DE2256313A1 - AZO CONNECTIONS, THEIR PRODUCTION AND USE - Google Patents

Description

ClBA-GEIGY AG, CH-4002 Basel V ^ iD / 'V """" vHEZlvH Y

Case 1-7847 / C1N 5V1 + 2 / B

Germany

Attorney file 22,946 November 16, 1972

Azo compounds, their manufacture and their uses

The invention relates to dyes

Formula. ,.

NH-CO-R ₂

D-N = N-

IH-CO-R ₁

where D is the remainder of a diazo component, R, a water

; atom, an aryl, alkoxy, aryloxy, alkylamino or

. Arylamino radical or an (alkyloxy or aryloxy) earbonyl

radical or (alkyloxy or aryloxy) earbonylalkyl radical or an (aryloxy, arylthio or arylamino) alkyl radical or a styryl radical or aralkyl, thiophenyl or pyridyl radical, Rp is an unsubstituted or substituted alkyl radical or the same as R and R, and R ₁ , optionally by

are at least one heteroatom interrupted and / or optionally substituted alkyl radicals. ^! According to the invention, the dyes are obtained by adding a diazonium compound of a diazo component

with a coupling component of the formula '

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'", ί'üi Λ τ j ■>'. '

CIBA-GEIGY AG

NH-CO-R

NH-CO-R

where R ,, R _? , R, and R ^ mean the same as above, clutch.

The dyes of the formulas are particularly preferred

NH-CO-R ₂

D-N = N

NH-CO-R -Χ-ΛΛ

wherein R ₁ - a straight-chain or branched lower alkylene

group, X is -0-, -S- or -NH and the radical A can be substituted, such as, for example

NH-CO-R

D-N = N

NH-CO-CH ₂ - {

also the dyes of the formulas

I0SI21 / 1078

CIBA-SEIGYAG - _

NH-CO-R ₂

D-N = N

NH-GO-CH = C-H-C ^ EL

NHCOR ₂ DN = N - / / - N

NHCOt (A NH-CO-R ₂ }

DN = N— ( V —— N

^R 4

NH-rCO-0-Rg

wherein R 1 is aryl or lower alkyl. As heteroatoms, which contain the radicals R_ and R ₁ ,

can interrupt, nitrogen, sulfur and especially oxygen atoms come into consideration. The radicals "R- and R ₁ ," derive as a rule from alkyl groups with 1-4 carbon atoms and the substituents preferably contain no more than 10 carbon atoms.

The radicals R., and R ₁ , are lower alkyl groups which can have up to 5 carbon atoms. They can be interrupted and / or substituted by heteroatoms such as sulfur, nitrogen and, above all, oxygen atoms

CIBA-GEIGY AG

be. Possible substituents are one or more Halogen atoms, alkylcarbonyloxy, arylcarbonyloxy, alkyloxycarbonyloxy, Aryloxycarbonyloxy, arylaminocarbonyloxy, alkylaminocarbonyloxy, cyano, phenyl, alkoxy, alkoxycarbonyl, Aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl, morpholinylcarbonyl, aminocarbonyl, dialkylaminoearbonyl, Alkylaminocarbonyloxy, arylaminocarbonyloxy, aryloxy, arylcarbonyl, alkylcarbonyl, or phthalimido radicals be substituted. The alkyl groups contained in the substituents preferably contain 1 to 5 Carbon atoms and can be replaced by halogen atoms, in particular chlorine or bromine atoms, alkoxy groups, such as methoxy or butoxy groups, Cyano groups, phenyl groups, or hydroxyl groups can be substituted. The aryl radicals mentioned in the list are preferably phenyl radicals. These phenyl radicals are either unsubstituted or by halogen atoms, such as fluorine, Bromine or chlorine atoms, methoxy or ethoxy groups, nitro, trifluoromethyl or alkyl groups, such as methyl, ethyl, isopropyl or butyl groups may be substituted.

Examples of groups R 1 and R 1 may be mentioned Benzyl-, ß-phenethyl-, ß-chloroethyl- ß, ß, ß-trifluoroethyl-, β, Ύ-dichloropropyl, ß-cyanoethyl, ß-ethoxyethyl or δ-methoxybutyl-, ß- (acetyl- or formyl) -aminoethyl-, formyloxyalkyl-, ß-Acetyloxyäthyl-, ß, 7-Diacetoxypropyl- and -y-Butyryloxypropyl -, - ß-Methanesulfonyläthyl-, ß-Ethanesulfonyläthyl-, Vinylsulfonylalkyl-, phenylsulfonyl-alkyl-

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CiBA-GEIGYAG

and β- (p-chlorobenzenesulfonyl) ethyl, ß-methylcarbamyloxyethyl, Butylcarbamyloxyäthyl- and ß-Phenylcarbarnyloxyäthyl-, Methoxycarbonyloxy- or Butoxyoarbonyloxyäthyl- and o-, m- or p- (methoxy-, ethoxy-, ß'-chloroethoxy-, isopropyloxy- or methyl) phenyl-earbonyloxyäthyl, 7-acetamidopropyl, Cy an a Ik oxy alkyl, ß-carboxyethyl, ß-cyanoacetoxyethyl, ß-Benzoyloxyäthyl- and ß- (p-Alkoxy- or phenoxy-benzoyl) -oxyäthyI groups.

As acidic in water dissociating., Water-solubilizing groups that are excluded in the new dyes are meant the known, the dyes Toggle • ionic character imparting substituents, for example Sui fonsäure-, or phosphoric acid groups. ₅

D preferably represents a halogen atom, hydroxyl, cyano, rhodane, nitro, lower alkyl, trifluoromethyl, lower alkoxy, formyl, lower alkylcarbonyl, benzoyl, methylbenzoyl, lower alkoxycarbonyl, benzyloxycarbonyl, cyclohexyloxycarbonyl -, Phenoxycarbonyl, lower, alkoxycarbonyloxy, Be'nzyloxycarbonyloxy, lower alkylcarbonyloxy, benzoyloxy, lower alkylcarbonylamirio, benzoylamino, lower alkylsulfonyl, chloroethylsulfonyl, hydroxyethylsulfonyl, mono-substituted or disubstituted by alkylsulfonyl groups, or , Difhydroxyäthyl) aminosulfonyl- _J Phenylarninosulfonyl-, (chloro- or methoxyJp. ^ Enylaminosulfonyl-,

