DE2555333A1 - AZO DYES - Google Patents

Description

L irL - MG. H. RO; ' ΙΟ.PL -IKO. S. STAEGfcrt 25553 33 MUNICH 5

31

Folder 23894 - Dr. K / by
ICI Case Dd. 27495/27682

IMPERIAL CHEMICAL INDUSTEIES LTD. London, UK

Azo dyes

Priority: 12/11/74 - Great Britain

The invention relates to new water-soluble azo dyes, to their preparation and to their use for ! Coloring synthe ti see polymeric materials in the form of Ribbons, fibers, films, yarns and textile materials in general. The dyes are particularly suitable for dyeing of polymers and copolymers of acrylonitrile and di-

60 9 8 25/0973

cyanoethylene and also, acid-modified polyesters and polyamides.

According to the invention, new azo dyes are proposed, which are free of carboxylic acid and sulfonic acid groups and the formula:

where A is the remainder of a quaternized triazole stands; Ir for a non-ionic substituent stands; η is 0, 1, 2 or 3; R for a hydrogen atom or an optionally substituted alkyl, alkenyl, cyclo

alkyl or aralkyl group stent; R ^, R ⁶ , R and R ⁸ each stand for a hydrogen atom or a methyl, ethyl or propyl group, where two or three of the symbols R ^, R,

1 8
R 'and R are hydrogen; and Σ stands for an anion.

A can be any substituted or unsubstituted radical Be triazoles in which one of the nitrogen atoms is quaternized.

Azotrxazole dyes can exist in several tautomeric forms, which as a result, when quaternized, more than can give a cationic isomer. Thus, in the case of 1,2,4-triazoles which are coupled in the 3-position, quaternization will yield a number of isomers drawn in various representational forms can, namely:

609825/0973

N-N ""

_b »-K > ^ y- X = ^K - ^K or

" ^K

. ■ Alk Alk Alk

^N - ^N. 0? - ¹ T "

N = NK * H ₁₁ JN -H- "Κ

(C) ^Alk (D)

H-N

U _n JLn = N - K or UnJ-N = N - K (E) Alk ( _F )

where E is a coupling component and Alk is a ternating radical stands. It is also clear that in cases where K is the remainder of a p-coupling amine as is the case with dyes of the present invention, other representational forms are also drawn can be, wherein the positive charge is arranged on the nitrogen atom of the p-coupling amine. In the above case A and D, B and F, C and E are different representational forms of three different isomers. In case of 1-substituted 1,2,4-triazole derivatives is of course the Number of isomers reduced.

The above is only an explanation of the variety of isomers and representative forms of triazolium dyes given that can be obtained. It will

609825/0973

However, it should be noted that the dyes according to the invention for the sake of convenience are shown in only one form, but that the invention is all isomeric and illustrative Forms of the dyes.

Preferred dyes according to the invention are those wherein A is the remainder of a quaternized 1,2,4-triazole stands, the azo group being bonded in the 3-position.

A particular class of dyes according to the invention comprises those of formula II:

• Ν - N

where R is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, thienyl or alkoxycarbonyl, R is alkyl, aryl, aralkyl or R ² , R ^{2 is} alkyl, alkenyl, cycloalkyl, aralkyl, 2-carbamoylethyl, 2-carbamoyl-2 -methylethyl, lower alkoxyethyl or mederalkylcarbonylethyl, R ^ is a non-ionic substituent, η is 0, 1, 2 or 3, R is hydrogen or optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl, R ⁵ , R ⁶ , R ⁷

and R have the meanings given above and Σ for is an anion.

Another class of dyes according to the invention comprises those of the formula III:

N-N

609825/09 7 3

wherein R, R ² , R ⁵ , r \ R ⁵ , R ⁶ , R ⁷ , R ⁸ , η and X have the meanings given above.

Another class of dyes of the invention comprises those of formula IV:

wherein R, R ¹ , R ² , R ⁵ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , η and X have the meanings given above.

When in this specification the term lower alkyl or Lower alkoxy is used, it should include alkyl or Alkoxy groups with 1 to 4 carbon atoms are understood.

Examples of R are in particular hydrogen, methyl, ethyl, propyl, butyl, phenyl, 4-nitrophenyl, 3-tolyl, cyclohexyl, 2-thienyl, benzyl, 4-chlorophenyl, 4-methoxyphenyl and methoxycarbonyl. R is preferably hydrogen.

1
Examples of R are lower alkyl, such as methyl and

Ethyl, and also benzyl and phenyl. R is preferably methyl or ethyl.

Examples of R are methyl, ethyl, propyl, butyl ; 2-chloroethyl, 2-bromoethyl, 2-acetoxyethyl, allyl, benzyl, cyclohexyl, 2-phenylethyl, 2-carbamoylethyl, 2-carbamoyl-2-methylethyl, 2-methoxyethyl, methylcarbonylethyl and 2-hydroxyethyl. R is preferably methyl, ethyl or benzyl and very particularly methyl or ethyl.

609825/0973

Ir is a non-ionic substituent. 1,2 or 3 such substituents in the invention Dyes may be present, depending on whether η is 0, 1, 2 or 3. If more than one substituent R is present then they don't have to be the same.

Examples of non-ionic substituents are halogens such as chlorine and bromine, lower alkyl such as methyl, Ethyl, propyl and butyl, alkoxy, such as methoxy, ethoxy, Propoxy and butoxy, nitro, carboxylic acid esters such as methoxycarbonyl and ethoxy carbonyl, acyl, such as methyl and ethyl carbonyl and methyl, ethyl and phenylsulfonyl, cyano, Trifluoromethyl, thiocyano, acylamino, such as formamido, Acetylamino and propionylamino, phenylsulfonylamino, methyl and ethylsulfonylamino, sulfonamido, alkylsulfonamido, such as e.g. monomethyl, monoethyl and dimethyl and diethyl sulfonamido, Carbonamide and alkyl carbonamide, such as methyl, ethyl and dimethyl and diethyl carbonamide, aryl acid amides, such as phenyl carbonamide and phenyl sulfonamide, and ureido.

E is preferably methyl, ethyl, methoxy, ethoxy or chloro, and η is preferably 0 or 1.

Examples of R are hydrogen, methyl, ethyl, propyl, Butyl, pentyl, hexyl, allyl, benzyl, 2-chlorobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 2-hydroxyethyl, 2-chloroethyl, 2-cyanoethyl, 2-bromoethyl, 2-methoxyethyl, 2-acetoxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-hydroxyisobutyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-ethoxypropyl, 2-hydroxy-3-propoxyethyl, 2-hydroxy-3-butoxypropyl, 2-hydroxy-3-allyloxypropyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-2-phenylethyl, 2-n-Amy 1 oxy ethyl, 2-n-butyl oxy ethyl, 2-t-butyloxyethyl, 2-cyclohexyloxyethyl, 2-benzoyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2- (p-methoxybenzoyloxy) ethyl, 2- (p-methoxycarbonylbenzoyloxy) ethyl, 2-phenoxyethyl, 2-benzyloxyethyl, 2- (2'-

