DE2360986A1 - Polycyclic azo dyes for synthetic fibres and polymers - and prepd. from diazotised 3-amino indazole coupled with substd. pyridines - Google Patents

Abstract

Polycyclic dyes of formula (I) (in which R1 is hydrogen or opt. substd. alkenyl, (ar)-alkyl, cycloalkyl, or aryl, R2 is cyan, carboxylic ester or amide, alkyl sulphone or aryl sulphone. R3 is prim. sec or tert. amino hydroxy or (thio) ether, and ring A may be further substd), are used as dispersion dyes for synthetic fibres, esp. polyamides and aromatic polyesters, and mass colouring of polymers. Soluble quaternised dyes are suitable for mordanted cellulose, silk, leather and synthetic fibres esp. polyacrylonitrile or polyvinylidene cyanide. (I) give intense, fluorescent yellow shades of high strength and brilliance with excellent temp. resistance and good light and wet fastness.

Description

FARBWERKE HOECHST AG formerly Master Lucius. &. Brüning

File number: HOE 73 / P 382

Date: December 6, 1973 Dr. ST / stl - ^; ; ..

Polycyclic dyes, process for their preparation and. their Usage: ■

Additional application to patent application P 23 55 967.3 (HOE 73 / F

The present invention relates to new polycyclic compounds, Process for their manufacture and their use.

Subject of the main application. P'23 55 967.3 (HOE 73 / F 3 ¹ II) are new compounds which correspond to the general formula (A)

wherein D is a mononuclear or polynuclear heterocyclic ring and B mean an aromatic or heterocyclic ring, preferably compounds of the formula (B)

^X 3

509830/0910

in which Y is a lower alkyl radical, V / hydrogen, a halogen atom, a nitro or cyano group and V is a lower alkyl radical, an alkoxy or aryloxy group or a primary, secondary or tertiary amino group, R 'a lower alkyl radical, an aralkyl or aryl radical, X is a secondary or tertiary amino group,

In a continuation of the inventive concept, new connections were made found that contain an indazolyl radical.

The new compounds of the present invention correspond to the general formula I.

wherein R. is hydrogen, an optionally substituted alkyl, Alkenyl, aralkyl, cycloalkyl or aryl radical, R "a cyano, Carboxylic acid ester, carboxamide, alkyl sulfone or aryl sulfone radical, R is a primary, secondary or tertiary amino group, a hydroxyl, ether or thioether group and the benzene nucleus A may optionally contain further substituents.

These substances can be obtained in such a way that compounds of the general formula II

X ¹

N = N ft ^ iC ^ Z

^ (II)

in which A, R., Rp and R have the meaning given above and Z is a removable group, for example a hydroxy, alkoxy or is an optionally substituted amino group, cyclized and then optionally quaternized or sulfated.

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2360988

The cyclization can be carried out by heating in a suitable solvent, for example in-water, or-an organic solvent, such as ethyl alcohol, amyl alcohol, ethylene glycol, acetone, Dichlorobenzene, chloroform, acetic acid, propionic acid or dimethylformamide, expediently in the presence of an organic acid or one Base.

The compounds of the formula II used as starting compounds can by coupling of .diazotized amines of the formula III

(III)

in which A has the meaning given above, with azo components of formula IV ■

(IV)

wherein R., Rp, -R, and Z have the meaning given above, will be preserved. . ·

Amines of the formula III are, for example, 3-aminoindazole itself or 3-amino-indazöle which have substituents in the benzene nucleus A,. for example halogen atoms, alkoxy, aryloxy, alkyl 1 , trifluoromethyl, nitro, alkylsulfonic, arylsulfonic, sulfonic acids, optionally substituted sulfonic acid amide, mono- or dialky1-amino, arylamino, cyano or acyl groups ,, where the alkyl radicals contained therein preferably have 1 to 4 carbon atoms and the aryl and acyl radicals preferably denote the phenyl or acetyl group.

Instead of a uniform diazo component, you can also use a Use a mixture of two or more diazo components *.

