DE2417302A1 - NEW AZO DYES AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

DR. BERG DIP L.-IN G. STAPF

Case 1-8720 + DIPL-INQ. SCHWABE DR. DR. SANDMAlR

PATENT LAWYERS

8 MÖNCHEN 80 · MAÜERKIRCHERSTR. 46

Germany 2417302

Attorney File 24 894 April 9 , 1974

New azo dyes and processes for their production

The present invention relates to new valuable azo dyes, those of acidic water-solubilizing Groups, especially sulfonic acid groups, are free and the general formula

correspond to where R-. is an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, but preferably an optionally substituted alkyl or aralkyl radical or a cyclohexyl radical, Z is a radical of the formulas = NH or -NH ₂ , Z _{2 is} a radical of the formulas -NR ₂ * "NHR ₂ *" ^NR 3 ^R 4>" ^0R 5 ^or " ^ Rg, where R ₉ , Ro and R, each hydrogen atoms, optionally substituted alkyl, aralkyl, cycloalkyl, aryl or are heterocyclic radicals, R "and R, together with the nitrogen atom connected to them, can form a five- or six-membered ring,

409844/0898

ORIGINAL INSPECTED

CIBA-GEIGYAG

JL a hydrogen atom, an alkyl, aralkyl, cycloalkyl,

I '

[Aryl or heterocyclic radical, R ^ is a hydrogen atom, an alkyl, aralkyl, cycloalkyl, aryl or hetero ^: cyclic radical, Z _{7 is} a radical of the formulas = NR, or -MiR. ι j. Λ A

j is, Y is a radical of the formulas -CONHp or, preferably, -CN is, and D is the residue of an aromatic or heterocyclic diazo component, the dihydropyridine ring A through only one

double bonded nitrogen atom is substituted and ι.

'contains two double bonds.

ι -

i The new dyes are obtained by adding the diazonium compound of an aromatic or heterocyclic Diazo component with a coupling component of the formula

wherein YL, 2,, Z ₀ , Z and Y are the same as above, couples, and optionally, if Y is a cyano group, ₃ converts this into a -CO-NH _{p group by treatment with concentrated sulfuric acid.}

The inventive dyes, which chemically represent uniform individuals are subject to the laws of tautomerism. · I

The tautomerism can be reproduced as follows:

4Q9844 / 0898

CIBA-GEIGY AG

-3 -

R-

D-N = N-

D-N = N-

RHN

HN / l> N R

HN

D-N = N-RHN '

R-i

Rr

^R l

RTJ ^ "^ Y

HN / / —N

D-N = N-

wherein Ri R , R ^ R ^ j R ₁ - ^ H ^ ₃ Y and D are the same as above. The tautomeric dyes represent preferred embodiments of the invention.

Among alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals are preferably alkyl radicals which are formed by oxygen or sulfur atoms or by groups of the formulas -NH- or -NAlkyl- or -NAryl- interrupted can be and / or can carry substituents, residues of the benzene series, optionally substituted benzyl, phenethyl, Cyclohexyl radicals and radicals of the thiazole, benzthiazole,

409844/089

CIBA-GEIGY AG

! Naphthothiaz-ol, isothiazole, benzisothiazole thiophene,

• imidazole, benzimidazole thiadiazole pyridine, quinoline,

Indazole, selenazoles oxazole, benzoxazole ^oxadiazoles: pyrazole or triazole understood.

j The radicals R ^ on the same nitrogen atom.

; and Ru can be used directly or via heteroatoms, in particular

Oxygen and sulfur, be linked together. Of the

The radical Zp can e.g. be a piperidine, pyrrolidine, '' Piperazine Morpholine, methylpiperazine or acetylpiper

be iazine ring, which via a nitrogen atom to the pyridine

^; ring is tied.

'As examples of the radicals R ₁ , R ₀ , R ^, R ,,,

-L d. J) H

R ^ and R / r come e.g. methyl, ethyl, propyl, isopropyl, Butyl, sec-butyl, n-pentyl and octyl radicals in question, which are interrupted by oxygen atoms and

i by hydroxy, cyano, carboxyl, carbalkoxy (with 2 to 6.

! Carbon atoms), alkoxy (with 1-8 carbon atoms),

^ Phenoxy, acyloxy (with 1-10 carbon atoms),

; if necessary by halogen atoms, lower alkyl * or lower

i '

! alkoxy, β-hydroxyethyl or lower carboalkoxy groups

! substituted phenyl groups or by benzyl, or phen

ethyl or cyclohexyl groups can be substituted.

j The acyl radicals include, for example; Fatty acids with up to 5 carbons

istoff atoms such as formyl, acetyl, propionyl, butyl radicals;

• Alkylcarbamyl radicals with up to 5 carbon atoms, such as methyl- "aminocarbonyl-, Ethylaminocarbonyl, propylaminocarbonyl

409844/0898

CIBA-GEIGY AG

or butylaminocarbonyl radicals; Alkyloxycarbonyl radicals with; up to 5 carbon atoms, such as methoxycarbonyl, ethoxy

! carbonyl, propoxycarbonyl or butoxycarbonyl radicals; ! Phenylcarbamyl or phenoxycarbonyl radicals, benzoyl,

'Phenoxyacetyl, chloroacetyl or phenylaeetyl radicals in

Question. R-, is preferably a cyclohexyl- or an opposing

! optionally substituted alkyl or aralkyl radical ..

! If R ₁ , R_, R- ,, RJ ,, R _c and R ^ - stand for aryl-: X ei j) 4 z> D

jreste, it is preferably an unsubstituted • one or mono- or polysubstituted ■ phenyl radical which is substituted by substituents of the following type can be halogen atoms, such as chlorine, bromine,

Fluorine, alkyl groups with 1-6 carbon atoms, which in turn are replaced by bromine, chlorine, lower alkoxy, cyano or Lower alkyloxycarbonyl groups can be substituted, lower alkyloxycarbonyl, lower alkoxysulfonyl, tri-

ifluoromethyl, acetyl, aminocarbonyloxy, aminosulfonyl,

Lower alkylaminosulfonyl, di (lower alkylamino) sulfonyl, , 'Alkylsulfone, alkylthio or arylthio radicals. Examples Such substituents on a phenyl radical are the! methyl, ethyl, propyl, butyl, isobutyl or amyl

! group, a methoxy, ethoxy, propoxy or butoxy radical,

Leine methoxymethyl, ethoxymethyl, ß-methoxyethyl or iß-ethoxyethyl group, a (methoxy, ethoxy, propoxy) -

imethoxy or ethoxy group, methoxycarbonyl, ethoxycarbonyl,

A09844 / 0898

-CtBA-GElGY AG

Propoxycarbonyl group, the methoxy- 'or ethoxy carbonyl (methoxy or ethoxy) radical, a methoxycarbonyl-amino group, an ethoxycarbonylamino group, a

Methylsulfonyl or methylsulfinyl group or a

Methyl, ethyl or phenylthio _{radical «R 1} - is preferably an optionally substituted phenyl radical.

