of from 5 to 60 minutes. Even in this case, the dyes, when the dyes used, contain metal complexing groups, can sometimes be improved for their authenticity with meta-lowering agents such as copper salts, e.g. copper sulphate or chromium, cobalt and nickel salts such as chromium acetate, cobalt sulphate or nickel sulphate.

The dyes obtained with the new dyes are generally distinguished by good to very good authenticity properties, especially by prominent wetness.

The new products of formula (I), in comparison with constitutionally almost comparable known chlorine or bromopyrimidinylamines, exhibit non-polar reactive dyes, for example, as described in Belgian patents 572 973, 573 299 and 578 742, significant technical advantages. Thus, the new dyes exhibiting a 2,6-difluoro-5-chloropyrimidinylamino or a 2-fluoro5,6-dichloropyrimidinylamino residue, surprisingly compared to the nearly comparable trichloropyrimidinylamino dyes, provide a better color yield on cotton and cotton dye on cotton fiber. superior to those of color strength when dyeing from long bathing solution.

In contrast to the known chloropyrimidine reactive dyes, the new fluoropyrimirine reactive dyes are also well suited for the so-called cold-potting storage method for cotton and regenerated fibers. In the printing process, the new dyes can be inserted for quick fixing. The bond between fibers and dyes is many times stronger in alkaline medium than for previously known dyes.

The new fluoropyrimidine reactive dyes further distinguish in comparison to the known chloropyrimidine dyes by providing valuable dyes with good washing, picking and potting properties on wool. Also on the silk and synthetic superpolyamide and polyurethane fibers, wet-resistant stains are obtained.

in the following examples, parts denote parts by weight, unless otherwise indicated.

Example 1

To a solution of 34.7 parts of 2-aminonaphthalene-4,3-disulfonic acid. sodium and 7 parts of sodium nitrite in 300 parts of water were added under ice-cooling 28 volumes of concentrated hydrochloric acid, after which the mixture was stirred for half an hour at 0-10 ° C. After removal of excess nitric acid, 10.7 parts of 3-aminotoluene dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water were added, and the coupling was carried out by adjusting the mixture to pH 3-5. The resulting aminoazo dye was salted, suctioned, washed, and then redissolved in 1400 parts of water and 200 parts of acetone with the addition of sodium hydroxide solution. at pH 7. To this solution was added dropwise at 20-30 ° C 19.2 parts of 2,4,6-trifluoro-5-chloropyrimidine and a pH of 5.5-6 was maintained by means of 2-n soluble solution. Upon completion of the reaction, the resulting dye was salted out by the probable formula

with 210 parts of saturated saline and the product crystallized into yellow needles was aspirated and washed with 2% NaCl solution and dried at 50 ° C in vacuo.

When cellulosic tissue was printed with a printing paste containing 15 g of the dye, 100 g of urea, 300 ml of water, 500 g of alginate thickening (60 g of sodium alginate per kg of thickening), and 20 g of soda and which was filled with water to 1 kg; dried, steamed for 1 minute at 105 ° C, rinsed with warm water and boiling saponified to obtain a strong, reddish-yellow print with good wash and light fastness.

Example 2

0.1 mole of the copper complex compound of the formula

19 334203 (prepared according to the disclosures of German patent 1,117,235) by coupling diazotated 1-amino-8- (benzenesulfonyloxy) -naphthalene-disulfonic acid (3,6) in soda alkaline medium with equivalent amount of 2-acetylamino-5 hydroxinaftalindisulfonsyra- (4.8) conversion of the monoazo compound to copper complex by oxidative copper treatment and hydrogenation of the acetyl and benzenesulfonyl group) was dissolved in 2500 parts by volume of water at a temperature of 60-65 ° C at pH 6-6.5 and added at 20-30 ° with 0.12 mol 2,4,6trifluor-5-chloropyrimidine.

During the condensation, a pH of 6-6.5 was maintained by the addition of sodium carbonate solution. After completion of the reaction, the dye was salted out and isolated. The dye consisted in dried form of a dark powder which dissolved in water of blue color.

100 parts by weight of a cotton wool fabric were foularded at room temperature with an aqueous solution containing 2% of the dye, 15 g per 1 sodium hydrogen carbonate and 150 g per 1 urea, medium dried, heated for 2 minutes to 140 ° C, then rinsed and boiling saponified. The tissue was stained wet in very clear, blue tones.

Example 3 parts of an analog of Example 1 by coupling diazotated 2-aminaphthalene-4,8-disulfo / acid to 3-methylamino toluene obtained monoazo dye were dissolved in 400 parts of water, 100 parts of acetone at 20-30 ° C, added dropwise. with 20 parts 2.4,

6-trifluoro-5-chloropyrimidine, maintaining a pH of 6-7 by means of a 2-n soda solution. The condensation was continued until a sample on acidification no longer showed color tone change. The dye obtained had the probable formula

and salted, suctioned, washed and dried in vacuo at 30 ° C,

Cotton fabric was impregnated with a solution having a temperature of 20-25 ° C

- 20 which per liter of bath solution contained 20 g of the above dye and 0.5 g of a nonionic wetting agent (eg a polyoxetylated oleyl alcohol, as well as 150 g of urea and 15 g of sodium hydrogen carbonate. Then, the tissue was pressed between two rubber rolls to a moisture content of about 100. After intermediate drying at 50-60 ° C, heated for 2 minutes to 140 ° C, after which the resulting staining was thoroughly rinsed with warm water and treated for 20 minutes boiling with a solution which liter contained 5 g of Marseiller soap and 2 g of soda. After rinsing and drying, a strong, red-tinted yellow color was obtained with good wet, tear and light resistance.

The following table lists the diazo components, the coupling components and the reactive components which can be coupled to the amino group, from which analogous to the data in Examples 1-3 dyes can be constructed, whose tints - obtained according to one of the described application procedures - are also indicated in the table.

Abbreviations for the reactive components:

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

Example diazo components Coupling components no

Reactive- Tint components

<td> 4</td><td>2-4,8-aminonaftalin disulfonic acid</td><td>1-amino no-2-methoxy-5-methylbenzene</td><td>- A</td><td>yellow</td>

<td> 6</td><td>l-aminonaftalin-3,6- disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>II</td>

<td> 8</td><td>2-aminonaftalin-5,7- disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>II</td>

<td> 10</td><td>2-aminonaftalin-6,8- disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>! f</td>

<td> 12</td><td>4-Amino noazobenzene-3,4'-disulfonic acid</td><td>l-amino-3-methylbenzene</td><td>A</td><td>buff cont.</td>

- 21 334203

<td colspan="2">Example diazocomponents No.</td><td>Clutch Components</td><td>Reactive- components</td><td>Hue</td>

<td> 13</td><td>1-aminobenzene-4-sulfonic acid 1-aminonaftalin6 acid</td><td>l-amino-3-methylbenzene</td><td>B</td><td>buff</td>

<td> 14</td><td>2- (3'-sulfo-4'-aminophenyl) 6-methyl-benzothiazol-7-sulfonic acid</td><td>TL</td><td>A</td><td>yellow</td>

<td> 15</td><td>2-aminonaftalin-4,8-di- acid</td><td>l-methylamino-3- methoxybenzene</td><td>B</td><td>TL</td>

<td> 16</td><td>II</td><td>I-amino-3-acetylamino- benzene</td><td>A</td><td>II</td>

<td> 17</td><td>u</td><td>aniline</td><td>A</td><td>II</td>

Example 18

To a solution of 36.5 parts of the sodium salt of 1-amino-8-hydroxynaphthalene

-3.67disulfonic acid in 20 parts of water was added dropwise at 8-10 ° C 20 parts of 2,4,6-trifluoro-5-chloropyrimidine, with constant neutralization of liberated fluorine hydrogen one.

The pH of 5.5-6 was maintained. The reaction was chromatographically followed. The resulting solution of the dye intermediate was added to 900 parts of water and coupled at a pH of 7-8 at 0-5 C with 17.5 parts of diazotized 2-aminobenzenesulfonic acid dissolved in 200 parts of water. At a final pH of 6.5, salted with 80 parts of saline, suctioned and washed with 10% saline. Dry in vacuo at 30-40 ° C. The dye

formed small red needles.

When cotton or regenerated cellulose tissue was dyed or printed according to one of the procedures described in Examples 1-3 with this dye, clear, streaky red stains and prints were obtained with good wet, tear and lightness.

- 22 Equally good results are obtained according to the following procedure:

g of cotton rope was dyed in 1 liter of dye bath solution containing 1.5 g of the above dye by adding 50 g of saline in several portions over a period of 30 minutes at 20-30 ° C, then adding 20 g of soda and treating the material under 60 minutes at this temperature. After rinsing, boiling saponification and drying, a blue-stained red stain was obtained with good wet, tear and light resistance.

The following tables indicate the tints of additional dyes which are constructed from the similarly indicated diazo components, coupling components, and with the amino group of the latter interconnectable reactive components analogous to the data of Example 18, or also by reacting the corresponding aminoazo dyes with the reactive components described above. be able to stain or print on cellulose material:

Abbreviations for the reactive components are the same as in the table for example 3.

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Reactive- components</td><td>Hue</td>

<td> 19</td><td>1-aminobenzene-2-sulfonic acid</td><td>l ^ amino-e-hydroxy-naphthalene Iin-3,6-disulfonic</td><td>B</td><td>RED</td>

<td> 20</td><td>aminobenzene</td><td>L- (3'-aminobenzoyl-amino) - 8-hydroxy-naphthalene-3,6-di- acid</td><td>A</td><td>II</td>

<td> 22</td><td>l-amino-2-carboxy-benzene-4-sulfonic acid</td><td>l-amino-8-hydroxinaftalin- 3,6-disulfonic acid</td><td>A</td><td> 11</td>

<td> 23</td><td>1- amino-4-methylbenzene 2-sulfonic acid</td><td>II</td><td>A</td><td>II</td>

<td> 24</td><td>1-ami ηο-3-acetylamide nobenzene-6-sulfonic acid</td><td> 11</td><td>B</td><td>tt</td>

<td> 25</td><td colspan="2">1-Amino-3- (2 '- / 4-sulphonated phenylaming7-4'-chlorotriazine-1 ', 3', 5'-yl-6 ') aminobenzene-6-sulfonic acid</td><td>A</td><td>II</td>

<td> 26 '</td><td>1-aminobenzene-2-sulfonic acid</td><td>2-amino-5-hydroxy-naphthalene-7-sulfoqsyra</td><td>A</td><td>Orange</td>

cont.

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Reactive components</td><td>Hue</td>

<td>26a</td><td>l-amino-3- (2 '- / 4-sulfophenyl aminö7-4'-methylamino-triazine-l', 3 ', 5'-yl-6') - amino-benzene-6sulfonsyra</td><td>2-amino-5-hydroxy-naphthalene lin-7-sulfonic acid</td><td>A</td><td>Orange</td>

<td> 27</td><td>l-aminobenzene-2-sulphone acid</td><td>2-methylamino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>A</td><td>Orange</td>

<td> 28</td><td>l-amino-4-acetyl-amino 6-sulfonic acid</td><td>II</td><td>A</td><td>scarlet</td>

<td> 29</td><td>al</td><td>2-amino-5-hydroxy-naphthalene</td><td>A</td><td>II</td>

lin-7-sulfonic acid

Example 30

In a solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 700 parts of water 20.0 parts of 2,4,6-trifluoro-5-chloropyrimidine were added dropwise with good stirring, then at 20-30 ° C was stirred under constant neutralization of the released hydrofluoric acid to pH 6-7, until a sample on diazotization and coupling with 1-hydroxy-naphthalene-4-sulfonic acid gave a clear, yellowish-red color. The resulting dye intermediate was diazotized after addition of ice directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then combined with a prepared solution of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxy-naphthalene-3,6-disulfonic acid and 12 parts of soda. parts of water, whereby coupling was made to one

which was salted out, suctioned. was washed and dried in vacuo at 30-40 ° C. The dye dissolved readily in water of red color and gave clear, blue-stained red stains and prints on cellulose material according to one of the methods described above.

The table below indicates the color tones and pH of the coupling media 334203

The dye 24 was prepared analogously to Example 30 from a diazocomponent containing an additional, preferably acylable amino group, from a coupling component. and from a reactive component which can be coupled to the diazocomponent. For dyeing and printing of cellulose materials with the dyes in the table, the above methods can be applied.

Abbreviations for the reactive components are the same as in the Table for Example 3.