The pyridines used as azo components, der- ■ Formula.-IV leave by reacting the corresponding 2,6-dichloro or 2,6-

5098307091Q

-n-

Dibromopyridines with the corresponding amines or hydroxy compounds obtain.

The halogen atoms can optionally be exchanged in two stages, with ^{a chlorine or bromine atom at a lower temperature, for example between about 30 and 100 °} C., and then at a higher temperature, for example between about 100 and 200 ° C., the second chlorine or bromine atom is exchanged. In this way, two different radicals R, and Z can be introduced. To introduce the same radicals R ^, and Z, the implementation is at about 100

ο
up to 200 C.

The reaction can be carried out in an inert organic solvent or in an excess of the amine or the hydroxy compound, possibly under pressure.

The primary and secondary amines are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic amines into consideration. Suitable primary amines are, for example:

Ammonia, methylamine, ethylamine, 2-hydroxyethylamine, 2-methoxyethylamine, 3-phenoxyethylamine, n- and iso-propylamine, 3-hydroxy-, 3-methoxy- and _; 3-iso-propoxypropylamine, 3-cyano-propylamine, allylamine, 1- or 2-methallylamine, n-, iso-, sea- and tert-butylamine, 2-amino-2-methyl-propanol- (l ), Crotylamine, 3-amino-pentane, n- and. iso-amylamine, aniline, methyl- and methoxyanilines, dimethylanilines, amino-naphthalenes, Ν, Ν-diethylethylenediamine, Ν, Ν-dimethyl- or Ν, Ν-diethylpropyl-diamine (1,3). Secondary amines are, for example, dimethylamine, diethylamine, N- (2-cyano-ethyl) -N- (2-hydroxyethyl) amine, N-di- (2-hydroxy-ethyl) amine, N-di - {2- cyano-ethy1) -amine, N-methyl-, N-iso-propyl-, Nn-butyl-, N-cyclohexyl- and N-benzyl- (2-hydroxy-ethyl) -amine, di-η- and di- isopropylamine, di-η- and diiso-b'utylamine, di-n-amyl- and di-n-hexylamine, morpholine, pyrrolidine, piperidine, N-methyl-piperazine, N-methyl- and N-ethyl-cyclohexylamine , N-methyl-benzylamine, N-methyl-3-methyl-benzylamine, N-methyl-, N-ethyl-, N-2-hydroxy-ethyl- and N-benzyl-aniline, N-methyl- and N-ethyl -2-chloro-aniline.

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Suitable hydroxy compounds for the reaction with the 2,6-halopyridines are aliphatic, araliphatic, cycloaliphatic, aromatic and heterocyclic hydroxy compounds, for example aliphatic alcohols with 1 to 8 carbon atoms, alkylene glycols and their ethers, cyclohexanols, phenylalkyl alcohols, Phenols, dihydroxybenzenes and their monoethers, naphthols and heterocyclic ones Hydroxy compounds into consideration.

The diazotization of the amines of the formula (III) can be carried out according to known methods Methods, for example using alkyl nitrite and an inorganic one Acid, for example hydrochloric acid γ sulfuric acid or phosphoric acid, or by means of nitro'sylsulphuric acid.

The coupling with the azo components of the formula (IV) can likewise in a manner known per se, e.g. in a neutral to acidic environment, optionally in the presence of sodium acetate or other known buffer substances which influence the coupling speed or catalysts, such as, for example, dimethylformamide, pyridine or its salts, can be carried out. ·. '".-

Of these new connections, those that should be emphasized are. do not have any water-solubilizing groups and are particularly suitable for dyeing; of polyester fibers. .

Of the new compounds of the present invention are as preferred to mention those of the formula (V)

in which A, R ₁ and R, have the above meanings. ; , - ■

• In particular, of the new compounds of the general formula (I) of the present invention, those dyestuffs which have the general formula (VI) '' ■. -'..- '..'. 'Are to be mentioned as preferred and advantageous. - ..

