DE1012009B - Process for the preparation of new monoazo dyes - Google Patents

Description

The invention relates to monoazo dyes of the product type of the formula

HO N = N- <

-NH-CO-CHo-Cl

Y-NH,

HO.S-

(1)

> -CH _a

Such dyes correspond to the general formula RN = NR ₁ -NH-CO-Z (2)

SO ₂ -Y

wherein R is the radical of a 2-aminonaphthalenesulfonic acid bonded in the 1-position to the azo group, R _{1 is} a benzene radical, Y is an aryl radical or the group

Method of manufacture
of new monoazo dyes

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney,
Hamburg 36, Neuer Wall 10

Claimed priority:
Switzerland of December 30, 1954 and November 8, 1955

Dr. Rene de Montmollin, Neu-Allschwil,

and Dr. Heinrich Zollinger, Binningen (Switzerland),

have been named as inventors

- n:

, Alkyl

'Aryl

and Z is an aliphatic, α-position to the —CO group means bonded radical which contains a halogen atom in the α- or ω-position.

In order to produce these monoazo dyes, according to the invention, diazo compounds are made from amino sulfones or Amino-sulfonic acid amides of the general formula

H ₂ NR ₁ -NH-CO-Z

SO ₉ -Y

(3)

where the meaning of the various symbols results from the formula (2) just explained, with 2-aminonaphthalenesulfonic acids coupled in acidic medium. The azo components are 2-aminonaphthalenesulfonic acids with secondary or primary amino group in 2-position, like 2-aminonaphthalene-3, 6- or -5, 7-disulfonic acid, but especially 2-aminonaphthalene monosulfonic acids, like 2-amino-3- or -S-oxynaphthalene-T-sulfonic acid, the 2-amino-7-oxynaphthalene-4-sulfonic acid, also 2-alkylamino-8-oxynaphthalene-6-sulfonic acids, z. B. the 2 - methylamino - 8 - oxynaphthalene - 6 - sulfonic acid, the 2-aminonaphthalene-7- or -6-sulfonic acid and preferably to mention the 2-amino-8-oxynaphthalene-6-sulfonic acid itself.

The amino-sulfones and amino-sulfonic acid amides, of the formula (3), which are used as starting materials in the present process, are new. You can z. B. produce so that the corresponding diaminosulfones or diamino-sulfonic acid amides of the general ^a 5 formula

H ₂ NR ₁ -NH ₂ (4)

SO ₂ -Y

with halides or with the anhydrides of the acids of the formula

HOOC - Z (5)

monoacylated, more uniform acylation products being obtained with the anhydrides as a rule. Examples of suitable acylating agents include: α- or β-chloropropionic acid chloride, chloroacetyl chloride and chloro- or bromopropionic anhydride and chloroacetic anhydride. The reaction of these amines with the specified carboxylic acid chlorides or anhydrides can be carried out in water and / or in the presence of an organic solvent, optionally with the addition of an acid-binding agent or a buffer such as sodium carbonate, magnesium oxide, calcium carbonate, pyridine or sodium acetate. The diaminosulfonic acid amides are preferably acylated with the anhydrides, while the diaminodiarylsulfones can generally be acylated in a satisfactory manner with carboxylic acid chlorides.

The acylation is advantageously carried out in the cold, e.g. B. between -10 and + 10 ° in a weakly acidic medium (pH 3 to 6) and with a small excess of the acylating agent, d. H. little more than is necessary to react with the amino group to be acylated.

709 587/374

The diamines of the formula (4) can be an —NH ₂

Aryl radical, e.g. B. a substituted or unsubstituted

Phenyl radical, such as a methylphenyl, chlorophenyl or / \. nt - n / \ NPr Γ Π

Methoxyphenyl radical, or the radical of a secondary ^x ■

Amine, e.g. an N-ethyl-N-phenylamino- or'N-methyl-5: N-chlorophenylamino group. contain. As examples of amino sulfones and amino-sulfonic acid amides, which are obtained from these diamines by the method just mentioned can be produced, the following should be mentioned:

2-Amino-5- (α- or ^ -chloropropionylamino) -4'-methoxy- io 1,1 '- diphenylsulfone, 2 - amino - 5 - (chloroacetylamino-1, l'-diphenyl sulfone and in particular ί-Αηύηο-δ- (chloracetylamino) -4'-methyl-l, l'-diphenyl sulfone, also 2-ami-

no-5- (bromoacetylamino) benzene-l-sulfonic acid-dimethyl- - - - · ■ - ■

or diethylamide and 2-amino-5- (chloroacetylamino) - 15 (see e.g. U.S. Patent 1,840,385 and U.S. Pat. No. 1,840,385 benzene-l-sulphonic acid-N-ethyl-N-phenylamide. German patent 842 975) have comparable

These amino-sulfones and amino-suÖonic acid amides can, however, have markedly better wet fastness properties, especially the customary compounds which are difficult to use, a significantly better wash fastness, and are diazotized to these common methods, for example also in terms of light fastness at least by adding water to them 20 finished or superior. They are suitable for dyeing and a suitable wetting agent, very finely pasted and printing on a wide variety of materials, in particular or or by diazotizing such animal origin as leather, silk and organic solvents mixed with water. With all wool as well as various synthetic fibers, '%. B. from 2-aminonaphthalenesulfonic acids, the coupling takes place in animalized rayon, super polyamides and super acids, for example weakly Congo acid to acetic polyurethanes, etc. The acidic agents obtained with these dyes. Here you can z. B. proceed in such a way that dyeings are distinguished by their valuable hues from the 2-aminonaphthalenesulfonic acid to be used and their good fastness properties. first converted into an alkali salt, this by adding In the following examples, the parts mean

Acetic acid converts back into the free acid, unless otherwise indicated, parts by weight and a free suspension is obtained, and then the diazo is the percentages by weight, compound combined with this suspension. Then it will be

the free example 1 resulting from the coupling reaction

Mineral acid partially blunted with sodium acetate 338.5 parts 2-amino-5-chloroacetylamino-4'-methyl-

and if necessary increase the temperature a little. The 1, l'-diphenylsulfone with 1800 parts of water in working up the coupling mass can in the usual; Finely pasted on the roller mill. Now the paste will be done in a known manner, e.g. -B. diluted by neutralization with 1200 parts of water, and it is added with sodium carbonate (care must be taken that 250 parts by volume of hydrochloric acid (d - 1.15) are added, the labile substituent of the radical Z is not split off to 0 to 5 ° and 250 Parts by volume of 4N sodium nitrite solution is added), filter off and dry. flow. The nitrite reaction is practical after 24 hours. The dyes according to the invention are new and have disappeared. In order to accelerate the diazotization, speak as free acids of the already explained eye-, acetone can be added.

my formula (2). Among these dyes have "'226 parts of 2-Ammo ^ 8-oxynaphthalene-6-sulfonic acid and those proved to be particularly valuable which are of the formula 73 parts 1, 3, 6-naphthalenetrisulfonic acid sodium

Suspended in 2400 parts of water from 60 to 70 ° and 45 with concentrated sodium hydroxide solution to weakly lacquer acid Reaction neutralized. This solution is at 70 to 80 °

> - NH - CO - CH ₂ --Cl heated and pour into the diazo suspension while stirring

calmly. After mixing the components

Y temperature ranging from 30 to 35 ° is maintained for 24 hours

'50 hold. A solution of 140 parts of crystallized

'Sodium acetate in 300 parts of warm water, which was made weakly lacquer wall with acetic acid, becomes _{very slowly after the addition of the 2-amino-8-oxynaphthalm-SO 3} H 6-sulfonic acid to correspond to the coupling mixture, where η is a whole number of 55 given. After the coupling has ended, the dyestuff is at most 2 and Y has the meaning given in the formula (2) suspension at room temperature with about 200 parts. These dyestuffs are constituted by calcined sodium carbonate up to weakly briUanttion-wise and technically dyed with the known coloring-alkaline reaction and filtered. The obtained substances of the formulas press cake is dried in vacuo at 50 to 60 °,

jq-jj 60 A dark red powder is obtained which dissolves in water

• ι dissolves and wool in an acidic medium in blue-tinged red tones

- ^: / - ~ ^ \ of good wet fastness and very good light fastness

-N = N- / N-NHCOCH ₃ colors.

