DE2263109A1 - NEW BASIC AZO DYES AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

New basic azo dyes and processes for their production

The present invention relates to new basic azo dyes which are derived from acidic water-solubilizing groups / in particular sulfonic acid groups are free and in general Formula ■

<ζ \ ζ

where zv / ei radicals Z mean groups of the formula -NR'R "■ and a radical Z means a group of the formulas -NR'R ⁿ , -OR" ¹ or _S-R " ^f , where R ^f , R" and R ¹ "each signify hydrogen, aryl ^ 7 ~ * alkyl, cycloalkyl or an aliphatic radical and R ¹ and R" can form a ring containing the amine nitrogen and the radicals -NR ^! R "can be the same or different from one another, Y is a radical of the formula -CN or -CONHp, and D is the radical of an aromatic or hetero-

309828/1042

cyclic diazo component and in which at least one radical Z and / or D is basic, optionally cationic Contains groups.

A preferred embodiment are the dyes of Form1

(Q) -D'-N = N q-1

^R 3 ^R 4
where D 'is the radical of an aromatic or heterocyclic diazo component and Y is a group of the formula -CN or -CONH "and R""R", R- "R ₁ . and R ₁ - each hydrogen or

d 1 dj 4 Z)

an aryl, aralkyl, cycloalkyl radical or an aliphatic radical, where R, with R _p and R with R ^, can form a ring containing the amine nitrogen and Q each is an optionally quaternized amino, hydrazino bonded directly or via a bridge -, etherified hydroxylamino or pyridine grouping and ρ and q are each 1 or 2, where, when ρ and q are both 1, D 'is a heterocycle with a quaternized ring nitrogen atom, and in which Z is an oxygen or sulfur atom or an imino group of the formula

-N-

309828/1042

is where FL- is hydrogen, aryl-, aralkyl-, cycloalkyl- or is an aliphatic radical. which with FL · or with Q can be linked. The basic radical Q can also be attached directly to the aromatic or heterocyclic nucleus be bound to the diazo component. However, it can also be attached to a substituent, e.g. an alkyl or alkoxy ~ group of the diazo component sit or via an alkylenearbonyl, Carbonyl oxy-.5 Carbonylaniino-, Aikyler-carbonylexy-,

Alkylencarbonylamino, alitylenesulfonylanino or alkylenesulfonyl bridge with the /
/ Dye molecule be linked. The basic group Q,

can also with R ^ - and Z together form a ring, for example a piperazine radical. . _: ,

Aryl, aralkyl, cycloalkyl and aliphatic radicals are preferably understood to mean radicals of the benzene series, benzyl, phenaethyl, cyclohexyl or alkyl radicals with a maximum of 12 carbon atoms, the latter being interrupted by oxygen, sulfur atoms or imino groups. The radicals R located on the same nitrogen atom can be linked to one another directly or via heteroatoms, in particular oxygen and sulfur, that is to say R ^! with R ", R, ..with R ₀ , R, with R ,, and in particular R, _ with R ^. The radical Z can therefore be, for example, a piperidine, pyrrolidine or morpholine radical.

As examples of the radicals R ¹ , R ", R '", R ₁ , Rg, R ₅ , R ^, R ₅

30 9 8 2Wto 42 ^; ·

jinr.a

and Rjr come, for example, methyl, ethyl, propyl, isop Butyl, sec. -Butyl, n-pentyl, and octyl radicals, in question, which are interrupted by oxygen atoms and by hydroxy, Carboxyl, carbalkoxy (with 2-6 carbon atoms), alkoxy (with 1-8 carbon atoms), phenoxy, Acyloxy (with 1-10 carbon atoms), optionally with halogen atoms, lower alkyl or lower alkoxy, ß-hydroxyethyl or lower carboalkoxy groups, substituted phenyl groups or benzyl, or phenaethyl, or cyclohexyl groups can be substituted or together to form a piperidine, pyrrolidine, morpholine, piperazine, or Methylpiperazine ring are linked.

Acyl residues include, for example, fatty acid residues with up to 5 carbon atoms such as formyl, acetyl, propionyl, butyl radicals; Alkylcarbamyl radicals with up to 5 carbon atoms, such as methylaminocarbonyl, Ethylaminocarbonyl, propylaminocarbonyl, or butylaminocarbonyl radicals; Alkyloxycarbonyl radicals with up to 5 carbon atoms, such as methoxycarbonyl., Ethoxycarbonyl, Propoxycarbonyl or butoxycarbonyl radicals; Phenylcarbamyl or phenoxycarbonyl radicals, benzoyl, phenoxyacetyl, Chloroacetyl or phenylacetyl residues in embossing.

Those dyes of the formula given are preferred in which D is a radical of the benzene series or a sulfur and / or nitrogen-containing heterocyclic radical, as well as dyes in which R ,, Rp, R ^, and R ^, hydrogen mean.

3 0 9 8 2 8/1042

According to the invention, the new dyes are prepared by coupling, condensation and Quaternization, with coupling also the oxidative Clutch is included.

In the production by coupling, one starts from diazo and coupling components, of which at least one component already contains a basic group. These basic groups are generally introduced before the coupling by reacting a corresponding coupling or diazo component, which has a reactive atom or group instead of the basic group, with amines, etherified hydroxylamines, hydrazines, pyridinecarboxylic acid chlorides or aminocarboxylic acid chlorides. Suitable reactive groups are those which are discussed below in connection with the preparation by condensation. Diazotized amines of the formula D — NH or (Q) —y — D '—NH _{p are} thus coupled with coupling components of the formula

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where D, Y, Ζ _χ , Z _g , Z ₃₃ D ¹ , R ₁ , R ₂ , R ₃ , R ₄ , RZ, q, ρ

and Q have the meanings mentioned above and ' ^: if necessary, when Y = CN, converts the cyano group with concentrated sulfuric acid to the -CONH group.

Basic groups Q include, for example, those of the formula

^R i

-NO'

[ ^R 2

in question, in which R 'and R ^ are hydrogen or an alkyl, in particular with 1-4 C atoms, aralkyl, especially benzyl or cycloalkyl, especially cyclohexyl, R 'denotes hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group and in which the nitrogen atom with R 'and or Rp and or Rl part of a heterocyclic ring. X is an anion and η 1 or 2. These radicals can be for example of the amines mentioned below in the preparation of the dyes by condensation, Derive hydroxylamines and hydrazines. The anions can be those of strong inorganic acids, e.g. Chloride, bromide, iodide, nitrate, sulfate, especially hydrogen sulfate and phosphate, especially dihydrogen phosphate. But there are also anions of organic acids

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In question., By which aryl and alkyl sulfonates and carbonates are understood, in particular benzenesulfonate and its with Nifcro, chlorine, bromine, C, to C ₂ , - alkyl and C, - Cj. - Alkoxy group-substituted 'derivatives, C, - Cu - alkylsulfonates, aliphatic carboxylic acids with 1 to 4 carbon atoms and benzoates, where the benzene ring can carry the same substituents as in the case of the benzenesulfonates. Of particular importance are the anions of the low molecular weight, ie 1 to 4,. Alkylsulfuric acid half-esters containing carbon atoms. ., In addition, the dyes can be present as double salts with eye metal halides ^ in particular with zinc and cadmium halides »

Examples of such anions are: Benzölsulfonate p-ioluenesulfonate, p-methoxybenzenesulfonate, methanesulfonate., Aetliansulfonat, Formiatj ,, Ac-etat, Chloraeetat, Propionat, Lactate, tartrate, benzoate, methyl benzoate, methyl sulfate, " Ethyl sulfate, ZnCl ~, CdCl ~, carbonate and bicarbonate.

• Basic ones are preferred. Remnants of the specified • Formula in which Rj, R ^ and R 'are low molecular weight. Alkyl radicals are, in particular methyl radicals. . . '

The basic groups can also be pyridine residues

28/10 ^ 2

be, where R \ is an alkyl radical, in particular with 1 to 4 Carbon atoms, cycloalkyl, especially cyclohexyl, or aralkyl, is in particular benzyl radical and X and η are the same as above.