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23609 * 6

in which R is a hydrogen atom, a chlorine or bromine atom, the methoxy, ethoxy, methyl, ethyl, nitro or cyano group, Z. and Z_ are identical or different and each is a hydrogen atom, an alkyl radical from 1 to 6 Carbon atoms, preferably from 1 to 4 carbon atoms, which by chlorine, hydroxy, cyano or alkoxy groups with 1 to Ά carbon atoms, preferably methoxy and ethoxy groups, amino, a monoalkylamino or a .Dialkylamino with 1 to ¹ J. Carbon atoms in the alkyl radical or by a trialkylamino group with 1 to 3 carbon atoms in each alkyl radical, or each a cyclo ^ hexyl radical, the benzyl or phenyl radical, which is in the nucleus by chlorine, methoxy, ethoxy, methyl, ethyl , Nitro, sulfo, amino, monoalkylamino or dialkylamino groups can be substituted with 1 to Ί carbon atoms in the alkyl radical, or Z ^ and Z "together with the nitrogen atom are a morpholine or piperidino ng form and R ^. is an alkyl group of 1 to 1J carbon atoms or the phenyl or benzyl group.

Of these, however, those compounds of the formula (VI) should be emphasized in which R ₁ , the methyl, ethyl or phenyl radical, Z. hydrogen, an alkyl radical with 1 to k carbon atoms or a hydroxyalkyl radical with 2 to 3 carbon atoms, Z ₂ hydrogen, an alkyl radical with 1 to M carbon atoms, a hydroxyalkyl radical with 2 or 3 carbon atoms, an alkoxyalkyl radical with 1 to H carbon atoms in the alkoxy radical and 2 or 3 carbon atoms in the alkyl radical, a cyclohexyl, benzyl, phenethyl, phenyl or naphthyl radical or Z ₁ and Zp together with the N atom is a morpholine ,. Mean piperidine or piperazine radical and R has one of the meanings given above.

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2360S86

Compounds of the formula (VI) in which R represents the sulfo group and Z ₁ and / or Z 'represents an alkyl radical which is substituted by the sulfato (- OSO, H) group are preferred compounds for dyeing wool and synthetic polyamide fibers.

The compounds of the formula (VI) can be prepared from amines of the formula (VII) according to the abovementioned process

(VII)

wherein R has the meaning given above, as diazo components or from pyridine compounds of the formula (VIII). "_

(VIII)

as coupling components in which Rk, 2.-, -Zp- and Z have the meanings given above, and subsequent cyclization of the Azo dye are produced. Preferred of the amines are of the formula (VIII) those in which the radical Z is a hydroxy, Methoxy or fithoxy group or an amino group of the formula

2
means in which Ί, and Z “have the above meanings.

The compounds of the formula I obtainable according to the invention represent new, "valuable dyes, which are, provided they are free from Sulphonic acid groups are excellent for dyeing and printing of synthetic fibers, for example of polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds,

5098 30/09

such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or Vinylidene chloride, or from copolymers of dicyanethylene and Vinyl acetate, as well as from aeryl nitrile block copolymers, fibers from polyurethanes, polypropylene, cellulose tri- and 2 1/2 acetate and in particular fibers made of polyamides, such as polyamide-6, polyamide-6,6 or polyamide-12 and from aromatic polyesters, such as those made from terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol, suitable. They produce predominantly yellow, intensely fluorescent colorations of high color strength and brilliance, which are excellent Temperature resistance and in some cases also have good light and wet fastness properties.

If the dyes of the formula I have water-solubilizing groups, such as sulfonic acid groups, they are suitable ■ for dyeing wool and polyamide fibers.

The new dyes of the formula I are also suitable for dyeing synthetic polymers such as polystyrene, polyvinyl chloride, polymethacrylate, polyethylene or polypropylene in the bulk.

For dyeing in aqueous liquors, the water-insoluble dyes of the formula I are expediently used in finely divided form and dyeing with the addition of dispersants at temperatures between 95 and 120 ^° C. ' . '

The dyes can also be used in dye baths that contain organic solvents included.

