CS209926B2 - Method of making the reactive dyes - Google Patents

Abstract

Reactive dyes of the formula <IMAGE> in which D1 is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R1 is hydrogen or C1-4-alkyl, the bridge member -N(R1)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C1-4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.

Description

(54) A method for producing reactive dyes

The invention relates to a process for the preparation of reactive dyes of the general formula (I)

Ri

H ₃ N OH

II and ^R L wherein

Di optionally substituted benzene or naphthalene residue,

D2 is an optionally substituted benzene radical, wherein C1-C4 alkyl, C1-C4 alkoxy, C1-C6 acylamino, amino-NH2, methylamino and ethylamino are suitable as substituents of D1 and D2; , ureidosyl, hydroxy, carboxy, and halogen atoms, and especially sulfonic acid groups,

R1 is hydrogen or alkyl of up to 4 carbon atoms, the bridging member of the formula being bonded to the carbon atom of the ring Dz,

R? a hydrogen atom or a (C1-C4) alkyl group optionally substituted by a chlorine atom, a hydroxy group, a cyano group, or an alkyl group having from 1 to 4 carbon atoms; methoxy and sulfo,

R 3 has the same meaning as R 2 or is cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl, or phenethyl, and in particular phenyl, optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy , acetylamino, ureido, carboxy, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, or is naphthyl, optionally substituted with sulfo, or groups

R 2 and R 3 together form a six-membered heterocyclic ring with nitrogen, which may optionally contain a heteroatom such as nitrogen, oxygen and sulfur.

209928

The residues D 1 and D 2 may have the substituents customary for azo dyes. Other substituents which may be mentioned are, for example: C1-C4-alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups, C1-C4-alkoxy groups such as methoxy, ethoxy, propyloxy, isopropyloxy C1-C6 acylamino, such as acetylamino, propionylamino and benzoylamino, carbamoyl, sulfamoyl, amino, such as amino-NH2, methylamino and ethylamino, ureldino, hydroxy, carboxylic acid, hydroxy, is a fluorine, chlorine and bromine atom, and a sulfonic acid group.

The D 1 and D 2 radicals contain, in particular, one or more sulfonic acid groups as further substituents.

R 1 in the meaning of an alkyl group is methyl, ethyl, propyl / isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

When R2 is an alkyl group, the alkyl group may be substituted by, for example, a chlorine atom, a hydroxy group, a cyano group, a methoxy group, a carboxy group and a sulfo group. Examples of R 2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, β-hydroxyethyl. β-chloroethyl, β-cyanethyl, cyanomethyl, γ-cyanopropyl, β-methoxyethyl, β-carboxyethyl, sulfomethyl and ε-sulfoethyl. '/

R 3 is: hydrogen, the same substituted and unsubstituted alkyl groups as defined for Ra, methoxypropyl, ethoxyethyl, ethoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-suifobenzyl, 4-methylbenzyl, phenethyl, and in particular phenyl, optionally substituted by C1 -C4 alkyl, C1 -C4 alkoxy, acetylamino, ureido, carboxy, halogen, sulfo, sulfomethyl,. trifluoromethyl, sulfamyl and carbamoyl, or naphthyl optionally substituted with sulfo.

They can also. the groups R2 and R3 form a six member. a heterocyclic ring with nitrogen, which may optionally contain another heteroatom, such as an atom. nitrogen, oxygen and sulfur.

Examples of the amino radical —NR @ 2 R @ 3 in formula I are:.

amino of formula -NH2, methylamino, ethylamino, polyamino, isopropylamino, butylamino, β-methoxyethylamino, γ-methoxypropylamino, Ν, dim-dimethylamino, N _; N-diethylamino, N-methyl-N-phenylamino, N-ethyl-4-phenylamino, β-chloroethylamino, ε-hydroxyethylamino, γ-hydroxypropyl · amino, benzylamino, cyclohexylamino, morpholino, amino, piperidino, piperidino phenylamino,.

toluidino, chloranilino, anisidino, phenetidino,

2-sulfoanilino,

3-sulfoanilino a

4-sulfoamino,

2,5-disulfo-4-iodo-4-carboxylic acid, sulfomethylanilino, N-sulfomethylanilino, 3-carboxyphenylamino, 4-carboxyphenylamino, 2-dihydro-5-sulfofof ( mylallyl, 2-carboxy-4-sulfephenylamino ^, and, 4-sulfonaphthyl- (1J-amino),

3,6-disulfonattyl- [1] -amino, 3,6,8-trisulfonaphthyl- (1) -amino and d.e.B-trisulfonaphthyl- (1'-amino).

