DE2158924A1 - MONOAZO DYES - Google Patents

Description

The present invention relates to new, valuable monoazo dyes, which in the form of the free acid of the general formula

-N = NKA (I) YXN-SO ₂

as well as their production and use for dyeing natural and synthetic fiber materials, especially those made from synthetic polyamides.

In the general formula '(I), R _{1 stands} for hydrogen or alkyl, Rp for hydrogen, halogen, alkyl, alkoxy «, nitro,

Cyan, carbonamide or carboxylic acid ester, Rx for hydrogen, halogen, alkyl or alkoxy, K for a phenylene or naphthylene radical, A for a substituted amino group in the p position to the azo group or a hydroxy or alkoxy group in the o or p position to the azo group,

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X for an -aralkylene or arylene radical and Y for SG ₃ FI or a disulfimide radical -SO ₂

₃
wherein

R ₁ P is alkyl or aryl.

Suitable alkyl radicals are, for example, those with 1 carbon atoms.

The alkyl radicals can optionally be further substituted, for example by hydroxy, cyano, alkoxy, in particular C. -Cr -alkoxy, acyloxy, in particular C ₁ -C ^ -Alkylcarbonylfc oxy or C.-C ^ -alkoxycarbonyloxy, halogen, in particular Cl and - Br, carbalkoxy with preferably 1-4 carbon atoms in the alkoxy group or by optionally further substituted phenyl.

Suitable alkyl radicals are in particular those with 1-4 carbon atoms in the CC chain, such as -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ Hg, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ -OH, -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CO-CH ₇ , -CH ₂ CH ₂ -O-CO-C ₂ H ₅ , -CH ₂ CH ₂ - O-CO-C ₃ H ₇ , -CH ₂ CH ₂ -O-CO-O-CH ₃ , -CH ₂ CH ₂ -O-OC-OC ₂ H ₅ , -CH ₂ CH ₂ -O-CO-OC ^ H ₉ , -CH ₂ -C ₆ H ₅ , -CH ₂ CH ₂ -C ₆ H ₅ , -CH ₂ CH ₂ -Cl, -CH ₂ CH ₂ -COO-CH ₃ , -CH ₂ CH ₂ -COOC ₂ H ₅ .

^ The preferred halogen is chlorine and bromine.

Suitable alkoxy radicals R ₂ and R ₃ are preferably those with 1-4 carbon atoms, for example -OCH ₃ , -OC ₂ H ₅ , 70-C ₃ H ₇ , -0-C ₄ H ₉ .

In addition to the carbonamide group, suitable carbonamide groups are, in particular, carboxylic acid mono- and dialkylamide groups, the alkyl groups preferably having 1-4 carbon atoms in the CC chain and optionally being able to have further substituents, for example hydroxy or cyano =

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Suitable carboxylic acid ester radicals are, in particular, alkoxy «- carbonyl radicals. with 1-4 carbon atoms in the alkoxy group.

Suitable aralkylene radicals X are, for example (f y-CH ₂ ~ and

Suitable aryl radicals are, in particular, phenyl radicals in Dyes can have customary substituents, for example Cj-C / -alkyl.

Suitable arylene radicals X are, for example, 1,2-, 1,3-, 1,4-phenylene and 1,2-, 1,4- and 1,5-Naph.thyl.en * The phenylene rings of the arylene and aralkylene radicals can be further substituted, for example by alkyl, in particular C ₁ -C ₄ -AlCy], such as CH ₃ -, C ₂ H ₅ -, C ₃ H ₇ -, aralkyl such as C ₆ H ₅ CH ₂ -, by ArjO, such as CgHf- , through C, -C. -Alkoxy, such as CH ₇ O-, CpHfO-, aralkoxy such as Cz-Ht-CHpO-, aryloxy such as phenoxy or phenoxy substituted by chlorine, bromine, cyano or nitro.

The phenylene and naphthylene radicals K can also have other substituents customary in azo dyes. The amino group A can be mono- or disubstituted.

Suitable. ! teste -K-A are, in particular residues of the formulas

5 "I) .Ij j

Le A 14 091-3 ~

3 0 Οι? "- '/ ΙΟυδ.

wherein

R / for hydrogen, halogen, an alkyl group, a Alkoxy group or an eylamino group,

Rj- for hydrogen, an alkyl group or a Alkoxy group,

R _{6 stands} for hydrogen or an alkyl group,

Rr ₇ for an alkyl group,

Rn and Rq for hydrogen, an alkyl group, an alkoxy group, a carboxyl group, a carbonamide group, a carbon ester group, an aryl group or halogen,

R _{10 represents} hydrogen or an alkyl group and

R _{11 represents} an aryl radical, halogen or an alkyl group.

Unless otherwise stated, the alkyl and alkoxy groups can have further substituents, for example Cyano, hydroxy, optionally substituted phenyl, alkoxy, acyloxy such as alkylcarbonyloxy and alkoxycarbonyloxy, where Alkyl and alkoxy preferably contain 1-4 carbon atoms.

Preferred alkyl groups R ₄ , R ₅ , Rg, Rg? R ₁₀ and R ₁₁ are not further substituted C 1 -C ₁ ^ -alkyl groups such as -CH- ,, -C ₂ Hp., -C, Hy, iso-C- ^ Hy, -C ^ Hg, 1SO-C ₄ Hg,

Preferred alkyl groups R ₅ ^ a R _{7 are} c

like -CH- ,, -C ₂ Hc * -C-zHU, -C ₄ Hg, iso-C ^ Hy, 1SO-C ₄ Hg, .see-C ₄ Hg, the other substituents like OH, CN, acyloxy, Alkoxy, alkoxycarbonyl, such as the following radicals: -C ₂ H ₄ CN, -C ₂ H ^ OH, -CH ₂ -C ₆ H ₅ , -CH ₂ CH ₂ -C ₆ H ₅ , -C ₂ H ₄ -O-ACyI, -C ₂ H ₄ -0-alkyl and -CgH ^ -COO-alkyl, where alkyl is preferably C ^ -C ₄ -alkyl and acyl is preferably C ₁ -C ^ -alkylcarbonyl or optionally substituted phenylcarbonyl.