The diazo components of the formula D-NH_ or (Q -) - - D ¹ -NH _{2 are} derived, for example, from amines of the naphthalene series and, in particular, from amines of the benzene series. In addition to the basic groups mentioned, the benzene nucleus can carry, for example, the following substituents: halogen atoms, hydroxyl, cyano, rhodan, nitro, lower alkyl, trifluoromethyl, lower alkoxy, formyl, lower alkylcarbonyl, benzoyl, methylbenzoyl , lower alkoxycarbonyl, benzyloxycarbonyl, cyclohexyloxycarbonyl, phenoxycarbonyl, lower alkoxycarbonyloxy, benzyloxycarbonyloxy, lower alkylcarbonyloxy, benzoyloxy, lower alkylcarbonylamino, benzoylamino, lower alkylsulfonyl or lower alkylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonyl, unsubstituted, unsulfonylsulfonylsulfonylsulfonylsulfonyl, lower alkylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonyls groups, mono- or disubstituted aminosulfonyl-, di (hv droxyäthyl) aminosulfonyl-, phenylaminosulfonyl-, (chloro- or methoxy) phenylaminosulfonyl-, benzylaminosulfonyl-,, N-piperidylsulfonyl-, N-morpholinosulfonyl-, lower alkyl

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sulfonyloxy, cyclohexylsulfonyloxy, chlorine thylsulfonyloxy, cyanoethylsulfonyloxy, phenylsulfonyloxy, aminosulfonyloxy, (chloro- or methoxy) phenylsulfonyloxy, N-. Morpholinosulfonyloxy, ethyleneiminosulfonyloxy, lower monoalkyl- or dialkylaminosulfonyloxy-, phenylaminosulfonyloxy-j N-phenyl-N (lower-alkyl) aminosulfonyloxy-j N- (methoxy or. and / or acetylaminophenyl groups, D or D ^{! can also} mean: a phenylazophenyl radical optionally substituted by chlorine or bromine atoms, hydroxyl, cyano, nitro, lower alkyl, trifluoromethyl, lower alkoxy or phenoxy groups, an optionally substituted by methoxy -, ethoxy, phenylazo or dimethylaminosulphonyl groups, a naphthyl radical optionally substituted by chlorine or bromine atoms, nitro, cyano, rhodane, lower alkyl, lower, alkoxy, lower alkylmercapto, phenyl, benzyl, phenethyl, lower alkoxycarbonyl , Trifluoromethyl, lower alkylcarbonyl and lower alkylsulfonyl groups substituted thiazolyl radical,

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an optionally by chlorine or bromine atoms, cyano, rhodan, nitro, lower alkyl, lower alkoxy, benzyl, Phenylethyl, lower alkylsulfonyl, phenyl, lower alkyltnercapto-, lower alkoxycarbonyl, lower alkylcarbonyl, trifluoromethyl, cyanoethylsulfonyl, aminosulfonyl or one with benzothiazolyl radical optionally substituted by lower mono- or dialkylaminosulfonyl groups, one optionally substituted by cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl or phenyl groups Pyrazolyl radical, an optionally lower alkoxy, lower alkyl, phenyl, lower alkylsulfonyl or lower Thiadiazolyl radical substituted by alkyl mercapto groups, one optionally substituted by nitro or lower alkyl groups Imidazolyl radical, an optionally by nitro, lower alkyl, lower alkylsulfonyl, lower alkoxycarbonyl or acetyl groups substituted thienyl, an optionally 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. Lower alkyl groups are sin e.g. methyl, ethyl, propyl, isopropyl and isobutyl estej 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 3 heteroato-

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have men, especially one nitrogen and one or two sulfur, oxygen or nitrogen ■ atoms as heteroatoms, and aminobenzenes, especially negatively substituted Arainobenzolen ,, in which the Substituenteh positive sigma values after Hammetgleichüng have, in particular those of the * \ formula '·

R "is hydrogen, bromine, a thiocyano, alkylsulfonyl, Alkoxycarbonyl, hydroxy, alkyl mercapto- ^ aryl mercapto-, Älkoxycarbonyloxy, aminosulfonyloxy, aeylarnino or preferably chlorine, a nitro, cyano, acyl, sulfcnamide, Carboxamide, alkoxy or aryloxy group. ■

; . R ^ is hydrogen, bromine, a carboxamide or, preferably, an alkoxycarbonyl or aminosulfonyloxy group. · - ■ - | '

R ' ¹ is hydrogen, bromine, a thiocyano, alkoxycarbonyl, alkoxy, aryloxy or acylamino group or preferably chlorine or a nitro, cyano, acyl, sulfonamide, carboxamide, trifluoromethyl or phenylazo - ■ group, the phenyl nucleus of which can in turn be substituted with alkyl, alkoxy, nitro groups and chlorine.

RjI 'is hydrogen, bromine, nitro, cyano, Thiocyano, acyl, carboxamide, alkoxy, aryloxy or

30982Ö / 10 4 2

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

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

5 '■■■■■■.' ^ι

one, nitro, cyano, thiocyano, acyl, alkoxycarbonyl, Trifluoroethyl or alkyl group.

'Examples of such acyl groups are:

Benzoyl, 4-chlorobenzoyl, 4-methylbenzoyl, benzenesulfonyl, formyl, acetyl, propionyl, chloroacetyi, methylsulfonyl, or (methoxy, ethoxy, propoxy, butpxyoxy) carbonyl radicals. I From the series of usable diazölioniponents
of the benzene series are, for example, the following: aniline,

l-amino-5- or -4-chlorobenzene,. ;

l-amino ~ 4-bromobenzene,

l-Araino-2-, -5- or - ^ - methylbenzene, _.)

l-Amino-2-, -3- or -4-nitrobenzene,. ·

l-amino - ^ - cyanobenzene,:

I l-aminobenzal-3- or -4-methylsulfone,,

l-amino-2-chlorobenzene-4-methylsulfone, i

i l-amino-2,5-diyanobenzene,. . '■

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

l-amino-2-methyl-4- or -6-chlorobenzene, 4-aminodiphenyl,

2- or 4-aminodiphenyl ether, -

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5- or 4-aminophthalimide., ■ ^:

l-Amino ^ -trifluoromethyl ^ -chlorobenzene, '·. '' 1-Amino ~ 2-cyano-4-chlorobenzene.,. '
l-Amino ~ 2-carbomethoxy-4-chlorobenzol, '' - "'" ■
l-AmIno-2-methylsulfonyl-4-ehlΌrbenzol _J.
l-amino-2-carboraethoxy-4-nitrobenzene,

l-amino-2-phenoxy-4-nitrobenzoΓ, ''^; · ■

l-amino-2-chloro-4-cyanobenzene _J. ■ 'l-Amino-2-chloro-4-nitrobenzene ·

l-Amino-2-methoxy-4-nitrobenzene _J ■ ^:

l-Amino - ^ - ehlor - ^ - carbethoxybenzene, -. :

l-amino-2-bromo-4-carbohexoxybenzene,. . ■
l-amino-2,4-dinitrobenzene,. ', "

l-amino-2 _i 4-dicyanobenzene,.

l-ArainΌ-2,6-dlchlor-4-cyanobenzene _ί ■.

l-Amino-2 _i 6-dichloro-4-nitrobenzene ·, ':

1-amino-2,5-dichloro-4-norrobenzene, ';

l-Amino-2,5- or 2,6-dlchlorobenzene-4-sulfonic acid dimethylamidj l-aminobenzene-4-sulfonic acid-ß-ehloräthylamid,: "

1-Amino-2-chlorobenzene-4-sulfonic acid diethylamide,
l-amino-2 _J 6-dibromobenzene-4-sulfonic acid amide _i -.
l-amino-2,4-dlnitro-6-chloro or ^{6-bromobenzene:}

■ ■. 9 - '

i-AmIno-2 _J 4-dicyan-6-chlorobenzene, ^x ■

l ~ Amino-5-chloro-cyano-2-nitrobenzene, ■>

i-amino-2,4, o-trichloro- or tribromobenzene,

. 309 828 ^ 1042

l-aminobenzene-3- or -4-sulfonic acid amide,

l-aniinobenzene -) - or -4-sulfonic acid ~ N-methyl ~ or -diethylamide,

l-amino-2-nitroben?, ol-4-sulfonic acid dimethylamide,

l-amino-2-nitrobenaol- ^J 4-äthylsulfon _i. ,,. ' ■

l-amino- ⁱ l-nitroben2ol-2-methylsulfone,. . ■ ■ 1-aminobenzene-4-carboxylic acid methoxyethyl ester, 1-amino-2-nitrobenzene-4-carboxylic acid ethoxyethyl ester, l-amino ^ -cyan ^ -nitrobenzene,

l-Amino-2-cyano-4-nitro-6-bromobenzene,.

l-Araino-2,6-dicyano-4-nitrobenzene _J 1-amino-2-cyano-4,6-din! trobenzol, l-amino-2, 4,5-trichlorobenzene.

^: As aminoazobenzenes come the compounds of the formula

H ² 'Jj;

/ Λ r \ _

^V 4 \ / ^{Ν = Ν} ~ \ ) - ·

wherein V, a hydrogen atom, a halogen atom or a methyl, a methoxy or ethoxy or nitro group> Vp a hydrogen atom, a halogen atom or a nitro group V-. a hydrogen atom, a halogen atom, or a nitro group Vj. a hydrogen atom, a halogen atom, a methoxy atom, a

Ethoxy, an alkoxycarbonyl, a cyano, or nitro group and V (- a hydrogen atom, a halogen atom, a methyl or

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"■ ■■ - ¹ · 'Λ f -

a methoxy group is * ££ 03109

• Suitable. Diasofconiponents of the azobenzene series are e.g. 4-amino-azobenzene,. . ■ _,

^ -S'-chloro-azobenzene,. -. '.

S ¹ , 4'-di chloro-azobenzenes' ■: - ..

4-Amino-2'-nitro-azobe £ izö ^r l,

il-Affiino-j'-nitro-azobenzolj
^ -Amino-S-methyl-azobenzene,.
^ Aiiiino - ^ '- methoxy-azobenzene,

-S ', ^' - dichloro-azobenzene,

4-Amirioazobenzol-4 ¹ -sulfonaäuredirfiethylamiä and 4-Amino-2-methyla3obenzQl-4 '-carbonsäureäthylestei ¹ -.

Ethyl ethers of aminophenols in the ß-position

of the ethoxy radical contain one of the stated basic groups Q, and can be derived, for example, from ■ ■,

4-nitro-2-arnineQphenol. ''. : _;

e-Nitro-'t-chloro-J-aminophenol: -

4-nitro-3-amino phenol · ._- .. '.

