DE2221989A1 - AZO BASIC DYES, METHOD FOR THEIR MANUFACTURE AND USE - Google Patents

Description

Basic azo dyes, process for their preparation and their use.

The present invention relates to basic azo dyes which are free from sulfonic acid groups and have the formula I,

D-N =

IN

Hal

(I)

where D denotes an aromatic or heterocyclic Diazo component containing a cyclammonium group, B hydrogen, an optionally substituted lower one Alkyl, cycloalkyl, aralkyl or aryl radical, Hai a chlorine or bromine atom and 3C ^ mean an anion and the benzene nucleus a optionally contain further nonionic substituents can. ■ ·

The. Dyes can be obtained in such a way that a) the diazoniumverbindunp- a quaternary amine of the formula II

D-NH,

(II)

wherein D and X have the meaning given above, with a coupling component of the formula III

Ν "- CH _? CH ₂ CN

(III)

Hal

309846/1022

in which R, Hal and a have the meaning given above, clutch, or that one.

b) an azo dye of the formula IV

R.
DN =. N-ZaV N - CH ₂ CH ₂ CN (IV>

Shark

where D is the radical of an aromatic or heterocyclic diazo component and R, Hal and a are those given above Have meaning, treated ait alkylating agents.

The quaternary amines of the formula II used for procedure a) can be obtained by treating suitable aromatic or heterocyclic amines with alkylating agents, for example, alkyl halides, aralkyl halides, haloacotamides, β-halopropylonitriles, halohydrins, 'alkylene oxides, acrylic acid amide, "alkyl esters of the Sulfuric acid or organic sulfonic acids.

Suitable quaternary amines of the formula II are, for example, those of the formula V,

-Y-

R, - Ν · «4 C - C h> C -

NILE

(V)

wherein R, an optionally substituted alkyl or aralkyl radical, Y a divalent atom or a divalent group required to complete a 5- or 6- _{membered ring, R 2} and R, hydrogen, alkyl radicals or substituents which complete a fused aromatic ring, η is zero or 1 and X is an anion. Such quaternary compounds can be derived from amines of the pyridine, pyrazole, imidazole, triazole-tetrazole, oxazole, thiazole, selenasole, oxdiazole, thiadiazole, fyrimidine or triazine series, and also the quinoline, tndazole, benzimidazole -, benzisothiazole, arylguanazole, naphthiraidazole, benzoxazole, naphthoxazole, benzthiazole or naphthothiazole series.

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Quaternary amines of the formulas VI and VII are also suitable

VI

- N A) —W -I- a

(VII)

wherein R, an optionally substituted alkyl or Aralkyl radical, A a 5- or 6-membered heterocyclic ring, for example a pyridinium, triazolium, pyrazolium, imidazolium or thiazolium radical, V / a direct bond or is a divalent bridge member and X is an anion and the benzene radical a is further substituents such as halogen atoms. Alkoxy, Aryloxy, alkyl, trifluoromethyl, nitro, alkylsulfone, May contain aryl sulfone, cyano or acyl groups.

Finally, quaternary amines of the formulas VIII and IX are suitable

VIII

(IX)

■ where A is a 5- or 6-membered heterocyclic ring, in particular a pyridinium ring, Z is a straight-chain or branched lower alkylene radical, an arylene. or aralkylene radical, B a -0-, -S-, -CO-, -SO ₂ -, -CONH-, -OCO- or -SO ₂ NH group, η O or 1 and X an anion and the benzene radical a further substituents, for example halogen atoms, alkoxy, aryloxy, alkyl, trifluoromethyl. May contain nitro \ alkylsulfone, arylsulfone, cyano or acyl groups.

Secondary or secondary azo components of the formula III are used tertiary amines into consideration. R can be hydrogen or a M-ethyl, ethyl, propyl or butyl radical, the other S substituents, such as halogen atoms, hydroxy, cyano, acyloxy, Carbalkoxy, carbamoyl, dialkylamino, alkoxy, trifluoromethyl, Acyl-, carbamic acid ester- ^ ·, alkylsulfone-, sulfamoyl- or may contain aryloxy groups.

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Ή can also be a cycloalkyl radical, for example a cyclohexyl radical, be an aralkyl radical, for example a benzyl radical, or an aryl radical, for example a benzene radical, the may contain further nonionic substituents. Of the Benzene radical a can also contain other substituents, for example halogen atoms, alkyl, alkoxy, carbalkoxy, Alkylsulfonyl, carbamoyl, sulfamyl, amino, trifluoromethyl, • acyl or acylamino groups.