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Reactive- components</td><td>The pH of the coupling medium</td><td>Hue</td>

<td> 31</td><td>1,3-diaminobenzene ·</td><td> 2-aminonaftalin-5,7-disulfide</td><td>A</td><td> 4-5</td><td rowspan="2">Orange</td>

<td colspan="2">4-sulfonic acid</td><td>acid</td><td></td><td></td>

<td> 32</td><td>II</td><td>2-aminonaftalin-3,6-disulfide acid</td><td>A</td><td> 4-5</td><td>II</td>

<td> 33</td><td>II</td><td>2-aminonaftalin-6-sulfonic acid</td><td>B</td><td> 4-5</td><td>II</td>

<td> 34</td><td> 11</td><td>2-N-methylamino-8-hydroxy- naphthalene-6-sulfonic acid</td><td>A</td><td> 4-5</td><td>tt</td>

<td> 35</td><td>1,3-diami nobenzene</td><td>1- (3 ', 5'-dichloro-1', 2'-thi</td><td>A</td><td> 7-8</td><td>RED</td>

<td></td><td>4-sulfonic acid</td><td>azole-4'-carbonamido) -8hydroxy to phthali n-3,6-di sulfonic acid</td><td></td><td></td><td></td>

<td> 36</td><td>II</td><td>L- (2 ', 4'-dihydroxy-triazin1', 3 ', 5', - 6'-yl-amino) -8hydroxinaftalin-3,6-disulfonic acid</td><td>B</td><td> 7-8</td><td>LF</td>

<td> 37</td><td>II</td><td>L- (3 ', 5'-dichloro-l', 2'-t.iazol-4'-carbonamido) -8hydroxinaftalin-3,6-disulsonsyra</td><td>A</td><td> 7-8</td><td>it</td>

<td> 38</td><td>II</td><td>2-hydroxy naphthalene n-3,6-di-</td><td>A</td><td> 8</td><td>scharla-</td>

<td> 39</td><td>II</td><td>1-acetylamino-8-hydroxynaphthalene-3,6-di sulfonic acid</td><td>B</td><td> 7-8</td><td>RED</td>

<td> 40</td><td>II</td><td>L- (3'-sulfophenyl) -3-methyl pyrazolone-5</td><td>A</td><td> 6</td><td>yellow</td>

<td> 41</td><td>II</td><td>L- (2 ', 5'-dichloro-4'7sulfofeny1) -3-methyl-5-pyrazolone</td><td>A</td><td> 6</td><td>II</td>

<td> 42</td><td> 11</td><td>1- (5 ', 7'-disulfonaphthyl-2'-) ·</td><td></td><td></td><td></td>

<td></td><td></td><td>3-methyl-5-pyrazolone</td><td>A</td><td> 6</td><td></td>

<td> 13</td><td> 11</td><td>L- (3'-sulfophenyl) -3-methyl-5- aminopyrazole</td><td>B</td><td> 6</td><td>al</td>

- 25 334203

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Reactive- components</td><td>Arrow of the coupling medium</td><td>Fary * TUU</td>

<td> 44</td><td>l, 4-diöminobei5-sei'- 3-sul Con-? Y u-</td><td>2-Amino-O-hy di oxy-naf to 1 in 6-sulfonic acid</td><td>A</td><td> 4-4,5</td><td>RED</td>

<td> 45</td><td>1,4-diami nobenzene-3-sulfonic acid</td><td>2-acetylamino-5-hydroxy- naphthalene-7-sulfonic acid</td><td>A</td><td> 6-7</td><td>schar- sheets</td>

<td> 46</td><td>it</td><td>1-acety lami no-5-new dx uxy-</td><td>B</td><td> 6-7</td><td>RED</td>

naphthalene-7-sulfonic acid

Example <17

51.6 parts of a by diazotizing 1-hydroxy-2-amino-benzene-4-sulfonic acid and coupling with 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper release coloring agent obtained by the formula

was dissolved in 1500 parts of water at pH 7. With careful stirring, 20.0 parts of 2,4,6-trifluoro-5-chloropyrimidine was added dropwise at 20 DEG C. and the hydrochloric acid released was continuously neutralized with soda solution to pH 6-7. When free amino groups could no longer be detected, salted, extruded, washed and dried in vacuo at 30-40 ° C, the reactive dye formed of the formula

Tissues of cellulose material can be stained or printed with this dye

- 26 according to one of the above procedures in wet, tear and light-resistant ruby tones.

The following table shows heavy metal complexes of additional amino acids dyes and the reactive components interconnected with the amino group, as well as the dyes of these dyes on cellulose material. The preparation of the aminoazo dyes, their metal complexes and their reaction with the reactive components can be carried out analogously to Example 47.

Abbreviations for the reactive components are the same as in the table for example 3.

Examples Amino azo dye Complex bottom- Reactive compo-

<td> 48</td><td>1-hydroxy-2-aminobenzene-4,6-disulfonic acid -2-amino-5-hydroxynaphthalene-7-sulfonic acid</td><td>Cu</td><td>A</td><td>Ruby</td>

<td> 49</td><td>1-hydroxy-2-aminobenzene-4-sulfonic acid - 2-ethylamino-5-hydroxynaphthalene ·. -7-sulfonic acid</td><td>Cu</td><td>A</td><td> «</td>

<td> 50</td><td>1-Amino-2-hydroxy-6-nitro-naphthalene-4-sulfonic acid-42-amino-5-hydroxynaphthalene-7-sulfonic acid.</td><td>Cu</td><td>A</td><td>II</td>

<td> 51</td><td>II</td><td>Cr</td><td>A</td><td>Green- scratchy gray</td>

<td> 52</td><td>l-amino-2-hydroxy-6-nitronaftalin- 4-sulfonic acid ^ l-amino-8-hydroxy- naphthalene-4-sulfonic acid</td><td>Co.</td><td>B</td><td>RED- scratchy black</td>

<td> 53</td><td>l-amino-2-hydroxy-5-methylsulfonyl- -benzene-l ^ aminoe-hydroxy-naphthalene 3,6-disulfonic acid</td><td>Cu</td><td>A</td><td>violet</td>

<td> 55</td><td>II</td><td>Cr</td><td>A</td><td>Green- scratchy black</td>

<td> 56</td><td>1-Amino-2-methylbenzene-4-sulfonic acid - 1-amino-2-hydroxy-5-methylbenzene-1-amino-8-hydroxy-Na-1-n-4,6-disulfonic acid</td><td>Cu</td><td>B</td><td>blue</td>

- 27 334203

Example Amino azo dye Complex Bun- Reactive Com- ColorNo the heavy components tons of numbers

<td> 58</td><td>it</td><td>Cr</td><td>A</td><td>Green- scratchy. black</td>

<td> 59</td><td>(1-Amino-2-chlorobenzene-4-sulfonic acid - 1-hydroxy-2-acetylaminobenzene), saponified 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid</td><td>Gu</td><td>A</td><td>navy</td>

<td> 60</td><td>it</td><td>Co.</td><td>A</td><td>Green</td>

<td> 61</td><td>1-ami ηο-8-hydroxy-naphtha 1-n-4- * sulfonic acid {- 1-hydroxy-2,6-diaminobenzene-4-sulphonic acid - 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 f-1-hydroxy-2,6-diaminobenzene-4-sulphonic acid 2,2-hydroxy-naphthalene</td><td>Co.</td><td>A</td><td>II</td>

<td> 63</td><td>1-amino-8-hydroxynaphthalene-4-sulfonic acid 1-hydroxy-2,6-diami nobenzene-4-sulphonic acid tonic acid-3-methyl-pyrazolone- (5) Example 64</td><td>Co.</td><td>A</td><td>hrs</td>

<td></td><td>96 parts (for 100% substance)</td><td colspan="2">off in the usual way</td><td>by inversion</td>

<td>can</td><td colspan="2">of chlorosulfonic acid and thionyl chloride on copper phthalocyanine</td><td colspan="2">freshly made copper</td>

parphthalocyanine tetrasulfochloride or its isomer, from 1-sulfobenzene-3,4-dicarboxylic acid over the corresponding copper phthalocyanine-tetrasulfonic acid, made up of copper phthalocyanine tetrasulfochloride was suspended in the form of its moist, well-washed suction cake and dissolved in 500 parts water and 500 parts water and 500 parts water 50 parts of 1,3-diaminobenzene in 500 parts of water, after which the pH of the mixture was adjusted with soda to 8.5. The suspension was stirred for 24 hours at room temperature with the pH constantly maintained at 8.5 by continuous addition of soda. The resulting condensation product was precipitated at pH 1-2 by the addition of saline, suction, washed and then redissolved neutral in 1000 parts of the aqueous solution. In the blue solution, 57 parts of 2,4,6-trifluoro-5-chloropyrimidine were introduced under intensive stirring, whereupon with continuous neutralization with soda solution to pH 6 was stirred for as long at 20-30 ° C until free amino groups could no longer be detected. The reactive dye thus obtained of the formula

salted, washed and dried in vacuo at 30-40 ° C. It consisted of a dark blue, water-blue soluble powder and colored cotton and regenerated cellulose according to one of the above-mentioned dyeing or printing procedures in clear blue tones with good wet, tear and light fastness.

Instead of the 96 parts of copper phthalocyanine tetrasulfochloride, otherwise, in the same way as in Example 64, 87 parts (with respect to 100% substance) of a copper or nickel phthalocyanine trisulfochloride obtained by the effect of chlorosulfonic acid on copper or nickel phthalocyanine can also be obtained. form of its moist, well-washed suction cake with ice water is inserted, thus obtaining clear blue-colored reactive dyes.

Sven when working analogously to Example 64 but starting from 87 parts of copper phthalocyanine trisulfochloride and instead of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonic acid, 90 parts of the sodium salt of 4,4'-diamino-diphenyl2,2'-substituted disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilben-2,2'-disulfonic acid, there are obtained reactive dyes which dye cellulose materials according to one of the above-mentioned processes in hydrogen, tear and light-resistant, clear blue tones.

If you start from 4 ', 4', 4 ', 4II ,,-tetrafenyl-Cu-phthalocyanine, after sulfochlorination and reaction with 1,3-phenylenediamine and acylation with 2,4,6 trifluoro-5-chloropyrimidine, a reactive dye is obtained which, in the presence of acid preparations, stains cellulose material in clear, wet and light green green.

Example 65 parts of 1-amino-4- (4'-aminophenyl) amino-anthraquinone-2,5,8-trisulfonic acid were dissolved in 630 parts of water, adjusted with sodium liquor to pH 6 and then added dropwise at 0-5 ° C with 18 parts of 2,4,6-trifluoro-5-chloropyrimidine, with a pH of

- 29 6-6.5 were maintained using soda solution. After completion of reaction, post-salt with 7 parts potassium chloride. was suctioned and washed with 3% potassium chloride solution. The dye obtained in the form of blue-green small needles was dried at 30 DEG-40 DEG C. in vacuo. It probably had the following formula

and colored cotton in green stained blue tones.

Example 66

When applied analogously to Example 47 but instead of the copper-containing amino monoazo dye used therein, the equivalent amount of a chromium complex of coupling diazotized 1-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid with 1- 3 '- ( 3-Aminophenyl) -sulfonylimido-sulfonyl-phenyl-3-methylpyrazolone- (5) obtained aminoazo dye, a reactive dye was obtained which stained cellulose material according to one of the above-mentioned processes in amber tones with good wet, tear and light resistance.

Example 67

0.1 mole of the copper complex compound of the formula

Sogna

was dissolved at pH 6 in 3000 parts by volume of water and combined with stirring at a temperature of 20-30 ° C with 16.8 parts by weight (0.1 mole) of 2,4,6-trifluoro-5-chloropyrimidine, using 2-n potassium carbonate solution a pH of 6 was maintained. The mixture is stirred

Until the condensation ends, the dye is separated by the addition of a small amount of sodium chloride and isolated. The residue was washed with acetone and dried at room temperature under reduced pressure. A dark powder was obtained which dissolved in water of green color and colored cotton according to the procedures in Examples 1-3 in green tones.

with a temperature

Cotton tissue was impregnated with a solution / of 20-25 ° C, which per liter of bath solution contained 25 g of the above dye and 0.5 g of a nonionic wetting agent (eg a polyoxetylated oleyl alcohol), 150 g of urea and 20 g. g of sodium carbonate Then the tissue was pressed between two rubber rolls to a moisture content of about 100%. After intermediate drying at 50 ° -60 ° C, the mixture was heated to 140 ° C for 2 minutes and the resulting dye was thoroughly rinsed with warm water and treated for 20 minutes boiling with a solution containing 5 g of marseiller soap and 2 g of soda. After rinsing and drying, a green stain was obtained with good wet, tear and light resistance.

Also according to one of the other dyeing or printing processes described in Examples 1-3, 18 and 30, clear greens were obtained with good authenticity on cellulose materials.

of the formula obtained by coupling the diazonium compound of 6-acetamino-2-aminonaphthalene 4,8-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound to copper complexes was dissolved at pH 6.5 in 2000 volumes of water and joined with 20 parts by weight of 2,4,6-trifluoro-5-chloropyrimidine. The reaction mixture was stirred at 20-30 ° C until the condensation was completed, maintaining the pH of the reaction solution with the addition of soda solution at 6-7. After completion of the reaction, the dye was salted off, isolated and vacuum dried.

The dried dye was a dark powder, which dissolved in water of violet color and dyed cotton in the presence of alkali in bluish-violet tones.

Example 69

An aqueous solution of 0.1 mole of the copper complex of the formula

prepared in accordance with the disclosures of German Patent Specifications 1,061,460 and 1,085,988, respectively, were reacted in the usual manner with 22 parts by weight of 2,4,6-trifluoro-5-chloropyrimidine. The pH of the mixture was maintained by adding soda at a value of 6-7 and the dye was isolated after completion of reaction by salting out. In a dried state, it formed a dark powder, which dissolved in water of violet color. Cotton fabric was dyed in light and wet-resistant violet tones.

Example 70

27.5 parts of 2-methylamino-5-hydroxy-naphthalene-7-sulfonic acid sodium were dissolved in 150 parts of water, added with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine and stirred at 30 ° C while constantly neutralizing the mixture. the resulting fluorine hydrogen with a total of 34 parts by volume of 16% soda solution to pH 6-7. The acylation was terminated after a short time, the pH being 6 and no longer changing.

Then 30 parts of sodium hydrogen carbonate were added and then dropwise added at 20 ° C over a period of 15 minutes a diazo suspension of 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulfonic acid in 200 parts of water. The immediately formed orange color reactive dye of the formula

was completely separated after one hour of stirring by addition of 80 parts of brine, then filtered off, washed with dilute brine and dried in vacuo at 35 ° C. The colored cellulose material according to the above-mentioned procedures in red-knit orange tones with very good wet resistance and good chlorine resistance.

Analogously, acylation of the aminonaphthanol sulfonic acids listed in column 3 of the table below was obtained with 2,4,6-trifluoro-5-chloropyrimidine and coupling of the acylaminophenol sulfonic acids formed with the orange diazocomponents listed in column 2 to red reactive dyes.