5-methanesulfonyl-2-aminophenol -. ·.

5-nitro-2-aminothiophenol

^ -Chlor ^ -aminophenol-S-sulfonic acid-N-methylamide

where the group Q is in particular trimethylammonium-30 982 8/1042

Chloride, triaethylammonium chloride, pyridinium chloride, N-methylpiperidinium chloride and N-methylmorpholinium chloride occur as well as the remains of the below in the production by

Condensation called amines, hydrazines and hydroxylamines. Condensation products of phenacyl chloride or bromide with the same amines, hydrazines and hydroxylamines, such as phenacyltrimethy1ammonium chloride, phenacyltriaethylammonium chloride .

However, the diazo components can also be derived from any diazotizable heterocyclic amines without derive acidic, water-solubilizing groups. These amines come, for example, from the thiazole, benzothiazole,

Naphthothiazole isothiazole, benzisothiazole imidazole,

Benzimidazole, thiadiazole, pyridine, quinoline, indazole, thiophene , /

/ Selenazole, oxazole, oxdiazole, benzoxazole, pyrazole or Triazole series. The nitrogen-containing heterocycles can be quaternized, with the anions in the description of the basic residues called representatives come into imprint.

In addition to the basic groups Q, possible substituents of these amines are:. .

Phenyl and phenylazo groups, the phenyl rings also bearing further substituents such as chlorine, nitro, alkyl, alkoxy and alkyl mercapto radicals each with 1 to 1 h carbon atoms

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can, halogen, especially bromine and chlorine, Sulfaifwyi-, ■ ^ " Trifluoromethyl, cyano, thiocyano, nitro, aralkyl, in particular Benzyl, cycloalkyl, especially cyclohexyl

residues, as well as alkyl, alkoxy, alkyl mercapto, alkylsulfonyl, Alkoxycarbonyl, alkanoyl and Ν, Ν-dialkylsulfonamide groups, especially those radicals with 1-4 carbon atoms.

Preferred are the amines which have a heterocyclic Five-membered ring with 2 or 3 heteroatoms, mainly one nitrogen and one or two sulfur, oxygen or have nitrogen atoms as heteroatoms, in particular So the amines of the thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole series.

Preferred substituents of these amines are:

Halogen, in particular chlorine or bromine, nitro, cyano, trifluoromethyl, alkyl and alkoxycarbonyl radicals, each with 1 to 4 carbon atoms, phenyl and the above substituted phenyl radicals.

Examples of such heterocyclic diazo components are:

2-amino thiazole, ■.: ■

• 2-amino-3-methyl-thiazolium chloride 2 ~ AniiriG-5 ~ nitrothiazole,

2-Amino-5-methylsulfonyl-thiazole, 2 ~ amino-f> -cyan thiazole,

309828/10 42 _(L.

2-Ami no- ^ l-methyl-5-nitrothiazole 2-Amino- ' ⁱ l-methylthiazole, 2-amino-4-phenylthiazole, 2-Ληιίηο-4- (4'-chloro) -phenylthiazole, 2-amino ~ 4- (V-nitro) -phenylthiazole, 3-aminopyridine,

jJ-aminoquinoline,. .

/ 3-aminopyrazole, · ·

5 ~ amino-1-phenylpyrazole, ·. '· ■

5-aminoindazole,

5-amino-2-methyl-5,7-dinitroindazole,. ;

5-amino-1,2,4-triazole ,

> -Amino-1- (4'-methoxyphenyl) -pyrazole,. ;

5- (methyl-, ethyl-, phenyl- or benzyl) -! ^, 4-triazole,
2-aminobenzothiazole, · ·; ■

2-amino-6-methylbenzthiazole _i

2-amino-6-methoxybenzthiazole, ]

2-amino-6-chlorobenzothiazole,
S-amino-o-cyanobenzothiazole, ".

2-Amino-6-nitrobenzthiazole,:

2-amino-6-carboathoxybenzothiazole, 2-amino-6-methylsulfonylbenzthiazole,

2-amino-l, _{3,4-thiadiazole:} i

2-amino-l, 5,5-thiadiazole,

2-amino - ^ - phenyl- or 4-methyl-l, 5,5-thiadiazole, 5-amino-3- (2 ^f -, 3'-or V-pyridyl) -1,2,4-thiadiazole,

2-amino-4-pheny] - or -4-methyl-1,3,5-thiadiazole,

309828/10 4 2

2-Amino ~ 4 ~ methylthio-1,3,5-thiadiazole 2-Amino-5-phenyl-ljJ, h- thiadiazole 2-Amino-3-nitro-5-methylsulfonylthiophene,

2 ~ amino -> - nitro-5 ~ acetylthiophene _J ·. , .

2-Amino-3i5-tois (methylsulfonyl) thiophene _i

i ^ -amino - ^ - methyl- ^ nitroisothiazole, '

3 ~ amino-5-nitro-2jl-benzisothiazole, ■ _; j

^ -Amino-T-bromo - ^ - nitro - ^, 1-benzisothiazole, -. '

5-amino ~ 4-nitro-l-methylimidazole _i '·

ⁱ l-Amino-5-t) roni-7-nitrobenzisothiazole _J. . _:

The coupling component is preferably a 3-cyano-4 _i 6-diamiriopyridine substituted in the 2-position. The two amino groups are preferably not further substituted. Aliphatic and aromatic amino, oxy or mercapto groups are in the 2-position. These compounds can be prepared by reacting the 2-bromo-3-cyano-4,6-diaminopyridine with a primary or secondary amine, a hydroxy or mercapto compound. ·

Examples of amines are: naphthylamines aniline and its derivatives, such as l-amino-3-chlorobenzene, l-amino-4-carbethoxybenzene, l-amino-2 _i , 4-di- · cyanobenzene, l-amineΌ -2-methoxy-4-nitrobenzene, 1-amino-2-. inethanesulfonyl-4-chlorobenzene, methylaminobenzene, ethylaminobenzene / 1-methylamino-J.-chlorobenzene. ^ -;

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1- (2'-chloroethoxy) -2-amino-4-nitrobenzene, ^{1- (2f} -chloroethoxy) -2-amino-4, 6-dinitrobenzene, ^{1- (2!} -chloroethoxy) -2-arnirio-5 -methanesulfonylbenzene, 1- (2 * -chloroethoxy) -3-amino-4-chloro-6-nitrobenzene.

Primary and secondary aliphatic amines such as methyl, ethyl, isopropyl, hexyl, octyl, decyl, methoxyethyl, methoxypropyl, isopropoxypropyl, dimethyl, dimethylaminopropyl, diethyl, chloroethyl, dimethylaminoethyl, ethanol , Diäthanoi-, propanol, benzyl or cyclohexylamine, morpholine, pyrrolidine, piperidine, piperazine and 3-Pi ° ^c ~ lyl amine.

Examples of alcohols that may be mentioned are: ethanol, propanol, isopro panol, butanol, 2-ethoxyethanol, cyclohexanol, benzyl alcohol, Phenol and its substituted derivatives.

Examples of mercapto compounds are: ethyl mercaptan, thiophenol.

Preferred coupling components are those 3-carboriamido- or 3-cyano-4,6-diaminopyridines, which are in the 2-position carry an amino group.

The starting products, in particular the diaminohalopyridines, are, for example, according to Boldt et al., Angew. Chemistry, volume 82: 392 (1970) W.J. Middleton, U.S. Patent 279-8-6; Sasaki et al., Tetrahedron Letters 1971 »p. 4593 available

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(cf. also Yokoyama Bull. Chem. Sog. Japan Volume 44 (1971),

s. 3195). '. '

The 3-Cyangruppe can be concentrated by saponification Convert sulfuric acid into the 3-CONHp group.

In those diazo and coupling components that are a reactive atom or group, e.g. chlorine, bromine, sulfonic acid ester, alkyl sulfate, hydroxyl or containing amino groups, as discussed below, by condensation before or after the coupling basic groups are introduced.

Components with quaternizable nitrogen atoms can before or after the coupling with quaternizing agents be treated.

Instead of a uniform diazo component

it is also possible to use a mixture of two or more of the diazo components according to the invention and, instead of a single azo component, a mixture of two or more of the azo components according to the invention.

The diazotization of the diazo components mentioned can be carried out by methods known per se, for example with the aid of mineral acid, in particular hydrochloric acid, and sodium nitrite

or, for example, with a solution of nitrosylsulfuric acid in concentrated sulfuric acid.

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The coupling can also be known per se Manner, e.g. in a neutral to acidic medium, optionally in the presence of sodium acetate or similar buffer substances that influence the coupling rate or Catalysts such as pyridine resp. its salts, are made.

In the event that a dye of the formula

or the formula

where X is an anion and R_ is an alkyl, cycloalkyl or aralkyl rest is to be produced, a hydrazone of the formula

/ ν

\ G = N-NH,

R ₇

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wherein R is the same as above with those given above Coupling components are reacted in the presence of oxidizing agents.

