CS205148B2 - Process for preparing reactive dyes - Google Patents

Abstract

The present invention relates to reactive dyes of the formula <IMAGE> in which R4 is C1-4-alkyl, C1-4-alkoxy, C1-4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula <IMAGE> in which A is a benzene or naphthalene radical which can contain further substituents, the benzene radical B can contain further substituents, R1 and R2 independently of one another are each a hydrogen atom or a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms and R3 is a hydrogen atom, a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, a substituted or unsubstituted benzyl, cyclohexyl or naphthyl radical, an unsubstituted phenyl radical or a substituted phenyl radical of the formula <IMAGE> is or are bonded to A and/or to the naphthalene nucleus, which carries one of the two complex-forming oxygen atoms.

Description

A benzene radical, optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 6 acylamino, amino -NH 2 C 1 -C 2 alkylamino, ureido, hydroxy, carboxy, atom halogen, sulfo, nitro, sulfamoyl, N-C 1 -C 4 alkylaminosulfonyl, C 1 -C 4 N-dialkylaminosulfonyl, phenyl or phenoxy, or a naphthalene radical, optionally substituted (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, (C 1 -C 6) acylamino, amino-NH 2, (C 1 -C 2) alkylamino, ureido, hydroxy, carboxy205148, halogen, sulfo, nitro,

(B) a benzene radical optionally substituted by a C1-C4 alkyl group, a C1-C4 alkoxy group and a halogen atom,

R1 and R2 are each independently hydrogen or C1-C4alkyl optionally substituted by chlorine, hydroxy, cyano, carboxy and sulfo,

R 5 is hydrogen or (C 1 -C 4) alkyl optionally substituted with chlorine, hydroxy, cyano, carboxy, sulfo and sulfate, (C 1 -C 4) alkoxyalkyl of up to about 4 carbon atoms in the alkoxy moiety , benzyl, optionally substituted sulfo and 'methyl, cyclohexyl, naphthyl', optionally substituted sulfo and hydroxy, unsubstituted phenyl or optionally substituted phenyl of formula

H

Kg where it means

R 4 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxyalkoxy, acetylamino, ureido, carboxy, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hyclroxyskupln,

R 5 is a hydrogen atom or a group represented by I <4 wherein, when several R 4 substituents are present, they have the same or different meanings, or

R 2 and R 2 together with the nitrogen atom form a morpholine, piperidine or piperazine ring and a radical or radicals of formula (II),

F (II) common suibstituents. Further substituents are, for example, C 1 -C 4 alkyl, such as methyl, ethyl, propyl, isopropyl and butyl, C 1 -C 4 alkoxy, such as methoxy, ethoxy, propyloxy, isopropyloxy and isopropyloxy. butoxy, C1 -C6 acylamino, such as acetylamino, propionylamino and benzoylamino, amino such as amino-NH2, methylamino and ethylamino, ureido, hydroxy and chloro, and carboxy, and a sulfonic acid group.

In particular, residue A contains, as further substituents, one or more sulfonic acid groups. The residue B contains further substituents as substituents, especially in the para position to the complexing oxygen atom.

When R 1 and R 2 are alkyl groups, these alkyl groups are optionally substituted; substituents include, for example, chlorine, hydroxy, cyano, carboxy and sulfo.

Examples of R 1 and R 2 are:

methyl, ethyl, propyl,.

isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, β-hydroxyethyl, β-chloroethyl, - -cyanethyl, Sk-scumethyl, χ-cyanopropyl, j-^-oxyoxyethyl, sulfomethyl and β-sulfoethyl.

As R-, for example:

a hydrogen atom, the same substituted or unsubstituted alkyl groups as mentioned for Rc and R2, a C1-C4 alkoxyalkyl group and a C1-C4 alkyl group such as methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl and methoxybutyl , cyclohexyl, beinzyl, 4-sulfobenzyl, 4-methylbenzyl, and in particular phenyl, optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, acetylamino, ureido, carboxy, halogen, sulfo, sulfomethyl The group A or the naphthalene ring have complexing oxygen atoms.

The groups A and B may have an ayl dye and a carbamoyl group for the azo dyes, provided that the conditions set forth in the general formula (I) are applicable, or it represents a naphthyl group optionally substituted by a sulfo group.

R 2 and R 5 may further form a six-membered N-heterocyclic ring which optionally contains an additional heteroatom such as an oxygen, nitrogen and sulfur atom.