Those dyes of the specified are preferred

i "

Formula, 'in which D is a residue of the benzene series or a

'Sulfur- and / or nitrogen-containing heterocyclic

Rest is. -

D preferably represents a lower one, optionally through halogen atoms, hydroxyl, cyano, rhodanic, nitro, lower Alkyl, trifluoromethyl, lower alkoxy, formyl, lower '' Alkylcarbonyl, benzoyl, methylbenzoyl, lower alkoxycarbonyl, Benzyloxycarbonyl, cyclohexyloxycarbonyl, Phenoxycarbonyl, lower alkoxycarbonyloxy, benzyloxycarbonyloxy, lower alkylcarbonyl, benzoyloxy, lower

409844/0898

CIBA-GEIGY AG

~ " Ύ -

Alkylcarbonylamino, benzoylamino, lower alkylsulfonyl, chloroethylsulfonyl, hydroxyethylsulfonyl, unsubstituted or mono- or disubstituted aminosulfonyl-, di (hydroxyethyl) aminosulfonyl-, phenylaminosulfonyl-, (chloroamino-sulfonyl- or methoxy) phenylaminosulfonyl-, (chloroaminoyl) or methoxy) , N-piperidylsulphonyl- N-morpholinosulphone3 ^r l ~, lower alkylsulphonyloxy, cyclohexylsulphonyloxy, chlorine

ι
■

methylsulfonyloxjr- _f Cyanäthylsulfonyloxy- , Phenylsulfonyloxy-, aminosulfonyloxy, (chloro- or methoxy) phenylsulfonyloxy, N-morpholinosulfonyloxy, Aetbyleniminosulfonyloxy, lower monoalkyl- or dialkylaminosulfonyloxy-, lower monoalkyl- or dialkylaminosulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, phenylaminosulfonyloxy-, lower-N- sulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, Phenosulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, N- sulfonyloxy-, Phenosulfonyloxy-, phenyl-N- phenylamino (lower- N- sulfonyloxy-, phenyl-phenylamino), aminosulfonyloxy, (chloro- or methoxy), N- (Methoxy or chlorine) phenylaminosulfonyloxy, phenylamino, nitrophenylamino, dinitrophenylamino, phenyl, phenoxy and / or acetylaminophenyl groups, a phenyl radical optionally substituted by chlorine or bromine atoms, hydroxyl, cyano, nitro, lower alkyl , Trifluoromethyl, lower alkoxy or phenoxy groups substituted phenylazophenyl

radical, a naphthyl radical optionally substituted by methoxy, ethoxy, phenylazo or dimethylaminosulfonyl groups, one optionally by chlorine or bromine atoms, nitro, cyano, rhodan, lower alkyl, lower alkoxy, lower Alkylmercapto, phenyl, benzyl, phenethyl, lower alkoxycarbonyl, trifluoromethyl, lower alkylcarbonyl and lower alkylsulfony! groups substituted thiazolyl radical,

409844/0898

CLBA-GEIGY AG

an optionally by chlorine or bromine atoms., cyano, Rhodan, nitro, lower alkyl, lower alkoxy, benzyl, Phenylethyl, lower alkylsulfonyl, phenyl, lower alkyl mercapto, lower alkoxycarbonyl, lower alkylcarbonyl, trifluoromethyl, Cyanäthy1sulfonyl-, aminosulfonyl- or a with optionally by lower mono- or dialkyl aminosulfonyl groups substituted benzothiazolyl radical, an optionally by cyano, lower alkyl, lower alkoxy,

lower alkoxycarbonyl or phenyl groups substituted pyrazolyl, an optionally by lower alkoxy, lower alkyl, phenyl, lower alkylsulfonyl or lower alkyl mercapto groups substituted thiadiazolyl, a optionally substituted by nitro or lower alkyl groups Imidazolyl radical, an optionally by nitro, lower alkyl, lower alkylsulfonyl, lower alkoxycarbonyl or acetyl groups, a thienyl radical optionally substituted by lower alkyl, nitro, lower alkylsulfonyl lower alkoxycarbonyl, cyano or phenyl groups substituted isothiazolyl, and optionally one

benzisothiazolyl radical substituted by lower alkyl groups, nitro groups or halogen atoms. Are lower alkyl groups e.g. methyl, ethyl, propyl, isopropyl and isobutyl rust; Analogously, alkoxy radicals are limited to 1 to 4 carbon atoms. I The diazo radical D is preferably derived from amines which have a heterocyclic five-membered ring with 2 or J heteroato-

9844/0898

CIBA-GElGY AG -

^: 9 ■

men, especially one nitrogen and one or two sulfur, Have oxygen or nitrogen atoms as heteroatoms, and aminotaenzenes, especially negatively substituted aminobenzenes, in which the substituents have positive Sigrna values according to the Hammet equation, especially those of the Formula ·. ■.

R ₁ I '

R 'is hydrogen, bromine, a thiocyano, alkylsulfonyl, Alkoxycarbonyl, hydroxy, alkyl mercapto, aryl mercapto, "Alkoxycarbonyloxy, aminosulfonyloxy, acylamino or preferably chlorine, a nitro, cyano, acyl, sulfonamides, carboxamides, alkoxy or aryloxy groups, i

; Rl is hydrogen, bromine, a carboxamide, or preferably an alkoxy carbonyl or aminosulfonyloxy group. _# '|

i R 'is hydrogen, bromine, a thiocyano, alkoxy, carbonyl, Alkoxy, aryloxy or acylamino group or, preferably, chlorine or a nitro, cyano, acyl, sulfonamide Carboxamides trifluoromethyl or phenylazo groups, their phenyl nucleus in turn with alkyl, Alkoxy, nitro groups and chlorine can be substituted.

RjI is hydrogen, bromine, a nitro, cyano,

Thiocyano-, acyl-, carboxamides, alkoxy-, aryloxy- or

409844/0898

- ίο -

Aeylamino group or, preferably, chlorine, a sulfonamide Alkoxycarbonyl, trifluoromethyl or alkyl group.

R 'is in particular hydrogen, chlorine or bromine, P.

"a nitro, cyano, thiocyano, acyl, alkoxy carbonyl,

Trifluoromethyl or alkyl group. *

\ Examples of such ayl radicals are:

Benzoyl, 4-chlorobenzoyl, 4-methylbehzoyl, benzenesulfonyl, Pormyl, acetyl, propionyl, chloroacetyl, methylsulfonyl, or (methoxy, ethoxy, propoxy, butoxyoxy) carbonyl radicals.

; ■ '-. . From the series of useful diazo components of the benzene series, the following may be mentioned, for example:

Aniline,

l-amino-3 ~ or -4-chlorobenzene, 1-amino-4-bromobenzene,

l-amino-2-, -3- or -4-methylbenzene, l-amino-2-, -3- or -4-nitrobenzene, 1-amino-4-cyanobenzene,

l-aminobenzene-3- or -4-methylsulfone, i-amino-2-chlorobenzene-4-methylsulfone,

l-amino-2,5-dicyanobenzene, _

1-amino-4-carbethoxybenzene, l-amino-2,4- or -2,5-dichlorobenzene,

l-amino-2,4-dibromobenzene, * * ■

1-amino-2-methyl-4- or -6-chlorobenzol,

4-aminodiphenyl,. ·

2- or 4-aminodiphenyl ether, - -

4098A4 / Q898

CIBA-GElGY AG ^-

5- or 4-aminophthalimide., 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene,

l-Amino ^ -carbomethoxy ^ -chlorobenzene, " ^:

1-amino-2-methylsulfonyl-4-chlorobenzene, 1-Amino-2-carbomethoxy-4-nitrobenzene

'l-Amino-2-phenoxy ~ 4-nitrobenzene,;

l-amino ^ -chloro ^ -cyanbenzene,. !

l-Amino-2-chloro-4-nitrobenzene _J ■

l-Amino-2-raethoxy-4-nitrobenzene _ί !