309 821/107 8

^ßA D ORIGINAL

CIBA-GEIGYAG

Benzylaminosulf oriyl-, N-piperidylsulfonyl, N-morpholinosulfonyl-, lower alkylsulfonyloxy, cyclohexylsulfonyloxy, chloromethylsulfonyloxy, cyanoethylsulfonyloxy, phenylsulfonyloxy, Aminosulfonyloxy, (chloro- or methoxy) phenylsulfonyloxy-, N-morpholinosulfonyloxy-, ethyleneiminosulfonyloxy, lower Monoalkyl or dialkylaminosulfonyloxy, phenylaminosulfonyloxy, N-phenyl-N (lower-alkyl) aminosulfonyloxy-, N- (methoxy- or chlorine) phenylaminosulfonyloxy-, phenylamino-, Phenyl radical substituted with nitrophenylamino, dinitrophenylamino, phenyl, phenoxy and / or acetylaminophenyl groups, an optionally by chlorine or bromine atoms, hydroxyl, Cyano, nitro, lower alkyl, trifluoromethyl, lower Phenylazophenyl radical substituted by alkoxy or phenoxy groups, an optionally substituted by methoxy, ethoxy, Substituted phenylazo or dimethylaminosulfonyl groups Naphthyl radical, a possibly by chlorine or bromine atoms, nitro, cyano, rhodan, lower alkyl, lower alkoxy, lower alkyl mercapto, phenyl, benzyl, phenethyl, cyano, lower alkyl, lower alkyloxycarbonyl, trifluoromethyl, substituted lower alkylcarbonyl and lower alkylsulfonyl groups Thiazolyl radical, one optionally by chlorine or JiVr ο ma to me, cyano, rhodan, nitro, lower alkyl, lower Alkoxy, benzyl, phenylethyl, lower alkylsulfonyl, phenyl, lower alkyl mercapto, lower alkoxycarbonyl, lower alkylcarbonyl, Tril'luoromethyl-, cyanrithy] suli'onyl-, aminosulfonyl-

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CIBA-GEIGY AG

or a rait if necessary by lower mono- or Benzthiazolyl radical substituted by dialkylaminosulfonyl groups, an optionally substituted by cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl or phenyl groups, an optionally substituted pyrazolyl radical by lower alkylsulfonyl, lower alkoxy, lower alkyl, phenyl, lower alkylsulfonyl or lower alkyl mercapto groups substituted thiadiazolyl radical, one optionally substituted by nitro or lower .Alkylgruppen Imidazolyl radical, one optionally substituted by nitro, lower alkyl, lower alkylsulphonyl, lower alkoxycarbonyl. or acetyl groups, one optionally substituted by lower alkyl, cyano or phenyl groups substituted isothiazolyl radical, and, one optionally by lower alkyl groups, nitro groups or halogen atoms substituted benzisothiazolyl radical »lower alkyl groups ■ are e.g. · 'methyl, ethyl, propyl, isopropyl and iso-

butyl residues.

i. ■

; The diazo radical D is preferably derived from

Amines that have a heterocyclic five-membered ring with 2 or 5 ■ Heteroatoms, mainly one nitrogen and one or two sulfur, Have oxygen or nitrogen atoms as heteroatoms,

'and aminobenzenes, especially negatively substituted amino

trenzolen, in particular those of the * formula ^; fa.

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CIBA-GEIGY AG

wherein a is a hydrogen or halogen atom, an alkyl or alkoxy, nitro., cyano, carbalkoxy or alkylsulphone group, b a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group, e a halogen atom, a nitro, cyano, Carbalkoxy, arylazo or alkylsulphonyl group, f is a hydrogen or halogen atom, a carbalkoxy or a carboxylic acid ami dgruppe mean.

Examples include: 2-aminothiazole,
2-Amino-5-nitrothiazole, 2-Amino-5-methylsulfonyl-thiazole, 2-Amino-5-cyanthiazole, 2-Amino-4-methyl-5-nitrothiazole, 3-Amino-benzisothiazole-2,1, 5- Amino-5-chloro-benzisothiazole-2, l,

, 7-dibromo-benzisothiazole-2,1, 2-cyano-4,6-dibromo-aniline, 2-cyano-4-chloro-6-bromo-aniline, 2-cyano-4,6-dichloro-aniline, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-Amino-4- (4'-chloro) -phenylthiazole, 2-Amino-4- (4'-nitro) -phenylthiazole,

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CIBA-GEIGYAG

3-aminopyridines

5-aminoquinoline,

5-aminopyrazole,

3-amino-l-phenylpyrazole, 5-aminoindazolj

3-amino-l, 2,4-triazole,

5- (methyl-, ethyl-, phenyl- or benzyl) -l, 2,4-triazole,

3-Amino-1- (4'-methoxyphenyl) pyrazole, 2-aminot) enz thiaz oil, 2-amino-6-methylbenzthiazole 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzothiazole, 2-amino 6-cyanobenzothiazole, 2-amino-6-rhodanobenzothiazole, 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, 2-amino- (4- or 6) -methylsulfonylbenzthiazole, 2-amino-1, 3 * 4 -thiadiazole, 2-amino-l, 5i5-thiadiazole, 2-amino-4-phenyl- or ~ 4-methyl-l, 3 * 5-thiadiazole 2-amino-5-phenyl-l, 3,4-thiadiazole, 2-Amino-3-nitro-5-methylsulfonyl-thiophene _ί , 2-Amino-3 * 5-bis (methylsulfonyl) -thiophene,. 5-amino-3-methyl-isothiazole,

2-amino-4-cyano-pyrazole, ''

2- (4'-nitrophenyl) -3-amino-4-cyanopyrazole,

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CIBA-GEIGYAG

5- odor 4-aminophthalimide, Aminobenzenes

1-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-2-cyano-4-chlorobenzene, l-amino - ^ - carbomethoxy - ^ - chlorobenzene, l-Amlno-P-carbomethoxy - ^ - nitrobenzene, l-Amino-2-chloro-4-cyanobenzene, l-Amino-2-chloro-4-nitrobenzene, l-amino-2-bromo-4-n-trobenzene, l-Amino-2-chloro-4-carbäthoxybenzolj l-Amino-2-chloro-4-methylsulfonylbenzene, 1-amino-2-methy1sulfonyl-4-chlorobenzene, l-Amino-2,4-dinltro-6-methylsulfonylbenzene, l-amino-2,4-dlnitro-6- (2'-hydroxyethylsulfonyl) benzene, l-amino-2,4-dinltro-6- (2'-chloroethylsulfonyl) benzene, l-amino-4-methylsulfonyl-2-nitrobenzene, l-amino-2-methylsulfonyl-4-nitrobenzene, l-Amino-2,4-dinitrobenzene, l-Amino-2,4-dlcyanbenzene, l-Amino-2-eyan-4-methylsulfonylbenzene, l-Amino-2,6-dichloro-4-cyanobenzene, l-amino-2,6-dichloro-4-nitrobenzene, l-amino-2,4-dicyan-6-chlorobenzene, 4-Amino-benzoic acid cyclohexyl ester, 1-amino-2,4-dinitro-6-chlorobenzene and in particular l-Amino-2-cyano-4-nitrobenzene, also -

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GiBA-GOGYAG - J.

l-AmInobenzol-2-j -3- or -4-sulfonic acid amides like that N-methyl- or N ^ N-dimethyl- or diethylamide,

N, 7-Isopropyloxypropyl ~ 2-aminonaphthalene-6-sulfonic acid amide

Nj ^ -Isopropyloxyproyl-l-aminobenzene - ^ - e ^ - or -4-sulfonic acid amide, - -

N-Isopropyl-1-aminobenzene-2 - ^ - 3- or -4-sulfonic acid amides

N _J 'Y-methoxypropyl-l-aminotienzol-2- _J -3- or -4-sulfonic acid amide,

N, N-bis (ß-hydroxyethyl) -l-aminot) enzene-2- ₅ -3- or -4-sulfonic acid amide,. .

