DEC0008849MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: February 6, 1954. Advertised on February 9, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22a GROUP 6

C 8849 IVb / 22a

Dr. Henri Riat, Ariesheim, and Dr. Oscar Weber, Reinach (Switzerland)

have been named as inventors

CIBA Aktiengesellschaft, Basel (Switzerland)

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

Ancestors for the production of new metal-containing azo dyes The priority of registrations in Switzerland from February 12th, 1953 and January 4th, 1964

is iii claim geiiorhirien

The invention relates to a process for the preparation of new metal-containing azo dyes which the general formula

R ₁ -N = N

ίο correspond, in which Me contains nickel or copper, X contains a, in which Y is a cation.

Oxygen atom, the grouping —COO— or -OCH ₂ GOO-, R ₁ -O- and R ₃ -O ^ - each denote the remainder of an oxynaphthalene monosulfonic acid bonded to a different azo group in d-position to the oxy group; each of these radicals being a YÖ as a further substituent ^; —Ö ₂ ^r S — O— alkylamino groups, e.g. B. One of the Forriel

YÖ-.O ₂ SO-CH ₈ -CHoNH

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C 8849 IVb / 22a

The metal-containing dyes of the formula (1) can be prepared by disazo dyes containing ester groups, which of the general formula

OH

R ₁ -N = N- <

N = NR ₂

correspond, in which U is an oxy, carboxy, carboxymethoxy group or the radical YO-O ₂ S — O—, in which Y stands for a cation, and the radicals R ₁ and R _{2 have} the meaning given above, with nickel- treated or copper-releasing agents.

Salts of divalent nickel or salts are expediently used as nickel or copper-releasing agents Used copper, "such as nickel (II) sulfate or copper (II) sulfate, and also compounds that contain these Contains metals in complex bonds. In particular, nickel or copper amine complexes are used for this purpose suitable e.g. B. those from ammonia, alkylamines, such as ethylamine, morpholine, ethanolamine, pyridine, picolines or piperidine available complexes Nickel or copper compounds.

Those containing ester groups required for treatment with nickel- or copper-releasing agents Disazo dyes of the formula (2) are ζ. B. obtained by coupling a tetrazotized di-. amines of the formula

HX

XH

NH,

in which XH denotes an oxy, carboxy or carboxy methoxy group with in the o-position to the oxy group coupling oxynaphthalenesulfonic acids, which have an oxyalkylamino group as further substituents, for example have an oxyethylamino group, and introduction of the acidic sulfuric acid ester group into the aliphatically bonded oxy groups of the disazo dyes thus obtained.

As diamines of the formula (3) there are 3, 3'-dioxy-4, 4'-diaminodiphenyl, 4,4'-diaminodiphenyl-3, 3'-dicarboxylic acid and 3,3'-di- (carboxymethoxy) -4,4'-diaminodiphenyl.

As oxyalkylamino-containing oxynaphthalene sulfonic acids are preferably those with a low molecular weight alkyl radical used, z. B. such

with a butyl, propyl or ethyl radical. There can also be two oxyalkyl groups on the same nitrogen atom be bound. The oxyalkyl groups are advantageously introduced in accordance with known methods Methods, for example by using the aminooxynaphthalene sulfonic acids on their amino groups Oxyhaloalkylenes such as epichlorohydrin, glycerol chlorohydrin or a-chloro-y-oxypropane converts. When α-chloro- / S-oxyethane proves to be particularly advantageous here (Glycol chlorohydrin, ethylene chlorohydrin).

In addition, certain aminooxyriaphthalenesulfonic acids can also be used with the help of alkali bisulfites with. Aminooxyalkyl compounds, such as ethanolamine, be condensed.

Oxynaphthalenesulfonic acids have proven to be particularly valuable of the formula ■

HO

HO ₃ S

I »| -NH ₂ _" (CH ₂ -CH ₂ OH) _{n 7 <J}

where η is an integer with a value of at most 2 and the group

-NH ₂ ^ (CH ₂ -CH ₂ OH) ₇₁

in a ^ position of the six-membered ring marked I. is located.

The following oxynaphthalenesulfonic acids all lead to valuable dyes:

2 - (/ 3-oxyethyl) -amino- 8-oxynaphthalene-6-sulfonic acid,

2-Di - (ß- oxyethyl) -amino-8-oxynaphthalene-6-sulfonic acid,

2- (ß - oxyethyl) - amino - 5 - oxynaphthalene - 7 - sulfonic acid.

