DE2065685A1 - Red and violet water-sol azo dyes - not contg acid water-solubilising gps, - for polyacrylonitrile etc - Google Patents

Abstract

Red and violet water-sol. azo dyes not contg. acid water solubilis ng gps. for dyeing/printing leather, tanned cotton, cellulose acetate, synthetic super polyamides and superpolyurethanes, lignin-contg. fibres, aromatic polyesters and esp. acrylonitrile (co)polymers, for colouring writing fluids and ball point inks and for off-set printing, have the formula (where D is an aromatic gp; E is H or organic radical; r11 is H or opt. substd. CH3, opt. substd. C2H5, opt. substd. >=3C alkyl, or alkenyl; r2 is alkylene; r3 is H, alkenyl, alkyl, cycloalkyl or aralkyl; r4 is H, alkenyl or alkyl; r9 is H, halogen, alkyl or alkoxy, r10 is H, halogen, cyano, lakyl, alkoxy, -NH-CO-alkyl, -NH-CHO, NH-SO2-alkyl, aryloxy, aralkoxy, -SO2-alkyl, -SO2-aryl or -CO- alkyl; X- is an anion); or cpd. (1) where r10 is replaced by ru2 and r11 by r' (where r' is H, alkyl or alkenyl; r12 is halogen, cyano, alkyl, alkoxy--NH-CO-alkyl, -NHCO-, -NH-SO2-alkyl, aryloxy, aralkoxy, -SO2-alkyl, -SO2-aryl or CO-alkyl).

Description

a phenyl, 1- or 2-naphthyl or 5- or β-tetrahydronaphthyl radical,

Hydrogen, an alkyl group with 1-17 carbon atoms which can be substituted by chlorine or cyano, an alkoxy group with 1-1.7 carbon atoms, which can be substituted by chlorine, nethoxy or ethoxy, an alkylthio group with 1-17 carbon atoms, an alkylsulfonyl group with 1-17 carbon atoms, cyclohexyl, cyclohexyloxy, benzyl, Benzyloxy, benzylthio, benzylsulfonyl, phenyl, the

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by nitro, methyl, methoxy, phenoxy, methyloxycarbonyl, Cyclohexyloxy or chlorine can be substituted, phenyloxy, phenylthio, phenylsulfonyl, a dialkylamino group 'with independently of one another 1-7 carbon atoms in the Alkyl chain, a Ν, Ν-diphenylamino group, an N, N-dibenzylamino group or piperidinyl,

r ^ hydrogen, an alkyl radical with 1-6 carbon atoms, that by halogen, hydroxy, cyano, by alkylcarbonyloxy with 1-4 carbon atoms, by alkyloxycarbonyl with 1-4 carbon atoms or by alkoxy with 1-4 carbon atoms can be substituted, or an alkenyl radical with 3-5 carbon atoms,

r _{2 is} an alkylene radical with 2-5 carbon atoms,

r. Hydrogen, an alkenyl radical with 3-5 carbon atoms, an alkyl radical with 1-6 carbon atoms, by cyano, hydroxy, halogen, by alkylcarbonyloxy with 1-4 Carbon atoms, by alkyloxycarbonyl with 1-4 carbon atoms or can be substituted by alkoxy with 1-6 carbon atoms, the cyclopentyl · ·, cyclohexyl, Cycloheptyl-, benzyl-, ß-phenylethyl-, phenylpropyl- (2,2) - or phenylpropyl radical,

r ^ hydrogen, an alkenyl radical with 3-5 carbon atoms or an alkyl radical with 1-6 carbon atoms, substituted by hydroxy, halogen or by alkoxy with 1-6 carbon atoms may be substituted or r, and r ^ together with the N atom is a piperidino radical,

T (j hydrogen, alkyl with 1-4 carbon atoms, benzyl, ß-phenylethyl, / "- phenylpropyl, phenylpropyl- (2,2), cyclohexyl, Phenyl, which can be substituted by fluorine, chlorine, bromine, methyl, ethyl, nitro, methoxy, ethoxy or cyano, Fluorine, chlorine, bromine, alkoxy with 1-3 carbon atoms, Benzyloxy, phenyloxy, acetyl, propionyl, benzoyl, nitro,

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• J. .

Cyano, trichlorinethy. 1, fluoromethyl, difluoroethyl, trifluoromethyl, Methyl carboxylate, ethyl carboxylate, carbamoyl, N-mono- or -di-alkylated carbamoyl, optionally with the same or different alkyl radicals with 1-6 carbon atoms, which are represented by chlorine, bromine or Cyano can be substituted, acetoxy, propionyloxy, methylsulfonyl, ethy! Sulfonyl, phenylsulfonyl, p-toluenesulfonyl, Acetylamino, propionylamino, ethylsulfonylamino, benzoylamino or phenylsulfonylamino,

r _g hydrogen, halogen, an alkyl radical with 1-6 carbon atoms or an alkoxy group with 1-6 carbon atoms,

m the numbers 1-4 and |

X "" mean an anion,

for bath dyeing and printing and materials dyed and printed therewith.

The anionic radicals X ~ * can be both inorganic and organic ions, for example:

Chloride, bromide, iodide, CH ^ SO / ", C ₂ H ₅ SO ₄ ", p-toluene sulfonate, CHjSOj "*, HSO ₄ ", benzenesulfonate, p-chlorobenzenesulfonate, phosphate, acetate, formate, propionate, oxalate, lactate, Xaleinate, crotonate, tartrate, citrate, NO, ", perchlorate and ZnCl,"".

