DE2064735C3 - Basic azine dyes, process for their preparation and their use - Google Patents

Description

ON

OH

wherein R ₃ and R _{4 have} the meaning given above, with an aminohydroquinone ether of the general formula III

(III)

in which R, R ₁ and R _{2 have} the meaning given above, or a compound of the formula IV

RO NO

(IV)

in which R, R ₁ and R _{2 have} the meaning given above, with a compound of the formula V

(V)

OH

wherein R ₃ and R _{4 have} the meaning given above. condensed in acidic medium.

The dyes can also be obtained in such a way that compounds of the formula IV ma 2-hydroxynaphthalenes in an acidic medium, optionally in the presence of a condensing agent, for example zinc chloride, condensed and the reaction product with a primary or secondary aliphatic amine or with a primary or secondary aromatic amine of the benzene series. The aliphatic or aromatic amine is expediently used in excess.

Suitable compounds of the formula II are 4-nitroso-3-hydroxymono- or -dialkylanilines, their alkyl radicals, where appropriate, nonionic substituents, namely Ilalogenatoms, hydroxy, Alkoxy, aryloxy, acyloxy, cyano, carbamyl, dialkylamino, carbalkoxy, acylamino, sulfone or Arykeste. may contain or together with the N atom a morpholine or piperidine ring or but together with the benzene ring a and the N atom a hydrogenated quinoline radical or a Benzomorpholine can form. Suitable connections of formula II are also 4-nitroso-3-hydroxy-diphenylamines, which contain optionally substituted alkyl radicals on the nitrogen of the diphenylamine and in the benzene nucleus a by nonionic substituents, namely by halogen atoms. Alkoxy, aryloxy. Alkyl, trifluoromethyl, nitro, alkylsulphone, arylsulphone, mono- or dialkylamino-. Arylamino, Cyano or acyl groups, may be substituted. Aminohydroquinone dialkyl ethers are used as compounds of the formula III into consideration, wherein the amino group by one or two lower alkyl groups may be substituted, which, like the alkyl group R., optionally also substituents, namely halogen atoms, Hydroxy, alkoxy or cyano groups. may contain or together with the N-Alom can form a morpholine or pipcridine ring. Compounds of the formula IV are 4-nitroso-1-aminohydroquinone dialkyl ethers into consideration, the amino group by one or two lower Alkyl groups can be substituted, the. like the alkyl groups A, optionally also substituents. namely halogen atoms, hydroxy, alkoxy or cyano groups, or together with know the N atom form a morpholine or piperidine ring.

Compounds of the formula V are 3-hydroxyanilines or 3-hydroxydiphenylamines Consider that may be substituted on the amino group by lower alkyl radicals, which together with the N atom or with the benzene ring and the N-Alom a heterocyclic radical of the above Can form mentioned type and the optionally non-ionic substituents, namely halogen atoms. Hydroxy, alkoxy, acyloxy, cyano. Carb amyl, dialkylamino, carbalkoxy, acylamino. SuI may contain fön or aryl radicals.

Fertilize the condensation of the respective Ausgangsvcrbin takes place at temperatures / wipe about 2 (and 120 C., preferably between about 50 and 100 C in an acidic medium. Suitably, one uses d'v hydrohalides, preferably the hydrochloride of the p-Nilrosoverbindungcn, and performs the organization Kondcn in the presence of an organic acid, for example in the presence of formic acid or acetic acid.

The dyes produced according to the invention contain the remainder of a powerful sauna as anion X.

preferably sulfuric acid or hydrochloric acid, or a chlorozincate residue. This according to the procedure Introduced anions can also be replaced by anions of other acids, for example the Phosphoric acid, acetic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, ammosulfonic acid, nitric acid, Carbon dioxide, lactic acid or tartaric acid, can be replaced.