Examples of the amino group of the general formula NNR 2 R 3 f in the general formula I are:

amino — NH2, methylamino, ethylamino, propylamino, isopropylamino and butylamino, n-methoxyethylamino, γ-methoxypropylamino, Ν, Ν-dimethylamino, N, N-diethylamino, N-methyl-N-N-ethyl-N-methyl-N -thenylamino, β-chloroethylamino, β-hydroxyethylamino, χ-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino and especially aromatic amino, such as phenylamino, up-phenylamino; , chloranilino, anisidine, phenethids, --sulimino, 4-sulfoanilino,

2.5- disuIfoi Ilin ^ i ^ ^ o ^ ^ r ^ Skupi N, sulfo ^ m ^ i ^ ^ l ^^ t ylanllinoskupina, N sullomethylanιillnoskupi _l,

3-kairbioxyphenylamino,

4-carboxyphenylamino;

2-S-kbrboxy sulfoPenylaminoskupma 2 - kbrhoxy -4-sulfonyl LF of one and up ammososk ^With 4-sulfonaftyl- [1 j - • amino,

3.6- disulfonaphths 1- (1) -amino,

3.6.8- Trisulfonaphthyl- (1) -amino group a

4.6.8- Trisulfonaphthyl- (1) -amino.

The reactive dyes of the formula I can have one or two groups of the formula II. When the reactive dyes of the formula I have only one group of the formula II, the group of the formula II is bonded to the group A or the naphthalene nucleus, wherein either the group A or the naphthalene nucleus has complexing oxygen atoms. If, however, "reactive dye of the formula I · two groups of the formula II is bonded one group of the formula II at ¹ A · radical and the other group of the formula II to the naphthalene nucleus.

Preferred are reactive dyes of the formula III,

where it means

X is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy. · 1 to 4 carbon atoms or halogen,

A, R1, R2, R3 have the meaning given by formula (I), and in particular reactive dyes of formula (III), where

A is a benzene group optionally substituted by a sulfo group, a methyl group, a methoxy group, a carboxy group, and a chlorine atom, or represents a naphthalene group optionally substituted by a sulfo group,

R 1 is a hydrogen atom, a methyl group or a (3-hydroxyethyl) group,

R2 is hydrogen, methyl or ethyl,

R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, β-hydroxyethyl, β-sulfoethyl, phenyl, optionally substituted with sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxy, chloro, bromo, , trifluoromethyl, sulfamoyl and carbamoyl, provided that the conditions set forth in formula (I) apply, or naphthylone is optionally substituted by a sulfonyl group and

X atom. hydrogen, methyl, ethyl, -methoxy, ethoxy or chloro.

Preference is given in particular to the dyes of the general formula IV,

О — Си, —O

I F where means

R1 is a hydrogen atom or a methyl group,

R2 is hydrogen, methyl or ethyl. group

R 3 is hydrogen, phenyl, optionally substituted with sulfo, methyl. ethyl, methoxy, ethoxy, acetylamino, carboxy, chloro, sulfamoyl. and a carbamoyl group, wherein the conditions of formula (I) are applicable, or is a naphthyl group optionally substituted with a sulfo group, and

X is hydrogen, methyl, ethyl, methoxy, ethoxy or chloro.

Valuable dyes of the formula IV are reactive dyes ^{1 of the} formula V.

S ° j ^w

The process for preparing the reactive dyes of the formula I '' is characterized in that the dye of the formula VI is condensed in any sequence.

20514В wherein the amino group (s) of the general formula (VII), -NH

AND

R1 (VII) is bonded or bonded to the group A and / or to the naphthalene nucleus, wherein the group A or the naphthalene nucleus has complexing oxygen atoms, or 2 moles of 2,4,6-trifluoromethyltriazine of formula VIII and 1, or 2 moles of the compound of formula IX,

HN — R3

AND

R2 (ix) wherein each symbol is as defined in Formula I.

A preferred embodiment is characterized in that dyes of the formula X are used as starting materials,

where

X is hydrogen, C 1 -C 4 alkyl or halogen;

A and R 1 are as defined for Formula I.

In particular, it is used as starting material in the general formula (X) where it is

A benzene radical optionally substituted by sulfo, methyl, methoxy, carboxy and chlorine, or a naphthalene radical optionally substituted by sulfo,

R1 is hydrogen, methyl or hydroxyethyl; and

X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and amino compounds of formula (IX) where

R2 is hydrogen, methyl or ethyl,

R @ 3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, .beta.-hydroxyethyl, .beta.-sulfoethyl, phenyl, substituted, optionally sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxy, chloro, sulfonyl, a trifluoromethyl group, a sulfamoyl group and a carbamyl group, the conditions of formula (I), or a naphthyl group optionally substituted with a sulfo group.

Preferred reactive dyes of formula (IV) are obtained when the dyes of formula (XI) are condensed in any sequence,

(XI)

2,4,6-trifluoro-sym-triazine of formula VIII and an amino compound of formula IX, wherein R 1, R 2, R 3 'and X in formulas XI and IX are as defined for formula IV.

