DEG0012614MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 9, 1953. Advertised on July 19, 1936

GERMAN PATENT OFFICE

The invention relates to the production of heavy metal-containing monoazo dyes, which are used for real dyeing of wool and of wool-like synthetic polypeptide fibers such as polyamide fibers or Casein fibers from neutral to weakly acidic dyebaths are excellently suited.

It is known that complex chromium compounds of metallizable monoazo dyes which do not contain any acidic water-solubilizing groups such as sulfonic acid or carboxyl groups are very suitable for real dyeing of wool and wool-like fibers, provided they have sufficient water solubility for dyeing purposes. If certain hydrophilic substituents are not present in the dye molecule, the water solubility of such dyes is usually insufficient. A hydrophilic substituent that is technically easy to introduce and therefore widely used is the sulfamide group - SO ₂ NH ₈ . However, its acidic character is already so pronounced that it has a drawability on wool from neutral

ÜB 550./397

G 12614 IVb / 22a

Bad is adversely affected. Complex chromium compounds of azo dyes that do not contain acidic, water-solubilizing groups and the sulfamide group as hydrophilic substituents When dyeing wool, depending on the constitution, a more or less high acid requirement, which the ability to combine such chromium-containing dyes is impaired. The substitution of the sulfamide group through hydrocarbon residues their

ίο The hydrophilic effect is greatly reduced, _{the acidic character of the monosubstituted sulfamide group - SO 2} - NH - R being only slightly influenced, while in the doubly substituted sulfamide group the acidic character and thus also its hydrophilic character is influenced

Properties are practically canceled; *

It has now been found that complex chromium and cobalt compounds of metallizable monoazo dyes without acidic groups, with the exception of any existing ones, on the complex metal formation

ao involved carboxyl group have sufficient water solubility and a very low acid requirement when dyeing wool, if they have sulfonic acid-N-oxalkyl-N-alkylamide groups as hydrophilic substituents in the dye molecule contain.

The metal-containing dyes according to the invention are obtained by treating monoazo dyes the general formula

-SO ₉ -N;

RAW

wherein A is the remainder of a diazo component, X is a hydroxyl or carboxyl group in the o-position to the azo group or a substituent which can be converted into such a group under the conditions of the metallization reaction and R and R 'are low molecular weight aliphatic or optionally also alicyclic hydrocarbon radicals mean, and in which the hydroxyl group in the naphthalene radical is in the o-position to the azo group, with chromium or cobalt releasing agents. The radical A can also be substituted in any non-ionic manner be, for example by halogen atoms, alkyl, alkoxy, aryloxy, nitro, acylamino, alkylsulfonyl, Arylsulforiyl, sulfonic acid dialkyl amide, sulfonic acid aryl ester, Carboxylic acid ester and carboxylic acid amide groups. However, it should not be acidic, water-soluble contain making substituents, except for a possibly involved in the complex formation carboxyl group. ■ '■■ _' ν

■■ Preferred diazo components are δ-oxy, 0-carboxy or δ-alkoxyamino compounds of the benzene and naphthalene series. The naphtholic azo component orientation is said to contain a sulfonic acid-N-oxalkyl-N-alkylkmid group; to this

suffices; can easily be achieved by converting sulfonic acid groups by customary methods in sulfonic acid halide groups and treat them with one

■■■■■ Excess of a securidary & alkanolamine. Preferential ^ The sulfamide group of methylamino or ethylamino-alkanols is said to be wise derive, in which the alkanol radical can contain 2 to & carbon atoms and the Hydroxyl and the amino group are advantageously bonded to adjacent carbon atoms. Especially valuable substituents are the sulfonic acid-N-methyl- or -N-ethyl-N-oxäthylamidgruppen.

Azo components with a sulfamide group according to the invention are obtained, for example, from acyloxynaphthalene sulfonic acid halides and alkylaminoalkanols and saponification of the acyloxy to hydroxyl groups. The diazotization takes place as usual in the cold in a mineral acid solution or suspension Sodium nitrite and the coupling in alkaline solution. Depending on the composition, red, brown, Produce violet, blue and gray dyes that turn into appropriately colored heavy metal complex compounds get convicted.