<td>Example No</td><td>diazo components</td><td>Aminonaftolsulfonsyra</td><td>Tint on cotton</td>

<td> 71</td><td>2-ami nonaphthalene-1,7disulfonic acid</td><td>2-ethylamino-5-hydroxy-naphthalene-7- acid</td><td>Orange</td>

<td> 72</td><td>II</td><td>2- (β-Hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>tt</td>

<td> 73</td><td> 11</td><td>2-amino-5-hydroxinaftalin-7-sulphate acid</td><td>tt</td>

<td> 74</td><td> 11</td><td>2-amino-5-hydroxinaftalin-7-sulphate acid</td><td>II</td>

<td> 75</td><td>n</td><td>2-am in ηο-8-hydroxy to ft a1i n-6-s phonic acid</td><td>scarlet</td>

<td> 76</td><td> 11</td><td>2-amino-8-hydroxinaftalin-3,6-di- acid</td><td>II</td>

<td> 77</td><td>2-aminonaftalin-l, 5disulfonsyra</td><td>2-methylamino-5-hydroxy-naphthalene 7-sulfonic acid</td><td>Orange</td>

<td> 78</td><td>II</td><td>2-ethylamino-5-hydroxy-naphthalene-7- acid</td><td>II</td>

<td> 79</td><td>II</td><td>2- (Phydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td> 11</td>

<td> 80</td><td>II</td><td>2-ami ηο-5-hydroxy-naphthali n-7-sulfonic acid</td><td>II</td>

cont.

- 33 334203

Aminonaftolsulfonsyra

diazo components

2-aminonaftalin-1,5disulfonsyra

2-aminonaphthalene-1,5disulfonic acid tf

2-aminonaphthalene-1,5,7 trisulfonic acid

II

2-aminobenzene sulfonic acid fr

II

2-ami nonaphthalic n-1sulfonic acid

2-ami nonaphthalene-1,5disulfonic acid

II

2-aminonaftalin-1,7disulfonsyra

II

2-Amino no-5-hydroxy naphtha 1 in n-1,7-di sulfonic acid

2-amino-8-hydroxinaftalin-6-sulfonic acid

2-amino-8-hydroxinaftalin-3,6-disulfonic acid

- 2-amino-5-hydroxynaphthalene in 7-sulfonic acid

2-methylamino-5-hydroxy-naphthalene-7sulfonsyra

2-amino-8-hydroxinaftalin-6-sulfonic acid

2-methylamino-5-hydroxy-naphthalene-7sulfonsyra

2- (Phydroxietylamino) -5-hydroxinaftalin ** 7-sulfonic acid

2-amiηο-8-hydroxinaftaliη-6-sulfonic acid

2-amino-8-hydroxinaftalin-3,6-disulfonic acid

2-amino-5-hydroxinaftalin-1,7-disulfonic acid

1-Amino-8-hydroxy-naphthalene n-3,6-di-sulfonic acid 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid

1-amino-8-disulfonic hydroxinaftalin33,6

1-ami ηο-8-hydroxy naphthalene-4,6-di sulfonic acid

1-amino-8-hydroxinaftalin-6-sulfonic acid

1-amino-8-hydroxinaftalin-3,6-disulfonic acid

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

1-amiηο-8-hydroxinaftalin-6-sulfonic acid

Tint on cotton orange scarlet

II orange scarlet orange η

scarlet

II

II bruised red u

II «

II u

farts.

<td>Example rir</td><td>diazo components</td><td>Aminonaftolsulfonsyra</td><td>Tint on cotton</td>

<td> 100</td><td>2-Aminones phthalin-1,5,7-t-trisulfonic acid</td><td>1-amine no-8-hydrox in naphthalene η-6-s ulonic acid</td><td>blåstickigt RED</td>

<td> 101</td><td>1-amino-4-chlorobenzene 2-sulfonic acid</td><td>1-ami ηο-8-hydroxy naphthalene in n-3,6-di sulfonic acid</td><td>II</td>

<td> 102</td><td>1-amino-2-methoxy-bensen5 acid</td><td>-1-Amino-8-hydroxinaftalin-3,6-disulfonic acid</td><td>II</td>

<td> 103</td><td>1-amino-benzene-2-carboxylic acid-4-sulfonic acid</td><td>1-amiηο-8-hydroxinaftalin-3,6-disulfonic acid</td><td>II</td>

<td> 104</td><td>1-amiηο-4-acety1-aminobenzene-2-sulfonic acid</td><td>it</td><td>violet</td>

<td> 105</td><td>LF</td><td>I-ami ηο-8-hydroxy naphthalene n-4,6-di sulfonic acid</td><td>blåstickigt RED</td>

Example 106

56.8 parts of a diazotized 1-amiηο-3-acetylaminobenzene-6-sulfonic acid on 2-aminonaphthalene-5,7-disulfonic acid in acetic acid and the alkaline or acidic hydrolysis of the acetylamino group obtained at diamino azo dye were dissolved at pH 7 in 450 parts water. After addition of 20 parts of 2,4,6-trifluoro-5-chloro pyrimidine, stirring was constantly neutralized with hydrochloric acid released with soda solution to pH 6-7 for about 1 hour at 30 ° C. After completion of acylation, the salts were filtered off, filtered off, redissolved in 4000 parts of water at 30 ° C and the reactive dye formed was filtered with the presumable formula

and then separated in completely pure form from the filtrate by the addition of 400 parts of saline. The dye was dried in the usual manner at 35 ° C in vacuo. The stained cellulose material according to one of the above-mentioned procedures in genuine yellowish orange tones.

- 35 334203

Exempsl-Xfi?

fill a neutral solution of 60 parts of the trisodium salt of one. by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 3-acetylamino-aniline in acetic acid obtained aminoazo dye in 500 parts of water, 20 parts of 2,4,6 trifluoro-5-chloropyrimidine were added and stirred for 1 hour at 30 ° C. , whereby a constant pH of 6 was maintained by constant addition of sodium liquor. The partially precipitated acylation product was completely separated at pH 7 by the addition of 100 parts of saline and filtered off. For purification, the reactive dye thus obtained could be redissolved in 2500 parts of water at 30 ° C, clarified and, again, by desalting the filtrate with 350 parts of saline. The dye had the formula

O and after filtering, drying at 35 ° C and painting a yellow powder which dissolved readily in water of yellow color and stained cellulose fibers according to one of the above staining procedures in the presence of acid binding agents in very genuine reddish yellow tones. Genuine yellow dyes are also obtained on wool and polyamide fibers.

Similar dyes are obtained when applied analogously to the above with, instead of 60 parts of 4'-amino-2'-acetylamino-phenyl- (1 ') - azo-naphthalene (2) -3,6,8-trisulfonic acid sodium, of the amino compounds listed in column 2 of the table below and the coupling components listed in column 3 in the usual manner obtained by diazotizing and coupling in acetic acid medium, the aminoazo dyes obtained and acylated with 2,4,6-trifluoro-5-chloropyrimidine.

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Tint on cotton</td>

<td> 108</td><td>2Taminonaphthalene η-1,5disulfinic acid</td><td>1-Amino-3-methyl-6-methoxy-benzene</td><td>strongly reddish. yellow</td>

<td> 109</td><td> (1</td><td>I-amino-3-metylhensen</td><td>yellow</td>

<td> 110</td><td>IN!</td><td>1-aminonaftalin-6-sulfonic acid</td><td>rödstickigt yellow</td>

<td> 111</td><td> 11</td><td>1-Amino-3-acetylamino-benzene</td><td>LF</td>

<td> 112</td><td> 11</td><td>3-aminofenylkarbamid</td><td> 1)</td>

<td> 113</td><td> 11</td><td>l-amino-3-hydroxiacetylaminobensen</td><td> 11</td>

<td> 114</td><td>2-aminonaftalin-: 5,7disulfonsyra</td><td>l-amino-3-methyl-6-methoxy-benzene</td><td>strongly reddish-yellow</td>

<td> 115</td><td> 11</td><td>1-aminonaftalin-7-sulfonic acid</td><td>rödstickigt yellow</td>

<td> 116</td><td> 11</td><td>l-amino-3-acetylaminobenzene</td><td> 11</td>

<td> 117</td><td>II</td><td>3-ami nofenylIcarbami d</td><td> 11</td>

<td> 118</td><td> 11</td><td>l-amino-3-hydroxyacetylamino-benzene</td><td> 11</td>

<td> 119</td><td>1-ami no to ft1i n-3,7disulfonic acid</td><td>l-amino-3-methyl-6-methoxybenzene</td><td>strongly reddish-yellow</td>

<td> 120</td><td>IN!</td><td>L-amino, 3-methylbenzene</td><td>rödstickigt yellow</td>

<td> 121</td><td>1-aminonaftaiin-3,7disulfonsyra</td><td>1-aminonaftalin-6-sulfonic acid</td><td>II</td>

<td> 122</td><td>2-ami nona Pt alin-3,6-disulfonic acid</td><td>1-amine no-3-methylbenzene</td><td>it</td>

<td> 123</td><td>hrs</td><td>1-Amino-3-methyl-6-methoxy-benzene</td><td>strongly reddish-yellow</td>

<td> 124</td><td> 11</td><td>in-Amino-3-acetylamino-benzene</td><td>rödstickigt yellow</td>

<td> 125</td><td> 11</td><td>3-aminofenylkarbamid</td><td>ff</td>

<td> 126</td><td> 11</td><td>1-amino-3-hydroxiacetylaminobensen</td><td> 11</td>

<td> 127</td><td>It.</td><td>1-aminonaftalin-6-sulfonic acid</td><td>tt</td>

<td> 128</td><td>2-ami nonaf ta 1 i n-6.8 ·; disulfonic acid</td><td>l-amino-3-acetylaminobenzene</td><td>If cont.</td>

IN

- 37 334203

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Tint on cotton11</td>

<td> 129</td><td>2-aminonaftalin-6,8- disulfonic acid</td><td>1-amino-2-methoxynaphthalene in η-6-sulfonic acid</td><td>strongly reddish-yellow</td>

<td> 130</td><td>TL</td><td>1-aminonaftaliη-6-sulfonic acid</td><td>red ic.kigt yellow</td>

<td> 131</td><td>2-4,8-aminonaftalin disulfonic acid</td><td>l-aminonaftalin-6-sulfonic acid</td><td>yellow</td>

<td> 132</td><td>TL</td><td>1-aminonaphthalene iη-7-sulfonic acid</td><td>II</td>

<td> 133</td><td>II</td><td>1-amino-2-metoxinaftalin-6-sulfonic acid</td><td>strongly reddish-yellow</td>

<td> 134</td><td>tt</td><td>1-metylamiηο-3-methylbenzene</td><td>yellow</td>

<td> 135</td><td>2-amine no. 1 in n-4,8disulfonic acid</td><td>In-ethylamino-3-methylbenzene</td><td>TL</td>

<td> 136</td><td>II</td><td>N-methylaniline</td><td>II</td>

<td> 137</td><td>II</td><td>N-ethylaniline</td><td>tt</td>

<td> 138</td><td>TL</td><td>N- (β-hydroxyethyl) aniline</td><td>II</td>

<td> 139</td><td>II</td><td>N-butylaniline</td><td>it</td>

<td> 140</td><td>2-aminonaftalin-3,6, 8-trisulfonic</td><td>Aniline</td><td>rödstickigt yellow</td>

<td> 141</td><td>TL</td><td>1-amino-3-methylbenzene</td><td> 11</td>

<td> 142</td><td>II</td><td>3-aminofenylkarbamid</td><td>II</td>

<td> 143</td><td>II</td><td>1-amino-3-hydroxiacetylaminobensen</td><td>II</td>

<td> 1444</td><td>II</td><td>1-amiηο 3-acetylamino-6-methoxybenzene</td><td>gulstickigt Orange</td>

<td> 145</td><td>II</td><td>1-amino no-3-acetylamino-6-methylbenzene</td><td>rödstickigt yellow</td>

<td> 146</td><td>II</td><td>1-ami no-3-methane-sulfoily 1-ami nobenzene</td><td>II</td>

<td> 147</td><td>II</td><td>2,5-dimethoxyaniline</td><td>gulstickigt Orange</td>

<td> 148</td><td>tt</td><td>3-mety1-6-methoxyaniline</td><td>II</td>

<td> 149</td><td>tt</td><td>N-methylaniline</td><td>rödstickigt yellow</td>

<td> 150</td><td>II</td><td>N-ethylaniline</td><td>II</td>

<td> 151</td><td>II</td><td>N-butylaniline</td><td>II</td>

cont.