The new dyes of the formula I, which have quaternary groups, can be obtained in such a way that the dyes of the formula I which contain quaternizable groups with alkylating Means treated. Preferred quaternary groups are ammonium radicals and the hydrazinium groups.

Alkylating agents are alkyl halides, aralkyl halides, Halogenacetamides, ß-halopropionitriles, halohydrins, alkylene oxides, Acrylic acid amide, alkyl esters of sulfuric acid or alkyl esters organic sulfonic acids into consideration.

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23609S8

Suitable alkylating agents are, for example, methyl chloride, ' -bromi-d or -iodide, ethyl bromide or -jödid, propyl bromide or -iodide, benzyl chloride, chloroacetamidj ß-chloropropionitrile, ethylene chlorohydrin, Dimethyl sulfate, benzenesulfonic 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 hydrocarbon, 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 * -Dime.thylsulfoxyd or in a ketone: such as acetone or methyl ethyl ketone. Instead of an organic solvent an excess of the alkylating agent can also be used.

The alkylation is at elevated temperature, optionally below Addition of acid-binding agents, such as magnesium oxide, magnesium carbonate, Soda, calcium carbonate or sodium bicarbonate and possibly under pressure. The cheapest Conditions can easily be determined by a preliminary test.

If appropriate, the alkylation can also; made in water will. ■ ": .- :. ',.

The new dyes that have quaternary groups contain as Anion preferably the remainder of a strong acid, for example "... ' sulfuric acid or its half-ester, an aryl sulfonic acid or a hydrohalic acid. This procedure was introduced according to Anions can also be replaced by anions of other acids, for example the Phosphoric acid, acetic acid, oxalic acid, lactic acid or tartaric acid ». be replaced. The dyes can also be in the form of their double salts obtained with zinc or cadmium halides. ':

The dyes of the formula I according to the invention with an optionally quaternized amino or hydrazino group are suitable for Dyeing or printing of tannin cellulose fibers, silk, leather or fully synthetic fibers, such as acetate silk, polyamide fibers or acid-modified polyamide or polyester fibers, in particular

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23809-86

however, from polyacrylonitrile or polyvinylidene-cyanide-containing fibers. The colors available on these pastes are mostly very strong in color and generally have good light and wet fastness properties, for example good washing, fulling, dyeing, carbonizing, chlorine and perspiration fastness, as well as good decatur, Steaming, ironing, rubbing and solvent fastness properties. The dyes are generally largely insensitive to a change in the pH of the dye bath and can therefore both can be used in weakly acidic as well as in strongly acidic baths. They are also at temperatures above 100 C, as they are at used in high-temperature dyeing. Wool becomes complete by the dyes under normal test conditions reserved.

The dyeing 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.

If the dyes of the formula I are reactive radicals such as vinylsulfone, ß-sulfatoethylsulfone, mono- or dichlorotriazine, di- or trichloro- or -bromopyrimidine, eC- or ß-chloroacetyl or propionyl, Ä, ß- Dichloro ~ or. oC, ß-Dibrompropionyl- or contain Fluorcyclobutancarbonylgruppen, they can be applied according to the usual dyeing methods with reactive dyes. ¹

To prepare the aqueous dye baths and printing pastes you can use the Use dyes in the form of powders. With the wassei'unlösliehen It is generally expedient to prepare the dyes for dyes to convert the dyeing into dyeing preparations which contain a dispersant and the finely divided dye in such a form, that when the dye preparations are diluted with water, a fine dispersion is formed. Such staining preparations can be used in known Manner-be obtained, for example by grinding the dye in dry or wet form with surfactants Dispersants and optionally further grinding aids.

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236Q9 # 6

- - li - ■ - ■■ - ■■■■ '■■. '-

Suitable anionic dispersants are, for example, alkylarylsulfonates, Condensation products of formaldehyde with naphthalenesulfonic acids or ligninsulfonates. Nonionogenic dispersants, for example, are the action products of ethylene oxide on fatty alcohols or alkylphenols with a higher alkyl radical into consideration,

The water-soluble dyes containing one quaternizable amino group or a quaternary ammonium group, can also in the form of powders, optionally adjusting means _s such as inorganic salts, / dextrin and optionally other additives, is used. .

