DE1644079B2 - PROCESS FOR THE PREPARATION OF WATER-SOLUBLE COLORS - Google Patents

Description

F - NH-CR-SO ₂ -Z, "

The compounds of the formula
O

Il

HaI-CR-SO ₂ -Z

can be according to the following method, which is known per se produce:

The cyclohexyl and endomethylene cyclohexyl radicals for R is produced by diene synthesis. As is well known, diene synthesis is understood to mean the reaction of a monounsaturated compound with a doubly unsaturated compound (see A. 3. Onishchenko: Diene Synthesis, Oldboume Press, London). The reaction partner for the production of the above-mentioned compound serves as a double unsaturated component butadiene or cyclopentadiene and, as a monounsaturated compound, acrylic acid.

Adding to the double bond of the diene adducts obtained from the components described above! one a thio compound de; general formula

25th

HaI-CR-SO ₂ -Z

where Hal is Cl or Br, acylated and in the latter case the azo dyes by diazotization and clutch builds up.

35

The present invention relates to a process for the preparation of new valuable water-soluble dyes the general formula

45 HS - CH ₁ - CH ₁ - Y

(H)

wherein F is the remainder of an azo, anthraquinone or phthalocyanine dye containing sulfonic acid groups, R is a cyclohexyl or endomethylene cyclohexyl radical, Z is a vinyl group or a // - bromine or / i'-chloroethyl radical, m means 1 or 2.

The dyes are prepared according to the invention by adding a dye of the general formula

F- (NH ₂ ) ,,,

or in the case of azo dyes, _{diazo and / or coupling components carrying the radical - NH 2} with an acid halide of the general formula

Il

Hai - C - R - SO ₂ - Z

where Hai is Cl or Br, acylated and in the latter In case the azo dyes are built up by diazotization and coupling.

where Y stands for chlorine, bromine or the hydroxyl group, oxidizes the thioether obtained in this way to the Sulfone and then converts the carboxyl group into the acid chloride group capable of reacting with the dye.

If Y in the compound II is not equal to chlorine or bromine, the conversion of the group Y can be the general formula II in chlorine or bromine both in the intermediate product and in the finished dye take place.

Dyes according to the invention in which Z is the vinyl group, if Y is chlorine or Bromine stands by splitting off HY from compounds of the general formula

- R - SO ₂ - CH ₂ - CH ₂ Y

produced with the help of basic agents.

If Y stands for the hydroxyl group, the vinyl group can be removed by the action of dehydrating agents or by conversion into the sulfuric acid half-ester and subsequent exposure to basic agents.

Some of the compounds of the formula which can be used according to the invention

Il

Hai - C - R - SO ₂ - Z

are listed below:
H

C-Cl

H, C

Cl

- C - Br

0, S- ¹

H ₂ CH, C

Br

O ₂ S-HC

I!

H, C

C-Cl

The dye residue contains at least one, in the Rain! but two to three or more sulfonic acid or carboxyl groups; in addition, other usual Substituents such as hydroxy, alkoxy, amino, acylamino, sulfamido, halogen, alkyl groups and the like. to be available.

Dyes containing amino groups or dye intermediates are used to produce the new dyes. which have a reactive hydrogen atom on the amine nitrogen, are reacted with the acid chlorides of the formula Hal-CO-R-SO ₂ Z and, in the case of intermediate products, are converted into dyes in a suitable manner.

The new dyes can belong to the class of the azo dyes, the anthraquinone or phthalocyanine dyes belong. They are very valuable as they face each other as a result of their great responsiveness Hydroxyl and amino groups are particularly good for dyeing and printing textiles, such as native and regenerated cellulose, wool and silk using the latest techniques in the present basic agents, such as short and long steaming, exhaust processes, cold dwell processes, two-phase pressure processes and the like. But the dyes are so stable that they can be of the type of alkali there is extensive freedom.

The dyes are also suitable for dyeing synthetic polyamide and polyurethane fibers. The dyeings and prints obtained with the new dyes are notable for their good quality to very good fastness properties, especially wet fastness.