<td>Example No</td><td>diazo components</td><td>Coupling components</td><td>Tint on cotton1</td>

<td> 152</td><td>2-aminonaftalin-3,6, 8-trisulfonic</td><td>N - ([3-hydroxyethyl) -a niline</td><td>rödstickigt yellow</td>

<td> 153</td><td>II</td><td>3- (N-ethylamino) -toluene</td><td>al</td>

<td> 15-1</td><td>II</td><td>2-aminotoluene</td><td>II ·</td>

<td> 155</td><td>II</td><td>1-amino-2,5-dimethylbenzene</td><td>strong red-streaked gu</td>

<td> 156</td><td> »</td><td>l-amino-2-methoxybenzene</td><td>II</td>

<td> 157</td><td> .11</td><td>l-amino-3-methoxybenzene</td><td>rödstickigt yellow</td>

<td> 158</td><td>TL</td><td>l-ethylamino-3-methoxybenzene</td><td> 11</td>

<td> 159</td><td>II</td><td>l-aminonaftalin-6-sulfonic acid</td><td>II</td>

<td> 160</td><td>II</td><td>l-aminonaftalin-7-sulfonic acid</td><td> 11</td>

<td> 161</td><td>2-aminonaftalin-4,6, 8-trisulfonic</td><td>1-amino-3-methylbenzene</td><td>II</td>

<td> 162</td><td>(t</td><td>l-amino-3-acetylaminobenzene</td><td>II</td>

<td> 163</td><td>1-aminonaphthalene-2,4,7-trisulfonic acid</td><td>1-amino-3-methylbenzene</td><td>yellow</td>

<td> 164</td><td>II</td><td>l-aminonaftalin-6-sulfonic acid</td><td>II</td>

<td> 165</td><td>4-nitro-4'-aminostil- bone-2,2'-disulfonic</td><td>1-amino-3-acetylaminobenzene</td><td>rödstickigt yellow</td>

<td> 166</td><td> 11</td><td>3-aminofenylkarbamid</td><td>II</td>

<td> 167</td><td>II</td><td>l-amino-3-hydroxiacetylaminobensen</td><td>II</td>

<td> 168</td><td>II</td><td>N-methylaniline</td><td>II</td>

<td> 169</td><td> 11</td><td>N-ethylaniline</td><td>LF</td>

<td> 170</td><td>II</td><td>'In-butylanilanilin</td><td>al</td>

<td> 171</td><td>it</td><td>N- (β-hydroxiety1) aniline</td><td>II</td>

<td> 172</td><td>II</td><td>L- (N-ethylamino) -3-methylbenzene</td><td> 11</td>

<td> 173</td><td>Aniline-2,5-disulfonic acid</td><td>l-aminonaftalin-6-sulfonic acid</td><td>II</td>

<td> 174</td><td>II</td><td>l-aminonaftalin-7-sulfonic acid</td><td>II</td>

<td> 175</td><td> 11</td><td>1-amino-3-methylbenzene</td><td>yellow</td>

<td> 176</td><td>II</td><td>1-amino-3-acetylaminobenzene</td><td> cont.</td>

Example Diazo Components Coupling Components no

Tint on cotton

177

An in 1 in-2,5-disulfonic acid

1-amiηο-2-methoxy-5-metylbeusen

178

179

II

Aniline-2,4-disulfonic acid

1-amine no-2,5-dimethoxybenzene 1-amine no-2-methoxy-5-methylbenzene red dot

II

Example 180 parts of the dye, of the formula

(prepared by coupling diazotized 1-hydroxy-2-eminobenzene-4,6disulfonic acid with 2-arino-8-hydroxynaphthalene-6-sulphonic acid and copper treatment of the azo dye obtained) was dissolved neutral, in 700 parts of water. 20 parts of 2,4,6-trifluoro-5-chloropyrimidine were added and stirred at 20-30 ° C while continuously neutralizing the liberated acid with soda solution to pH 6-7 until free amino groups could not be detected. The resulting reactive dye of formula

salted, filtered, washed and dried at 30-40 ° C. It stained cellulose material in very genuine ruby tones according to one of the above procedures.

Dyes with similar properties are obtained by analogy with the above described working methods from the copper complexes of the azo dyes prepared from the diazo and azo components listed in the table below:

- 40 No. Diazocomponents

Clutch Components

Tint on cotton

<td> 181</td><td>l-hydroxy-2-aminobensen- 4-sulfonic acid</td><td>2-methylamino-5-hydroxy-naphthalene * 7- acid</td><td>Ruby</td>

<td> 182</td><td> »</td><td>2-ethyl-amino-5-hydroxy-naphthalene-7- acid</td><td>tt</td>

<td> 183</td><td>tt</td><td>2- (1-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid</td><td>IT</td>

<td> 184</td><td>it</td><td>2-ami ηο-8-hydroxynaphthalene in n-3,6-disulfonic acid</td><td>it</td>

<td> 185</td><td>1-hydroxy-2-disulfonic aminobensen4,6</td><td>2-aminor5-hydroxinaftalin-1,7-disulfonic acid</td><td>tt</td>

<td> 186</td><td> 11</td><td>2-amino-8-hydroxinaftalin-3,6-disulfide acid</td><td>it</td>

<td> 187</td><td> 11</td><td>2-methylamino-5-hydroxinaftalin-7-sulphate acid</td><td>tt</td>

<td> 188</td><td>II</td><td>2-ethylamino-5-hydroxy naphthal η-7-sulfonic acid</td><td>II</td>

<td> 189</td><td>II</td><td>2- (3-Hydroxyethylamino) -5-hydroxinaftalin-7-sulfonic acid</td><td>tt</td>

<td> 190</td><td>l-hydroxy-2-disulfonic aminobensen4,6</td><td>l-amino-8-hydroxinaftalin-3,6-disulfide acid</td><td>violet</td>

<td> 191</td><td>II</td><td>l-amino-8-hydroxinaftalin-4,6-disulfide acid</td><td>t</td>

<td> 192</td><td>l-hydroxy-2-aminobensen- 5-sulfonic acid</td><td>I-amino-8-hydroxinaftalin-3,6-disulfide acid</td><td>IT</td>

<td> 193</td><td>II</td><td>l-amino-8-hydroxinaftalin-4,6-disulfide acid</td><td> 11</td>

<td> 194</td><td>1-hydroxy-2-amine ηο-4-acetylaminobenzene-6-sulfonic acid</td><td>1-amino no-O-hydroxy to phthali n-3,6-di-sulfonic acid</td><td>blåstickigt violet</td>

<td> 195</td><td>1-hydroxy-2-amine ηο-4-ace-.</td><td>l-ethoxy-8-hydroxinaftalin-3,6-disulfide</td><td>LF</td>

tylaminohensene-6-sulfonic-phonic acid (Acetylamino group in 4-position saponified afterwards)

<td> 196</td><td>tt</td><td>1-amino-8-hydroxynaphthalene-2,4-disulblue acid</td>

<td> 197</td><td>tt</td><td>l-amino-8-hydroxinaftalin-2,4,6-tri- acid</td>

<td> 198</td><td>1-Hydroxy-2-amiηο-6-acetylaminobenzene-4-sulfonic acid</td><td>l-amino-8-hydroxinaftalin-2,4-disulfide acid</td>

(Acetylamino group in 6 position saponified)

- 41 334203

No. Diazocomponents

Clutch Components

Tint on cotton

199 i-amino-2-hydroxy-6-nitro-1-amino-8-hydroxynaphthalene-2,4-disulbable naphthalene-4-sulfonic acid phonic acid

200 1-amino-2-hydroxy-6-nitro-1-amino-8-hydroxyphthalene-2,4,6-triaphthalene-4-sulfonic acid silicic acid (The 6-position nitro group is subsequently reduced to -NH

201 1-hydroxy-2-amino-6-ethylethylaminobenzene-4-sulfonic acid (Acetylamino group in 6-position saponified)

Example 202

By analogy to Example 30, however, the diazotized, reactive group-containing intermediate in soda alkaline medium is coupled to 40 parts of the sodium salt of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid instead of 47 parts of the sodium salt of 1-benioylamino. -8-hydroxynaphthalene-3,6-disulfonic acid and isolated the formed dye of formula

in the manner set forth in Example 30. The water-soluble dye stained cellulose material according to the scribbling steam and scrubbing thermofixing method, respectively (at 140 ° C) in whiteable, wet, tear-and-light bluish red-tinted red tones.

Example 203

A solution of 19.5 parts of the sodium salt of 1-aminobenzene-4-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water was allowed to flow to a mixture of 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid, then stirred for 1 hour.

0 -10 ° C and then excess nitric acid was removed. To the thus obtained diazo suspension was added a cooled and thus partially partially crystallized solution of 26.2 parts of the potassium salt of 1-amino-naphthalene-8-sul-334203.

42 phonic acid in 250 parts of warm water and neutralized the strongly acidic coupling mixture at 10-20 ° C by careful addition of sodium liquor to pH 4. The coupling was completed quickly and the resulting aminoazo dye completely desalted with 100 parts of saline, suction, washed and redissolved. in 500 parts of water at 10 ° C and pH 6-7. The aqueous solution was added dropwise with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine and stirred for 1 hour at 20-30 ° C while continuously neutralizing the liberated acid with soda solution to pH 6-7. When aminoazo dye could no longer be detected, the partially precipitated reactive dye of formula

with 40 parts of saline, filtered off and dissolved in and for purification again in 800 parts of hot water. After clarification of the solution, the pure dye was separated from the filtrate by the addition of 80-100 parts of saline. After filtering, drying at 35 ° C and grinding, a yellow powder was obtained which dissolved readily in water of yellow color and stained cellulose fibers according to one of the above staining procedures in the presence of acid binding agents in very good wet, light and chlorine-rich yellow tones . Genuine yellows are also obtained on wool and polyamide fibers.

By analogous to the above but instead of 19.5 parts of the sodium salt of 1-aminobenzene-4-sulfonic acid, equivalent amounts of the diazo components listed in the following table with 1-amino-naphthalene-8-sulfonic acid were obtained after acylation with 2 , 4,6-Trifluoro-5-chloropyrimidine likewise valuable yellow to brown reactive dyes.

Diazo components. Color theory on cellulose fiber reddish yellow

1- aminobenzene-2,5-disulfonic acid

2- amino-naphthalene-4,8-disulfonic acid strongly reddish yellow

- 43 334203 cont.

diazo components

2-amino-naphthalene-5,7-disulfonic acid

2-amino-naphthalene-6,8-disulfonic acid

2-amino-naphthalene-3,6,8-trisulfonic

2-amino-naphthalene-4,6,8-trisulfonic

4-amino-azobenzene-3,4'-disulfonic

4-amiηο-2-acetylamino-azobenzene-2 ', 5'-disulfonic acid

Tint on cellulose fiber strong reddish yellow

II

II yellow prickly brown orange-red red prickly brown

SO 2

reddish brown (1-aminobenzene-2,5-disulfonic acid coupled acid to a technical mixture of 1-aminonaphthalene-6 and -7-sulfonic acid) cont.

violet stained brown (1-amino-naphthalene-2,5,7-trisulfonic acid coupled acid to 1-amino-naphthalene-6-sulfonic acid)

reddish brown (1-amino-naphthalene-2,5,7-trisulfonic acid linked acid to 1-amino-2-methoxy-5-methylbenzene)

Example 204

When printing cellulose tissue 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 alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzene sulfonic acid, which was filled with water to 1 kg, then medium-dried and then steamed in a suitable vapor container for 30 seconds at 103-115 ° C, obtained after rinsing and boiling saponification a strong bluish red printing with good wet, tear and light fastness.

Example 205

A mixture of solutions of each 65.5 parts of chromium - 2: 1 complex and

In each 400 parts of water stirred for about 2 hours at 30-40 ° C while maintaining! those of a pH 6-7 with 40 parts of 2,4,6-trifluoro-5-chloropyrimidine. When aminoazo dye could no longer be detected chromatographically (Co-complex: blue; Cr-complex: blue-green), the resulting mixture of the two reactive dyes was precipitated with potassium chloride, filtered off and dried.

The dye gave strong black tones with very good wet and light resistance to cellulose material according to the scribble staining process or when printed in the presence / acid binding agent.

When similarly sedated but a mixture of the chromium-2: 1 and cobalt-2: 1 complexes of the following aminoazo dyes was added, valuable black dyes were also obtained:

Diazo Components Coupling Components Coupling pH 1-hydroxy-2-amino-4-nitrobenzene 1-hydroxy-8-amino-naphthalene-3,6- 9 disulfonic acid 1-hydroxy-2-amino-4-nitronaphthalene 11 9

7-sulfonic acid

Example 206

To a neutral solution of 53.15 parts of the disodium salt of a by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5'-sulfophenyl)

3-methyl-pyrazolone (5) and subsequent reduction of the nitro group with sodium sulfite obtained aminoazo dye in 300 parts of water were added 20 parts of 2,4,6-t, rifluoro-5-chloropyrimidine, and the mixture was stirred for 1 hour at 30 ° C. whereby the released acid was continuously neutralized with soda solution to a pH of 6.0. The separated dye of formula

46 334203 was filtered off, dissolved / 3000 parts water at pH 6-7 and again precipitated from the filtered solution by adding brine. After filtration, drying and pulverization, a yellow, water-soluble powder was obtained, which stained cellulose material in long bath solution at 30 ° C or according to the soda-cold storage procedure with acid as an acid-binding agent in clear, wash-, tear- and light-yellow yellow tones.

When applied analogously to the above but + instead of the amino-azo dye inserted, equivalent amounts of the amino-azo dye-derived components listed in the table below were added, valuable new reactive dyes were also obtained.

In the table, the term saponified means that an acylamino group contained in the aminoazo dye is subsequently saponified, while the term reduced means that a nitro group included in the diazo component after coupling is reduced to amino group, thereby forming the desired aminoazo dye.

<td>Example No</td><td>diazo components</td><td>Azo Components the pH of the media</td><td>Tint on cellulose</td>

<td> 207</td><td colspan="2">1- amino-4-nitrobenzene-1- (4'-sulfophenyl) -3-methyl-5-6 2-sulfonic acid tyl-pyrazolone- (5) (Nitro group in 4-position retrospectively reduced)</td><td>yellow</td>

<td> 208</td><td>II</td><td>1- (4'-sulfophenyl) -3-carboxy-6-boxy-pyrazolone- (5)</td><td>rödstickigt ugly</td>

<td> 209</td><td>II</td><td>1- (3'-sulfophenyl) -3-meth-6-7 ty1-5-ami no-pyrazole</td><td>yellow</td>

<td> 210</td><td>1-amino-3-acety1-amino</td><td> 6-7</td><td>II</td>

no-benzene-6-sulfonic acid (Acetylamino group in 3-position afterwards saponified)

211 1- (β-hydroxyethyl) -3-methyl-5-6 pyrazolone- (5)

212 2 moles of 1-aminothio-3-acetyl-1 mole of pyrazolone from 5-6 amino-benzene-6-sulfonic-4,4 '- hydrazinadibenzoic acid (saponified) syl-2T2'-disulfonic acid and acetacetic ethyl ester

213 1 mole of 1-amino-3-acety-1- (4'-sulfophenyl) -3-carboxy-5-6-amino-benzene-6-sulfonboxy-pyrazolone (S) acid (saponified)

214 1-Amino-5-acetyl-amino-1- (4'-sulfophenyl) -3-carboxy-5-6-naphthalene n-3,7-di-sulfoxy-pyrazolone (5) phonic acid (saponified)

215 1-amino-2-methyl-benzene-2-acetylamino-5-naphthol-7- 7-8 4,6-disulfonic acid. sulfonic acid (saponified) reddish yellow orange

- 47 334203 cont.

