DE2515662A1 - HYDRO-SOLUBLE AZO DYES - Google Patents

Description

where D

R ^ to

LeA15945

the radical of an aromatic carbo- or heterocyclic diazo component is independently hydrogen, optionally substituted alkyl, cycloalkyl, aryl or aralkyl or each R ₁ with Rp, R ^ with R ^ and R ₁ - with Rg together with the respective N atom 5- to 7-membered heterocycle can form,

represents SO ₃ H, OSO, H or B -SO ₂ -NH-SO ₂ and represents C ^ -C ^ -alkyl or optionally substituted aryl,

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Ί Ο. Hydrogen, CN, CONH ₂ , CONT ₁ T ₂ , SO ₂ T ₁ , C0 ₂ T _£ , COT ₁ ,

NO ₂ , halogen or SO ^ H, where T _{1 is} alkyl, cycloalkyl, aryl or aralkyl and T _{2 is} hydrogen or T ₁ or, together with T ₁ and the N atom, forms a 5- to 7-membered heterocycle and
η means the numbers 1, 2, 3 or 4.

Suitable diazo components D are, for example, those of the benzene or naphthalene series, of the azobenzene, phthalimide, thiazole, benzthiazole, 2-phenylbenzthiazole, triazole or thiadiazole, which are replaced by halogen, C ^ -C ^ -alkyl, trifluoromethyl, C ₁ -C ^ -AIkOXy , C ₁ -C.-alkylsulphonyl, cyano, phenylsulphonyl, nitro, carboxyl, sulfo, C ₁ -Cλ-alkylsulphonylaminosulphonyl, _{phenylsulphonylaminosulphonyl optionally substituted by halogen or C 1} -C, -alkyl, carbonamide, sulphonamide, by C ₁ - C / alkyl, which can also be hydroxy-, C ₁ -C ^ -alkoxy- or cyano-substituted, cyclohexyl or phenyl mono- or di-substituted carbonamide or sulfonamide, carboxylic acid piperide, morpholide, pyrrolidide, sulfonic acid piperide, morpholide, - pyrrolid, C ₁ -C ^ - alkylcarbonylamino, phenylcarbonylamino, which can also be substituted by halogen, methyl, methoxy or nitro, C ₁ -C, -alkylsulfonylamino, phenylsulfonylamino, which can also be substituted by halogen, methyl, methoxy or nitro or Benzothiazole yl can be substituted.

The alkyl radicals R ₁ to Rg as well as T ₁ and T ₂ are saturated or unsaturated, preferably have 1 to 8 carbon atoms and can, for example, by cyano, hydroxy, C ₁ -C ₈ -alkoxy, carboxyl, C ₁ -Cg-alkOXycarbonyl , SuIfο, SuIfato, optionally by C ^ C ^ -alkyl, cyclohexyl or phenyl mono- or di-substituted amino, ^ -C ^ -Alkylcarbonylamino, Phenylcarbonylamino, C ₁ -C ^ -AlkyIsulfonylamino, Phenylsulfonylamino, Carbonamid, Phenoxy, Benzyloxy, Sulfonamide, F, Cl or Br may be substituted. Particularly preferred alkyl radicals are C ₁ -C ^ -alkyl radicals substituted by CN, OH, C ₁ -C ^ -AIkOXy or optionally

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mono- or di-substituted amino, morpholino, piperidino or pyrrolidino can be substituted by C ₁ -C 6 -alkyl, cyclohexyl or phenyl.

Cycloalkyl radicals for R. to Rg and also T ₁ and T _{2 are} preferably cyclohexyl radicals, which can be substituted, for example, by 1 to 3 methyl radicals.

Suitable aryl radicals R ₁ to Rg as well as T ₁ and T ₂ are especially optionally 1 to 3 times by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, sulfonyl, C 1 -C 4 -alkylsulfonylaminosulfonyl Phenylsulfonylaminosulfonyl or cyano-substituted phenyl radicals, optionally substituted by halogen or C1- (V-alkyl, where halogen is preferably understood to mean chlorine. Preferred are phenyl and tolyl).

Suitable aralkyl radicals R ₁ to Rg and T ₁ and T ₂ are preferably benzyl or phenylethyl radicals which are substituted, for example, 1 to 3 times by chlorine, sulfo, C ^ Cλ-alkylsulphonylaminosulphonyl, optionally by halogen or C ₁ -C, -alkyl Phenylsulfonylaminosulfonyl, C.-C / -alkyl or C, -C ^ -alkoxy can be substituted.

Suitable heterocycles which R ₁ and R ₂ , R, and R ^, R ₅ and Rg as well as T ₁ and T ₂ , including the N atom, can form together are unsaturated heterocycles such as pyrazole, imidazole, benzimidazole, indole or indazole, and - preferably - saturated heterocycles such as pyrrolidine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, hexamethyleneimine and pyrazolidine.

Suitable halogen are in particular fluorine, chlorine and bromine. Suitable aryl groups B are phenyl radicals which are optionally substituted _{by halogen or C 1 -C 4 -alkyl.}

In the dyes of the formula I according to the invention, Z is preferably either alone in the radical D or alone in the radicals R ₁ to Rg, in particular if these contain a phenyl radical.

