DE1769184A1 - Dyes of the anthraquinone series, their manufacture and use - Google Patents

Description

Patent attorneys

Dr. W. Schalk, Did .-! Ng. P. Wirth

DIpL-lr.-. C. · ■ · -: ■ - ■■ - ^. Iwrg

Dr. V. o-r'r:. ··. :: = - '-ov / arzik

Dr. P-V / tinh J-, Dr. D. Gudel Frankfurt / '.' A-, Gr. Eschenheimer Str.

SAHT) OZ AG
Basel, Switzerland

Case 2671 / a

Dyes of the anthraquinone series, their production and use . ^; .- ■ "

The invention relates to dyes of the anthraquinone series the formula

O NH-CH-X-C-R., -SC> H

ι ^Λ s-

R-,

O NH-CH-XCR "-SO, H j I ⁴ 5

R ₁ ^R 2

wherein R is an optionally substituted hydrocarbon radical,

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Rp is a hydrogen atom or an optionally substituted one Hydrocarbon residue,

R is an optionally substituted hydrocarbon radical,
Rji, an optionally further substituted arylene radical, preferably a phenyl radical,

and X is an optionally substituted alkylene radical

and the aromatic ring A carries at least one halogen atom »
The process for the preparation of the dyes of the formula (I) is characterized in that 1 mol of a compound of
formula

0 W

(II),

wherein W is a substituent which can be exchanged for an amino group, or 1 mol of the leuco form of a compound of the formula (II) or 1 mol of a mixture of one
Compound of formula (II) and its leuco form with 2
Moles of a compound of the formula

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(in),

in which T denotes a mass atom or the sulfonic acid group, -reacts _f oxidizes if the compound of formula (II) was used in its leuco form, and sulfonates if T denotes a hydrogen atom.

Particularly good dyes correspond to the formula

O NH-CH-CH ₀ -C- ^ A-

I ■ ^ l \ _> SO, H

^R 5 ^R 6 ■?

wherein each of the radicals' Rj-, R ^ - and R "is an optionally substituted alkyl radical having, for example, 1 to 12, or 1 to 8 and preferably 1 to k carbon atoms, Y is a chlorine atom

and Z represents a hydrogen or chlorine atom.

An excellent dye is the formula dye

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BATH ORIGINAL

ϊ / 69184

SO-, Η O

I ι 3

iH-CH-CH ₀ -C /

The implementation of a compound of the formula (III), if T is for is a hydrogen atom, with a compound of the formula (II) is advantageously carried out in an organic medium. The base (III) or a mixture of bases can with a compound of Formula (II) or its leuco derivative or with a mixture of compounds of the formula (II) or their leuco forms for Reaction to be brought. The reaction products obtained in this way are optionally oxidized and then sulfonated, the sulfonation e.g. in oleum or with concentrated sulfuric acid from $ 80-100, preferably $ 92-100, or with chlorosulfonic acid can be carried out.

The reaction of a compound of the formula (III) or a mixture of such compounds, if T for the sulfonic acid group with a compound of the formula (II) or its leuco derivative or with a mixture of compounds of the formula (Ii) or their leuco form, preferably in an aqueous medium carried out.

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Suitable organic media are, for example: high molecular weight alcohols such as butyl alcohol, isobutyl alcohol, amyl alcohol, octyl alcohol, dodecyl alcohol, etc. Nitrobensol, Ghlorbcnzol or mixtures of such solvents, in which "ren the reaction at temperatures of _r 8O-l4O ° C, preferably at temperatures from 100-130 ⁰ C, can be carried out.

In most cases, the reaction product obtained is obtained in the leuco form and must therefore be oxidized in order to convert it into the final dye. The oxidation can also be carried out in the abovementioned solvents at temperatures of 100-l80 ° C, preferably 130-170 ⁰ C, for which purpose air can be introduced into the organic medium; If nitrobenzene is used as the solvent, it is not necessary to introduce air. ·

R ₁ and R., and R ₂ can represent an optionally substituted hydrocarbon radical, advantageously an alkyl radical with, for example, 1 to 12, preferably 1-8, or. 1-5 carbon atoms, for example an optionally substituted alkyl or cycloalkyl radical, for example an alkylcyclohexyl radical. If these radicals are substituted, they contain, for example, a hydroxyl or cyano group or a halogen atom, such as a chlorine or bromine atom

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can, for example, by halogen, optionally substituted alkyl or alkoxy or by an amino, nitro, cyano or hydroxyl group be substituted. The optionally substituted alkylene radical X can be straight-chain or branched and can be 1 to 6 and preferably contain 1 to 4 carbon atoms. It can for example be substituted by the hydroxyl group.

The aromatic radical A carries at least one halogen atom, before -P partly, however, 2 halogen atoms in the 6- and 7-positions.

In each pail, halogen preferably denotes chlorine or bromine.

W denotes a substituent which can be exchanged for an amino group, e.g. the hydroxy group, an amino or alkoxy group or a halogen atom.

The new dyes are used for dyeing, padding or printing of fibers of animal origin, e.g. wool or silk, of synthetic polyamide fibers, e.g. nylon, and of leather. the Dyes reserve cotton and regenerated cellulose.

When dyeing, padding or printing you can usually do it used mesh, leveling, thickening or other

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Use textile or leather auxiliaries. .