. ■ i

Of the anions, the halides such as chloride, bromide, and iodide, hydrogen sulphate, sulphate, phosphate and methosulphate are of particular importance, since they are used in the representation of the according to the invention Dyes are produced immediately. The dyes obtained in this way can be "exchanged" in known manner be converted into other anions containing dyes. The type of anionic radicals is irrelevant for the application of the dyes, insofar as they are largely coloring, is loose residues that do not adversely affect the solubility of the dyes.

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-N-

Notable alkyl radicals are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, 2 ^ methyl-propyl-1, Isoamyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl and n-heptadecyl.

CH
ι

Suitable alkylene radicals with 2-5 carbon atoms are: -c:

CH, CH, CL H _c C ₉ H ₁ .

»3 ι 3 12 5 12 5

-CH ₂ -CH-, -CH-CH ₂ -, -CH-CH ₂ -, -CH ₂ -CH-, -CH ₃ -CH

CH, CH, 0

n "U AU _PU - Ptl _PU _PU_ —PU

» ^E t " wil ™ vfl «Uli« "9 wXIq wIIa Uli 5 vua

ί ^Η 3

CH, 1 3

-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH-CH ₂ -CH ₂ -, -CH-

- CHp-CHp- CH «- CHp- .

Preferred dyes for use are those of the formulas

R ₂ '- ν - CH ₂ - ('y>

K '

R ₁ ^{1 is} an alkyl radical with 1-5 carbon atoms, R ₂ ¹ ethylene or propylene (1,3) R ₃ ^{1 is} an alkyl radical with 1-3 carbon atoms, Rij ^{1 is} an alkyl radical with 1-3 carbon atoms, Hydrogen, methyl, methoxy, chlorine or bromine,

Hydrogen, methoxy or ethoxy, R ₇ ^{1 is} phenyl, benzyl, benzyloxy or benzylthio and X is an anion, and

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-ΓΓ—?

-N- CHo - <'^

X "
(III)

wherein

R _{1 is} hydrogen or an alkyl radical with 1-5 carbon atoms which can be substituted by halogen, cyano or an alkoxy group mvfc 1-4 · carbon atoms, |

R _{2 is} an alkylene radical with 2-5 carbon atoms,

R ^ hydrogen, an alkenyl radical with 5-5 carbon atoms, an alkyl radical with 1-5 carbon atoms, which is represented by hydroxy, halogen, cyano, by alkylcarbonyloxy with 1-4 carbon atoms or by alkyloxycarbonyl with 1-4 Carbon atoms can be substituted,

R ^ hydrogen, an alkenyl radical with 5-5 carbon atoms or an alkyl radical with 1-5 carbon atoms,

R 'Wa-ss only off, methyl, methoxy, chlorine or bromine,

R _fi hydrogen, halogen, methyl or an alkoxy j

group with 1-3 carbon atoms,

R _{7 is} a di-alkylated amino group with identical or different alkyl radicals with 1-7 carbon atoms, which can be ring-closed to form a heterocyclic system, K, N-di-phenylamino or N, N-di-benzylamino and

X "mean an anion.

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The dyes of the formula (I) to be used according to the invention can be prepared by several known methods. The following two procedures should be emphasized:

1. Quaternization of azo dyes of the formula

^r 6 E-. N / ^. r-

^N -S - ^ - ^{N s Ν} - \ ^ / - Ν / ^Γ 3 (IV)

E, r ₁ , r_, r ,, τ ^ and v <have the meaning given above,

with compounds of the formula

X-CH ₂ -B (-r ₅ ) _m . (V)

B, Tc and m have the meaning given above and X denotes a radical which can be split off as an anion.

2. Diazotization of amines of the formula

.N

E has the meaning given above »

and subsequent coupling with ammonium compounds of the formula

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(VII)

where B, T ₁

r ₆ , m and X those already given

Have meaning.

The dyes of the formulas (II) and (III) can be prepared in the same way.

The following 1,2,4-thiodiazoles are particularly suitable as diazo components of the formula (VI):

5-amino-1,2,4-thiodiazole, 3-phenyl-5-amino-1,2,4-thiodiazole, 3-p-tolyl-5-aaino-1,2,4-thiodiazole, 3-2 ', 4'-dimethyl-piienyl-5-amino-1,2,4-thiodiazole, 3-p-chlorophenyl-5-amino-1,2,4-thiodiazole, 3-m-chlorophenyl-5-amino-1,2,4-thiodiazole, 3-2 ', 4'-dich.lor-plienyl-5-ainino-i, 2,4-thiodiazole, 3-p-nitrophenyl-5-anino-T, 2,3-thiodiazole, 3-m-nitroplienyl-5-aiaino-1,2,4-thiodiazole, 3-p-methoxycarbonylphenyl-5-amino-1,2,4-thiodiazole, 3-methyl-5-amino-1,2,4-thiodiazole, 3-ethyl-5-ainino-1,2,4-thiodiazole, 3-n-hexyl-5-amino-1,2,4-thiodiazole, 3-methoxy-5-amino-1,2,4-thiodiazole, 3-ethoxy-5-amino-1,2,4-thiodiasol, 3-ß-chloroethoxy-5-amino-1,2,4-thiodiazole, 3-cyclohexoxy-5-anir.o-1,2,4- thiodiazole, 3-phenoxy-5-amino-1,2,4-thiodiazole, 3-benzyl-5-amino-1,2,4-thiodiazole, 3-benzyloxy-5-anir.o-1,2,4-thiodiazole, 3-methylthio-5-amino-1,2,4-thiodiazole, 3-ethylthio-5-amino-1,2,4-thiodiazole, S-n-propylthio-S-anino-1,2,4-thiodiazole, 3-n-butylthio-5-amino-1,2,4-thiodiasol, 3-tert-butylthio-5-amino-1,2,4-thiodiazole, 3-n-hexylthio-5-aaino-1; 2,4-thiodiazole, 3-n-dodecylthio-5-amino-1,2,4.-