^; The ^ -Ammo-S-chloracetylaniino ^ '- methyl-l, l'-di- • OH .. I- 65 phenylsulfone can, for. B. obtained in the following manner

, ² become:

c _n -ü '■ -' ■ '"398 parts of 2,5-diamino-4'-methyl-l, l'-diphenyl sulfone

bU ₃ ± i χ in 1200 parts of water and 900 parts of glacial acetic acid

wherein X is an ethylphenylamine or a p-toluene residue dissolved warm and cooled to -0 °. After adding represents, and. '- - ■; ■ ■ 70 410 parts of crystallized sodium acetate are under

Claims (4)

5 6 Stirring to increase 186 parts of chloroacetylity within about 1 hour. The dye thus obtained stains chloride, dissolved in 200 parts of toluene, was added. One wool from acidic medium in red-violet tones from Takes 30 minutes and drips within 30 minutes of marked washfastness and good lightfastness. 3200 parts of water are added, the mixture is stirred again for 30 minutes and. . filtered. The residue is mixed with plenty of water from 30 to 5 Example 5 Washed 40 ° and dried in vacuo at 80 to 90 °. 383 parts of 2-amino-5-bromoacetylamino- 470 to 480 parts of a light gray, violet-4'-methyl-l, Γ-diphenylsulfone are obtained and coupled with 226 parts puncture powder, which 70 to 75 ° / ₀ 2-amino-S-chloro-2-amino-8-oxynaphthalene-6-sulfonic acid exactly after the contains acetylamino-4'-methyl-l, Γ-diphenyl sulfone. The method described in Example 1. One receives a Purified product melts at 170 to 171 °. io water-soluble, dark red powder, the wool in acid You can also work as follows: 394 parts of medium in blue-tinged red tones of good wet and dry 2, 5-diamino-4'-methyl-l, l'-diphenyl sulfone are colored in lightfastness. 4000 parts of hot ethyl acetate dissolved, down to 0 ° Example 6 cooled and, while stirring, added dropwise with " 269 parts of chloroacetic anhydride, dissolved in 500 parts 15 352.5 parts of 2-amino-5- / S-chloropropionylamino-4'-me-ethyl acetate, keeping the temperature 5 ° not thyl-1, Γ-diphenyl sulfone are diazotized and may geübersteigen · . After all the anhydride has been added, the mixture is coupled with 226 parts of 2-amino-8-oxynaphthalene-6-sulwis stirred for 1 hour at Ό to 5 °, the precipitated fatty acid analogously to the pre-2-amino-5-chloro described in Example 1 acetylamino-4'-methyl-1, Γ-diphenyl font. A dark red powder is obtained which is sulfone filtered and dissolved in water with 500 parts of ethyl acetate and wool is washed in an acidic medium with a bluish tinge from 0 to 5 °. The acylated product is dyed in red shades of good wet and light fastness. 4000 parts of water at 30 ° slurried, filtered again and dried in vacuo at 60 °. Example 7 is obtained
430 parts of a crystalline product, which at 169 to 171 ° melts. 25 367.5 parts of 2-amino-5-chloroacetyl are diazotized Example 2 'ammobenzene-.l-sulfonic acid-N-ethyl-N-phenylamide and coupled with 226 parts of 2-amino-8-oxynaphthalene-6-sul- 338.5 parts of 2-amino-5-chloroacetylfonic acid are diazotized exactly as described in Example 1 amino-4'-methyl-l, l'-diphenyl sulfone, as in Example 1 regulation. A dark red powder is obtained which is described, and couples the diazo compound obtained 30 dissolves in water and wool in an acidic medium in bluish tint in the manner described in Example 1 with 223 parts of red shades of good and very good wet fastness properties 2-aminonaphthalene-6-sulfonic acid. An orange lightfastness color is obtained. red powder that dissolves in water and turns wool into 2-amino-5-chloroacetylaminobenzene-l-sulfonic acid acidic agent in orange tones of very good wet N-ethyl-N-phenylamide can be used, for. B. shown as follows and color fastness to light. 