Since the individual process steps mentioned above, namely multiple condensations, can be carried out in a different sequence and possibly also partially simultaneously, different variants of the process according to the invention are possible. For each partial reaction used the default. In general, the reactions are carried out in successive steps, the sequence of the individual reactions being simple between the reactants of the formulas VI, VIII and IX as desired.

The two most important variants of the process according to the invention are characterized in that they are condensed

1. a dye of formula (VI) with 1 or 2 moles of a 2,4,6-trifluoromethyl-triazine of formula (VIII) and the obtained monoprimary or diprimary condensation product is condensed with 1 or 2 moles of an amino compound of formula (IX);

2. 2,4,6-Trifluoro-sym-triazine of formula VIII with an amino compound of formula IX and 1 or 2 moles obtained. the primary condensation product is condensed with the colorant of formula VI.

A preferred process for preparing dyes of reactive formula V is characterized by condensing a dye of formula XII

(XII) with 2,4,6-trifluoro-sym-triazine and the obtained primary condensation product is condensed with ammonia.

Dyes of general use used as starting materials. of formula VI are obtained by coupling a diazotized aminobenzene or aminonaphthalene, which is optionally further substituted as described above, to form an ortho-alkoxyaminobenzene. or. to the ortho-hydroxyaminobenzene, which is also optionally further substituted as described above, such as o-anisidine, cresidine, 2,5-dimethoxyaniline, or to the 2-acetylaminophenol obtained by the monoazo compound, optionally after saponification of the diazotizing amino group, is diazotized and coupled with naphthosulfonic acid, optionally with amiinonaphtholsulfonic acid, and the resulting diazo dye is formed. it is reacted with a copper transfer agent, particularly a copper transfer agent dealkylation agent.

The diazotization of the diazo components is generally carried out by treatment with nitric acid in. aqueous medium acidified with mineral acid at low temperature, coupling to the coupling components is carried out in a slightly acidic, neutral to slightly alkaline medium.

Salts containing copper as a cation, for example, copper sulfate, can be used as the copper transfer agent. cuprous chloride or cuprous acetate. In many cases, it is preferable to use complex copper compounds, for example copper in the form of amine complexes such as copper tetramine sulfates from copper sulfate and ammonia, pyridine or monoethanolamine, or copper in the form of compounds containing copper complexed, e.g. aminocarboxylic acids or hydroxycarboxylic acids, such as glycol, lactic acid, and especially tartaric acid, such as sodium copper tartrate.

Processing of the submitting means of copper is carried out in an aqueous or aqueous organic medium, for example at room temperature in the case of easily · metalizovatelných starting compounds, or in the case where simultaneously with meta-tion desalkylaice be performed by heating at 50 to 120 ^Q C in open containers, for example using a reflux condenser or, optionally, in a closed container under pressure at pH values given by the type of metallization process chosen; for example, acidic copper copper sulfate, alkaline copper copper tetramine sulfate.

Optionally, solvents such as, for example, can be added during metallization. alcohol or dimethylformamide.

The following compounds can be used, for example, as coloring compounds of the formula VI:

and)

Aminobenzenes and aminonaphthalenes (residue A)

Aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-chloroaniline, m-chloroaniline, p-chloroaniline,

2.5-diichlor aniline, α-naphthylamine, Jnaltylamine,

2.5- dimethylarnlin,

Iso-1,4-aminodiphenyl, nniline-2-carboxylic acid, nnilm-3-carboxylic acid aniline-4-carboxylic acid, 5-nitro-α-aminoanane, and mminod if enelet he г,

2-amino-benzenesulfonamide, 3-aminobenzenesulfonamide, 4-amincibenzene sulfonamide,

2-Nminobenzenesulfoimonomethylamide

3-nmie · obeezeesulfomoinomethylmid, α-amino-benzenesulfon-o-methyl,

2- nmlnobenzenesulfoethylnmid,

3-Aminobenzyl-1,3-dimethyl-ethylamide,

4-aminobenzenesulfoethylamide,

2- nminobenzenfullondimethyl] nmid,

3-amnobenzene nondondimethylamide,

4-Methylbenzenesulfoedimethylnamide, 2-aminobenzenulphenimide, amide,

3-aminobenzenesulfonamide ^, 4-aminobenzenesulfonamide ^, neilin-2-sulfonic acid, aniline-3-sulfonic acid and nniline-4-sulfonic acid, aniline-2,5-disulfonic acid,

2,4-dimethylnniline-6-sulfonic acid, 4'-Chloro-5-methylenediene-2-sulfonic acid, neiln-2,4-dinulfonic acid, neilm-3,5-dilsulfonic acid, amine-4-sulfonybenzoic acid or