The metallization is expediently carried out in an aqueous solution or suspension under the influence of heat of salts of cobalt or of trivalent chromium, whereby one is based on two dye molecules allows at least 1 atom of heavy metal to act. It is advantageous to use alkali salts for chroming of chromium salicylic acid. The metallization can be done openly under reflux or in a closed vessel Carry out under pressure, if necessary with the addition of dispersants, for example Turkish red oil, or work in high-boiling organic solvents and diluents, for example in formamide, Dimethylformamide or in the urea melt. Working at over ioo ° and under pressure is particularly recommended when substituents o-position to the azo group, such as alkoxy groups or halogen atoms to be replaced by the hydroxyl group during metallization.

The complex chromium or cobalt compounds of the above-defined monoazo dyes according to the invention usually already have sufficient water solubility for dyeing purposes. Possibly this can be achieved by mixing with alkaline inorganic salts such as sodium carbonate or trisodium phosphate, as well as organic, non-active wetting agents: and; Dispersants, such as soaps and synthetic detergents, are still to be improved.

The new chromium or cobalt-containing dyes dye the wool from neutral to weak acidic bath, for example from the Glauber's salt bath containing ammonium sulfate, with very good exhaustion the baths very evenly and can be mixed with or with other similar dyes combine very well thanks to their very similar coloring behavior.

The chromium complex compound according to the invention of the dye from diazotized 2-amino-i-oxy-4-methoxybenzene and α-oxynaphthalene-δ-sulfonic acid-N-methyl-N-oxyethylamide exhibits opposite the chromium complex compound of the dye from diazotized 2-Amino-i, 4-dimethoxybenzene and 2-oxynaphthalene-'6-sulfonic acid methylemide according to the German patent application P 4955 IVd / 22 a, Example 2, a better one Water solubility and better rub fastness.

'^ ■ 609 550/397

G 12614 IVb / 22a

The following examples illustrate the invention. The parts mean, if nothing otherwise noted is parts by weight. Parts by weight are in the same proportion to parts by volume as Kilograms to liters.

example 1

OH

NH,

SO ₂ -N-.CH ₂ CH ₂ OH
CH ₃ .

Cr complex compound

14.4 parts of 4-chloro-2-amino-i-oxybenzene are diazotized in 100 parts of water and 17 parts concentrated hydrochloric acid with 20 parts by volume of 5 N sodium nitrite solution at 0 to 5 ⁰ and after neutralization with sodium carbonate at 0 to 3 ° in a Poured a solution of 29.5 parts of i-oxynaphthalene-3-sulfonic acid-N-methyl-N-oxyethylamide, 10.5 parts by volume of 10 N sodium hydroxide solution and 300 parts of water. When the dye has formed, sodium chloride is added, nitrated, the dye is suspended in 800 parts of water, 200 parts by volume of a solution of chromium salicylic acid ammonium (corresponding to 7.6 parts of Cr ₂ O ₃ ) are added and the mixture is refluxed for 20 hours. The chromium-containing dye falls through

Adding table salt, filter it off and dry him. It represents a blue-black powder, the wool from neutral or weakly acidic bath in navy blue Tones colors.

The ι - oxynaphthalene - 3 - sulfonic acid - N - dxyäthyl-N-methylamide is represented as follows: i-Oxynaphthalene-3-sulfonic acid is esterified with toluene sulfochloride and, after thorough drying with phosphorus pentachloride, converted into i-toluenesulfonyloxynaphthalene-3-sulfonic acid chloride. This is then ^{condensed with methylethanolamine:} · ■ and the toluenesulfonyl residue is split off by heating with dilute sodium hydroxide solution. F. (from Diluted Alcohol) 134 to 135 ⁰ . ■ -. : '.;"'■■ ■:

Example 2

OH

HO

NH ₉

SO ₂ -N- CH ₂ - CH ₂ - OH
CH,

Cr complex compound

14.4 parts of 4-chloro-2-amino-i-oxybenzene are diazotized and after neutralizing with sodium bicarbonate at 15 ° in a solution of 29.5 parts 2-Oxynaphthah'n-6-sulfonic acid-N-oxyethyl-N-methylamide, 4.4 parts of sodium hydroxide and 12 parts anhydrous soda poured into 600 parts of water. Then it is heated to 20 ° and stirred for so long at this temperature until the coupling has ended.