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thiodiazole, 3-PHenylthlo-5-amino-1,2,4-thiodiazole, 3-3enzyl- ■ thio-5-amino-1, 2,4-thiodiazole, 3-U, N-dimethylaiaino-5-a: 3ir : o- '1,2,4-thiodiazole, 3-piperidino-5-amino-1,2,4-thiodiazole, 3-N, K-di-benzylamino-5-amino-1> 2,4-thiodiazole, 3-N _f -N-diphenylamino-5-amino-1,2,4-thiodiazole, 3-methylaulfonyl-5-amino-1,2,4-thiodiazole, 3-ethylsulfonyl-5-amino-1,2,4 -thiodiazole, 3-n-butyl3ulfonyl-5-amino-1,2,4-thiodiazole, S-tert.-butylsulfonyl-S-amino-i, 2,4-thiodiazole, 3-3enzylsulfonyl-5-amino-1, 2,4-thiodiazole.

According to J. Goerdeler et al, diazo components of the formula (VI) can be prepared from guanidines, nitriles, cyanic acid esters and thiuronium compounds by reaction with rhodanide and chlorine under alkaline conditions / Chem. Ber. ^ 8 (1955) 1071, Chem. Ber. . Ber 87 (195 ¹ O 57, Chem. Ber. 88 (1955) 843, Chem. £ 8 (1956) 10,337th

Suitable starting amines of the formula (VII) are, for example: β-CN-ethyl-N-phenyl-aminoethyl-dimethyl-benzyl-ammonium-chloride / β- [N-propyl-N-phenyl] -aminoethyl-di-n-propyl - (II-nitrobenzyl) ammonium chloride, ß- [N-ethyl-N-phenyl] -aminoethyl-dimethyl- (3-nitrobenzyl) -ammonium-chloride, ß-CN- (ß-ethoxyethyl) -N-phenyl ] -aminoethyl-dimethyl-M-methylbenzyl-ammonium chloride, ß- [N- (ß-Cyanäthyli-N-phenylj-aminoethyl-dimethyl-benzyl-ammonium-chloride, ß- [N-Xthyl-N-phenyl] - aminoethyl-dimethyl-2, ¹ l, 6-trichlorobenzylammonium chloride, ß-CN-ethyl-N-phenylJ-aminoethyl-dimethyl-2,4,6-trimethylbenzylammonium chloride, ß- [N-Äthy1-N- pheny1] -aminoethyl-dimethyl - ^ - bromobenzyl-ammonium-chloride, ß- [N-ethyl-N-phenyl] -aminoethyl-benzyl-ammonium-chloride, ß- [N-Äthy1-N-pheny l] -aminoethyl- methyl-benzy 1-ammonium chloride, γ- [Ν-η-Buty1-N-phenyl] -amino-propyl-dimethyl-benzy1-ammonium-chloride, Y- [N-Methy1-N-phenylj-aminopropyl- (di -ß-chloroethyl) -benzylammoniumchloride, ß- [N-2-methyl-propyl-N-phenyl] -aminoäthylmethy1-ß-hyd roxyethyl-benzy1-ammonium-chloride, ß-CN-ethyl-N-phenyl] -aminoethyl-methyl-ß-cyanoethyl-benzy1-ammonium-chloride,

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ß-CN-ethyl-N-phenylj-aminoethyl-ß-cyanoethyl-il-chloro-benzylammonium chloride, v-CN-methyl-N-phenyl-amino-propyl-C ^ -tert. butyl-benzyl] -anunonium-chloride, ß- [N-ethyl-N-phenyl] -aminoethyl-dimethyl-CM-benzyl-benzyl-ammonium-chloride, ß- [N-ethyl-N-phenyl] -dimethyl- ( M-methyl-diphenylJ-ammonium chloride, ß- [ß-ethoxy-ethyl-N-phenyl-amino-ethyl-methyl-ß-carbomethoxyethyl - ^ - nitrobenzyl-aramonium chloride, ß- [Nn-butyl-N- phenyl] -araino-ethyl-methyl-allyl-C2, M-dimethyl) -benzyl-ammonium chloride, Y-CN-propyl-N-phenylJ-araino-propyl-bis-allyl-iM-chlorobenzyD-ammonium chloride, ß- Cß-chloroethyl-N-phenylJ-aniinoäthylmethyl-ß-chloroethyl- (M-ethoxy-benzyl) -ammoniura-chloride, ß- [N-ethyl-N-phenylj-aminoethyl-dimethyl-tetrahydronaphthyl-CS) - * methyl] - ammonium chloride, ß-CN-ethyl-N-phenyl] -aminoethyldimethyl-C4-chloro-naphthyl- (l) -methyl] -ammonium-chloride, ß- [N-ethyl-N-phenyl] -aminoethyl-methyl- carbomethoxymethyl ( k fluoro-benzyl) ammonium chloride, β- [N-ethyl-N-phenyl] -aminoethyldimethyl - (^ - cyano-benzyl-ammonium chloride, β- [N-ethyl-N-phenyl-aminoethyl -dimethyl-4-isopropyl-benzyl-ammonium chloride, ß- [N-ethyl-N-pheny 13 -aminoethyl-d imethy 1-C * ♦ - (^ '-methyl-phenoxy) -benzyl] -ammonium-chloride, ß- [N-ethyl-N-phenyl] -aminoethyldimethyl- (3-carbomethoxy-benzyl) -ammonium-chloride, ß - [N-Xthyl-N-phenyl] -aminoethyl-dimethyl- (3-benzoyl-benzyl) -ammonium chloride, ß-CN-ß-bromo-ethyl-N-phenyl3-aminoethyl-dimethyl- (3-acetyl-benzyl) ammonium chloride, γ-CN-ethyl-N-phenyl-amino- j propyl-dimethyl-cnaphthyl-dJ-methylj-amraonium chloride, ß- [N- '-allyl-N-phenylj-amino-ethyl-dimethyl -CM-phenoxy-benzyl) -ammonium-chloride, ß- [N-3-methyl-butyl-N-phenyl] -aminoethyldimethyl-benzyl-ammonium-chloride, ß-CN-Xthyl-N-phenyl] -aminoethyl- methyl-methylcarbonyloxyethyl-benzyl-ammonium-chloride, ß-CN-butene- (3) -yl-lN-phenyl] -aminoethyl-dimethyl-benzylamraonium-chloride, ß- [N-butene- (2) -yl-lN- phenyl] aminoethyldimethylbenzylammonium chloride and the corresponding bromides, iodides and sulfato compounds.