In the production by condensation one uses one Dye of the formula

wherein D ₁ Z ,, Z, Z and Y have the meaning given above, but at least one radical Z and / or D instead of a basic group contain a reactive atom or a reactive radical which is etherified with an amine, hydrazine, or etherified hydroxylamine can react with a carboxylic acid halide, or a dye of the formula

where D ', R ,, Rp, R- ,, R ^ R ^ -, Y, Z, ρ and q' have the meaning given, but ρ j-q must be at least 3 and V is a reactive atom or group mean, with an amine, hydrazine, etherified _n HydroxylarrJn, a pyridine carboxylic acid chloride or a-

30982 8/10 A 2

optionally quaternary aminocarboxylic acid chloride. Possible reactive atoms and groups are:

Halogen atoms, especially chlorine or bromine, benzenesulfonic acid ester groups, such as p-toluenesulfonates and benzenesulfonates, low molecular weight, i.e. 1 to 4 carbon atoms containing alkylsulfonic acid ester and alkylsulfuric acid half-ester groups like methyl sulfate and methanesulfonate, Hydroxyl and amino groups.

Preference is given to using tertiary amines, hydrazines or hydroxylamines for the condensation, as these are used Way directly to cationic dyes with quaternary nitrogen. The anion of these dyes corresponds to as long as it is not subsequently exchanged, one of the reactive radicals V. The dyes used in the preparation by condensation are expediently 'by coupling manufactured. This is based on compounds that correspond to the components used in the coupling process, but the above-mentioned split-off groups in the basic groups

containable atoms or groups.

The dyes prepared from these components by coupling are according to the invention with pyridine or optionally quaternary aminocarboxylic acid chlorides, amines, hydrazines or etherified hydroxylamines.

309828 / 104.2

Such compounds include, for example, the following:

Amines : primary and secondary such as methyl, ethyl,. Isopropyl, methoxyethyl, methoxypropyl, dimethyl, diethyl, A ethyl phenyl ,. Diethanoi-, propanol-, benzyl-, cyclohexylamine, pyrrolidine, piperidine, piperazine, morpholine, tertiary such as trimethylamine, triethylamine, dimethylaniline, "triethanolamine, pyridine ^ picoline, lutidine, U-methyl-P.iperidine, N-methyl-piperazine, N-methylmorpholine, quinoline or pyrimidine.

Hydrazines; N-methylhydrazine, Nj.N-dimethylhydrazine, N, N ¹ -diethylhydrazine, N, N, N'-trimethylhydrazine, N / N, N, N'-tetramethylhydrazine , N-aminopiperidine, N-aminopyrrolidine, 1,5 -Diaza-

Etherified hydroxylamines:

N-OC ₀ H ₁

HN-OCH ₅

STILL,

CH

H ₀ C /

CH

H ₀ C

. '· CH ₀ -CH ₉

■ NO— GBT ^ά ^ N) H. CH,

309828/1042

NIi-OCH,

CH

NiH

ClCH ₀ CH

H ₀ C CH
² N

or

H, C- <I> - ⁰

0 CH

S0 _o 0-CH _o CE

Carboxylic acid chlorides

(m-N CH ₀ -COCl

CH, Cl

CH,

COCl,

COCl,

COCl

The reaction of the dye containing, for example, a halogen or sulfatoalkyl group with the amine, Hydrazine or etherified hydroxylamine takes place in a neutral solvent, e.g. in chlorobenzene, alcohols or aqueous alcohol mixtures or dimethylformamide, or even without a solvent, useful in the case of increased Temperature in an excess of the hydroxylamine and • optionally with the addition of catalysts, e.g. NaI.

309828/1042

The acylation of an acylatable hydroxyl or amino group containing dyes with the mentioned carboxylic acid chlorides is preferably in the presence of acidic agents such as alkali and Alkaline earth acetates, hydrogen carbonates and carbonates or pyridine in an organic or organic-aqueous Medium carried out according to methods known per se.

Those new dyes which contain a quaternized nitrogen atom can, according to a further production variant, also be obtained by treating the corresponding dyes which contain a non-quaternized amino, hydrazino or etherified hydroxylamino group or nitrogen-containing heterocyclic group quaternized with alkylating agents. As such alkylating or quaternizing can be used as: esters of strong mineral acids _s in particular, low molecular Schwefelsäureester, or organic sulfonic acids, such as dimethyl sulfate, diethyl sulfate, Alkylhaloge, halides, such as methyl chloride, bromide or iodide, aralkyl halides. for example benzyl chloride, esters of low molecular weight, ie .. ■ 1 to 4 carbon atoms having alkane sulfonic acids, such as

Methyl ester. Methane, ethane or butanesu.1 folic acid, .. and esters of benzenesulfonic acids,

"309828/1042

may have additional substituents, for example methyl] -, Λethyl-, propyl or butyl esters of benzenesulfonic of 2 or ^J [-Methylbenzolsulf oic acid, 4-Chlorber.zolsul'i'onsäure or 3- or 4-nitrobenzene sulfonic acid.

The alkylation is conveniently carried out by heating in an inert organic solvent, for example hydrocarbons such as benzene, toluene or Xylene, halogenated hydrocarbons, such as carbon tetrachloride, tetrachloroethane, chlorobenzene, o-dichiorobenzene, or ^ • Nitro hydrocarbons such as nitromethane, nitrobenzene or nitronaphthalene. Also acid anhydrides, acid amides or nitriles, such as acetic anhydride, dimethylformamide or acetonitrile or dimethyl sulfoxide can be used as solvents in the alkylation. Instead of A large excess of alkylating agent can also be used in a solvent. In this case it is However, care should be taken that the mixture does not heat up excessively, as the reaction is strongly exothermic. Nevertheless, in most cases, especially in the presence of organic solvents, it is necessary to clean the reaction mixture to be heated from the outside in order to set the reaction in motion. In special cases, the alkylation can also be carried out in aqueous Medium or using an alcohol, possibly in

309828 / 10-2

The presence of small amounts of potassium iodide can be carried out. If necessary, the dye salts are expediently purified by dissolving them in water, with any unreacted starting dye being filtered off as an insoluble residue. Water-soluble salts can be added to the aqueous solution , for example sodium chloride, the dye can be deposited again.

The dye salts obtained can according to the process Introduced anions contain. However, this can also be done subsequently by other of the anions specified further on be replaced. -

The dyes or dye salts obtained according to the invention with an optionally quaternized Amino, hydrazino-etherified hydroxylamino group or -. nitrogen-containing heterocyclic group are suitable for Coloring and printing of a wide variety of fully synthetic fibers, such as polyvinyl chloride, polyamide, Polyurethane fibers, as well as fibers made from polyesters of aromatic dicarboxylic acids, such as polyethylene terephthalate fibers as well as anionically modified polyester and polyamide fibers in particular but of polyacrylonitrile fibers or from polyvinylidenedenide fibers (Darvan).

Under Polyacrylnitrilasern is meant especially polymers which more than 80%, for example 80 to 95 <fo contain acrylonitrile; they also contain 5 to 20 % ''

309828/1042.

Vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, etc. These products are sold, for example, under the following brand names: "Acrilan I656" (The Chemstrand Corporation, Decatur, Alabama, USA), "Acrilan 4l" (The Chemstrand Corporation), "Creslan" (American Cyanamid Company), "Orion 44" (Du Pont), "Crylor HH" (Soc. Rhodiacdta SA, France), "Leacril N" (Applicazioni Chimice Societa per Azioni, Italy), "Dynel "(Union Carbide Chem. Corp.)," Exlan "(Japan Exlan Industry Co., Japan)," Vonnel "(Mitsubishi, Japan)," Verel "(Tennessee Eastman, USA)," Zefran "(Dow Chemical, USA ), "Wolcrylon" (Agfa film factory, Wolfen), "Ssaniw" (USSR) and also "Orion 42", "Dralon", "Courtelle" etc.

These fibers, which can also be dyed in a mixture with one another, are obtained with the new dyes intensive and level dyeings with good lightfastness and good all-round fastness properties, especially good washing, Sweat, sublimation, crease-proof, decatur, ironing, friction,

Chlorinated water, / carbonizing, water, / sea water, dry cleaning,

Fastness to over-dyeing and solvents. The inventive novel dyes have including good stability in a larger p _H range, a good affinity for example, in aqueous solutions of various _IT p values and -

309828 / 10A2

good bench fastness. Another advantage "is the good reserve for wool and other natural polyamide fibers as well as cotton. Draw the colors are characterized by bright nuances.

The quaternized, water-soluble dyes are generally not very sensitive to electrolytes and show partly an extremely good solubility in water or polar solvents. The staining with the quaternized / Water-soluble dyes generally take place in an aqueous, neutral or acidic medium, at the boiling point under atmospheric pressure or in a closed vessel under elevated temperature and pressure. . .

They can also be applied by printing on dB fibers be, "For this purpose one uses, for example a printing paste which contains the dye in addition to the auxiliaries customary in printing. You are suitable also for the mass coloring of polymerization products of acrylonitrile, as well as of other "plastic, possibly dissolved masses, in lightfast and washfast". Nuances, also for the coloring of oil paints or. Lacquers ,. or finally for the coloring of paper and of stained cotton ..-.-. · -. ■ _'- ■ ■ · .. ■

30 9828/1042

]) ie, jiMii ( ^r / Mi HDt (Ji "the new FarboloiTcn, whose construction" always contains non-quateniiized Hti ck.slof i'atotiie and which are not or little; water-soluble / have been intended Ig in fcinverto In the form and with the addition of dispersants such as fUijfo, sulphite cellulose blue or synthetic detergents, or a combination of different wetting and dispersing agents. As a rule, it is advisable to convert these dyes into a dye preparation before dyeing ( has let a Diapci ^ greed medium and feinvertellten dye in such a form that upon dilution of. Färbst of fprtiparate V / produced ater a fine dispersion. such PärtofStoff »· preparations can in a known catfish, for example ^by! grinding ·. of the dye in highly effective milling devices are obtained in dry or wet form with or without the addition of dispersants during the grinding process. They are also used for dyeing and printing a wide variety semisynthetic un d fully synthetic fibers are suitable, such as cellulose acetate, polyolefin, for example modified polypropylene, polyester, polyvinyl chloride, polyamide or polyurethane fibers, but especially fibers made from polyacrylonitrile.

