DE2222042A1 - AZO BASIC DYES, METHOD FOR THEIR MANUFACTURE AND USE - Google Patents

Description

PAHBWEiIKE HOECHST /> Γ _Τ formerly master. Lucius Si Brüning

File number: - HOE 72 / F 135 2222042

Date: May 2, 1972

Dr.OT / ^ i;

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

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

D- N = N-A-N- CH -CH- COOR-,

ι- ι -

Y ζ

where D is a thiazolium, benzthiazolium, triasolium, beiiztriazolium, pyrazolium, indazolium, pyridinium, quinoliniura or benzimidazolium radical, A is an optionally substituted phenol or kaphthylene radical or, together with _T ' _T, a 1,6- (1 , 2,3 ^ - Tetrahydro) -quinolinylen ~, 1,6-benzomorpholinylene or 1,3-Ir: dolylene radical, E is hydrogen »an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, Y and Z are hydrogen or a Likewise substituted alkyl radical, R-, a given; .cnfa.ll substituted Αΐίςνΐ-, Cycloaliqyl ™, aralkyl or aryl radical and X- is an anion.

The dyes can be obtained in the manner that one a) the Diazonius compound of a 'quaternary amine of the formula II

D ~

X ^Θ II

where D and X have the meaning given above, kit

a coupling component of the formula III

R ι

AN-CH-CH-- COOR ₁ III

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wherein Λ, R, X, Z and R- have the meaning given above own, couple, or that one b) an azo dye of formula IV

RID-N = N-A-N-CH-CH

• I i Y Z

COOR ₁

IV

wherein D is a thiazole, benzthiazole, triazole, benzotriazole, Pyrazole, indazole, pyridine, quinoline or benzimidazole radical means and A, R, Y, Z and R-. the one given above Have meaning, treated with alkylating agents, or that c) an azo dye of the formula V

= N-A-

R. - CH - CH - COOH I. I. I. N Y Z

wherein D, A, R, Y, Z and ΊΡ have the meaning given above, esterified with an aliphatic, eyeloaliphatic or araliphatic alcohol or an aromatic Oxyverbi.

The quaternary amines used for procedure a) of the formula II can be obtained by treating the heterocyclic amines with alkylating agents, for example alkyl halides, Aralkyl halides, haloacetamides, ß-halopropionitriles, Halohydrins, alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or organic sulfon- ^ acids.

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

- C-

VI

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in which R. is an optionally substituted alkyl or aralkyl radical, B is a divalent atom or a divalent group required to complete a 5- or 6-ring, ■ Rp and R ^ are hydrogen, alkyl radicals or substituents which add to a fused aromatic ring, η denotes the number O or 1 and ΎΡ 'denotes an anion. Such quaternary compounds can be derived from amines of the pyridine, pyrazole, triazole, thiazole, quinoline, indazole, benzimidazole, arylguanazole, naphthimidazole, benzthiazole or naphthothiazole series.

Quaternary amines of the formula VII are also suitable

X ^Θ VII

where R ^ is an optionally substituted alkyl or aralkyl radical, C is a 5 "or 6-membered heterocyclic ring, for example a pyridinium, triazolium, pyrazoline or thiazole iurarest and ItP is an anion and the benzene test a further substituents, such as halogen atoms, alkoxy, aryloxy, alkyl, trifluoromethyl, nitro, alkylsulfone, arylsulfone, cyano or acyl groups.

Secondary or secondary azo components of the formula III are used tertiary amines of the benzene or naphthalene series into consideration. R can be hydrogen or a methyl, ethyl, propyl or Be butyl radical, the further substituents, such as halogen atoms, Hydroxy, cyano, acyloxy, carbalkoxy, carbamoyl, dialkylamino, Alkoxy, trifluoromethyl, acyl, carbamic acid ester, alkyl sun, sulfamoyl or aryloxy groups. R can also be a cycloalkyl, for example a cyclohexyl radical, an aralkyl, for example a benzyl or .'Phenäthyl- ■ radical, or an aryl radical, for example an optionally substituted phenyl radical. A can also be used together with 8 is a l, 6- (l, 2,3,4-tetrahydro) -quinolinylene or -7,8-benzoquinolinylene radical, a 1,6-benzomorpholinylene radical or be a 1,3-indolynylene rust. The 'remainder A can also further

309847/0975 '. ~ ⁴ ~

Contain 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 be carried out according to known methods Methods, for example by means of alkali nitrite and an inorganic acid, for example hydrochloric acid, sulfuric acid or phosphoric acid, or means. Nitrosylsulfuric 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 can be made.