Example Diazocomponents Azocomponents no

Coupling Color tone of the medium pH cellulose

<td> 216</td><td>l-amino-2-methyl-benzene-4, 6-disulfonic acid</td><td>2-acetylamino-8-naphthol6-sulfonic acid (saponified)</td><td> 7-8</td><td>RED</td>

<td> 217</td><td>II</td><td>1-Chloro-2-acetyl-amino-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-disulfonic acid (saponified)</td><td> 7-8</td><td>RED</td>

<td> 219</td><td>2-aminonaftalin-3,6-disulfonic acid</td><td>II</td><td> 7-8</td><td>blåstickigt. RED</td>

<td> 220</td><td>2-aminonaftalln-3,7-disulfonic acid</td><td>II</td><td> 7-8</td><td>II</td>

<td> 221</td><td>2-aminonaftalin-4,8-disulfonic acid</td><td>II</td><td> 7-8</td><td>II</td>

<td> 222</td><td>2-aminonaftalin-3,6-disulfongyra</td><td>1-Acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (saponified)</td><td> 7-8</td><td>II</td>

<td> 223</td><td>2-aminonaftalin-4,8-disulfonic acid</td><td>1-Acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (saponified)</td><td> 7-8</td><td>Π</td>

<td> 224</td><td>1- amino-4-methoxybenzene 2-sulfonic acid</td><td>2- (N-acetyl-N-methylamino) 5-hydroxy-naphthalene-7-sulfonic acid (saponified)</td><td> 7-8</td><td>gulstickigt RED</td>

<td> 225</td><td>II</td><td>2- (N-acetyl-N-methyl) amino) 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>II</td><td> 7-8</td><td>TL</td>

<td> 227</td><td>1-aminobenzene-3-sulfonic acid</td><td>II</td><td> 7-8</td><td>II</td>

<td> 228</td><td>l-aminobenzene-4-sulfonic acid</td><td>II</td><td> 7-8</td><td>II</td>

<td> 229</td><td>1-amino-4-methyl-benzene-2-sulfonic acid</td><td> 11</td><td> 7-8</td><td>II</td>

<td> 230</td><td>1-amino-2,4-dimety1-bensen6 acid</td><td>2- (N-acetyl-N-methyl-amino) 8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td> 7-8</td><td>II</td>

<td> 231</td><td>II</td><td>2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid (saponified)</td><td> • 7-8</td><td>II</td>

<td> 232</td><td>1-amino-2,4-dimety1-bensen6 acid</td><td>2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td> 7-8</td><td>II</td>

A.D)

- 48 cont.

<td colspan="2">Example Diazocomponents no</td><td>Azokomponenter</td><td colspan="2">Coupling Color tone of the medium pH cellulose</td>

<td> 233</td><td>4-aminoazobenzene-3,4'-di- acid</td><td>1-amino-3-acetyl-aminobenzene</td><td> 5-6</td><td>yellowish brown</td>

<td> 234</td><td> 11</td><td>l-amino-3-acetyl-ftydroxi aminobenzene</td><td> 5-6</td><td> 11</td>

<td> 235</td><td>tt</td><td>l-amino-naphthalene-6-sulfonic acid</td><td> 5-6</td><td></td>

<td> 236</td><td> 11</td><td>1-Amino-naphthalene-7-sulfonic acid</td><td> 5-6</td><td> 11</td>

<td> 237</td><td> 11</td><td colspan="2">1-amino-2- (4'-amino-2'-sulfophenyl) - (1 ') azo) -8-hydroxynaphthalene-3,6-disulfonic acid</td><td>black</td>

Example 238.

52.4 parts of the disodium salt of 4- (4-aminophenyl / amino) -2'-nitro-diphenylamine-3,4'-disulfonic acid was dissolved in 1000 parts of water and stirred for 1 hour at 20-30 ° C with 20 parts 2 , 4,6-trifluoro-5-chloropyrimidine. Thereby, the released acid was continuously neutralized with soda to a pH of 5.5-6. The formed reactive nitro dye of formula

salted, filtered, washed and dried. It stained cellulose fibers from long bathing solution or according to one of the usual spotting methods in the presence of soda as an acid binding agent in wet and tear-proof, deep violet tones.

Example 239 parts of 1-amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,2'-disulfonic acid were dissolved in 550 parts of water and adjusted with sodium hydroxide solution to pH 6. Then 18 parts 2.4 were added dropwise at room temperature. 6-trifluoro-5-chloropyrimidine, whereby pH 6 was maintained by means of 2-n soda solution. The reaction was followed chromatographically. The crystallizing reaction product in blue needles was aspirated and the filter residue was washedMed 3% saline. On cotton, clear blue colors were obtained with good wetness and good lightfastness.

The dye obtained corresponded to the probable formula

<td>Example No</td><td>Water-soluble amino-anthraquinone derivative</td><td>Hue</td>

<td> 240</td><td>1-Amino-4- (4'-N-methylaminoethylamino) -anthraquinone-2,6,2Γ-trisulfonic acid</td><td>greenstick really blue</td>

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

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

<td> 243</td><td>1-Amino-4- (4'-Amino-amino) anthraquinone-2,6-disulfonic acid</td><td>blue-green</td>

<td> 244</td><td>1-Amino No-4- (4-Amino Noanyl) -antraki Non-2,5-Di Sulfonic Acid</td><td>grönst. 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'-aminoalino) anthraquinone-2,5-disulfonic acid</td><td>II</td>

<td> 247</td><td>l-amino-4- (3'-aminoanilino) anthraquinone-2,4'-disulfonic</td><td>something red st.ickigt blue</td>

<td> 248</td><td>l-amino-4- (3'-aminoanilino) anthraquinone-2,4'-6'-trisulphonic</td><td>rödst. blue</td>

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

<td> 250</td><td>1-Amino-4- (4'-N-methylaminoethylanilino) anthracite non-2,3'-disulfonic acid</td><td>blue</td>

<td> 251</td><td>1-ami no-4- (4 '- ^ - ami nobensoy lami nq7 ~ ani 1 i no) -a ntraki non-2,5,8trisulfonic acid</td><td>blue-green</td>

<td> 252</td><td>l-amino-4- (4 '- ^ 3 aminobensensulfamid (7-anilino) -antrakinon2,5,8-trisulphonic</td><td>grönst. blue</td>

- 50 cont.

Example Water-insoluble amino-anthraquinone derivative Color tone no

253 1-amino-4- (4-aminostilbenamino) -anthraquinone-2,2 'IN2-tri-green sulfonic acid

Example 255

When analogous to Example 18, but the resulting dye intermediate was coupled with a diazo compound of 20.8 parts of 3-claraniline-6-sulfonic acid instead of the diazo compound of 17.5 parts of 2-aminobenzene sulfonic acid - in the presence of 12 parts of soda at a final pH of 7, a reactive dye of the formula was obtained

with which cellulose material from long bathing solution at 40 ° C or according to the standard soda-scrubbing or printing processes as soda as an acid-binding agent could be stained or printed, respectively, in wet, brilliant red tones.

Analogously, the coupling components listed in the table below were obtained by acylating their amino group with 2,4,6-trifluoro-5-chloropyrimidine and coupling the resulting dye intermediate with the indicated diazocomponents valuable reactive dyes with which cellulose feed materials - soda - could be colored or printed in specified tones:

- 51 334203

<td>Example No</td><td>diazo components</td><td>Clutch Components</td><td>Switching pH</td><td>Hue</td>

<td> 256</td><td>1 1-amino-4-methoxy-bensen6 acid</td><td>l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid</td><td> 7-8</td><td>violet</td>

<td> 257</td><td>II</td><td>l-amino-8-ltydroxi-naphthalene-4,6-disulfonic acid</td><td> 7-8</td><td>rödstickigt. violet</td>

<td> 258</td><td> 11</td><td>2-ami ηο-5-hydroxy-naphthalene-1,7-disulfonic acid</td><td> 7</td><td>scarlet</td>

<td> 259</td><td>1-amino-5-chloro-benzene-2sulfonsyra</td><td> 11</td><td> 7</td><td>Orange</td>

<td> 260</td><td>1-aminobenzene-3-sulfonic acid</td><td>II</td><td> 7</td><td> 11</td>

<td> 261</td><td>l-aminobenzene-4-sulfonic acid</td><td>tt</td><td> 7</td><td>II</td>

<td> 262</td><td>tt</td><td>2-amino-8-hydroxy-naphthalene-3,6-disulfonic acid</td><td> 7-8</td><td>scarlet</td>

<td> 263</td><td>4-ami nobensoic acid (βsulfoethylD-amide</td><td>1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid</td><td> 7-8</td><td>RED</td>

<td> 264</td><td>1-amino-4-sulpho-acetylamino-benzene-6-sulfonic acid</td><td>II</td><td> 7-8</td><td>violet</td>

<td> 265</td><td>1-amino-3-sulfo-acetylamino-benzene-6-sulfonic acid</td><td>2-amino-5-hydroxy-naphthalene-1,7-disulfonic acid</td><td> 7</td><td>Orange</td>

<td> 266</td><td>1-amino-4-sulfo-benzene acety1amino</td><td>2-amino-5-hydroxy-naphthalene-J, 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) -8-methylpyrazolone- (5)</td><td> 6</td><td>yellow</td>

<td> 268</td><td>* 2-amino-4,8-naphthalene disulfonic acid</td><td>II</td><td> 6</td><td>II</td>

Example 269

When analogous to Example 30, but the intermediate of the dye obtained after diazotization at 10 ° C and pH 7.5 - 6.5 was coupled to the 1,3-diaminobenzene-6-sulfonic acid and 2,4,6-trifluoro-5-chloropyrimidine. solution of 40.5 parts of the disodium salt of 2-sulfoacetylamino-5-hydroxynaphthalene-7-sulfonic acid gave a reactive dye of the formula

as colored eellulose materials according to the usual soda application procedures as acid binding agents in genuine orange tones.

Example 27OJ

When applied analogously to Example 206 but instead of the one where the aminoazo dye inserted, 53.15 parts of the disodium salt acylated by it by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5 ') -sulfophenyl) -3-methyl pyrazolone- (5) and subsequent reduction of the nitro group with the sodium sulfide obtained aminoazo dye with 2,4,6-trifluoro-5-chloropyrimidine also obtained a valuable reactive dye. with which cellulose material could be printed in true yellow tones according to the usual dyeing and printing methods.

Similar reactive dyes are obtained when, instead of the aforementioned aminoazo dye, one of the aminoazo dyes built up from the components listed in the table below is acylated with 2,4,6-trifluoro-5-chloropyrimidine:

Example Diazocomponents Azo Components Tint no

271 1-Amino-4-nitrobenzene-2-sulfonic acid (reduced)

272

273

274 1-Amino-4-nitrobenzene-2-sulfonic acid (reduced)

275 1-amino-3-acetylamino-benzene-6sulfonic acid (saponified)

276 1- (2'-methyl-4'-sulfophenyl) - yellow 3-methyl-pyrazolone- (5) 1- (2 ', 5'-disulfophenyl) -3- methyl-pyrazolone- (5) 1- (2) '-methyl-4'-sulfo-6'-chlorophenyl) -3-methyl-pyrazolone- (5) 1- (2', 5 * -dichloro-4'-sulfophenyl) -3-methyl-pyrazolone (5) ) 1- (2'-methyl-4'-sulfophenyl) - green stick 3-methyl-pyrazolone (5) yellow

1- (4'-sulfophenyl) -3-methyl-pyrazolone- (5)

- 53 334203 cont.

Examples Diazocomponents Azo Components Ego tone no

277 1-Amino-3-acetylamino-benzene-6- 1- (2'-methyl-4'-sulfophenyl) - succinic sulfonic acid (saponified) 3-carboxy-pyrazolone (5) yellow

270 L- (2'-chloro-4'-sulfophenyl) -

3-karboxipyrazolon- (5)

Example 279 parts of a dye of formula

(prepared by coupling diazotized 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid to 2-methylamino-8-hydroxy-naphthalene-6-sulfonic acid and copper treatment of the azo dye thus obtained) was dissolved neutral in 700 parts water. 20.0 parts of 2,4,6-trifluoro-5-chloro-pyrimidine were added dropwise and stirred at 20-30 ° C with continuous neutralization of liberated hydrofluoric acid with soda solution to pH 6.0-6.5 until reactive free amino groups were not added. longer could be detected. The formed / dye of formula

salted, filtered, washed and dried at 30-40 ° C. It stained cellulose material in very genuine violet tones according to one of the above methods.

Dyes with similar properties are obtained by analogy with the above methods from - by simple demethylating or oxidizing copper treatment, copper complexes of mono- and disazo dyes obtained from the diazo and azo components listed in the table below:

Examples Diazocomponents Azocomponents Coupling Tint No. pH

<td> 280</td><td>1-hydroxy-2-amino-4-chloro-2-amino-8-hydroxypnafbenzene-5-sulfonic acid talin-3,6-disulfonic acid</td><td> 10</td><td>rödstickigt violet</td>

<td> 281</td><td>11 l-amino-8-hydroxy-NAF talin-3,6-disulfonic acid</td><td> 10</td><td>blåstickigt violet</td>

<td> 282</td><td>2-amino-naphthalene-4,6,8-2-hydroxy-6-acetylaminotrisulfonic acid (oxidative naphthalene-4-sulfonic acid copper-treated) (saponified)</td><td> 8-9</td><td>rödstickigt blue</td>

<td> 203</td><td>1-amino-2-hydroxy-6-nit-1-hydroxy-8-ethoxy-naphronaphthalene-4-sulfonic acid talin-3,6-disulfonic acid (reduced)</td><td> 10</td><td>blue</td>

<td> 284</td><td>1-hydroxy-2-amino-benzene-2-hydroxy-3-amino-naf4,6-disulfonic acid talin-5,7-disulfonic acid</td><td> 10</td><td>RED</td>

<td> 285</td><td>2-amino-naphthalene-4,8 ~ di sulfonic acid (oxidative copper treated)</td><td> 8-9</td><td>blue</td>

<td> 286</td><td>2-ami nonaphthalene n-4,6,8-2-hydroxy-3-amine no-na trisulfonic acid (oxidative talin-7-sulfonic acid copper-treated)</td><td> 8-9</td><td>ii</td>

<td> 287</td><td>3-Methoxy-4-amino ηο-6-methyl-2-methylamino-5-hydroxiazobenzene-2'4'-disulfonaphthaphthalene-7-sulfonic acid (demethylating copper) parbehandlad)</td><td> 10</td><td>navy</td>

<td> 288</td><td>1 2-amino-8-hydroxy-NAF talin-3,6-disulfonic acid</td><td> 10</td><td>II</td>

<td> 289</td><td> 2-amino-5-hydroxy-NAF talinic, 7-disulfonic acid</td><td> 10</td><td>II</td>

<td> 290</td><td>3-methoxy-4-amino-6-methyl-2-methylamino-5-hydroxiazobenzene-2 ', 5'-disulfonaphthalene-7-sulfonic acid (demethylating copper) parbehandlad)</td><td> 10</td><td>II</td>

<td> 291</td><td>3-methoxy-4-amino-6-methyl-2-amino-O-hydroxy-nafazobenzene-2 ', 5'-disulfonyl-3,6-disulfonic acid (demethylating copper) parbehandlad)</td><td> 10</td><td>(f</td>

<td> 292</td><td> 2-amine no-5-hydroxy-naphthalene talin-1,7-disulfonic acid</td><td> 10</td><td>II</td>

Example 293

62.0 parts of trisodium salt of a dye-alkaline coupling from diazotized 4-chloro-2-amino-1-hydroxybenzene ~ 6-sulfonic acid and 1-amino-8-hydroxynaphthalene ~ 3.6disulfonic acid were added in 300 parts of water at 70-80 ° C and one. pH of 8-9 with 54.2 parts of the 1: 1 chromium complex of a dye from 6-nitro-1-diazo-2hydroxinaphthalene-4-sulfonic acid and 2-hydroxynaphthalene. After 10 minutes, a deep blue solution was formed.