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In the context of the formula I, dyes which are not preferred are those of formula

(II)

wherein

for CN, CONH ₂ , CONT ₃ T ^ or hydrogen, for C -C alkyl, cyclohexyl, phenyl or benzyl which is optionally substituted by C 1 -C 4 alkoxy; for hydrogen or T-, stand or

T, and Tr together with the N atom form a pyrrolidine, piperidine,

Can form morpholine or N-methylpiperazine ring, ρ denotes the numbers 1 or 2 and D, R ₁ - Rg and Z have the meaning given above.

Dyes of the formula are particularly preferred

NHR

-N = N

(III)

wherein

Ry and Rg are hydrogen or C ^ -Cg-alkyl which _{can be substituted by C 1} -C ^ - alkoxy and

Mean Rq and R, Q is hydrogen, optionally substituted by C ₁ -Cr alkoxy, CN, OH, ΝΤ-, Τ ^ or phenoxy-substituted C ₁ -CG alkyl, cyclohexyl, phenyl or benzyl and

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D, Z, ρ, Q ₁ , T, and T, have the meanings given above.

In the context of the formula II, very particularly preferred dyes are again those of the formula

NHR _C

(IV)

wherein

Z, p, Ry, Rg, Rq and R ₁ Q have the meaning given above and

D _{1 represents} a diazo component of the benzene, azobenzene or naphthalene series which is optionally substituted by the substituents mentioned on page 2.

Of the dyes of the formula IV, preference is given to those in which the water-solubilizing groups Z are bonded _{to the diazo component D 1. D 1 is} very particularly preferably a sulfophenyl radical which is optionally substituted by chlorine, bromine, C ₁ -C 4 -alkyl, C ₁ -C 4 -alkyl, trifluoromethyl or cyano.

The dyes of the formula I are prepared by adding amines of the formula

D-NH.

(V)

wherein
D.

has the meaning given above,

diazotized and with coupling components of the formula

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- 5th
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K NR /

^R 6

wherein

R. to Ra and Q have the meaning given above,

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and the components V and VI are chosen so that the dyes contain 0 to 4 groups Z, where Z is the above Has meaning and, in the event that the dyes have no group Z, the dyes sulfonated with sulfuric acid or sulfated.

Diazotization and coupling take place according to methods known per se.

The sulfonation or sulfation is expediently carried out at about 70 to 100% sulfuric acid or oleum with up to 25% SO ^ content at temperatures of about 0 to 100 ⁰ C, preferably below about 40 C by methods known per se.

Suitable amines of the formula V are, for example:

Aniline, 2-, 3- and 4-chloro-aniline, 2-, 3- and 4-bromoaniline, 2-, 3- and 4-nitroaniline, 2-, 3- and 4-toluidine, 2-, 3- and 4-cyananiline, 2,4-dicyano-aniline, 3,4- or 2,5-dichloro-aniline, 2,4,5-trichloro-aniline, 2,4,6-trichloro-aniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline, 4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 2-methoxy-4-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-amino-2-nitrobenzene-4-sulfonic acid- (n) -butylamide or -ß-methoxyethylamide, 1-amino-benzene-4-methylsulphone, 1-amino-2,6-dibromobenzene-4-methylsulphone, 1-Amino-2, ö-dichlorobenzene ^ -methylsulfone, 3,5-dichloroanthranilic acid methyl ester, propyl ester, β-methoxyethyl ester, -butyl ester, 3,5-dibromanthranilic acid methyl ester, ethyl ester, (n) or (i) propyl ester, (n) or (i) butyl ester, -ß-methoxy-ethyl ester, N-acetyl-p-phenylenediamine, N-acetyl-m-phenylenediamine, N-benzenesulfonyl-p-phenylenediamine, 4-amino-acetophenone, 4- or 2-aminobenzophenone, 2- and 4-aminodiphenyl sulfone, 2-, 3- or 4-aminobenzoic acid methyl ester, ethyl ester, propyl ester, butyl ester, isobutyl ester, β-methoxyethyl ester, -ß-ethoxyethyl ester, -methyl diglycol ester,