Advantageously, however, easier-to-use concentrated aqueous solutions of the dyes containing 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, the ethers or esters of which contain polyethers, aliphatic carboxamides, lactams, lactones, nitriles, dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or urea and water.

If the new dyes contain sulfonic acid or sulfate groups as water-solubilizing groups, they can be used for preparation of the dyebaths and printing pastes also in a more concentrated form Solutions are used which, in addition to the dye, have a water-soluble anionic, cationic or ni cn ti onogenic surface-active Agents and a water-soluble organic solvent, for example one of the solvents mentioned above, •contain.

The following examples serve to illustrate the invention. The parts are parts by weight, the percentages of solutions or mixtures are percentages by weight. Parts by weight and Parts by volume are related to the kilogram to the liter.

509830/0910

Example 1:

6.6 parts of 3-aminoindazole are diazotized in the usual way. The dxazonium salt solution is added dropwise to a solution of 13 »1 parts of 2- (β-hydroxyethylamino) -3-cyano-4-methyl-6-morpholinopyridine in 200 parts by volume of glacial acetic acid. The whole is stirred for 1 hour at room temperature. The mixture is then heated to 80-90 ° C. for 1 hour. The yellow dye which has precipitated is filtered off with suction, washed with bicarbonate solution and dried. After recrystallization from dimethylformamide, 15.5 parts of a dye of the formula are obtained

i NH-CH ₂ -CH ₂ -OH

in the form of yellow, felted needles with a melting point (with decomposition) of above 330 ° C. This dye dyes polyester fibers from aqueous dispersion in a conventional manner known in the art in bright yellow tones.

Analysis: C. MG = 319 H 3, 08 C ₁₆ H ₁ N ₇ O C. 60, 2 <fo _r H 97 Calculated: 60, $ 12, Found:

N 30.7 Io N 30, 2 ° / o

Examples 2-15:

Polycyclic ^ dyes of similar constitution, which also Able to dye polyester fibers, are obtained if one

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236O98S

instead of the diazo and coupling components given in Example 1 equivalent amounts of a diazo and coupling component given in Table I below as a reactant uses:

Table I.

Example diazo component coupling component

hue

a.Polyester

fiber

3-Amino-indazole 2- (3 '-Methoxypropylamino) <-3-cyano-4-methyl-6-diethylamino-pyridine

■ 3

3-amino-indazole

3-amino-indazole, 2-phenylamino-3-cyano-4-methyl-6-dimethylamino-pyridine yellow

2,6-bis-morpholino-3-cyano-4-methyl-pyridine yellow

3-amino-indazole, 2-propylamino-3-cyano-4-methyl -6-piperidino-pyridine

yellow

3-amino-5-nitro indazole

Z- (β-Hydroxyeth3> -) cyano- k -me thy1-6-dimethylamino-pyridine

yellow

3-amino-5-n ± trο ■ indazöl

2-phenylamino-3-cyano-4-me ■ thy1-6-morpho1ino-pyridiri

yellow

3-amino-5-nitro ■ indaz'ol

2- (3'-methoxypropylamino) -3-cyano-4-me ethyl 6-morpho1ino pyridine .

yellow

3-amino-5-nitro ■ indazole

2,6-Bi s- (N-methyl-N-ß-hydroxyethylamino) -3-4-me thyl-pyridine

yellow

10

3-amino-5-kitroindazole

2,6-bis-morpho1ino-3-cyano-; 4-methyl-pyridane

yellow

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Example diazo component coupling component

Shade a. Polyester fiber

11 3-amino-5-chloro
indazole 12th 3-amino-5-chloro
indazole 13th 3-amino-6-chloro
indazole 14th 3 - amino-6-chloro
indazole 15th 3-amino-6-chloro
indazole

