DE1024652B - Process for the preparation of dyes of the oxazine series - Google Patents

Description

kl. 22 c 4

INTERNAT. KL. C 09 L

PATENT OFFICE

C 10477 IVb / 22 c REGISTRATION DATE: DECEMBER 23, 1954

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EXPLAINED: FEBRUARY 20, 1958

It has been found that new, valuable dyes of the oxazine series are obtained if 2 mol Cyanuric halide on the one hand with 1 mol of a diaminodioxazine of the formula

Cl

N Λ .0,
H ₂ NR ₁ -HN-R ₂ I jj I

0, ^V N ^
Cl

R ₂ -NH-R ₁ -NH ₂ (D.

IO

where R _{1 is} a benzene radical and R _{2 is} a sulfonic acid group-containing benzene ring condensed with the hetero ring I, and on the other hand condenses with 2 moles of a cyclic monoamine free of oxazine rings and optionally exchanges the halogen atoms still present on the triazine radicals for amino groups.

Dioxazines of the above composition, e.g. B. those of the formula

Process for the preparation of dyes of the oxazine series

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

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

Claimed priority: Switzerland from December 28, 1S53

Dr. Karl Seitz, Neu-Allschwil,

and Dr. Walter Anderau, Binningen (Switzerland),

have been named as inventors

Cl

HO ₃ S-

H ₂ NR ₁ -HN-

Ό '

/ ⁰ V

^: N

/ '■■

-NH-R ₁ -NH ₂ -SO ₃ H

(2) Tetrachloroquinone (chloranil) with 2 moles of a compound of the formula

H SOoH

Cl

30th

in which R _{1 has} the meaning given can be prepared by methods known per se. For example, by condensing 1 mole of 2,3,5,6-

HOoS HN-R ₂ -NH-R ₁ -NH-ACyI

where R ₁ and R _{2 represent} benzene radicals, the —NH groups are everywhere in the p-position to one another and the sulfonic acid group is in the o-position to the —NH — R ₁ group, compounds of the formula

Cl

ACyI-HN-R ₁ -NH-R ₂ -NH- / ' ^X =

O = I

Cl HN-R ₂ -HN-R ₁ -NH-ACyI

SOoH

produce, treat them with ring-closing agents and split off the acyl groups. The ring closure is advantageously carried out with free sulfur trioxide containing Sulfuric acid (oleum), and for splitting off the acyl groups, z. B. a treatment at higher Temperature with dilute hydrochloric acid as appropriate. As already indicated, the cyanuric halide can e.g. B. reacted in a molecular ratio of 2: 1 with the diaminodioxazines of the formula (1) and the condensation products thus obtained then further condensed in a molecular ratio of 1: 2 with cyclic monoamines will. However, the halogen compounds can also be used in an equimolecular ratio in reverse order condense with oxazine ring-free cyclic monoamines and then these in a molecular ratio of 2: 1 React condensation products with diaminodioxazines of the formula (1).

Primary or secondary cyclic monoamines can be used, e.g. B. those which are heterocyclic Rings or aromatic rings, such as naphthalene or benzene rings or more highly condensed ring systems, possibly also two or more non-condensed,

709 280/332

identical or different rings. By choosing the monoamines, the color of the end products can be determined of the present proceedings. So you can z. B. colorless to slightly colored monoamines or those without dye character, such as aminobenzenes, aminonaphthalenes, aminodiphenyl compounds, amino-aroylaminobenzenes, Aminochrysen, aminopyrene, aminobenzenecarboxylic acids, aminooxybenzenecarboxylic acids, cyclohexylamine or aminophenylbenzothiazoles.

Of the colored monoamines, the yellow, amino group-containing dyes of Meaning. These can be chosen from different classes of dyes, for example monoamines the azine series or the anthraquinone series into consideration. Particularly noteworthy are the yellow monoaminoazo dyes, and among these are especially the amino monoazo dyes of the formulas

H ₂ N - R ₃ - N = N - R ₄

H ₉ N - R, - X - R, - X - R _d

(5)

(6)

to mention. In these formulas, R ₃ , R ₄ and R _{5 are} benzene radicals, and in formula (6) one X is an azo group and the other X is a - CO - N H group. The bridge members (- N = N - and ■ —-CO —- NH—) between the benzene radicals and the amino groups are preferably in the m- or p-position to one another. The benzene radicals can also contain other substituents; For example, the radical R ₄ in the p-position to the - N = N - or - CO - N Η group by an oxy group and in

ίο o-position to this through a carboxylic acid group be substituted.