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Preferred alkoxy groups are those with 1-4 carbon atoms, such as -OCH ₃ , -OC ₃ H ₇ , -OC ₄ H ₉ , -OCH ₂ CH ₂ OH, -OC ₂ H ₅ .

Acylamino groups R ₄ are in particular taken to mean formylamino, alkylcarbonylamino, phenylcarbonylamino, alkylsulfonylamino and phenylsulfonylamino groups, where the alkyl and phenyl radicals can be further substituted, for example by chlorine or bromine, and the alkyl groups preferably contain 1-4 carbon atoms.

Preferred acylamino groups Rr are for example formylamino, 'acetylamino, propionylamino, butyrylamino, Methylsulf onylamino-, phenylsulfonylamino, Hydroxyacetylamino-, Phenoxyacetylamino-, p- ^c hlorbenzoylamino-, benzoylamino, 2,5-Dichlorbenzoylamino- and Phenylacetylaminogruppen.

Preferred halogen atoms are chlorine and bromine.

Suitable aryl radicals Rg, Rg and R ₁₁ are, in particular, phenyl radicals which can have substituents customary in dyes, for example alkyl, alkoxy, halogen.

In the context of the formula I, those dyes are preferred which are in the form of the free acid of the formula

YXN- O ₃ SAN = NKA (II)

correspond, in which X, Y, R ₁ , R ₂ , R ₇ , K and A have the meaning given above.

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Particularly preferred dyes are those of the formula

YXNO ₂ R,

, -N = NKA R ₃ '

(III)

where X, Y, FLj, K and A have the meaning given above, for hydrogen, chlorine or bromine and

stands for chlorine or bromine,

especially those of the formula

YXNO ₂

R ₂ "

(IV)

Cl

in which X, Y, R ₁ , K and A are as defined above and R ₂ ″ is hydrogen or chlorine.

In the context of the formulas (II) - (IV), those dyes are preferred in which -K-A radicals of the formulas

0-R _IÖ and

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represents, wherein R ^, R, -, Rg, R ₁ - ,, Rg, R ₀ , R ^ ₀ and R ^ _{1 have} the meaning given above.

The new dyes of the formula (I) are produced by taking amines of the formula

R ₃

Y-X-X-O

R ₁

where X, Y, R ^, Rp and R ^ have the meaning given above,

diazotized and with coupling components

H-K-A '(VI)

wherein

A 'is a hydroxyl group or a substituted amino

group represents and
K denotes a phenylene or naphthylene radical,

couples in the o- or p-position to the hydroxyl group or in the p-position to the substituted amino group and then, in the event that A ^{f is} an alkoxy group, alkylates the hydroxyl group.

The diazo components of the general formula (V) are obtained by adding acetylaminobenzene sulfochloride or nitrobenzene sulfochloride of the formula _r

ClO ₂ S

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309022/1 Ü 0 B.

wherein

Z = NOp. Or acetylamino, with amines of the formula

Y-X-N-H

^R 1

where X, Y and R * have the meaning given above,

amidated and the acetyl group is split off by saponification, or the nitro group is converted into the amino group by reduction.

Amines of the formula

R ₁₂ SO ₂ NHSO ₂ -XNH

is obtained in a known manner by reacting sulfonamides of the formula

R ₁₂ SO ₂ NH ₂

with sulfochlorides of the formula

ClO ₂ SXW

wherein

W denotes a nitro group or an acetylamino group,

and. subsequent reduction of the nitro group or splitting off of the acetyl group.

Suitable aminobenzenesulfonamides of the formula (V) are at = for example:

N- (4-Amino-phenyl-sulfonyl) -3-aminophenyl-sulfonic acid, N-methyl-N- (4-amino-2-chlorophenylsulfonyl) -3-aminophenyl-

sulfonic acid, N-ethyl-N- (4-amino-3-chlorophenyl-sulfonyl) -3-aminophenyl-

sulfonic acid,

N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -3 ~ aminophenyl-sul =

fonsäure,

N-methyl-N- (4-amino-2.5-dichloro ~ phenyl-sulfonyl) -3-amino--

phenyl sulfonic acid,

N-methyl-N- (4-amino-3.5-dichloro-phenyl-sulfonyl) -3-amino-

phenyl sulfonic acid,

N-propyl-N- (4-aiiino-3.5-dichloro-phenyl-sulfonyl-3-amino-

phenyl sulfonic acid,

N- (4-Aein © -3-methyl-phenyl-sulfonyl) -3-aminophenyl-sulfon =

acid,

N- (4-Amino-3-i-methoxy-phenyl-sulfonyl) -3-aminophenyl-sulfone =

acid,

N- (4-Amino-3-trifluoromethyl-phenyl-sulfonyl) -3-aminophenyl-

sulfonic acid,

N- (4-Amino-pbenyl-sulfonyl) -4-aminophenyl-sulfonic acid, N - (^ - Amino ^ -chlorophenyl-sulfonyl) -4-aminophenyl-sulfonic acid, N-methyl-N- (4-aeino-3-chloro-phenyl-sulfonyl) -4-aminophenyl-

sulfonic acid,

N- (4-amino-2.5-dichloro-phenyl-sulfonyl) -4-amino-phenyl-sul =

fonsäure, N-Methyl-N-i ^ -aeiino ^ .S-dichlorophenyl-sulfonylJ - ^ - amino-

phenyl sulfenic acid, N-Aethyl-N-i ^ -aeino ^ .S-dichloro-phenyl-sulfonylJ - ^ - amino-

phenyl sulfonic acid, N-methyl-N- (4-amino-3.5-diehlor-ph.enyl-sulfonyl) -4-amino-

phenyl sulfonic acid,

N- (4-Amino-3-aethyl-phenyl-sulfonyl) - ^/ j-aminophenyl-sulfone =:

acid, N - <^ - amino-3-meth »xy-phenyl-sulfonyl) -4-aminophenyl-sulfone =

Le A 14 091 309822/91 & 05 ^acid '