The diazotization of the amines of the formula II can by known methods, for example by means of alkali metal nitrite and a inorganic acid, for example hydrochloric acid, ivory acid or phosphoric acid, or using nitrosulfuric acid,

The coupling with the azo components of the formula III can also be carried out in a manner known per se, for example in neutral to acidic medium, optionally in the presence of sodium acetate or the like, influencing the coupling speed Buffer substances or catalysts, such as Dimethylformamide, pyridine or its salts, are made,

The starting dyes used for procedure b) of the formula IV can by coupling the diazotized amines of the formula D - NF ^ with the coupling components or by condensation of the amines with the corresponding p-nitroso compounds the amines of the formula III are obtained.

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«. 5 -

Procedure b) is particularly useful for amines of formula X.

Γ * ■ 1

Η4 C - 0 ^ i C - NH ₂ ^ *

do ...

in which Y, η, Rg uR ^ have the meaning given above, are suitable. As amines of the formula X in particular, those of the pyridine _t I> ~ yrazol, imidazoles triazole, tetrazole, · oxazole, thiazole, selenazole, oxadiazole, thiadiazole or triazine Pyriißidin- _t, further the quinolines, Indazql-, benzinidazole, benzisothiazole, arylguanazole, • haphthimidazole, benzoxazole, naphthoxazole, benzthiazole or naphthothiazoles into consideration.

As aTkylierende agents are alkyl halides, aralkyl halides, Halogenacetaniide, "halohydrins, alkylene oxides _T acrylamide, alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids ß-Halogenpropionitrile in. Considered.

Suitable alkylating agents are, for example, methyl- ^ chloride, bromide or iodide, ethyl bromide or iodide, propyl bromide or iodide, benzyl chloride, chloroacetamide, ß-chloropropionitrile, Ethylene chlorohydrin, dimethyl sulfate, benzene sulf onic acid methyl ester, p-toluenesulfonic acid methyl-, -ethyl-, · propyl or butyl ester. The alkylation is expediently carried out in an inert organic solvent, for example in a hydrocarbon, chlorinated hydrocarbon

or nitro hydrocarbons, such as benzene, toluene, xylene, tetrachloroethane, Chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, in an acid amiS. or Acid anhydride, such as dimethylformamide, N-methylacetaiaid or . Acetic anhydride, in dimethyl sulfoxide or in a ketone, like acetone or methyl ethyl ketone, instead of an organic one Solvent can also be an excess of the alkylating agent be used.

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Depending on the number of alkylatable nitrogen atoms in the starting dye one or more alkyl groups are introduced into the dye molecule. The alkylation is increased at Temperature, if necessary with the addition of acid-binding agents such as magnesium oxide, magnesium carbonate, soda, calcium, carbonate or sodium bicarbonate and optionally, made under pressure. The most favorable conditions in each case can easily be determined by a preliminary test.

If appropriate, the alkylation can also be carried out in water. . .

The new dyes can be used in modification of the above Process can also be obtained so that one

Hydrazone or benzenesulfonylhydrazone of the general formula XT

Γ ^Α I.

R ₄ - N 4 C »O f _n C a N - NH - E ι

R ₂ R ₅

where γ, red R * ι R ^. and η has the meaning given above and E represents a hydrogen atom or a benzylsulfonyl radical is, with an azo component of the formula III under the action of oxidizing agents.

4 »

The new dyes preferably contain the remainder of a strong acid, for example sulfuric acid or its H & lbester, an arylsulfonic acid or a hydrohalic acid, as the anion X ~ *. These anions introduced according to the method can also be replaced by anions of other acids, for example phosphoric acid, perchloric acid, acetic acid, oxalic acid, lactic acid, propionic acid. Maleic acid, malonic acid or tartaric acid can be replaced. The dyes can also be in the form of their double salts with zinc or cadmium halides β, β ^ οηηβη . The nature of the anionic residue is irrelevant for the properties of the dyes, as long as it is colorless residues which do not impair the solubility of the dyes in undesirable wines.