1-Amino-4-chlorobenzene-2-sulfonic acid amides and the N-substituted derivatives 2-j 3- or 4-aminophenyl sulfamate, 2-anaino-4-e -5- or -6-methylphenyl sulfamate ^ 2-AmInO-S-IHe ^ OXy-phenylsulfamate 3-Amino-6-ehlorphenylsulfamat ₃ 3-Amino-2,6-dichlorophenylsulfamat, 4-Amino-2- or -3-methoxyphenylsulfamat, N, N-Dimethyl-2-aminophenylsulfamate Ν, Ν-Di-nt ) utyl-2-aminophenylsulfamate N, N-dimethyl-2-amino-4-chlorophenylsulfamate j, N, N-propyl-3-aniinophenylsulfamat _; , N, N-Di-n-butyl-3-aminophenylsulfamate O (3-aminophenyl) -N-morpholine-N-sulfonate, O (3-aminophenyl) -N-piperidine-sulfonate, N-cyelohexyl-O- (3 -aminophenyl) -sulfamatj N (N-methylaniline) -O- (3-aminophenyl) -sulfonate

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A.

N, N-diethyl-3-amino-6-methylphenyl sulfamate, N-ethyleneimine-Ö- (4-aminophenyl) -sulfonate, NjN-dimethyl - ^ - aminophenyl sulfamate, 0- (n-propyl) -O- (3-aminophenyl) sulfonate, 0, ß-chloroethyl-O- (2-aminophenyl) sulfonate, O-benzyl-0- (3-aminophenyl) sulfonate and O-ethyl-0- (4-amino-2,6-dimethyl-phenyl) -sulfonate, 4-aminoazobenzene,

3i 2'-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 4-amino-2-n-troazobenzene,

2, ^ - Dimethoxy - ^ - aminoazobenzene, 4 ^f -methoxy-4-aminoazobenzene, 2-methyl-4'-methoxy-4-aminoazobenzene, 5, 6, ^ trimethoxy-'ty-aminoazobenzene, 4 '- chlorine- 4-amlnoazobenzene,

ί
2 .'- or 3'-chloro-4-aminoazobenzene, 3-nitro-4i-amino-2 ', 4'-dichloroazobenzene and 4-aminoazobenzene-4'-sulfonic acid amide.

Instead of the above, ionogenic, water-solubilizing agents Groups free diazo components can those which contain fiber-reactive groups can also be used contain, such as s-trlazinyl residues on the triazine ring 1 or 2 chlorine or bromine atoms, pyrimidyl radicals that have one or two chlorine atoms or one or two arylsulfonyl or carry alkanesulfonyl groups on the pyrimidine ring, mono- or

309821/1078

CLBA-GEIGY AG

.A

Bis- (7-halo-ß-hydroxypropyl) -amino groups, ß-haloethylsulfamyl groups, ß-haloethoxy groups., Ss-haloethyl mercapto groups, 2-chlorobenzthiazolyl-6-azo groups, 2-chlorobenzothiazolyl-6-amino groups, 7-halo groups -ß-hydroxy-propylsulfamyl radicals, chloroacetylamino groups, <x, ß-dibromopropionyl groups, vinylsulfonyl groups and 2nd, 3-epoxypropyl groups.

Suitable fiber-reactive diazo components are e.g. Ν, ß-chloroethyl-5-chloro - ^ - amino-benzenesulfamide (hydrochloride), N, ß-chloroethyl-4-aminobenzene-sulfamide (hydrochloride), 5_.BrOm-4-amino-m-chloroacetophenone, "'

N, 7-chloro-ß-hydroxypropyl-4-aminobenzpl-sulfamidj N, ß-chloroethyl-1-amino-4-naphthylsulfonamide, N, ß-chloroethyl-l-amino-3i5-dichlorobenzenesulfamide and 2f_ (7-chloro-ß-hydroxy-propoxy) -aniline.

The diazotization of the diazo components mentioned can correspond to the position of the amino group in question, e.g. with the help of mineral acid and sodium nitrite or e.g. with a solution of nitrosylsulfuric acid in concentrated Sulfuric acid.

The coupling can also be carried out in a manner known per se, 25.B. in a neutral to acidic medium, if necessary in the presence of sodium acetate or similar, the coupling ' speed-influencing buffer substances or catalysts, such as dimethylformamide, pyridine or their Salting, can be made. :

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CIBA-GEIGY AG

The coupling components are obtained, for example, by converting 3,5-nitro-aniline to 5-nitro-1,3-m-phenylenediamine reduced. The dianiine is then diacylated and kata Lytically reduced to 1,3-diacylamino-5-aminobenzene. the the latter connection, which of the B'ormel

NH-CO-R

corresponds, can be alkylated on the free amino group in a manner known per se, for example by reaction with
Ethylene oxide or by reaction with halogen compounds (eg chloroacetic acid esters), reaction with higher epoxides and optionally acylation of any hydroxyl groups that may have formed.