The co-complex was acylated for about 1 hour at 30-40 ° C and one. pH of 6.57.5 with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine. In this case, the pH was kept constant by dropwise addition of soda solution. The acylated dye was separated with 20% sodium chloride, suction filtered and dried at 30 ° C.

In cotton, according to the method of Example 3, a bi-black print was obtained with excellent light and washability.

Example 294

30.4 parts of 2-amino-8-oxinaphthalene-3,6-disulfonic acid were neutral dissolved in 300 parts of water, heated to 60-65 ° C and added with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine. Over the course of 1 hour, 40 parts of 50% soda solution were added, so that the pH was at 6-6.5. The acylation product partially precipitated.

A freshly prepared diazonium salt solution of 13.6 parts of p-aminobenzylsulfonic acid was added dropwise at 0-5 ° C to the suspension containing the acylation product with 12.5 parts of soda. After 5 hours of stirring at ice-bath temperature, salted with boiled salt, suctioned, rinsed with dilute saline and dried at 30 ° C in a vacuum dryer. The dye obtained corresponded to the formula

When applied analogously to the above but instead of 30.4 parts of 2-amino8-oxinaphthalene-3,6-disulfonic acid, 30.4 parts of 2-amino-5-oxinaphthalin-7-disulfonic acid with 2,4,6-trifluoroacetic acid were acylated. 5-chloropyrimidine and coupling the reactive group-containing coupling component with diazotized p-aminobenzylsulfonic acid yielded a readily soluble reactive dye, which stained tissue, containing cellulose fibers, in brilliant red-knit orange tones.

O

Cotton or cell wool tissue was impregnated on a foulard at 20-25 C with a solution containing per liter of bath solution containing 30 g of the dye described in this first paragraph, 100 g of urea and 20 g of soda, extruded to a moisture content of approx. 100% and coiled the moist tissue. After 4 hours of storage at room temperature, the tissue was rinsed, saponified in the usual manner and dried. They obtained a brilliant, scarlet colored stain with good wet and light fastness. '

Cotton or cell wool fabric was impregnated on a foulard at 20-25 ° C with a solution containing per liter of 30 g of the dye described in the present example, first paragraph, 100 g of urea and 20 g of soda, extruded to a moisture content of approx. 100% and steam treated for 30 seconds at 103 ° C. After rinsing, boiling saponification and drying, they also obtained a brilliant, scarlet-colored stain with good wet and light fastness.

Cotton fabric was impregnated with a solution having a temperature of 20-25 ° C, which contained per liter of bathing solution 20 g of the dye obtained according to this example, the first paragraph dye and 0.5 g of a non-ionic wetting agent (e.g. polyoxetylated oleyl alcohol) and 150 g of urea and 15 g of sodium hydrogen carbonate. Subsequently, the tissue between two rubber rolls was pressed down to a moisture content of about 100%. After intermediate drying at 50-60 ° C, it was heated to 140 ° C for 10 minutes, after which the thus obtained staining was thoroughly rinsed with warm water and treated for 10 minutes boiling with a solution containing 5 g of marseille soap and per liter. 2 g of soda. After rinsing and drying, a strong scarlet color was obtained with good wet and light fastness.

When printing cellulose tissue with entry paste, which contained per kilogram of 30 g of the dye described in the first paragraph, the first paragraph, 100 g of urea,

300 g of water, 500 g of alginate thickening (60 g of sodium alginate. per kilogram of thickening) g of soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid, which was filled with water to 1 kg, then dried and then steamed in a suitable steam container for 30 seconds at 103 115 ° C, after rinsing and boiling-colored saponification, a strong scarlet / annoyance with good authenticity was obtained.

100 parts of wool were introduced at 40 ° C in a bath containing 5000 parts of water

1.5 parts of the dye described in the present example, the first paragraph and 6 parts of 30% acetic acid and 0.5 parts of a polyoxetylated hydroxyl group-containing stearylamine derivative. The dye bath was brought to boiling for 30 minutes, after which the boiling was stained for one hour. After rinsing and drying, a brilliant scarlet-colored stain was obtained with good wash, whitewash and light fastness.

Example 295

28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid (monosodium salt) were diazotized and the diazo compound was coupled with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in slightly acidic medium. The monoazo dye obtained was isolated and then diazotized or optionally without isolation in solution and coupled alkaline with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid. The resulting disazo dye was salted out by the addition of sodium chloride and suctioned and the isolated product was metallized for 5 hours at 95-100 ° C with about 50 parts of crystallized copper sulfate, 40 parts of diethanolamine and 50 parts of ammonia (D: 0.88). From the copper solution, the dye was isolated by salt addition and gentle acidification.

The copper-treated amino-disazo dye was then acylated in aqueous solution at pH 6-7 at a temperature of 20-30 ° C with 20 parts of 2,4,6-trifluoro-5-chloropyrimidine, keeping the pH within the indicated range by addition of seed. After av334203

After 58 acylation, the dye was isolated with sodium chloride and dried at 35 ° C. The dye corresponded to the formula of the free sulfonic acid in the formula:

the stained cellulose tissue according to the methods known for reactive dyes in wet and light-resistant, navy tones.

Similarly, additional dyes of the invention may be prepared by combining, by analogy with the above, the above monoazo dye from 2-amino-1-methylbenzene-3,5-disulfonic acid and 1-araeno-2-methoxy-5-methylbenzene with those of the following table indicated the aminonaphthol sulfonic acids and 2,4,6-trifluoro-5-chloropyrimidine.

Cooplintic components di2-ami no-5-hydroxy naphthal in η-1,7-

2-amiηο-8-hydroxinaftalin 3,6ydisulfonsyra

The dyes obtained were blue.

Example 296

0.1 mole of 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid was diazotized and soda-alkaline coupled with 0.1 mole of 1-amine-8-hydroxy-naphthalene-2,4-disulfonic acid. The coupling solution was adjusted with sodium hydroxide to a content of 2 moles per liter and then boiled for 3 hours under reflux and in the saponification of the ureido group. After cooling, the hydrochloric acid was neutralized. By adding 25 parts of copper sulphate and 100 parts of 2-n sodium liquor, the dye was metallized at 45 ° C and a PII value of 4-6 and acylated after 30 minutes at pH 6-7 and temperatures of between 20 ° and 30 ° C at 0 ° C. 1 mole of 2,4,6-trifluoro-5-chloropyrimidine. The resultant dye of formula

- 59 334203 t

salted out. On cotton, a blue dye was obtained.

Example 297

A neutral paste of 600 g of technically 96% copper phthalocyanine prepared from copper phthalocyanine 3,3 ', 3-trisulfonic acid chloride was stirred with a small amount of water, filled to 4 liters and reacted at a pH of 3.5 - 6.0 with 216 g of N-methyl-N- (4 '' amino-2'-sulfobenzyl) -amine at initially 0-3θ0 and finally 20-35 ° C, with the addition of 300 ml (295 g) of pyridine, then the pyridine at pH 9.0 was distilled off with water vapor from the resulting solution of copper phthalocyanine disulfonic acid monosulfonic acid (3'-sulfo-4'-methyl-aminomethyl-anilide). To the 20 ° -30 ° C hot solution was added dropwise and portionwise over 1-2 hours 300 g of 2,4,6-trifluoro-5-chloropyrimidine, maintaining a pH of 6-7 by the addition of dilute sodium liquor. The reaction mixture was immediately diluted as needed with so much water that the dye remained in solution at all times. 10 liters of dye solution, which was separated from excess acylating agent, with the help of acetic acid was adjusted to a pH of 7.0 and precipitated by stirring 2.5 liters of concentrated saline solution.

After suction and drying at 3D ° C, a clear turquoise blue dye was obtained, which from soda-alkaline solution at 40-60 ° C with very good yield and washing.

Using \ iPc-3,3 ', 3-trisulfonic acid chloride as a starting material, a slightly greener turquoise blue color was obtained with equally valuable properties.

Example 298

0.1 mole of an aminoazo dye of the formula

prepared according to the information in German patent 1,115,865 by coupling the diazonium compound from 2-aminonaphthalene-4,8-disulfonic acid with 1-aminonaphthalene-6sulfonic acid, further diazotizing the obtained aminoazo dye, coupling with equivalent amount of 2,5-diaminonaphthalene-4,8 -disulfonic acid and conversion to aminotriazole, dissolved at pH 6 in 1000 parts by volume of water and stirred at a temperature of 20-30 ° C with 21 parts of 2,4,6-trifluoro-5-chloropyrimidine. The slowly released hydrofluoric acid was neutralized with soda solution until the reaction stopped. Then the dye was separated by the addition of sodium chloride, isolated and dried in vacuo at about 50 ° C. It consisted of a yellow, in water of yellow color easily soluble powder.

Example 299

30.9 parts of a dye-alkaline coupling from 6-nitro-2-diazo-1-hydroxybenzene-4-sulfonic acid and 2-hydroxynaphthalene dye were stirred in 200 parts at water / pH 8 at a temperature of 70-80 ° C. In this suspension, 67.9 parts of a one-molecule dye was introduced into a chromate atom containing a chromium complex compound of an azo dye from 4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6. disulfonic acid, whereby the pH value by dropwise addition of soda solution was kept between 7 and 9. After 20 minutes at 70-80 ° C, a dark blue solution had formed. Paper chromatography showed that a uniform co-complex has occurred. The co-complex was acylated over the course of 1 hour at 40 ° C and pH 6.5 - 7.5 with 22.0 parts of 2,4,6-trifluoro-5-chloropyrimidine, keeping the pH by dropwise addition of soda solution within the range indicated. . The acylated dye was salted out with 20% potassium chloride, filtered off and dried at 30 ° C. A dark powder was obtained, which dissolved in water of blue-gray color.

The dye corresponded in the form of the pentane sodium salt formula

The colored cotton according to the procedure in Examples 1-3 in gray in response take tones.

Equally valuable dyes could be obtained from the starting components listed in the table below in the manner described in these examples. For the preparation of these dyes, the azo dye was always used, which in the 2: 1 co-complex showed the reactive group, as 1: 1-chromium complex.

1: 1 chromium complex metal-free dye

Tint on cotton

<td> 300</td><td>4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid · 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid</td><td>4-nitro-2-amino-1-hydroxybenzene - -2-hydroxynaphthalene</td><td>black</td>

<td> 303</td><td>II</td><td>4-nitro-2-amino-1-hydroxybenzene - + 2-hydroxynaphthalene-6-sulfonic acid</td><td>II</td>

<td> 305</td><td>II</td><td>4-njtro-2-amino-hydroxybenzene -? L-hydroxinaftalin-4-sulfonic acid</td><td>marine</td>

cont.

- 62 1: 1 chromium complex metal free dye cotton tint

<td> 306</td><td>4-Nitro-2-amino-1-hydroxybenzene-6-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid - 1-amino-8- 4-sulfonic acid - 2-hydroxynaphthalene hydroxynaphthalene-3,6-disulfone - acid</td><td>black</td>

<td> 307</td><td>11 4-nitro-2-amino-hydroxybenzene -> 1-acetylamide no-7-hydroxy naphthalene</td><td>II</td>

<td> 308</td><td> 6-nitro-l-amino-2-hydroxinaftalin- 4-sulfonic acid 2-hydroxy naphthalene</td><td>II</td>

<td> 309</td><td>4-nitro-2-amino-1-hydroxybenzene-4-nitro-2-amino-1-hydroxynaphthalene-6-sulfonic acid-1-amino-8- 6-sulfonic acid -2-hydroxy-naphthalene hydroxynaphthalene -4,6-disulfonic acid</td><td>II</td>

<td> 310</td><td>4-Chloro-2-amino-1'-hydroxybenzene-4-nitro-2-amino-1-hydroxybenzene seu-6-sulfonic acid-β-amino-2-hydroxyphthalene 8-hydroxynaphthalene-3,6-disulphide acid</td><td>biåsvart</td>

<td> 312</td><td> 4-nitro-2-amino-hydroxybenzene</td><td></td>

<td></td><td>2-hydroxinaftaliη-6-sulfonic acid</td><td>it</td>

<td> 313</td><td> 4-chloro-2-amino-hydroxybenzene - ·) 2rhydroxinaftalin</td><td>navy</td>

<td> 314</td><td> 4-nitro-2-amino-hydroxybenzene 1-acetylamide no-8-hydroxy talin-3,6-disulfonic acid</td><td>blue</td>

<td> 315</td><td> 4-nitro-2-amino-hydroxybenzene 1-ami no-8-hydroxy naphtha lin 2,4-disulfonic acid</td><td>navy</td>

<td> 316</td><td> 6-nitro-l-amino-2-hydroxinaftalin- ^ 4-sulfonic acid 2-hydroxinaft.alin</td><td>biåsvart.</td>

<td> 317</td><td> 2-aminobenzene-l-carboxylic acid-5-sulfonic tartaric acid — 1H-phenyl-3-methyl-5-pyrazolone</td><td>greyish green</td>

<td> 318</td><td>4-Nitro-2-amino-1-hydroxy-6-nitro-1-amino-2-hydroxinaflalinbenzene-6-sulfonic acid - 1- 1- 4 -sulfonic acid -2-hydroxy naphthalene amino-O-hydroxy naphthalene - 3,6-disulfonic acid ι</td><td>black</td>

<td> 319</td><td>4-Chloro-2-amino-I-hydroxybenzene-4-chloro-2-amino-1-hydroxybenzene sen-6-sulfonic acid-1 H-amino-1 H -1- (4'-sulfophenyl) -3-methyl-58 hydroxy naphthalene in n-3,6-di sulpyrazolone acid</td><td>violet</td>

- 63 334203 tint on cotton I.

cont.