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Suitable compounds of the formula (V) are, for example: benzyl chloride, 2-chlorobenzyl chloride, Jj-methylbenzyl chloride, 4-chlorobenzyl chloride, ^ -benzyl-benzyl chloride, diphenyl chloride, methane, 4-nitrobenzyl chloride, ^ -methoxybenzyl chloride, 4-bromobenzyl chloride, Ί-tert. benzyl, 1-chloromethylnaphthalene, 2-chloromethylnaphthalene, 2, ¹ '-Dichlorbenzylchlorid, 2,11-dimethylbenzyl chloride, ll-Äthoxybenzylchlorid, 4-n-Propoxybenzylchlorid, 2,4,6-Trichlorbenzylchlorid, 5-Chlormethyltetrahydronaphthalin, l-chloromethyl ^ -chloronaphthalene, k- fluorobenzyl chloride, 3-cyanobenzyl chloride, i | - (2'-methyl) ™ ethylbenzyl chloride, 3-methoxycarbonylbenzyl chloride, 4 ™ benzyloxybenzyl chloride, ^ -trifluoromethylbenzyl chloride, 3-benzoylbenzyl chloride, 3-acetylbenzyl chloride.

The dyes of the formula (I) are extremely valuable dyes which are used for dyeing and printing materials made of leather, tannier ter cotton, cellulose acetate, synthetic super polyamides and polyurethanes, as well as for dyeing lignin-containing fibers, such as coconut, jute and sisal, can be used. they are further suitable for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in the Use rubber pressure.

The dyes of the formula (I) are particularly suitable for dyeing of fibers and moldings, such as flakes, threads, tapes, woven or knitted fabrics made of polyacrylonitrile, copolymers Acrylonitrile with other vinyl compounds, such as vinyl chloride, Vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and amides and as. Dicyanethylene, or flakes, fibers, tapes, woven or knitted fabrics made from acid-modified aromatic polyesters and acid modified polyamides. Acid-modified aromatic polyesters are, for example, polycondensation products from sulfoterephthalic acid and xethylene glycol, i.e.

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polyethylene glycol terephthalates containing sulfonic acid groups (type DACRON 6H from E. I. Du Pont de Nemours and Company) such as see them in Belgian patent specification 5 ^ 9,179 and US patent specification 2 893 816 are described.

The dyeing may be carried out slightly acidic liquor, wherein, in the dyeing bath conveniently at MO - received 60 ⁰ C and then dyed at the boil. You can also dye at temperatures above 100 ^{0 C under pressure.}

The aralkylammonium dyes of the formula (I) have at | Their use from aqueous dyebaths is a surprising one high drawing speed on polyacrylonitrile and acid-modified polyesters and polyamides compared to the corresponding known alkylammonium and arylammonium dyes. For example, the first dye in the table examples shows the last dye on page 27 of BE-PS 702,737 a higher pull rate on polyacrylonitrile.

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■ Al

Example 1 :

100 g piece goods made of polyacrylonitrile are treated with the following dye liquor:
0.65 g of dye of the formula

CH ₂ -CH ₂ -O-CH ₃

Cl "

be with. Make a paste with water and dissolve it with 500 ml of hot water. The dye liquor contains an addition of 0.5 g des Reaction product of 50 moles of ethylene oxide with 1 mole of toloyl alcohol and 12.5 g sodium sulfate. The pH is then adjusted to 4.5 with acetic acid and a further 1 g of sodium acetate is added. The fabric is dyed at 100 ° C. and a yellowish tinge is obtained Red tone, with all of the dye absorbed onto the fiber after just 15 minutes.

Example 2:

In a staining beaker of 500 ml, which is located in a heatable water bath, 0.055 g of the dye with the formula given in Example 1 are made into a paste with 20 times the amount of hot water, with the addition of a little acetic acid and dissolved with hot water Dye liquor is also given an addition of 0.5 g of the action product of 50 moles of ethylene oxide to 1 mole of oleyl alcohol and is made up to 500 ml with cold water. The pH of the dye liquor is adjusted to 4.5 to 5 with acetic acid or sodium acetate.