609825/0973

Phenylethyloxy) ethyl, 2- (3'-phenylpropoxy) ethyl, 2- (2 '-phenyloxyethyloxy) ethyl, 2- (p-chlorophenoxy) ethyl, 2- (chlorobenzoyloxy) ethyl, 2- (o-chlorophenoxy) ethyl, 2 - (p-methylphenoxy) ethyl, 2- (o-methylphenoxy) ethyl, 2- (p-ethylphenoxy) ethyl, 2- (o-ethylphenoxy) ethyl, 2- (m-methylphenoxy) ethyl, 2- (p- Cyclohexylphenoxy) ethyl, 2- (2 ^f -naphthoxy) ethyl, 2- (o-isopropyloxyphenoxy) ethyl, 2- (ο, p-dichlorophenoxy) ethyl, 2- (p-phenylphenoxy) ethyl, 2- (o-benzylphenoxy) ethyl, 2- (p-benzylphenoxy) ethyl, 2- (p-tert-butylphenoxy) ethyl, 2-phenyltMoäthyl, 2-Pentacllloroplenyltllioätl3yl, 2- (p-Chloro-m-methylphenoxy) ethyl, 2- (p-Methoxyphenoxy) ethyl, 2- (3,5-dimethylphenoxy) ethyl, 2- (3,5-dimethyl-4-chlorophenoxy) ethyl, 2- (o-isopropylphenoxy) ethyl, 2- [p- (2-phenylisopropyl ) phenoxy] ethyl, 2- (1,2,3,4-tetrahydronaphth-6-oxy) ethyl, 2- (1,2,3,4-tetrahydronaphth-1-oxy) ethyl, 2- (phenylaminocarbonyloxy) ethyl and the ethyl, methyl, propyl, butyl ■ ami. Benzyl succinic, maleic "and adipic acid half-esters of the 2-hydroxyethyl group.

R is preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-cyanoethyl, 2-acetoxyethyl, benzyl, 4-chloro, 4-methoxy- or 4-methylbenzyl, ethoxycarbonylethyl, propoxycarbonylethyl, Butoxycarbonylethyl, phenoxycarbonylethyl or benzyloxycarbonylethyl.

E ⁵ , R ⁶ , R ⁷ and R ⁸ are each hydrogen, methyl, ethyl or propyl, with the restriction that two or three of them are hydrogen.

Examples of the anion X are inorganic anions such as e.g. chloride, bromide, iodide, tetrachlorozincate, bisulfate, Nitrate, sulfate, sulfamate, phosphate, borate or tetrafluoroborate, and organic anions such as acetate, propionate, methosulfate, methyl sulfate and p-tolyl sulfonate. In the! Cases » in which the anion is polyvalent it becomes the dye

- 7 609825/0973

contain a corresponding molar proportion of the cationic part of the dye.

Particularly valuable classes of dyes according to the invention include those dyes in which the tetrahydroquinoline radical of the formula:

.8th

, 7, 6 -

(a) R ⁶ , R ⁷ and R ^{8 represent} hydrogen, R ^{5 represents} methyl and R, R and η have the meanings given above;

(b) R ⁵ , R ⁶ and R ^{7 represent} hydrogen, R ^{8 represents} methyl and R ^, R and η have the meanings given above;

(c) R ⁶ and R ^{7 represent} hydrogen, R ⁵ and R ^{8 represent} methyl

■ Z lL

stand and R ^, R and η have the meanings given above;

(d) r5 stands for ethyl, R ⁶ , R ⁷ and R ⁸ stand for hydrogen and R *, R and η have the meanings given above;

(e) R ⁷ stands for methyl, R ⁵ , R ⁶ and R ⁸ stand for hydrogen

• 5 4-

hen and R, R and η have the meanings given above; and

(f) R ⁵ and R ^{6 represent} methyl, R ⁷ and R ^{8 represent} hydrogen

2 IL

stand and R-% R and η have the meanings given above.

Examples of such tetrahydroquinoline radicals are:

- 8 609825/0973

• Ν ' XIL

(IT)

(IT)

(RO

CIL

R · ⁵ is preferably methyl, ethyl, methoxy, ethoxy or chloro, and η is preferably O or 1.

A preferred class of dyes according to the invention comprises those of the formula:

A ^x - N = N

in which A stands for a quaternized 1,2,4-triazole which is connected to the azo group in the 3-position, R ^{y stands} for butyl, pentyl, hexyl or benzyl and X has the meaning given above.

609825/0973

Another preferred class of dyes according to the invention includes those of the formula:

A ¹ - N =

wherein A, ü "and X have the meanings given above.

Another particularly valuable class of dyes according to the invention comprises those of the formula:

A ^A - N = N

1 9
wherein A, Ir and X have the meanings given above

Finally, encompasses yet another such class of particularly valuable dyes according to the invention are those of the formula:

A ¹ - N

- 10 -

609825/0 973

wherein A and X have the meanings given above and R ^{10 is} methyl or ethyl.

In the above preferred classes of the invention A particularly preferred quaternized 1,2,4-iriazole dyes has the formula:

NT-N

, 11

where E is methyl or ethyl.

According to the invention, a method for producing the dyes according to the invention is also proposed, which is carried out by adding a compound of the formula:

tr - ν = ν

(V)

where E,

UC CL TJ Q

E, E- ⁷ , E, E, E and η the above given

ό
Have meanings and A stands for the best of a triazole ring with at least one unsubstituted nitrogen atom, alkylated.

The preferred classes of dyes according to the invention can be prepared by diazotization the corresponding triazoles, such as the 3-ami-

- 11 -

609825/09 7 3

no-1,2,4-triazole, azo compounds obtained are alkylated and couples with a corresponding tetrahydroquinoline.

Examples of alkylating agents are alkyl halides, such as e.g., methyl, ethyl, propyl and butyl chlorides, and the corresponding bromides, alkenyl halides such as allyl chloride or bromide, aralky halides such as benzyl chloride or bromide, dialkyl sulfates, such as dimethyl sulfate, Diethyl sulfate, dipropyl sulfate and dibutyl sulfate, alkyl esters of aryl sulfonates, such as methyl and ethyl ptoluenesulfonate, and other lower alkyl esters of strong mineral acids or organic sulfonates. Other alkylating agents can in turn carry substituents, as is the case, for example, with chloropropionitrile or bromopropionamide and bromohydrin is the case.

The reaction between the alkylating / quaternizing agent and the dye of the formula V can take place without the addition of other solvents or can be carried out in an inert organic solvent, such as benzene, toluene, xylene, chlorobenzene, nitrobenzene, acetone, carbon tetrachloride, tetrachloroethane, perchlorethylene, Chloroform, dimethylformamide, acetonitrile, acetic acid, formic acid or 2-ethoxyethanol. The alkylation can also be carried out in the aqueous phase and, if appropriate, in the presence of an organic solvent. The alkylating agent can be used in substantial excess, for example up to 6 moles per mole of dye can be used. Suitable temperatures are from 20-150 ⁰ C and particularly 20-90 ⁰ C. The incorporation of an acid-binding agent is often useful. Such agents are magnesium oxide, sodium and potassium carbonate, sodium and potassium bicarbonate, magnesium and calcium carbonate, potassium acetate, and mixtures of such agents.

The alkylation of the dyes of the formula V can also

- 12 -

609825/0973.

be carried out by reaction with, for example, acrylamide in an organic acid or a mineral acid, such as acetic, formic or hydrochloric acid or a mixture thereof, from 50 to 100 ⁰ G.

The alkylation can also be carried out that a dye of the formula 7 with ethylene oxide or a Derivative thereof with the formula:

wherein Ir and E represent hydrogen or an optionally substituted one Lower alkyl group, converts.

