DE3939700A1 - New bis:amino-tri:phenyl dioxazinyl-amino S-triazine dyestuff cpds. - Google Patents

Abstract

New 2,4-bis (10-amino-tripheno dioxazin-3-yl-amino) -s-triazine dyestuffs are of formula 8I): R = H or (substd.) 1-4C alkyl; R' and X = H or a substit.; T1 and T2 = H, Cl, Br, (substd.) 1-4C alkyl, 1-4C alkoxy, phenyl or phenoxy; and n = 0 or 1. (I) are prepd. (claimed) by reacting 1 mole 3,10-diamino-triphenodioxazine dyestuff (II) with 1 mole halo-triazone (III) to a monoacylation prod. (IV) and condensing this with 1 mole (II): Hal = Cl, Br or F.

Description

The present invention relates to triphendioxazine dye substances of the formula

and their use for dyeing and printing cellulosic materials and leather.

In (1) means
R = hydrogen or optionally substituted C₁-C₄ alkyl
R ′ = hydrogen or substituent
T₁, T₂ = hydrogen, chlorine, bromine, optionally sub-substituted C₁-C₄ alkyl, C₁-C₄ alkoxy, phenyl or phenoxy
X = hydrogen or substituent
n = 0 or 1.

If n = 1, the sulfo group is in the o position Substituents

Examples of R are: CH₃, C₂H₅, n-C₃H₇, i-C₃-H₇, n-C₄H₉, n-C₆H₁₃, for example by OH, OCH₃, OC₂H₅, COOH, SO₃H, OSO₃H, CN, Cl can be substituted can.

Substituents of the optionally substituted C₁-C₄- Alkyl and C₁-C₄ alkoxy radicals T₁ and T₂ are examples as C₁-C₄ alkoxy or OSO₃H.

Substituents of the optionally substituted phenyl and phenoxy radicals T₁ and T₂ are, for example, Cl, Br, C₁-C₄ alkyl, C₁-C₄ alkoxy and SO₃H.

Suitable substituents R 'are, for example, the following: Halogen such as Cl, C₁-C₄-alkyl, C₁-C₄-alkoxy, COOH.

Examples of substituents X are: halogen atoms such as fluorine, chlorine or bromine; the sulfonic acid group, lower alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, a thioether group, for example one of the general formula -S-R₁ or an ether group, for example one of the general Formula -O-R₂, in which
R₁ is a substituent from the group alkyl or substituted alkyl, such as substituted by substituents from the group hydroxy, lower alkoxy, sulfato, sulfo, carboxy and phenyl, lower alkyl or phenyl or substituted phenyl, such as by substituent from the group nitro, Sulfo and carboxy substituted phenyl, means and
R₂ is a hydrogen atom or has the abovementioned meaning of R₁, an optionally substituted amino group, for example one of the general formula -NR₃Kr₄, in which
R₃ is a hydrogen atom, an aliphatic radical, an araliphatic radical or a cycloaliphatic radical, such as a lower alkyl radical which can be substituted by one or two substituents from the group consisting of hydroxyl, sulfato, lower alkoxy, sulfo, carboxy and phenyl or a Cyclohexylrest and
R₄ represents a hydrogen atom, an aliphatic radical, for example a lower alkyl radical, which can be substituted by hydroxyl, lower alkoxy, sulfato, sulfo and carboxy or an optionally substituted aromatic radical, such as for a phenyl or naphthyl radical, by a or two substituents from the group consisting of hydroxyl, carboxy, sulfo, lower alkyl and lower alkoxy may be substituted or for an optionally substituted araliphatic radical, such as, for example, a lower alkyl radical which is substituted by phenyl or naphthyl or for a hydroxy or a lower alkoxy group or for an optionally substituted amino group, such as the amino group or a phenylamino or lower alkylamino group, or in which
R₃ and R₄ together with the nitrogen atom are a heterocyclic ring with an alkylene radical of 2 to 8, preferably 5 to 7, C atoms or one, two or three lower alkylene radicals and 1 or 2 heteroatoms, such as a nitrogen or oxygen atom, form containing heterocyclic ring, such as the morpholine, piperidine or piperazine ring.