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ethyl diglycol ester, methyl triglycol ester, 3- or 4-aminophthalic acid, 5-amino isophthalic acid or aminoterephthalic acid dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, 3- or 4-aminobenzoic acid amide, -methylamide, -bpropylamide, - isobutylamide, -cyclohexylamide, ß-ethyl-hexylamide, -jf-methoxy-propylamide, 2-, 3- or 4-aminobenzoic acid-dimethy1-amide, -diethylamide, -pyrrolidide, -morpholide, 5-amino-isophthalic acid diamide, 3- or 4-Amino-phthalic acid imide, -ß-hydroxyethylimide, methylimide, ethylimide, tolylimide, 4-aminobenzenesulfonic acid dimethylamide, diethylamide, pyrrolidide, morpholide, 3- or 4-aminophthalic acid hydrazide, 4-amino naphtha 1 acid ethylimide, butylimide, methoxyethylimide, 1-amino-anthraquinone, 4-amino-diphenylene oxide, 2-amino-benzothiazole, 4- and 5-nitronaphthylamine, 4-amino-azobenzene, 2 ', 3-dimethyl 4-amino-azobenzene, 3 ', 2-dimethyl-4-amino-azobenzene, 2,5-dimethyl-4-amino-azobenzene, 2-methyl-5-methoxy-4-amino-azobenzene, 2-methyl-4 ', 5-dimethoxy-4-amino-az topzol, 4'-chloro-2-methyl-5-methoxy-4-amino-azobenzene, 4 '-nitro ^ -methyl ^ -methoxy ^ -amino-azobenzene, 4 ^! -Chlor-2-methyl-4-amino-azobenzene, 2,5-dimethoxy-4-amino-azobenzene, 4'-chloro-2,5-dimethoxy-4-amino-azobenzene, 4'-nitro-2,5 -dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethyl-4-amino-azobenzene, 4'-methoxy-2,5-dimethyl-4-amino-azobenzene, 4'-nitro-4-amino- azobenzene, 3,5-dibromo-4-amino-azobenzene, 2,3'-dichloro-4-amino-azobenzene, 3-methoxy-4-amino-azobenzene, 1-amino-naphthalene-4-sulfonic acid, i-amino -2-, -3- or -4-benzenesulfonic acid, i-amino-4-chlorobenzenesulfonic acid- (2), 1-amino-4,5-dlchlorobenzenesulfonic acid- (2), 1-amino ^ -methyl-S- chlorobenzenesulphonic acid (2), 1-amino-2,5-dichlorobenzenesulphonic acid (4), 1-amino-4-ethylbenzenesulphonic acid (2), 2-amino-naphthalene- (1) -sulphonic acid, 1-aminobenzene- 2,4-disulfonic acid, 3- (4-aminophenylazo) -4-chlorobenzenesulfonic acid, 3-chloro-, 4- (3-sulfo-4-aminophenylazo) -benzenesulfonic acid, N- (4-methyl-x-sulfophenyl) -3 -aminophthalimide, N- (2-sulfatoethyl) -3-aminophthalimide, 2-methyl-4- (2-methylphenylazo) -aniline, 3-methyl-4- (3-methylphenylazo) -aniline, 3-methyl-4- ( 4-chlorophenyl azo) -aniline, 4- (4-sulfophenylazo) -aniline, 2,5-dimethyl-4- (4-sulfophenylazo) -aniline, 2,5-dimethoxy-4- (4-sulfophenylazo) -

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aniline, 2-methoxy-4- (4-sulfophenylazo) -5-methylaniline, 4- (3-sulfophenylazo) -aniline, 2,5-dimethyl-4- (3-sulfophenylazo) -aniline, 2,5-dimethoxy- 4- (3-sulfophenylazo) -aniline, 2-sulfo-4- (4-sulfophenylazo) -aniline, 1-amino-4- (4-sulfophenylazo) -naphthalene-6-sulfonic acid, 1-amino-4- (4 sulfophenylazo) naphthalene-7-sulfonic acid, 2- (4-aminophenyl) -6-methyl-7-sulfobenzothiazole, 2- (3-sulfo-4-aminophenyl) -6-methyl-7-sulfobenzothiazole, 2-amino xsulfobenzthiazole, 2-, 3- and 4-amino-benzoic acid methyl ester, -ethyl ester, - (η) - and - (i) -propyl ester, -β-methoxyethyl ester, 2-amino-3,5-dichlorobenzoic acid methyl ester , -ethyl ester, - (i) -propyl ester, 2-amino-3,5-dibromo-benzoic acid methyl ester, -ethyl ester, -β-methoxy-ethyl ester, 3-bromo-4-aminobenzoic acid ethyl ester, aminoterephthalic acid diethyl ester, 2 -Amino-benzonitrile, 2,4-dicyan-aniline, 2-amino-5-chlorobenzonitrile, 2-amino-5-bromobenzonitrile, 2-amino-3-bromo-5-chlorobenzonitrile, 2-amino-3 , 5-dibromo-benzonitrile, 2-amino-3,5-dichloro-benzonitrile, 2-amino-1-trifluorometh yl-benzene, 2-amino-5-chloro-trifluoromethylbenzene, 4-aminobenzene-1-methylsulphone, 3-chloro-4-aminobenzene-1-methylsulphone, 2-amino-diphenylsulphone, 4-amino-diphenylsulphone, 3- and 4 Aminophthalic acid-ß-hydroxyethylimide, 3- and 4-aminophthalic acid-ß-methoxyethylimide, 3- and 4-aminophthalic acid-butylimide, -tolylimide, 1-amino-4-nitrobenzene, 1-amino-4-acetylamino-benzene, 1- Amino-3-acetylaminobenzene, 4-amino-benzoic acid amide, 4-aminobenzoic acid-N-methylamide, -N-butylamide, N-ß-ethylhexylamide, 4-amino-benzoic acid-N, N-diethylamide, 3- and 4- Amino-benzenesulfonic acid amide, 3- and 4-Amino-benzenesulfonic acid-N-butylamide, 3- and 4-Amino-benzenesulfonic acid-morpholide, 2-Amino-5-chlorobenzenesulfonic acid- (1), 2-Amino-4,5- dichlorobenzene sulfonic acid (1), 2-amino-4-chloro-5-methyl-benzenesulfonic acid (1), 4-amino-3,6-dichlorobenzenesulfonic acid (1), 4-amino-3,6-dibromobenzenesulfonic acid (1), 4-amino-azobenzene, 4-amino-3,5-dibromo-azobenzene, 2,5-dimethyl-4- (2-chloro-5-sulfophenylazo) -aniline, 2,5-dimethyl-4- (2-methoxy-5-sulfophenylazo ) -aniline, 2,5-dimethoxy-4- (2-chloro-5-sulfophenylazo) -aniline, 2-methoxy-4- (3-sulfophenylazo) -aniline, 2-methoxy-4- (2-chloro-5 -sulfophenylazo) -5-methylaniline, 2,5-dimethoxy-4- (2,5-dichloro-4-sulfophenylazo) -aniline, 1-amino-4- (2,5-

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dichloro-4-sulfophenylazo) -naphthalene-7-sulfonic acid, 1-amino-4- (2,5-dichloro-4-sulf ophenylazo) -naphthalene-7-sulfonic acid, 1 amino-4- (3-sulfophenylazonaphthalene-7-sulfonic acid and 1-amino-4-phenylazonaphthalene-6- or -7-sulfonic acid.