This reaction is carried out in a solvent in the presence of a mineral acid or an organic acid which provides the anion X at temperatures of 10-10O ⁰ C, preferably 40-90 ⁰ C. Suitable acids are sulfuric, hydrochloric, hydrobromic, phosphoric, benzenesulfonic, toluenesulfonic, formic, acetic or propionic acid. Such acids can also serve as solvents or can be used as a mixture with one another or with other organic solvents, such as dimethylformamide, acetonitrile, dioxane, tetrahydrofuran, chlorobenzene, toluene, xylene, nitrobenzene, acetone or methyl ethyl ketone.

If the reaction is carried out in hydrophobic organic solvents then the alkylated dye is usually insoluble and can be separated by filtration. If necessary, the alkylated dye can pass through from aqueous solution Precipitation in the form of a salt can be isolated, for example as tetrachlorozincate, which is obtained by adding zinc chloride to the aqueous solution is obtained.

As a result of the alkylation, the dye is exemplified

- 13 -

60982b / ü9 7 3

wisely in the form of chloride, bromide or methosulphate, each according to the alkylating agent used. If the dye is desired as a salt of another anion, then one anion can be replaced by another anion using known metathesis methods.

Insoluble azo dyes used as starting materials for the above procedures are useful can be obtained by diazotizing an aminotriazole and then diazotizing the diazo compound with an appropriate tetrahydroquinoline derivative clutch.

Examples of aminotriazoles that can be used as diazo components are:

3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole, 3-amino-5-ethyl-1,2,4-triazole, 3-amino-5-propyl-1,2,4-triazole, 3-amino-5-butyl-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole, 3-amino-5- (p-nitrophenyl) -1,2,4-triazole, 3-amino-5- (m-tolyl) -1,2,4-triazole, 3-amino-5-cyclohexyl-1,2,4-triazole, 3-amino-5- (2-thienyl) -1,2,4- triazole, 3-amino-5-benzyl-1,2,4-triazole, 3-amino-5- (p-chlorophenyl) -1,2,4-triazole, 3-Amino-5- (p-niethoxyph.enyl) -1,2,4-triazole, 3-Amino-5-methoxycarbonyl-1,2,4-triazole (+ higher ester homologs),

1-methyl-3-amino-i, 2,4-triazole, 1-ethyl-3-amino-1,2,4-triazole, 1-benzyl-3-amino-1,2,4-triazole, 1-benzyl-5-methyl-3-amino-1,2,4-triazole, 1-phenyl-3-amino-1,2,4-triazole, 1,5-dimethyl-3-amino-1,2,4-triazole,

-amino-i, 2,4-triazole,

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1-ethyl-phenyl-1-amino-1, 2,4-triazole, 1,5-diphenyl-3-amino-1,2,4-triazole, 1-phenyl-5-ia ^e 'fchyl-3-amiiio 1,2,4-triazole, 1-benzyl-5-plienyl-3-amino-1,2,4-triazole and 1,5-dibenzyl-3-amino-1,2,4-triazole.

Examples of tetrahydroquinolines that are used as coupling components can be used are the following, where THQ stands for tetrahydroquinoline:

2-methyl-THQ,

N-methyl-2-methyl-THQ, N-ethyl-2-methyl-THQ, N-n-Propyl-2-methyl-THQ, N-n-Butyl-2-methyl-THQ, N-n-Pentyl-2-methyl-THQ, N-n-Hexyl-2-methyl-THQ, N-allyl-2-methyl-THQ, N-benzyl-2-methyl-THQ, N-2'-chlorobenzyl-2-methyl-THQ, N-4- '-chlorobenzyl-2-niethyl-THQ, N-4- '-Me thy Ib enzyl-2-methyl-THQ, N-4-methoxybenzyl-2-methyl-THQ, N-2-phenylethyl-2-methyl-THQ, N- (2-hydroxyethyl) -2-methyl-THQ, N- (2-chloroethyl) -2-methyl-THQ, N- (2-cyanoethyl) -2-methyl-THQ, N- (2-bromoethyl) -2-methyl-THQ, N- (2-methoxyethyl) -2-methyl-THQ, N- (2-methylcarbonylethyl) -2-methyl-THQ, N- (2-acetoxyethyl) -2-methyl-THQ, N- (2-hydroxypropyl) -2-methyl-THQ, if- (3-hydroxypropyl) -2-methyl-THQ, N- (2-hydroxybutyl) -2-methyl-THQ, N- (4-hydroxybutyl) -2-methyl-THQ, N- (2-Hydroxyisobutyl) -2-methyl-THQ,

- 15 6 0 9 8 2 b / over 9 7

N- (2-Hydroxy-3-methoxypropyl) -2-methyl-THQ, N- (2-Hydroxy-3-ethoxypropyl) -2-methyl-THQ, N- (2-Hydroxy-3-propoxypropyl) -2-methyl-THQ, N- (2-Hydroxy-3-butoxypropyl) -2-methyl-THQ, N- (2-Hydroxy-3-allyloxypropyl) -2-methyl-THQ, N- (2-Hydroxy-3-phenoxypropyl) -2-methyl-THQ, N- (2-Hydroxy-2-phenylethyl) -2-methyl-THQ, N- (2-η-amyloxyethyl) -2-methyl-THQ, N- (2-n-butyloxyethyl) -2-methyl-THQ, N- (2-t-butyloxyethyl) -2-methyl-THQ, N- (2-Cyclohexyloxyethyl) -2-methyl-THQ, N- (2-benzoyloxyethyl) -2-methyl-THQ, N- (2-methoxycarbonylethyl) -2-methyl-THQ, N- (2-Äthoxycarb onyläthyl) -2-methyl-THQ, N- (2-propoxycarbonylethyl) -2-methyl-THQ, N- (2-Butoxycarb oxyäthyl) -2-methyl-THQ, N- (2-benzyloxycarbonylethyl) -2-methyl-THQ, N-2- (p-methoxybenzoyloxy) ethyl-2-methyl-THQ N-2- (p-methoxycarbonylbenzoyloxy) ethyl-2-methyl-THQ, N- (2-phenoxyethyl) -2-methyl-THQ, N- (2-benzyloxyethyl) -2-methyl-THQ, N-2- (2-phenylethyloxy) ethyl-2-methyl-THQ, N-2- (3'-phenylpropoxy) ethyl-2-methyl-THQ, N-2- (2'-phenyloxyethyloxy) ethyl-2-methyl-THQ, N-2- (p-chlorophenoxy) ethyl-2-methyl-THQ, N-2- (chlorobenzyloxy) ethyl-2-methyl-THQ, N-2- (o-Chlorophenoxy) ethyl-2-methyl-THQ, N-2- (p-Kethylphenoxy) ethyl-2-methyl-THQ, N-2- (o-methylphenoxy) ethyl-2-methyl-THQ, N-2- (p-ethylphenoxy) ethyl-2-methyl-THQ, N-2- (o-ithylphenoxy) ethyl-2-methyl-THQ, N-2- (m-methylphenoxy) ethyl-2-methyl-THQ, N-2- (p-cyclohexylphenoxy) ethyl-2-methyl-THQ, N-2- (2'-naphthoxy) ethyl-2-methyl-THQ, N-2- (o-Isopropyloxyphenoxy) ethyl-2-methyl-THQ,

