DE1150473B - Process for the preparation of unsymmetrical polyazo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

F30197IVc / 22a

EDUCATE: DECEMBER 28, 1959

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: JUNE 20, 1963

Unsymmetrical polyazo dyes are generally used built up by stepwise coupling in such a way that one mole of a tetrazo compound initially combined with 1 mol of a first azo component and then the resulting diazo compound can react with 1 mole of a second azo component. This procedure results in numerous In cases of unsatisfactory results, because whenever the half-sided coupling does not work exactly, Mixtures of dyes arise. If the azo components used couple very quickly, is this procedure is not applicable at all. In this case you get exclusively or predominantly the symmetrical polyazo dye with the first Phase used azo component.

It has now been found that these difficulties can be avoided by using the tetrazo compound first with HiKe of a suitable amine component on one side into a diazoamino compound converts, this then couples with any azo component to the diazoaminoazo dye, in this splits the diazoamino group with acid to form the diazoazo compound, which then in turn with any azo component different from the first azo component to the unsymmetrical one Polyazo dye can be further implemented.

The diazoaminodiazo compound obtained in the first stage from a tetrazo compound and a suitable stabilizing amine corresponds to the general formula

R ₃ -NN = NR ₂ -XR ₁ -N = N

in which R ₁ and R _{0 represent} aromatic radicals which can carry substituents customary in azo compounds, such as halogen, nitro, alkyl, alkoxy, sulfonic acid or carboxyl groups, R ₃ · N— is the radical of one primary or secondary amine of the aliphatic, cycloaliphatic or aromatic series, and in which X is a single bond or a bridge member, such as _N = N-, —NH-CO — NH-, -NHCO, -SO ₂ -, —CO—, - CH = CH-.

For example, the tetrazo compounds of benzidine, tolidine, dianisidine, 4,4'-diaminoazobenzene, 4-4'-diaminostilbene, 4-4 ^/ -diaminodiphenylurea, 4-4'-diaminobenzoylaminobenzene and their substitution products are suitable for the process.

The primary or secondary amines which are used as stabilizing amines according to the method come, must be matched to the constitution of the tetrazo compound in order to achieve the best possible results to achieve. Tetrazo compounds can thus be produced using processes for production unsymmetrical polyazo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Kurt Breig, Cologne-Flittard,

and Dr. Fritz Suckfüll, Leverkusen, have been named as the inventor

lower coupling energy most suitable with aliphatic amines in the corresponding diazoaminodiazo compounds transfer, while with tetrazo compounds with stronger coupling energy, aromatic amines can also be used. These considerations are also important in terms of durability and, on the other hand, cleavage the diazoamino group in the diazoaminoazo dyes. Suitable stabilizing amines are primary and secondary amines of the aliphatic, cycloaliphatic and aromatic series as well their substitution products, including sarcosine, methyltaurine, alkylethanolamine, diethanolamine, S-sulfo ^ -aminobenzoic acid, 5-sulfo-2-alkylaminobenzoic acid, S-chloro-1-aminobenzoic acid and phenylglycine carboxylic acid.

The azo components used in azo chemistry customary compounds are used, such as pyrazolones, pyrazolone sulfonic acids, acetoacetanilides and arylides of 2,3-oxynaphthoic acid, naphthols, aminonaphthalenes, naphtholsulfonic acids, naphthylamine sulfonic acids, Aminonaphthols, aminonaphtholsulfonic acids.

A particular embodiment of the process consists in that a tetrazo compound stepwise with two suitable amines of different composition into an unsymmetrical bisdiazoamido compound convicted. As a result of the different stability of the diazoamide groups, this bisdiazoamido compound can form one side of one Diazoaminodiazo compound are split, their immediate production difficulties prepares. Such a reaction path can be advantageous, for example, if the stability of the

309 617/233

permanent diazoamido groups are subject to special requirements.

The new process enables the production of a very large number of known and previously not described unsymmetrical polyazo dyes. In many cases the procedure offers the possibility of known asymmetrical dyes, which so far only under difficult or considerable conditions Labor could be represented in the desired purity, in a simple manner and greater Build purity.

From the German patent specification 87 616 it is already known that one diazoaminodiazo compounds of Diphenyl series can couple on one side by means of the free diazo group; but there is no possibility here discussed building asymmetrical polyazo dyes with half-stabilized tetrazo compounds. Rather, it has been expressly pointed out in the example of the patent that a

COO

"O ₃ S

NH-N = N-

to precipitate in red crystals. After stirring for 1.5 hours, the reaction is complete, and so is the diazoaminodiazo compound can be isolated. It is expediently processed further as a paste.

Instead of 5-sulfo-2-aminobenzoic acid you can, for. B. also the 5-sulfo-2-methylaminobenzoic acid or use 5-sulfo-2-ethylaminobenzoic acid.