35 become: ". · Ιο 436 parts of 2,5-diaminobenzene-l-sulfonic acid-N-ethyl- ^ice P ^ie N-phenylamide are in a mixture of 1200 parts 338.5 parts of 2-ammo-5-chloroacetylamino-4'-methyl water and 900 parts of glacial acetic acid dissolved, to 70 to 80 ° er-1,1'-diphenylsulfone are diazotized according to Example 1. warms and filters. The filtrate is set to 0 ° and 253 parts of 2-N-methylamino-8-oxynaphthalene-6-sulfone 40 acid and 73 parts of 1, 3, 6 -naphthalenetrisulfonic acid with 257 parts of chloroacetic anhydride, dissolved in 350 parts of sodium are in 2800 parts of water from 60 to 70 ° len ethyl acetate. The ^{mixture is stirred for a further 1} J ₂ hours and slurried and neutralized with concentrated sodium hydroxide solution within a further half an hour, the weak lacquer acid reaction is neutralized. This solute up to the weakly brilliantly alkaline reaction with solution is heated to 70 to 80 ° and the diazo suspension is allowed to flow with stirring in 45,726 parts of sodium hydroxide, dissolved in 1200 parts. The temperature reached after the water, whereby it should be noted that the temperature not mixing the components rises above 5 °. The mixture is stirred for a further 2 hours, filtered and 30 to 35 ° is held for 24 hours. A solution of washes with 4000 parts of water and dries in vacuo 140 parts of crystallized sodium acetate in 300 parts at 60 to 70 °. 505 parts of warm brownish water are obtained, which with acetic acid pale lacquer- 5 ° colored powder, which was 88 to 92 ° / ₀ 2-amino-5-chloromus acid, is acetylaminobenzene-1-sulfonic acid-N-ethyl- N-phenylamide which contains 2-N-methylamino-8-oxynaphthalene-6-sulfonic acid very much. The purified product melts at 102 to 103 °. slowly added to the coupling mixture. After the coupling has ended, the dye suspension in room example 8
temperature with about 200 parts of calcined sodium 55 carbonate up to the weakly brilliant alkaline reaction. 367.5 parts of 2-amino-5-chloroacetylamino are diazotized added and filtered. The press cake obtained is with benzene-1-sulfonic acid-N-ethyl-N-phenylamide according to the im 50 to 60 ° dried in vacuo. A procedure described in blue Example 1 is thus obtained and coupled with it purple powder that you can use e.g. B. mixed with urea, 253 parts of 2-N-methylamino-8-oxynaphthalene-6-sulfone to improve solubility. The coloring acid thus obtained, as indicated in Example 3. You get a blue fabric dyes wool from an acidic medium in red-violet tones violet powder, which you can use for. B. mixed with urea, of good wash and lightfastness. to improve solubility. The color thus obtained _R. · ₁₄ ^st ° ff dyes wool from acidic agents in purple tones eispie Ί _{of froM} g _ez eichneter wash fastness and good light 338.5 parts of 2-amino-5-chloroacetylamino-4'-methyl-65 fastness.
1, Γ-diphenyl sulfone are diazotized according to Example 1 and with 267 parts of 2-N-ethylamino-8-oxynaphthalene claims:
6-sulfonic acid analogous to that described in Example 3 Procedure coupled. A blue-violet powder is obtained, 1. Process for the production of new mono-soft one z. B. mixed with urea to the solvent 70 azo dyes, characterized in that one 2-aminonaphthalenesulfonic acids with diazo compounds from amines of the general formula H ₂ NR ₁ -NH-CO-Z SO ₂ -Y couples in which R _{1 is} a benzene radical, Y is an aryl radical or the group -N ' , Alkyl Aryl IO and Z denotes an aliphatic radical bonded to the - CO group in the α-position, which is a Contains halogen atom in α- or ω-position. 2. The method according to claim 1, characterized in that that 2-aminonaphthalene monosulfonic acids in acidic agents with diazo compounds Amines of the formula H ₉ N NH-CO-Z SO ₉ -Y couples in which Y is an aryl radical or the group - N: , Alkyl 'Aryl and Z is a halogenated alkyl radical which contains a chlorine atom in the α or ω position. 3. The method according to claim 1 and 2, characterized in that the 2-amino-8-oxynaphthalene-6-monosulfonic acid, which may optionally be alkylated in the amino group, in an acidic medium with diazo compounds from amines of the general formula H ₉ N- I /
SO ₂ -Y NH-CO-CH ₉ -Cl couples in which Y is an aryl radical or the group ,, alkyl ■ n: Aryl means. 4. The method according to claim 1 to 3, characterized in that the diazo compound is diazotized tes 2 - Amino - 5 - (chloroacetylamino) - 4 '- methyl-1, l'-diphenylsulfone is used. Considered publications:
German Patent No. 842,975;
U.S. Patent No. 1,840,385. © 709 587/374 7.57