- 16 609825/097 3

N-2- (o, p-dichlorophenoxy) ethyl-2-methyl-THQ, N-2- (p-phenylphenoxy) ethyl-2-methyl-THQ, N-2- (o-Benzylphenoxy) ethyl-2-methyl-THQ, N-2- (p-Benzylphenoxy) ethyl-2-methyl-THQ, N-2- (p-tert-butylphenoxy) ethyl-2-methyl-THQ, N- (2-phenylthioethyl) -2-methy1-THQ,

N- (2-pentachlorophenylthioethyl) -2-methyl-THQ, N-2- (p-chloro-m-methylphenoxy) ethyl-2-methyl-THQ, N-2- (p-methoxyphenoxy) ethyl-2-methyl-THQ, N-2- (3,5-dimethy! Phenoxy) ethyl-2-methyl-THQ, N-2- (3,5-dimethyl-4-chlorophenoxy) ethyl-2-methyl-THQ, N-2- (o-Isopropylphenoxy) ethyl-2-methyl-THQ, N-2-Cp- (2-phenylisopropyl) phenoxylethyl-2-methyl-THQ, N-2-C 3,5-dimethylphenoxy) ethyl-2-methyl-THQ, N-2- (3,5-Dimethy1-4-chlorophenoxy) ethyl-2-methyl-THQ, N-2- (o-Isopropylphenoxy) ethyl-2-methy1-THQ, N-2- [p- (2-phenylisopropyl) phenoxy] ethyl-2-methyl-THQ, N-2- (1,2,3,4-tetrahydronaphth-e-oxy) ethyl-2-methyl-THQ and H-2- (1,2,3,4-tetrahydronaphth-1-oxy) ethyl-2-methyl-THQ.

Analogs of the above compounds can also be used as coupling components can be used, such as 4-methyl-THQ, 2,4-dimethyl-THQ, 2-ethyl-THQ, 3-methyl-THQ and 2,2-dimethyl-THQ and N-substituted derivatives thereof attached to the nitrogen atom Have substituents, such as those listed above for the coupling components.

Analogs of all the above compounds in which methyl, ethyl, Methoxy, ethoxy or chloro substituents are present in the non-heterocyclic ring of the tetrahydroquinoline, and although preferably in the 7-position of the tetrahydroquinoline nucleus.

Insoluble azo dyes that are useful as starting materials can also be prepared in other ways,

- 17 609825/09 7 3

for example by condensation of a 6-nitrosotetrahydroquinoline compound with an iminotriazole or by oxidative coupling of a triazole hydrazone with tetrahydroquinoline.

You can, for example, by diazotizing and coupling 3-amino-5-carboxytriazoles and subsequent decarboxylation getting produced.

The diazotization of an aminotriazole and the subsequent Coupling is the preferred method.

The dyes of the invention can also be used for dyeing synthetic polymeric materials can be used, being applied from an aqueous bath. The invention Dyes produce valuable, luminous shades with high color strength.

The dyes according to the invention are particularly suitable for coloring polyacrylonitrile materials. They can be applied to Polyacrylonitrilmaterialien from acidic, neutral or slightly alkaline dyebaths (ie, pH 3-8) at temperatures between ⁰ 4-0-120 G, and preferably between 80 and 120 ⁰ G, or by printing techniques using thickened printing pastes. Bright red to bluish-red dyeings with excellent fastness to washing, sweating, steam ironing and light are obtained.

The dyes according to the invention have an excellent one Lightfastness and are particularly in this regard other basic dyes with similar shades, such as e.g. magenta, superior.

In particular, the preferred dyes have moderate dyeing speeds so that they are compatible with the dyeing speeds of other known commercially available dyes, such as Basic Yellow 28, Basic Red 46

- 18 60982b / 09 7 3

and Basic Blue 4-1 listed in the Color Index will.

The dyes of the present invention can be prepared by a wet transfer printing process can be applied, in which, for example, a support such as paper, with a dye containing printing ink is printed, the printed carrier is brought into contact with a textile material and the Whole under damp / wet conditions is exposed to heat and pressure in order to apply the dye to the textile material transfer.

The invention is illustrated by the following examples, in which all parts and percentages are expressed in weight unless otherwise stated. When speaking of parts by volume, then the ratio is Weight to volume is the ratio of grams to milliliters.

example 1

0.84 parts of 3-amino-1,2,4-triazole are dissolved in a mixture of 4 parts by volume of water and 1.1 parts by volume of concentrated sulfuric acid. 4 parts by volume of glacial acetic acid are added and the solution is cooled to below 5 ° C. The aminotriazole is diazotized by dropwise addition of 2.1 parts by volume 5 π sodium nitrate solution with stirring at 0-5 ⁰ C. After stirring for a further 4 hours below 5 ° C, the excess nitrite is destroyed by adding sulfamic acid solution.

1.74 parts of N-ethyl-2-methyl-tetrahydroquinoline are dissolved in 150 parts of water and 15 parts of concentrated hydrochloric acid. The coupling bath is cooled at 5 ⁰ C, and the diazo solution is added minutes with stirring at 0-5 ⁰ C for 10th Excess acidity compared to Congo red paper is destroyed by adding sodium acetate, and

- 19 -

6098 25/0973

the resulting orange dye is filtered off, washed with water and dried. 1.46 parts of the dye Formula:

N-N

will get.

1.54 parts of the above dye are added to 25 parts of glacial acetic acid containing 0.52 parts of magnesium oxide. After heating to 90 ^° C., 2.8 parts of dimethyl sulfate are added with stirring. The quaternization is over in 1 hour at 85-90 ° C. The reactants are then cooled, poured into I50 parts of water and heated to 75-80 ⁰ C. The aqueous solution of the cationic dye is filtered through a bed of "Hyflo" supercel and cooled, and then the cationic dye is isolated by adding 3 parts of 100% aqueous zinc chloride solution and adding salt to a concentration of 10%. There are 0.8 parts of dye of the formula:

H-N

CH

obtained, the polyacrylonitrile from a weakly acidic dye bath dyes in bright bluish-red shades with excellent fastness properties.

- 20 -

609825/0973

Example 2

0.84 parts of 3-amino-1,2,4-triazole are dissolved in a mixture of 4 parts by volume of water and 1.1 parts by volume of concentrated sulfuric acid. 4 parts by volume of glacial acetic acid are then added and the amine solution is cooled to below 5 ° C. The Aminotriazöl is then diazotized by the dropwise addition of 2-VoI. parts 5 η sodium nitrite solution with stirring at 0-5 ⁰ C. The mixture is then ^{stirred below 5 °} C. for a further 3 hours.

2.03 parts of nin-butyl-2-methyltetrahydroquinoline are dissolved in 100 parts of acetone and 50 parts of water. 1 part of urea is added and the coupling solution is cooled to below 5 ° C. The above diazo solution is added to the coupling bath at 0-5 ⁰ C with stirring. After stirring for a further 15 min, the acidity compared to Congo red paper is neutralized by adding sodium acetate, the temperature being kept ^{below 5 ° C. throughout.} After stirring for a further 20 minutes, the bath is diluted by adding 200 parts of water, whereupon the yellow dye base is filtered off, washed with water and dried. The yield of the yellow dye base is 2.46 parts.