N- (4-Amino-3-trifluoromethyl-phenyl-sulfonyl) -4-amino-phenyl-

sulfonic acid,

N - (* i-Amino-phenyl-sulfonyl) -3-aminophenylmethane-sulfonic acid, N-ethyl-N- (A-aminophenyl-sulfonyl) -3 - aminophenylmeth.an-

sulfonic acid, N - (* i-amino-2-chlorophenyl-sulfonyl) -3- * aminophenylmethane-sul =

Fonsäure, N- (4-Amino-3-chloro-phenyl-sulfonyl) -3-aminophenylmethane-sul =

fonsäure,

N- (4-Amino-2.5-dichlorophenyl-sulfonyl) -3-aminophenylmethanesulfonic acid,

N-methyl-N- (4-amino-2,5-dichloro-phenyl-sulfonyl) -3-amino-phe =

ny! methane sulfonic acid,

N-ethyl-N - (^ - amino-2.5-dichloro-phenyl-sulfnnyl) -3-amino-phe =

nylmethane sulfonic acid,

N-methyl-N- ( ⁱ -amino-3,5-dichloro-phenyl-sulfonyl) -3-amino-phe =

nylmethane sulfonic acid,

N- (4-Amino-3-trifluoromethyl-phenyl-sulfonyl) -3-aminophenyl =

methane sulfonic acid,

N-i ^ -amino-phenyl-sulfonyl) -4-aminophenylmethane-sulfonic acid, N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -4-aminophenylmethane

sulfonic acid,

N-methyl-N- (4-amino-2.5-dichloro-phenyl-sulfonyl) -4-amino-phe = ψ nylmethane-sulfonic acid,

N - (^ - Aaino-3-ethoxy-phenyl-sulfonyl) - ^ - amino-phenylme than-sul =

fonsäure, N - (^ - Amino-3-trifluoromethyl-phenyl-sulfonyl) - ^ - aminophenyl =

methane sulfonic acid, N - (^ - amino-2-chlorophenyl-sulfonyl) -3-amino - ^ - methy1-phenyl-

sulfonic acid, N- (4-amino-3-chloro-phenyl-sulfonyl) -3-amino - ^ - methyl-phenyl-

sulfonic acid,

N- (ii-Amino-2.5-dichloro-phenyl-sulfonyl) -3 ~ amino-4-methyl-phe =

nylon sulfonic acid,

methyl-phenyl-sulfonic acid,

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309822/10 Ob

N ~ ethyl-N- (4-amino-2.5-dichloro-ph «nylsulfonyl) -3-

methyl-phenyl-sulfonic acid, N- (4-amino-3,5-dichloro-phenyl-sulfonyl) -3-amino- ^/ i-methyl-phe =

nylon sulfonic acid,

N- (4-amino-3-trifluoromethyl-phenyl-sulfonyl) -3-amino- * t-methyl-

phenyl sulfonic acid, N - (^ - Amino-phenyl-sulfonyl) -4-amino-3-methyl-phenyl-8ulfon =:

acid, N ~ (4-Amino-2,5-dichloro-phenyl-sulfonyl) -4-amino-3-methyl-phe =

nylon sulfonic acid,

N- (4-Amino-3-trifluoromethyl-phenyl-sulfonylJ - ^ - amino ^ -methylphenyl-sulf onic acid,

N- (d-Amino-phenyl-sulfonyl) -3-amino-4-methoxyphenyl-sulfone =

acid, N- (4-amino-2.5-dichloro-phenyl-sulfonyl) -3-amino- ^< »-niethoxy-

phenyl sulfonic acid, N- (4-ABino-3.5-dichloro-phenyl-sulfonyl) -3-amino - ^ - methoxy-

phenyl sulfonic acid, N- (4-Aeino-3-trifluoromethyl-phenyl-sulfonyl) -3-amino-4-methoxy-

phenyl sulfonic acid,

N- (At-AiBino-2-ohlor-phenyl-sulfonyl) - ⁱ i-aiiiino-3-niethoxy-phenyl

sulfonic acid,

N- (4-Aoino-3-methyl-phenyl-sulfonyl) -4-amino-3-methoxy-phenyl-

sulfonic acid, N- (4-Aaino-3-B »ethoxyphenyl- * sulfonyl) -4-amino-3-methoxy-phenyl-

sulfonic acid,

N - (^ - Amino-2-chloro-phenyl-8Ulfonyl) -5-amino-2-methoxy-phenyl-

sulfonic acid,

N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -5-aiBino-2-yneth.t> xy-phea

nylon sulfonic acid,

N-methyl-N - (^ - aBino-2.5-diohlor-phenyl-8ulfonyl) -5-amino-2-

methoxy-phenyl-sulfonic acid,

N- (4-Amino-2.5-dichlorophenyl-8ulfonyl) -5-amino-2-ethoxy-phe =

nyl-sulfonic acid, N-methyl-N - (^ - amino-2.5-dichloro-phenyl-sulfonyl) -5-amino-2-

ethoxy-phenyl-sulfonic acid,

^LeA14091 309822? «OS

N- (4-Amino-phenyl-sulfonyl) -5-amino-2-phenoxyphenyl-sulfone =

acid, N-methyl-N- (4-amino-3-chloro-phenyl-sulfonyl) -5-amino-2-phen =

oxy-ptienyl-sulfonic acid, N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -5-amino-2-phenoxy-phe =

nylon sulfonic acid, N-methyl-N- (4-amino-2.5-dichloro ~ phenyl-sulfonyl) -5 - aniino-2-

phenoxy-phenyl-sulfonic acid,

N- (4-Amino-3,5-dichloro-phenyl-sulfonyl) -5-amino-2-phenoxy-phe = ^ nyl-sulfonic acid,