2-Amino-5-suifobenzoic acid

2-metethafailώИniЗ, ninlsulfonic acid,

2-thiophenoic acid, 2-thiophenol-2-yl-2-thiophenol;

2-Methoxyoxyaniline-3,5-disulfonic acid,

2-chloroilie-4-sulfolinic acid,

2,3- · Dimethylneilin-4,6-ninulfonic acid

2,5-Nimethyl-4,6-disulfonic acid

5-chloro-4-methylneiline-2-suifonic acid,

3-acetylamin: 1-amino-6-sulfonic acid, 4-acetylaminoannin-2-sulfonic acid,

4-Chloro-n-n-2-sulfonic acid,

3,4-Dichloroanine-6-sulfonic acid,

4-Methyl-amino-2-SL-11fonic acid, 5-methylneilie-6-nuifonic acid,

2,4-non-methoxyphenyl-6-sulfonic acid,

4-Methoxyaniline-2-sulphonic acid,

5- methyl ^and thoxyanШn-2-sulfonic acid,

2.5-Nichloginine-4-suifonic acid

2,4-dimethylaninin-5-sulfoic acid,

2- · methoxyanilium-5-sulfoic acid,

2-methylianiline-4-sulfonic acid, 4-methyl-2-sulfonic acid, 4-ethoxyalmine-2-sulfonic acid, 4-ethyleniline-2-sulfonic acid, 4-methyl-amino-phiamine, 4-ethoxyan-e-3 -sulfoeic acid,

3,4-dichloroaniline, o-nitroaniline, m-mttoamlin, p-niteonniiin, m-aminoacetan ilide, p-aminoacetanilide,

4-amino-2-acelylnminotoluene-5-sulfonic acid,

4-Methoxyaniline-3-sulfonic acid, 1-Aminoenaphthene-2-sulfoic acid, 1-aminionaphthalene-4-sulfonic acid, aminonaphthalene-S-sulfonic acid,

1- nmøenenftaten-6sulfoeová,

-aminonaphthalene-7-sulphonic acid and 1-aminonaphthalene-8-sulphonic acid, 2-aminonaphthalene-1-sulphonic acid, 2-aminonaphthalene-5-sulphonic acid or 2-aminonaphthalene-8-sulphonic acid; di suttoic acid, 1-amino-naphthalene-5,7-nisgylphonic acid,

2- ηω; ίη onaHa ten-1,5 ^ isulfonová, * 2-amlnonaftatee-1,7-dinuff · onová,

2-anenonaphthalene-3,6-diisulfonic acid, 2H-mononaltalene-5,7-d isulfonic acid, 2-aminonaphthalene-4,8-di; sulfonic acid, or 2-aminonaphthalene-6-, 8-disuldoic acid,

1-amlnonaphthalene-2,5,7-risisulfonic acid,

2-aminonaphthalene-1,5,7-tetraisulfonic acid, 2-aminonaphthalene-3,6,8-risulfonic acid or 2-aminonaphthalene-4,6,8-trisulfonic acid, 1-amino-2-hydroxy-6-mitronaphthalene-4-Sulfuronic acid,

2-Amino-1-hydroxy-naphthalenyl-4,8-ninulfonic acid, 1-nmino-3-acetylaminobenzene (saponified), 1-amtooameothytemobenzene-O-sulfonyl or 1-amino-3-acetylamphenobenzene 6-sulfonic acid (saponified), 1-aminOr4-acetylaminobenzene-2-sulfonic acid (saponified),

1- (4-Chloro-3- (N-acetyl-N-methylamino) benzene (saponified),

3-eitгoanilie (reduced),

4-methoxyphenyl (reduced), Z-methoxy-4-nitroamlin (reduced),

2-methoxy-r-nitrooanilium (reduced), 2-O-O-O-1-3- (110-5-) 0111113 ^ 111 (reduced), and

2-methΌxy-rmitge · -5-rhl · oгanilm ..

b) o-Aoxyxybenzene or o-hydroxyaminobenzene (residue B) 1-Amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethoxybenzene,

-amino-2-methyloxybenzene, 1-nmmo-2-methoxy-5-chloro benzene, 1-111111102 (161110X1-5-611111) 61 ^ 61,

1-amino-2,5-diethoxybeezee, 1-arao-2-ethoxybeenene a

2- N-ethylaminophenol (saponified)

C)