1.97 parts of the above dye base are dissolved in 30 parts of glacial acetic acid, whereupon 0.7 parts of magnesium oxide are added. The dye ^{solution is heated to 60 °} C. with stirring, whereupon 5 parts of dimethyl sulfate are added dropwise. After a 2 1/2 permanent stirring at 80-85 ⁰ C st, the total disperse dye base quaternized. The reactants are then cooled and poured into 100 parts of water, 1 part of "Hyflo ⁿ -Supercel is added, and the cationic dye solution is ^{filtered through a bed of" Hyflo n} -Supercel. The resulting cationic dye is made by adding 3 parts by volume of a 100%

- 21 6ü982b / üS7 3

ZnClo solution and aurcli addition of salt up to a concentration of 20 % isolated.

1.7 parts of dye of the formula:

N-N

CH

-f Il

[ZnC

CH,

obtain. He dyes polyacrylonitrile fibers from a weak acid dye bath in bright reddish-violet shades, including excellent all-round fastness properties Have lightfastness.

In the following examples, THQ is used as an abbreviation for 1,2,3,4-tetrahydroehinoline.

Example 3

0.84 parts of 3-amino-1,2,4-triazole are dissolved in a mixture of 8.5 parts of acetic acid and 5.5 parts of water. 1 part concentrated sulfuric acid is added and the amino tr iazollö solution is cooled to below 0 ⁰ C. 0 * 71 parts of sodium nitrate are dissolved in 14 parts · concentrated sulfuric acid and then added dropwise under stirring at 0-5 C ^e. The diazotization is continued by stirring at 0-5 ° C. for a further 60 minutes. The excess nitrite is then destroyed by adding a little urea.

2.17 parts of N-pentyl-2-methyl-THQ are dissolved in 20 parts of acetic acid, and the solution is then slowly added to the above diazo solution under vigorous stirring at 0-5 ⁰ C. After a further 30 minutes, the coupling bath is slowly neutralized by gradually adding 12 parts of ammonium acetate,

- 22 -

60982b / 0973

keeping the temperature below 5 ° C at all times. After stirring for a further 60 minutes at 0-5 ° C., the The reaction mass is poured into 20 parts of water, whereupon the resulting yellow dye base is filtered off, with water washed and dried.

2.06 parts of this dye base are quaternized according to Example 2, a cationic dye of the formula:

CH

is obtained. It colors polyacrylonitrile from a weak acid dye bath in bright red-violet shades, with the dyeings having excellent all-round fastness properties exhibit.

If in the above example the dimethyl sulfate by the equivalent amount of diethyl sulfate, dibutyl sulfate, ethyl p-toluenesulfonate or methyl p-toluenesulfonate is replaced, then similar dyes are obtained.

Similar dyes can also be obtained by using the N-pentyl-2-methyl-THQ used in the above example replaced by the equivalent amount of the coupling components indicated in column 2 of the following table and proceed in the same way as in the example above. The colors on polyacrylonitrile are in column 3 of the table specified.

609825/0973

at
game Coupling component Hue on
Polyacrylonitrile 4th N-hexyl-2-methyl-THQ reddish purple 5 N-propyl-2,4-dimethyl-THQ Il 6th N-butyl-2,4-dimethyl-THQ , Il 7th N-pentyl-2,4-dimethyl-THQ Il 8th N-hexyl-2,4-dimethyl-THQ dd 9 N-propyl-2,2-dimethyl-THQ Il 10 N-butyl-2,2-dimethyl-THQ Il 11 N-pentyl-2,2-dimethyl-THQ M. 12th N-hexyl-2,2-dimethyl-THQ Il 13th N-propyl-2-ethyl-THQ Il 14th N-butyl-2-ethyl-THQ Il 15th N-pentyl-2-ethyl-THQ dd 16 N-hexyl-2-ethyl-THQ Il 17th N-propyl-4-methyl-THQ bluish red 18th N-Butyl-4-methyl-THQ It 19th N-pentyl-4-methyl-THQ It 20th N-hexyl-4-methyl-THQ Il 21 N-propyl-2,7-dimethyl-THQ reddish purple 22nd N-butyl-2,7-dimethyl-THQ Il 23 N-pentyl-2,7-dimethyl-THQ Il 24 ' N-hexyl-2,7-dimethyl-THQ It 25th N-propyl-2,4,7-trimethyl-THQ Il 26th N-butyl-2,4,7-trimethyl-THQ ti 27 N-pentyl-2,4,7-trimethyl-THQ dd 28 N-hexyl-2,4,7-trimethyl-THQ It 29 N-propyl-2,2,7-trimethyl-THQ Il 30th N-butyl-2,2,7-trimethyl-THQ dd 31 N-amyl-2,2,7-trimethyl-THQ It 32 N-hexyl-2,2,7-trimethyl-THQ dd 33 N-propyl-2-ethyl-7-methyl-THQ It 34 N-butyl-2-ethyl-7-methyl-THQ It 35 N-Pentyl-2-ethyl-7-methyl-THQ ti

- 24 -

609825/0973

Porting the table

at
game Coupling component Hue on
Polyacrylonitrile 36 N-hexyl-2-ethyl-7-methyl'-THQ reddish purple 37 N-butyl-4,7-dimethyl-THQ bluish red 38 N-pentyl-4,7-dimethyl-THQ dd 39 N-Benzyl-2-methyl-THQ Il 40 N-benzyl-2,4-dimethyl-THQ Il 41 N-benzyl-2,4-dimethyl-THQ Il 42 N-benzyl-2,4,7-trimethyl-THQ Il 43 N-benzyl-2,2-dimethyl-THQ Il 44 N-benzyl-2,2,7-trimethyl-THQ ti 45 N-benzyl-2-ethyl-THQ H 46 N-Benzyl-2-ethyl-7-methyl-THQ Il 47 N-Benzyl-4-methyl-THQ Red 48 N-3utyl-2-methyl-7-ethyl-THQ reddish purple 49 N -Butyl-2-methyl-7-methoxy-THQ bluish red 50 N-Butyl-2-methyl-7-chloro-THQ Il 51 N- (2-phenylethyl) -2-methyl-THQ reddish purple 52 N- (butoxycarbonylethyl) -2- bluish red methyl THQ 53 N- (Benzyloxycarb onylethyl) -2- It methyl THQ 54 N-propyl-2-methyl-THQ reddish purple 55 N-allyl-2-methyl-THQ bluish red 56 N-isopropyl-2-methyl-THQ reddish purple 57 N-Cyclohexyl-2-methyl-THQ Il 58 2-methyl-THQ bluish red 59 2,4-dimethyl THQ η 60 N- (2-chloroethyl) -2-methyl-THQ reddish purple 61 N- (2-cyanoethyl) -2-methyl-THQ bluish red 62 N- (4-chlorobenzyl) -2-methyl-THQ It - 63 N- (4-methylbenzyl) -2-methyl-THQ Il 64 N- (4-methoxybenzyl) -2-methyl-THQ dd

609825/0973

Continuation of the table

Coupling component

Color on polyacrylonitrile

N- (2 ~ chlorobenzyl) -2-methyl-THQ N- (2-hydroxyethyl) -2-methyl-THQ IT- (2-bromoethyl) -2-methyl-THQ N- (2-methoxyethyl) -2-methyl-THQ N- (2-acetoxyethyl) -2-methyl-THQ N- (2-Hydroxypropyl) -2-methyl-THQ N- (2-Hydroxybutyl) -2-methyl-THQ