16 parts of sulfonated castor oil and 120 parts by volume of a solution of chromium salicylic acid ammonium (corresponding to 4.55 parts of Cr ₂ O ₃ ) are then added and the mixture is refluxed for 3 hours. The mixture is then allowed to cool to 95 °, 90 parts of sodium chloride are added, the mixture is heated ^{to boiling again for x} / ₂ hours and finally the dyestuff which has precipitated out is filtered off while hot. After drying, he presents a blue-violet powder that dyes wool from a neutral bath in clear violet tones with very good fastness properties. The 2-oxynaphthalene-6-sulfonic acid-N-oxyethyl-N-methylamide is represented as follows: 2-oxynaphthalene-1-carboxylic acid-6-sulfonyl chloride is condensed with methylethanolamine and the carboxyl group is split off by heating in a weakly acidic agent . F. (from alcohol) 184 to 185.5 °.

609 550/397

G 12614 IVb / 22 a

According to the information in the above examples, the following dyes can also be represented:

table

LO 2 20th 8th Diazo component Azo component metal Hue of ⁵ no: 3 4-chloro-2-amino-i-oxybenzene ι-Oxynaphthalene-4-sulfonic acid e- Cr Metal complex
connection on
Wool I. 4th 9 N-methyl-N-oxyethylamide Reddish 4-nitro-2-amino-i-oxybenzene the same Cr violet 15 5 35 10 5-nitro-2-amino-i-oxybenzene the same Cr Bordeaux red II o-nitro- ^ methyl ^ -amino-i-oxy- i-oxynaphthalene-3-sulfonic acid Cr Blue violet 6th benzene N-methyl-N-oxyethylamide Navy blue 4-chloro-5-nitro-2-amino-i-oxybenzene i-oxynaphthalene-5-sulfonic acid Cr 7th N-methyl-N-oxyethylamide Greenish 4, o-Dinitro - ^ - amino-i-oxybenzene 2-oxynaphthalene-8-sulfonic acid Cr. Gray N-methyl-N-oxyethylamide Purple brown 4-chloro-2-amino-i-oxybenzene a-oxynaphthalene-o-sulfonic acid Co N-methyl-N-oxyethylamide Ruby red o-nitro ^ -methyl ^ -amino-i-oxy- 2-oxynaphthalene-4-sulfonic acid Cr benzene N-methyl-N-oxyethylamide Gray 4-chloro-2-amino-i-oxybenzene the same Cr Reddish 4,6-dichloro-2-amino-i-oxybenzene the same Cr navy blue z-Amino-i-oxybenzene ^ -sulfonic acid- 2-oxynaphthalene-6-sulfonic acid Cr Violet-
pungent gray
Reddish N-dimethylamide N-methyl-N-oxyethylamide violet

Claims (1)

PATENT CLAIM: Process for the production of heavy metal-containing monoazo dyes, characterized in that that on sulfonic acid group-free dyes of the general formula OH A-N = N- , R -so ₉ -n; '—OH wherein A is the remainder of a diazo component, X is a hydroxyl or carboxy group in the o-position to the azo group or a substituent which can be converted into such a group and R and R 'are low molecular weight aliphatic hydrocarbon radicals with not more than 8 carbon atoms together mean and in which the hydroxyl group in the naphthalene radical is in the o-position to the azo group and the radical A can still not be ionically substituted, with chromium or cobalt treated in such quantities that for every 2 dye molecules at least 1 atom Heavy metal is omitted. Considered publications:
German patent applications G 5761 IVd / 22a and P 4955 IVd / 22a. © 609550/397 7.56