The new dyes are suitable for dyeing or printing tannier cellulose fibers, silk, leather or fully synthetic fibers such as acetate silk, polyamide fibers or acid-modified polyamide or polyester fibers, but especially fibers containing polyacrylonitrile or polyvinylidenecyanide. The dyeings obtainable on these fibers are usually very clear and strongly colored and generally have good light and wet fastness properties, for example good wash, milled, overdyeing, carbonizing, chlorine and perspiration fastnesses, as well as good decatur, steaming and ironing fastnesses -, rubbing and solvent fastness. The dyes are generally largely insensitive to a change in the pH of the dyebath and can therefore be used in both weakly acidic and strongly acidic baths. They are also stable at temperatures above 100 ^° C., as used in high-temperature dyeing.

example 1

10.3 parts by weight of 2- (fi- cyanoethylamino) -hydroquinone dimethyl ether are dissolved in 100 parts by weight of 70% acetic acid and 11.3 parts by weight of 4-nitroso-3-hydroxy-Ν, Ν-dimethylaniline hydrochloride are added. The mixture is ^{heated to about 50 °} C. and kept at this temperature for 1 hour. 150 parts by weight of water and 3 parts by weight of kieselguhr are then added, the mixture is filtered and the dye of the formula is obtained from the filtrate by adding 10 parts by weight of 30% strength hydrochloric acid and zinc chloride

H ₃ CO

HN

CH ₁

C ₂ H ₄ CN

ZnCIi-

1 g of the dye is mixed with 2.5 g of 50% acetic acid and dissolved in 6 liters of water. The dye bath 1 g of crystalline sodium acetate and 10 g of calcined sodium sulfate are added ». Then goes 100 g of prewashed polyacrylic nitrile staple fiber yarn in the 60 C dyebath one, increases the temperature slowly to 100 C and colors 1 hour at boiling temperature. Subsequently the dyed material is allowed to cool slowly to about 60 ° C., rinsed and dried. You get a clear. greenish blue coloration with very good light and wet fastness properties.

Example 2

9.3 parts by weight of 3-hydroxydiphenylamine are dissolved in 100 parts by weight of 70% acetic acid and 13.6 parts by weight of 5-nitroso-2 - (/ i-cyanoethylamino) hydroquinone dimethyl ether hydrochloride are added. The mixture is ^{heated to about 80 °} C and held at that temperature for 1 hour. The blue solution is then added to a mixture of 1000 parts by weight of water, 5 parts by weight of kieselguhr and 10 parts by weight of 30% hydrochloric acid, filtered and the dye of the formula is obtained from the filtrate by adding sodium chloride

Cl

40

45

precipitated, suctioned off and dried. This gives 21.5 parts by weight of a dark powder which is mixed with blue color dissolves in water and diluted acids.

H ₃ CO

XOO

HN NH

C ₂ H ₄ CN

deposited, vacuumed and dried. 9.5 parts by weight of a dark powder are obtained which dissolves with blue color dissolves in water and diluted acids.

1 g of the dye is mixed with 2 g of 50% acetic acid and dissolved in 5 l of water which contains 1 g of crystalline sodium acetate. Then one proceeds with 100 g pre-washed material from acid-modified polyester fiber in the dyebath at 60 ⁰ C., the temperature is raised slowly and stained for 1 hour at 115 to 120 ⁰ C. Then the product is cooled, rinsed and dried at about 70 C. A clear greenish blue coloration with good light and wet fastness properties is obtained.

The table below contains further dyes obtainable according to the invention and the color shades the dyeings available with the dyes on polyacrylonitrile fibers.