Several synthetic routes are possible for the preparation of the coupling components VI.

One method is characterized in that compounds of the formula

(VII)

wherein

Q ¹ is CN or a carbonamide group, by treatment with POCl, and / or PCI, - - expediently in the presence of tertiary organic bases such as pyridine or dime thy lanilin and temperatures from 100 to 160 ⁰ C - in the compound of formula

(VIII)

Cl ' N "Cl

transferred, then the halogen atoms contained therein against amino groups or radicals defined in more detail above Exchanges nitrogen heterocycles and, if desired, then the cyano group in a manner known per se in a Amide or ester group (see e.g. Dutch patent application 7 216 930).

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-A4-

The conversion of the cyano group into an amide group can also be after the substitution of the chlorine atoms are made to amino groups, for example by treatment with 70-90% sulfuric acid at 70-100 ⁰ C (cf., for example German Offenlegungsschrift No. 2,062,717.).

The compounds of the formula VII are known (cf. Arch. Pharm. 296 , 501 (1963)).

Suitable solvents for the exchange reaction of the chlorine atoms for the amino groups are, for example, methanol, ethanol, butanol, acetone, β-methoxyethanol, dimethyl sulfoxide, dimethylformamide or ethylene glycol dimethyl ether. The reactions can also be carried out under pressure. To bind the hydrogen chloride released during the reaction with amines, either excess amine or acid-binding agents such as Na ₂ CO ^, NaHCO, or MgO are used.

Another method of representing VI is characterized by that one pyridinium salts of the formula

(IX)

egg (-)

with at least 2 equivalents of an amine HNR ₅ R g at temperatures of 80 to 200 ⁰ C, preferably 100 to 150 ° C, reacting and converting the cyano group in manner known per se in ester or amide groups.

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Suitable amines HNR ₅ Rg are, for example, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, n-hexylamine, n-octylamine, 2-hydroxyethylamine, 2-cyanoethylamine, 2-methoxyethylamine, 2-ethoxyethylamine , 3-hydroxypropylamine- (1), 3-methoxypropylamine- (1), 3-ethoxypropylamine- (1), 3-butoxypropylamine- (1), 3-aminopropyl-2-ethyl-hexyl ether, 4-hydroxyidutylamine- (1) , 4-ethoxybutylamine- (1), 1, 4-diaminot> utane, 1-amino-4-dimethylaminobutane, dimethylamine, diethylamine, di-i-propylamine, di-n-propylamine, di-n-butylamine, methylbutylamine, ethylbutylamine , Methylhexylamine, pyrrolidine, piperidine, morpholine, N-methylpiperazine, cyclohexylamine, 4-amino-1-methylcyclohexane, aminomethylcyclohexane, aniline, o-, m- or p-aminotoluene, benzylamine, 1-amino-1-phenylethane, 1-amino -2-phenylethane.

The reaction of IX with these amines takes place either in excess amine or in the presence of an inert one Solvents such as chloroform, acetonitrile, tetrahydrofuran, ethanol and others - if necessary under pressure.

The pyridinium salts IX are partly from Angew. Chemie 84, 1184 (1972) known or according to the method described there available.

Suitable coupling components are, for example, the compounds listed in the tables below.

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NHR

R,

R ₉ ^R 10 CH ₃
C ₂ H ₅
C ₃ H ₇
C ₄ H ₉ R ₇ - (CH ₂ ) ₃ -0-CH (C ₂ H ₅ ) - (CH ₂ ) ₄ -
-CH ₃ C ₄ H ₉
^C 6 ^H 13
C ₄ H ₉
CH ₃ ^R 8 3 KKKK CH ₂ phenyl
CH ₂ -CH ₂ -phenyl -CH ^ -CH ^ -CH ^ -OH CH ₃
CH ₃ C ₄ H ₉
^C 6 ^H 13
^C 4 ^H 9
CH ₃ CH ₃ H
H LfM CT \
K ^ CM ^
BB 8
CM CM CM
KKK
CM CM CM
KKK WlIQ VlIn vliQ \ Ji 1 CH ₃
CH ₃
CH ₃ CH ₃
CH ₃ CH ₃ KKK CH ₂ -CH ₂ -CH ₂ -OCH ₃
CHp —CHp — CHp — OC pH (-
CHp-CHp-CHp-OCλHq -CH ₂ -CH ₂ -CH ₂ -CH ₂ -OH C ₂ H ₅
CH ₃ KM KM KM
WK, K CH ₃ KKK CH ₂ -CH ₂ -CH ₂ -CN C ₃ H ₇ LfM LO
KMK K
K CM CM ^C 4 ^H 9 H CH ₂ -CH ₂ -CHp-CH ₂ -NH ₂ CH ₃ C ₃ H ₇ CH ₃ H CH ₂ -CH ₂ -CH ₂ -NHCH ₃ CH ₃ CH H CH ₂ -CH ₂ -OCOOCH ₃ CH ₃ H CH ₃ H H CH ₃ H