The starting dyes of the formula IV used for procedure b) can be obtained by coupling the diazotized amines of the formula D-NH ₂ with the coupling components or by condensation of the amines with the corresponding p-nitroso compounds of the amines of the formula III.

Procedure b) is particularly useful for amines of the formula VIII

in which B, R ₂ , R and η have the meaning given above, are suitable. Particularly suitable amines of the formula VIII are those of the pyridine, pyrazole, triazole, thiazole, quinoline, indasole, benzimidazole, arylguanazole, naphthimidazole, benzthiazole or naphthothiazole series.

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Alkylating agents are alkyl halides, aralkyl halides, haloacetamides, ß ~ halopropionitriles, halohydrins, Alkylene oxides, acrylic acid amide, alkyl esters of Sulfuric acid or alkyl esters of organic sulfonic acids in Consideration.

Suitable alkylating agents are, for example, methyl chloride, bromide or iodide, ethyl bromide or iodide, propyl bromide or -o'odide, benzyl chloride, chloroacetamide, ß-chloropropionitrile, Ethylene chlorohydrin, dimethyl sulfate, methyl benzenesulfonate, methyl p-toluenesulfonate, ethyl, propyl or butyl ester. The alkylation is expedient 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 amide or Acid anhydride, such as dimethylformamide, N ^ -methylacetamide or Acetic anhydride, in dimethyl sulfoxide or in a ketone, such as acetone or methyl ethyl ketone. Instead of an organic solvent, it is also possible to use an excess of the alkylating agent be used.

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, optionally with the addition of acid-binding agents such as magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and optionally 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. _r .

The new dyes can, in a modification of the abovementioned processes, in some cases also be obtained in such a way that one

- 6 309847/0975

Hydrazone or benzenesulfonylhydrazone of the general formula IX

R ₄ -K- (C = C ^ C = N-KH-E IX

wherein B, R ₂ , R 1, R ^, and η have the meaning given above and E is a hydrogen atom or a benzenesulfonyIrost, couples with an azo component of the formula TII under the action of oxidizing agents.

The new dyes preferably contain the anion X ~ Remainder of a strong acid, for example sulfuric acid or its half-ester, an arylsulfonic acid or a hydrogen halide acid. These anions introduced according to the method can also be replaced by anions of other acids, for example the Phosphoric acid, perchloric acid, acetic acid, oxalic acid, lactic acid, propionic acid, maleic acid, malonic acid or tartaric acid replaced will. The dyes can also be obtained in the form of their double salts with zinc or cadinium halides. The kind of the anionic residue is for the properties of the dyes irrelevant insofar as they are colorless residues which do not adversely affect the solubility of the dyes impaired.

The new dyes are used for the production of writing fluids, Stamp inks or ballpoint pen pastes are suitable and can also be used in rubber printing. Sio are also suitable for dyeing, printing or mass dyeing of tannin cellulose fibers, 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 generally very intense in color and generally have good ones Light and wet fastness, for example good washing, fulling, Over-dyeing, carbon dioxide, chlorine and perspiration fastness, as well as good decatur, steam, ironing, rubbing and solvent fastness properties. The dyes are generally largely insensitive to a change in the pH of the dyebath

309847/0975 - 7 -

and can therefore be used in both weakly acidic and strongly acidic baths. They are also at temperatures above 100 C, as used in high-temperature dyeing become permanent. Full is made by the dyes. Fully reserved 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.

For the preparation of the aqueous. Dyebaths and printing pastes, the dyes can be used in the form of powders which, if appropriate, contain adjusting agents, such as, for example, inorganic salts, dextrin and, if appropriate, further 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 carboxylic acids, such as formic acid, acetic acid, propionic acid or lactic acid, and optionally other additives such as water-soluble polyhydric alcohols, their ither or Esters, polyethers, aliphatic carboxamides, lactams, lactones, nitriles, dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or urea as well as water contain. To prepare the dye baths which contain only organic solvents, for example chlorinated hydrocarbons, it is advantageous to use concentrated solutions which contain the dye as a free base or as a salt of a monobasic organic acid, chlorinated hydrocarbons, organic acids and polar organic solvents.

The new dyes form with anionic precipitants, such as clay, tannin or heteropoly acids such as phosphotungstic or molybdic acids, lightfast Pigments that can be used to advantage in paper printing.

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The following examples serve to illustrate the invention.