In order to achieve strong stains, it is advisable to start the staining process at higher temperatures, for example at boiling point to perform.

309828 / 1OA2

BADORiGfNAL

A dispersant is advantageously added and that The dyebath is made slightly acidic, for example by adding a weak acid, e.g. acetic acid.

The present dyes can also be applied by printing. For this purpose, for example, a printing ink is used which, in addition to the auxiliaries customary in printing, such as wetting agents and thickeners, contains the finely dispersed dyestuff, if necessary in a mixture with other dyestuffs.

In the examples below, the parts, unless otherwise indicated, mean parts by weight that

Percentages by weight, 'and the temperatures are in Degrees Celsius. ·

309828/1 042, ... . - BATH

? 263109

Before \ schr.t Π

ΙΟ, 6 ^ ¹ ^ parts -Brorn-JJ-cyano- ^, 6-di aminopyr idin parts alcohol and l6 ^r Leile 70 $ aqueous sodium Aethylamiri be during H hours heated in an autoclave at 100 °. Excess atriiri and the other volatile constituents are evaporated in vacuo and the residue, which is the compound of the formula

H ₀ N

ON ■

contains, is used as a coupling component without further purification

Regulation 2 ■

10.65 parts of 2-bromo-3-cyano-4,6-diaminopyridine and 24 parts of aniline are heated at 140 for 4 hours. The mixture is cooled, provided with Natriurnhydroxydlösung to pH 7-8 and the excess aniline ii is driven off with steam. The unusual product of the formula

309828/1042

is separated, and air without purification. Coupling components - You get a yellow powder with a melting point,

147 °.

Vor.'u: h.r-j ft 3

4.26 parts of 2-broin-j5 ~ cyano-4,6-diamiriopyridine become 3 η 120 parts of methyl alcohol ho is κ dissolved. J5 parts of sodium methyl acetate are added and the mixture is refluxed until there are no more starting substances in the thin-layer chromatogram is detectable. The .solvent will removed in vacuo, the residue stirred with ice water, the insoluble product separated by filtration, the .. crystalline, ge] he filter cake washed with cold water and dried. The compound has the formula

and has -eiiieri .iichjnelz-purikt: from Yf ¹ I

309828/1042 '·'

BATH ORIGINAL Regulation 4

6.4 parts of 2-bromine-3-cyano-4,6-diaminopyridine _J, 14.5 parts of phenol and 2.5 parts of potassium carbonate are heated at 140 ° until no more starting substance can be detected in thin-layer chromatography. The mixture is poured into water and adjusted to pH 9 with sodium hydroxide solution. The precipitated compound of the formula

CN

is filtered off, washed with water and dried. The melting point is ΐγ6

30982 8/1042

• -ή

Regulation 5

8.4 parts of 2-chloro-3-cyano- ² l-, 6-diaminopyrldine and 20 parts of 3-dimethylamino-l-propylamine are at 100 for 6
Heated for hours. Excess arnine is evaporated in vacuo and the viscous residue, which is the compound of the formula

contains, is used as a coupling component

309828/10

example 1

h, 57 parts of ^ -aminophenacyltrimethylammonium chloride, obtained by reacting ^ -aminophenacyl chloride with trimethylamine v / earth dissolved in 20 parts of v / water and the whole solution is mixed with 8 parts by volume of concentrated hydrochloric acid. The solution is diazotized at 0-5 by adding ¹ ': of 5 parts by volume of sodium nitrite solution. The diazo solution is added at 0-5 to a solution of 4.5 parts of 2-anilino-3-cyano-4,6-diaminopyridine in JO parts of alcohol. The coupling mixture is by adding
Sodium acetate solution made Congo-neutral. After the coupling has ended, the mixture is diluted with 10 ^ iger sodium chloride solution. The dye is filtered off, dissolved in hot water and, after filtering the solution, salted out from the filtrate. The unusual dye of the formula

(CH) N-CH ₂ -C

he

filtered off and dried. He dyes polyacrylonitrile fibers in red-yellow shades of excellent
Fastnesses.

309828/1042

■ Example 2 _ * - -

Parts of 5-Amirio-3-phenyl'-l> 2 _J ⁱ l -thiadiazole are dissolved in 20 parts of formic acid. 1.4 parts of sodium nitrite are introduced at 0 to 5 ° and the mixture is stirred for 30 minutes. Then 0.1 OS parts of sulfamic acid are added. Then 6.9 parts of 3 (3'-cyano-4 ', 6'-diaminopyridine-2 ^t -) aminopropyl-1-trimethylammoniummethosulf.at are added and rinsed with 10 parts by volume of formic acid. The mixture is slowly heated to 60 and stirred at this temperature for 2 hours. The paste is diluted with water , dissolved while hot and, after filtering the solution from the filtrate, salted out with sodium chloride and zinc chloride.

The unusual dye of the formula "■"

will ^J atof iltrier't and. dried. It dyes polyacrylonitrile fibers in reddish yellow shades with very good fastness properties.

The coupling component is obtained by alkylation of the intermediate described in instruction 5 with dimethyl sulfate in chlorobenzoliseher'Lösung ·. - "■ ■ '- ■' ■ _. ·

Further dyes of the formula are obtained in an analogous manner

D-N =

B E

in which the symbols D, A, B, C, E and X have the meaning given in Table 1.

309828/1042

Table 1

(CH ₃ J ₃

A.
NH ₂ B.
NH ₂ C.
Piperidyl E.
CN ' x ■
Br hue
■ golden yellow NH ₂ NHC ₆ H ₅ CN Cl golden yellow

O CD OO PO OO

(CH ₃ )

NHCOCH ₃

OC ₂ H ₅

CH NH ₀ NH,

NH ₀ 'NH,

NHCgH ₄ OC ₆ H ₅ CN, "Cl yellow,

CN Cl '' golden yellow

NHCH ₂ CON (CH ₃ )

CN Cl orange

• Η

Cl OQH- ■ 2

CN CH ,, COO goldgiU)

Xi u d

H Φ

cd ο

H fctO

, Ω

H Φ M

HO

HO

HO

fi

CNJ

CM O ISS

CQ

CXJ

C \ J

OJ

CM

CVi

CM

CM

309828/1 O4 2

■ j-

IHC: H ₀ OH 4 ο

-HHOH (GHj) ₂

E X

CI Cl

orange

IH,

IH.

CI I

golden yellow

CD CO,

(-CH ₅ V ₅ C ₂ H ₄ OOC

CH.

IH.

IH.

IH.

1 (CH,),

CI \ CE "SO. golden yellow

IHC ₂ H ₄ Cl CI C ₇ H ₇ SO ₅ • yellow V

OC ₀ HI 2

IH.

NHC ₃ H

. G ^ -Hj. 'CI GEL ¹ SO- orange

CH

IH ₂ HHCgHp

NS-

lHC.H _e
6 "5

CI Cl. , yellow

CI

yellow

A-B C

X shade

O,

OCH,

NH NH, OC.H

ά £ ■ O 5

CN

yellow

NH-cyclohexyl CN HSO. yellow

CH

(CHj) ₃ NCH ₂ COHKiCH ₂

NH ₂ NH ₂ SC ₂ H ₅

CN Cl yellow

H-N = H

NH

CN

CH-SO.
-5 4

yellow

CM I ^:

4s-

ω E (D

H ω

ω ftf

ce ο

, α H

KD E (D

H ο

HO

H O

CV

i;

Q O

S5 O

309828/1042

CVJ

CM

O O

(M

OJ

CM·

in

(M

in .W

(M O

τα

CM

ta

ο ο

cn o

'"us Μ

iU O CM -φ

ο W

- ^ CM

H Φ

CD

, α ^ a H H Φ Φ «Ιθ «Ιθ

Kl

ω ο

CM O O

H O

■ a

OJ

OJ

CU O O

! 25 - O

309828/1042

2283109

H φ

, Ω

H Φ

O CO

Oil

c m

ro

Q CQ

OJ

O- Hj-t J-H

■ o

OJ

in

IN THE

O4

W *

O O

OJ O

O -

-Q

OsI

Cvj

30 98 28 / 10A2

H (υ to

ti

HO

- «rf- ο to
• Η • Hf. O ω CO., JQ • Η ö,, ·; -PH co ^ a H O Φ ■ Ρ H ^ i ' Φ h * 0 ο ω ο «» O ο O Wt approx CQ in in C- CM VO O H ο ο O

CM

125
O

O O

OO O
O

O
O

O
O

IT »

CM O

in

CM

to

CM ο »Ρ"
ο νο ο ίο
O

in

CM O

CM

in M

CM O

CM

CM

• Λ

VO
O

CM O

CM O CM

ο *

CM

309828/1042

E X hue

4-nitrophenyl

HH, CN Cl ■ orange

5-nitrothiazolyl-2-

. NH

2

IiH

4-nitro-2-trifluoromethyl-, EHCH CH ₉ I \ N (CH ). '■ phenyl. ^{ά N} - ^/ ->

O CO CO ΓΌ OO

4 (4 '-nitrophenyl) azophenyl

_ »2-chloro-4-nitrophenyl

NH,

NHC ₂ H ₄ N (CH ₃ ) 2 · N (C ₂ H ₅ )

NH,

2,5-dichloro-4-dimethylamino 'sulfony! phenyl.