Acylating agents are, for example, carboxylic acid halides, especially chlorides such as benzoyl chloride, and the compounds of the formulas

ClCOOC ₀ H ₁

CICOOCH ₂ CH ₂ OCh

ClCOOC ^ -H _n ο 5

ClCOOC ₆ H ₄ OCH ClCOOC ₆ H ₄ Cl 0CN-C _o H _c

OCN-C ₄ H ₉

6 5

309821/1078

CIBA.GEIGYAG

Possible residues -CQ-R. ,, are:

the half-esterified dicarboxylic acid residues of the general one formula

(Aryloxy- or lower alkoxy) -CO- (CH ₂ ) ..- CO-., Where m = 1-9. Examples of these are, for example, the methoxycarhonylcarbonyl radical, the C ₂ H ₅ -O-CO- (CH ₂ K-CO radical and the p-CH -CgH ^ -O-CO-CHgCHg-CO radical, half-esterified acyl radicals of oxalic acid, such as the radicals of the formulas CH-O-CO-CO-, C ^ HO-CO-CO-, p-Cl-CgHw-O-CO-CO-, o-CH ^ -CgHjj-O-CO-CO-., p-CH ₁ CgH ₁ , 0-CO-CO- and PC ₂ H ₅ -OC ₆ H ^ -O-CO are the radicals of cyoloaliphatic carboxylic acids, such as the cyclohexanecarbonyl, methylcyclohexanecarbonyl and dimethylcyclohexanearbonyl radical; the radicals of araliphatic carboxylic acids, such as phenylacetyl -, ß-phenylpropionyl-, phenoxyacetyl-, (p-nitro-, p-acetyl-, o-butoxycarbonyl, o-methoxy-, - p-butoxy-, p-methyl-, p-bromo, 5.5- Dichloro, p-ethyl, p-chloro) phenoxyacetyl, phenoxypropionyl, phenoxybutyryl, phenoxythioacetyl, 5 ^ 5-dichlorophenylthioacetyl, p-methoxyearbonylphenylmercaptoacetyl, o ^ -phenylmercapto-propionyl, 7 (p-nitrophenylmeryl, p-nitrophenylmeryl, 7 (p-nitrophenylmeryl) -Chlorophenylaminoacetyl, m-Aethylphenylaminoaoetyl ,, N, Morpholinoacetyl, Styrylcarbonyl- and the cinnamyl carbon ylrest; the residues of aromatic carboxylic acids such as benzoyl, methylbenzoyl, p-chlorobenzoyl, p-nitrobenzoyl, 5,5-dinitrobenzoyl, methoxybenzoyl, ^ phenoxybenzoyl - ^ - phenyrbenzoyl-., 4-phenylmercapto-benzoyl- ^ - phenylazobenzoyl, a -Naphthoyl- and the

309821/1078

β-naphthoyl radical; and the radicals heterocyclic carboxylic acids such as the furyl, nicotinyl, thiophene-2-carbonyl or pyridine 3- or -4-carbonyl radical. The acyl radicals can be derived from dicarboric acids or their half-esters, such as ζ.B * the radical “CO” (CH ₂ J _n ^ ₁ -CO-, where n = 1-7, each # B, radicals of the formulas - CO-CO-0-alkyl or -CO- (CH ₂ ) ^ - CÖ-O-alkyl *

The acyl radicals can also be derived from alkyl or aryl semiesters of carbonic acid, and Rj and Rp then stand for C 1-6 alkoxy or optionally substituted phenoxy groups, such as methoxy, ethoxy, h-propyloxy, isopropyloxy, ß-chlorathoxy, ß-methoxyathoxy, n-butoxy _# isobutoxy and hexyloxy groups, also phenyl ^m t "chloro * phenyl ^ bromophenyl, nitrophenyl, carbethoxyphenyl, methoxyphenyl, methylphenyl or ethylphenyl radicals.

The remainder-CORg has the same meaning as -COR. and can be the same or different from -COR- * It can also stand for an unsubstituted or substituted fatty acid radical with at least 2 carbon atoms, such as acetyl, propionyl, butyryl, l-methylbutyryl, hexanoyl, crotonyl, octanoyl, Decanoyl, dodecanoyl, hexadecanoyl, palrnityl or stearyl radical, also a glycol or methyl mercaptoacetic radical, chloroacetyl, α, ß-dibromo- or dichiorpropionyl, ß-bromopropionyl, 4-chlorobutyryl, acetoacetyl, - ^,; B-formacetyl, 2-phenylbutyryl, 4-benzoyi-butyryl, 4-phenyl • butyryl, cyclohexane butyryl, 2-bromostearyl, 11-bromundecanoyl,

309821/1078

CLBA-GEIGY AG

Palmitoylglycoyl and 3- and 4-hydroxybutyryl radicals.

The term "lower" before the term "alkyl", "Alkoxy" or "alkanoyl" means the group or the organic group component has a maximum of 5 carbon atoms having.

The new compounds, their mixtures with one another and their mixtures with other azo dyes are suitable excellent for dyeing and printing leather, wool, Silk and especially synthetic fibers, such as Acrylic or acrylonitrile fibers, polyacrylonitrile fibers and copolymers made from acrylonitrile and other vinyl compounds, such as acrylic esters, acrylic amides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanethylene ■ and Vinyl acetate, as well as acrylonitrile block copolymers, Pipes made of polyurethanes, polyolefins, such as basic modified, nickel modified or urimodified Polypropylene, cellulose tri- and 2 l / 2-acetate ' and especially polyamide filaments such as nylon-6> Nylon 6,6 or nylon 12 and from aromatic polyesters such as from terephthalic acid and ethylene glycol or 1,4-dimethyl

309821/1078

CIBA-GEIGY AG 2 2 5 6 3 I O

'Cyclohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol.

The fiber materials mentioned are preferably dyed with the inventive fiber materials with difficulty in water soluble azo dyes from aqueous dispersion. When the dyes according to the invention have hydrophilic groups such as e.g. contain one or more hydroxyalkyl or sulfonamide groups, they are best removed from a solvent liquor applied. It is therefore useful to use them as disperse dyes usable representatives by mixing with textile auxiliaries, such as dispersants and possibly other grinding aids to be finely divided. By Subsequent drying gives dye preparations consisting of the textile auxiliary and the dye.

For example, dispersants of the non-ionic group which can be used advantageously may be mentioned: addition products of 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol, of 15 or 6 moles of ethylene oxide with castor oil, of 20 moles of ethylene oxide with the alcohol C 1, -H ..-. 0H, ethylene oxide addition products to di- (a-phenylethyl) phenols, polyethylene oxide-turt-dodecyl-thioether, polyamol-polyglycol ether or products of 15 or 50 mol of ethylene oxide to L MoL Aline in C ₁₀ FI _0n -NH ₀ or C _iQ IU "NH _o .