I. , j

l-Amino-2-chloro-4-carbethoxybenzene _J · i

l-amino-2-bromo-4-carbohexoxybenzene, I.

l-amino-2 _J 4-dinitrobenzene. ■ j.

l-amino-2,4-dicyanobenzene _i ;

l-Amino ^ jo-dichlor ^ -cyanbenzene, j

! j

l-amino-2,6-dichloro-4-nitrobenzene,. j

l-amino-2 _J 5-dichloro-4-nitrobenzene _J. ·;

1-amino-2 _{J i} 2 5- or 6-dichlorobenzene-4-sulfonic acid dimethylamide _i

l-aminobenzene-4-sulfonic acid-ß-chloroethylamide, 1-amino-2-chlorobenzene-4-sulfonic acid _{dimethylamide, l-amino-2 i} 6-dibromobenzene-4-sulfonic acid amide, l-amino-2,4-dinitro-6- chloro- or -6-bromobenzene, l-amino-2,4-dicyano-6-chlorobenzene _s l-amino ^ -chloro ^ -cyan ^ -nitrobenzene, l-amino-2,4, β-trichloro- or -tribrornobenzene ,

4098 4 ^ / 08 9.8

CIBA-GEIGY AG

l-aminobenzene-5- or - ^ - sulfonic acid amide,

L-aminobenzene-3- or -4-sulfonic acid-N-methyl or diet hy la mid,

1- ^{Amino-2-nitrobenzene- 1} \ - sulfonic acid dimethyl amide, l ^ amino-2-nitrobenzene- ^; 1-ethyl sulfone, 1-amino- ■ 'I-nitrobenzene-2-methyl sulfone,

1-aminobenzene-4-carboxylic acid methoxyethyl ester, ]

l-amino-2-nitrobenzene- h- carboxylic acid ethoxyethyl ester,

l-Amino ^ -cyan - ^ - nitrobenzene,;

l-amino-2-cyano-4-nitro-6-bromobenzene,

l-amino-2,6-dicyano-4-nitrobenzene, - ■ "

l-anlino-2-cyan - '' +, 6-dinitrobenzene, l-amino-2, ^ l, 5-trichlorobenzene.

: As aminoazobenzenes come the compounds of the formula

N-N- / \

wherein V, a hydrogen atom, a halogen atom or a methyl, a methoxy or ethoxy or nitro group, Vp is a hydrogen atom, a halogen atom or a nitro group, V_ is a hydrogen atom, a halogen atom, or a nitro group, V ^. a hydrogen atom, a halogen atom, a methoxy, a

Aethoxy, an alkoxycarbonyl, a Cypii, or Nitrogruppo and Vj- a hydrogen atom, a halogen atom, a methyl or

409844/0893

CLBA-GEIGY AG

is a methoxy group.

Suitable diazo components of the azobenzene series
are e.g. 4-A.mino-azobenzol.,. _ '·

^ -Amino-S'-chloro-äzobenzor, /. "

4 ~ Amino-2 ', V-dichloro-azobenzene.,. ;

^ -Amirio - ^ '- chloro-azobenzene,',

4 ~ amino-2'-nitro-azobenzene,

^J i ~ amino -> - nitro-azobenzene, ■. '. .

4 - Amirio-3 ^f -nitro-azobenzene,. ^:

^ -Amino-S-methyl-razobenzene, ■ / -,

4-Amino-4'-methoxy-azobenzolj ^ -Amino-3-nitΓo-2'-chloro-azobenzene,

-S ¹ , H '-dichloro-azobenzene, ^ -amino - ^ - nitro - ^' - methoxy-azobenzene, ^ -aminoazobenzene- ^ ¹ -sulphonic acid dimethylamide and 4-arr) ino-2-methylazobenzene-4'-carboxylic acid ethyl ester.

Any diazotizable heterocyclic amines can also be used as diazo components,
which do not contain any acidic, water-soluble substituents. These amines come, for example, from the thiazole. Benzthiazole, naphthothiazole, isothiazole, benzisothiazole thiophene, imidazole, benzimidazole, thiadiazole, pyridine
Quinoline, indazole, selenazole, oxazole, oxdiazole, benzoxazole, pyrazole or triazole series.

• 'As substituents of these amines in'

409844/0898

'ORIGINAL INSPECTED

CIDA-GEIGY AG

- i4 consideration:

Phenyl and phenylazo groups, the pheriyl rings carry further substituents, such as chlorine, nitro, alkyl, alkoxy and alkyl mercapto radicals each having 1 to 4 carbon atoms can, halogen, especially bromine and chlorine, sulfamoyl, Trifluoromethyl, cyano, thiocyano, nitro, aralkyl, in particular Benzyl, cycloalkyl, especially cyclohexyl radicals, as well as alkyl, alkoxy, alkyl mercapto, alkylsulfonyl, Alkoxycarbonyl, alkanoyl and Ν, Ν-dialkylsulfonamide groups, in particular those radicals with 1-4 carbon atoms:

•. Preference is given to the amines which have a heterocyclic five-membered ring with 2 or J heteroatoms, especially

one nitrogen and one or two sulfur, oxygen

'' ■■ * -. - ■

or have nitrogen atoms as heteroatoms, in particular

So the amines of the thiazole, benzothiazole, isothlazole, Benzisothiazole and thiadiazole series.

Preferred substituents of these 'amines are: halogen, in particular chlorine or bromine, nitro, cyano, trifluoromethyl, Alkyl and alkoxycarbonyl radicals each having 1 to 4 carbon atoms, phenyl and the substituted phenyl radicals mentioned above. Examples of such heterocyclic diazo components are:

2-aminothiazole, "

2-amino-5-nitrothiazole, ■. _:

2-amino-5-methylsulfonyl-thiazole,

2-Amino-5-cyanthiazole, - ■

A0984A / 0898

OR ^ GI ^ 3AL INSPECTED

2-Amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole 2-Amino-4- (4 ^f -chlor) -phenylthiazole, 2-amino-4- (4 '-nitro) -phenylthiazole 3 ~ amin'opyridine, 3 * -aminoquinoline,, 3- arainopyrazole , 5-amino-1-phenylpyrazole, 3-aminoindazole, 3-amino-2-methyl-5J7-dinitroindazole, 3- amino-l, 2, 4j-triazole, 3-amino-l- (4'-methoxyphenyl) -pyrazole,

5- (methyl, ethyl, phenyl or benzyl) -1, 2 _i 4-triazole _i 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzthiazole , 2-amino-6-cyanobenzothiazole _J 2-amino-6-nitrobenzthiazole, S-amino-6-carboethoxybenzthiazole, 2-amino-6-methylsulfonylbenzthiazole, 2-amino-1,3,4-thiadiazole, 2-amino-1 , 3,5-thiadiazole,

^ phenyl or 4-methy.l-1,3, ¹ J thiadiazoles

409844/0898

2-amino-4-methyl thio-1,3,5-thiadiazole, 2-amino-5-phenyl-1,3,4-thiadiazole, 2-amino-3-nitro-5-methylsulfonylthiophene, 2-amino-3-nitro-5-acetylthiophene, 2-amino-3,5-bis (methyl sulfonyl) thiophene, 5-amino-3-methyl-4-nitroisothiazole, 3-Amino-5-nitro-2, l-benzisothiazole, 3-amino-7-bromo-5-nitro-2, l-benzisothiazole, 5-amino-4-nitro-l-methylimidazole, 4-amino-5-bromo-7-nitrobenzisothiazole, 4-amino-7-nitrobenzotriazole.

The coupling component is preferably an o-amino-S-cyano-1-alkyl ^ -alkylaminodihydropyridine substituted in the 2-position, which has an imino group in the 2-, 4- or 6-position. In the 2-position are aliphatic and aromatic amino, oxy or mercapto groups. These compounds can be obtained by reacting the o-amino-S-cyano-1-alkyl ^ -alkylaminopyridinium chloride with a primary or secondary amine, a hydroxy or mercapto compound.

Examples of aromatic amines are: naphthylamine, aniline and its derivatives, such as l-amino-3-chlorobenzene, l-amino-4-carbethoxybenzene, 1-amino-2,4-dicyanobenzene, l-amino ^ -methoxy ^ -nitrobenzene, l-amino-2-methanesulfonyl-4-chlorobenzene, Methylaminobenzene, ethylamino-

409844/0898

GIBA-GEIQY AG "

- 17 -

! benzol / 1-methylamino-3-chlorobenzene. Then come the above

long-established diazo components of the aromatic and heterocyclic

'lischen series in question as amines to be deposited.