2- (ß-hydroxy-ethylamino) -3-cyano - ^ - methyl-o-dimethylaminopyridine yellow

2-phenylamine-p-3-cyano-4-raethyl-6-diethylamino-pyridine yellow

2-Cyclohexylamino-3-c3'-ano-4-meth.yl-6-morpho lino-pyridine yellow

2-Phenylamino-3-cyano-4-methyl-6 ~ N-nieth.yl-N-ph.enyl aminopyridine yellow

2- (3'-Hydroxy-propylaraino ) ~ 3 ~ cyano-4-methyl-6-morpholinopyridine yellow

Example 16: -

16 parts of the dye obtained according to Example 1 are in 20 C in portions in 50 parts of concentrated sulfuric acid entered and stirred therein for 3 hours. The clear solution obtained is poured onto 200 parts of ice powder with stirring. The precipitated yellow dye is filtered off and in 200 part oi water at 80 C with the addition of caustic soda or Sodium bicarbonate dissolved so that a neutral solution is obtained will. During the cooling of this solution, ge3.be crystals precipitate, which are filtered off with suction, washed with 10% sodium chloride solution and then be dried. 12 parts of a yellow dye of the formula are obtained

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NH-CH ₂ -CH ₂ -OSOH

which dyes polyamide fibers and wool in fluorescent yellow tones. ".

Example 17-19:

Table II below contains further examples according to the invention Dyes in an analogous manner - according to the information in Example 16 are available * They are also capable of wool or polyamide fibers to be colored in clear, brilliant tones.

Table II '■ _ .

example

dye

Color on polyamide fiber

Cl

H,

■ Ν

NH-CH ₂ -CH ₂ -OSO ₃ H

yellow

example

dye

Color shade on polyamide fiber

yellow

NH- CH _? - CH ₂ - O S.0 "H

yellow

NH-CH ₂ -CH ₂ -OSO ₃ H

Example 20: '""

10.6 parts of 3-aminoindazole-5-sulfonic acid are dissolved in 200 parts of water and 18 part oil-concentrated hydrochloric acid slurried and with 0-5 C diazotized with 10 parts by volume of 5 * i-sodium nitrite solution, The diazonium salt solution is left in a solution of 13.1 parts 2- (β-Hydroxy-ethylamino) -3-cyano-4-methyl-6-morpholinopyridine drop into 200 parts of methanol. After the coupling is completed Methanol is distilled off and the remaining reaction mixture is heated to 90-95 ° C. for one hour. Then you let up Cool to room temperature, filter the precipitate formed

,O

and dried at ^ OC in \ ^r acuum. Yellow-brown crystals of a dye of the formula are obtained

CN

NH-CH ₂ -CH ₂ -OH

obtained that dyes polyamide fibers in fluorescent yellow tones. ■■■ "" ■. '

The 3-amino-indazole-5-sulfonic acid used as starting material is obtained according to the specifications of the DT-AS 19 * H 5 ^ 2, example ^ 2. _ "." "....-. ■

Example 21: / ■; -. ·· -

13> 3 parts 3-amino-indazole, suspended in ^ O parts concentrate ter hydrochloric acid and 100 parts water, at 0 to 5 -C with 20.5 Volumes, a 5N sodium nitrite solution diazo tier t. the Diet salt solution is added to a solution of 28.8 parts ■ 2,6-bis-morpholino-3-cyano-4-methyl-pyridine in 100 parts of glacial acetic acid; this solution is left to rest for 3 hours at room temperature, then sucks off the precipitated yellow dye, washes it with water and dry at 80 C in a vacuum. ·

28.2 parts of a yellow dye of the formula are obtained

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CD

the Polyethylene terephthalate fiber from an aqueous dispersion in colors fluorescent yellow tones.

Analysis: : N MG 28.4 C ₁₈ H ₁₅ N ₇ O N 28.2 Calculated 22 - -. Found: 41 Examples

The following table III contains further inventions like ate Dyes, for example in analog. Way according to Example 21 and polyethylene terephthalate fibers in coloring brilliant yellow tones:

Table III

Example diazo component

Coupling component

Shade a, polyester fiber

22 3-Aminoindazole 23 3-Aminoindazole

2,6-bis-piperidino-3-cyano-4-raethyl-pyridine yellow

2- (3-methoxypropylaraino) -3-cyano ~ 4-methyl-6-dimethyl ~ aminopyridine yellow ·.