1: 1 chromium complex metal-free dye

<td> 320</td><td>4-methyl-2-amino-1-hydroxybenzene-6-sulfonic acid-41-aminothio-8-hydroxy-naphthalene in n-3,6-disulfonic acid,</td><td>4-Chloro-2-amino-1-hydroxybenzene · 2) hydroxy naphthalis-6-sulphonic acid</td><td>rödstickigt BIA</td>

<td> 321</td><td>4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid-amylamino-8-hydroxy-naphthalene in n3,6-disulfonic acid</td><td>5-nitro-2-amino-1-hydroxybenzene-2-hydroxy to phenyl-6-su acid</td><td>black</td>

<td> 322</td><td>II</td><td>4-Nitro-2-amino-1-hydroxybenzene 2-hydroxinaphaline-8-sulfonic acid</td><td>II</td>

<td> 323</td><td>II</td><td>4-Nitro-2-amino-1-hydroxybenzene 1-hydroxynaphthalene-5-sulfonic acid</td><td>II</td>

<td> 324</td><td>al Example 325</td><td>6-Nitro-4-chloro-1-hydroxybenzene - (1) hydroxynaphthalene in 5-sulfononic acid</td><td>II</td>

<td></td><td colspan="2">8.2 parts of 1-amino-4β / 3'-amino-aniline-4-anthraquinone-2-sulfonic acid</td><td>was resolved under</td>

addition of 1.05 parts of sodium carbonate in a mixture of 160 parts of water and parts of dioxane. At 0 ° C, 3.8 parts of 2,4,6-trifluoro-5-chloro-pyrimidine were added dropwise, maintaining a pH of 6 - 6.5 by the addition of 2-n soda solution. Upon completion of acylation, the dye was desalted at 20 ° C with 25 parts of saline and the crystalline product was suctioned, washed with 2% saline and dried in vacuo at 30 ° C.

The dye is colored wool / very wet blue tones.

Example 326

8.3 parts of 1-amino-4- [4'-amino-cyclohexylamine 3-anthraquinone-2-sulfonic acid were dissolved in 160 parts of water and 80 parts of dioxane with the addition of 1.3 parts of 45%

- 64 sodium hydroxide solution was added dropwise at 0-5 ° C with 3.0 parts of 2,4,6-trifluoro-5-chloropyrimidine. By adding 2-n soda solution, a pH of 9-10 was maintained. After completion of acylation, pii was adjusted to 4.5 by addition of hydrochloric acid. The crystalline product was suctioned and washed with 2% g of brine until the washing solution was colorless. The dye obtained was dried at 30 DEG-40 DEG C. in vacuo, including the dyed wool in clear, washable, blue tones.

Example 327

15.9 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid were dissolved in 150 parts of water and acylated at 20 ° C and a pH of 5.5-6 with 10.2 parts of dichlorodifluoropyrimidite. The liberated fluorine hydrogen was neutralized with 2-n sodium hydroxide solution. For coupling, the batch was diluted with 450 parts of water, then 10 parts of soda was added and then a suspension containing 9.9 parts of diazotized 2-aminobenzenesulfonic acid was allowed to flow at 0 ° C. pH. Idols at 7-8. After completion of reaction, adjusted to pH 6, salted with 100 parts of saline, suctioned and washed with 20% saline. A red dye of the formula was obtained

Example 328

15.9 parts of 1-amino-8-hydroxy * -naphthalene-3,6-disulfonic acid were dissolved in 150 parts of water and acylated at 20-25 ° with 8.3 parts of 2,4-difluoro-6-chloropyrimidine. The liberated fluorine hydrogen was neutralized with sodium hydroxide solution. The further process was analogous to Example 327. A red dye of the formula was obtained

like colored cotton at about 30-50.

Example 329

8.2 parts of 1-amino-4- (p-amino-anilino) anthraquinone-2-sulfonic acid were dissolved in a mixture of 160 parts of water and 80 parts of dioxane and reacted at 0 ° C and a pH of 6-7 with 3 , 8 parts trifluorochloropyrimidine. The pH was maintained using 2-n sodium hydroxide solution. After completion of the reaction, the mixture was aspirated at 20 ° C and washed with 2% saline. Dry at 60 ° to obtain a dye of the formula

Cl F

like colored wool in green stained blue tones with good wetness.

Example 330

7.6 parts of 2-oxinaphthalene-6,8-disulfonic acid were dissolved in 100 parts of water by the addition of soda. Then, a suspension of the diazonium salt of 1-amino3- (2 ', 6'-difluoro-5'-chloro-pyrimidinyl) -4' - aminobenzene-4-sulfonic acid (prepared from

4.7 parts 1,3-diaminobenzene-4-sulfonic acid, corresponding to Example 30) at 0 ° C, maintaining a pH of 8. After acidification, salted off with 20 parts of sodium chloride, after which the crystalline reaction product was aspirated and washed with 20% sodium chloride solution. The dye was dried at 60 °. The colored wool with good choice and

- 66 pot fasteners in clear orange tones.

Example 331

9.5 parts of 1-amino-4- (p-amino-phenylamino) anthraquinone-2,6,2'-trisulfonic acid were dissolved in 95 parts of water and added dropwise with 5.0 parts 2.4 at 20-25 °. 6trxfluor-5-chloro-pyrxmidin. The pH was maintained between 6 and 7. After completion of the reaction, the precipitated reaction product of formula

which was washed with 5% saline. The product was dried in vacuo at 60 °.

Example 332 Parts I-Amino-4- (p-amino-phenylamino) anthraquinone-2.6t3'-trisulfonic acid was dissolved in 600 parts of water and added with 19 parts of trifluorochloropyrimidine. With the help of sodium liquor, a pH of 6-7 was maintained. The work-up was done analogously to Example 331. A blue-green dye of the formula was obtained

Example 333

15.9 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid were dissolved in 150 parts of water and reacted at pH 6-7 with 10 parts of 2,4-difluoro-5-chloropyrimidine. The liberated fluorine hydrogen was neutralized with 2-n sodium hydroxide solution. connection and reprocessing

67,334,203 were made analogously to Example 327. A dye of the formula was obtained

Example 334

15.9 parts of 1-amino-8-hydroxy-naphthalene-4,6-disulfonic acid were dissolved in 150 parts of water and acylated at pH 6-7 with 6 parts of difluoropyrimidine. The coupling and working up were made analogously to Example 327. A dye of the formula was obtained

which on cotton gave red prints with good wetness.

Example 335

15.9 parts of 1-amino-8-hydroxy-naphthalene, n-3.6-disulfonic acid were dissolved in 150 parts of water and reacted at pH 5.5-6 with 9 parts of tetrafluoropyrimidine. The coupling and further processing took place analogously to Example 327. A dye of the formula was obtained

like colored cotton from long bathing solution in genuine red tones.

- Example 336

12.2 parts of amino-4- (p-amino-phenylamino) anthraquinone-2,6'-disulfone-6-carboxylic acid were dissolved in 360 parts of water and acylated at pH 6 with 3.7 parts of difluorodichloropyrimidine. The. the resultant dye of formula

salted with 10 g of saline, suctioned and washed with 10% saline. The colored wool in a green stained blue color with very good picking and potting strength.

Example 337

To a solution of 15.1 parts acidic coupling product of 1-amino-8-hydroxynaphthalene ~ 3,6-disulfonic acid and diazotated o-sulphanilic acid in 150 parts of water was added at pH 8 and a temperature of 0-5 ° C a suspension of the diazonium salt. of 1-amino-3- (2 ', 6'-difluoro-5'-chloro-pyrimidinyl-4') -amino benzene sulfonic acid (prepared from 5.7 parts of 1,3-diamino-benzene-4-sulfonic acid analogous to Example 30 ). Under the coupling, a pH of 8 was maintained and adjusted after completion of the reaction to pH 6. The dye of the formula

salted with 100 parts of saline, suctioned and dried in vacuo at 60 °. On cotton, when dyeing from a long bath solution, a black tone was obtained.

Example 338 parts of 1-amino-4- (3 '- 2,6-difluoro-5-chloro-pyrimidinyl-3min-anilino) anthraquinone-2-sulfonic acid were introduced at 0 ° in 70 parts of 13% oleum. Towards the end of

The reaction was brought to 20 ° and after complete cooling the mixture was introduced into a mixture of 220 parts of ice water and 30 parts of potassium chloride. The highly crystallizing product was aspirated and washed neutral with saturated potassium chloride solution. The dye, with the probable formula

colored cotton and wool in red stained blue tones with good wetness.

IN

Example 339 divides 1-amino-4- (3 '- 2,6)II-Difluoro-5-chloro-pyrimidinyl] -anilino) -anthraquinone-2,6-disulfonic acid was dissolved at 0 ° C in 65 parts of 13% oleum and after completion of sulfurization was introduced into a mixture of 220 parts of ice and 30 parts of potassium chloride. The substance was aspirated, washed with saturated potassium chloride solution and dried in vacuum at 60 °. On cotton, blue prints were obtained with good wetness.

Example 340

79.7 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid were dissolved in 500 parts of water and then added with a suspension of the drazo salt of 1-amino-3- (2 ', 6'-difluoro-5'-methyl). chloro-pyrimidinyl-4 ') - amino-benzene-6-sulfonic acid (prepared from 47 parts of 1,3-diamino-benzenesulfonic acid analogous to Example 30). With sodium acetate solution, a pH of 4.5 was adjusted and the crystalline reaction product was suctioned after completion of coupling and washed with 10% sodium chloride solution. The dye was dried in vacuo at 60 °.

Example 341

36.6 parts of monoazo dye from Example 340 were dissolved in 460 parts of water and

6.7 parts of soda and added at 0-5 ° while maintaining a pH of 8-8.5 with a diazonium solution of 4.7 parts of aniline. The mixture was stirred for about 3 hours, adjusted with a hydrochloric acid to a pH of 5.5, aspirated and washed with 5% saline solution. The dye of formula

dried in vacuo at 60 ° and at 8-10% staining gave a black color on cotton and cell wool.

When in this example, instead of aniline, the diazo components listed in the following table were used in equivalent amounts, valuable dyes were also obtained:

Hue

diazo components

<td> 342</td><td>2-amino-benzene-l-sulfonic acid</td><td>black</td>

<td> 343</td><td>2-amino-5-chloro-benzene-l-sulfonic acid</td><td>II</td>

<td> 344</td><td>2-amino-5-methyl-benzene-l-sulfonic acid</td><td>it</td>

<td> 345</td><td>2-amino-5-nitro-benzene-l-sulfonic acid</td><td>II</td>

<td> 346</td><td>2-amino-naphthalene-l-sulfonic acid</td><td>II</td>

<td> 347</td><td>dehydro-p-toluidindisulfonsyra</td><td>II</td>

<td> 348</td><td>2-Amino-naphthalene-1,5-di sulfonic acid</td><td>II</td>

Example 349

Analogously to Example 340, a dye of the formula of 1,4-diaminobenzene-2-sulfonic acid was obtained

When coupling this dye with the following diazo components, black dyes were also obtained:

- 71 334203

Diazo components Hue

<td> 350</td><td>2-amino-benzene-l-sulfonic acid</td><td>black</td>

<td> 351</td><td>2-amino-5-nitro-benzene-l-sulfonic acid</td><td>II</td>

<td> 352</td><td>2-amino-5-methyl-benzene-l-sulfonic acid</td><td>II</td>

<td> 353</td><td>2-amino-naphthalene-l, 6-disulfonic acid</td><td>II</td>

<td> 354</td><td>2-amino-naphthalene-1,7-disulfonic acid</td><td>II</td>

<td> 355</td><td>p-toluidine</td><td>II</td>

Example 356

9.4 parts of p-phenylenediamino-2-sulfonic acid were dissolved at pH 7 in 95 parts of water and acylated at 0-5 ° with 9.3 parts of 5-chloro-2,4,6-trifluoropyrimidine while maintaining the pH through dropwise addition of 2-n sodium hydroxide solution. Dilute with 70 parts of water, add 3.5 parts of sodium nitrite and allow the mixture to flow well at 0-5 ° to a mixture of 150 parts of water and 13 parts of concentrated hydrochloric acid. After 1 hour, the excess nitrite was decomposed with amidosulfonic acid and the suspension of the diazonium salt was added at 0-5 ° to a solution of 15.9 parts of 1-amino-8-oxinaphthalene-2,4-disulfonic acid in 100 parts of an 8% soda solution. The pH was kept at 8 until the coupling was completed, after which the pH with hydrochloric acid was adjusted to 5.5 and the dye was salted out. The product was aspirated, washed with brine and dried in vacuo at 60 °. On cotton or wool, violet dyes were obtained with good wetness.