Compared to the one from the Belgian patent specification

6 61 532 and the British patent 10 22 756 known comparable dyes stand out the dyes according to the invention are characterized by a significantly better fixing behavior.

example 1

a) 188 g of 2,4-diaminobenzenesulfonic acid are dissolved neutrally with 1 liter of water. After 122 g of bicarbonate have been added, 341 g of i -chloroethylsulfonyl-endomethylene cyclohexanecarboxylic acid chloride, dissolved in 500 ml of acetone, are added in portions at 5 to 10 ° C. After several hours, the diamino acid can only be detected in traces by chromatography.

b) 69 g of sodium nitrite are now added to the solution of the acid acylated in the 4-position, and the mixture is stirred into 300 ml of 10N hydrochloric acid ^{at 15 to 20 3 C.} The diazo suspension obtained is added to a neutral solution of 330 g of 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone-5. The solution is adjusted to pH 7 by adding about 150 g of soda The coupling is finished after a short time. It separates the dye by the addition of about 15 volume percent potassium chloride, and dried at 40 to 5O ⁰ C in vacuo. It is a water-soluble, yellow powder which, when applied in the presence of alkali, provides wet-fast, clear, greenish-yellow dyeings and prints on cellulose materials using all known techniques.

so The acid chloride used is made by Addition of mercaptoethanol to the diene adduct of cyclopentadiene and acrylic acid. One oxidizes with hydrogen peroxide and then sets the carboxylic acid thus obtained with thionyl chloride to the acid chloride around.

The following table lists other dyes that contain the diazo component just described can be produced:

Coupling component

Hue on
cotton

3-carboxypyrazolone-5

l- (4'-sulfophenyl) -3-methyl-

pyrazolone-5

1 -hydroxy-naphthalene-4-sulfo-

greenish yellow
yellow

scarlet

5 6

Continuation b) Now is diazotized in the usual way. the

Diazo suspension is added to a concentrated one

"_ Solution of 284 ε 1 - (4'-sulfophenyl) -3-carboxy-

Coupling component Baumln "pyrazolon-5. Adding soda becomes neutral

5 and the dye after coupling has ended

deposited by adding potassium chloride.

! -H} droxy-naphtha! In-4,6-di- scarlet red ^He l ' ^ef " ^{ert on} cotton after the reactive

sulfonic acid dyes usual principle light- and wet-fast roi-

2-Hydroxy-naphthalene-3,6-di-scarlet red, pale yellow dyeings and prints. Further coupling

sulfonic acid ¹⁰ solution components, which with the diazo component a)

, _ ίο .. ,, ·, · valuable dyes are in the following

l-Benzoylarnino-8-hydroxy- blaustichigrot _{Tabe "e} r _{au aeführt:}

naphtha-3,6-disulfo acid

2-ureido-5-hydroxynaphthalene- orange l- (4'-sulfophenyl) -3-methyl-

7-sulfonic acid, _s pyrazolone-5 '. yellow

1 - Phenyi-3-carboxy-

Example 2 pyrazolon-5 rotstichiggclb

2-dichlorotriazinyl-amino-

a) 319 g of 1-amino-S-hydroxy-naphthalene ^ o-di- 5-hydroxynaphthalene-

sulfonic acid with 1 1 H ₂ O and 122 g bicarbonate 20 sulfonic acid-7 scarlet fever

touched. To do this, add about 2-ureido-5-hydroxy-naphtha-

5 ° C in the course of several hours 328 g / i-chlorine-insu (fonsäure-7 scarlet fever

ethylsulfonyl - cyclohexanecarboxylic acid chloride, produced 2-acetamino-5-hydroxy-

represents analogous to the acid chloride from Example 1, with naphthalenesulfonic acid-7 .... scarlet

the difference is that here the addition of 25 1-hydroxy-naphthalene

Cyclohexene-4-sulphonic acid, red, obtainable from acrylic acid on butadiene

carboxylic acid used as the starting material. One l-acethylamino-8-hydroxy-

stir for a further 3 hours until the acylation mixture is naphthalene-disulfonic acid-3.6 ruby

can only be diazotized in traces. l-benzoylamino-8-hydroxy-

b) 173 g of 2-aminobenzenesulphonic acid are like 30 naphthalene-disulphonic acid-4,6 ruby
Usually diazotized and with the coupling component described above from

Coupling component a) with the addition of soda Example 2a) ruby

coupled. After the coupling has ended, the pH

the solution to 7 and the dye by Example 4

Adding 18 percent by volume of rock salt salted out. 35

After drying, it provides a red, well watered 503 g of 1-amino-4- (4'-methyl-3'-amino-5'-sulfo-

soluble powder that becomes clear, phenyl) - aminoanthraquinone - 2 - sulfonic acid on cellulose fibers

Red dyeings and prints of good light and dissolved neutrally with about 4 liters of water. In addition one gives

provides very good wet fastness. In the following 130 g bicarbonate and at about 10 ° C in portions

The table lists other dyes that contain 40 341 g / i-chloroethylsulfonyl-cyclohexanecarboxylic acid

the described coupling component a) herged chloride, dissolved in acetone. The mixture is stirred for a few hours

can be adjusted: after and then separates the dye by adding

of potassium chloride. He colors hydroxyl groups

~~ containing materials with the addition of alkali in clear,

Diazo component color on 45 lightfast blue tones.