NH, NHC ₃ H ₆ N (CH ₅ ) ₂
C ₂ H ₅

CH
^4th

NHC ₀ H

OC ₄ H ₉
)

2 "5 '2

CN C ₂ H SO ruby

CN Cl scarlet fever

CN Br "orange

CN CH, SO "Scarlet 3 3 ' ,

₆ H ₄ OC ₂ H ₄ N (0H ₃ ) ₃ (-.p) CN CH ₃ SO ₄ 'orange

4-phenylazophenyl

'NHC ₅ H ₆ N (OH ₅ ) ₂ OCH, N (CH ₃ ),

CN C ₅ H ₅ SO ₃ golden yellow

4-nitro-2-thiocyanphenyl NH,

NHC H ₆ N (CH ₃ )

NH.cyclohexyl

CN CH "SCN" orange

ο
co

5 -Ni t ro-7-bromo-2, l-benz isothiazoiyi-3

NH,

E. X ■ Parta volume CN Br Red

-Chlor-2-trifluoromethyl-OC

phenyl

2,6-dichloro-4-nitrophenyl "NH ₂

co .... ·· ■. /

οο S-Acetyl-J-nitrothiophenyX ■ NHO ₀ H, Ν— N κ ». ^d 4 \ /

οο 'C «.H ^

ο 3-Buxylthio-1,2,4-thia-: · NH

4- (2'-hydroxyl'-methylphenyl) azophenyl

6-methylsulfonylbenzthiar

1-anthraquinonyl

NH,

morpholino morpholino
ι NH ₂ NHC ₂ H ₄ N (C ₂ H ₅ ) N (GH). N (CH)

NHC ₂ HN (C ₂ H ₅ ) ₃

NH ₂

NHC ₀ H.OCOCH ₀ (CH,), N (CH,)

"NH,

N (CH,),

C ₀ HN H 0
4i \ /

CN

CN I orange

CN CH SO Br rub in CN Br) Cl red f. ti O 1 / 3K) ₄ Sib CN orange CN 109 sharp
laugh CN Crowd
laugh

CD C £> OO, NJ CO

5 ~ chloro-2-methylthio-n "phenyl

2-ethoxy carbonyl r-4 τ nltrophenyl

1-naphthyl

NHCH

phenyl

6-bromo ~ 2-oyan-4 "-nitro-

phenyl

l-methyl-4-nitroimida-. zolyl ~ 5 <-

^{2-methoxy-5-i} niti ophenyl

2,6-dichloro-4-aminosul ~ _r NH fonylphenyl. ^f

j;

C ₂ H ₄ OH

.. B • c piperidino piperidino NH ₂ , NHC.H.NHCb
D 4 N (OH ₃ I ₂ N (CH ₃ J ₂ · SC ₂ HN (C ₂ H, -) NH ₂

EX '■' · shade CN Cl ; "· yellow

) ₃ (-m) CN HSO ₄ scarlet

NHC ₂ H, N

S>

CH

NHCH (CH ^) ₉ NHCH (CH,), NHC ₃ H ₆ N (CH ₃ ) ₃ NHC ₂ H ₄ C ₆ H ₅

CN CIHLSG ₃ orange

CN

CN Cl ruby

CN 1/2 SO ₂₁ scarlet

CN CH ₃ SO ₄ yellow

NHC _fi HCH ₉ N (CH,) (-P) CN ' Cl KJ 263 ' CD
.CD

4-Azophenyl-2-nitro-NHC-H ₀ N (C ₀ He.), Phenyl ^{4 ö |} * ⁵ '

NH,

2,4-dicyanophenyl B
N (CH-),

E X

CN Cl

CN

Colors οι Red;

C ₃ H ₅ SO ₄ orange

1-phenyl-3-methylpyra- OC ₀ HK (CX) zolyl-5 ⁴

5,6-dichlorobenzthia-NH zolyl-2

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

NHC

C ₆ H ₄ OCH (-ρ)

5-thiocyan1; hiazolyl-2 NH,

2-methyl-4-nitrophenyl

4-Pyrrolidinocarbony1- NHC ₀ H. (C.

phenyl ^ά

NHCH (CH) ₂ NHCH (CH ^) ₂ CN Br yellow NH ₂ NHN (CH ₃ ) ₂ C * CH ₃ SO ₄ orange pyrrolidino pyrrolidino - ■ C ₇ H ₇ SO ₃ ruby NHC ₃ H ₆ N (CH ₃ ) - NHC ₃ H ₆ N (CHj) ₃ - CH ₃ SO ₄ orange NH ₂ OC ₂ H ₄ N (C ₂ H ₅ J ₃ CN C ₂ H ₅ SO ₄ yellow NHC ₂ H ₅ NHC ₂ H ₅ CONH ₂ 1/2 SO ₂ ^ yellow 263

D.
2,4-DinitiOphenyl

IiH.

B NH ₀ NHC,

C ₀ H

4- (4 ^I -chlorophenyl) azo-2 UEC ₉ HNC ₉ H. NN (CHj ₉ N (CHj ₀ EX
CN Cl *

CN 'Cl

methoxy-5-methylpheny1 4-methoxy-2-nitrophenyl

° 2 ^H 4

NH, CN

¹ shade of red

Scarlet fever

CH ₃ COO orange

2-methyl-5-ni.trophenyl NHC ₉ H _A N.

4-ethylamino sulfonyl

phenyl

5-phenyl-l, 3, 4-thiadia-

zolyl-2

2-'ethoxy-4-nitrophenyl

H>

NH

4-phenoxycarbonyylphenyl NHC-HgN

t--) N (C ₉ H ^) CN, Cl ■ · 'yellow

NH, NHC ₂ H ₄ N (C ₂ H ₅ ) ₂ CN Br

.CN Cl

NHCH,

CN

-N-CH

CH ₃ ) ₂

orange

reddish yellow

0 «H, -. SO- orange

CONH ₂ Cl

reddish gray?

C3- CO

3-phenyl-1,2,4-thiaaia- ■ zolyl-5

C EX

ι * CONH ₂ I.

Golden yellow color

2,6-dibromo-4-nitrophenyl

NH,

NH,

SC ₂ H ₄ "N (C ₂ H ₅ ) ₃ CN

1/3 PO4 yellow

2,4,5-triehlophenyl NH,

1-methylbenztriazolyl-4-NHC

2-cyano-4-nitrophenyl NH,

NH,

5-nitro-indazolyl-3

NHC ₀ H.OC 2

NH,

NHC ₂ H ₄ N (CH ₅ )

OCH,

N (CBL) ₂

CN HSO, yellow

CN Cl

CN

CN Cl

yellow

^ -SO. scarlet 0 4

orange

2,6-bicyano-4-nitropiienyl

NH,

NHC H ₆ N (i

OT HCO ₃ ruby

5-methyl-1,2-oxazoyl-3 SC ₂ H ₄ N (CH ₃ )

C ₂ H ₄ CONH ₂

CN Cl

2,4,6-tribromophenyl.

6 '3 ^y 3

,: X shade CH ^ SO. yellow

J? 4 *

5'-nitro- ⁱ 2., l-benzisQ-
thiazolyl-3 co
OQ 4-phenylamino-3-ni-
tropiie.nyl OO
O 4 «Butylsulfony1-
phenyl KJ 2-cyano-4,6-dinitro-
phenyl 3-pyridyl Quinolinyl-8

.MEL

HH,

NH.

NH

/ i ^H g) 2

N H

CN

CN Cl

NiCH ₃ ) ₃ SCH

NH,

CN
■ CN

yellow

rub in

CH ^ SO 'yellow-

CN '■ Cl

orange

CN 'C ₇ H ₇ SO ₃ seharlaoh.

NH ₂ ,, NHC ₆ H ₄ CH ₂ N (CH ₃ ) ₃ (p) PN, Br yellow

Cl
Cl

orange

yellow

Example 3

2.76 parts of 4-nitroanlline are made into a paste with 8 parts by volume of concentrated hydrochloric acid and mixed together
stirred in by 80 parts of ice and water. The suspension
is mixed with 5 parts by volume of 4N sodium nitrite solution at 0
to 5 diazotized. The diazo solution becomes a solution
of 4.68 parts of 2-dimethylaminopropylamino-3-cyano-4 _> 6-diaminopyridine in 20 parts of alcohol. After the coupling has ended, the mixture is adjusted to pH 8.9 with sodium hydroxide solution. The precipitated dye is filtered off, washed with water and dried. It dyes polyacrylonitrile fibers in red-yellow shades with excellent fastness properties.

Further dyes of the formula are obtained in an analogous manner

BE

wherein the symbols D, A, B, C and B are used in the following Meaning given in the table.