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-CHq-CHq "CH

2-

-CH ₂ - (CH ₂ ) 3-CH ₂ - -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - -CH ₂ -CH ₂ -NCH ₃ -CH ₂ -CH ₂ - -CH = N-CH = CH-

R ₉ ^R 10 R ₇ ^R 8 H CH ₂ -CH ₂ -CH ₂ -OCOC ₂ H ₅ CH, CH ₃ H CH ₂ -COOCH ₃ C ₂ H ₅ CH ₃ H CH ₂ -CH ₂ -COOCH ₃ CH, CH ₃ H CH ₂ -CH ₂ -COOC ₂ H ₅ C ₂ H ₅ C ₂ H ₅ H CH ₂ -CH ₂ -COOH CH ₃ CH ₃ H Cyclohexyl Cyclohexyl Cyclohexyl H CH ₂ cyclohexyl CH ₃ CH ₃ CH, CH ₃ C ₄ H ₉ C ₄ H ₉ C ₂ H ₅ C ₂ H ₅ CH ₃ CH ₃ C ₃ H ₇ C ₃ H ₇ CH ₃ C ₂ H ₅ C ₄ H ₉ C ₄ H ₉ CH ₃ CH ₃ CH ₃ ^C 4 ^H 9 CH ₃ CH ₃ CH ₃ CH ₂ -CH ₂ -CH ₂ -OCH ₃ CH ₃ CH,
3

CH ₃ CH ₃ C ₂ H ₅ C ₂ H ₅ CH ₃ CH ₃ CH ₃ CH ₃ C ₂ H ₅ C ₂ H ₅

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NH- (CH _{2) n} -0- (CH _{2) m} CN -H

(CH ₂ ) _n -0- (CH ₂ ) _m -H

R ₉ ^R 10 CH ₃ η m H C ₂ H ₅
C ₃ H ₇
^C 4 ^H 9 3 2 H
H
H CH ₂ phenyl
CH _£ -CH ₂ -phenyl 3
3
2 2
1
1 H
H . CH ₂ -CH ₂ -OCH ₃ 2
2 1
2 H CH ₂ -CH ₂ -OC ₂ H ₅ 2 2 H CH ₂ -CH ₂ -OC ₄ H ₉ 3 2 H CH ₂ -CH ₂ -CH ₂ -OCH ₃ 2 1 H CHo — CHo -CHo — 00 oHp- 2 1 H CH ₂ -CH ₂ -CH ₂ -OC ₄ H ₉ 2 1 H - (CH ₂ ) ₃ -0-CH (C ₂ H ₅ ) - (CH ₂ ) ₄ -CH ₃ 2 1 H -CH ₂ -CH ₂ -CH ₂ -OH
-CH ₂ -CH ₂ -CH ₂ -CH ₂ -OH 2 1 H
H CH ₂ -CH ₂ -CH ₂ -CN 3
2 OvJ OJ H CH ₂ -CH ₂ -CH ₂ -CH ₂ -NH ₂ 3 2 H CH ₂ -CH ₂ -CH ₂ -NHCH ₃ 3 2 H 2 2

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R ₉ ^R 10 CH ₂ -CH ₂ -OCOCH ₃ η m H CH ₂ -CH ₂ -CH ₂ -OCOC ₂ H ₅ 3 1 H CH ₂ -COOCH ₃ 3 1 H CH ₂ -CH ₂ -COOCH ₃ 3 2 H CH ₂ -CH ₂ -COOC ₂ H ₅ 2 1 H CH ₂ -CH ₂ -COOH 2 1 H Cyclohexyl 3 2 H CH ₂ cyclohexyl 3 2 H CH ₃ 3 2 CH ₃ ^C 2 ^H 5 3 2 C ₂ H ₅ C ₃ H ₇ 3 2 C ₃ H ₇ C ₄ H ₉ 2 2 C ₄ H ₉ C ₄ H ₉ 2 1 CH ₃ CHp-CHp- CHp- OCH ·? 0 2 2 CH ₃ 3 . 1

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^R 9 ^R 10 n m "CHp-CHp-CHp ^e CHp— 3 1 3 1 -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - 3 1 -CH ₂ -CH ₂ -NCH ₃ -CH ₂ -CH ₂ - 2 1 -CH = N-CH = CH- 2 1

The new dyes are very suitable for dyeing and printing natural and synthetic polyamide materials. They then give yellow to red dyeings and prints with good results using the customary dyeing and printing processes Fastness properties, especially good light fastness. The good pulling and building ability of the Dyes when dyeing from aqueous liquor in the exhaust process.

The dyes can be in the form of the free acids or their salts, for example the alkali, alkaline earth or ammonium salts are used. Suitable cations are, for example, those of des Lithium, sodium or potassium as well as ammonium, trimethylammonium, Methoxyethylammonium, diphenylbenzylammonium, tetra- (ß-hydroxyethyl) -ammonium or guanidinium.