Example 1:

14.4 parts by weight. 4-chloro-2,6 ~ diamino-N-methylaniline sulfate as mononydrate are dissolved in 25 parts by volume of 95% sulfuric acid with stirring. After cooling to 0-5 ° C is allowed to 16.6 Voluraenteile Mtrosylschwef elsäure (approx.41% strength) are added dropwise so that the temperature is maintained at 8-10 ⁰ 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 is allowed in the course of about 30 minutes to the filtered solution of the thus obtained diazotized 5-chloro ~ 7-amino-l-methyl-benzotriazole at 10 ⁰ C, a solution of 13 parts by weight ß (N ~ ethyl-N-phenyl) -amino-propicnsäurebutylester in 50 parts by volume of glacial acetic acid. After the coupling has ended, the dye is filtered off with suction, washed with a little water and again stirred with water. The dye suspension is then made alkaline with approx. 50 parts by volume of 2N soda solution, and after 1 hour the dye of the formula is sucked off

^ CH _t

N ^d ■

N-CH

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

16 parts by weight of the dried material are used for quaternization Dye dissolved in 250 parts by volume of chlorobenzene. To the Removal of the last traces of water, about 80 parts by volume of chlorobenzene are distilled off, 0.5 parts by weight are added Magnesium oxide and drop in about 30 minutes at 80 ~ 85 ° C Add 5 parts by volume of dimethyl sulfate. One stirs until

~ 9 3Q9847 / 0975

Completion of quaternization approx. 5 hours after. The chlorobenzene is driven over with steam. The remaining aqueous dye solution is made up to 600 parts by volume and precipitated with 27 parts by weight of common salt and 5 parts by volume of zinc chloride solution (about 64%). After suctioning off and drying at 50 ⁰ G , 17 parts by weight of the dye of the formula "'

fl, C-N ® "N-CH, 3 ν jj χ 5

n:

.C ₂ H ₅ ; CH ₂ -CH ₂ -COOC ₄ Hq

ZnCl,

which is bluish-red in water as well as in aliphatic Carboxylic acids, such as acetic or formic acid, optionally also in mixtures of these acids with other solvents, such as alcohols, ketones, 'carboxamides or carboxylic acid esters, dissolves. He dyes polyacrylonitrile fibers from weak acidic bath in light and wet-fast Bordo tones.

Example 2:

4-5 »4 parts by weight of 5-chloro-7-amino-1-methylbene; isimidazole are mixed with 7» 5 parts by weight of magnesium oxide in 125 parts by volume of water and stirred at 50-60 ° C. for about 1 hour 38.8 parts by volume of dimethyl sulfate are added. 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, rapid addition of 52 parts by volume of ρμ sodium nitrite solution is diazotized. After destroying a small amount of nitrite

309847/0975

- IU -

The yellow-brown, clear Diazolösimg is mixed with a little amidosulfonic acid in a mixture of 58 parts by weight ß- (N ~ ethyl ~ N-m-toluyl) ~ arainopropionic acid ethyl ester, 1200 Parts by volume of water and 100 parts by volume of 5N hydrochloric acid come in. The pH value is concentrated with sodium hydroxide solution. to 1.5 posed. After adding 80 parts by weight of sodium chloride

the dyestuff which has precipitated out in red crystals is filtered off with suction.

washed with a little water and dried.

87 parts by weight of the dye of the formula are obtained

N = N- / V ^N \ ^C1

CH ₀ -CH ₀ -COOCH

H _x CN @ N-CH _x

θ ' ^j

H ..

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 lightfast and wetfast yellowish red tones. The dye can also be obtained by coupling diazotized 1-methyl-5-chloro-7-aminobenzimidazole with β- (N-ethyl-N-m-toluyl) -amino-propionic acid and subsequent quaternization and simultaneous esterification with dimethyl sulfate in water in the presence of sodium bicarbonate or in acetone in the presence of potassium carbonate, or by coupling of diazotized 1,3-Dimethyl-5-chloro-7-amino-benzimidazolium methyl sulfate with ß- (N-ethyl ~ N ~ iB-toluyl) -aminopropionic acid and then Establish esterification with dimethyl sulfate in water in the presence of sodium bicarbonate.