AriLonlnche DLspergators are: Sulfuric acid esters of alcohols of the fatty series with 8 to. 20 carbon atoms, from the ethylene oxide adducts from the

309821/1078

corresponding fatty acid ami den., or ¹ of alkylated Phenalett with 8 to 12 carbon atoms in the alkyl radical; Sulfonic acid esters with alkyl radicals having 8 to 20 carbon atoms; Sulphation products of unsaturated fats and oil phosphoric acid esters with alkyl radicals mat B Ms 20 Kohl narrows offatomelij Fettsäuireseifeni also Mfeylaryl sulfonate. Condensate! osg · »des Formalde & yds with UajsiitihäilßsiJiföiigatire

ternare Ämffloni-ym ¥ @ 2 * teiödnfigeft> Welefee-Alkyl " öiit 8 to 20 Köfalenstöffatöfags efit

Me dye ppapsrat © Könfiea 2UB'äfczli & k zn ά & α atorefi noeb orgaiiisehe iiös-taigsffiittg 100 C boiling solvents * which are miscible with wateri such as mono- and moxati, methyl-form-fluid or -acetamide, ^ fön or 0in the man advantageously contains dye, * * Mgpergator and solvent with one another

The dyeing of the polyester fibers with the dyes of the invention that are sparingly soluble in water from aqueous dispersion is carried out according to the "procedure" for polyester-aromatic polycarboxylic acid with polyhydric alcohols, and dyeing is preferably carried out at temperatures above 100 ° 0 with dryness. Coloring can also take place at the boiling point of the dyeing ice in the presence of

309821/1078

CIBA-QEIGYAG

/, /, OOQ \ O

Dye transfer agents, for example phenylphenols, polychlorobenzene compounds or similar auxiliaries, are carried out using the thermosol process, ie padding with subsequent heat treatment, e.g. thermosetting, at 180-210 C, cellulose 2 l / 2 acetate fibers are preferably dyed at temperatures from 80 - 85 t while cellulose triacetate fibers are advantageously dyed at the boiling point of the dye bath. When dyeing cellulose-2 1/2 acetate or polyamide fibers, there is no need to use color carriers.

The method according to these dyeings obtained may be subjected to post-treatment, for example by heating with an aqueous solution>"j
■ an ion-free detergent.

I Instead of impregnation according to the present process, the compounds indicated are applied by printing. For this purpose, for example, a printing ink is used which, in addition to the auxiliaries customary in printing, such as wetting agents and thickeners, contains the finely dispersed dye.

Synthetic fibers such as polyesters and polyamides can also be used in organic solvent liquors like a mixture of perchlorethylene and di-

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CLBA-GElGY AG * - ..: ..,

3-f

methylformamide or in pure perchlorethylene. '· According to the present process, strong dyeings and prints with good fastness properties are obtained, in particular good thermosetting, subliming, pleating, flue gas,

- I.

Over-dyeing, dry cleaning, chlorine and wet fastness,

such as water, washing and perspiration fastness.

.: 'You can use the new water-insoluble compounds also for spin dyeing polyamides, polyesters and polyolefins use. The polymer to be colored becomes appropriate in the form of. Powder, 'grains or cutlets, as ready-to-use spinning solution or in the molten state mixed with the dye, which in the dry state or in Is introduced in the form of a dispersion or solution in an optionally volatile solvent. After more homogeneous Distribution of the dye in the solution or melt of the Polymers is the mixture in a known manner by (Hessen ^ Compression or extrusion into fibers, yarns, monofilaments, films, etc. processing. ■ ·.

In the examples below, the parts, unless stated otherwise, are / parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius. - - ^; ■. '· ■ *

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CIBA-GEtGYAG Δ Δ Ό Ό Ο [

Regulation 1

a) 150 parts by volume of aqueous-methanol solution of Sodium hydrogen sulfide are prepared according to Hodgson's instructions and Ward, J. Chem. Soc. 19 ^ 8 242, slowly to one low-boiling solution of 22.5 parts of 3 * 5-dinitroacetanilide given in 550 parts of methanol. After the addition (i.e. after about half an hour) the mixture will

refluxed for another two hours. It gets hot filtered off and the filtrate is concentrated and cooled, whereupon 5-amino-5-nitro-acetanilide in orange leaflets, P.p. 202 - 204 °, crystallized out.

b) 19.0 parts of phenoxyacetyl chloride are slowly added to a solution of 19.5 parts of 5-amino-5-nitro-acetanilide in 100 parts of pyridine, the mixture being cooled to 10-15. The mixture is stirred for a further hour and then poured into 1000 parts of ice-cold dilute hydrochloric acid. (800 parts of ice water: 200 parts of concentrated hydrochloric acid). The precipitated ^ -acetamino - ^ - phenoxyacetamidonitrobenzene is filtered off, washed and dried. After recrystallization from alcohol, the product melts at 192-195 °. ^!

c) 150 VolumeriteiLe LN sodium hydrogen sulfide solution are added to a solution of 100 parts of the product obtained in (b) in 100 parts of dimethylformamide, soft in a bath. is kept at 100 °. When the addition is complete, the mixture is set to 100 for a further two hours

309821/1078

CIBA-GEIGYAG- '£ 2 5 U V I

held. The mixture is filtered hot and das.Flltrat is evaporated to dryness. A glassy residue is obtained, which is stirred with water. The .entstand.ene crystal mass is filtered off and the resulting ^ huetamiat 5 ^ phe: rio ± yacetamido-aniline is recrystallized from acetonitrile, F, p, 206-208 ^Q _f

d). A mixture of £ 9.9 parts of the product of ■ Section (a),. 100: parts of acetic acid, and 5.0 parts of liquid. Ethylene oxide is stirred in a closed vessel at room temperature until one recognizes by thin-film chromatography that the reaction is complete, which takes about 6-7 hours. The solvent is distilled off and the resulting Big
is used in the usual way with acetic anhydride product, of the formula .- .. "■

NHQOGEE,

K ((SBgCHgQ * GClCH ₅ ) _a

is isolated in oily form and without further treatment used for the production of the azo dye "

18 «0 parts of Cinnamo ^ lahlorid such as; in. 'Provision 1 (b) a give * aeyliert «Das ,, received J ^

309821 / 1Q78

CIBA-QEIGY AO

£ 4 b O 41 g

aeetanilid is recrystallized from acetonitrile and
melts at 268 - 269 °.

32.5 parts of the cinnanioylamino compound are then reduced with sodium hydrosulfide solution as in regulation 1 (o),
The amino compound is then ethylated bishydroxy: and
aeetylated. The compound of the formula is obtained

NHCOCH,

NHCOCH = CH- / \ I

as a colorless oil, j

Regulation 3 . _;

j 3-Amino »5-nitro-acetanilide is as in regulation

l acylated, but instead of l8 parts Phenoicyacetylchl © «rid be 15.5 parts Benzoylehlorld used" Dag get "■ ^ ne acetamido-S-benzamidonitrobenzol (F ρ, β ~ $ 2 * · 235)
is reduced as in procedure 1 until it is hydrojtySfchylated;

and acetylated, so that the coupling components of the

j formula j

NHCOCH ₅ ■

309821/1078

CIBA-GEIGYAG

receives, which is used as an oil. Regulation 4 . '

A mixture of 19 * 5 parts of 3-amino-5-nitroacetanilide and 70 parts of 85% formic acid is heated on a boiling water bath for 1 hour. After cooling, the crystalline precipitate of ^ -acetamido-.S-formamido-nitrobenzene is filtered off, washed and dried. The melting point is 260-262 ° _. The product is then reduced as described in instruction 1, doubly hydroxyethylated on the amino group formed and finally acetylated. The coupling component is finally obtained

Formula ^

. / \ N (CH ₂ CHgO-COCH ₅ ) ₂ . >/,:; ■. =

as a colorless oil. ■ _; -.