N- (2-Hydroxy-3-methoxypropyl) -2-methyl-THQ

N- (2-Hydroxy-3-ethoxypropyl) -2-methyl-THQ

N- (2-Hydroxy-3-allyloxypropyl) -2-methyl-THQ

N- (2-Hydroxy-3-phenoxypropyl) -2-methyl-THQ

N- (2-Hydroxy-2-phenylethyl) -2-methyl-THQ N- (2-n-pentyloxyethyl) -2-methyl-THQ

N- (2-n-Butyloxyethyl) -2-methyl-THQ

N- (2-t-butyloxyethyl) -2-methyl-THQ

N- (2-Benzoyloxyethyl) -2-methyl-THQ

N- (2-methylcarbonylethyl) -2-methyl-THQ N- (2-methoxycarbonylethyl) -2-methyl-THQ N- (2-phenoxyethyl) -2-methyl-THQ N- (2-phenylethyloxy) ethyl-2-methyl-THQ

N-2- (3-phenylpropoxy) ethyl-2-methyl-THQ

- 26 bluish red reddish purple

bluish red reddish purple

Il
If

bluish red

reddish purple

609825/09

Continuation of the table

at
game Coupling component Hue on
Polyacrylonitrile 86 N-2- (2-phenyloxyethyloxy) ethyl
2-methyl-THQ reddish purple 87 N-2- (p-chlorophenoxy) ethyl
2-methyl-THQ Il 88 N-2- (chlorobenzyloxy) ethyl
2-methyl-THQ Il 89 N-2- (o-chlorophenoxy) ethyl
2-methyl-THQ η 90 N-2- (p-methylphenoxy) ethyl
2-methyl-THQ It 91 N-2-C o-methylphenoxy) ethyl
2-methyl-THQ It 92 N-2- (p-ethylphenoxy) ethyl
2-methyl-THQ dd 93 N-2- (o-lthy! Phenoxy) ethyl
2-methyl-THQ It 94 N-2- (m-ethylphenoxy) ethy1-
2-methyl-THQ It 95 N-2- (p-Cyclohexylphenoxy) ethyl
2-methyl-THQ dd 96 N-2- (2-naphthoxy) ethyl-2-methyl-
THQ π 97 N-2- (o-isopropyloxyphenoxy)
ethyl-2-methyl-THQ ti 98 N-2- (o, p-dichlorophenoxy) ethyl
2-methyl-THQ Il 99 N-2- (p-phenylphenoxy) ethyl-2-
methyl THQ Il 100 N-2- (o-Benzylphenoxy) ethyl Il 2-methyl-THQ 101 N-2- (p-Benzylphenoxy) ethyl-2-
methyl THQ It 102 N-2- (pt-butylphenoxy) ethyl-2-
methyl THQ It $ 10 N-2- (phenylthio) ethyl-2-methyl-
THQ ti

- 27 -

609825 / 0.973

Continuation of the table

at
game Coupling component Hue on
Polyacrylonitrile 104 N-2- (pentachlorophenol thio) - reddish purple ethyl-2-methyl-THQ 105 N ^ -Cp-chloro-m-methylphenoxy) - Il ethyl-2-methyl-THQ 106 N-2- (p-methoxyphenoxy) ethyl-2- It methyl THQ 107 N-2- (3,5-dimethylphenoxy) - It ethyl-2-methyl-THQ 108 N-2- (3,5-dimethyl-4-chlorophene- It oxy) ethyl-2-methyl-THQ 109 N-2- (o-isopropylphenoxy) ethyl ti 2-methyl-THQ 110 N-2- [p- (2-phenylisopropyl) phen- Il oxy] ethyl-2-methyl-THQ 111 N-2- (1,2,3,4-tetrahydronaphth- ti 6-oxy) ethyl-2-methyl-THQ 112 N-2- (1,2,3,4-tetrahydronaphth- dd 1-oxy) ethyl-2-methyl-THQ 113 N-ethyl-2-methyl-7-ethoxy-THQ bluish red 114 IT-ethyl-2-methyl-7- "bromo-THQ Il

If in the above examples the 3-amino-1,2,4-triazole is replaced by the equivalent amount of the following aminotriazoles, then similar dyes with similar Preserved coloring properties.

3-amino ~ 5-methyl-1,2,4-triazole, 3-amino-5-ethyl-1,2,4-triazole, 3-amino-5-propyl-1,2,4-triazole, 3-amino-5-butyl-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole, 3-amino-5- (p-nitrophenyl) -1,2,4-triazole, 3-amino-5- (m-tolyl) -1,2,4-triazole,

- 28 -

609825/09 7 3

3-amino-5-cyclohexyl-1,2,4 ~ triazole, 3-amino-5- (2-thienyl) -1,2,4 ~ triazole, 3-amino-5-benzyl-1,2,4- triazole,
3 ~ amino-5- (p-chlorophenyl) -1,2,4-triazole, 3-amino-5- (p-methoxyphenyl) -1.2 _t 4-triazole, 3 ~ amino-5-methylthio-1 , 2,4-triazole and 3-amino-5-methoxycarbonyl-1,2,4-triazole.

Example 115

0.93 parts of i-methyl-3-amino-i, 2,4-triazole are dissolved in a mixture of 8.5 parts of glacial acetic acid and 5.5 parts of water. 1 part of concentrated sulfuric acid is added and the aminotriazole solution is cooled to ^{below 0 ° C.} 0.71 parts of sodium nitrite in concentrated sulfuric acid 14 parts are dissolved, are added dropwise with stirring below ^{0 0} C, and the diazotization is continued minutes with stirring at 0-5 ⁰ C for a further 60th The excess nitrite is then destroyed by adding sulfamic acid.

2.03 parts of N-butyl-2-methyl-THQ are dissolved in 20 parts of glacial acetic acid and the solution is then added slowly with vigorous stirring below 0 ⁰ C to the diazo solution. After stirring for a further 30 minutes, the coupling solution is neutralized by gradually adding 12 parts of ammonium acetate, the temperature being kept below 5 ° C. throughout. After another 90 min of stirring, at 0-5 ⁰ G, the reaction mass is poured into 200 parts of water, filtered off and then the resulting dye base, washed with water and dried.

2.08 parts of the above dye base are dissolved in 30 parts of glacial acetic acid containing 0.7 parts of magnesium oxide. 1.7 parts of dimethyl sulfate are added under stirring at 85 to 90 ⁰ C, and the Quateraisierung is continued until completion. The resulting cationic 3?

- 29 60982b / üÖ7 3

to

substance is isolated according to Example 17 and has the formula:

It dyes polyacrylonitrile from a weakly acidic dye bath in bright bluish-red shades. Own the colorations excellent all-round fastness properties. Similar dyes can be obtained when the above Example used dimethyl sulfate by the appropriate amount of diethyl sulfate, ethyl p-toluene sulfonate or benzyl chloride is replaced.