COO

Excess of azo component (naphthionic acid) must be avoided in order to prevent the formation of a disazo dye to prevent in place of the monoazo connection. Disazo dyes, the formation of which occurs during Application of excess naphthionic acid would allow them to be constructed asymmetrically and as undesirable by-products have been considered.

example 1

18.4 parts by weight (0.1 mol) of benzidine are diazotized in a known manner. The tetrazo solution is poured, with thorough stirring, into a solution which contains 23.9 parts by weight (0.11 mol) of 5-sulfo-2-aminobenzoic acid, 20 parts by volume of 36 ° Be sodium hydroxide solution and 25 parts by weight of sodium acetate dissolved in 120 parts by volume of water. After combining the two solutions the _pH value is 4.5 to 4.7. In a short time, the diazoaminodiazo compound of the following formula starts

25.4 parts by weight (0.1 mol) of 1- (4'-sulfophenyl) -3-methylpyrazolone- (5) are dissolved with 10 parts by volume of 36 ° Be sodium hydroxide solution in 70 parts by volume of water. While stirring vigorously and adding at the same time from 35 parts by volume of 15% soda solution, the paste of the diazoamhiodiazo compound is carried into this Solution one. After complete dissolution has occurred, the diazoaminoazo dye of the formula

"O ₃ S-

- NH - N = N ■

-N = N-C-

CH ₃

HO

^X N

.N

SO ₃

be isolated with salt. The dye paste obtained is then dissolved in about 500 parts by volume of water 50 ° C and heated by adding 50 volume

share hydrochloric acid (rf = 1.19) made Congo acidic. Of the rapidly forming diazoazo dye of the formula

CH _a

fails completely and can be isolated immediately. It is transformed into a solution as a paste with vigorous stirring of 26.3 parts by weight (0.1 mol) of 2,3-oxynaphthoic anilide in 10 parts by volume of 36 ° Be sodium hydroxide solution,

Entered 20 parts by volume of alcohol and 80 parts by volume of water. After stirring for 4 hours, the Clutch finished. The reaction can be accelerated somewhat by adding 5 parts by volume of pyridine. The obtained dye of the formula

N = N

CO OH

NH

N = N-C --- C-CH,

HO - C _x , N

SO _S

has failed completely and can be isolated. When dried, it is a dark powder that can be found in rubbing in oil gives a corinth shade.

Used instead of 2,3-oxynaphthoic anilide the equivalent amount of 2,3-oxynaphthoic acid-2'-methylanilide, a dye is obtained which gives a similar shade.

At & piel 2

18.4 parts by weight (0.1 mol) of benzidine with 23.9 parts by weight of 5-sulfo-2-aminobenzoic acid, such as given in Example 1, converted into the diazoaminodiazo compound.

The paste obtained is, with vigorous stirring, in a solution of 27.1 parts by weight (0.1 mol) of acetoacetic acid-4'-chloro-2 ', 5'-dimethoxyanilide and 10 parts by weight of soda in 10 parts by volume of 36 ° Be sodium hydroxide solution, 20 parts by volume of alcohol and 90 parts by volume Water entered. The coupling can be accelerated by adding 5 parts by volume of pyridine.

The reddish-tinged yellow diazoaminoazo dye obtained is, after isolation, stirred with 400 parts by volume of water and heated to 50.degree. 50 parts by volume of hydrochloric acid (d = 1.19) are then added with vigorous stirring. The hue of the suspended dye changes to dark red. The resulting diazo dye remains precipitated and can be coupled on immediately after isolation. For this purpose, the dye paste is introduced into a solution of 0.1 mol of 2,3-oxynaphthoic anilide, as described in Example 1, with stirring. After the coupling is complete, the isolated and dried pigment dye is a dark red powder, the color of which is corinthian when rubbed with oil.

Example 3

Following the procedure of Example 1 makes a paste of the diazoazo dye of the formula

SO ₃

prepared and this with thorough stirring in a solution of 38.4 parts by weight of l- [4 ', 8'-disulfonaphthyl- (2')] -3-methylpyrazolone- (5) entered in 20 parts by volume of sodium hydroxide solution 36 ° Be and 300 parts by volume of water. As the clutch progresses the diazoazo compound goes into solution. The resulting dye can then be isolated with salt. When dried, it is a light red powder that dyes cotton and wool in orange tones.

If one uses in place of the l- [4 ', 8'-disulfonaphthyl- (2')] -3-methylpyrazolon- (5) as azo component the corresponding amount of acetoacetic acid-4'-chloro-2 ', 5'-dimethoxyanilide, in this way a dye is obtained which, when rubbed in oil, has a yellow-brown color shows.