Cotton can be dyes of similar properties

obtained if one in place of the above

. ... ... .. "-,. the condensation product of 1 -amino-4-bromo-

Aniline-3-sulfuric acid yellowish red anthraquinone-2-sulfonic acid with one of the following

Anihn-4-carboxylic acid red ₅₀ diamines used:

⁴ - ^toluidine bluish red 2,4-diaminobenzenesulfonic acid,

4-methoxyanine-2-sulfonic acid bluish-tinted red 2,5-diaminobenzenesulfonic acid,

4-methylaniline-2-sulfonic acid red 3,5-diamino-4-methyl-benzenesulfonic acid,

Diazo component made of blue tint 3,3'-diamino-4'-methyl-l, r-diphenylsulfone-

spiella) "5'-sulfonic acid.

Example 3

a) 188 g of 2,5-diaminobenzenesulfonic acid are dissolved neutrally with 1.2 l of water and 14 gkrist. Sodium acetate offset. 398 g / f-bromoethylsulfonylcyclohexanecarboxylic acid bromide are simultaneously added dropwise to the solution at 10 to 15 ° C. dissolved in 500 ml of ethylene chloride, and 100 ml of 10n sodium hydrochloride solution, a pH of about 6 is maintained. The mixture is stirred for several hours until the diamino acid only sDurable can be proven.

Example 5

60 300 g of 2-aminonaphthalene-4,8-disulfonic acid are diazotized in the usual way and in acetic acid Solution coupled to 137 g of 2-methoxy-5-methyl-aniline. The dye solution is neutralized and after adding 100 g of bicarbonate with 341 g

65 β- chloroethylsulfonyl-cyclohexanecarboxylic acid chloride acylated. With the monoazo dye obtained after separation and drying, cotton can be processed using one of the methods customary for reactive dyes

η dyed or printed on wet-fast yellow shades will.

Other valuable dyes are obtained if the following diazo and zo components are coupled in an analogous manner and reacted with one of the acid chlorides A or B, where A stands for β-chlorithylsulfonyl-cyclohexanecarboxylic acid chloride and B iir β- chloroethylsulfonyl-endomethylene cyclohexane : carbonic acid chloride stands.

Diazo component

Azo component acid color chloride

2-amino-naphthalene-4,8-disulfonic acid
Aniline-2,5-disulfonic acid

m-toluidine

2,5-dimethylaniline

yellow yellow

Example 6

neutral solution of 319 g of 1-amino-8-hydroxynaphthalene - 3,6 - disulfonic acid. As soon as the acidic coupling is complete, an excess of soda is added to the solution of the intermediate dye product, 1 mol of the 2 - amino - 4 - {β - chloroethylsulfonyl - endomethylene - cyclohexanecarbonyl) - aminobenzenesulfonic acid diazo compound described in Example 1 a) is added and allows the alkaline coupling to come to an end at a pH of about 8.5. The pH is adjusted to 7 and the dye is separated off by adding salt and potassium chloride. This gives a disazo dye which gives black dyeings and prints of good wet fastness on cotton. If the following diazo compounds are used instead of sulfanilic acid for the acidic coupling, valuable dyes are also obtained:

Diazo component of the acidic
coupling

Hue on
cotton

173 g of sulfanilic acid are mixed in the usual way with 270 ml of 10N hydrochloric acid and 69 g of sodium nitrite diazotized. The diazo suspension is added

p-nitroaniline violet

2-Nitraniline-4-sulfonic acid black

4-nitroaniline-2-sulfonic acid black

509 584,

Claims (1)

Claim: Process for the preparation of new water-soluble dyes of the general formula F - \ NH - C - R - SO ₂ - Z /, " wherein F is the radical of an azo, anthraquinone or phthalocyanine dye containing sulfonic acid groups, R is a cyclohexyl or endomethylene cyclohexyl radical, Z is a vinyl group or a / »'- bromine or p'-chloroethyl radical, m 1 or 2, characterized in that one Dye of the general formula F- (NH ₂ ). or in the case of azo dyes, _{diazo and / or coupling components carrying the radical - NH 2} with an acid halide of the general formula