If in the above example the 1-methyl-3-amino-1,2,4-triazole is replaced by the appropriate amount of the following 3-aminotriazoles, then cationic dyes with similar Properties obtained:

1-ethyl-3-amino-1,2,4-triazole,
1-benzyl-3-amino-i, 2,4-triazole,
1-phenyl-3-amino-1,2,4-triazole,
1-benzyl-5-methyl-3-amino-1,2,4-triazole, 1,5-dimethyl-3-amino-1,2,4-triazole,
1-methyl-5-benzyl-3-amino-1,2,4-triazole, 1-ethyl-5-phenyl-3-amino-1,2,4-triazole, 1,5-diphenyl-3-amino- 1,2,4-triazole,
1-phenyl-5-methyl-3-amino-1,2,4-triazole, 1-benzyl-5-phenyl-3-amino-1,2,4-triazole and 1,5-dibenzyl-3-amino- 1,2,4-triazole.

When the above 3-aminotriazoles with any of the above

- 30 -

6098 2 5/0973

mentioned THQ coupling components are used according to the method described in the example above, then dyes with similar coloring properties are obtained.

Example 116

1.98 parts of the dye base, whose preparation is described in Example 2 are dissolved in 30 parts of dimethylformamide, and then 5 parts of dimethyl sulfate are added dropwise under stirring at 85-90 ⁰ C. The quaternization is continued by stirring at 85-90 ⁰ C until completion, whereupon the liquids in 200 parts of water are poured. The dye is isolated in the usual way as tetrachlorozincate according to Example 2 and has a similar hue and similar coloring properties.

If the dimethyl sulfate used in the above example is replaced by the corresponding amounts of diethyl sulfate, dipropyl sulfate, Dibutyl sulfate, ethyl p-toluene sulfonate or benzyl chloride is replaced, then similar dyes are obtained.

Example 117

3.1 parts of the dye base obtained from 1-methyl-3-amino-1,2,4-triazole and N-butyl-2-methyl-THQ is obtained dissolved in 30 parts of dimethylformamide, and then 2.5 parts of dimethyl sulfate are added dropwise with stirring 9O-95 ° C added. The quaternization will take place at this temperature continued until completion, whereupon the liquids are poured into 200 parts of water and the Dye in the usual way with the addition of sodium chloride and subsequent addition of zinc chloride as tetrachlorozincate is isolated. The dye obtained has the formula:

- 31 -60982b / ü9 7 3

'N N

N = N

• CH,

and dyes polyacrylonitrile from a weakly acidic dye bath in bright bluish-red shades, the excellent one
Show all-round fastness properties.

If the dimethyl sulfate used in the above example is replaced by the corresponding amount of diethyl sulfate, dipropyl sulfate, dibutyl sulfate or ethyl p-toluenesulfonate is replaced, then similar dyes are obtained.

Example 118

3.1 parts of the dye base obtained from 3-amino-1,2,4-triazole and Nn-butyl-2,4-dimethyl-THQ are refluxed with 7.5 parts of dimethyl sulfate in 50 parts
Stirred with chloroform. After quaternization is finished,
the chloroform was removed by distillation. The cationic dye obtained as methosulfate is in 200 parts
Dissolved water, filtered and used in the usual way as
Tetrachlorozincate isolated. It has the structure:

N-N

N ₌ ν

CH,

and dyes polyacrylonitrile from a weakly acidic dye bath in bright reddish-violet shades, the excellent Have all-round fastness properties.

- 32 609825/0973

If the dimethyl sulfate used in the above example is replaced by the equivalent weight of diethyl sulfate, dibutyl sulfate, Ethyl p-toluenesulfonate, benzyl chloride, allyl bromide, chloropropionitrile, Bromopropionamide or bromohydrin is replaced, then similar dyes are obtained.

If the chloroform used in the above example is replaced by an equivalent volume of benzene, toluene, xylene, nitrobenzene, Acetone, carbon tetrachloride, tetrachloroethane, perchloroethylene, acetonitrile or 2-ethoxyethanol replaced then similar dyes are obtained.

Example 119

3.6 parts of the dye base obtained by diazotization of 1-Benzyl-3-amino-1,2,4-triazole and coupling with IT-ethyl-2-methyl-THQ is obtained, are stirred under reflux with 2.5 parts of dimethyl sulfate in 50 parts of chloroform. To When the quaternization is complete, the chloroform is removed by distillation, whereupon the cationic dye is converted into 200 Part of water is dissolved, filtered and isolated in the usual manner as tetrachlorozincate. He owns the Structure:

It dyes polyacrylonitrile from a weakly acidic dye bath in bright bluish-red shades.

60982b / 09 7

Example 120

2.8 parts of the dye base, which is obtained by diazotizing 3-amino-1,2,4-triazole and coupling with N-ethyl-2,7-dimethyl-THQ, are concentrated in 20 parts of glacial acetic acid and 2.0 parts Dissolved hydrochloric acid. 14.4 parts of acrylamide are added dropwise under stirring at 60-65 ⁰ C, whereupon the reaction mixture is stirred at 85-90 ⁰ C until the quaternization has ended. The reaction mixture is then poured into 200 parts of water and filtered, and the cationic dye is isolated in the usual way as tetrachlorozincate. It has the structure:

CZnCl

and dyes polyacrylonitrile from a weakly acidic dye bath in bright bluish-red shades that have good all-round fastness properties demonstrate.

Example 121

5.0 parts of the dye base obtained by diazotizing 1,5-dimethyl-3-amino-1,2, A-triazole and coupling with N-ethyl-2-methyl-THQ is obtained in 20 parts of glacial acetic acid and

1.1 parts of hydrochloric acid dissolved. 7.2 parts of acrylamide will be then added dropwise with stirring at 65-7O ° C, and the quaternization is carried out with stirring at 85-90 ° C until Termination continued. The reactants are then cooled and poured into 200 parts of water, whereupon the dye in the usual way as tetrachlorozincate

- 54 -

609825/0973

is isolated. It has the structure:

It dyes polyacrylonitrile fibers in bright bluish-red shades, the excellent all-round fastness properties demonstrate.

Example 122

2.98 parts of the dye base, whose preparation is described in Example 2, in 20 parts of ethanol under pressure with 6.5 parts of ethyl bromide 4- st heated to 100-110 ⁰ C. After the ethanol has been separated off by distillation, the cationic dye is a bromide of the formula:

N - N

obtain.

It can be dissolved in water and isolated as tetrachlorozincate will. It dyes polyacrylonitrile from a weakly acidic dye bath in bright reddish-violet shades. the Dyeings show excellent all-round fastness properties.

- 35 -

60982S / U9 7 3

Similar dyes are obtained by using the Ethyl bromide by equivalent amounts of methyl bromide, propyl bromide, Butyl bromide, allyl bromide, benzyl bromide or their corresponding chlorides replaced. Similar dyes are also obtained if the ethyl bromide is replaced by equivalents Amounts of chloropropionitrile, bromopropionamide or bromohydrin replaced.

Example 125

4.2 parts of the dye base, "* which is obtained from 1-benzyl-3-amino-1,2,4-triazole and N-benzyl-2-methyl-THQ, are dissolved in 20 parts of ethanol and mixed under pressure with 3.2 parts of ethyl bromide 5 st heated to 110-120 ⁰ C. After removal of the ethanol by distillation, the cationic dye is of the formula..:

/ \ V_CH_ — N-N

Br "

obtain. It dyes polyacrylonitrile fibers from a weakly acidic dye bath in bright red shades.

example

12.5 parts of the dye base of the structure:

CH ₃ -

- 36 -609825/0973 '

are dissolved in 50 parts of glacial acetic acid. Ethylene oxide is passed through this solution with stirring at 80-85 ° C, until the quaternization is over. The liquids are then poured into 150 parts of water, and the cationic The dye is isolated as tetrachlorozincate in the usual way. He colors polyacrylonitrile from a weakly acid dye bath in bright bluish-red shades.