; Primary and secondary aliphatic amines such as

Methyl-., Ethyl-, isopropyl-, hexy-1- ,. Octyl, decyl, methoxy

ethyl, isopropoxypropyl, dimethyl, diethyl, chloroethyl, iAethanol, diethanol, propanol, benzyl or cyclohexyl amines Morpholine, pyrrolidine and piperidine.

I Examples of alcohols include: ethanol, propanol, Isopropanol, butanol, 2-ethoxyethanol, cyclohexanol, benzyl alcohol, Phenol and its substituted derivatives. i Examples of mercapto compounds are: Ethyl mercaptan, thiophenol.

Preferred coupling components are those 3-carbonamido or 3-cyano (4-amino-6-imino- or 4-imino-6-amino) dihydropyridines, which carry an amino group in the 2-position, in particular a morpholino, pyrrolidino or Piperidino group.

ι I ι ■ ·

The starting products, especially the diaminohalogenpyridinium chloride, are e.g. according to A.L. Cossey et al., Angew. iChemie, Vol. 84 (1972), p. Il84. ,

The 3 cyano group can be converted into concentrated sulfuric acid into the 3-CONHp group.

Instead of a uniform diazo component,

j. Ί

^; one also uses a mixture of two or more of the diazo components according to the invention and instead of a uniform one

409844/0898

CIBA-GEIGYAG

- 18 -

Azo component use a mixture of two or more of the azo components according to the invention.

The diazotization of the diazo components mentioned can be done according to methods known per se - e.g. with the help of Mineral acid, especially hydrochloric acid, and sodium nitrite or e.g. with a solution of nitrosylsulfuric acid in. concentrated sulfuric acid, made * '

The coupling can also be carried out in a manner known per se, e.g. in a neutral to acidic agent, if appropriate in the presence of sodium acetate or the like, the coupling rate influencing buffer substances or catalysts, such as pyridine resp. its salts, made will.

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, for example Acrylic or acrylonitrile fibers, polyacrylonitrile fibers and copolymers made from acrylonitrile and other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanethylene and vinyl acetate, and of acrylonitrile block copolymers, Fibers made from polyurethane, polyolefins, such as base modified, with nickel modified or unmodified

4098U / 0898

CIBA-GEIGY AG

Polypropylene, cellulose tri- and 2 l / 2-acetate and in particular Pipes made from polyamides such as nylon-6, nylon-6,6 or Nylon 12 and aromatic polyesters such as those made from terephthalic acid and ethylene glycol or 1,4-dirne thylcyclohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol.

ι. The above-mentioned are preferably colored

Fiber materials with the inventive, in water j

sparingly soluble azo dyes from aqueous dispersion. If the dyes according to the invention in the diazo component have hydrophilic groups such as one or more hydroxyalkyl Contain carbonamide or sulfonamide groups it is best applied from a solvent liquor .. It is therefore advisable to use them as disperse dyes usable representatives by grinding with textile auxiliaries, such as dispersants and possibly to finely divide further grinding aids. By subsequently

Send drying is obtained from the textile auxiliary and the

Dye existing dye preparations.

Examples which may be mentioned as advantageously usable dispersants of the nonionic group are: addition products of 8 moles of ethylene oxide to 1 mole of p-tert-octylphenol, of 15 or 6 moles of ethylene oxide to castor oil, of 20 moles of ethylene oxide to the alcohol Ο., - Η, -, ΟΗ, ethylene oxide Addition products to di [a-phenylethyl] phenols,

409844/0898

CIBA-GEIGY AG

Polyethylene oxide tert-dodecyl thioether, polyamine polyglycol ether or addition products of 15 or 50 mol of ethylene oxide to 1 mole of amine C-pELj-NHp or C

^ ₂₇ p

: The following may be mentioned as anionic dispersants: Sulfuric acid esters of alcohols of the fat series with 8 to 20 carbon atoms, from the ethylene oxide adducts from the corresponding fatty acid amides, or from alkylated phenols with 8 to 12 carbon atoms in the alkyl radical; Sulfonic acid esters with alkyl radicals with 8 to 20 carbon atoms; Sulphate decomposition products from unsaturated fats and oils;

■ phosphoric acid esters with alkyl radicals with 8 to 20 carbon atoms; Fatty acid soaps, also alkylarylsulfonates,

: Densation products of formaldehyde with naphthalenesulfonic acid and lignosulfonates.

^: Suitable cationic dispersing agents are quaternary ammonium compounds containing alkyl or aralkyl radical containing from 8 to 20 carbon atoms.

In addition to the dispersants, the dye preparations can also contain organic solvents, in particular Solvents boiling above 100 C, which are preferably are miscible with water, such as mono- and dialkyl glycol ethers, dioxane, dimethylformamide or acetamide, tetramethylene

■ contain sulfone or dimethyl sulfoxide. One can benefit. Adhesive dye, dispersant and solvent to one another

marry.

409844/0898

CIßA-GEIGY AG

24173Q2

- 21 -

The dyeing of the polyester fibers with the inventive In water sparingly soluble dyes from aqueous dispersion is carried out according to the procedure for polyester materials customary processes, polyesters of aromatic polycarboxylic acids with polyhydric alcohols .man preferably dyes Temperatures of over 100 C under pressure. The coloring can but also at the boiling point of the dyebath in the presence of color carriers, for example phenylphenols, polychlorobenzene compounds or similar aids or by the thermosol process, i.e. Padding with subsequent post-treatment in the heat, e.g. thermosetting, at 180 ~ 210 ° C. Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures from 80-85 °, while cellulose triacetate fibers are advantageously dyed at the boiling point of the dyebath. At the Dyeing of cellulose-2 l / 2-acetate or polyamide fibers the use of color carriers is unnecessary. Dyes according to the invention can also be used for printing materials mentioned are used according to customary methods ♦:

The dyeings obtained according to the present process can be subjected to an after-treatment, ' for example by heating with an aqueous solution of an ion-free detergent. . ■

Instead of impregnation,

A09844 / 0898

ommA inspected

CIBA-GEIGY AG

- 22 -. According to the method, the 'specified compounds are also carried out

Printing applied v / ground. Used for this purpose
For example, a printing ink that contains the finely dispersed dye in addition to the auxiliaries customary in printing, such as wetting agents and thickeners] !,.

Synthetic fibers such as polyesters and polyamides can also be used in organic solvent liquors color, like a mixture of perchlorethylene and dimethylformamide or in pure perchlorethylene.

The present process gives vivid, brilliant dyeings and prints of excellent quality Fastness properties, in particular light, thermosetting, subliming, Pleated, flue gas, over-dyeing, dry cleaning, ironing, rubbing, chlorine and wet fastness, such as water, washing and waterproof properties. ·.

'You can use the new water-insoluble dyes Also use for spin dyeing of polyamides, polyesters and polyolefins ". The polymer to be colored is zxtfeekmäs— sig in the form of powder, grains or chips, as a ready-to-use spinning solution or in the molten state with the dye mixed, which in the dry state or in the form of a dispersion or solution in an optionally volatile Solvent is introduced. After homogeneous distribution of the dye in the solution or melt of the polymer the mixture is poured in a known manner,

409844/0898

CIBA-GEIGY AG

Pre-pressing or extrusion to form fibers, yarns, monofilaments, Films etc. processed.

In the following examples, the mean Unless otherwise indicated, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius.

4098A4 / 0898

ORIGINAL INSPECTED

CLBA-GEIGY AG

Regulation 1

4.66 parts of 6-amino-2-chloro-3 ~ ^c y ^an ~ l ~ ^met hyl ~ 4-! methylaminopyridinium chloride, 10 parts of alcohol and

i 11.7 parts of isopropoxypropylamine are added for 10 hours ί

; heated in an autoclave at 130 °. After cooling, 'are 2 parts of sodium carbonate was added and the ^over-: schüssige amine and the remaining volatiles I are distilled off with steam. The residue is ^: extracted with chloroform, the extract with calcined

Sodium sulfate dried and the solvent im. Distilled off under vacuum. The residue, which is through

the formula

HN ^{/ x} K
2

. and as a viscous, colorless oil ; is used as a coupling component.