2-di- (j8-oxyethyl) -amino-5-oxynaphthalene-7-sulfonic acid,

2- (ß- oxypropyl) - amino - 5 - oxynaphthalin-y ^ sulfonic acid,

2- (γ - oxypropyl) - amino -.5 - oxynaphthalene-7-sulfonic acid,

2- (oxybutyl) amino-5-oxynaphthalene-7-sulfonic acid and

2 ~ (β, γ.- Dioxypropylamino) -5-oxynaphthalene-7-sulfonic acid.

The conversion of the aliphatically bonded oxy groups present in the azo dyes into the acidic sulfuric acid ester groups is usually expedient with chlorosulfonic acid in the presence of a tertiary base, e.g. B. a pyridine base, such as picoline or pyridine, carried out itself. Those to be esterified Dyes still contain aromatically bound oxy groups, and it generally means none Disadvantage if these are also esterified. In the case of the oxy groups, which are part of a subsequent Participate in metallization and o, o'-dioxyazo metal complex compounds should result, the sulfuric acid ester group in the treatment with the metal donor Middle easily split again. The esterification can also take place in concentrated sulfuric acid be carried out, the aromatic oxy groups generally not being esterified.

As can be seen from the above, those are obtainable by the method metal-containing dyes of particular interest, which of the formula

-Me -— O

O-

R ₁ -N = N

correspond, in which Me one of the metals nickel and copper and R ₁ —O— and R ₂ —O— each have the remainder of one in the o-position to the —O — Me group on the azo

657/165

C 8849 IVb / 22 a

oxynaphthalene monosulfonic acid bonded to a group, each of these radicals containing a YO — O ₂ S — O — alkylamino group as a further substituent, in which Y represents a cation.
The formulation used here for the metal-containing dyes undoubtedly reflects the correct stoichiometric amounts of metal and the correct position of the metal atom in the complex. In contrast, the distribution of major and minor valences in the complex bond of the metal is not yet clearly established.

The new metal-containing dyes of the formula (i) are suitable for dyeing and printing a wide variety of materials Materials, especially made of fibers containing cellulose, such as linen, cotton or rayon and rayon made of regenerated cellulose. This is where they stand out

.. · both by good drawing power and by a good leveling power and result in interesting, in some cases very pure shades of good lightfastness, which is retained even with the usual anti-crease treatments.

From the patent specification 889 662 a dye is known which is obtained by coupling 1 mol of a tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with 2 moles of 2- (4'-carboxymethoxyphenyl) -amino-5-oxynaphthalene-7-sulfonic acid and then

... ßende treatment of the resulting disazo dye with copper-releasing agents. Farther a copper-containing disazo dye is known from the patent specification 858 438, which is obtained by Coupling of 1 mol of the above-mentioned tetrazo component with 1 mol of 2, S-dioxynaphthalene-o-sulfonic acid and 1 mole of a-phenylamino-S-oxynaphthalene-4 ', 7-disulfonic acid and subsequent exposure to copper-releasing agents.

Compared to these dyes, the dyes obtained according to the process show the preference on cotton To result in colorations that are more washable and can be etched in pure white.

In the following examples the parts mean, unless otherwise stated, parts by weight,

_; the percentages percentages by weight.

example 1

18 parts of chlorosulfonic acid are added dropwise to 70 parts of pyridine with cooling. In this mixture contributes 30 to 40 ⁰ with good stirring, 18 parts of by alkaline coupling of 1 mole of tetrazotised 3, 3'-dioxy-4, 4'-diaminodiphenyl with 2 moles of 2- (di- (S - oxyäthyl) - amino-5-oxynaphthalene-7-sulfonic acid available powdered disazo dye and stirred for 1 hour at 40 ⁰ and 2 hours at 50 to 55 °. the viscous blue solution is diluted with a little water, made alkaline with sodium carbonate, the pyridine under reduced pressure distilled off and the dye salted out and filtered off.

To convert the paste into the copper complex compound, it is dissolved in 300 parts of warm water and an ammoniacal copper sulfate solution (corresponding to 10 parts of CuSO ₄ —SH ₂ O) is added at 70 °. It is kept at 70 ° for a few minutes, saturated with sodium chloride and allowed to cool, the dye separating out completely over the course of several hours. It is filtered off and dried in vacuo. It dissolves very easily in water with a blue color and dyes cotton in very pure blue tones. The coloring is extremely lightfast.

16 parts of the disazo dye obtained by coupling are used as the starting dye of ι mol of tetrazotized 3, 3'-dioxy-4, 4'-diaminodiphenyl with 2 moles of 2 - (/ 9-oxyethyl) amino-8-oxynaphthalene-6-sulfonic acid, and if you proceed according to the information in the example, you also get one Easily soluble dye that dyes cotton in very lightfast, gray-blue tones.