The dazo dyes of the formula I are reactive with the fiber since they contain a leaving atom of fluorine in the symtriazine residue.

Fiber-reactive compounds are compounds which are capable of reacting with the hydroxyl groups of cellulose or the amino groups of natural or synthetic polyamide fibers to form a cosmodic chemical bond.

Residue. Di contains no fiber-reactive group.

Preferred are reactive dyes of the formula II,

wherein one Y is a hydrogen atom and the other Y is a sulfo group and D 1, R 12 and R 3 are as defined for formula (I).

Particularly preferred are reactive dyes of the general formula (II) where

A di-benzene group optionally substituted by a sulfo group, a methoxy group and a chlorine atom, or a naphthalene group optionally substituted by a sulfo group and a nitro group,

R @ 2 is hydrogen, methyl or ethyl; and

R 3 is hydrogen, ethyl, β-hydroxyethyl, butyl, phenyl optionally substituted with methyl. methoxy, ethoxy, chloro, acetylamino, ureido, carboxy and sulfo; or wherein the amino group of the formula

NR2R3 is morpholino. .

Particularly preferred are reactive dyes of the formula III,

(Ш) where · means

R2 is hydrogen, methyl or ethyl,

R3 is hydrogen or phenyl, optionally substituted by methyl, methoxy, chloro and sulfo.

A valuable reactive dye of formula III is a reactive dye of formula IV.

/ f 7

\ ...... /

and.

A process for the preparation of reactive dyes of the formula I is characterized in that the coupling component of the formula V is diazotized, coupled and condensed,

diazo component of formula VI,

Di-NH2 (VI) another diazo component of formula VII, H2N-D2-nh

I ‘

Ri (VII)

2,4,6-trifluoromethyl-VIII of formula VIII

AND

F (VIII) and amino compound of formula IX,

HN — R3

R2 wherein the individual meanings of the symbols are given in the general formula I.

A preferred embodiment is characterized in that -compounds of formula X are used as coupling components of formula V,

wherein one Y represents a hydrogen atom and the other a sulfo group, and as a diazo component of formula VII a compound of formula XI.

In particular, the compounds of the general formulas (VI) and (IX) are used as starting materials. wherein D 1 is a benzene radical optionally substituted by a sulfo group, a methoxy group and a chlorine atom, or a naphthalene radical optionally substituted by a sulfo group and a nitro group, R 2 is hydrogen, methyl or ethyl and R 3 is hydrogen, ethyl, n-hydroxyethyl, butyl, phenyl optionally substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureldio, carboxy, and sulfo, or R3 is naphthyl, optionally substituted with -sulfo, or amino substituted by -OR2R2 .

Preferred reactive dyes of the general formula (III) are obtained if, in any sequence, diazotized, coupled, and condensed, the diazo component of general formula (XII),

SO4H

(xii) 1-Amino-8-hydroxynaphthalene-3 _/ 6-dsulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, cyanurofluoride, and an amino compound of formula IX, wherein - R 2 and R 3 are as defined for formula III.

Since the individual preparation steps mentioned above, namely diazotization, coupling and condensation can be carried out in any desired sequence, possibly also at the same time, different variants of the process for preparing the dyes of the general formula I are possible. In general, the reaction is carried out sequentially, wherein the sequence of individual simple reactions between the individual reaction components of the formulas V to IX is arbitrary.

Important variants of the method are indicated by:

1. A coupling compound of formula (V) is reacted with a diazotized -diazo component of formula (VI) and (VII). to form a diazo compound, the diazo compound is condensed with 2,4,6-trifluoro (or-sym-triazine VIII) and the primary condensation product is condensed with the amino compound of formula IX.