30 9828/1

■ Table 2 ABC

E shade
Pyrrolidino CN golden yellow

Cl

WH NH, EHC. H_

2.2 49

CN golden yellow

OO NJ OO

'ca,'

GN yellow

: ₂ . NH ₂ NHC ₆ H ₄ OCH ₃ (m) CN yellow

<H>

NH ₂ SC ₆ H ₃ Cl ₂ (2.5) ■ CN yellow '

E shade

⁰ A _x

C ₂ E ₅ O

-N = H-

Cl

N (C ₂ H ₅ ) ₂

CN yellow

O CO OO IO CO

(CH) ₂ NH ₆ C-HNO

N = N

OCK

-N = N-

OH, NH,

NH ₀ NH

NHCH ₂ C ₍

CN orange

NHC, H, OCH "
6 3

CN orange

■ COQEji HO 2 s. •

HHC ₆ H IHC ₂ H ₅ NHC ₂ H ₅ . CN orange

B shade.

-COCE ₀ N (ι WH-CH,

H
0

CF orange

ep; approx

(CH,

(CH) NH.C ^ OOC

NHCH.

NH.

NH,

NHCH ₁

CN ¹

orange

yellow

CN yellow

NH-cyclohexyl NHCH (CH} ₀ NHCH ( QgL).

'Mp .. NHC-H ₀ OH

CN reddish yellow

CN yellow

U, O

-ο

, Q

H Φ

fei O

CJ

O in O M. O VO O O W. CJ O

CM

ITS O

CM O O

ft

HO -a IN THE

fit JEl

(M

in

«M

ÜQ.

CM

CM

309828/1042

■ ttö

= 8 O O

CM

■ CM

if

NHCH CM

CM O

'Bi CM

CM

CM O

LTv-

f-r *

HH
CM

O O cn

CM

CM Ο

CM O

28/1042

2-bromoH- nitrophenyl

ABC E shade

NH ₂ NHC H ₆ N (CH) ₂ CN orange

4-phenylazophenyl NH ₂

NHC ₃ HN (C ₅ H) ₂ CN orange

4-chloro-2-cyano
phenyl 3098 6-nitrobenzthiazo-
lyl-2 IO co
- »^
O 4-ethoxycarbonyl
phenyl K * 2-methyl-4-nitro-
phenyl 4-C4'-nitrophenyl]
azophenyl

NH ₉ NH NHC ₀ H. N <

GCH

CN reddish yellow

CN scarlet

Nile

CH ₃

CL
^4th

NH ₉ NHC.H N < ^{4 y} CN 'golden yellow

OC H

NHC ₂ H ₄ N

HH ₂ NHC H ₆ NH

CN orange

CN orange

sulfonylphenyl - NH NH NHC H. N HO CN orange

^N - ^/

3-phenyl ~ 1,2,4 ~ thiadiazolyl

BHÖ ^ H.U. Η HCH *

E shade

4-diphenyl

NH _r

CN

5-chloroindazolyl-3 orange

S-acetyl ^ -nitrothio- NHO ₉ H. N (CH,),, '. phenyl-2 ^? '

5-methylsulfonylthia * "έ oly 1-2

3-phenoxy B "ialf © nyl- ^; phenyl

-Η ^

Floor Η

NHGH (GH).

H IiC ₀ H _n - NHG _O H NHGH (CH ₅ ),

GN

GN yot 'is * ¹

CN

Quinolinyl-S

NHG ₀ H ₇₁ NH NH. NHCH-

4 -Buty! Amino earls onyl NH, NHGH ^ "

₅ ) ₂

CN orange GN

2-ethyl-5-nitrophenyl

NH,

NHC

CN

hue

yellow

2-chloro-4-nitrophenyl

NH

CN

yellow

2-ethoxycarbonyl-4-nitrophenyl

NH,

SC ₂ HN (C ₂ H ₅ ) ₂

CN

yellow

UD CO ΙΌ CD

isothiazolyl-5

OC H ₄ N (CH,) ₂ piperidino piperidino

thiazolyl-3

2-cyano-4-nitrophenyl

NHCH (CH,) _?

NHC ₂ H

CH ₃

CN

CN

Red

Scarlet fever

orange

Z , 4,6-trichlorophenyl

SC ₂ H ₄ IC C ₂ H ₅ ) ₂ IH,

yellow

2-methyleulfonyl-4-

nitrophenyl

IHC

HHC ₂ H ₄ C ₆ H ₅

Scarlet fever

rf -P -P ο · H O O O ω -P ti U ftf CD O Pm EiO

(M

CM

O O

! = 5

(M

in W.

(M O

CM

M o

(M

LPv

CM

V £

M to O

(M

LT \ Ph

CM O

CM

CM

! 25

CM

CM

CM

CM

H -P I. H H ci O & pj -P P) •H φ ω r | -N / A a <r \ Xi Pt d pi P ₁ CD H H O ■ rf |> j fn I. -P -P H ω • Η I. ω CJ rf O a co • Η · •H pi O I. •H
I.

CM

CM

3.09028 / 1042

CIBA-UEIUY AU "» · Example 4

3.83 parts of the dye described in Example 3 are dissolved in 150 parts of hot chlorobenzene. 1.9 'parts Dimethyl sulfate, dissolved in 10 parts of chlorobenzene, are added dropwise and the reaction mixture for 3 hours at 95 - 100 stirred further. After cooling, the suspension is filtered off. The filter residue is in helsse'tn ■ Dissolved water and, after filtering the solution from the filtrate, salted it out with sodium chloride and zinc chloride. The precipitated dye of the formula "■

^ -NiIC ₃ H ₆ N (CH) CN,;

is filtered off and dried. It dyes polyacrylonitrile fibers in red-yellow tones of excellent fastness properties. Other dyes are obtained in an analogous manner by alkylation of the dyes of the formula designated below

D-N = N- <T y- c

B E

with those given in the penultimate column of the table Alkylating agents.

30 9 8 2 8 / 1'0 A 2

Table III

D '

B Medium alkylation shade;

MHCH CM

golden yellow

N '

MHC

MH,

2,

CM GJEt ₇ SO ^ CH ,. 7 5

., golden yellow

-C ₂ H ₄ MHO ₃ S '

: M

—Ν

, J-

M ' ¹ M

.JL

* S

-S MH _n NHCH ₀ C; H _c . "■ CM ..: 2 6 5

'golden yellow' ^v

MHGH ^ - ^ ₀ ^ MHG ₂ H ₅

CM

red; tichig 'f oraiige ■

CM

golden yellow

SCH ₅ MH _2; ■; _ GM

,yellow

, α H φ H Φ CiO

, α H Φ

ra

ÖD

d H Ρ Φ

! >> Jh -H M φ + ^

H · Η · Η

<4 η a

CM

O CM

O O

O H O

CM

I AM

CM O

52! O

O O

CM W

CM

in

CM W

CM

W * CM

309821/1042

H H , Ω H Φ Φ H Φ ftf ftf Φ ftf Sl

I. O O O J-iH
HH O ω - χη CQ CQ - O CQ ftf CvJ CM CM to CM £ ί ι — I ..— s O 3 φ ■ nT to
W. CQ " ? Η -P
Φ · Ρ ο O ο dd HH
CM • Η · Η ^^ * - ' C- O η a Ό ^v ~ ' CvJ ItH HH O O O O S O O

to OJ t H , - ^ ' W. to V VO M. O O O O W.

IT \

LH

CM
O

I-tH

CvJ

to

CvJ

CM

to

W.
O

CM
W.

HH
CvJ

CM

to

W O

CM

CvJ

CM

CvJ

to W-

H-)

MD O

HH

CvJ O

30 9 8 2 8/10 4

2, S-dichloro ^ -nitrophenyl

NH,

NHC ₂ H ₄

E Alky shade

lation

middle

CN (CH_) ₂ S0. οrange

4-phenylazo-2-nitro- NHC H <^ N phenyl ⁴ ^ - '

NHC ₂ H

CN (C-Hj ₀ SO. Red 2 ο ε . 4

σ co oo

2, S-Tue thylaminosulfonylphenyl

4-chloro-2-trifluoromethyl phenyl

NH,

5-chloro-2-phenoxy-NHC ₂ H OC phenyl

NH.

NH

N (CH

NH,

NHC H N-CgH OCH (p) CN C H S0, CH ■ orange

N (CH) ₂

CN C ₇ H ₇ SO ₃ C ₂ H ₅ yellow

CONH

(CH) ₂ S0

yellow '

(CIL ,.) NNHC

NH,

NH,

NHC ₂ H ₄

CONH

yellow

VjJ-

Dyes with similarly good properties are obtained if one of the items listed in Table 2 is used . Dyes quaternized with one of the following quaternizing agents: dimethyl sulfate, Diethyl sulfate, ethyl iodide, butyl bromide, benzyl chloride, 2-chloroethanol, 2-chloropropionic acid ethyl ester, 2-bromopropionic acid amide, p-toluenesulphonic acid methyl ester and benaolsul-

ethyl acetate.