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Example 3:

36 parts by weight of 2-amino-6-methoxy-benzothiazole are introduced into 300 parts by volume of glacial acetic acid. After adding 200 parts by weight of ice, 40 parts by volume of 5N sodium nitrite solution are added all at once. The mixture is stirred for 15 minutes with good external cooling, 4-5.5 parts by weight of methyl β- (N-ethyl-N- (5 ^l -methyl-phenyl) -amino-propionate) are added, and the mixture is stirred at room temperature for 30 minutes and heated to 40.degree and stirred for 1 hour at 40 ° C. The coupling device is diluted with 1000 parts by volume of water, the precipitated dye is filtered off with suction, washed with water and dried, giving about 32 parts by weight of dye of the formula

CH ₂ -GH ₂ -COOCH ₅

For quaternization, 32 parts by weight of dye are introduced in 200 parts by volume of glacial acetic acid and 6 parts by weight of magnesium oxide are added. Then, the Färbstofflösung is heated to 50 ⁰ C, is added at 50-60 C with 30 parts by volume of dimethyl sulfate and stirred for 1 hour at 60 ° C "and 2 hours at 90 ⁰ C. After distilling off 100 parts by volume of glacial acetic acid is diluted with 1,000 parts by volume water, filtered, the dyestuff precipitated by adding sodium chloride and zinc-chloride solution, filtered off with suction and dried, giving 35 parts by weight of dyestuff of the formula.

N " _{n T} , ZnC l,

\ < ^{2 5} ^

η ηη ^ ν ^ ς / V = ⁷ CH ₀ -CH ₀ -COOCH ^H 5 ^{C0 S} CH ₇ .2 2

- 12 -

309847/0975

which turns blue in water as well as aliphatic Carboxylic acids, such as acetic or formic acid, optionally 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.

Example 4-:

11 parts by weight of N-methyl-benzthiazolon-2-hydrazone and 21.4 parts by weight of ß- (N- (2'-chloro-phenyl) -amino-propionic acid methyl ester are in 640 "parts by volume of water and 160 parts by volume 5N hydrochloric acid dissolved at approx. 4-5 ° C with stirring. then a solution of 64 parts by weight of crystalline is added dropwise. Iron III ™ chloride in 100 volumes ilen V / ater and stir until the end of the reaction (approx. 6 hours). The resulting Solution is filtered with animal charcoal and kieselguhr, through Zugsoe The dye is precipitated from zinc chloride and sodium chloride and acidified washed with 5% sodium chloride solution and dried at 60.degree. About 21 parts by weight of the dye of the formula are obtained

N - \ V NH-CH ₀ -Ch ₀ -COOCH, Cl

₀ -Ch ₀

which is blue in water as well as in aliphatic Carboxylic acids, such as acetic or formic acid, optionally 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.

309847/0975

Example ^:

8.4 parts by weight of 3-amino-l, 2,4-triazole are dissolved in 12 parts by volume of water and after 30 min slowly with 30% parts by volume% sulfuric acid was added such that the temperature does not exceed 50-6O ⁰ C. The clear solution is cooled to 0-5 ° C. and the amine is diazotized at this temperature by dropping 15.2 parts by volume of nitrosylsulfuric acid (approx. 41%) in the course of approx. 15 minutes. The mixture is stirred at 5-10 ° C. for a further 30 minutes and the nitrosyl melt is then poured onto a mixture of ice and water. After a slight excess of nitrite has been destroyed, the diazo solution is added dropwise to a solution of 21.0 parts by weight of methyl β-(N-ethyl-N-phenyl) -amino-propionate in 20 parts by volume of glacial acetic acid. Part of the mineral acid is taken back by dropwise addition of 2N sodium acetate solution, the precipitated dye is filtered off with suction and washed with water. The filter cake is again mixed with approx. 500 parts by volume V / water, then made alkaline with soda solution, the dye of the formula

CH ₀ -CH ₀ -COOCH

filtered off, washed and dried at about 60 ⁰ C.

For quaternization, 24 parts by weight of the dried dye are dissolved in 350 parts by volume of chlorobenzene. To remove the last traces of water, about 50 parts by volume of chlorobenzene are distilled off, 10 parts by weight of magnesium oxide are added and in about 10 minutes at 80 ^ 3 20 parts by volume. Add dimethyl sulfate. The mixture is stirred for a further 5 hours at 95-10O ⁰ C until the quaternization has ended. The dye is isolated from the chlorobenzene, dissolved in hot water, the solution is adjusted to pH 2-3 with hydrochloric acid and, after the addition of animal charcoal and kieselguhr filtered. · '

309847/0975 ~ ^1M ~

The dye is precipitated by addition of zinc chloride solution and sodium chloride, filtered off with suction, washed with 5% brine and dried at about 60 ⁰ C. About 15 parts by weight of the dye of the formula are obtained

N-N- CH,

Il Θ II ° / j ~ x ^ CpH, ZnCl ^θΘ

CH CN = N- / VN ^d ? ^{Lmj 1} H-

2 ·

CH

in the form of a red powder that dissolves in water and in dilute acetic acid or formic acid with a red color and dyes polyacrylonitrile fibers in lightfast and wetfast red tones.