Example 2

I. II Diazo component ■ Azo component I. 3, 3'-dioxy-4, 4'-di- 2- (ß-oxyethyl) -amino- aminodiphenyl 5-oxynaphthalene-7-sulfone acid 2 the same 2 - (/ 3-oxypropyl) -amino- S-oxynaphthalene - ^ - sulfone- acid 3 the same 2- (y-oxypropyl) -amino- 5-oxynaphthalene-7-sulfone acid 4th the same 2-oxybutyi-amino- 5-oxynaphthalene-7-sulfone acid 5 the same 2 - ((S, y-dioxypropyl) - amino-5-oxynaphthalene-. 7-sulfonic acid

18 parts of the finely powdered dye from 1 mole of tetrazotized 3,3'-dioxy-4,4'-diaminodiphenyl and 2 moles of 2- (di- / 3-oxyethylamino) -5-oxynaphthalene-7-sulfonic acid (see Example 1) registered in 150 parts of concentrated sulfuric acid, the temperature being kept at about 30 ⁰ by external cooling. After 2 hours, the mixture is poured onto ice water and saturated with sodium chloride. The dye is filtered off after several hours, washed with saturated sodium chloride solution and converted into the copper complex compound according to the method of Example 1; which has practically the same properties as the dye of Example 1, 2nd paragraph.

One arrives at dyes with similar properties if one follows the information in the example 2, but starts from disazo dyes, which are listed in the table below. They can be obtained by coupling 1 mol of the tetrazo compound of the diamine mentioned in column I. with 2 moles of the azo component listed in column II.

Finally, the dye obtained by coupling 1 mole of tetrazotized material is used 3,3'-Dioxy-4, 4'-diaminodiphenyl with 2 moles of i - (/ S-oxyethyl) amino-8-oxynaphthalene-4-sulfonic acid, so receives

509 657/165

Claims (2)

ihan a copper complex, the Bäuriiwölle - iti colors green-blue Törieri. If one leaves nickel sulfate instead of Küpfersülfät to the dyes esterified according to the above information have an effect, so that easily soluble nickel complex compounds are obtained, the Bäürnwölle in reddish blue Coloring shades with very good lightfastness. Example 3 io parts of the feinpülyerisierti dye from 1 mol tetra-doped 4,4'-oil iodiphenyl-3; 3'-dicarb brisic acid . ·: And 2 mol of 2 - (/ 3-Öxyäthyl) -ämiriö-5-oxyriäphthaliri-7-sulfohäure are dissolved in 10 parts concentrated sulfuric acid. After 1 hour the solution will be poured into ice water. The dye deposited with sodium chloride is then made more ammoniacal with Copper sulphate is dissolved in the copper body convicted. This dissolves in water with red-blue color urid dyes Baüiri wool in blue ao purple tones. If you use .in .place "of the described output the disazöf arbstdff that mäh receives by coupling 1 mole of tetrazotized 3,3'-di- (carboxyrüethöxy) -4, 4'-diäminodiphenyl with 2 moles of 2 - (di-ß- oxyethyl) - ämirio- 5 - oxynaphthälin- 7 - sulforic acid, in this way a dye is obtained which produces reddish blue tones on cotton. ^ ÄTENTÄNSPRÖCHE: i. Process for the production of current metal-containing Azo dyes, characterized in that that mäh disazo dyes of the general formula R ₁ -N = , _ N = N-Rs in which U denotes an oxy, carboxy, carboxymethoxy group ¹ or the radical YO-SO ₂ —0—, in which Y is a cation, R ^ and R | each denotes the remainder of an iri ö -stellurig to the oxy group to the azo group bonded Öxyriäphthalmriiöribsülfonsäure, each of these remainders as a further Sübstitueriten one YO-O ₂ S-O-alkylamino group e.g. B. one of the Forriiel YO-O ₂ SO-CH ₂ CH ₂ -NH- contains, where Y is a cation, treated with rii'ckel- or kupferäbgeberiden Mittelri. 2. Method gerriäß Ärisprüch i, characterized in that that rriari an initial color of the formula OH (YO-O ₂ S - O - CH ₂ CH ₂ ) "H ₂ _ _B N - NH ₂ __ _Ä (CH ₂ CH ₂ -O-SO ₃ -OY) _Ä is used, in which U has the meaning given, Y is a cation, η is an integer with a value of at most 2 and the substituents - NH ₂ _ "(CH ₂ CH ₂ O —SO ₂ —OY) _W are in a ^ -Position of the naphthalene nuclei. '· ■ · Referred publications: German patent specifications No. 889 662, 858 438. 509 657/165 1.56