N-ethyl-N- (4-amino-3.5-dichloro-phenyl-sulfonyl) -5-amino-2-

phenoxy-phenyl-sulfonic acid,

N- (4-amino-3-trifluoromethyl-phenyl-sulfonyl) -5-amino-2-phenoxy-

phenyl sulfonic acid, N-methyl-N- (4-aminophenyl-sulfonyl) -3-amino-4-chlorophenyl-

sulfonic acid,

N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -3-amino-4-chloro-phenyl-

sulfonic acid,

N - (^ i-Amino-2.5-dichloro-phenyl-8Ulfonyl) - ⁱ i-amino-3-chloro-phenyl

sulfonic acid,

N- (4-Attino-phenyl-8ulfonyl) -3-amino-methane-phenyl-sulfonic acid, N- (4-Amino-2-chloro-phenyl-sulfonyl) -3-amino-methane-phenyl-sul = \ sulfonic acid ,

N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -3-amino-methane-phenyl-

sulfonic acid, N-methyl-N- (4-amino-2.5-dichloro-phenyl-sulfonyl) -3-amino-methane

phenyl sulfonic acid, N- (4-amino-3-trifluoromethyl-phenyl-sulfonyl) -3-amino-methane

phenyl sulfonic acid, N-Aethyl-N - (^ - amino-phenyl-sulfonyl) - * t-amino-methane-phenyl-

sulfonic acid,

N- (4-Amino-2.5-dichloro-phenyl-sulfonylJ - ^ - amino-methane-phenyl-

sulfonic acid, N-methyl-N- (4-amino-2.5-diochlorophenyl-sulfonyl) - ^ - amino-me =

than-phenyl-sulfonic acid,

N- (4-Amino-3-trifluoromethyl-phenyl-sulfonyl) -4-amino-raethane-Tp a 14 DQ1 19 phenyl sulfonic acid,

^{Le A 1} ^ ° ⁹¹ 3098227 ^ 05

[^ (it-Amino ^ .S-dichloro-phenyl-sulfonyl ^ -amino-phenyiJ-sul = ~ fonyl-phenylsulfon-amide,

JN- (4-Amino-2,5-dichloro-phenyl-eulfonyl) -4-amiuo-phenyl [-sul =

fonyl-methylsulfon-amide, fN- (4-Amino-2,5-dichloro-phenyl-sulfonyl) -3-aminophenyl] -sul =

fonyl-phenylsulfon-amide, [N _ (/ _l . amino-2,5-dichloro-phenyl-sulfonyl) -3-aminophenyl-sul =

fonyl-butylsulfon-amide, [N- (4-Amino-2.5-dichloro-phenyl-sulfonyl) -2-aminophenyl-sul =

fonyl-p-tolylsulfon-amide,

Suitable coupling components of the general formula (VI) are for example aniline derivatives of the formula

E «τ

in which R ₄ , R ₅ , R _e and R _{7 have} the meanings given above, phenols of the formula

/ JVOH (VIII)

R ₉ .

in which R ₈ and R _{9 have} the meaning given above and which couple in the p-position to the phenolic hydroxyl group or phenols of the formula

OH

(IX)

wherein R _{11 has} the meaning given above and the couple in the o-position to the phenolic hydroxyl group.

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215892Λ

Examples of suitable anilines of the formula (VIl) are mentioned:

N.N-Dimethylaniline, N.N-Diethylaniline, N-Methy1-N-n-butyl = aniline, N.N-diethyl-m-toluidine, N.N-diethylamino-3-chlorobenzene, N.N-diethyl-N'-formyl-m-phenylenediamine, N.N-diethyl-N'-acetyl-m-phenylenediamine, N.N-diethylaroino-3-methoxybenzene, l-N.N-diethylamino-2.5-dimethoxybenzene, 1-N.N-diethylanino-2.5-diethoxybenzene, l-N.N ~ diethylamino-2-raethoxy-5-acetylami = no-benzene, N-ethyl-N-ß-chloroethyl-aniline, N.N ~ bis- (ß-chloroethyl) -aniline, N- (ß-chloroethyl) -N-butyl-aniline, N- (ß-chloroethyl) -N-ethyl-m-toluidine, N.N-Bis- (ß-chloroethyl) -m-toluidine, N-methyl-N-ß-hydroxyäthy1-ani1in, N-Ethy1-N-ß-hydroxyäthy1-aniline, N.N-bis- (ß-hydroxyethyl) -anllin, N-butyl-N- (ß-hydro = xy-ethyl) -aniline, N.N-bis- (ß, y-dihydroxypropyl) -aniline, N-ethyl-N-benzyl-aniline, N-ethyl-N-benzyl-m-toluidine, N-ethyl-N-ß-hydroxyethyl-m-toluidine, N.N-bis- (ß-hydroxy = ethyl) -m-toluidine, 1-N-ethyl-N-ß-hydroxyethylamino-2-methoxy-5-ethylbenzene, N-ethyl-N-ß-hydroxyethyl-N'-aoetyl-m-pheny =: len-diamine, N.N-bis- (ß-hydroxyethyl) -N'-acetyl-m-phenylene = diaain, l-N.N-bis- (ß-hydroxyethyl) -amino-2-methoxy-5-acetyls!

aminobenzene, l-N.N-bis- (ß-hydroxyethyl) -amino-2-ethoxy-5-acetyl-amino-benzene, l-N.N-Bi8- (ß ~ hydroxyethyl) -amino-2-methoxy- 5-propionylamino-benzene, N-ethyl-N-ß-acetoxyethylaniline, N.N-bis- (ß-acetoxyäthy1) -aniline, N-butyl-N-ß-acetoxyäthylaniline, N-Aethyl-N-ß_aoetoxyäthyl-m-toluidine, N.N-Bis- (ßaeetoxy-ethyl) -m-toluidine, 1-N-ethyl-N-ß-acetoxyethylamino-2-methoxy-5-methylbenzene, N-ethyl-N-ß-a.cetoxyäthyl-N * -ace = tyl-m-phenylenediamine, N.N-bis- (ß-acetoxyethyl) -N'-acetyl-mphenylenediamine, l-N.N-bis (ß-acetoxyethyl) -amino-2-methoxy-5-acetylaniino-benzene, l-N, N-bis (ß-acetoxyethyl) -amino-2-ethoxy-5-acetylamino-benzene, l-N. N-bis (ß-acetpxyäthyl-amino-2-methoxy-5-propionylamino-benzene, N.N-Bis- (ß-ethoxycarbonyl = oxyethyl) -aniline, N.N-Bis- (ß-methoxy-carbonyloxyäthy1) -aniline, N, N-bis- (ß-ethoxycarbonyloxyethyl) -m-toluidine, N.N-bis- (ßmethoxycarbonyloxyäthyl) -m-toluidine, N.N-Bis- (ß-ethoxycarbo = nyloxyethyl) -N'-acetyl-m-phenylenediamine, N.N-Bis- (ß-methoxy = carbonyloxyäthylJ-N'-acetyl-m-phenylenediamine, l-N.N-bis- (ß-