The last two reaction steps may also be carried out in a different sequence by first condensing 2,4,6-trifluoro-syim4riazm with the amino compound of formula (IX) -

The foregoing primary condensation product is condensed with the above-described disazo compound.

In the preparation of the aforementioned disazo compound, it is preferred to first coupling the diazotized diazo component of formula VI with a coupling component of formula V, and then obtaining the monoazo compound with a diazotized diazo compound. of formula VII.

2. Diazotize the diazo component of formula (VI) and coupled to the coupling component of formula (V), further condensing 2,4e-trifluoro-sym-triazine of formula VIII with an -amino compound of formula (IX), a primary condensation the product is then condensed with a diazo component of formula VII and the secondary condensation product obtained is diazotized and coupled to the initially prepared monoazos compound.

A preferred process for the preparation of the reactive dyes of formula IV is characterized by diazotizing the sulfanilic acid and 1,3-phenylenediamine-4-sulfonic acid and coupling to 1-aimino-4-hydroxynaphthalene-4-disulfonic acid, the intermediate of formula XIII obtained.

is condensed with cyanurofluoride and the primary condensation product is condensed with m-chloroaniline. ’

The diazotization of the diazo components is generally carried out by treatment with nitrous acid in an aqueous solution acidified with mineral acid at low temperature.

The coupling of the diazo components of the formula VI to the coupling compounds of the formula V in ortho position to the - NH2 - group is carried out in a strongly acidic solution, at a pH of 1 to 2; The coupling of the diazo compounds of formula VII to the coupling compounds of formula V in ortho position to the hydroxyl group is carried out in a weakly acidic, neutral to weakly basic medium, at a pH of 6.5 to 8.

In general, it is desirable to first carry out the coupling in an acidic solution. In many cases, it is expediently used for couplings in which the diamine-benzenesulfonic acid is used as the diazo component of formula (VII), not the component itself, but instead the amino-amino-isobenzenesulfonic acid, for example 5-acetylamino-aniline-2-sulfonic acid, after completion of the coupling, the acetyl group is cleaved by saponification before further condensation is carried out. In addition, nitroamino compounds, for example 5-tetramino-2-sulfonic acids, can also be used as diazo components of formula VII, and the nitro group is then reduced to -am by sodium sulphide or sodium sulphate after completion of the coupling.

The condensation of 2, .4 ,, ^ - ^ tl ^ j IFL ^<ι ^ f ^ i ^^ <^ 1 ^ i ^^ - t]? 'Azine of Formula VIII with dlazosložk.ami -obecného- VII and -S The amino compounds of the formula IX are preferably carried out in an aqueous solution or suspension, at a low temperature and at an acidic, neutral to weakly alkaline pH, so that at least one atom remains in the finished reactive dye of the formula I fluorine as a leaving group. Preferably, the hydrofluoric acid released by condensation is continuously neutralized by the addition of an aqueous solution of an alkali hydroxide, carbonate or bicarbonate.

The production of diazo intermediates is not always described in the following examples, but is always apparent from the foregoing.

The starting materials for the preparation of the reactive dyes of the general formula I are exemplified by:

a] Coupling components of formula V

Acids: 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 1-amino-8B-hydroxy-naphthalene-4-disulfonic acid (K-acid and 1-amino-8-hydroxynaphthalene) -4-sulfonic acid (K-acid-and _t

b] Diazo components of formula VI

Aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, nmamsidine, p-anisidine, o-chtoraniline, m-chloroaniline,.

p-chloroaniline,

2.5-dichlorazinine, α-naphthylamine, β-naphthylamine,

2.5- dimethylaniline,

-n i t г о - 2-aminoa n i sol

4-aminodifeethyl, aniline-2-carboxylic acid, aniline-3-carboxylate and α-β-4-carboxylic acid, 2-aminodiphenyl ether,

2-aminobenzenesulfonanild,

3-Aminobenzenesulfonamide or

4-aminobenzenesulfonamide or sulfomonomethylamide or sulfonaonoethylamide or sulfondimethylamide or sulfondiethylamide, anilino-2-sulfonic acid, aniline-3-sulfonic acid and aniline-4-sulfonic acid, aniline-2,5-disulfonic acid,