dye

Color ion

CH ₃ O

blue

ZnCl., Greenish blue

continuation

dye

C H, O

HN

C ₂ H ₄ CN CH ₃ O

CH ₃

CH,

HN

C ₂ H ₄ CN CH ₃ O

N CH ₃

CH,

HN

C ₂ H ₄ CN CH ₃ O

NH

Cl

Cl

oV

OC ₂ H ₅

HN

C ₂ H ₄ CN CH ₃ O

NH

Cl--

CH ₃

HN

C ₂ H ₄ CN

NH

CH ₃

NCCH ₂ CH ₂ HN CH ₃ O

NCCH ₂ CH ₂ HN C ₂ H ₅ O

NCCH ₂ CH ₂ HN

NH

CH ₁

NHCH ₂ CH ₂ CN C ₂ H ₅

C ₂ H ₅

hue

ZnCl ₃ greenish blue

greenish blue

greenish blue

greenish blue

crusty blue

crusty blue

Z _n Cl ₃ greenish blue

Z _n Cl ₃ greenish blue

continuation

10

dye

hue

C ₂ H ₅ O

NCCHXH ₂ HN

ZnCl, greenish blue

C ₂ H ₅ O

NCCHXH ₂ HN

CH ₃

CH ₃

CH ₃

ZnCl ₃ greenish blue

C ₂ H ₅ O

NCCHXH ₁ HN

C ₂ H ₅ O

H ₂ N

/ V ^N O

Tt

NH

NH

Greenish blue

blue

C ₂ H ₅ O

NCCH ₂ CH ₂ HN

NHCH ₂ CH ₂ CN

ZnCl ₃

eriinstichiaes blue

CH ₃ O

NCCHXH ₂ HN

CH ₃ O,

NCCH ₂ CH ₂ HN

CH, O

: xx

NH

CH ₃ CH-CH ₂

NH (

NCCHXH ₂ HN

/ \ A

NH

CH ₂

CH,

reddish blue

blue

blue

11th

continuation

dye

CH ₃ O

NCCH ₂ CH ₂ HN

NH

H ₂ C /
^X CH

OH

CH ₂

Color ion

blue

CH ₃ O

CH ₃ HN

Tr

NH

C ₂ H ₅ HN '

/ Λ ο

NH

Cl

HOCHXH ₂ HN

NH

Cl

blue

blue

blue

Claims (4)

Patent claims: 1. Basic oxazine dyes of the formula
RO where R is an optionally substituted lower alkyl group, R ₁ and R _{2 are} hydrogen or optionally substituted lower alkyl groups which, together with the N atom, can also form a heterocyclic radical, R _{3 is} hydrogen © which is an optionally substituted lower alkyl group, R _{4 is} hydrogen optionally substituted lower alkyl group or an optionally substituted phenyl radical, where R ₃ and R ₄ , optionally via a heteroatom, together with the N atom or R ₄ together with the N atom and the benzene ring, optionally via a heteroatom, a heterocyclic radical can form, X both mutet an anion and the benzene ring a can contain further nonionic substituents or a fused-on benzene ring. 2. Process for the preparation of the dyes according to Claim 1, characterized in that one compound of the formula OH wherein R ₃ and R _{4 have} the meaning given in claim 1, with an aminohydroquinone ether of the formula wherein R, R and R _{2 have} the meaning given in claim 1, or a compound of the formula Have meaning with a compound of the formula OH wherein R ₃ and R _{4 have} the meaning given in claim 1, condensed in acidic medium .n. 3. Process for the preparation of basic oxazine dyes of the formula wherein R is an optionally substituted lower alkyl group, Rj and R _{2 are} hydrogen or optionally substituted lower alkyl groups. which together with the N atom can also form a heterocyclic radical, R _{3 is} hydrogen or an optionally substituted lower alkyl group, R _{4 is} hydrogen, an optionally substituted lower alkyl group or a phenyl radical and X is an anion, the benzene ring a containing further nonionic substituents can, characterized in that a compound of the formula wherein R, R ₁ and R _{2 have} the meaning given above, condensed with a 2-hydroxynaphthalire in an acidic medium and the reaction product is reacted with a primary or secondary aliphatic amine or with a primary or secondary amine of the benzene series. 4. Use of the dyestuffs according to Claim I or according to Claim 2 or Claim 3 provided dyes for dyeing or printing on tannin Ccllulose fibers. Silk. Leather. Acc silk. Polyamide fibers, acid-modified poly amide or polyester fibers or from polyacrylic fibers containing nitrile or polyvinylidenecyanide. Wherein R, R ₁ and R _{2 are} those given in claim 1 The invention relates to basic oxazine dyes _C r Forme! 1 (I) "Rorin R represents an optionally substituted lower AlkylgruPP ^{0 'R} i ^{and R} 2 ^Wasserst often or given-I ₁ IIs substituted lower alkyl groups, the well-N-atom can lüden also a heterocyclic radical together the, R ₃ is hydrogen or a gegebenenfclls substituted lower alkyl group , R ₄ denotes hydrogen, an optionally substituted lower alkyl group or an optionally substituted phenyl radical, where R ₃ and R ₄ , but optionally a heteroatom, together with the N atom or R ₄ together with the N atom and the benzene ring, optionally above a heteroatom, can form a heterocyclic radical, and X is an anion, where the benzene ring a can contain further nonionic substituents or a fused-on benzene ring. These dyes differ from the prior art in that they have a lower alkoxy group. The dyes can be obtained in accordance with the invention by adding a compound of the general Formula 11