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methoxycarbonyloxyethyl) -amino-2-methoxy-5 ~ acetylamino-benzene, lN.N-bis (ß-athoxycarbonyloxyethyl) ~ amino-2-ethoxy-5-acetylaminobenzene, lN.N-bis- (ß-methoxycarbonyloxyethyl) -ami = no ^ -ethoxy-S-acetylaminobenzene, NN-bis- (ß-carbomethoxy-ethyl) -N ^f -acetyl-m-phenylenediamine _f N-methyl-N-ß-cyanoethyl-aniline, NN-bis- ( ß-cyanoethyl) -aniline, N-ethyl-N-ß-cyanoethyl-m-tolui = din, N-ethyl-N-ß-cyanoethyl-N'-acetylamino-m-phenylenediamine, N-ß-hydroxyethyl-N- ß-cyanoethyl-aniline, N-ß-acetoxy-ethyl-N-ßeyanäthyl-m-toluidine, N-ß-methoxy-carbonyloxyethyl-N-ß-cyano = ethyl-N'-acetylafflino-m-phenylenediamine, NN-bis - (ß-cyanoethyl) -N'-benzoyl-m-phenylenediamine, N-ß-hydroxy ~ ethyl-N-ß-cyanoethyl-N'-phenacetyl-m-phenylenediamine, NN-diethyl-N'-phenoxyacetylm-phenylenediamine, N-ethyl-N-ß-cyanoethyl-N'-phenoxyacetyl-mphenylenediamine, NN-bis- (ß-cyanoethyl) -N'-p-chlorobenzoyl-mphenylenediamine.

N-methyl-eniline, N-ethyl-aniline, N-butyl-aniline, N-ß-cyanoethyl-aniline, N-ß-chloroethyl-aniline, ß-hydroxyethyl- aniline, N-ß-acetoxyethyl-aniline, N-ß-methoxy and N-ß-ethoxycarbonyloxyethyl aniline, N-ß-Oarbomethoxyäthylanilin, N-ß-0yanätbyl-2-methyl-aniline, N-methyl-m-toluidine, N-ethyl-m-toluidine, N -ß-cyanoethyl-m-toluidine, N-ß-chloroethyl-mtoluidine, N-ß-hydroxyethyl-m-toluidine, N-ß-acetoxyethyl-m-toluidine, N-ß-methoxycarbonyloxyethyl-m-toluidine, IT-ethyl -5-ethylaniline, Nn-propyl-3-ethyl-aniline, N ~ ß-cyanoethyl-3-ethyl-aniline, N-ß-cyanoethyl-3-methoxy-aniline, N-ß-chloroethyl-3-methoxyaniline, N -ß-cyanoethyl-3-ethoxy-aniline, NB-chloroethy'1-3-ethoxy-anilxn, N-ethyl-3-chloro-aniline, N-ß-cyanoethyl-3-chloroaniline, N-ß-chloroethyl-3 -chloro-aniline, N-ß-hydroxyethyl-3-chloro-aniline, N-ß-acetoxyethyl-3-chloro-aniline, N-ß-cyanoethyl-3-bromo-aniline, N-ethyl-N'-formyl-m- phenylenediarainjN-Ätliyl-N'-acetylm-phenylenediamine, N-ß-cyanoethyl-N ¹ -formyl-m-phenylenediamine, N-ß-cyanoethyl-N'-acetyl-m-phenylenediamine, N-ß-Cya näthyl-N ¹ -hydroxyacetyl-ra-phenylenediamine, N-ß-cyanoethyl-N ¹ -propionyl-m-phenylenediamine, N-ß-cyanoethyl-N ¹ -benzoyl-m-phenylenediamine, N-ß-cyanoethyl-N'- methoxycarbonyl-m-phenylenediamine, N-ß-cyanoethyl-II ¹ -ethoxy-Le A 14 091 - 15 -

309822/1006

carbonyl-m-phenylenediamine N-ß-cyanoethyl-N'-benzenesulfonyl-m-phenylenediamine ,. N-ß-cyanoethyl-K'-toluenesulfonylm-phenylenediamine, N-ß-cyanoethyl-N'-methylsulfonyl-phenylenediarain, N-ß-cyanoethyl-N ¹ -ethylsulfonyl ~ m-phenylenediamine, N-ß-chloroethyl-N ¹ - acetyl-m-phenylenediamine, NB-. Hydroxyethyl-N'-acetyl-m-phenylenediamine, N-ß-acetoxyethyl-N'-acetyl-m-phenylenedianiine, N-ß-methoxycarbonylethyl- -N-acetyl-m-phenylenediamine, N-ß-Oarbomethoxyethyl-N ' -acetylm-phenylenediamine, N-ethyl-2-methoxy-5-niethj ^r l-aniline, iJ-ß-cyanoethyl-2-methoxy-5-ynethyl-aniline _f N-ß-cyanoethyl-2-ethoxy-5-methyl -aniline, N-ß-cyanophyl-2,5-dimethyl-aniline, li / ithyl-