: I.

309821

example 1

13.8 parts of p-nitroaniline are dissolved in 30 parts of water and 30 parts of concentrated hydrochloric acid with heating dissolved.

The solution is crushed to 80 parts Poured ice and the resulting suspension is treated with 6.9 parts of sodium nitrite. The mixture is stirred until a clear, colorless diazo solution has formed. It slowly becomes a solution of 44.3 parts of N-acetoxyethyl N-methoxyethyl-3-acetamido-5-phenoxyacetamido-aniline in 300 parts of a mixture of acetic acid and propionic acid (5: 1), which is kept at 0-5 .. The mixture is stirred at this temperature for some time and finally diluted with water, the dye being of the formula

j NHCOCH

H CH ₂ O-COCH

NH-COCH ₂ O

precipitates, which is filtered off, washed and dried will. It dyes polyester fibers in brilliant bluish-red shades with excellent fastness properties.

'Vl ./^' i'viile 6-chloro-l ?, 4-diri! tro - mi Lin v / erden 3098 2171078 ^ t BADORiGlNAL

OIBA'GEIQY AQ

1 N nitrosol sulfuric acid slowly added at room temperature with stirring to IQO advantages. After half an hour of stirring, the solution is poured onto 500 parts of 3§rstqssenes ice. Excess nitrous acid is destroyed if appropriate in. Conventional manner durch.Zugabe of-SuIfaminsäure, wir4langsam The clear solution to a solution of 4 _r ^ * 8 parts

amido-aniline in JOO parts one

Mixture (5; 1) given «You get naoh the

the dye of the formula. ..

HHCOCH,

NHCOCH,

which polyester fibers in bluish yellow tones with; good fastness properties »'' '-

ι Example 3. . \

In a manner analogous to Example 3 is 6 S, 4-ainltroaniline diagofcl # rt and with JfjN bonyläthy 1 «5 ™ aeetamido« §
The dye of the formula is obtained

30982-1- / 1078.

CIBA-GEIGY AG

Cl

NHCOCH.

0, -tV «

Cl

NH-COCH-O- / \

which dyes polyester fibers in ruby red shades with good lightfastness and good dry heat resistance. Example 4

17.7 parts of 2-amino-4-phenyl- 1,3,5-thiadiazole are dissolved in 250 parts of 85% -lgev phosphoric acid by stirring at room temperature. The solution is cooled to -10 to -12 ° and 0.1 part of potassium bromide, 6.9 parts

nitrite/
dry sodium / added and stirred for 5 hours at the same temperature. The mixture is then slowly added to a solution, cooled to 5, of 47.1 parts of N, N-di-ß-ace-.toxyethyl-3-acetamido-5-phenoxyacetamido-aniline in 500 parts of an acetic acid-propionic acid mixture (5 ' · L) added with stirring. The mixture is stirred for 2 hours and then the dye is precipitated in the usual way with water. The dye of the formula is obtained

NHCOCH

■ Ν

J N = N

N (CH ₂ CH ₂ O-COCIL

NH-COCH - (

309821/1078

which dyes polyester fibers in red shades with good fastness properties.

The dyes indicated in the table below are obtained in an analogous manner, the symbols referring to the. refers to the first formula given in the definition of the invention.

3 098 21/1078

CIBA-GEIGY AG

CW E-

O (O CO IM

- r-l -P —Τ P. XJ -P CJ co OJ ■ P 4-5 40 I. -P pi M. -P C) ft; -P O O O ■ rl H O O ■ P O r-l CO ■ rl P. Ci 2 cl Q) S ^ co U r-l Xi ^u (D U >> ω r-J- X ^ O) cd CD t rH Tt I. rH CJ r-l .XJ O f — 1 ρ > φ C. [J O Q) r-l O •H O QJ W W) CVi nt KN tn τ-! X! O • rH -P -H O (D KN ti XJ O [Xj VO > Ch N ί> w 2 > Ch ri O ctf O Ci O O I (Vl
KN -rl I. + J CO CO r ~ - \ O Ci ω -P O O ι · χί + S O rH "~ i O Ü O • rl Oil 0 .p O Ch XJ δ P-i O el ti r-tH CJ I Ch - = * -j- CVJ O KN in I. ϋ O Fig.> O -J- OJ Century KN e-ζ CVJ O c ~ O O O if! JtJ I · » O _t KN -J- rH OJ IQ. Η O b X) O Oil O OJ O rl [T] O ο I. OJ O CVJ O -l · ~ ■ KN [Xj Sz 00 I. ⁼ O OJ rl in O KN O r * 5 W. O pr; . — Ν XJ rl OJ Ü O • D. P C) U I. Φ Μ JtJ - H (ti 'ft CVJ OJ I -rl
vo x! I. O O I P v_ ^ O O 0 , -. CJ W ilJ P. • H-rl Ü σ \ I. Egg M O tn tn ¹ IfN <C Cl O - ^ j- VO UJ rH I QJ I. U 0 VO O KN, n O 0 O I. 0 ti, ' • O VO 0 in 0—— CVJ CVJ [Xj O I. [T] VO O —J " - VO lf \ O O Oil JrI O ti; ι O tri 'vo O CXl O CVJ O Ü ^ J- O P. O trj in φ d CVJ OJ Ü ο ΐΐ tr; r- |
C) 0 α] IfV N I. M * I. CD He O O CVl O τ) I. Cl rH C) j., C! Cj M. | J XJ r P. •H P. CJ Tj O I. • rl r-l O (D Yy O Cl Tl Cl Xl rl Tl I. c! I. CJ P. I. r— ■ XJ O • rl -J- CU ■ rl O I. I. egg I.
rl O CJ I. Ci Cl] Tl Ol i! [> j Fl CJ I.
IfN —J * P. O O? r-l-rl O 4-3 Tl I. I. • rl C | I. < J> jrl N CJ Tl rH O CJ 4) U I. id -rl CJ -rl CJ • rl C! ^ J> J VO Tl O CJ P C! Φ r-l ^ f CJ ■ rl O CJ I. [35 rH τ! OJ cd
E rt fT) I. ai egg I -H
CVJ H O r-l I. XJ ii "rl r ¹ ^} I f J r < p I · Η Ci O -J " O -H Π CJ CvI Ct) cvJ P. I. C. CJ • rl M ^ ._ I Ci I O O • rl CVi O C (J E: «J rl VO qj β S3 XJ r-l O C! -t HO <C tI O * a I. -rl r-l " XJ Ci I Xi m Cl tZ \ > ~ 1 CVj_ ^ O -P CU P Oil I "Ί r-l I. I Tl VO XJ ^ J- ti) rl vp c; r-l μ in rH ' KN r-l