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Production of the starting connections to the coupling components Example 1-

2,4,6-trihydroxy-nicotinic acid nitrile

To a solution of 11.5 g of sodium in 400 ml of absolute ethanol are added 40 g of diethyl malonate, 28.2 g of ethyl cyanoacetate and 4.25 g of ammonia (as an approx. 25% ethanol solution) and the mixture is heated for 8 to 10 hours autoclave at 110-120 ⁰ C. After cooling, the reaction product is filtered off and dissolved in water. The reaction product is precipitated by adding hydrochloric acid to the aqueous solution. After filtering off with suction and drying, 29 g (77.5 % of theory) of crude 2,4,6-trihydroxy-nicotinic acid nitrile are obtained, which is sufficiently pure for further processing to 2,4,6-trichloro-nicotinic acid nitrile. A sample purified according to the information provided by KE Schulte and R. Mang (Arch. Phar. 296 (1963) 509) was found to be identical to the product obtained by the same authors from diethyl malonate and cyanoacetamide in the presence of sodium ethylate.

Example 2

2,4,6-trichloro-nicotinic acid nitrile

304 g of 2,4,6-trihydroxy-nicotinonitrile be heated together with phosphorous oxychloride in 2 1 autoclave for 6 hours at 150 ⁰ C to give not allowed to rise atm by venting the hydrogen chloride formed the pressure on 10th The phosphorus oxychloride is then distilled off as far as possible from the clear brown solution under reduced pressure and the residue is then poured into ice water. The mixture is then stirred for 2 to 3 hours until the phosphorus compounds are completely hydrolyzed, the temperature of the aqueous suspension not being allowed to rise above 25 ° C. by adding ice. Then the crystalline

Le A 15 945 - 17 -

6098 k 3/0962

251S662

precipitated substance sucked off and washed thoroughly with water. After drying in vacuo 331 g of crude 2,4,6-trichloro-nicotinonitrile ₍₈₀ ^ _theory) of melting point 110 - 115 ⁰ C obtained which can be purified by reprecipitation from about 3 1 benzine. Yield after redissolving with work-up of the mother liquor: 304 g (70 % of theory).

Light brown crystals of melting point 112-115 ° C (literature: 112 ⁰ C 117 ⁰ C).

Production of the coupling components Example 3

16 g of diethylamine are gradually added to 20.75 g of 2,4,6-trichloronicotinic acid nitrile in 150 ml of dimethylformamide, external cooling being used to ensure that the temperature of the reaction mixture does not rise above 40.degree. Stirring is continued at this temperature until thin layer chromatography (silica gel, flow agent methyl chloride, observation under UV light, wavelength 254 nm) no longer shows any starting product. The reaction mixture is then poured into ice water and filtered off with suction. After drying, about 21 g of a crude product, which at 106 - 116 ⁰ C melts. By reprecipitation from methanol 17 g obtained from a melt at 124 C 126 ⁰ compound of the probable formula

The mother liquor contains small amounts of the isomeric compounds

Le A 15 945 - 18 -

609843/0962

24.4 g of 2-diethylamino-3-cyano-4,6-dichloropyridine are suspended in about 250 ml of 30% aqueous methylamine solution in an autoclave for 5 hours at 140 - 150 ⁰ C heated. It is then cooled to about O ⁰ C, suction filtered, and the yellow crystal obtained after drying about 19 g of a compound of the probable formula

NHCH ₃

C H 2 5

^C 2 ^H 5

after recrystallization from ethanol at 130 - 132 ⁰ C melts with decomposition.

Example 4

23.3 g of 2-chloro-3-cyano-4-methylamino-6-amino-N-methyl-pyridinium chloride (prepared according to AL Cossey et al., Angew. Chem. 84 , 1184 (1972)) are in about 100 entered g of benzylamine and ^{heated to 130 0} C for 3 to 4 hours. After cooling to approx. 50 ^° C., the solution is added to approx. 300 ml of ice water, a yellowish oil separating out and slowly crystallizing. It is filtered off with suction, washed with water and dried, and 19-20 g of the compound are obtained

Le A 15 945 - 19 -

6098 4 3/0962

-Ur

NHCH,

ι D

CH ^ -NH

after recrystallization from ethanol at 148 - 153 ⁰ C melts with decomposition.

Example 5

32.1 g of 2-chloro-3-cyano-4- (ß-methoxyäthylamino) -6-amino-N- (ßmethoxyäthyl) pyridinium chloride are used in approximately 120 g of n-butylamine in an autoclave for 4 hours at 130 ⁰ C heated.

The excess n-butylamine is then distilled off and the light brown oil that remains is dissolved in approx. 200 g of glacial acetic acid. This solution contains 27 g of the compound

NH-CH ₂ -CH ₂ -OCH,

ί- (CHo), -CH, CH ₂ -CH ₂ -OCH,

and is used for further reactions without purification. Example 6

20.7 g of 2-chloro-4-aminobenzenesulfonic acid are _{diazotized with aqueous NaN0 2} solution and treated with 23.3 g of 4,6-bis (methylamino) -3-cyano-2-butylamino-pyridine, dissolved in approx 100 ml of glacial acetic acid, coupled at pH 3-4. After the coupling has ended, the dye is precipitated by adding sodium chloride, filtered off with suction and dried at about 50 ° C. in a vacuum. In the form of the free acid, it corresponds to the formula

Le A 15 945 - 20 -

609843/0982

NHCH ₃ NHC ₄ H ₉

and results in polyamide and base modified polyacrylonitrile fibers strong yellow colorations with good light and wet fastness properties.