2-methoxy ~ 5-acetylamino-aniline, N-ß-chloroethyl-2-inethaxy-5-acetylaniino-aniline, N-ß-cyanoethyl-2-methoxy ~ 5-acetylamino-aniline, N-ß-cyanoethyl-2-ethoxy-5-acetylaraino-aniline, N-ß-Cyanoätbyl-2-Inethoxy-5-forInylamino-aniline, N-ß-Cyanoethyl-2-methoxy-5-hydroxyaoetylamin'o-aniline, N-ß-cyanoethyl-2-methoxy-5-propionylamino-aniline, N-ß-cyanoethyl-2-ethoxy-5-propionylamino-aniline, N-ß-Gyanäthyi-2-ethoxy- ~ 5-hydroxyacetylamino-aniline, N-ß ~ Gyanätbyl-2-methoxy-5-benzoylamino-aniline, N-ß-cyanoethyl-2-raethoxy-5-niethoxycarbonylamino-aniline, N-ß-cyanoethyl-2-methoxj '--- 5-ethoxycarbonylamino-aniline, N-ß-cyanoethyl-2-methoxy-5-ynethylsulfonylamino-aniline, N-ß-cyanoethyl ^ -methoxy-S-ethylsulfonylamino-aniline, N-ß-Hydrox.yäthyl-2-methoxy-5-acetylamino-aniline, N-ß-acetoxyethyl-2-methoxy-5 ~ 'acetylamino-aniline, N-ß-Methoxycarbonyloxyäthyl-2-ynethoxy-5-acetylamino-aniline, N-ß-cyanoethyl-2-methyl-5-acetylaraino-aniline.

Suitable phenols of the formulas (VIII) and (IX) are for example mentioned:

Phenol, o-cresol, m-cresol, p ~ cresol, l-hydroxy-4-ethylbenzene, l-hydroxy- ^ i-tert-butyl-benzene, l-hydroxy-2-ethylbenzene, l-hydroxy-2- isopropyl-benzene, 1-hydroxy-2-sec.-bu = tyl-benzene, 3-hydroxy-1,2-dimethyl-benzene, 2-hydroxy-1,4-dimethyl-benzene, ^/ t-hydroxy-1,2- dimethyl benzene, 2-hydroxy-1,3-diethyl benzene, l-hydroxy-2-methoxy-benzene, l-hydroxy-3-meth =

Le A 14 091 - 16 -

309822/1005

oxy-benzene, 1-hydroxy-3-ethoxy-benzene, l-hydroxy-4-butoxybenzene, 1-Hydroxy-3-butoxy-benzene, 2-hydroxy-biphenyl, 4-Hy = droxy-biphenyl, salicylic acid, methyl salicylate, ethyl salicylate, 2-chlorophenol, 4-chlorophenol, 2-Me = ethyl-5-chlorophenol.

Examples of suitable alkylating agents are: Dimethyl sulfate, diethyl sulfate, methyl chloride, methyl iodide, Ethyl chloride, propyl bromide, isopropyl bromide, butyl chloride and benzyl bromide, ethylene oxide, 2-chloroethanol.

The alkylation is carried out in a manner known per se in an aqueous, aqueous-organic or organic medium at room temperature or elevated temperature.

The dyes according to the invention are suitable for dyeing natural = Licher and synthetic fiber materials, especially .zu «dyeing polyamide fibers in level, extensive, yellow to orange tones of very good lightfastness. They already pull well on poly = in the neutral to weakly acidic dye bath amide fibers. Polyamide fibers are in particular those made from synthetic polyamides such as £ -Polycapro = lactam or condensation products of adipic acid and hexa = methylenediamine understood.

The dyes were used in the form of the free acids or in the form of their salts. Preferred salts are the alkali salts, especially the Na salts and the ammonium salts.

In the following examples, parts mean parts by weight.

example 1

39.7 parts of N- (4-amino-2,5-dichloro-phenyl-sulfonyl) - * t-aminophenylsulfonic acid are dissolved in 200 parts of water with sodium hydroxide solution at pH 7, 7.0 parts of sodium nitrite are added, after Cooling to 5 ° C. 30 parts of hydrochloric acid (37%) collapsed and diazotized at 0-5 ° C. for 15 minutes. A small excess

Le A 14 091-17 - *

309822/1005

of nitrous acid is destroyed with sulfamic acid. The solution of 16.5 parts of Ν, Ν-diethyl-m-toluidine in 200 parts of 10 ^ iger hydrochloric acid is then added to the clear diazo solution and completes the coupling, which starts immediately, by adding sodium acetate. The precipitated dye the formula

Cl

/ ^C 2 ^H 5

Ho ₃ s- ^ ~ Vhn-o, s- / ~ V ^{N = N} - <f ~ V ^N

J f ° 2 ^H 5

Cl CH ₃

is sucked off and dried. He dyes polyamide fibers and Polyamide fabric made from weakly acidic or neutral bath blue; chig red with very good lightfastness.

If you proceed as indicated in Example 1, but as Diazo component the compounds listed in column I and, as coupling components, the compounds listed in column II of the following table when used, valuable water-soluble azo dyes are also obtained, the polyamide having an orange to bluish tinge dye red, lightfast shades.

Le A 14 091 - 18 -

309822/1005

co

II

Color on polyamide

N> lsi

4> O

2.) HO ₈ S

3.)

4.)

5.)

6.)

7.)

8.) HO ₃ SQ-HN-O ₂ S- {3-

Cl

CH,

CH ₃

^ CH ₂ -CK ₂ -CH ₃

^ CH ₂ -CH ₂ -CH ₃

, C ₂ H ₅

C ₂ H ₅

, C ₂ H ₅

-CH ₂

orange

rotst. orange

orange

Scarlet fever

CJI OO CO

Color on polyamide

9.)

HO.

> - 'Hg "-CH ₂ " OH ₃ -Liig -OiLj

Scarlet fever

10-;

J.1. /

EO

₃ S-J [

CHg

^ Z

/ ΓΛ ^

( H

C ₂ H ₅

Red

orange

Tue 12.)

= * / ^ CH ₂ -CH ₂ -OH

CH.

i6.).