2,4-dimethyl.almil-6-sulfonic acid,

4-chloro-5-methylaniline-2-sulphonic, and ^even Nilin-2,4-di- ^l sulphonic acid, aniline-3,5-disulfonic acid, 2- »amino-4-sulfoben.zoová, 2-amino-5-sulfobenzoic , 2-methylaniline-3,5-disulfonic acid, 2-methylaniline-5-sulfonic acid, 2-methoxyaniline-3,5-disulfonic acid,

2-Chlonaniline-4-sulfonic acid,

2,3-dimethylanilm-4,6-disulfonic acid,

2.5- di methyla.nilin ^{L-4,6-disulfonic} acid,

5-chloro-4-methylaniline-2-sulfonic acid,

3- acetylaminoanilin ^j-6 sulfonic acid,

4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid,

3.4-dichloroaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid,

3-methylaniline-6-sulfonic acid,

2,4-dimethoxyaniline-6-sulfonic acid,

4-Methoxaniline-2-sulfonic acid,

5-methoxane-2-sulfonic acid,

2,5-Dichloro-niline-4-sulfonic acid,

2,4-dimethylaniline-5-sulfonic acid, 2-mothoxane-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid and 4-ethylaniline- 2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxyaniline-3-sulfonic acid,

3.4-dichloroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, m-ammoacetanilide, p-aminoacetanilide, 4-amino-12-acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, 1-anainonaphthalene-2 -sulfonic, aminoaminophthalen-4-sulfonyl, 1-aminonaphthalene-5-sulfonic, 1-aminonaphthalene-6-sulfonic, 1-aminonaphthalene-7-sulfonic,

1-aminonaphthalene-8-sulfonic acid,

2-Amino-naphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-3,6-disulfonic acid,

1- ami ^! nonaphthalene-5,7-disulfone,

2-aminonaphthalene-1,5-disulfonate, 2-aminonaphthalene-1,7-disulfonate ^| 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-6,8-diisone u 1 phono v á,

1-ammonaphthalene-2,5,7-trisulfonic acid,

2-aminonaphthalene-l ₅ 5,7-trisulfonic, 2-amiinonaftalen-3,6,8-trisulfonic, 2-aminonaftale.n-4,6,8-trisulfonic,

1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid a

2-amino-1'-hydroxy-naphthalene-4,8-disulfonic acid, 1-amino-3-acetylaminobenzene (saponified), 1-amino-3-acetylaminobenzene-5-sulfoic acid, (saponified), 1-amino acetylaminobenzen -3-6-sulfonic acid (saponified) and i-amino-4-acetyl-aminobenzene _and 2-sulfonic acid (saponified),

1-amino-3- (N-acetyl-N-methylamino) benzene (saponified),

3-: nitroaniline (reduced),

4-metroaniline (reduced),

2-methoxy-4-nitroaniline (reduced 2-methoxy-5-nitroaniline (reduced 2-methoxy-3-nitro-5-methylaniline (reduced)),

2-methoxy-3-nitro-5-chloroaniline.

c) Diazo components of formula VII

1,3-diaminobenzene,

1,4- diaminobenzene,

1.3- diaminoantsol,

1,4 -d i a m inoan i s o 1,

1,3 - d i a mi n ot o 1 u e n,

1,4- diamino toluene,

1,3-diamino-4-chlorobenzene,

1,3-diam: no-4-ethylbenzene,

1,3-diamino-4-ethoxy benzene, acid

1,3-diaminobenzene-4-sulfonic acid,

1,4-diaminobenzene-2-sulfonic acid,

1,4-diaminobenzene-2,5-disulfone,

1,4-diamine-2,6-disulfone and 1,3-diamino-benzene-4,6-disulfone.

d) 2,4,6-Trifluoro-sym-triazine of formula VIII (cyanurfluoride)

e) Amino compounds of formula IX

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec-butylamine, tert-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chlorethylamine, hydroxyethylamine, hydroxyethylamine, hydroxyethylamine, hydroxyethylamine, hydroxyethylamine , aminoethanesulfonic acid, z-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-to-lidine, m-toduidine, p-toluidine,