40384 ^ / 0898

CIBA-GEIGYAG

Regulation 2

4.66 parts of 6-amino-2-chloro-3-cyano-l-methyl-4-methylaminopyridiniurnchlorid, 10 parts of alcohol, and 8.5 parts of piperidine are heated for 12 hours in an autoclave at I30 ^0th It is cooled, 2 parts of sodium carbonate are added and the excess amine and the other volatile constituents are distilled off with steam. The residue is extracted with chloroform. The chloroform extract is dried with calcined sodium sulfate and then the solvent is distilled off in vacuo. The residue, which is represented by the formula

and as a viscous, colorless oil is used as a coupling component.

409844/0898

Regulation 3

4.66 parts of o-amino - ^ - chloro-S-cyano-l-methyl - ^ - methylate ninopyridinium chloride and 12 parts of aniline are heated to 160 to 170 ° for 12 hours. After cooling down 4 parts of sodium carbonate are added and the excess amine is distilled off with steam. The unusual product is filtered off, washed neutral with cold water and dried. The pale brown colored powder, which

by the formula

NHCH

is used as a coupling component.

Regulation 4

7 parts of o-amino ^ -chlor-S-cyano-l-methyl ^ -methylaminopyridinium chloride, 21 parts of phenol and 3.5 parts of potassium carbonate are heated to 160 ° to 170 ° for 24 hours. After this The reaction mixture is cooled with 2N sodium hydroxide solution Made phenolphthalein-alkaline and the precipitated product was filtered off, washed with water and dried. The brown one Powder is extracted with hot acetone. The extract is separated off and the solvent is distilled off in vacuo. Of the residue thus obtained, which is represented by the formula

409844/0898

KHGH CN

can be shown and is obtained as a pale brown colored powder, is used as a coupling component.

If the corresponding amount of thiophenol is used instead of phenol, the corresponding thio product is obtained,

Regulation 5

62.4 parts of cyanoacetic acid methoxypropylamide are dissolved in 125 parts by volume of chloroform, and at 50 to 55 parts are 61.4 parts of phosphorus oxychloride were added dropwise. The mixture is refluxed for 12 hours. Then that will The solvent is distilled off in vacuo and 30 parts by volume of methyl alcohol are added to the residue. The tough mass will stirred at 0 to 5 for 3 to 4 hours until crystallization has ended. The product is filtered off, with a little cold Washed methyl alcohol and squeezed well. The pale yellow crystals obtained in this way, having a melting point of 160 to 165, the

^formula

he-

are used to manufacture the coupling components. 4Q9844 / 0898

Regulation 6

66.4 parts of cyanoacetic acid cyclohexylamide are dissolved in 200 parts by volume of chloroform and at 50 to 55 ° 61.4 parts of phosphorus oxychloride were added dropwise. The mixture is refluxed for 12 hours. Then that will The solvent is distilled off in vacuo and 100 parts by volume of methyl alcohol are added to the residue. After 2 to 3 hours Stirring, the crystallized product is filtered off and washed with cold methyl alcohol. That recrystallized from methyl alcohol light yellow product has a melting point of 195 to 196 and corresponds to the formula

It is used to manufacture the clutch components.

Regulation 7

75.2 parts of cyanoacetic acid phenyl methylamide are used in 200 parts by volume of chloroform dissolved, and 61.4 parts of phosphorus oxychloride are added dropwise at 50 to 55 °. The mixture will heated under reflux for 12 hours. Then the solvent is distilled off in vacuo and the residue in 30 parts by volume Methyl alcohol added. After 3 hours of stirring at 5 to, the product which has crystallized out is filtered off and washed with cold Washed methyl alcohol. That recrystallized from methyl alcohol

A09844 / 0898

light yellow product has a m.p. from 234 to 235 and corresponds to the formula

el · ·

° 2 ^H 4

It is used to manufacture the clutch components.

Regulation 8

10.5 parts ö-amino - ^ - chlor-S-cyano-l-inethoxypropyl - ^ - methoxypropylaminopyrridinium chloride, 15 parts alcohol and 26.6 parts of 35% strength methylamine solution are heated to 17.0 in an autoclave for 12 hours. After cooling down 3 parts of sodium carbonate are added, and the excess amine and the other volatile constituents are vaporized distilled off. Of the. The residue is extracted with chloroform, the extract is dried with calcined sodium sulfate and the solvent distilled off in vacuo. The residue, which is represented by the formula NHC HgOCH

CN,

can be represented and is obtained as a viscous oil, is called Coupling component used.

409844/0898 QRlGJNAL INSPECTEO

Regulation 9

9.8 parts of methyl cyanoacetamide are dissolved in 50 parts by volume of chloroform while warm. Then it is cooled down. and 28.7 parts of phosphorus oxybromide were added. The reaction mixture is slowly warmed to 60 ° and refluxed for 12 hours. The suspension is cooled to 0-5 and filtered off. The residue is recrystallized from methyl alcohol. The yellow product, which has a m.p. of 242 to 244 owns and the formula

NHCK ₂ ι 3

Βγ ^Θ

"Br

corresponds to, can be with nucleophilic agents analogous to the React chlorine product to coupling components.

409844/0898

CIBA-GEIGYAG

- 31 -

Example 1. ·

17.2 parts of 2-chloro-4-nitroaniline are with 39 parts by volume conc. Hydrochloric acid made into a paste and stirred into a mixture of 400 parts of ice and water. The suspension is mixed with 25 parts by volume of 4N sodium nitrite solution diazotized at 0-5. The diazo solution becomes a solution of 27.7 parts according to the instructions 1 obtained o-amino ^ -cyan ^ -isopropoxypropylimino-1-methyl-4-methylamino-1,2-dihydropyridine given in 150 parts of ethyl alcohol. The clutch mix is neutralized against Congo red with sodium acetate solution. After the coupling has ended, the failed one becomes Dye made up by the formula

Cl CH ₃ HN GN

can be represented, · filtered off, washed with water and dried. It dyes polyester fibers in brilliant red-orange shades with very good fastness properties.

409844/0898

ORiGlNAL INSPECIED

CBA-GEIGYAG

- 32 -

Example 2

18.3 parts of 2,4-dinitroariiline in 55 parts conc. Entered sulfuric acid and dissolved. At 20 3-1 * 8 parts of 42-oil nitrosylsulfuric acid are added dropwise and stirred for a further 2 hours at 20-22. The diazo solution becomes a solution of 24.5 parts of the 5-cyano-2-imino-I-methyl- obtained according to instruction 2 ^ -methylamino-ö-piperidino-l, 2-dihydropyridins in 150 parts of alcohol given at 0-5. The clutch mix is stirred for 2 hours and neutralized against Congo red with sodium acetate solution. To When the coupling is complete, the precipitated dye, which is represented by the formula

NO ₂ CH HN CN

JK

-N — C "> —N

can represent, filtered off, washed with water and dried. It dyes polyester fibers in red shades with very good fastness properties.

4098 4 4/0898

CLBA-GEJGY AG

- 33 -

Example 3.

1.5 parts of sodium nitrite are used at 0 to 10 ° in l8 parts conc. Sulfuric acid interspersed. The mixture is heated to 65 until everything is dissolved, then up 0 cooled and added dropwise with 20 parts by volume of a

Mixture of 4 parts of glacial acetic acid and one part of propionic acid A solution of 2.9 parts of 2-amina-5-nitrothiazole in 20 parts by volume is added to the solution obtained a mixture of glacial acetic acid and propionic acid (4: 1) was added dropwise and the reaction mixture over 3 hours stirred further at 0 to 5. 1.5 parts of urea will be added in portions to this diazo solution. The diazo solution thus obtained becomes a solution of 5.08 parts 5-cyano-2-imino-6-phenoxy-1-methyl-4-methylamino-1> 2-dihydropyridine was added in 20 parts of alcohol. The mixture is stirred for a further 2 hours and then made Congo-neutral with sodium acetate solution. After the coupling is completed the precipitated dye is filtered off with water washed and dried. The dye, which is represented by the formula

_{HC N} CH ₃ HN CN

O ₀ NC C — U = NC> —OC.H ₁ -

² V Vn / ^{6 5}

CH ₅

ORIGINAL IMSPECTEÖ

4G98U / Q898

CISA-GEIGYAG

- 34 -;

show, dyes polyester and cellulose acetate fibers in red shades of very good fastness properties.