Example 4

The paste of the diazoazo dye, which was prepared according to the instructions in Example 1, is stirred into the solution of 18 parts by weight of the chlorohydrate of 0.1 mol of a-naphthylamine in 200 parts by volume of water. Were to admit by 8 parts by weight of sodium acetate the _pH value is adjusted to 6.7. After stirring for 4 hours, 10 parts by volume of pyridine are added. The obtained dye can after stirring overnight

7 8

to be isolated. In an oil rub it shows a tene dye which differs in color from that

brown hue. described above is not essential, however

If you use a little more water-soluble instead of a-naphthylamine.

26.7 parts by weight of l-amino ^ -ethoxynaphthaun-o-. ,

sulfonic acid, 5 examples are obtained with the same procedure

a water-soluble dye which, after staining, yields a tetrazonium salt solution of 24.4 (0.1 mol)

Cotton, diazotization on the fiber and parts by weight of dianisidine is poured into a

treatment with 1,3-diaminobenzene gives a deep brown. Solution of 8.3 parts by weight (0.11 mol) of N-methyl

. -ι, - N-ethanolamine and 25 parts by weight of sodium acetate

Example S ₁₀ J _{n 2} qo parts by volume of water poured in. The _pH value

26.4 parts by weight (0.1 mol) of 4,4'-diaminodiphenyl- is then 4.5 to 4.7. By adding in parts

3-sulfonic acid with 5.3 weight parts of sodium carbonate in the sodium carbonate solution of dilute _H p is the value

250 parts by volume of water at 60 ° C dissolved. The set on solution to 6.5 to 6.7. After the approach

Ice-poured solution is mixed with 28 parts by volume of salt with 20% sodium chloride, begins after

acid (J = 1.19) and at 5 ° C with 21 vol- 15 a short time the diazoaminodiazo-

share 33% sodium nitrite solution diazotized. The connection in deep red crystals. After an hour

clarified diazotization solution is added with thorough stirring, the compound can be isolated.

Stirring into a solution containing 23.9 parts by weight. The paste obtained is stirred into a

(0.11 mol) 5-sulfo-2-aminobenzoic acid, 20 parts by volume solution of 17.4 parts by weight of l-phenyl-3-methyl-

36 ° Be sodium hydroxide solution and 25 parts by weight of sodium pyrazolone (5) in 10 parts by volume of 36 ° Be sodium hydroxide solution,

contains acetate dissolved in 80 parts by volume of water. After 10 parts by volume of pyridine and 100 parts by volume of water

the union of the two solutions is added to the _pH value. The resulting orange diazo

5.5. After stirring for 1 hour, the diazoamino-aminoazo dye can be used after stirring overnight

diazo compound isolated isolated by addition of salt. To split the diazoamido group is

will. 25 add the dye paste with 200 parts by volume of water.

The paste obtained is stirred for further coupling and heated to 50 ° C., with complete

enters a solution of 17.4 parts by weight (0.1 mole) of solution. In this solution are added 50 volumes

l-Phenyl-3-methylpyrazolone- (5) in 10 parts by volume parts hydrochloric acid (d = 1.19). Immediately afterwards occurs

Sodium hydroxide solution 36 ° Be, 10 parts by volume of pyridine and a color change to dark red. With Na-

100 parts by volume of water with thorough stirring. 30 trium chloride can be the resulting diazoazover-

After stirring for 2 hours, the diazoamino dye bond can isolate.

insulated with salt. The dye paste is The paste obtained is stirred into a

dissolved in 400 parts by volume of water and heated to 50 ° C. solution of 30.4 parts by weight (0.1 mol) of 2-oxy-

warms. Then 50 parts by volume of naphthalene-3,6-disulfonic acid and 16 parts by weight are added

share hydrochloric acid (J = 1.19) made Congo acidic. The 35 soda added in 100 parts by volume of water. Of the

The diazoamino group is split up immediately after stirring overnight with sodium chloride

tan, the resulting diazoazo dye producing a completely isolated dye on wool

keeps failing and can be isolated. exercise.

For further coupling, the paste thus obtained is used in place of the 2-oxynaphthalene-3,6-

while stirring in a solution of 29.3 weight- 4 ° disulfonic acid the corresponding amount of 2,3-oxy-

share (0.1 mol) 2,3-oxynaphthoic acid-2'-methoxy-naphthoic acid-2'-ethoxyanilide as azo component,

anilide in 10 parts by volume of caustic soda 36 ° Be, 20 vol- so you get a water-insoluble disazo

by volume of alcohol and 80 parts by volume of water.

wear. After stirring overnight the colored tone will show

fabric insulated; he gives a corinth-colored oil rub. 45 _B. . ..