Example 125

A polyacrylonitrile textile material is placed in a dye bath containing 0.15 g / l of that described in Example 2 Contains dye, 0.75 g / l of 30% strength aqueous acetic acid and 0.38 g / l of sodium acetate. It becomes a liquor ratio 1:40 used. The dyeing is carried out by slowly heating the dyebath for 0 minutes until it boils. That The dyebath is exhausted by boiling for a further 45 minutes. The colored ifeterial is rinsed in warm water and dried to obtain a bright red-violet hue which has excellent fastness properties having.

Example 126

A printing paste is made from 30 parts of that described in Example 2 Dye, 50 parts of ethylene thiodiglycol, 30 parts of cyclohexanol and 30 parts of 30% strength aqueous acetic acid manufactured. After diluting with 300 parts of warm water, the solution becomes 500 parts of gum arabic as Thickener added. Finally, 30 parts of zinc nitrate are added to the printing paste.

A Polyacrylonitriltextilmaterial is printed with the above printing paste and 20 min steamed at 100-105 ⁰ C. After washing with warm water and drying, a

- 37 -60982S / 0973

bright red-violet imprint received, the excellent one Has authenticity properties.

Example 127

An acid-modified polyethylene terephthalate textile material is introduced into an aqueous dyebath at 20 ⁰ G, the dimethyl benzyl-dodecyl 10 parts / 1 of sodium sulfate, 1 part / 1 PoIyglykolather of oleyl alcohol (50 moles of ethylene oxide / mole of oleyl alcohol), 10 parts / 1 ammonium chloride and 0.15 part / l of the dye of Example 2 contains. After the pH has been adjusted to 4-5 with acetic acid, the textile material is dyed with a liquor ratio of 1:40, the temperature of the dyebath being slowly raised to boiling over 30 minutes and this temperature being maintained for 60 minutes. After rinsing and drying, a bright red-violet shade is obtained.

Example 128

An acid-modified polyamide textile material is introduced into an aqueous dyebath at 40 ⁰ C, which the described 10 parts / 1 of sodium acetate, 2 parts / 1 polyglycol ethers of oleyl alcohol (50 moles of ethylene oxide / mole of oleyl alcohol) and 0.3 parts / 1 in Example 2 Contains dye. After the pH has been adjusted to 4.5 with acetic acid, the textile material is dyed with a liquor ratio of 1:40, the temperature being slowly raised to boiling over 30 minutes and this temperature being maintained for a further 60 minutes. After rinsing and drying, a bright red-violet color is obtained.

- 38 6098 25/09 7 3

Claims (1)

PATENT CLAIMS: 1. Azo dyes that are free from carboxylic acid and sulfonic acid groups are and the formula: A-N = where A is the remainder of a quaternized ■ z
Triazole, R ^ is a non-ionic substituent, η is 0, 1, 2 or 3; R for a hydrogen atom or an optionally substituted alkyl, Alkenyl, cycloalkyl or aralkyl group; R, R, 7 β
R 'and R each represent a hydrogen atom or a methyl, ethyl or propyl group, two or three of the symbols R ^, R ⁶ , R ⁷ and R ^{8 being} hydrogen; and X stands for an anion. Azo dyes according to Claim 1, characterized in that A is the radical of a quaternized 1,2,4-triazole, which is bonded to the azo group in the 3-position. Azo dyes according to Claim 2, characterized in that they have the formula II R I II - 39 609825/09 7 3 have, wherein R is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl, thienyl or alkoxycarbonyl group R represents an alkyl, aryl or 2 2 Aralkyl group or R represents, R represents an alkyl, alkenyl, cycloalkyl, aralkyl, 2-carbamoylethyl, 2-carbamoyl-2-methylethyl, lower alkoxyethyl or lower alkylcarbonylethyl group, R "^ represents a non-ionic substituent , η stands for 0, 1, 2 or 3, R stands for a hydrogen atom or an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group and R ^, r5, r ⁶ , r ⁷ , r ⁸ , χ and η have the meanings given in claim 1. Azo dyes according to Claim 2, characterized in that that they have the formula III: N-N .8th R ' have, wherein R, R, R ^, , R, R ⁷ , R, η and X have the meanings given in claim $. 5. azo dyes according to claim 2, characterized in that they have the formula IV: - 40 - 609825/09 7 3 Hi fi \ 3 _R 6 R ⁸ , have, wherein R, R, R, R
η and X have the meanings given in claim 3. 6. Azo dyes according to one of claims 3, 4- or 5 » characterized in that R represents a hydrogen atom Ί 2
R and R stand for a methyl or ethyl group, η stands for 0 or 1 and R, if present, stands for a methyl, ethyl, methoxy or ethoxy group or a chlorine atom and occupies the 7-position of the tetrahydroquinoline ring. 7- azo dyes according to claim 6, characterized in that that R represents a hydrogen atom or a methyl, ethyl, Propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 4 — hydroxybutyl, 2-cyanoethyl, 2-acetoxyethyl, Benzyl, 4-chloro, 4-methoxy or 4-methylbenzyl, Ethoxycarbonyläthyl-, Propoxycarbonyläthyl-, Butoxycarbonyläthyl-, Phenoxycarbonyläthy1- or Benzyloxycarbonyläthylgruppe stands. 8. azo dyes according to claim 2, characterized in that they have the formula: - N = N in which A stands for the residue of a quaternized 1,2,4-triazole which is bonded to the azo group in the 3-position, R ^{7 stands} for a butyl, pentyl, hexyl or benzyl group and X stands for an anion stands. - 4-1 - 60982b / 09 7 9. Azo dyes according to. Claim 2, characterized in that that they have the formula: 1 9 wherein A, R and X are as recited in claim 8 Have meanings. Azo dyes according to Claim 2, characterized in that they have the formula: 1 Q wherein A, R ^ and X are those given in claim 8 Have meanings. 11. Azo dyes according to claim 2, characterized in that they have the formula: A ¹ -N have, in which A and X have the meanings given in claim 8
Ethyl group. 10
nen meanings and R is a methyl or _ 42 609826/0973 12. Azo dyes according to one of claims 8, 9, 10 or 11, characterized in that A has the formula: K ¹¹
N - / - N has, wherein R stands for a methyl or ethyl group. Process for the preparation of the azo dyes according to Claim 1, characterized in that a compound the formula: A - - N = N (V) Ti h_ c. f. η Q wherein R, R, R, R, R _1, R and η are those in claim 1 Have given meanings and A stands for the remainder of a triazole with at least one unsubstituted Nitrogen atom, alkylated. 14. Use of the dyes according to claim 1 for dyeing synthetic polymeric materials from a aqueous dye bath. 15. Use according to claim 14, characterized in that that the synthetic polymeric material consists of a polyacrylonitrile material and the dye consists of an acidic, neutral or weakly alkaline dye 60 9825/0973 bath is applied at a pH of 3 to 8 and at a temperature between 4-0 and 120 ⁰ C or by a printing technique using a thickened printing paste. PA7WTAHWM.TE ML-HM. H. FINCKE, OIPL-ING. H. BOHR Mf) UIIG. LSTAEOHt 09826/09 7 3