The above formula radical R₁, but not the formula radical R₂, can also mean the benzthiazolyl (2) radical.

Aliphatic residues are very general, for example optionally substituted alkyl radicals with 1 to 10 carbon atoms, optionally by heteroatoms or hetero atomic groups can be interrupted, for example by O, N, S, CONH, SO₂NH, SO₂.

Lower alkyl or alkoxy radicals are those with 1 to 4 carbon atoms.

Preferred dyes in the context of the formula (1) speak the formula  

wherein T₁, T₂ and X have the meaning given. Furthermore, dyes of the formulas (1) or (2) preferred, in which T₁, T₂ = Cl or OCH₃.

X preferably represents a chlorine atom or a sulfo group or a radical of the formula -S-R₁ or -O-R₂, in which R₁ preferably a phenyl radical, which is chlorine or nitro may be substituted, or a lower one Alkyl radical which is substituted by hydroxy or carboxy can be means and R₂ is preferably a hydrogen atom or is a lower alkyl radical or a phenyl radical which can be substituted by sulfo or carboxy. The Formula radical X furthermore preferably denotes an amino group of the formula -NR₃R₄, in which R₃ is preferably a Means hydrogen atom or a lower alkyl group, which are substituted by a carboxy or sulfo group can be and in which R₄ is preferably a hydrogen atom or a lower alkyl group means by a hydroxy, sulfato, carboxy, sulfo, lower alk oxy group, a phenyl radical or a cyclohexyl radical can be substituted.

Also preferred are amine residues -NR₃R₄, in which R₃ and R₄ optionally including another Heteroatoms form a ring.  

Examples of preferred radicals X are:

The invention further relates to a method for Preparation of the dyes of the formula (1). It is characterized in that 1 mol of a triphendi oxazine dye of the formula  

wherein T₁, T₂, R, R 'and n have the meaning given have, with 1 mole of a halotriazine of the formula

where Hal is chlorine, bromine or fluorine and X is has given meaning to a monoacylation product of the formula

and then implement this with another mole of one Triphendioxazine dye of formula (3) to one Dye of the formula (1) condensed.

The condensation of the dyes (3) with the halogen triazines (4) is preferably carried out in aqueous or aqueous organic medium and depending on the  Halogen triazine reactivity at temperatures of 0 ° C to 40 ° C, where appropriate, the condensation liberated hydrohalic acid by adding acid-binding agents is intercepted.

The further condensation of the monoacylation products (5) with a dye (3) is also in aqueous or aqueous-organic medium at temperatures of 20 ° C up to 100 ° C, the condensation Released hydrogen halide by adding acid binding funds is neutralized. Acid binding Agents are in particular the alkali or alkaline earths hydrogen carbonates, carbonates, hydroxides, phosphates or borates.

If X in the halotriazines of the formula (4) for Halogen is present in a further condensation reaction in dyes of formula (1) X (= Hal) against Ether, thioether or amine residues of the formula -OR₂, -SR₁ or -NR₃R₄ are exchanged.

This condensation is also in aqueous or aqueous-organic medium at temperatures from 60 ° C to 100 ° C, the condensation free Expectant hydrogen halide by adding acidic bin funds is neutralized. Acid-binding agents are in addition to the above-mentioned alkali or alkaline earth metal Bindings also amines of the formula NHR₃R₄ (6), which in about shot are used. There are also tertiary ones Amines such as triethylamine or pyridine bases such as pyridine, Picoline or quinoline can be used.  

A preferred method of manufacture is that to dye (3) with cyanuric chloride to dye (4) condensed with X = Cl and then X = Cl against residues OR₂, SR₁ or NR₃R₄ exchanged.

For the condensation reactions, the triphendioxa tin dyes (3) preferably in the form of their neutral Alkali salts, especially their lithium salts.

Dyes of the formula (3) are from the literature knows. For example, their manufacture is in the European Patent 1 70 838 described.

Examples of halotriazines (4) are:

2,4,6-trichlorotriazine (cyanuric chloride),
2,6,6-trifluorotriazine,
2,4,6-tribromotriazine,
2-methyl-4,6-dichlorotriazine,
2-β-methoxyethoxy-4,6-dichlorotriazine,
2-methoxy-4,6-dichlorotriazine.