Tabel

No. D. ^R l CH ₅ (CH ₂ J ₅ OCgH ₅ C ₂ H ₄ OCOCH ₅ dd • H ₄ Nuance on
polyester ■ 18 2,6-dichloro-4-nitro-
aniline dd ft It C _A OCH ₅ O ₂ H ₄ CN. Ruby red ; i9 2-chloro-4-methyl-
sulphonylaniline °? ^H 7 CH ₂ SO ₆ H ₅ O ₂ H ₅ ^
TT ■ orange-red , 20: 2-cyan-4-n ± trQ-anIl ± n ff ' ff tf C ₂ H ₄ OCH ₅ Red ¹ L ₁ OH,. CH ₂ SCgH ₅ Cl ₂ (-2.5) 'tt red ■ 22nd 2-araino-l-methyl-
thiazole tr CH ₂ SCgH ₄ -COOCH, - tf ' purple 25th 2-amino-6-dimethyl-
aminosulfonylbenz-
thiazole H CH (CH ₅ ) SCgH ₄ . C ₀ H ₂₁ OCOCH, dd Red 24 2-amino-6-ethoxy
benzthiazole ft Λ ff TT Λ Of TT "KT ^^ f <w Λ
\ W Jn ^^ / · ^ OW ^ JCi '! ι XN ^ /> s V *** (J 7 C _o H, .C00CH,
ώ 4 ρ C ₂ H ₄ OCOCH Orange red 25th 4-nitro-2-trifluoro
methylaniline OH, ■ ■ CH ₂ NHC ₆ H ₅ , ji '9 C ₂ H ₄ COOCH bluish tint
violet 26th 6-chloro-2,4-dinitro-
aniline' dd CH ₂ NHCgH ₄ CK-P) ' C ₂ H ₄ CN Red 27 2-methylsulfonyl-4-
nitroaniline tf CH ₂ NHCgH ₄ -C ₂ H ₅ (-m) ft yellowish
Red 28 acid blue ■ '
I. 3-amino-5 ,, 7-dibromo-
benzisothiazole-2,1.

Tabel

No. D. ^R l tf ^R s CH ₃ CgH ₅ ^R 3 C ₂ H ₄ CN Nuance on
polyester 29 ^ -Nitroanilln rt CH ₂ CgH ₄ CK-P) C ₂ H ₄ CN C ₂ H ₄ OCOCH Red 30th 2-cyano-4-nitroaniline ft CH ₂ C ₆ H ₄ HO ₂ (-p) C ₂ H ₄ OCOCH it violet 31 If dd ^C 6 ^H 5 ft dd dd 52 • t ^; η CgH ₄ CK-O) π dd dd 33 2,6-dichloro-4-nitro-
aniline ft C ₆ H _? (N0 ₅ ) _a (-3.5) ft ft Ruby red 34 η ^C 6 ^H 5 ^C 6 ^H 5 tt ■ dd dd 35 Tt UH-. π It 36 S-chloro-2,4-dinitro-
aniline. dd ff C ₂ H ₄ CN bluish tint
violet 37 S-chloro-2-cyano-4-ni-
fcroaniline dd C ₂ H ₅ C ₂ H ₄ OCOCH blue 38 2-3enzoyl-4-nitro-
aniline η CH = CHC ^ H ₅ C ₂ H ₄ OCOCH dd Red 59 4-nitroaniline ft tf dd .40 2,6-dichloro-4-nitro-
aniline ft Ruby red

Tabel

No. D. ^R l H ■ ^R 2 - ^R ₅ R ₄ Nuance on
polyester 41 2,6-dichloro-4-nitro-
aniline dd Γ> υ ΠΙΤΓ ¹ TJ
b 5 C ₂ H ₄ OCOCH C ₂ H ₄ OCOCH Ruby red j 42 6-Br οm-2-c yan-4-
nitroaniline dd - ^CH 3 C ₂ H ₄ COOCH ₃ C ₂ H ₄ COOC ₂ H ₅ navy blue 45 dd CH ₅ H dd dd tt · ■. 44 2-amino-4-pnenyl-
1> 5j 5-thiadiazole dd CH ₂ CN C ₂ H ₄ OCOCH ₃ C ₂ H ₄ OCOCH Red 45 2-chloroethylsulfonyl-.
aniline dd dd dd Orange red 46 4-nitroaniline ti OC ₂ H ₅ C ₂ H ₅ C ₂ H ₄ OCH ₃ Red 47 2-amino-6-nitro-
benzthiazbl It dd dd It violet 48 2-cyano-4-nitroaniline H COOCJHL
2 5 C ₂ H ₄ OCOCH ₃ . C ₂ H ₄ OCOCH · · violet ' 49 Il ι ' CH,
5 dd dd it ' purple. 50 2., 6-dichloro-4-nitro-
aniline' » NHC ^ H ₁ -
• 0 0 C ₂ H ₄ CN H Ruby red, 51 dd dd NHC ₆ H ₄ CH ₃ (-p) dd dd ruby red ^ 52 2-methoxy-4-nitroani-
lin NHC ₄ H ₉ NHC ₄ H ₉ ° 5 β 5 C ₅ H ₆ OCOCH ₅ Red 55 4-nitroaniline
■ NHC ₄ H ₉ dd dd Red

Tabel

No. D. ^R l CH, ... CH ₂ OC ₆ H ₅ ■ ''' C ₂ H ₄ OCO ₂ CH ₅ 56 25 0 ^R. to It Nuance on
Polyester j 2-amino-5-acetyl-5-
nitrothiphene dd dd dd C ₂ H ₄ OCOCH ₅ dd blue 55
i 5-amino-1-methyl-4-
nitroimidazole << H dd dd
dd C ₂ H ₄ CCOC ₆ H ₅ violet I 56
i 2- .-. Rr.inc- β- carbethoxy-
'' i en ζ ¹ J Ii i 3. ξ c 1 Il Il C ₅ HgCOO ₂ H ₅ violet j 57 5-arr.ir.opyridine Il it
* C ₂ H ₄ OCOCH ₅ ce ¹ letter
ror I.
58 S-amino-J-methyl-l-
phenylpyrazole It dd ti
dd yellowish
Red 59 4-aminobenzoic acid
bensyl ester ti
ti ti rpt 60
61 l-amino-2,5-dichloro
4-sulfonic acid dim
thyl amide
It Red
Red 309821- ^^
O OO

CIBA-SElGY AG

'' Dyeing instructions (water-based polyester) :

1 part of the dye obtained in Example 1

- fes is mixed with 2 parts of a 50 $ aqueous solution of the Wet grinding of the sodium salt of dinaphthylmethane disulphonic acid and dried. ·

This dye preparation is 40 parts of a 10_ 5 ^ aqueous solution of the sodium salt of N-benzyl-μ-heptadecyl-benzimidazole disulfonic acid stirred and 4 parts of a 40 ^ strength acetic acid solution added. By diluting " With water it becomes a dyebath of 4000 parts prepares.