S G S £ 4 S / 1 C- 2 2

The new dyes Bind for the production of writing fluids, Stamp inks or ballpoint pen pastes are suitable and can also be used for rubber printing. You ■ are also suitable for dyeing, printing or mass dyeing of tannin cellulose fiber ^ silk, hair, leather, coconut, Jute, sisal or fully synthetic fibers such as acetate silk, Polyamide fibers or acid modified polyolefin, polyamide or Polyester fibers, but in particular polyacrylonitrile or polyvinylidene-containing fibers. The on The dyeings and prints obtainable from these fibers are usually very intense in color and generally have good properties Light and wet fastness, for example good wash, fulling, over-dyeing, carbonisior, chlorine and perspiration fastness, and good decatur, steam, ironing, additive and solvent fastness. The dyestuffs Bind 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 at temperatures above 100 ⁰ C, such as are'wendet ange-in high-temperature dyeing, resistant. Wool is completely reserved by the dyes under normal dyeing conditions.

The dyeing with the new dyes is generally carried out in an aqueous medium at the boiling point or in closed vessels at temperatures above 100 ^° C. and under pressure. The dyes can also be used from organic solvents.

To prepare the aqueous dyebaths and printing pastes, the dyes can be used in the form of powders, the optionally ■ adjusting agents, such as, for example, inorganic salts; Use dextrin and possibly other additives. However, it is more advantageous to use concentrated aqueous solutions of the dyes that are easier to handle and contain about 20 to 60 % dye, one or more lower aliphatic ^

309846/1022 -β "-

Carboxylic acids, vfie formic acid, acetic acid, propionic acid or lactic acid, and if necessary other additives, such as water-soluble polyhydric alcohols, their ethers or esters, Polyethers, aliphatic carboxamides, lactams, lactones, Nitriles, dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or contain urea and water. For the preparation of the dye baths, which only contain organic solvents, For example, chlorinated hydrocarbons contain, it is advantageous to use concentrated solutions containing the dye as free base or as a salt of a monobasic organic acid, chlorinated hydrocarbons, organic acids and polar acids contain organic solvents.

The new dyes form _{lightfast pigments with anionic precipitation initiators 1} such as, for example, clay, tannin or heteropoly acids such as phosphotungstic or molybdic acids, which can advantageously be used in paper printing.

The following examples serve to illustrate the invention.

309846/1022

Example 1:

14.4 parts by weight of 4-chloro-2,6-diamino-N-methylaniline sulfate as Monohydrate are 95% sulfuric acid in 25 parts by volume dissolved with stirring. After cooling to 0-5 ° C., it is left 16.6 Add parts by volume of nitrosylsulfuric acid (about 41%) so that ' that the temperature is kept at 8-10 ° C. The mixture is stirred for a further 1 hour and the nitrosyl melt is poured onto ice and Water. A small excess of nitrite is destroyed with a little sulfamic acid. Then left for about 50 minutes into the filtered solution of the diazotized 5-chloro-7-amino-1-methyl-benzotriazole thus obtained at 10 ° C a solution of 10.7 parts by weight of 3 ~ chlorine-N-ethyl-N-ß-cyanoethylaniline Add dropwise in 50 parts by volume of glacial acetic acid. The dye. ' is filtered off with suction after the coupling is complete, washed with a little water and again stirred with water. Then you ask the dye suspension with approx. 50 parts by volume of 2N Söda solution alkaline, absorbs the dye of the formula after 1 hour

N N-CH, ^υχ

ν, " ⁵ ·

off, washes neutral with water and dries at about 60 C,

20 parts by weight of the dried material are used for quaternization Dye dissolved in 800 parts by volume of chlorobenzene. To remove the last traces of water, distill approx. 80 parts by volume of chlorobenzene are 0.5 parts by weight Magnesium oxide is added and 7.3 parts by volume of dimethyl sulfate are added dropwise over a period of 30 minutes at 80-85. One stirs until

- 10 -

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Completion of quaternization approx. 5 hours after, cools down to 4-0 ⁰ C, sucks the,
washes with chlorobenzene.

to 4-0 C, sucks off the deposited dye and

After drying at 60 ⁰ C is obtained 15i5 parts by weight of dye of the formula

/ χ ι ² " ⁵

N- / Vn-CH ₀ -CH ₀ -CN CH, SO. \ / c. dy

WC-N © N-CH

which has a blue-red color in water and in aliphatic carboxylic acids, such as acetic or formic acid, if appropriate also in mixtures of these acids with other solvents, such as alcohols, ketones, carboxamides or carboxylic acid esters, solves. It dyes polyacrylonitrile fibers as well as acid-modified polyester fibers from schv / ach acidic bath in light and wet-real Bordo tones.