2.3- dimethylanirine,

2,4-dimethylaniline, 2,5 ^ 1те1Ьу1ат1гп,

2,6-dimethylaniline,

3.4- dimiethylamine,

3,5-dimethylaniline, o-haloniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline,

3-acetylaminoaniline,

4- acetone Lamanone aniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenod, p-aminophenod, 2-methyl-4-nrtronniline,

2-Methyl-5-nitroaniline ₃

2,5-dimethoxy aniline,

3-Methyl-4-nitroaniline

2-nitro-4-methylaniline,

3-nitro-4-methylanilino-o-anisidine, m-anisidine, p-anisidine, o-phenetidine, n-phenetidine, p-phenetidine,

- me t hox у - 5-m eth у l an i 1 i π,

2-ethoxy-5-methoxyethoxy, α-bromoimine,

3- ammobenzamine,

4-aminophenylsulfamide,

3-trlf luo-rmethy bánili n,

-a minof en у 1 power in a,

4-amine of e ny lm o δονin a,

1- Naphthylamine,

2-naphthylamine, 2-amino-1-hydroxynaphthalene, 1-amine-o-4-hydroxynaphthalene, 1-amhio-5-hydroxynaphthalene, 1-amino-2- hydroxynaphthylen, ^la.m: .no-7'hydroxyn-aftalen acid ortanilová, metanilová, sulfanilic or 1 s л - 2 ₇ 4 - di Square F 1 on the OC and aniline-2,5-disulfonate-OVA Amlin -3,5-disulfonate, anranil, m-aminobenzone, p-amine-o ben zoo,

4-Aminophenylmethanesulfonic acid, aniline-N-methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotodon-5-sulfonic acid, p-amine Gabycyl, 1-amino-4-carboxybenzene-3 sulfonic acid, 1-amino-2-carboxybenzene-5-sulfonic acid, 1-amino-5-carboxybenzene-2-sulfonic acid, 1-naphthalenin-2-sulfonyl, 1- naphthylamine-3-sulfone,

- na f t am 1-amine - 4 - s-phenylane, 1. - n-phthyl in-in - 5 - s-phenylane, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-surfonic acid,

1-naphthylamine-8-sulfonic acid,

2-naphthyl-1-sulfonic, 2-naphthylamino-3-sulfonic, 2-naphthylamine-4-sulfonic, 2-naphthylamine-5-sulfonic, 2-naphthylamine-6-sulfonic,

-fromo-7-sulfonate, 2-naphthylamine-8-sulfonic acid, 1-naphthylamine-2,4-disulfonic acid, 1-naphthylamine ^. ftyl-amino-2,5-disulfonic acid, L-2,7-naftyiamin dIsulf'ono'Vá l ^j naphthylamine-2,8-disulfonic LN-aftylamin-disulfonic S ^ l-naphthylamine-3,6 -disulfonic, 1-naphthylamine-3,7-disulfonic, 1-naphthylamine-3,8-disulfonic, 1-naphthylamine-4,6-disulfonic, 1-naphthylamine-4,7-disulfonic, 1-naphthylamine-4,8-disulfonate,

1-naphthylamine-5,8-disulfonate, 2-n-thiophen-1,5-diisophenone,

2- naftybamln-l, 6-di.su.lřono acid, 2-naphthylamine-l, 7-disulfonic _{3 2-naphthylamine-3)} 6-d'Sulfono acid, 2-naphthylamine-3,7-disulfonic acid, 2-naphthylamine-4,7-disulfonic acid, 2-naphthylamine-4,8-'dLsnlfcnoivá ^{2-inaftylamin-5,7-dlsulfono:} acid, ^{2-naphthylamine-6s8-d:} snlfonová, naphthylamine-.2 4,6-trisulfonic, 1-naphthylamine-N, N-trisulfonic, 1-naphthylamine-2,5,7-trisulfonate, 1-naphthylamine-3,5,7-thisulfonyl, 1-naphthylamine-3 , 6 ₅ 8-trisulfone,

1- naphthyl ^; amine-4,6,8-trisulfonic acid,

2- naphthylamine-l, _3: 7-'tT] siilfonová, 2-naphthylamine-l, 5,7-trisulfonic ₃ 2-níaftylamin-3,5.7-trlsulfono acid, 2-naftylamln-3,6,8-tri- sulfonated, 2-naphthylamine-3,6,7-trisulfone and 2-naphthylamine-4,6,8-trisulfone;

2-Amino-pyridine

3-ammo-pyridine,

4-aminopyridine,

2- a ^; m vnobenzthia-zol,

5-aminoquinoline.n,

6-aminoquinoline, 8-aminoquinoline, 2-aminopyrimidine, morpholine, ..

plperidine, piperazine.