Naphtholsulfonic acids or aminonaphtholsulfonic acids

2-Amino-8-hexanoic acid-6-sulfoic acid,

2-Amino-6-hydroxynaphthalene-8-sulfonic acid,

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

2-Amino-5-hydroxy-phthalene-1,7-disulfonic acid,

2-Amino-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid,

2- (4'-am.inof phenylamino) -5-hydroxynaphthalen-3 ', ^7-D: sulfoinová acid,

2-amino-8-hydroxy-naphthalene-3,6-disulfonic acid,

1-Amino-benzoylamino-8-hydroxynaphthalem-3,6-disulfonic acid,

2-amino-5-hydroxynaphthalene-4,8-disulfonic acid, amino-8-hydroxynaphthalene-3,6-disulfonic acid,

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

2-N-phanylamino-5-hydroxynaphthalene-7-sulfonic acid,

2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid,

2-N-acetyl-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid,

2-N- (2‘-hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid,

2-N-methylamino-8-hydroxynaphthalene-6-sulfonic acid,

3-Amino-2-hydroxynaphthalene-7-sulfonic acid, 1-hydroxynaphthalene-3,6-disulfonic acid, 1-hydroxynaphthalene-4,8-diisulfonic acid, 1-hydroxynaphthalene-3,8-disulfonic acid, 1-hydroxynaphthalene-3,6,8-trisulfonic acid and 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-5-sulfonic acid and 1-hydroxynaphthalene-8-sulfonic acid.

The process for the preparation of the dyes of the general formula (VI) is not always described in the following examples, but it is clear from the above.

Other starting materials which can be used for the preparation of reactive dyes of the formula I include 2,4,6-trifluoromethyl-triazine of the formula VIII (cyanurofluoride) as well as, for example, the following amino compounds of the formula IX:

ammonia, methylamine, dimethylamine, ethylamine, d'ethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.butylamine, tert-butylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chlorethylamine, hydroxyethylamine, aminoethanoic acid, dihydroocylamine, dihydroocylamine, / Z-sulfatoisthylamine, benzylamine, cyclohexylamine, aniline, m-toluidine, p-toluidine,

2.3- dimethylainiliin,

2.4- dimethylaniline,

2.5- dimiethylaniHn,

2,6-dimethylanil.n

3,4-dimethylaniline a

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

3-acetylamtnoaniline,

4-acetylaminoaniline, m-nitroaniline, p-nitroaniline, m-aminophenol, p-aminophenol-2-methyl-4-nitroaniline,

2-Methyl-5-nitroaniline

2.5-dlmethoxyaniline,

3-Methyl-4-nitroaniline

2-nitro-4-methylaniline,

3-nitro-4-methylaniline,

3-amtoo-4-methylaniline,

4-aminio-3-methylaniline, 2-amino-4-methylaniline, m-anisoline, p-anisidine, m-phenetidine, p-phenetidine, 2-methoxy-5-methylaniline,

2-ethoxy-5-methoxyaniline,

4-broananilijn,

3-aminobenzamide,

4-aminophenylsulfamide,

3-Trifluoromethylanine,

3-aminophenyl urea

4-aminophenyl urine,

1- diesel laminate,

2-naphtha laminate,

2-aminol-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-8-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene,

1-Amino-7-hydroxynaphthalene, methanilic acid, sulfanilic acid, aniline,

2,4-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, m-amlnobenzoic acid, p-aminobenzoic acid,

4-aminophenylmethanesulfonic acid, aniline-N-methanesulfonic acid,

2-amtootoluene-4-sulfonic acid, 2-a: minotoluene, n-5-sulfonic acid, p-amiinosallcylic acid, 1-amino-4-carboxybenzene-3-sulfonic acid, 1-amino-2-carboxybenzene-5- sulfonic acid, 1-amino-5-carboxybenzene-2-sulfonic acid, 1-naphthylamine-2-sulfonic acid, 1-naphthylamine-3-sulfonic acid, 1-naphthylamine-4-sulfonic acid, 1-naphthylanine- 5-sulfoic acid, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid,

1-naphthylamine-8-sulfonic acid,

2-naphthylamine-1-sulfonic acid, 2-naphthylamine-3-sulfonic acid, 2-naphthylamine-4-sulfonic acid, 2-naphthylamine-5-sulfonic acid, 2-naphthylamine-6-sulfonic acid,

2-naphthylamine-7-sulfonic acid, 2-naphthylamine-8-sulfonic acid, 1-naphthylamine-2,4-disuccinic acid, 1m-aftylamino-2,5-disulfonic acid, 1-naphthylanine ^ 1'-disulfonic acid, 1'-naphthylamine-2,8-disulfonic acid, 1'-R '', 4'-aylamino-3,5'- (1''''''-phthalic acid), 1'''-r'y ' ltyla ^ mnn4365 ^ dlrs ^ Ulfoinic acid, naphthylamine * n-3,7-disulfonic acid,

Naftylam 1-yn-3,8-disulfonic acid, lmattylamin-4,6-disulfonic acid, linaftylam2n 4,7ndislιlf ^ι-sulfonic acid, l ^ · ^ ^^ r ^ ftvk mJ.r ^ -4,8- ' di-sulfonic acid, 1-raftylamin-5,8-disulfonic acid,

2-naphthylamine-2,5-disulfonic acid,

1-naphthylamino-2-naphthylamine-2-naphthylamine-4-disulfonic acid, ornaphthyl-5-dimin-3, 6-naphthylamino-4-disulfonic acid,

2-naphthylamine-4,7-disulfonic acid,. .