In an analogous manner, the dyes of the formula listed in the table below

EHN Y

DN = H— <ζ y —Z -N '

E received.

4098 U / 08-9 8 OR ₁ G ₁ NAL! NSPECTED

3

cn

co

OO

O
00
CO

CO

ί 5

! 6 ! ι

7 "

8th

10

11

12th

13th

14th

2-bromo-6-methoxy-4-nitro-phenyl

4-phenylazophenyl

2-chloro-4-nitrophenyl

5-nitrothiazolyl-2

ί 3-phenyl-1,2,4-thiadiazolyl-5

(2,6-dichloro-4-nitrophenyl j 5-phenyl-1,3,4-thiadiazolyl-2

6-nitrobenzthiazolyl-2 2,4,6-tribromophenyl

2,4-dinitrophenyl

4- (2'-Hydroxy-5'-methylphenyl) azo-phenyl

4-butylsulfonylpheny1 2-methoxy-4-nitrophenyl

2,6-dibromo-4-nitrophenyl

CH,

C ₂ H ₄ C ₆ H ₅

C ₂ H ₅

^C 2 ^H 5
C ₃ H ₆ OCH ₃

CH _n

C ₃ H ₆ OC ₂ H ₅
C ₃ H ₇ _

CH,

Cyclopentyl

C ₂ H ₅

-CH

C ₃ H ₆ OCH ₃

SC ₆ H ₄ CH ₃ (4)

NHC ₈ H ₁₇

OC ₆ H ₅

N (C ₄ H ₉ ),

NHC ₆ H ₁₃ N (CH ₃ ) ₂ NHC ₆ H ₄ Br (4) NHCH ₃

Ή Η

NHC ₂ H ₄ Cl

NH-cyclopentyl

PH

NH-CH "" 3

CN CN CN

CN CN ■ CN CN CN

Color shade on j polyester fibers j

> <H «~ 4

golden yellow ir

bluish red

golden yellow

Scarlet fever

golden yellow

Scarlet fever

yellow

red scarlet

yellow orange

orange.

CO O K)

\ 4-cyanophenyl

J16

j 2,5-dichloro-4-dimethylamino} sulfonylphenyl

! 17 j 3-nitro-4-phenylaminophenyl

Cyclohexyl

C ₂ H ₅

C ₂ H ₄ C ₆ H ₅

3-methyl-1,2,4-thiadiazolyl-5 \ CH ₂ C ₅ H ₅

j 19 j 2-methylsulfonyl-4-nitrophenylj CH ₃

^; 20 j 2-methyl-4-nitrophenyl

v _O j21 5-nitro-2,1-benzisothiazolyl-3

C ₃ H ₆ OCH (CH ₃ )

NHC ₂ H ₄ COOH NHC ₃ H ₆ OCH ₃

-EE NCOCH

-NHO

NHCH ₂ C ₆ H ₅ NHC ₄ H ₉

^C 2 ^H

j 4-acetylphenyl

2 ^H 5

C ₃ H ₆ OC ₂ H ₅

* "* i 23

£ j 24

cd: 26

! 28

4-ethoxyethoxycarbonylphenyl \ C ^ H ₇

3-methyl-4-nitro-1,2-isothiazolyl-5

4- (4'-nitrophenyl) azo-phenyl

2,6-dichloro-4-ethylsulfonylphenyl

4-aminosulfonylphenyl

5,6-dichlorobenzothiazolyl-2

C ₃ H ₆ OCH ₃

CH,

CH,

N H

NHC ₂ H ₄ C ₆ H ₅

NHC ₆ H ₄ Cl (3)

C ₃ H ₇

NH-Cyclohexyl N (C ₂ H ₄ OCOCH ₃ )

NHC ₆ H ₄ OCH ₃ (2) SC ₆ H ₃ C1 ₂ (2.5)

Y \ color tone on
■ 1 polyester fibers

golden yellow
golden yellow

orange

yellow

Scarlet fever
orange

reddish blue

CN yellow CN yellow CN Red CN orange CN orange CN golden yellow CN Red Yellow

J 29 ί 30

31

32 33

134

5-nitr οindazοIy1-3 4-benzoylphenyl 2-cyano-4-nitrophenyl 4-N-Prapy! Phthalimide 2,4,6-triehlophenyl

4-chloro-2-trifluoromethylphenyl

co

j I f38

• O
CD i 39 CO O 3D *> ■ O Z O, | - OO 40 co Ic? cc f 41 Q m σ

4-butylaminocarbonylphenyl

4-phenylazo-2-nitrophenyl 5-chloro-2-methylthio-phenyl

GH

^C 2 ^H 4 ^C 6 ^H 5

Cyclopenty1

j 2,5-bis-methoxycarbonylphenyl [ i

I ^CH 2 ^C 6 ^H 5

2-cyano-4,6-dinitrophenyl 1-: methyl-4-nitroimidazolyl-5 j

2-chloro-5-methoxy-4-nitro- j CH ₃ phenyl. }

CH (CH ₃ )

^C 2 ^H 5

C ₃ H ₇

NHC ₄ H ₈ OH

NHCH ₂ CON (CH ₃ )

NHC ₂ H ₄ OC ₆ H ₅

NHC ₅ H ₁₁

N (C ₃ H ₇ ) ₂

0C ₆ H ₃ (CH ₃ ) ₂ (3.4)

OC ₆ H ₄ OCH ₃ (4)

Color on j polyester fibers

CN

CQNHr CN

CN

CN CN.

orange

golden yellow

Scarlet fever

golden yellow.

golden yellow

golden yellow

yellow j

[bluish red]

Scarlet j red yellow

Red Yellow

Red

yellow

co σ ro

T "

cn 45 ί 46 ! ■
47 ο 48 co 49 OO Ns 50 O 00
CO 51 GC O 52 Ω 2 >
Γ " 2
ω 53 -σ m ο m D.

2,4,6-trinitraphenyl

S-methylpyrazolyl-5

4-phenoxycarbony! Phenyl

■ 5-nitro-7-bromo-2,1-benzisothiazolyl-3

3-phenoxysulfonylpheny1

4-hexylaminosulfonylphenyl 4-benzyloxycarbonylphenyl

6-methylsulfonylbenzthiazolyl-2

2 _r , 6-dicyan-4-nitrophenyl 2,4-dinitro-6-chlorophenyl

2 ^ ösulfonylphenyl

l-phenylpyrazolyl-5

CH ₂ CH (CH ₃ )

^C 2 ^H 5

CH ₃ 1 C »H _ft OCH (CH,) ₉ t

Cyclohexyl

CH ₃ CH ₃

C ₃ H ₇

CH.

CH.

WHGH,

NHOH,

NHC _Ä H / OCH, (4)

Tue + J

NHC ₄ H ₉

NHCH (CH ₃ )

₃ ) ₂

NHC ₃ H ₆ OCH ₂ CHC ₄ H ₉

Y t shade on FoIy- j j. ester fibers j

CONH ₂ purple

CN yellow

CN j golden yellow

CN I red-tinged, blue l

CN j yellow

CN j red yellow

CN ' _: red-yellow CONH ₂ sharp

CN bluish red CN orange CN orange

CN ■ yellow

co
co

_ -Fc-

J54 f 4-nitro-2-trifluoromethyl 155

ί56 157

! 58 | 59

160 J61! 62

3-butylthio-1,2,4-thia- | CH ₃

diazolyl-5 i

2-Bromo-6-cyano-4-nitrophenyl j CH ₃

S-cyano ^ -methyl-S-methoxy-1 C ₂ H ₁

carbonyl-thiophenyl-2!