After the condensations with the diaminodioxazine and the monoamine have taken place, the can third halogen atoms still present in the two triazine rings, if desired in a manner known per se Way to be replaced by amino groups. As a result, an improvement in the drawability can still be achieved are, but the other coloring properties are not significantly changed. The consortium

ao densations of the halogen compounds with the aminooxazines or the other amines can in itself be carried out in a known manner.

The dyes obtainable by the present process correspond to the formula

ii [. '

R ₆ -NH-C _x X-HN-R ₁ -NH-R ₂ I.

^X NO

Cl

Cl

N '"' N

R ₂ -HN-R ₁ -NH-C

C-HN-R ₆

wherein R _{1 is} a benzene radical, R _{2 is} a benzene ring containing sulfonic acid groups and fused to the hetero ring I, R _{6 is} an oxazine ring-free cyclic radical and Y is an amino group or a halogen atom.

These new dyes are suitable for dyeing and printing a wide variety of materials, e.g. B. such of animal origin, such as leather, silk and wool, or of synthetic fibers made from casein, from super polyamides or Super-polyurethanes. Above all, they have good drawability for cellulosic materials such as paper, Linen, cotton, or products made from regenerated cellulose, such as rayon, rayon and cellulose films, on. The colorations produced on cellulosic materials with the new dyes are noticeable in the Usually characterized by the purity of the shade and good lightfastness. The lightfastness is generally also not significantly affected by the usual treatment with anti-crease agents.

The dioxazine dyes of the formula ( 7), the residues of which R _{6 represent} benzene residues, due to a significantly better drawability on cellulose-containing fibers. The dyeings obtained on cellulose-containing fibers with these new dyes are better washfast than those obtained with the dye obtained from Publication Board No. 83573, p. 3311; the composition of the latter corresponds to the dye mentioned in US Pat. No. 2,134,505, but contains two benzoylamino groups instead of the acetylamino groups.

In the following examples, unless otherwise noted, the parts mean parts by weight and the Percentages by weight.

example 1

A solution of 200 parts of water, 100 parts of acetone, 5.14 parts of 4-amino-4'-oxy-l, l'-azobenzene-3'-carboxylic acid and 1.8 parts of anhydrous sodium acetate is stirred at 0 ° with a solution of 4 parts of cyanuric chloride added in 50 parts of acetone. A yellow suspension is formed, and after a few minutes it leaves no more free amine can be detected.

The primary condensation product thus obtained is then added, with stirring, to 900 parts of the blue, sodium carbonate-alkaline solution of dioxazine sulfonic acid, the preparation of which is described below. The whole is heated to 40 to 45 ° and stirred for 2 hours at this temperature. By temporarily dropwise addition of saturated sodium carbonate solution it is ensured that the _pH value of the solution is 8 to 9 25 parts now to be 20 ° / ₀ aqueous ammonia was added and the reaction mixture is stirred for a further 2 hours at 70 to 75 °. It is allowed to cool, the precipitated dye is filtered off and washed with saturated sodium chloride solution. The dye dyes cotton in green shades of good lightfastness.

Claims (2)