Example 6:

To a suspension of 8.8 parts by weight of 1-Phenylguanazol in 6.2 Volurnenteilen water is added dropwise at about 60 ⁰ C 14.75 VoluBienteile sulfuric acid 95% "said solution occurs. When cooling to 5 C, the sulfate of the l-phenylguanazole separates out. At 5-10 ^° C., 7 * 6 parts by volume of nitrosylsulphuric acid (approx. 41%) are diazotized, stirring is continued for 30 minutes at 5-10 ° C., the excess nitrite is eliminated with amidosulfoεäare and the diazo melt is converted into a solution of 10.4 parts by weight - (N-Ethyl-N-phenyl) -amino-propionic acid methyl ester added to 50 volumes of ilen glacial acetic acid. After stirring for 3 hours, the coupling mixture is poured onto ice water and made alkaline by dropping 2N soda solution. The deposited dye of the formula

CH ₂ -CH ₂ -COOCH ₅

is isolated, washed neutral and dried.

309847/0975

11.3 parts by weight of the dye are used for quaternization and 10 parts by weight of magnesium oxide in 200 parts by volume of chlorobenzene entered, at 70 C one drips in 60 minutes Add 20 parts by volume of dimethyl sulfate and stir until the end the quaternization (approx. 6 hours) at 90-95 ° C. After this Cooling to room temperature, the separated dye is separated from the chlorobenzene, washed several times with chlorobenzene, dissolved in water and hydrochloric acid and added Table salt precipitated.

After drying, 15.6 parts by weight of the dye are obtained the formula

O -N - N- CH,

HN = C CN = N- (Z VH ^ ^ ^p C1 ^u

\ '\ - = / "CH ₀ -CH ₀ -COOCH,

CH ₂

of polyacrylonitrile fibers in light and wet-fast red tones colors. ■

Example ?:

15.8 parts by weight of 5-amino-3-phenyl-pyrazole are added in 60 volumes share glacial acetic acid and 4-0 parts by volume of 5N sulfuric acid. At 15 ~ 25 ° C, 20 parts by volume of 5n ~ sodium nitrite ~ solution diazotized. The resulting diazo suspension is left into a mixture of 25 parts by weight of β- (N ~ ethyl-N-phenyl) ~ Amino-propionic acid ethyl ester iind 100 parts by volume of water enter. It is adjusted to a pH value of with sodium hydroxide solution and separates the dye of the formula

away. ·

.30984 7/0 97 5 ~ ¹⁶

The dye is used for methylation and quaternization 300 parts by volume of toluene taken up, azeotropically dehydrated ■ and filtered. The filtrate is 14 parts by weight Magnesium oxide added. 29 parts by volume of dimethyl sulfate are added dropwise at the boiling point and the mixture is stirred until the end quaternization after 5 to 6 hours at the boiling point. The deposited dye is separated from the toluene, dissolved in water and acidified with dilute hydrochloric acid. To Filtration and precipitation with common salt and zinc-chloride solution separates the dye.

After suctioning off and drying, about 10 parts by weight are obtained Dye of the formula -. ·

C - C-H / CVA

H ₅ CN ^ CN = N- / VN ^ ² ^

^V N ^X · ^ "^^ ^ ^CH 2 ~ I
CH ₅

which are in water and aliphatic carboxylic acids, such as acetic or formic acid, optionally also in mixtures of the acids with other solvents, such as alcohols, ketones, carboxamides or carboxylic acid esters, easily dissolves and Polyacrylonitrile fibers in light and wet-fast orange tones colors.

Example 8:

55 ₁ 5 parts by weight of 6-chloro ~ 3-3mino-indazole are added to 400 parts by volume of water and 560 Voluraenteile 5N sulfuric acid. At 35-40 C, 41 parts by volume of 5N sodium nitrite solution are diazotized, stirred for 1 hour and the excess nitrite is destroyed with sulfamic acid. The filtered diazo solution is allowed to run into 3500 parts by volume of water and 45.4 parts by weight of β- (i-ithyl-N- (3'-methylphenyl) aminopropionic acid methyl ester

309847/0975 - 17 -

- ■ 37 -

is crystallized with 190 parts by weight. Buffered sodium acetate. After the coupling has ended, it is filtered off with suction, washed with water and dried. 72 parts by weight of dye are obtained the formula

N ^

CH ₂ -CH ₂ -COOCH ₃

CH

For methylation and quaternization, 36 parts by weight of the Dye azeotropically dehydrated in 500 parts by volume of toluene. Then 14 parts by weight of magnesium oxide are added and at Boiling temperature over the course of about 90 minutes with 29 parts by volume Treated dimethyl sulfate. The reaction is after approx Hours ended. The deposited dye is from the toluene

separated and by dissolving in water and hydrochloric acid and subsequent Precipitation cleaned with zinc chloride solution.