Cyanuric chloride has a preferred meaning. Connection gene of the formula HOR₂ (7), HSR₁ (8) and HNR₃R₄ (6) for example the following

Alcohols HOR₂:
Methanol, ethanol, isopropanol, β-methoxyethanol, β-ethoxyethanol, glycolic acid;

Phenols HOR₂:
Phenol, 4-nitrophenol, 4-sulfophenol, 4-carboxyphenol, p-cresol, salicylic acid;

Alkyl mercaptans HSR₁:
Mercaptoethanol, mercaptoacetic acid, β-mercaptopropionic acid, 1-mercapto-2-hydroxypropane, 1-hydroxy-2-mercapto propane;

aryl- and heterocyclic mercaptans HSR₁:
Thiophenol, 4-nitrothiophenol, 4-sulfothiophenol, 4-carboxythiophenol, 2-mercaptobenzthiazole, 2-mercapto benzothiazole-x-sulfonic acid;

aliphatic amines HNR₃R₄:
Ammonia, methylamine, ethylamine, diethylamine, isopropylamine, taurine, methyltaurine, aminolsulfate, N-methyl-β-sulfatoethylamine, ethanolamine, bis- (β-hydroxyethyl) amine, β-methoxyethylamine, bis- (β-methoxyethyl) amine , Aminoacetic acid, sarcosine, β-aminopropionic acid, amino succinic acid, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine;

aromatic amines HNR₃R₄:
Aniline, p-toluidine, 4-methoxy-aniline, 4-ethoxyaniline, N-ethylaniline, m-sulfanilic acid, 4-aminophenyl-ω-methane sulfonic acid, p-sulfanilic acid, 4-aminobenzoic acid;

cycloaliphatic amines HNR₃R₄:
Cyclohexylamine, cyclopentylamine;

araliphatic amines HNR₃R₄:
Benzylamine, N-methylbenzylamine, N-methylbenzylamine-x-sulfonic acid;

ring-closed amines HNR₃R₄:
Morpholine, piperidine, pyrrolidine, N-methylpiperazine.

The dyes are e.g. B. isolated after adding salt and dried. But it can also be the condensation solutions or suspensions via a roller or Spray dryer can be performed.

The moist pastes of the dyes can just as well concentrated, aqueous solutions are prepared, e.g. B. by making suspensions or solutions of these dyes in water of desalination, e.g. B. by pressure permeation submits.

The dyes dye cellulosic materials, especially paper, cotton and viscose as well as leather in blue tones with good wet and light fastness.

The dyes can after all in the paper and Textile industry used for substantive dyes Lichen procedures are used, especially in the Bulk as in the surface coloring of paper for glued or unsized varieties, starting from bleached different or unbleached pulp Provenance such as softwood or hardwood sulfite and / or -sulfate pulp. You can also in the yarn and  Garment dyeing of cotton, viscose and linen after the Extraction process from a long fleet or in continuous driving can be applied.

The obtained with the dyes of the invention Paper dyeings are characterized by good light and wet authenticity (fastness to bleeding). Also on the brilliance and clarity of the color tones must be emphasized. Furthermore is the combination behavior with suitable dyes very well.

The temperature data in the examples are ° C. The formulas of water-soluble dyes in the description and in the examples are those of free acids. The colors are isolated and applied substances in general in the form of their alkali salts, esp special of the lithium, sodium or potassium salts.

Get the color codes given in the examples refer to the Color Index Hue Indication Chart (Indicator Numbers).

The formulas given in the following examples each relate to one of the implementation resulting isomeric reaction products, with respect to of the substituents in the two outer aromatic Rings of the triphendioxazine system of the isomeric reak tion products referred to what has been said under formula (1) becomes.  

example 1

0.1 mole of 2,9-diamino-6,13-dichloro-triphendioxazinedi sulfonic acid (obtained according to example 1 of the European Patent 1 70 838) are stirred in 1.5 l of water and neutralized with lithium hydroxide, the Dye goes into solution. 500 g of ice are then added, sprinkles in 0.05 mol of cyanuric chloride and stirs at 0 ° C to 5 ° C to about 50% of the triphendioxazine used are acylated. You hold out during the acylation Drop of lithium hydroxyl solution the pH between 6 and 7. Then heated to 60 to 70 ° C, wherein the second chlorine atom is exchanged.