Instead of the l-phenyl-3-methylpyrazolone- (5), example 7

one also the equivalent amount of l- (4'-sulfophenyl) - The obtained according to the data of Example 6

Use 3-methylpyrazolone- (5). The resulting paste of the diazoaminodiazo compound of the formula

CH ₃

OH-CH ₂ -CH ₂ -NN = N - / V ~ / \ -N = N

H ₃ CO OCH ₃

is mixed with 100 parts by volume of water. This after for further coupling as a paste with stirring in

Slurry is added with stirring to a solution of 27.1 parts by weight of acetoacetic acid

Solution of 25.4 parts by weight of 1- (4'-sulfophenyl) -3- 4'-chloro-2 ^/ , 5'-dimethoxyanilide and 10 parts by weight

methylpyrazolon- (5) and 15 parts by weight of soda in 60 soda, in 10 parts by volume of caustic soda 36 ° Be, 20 vol-

Parts by volume of water. The resulting diazolum parts alcohol and 100 parts by volume water.

aminoazo dye precipitates and will wear after isolation. To speed up the clutch will be

tion for splitting the diazoamino group with 10 parts by volume of pyridine added. After stirring

Parts by volume of water are stirred up and the dye can be isolated at 50 ° C. overnight. He gives

warms. Almost complete solution occurs here. 65 after drying in an oil grind, a yellow-

Adding 50 parts by volume of hydrochloric acid (d = 1.19) gives a pungent brown.

If the water-insoluble di-

azoazo dye. This is isolated and the dimethoxyanilide as the azo component is the 2,3-oxy-

naphthoic anilide, a dye is obtained which has a bluish tinge when rubbed with oil Corinth tone shows.

Example 8

A tetrazo solution of 24.4 parts by weight (0.1 mol) of dianisidine is stirred into a solution of 25.7 parts by weight (0.15 mol) of 5-chloro-2-aminobenzoic acid and 25 parts by weight of sodium acetate in 15 parts by volume of sodium hydroxide solution 36 ° Be and 400 Parts by volume of water entered. The _pH value is set to 6.5 to 6.8 by addition of a little sodium carbonate solution. After stirring for about 2 hours, the diazoaminodiazo compound has completely precipitated. It can be isolated as a paste and, as described in Examples 6 and 7, processed further.

Instead of 5-chloro-2-aminobenzoic acid, diethanolamine can also be used as a stabilizing amine will. The diazoaminodiazo compound obtained therefrom has a somewhat better durability compared to the analogous compound prepared from 5-chloro-2-aminobenzoic acid.

Example 9

The tetrazo compound of 21.2 parts by weight of tolidine is, as described in Example 1, with 23.9 parts by weight of 5-sulfo-2-aminobenzoic acid converted to the diazoaminodiazo compound.

Instead of 5-sulfo-2-aminobenzoic acid, for example, 5-sulfo-2-methylaminobenzoic acid can also be used use.

By coupling the diazoaminodiazo compound with l- (4'-sulfonphenyl) -3-methylpyrazolone- (5) the corresponding diazoaminoazo dye is obtained. This can be with acid at 50 ° C for Split diazoazo dye, which in turn by coupling with 2,3-oxynaphthoic acid-2'-methoxyanilide is converted into the unsymmetrical disazo dye. This results in an oil grinding a Corinth.

Example 10

The tetrazo compound of 21.2 parts by weight of 4,4'-diaminoazobenzene can be, as in Example 1 described, with 23.9 parts by weight of 5-sulfo-2-aminobenzoic acid into the corresponding diazoaminoazo compound convict. If you now use the method of the previous examples as the first azo component l- (4'-sulfophenyl) -3-methylpyrazolon- (5) and, as the second azo component, 2,3-oxynaphthoic acid-2-ethoxyanilide, in this way a dye is obtained which, when rubbed in oil, produces a corinth.

A water-soluble asymmetrical trisazo dye is obtained if one takes the place of the 2,3-oxynaphthoic acid-2'-ethoxyanilids the corresponding amount of l-oxynaphthalene-4-sulfonic acid is used. This dye dyes wool in red tones.

Claims (1)

PATENT CLAIM: Process for the preparation of asymmetrical polyazo dyes, characterized in that a diazoaminodiazo compound of the formula R ₃ -NN = NR ₂ -XR ₁ -N = N wherein R ₁ and R _{2 represent} the aromatic radicals, R ₃ -N— denotes the radical of a primary or secondary amine of the aliphatic, cycloaliphatic or aromatic series and X represents a single bond or a bridge member, couples with an azo component in the diazoaminoazo compound obtained splits the diazoamino group to form the diazo group and then couples it with an azo component different from the first azo component. Considered publications:
German patent specification No. 87 616. A coloring table was displayed when the application was announced. © 309 617/233 6.63