In this bath you go at 50 ° with 100 parts a cleaned polyester fiber, the temperature increases within half an hour to 120 to 150 ° and stains an hour in a closed vessel at this tem- » temperature. Then it is rinsed well. A strong orange-red coloration with excellent fastness to light and sublimation is obtained. "-

309821/1070

Claims (1)

Claims 1. Azo compounds of the formula which are free from water-solubilizing acidic groups NH-CO-R NH-CO-R ₁ where D is the residue of a diazo component, R, © in hydrogen atom, an aryl, alkoxy, aryloxy, alkylamino or Arylamino radical or (alkoxy or aryloxy) carbonylr @ st or (Alkyloxy or aryloxy) carbonylalkyl radical or an (aryloxy, arylthio or arylamino) alkyl radical or © in styryl radical or aralkyl, thiophenyl or pyridyl radical, R _{g is} an unsubstituted or substituted alkyl radical or the same as R, and R- , and R ^ are optionally interrupted and / or optionally substituted alkyl radicals by at least one heteroatom.
2. azo compounds according to claim 1, characterized by the formula NH-CO-alkyl D-N ^ N wherein R, - a straight or branched Nledalkylengruppe, X j = -S-, -NH- or -0-, and the radical A is substituted can be. 309821/1078 3. Azo compounds according to claim 1 of the formula NHCO-R ₂ D-N = N NHCO wherein the radical A can be substituted. 4. azo compounds according to claim 1, characterized by the formula · ■ NHCOR ₂ D-N = N NHCO-CH = CH 5 · Compounds according to claims 1 to h _3, characterized in that the radical D is a radical of a "benzene, quinoline, Benzthiazo.is, thiazole, isothiazole,. Is benzisothiazole, benzoxazole, imidazole, triazole, pyrazole or thiadiazole, 6. Process for the preparation of azo compounds which are free from acidic groups which make them soluble in water are and the formula 309821/1978 CIDA-GEIGY AG Z Z O O O I 0 NH-CO-R ₂ D-N-N NH-CO-R, wherein D is the remainder of a diazo component, R is a hydrogen atom, an aryl, alkoxy, aryloxy, alkylamino or arylamino radical or (alkoxy or aryloxy) carbonyl radical or (Alkyloxy or aryloxy) carbonylalkyl radical or an (aryloxy, Arylthio or Arylaminojalkylrest or a Styrylrest or Is aralkyl, thlophenyl or pyridyl radical, Rp is an unsubstituted one or substituted alkyl radical or the same as R, is and R., and R ^, optionally by at least a heteroatom are interrupted and / or optionally substituted alkyl radicals, characterized in that one a diazonium compound of a diazo component with a coupling component of the formula NHCOR ₂ NHCOR ₁ clutch. 7. The method according to claim 6, characterized in that one of a coupling component of the formula 309821/1078 CLBA-GEIGY AG 33 NH-CO-R HB-CO-R ₅ -X - (A} where Rp is a straight or branched chain group, X «is -S-, -MH- or -0- and the reading A can be substituted> going out «· 8. Process for the preparation of azo compounds according to claim 6, characterized in that coupling components of the formula NHCOR, NHCO starts, [in which A can be substituted * I.
9. The method stur production of azo compounds according to claim β, characterized in that coupling components of the formula NHCOR ₀ NHCOCH eCH --- (T \ goes out 309821 '/ 1078 / Z O Π J I 0 CIBA-GEIGY AG Case 1-7847 / CIN 5 ^ / n2 / o 10. Procedure according to claims 6 to 9> characterized in that a diazonium compound of a benzene, Quinolines, benzothiazoles, thiazoles, isothiazoles, benzisothiazoles, benzoxazoles, benzimidazoles, triazoles, Pyrazoles or thiadiazoles are used. 11. The method according to claims 6 to 9 *, characterized in that that one starts from coupling components and diazo components that do not have ion-forming substituents contain. 12. Process for dyeing and printing hydrophobic synthetic fibers, especially those containing ester groups Fibers, characterized in that dyes according to Claims 1 to 5 are used. 23 · Method according to claim 10, characterized in that that you dye polyester fibers. lH. Dye preparations, characterized in that they contain at least one azo compound free from sulfo groups the form] IJH-CO-R ₀ η q ft? 1/1 0 7 8 _{0RlQlNAL 1NSPEC} ted CIBA-GEIGY AG Δ L-Op ό Ι J contain, wherein D is the remainder of a diazo component, R is a hydrogen atom, an aryl ,. Alkoxy, aryloxy, alkylamino or arylamino radical or (alkoxy or aryloxy) carbonyl radical or (alkyloxy or aryloxy) carbonylalkyl radical or an (aryloxy, arylthio or arylamino) alkyl radical or a styryl radical or aralkyl, thiophenyl or pyridyl radical, R "is an unsubstituted or substituted alkyl radical or the same as R and R ^, and R ₁ . are optionally interrupted and / or optionally substituted alkyl radicals by at least one heteroatom. 15 · Dyestuff preparations according to claim 14, characterized in that that they contain a dispersant. l6. Dye preparations according to Claims L 4 to 15 > characterized in that they contain an organic solvent. 17 · Amines of the formula NH-CO-R ₂ - N NH-CO-R ₁ ^R 4 .L 1 wherein R, a hydrogen atom, an aryl, alkoxy, aryloxy, alkylamino or arylamino radical or a (Alkoxy- or aryloxy) carbonyl radical or (AlkyLoxy- 309821/1078 CIBA-GEIG * AG? 2 5 R 1 or aryloxy) carbonylalkyl radical or an (aryloxy, Arylthio- or Arylaini.no) alkyl radical or a Scyryl radical or aralkyl, thiophenyl or pyridyl radical, R is an unsubstituted or substituted alkyl radical or the same as R and R and R ^, optionally alkyl radicals interrupted and / or optionally substituted by at least one heteroatom are. 309821/1078