The dyes can be prepared from an acidic or neutral * but also from an alkaline medium at temperatures of TO-IOO ⁰ C, preferably at Koehtemperatür, color. They have a good build-up capacity on the specified substrates and are excellent in leveling. The dyeings and prints obtained are of excellent brilliance and have good lightfastness and good VIaIk, λ Sehwelss, washing, water, seawater, rub, acid and soda fastness.

In the French patent 1 2 ^ 2 669 the dye the formula

CH _{3 s} I / -v * " 2

O NH-CH-CH ₂ - (

ι 3
O NH-CH-CH ₀ -C- ( 5th

3 3

described. It is used to dye Violle. It is surprising that the dyes of formula (I), also dyed on wool have better wash and boil fastness.

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" ⁸ " ί /69.184

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are in Celsius-. degrees indicated.

example 1

8 parts of l ^ -dihydroxy-ö ^ T-dichloro-anthraquinone in the leuco form and 18 parts of 2-phenyl ~ 2-methyl-4-aminopentane, in 40 parts of normal Butanol dissolved, are for 28 hours at 100 ° in a fc heated nitrogen atmosphere and the product obtained with a Oxygenated air stream. The solution is diluted with ethanol, the dye obtained is filtered off and washed with ethanol.

10 parts of dried dye are dissolved in 80 parts of sulfuric acid monohydrate sulfonated at room temperature. The mass is poured onto ice and the precipitate is filtered off. The residue we is washed with a sodium chloride solution and then dried.

^ A powder is obtained that contains wool and nylon, in greenish blue, dyes brilliant shades with good light fastness and good wet fastness properties.

The same dye is obtained if 8 parts of 1,4-dihydroxy-6,7-dichloroanthraquinone are used in the leuco form and 22 parts of 2-phenyl-2-methyl-4-amine pentane sulfonic acid Sodium converts in water at elevated temperature and then eating the reaction product oxidized.

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-Q-

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Dyeing prescription

A dyebath consisting of 10,000 parts of water, 2 parts of dyestuff of Example 1/10 parts of Glauber's salt and 2 parts of glacial acetic acid is admixed with 100 parts of wool at a temperature of 4-0-50 °. The bath is heated to the boil within 3> 0 minutes and the bath is left at the boiling temperature for several minutes. After this time, another 2 parts of glacial acetic acid are added to the dye bath and dyeing is ended after a further 50 minutes of cooking. The woolen cloth is dyed in a very lightfast, brilliant, greenish blue shade and has good lightfastness and good wet fastness properties, for example good wash and milled fastness.

If 100 parts of nylon are dyed as indicated above, one obtains a similarly good coloring.

The following table shows the structure of the other Dyestuffs indicated, which were prepared according to the information in Example 1 will. They correspond to the formula

0 NH-CH-XC-Rj ₁ -SO ₇ H
.R,

O NH-CH-OC-C-H., -SO, H

i \ .4 y

X3 "D

R ₁ R ₃

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-ιο ί / 6yi84

wherein R, to R ^, have the meanings given in the table.

Position of 1 O - ^CH 3 X ^R A nuance E.g. Substituents X C. 'r the Fär No. ten in the ring -C ₂ H ₅ exercise on A. -CH, -CHj CH ^ -CH ₂ - - (J) -CH ₃ Wool 2 6,7-dichloro CH ₃ chiges -CHj -C ₂ H ₅ CH ₅ -CH ₂ - -Λ blue 3 ^6,7-D ichlor -CHj CHj -CH ₂ - do 4th 6,7-dichloro -CH CHj -CH ₂ - Of do 5 6-chlorine -CHj CH,
3 -CH ₂ - "9 ^ ° ^Η 3 do 6th 6-bromine do

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Claims (1)

IJ dyes of the anthraquinone series of the formula f ₂ h-SO H (D. 0 ΚΉ-CH-X-C-R ^ -SOJH R ₁ A ₂ wherein R, an optionally substituted hydrocarbon radical, R _{p is} a hydrogen atom or an optionally substituted hydrocarbon radical, R is an optionally substituted hydrocarbon radical, R ₁ denotes an optionally further substituted arylene radical and X denotes an optionally substituted alkylene radical
and the aromatic ring A carries at least one halogen atom. 2. Anthraciiinone dyes according to claim 1 of the formula 0 NH-CH-CH ₀ -C _(v) 109845 / U 32 wherein each of the radicals R ^ * Rg and R "is an optionally substituted alkyl radical,
Y is a chlorine atom
and Z represents a hydrogen or chlorine atom. . Anthraquinone dyes according to claim 1 of the formula (VII) 0 NH-CH-CH ₀ -C 4. Process for the preparation of anthraquinone dyes of the formula (I), characterized in that 1 mol of a compound is used the formula in which W is a substituent which can be exchanged for an araino group means, or 1 mole of the leuco form of a compound of the formula (II) or 1 mole of a mixture of of a compound of the formula (II) and its leuco form with 2 moles of a compound of the formula 10 9 8 k 5 / H 3 2 ι ² C-R ^ -T (III), in which T denotes a hydrogen atom or the sulfonic acid group, reacts or, if so, oxidizes the compound of the formula (II) was used in its leuco form, and sulfonated, if T is a hydrogen atom " 5. Use of the dyestuffs of the formula (I) for dyeing or printing of natural and synthetic polyamides. 6 »Use of the dyes of the formula (I) for dyeing or printing leather. . 7. According to claims 7 and 8 colored or printed Materials. 109845/1432 ι . ■ ■ ■