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In this dye liquor 10 g of piece goods made from acid modified The polyamide was kept in motion while the temperature was increased to 100 ° C. in 15 minutes. At cooking temperature if you dye it for 15-20 minutes, the material is rinsed with cold water and then dried, e.g. B. by Iron or in the drying cabinet at 60 - 70 ° C. The result is a red-colored material.

Example 3

In a staining beaker of 500 ml, which is in a heatable Water bath is, 0.07 g of the dye with the formula given in Example 1 with the 20 times the amount of hot water, with the addition of a little acetic acid, made into a paste and dissolved with hot water. the Dye liquor also contains an addition of 0.5 g of the action product of 50 moles of ethylene oxide to 1 mole of oleyl _ alcohol, and 1.5 g of a customary aromatic o-oxycarboxylic acid methyl ether. The pH of the dye liquor is then adjusted to 4.5 to 5 with acetic acid or sodium acetate. In this dye liquor, 10 g piece goods made of acid-modified aromatic Eolyester are kept constantly in motion, while the temperature is increased to 100 ° C. in 15 minutes. You dye at boiling temperature for 60 minutes, rinse Material with cold water and then dry it z. B. by ironing or in a drying cabinet at 60 - 70 ° C. Finally, red-colored material is obtained.

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example

East Indian bastard leather, which is prepared in the usual way for dyeing, is mixed in a plotting ratio of 1:10 with 1 % of the dye with the formula given in Example 1, which was previously made into a ^{paste with the same amount of 1} JO Jiiger acetic acid, at HO ⁰ C 1 * Dyed for 5 minutes in a full barrel. The leather is prepared in a known manner. A red dyeing with good fastness properties is obtained.

Following the procedure of Example 1, the specified dyes are obtained on polyacrylonitrile materials using the following dyes Color shades:

formula

Color on polyacrylonitrile fiber

Vc- N \ - / μ η

N C-N = N-

CH,

Cl "

Red

Oi

N ι

CH ₂ -CH ₂ = CH ₂

H ₂ PO ₄

Red

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formula

Paint on polyacrylonitrile fiber

CH ₅

CH

H ₂ PO ₄

Red

-c N

, CHp-CHp ^- CH,

CH ₅ 'CH ₂ -CH ₂ -CH ₂ -CH ₂ -N-CH ₂ - / ~ \

(SO ₄ ") 1/2,

Red

// Λ-σ — N

H ^; c-H

• Η

CH ₅

C ₂ H ₄ -If-CH ₂ -CH,

CH

CH ₂ -CH = CH

CH ₅

H ₂ PO ₄

RoI

H ₂ PO ₄

Red

Ql - // ^ -C --N

-N = N- /

CH

CH ₂ -CH ₂ -CH ₅ ^ CH ₂ -CH ₂ -CH ₂ -N-CH ₂ -J ~ \ -Cl

⁵ cl

Λ Ot

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formula

Part on poly "acrylonitrile fiber

"n H

N ^ C-N

CH,

= N-

CHr) CHo

² I ²

Ho

Red

CH ₃ -OCO-f> -CN

CH ₂ -CH ₂ -CH ₂ -CH ₃

c ₂ H ₄ -K-CH ₂ - ■ ^

H ₂ PO ₄

Ro-

CH, -

^J V- J Il

Il

C-N

H ₂ PO ₄ "

CH

CH,

Red

\\ - 0- ^ VC - N

it H CH

-N = N-

CH ₃

-N-C

CH,

Red

CH, O-C N

CH,

"CHo-

-CH ₂ -N-CH ₂ -C ₂ H ₅

Red

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formula

Paint on polyacrylonitrile

C ₂ H ₅ OC N

-N = N-

C ₂ H ₄ -N-CH ₂ -CH,

-OC ₂ H ₅

H ₂ PO ₄

Red

H-C N

CH ₉ -CH

'-N = N-

PTT

ν «· ζ η τι

CH ₂ -CH ₂ -CH ₂ -N-CH ₂ - • ^ 2 ^Η 5

-OC ₂ H ₅

-CH ₉ ) -NC N _ CH,

² I τ Vc-N, H-fV </ 'C ₂ H ₄ -NH ₂ -CH ₂ -

Red

H ₂ PO ₄ "

Red

CH,

? ^Η

H ₂ PO ₄

Red

1/2

(Γ \. \ -NC N

■ U 11

12. N ^ e. .0

.CH,

-N = N- /

Red

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dye

Color on polyacrylonitrile fiber

N S-N = N-

C ₂ H ₅ SO ₂ -C - N

C-N = N-

CH, CH, ι 3 + ι 3

-NC ₀ H ^ -N-CH ₉ 2 4 ι £

CH ₃

Red

- N- / Λ-N-C (Σ CH,
. + J 3 CH,
/ —Λ ι J TI-C ₄ HqSO ₂ -C- ₉ H.-N-CH ₉ -
2 4 ι 2 G> -? - ^c CH ₃ ! - 'CHj - Ν
η

CH, -C- _{SO 2} -CN CH ₃ CH _{3 -CH 3}

CH, N ^ CN = N- f \ -NC ₂ H ₄ -N ⁺ -CH ₂ - / 3 -C-CH ₃

₂ H ₄

CH ₃

CH

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dye

Color on polyacrylonitrile fiber

-CH ₅ -SO ₅ -CN

^ * - It It

1/2

CH ₃ CH ₃

CH

CH

CH

Red

-C N

Tim

■) 1/2 <

Red

V- / ii

3-N = N-

CH, - <! ^x > -C

3-N = Nf ^ -N CH ₂ -CH ₂ OH

CH, ι P

C ₂ H ₄ -K-CH ₂ CH ₂ -CH ₂ -OCOCH ₃

(H ₂ PO ₄ red

■ N

ILoJJ-N = N-T

CH ₂ -CH ₂ -COOCH

C ₂ H ₄ -N-CH ₂ -T CH,

(H ₂ PO ₄ "") Red

> 1/2

Red

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formula - N
ti
, CN = N- / ~ \ -N ^ Color on poly
acrylonitrile fiber Cl " CH, - / "Λ-C— C ₂ H ₄ -N-CH ₂ -1 / \ -CH ^
CH, ~ Red