2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-5,7-disulfonic acid, 2-naphthylainine-6,8-disulfonic acid, 1-naphthylamine-6,8-disulfonic acid imine-2,4,6-trifluorophthalic acid, 1-methyl-2,4,6-trifluoroacetic acid; -naphthyl-2,5,7-trifluorulfonic acid, l'naphthyl-l-phthalin-3,5,2-thiophenesulfonic acid,

1-naphthylamine-4-S-trisulfonic acid, 1-naphthylamine-4,6,8-toluenesulfonic acid, 2-naphthylamine-1,3,7-trliulfonic acid,

2- naftýlamintl, 5,7ttrSulfonová acid, 2-naphthyl] ^ and ^ ^í ml nt3,5, '^' ^ l 1tгisul ^ ^ o ^ ιnová acid, 2-naftylam ^{N-3,6,7-triisulfonová} acid, 2 - raftylam ^of N-4,6,8-trliulf sulfonic acid moofolin, a piperazine and piperidine ·.

The condensation of the 2,4-trifluorotriymtriazine of formula (VIII) with the dye of formula (VI) and the amino compounds of formula (IX) is preferably carried out in aqueous solution or suspension, at low temperature and at a slightly acidic, neutral to slightly alkaline pH And so that at least one fluorine atom remains as a leaving group in the finished reactive dye of formula (I). Preferably, the condensation released by hydrogen condensation is continuously neutralized by the addition of an aqueous solution of alkali hydroxide, carbonate and bicarbonate.

The copper complex dyes of the general formula I are reactive with the fiber, since in the symtriazine residue or in both symtriazine residues it always contains one leaving fluorine atom.

Fiber-reactive compounds are those which are capable of reacting with the hydroxyl groups of cellulose with the amino-upins of natural or synthetic polyamides to form a covalent chemical bond.

The reactive dyes of formula (I) may be isolated and processed to form useful dry dye preparations. Isolation is preferably carried out at low temperatures by salting out and filtration. The filtered dyes may be dried, if desired, after addition of buffing agents and / or buffers, for example by addition of a mixture of the same moiety of bisphosphate and disodium phosphate; preferably, the drying is carried out at not too high temperatures and under reduced pressure. In certain instances, dry formulations can be prepared by spray-drying the composition as a whole directly according to the invention, i.e. the dye need not be isolated as such.

The reactive dyes of the formula (I) produced by the process according to 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 draw properties and have a high · fixation · dye, with unfixed fractions readily removed.

Reactive dyes of general formula I are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, polyamide fibers, polyamide urethanes, but particularly suitable for fibrous webs containing cellulose such as flax, pulp, regenerated cellulose and, in particular, cotton. They are suitable for both pull-out dyeing and foul-dyeing, whereby the textile material is impregnated with an aqueous and optionally salt-containing dye solution and the dye is alkaline or in the presence of an alkali, optionally under the action of heat.

The reactive dyes of the formula I are also suitable for printing, in particular cotton, but also for printing nitrogen-containing fibers, such as wool, silk or wool-containing mixed fabrics.

It is recommended to thoroughly rinse the dyeings and prints with cold and hot water, optionally with the addition of dispersing agents and diffusing non-fixed proportions.

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

Example 1 Dye Parts of Formula

N = N

SO, H

se '. Dissolve in 70 parts water at pH. 7. and the solution is cooled to a temperature by adding 40 parts of ice. 0 ° C. While stirring well, 2 parts of 2,4,6-trifluoromethyltriazine are added dropwise while maintaining the pH at 6.5 by the simultaneous addition of sodium carbonate solution.

Then 3 volumes of concentrated aqueous ammonia solution were added and stirred. is kept for two hours at 5. to 10 ° C. Reactive dye formed. with pouring. sodium chloride precipitated and filtered. The dye paste is mixed with disodium phosphate solution and dried.

The dye obtained dyes cotton from a long bath. for intense navy blue shades.

If the site. ammonia using the amines listed in the following table to give navy blue dyes of similar properties.