5 6 Green dyes with similar properties become benzene-3'-carboxylic acid a yellow amine monoazo dye obtained when the following formulas are used in place of 4-amino-4'-oxy-l, l'-azo-: H ₂ N- '^ -N = N- / -OH H ₂ N- ^ -CONH- -N = N-> I ι Cl COOH SO ₃ H COOH and H ₂ N-; > N = N-; ' \ ι j OCH ₃ SO ₃ H The above-mentioned blue dye solution is prepared as follows. Dyes having similar properties are prepared : hold if you replace 4-amino-1-oxybenzene-2-car- 24.6 parts of chloranil, 64.2 parts of 4-amino-4'-acetylamino-20 bonsäure aminobenzene, cyclohexylamine, 1-aminobenzene diphenylamine-2-sulfonic acid and 9.3 parts of magnesium 4-carboxylic acid, l-amino-4-acetylaminobenzene, 4-amino oxide are in 500 parts of water for 6 hours at 60 to 1,1'-diphenyl, l-amino-4-benzoylaminobenzene, 1-amino 65 ° stirred. A dark blue colored 4-cinnamoylaminobenzene, 2-aminochrysen, 4-aminopy- Suspension. After cooling, the separated or 2- (4'-aminophenyl) -6-methylbenzthiazole is The condensation product is filtered off, washed with water 25 turns, and dried in vacuo at 90 to 100 °. A similar dye that also turns blue is 8.37 parts of the condensation product thus obtained obtained if the in the second paragraph of the present are mixed with ammonia in a mixture of 15 parts of monohydrate and example 15 parts of 27 ° / ₀ oleum entered and remains 12 hours stirred at room temperature. After discharging 30 The dioxazine sulfonic acid is filtered off with suction onto 250 parts of ice
and washed with saturated sodium chloride solution. The dye paste is then with 165 parts of 10 ° / ₀ hydrochloric A solution of 4 parts of cyanuric chloride in 100 parts of Hydrochloric acid stirred for 3 hours at 90 to 95 °, whereby the acetone is added at 0 ° with stirring to 900 parts of a Acetylamino groups are saponified. The obtained 35 weakly acetic acid solution of dioxazine sulfonic acid, Sodium carbonate is added to the dye solution until its preparation has been described in Example 1 and alkaline reaction occurs on brilliant yellow paper, and 1.8 parts of anhydrous sodium acetate diluted with water to 900 parts by volume. has set. The mixture is stirred at 0 to 5 ° for 1 hour. Then pour . . the above solution to a sodium carbonate alkaline Example 2. _{40 sc} h _s solution containing in 500 parts of water 5.04 parts of 4-amino- Heated to a solution of 200 parts of water containing 50 parts of 4'-oxy-l, l'azobenzene-3'-carboxylic acid Acetone, 3.06 parts of 4-amino-1-oxybenzene-2-carboxylic acid 40 to 45 ° and stirred for 2 hours at this temperature, and 1.8 parts of anhydrous sodium acetate are added at 50 parts of 20% ammonia are then added 0 ° with stirring a solution of 4 parts of cyanuric chloride and stirred for a further 2 hours at 70 to 75 °. Through a- in 50 parts of acetone. After 15 minutes of stirring at 0 ° 45, sprinkle with sodium chloride, the dye is removed. the primary condensation product has formed, separated, filtered off after cooling and filled with saturated and free 4-amino-1-oxybenzene-2-carboxylic acid can be washed ter sodium chloride solution. The dye can no longer prove. dyes cotton in similar green tones as the The primary condensation product is then in the one according to Example 1, paragraphs 1 and 2, obtained the manner indicated in Example 1 with the Dioxazin- 50,
sulfonic acid condensed, its production also in
Example 1 has been described, and finally will be using Using ammonia, again according to the instructions of ^{[atentanspruche}
Example 1, the two chlorine atoms still bound to the triazine rings replaced by H ₂ N groups. 55 1. Process for the preparation of dyes the The dye obtained in this way dyes the oxazine series, characterized in that 2 mol Cotton in pure, blue tones of very good light cyanuric halide on the one hand with 1 mole of a diamino authenticity. dioxazins of the formula Cl
H ₂ NR ₁ -HN-R ₂ I j IR ₂ -NH-R ₁ -NH ₂ Cl where R _{1 is} a benzene radical and R _{2 is} a condensed benzene ring, and on the other hand sulfonic acid group-containing, with the hetero ring I 70 with 2 moles of a cyclic one free of oxazine rings Monoamines condensed and possibly the halogen atoms still present on the triazine residues against Exchanges amino groups. HO ₃ S -
H ₂ NR ₁ -HN- -N ILN-IL-XR ₁₅ -XR ₄ used, wherein R _{1 is} a benzene radical and the sulfonic acid groups are in o-position to the - NH groups. 3. The method according to any one of claims 1 and 2, characterized in that one is a cyclic Monoamine used without coloring character. 4. The method according to any one of claims 1 and 2, characterized in that there is used as monoamines a yellow aminoazo dye is used, preferably one of one of the formulas 2. The method according to claim 1, characterized in that there is a diaminodioxazine of the formula , 0 -NH-R ₁ -NH ₂
-SO ₃ H corresponds, in which R ₃ , R ₄ and R _{5 are} benzene radicals and one X is an azo group and the other X is a - CO - NH group, in particular those aminoazo dyes of this composition are used in which the benzene radical R ₄ in p- Position to the group - N = N - or - X - is substituted by an oxy group and in o-position to this by a carboxylic acid group. Considered publications: U.S. Patent Nos. 1663474,2139617,2187,853, 134 505. When the application was announced, two staining tables were displayed. © 709 880/382 2.