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Example,

Diazo component coupling component

Shade a. Polyester fiber

24

3-amino indaz ο1

3-Amino indaz o'l 2, ö-Bis-dimethylamino - ^ -
cyano-4-methyl-pyridine

2-phenylamino 3-cyano-4-me ·
thy1-6-morpho1ino-pyridin

yellow

yellow

26th

3-aminoindazο1

3-aminoindaz oil

28 3-amino-5-chloro
indazole 29 3-amino-5-chlorine
indazole 30th 3-amino-5-chloro
indazole ' 3 ¹ 3-amino-5-chloro
indazole 32 "3 -Amino - 5 - chi ο r
indazole 33 3-Amino-S-iiit ^ o
indazole \ 3k ■ 3-aniino - 5-ni tr ο
indazole 55 3-amino-5-nitrο
indazole 36 3-amine ο-5-ni trο
indazole

2-Benzylamino-3-ethoxycarbonyl-4-methyl-6-diethylaminopyridine yellow

2,6-bis-morpholino-3-ca rhonamido-4-phenyi-pyridine yellow

2 i 6-bis-morpholino-3-cyano-

4-methyl-pyridine yellow

2,6-bis-diethylamino-3-cyano-4-methyl-pyridine yellow

2--U.--.Methyl -N- phenyl -amino -3-

cyano - ^ - methyl-6-dimethyl-

aminopyridine yellow

2- (3-acetoxypropylamino) -3-cyano - 4-methyl-6- ^ N-methyl-N-phenyl-aminopyridine yellow

2,6-bis-piperidino-3-cyano-4-

methyl pyridine yellow

2, ö-bis-morpholino - ^ - cyano - ^ -
methyl pyridine yellow

2, ö-Bis-diethylainino- ^ - cyano-4-methyl ^ pyridine yellow

2, ö-bis-piperidino-J-cyano-4-methyl-pyriaine yellow

2-propylamino-3-cyano-4-methyl-6-dimethylamino-pyridine yellow

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Example diazo component

Coupling component

Shade a, polyaraid

iaser

3-Amiiio-5-nitroindazole

3-Amxno-5-nitroindazole

3 - A.minp ~ 6-chloroindazole

kO 3-amino-6-chloro

indazole

3-amino-6-chloro

indazole

2-phenylamino-3-cyano-4-methyl-6-morpholinopyridine

gelh

2-Benzoyl amino-3-cyajao- h -methyl -6-N-methyl-N-phenyl-aminopyridine. yellow

2,6-bis-morpholino-3-cyano-4-methyl-pyridine . yellow

2- (1-Naphthylamino) -3-cyano-Jf-me tliyl-6-dime th.ylamirio -

pyridine yellow

2- (β-Hydroxy-ethylamino) -3-cyano - '^ - metllyl-6 - πlor · pholinopyridine - yellow

example

13 »3 parts of 3-amino-indazole are diazotized and coupled with 30.4 parts of 2- (3 ¹ -dimethylaminopropylamino) ~ 3-cyano-4-methyl-6-morph.olin.opyridine. A solution of sodium tetrachlorozincate is added to the dye solution obtained, and the dye salt thus obtained is precipitated with sodium chloride, then filtered off with suction and dried. ... "

The dye containing iiatrium chloride obtained as a brownish-yellow powder has the formula

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(CII) rN
(

and dyes polyacrylonitrile and acid modified polyester fibers in fluorescent yellow tones "

Examples ^ 3-59: .. · -

The following table IV contains further according to the invention Dyes of the general formula below

to dye the polyester fibers in brilliant shades

fortune. ': ■

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Table IV

Example,

R.

Substituent xn
A. - • Colors - 6- OCH yellow - - yellow 6-Br - yellow yellow yellow yellow yellow yellow

hk

hey
k ₇

CH

CH

CH

CH ₃ ;

CH _r

CH,

CH.