Example 2:

45.4 parts by weight of 5-chloro-7-amino-l-methylbenzimidazole are mixed with 7.5 parts by weight of magnesium oxide in 125 parts by volume of water and at 50-60 ° C. with stirring over the course of about 1 hour with 30.8 parts by volume of dimethyl sulfate offset. The mixture is stirred for about 2 hours at 50-60 ° C. (pH 7.5-8.5), 2.5 parts by weight of kieselguhr and 2.5 parts by weight of carboraffin C are added, and the mixture is filtered off with suction and washed with 100 parts by volume of hot water. The filtrate is mixed with 120 parts by volume of 30% hydrochloric acid and cooled to ⁰ ° C. After adding 75 parts by weight of ice, diazotization is carried out by rapidly adding 52 parts by volume of 5N sodium nitrate solution. After the destruction of a small amount of nitrite

- 11 309846/1022

Excess with a little sulfamic acid is allowed to steep the yellow-brown, clear diazo solution in a 50 weight unit. ^ -Chlor-N-raethyl-N-ß-cyanoethylaniline, 4-00 parts by volume Pour in water and 100 parts by volume of 5N hydrochloric acid. Of the The pH value is adjusted to 1.5 with concentrated sodium hydroxide solution. The in The dye which has precipitated out red crystals is filtered off with suction, washed with a little water and dried. 95 parts by weight of dye of the formula are obtained

N-CH ₂ -CH ₂ -CN Cr

which is red in water and in aliphatic carboxylic acids, such as acetic or formic acid, if appropriate also in mixtures of these acids with other solvents, such as alcohols, ketones, carboxamides or carboxylic acid esters, dissolves and dyes polyacrylonitrile fibers from a weakly acidic bath in light- and wet-fast reddish orange tones.

example

11 parts by weight of N-methyl-benzthiazolon-2-hydrazone and 19 * 4-5 parts by weight of ^ -chloro-N-methyl-N-ß-cyanoethylaniline v / earth in 64-0 parts by volume of water and 160 parts by volume 5N hydrochloric acid dissolved at approx. 45 ° C. with stirring. Then drips a solution of 64 parts by weight of crystalline. Iron III chloride in 100 parts by volume of water and stir until the reaction has ended (about 6 hours). The crystalline deposited

309848/1022

dye is filtered off, washed with a little water and normally recrystallized with water and a little hydrochloric acid, 10 parts by weight of dye of the formula are used

CV-,

-N-CH ₂ -CH ₂ -CN

which is blue in water and in aliphatic carboxylic acids, v / ie acetic or formic acid, if appropriate also in mixtures of these acids and other solvents, such as alcohols, ketones, carboxamides or carboxylic acid esters, dissolves and dyes polyacrylonitrile fibers in light- and wet-fast blue tones.

The table below contains further inventions Dyes and the shades of the dyeings available on polyacrylonitrile fibers:

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dye

hue

1-CH ₂ CH ₂ CN

H ^ CN ©
CH

Cl orange

dito

dito

dito

dito

/ V

Cl

CH

N-OH ₂ CH ₂ CN

Cl

Cl

CH ₂ CH ₂ CN

Cl he

C Γ

orange

orange

GHF - orange

orange

dito

/ "VnY V CH. Cf

orange

Cl

dito

dito

Br

v Vn-Zh

Cl CHpCH ₂ CN er

orange

orange

309846/1022

dye

hue

Cl

-N =

CH-

N-CH ₂ CH ₂ CN

01 ^Θ Wine red

H, C-N © N-CH-, Cl

dito

C ₃ H ₇

Cl® wine red

Cl

CH-,
ι 0

^S C - N - NV

C ₂ H ₅ N-CH ₂ CH ₂ CN

Cl

dito

N-CH ₂ CH ₂ CN

Cl

CH,

blue

blue

Θ C-N =

CH., SO.® Blue

CH

© c

30 ^Θ

CH 30 _{/ +}

blue

Cl

3098 46/1022

Dye hue

CH-

N ^

Il © C-N = N-

Br

blue

-C - CH H _x CN ^w C -

CH,

CH,

s N-

Cl CH _x SO /
4th

'' yellowish red

C-CH

H _x CN CN =

N-CH ₂ CH ₂ CN

Cl yellowish red

'CH

N-CH ₂ CH ₂ CN

N ": ^ CH _x ^C1 i

CH

-Γ Vn-V /

² " ⁵ CH _x S (
3

CH _x Cl

violet

Violet..