N - N
ti ff-
CN = N- / CH, N -N-CHp- CH, Λ> _Ν / ^G 2 ^H 5 Y ^N G ₂ H ₄

Cl

Red

Le A 13 087-1

- 20 -

409884/1181

formula

Paint on polyacrylonitrile fiber

( ^s0 4 h / 2

ff Ve— N

CH

- CH ₂ -

Red

(H ₂ PO ₄ ")

/ \ V-C-N

ti II

N ^ C

CH ₃

CH ₂ -CH ₂ -CH ₂ -N - CH ₂ -. CH ₃

Red

// Vc- N

J ^ ₃ JHH

C ₂ H ₅

₅
-NC ₂ H ₄ -N ₄₇ CH ₂

C ₂ H ₅

Red

(H ₂ PO ₄ ")

CH,

Red

^ ft H 087- ] - 21 -

0.9 8 8 A / 1 1 8 1

formula

It Il

v <

CH,

Paint on polyacrylonitrile fiber

Red

(H ₂ PO ₄ ")

VC-N

C ₂ H ₅

V ₄ -N-CH ₂ - <Q -CH ₃ C ₂ H ₅

Red

/ A-C N

CH

Red

(H ₂ PO ₄ ")

-C - N

/ ^C 2 ^H 5

₃ C ₂ H ₄ -N-CH ₂ -

CH

\ -0CH,

Red

- 22 -

409884/1181

Pormel

Paint on polyacrylonitrile fiber

OCN (so

^CH

CH,

CH

Red

(H ₂ PO ₄ ")

// Vc- N

C ₂ H ₄ CN

-CH,

Red

'4

C ₂ H ₅

C ₂ H ₄ Cl

Red

(H ₂ PO ₄ ")

/ 2 = 5

CH ₃

C ₂ H ₄ -N-CH ₂ - ^
CH

Red

Le A 13 087 -I - 23 -

409884/1181

formula

Paint on polyacrylonitrile fiber

-σ-ν

It It

N C-N = N-

-N GH,

ζ \ -CH ₂ -

Red

S-O N

¹¹ "

CH

Red

-C-N

η ti

N ^ .C-

Red

Le A 13 087-1

- 2 * 4 -

409884/1181

formula

. «Τ

Paint on polyacrylonitrile fiber

(H ₂ PO ₄ ")

PCN it ti / N ^ C ^ CN = N- <f

NO ₂ ^{ö X}

CH CH

, _{/ 2}

iC N

Il It

N _σ .CN = N-

/ ° 2 ^H 5

CH

-CH,

Red

Red

(H ₂ PO ₄ ")

³  ^W S / c C ₂ H ₅

A CH ₅

^C 2 ^H 4 1+ 2 W CH ₅

Red

1/2

CH ^ OCO- f ~~ \ -C - N ^ = " ⁷ NC

-N

CH,

ι -

-N ₊ -C CH,

Red

Le A 13087 -I

- 25 -

40.9884 / 1-181

Pormel

Paint on polyacrylonitrile fiber

; -Q-N

(H ₂ PO ₄ ")

CH,

_t » _rO

Red

-C-N

GH

(SO ₄ -) _1/2 C ₂ H ₅

% -n 'CH ₅

CH,

Red

-C N

N _n <_ SN = N-

CH,

(H ₂ PO ₄ ")

CoH ₁

CH ₅

"C ₂ H ₄ - ^ - CH ₂ -CH ₅

Red

/% - 0-C N

ti ff

N-O ^ C-

CH ₅

'C ₂ H ₄ -N-CH ₂ . CH,

Red

Le A 13 087-1

- 26 -

409884/1181

Pormel

Paint on polyacrylonitrile fiber

H> -OC N

• I Il

N ^ g, C-N = N-

/ 2 ^H 5 -N CH,

CH,

Red

CH-O-C N

Ν _{νσ y} CN = N- / \ -N

CH _x CH

Red

CH, -C- N

V Il M

CH ₂ -CH-C CH ₅

C ₂ H ₅

Red

Le A 13 087-1

- 27 -

A0988A / 1181

Formula -tf

Paint on polyacrylonitrile fiber

N ^ ₅ , CN = N- f ~ \ -N

CH-

CH,

Red

CH ₅ (CH ₂ ) 5-0 -N

N-C-N = N- / Λ-Ν CH,

CH

Red

HC-

? 3
C ₂ H ₄ -N-CH ₂ /

CH ₃

Red

N _vS ^ C-Nf = N-

, ^C 2 ^H 5

CH,

CH.