Example. Amin. N-ffléttfrjýlamln

3 'N-methylanine lin. 3,5-dimethylamine. 4-methoxyaniline

3-Aminobenzenesulfonic acid

4-a: Minobenzoic acid

4-methylaniline ^and n-ili

3-methylaniline

4-Aminobenzenesulfonic acid

2-amino-4-n-methylmethylbenzene

3-Trifluoromethylamine

4-Aminobenzylsulfonic acid butylamine

2-Aminoethane sulfonic acid

2-aminoethanol aniline

3-aminoaaetanilid

4-Aminophenyl urea

2-aminonitrile.

The 2-amino-naphthalene-4,8-disultonic acid is diazotized in a conventional manner and coupled in a weakly acidic solution with 13.7 parts of 3-amino-4-methoxytoluene. The resulting aminoazo dye is precipitated by the addition of sodium chloride, filtered off and redissolved in. water. Diazotized by the addition of hydrochloric acid and. sodium nitrite and coupled at pH 8 to 8. 8,5 s. 29.5 parts of N-acetyl-N-methyl-2-amino-5-hydroxynaphthalene-7-sultonic acid. 100 parts by volume of concentrated aqueous ammonia solution and 140 parts by volume are now added to the resulting violet solution. 1N copper sulfate solution and stirred at 95 ° C for 12 hours. The copper complex is precipitated from the deep blue solution by addition of sodium chloride and filtered off with suction. To saponify the acetyl group, the dye is heated at 85 ° C in 1 N sodium hydroxide solution for two hours, then acidified to pH 3 with hydrochloric acid after cooling to 25 ° C and aspirated.

35.5 parts of copper complex dye are dissolved in 250 parts of water under neutral reaction and cooled to 0ac. 150 parts of ice are added and 7.1 parts of 2,4,6-hex-1,3,5-triazine are added dropwise to the solution at a pH of 6-7. After completion of the condensation, a solution of 5.4 parts of 4-aminotoluene in acetone was added. and condenses at temperature. 5-10 ° C and at pH 7.5. Evaporation of the reaction mixture to dryness gives a dye in the form of a blue-black powder. It dyes cotton to permanent navy blue shades.

In a similar way, the ingredients

A = starting component B = intermediate C - final component by double coupling. and demethylating the introduction of copper to obtain an aminodisazothiol dye which is condensed with cyanurfluoride and the other. The triad with the new substituent 'T provides additional stable dyes.

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205148 21 22nd Example 50

parts of the copper complex. disazo dyes formulas

as the trisodium salt was dissolved in 100 parts of water and cooled to 0 ° C by the addition of ice. 1.4 parts of disodium hydrogen phosphate are added and 2.75 parts of 2,4,6-trifluoro-1,3 is added dropwise with good stirring.

5-triazine, while maintaining the pH of the reaction mixture at 6.5 with simultaneous addition of sodium hydroxide solution. After completion of the reaction, which is monitored by thin-layer chromatography, 2.2 parts of 3-aminotoluene are added and allowed to warm to 20 ° C, again releasing the hydrogen fluoride released continuously by condensation. Concentration of the obtained dye solution in vacuo gives a dark dye powder. The dye dyees cellulose fiber fabrics to permanent blue shades.

Example 51 parts of a copper-disazo dye complex of the formula

SO _K H o

Dissolve in 100 parts of water at pH 7. A solution of 3.3 is added. of 2- (4'-methylphenylamino) -4,6-difluoro-1,3,5-triazine in 15 parts of acetone and the mixture is stirred for 8 hours at 15 [deg.] C. while the solution of 1N hydroxide solution is added dropwise. NaCl maintains a pH of 6.5-7. After a given reaction time, no starting material is chromatographically detectable. The colorant is precipitated by pouring sodium chloride into the solution, - filtered - and dried. It is identical to the product obtained in the manner described in Example 8.

Example 52

To a solution of 34.6 parts of the disodium salt of the dye of the formula

cw ₃

After completion of the reaction, 19 parts of 3-aminobenzenesulfonic acid are added and stirred for three hours at pH 7.5 at 25 ° C. The resulting dye of the formula in 600 parts of water was added dropwise at -0 ° C with good stirring of 14 parts

Of 3,5-thiazine, maintaining the dropwise addition of the sodium tri-nicotartartonate solution - hr205148

dyes cotton to a permanent deep blue shade.

Dye prescription Dissolve 1 part of the dye obtained in the manner described in Example 1 with 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonic acid. The obtained solution is impregnated with a cotton fabric so that its weight increases by 75% and then dried.

Then the fabric is impregnated with a solution at 20 ^Q C, which contains per liter 5 g of sodium hydroxide and 300 g of sodium chloride odmáčkine the weight increase of 75%, dyeing is steamed for 30 seconds at 100 to 101 DEG C., rinsed , soap for 15 minutes in a boiling -0.3% nonionic detergent solution, rinse and dry.