Example 7

24.1 g of 2-amino-4,5-dichlorobenzenesulfonic acid are diazotized as usual and, in the weakly acidic range, with 26.7 g of 4,6-bis- (methylamino) -3-cyano-2-benzylamino-pyridine, dissolved in 100% ml glacial acetic acid, coupled. After coupling, the dye is precipitated by adding sodium chloride, filtered off with suction and ^{dried at about 60 °} C. in vacuo. In the form of the free acid, it corresponds to the formula

Cl. ^ SO, H

3 "NHCH ₃

and produces strong yellow dyeings with good light and wet fastness properties on polyamide fibers.

Example 8

42.9 g of the dye of the formula

Le A 15 945 - 21 -

6 0 9 8 4 3/0962

2b15662

NHCH,

- (CH ₉ ), -OH

produced by coupling diazo-filled 2,4-dinitroaniline to 4,6-bis (methylamino-3-cyano-2- (3-hydroxypropyl) aminopyridine, are introduced into about 120 g of 100% sulfuric acid at room temperature and The mixture is then poured onto a mixture of 500 g of ice, 100 ml of 50% strength sodium hydroxide solution and 50 g of sodium chloride and, after cooling to 0 to 10 ^° C., the precipitated dye of the formula is filtered

NHCH ₃ NH- (CH ₂ ) ₃ -0-S0 ₃ Na

off, washed with NaCl solution and dried. You get so a dark red powder that dyes polyamide fibers in strong red tones with good fastness properties.

Analogously to the procedure described in the examples, the in the following table by specifying diazo and coupling component to produce characterized dyes.

Le A 15 945

22 -

6 0 9 8 '. 3/0 9 B 2

VJl

-P- VJl

NHR ₁

D-N = N

CN

No.

CO 00 -ίου

* ■ * ·> ro σ v> j CD,

2)

4)

5)

H0, S

Cl

H0, S-

f ~ \

Cl

^: 4 ^H 9

C ₄ H ₉

CH ₂ -CH ₂ -OCH ₃

CH ₂ -CH ₂ -OCH,

CH,

R.

^C 4 ^H 9

C ₄ H ₉

CH ₂ -CH ₂ -OCH ₃

CH ₂ -CH ₂ -OCH,

CH

R,

CH ₂ -C ₆ H ₅

(CH ₂ ) ₃ -0CH ₃

C ₄ H ₉

C ₄ H ₉

CH ₂ -C ₆ H ₅

hue

yellow

yellow

yellow

yellow

yellow

f ¹ ft

VJl

VO .ρ-VJi

No

OT -p-

6)

7)

8th)

9)

10) 11) 12)

^C1

Cl

Cl

CH

CH

CH ₂ -CH ₂ -OCH ₃

C ₂ H ₅

C ₄ H ₉

₃ H ₇

CH ₂ -CH ₂ -OCH

CH

GH

CH ₂ -CH ₂ -OCH

C ₂ H ₅

C ₄ H ₉

₃ E ₇

CHp- CHp- OCH

H ^-

C ₄ H ₉

CH ₂ -C ₆ H ₅

CH ₂ -C ₆ H ₅

CH ₂ -CH ₂ -OCH

₄ H ₉

C ₄ H ₉

CH ₂ -C ₆ H ₅

hue

yellow

yellow

yellow

yellow

yellow

yellow

yellow

VD -Ρ " VJl

No. D. R ₇ ^R 8 R ₉ ^R 10 hue Cl SO ₃ H 13) C / · CH ₃ CH ₃ H CH ₂ -CH ₂ -OCH ₃ yellow ClSO ₃ H 14) Kr C ₂ H ₅ C ₂ H ₅ H C ₄ H ₉ yellow ά 15) HO ₃ S ^ CH ₃ CH ₃ H (CHg) ₃ -OCH ₃ yellow 16) ° 2 ^Ν \ / CH ₃ CH ₃ H CH ₂ -C ₆ H ₅ orange SO ₃ H 17) CH ₃ CH ₃ H C ₄ H ₉ Red

cn cn K:

ir ¹

(O

vji
vo

VJl

cn I. σ IV) CD cn OO ■ ί CD CD

No.

18)

19)

20)

21)

22)

23)

F?

CH

OCH

ci

CH ₂ -CH ₂ -SO ₃ H

CH

CH

CH

C ₂ H ₅

CH

CH

CH

CH ₃

CH

C ₂ H ₅

CH

CH

CH ₂ -C ₆ H ₅

C ₂ H ₅

(CH ₂ ) ₃ -OCH

₄ H ₉

CH ₂ -CH ₂ -OCH ₃

4 ^H 9

hue

Red

Red

yellow

yellow

yellow

golden yellow

■ ro cn

-eco

No.

24)

25)

26)

27)

28)

29)

Cl

O ₂ N

H ₃ C

Cl

Cl

Cl

•8th

CH

CH

CH,

CH

CH

CH

10

hue

C ₄ H ₉

(CH ₂ J ₃ -OSO ₃ H

C.

~ CHp ~ * CHp ^- CHp ""

SO.H

orange

yellow

Scarlet fever

orange

yellow

orange

cn cn cn

VJl VO VJl

No.

30)

3D

σ> I. 32) σ IV) CD 00 33) QO ο CD CD ro

C ₆ H ₅ -SO ₂ -

SO ₂ -O

R ₇

CH ₂ -CH ₂ -OCH

CH

CHp-CHp-OCH

^{1 line}

CH

R,

H
H

R,

10

(CH ₂ ) ₃ -0S0 ₃ H.