Red

Le A 15 087 -I - 28 -

40-98 84/1 181

formula m , -CNC ₉
N _N g "CN = N - ^ \ - N _x
* - ft (SO Color on poly
acrylonitrile fiber Red CH ₅ 4 "" ^} i / 2 / "" "V-CH, CH ₃ -ΖΛ

(H ₂ PO ₄ ")

-CH ₀ O-C'-N

-N

CH,

CH

Red

(OHj) ₂ SCK ■

CH, CH ^ -CHo-CH _n -NrCH,

(OH ₃ J ₂ NON

/ 2 5

CH ₃

Red

Le A 13 087-1

- 29 -

09884/1181

formula

-V)

Paint on polyacrylonitrile fiber

C ₂ H ₅

⁵ CH ₃

ρ "-N-CHp- / ~ \ -CH, υρΗ _Λ ι + <- \ / - J

^{ά Λ} CH, / ³ CH,

Red

CH, S-C-N 3 ιΐ it

C-N = N-

Red

CH, S-C-N

o. C-N = N-

AN ⁷

C ₀ Hc / 25

Red

C ₉ H ₁ -SC-N
2 5 n

(H ₂ PO ₄ ")

-N = N- / \ -N W λ

oHc 2. 5

LeA 13087-

Red

- 30 -409 884/1

formula

-TA paint on polyacrylonitrile fiber

n-C, H-S-C N

-> * t ir

f "

N _vt , ^ CN = N-

. ^C 2 ^H 5

CH ι

CH,

Red

n-C, H ~ S-C N

j ι ν «

• ^C 2 ^H 4-? T ^CH 2- CH ₃

Red

CH ₃

CH, -CSC
ι if

CH, N

--N

U = N- <Q

C ₂ H

₂ H ₅

OH,

Red

CH ₃ ■ CH ₃
-CSC-N
I Ί Ii ^W V ₄ ( CH ₃
-N ₊ -CH ₂ - W. CH ₃ N _{x S} , CN = 1 CH ₃ - T1 Le A 13 087 -I 409 88 4 / 1181

' Red

formula

Color on polyacrylonitrile fiber

Ti-C ₆ H ₁₃ SCN

-N = N- / ~ Λ -Ν / ^C 2 ^H 5.

C ₂ H ₄ -N ₊ -CI CH,

Red

n-C, -Hi, S-C-N

C ₂ H ₅ -N-CH ₂ - / Λ

Red

(SO

\ _S-C— N

Ν _{ν q} , CN = N- /

C ₂ H ₅

CH

Red

• Ν CN = NZ ^ -N ⁷ CH N-CH

Red

Le A 13 087-1

- 32 4.0 9 8 8-4 / 1 181

formula

Paint on polyacrylonitrile fiber

^ -CH ₉ SC -Ν 2 ι κ

N ^ C-N = N-

-N CH,

CH

Red

-CH ₀ SC 2 κ

- Ν

CoHc-

Q- CH

\ ι

C ₂ H ₄ -N-CH ₂ - /

Red

CH-SO ₅ -C— N 3 2 ι, ι

/ 25
N CH,

C ₂ H ₄ -N ₊ -CH ₂ -CH,

(H ₂ PO ₄ ')

Red

CH, S0 _o -C - Ν 3 2 it η

N _x ς .CN = N-

-N CH,

Le A 15 087-1

- 33 - red

409884/1181

formula

Paint on poly- ^ acrylonitrile fiber

(H ₂ PO ₄ ")

C ₉ Hc-SO ₀ -C- N-

CH

Red

hh

A h / 2

CH,

CH

Red

HC ₄ H ₉ SO ₂ -CN

_s ^

'2 ⁿ 5

(H ₂ PO ₄ -)

C-N = N- / \ -n: ch.

^K C ₂ H ₄ -N ₊ -CV _V- CH ₃

Red

HC ₄ H ₉ SO ₂ -CN

C ₂ H ₅ -N { CH

CH

Red

Le A 13 087-1 40988A / 1181

formula

Color on polyacrylonitrile fiber

CH ₃

• C-S (

CH, (H ₂ PO ₄ -)

-σ - ν

i Il /, -? v

N, 3, CN = N- (J *)

. ^C 2 ^H 5

CH

CH,

Red

CH ₃

CH ^ -C-SO ₀ -C · CH ₃ N.

Il

yN CH,

CH

Red

O-CH _{9 -SO 9} -C -N

N _ns ^ CN = N

(H ₂ PO ₄ ")

CH, 1 3 CH

Red

-HC ₂ H ₅

CH ₃ CH

Red

Le A 13 087-1

- 35 -

A O 9 8 8 A / 1 1 8

formula

Paint on polyacrylonitrile, !fiber

CH ₂ -CH ₂ -OH

CH

-Br

Red

(so _A "~)

N \ -N -

4 M / 2

^C 2 ^H 4it ^CH 2-O- \ CH,

Red

Le A 15 087-1 - 36 -

4.09884 / 1 18 1

-YI

Preparation example 1 :

88.5 g of 3-phenyl-5-amino-thiadiazole-1,2,4 · be finely powdered and under stirring in 1 kg of 85-90 follow phosphoric acid added. After the whole thing is homogeneous, it is cooled to 0 "to -5 ° C and 85 ecm nitrosylsulfuric acid is added dropwise at this temperature (50 ecm nitrosylsulfuric acid contain 21 g nitrite). The colorless mixture then turns an intense orange-yellow color very quickly Stirred in closed apparatus at this temperature for another 5 hours, at the end of which a syrupy diazo solution is present. N-phenyl7-affiinomethyldimethyl-benzylammonium chloride is added to 750 ecm of water, which is gradually poured into ice. the amount is added so that the temperature does not rise above 0 ° C. The pH is then adjusted to 5.5-6 with about 900 g of concentrated sodium hydroxide solution over the course of 3 hours with the addition of ice at 0 ° C. The mixture is stirred overnight and then suctioned sharply and dried at 60 ° C.