Here, too, the hydrogen chloride released is included Neutralized lithium hydroxide solution. The one in solution present dye has the specified for Example 1 Constitution. By adding 4% by volume sodium chloride, the dye is separated. After this Vacuuming, drying and grinding are obtained in water with clear blue color soluble dye powder that Cotton according to one of the substantive dyes usual dyeing procedures in clear reddish blue Tones colors (color code 13).

Example 2

The solution of that obtained in Example 1 is added Monochlorotriazine dye with 0.15 mol of N-methyl taurine and heated to 85 ° C to 95 ° C, the pH between 7.5 and 9.5 should be until the exchange of the chlorine atom  against the amine residue. The dye is through Add 4% by volume of sodium chloride. To after suction, drying and grinding you get an in Water with clear blue color soluble dye powder ver, the cotton after one of the for substantive color usual dyeing processes in clear reddish tones colors blue tones (color code 13). The dye has the constitution given for example 2.

In Example 2, N-methyl taurine is replaced by the equi molar amount of one of the amines listed below, so you also get valuable substantive color fabrics containing material in cellulose fibers clear shades of blue (color code 13).

Example 3

Morpholine

Example 4

Diethanolamine

Example 5

Methylaminoethanol  

Example 6

Taurine

Example 7

Mono (2-aminoethyl) sulfuric acid

Example 8

Mono (2-methylaminoethyl) sulfuric acid

Example 9

Amino acetic acid

Example 10

Methylaminoacetic acid

Example 11

β-aminopropionic acid

Example 12

Bis (2-sulfatoethyl) amine  

Example 13

The solution of the monochlor obtained in Example 1 is added triazine dye with 0.15 mol mercaptoethanol and heated to 80 ° C. to 85 ° C, being by dropwise addition of dilute lithium hydride solution keeps the pH between 7.5 and 8.5. After the condensate has ended The dye is obtained by adding 2% by volume of sodium salted out chloride. After vacuuming, drying and grinding a blue dye powder containing cellulose fibers Material in clear shades of blue colors (color code 13).

Example 14

In Example 13, mercaptoethanol is replaced by an equimolar one Amount of mercaptoacetic acid and proceed as described in Example 13, this also gives a dye which contains cellulose fibers holding material in a clear blue color (color code 13).

In the table below, the dye constitutions are the Examples 1 to 14 given:

In Example 1, 2,9-diamino-6,13-dichlor is replaced triphendioxazine disulfonic acid by the equimolar amount 2,9-diamino-6,13-dimethoxy-triphendioxazine disulfonic acid or 2,9-diamino-6,3-diethoxy-triphendioxazine disulfone acid and otherwise operates as in Examples 1 to 14, you also get substantives Dyes, the material containing cellulose fibers color in clear strong reddish blue tones.

Claims (6)

1. Triphendioxazine dyes of the formula wherein
R = hydrogen or optionally substituted C₁-C₄ alkyl
R ′ = hydrogen or substituent
T₁, T₂ = hydrogen, chlorine, bromine, optionally substituted C₁-C₄-alkyl, C₁-C₄-alkoxy, phenyl or phenoxy
X = hydrogen or substituent
n = 0 or 1
means. 2. Dyes of claim 1 of the formula 3. Dyes of claims 1 and 2 with T₁ = T₂ = Cl or OCH₃. 4. dyes of claims 1 to 3 with X = halogen, Sulfo, C₁-C₄ alkyl, a thioether, ether or optionally substituted amino group. 5. A process for the preparation of the dyes of claim 1, characterized in that 1 mole of a triphendioxazine dye of the formula wherein T₁, T₂, R, R 'and n have the meaning given, with 1 mol of a halotriazine of the formula where Hal is chlorine, bromine or fluorine and X has the meaning given, to a monoacylation product of the formula reacted and this then condensed with a further mole of a triphendioxazine dye of the formula (3). 6. Use of the dyes of claims 1 to 4 for Dyeing and printing cellulosic materials and leather.