About 30 parts by weight of dye of the formula are obtained

C ₂ H ₅ CH ₂ -CH ₂ -COOCH ₅

ZnCl

ΘΘ

which in water and aliphatic carboxylic acids wi _t "acetic or formic acid, optionally in mixtures of the acids with other solvents such as alcohols, ketones, carboxylic acid amides or Carbonsäureestern, readily dissolves and Polyakrylnitrilfasern in light- and wet-fast colored bright" Bordotönen.

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The table below contains more according to the invention Dyes and the shades of the dyeings obtainable with them on polyacrylonitrile fibers:

dye

hue

ZnCl ₄

Vnhch ₂ ch ₂ cooch ₅ —g ---

CH _x -N © N-CH,
CH

Cl

Golden yellow

dito

Cl

ZnCV ³ * = 'golden yellow

dito

ZnCl

CH ₂ CHpCOOC ₄ H ₀ 2

4___ orange

dito

n:

ZnCl

CH ₀ CH ₀ COOCH
dd

4 orange

dito

CH-,

ZnCl;

Red

dito

CH ₅

CH ₀ CH ₀ CN
CH ₂ CH ₂ COOC ₄ Hq

orange

309847/0975 ^v

~ 19 -

dye

hue

ν = N- / Vn!

orange

CH -, - Ν © N-CH- ^ CH

dito

ZnCl

■ 4

CH CH ₂ CH ₂ COOC ₂ H

Red

dito

Cl

^ C ₂ H ₅ ZnCl ₄ ^ ⁰

N ^ 5 ¹ yellowish tinge

^ CH ₂ CH ₂ COOC ₄ Hq ^d Red

dito

ZnC 1 "™ yellow

CH ₀ CH ₀ COOCH,

dito

-CH ₀ CH ₀ COOCH

Red

dito

dito

OH

N-CH ₀ CH ₀ COOCH,

CH ₀ CH ₀ OH

²

CH ₀ CH ₀ COOCH,

^ ⁰ - ¹ *** purple

^Znül 4 yellowish 2 red,

dito

Cl ^ZnC1 l orange

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Dye hue

Cl

VV ~ N = N CH _x -N © N-CH _x CH _x ZnCl,

NHCH ₀ CHCOOCH _x

² I.

CH _x yellowish! Red

dito

CH,

n;

CH ₀ CH ₀ COOCH ₀ CHCH OH reddish orange

dito

-CH ₀ CH ₀ COOCH blue

dito

^ CH ₄ OH

^ -N ^ Cl ^u Orange

^ CH ₂ CH ₂ COOCH ₂ CH (Ch,) ₂

dito

-CH _x

Vn-c? I ₂ ch _? cooch ₂ chc _/} Hq orange

dito

dito

CH ₀ CH ₀ Cl

CH

CH ₃

CH, ZnCl,

Rotoran ^ e

ZnCl,

'11VyIl _x

OH

Red

3098Λ7 / 0975 '

Dye hue

Cl

CH

N = NC Vn-CHCH ₂ COOCH ₇

CJ

CH,

CH ₂ -N © N-CH ₇ \ / ZnCl,

orange

dito

CH

\ _ N-CHCH ₂ COOCH ₅

CH ₇ 3-ZnCl,

Red

dito

CH ZnCl;

orange

Cl

C ₂ H ₅ - w_A Vn-CH ₀ CH ₀ COOCH,

CH ₇ -N N-CH ₃ ZnCl,

Bordo

dito

N-CTI ₀ CH ₀ COOCH ₇

CH, ZnCl,

violet

d j to ZnCl,

violet

309847/0975

-

dye

CH ₀ CH ₀ CN

C-

₀ CH ₀

C. C

= K

CH _x -N N-CH ■>% / '-

' IT

dito

CH.

hue

ZnCl,

Board o

Bordo

ditto -f ~ \ ~ N-CPI ₀ CH ₀ COOC (CH _x ), Cl *

ν = '

CH-

violet

dito

? 2 ^H 5

/ VN-CIi ₀ CH ₀ COOCH ₀ CH-CH

ei d d ^

Cl ^w purple

CH _x

OH

, —Ν I ^ - ^ ΖηΟΐΛ ^

ditto ~ </ VN-CH ₀ CH ₀ COOCh ₀ CH ₀ OCOCH ₇ - ~ _ο ~ -ί- ~ -

^{λ /} 22 22 52

Board ο

dito

Bordo

dito

CH

ZnC I

Bordo

~ 27)

3098 4.7 / 0976

~ 25 -

dye

hue

- N = N

CH _x -N N-CH

IT

ZnCl ₁

Bordo

CH ₇

N.