2,4,5-trichlorophenyl j CH ₃

S j

\ 4-pyrrolidinocarbonylphenyl I CHo

1 I.

f 2-methoxy-5-nitrophenyl j C ₉ H ₁ 4-nitro-2-thiocyanophenyl

4- (4'-chloropheny1) -azo-2-me thoxy-5-me thy! phenyl

164

j 63 f 4-phenylsulfonyl phenyl

3-cyano-4,5-tetramethylenethiophenyl-2

2-ethoxycarbonyl-4-nitrophenyl

C ₃ H ₆ OC ₂ H ₅ .

s ⁶⁵

CD {

66

67

5-acetyl-3-nitrothiophenyl-2 5-phenyl-1,2,4-triazolyl-3

NHC ₈ H ₁₇ NHCH (CH ₃ )

NHC ₃ H ₆ OCH (CH ₃ O ₂

NHC ₆ H ₁₃

NH-cyclohexyl

N (C ₂ H ₄ OH) ₂

NHC ₃ H ₆ OCH (CH ₃ ) NHC ₆ H ₄ OCH ₃ (4)

NHC ₂ H ₅

NHC ₆ H ₁₃
NHC ₆ H ₄ Br (4)

Hue. On poly )

CN CN

CN

CN CN

yellow orange orange

Scarlet fever

bluish red yellow,

- 39a -

_f j j

J71 J72 J

! 74

phenyl i76 j 3-pyridyl

C ₂ H ₅

CoH / OCrtHr

CHo

5-cyanthiazole-2 4-ethoxy-2-nitrophenyl 2,4-dicyanophenyl

4-methyl-2-nitrophenyl 4-propoxycarbonylpheny1 2-methyl-5-nitrophenyl j CH ₂ C ₆ H ₅ 4-nitrophenyl 4-hexoxycarbonyl-2-nitro-

.._ i_

C ₃ H ₇ C ₂ H ₅

C ₂ H ₅

C ₃ H ₆ OCH ₃

^C 6 ^H 13

NHCH

NHC ₂ H ₄ C ₆ H ₅

C ₂ H ₅

NHC ₆ H ₄ Cl (3)

oH _n OCH ₀ 3 6 3

NHC ₅ H ₁₁

NHC ₂ H ₅

NHC ₄ H ₉

NHC ₆ H ₄ CH ₃ (4)

NHC ₃ H ₆ OCH ₂ CHC ₄ H ₉

CN CN CN CN CN

Color on polyester fibers i

Ή I * "" S * · -I · "I * ·!» - · r * JLVW .IT.. ^ Ii ing 1 if 1—.TM 1-MIMJJI HWIMHMIIll HI M '"*

Red

orange

orange

golden yellow

golden yellow

yellow

golden yellow

orange

yellow

Example 4

2 parts of 5- (2 ', 4'-Dinitrophenyl) -a2o-2-hexylamino-6-imino-4 "methyl! Amino-i-methyl 1-3 -cyanedihydropyridine are dissolved in 10 parts of 90% sulfuric acid and at 60 ° during Stirred for 12 hours. The solution is then allowed to cool and poured onto 60 parts of ice. and water ". The precipitated dye of the formula

ELCHN COWH,

is filtered off, washed neutral with water and dried, It dyes polyester fibers in ruby red tones.

In the same way, the other 3-aminocarbonyl group dyes described in the present examples were made obtain.

409844/0898

Cl BA-GlI SY AG

• Coloring instruction

1 part of the dye obtained in Example 1 is mixed with 2 parts of a 50% aqueous solution of the sodium salt of dinaphthylmethanedisulphonic acid wet grinding and drying »

This dye preparation is made with 40 parts

a 10% aqueous solution of the sodium salt of i

N-Benzy! -Μ-heptädecyl-benzirnidazoldlsulfonic acid stirred and 4 parts of a 4o ^ acetic acid solution added. A dyebath of 4000 parts is prepared from it by diluting it with water.

100 parts of a purified polyester fiber material are added to this bath at 50 °, which increases Temperature within half an hour to 120 to IjK) and stains it for an hour in a closed vessel

Temperature. Then it is rinsed well. You get one

red orange /
strong / coloring of excellent sealing and sublimation

mierechtheit *

403844/0898

Claims (1)