In this example, when using the compounds listed in the following table as valuable components, valuable reactive dyes were obtained:

Coupling components Color tone

357 2-methylamino-8-oxinaphthalene-6-sulfonic acid bluish red

358 2-oxinaphthalene-6,8-disulfonic acid orange

359 1-Acetylamino-8-hydroxynaphthalic n-4,6-disulfonic acid red

Example 360

15.9 parts of 1-amino-8-oxinaphthalene-4,6-disulfonic acid were dissolved in 100 parts of water and acylated at 0 ° C with 9.3 parts of trifluorochloropyrimidine. One maintained one.

72 pH - 6.5 - 7. A solution of diazotized aniline was then coupled at 0 ° C and a 7-0 arrow. After completion of the reaction, the pH was adjusted to 6, after which the reaction product was suctioned and washed with 5% saline. The resultant dye of formula

S03h was dried in vacuo at 60 ° and stained cotton in wet, red tones.

Example 361 parts I-amino-4- (4'-1'-methylaminomethyl «anilino) anthraquinone-2,6,2'-trisulfonic acid was dissolved in 160 parts of water and acylated at 0-5 ° with 2 parts of 5-nitro -2,4difluor-pyrimidine. The pH was maintained with the aid of sodium hydroxide at 6.5-7. After completion of the reaction, it was salted out with brine, suction filtered and dried in vacuo. On wool gave the resultant dye of formula

blue tones.

Example 362 one

12.3 parts of dye produced by coupling 1- (5'-chloro-2 ', 6'-difluoropyrimidinylamino) -8-hydroxynaphthalene-3,6-disulfonic acid with diazotized aniline, was dissolved in 160 parts 10% oleum at 0 ° and after completion of sulfurization was added to a mixture of 500 parts of ice and 120 parts of saline, after which suction and washing with

- 73 334203 Saturated Coke Solution. The product was dried in vacuo at 80 °. Cotton was dyed in genuine, red tones.

Example 363

10.0 parts of 1-amino-4- (2 ', 6'-dimethyl-anilino-3'-sulfonamido) anthraquinone-2sulfonic acid were dissolved in 150 parts of water and adjusted to pH 12. Acylated with

3.7 parts trifluorochloropyrimidine and, after completion of reaction, adjusted to pH 5, salted with 25 parts potassium chloride, suction and washed with ice-cold 15% potassium chloride solution. The resultant dye of formula

Example 364 parts of 1-amino-4- (4'-N-methylaminomethyl-anilino) anthraquinone-2,2'-disulfonic acid were dissolved in 560 parts of water and acylated at 0-5 ° with 10.2 parts of difluorodichloropyrimidine. Using a 2-n sodium hydroxide solution, a pH of 6-6.5 was maintained. Then, using 10 parts of concentrated hydrochloric acid, a pH of 1.5 was adjusted, then suctioned and washed with 5% saline. The dye of the formula is dried at 60 ° in vacuo

colored cotton in genuine, clear, blue tones

- 74 Example 365

13.3 parts of 1-amino no-4- (4'-N-methylamomethyl-anil in no) -antraki non-2,6,2'-trisulfonic acid were dissolved in 360 parts of water and acylated at 20-25 ° with 6 parts 2,4,6 trifluoro-pyrimidine. The arrow value was maintained using 2-n sodium hydroxide at 6-7. After completion of the reaction, salt was rapidly salted with 65 parts of saline and dried in vacuo at 60 °. The resultant dye of formula

gave the wool a green stained blue color.

Analogously, valuable dyes could be obtained from the following components:

<td></td><td>Dye</td><td>reactive Components</td><td>Hue</td>

<td> 366</td><td>1-Amino-4- (4'-N-methylaminomethyl-nilino) -traki non-2,6,2'-trisulfonic acid</td><td>2,4-difluoro-6-chloro-pyrimidine</td><td>greenish blue</td>

<td> 367</td><td>l-amino-4- (4'-N-methylaminomethyl anilino) -anthraquinone-2,7,2'-tri- acid</td><td>2,4-difluoro-5-chloro-pyrimidine</td><td>blue</td>

<td> 363</td><td>1-Amino no-4- (4'-Amino no-a-nilino) -tracial non-2,7-di sulphonic acid</td><td>2,4-di fluoro-6-difluoromethyl-5-chloro-pyrimidine</td><td>blue-green</td>

<td> 369</td><td>1-Amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,6,2'-tri</td><td>2,4-di fluoro-6-tr in fluoromethyl-15-chloro-pyrimidine</td><td>blue</td>

acid

Example 370

To a solution of 15.6 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid in 100 parts of 3% soda solution was obtained at 0-5 ° a suspension of the diazonium salt of 1-amino-5- (2). ', 6'-difluoro-5'-chloro-pyrimidinylamino-4') - benzene-2-sulfonic acid (prepared from 18.8 parts of 1,5-diamino-benzene-2-sulfonic acid analogous to Example 30), by the addition of Na-acetate a pH of 4-4.5 was maintained. Ef334203

- 75 quarters of finished coupling was added 5.7 parts of soda solution and stirred at a pH of

7.5 - 8 for another 3 hours. The resultant dye was salted with 100 parts of saline, suctioned and washed with 15% saline. Dry in vacuo at 60 °. On cotton, the resulting dye gave a black color with very good wetness. äktheter.

Similar dyes are obtained when the following diazo components are added in this example:

371 1-Amino-4- (2 ', 6'-di-fluoro-5'-chloro-pyrimidinylamino-4') - benzene-2-sulfonic acid

372 1-Amino-3- (2'-fluoro-5 ', 6'-dichloropyrimidinylamino-4') - benzene-2-sulfonic acid

373 l-methyl-2- (2 ', 6'-difluorpyrimidinylamino-4') - 4-amino-benzene-5-sulfonic acid

374 l-amino-4- (2'-fluoro-5'-chloro-pyrimidinylamino-4 ') - benzene-2-sulfonic acid

Example 375

6.1 parts of 1-amino-4- (3'-aminomethyl-1-2 ', 6'-dimethyl-anilino) anthraquinone-2,0,5'-trisulfonic acid were dissolved in 65 parts of water and acylated at pH 6 with 2 divides chlorotrifluoropyrimidine. The pH was adjusted using 2-n sodium hydroxide solution. The resulting dye was salted with 10 parts of potassium chloride and washed with 20% potassium chloride solution. Dry in vacuo at 60 °. The resultant dye of formula

colored wool in clear, blue tones with good selection and sweat resistance.

Example 376

10.6 parts of 1-amino-4- (3'-aminomethyl-2 ', 6'-dimethyl-anilino) anthraquinone-2,5'-disulfonic acid were dissolved in 110 parts of water. Acylated with 4.4 parts of trifluorochloropyrimidine at 20-25 ° and a pH of 6-6.5. The pH was maintained using 2-n sodium hydroxide solution. After completion of the reaction, the resulting dye was salted out of the formula

with 20 parts of saline, suction and washed with 10% saline. The dye dried at 60 ° in vacuo gave cotton or wool wet, clear, reddish blue stains.

Example 377

7.8 parts of 1-amino-4- (3'-N-methylaminomethyl-2 ', 6'-dimethyl-anilino) anthraquinone2,6,5'-trisulfonic acid were dissolved in 85 parts of water at 20-25 ° with 2, 3 parts 2,4,6-trifluoro-5-chloro-pyrimidine. (During the reaction, a pH of 6-6.5 was maintained using 2-n soda solution. Prior to a rapid addition of 20 parts of saline, a pH of 3.5 with 1 part of concentrated hydrochloric acid was adjusted. formula

colored wool or cotton in wet, clear, blue tones.

Example 378

7.6 parts of 1-amino no-4- (3'-N-methylamomethoxy 1-2 ', 6'-dimethyl-1-ain-1) no-anthracione 2,6-disulfonic acid were dissolved in 250 parts of water and acylated with 3.1 parts of trifluorochloropyrimidine under the following conditions: pH 6-6.5, temperature 20-25 °. The pH was maintained by the addition of 2-n sodium hydroxide solution. After completion of the reaction, the batch was salted with 10 parts of saline and washed with 2% saline. On bo334203 mull or wool, wet, clear, blue tints were obtained.

Analogous to the procedures described in Examples 375 - 378, we obtained the use of the components listed in the following table as valuable dyes, which dyed cotton and wool in red-stained to green-stained blue, clear color tones:

Dye Keactive components

<td> 379</td><td>1-Amino-4- (3'-N-methylaminomethyl-2 ', 6'-dimethylamino) anthraquinone-2,7-disulfonic acid</td><td>2,4-difluoro-5,6-dichloro-pyrimidiri</td>

<td> 380</td><td>1-Amino-4- (3'-N-methylaminomethyl-2 ', 6'-dimethylamino-amino) anthraquinone-2,7,5'-trisulfonic acid</td><td>2,4-difluoro-6-chloro-pyrimidine</td>

<td> 381</td><td>1-Amino-4- (4'-1-methylamino-1-2 ', 6'-dimethylamino) -tracial non-2,6,5'-tri sulphonic acid</td><td>2,4,6-trifluoro-pyrimidine</td>

<td> 382</td><td>1-Amino-4- (3'-N-methylaminoethyl-2 ', 6'-dimethylanilino) -anthraquinone-2, α, (T-trisulfonic acid</td><td>2,4-difluoro-5,6-dichloro-pyriinirlin</td>

<td> 383</td><td>l-amino-4- (3'-aminomethyl-4'-methyl-anilino) anthraquinone-2,6,6'-trisulfonic</td><td>2,4,6-trifluoro-5-difluorme- methyl-pyrimidine</td>

<td> 384</td><td>l-amino-4- (3'-aminomethyl-4'-methyl-anilino) anthraquinone-2,6'-disulfonic</td><td>2,4,6-trifluoro-5-trifluoromethyl 1-pyrimidine</td>

<td> 385</td><td>1-Amino No-4- (3'-Aminomethyl-4'-methylamino) anthraquinone-2,7,6'-trisulfonic acid</td><td>2,4-difluoro-5-trifluormety1pyrimidin</td>

<td> 386</td><td>1-Amino-4- (3'-methylamino-4'-methoxy-anilino) anthraquinone-2,7,6'-trisulfonic acid</td><td>2,4-difluoro-5-carbonamide dopyrimidine</td>

<td> 387</td><td>1-amino-4- (4'-amino-anilino) anthraquinone-2,3 ', 6-trisulfonic acid</td><td>2,4-difluoro-5-chloro-6-phenyl pyrimidine</td>

<td> 388</td><td>1-amino-4- (3'-amino-ailino) anthraquinone-2,6-disulfonic acid</td><td>2,4-difluoro-5-cyano-pyrimidine</td>

<td> 389</td><td>1-Amino No-4- (4'-Amino-Alieno) -Antraki Non-2,6disulfonic Acid</td><td>2,4-di fluoro-5-carbonethyl ester pyrimidine</td>

<td> 390</td><td>1-Amino-4- (4'-amino-a-amino) anthraquinone-2,7disulfonic acid</td><td>2,4-difluoro-5-methyl-sulfony1pyrimidin</td>

<td> 391</td><td>1-Amino No-4- (3'-Amino No-Alino) -intraki non-2,7disulfonic acid</td><td>2,4,6-trifluoro-5-bromo-pyrimidine your</td>

<td> 392</td><td>1-amino-4- (2 ', 4', 6'-trimethyl-3'-amino-a-amino) anthraquinone-2,5'-disulfonic acid</td><td>2,4,6-trifluoro-5-chloro-pyrimidine your</td>

32 members in 18 offices

This recordMember, by publication datePriority claim8 more offices are in the list below

Priority claims2

Priority claims
Document	Office	Kind	Date
F0050181	Germany	A	1966-09-10
F0051942	Germany	A	1967-03-25

Members32

Family members, oldest first
Document	Office	Kind
BE703598A	Belgium	A	1968-03-07
NL6712369A	Netherlands (Kingdom of the)	A	1968-03-11
ES344891A1	Spain	A1	1969-01-01
FR1563661A	France	A	1969-04-18
AT274983B	Austria	B	1969-10-10
GB1169254A	United Kingdom	A	1969-11-05
CH495463A	Switzerland	A	1970-03-31
CH878567A4	Switzerland	A4	1970-03-31
DE1644171A1	Germany	A1	1970-07-30
CH494266A	Switzerland	A	1970-07-31
CH494267A	Switzerland	A	1970-07-31
CH501101A	Switzerland	A	1970-07-31
CH594668A4	Switzerland	A4	1970-07-31
AT284774B	Austria	B	1970-09-25
IL28188A	Israel	A	1970-10-30
SE334203BThis record	Sweden	B	1971-04-19
AT291180B	Austria	B	1971-07-12
FI44650B	Finland	B	1971-08-31
FI44650C	Finland	C	1971-12-10
DE1644204A1	Germany	A1	1972-03-16
US3669951A	United States of America	A	1972-06-13
DK128168B	Denmark	B	1974-03-11
JPS4930502B1	Japan	B1	1974-08-13
PL72556B1	Poland	B1	1974-08-30
NO133369B	Norway	B	1976-01-12
NO133369C	Norway	C	1976-04-21
NL150839B	Netherlands (Kingdom of the)	B	1976-09-15
DE1644204B2	Germany	B2	1977-09-22
US4052386A	United States of America	A	1977-10-04
DE1644204C3	Germany	C3	1978-06-01
BG25101A3	Bulgaria	A3	1978-07-12
CS194801B2	Czechoslovakia (until 1993)	B2	1979-12-31

Reactive Dyestuffs

Abstract

Term

SWEDEN

PATENTS AND REGISTRATION OFFICE

FARBENFABRIKEN BAYER AG, LEVERKUSEN, FEDERAL REPUBLIC OF GERMANY DT

N (R ') - A; C1; NO

0-2 (SO 2 H)

A HM

HO -

POOR QUALITY

II

II

II

II

II

II

II

IN

II

II

II

II

SO 2

A.D)

O

IN

Priority claims2

Members32

Numbers

Classification