C -

N = ·· N- / Vn-CH ₂ CH ₂ COOCH,

blue

CH

dito

N-CH ₂ CH ₂ COOC ₂ H ₅

ZnCl,

B181J

ditto CH ₇
ί ' Vn-CH ₂ CH ₂ COOCH-

ZnCl,

Cl

blue

CH-

I -

© c

CH

N = N- ^ ~ Vl

ZnCl ₁

2

blue

dito

blue

309847/0975

Dye hue

CH ₂ ι 3

0C-

-N-CH ₂ CH ₂ COOCH

CH, he

blue

dito

CH

-N-CR ₀ CH ₀ COOCH er

blue

dito

CH ₅ N '

CH ₀ CH ₀ COOCH-, blue-red

CH,

3C-N =

CH

N =

CH,

dito

° 2 ^H 5

CH, ZnCl

blue

ZnCl,

blue

ZnC I T

blue

dito

/ 49

- / ~~ \ - N-CH ₂ CH ₂ COOC ₂ II ₅ ZnCl,

blue

309847/0

Dye hue

H _$ C - N ©> - N

dito

Cl

C.

cn / ⁿ \

ZnCl, ZnCl,

blue

blue

dito

/ "Vn / ηΛ

. ch ₂ ch ₂ cooch, ZnCl,

blue

H ₂ C -

Cl ZnCl,

Yiolet

H-C - S

H-C ^ C

CH,

N = N- /

2 = 5 ZnCl ₇ ΊΓ

blue

N-N-CH ₃

It © Il CH CN = N-

CH,

, ^C 2 ^H 5

H ₂ CH ₂ COOC ₂ PI ₅ ZnCl,

Red

- 26 -

309847/0975

dye

hue

N - N-CH-

CH C - N

CH,

= n- / ~ Vn- (

OH"

ZnCl,

RoI

f> -N - N-CH, CpH ₁ -

" 1-N = NC Vn-CH ₂ CH ₂ COOC ₂ H,

CH,

Red

dito

N-CH ₂ GH ₂ COOC ₂ H ^

CH _V

Red

dito

- N-CH ₂ CH ₂ COOC ₄ H ₉ er

Red

OH,

H-C N-CH,

N = N

N-CH ₀ CH ₀ COOCH ZnCl,

orange

ditto ~ <f ^x > -N-CH ₂ CH ₂ COOCH, CH,

ZnCl ,, ^ Red

309847/0975 - 27 -

Dye. hue

CH, ι 3

H-C N-CH.

CH

= N- / ~ V N-CH ₂ CH ₂ COOCH ₅ ZnC ΙΛ ^ orange

ditto '- / VNHCH ₂ Ch ₂ COOCH ₃

Cl

. Cl ⁰ golden yellow

/ Vc-C-H II ^ Il

CH

orange

CH,

dito

CH, ZnCl ,, ⁰⁹ scarlet fever

CH - CH H ₇ CN

CN = N - / "Vn-CH ₂ CH ₂ COOCH ₃ CH _V

dito

Red

Red

309847/0975 - 28

Dye hue

H, C-C -

Θ H _x CN CN = N-

w-CH ₀ CH ₀ COOCH- ²

CH, ZnCl ₁₁ ^ red

© N-CH "N ^

CH,

N =

~ ζ ~ \ ~ N-CH ₂ CH ₂ COOCH ₇

3 CH-ZnCl ,, ® ⁹ . Bordo

CH

- N - <f ~~ V N-

^ N-CH.