CH,

-NH-CH,

NH-C _O H_NH-CH (GH) ₂ NH-C ₄ H ₉

-NH-CH ₀ -CH ₀ -OCH,

-NH-CH ₂ -CH ₀ -OC ₄ H ₉

-NH-CH-CH \

CH ₃

C _n H ₁ .

-N-CH-CH-OH

-N (CH ₀ -CH ₀ -OH).

CH,

-Nv H 6-Cl
6-Cl

6-Cl
6-Cl

6-Cl

ge3.b yellow

yellow yellow

yellow

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Ex.

Substituent in
A.

hue

CH,

Π.

"N-H

6-Cl

yellow

57 58

^CH

CH

NH-CH ₂ -CH ₂ -CH ₂ -OH

6-Ci

6-CN

yellow yellow

59.

-NH-

-T QH _? -: ÖCH ^.

6-CN

yellow

Example 60:

2 g of the dye described in Example 1 are finely suspended in 2000 ml of water containing hg oleyl polyglycol ether in a printing ink apparatus. The pH of the dyebath is adjusted to 5 to 5 with acetic acid.

100 g of fabric made of polyethylene glycol terephthalate are added at 50 ° C., the bath is heated to Ι4θ ° C. within 30 minutes and dyed for 50 minutes at this temperature. The dye is then rinsed with water, soaped and dried. If these conditions are observed, a pure, fluorescent, yellow coloration is obtained which is fast to washing, perspiration, light and suhlimation . ■■ - "."".■■■""-

The dyes described in the other examples result after this process, dyes are of equal quality!

9 8 30/0910

Example 61:

2 g of the dye obtained in Example 1 are dispersed in 4000 ml of water. This dispersion is added as a swelling agent 12 g sodium ο-phenylpheno 1 at and 12 g Diammoniumph.osph.at and dyes 100 g of polyethylene glycol terephthalate 1 1/2 yarn Hours at 95 to 98 C. The dye is rinsed and with post-treated with diluted sodium hydroxide solution and a dispersant.

The result is a brilliant, fluorescent yellow color that is washable, lightfast and sublime.

In the above example, if 100 g of polyethylene glycol terephthalate are replaced yarn through 100 g cellulose triacetate fabric, dyes under the specified Conditions and then rinsing with water, the result is a yellow, very lightfast and sublimationfast coloration ■ of the highest brilliance,

509830/0910

Claims (1)

HOE 73 / - ^πτ 382 23609 & 6 Patent claims: 1. Compounds of the general formula N ' wherein -R _{1 is} hydrogen, an optionally substituted alkyl, alkenyl, aralkyl, cycloalkyl or aryl radical, 'Ή'. a cyano, carboxylic acid ester, carbonic acid amide, alkyl sulfone or aryl sulfone radical, R "denotes a primary, secondary or tertiary amino group, a hydroxyl, ether or thioether group, and the benzene nucleus A optionally contains further substituents can. 2, compounds according to claim 1, characterized in that they are free from water-solubilizing groups. 3. A process for the preparation of as defined in claim 1. Links, characterized in that a diazonium compound of an amine of the formula wherein A has the meaning given in claim 1, with an azo component of the formula 30/0910 where R ₁ , R _? and R has the meaning given in claim 1 and Z is a hydroxy, alkoxy, optionally substituted amino or sulfo group or a chlorine atom »to an azo compound of the formula / -N = N ^N R in which A, R ₁ , R ", R" and Z have the meaning given, couples, these cyclized with elimination of HZ "and then optionally quaternized or sulfated. k. Use of the compounds produced in claim 1 or 2 or of the compounds prepared in accordance with claim h for dyeing and printing synthetic fibers. 5. Use of the compounds prepared in claim 1, 2 or in accordance with claim h for dyeing synthetic polymers in bulk. 6. Solid or liquid dye preparations, characterized in that that they have one or more dyes according to claim. 1 to 3 included. 509830/0910