The reactive dyes of the formula I can be isolated and processed into useful, dry dye preparations. The isolation is carried out, preferably at low temperatures if possible, by salting out and filtration. The filtered dyes may optionally be dried after the addition of buffing agents and / or buffering agents, for example after addition of a mixture of equal parts of mono-sodium phosphate and disodium phosphate. Preferably, the drying is carried out at not too high temperatures and under reduced pressure. In certain cases, spray-dried mixtures as a whole can be prepared according to the invention directly with dry dye preparations, i.e. without dye isolation.

The reactive dyes of the formula I prepared according to the process of the invention are novel. They are characterized by high reactivity and provide coloring with good fastness to wet and light. In particular, it is emphasized that dyes have good solubility in electrolytes with good drawing properties and a high degree of dye fixation and that unfixed dye fractions are easily removed. The colors are etchable.

The reactive dyes of the formula I are suitable for dyeing and printing the most important materials, such as silk, leather, wool. polyamide and polyurethane fibers, but are particularly suitable for dyeing and printing cellulose-containing fibrous web materials such as flax, cellulose staple, regenerated cellulose and, in particular, cotton. They are suitable for both dye-drawing and blower-dyeing, wherein the textile material is impregnated with an aqueous and optionally also salt-containing dye bath and a dye with an alkaline treatment or in the presence of an alkali, optionally under the action of heat. fixuje.

They are also suitable for printing, especially cotton, but also for printing fibers containing-nitrogen, such as wool, silk, or mixtures containing wool.

It is recommended that the dyeings and prints be thoroughly rinsed with cold and hot water, optionally with the addition of dispersing agents and promoting the diffusion of non-fixed fractions.

In the following examples, parts are by weight and temperatures are in ° C.

Example 1

Neutral solution of 70.2 parts disazo dye of formula

HOJ

in 500 parts water, cooled to 0-5 ° C by adding 300 parts ice. During 5 to 10 minutes, 10 parts of cyanurofluoride are added with vigorous stirring and the pH of the reaction mixture is simultaneously maintained by dropwise addition of 2N sodium hydroxide solution to 6-7. 10.7 parts of o-toluidine are added to the difluorotriazine dye solution, heated to 30-35 ° C and the pH of the reaction mixture is maintained at 7-8 by dropwise addition of 2N sodium hydroxide solution. After complete reaction, the mono- The fluorotriazine dye is mixed with 5 parts of sodium hydrogen phosphate and the solution is evaporated in a rotary evaporator at a temperature of 40 to 45 ° C to dryness.

The dye thus obtained dyes cotton to navy blue shades.

Similar dyes, which also dye cotton to navy blue shades, are obtained when the procedure described in this example is followed, but instead of o-toluidine, an equivalent amount of the below amine is used.

Example Amin 2 m-toluidine 3 p-toluidine 4 2,4-dimethylaniline 5 2,5 -dirnethylaaiiiin 6 2, f: - - 7 ethanolamine 8 aniline 9 N-methylaniline 10 N-ethylaniline 11 m-chloroaniline 12 p-chloroaniline 13 acetyl- m- phenyltenediamine 14 acetyl-p-phenylenediamine 15 Dec ocanisidine 16 p-anisidine 17 4-m mmon enm Imocated a 18 3- 4-mieophenylurea 19 Dec p-amine benzoic acid 20 May motavilioic acid 21 2c4minonaphthalene-6-sulfo- new acid 2-2 23 ⁱ mcanisidl · n 24 4-methoxyphenol 25 morpholine 26 Taiir In

Next . dyes that dye cotton. to the shades listed in column III, are obtained when the amine-containing disazo dye mentioned in. column I, reacted with cyanurfluorld and the amines listed in column II.