Godfather tan sayings 1. Free from acidic water-solubilizing groups Azo dyes of the formula wherein R, is an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, Z-, a radical of the formulas = NH or -NH ₂ , Z _{2 is} a radical of the formulas = NR ₂ , -NHR ₂ , -NRoRa ₅ -OR, - or -SR / -, where R ₂ , R, and R, are each hydrogen atoms or optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radicals, R- and R, together with the nitrogen atom connected to them can form a five- or six-membered ring, R _{5 is} a hydrogen atom, an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, R - is a hydrogen atom, an optionally substituted alkyl , Is aralkyl, cycloalkyl, aryl or heterocyclic radical, Zo is a radical of the formulas = NR ₁ "or -NHR ^, Y is a radical of the formulas -CONH ₂ or -CN, and D is the radical of an aromatic or heterocyclic radical Diazo component is, the dihydropyridine ring A being substituted only by a double-bonded nitrogen atom is and contains two double bonds. 2. Azo dyes according to claim 1, characterized in that that R, an optionally substituted alkyl or aralkyl radical or is a cyclohexyl radical. A0984 4/0898 OflfG JWSPECTED 3. Azo dyes according to Claims 1 or 2, characterized characterized in that Zr is a residue of the formulas -NIIRo or = NR ", wherein R ~ is the same as in claim 1. 4. Azo dyes according to Claims 1 or 2, characterized / " ^R 3 characterized in that Z _{0 is} a radical of the formula -N-. _p is where Z ^ K ₄ R ~ and R mean the same as in claim 1. 5. Azo dyes according to Claims 1 or 2, characterized in that Z _? is a radical of the formula -0-R- in which R 1 is the same as in claim 1. 6. Azo dyes according to Claims 1 or 2, characterized in that Z ^ is a radical of the formula -O-Rc, in which R _{5 is} an optionally substituted phenyl group. 7. Azo dyes according to claims 1 or 2, characterized in that Z2 is a radical of the formula -S-R, -, wherein Rg means the same as in claim 1. 8. Azo dyes according to claims 1 to 7, wherein Y is a cyano group. 9. Azo dyes according to Claims 1 to 7, wherein D is a radical of the benzene series, the azobenzene series or a sulfur- and / or nitrogen-containing heterocyclic radical. 409844/0898 MS * 10. Azo dyes according to claim 1, wherein R _T and Rj, each hydrogen, radicals of the benzene series, benzyl, cycloalkyl or alkyl radicals with at most 12 carbon atoms, the latter optionally being interrupted by oxygen, sulfur atoms or imino groups and directly or can be linked to form a ring via an oxygen or sulfur atom. 11. Azo dyes according to claim 1 of the formula wherein D and R- ^ have the meaning given in claim 1 and Zp the residue of an aniline, cyclohexylamine. Benzylamine, Is phenethylamine or an aliphatic amine with a maximum of 12 carbon atoms. 12, azo dyes according to claim 1 of the general formula wherein D and R. are the same as in claim 1 and Zg a morpholine bonded via the ring nitrogen atom, Pyrrolidine, piperidine., Piperazine, N-methylpiperazine 844/0898 ORIGINAL IMSPECTED CiBA-GEtGVAG λ / λ η q η O or N-acylpiperazine radical, ! J. Azo dyes according to claim 9, wherein D is heteroeyelic residue of the thiazole, benzothiazole., thio- ' phen, imidazole, pyridine, indazole, pyrazole ^ triazole, Benztriazole, Thiadiazole, Isothiazole or Benzisothiazole series is. 14 «azo dyes according to claim 9, where D is a residue the benzene or azobenzene series, which is unsubstituted or by halogen atoms, nitro, cyano ^ thiocyan, Trifluoromethyl, alkyl, alkoxy, aryloxy, alkyl mercapto, Aryl mercapto, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, Alkylsulfonyl, aminosulfonyloxy, sulfonamide, Carboxamide, acyl, acylamino and phenylazo groups, in which the phenyl nucleus contains chlorine atoms and cyano, nitro, alkyl, alkoxy, alkoxycarbonyl and sulfonamide groups can carry, is substituted. 15 · Process for the preparation of azo dyes that are free from acidic water-solubilizing groups and are of the formula 4Ö9844 / Ö898 correspond, in which R- is an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, Z-, a radical of the formulas = NH or -NtU, Z _{2 is} a radical of the formulas = NR ₂ , - NHR ₂ , -NR ₃ R ^, -OR ₅ or -SR ₆ , where R ₂ , R ₃ and R ^ are each hydrogen atoms or optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radicals, R ^ and R, together with the nitrogen atom connected to them, can form a five- or six-membered ring, Rr is a hydrogen atom, an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, R 1 is a hydrogen atom, an optionally substituted one Is alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, Zo is a radical of the formulas = NR-, or -NHR. Y is a radical of the formulas -CONH ₂ or -CN, and D is the radical of an aromatic or heterocyclic diazo component, the dihydropyridine ring A being only substituted by a double bonded nitrogen atom and containing two double bonds, characterized in that the diazonium compound of an amine of the formula D-NH ₂ with a coupling component of the formula couples and optionally, when Y = CN, the cyano group in concentrated sulfuric acid to the -CONH ^ group. 409844/0 8 9 8 ' ORIGINAL INSPECTED cioa-geigyag 9 Λ 1 7 Ί Π? 16. The method according to claim 15, characterized in that that one starts from coupling components in which R, an optionally substituted alkyl or aralkyl radical or is a cyclohexyl radical. 17. The method according to claim 15 or 16, characterized characterized by the fact that coupling components are used as the starting point, in which Z "is a remainder of the formulas -KHFU or = NFL · is wherein R "means the same as in claim 15. 18. The method according to claim 15 or 16, characterized in that one starts from coupling components in which Z "is a radical of the formula -NT _D , wherein R-, and R ^, are the same as in claim 15. 19 «The method according to claim 15 or 16, characterized in that one starts from coupling components in which Z _{p is a} radical of the formula -O-Rp. in which R is the same as in claim 15, but is preferably an optionally substituted phenyl radical. 20. The method according to claim 15 or 16, characterized characterized in that one starts from coupling _{components in which Z p is} a radical of the formula -SR, -, where R, - is the same as in claim 15. 21. The method according to claim I5, characterized in that that one starts from a coupling component in which Y is -CN. 9844/089 22 «Method according to claims 15 to 21, thereby characterizedj that one of the diazotized amines Benzene series or sulfur- and / or nitrogen-containing heterocyclic compounds " 2Y. The method compliant with claim 15 » characterized in that one starts from coupling components in which PL · and Ru are each hydrogen, radicals of the benzene series, benzyl, phenethyl, cycloalkyl or alkyl radicals with at most 12 carbon atoms, the latter optionally being replaced by oxygen -, sulfur atoms or imino groups can be interrupted and linked directly or via an oxygen or sulfur atom to form a ring. 2Ά . Process according to claim 15 *, characterized in that coupling components of the formula HK R ₁ R ₁ HN starts in which Z _{p is} the radical of an aniline, cyclohexylamine, benzylamine, phenethylamine or an aliphatic amine with at most 12 carbon atoms and R _{1 is} the same as in claim 15. 25. The method according to claim 15 ₃ characterized in that coupling components of the formula • 409844/0898 in R ₁ \ _J-h where Z _{n is} a morpholine, piperaziri, N-methylpiperazine, N-acylpiperazine or piperidine radical bonded via the ring nitrogen atom. 26. The method according to claim 22, characterized in that that one of diazotized amines of thiazole, thiophene, imidazole ,. Pyridine, indazole, pyrazole, Triazole, benzotriazole, benzthiazole, thiadiazole, isothiazole or benzisothiazole series starts. 27. The method according to claim 22, characterized in that that one starts from diazotized amines of the benzene series, in which the benzene ring has one or more halogen atoms, Nitro, cyano, thiocyanate, trifluoromethyl, alkyl, alkoxy, aryloxy, alkyl mercapto, aryl mercapto, alkoxycarbonyl, Aryloxycarbonyl, alkoxycarbonyloxy, aryloxy. ' carbonyloxy, alkoxysulfonyl, aminosulfonylcxy, sulfonamide, Carboxamide, acyl and acylamino radicals and phenylazo groups can carry, the phenyl nucleus with Cyano, chlorine, nitro, alkoxycarbonyl, sulfonamide, alkyl and alkoxy groups can be substituted * 40 9 8 4 4/0898 ~, -ι 7 o η ο 28. Process for dyeing and printing hydrophobic synthetic Fibers, in particular fibers containing ester groups, characterized in that dyes are used Claims 1 to 14 used. 29- The method according to claim 28 for dyeing and Printing of fibers made of cellulose acetate or aromatic polyesters, in particular made of polyethylene terephthalate, characterized by the use of the dyes defined according to claims 1 to 14. 30. The method according to claims 28 to 29 * thereby characterized in that dyeing is carried out in an organic solvent. 31. The colored obtained according to claims 28 to 30 Material. 32. Dye preparations, characterized in that they have at least one sulfo-free azo compound of the formula contain, in which R ^ is an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, Z, a radical of the formulas = NH or - is, Z ₂ "is a residue of the formulas = NR ₂ , -NHR ₂ , - 409844/0898 j- or -SR, -, where R. ,, R-? and R _; in each case hydrogen or optionally substituted Atoms / alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radicals are, R 1 and Rj, together with the nitrogen atoms connected to them, can form a five- or six-membered ring, R ^ is a hydrogen atom, an alkyl, aralkyl -, Cycloalkyl, aryl or heteroeyelic radical, R, - is a hydrogen atom, an alkyl, aralkyl, cycloalkyl, aryl or heteroeyelic radical, Z _{v is} a radical of the formulas -NHR ₁ ISt, Y is a radical of the formulas -CONH ₂ or -CN, and D is the radical of an aromatic or heterocyclic diazo component, the dihydropyridine ring A being substituted only by a double-bonded nitrogen atom and containing two double bonds. 33 · Dye preparations according to claim 32, characterized in that characterized in that they contain a dispersant. 3 ^. Dye preparations according to claims 32 and 33j characterized in that they contain an organic solvent. 35 · Amines of the formula 409844 / 089H where R- is an optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, Z is a radical of the formulas = NH or -NH ₂ , Z _{2 is} a radical of the formulas = NR ₂ , -NHR ₂ , -NRoRa, -ORc or -SR, -, where R ^, Ro and R, each hydrogen atoms or optionally substituted alkyl, aralkyl,
Are cycloalkyl, aryl or heterocyclic radicals, R ₀ and R,
together with the nitrogen atom connected to them one
Can form five- or six-membered rings, R ₁ - is a hydrogen atom, an alkyl-j aralkyl, cycloalkyl, aryl or heterocyclic radical, R / - is a hydrogen atom, an alkyl, aralkyl, cycloalkyl, aryl or is a heterocyclic radical, Z- is a radical of the formulas
= NR or -NHR, Y is a radical of the formulas -CONH ₂ or -CN,
wherein the dihydropyridine ring A is only substituted by a double bonded nitrogen atom and contains two double bonds. 409844/0898