// VwN ''

_{/ 7} _ ^ CH ₂ -CH, -CH ₃

V ^{&quot; ιΝι} ^

H ₂ -CH ₂ -CH ₃

yellow. Red

yellow. Red

f ¹ Φ

4>

II

Color on polyamide

17) HO ₃ S-

TTTT «· fi Rm * ff Vs« .Τ

^j 2r ^ \ = j ' ^m 2

gelatin. Red

18)

jH ₂ -CH ₂ -OH

Red

19) Soharlacii

ο ο on

20) CH ₉ -CH ₉ -O-CO-CH,

CH ₀ -CH ₀ -O-CO-CH
cc.

yellow. Red

21)

22)

Cl

^! 2 ^H 5

C ₂ H ₅

_/ CH ₂ -CH ₂ -0-CH ₃
CH ₂ -CE ₂ -O-CH ₅

■ ro cn

• OO NJ>

tr ¹

(D

O VD

II

Color on polyamide

23)

HO ₃ S

Cl

yellow. Red

O ro co I. co ro NJ CD O on

24)

25)

26)

CH ₂ ^ DH ₂ -O-CO-OCH ₃

/ ° 2 ^H 5

CH ₂ -CK ₂ -COO-CH ₅

/ ° 2 ^H 5

27)

cn co co

215892A

- 4 * 4 * τ
O
w α O
m i P =! • ω U)
Ρ « W. H tiü ,Egg

tn ι m U1 C \ J it} W. W. ο t.5

CV W "

5 = 5

C \ J

CM

rs te O CM W. j i CM CM W. O O S. I. te * S. i

f \ j

i] I? j S. ·> ^ V. I. Ui
f O

crt

(JO CM

(51 f CVl

J λ / 1Ί f J ¹ J -

3 o a ti;. · 2 • ι ο ο ii

tr ¹
φ

VO

34)

35)

ω I. 36) σ tV) cc
cc • f-
I. r-o 37) _ \ O
O 38) cn

HO ₃ S-

39)

Cl

II

OCH ₃

/ 3-NH-CH ₂ CH ₂ -CN
CH ₃

C ₂ H ₅

NH-CO-CH,

CH,

OH

CH,

VOH

CH,

Color on polyamide

yellow, red

red orange orange

Ul CQ CQ

O
Ph

«Η
CO

co Et,

BJ

-P CO

■ Q

- I Q) bO

■ ρ -P -P O O O DS pi -P + J co co O I-I co OS Φ r-l bß

of

(M

ITi

Le A 14 - 25 -

309822/1005

II

Color on polyamide

"^ -0-CH ₃ CH ₃

/ "VNH-CH ₈ CH ₂ -CN Cl

CHg CH2 -CH ₃

- ^C 2 ^H 5

C ₂ H ₅
Co Η _κ

^ H ₂ CH ₂ -OH

C ₂ H ₅

CH ₂ CH ₂ -CN

Orange yellow. Red

Orange orange

Orange orange

Orange orange

tr ¹ φ

47)

48)

HO ₃ S-CH ₂ -Q-NH-O ₂ S-Qr-NH ₂

Cl

HO ₃

Cl

Cl

CH,

50)

51) HO ₃ 8- / 3-NH- ⁰ S S- / 3 " ¹¹¹¹ !

52)

53) HO ₃ SZ ^ -NO ₂ S ^ Q) -NH ₂

CH "

54)

TJ • Ρ • Η O B. CO
>> • r- (
O ■ Ρ α « CQ Ή ,O - I CO α) W) S3 O -P , α U CO fe.

+ O PS

-P -P O O « * φ ■ Ρ -ρ CO CQ & CO r-l CC D. Φ
IaC γΗ

rf

ϋ «Q O

in

ir

αο in ITv

Le A 14 091

-

30982 2/1005

(O

62)

ro α

6k)

65)

• 66) 67)

, 68) 69)

CH,

HO ₃ S-CH ₂ -Q-NH- O ₂ S ^ f ^ \ -

CH ₃ Cl

63) HO ₃ S

- ^ VNH-

Cl .Cl

O ₂

Cl

Cl

io ₂ ShQ-NH ₂

SO ₃ H Cl

II

st

"ti

^{2 5}

C ₂ H ₅

/ C ₂ H ₅

N.

Ö- »

CH ₂ CH ₂ -CH ₃

CH ₂ CH ₂ ""

CNH-CH ₂ CH ₂ -CN

^H 5

^ ⁷ CH ₂ CH ₂ -

OH

CH ₂ CH ₂ -OH ²

CH ₂ CH ₂ -CN

Color on polyamide

bluish red

yellow, red

Red

Scarlet fever

00 CO NJ

QS

m +3 cn, Q r-i (D W)

-P -P Sl P. O O O O S3 03 I— ( CS Φ -P P. bC Ου co OJ , η , 0 CO O r-f Φ co Φ O bß

a " a " a a a " a a 52! a " Sz; a Ol Oi ϋ m η 0-0 O O α O U ^ P
525 ο egg V a ¹ a ¹ m <i O O
■ ϋ
f O
I. ϋ O i a _M a et a ν O ό I. I. ο · a Μ a μ a I. I. EtT a " Jz; V ^ P
Sz; OJ
a a ¹ O O cm Oil a a a a \

Cl

IA

VO

Le A 14

- 29 -309822/1005

S. +3 O) co O bO ι — Ι
O ⁰ I. d d. • p co "H CO S. • Q O co rH β Φ O hss -yy , Q (η CO Cl,

GO

OI a ^w rf, "

! 25

CS

• ο

CM CC

OO

»Η

QO

Le A 14 091

309822/1005

pi

+3

ΐΗ Φ

bü

ro

CO

+3

+3

cn

(η O

+3

VO OD

QO

CO

r σ · »