SO.H

3-Aminot-oluene blue with a green tinge

N ~ N

OH

so _b H

N.vX

S (° H NHz n-butylamine blue with green tint)

HOf

aniline-3-sufonic acid blue with a green tinge

4-Aminoanisole blue

2-chloroaniline strongly green-blue

2a

AND

II

III

ethylamine

N-methylanine blue-green strongly green-blue

3-aminotoluene strongly green-blue

metanilic acid strongly green-blue

Example 2

Neutral solution of 17.3 parts of ortanilic acid in 200 -. It is cooled to 0 DEG C. by adding 250 parts of ice. Leave to stand with vigorous stirring. 9 parts of cyanurfluoride flow in over 10 minutes and the pH-value is maintained dropwise by dropping -2N sodium hydroxide solution at 6-. - to 7. If no more unreacted ortanilic acid is detectable, - mix - the solution - of the primary condensation product with the - neutral solution

18.8 parts of m-fenylendiaminsulfono-acid ethyl ester in 50 parts - water, the temperature was allowed to rise: ²⁰ to 25 ° C and the p ^H value REA ^ ack mixture was maintained at 6.5 to 7.0. After complete reaction, the secondary condensation blue product is salted out by addition of 15% by volume sodium chloride and filtered off.

A neutral suspension of 45.6 parts of the above secondary condensation product in 150 parts of water was mixed with 25 parts of 4N sodium nitrite solution and cooled with ice to 0-5 ° C. 30 parts of 10 N hydrochloric acid were added and after several hours the excess nitrite was destroyed with sulfamic acid.

The thus obtained yellow diazo compound suspension is then poured into an ice-cold neutral solution of 50.3 parts of the dye "sulfacidic nile -Hnn acid ----> H-acid" in 150 parts of water, which is mixed with 30 parts of sodium hydrogen carbonate before coupling. .

A clear solution of about 750 parts by volume is formed, from which the dye formed is salted out by adding 10% by volume of a 1: 1 mixture of sodium chloride and potassium chloride. After filtering · the dye paste · is mixed with a concentrated aqueous solution of 5 parts of disodium hydrogen phosphate and dried under vacuum at 50 ° C.

The dye thus obtained dyes cotton to the sailor's. Blue shades.

Example '3

10 parts of cyanurofluoride are added dropwise to the ice-cold, neutral solution of 17.3 parts of ortanilic acid in 400 parts of water over a period of about 10 minutes, while maintaining the pH of the reaction mixture at 6-7 by simultaneous addition of 1N sodium hydroxide solution.

The primary condensation product thus obtained is then poured into a neutral solution of 70.2 parts of the disazo dye of the formula

in 500 parts of water, heated to a temperature of 30 to 35 ° C and maintaining the pH of the reaction mixture at 7 to 8 by dropwise addition of 1N sodium hydroxide solution.

After the acylation is complete, the monofluorotriazine dye solution is mixed with 5 parts of disodium hydrogen phosphate and the solution is evaporated in a rotary evaporator at 40-45 ° C. to dryness. The dye thus obtained is colored. cotton on navy blue shades.

If 18.72 parts of 4-aminotoluene-3-sulfonic acid are used instead of ortanilic acid, a dye is obtained. which also dyes cotton to navy blue.

Dye prescription

Two parts of the dye prepared as described in Example 1 were dissolved in water with the addition of 0.5 parts of m-nitrobenzenesulfonic acid as the sodium salt, using 100 parts of water. The obtained solution is impregnated with a cotton fabric so that its weight is increased by 75% and then dried.

Then the fabric is impregnated with a solution temperature of about .20 ° C, which contains, per liter of sodium hydroxide and 300 g of sodium chloride, squeezed to a ^75% increase, coloration Mr. ^P .dobu about ³⁰ seconds at 100 to 101 ° C, rinsed, soaped for 15 minutes in a 0.3% boiling wash solution. a simple device. The ions are rinsed and dried.

Dye regulation II

Two parts of the dye prepared as described in Example 1 are dissolved in 100 parts of water.