ι
CJH,

N = N

-CH- "

N-CH ₂ CH ₂ CN CH _;

Cl violet

16 -

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Dye hue

H _x CO

N ""

CH.

Ί1

• ^C 4 ^H 9

N-CHpCHpCN

Cl violet

H ₂ CN ffi 7

N = N

CH.

N-CH ₂ CH ₂ CN

Cl ZnCl

reddish blue

H, C-N ©,) - N = N

Cl ZnCl ₁

reddish blue

N - N-CH,

CH C-N = N

CH

Cl

CH-

N-CH ₂ CH ₂ CN ZnCl,

Red

N - N-CH ₅

Ii Θ I!

CH C-N

CH _x 5

= N

Cl

ZnCl,

Red

N - N-CH ₅

II Θ II CH CN =

CH ₂

ν- ^J

N-CH ₂ OH ₂ CN

Cl ZnCl,

Red

309846/1022

dye

hue

CH-S I! t CH ® C

CH-

N = N

CH,

Cl blue

.N-CH ₂ -CO

= N

Cl

CH ₃

CH © N-CH,

GH,

N = NC Vn-CH ₂ CH ₀ CN

Cl

CH, -N © N-CH \

? 2 ^H 5

N = N / V N-CH ₂ CH ₂ CN

Cl

ZnCl

2 ~ "

orange

orange

orange

CH - CH 'II Il

CH ₇ -N © C-N = N

Cl

GH-C - C S Il ^ n Il

OH -, - N C-N = N

N \

CH ₂

Cl

ZnCl,

N-CH ₂ CH ₂ CN 2

ZnC I,

yellowish red

yellow :) cnip; ec. Red

-

309846/10

dye

GH

CH

CH,

I - N ^

N = N-

Eq

ZnCl _{/ (} ⁰⁹

hue

Golden yellow

N - N-GH-,

© II ⁵

HN = C C-N

CH

= N

Cl scarlet fever

N
CH-. -N © N-CH-

N = N

Cl CH-, SO

Red

Cl

CH ₂ -C ^ ® ^X N-CH,

⁶ W Il ³

CH - C-CH,

Θ, N-

Cl

CH-,

I.

N-CH ₂ CH ₂ CN

CH-

Cl

CH,

Cl

GH,

N - N- / Vn-OH ₂ CH ₂ CN Cl Cl ⁽

g; e lbs t i ige s red

orange

orange

Oranpe

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Claims (1)

Patent claims ; 1) Basic azo dyes that are free from sulfonic acid groups are and have the formula D-N N / aVN \ asaa / Shark CH ₂ CH ₂ GN in which D is the residue of an aromatic or heterocyclic diazo component which contains a cycloammonium group, R is hydrogen, an optionally substituted lower alkyl, cycloalkyl, aralkyl or aryl rust, Hal is a chlorine or chromate atom and X is an anion and the benzene ring a is optionally others non-ionic substituents contain ident. 2) Process for the production of basic azo dyes, which are free from Sudfonsäuregrurspen and have the formula, B.
I. H - CH ₂ CH ₂ CN Shark where D is the residue of an aromatic or heterocyclic one Diazo component, which contains a CyclaEsmoniuisgruppe, R is hydrogen, oinone optionally substituted lower Alkyl, cycloalkyl, aralkyl or aryl radical, Hal is chlorine or Bromine atom and X ^ mean an anion and the Bonzol nucleus a may optionally contain further nonionic substituents, characterized in that 309848/1022 ρ) the diazonium compound of a quaternary amine of the formula D - © jo
wherein D and A have the meaning indicated above, with a coupling component of Fonael R.
ι N - CH ₂ CH ₂ CH Shark where R, Hai and a have the meaning given above, clutch, or that one b) an azo dye of the form 1 R.
DNN - / aV N - CH ₂ CH ₂ CN Shark wherein D is the residue of an aromatic or heterocyclic Diazo component means and R, Hai and a have the meaning given above, treated with alkylating agents. 5) Use of dyes according to claim 1 for dyeing or Printing of textile material made from natural and synthetic fibers. 4-) Use of dyes according to claim 1 for dyeing or printing textile material containing acidic groups synthetic fibers. 5) means for dyeing textile material made of natural or synthetic fibers containing one or more dyes according to claim 1. 309848/1022