CH ₂ -C ₅ H ₅

^CH 4 " ^C 6 ^H 5

^C 4 ^H 9

hue

Red

yellow

yellow yellow

Claims (8)

Patent claims: where D R ₁ to the remainder of an aromatic carbo- or heterocyclic diazo component is independently hydrogen, optionally substituted alkyl, cycloalkyl, aryl or aralkyl or R ₁ with R2, R- * with Rr and Rc with Rg together with the respective N atom a 5- can form up to 7-membered heterocycle, _a represents SO ₃ H, OSO ₃ H or B-SO ₂ -NH-SO ₂ and represents C ₁ -C ^ -alkyl or optionally substituted aryl, Hydrogen, CN, CONH, CO ₂ T ₂ , COT. 1' for alkyl, NO ₂ , halogen or SO ₃ H, where _{1 is} cycloalkyl, aryl or aralkyl and T _{2 is} hydrogen or T ₁ or, together with T ₁ and the N atom, forms a 5- to 7-membered heterocycle and
the numbers 1, 2, 3 or 4 means. Le A 15 945 -29- 609843/0962 2. Azo dyes according to claim 1, which are in the form of the free acid the formula correspond, wherein Q ₁ is CN, CONH _2, CONT ₃ T ₄ or hydrogen, T ₃ is optionally substituted by C ₁ -C -alkoxy-substituted C ₁ -CG-AIlCyI, cyclohexyl, phenyl or benzyl; T ^ stand for hydrogen or T ₅ or T, and T ^ together with the N atom is a pyrrolidine, piperidine, Can form morpholine or N-methylpiperazine rings, the numbers 1 or 2 means and Rg and Z have the meaning given in claim 1. 3. Azo dyes according to claim 1, which are in the form of the free acid of the formula -N = N NHR correspond Le A 15 -30- 609843/096 2 R ₇ and R _{8 are} hydrogen or C ^ Cg-alkyl which can be substituted _{by C 1 -C ^ and} Hydrogen, optionally by C ₁ -C ₄ -AlkOXy, CN, OH, ΝΤ-, Τ / or phenoxy-substituted C ₁ -C / - alkyl, »3 4" 10 Mean cyclohexyl, phenyl or benzyl and and T _{4 has} the meaning given in claim 2 R _g and D, Z, p, *1'
to have. 4. Azo dyes according to claim 1, which are in the form of the free acid of the formula NHR _C - Z. wherein
Z, p, R ₇ Rg, Rq and R _{10 have} the meaning given in claim 3 have and D ₁ for optionally by halogen, C ₁ -C ₄ -A ^ yI, trifluoromethyl, C ₁ -C ₄ -AIkOXy, C ₁ -C ₄ -alkylsulfonyl, cyano, phenylsulfonyl, nitro, carboxyl, sulfo, C ₁ -C ₄ -Alkylsulfonylaminosulfonyl, optionally substituted by halogen or C ₁ -C ₄ -A ^ yI-substituted phenylsulfonylamino sulfonyl, carbonamide, sulfonamide, by C ₁ -C ₄ -alkyl which is also hydroxy-, C ₁ -C ₄ -alkoxy- or cyano-substituted can, cyclohexyl or phenyl mono- or di-substituted carbonamide or sulfonamide, carboxylic acid piperide, morpholide, pyrrolidide, sulfonic acid piperide, morpholide, pyrrolide, C ₁ -C ₄ -alkylcarbonylamino, phenylcarbonylamino, which is also replaced by halogen, methyl, methoxy or Nitro can be substituted, C ₁ -C ₄ -alkylsulfonylamino, phenylsulfonylamino, which is still by Le A 15 945 -31- 609843/0962 Halogen, methyl, methoxy or nitro can be substituted or benzothiazolyl-substituted phenyl, phenylazophenyl or naphthyl. 5. azo dyes according to claim 4, wherein D ₁ denotes a sulfophenyl radical which is optionally substituted by chlorine, bromine, C _{1 -C alkoxy, trifluoromethyl or cyano.} 6. Process for the production of azo dyes, characterized in that that one diazotized amines of the formula D - NH ₂ wherein D is the radical of an aromatic carbo- or heterocyclic Diazo component means with coupling components of the formula wherein R ₁ to Rg independently of one another denote hydrogen, optionally substituted alkyl, cycloalkyl, aryl or aralkyl or in each case R ₁ with R ₂ , R, with R, and R ₅ with Rg together with the respective N atom are 5- to 7-membered Can form heterocycle, and Q is hydrogen, CN, CONH ₂ , CONT ₁ T ₂ , SO ₂ T ₁ , CO ₂ T ₂ , COT ₁ NO ₂ , halogen or SO ₅ , where T _{1 is} alkyl, cycloalkyl, aryl or aralkyl and T _{2 is} water - Le A 15 945 -32- 609843/0962 substance or T. means or together with I. and the N atom forms a 5- "to 7-membered heterocycle converts and selects the components so that the dyes contain 0 to groups Z,
whereby Z is SO, H, OSO, H or B -SO ₀ -NH-SO ₀ and B is Cj-C ^ -alkyl or optionally substituted aryl and in the event that the dyes do not contain a group Z, the dyes sulfonated or sulfated. 7. A method for dyeing and printing natural and synthetic textile materials, characterized in that one
Dyes according to claim 1 used. 8. With the dyes according to claim 1 dyed or printed natural or synthetic fiber materials. Le A 15 945 -33- 609843/0962