Dye regulation II

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

The solution is added to 1900 parts cold water, 60 parts sodium chloride is added and 100 parts of cotton fabric are added to this dye bath. ¹

The temperature was raised to 40 ° C, after which 4 parts by volume of 30% sodium hydroxide solution, 10 parts of soda ash and 60 parts of sodium chloride were added after 30 minutes. The temperature is maintained at 40 ° C for 30 minutes, rinsed and soaped for 15 minutes in 0.3 l of boiling nonionic detergent solution, rinsed and dried.

OBJECT OF THE INVENTION

Claims (2)

OBJECT OF THE INVENTION 1 or 2 moles of the amino compound of formula IX, HN — R3 Wherein each symbol has the meaning given in general formula I. 2. Process according to claim 1, characterized in that the dyes of the general formula (X) are used as starting materials, wherein X is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or halogen, and A and R 1 are as defined in 1. 3. Process according to claim 2, characterized in that the dyes of the general formula (X) are used as starting materials A benzene radical, optionally substituted with sulfo, methyl, methoxy, carboxy, chlorine, or a naphthalene radical, optionally substituted with sulfo, R 1 is a hydrogen atom, a methyl group or a θ-hydroxyethyl group, X is hydrogen, methyl, ethyl, methoxy, ethoxy or chloro, an amino compound of formula (IX) wherein R2 is hydrogen, methyl or ethyl, R 5 is hydrogen, methyl, ethyl, butyl, methoxypropyl, β-hydroxyethyl, β-sulfoethyl, phenyl, optionally substituted with sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxy, chloro, bromo, trifluoromethyl, sulfamoyl and carbamoyl, the conditions set forth in point 1, or naphthyl optionally substituted with sulfo. 4. The process of item 2 for preparing a reactive dye of formula IV, ^F (IV), wherein the conditions set forth in item 1, or a naphthyl group optionally substituted with a sulfo group, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chloro. characterized in that a dye of the general formula (XI), where denotes, is condensed in any sequence R1 is a hydrogen atom or a methyl group, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, phenyl, optionally substituted with sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxy, chloro, sulfamoyl and carbamoyl, 5. The process of item 4 for preparing a reactive dye of formula V, 1 or 2 moles of 2,4,6-trifluoro-sym-triazine of formula VIII —NH 1 F-C ^ C-F Rl I, !! (VII) is bonded or bonded to the group A and / or to the naphthalene ring, the group A or the naphthalene ring having complexing oxygen atoms, jr (Vlil) CLAIMS 1. A process for the preparation of reactive dyes of the general formula I, wherein h is A benzene radical, optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 6 acylamino, amino -NH 2, C 1 -C 2 alkylamino, ureido, hydroxy, carboxy, atom halogen, sulfo, nitro, sulfamoyl nominal aware of both N - and 1 к у 1 mi 1 -sulfonyl nose of ^L 1 is hydrocarbyl of 1 to 4 carbon atoms in the proportion alkyllovém, NN-di-alkylaminosulfonyl group having 4 carbon l.až or a naphthalene radical optionally substituted by a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C6 acylamino group, an -NH2-amino group, a C1-C6 alkylamino group up to 2 carbon atoms, ureido, hydroxy, nitro, carboxy, halogen, sulfo, A benzene radical optionally substituted by a C1-C4 alkyl group, a C1-C4 alkoxy group and a halogen atom, R 1 and R 2 are each independently hydrogen or C 1 -C 4 alkyl optionally substituted by chlorine, hydroxy, cyano, carboxy and sulfo, R5 is hydrogen or C1-C4alkyl optionally substituted by chlorine, hydroxy, cyano, carboxy, sulfo and sulphate, C1-C4alkoxyalkyl and C1-C4alkoxy, benzyl , optionally substituted sulfo and methyl, cyclohexyl, naphthyl, optionally substituted sulfo and hydroxy, unsubstituted phenyl or optionally substituted phenyl of the formula wherein Rd C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxyalkoxy, acetylamino, ureido, carboxy, halogen, sulfo, sulfOmethyl, trifluoromethyl, sulfamoyl, carbamoyl a nitro group or a hydroxyl group, R @ 5 is hydrogen or R @ 4, where, when several R @ d is present, they have the same or different meanings, or R @ 2 and R @ 3 together with the nitrogen atom form a morpholine, piperidine or piperazine ring and a radical or radicals of formula II; Rf c '' I are bonded to the group A and / or to the naphthalene ring, wherein the group A or the naphthalene ring have complexing oxygen atoms, characterized in that the dye of the general formula VI, in which the amino group or amino groups of the formula VII 2,4,6-trifluoro-sy-triazine of formula VIII and an amino compound of formula IX wherein R 1, R2 and R3 are as defined above.