ι
CH-

OCH. _p '= N- ^ VN-CH ₂ CH ₂ COOC ₂ H ₅

CH. B or do

violet

dito

- / ~~ V NHCH ₂ CH

NHCOCH-, 5

Cl ^w Bordo

0 9 8 4 7/0975 '

Dye hue

N =

jl Θ N-CH ₇

CH,

dito

OCH ₃

^ - N-CH ₂ CH ₂ COOCH,

OCH,

• NHCOCH,

CIL violet blue

Cl ^w purple

N CH

N = N

ZnCl

Ά orange

dito

CH ZnCl,

CH-S Il ^ I CH ^ C - N

CH,

Ν- / Λ-Ν

CH ₀ CH ₀ COOC ₀ H ₁ purple

ditto - / \ nHCH ₂ CH ₂ C00CH ₅

dito

/ ΓΛΙ

■ IT

CH ₀ CH ₀ COOCH violet

Cl ^ bluish red

309847/0975 - 7,

Dye hue

CH _x

HC "- S ^ / -λ I ^ Il © CN = Ή-V VNHCHCH ₀ COOCH _x

HC- N ^ \ = ^ ^d -> ι ZnCl.

reddish blue

dito

OCH _x CH _x 3 |.

NHCHCHoCOOCH-ZnCl,

reddish blue

dito

2 ^Η 5

NHCHCh ₀ COOCH ₇ 2 blue-violet

CH ₃ , ι

NN II @ Il

HC CN ^V N "I.
CH,

dito

OCH _x CH _x J

NHCHCH ₀ COOCH _x 2 ZnCl,

ZnCl,

yellowish? Hot

blue i ge s red

ditto • ■ H

0C _o H _c CH ₇

25 ι

NHCHCH ₀ COOCH 2 ZnCl,

blues ichitre? Red

H ₇ CN N-CH-

/ i Vn =

Cl ditto

dito

CIL

OCH _x CH ₇ (3.3

NHCHCH ₀ COOCH

NHCHCH ^ COOCH-ZnCl,

ZnCl,

yellowish orange

orange

Scarlet fever

309847/0

Claims (3)

Claims ^. ? 9? ? O &? 1) Basic azo dyes that are free from sulfonic acid groups are and have the formula Θ f DNN.-AN- CH -CH- COOR ₁ Il Y Z- where D is a thiazolium, benzthiazolium, triazolium, benztriazolium, pyrazolium, indazolium, pyridinium, quinolinium or benzisidazolium radical, A is an optionally substituted phonylene or naphthylene radical or together with J £ _ a 1,6- ( 1,2,3, ^ - Tetrahydro ^ quinolinylene, l, 6 ~ BenzoHorpholinylen- or 1,3-indolylene radical, B hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, Y and Z hydrogen or a optionally substituted alkyl, R-, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical and] 1 denote an anion. 2) Process for the preparation of basic azo dyes ^ which are free of sulfonic acid groups "and have the formula D-N-Jf-A-N-. CH-CH- COOE, II ^λ _ Y ί. ■ '_ where D is a thiazolium, benzthiazolium, triazolium, benztriazolium, pyrazolium, indazolium, pyridinium, quinoliniuia or benaimidazolium, A is an optionally substituted phenylene or haphthylene rust or together with _ | j__ a l, 6- (1,2,3,4-tetrahydro) -quinolynylene, 1,6-benzoinorpb.olinyle'n- or 1,3-indolylcnrest, R is hydrogen, an optionally substituted alkyl, cycloalkyl, aralkylTM or aryl radical, Y and Z denotes hydrogen or an optionally substituted alkyl radical, Ji ₁ denotes an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical and 51 "denotes an anion, nn ^r ~ lv-" denotes that 0 984 7 / OSTS BAD OBIGlNAt a) the diazoniim compound of a quaternary amine of the formula D - NH, wherein D and T ^ have the meaning given above, with a coupling component of the formula R.
A - N - CH - "CH - COOR ₁ Il J- Y Z in which A, R, Y ₁ Z and R. have the meaning given above, coupling, or that b) an azo dye of the formula IV D-N A - N - CH -.CH - COOR, IV where D is a thiazole, benzthiazole, triazole, benzotriazole, pyrazole, indazole, pyridine, quinoline or benzimidazole radical and A, R _1, Y, Z and R, as defined above, are treated with alkylating agents , or that c) an azo dye of the formula V R.
A-N-CH-CH-COOH D-N = N-A-N-CH-CH-COOH X wherein D, A, R, Y, Z and X ^ have the meaning given above have, with an aliphatic, cycloaliphatic ^ or araliphatic alcohol. or an aromatic oxy compound; esterified. 3 Ü yb ¹ 4 7 / (i 9 7 3) Use of dyes according to claim 1 for dyeing odor Printing of textile material made from natural and synthetic fibers. Use of dyes according to claim 1 for dyeing or Printing of textile material made from synthetic fibers containing acidic groups. Agent for dyeing textile material made from natural or synthetic fibers, containing one or more dyes according to Claim 1 ^: 7/0975