Le A 14

3098 2 2/1006

Su O

οι

Cfi

in

C. O O CS CS B = α • • Ο W. W. W. X- i-G K. i-i ω St. St.

on

α ο

O Ci ^

VD

Ι

00 ο ο

Le A 14 0 ^ι ) Ί

J3

CJ

CO

ι — ι U

+3 O OS

-P O 03

03

foss

w ³ rf

O S. W. O ο 1 W. 8th O O O O O O ö t j W. td C. Ü

oil

cn o ¹ sz: as

3 rf

ta I. «- W. I. in W. W. W. W- O IO CV) ?! C4 W. \ W. C! CM s O

r-l

Le A 14

ο - CO

309822/1005

Color on polyamide

V OCH,

orange

NH-CO-CH,

yellow, red

H ₄ -0-CO-C ₂ H ₈

fy <

C ₂ H ₄ Cl

/ C ₂ H ₅

¹ N

C ₂ H ₅

^H 5

'C ₂ H ₅

Red

CJl OO

111)

Cl

<fVs O ₂ -N-SO ₂

\ y _H

Cl

112)

113)

Cl

ANO ₂ H

Cl

Cl

115) CH ₃ -SO ₂ -NO ₂ Sf ^ -N-0 ₂ Sf \ -NH ₂ H ^ = ⁷ H ■ ^ Λ

116)

117)

118)

2158324

The diazo component used in Example 5 is in iolperider Way represented:

To a mixture of 173 parts of Suii aiii 1 acid and 3 <> 5 parts of 2. 5 * -Üichlor- ^/ i * 'a "C5fit3'ininiiio - beflzöl-su] foohl orid in 1500 parts of benzene are added at 50 ° 150 parts of tri äthylaritin ziiftei ropjf i. 'The mixture is heated for 1 hour liilokf Ittjl cooled abf liltriert and wäöolit according with benzene The fMickstand is l · Stinide in water at 50 ⁰ O stirred ^ cooled, leached and getrodkiiet, Man erlial i HUO parts of the Triäthyjammonium-iialzes dei- Ή ~ (2.5 ⁱ -iÜlülilor '- ^ - amino -]) heiiy 1 * - suliony])

The other part can be found in the table in an analogous way mentioned, DiazokötnpoDeiiteii. ·.

Le Λ 14 091 - 35 -

ORIGlNAL BATHROOM

I 00S

Claims (7)

Claims: ^ ι O ο Ό Z 4 1.) Monoazo dyes in the form of the free acid of the general formula YXNO ₂ S correspond, where \ R _{1 is} hydrogen or alkyl, R ₂ for hydrogen, halogen, nitro, cyano, alkyl, alkoxy, a carbonamide or a carbon ester group, R ₇ for hydrogen, halogen, alkyl or alkoxy, K for a phenylene or naphthylene radical, A for a substituted p-to the azo group Amino group or a hydroxy or alkoxy group in the o- or p-position to the azo group, X for an aralkylene or arylene radical and Y for -SO ₃ H or a disulfimide radical -SO ₂ -NH-SO ₂ -R ₁₂ wherein
R. _{9 is} alkyl or aryl. 2.) Monoazo dyes, which in the form of the free acid of the general ' formula R ₂ YXNO ₂ SQ) -N = NKA R ₁ T R ₃ in which R .., R ₂ , R ^, K, A, X and Y have the meaning given in claim 1. Le A 14 091 - 36 - 3098 2 2/1005 31 3.) Monoazo dyes in the form of the free acid of the general formula -Z ² ' YXNO ₂ SQ ^ -N = NKA R, wherein R ^, K, A, X and Y correspond to those in claim 1 have given meaning, Rp 'is hydrogen, chlorine or bromine and R-, ^{1 is} chlorine or bromine. 4.) Monoazo dyes, which are in the form of the free acid of the general formula R ₂ " ^Ul ei where R,., K, A, X and Y correspond to those in claim have genanribe meaning and Rp "stands for hydrogen or chlorine. 5.) Dyes of claims 1-4, wherein -K-A for a Reut of the formula R ₁₀ and -J ~ \ H ₅ R ₉ V ₁ Le A 14 091 "- 37 - 3 0 ^C J 8 2 2 i 1 0 Ü b S * is where R- stands for hydrogen, halogen, an alkyl group, an alkoxy group or an acylamino group, Rc represents hydrogen, an alkyl group or a Alkoxy group, Rg for hydrogen or an alkyl group, Ry for an alkyl group, Rg and Rg for hydrogen, an alkyl group, a kllioxy group, a carboxyl group, a carbonamide group, a carbon ester group, an aryl radical or halogen, R _{10 represents} hydrogen or an alkyl group and "R ^ represents an aryl radical, halogen or an alkyl group. 6.) Process for the production of monoazo dyes used in Form of the free acid of the general formula A ₁ correspond to worm Ry, for hydrogen or ALkyL, R ₂ for hydrogen, halogen, HLtro, cyano, alkyl, alkoxy, a carbonamide or υίηε carbottostor group, R-, for Waf3serstoi'f, Halogon, AlkyL or Alkoxy, K for a phenylene or naphthyl -.- ures t, A for ei.rift to the azo group p-ständLgo, substituted Amino group or a - '. Lic ¹ azo group o- or p-stan- dige hydroxyl or alkoxy group, Le A 14 091 - 38 - 309822/1005 _ _At BAt) ORIGINAL SB X is an aralkylene or arylene radical and Y for -SO ^ H or a disulximide radical -SO ₀ -NH-SO ₉ -FL wherein
RP denotes alkyl or aryl, stands, characterized in that one diazotized amines of general formula R ₂ * R wherein R ₁ , Rp ₅ R- ?, X and Y have the meaning given above, with coupling components of the general formula H-K-A ' united, wori] j A 'is a Hydro :: y group or a substituted amino group and K has the meaning mentioned, in o- or p-position to the hydroxyl group or in p-position to the substituted amino group and then in the event that A is an alkoxy group, the hydroxy group is alkylated. Le Λ 14 091 - 39 - 3 0 9 S 7.2 / 1 O.Ü 6 to 7.) Use of the dyes of claims 1-5 for dyeing natural and synthetic fiber materials. ⁸ ·) Use of the dyes of claims 1-5 for dyeing fiber materials made from synthetic polyamides. 9 ·) Natural and synthetic fiber materials dyed with the dyes of claims 1-5. Le A 14 091 - 40 - 309822/1005