The solution was added. to 1900 parts cold water, 60 parts chloride are added. sodium. and 100 parts of cotton fabric are introduced into this. coloring bath.

The temperature is raised to 43 ° C, after which 4 parts by volume of 30% sodium hydroxide solution, 10 parts of soda ash and 60 parts of sodium chloride are added after 30 minutes. The temperature is maintained at 40 ° C for 30 minutes, rinsed and then the dye is soaped for 15 minutes in 0.3% boiling detergent-free solution. ions, rinsed and dried.

Claims (5)

BEFORE THE INVENTION CLAIMS 1. A process for the production of reactive dyes of the general formula I, in which: Di an optionally substituted benzene or naphthalene residue, D 2 is an optionally substituted benzene radical, the substituents of the radicals D 1 and D 2 being alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acylamino groups having 1 to 4 carbon atoms. 6 carbon atoms, amino group of formula -NH2, methylamino and ethylamino, ureido, hydroxy and carboxy, and halogen atoms, and in particular sulfonic acid groups, Ri. a hydrogen atom or a (C1-C4) alkyl group, the bridging member of the formula --N-- R 1 is bonded to the carbon atom of ring D 2, R2 is hydrogen or C1-C4alkyl optionally substituted by chlorine, hydroxy, cyano, methoxy and sulfo, R3 has the same meaning as R2 or. is cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl, or phenethyl, and in particular phenyl, optionally substituted with C1-C4 alkyl, C1-C4 alkoxy, acetylamino, ureldlamino, carboxy, halogen, sulfo, sulfomethyl, trifluoromethyl, 4-sulfamonyl and carbamoyl, or is naphthyl, optionally substituted with sulfo, or groups R 2 and R 3 together form a six-membered hetero-nitrogen ring, which may optionally contain a heteroatom, such as an atom. nitrogen, oxygen and sulfur, characterized in that the coupling component of formula V, the diazo component of formula VI is diazotized, coupled and condensed; Di-NH 2 (VI) wherein Di is as defined above, another diazo component of formula VII, H2N — D2 — NH R 1 (VII) wherein D 2 and R 1 are as defined above, 2. Method according to claim 1, characterized in that:. A compound of formula X wherein one Y is hydrogen and the other sulfo group is used as the coupling component of formula (V) and a diazosyl group of formula (VII) is used as the diazosyl component of formula (VII). (XI) ^2,4,6-LR-ι fluortrym -triazi'n VIII F- ^F (VIII) and amino compound of formula IX, HN — R3 AND R2 [ix] wherein R2 and R3 are as defined above. 3. Process according to claim 2, characterized in that the starting materials used are compounds of the formulas VI and IX, where they are A di-benzene radical, optionally substituted with a sulfo group, a methoxy group and a chlorine atom, or a naphthalene group, optionally substituted with a sulfo group and a nitro group, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, ethyl, beta-hydroxyethyl, butyl, phenyl, optionally substituted with methyl, methoxy, ethoxy, chloro, acetylamino, ureido, carboxyRupine and sulfo, or is optionally substituted with sulfo , or an amino group of formula -NR 2 R 3 is a morpholino residue. 4. The process according to item 3 for the preparation of reactive dyes of the general formula III, wherein it is R2 is hydrogen, methyl or ethyl, R3 is a hydrogen atom or a phenyl group optionally substituted by a methyl, methoxy, chlorine and sulfo group, characterized in that the diazo component of the formula (XII), 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, is diazotized, coupled and condensed; 1,3-diaminobenzene-4-sulfonic acid or 1-amino-3-acetylaminobenzene-6-sulfonic acid from which the acetyl group is cleaved after saponification by saponification, the cyanurofluoride and the amino compound of the formula IX, wherein R2 and R3 have the aforementioned importance. 5. The method of item 4 for producing reactive dyes of formula IV, SCLH (XII) characterized in that the sulfanilic acid and 1-amino-3-acetylaminobenzene-6-sulfonic acid are diazotized and coupled to 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, the acetyl group is cleavage by saponification and the intermediate of formula XIII obtained is condensed with cyanurfluoride and the primary condensation product is condensed with m-chloroaniline.