The resulting dye of the formula

ACN / Il Il

dyes polyacrylonitrile fibers in bluish red tones.

Le A 13 087 -I

- 37 -

A O 9 8 8 4/1 1 8 1

Preparation example 2 : 367.5 g of dye of the formula

CH ₉ -CH ₉ -O-CH ² *

\ N

(produced by diazotizing 3-phenyl-5-aminothiodiazole-1,2,4 - and coupling on ß-N-ß'-methoxyethyl-N-phenylaminoethyl-dimethylamine) are heated to 95 ° C with 200 ecm of water, then 128 g of benzyl chloride are added with stirring at this temperature in about 1 hour and the mixture is stirred for a further 1 hour. The resulting dye has the formula given in Example 1.

Le A 13 087-1 - 38 -

409884/1181

Claims (3)

Patent claims : a phenyl, 1- or Z- naphthyl or 5- or S-tetrahydronaphthyl radical, 'Hydrogen, an alkyl group with 1-17 carbon atoms substituted by chlorine or cyano can, an alkoxy group with 1-17 carbon atoms, which is substituted by chlorine, methoxy or üthoxy can be an alkylthio group with 1-17 carbon atoms, an alkylsulfonyl group with 1-17 carbon atoms, Cyclohexyl, cyclohexyloxy, benzyl, benzyloxy, benzylthio, benzylsulfonyl, fhenyl, the by nitro, .methyl, methoxy, phenoxy, methyloxycarbonyl, Cyclohexyloxy or chlorine can be substituted, phenyloxy, Phenylthio, phenyleulfonyl, a dialkylamino group with independently of one another 1-7 carbon atoms in the alkyl chain, a Ν, Ν-diphenylamino group, an N, N-dibenzylamino group or piperidinyl, Le A 13 087-1 - 39 - 40988WM81 T _{1 is} hydrogen, an alkyl radical with 1-6 carbon atoms which can be substituted by halogen, hydroxy, cyano, by alkylcarbonyloxy with 1-4 carbon atoms, by alkyloxycarbonyl with 1-H carbon atoms or by alkoxy with 1-4 carbon atoms, or an alkenyl radical with 3-5 carbon atoms, r _{2 is} an alkylene radical with 2-5 carbon atoms, r. Hydrogen, an alkenyl radical with 3-5 carbon atoms, an alkyl radical with 1-6 carbon atoms, which is substituted by cyano, hydroxy, halogen, by alkylcarbonyloxy with 1-h carbon atoms, by alkyloxycarbonyl with 1-k carbon atoms or by alkoxy with 1-6 carbon atoms can be the cyclopentyl, cyclohexyl, cycloheptyl, benzyl, ß-phenylethyl, phenylpropyl (2,2) or phenylpropyl radical, rjj hydrogen, an alkenyl radical with 3-5 carbon atoms or an alkyl radical with 1-6 carbon atoms, which can be substituted by hydroxy, halogen or by alkoxy with 1-6 carbon atoms, or r, and Tu together with the N atom are a piperidino radical, T ^ hydrogen, alkyl with 1-k carbon atoms, benzyl, ß-phenylethy 1, / '' - phenylpropyl, phenylpropyl- (2,2), cyclohexyl, phenyl, which by fluorine, chlorine, bromine, methyl, ethyl, nitro, Methoxy, ethoxy or cyano can be substituted, fluorine, chlorine, bromine, alkoxy with 1-3 carbon atoms, benzyloxy, phenyloxy, acetyl, propionyl, benzoyl, nitro, cyano, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, methyl carboxylate, ethyl carboxylate, carbamoyl, N-mono- or -di-alkylated carbamoyl, optionally with identical or different alkyl radicals with 1-6 carbon atoms, which can be substituted by chlorine, bromine or cyano, acetoxy, propionyloxy, methylsulfony1, ethylsulfony1, phenylsulfonyl, p-toluenesulfonyl, acetylamino, Propionylamino, ethylsulfonylamino, benzoylamino or phenylsulfonylamino, Le A 13 087 -I - * 0 - 4 0 9 8 8 4/1181 Tg hydrogen, halogen, an alky Ires t with 1-6 "crude lead atoms or an alkoxy group with 1-6 carbon atoms, m the numbers 1-4 and
X ~ mean an anion, for bath dyeing and printing of moldings made from polymers or copolymers of acrylonitrile or as. dicyanoethylene or from acid-modified aromatic polyesters and polyamides. 2.) Use of dyes of claim 1 for dyeing leather, tannic cotton, synthetic superpolyamides and polyurethanes, of, writing fluids, of lignin-containing Fibers and for coloring printing pastes. 3.) Use of azo dyes of the general formula R ₇ -. N. JLn N / A * Rt-N- CH, 2, wherein R ₁ 'is an alkyl radical having 1-5 carbon atoms, R ₂ ¹ ethylene or propylene (1,3) R · » ^{1 is} an alkyl radical with 1-3 carbon atoms, Ru ^{1 is} an alkyl radical with 1-3 carbon atoms, hydrogen, methyl, methoxy, chlorine or bromine, hydrogen, methoxy or ethoxy, phenyl, benzyl, benzyloxy or benzylthio and an anion, V VR ₇ . Le A 13 087 - ORIGINAL INSPECTED 09 8 84/1181 2055685 for bath dyeing and printing of moldings made from polymers or copolymers of acrylonitrile or as. Dicyanäthylens or of acid-modified aromatic polyesters and polyamides. Le A 13 087 -I - k2 - 4 09884/1181