OJ

■ '. ■ - ■ ·.'"· Example 5 X ^

-1 ^ 5 parts. Sodium nitrite will be at 0-10 'in l8 Parts of concentrated sulfuric acid sprinkled in,

The mixture is heated to 65 ° until everything is dissolved,

ο
then cooled to 0 and 20 parts by volume of a mixture of glacial acetic acid and propionic acid in a ratio of 4: 1 were added dropwise. In -the 'solution obtained becomes a solution.' of 2 parts .2-AminothiaZ'Ol in 20 parts by volume of one,; Mixture of glacial acetic acid and / propionic acid (4: 1) was added dropwise

■ ο

and the reaction mixture for 3 hours at 0-5

far from it. 1.5 parts of urea are added in portions to this diazole solution Parts of alcohol are added. The mixture is stirred for a further 10 hours and adjusted to pH 8 with sodium hydroxide solution. The precipitated dye ^: is filtered off, washed with water and .. dried .. -. -

2.88 parts of the dye obtained above are dissolved in 150 parts of hot nitrobenzene. A> 9 parts of dimethyl sulfate '"dissolved in 10 parts of nitrobenzoi are added dropwise and the reaction mixture is stirred for 3 hours at ^: 95-10%. After cooling, the suspension is added

309828 / IP

CIBA-GEIGYAG - 72 -

filtered off. The filter residue is dissolved in hot water and after filtering the solution from deiti filtfat salted out with sodium chloride and zinc chloride

The unusual dye of the formula

-NHCLH.- ZnClJ-

is filtered off and dried. He dyes polyacrylni- ' trile fibers in brilliant orange tones with excellent fastness properties. Further quaternized ones are obtained in an analogous manner Dyes by alkylating the dyes of the formula given below ail *

DN = N - * ζ V- C

with the alkylating agents given in the penultimate column.

309828/10 ^ 2

Table 17

309 8 . D. - ro
OO Benzothiazole-2 1,3,4-Tiiiadiazo-
lyl-2 1,2,4-Tiiiadiazo-
■ lyl-5
Pyridine-3

NH,

NH ₂ NHCH

NH ₂

4- (6'-methyl-2 • -benz-NH, thiazolyl) phenyl ^c

3-methyl-1,2-isdthia-zolyl-5.

3-methyl-l-phenylpy- ΝΗβ, Η ^ SCH, NH razolyl-5 ° E Alky-

agents

CN (C ₀ H ^) ₀ SO,

NH ₂ NHC ₂ H ₄ C ₆ H ₅ CN C ₇ H ₇ SO ₃ CH ₃

CN C -EL SO, CH

NH ₂ NS CN. ^C 4 ^H 9 ^B r NH ₂ NHC ₂ H OH CN BrCH ₀ CONH ₀
2 2 NH ₂ NH ₁ C ₄ H ₉ . CN (CH ₃ ) ₂ SO

CN ■ (C ₂ H ₅ ) ₂ SO ₄

1,2,4-triazolyl-3

NH, shade of scarlet

orange

yellow

yellow

orange

orange

yellow

NH ₂ NHcyclohexyl 'CN (CH ₃ J ₂ SO ₄ yellow

l-methylimidazolyl-5

AWAY

NH, NHC-H, -0C _o H _c CONH,

Alkylating agents CH-J

hue

yellow

Indazolyl-3

SC ₂ H ₅ NHC ₂ H ₅ NHC ₂ H ₅

CN

C ₇ H ₇ SO ₅ CH- orange

Benz-2,1-isothiazolyl-3

Thiazolyl-2

NH ₂

NH,

NH, piperidino CN

N (CH ₃ ),

CN

(CHj) ₂ SO ₄ red

(CH_) ₂ S0. orange

6-methoxybenzthiazo- NH ₉ lyl-2 ^ά

CN

orange

5-methyl-1,3,4-thia- NH _? zolyl-2

NH,

CN

yellow

J-methyl-l ^^ - thia- GC ₂ H ₅ NHCH (CH ₃ J ₂ CN

C ₇ H ₇ SO ₃ CH ₃ yellow

2-methoxypyridyl-4

NH, CN

..Scarlet fever

ISJ N)

5-methyl-1,2-isoxazQlyl-3

l-phenylpyrazolyl-5, HH,

5-imino-l ,, 2,4-tri-OC.H

4-Methyltiiia.zQlyl-2 HH

3-methoxyTl, 2,4-thiadiazolyi ~ 5

OH

HH

'2 ■

HHCH

2-methylquinolinyl-4 HHC ₆ H ₄ CH ₅ (p)

-H-

Ό Ό.

HHCH.

HHCH (CH J

COHH.

Alky-
lation
middle
. ^C 6 ^H 5 ^CH 2 ⁰¹ :,. ,,. ; .. hue
yellow ClC ₂ H ₄ OH yellow '■ .CCEHj) ₂ SO ₄ yellow

COHH

orange

yellow

Scarlet fever

3-methylpyrazolyl-5 HH ₂

yellow

5-methylthio-1,2,4-HH. triazoiyl-J ^Ä COHH ₀ / C ₇ H ₇ SO-CH- yellow

O CO OO K> OO

5-methylthiothiazolyl-2

NHCH-

NH

Alkylating agent (CH_) _o S0.

hue

yellow

3-methylthio-1,2,4-thiadiazolyl-5

NH,

CN (C.HJ.SO, yellow

CI ₈ AGE ₁ GVAG 2 28 # 10

Example 6

l8,5 parts 5- [4 ^T -Chloracetylphenyl] A2O-2-b _e utylamino-4,6-diamino-3-cyanopyridine are with 53 parts of 40 follower wässe engined · trimethylamine and 20 parts of water for 20 hours at 20 to 25 . stirred and then heated at 60 to 65 for 5 hours. The mixture is then cooled, 500 parts of water and dilute hydrochloric acid are added until the reaction is weakly acidic. The mixture is heated, filtered hot and the piltrate is salted out with sodium chloride. The unusual dye of the formula

f ² '

⁰ IiR

dyes polyacrylonitrile fibers in reddish yellow shades of very good fastness properties.

Other dyes are made according to the work given above wisely obtained by condensation of a dye of formula 4

D- - IT = N -χ y-0,

B E

wherein the symbols D, A, B, C and E are used in the following ■ Table have the meaning given in the penultimate Compounds specified in the column.

309828/1042

2-chloro-4-nitrophenyl A. CVl Tabel B. V C. E. Reaction
partner N (C ^) ₂ NH ₂ NHC ₂ H ₄ NH ₂ CN (CH -), NCH ₀ COCl
3 3 j 2 OCH 4-nitrophenyl .NHC ₂ H Cl Cl " Pyridine - NiC ^ Jg N (CH ₃ ) ₂ CONH ₂ H ₂ NN (CH ^) ₂ Chloroethylaminosulfo-
nylphenyl NHCH, 2,4,5-trichlorophylene enyl J ^ j J ^ \ y j-, fi ι w ^ L
2 ^ L SCH ₃ NH ₂ CN 39828 N (C ₂ H ₅ ) ₂ N (C ₂ H ₅ ) ₂ CN / 10 ro

hue

orange

orange

Example 7

3.6 parts of 3-methylbenzthiazolon-2-hydrazone are dissolved in 4-0 parts of glacial acetic acid. 4.3 parts of 4,6-diamino-3-cyano-2-piperidinopyridine and O ₃ 5 parts of conc. Hydrochloric acid are added. A solution of 26.9 parts of ferric chloride

, hexahydrate in 35 parts of water will slow at 15-20 added dropwise and the reaction mixture 'for 3 hours

• continued to stir. The precipitated product is filtered off and washed with a little sodium chloride solution. Of the The filter cake is dissolved in hot water, filtered clear and salted out from the filtrate with sodium chloride.

The unusual dye of the formula

f3

.CN

is-filtered off and dried. It dyes polyacrylonitrile fibers in scarlet shades of very good fastness properties.

If instead of the benzothiazolone hydrazone one ent-.

speaking amount of

3-methylthiazolone-2-hydrazori

_a 4-Methy1-1,2,4-thiadiazolon-5-hydrazone

309828/1042

CIBA-GEIGYAG - SUN -

3-methyl-1,3> ^ -thiadiazolone-2-hydrazone l-methylquinolone-2-hydrazone 2-methylpyridazone-3-hydrazone or 1 _J 2-dimethyl-3-indazolone hydrazone, dyes with similarly good properties are obtained.

309828 / 10A2

'CIBA-GEIGYAG. - Bl -

. Dyeing regulations I

1 part of the dye obtained in Example 1 is dissolved in 2000 parts of water with the addition of ^} i parts of Λο ^ ίβ

Acetic acid, 1 part crystallized sodium acetate and 10 parts Dissolved anhydrous sodium sulfate ·. In this dyebath you go at 60 ° with 100 parts of dried yarn made of polyacrylic

nitrile staple fibers, increases the temperature within half an hour to 100 ° and colors temperature. Then the dye is rinsed well and dried.

309828/1042 bath

Dyeing instructions II

1 part of the dye obtained in Example 3, 1 part of 50% neutralized reaction product of 1 mol a 'higher alkylamine with about 20 carbon atoms with

30 moles of ethylene oxide, 1 part of concentrated acetic acid and

... _t * - 7 parts of water become fine in a ball mill

Grind dispersion.

To a dyebath of 400 parts of water and 4 parts of a 50 # strength solution of a condensation product of 1 mol ^- "1-methyl-2-heptadecylbenzimidazole with 7 mol of ethylene oxide, which is adjusted to a ρ value of 4 with acetic acid

was, the dye composition described above is added, there will be discussed with 100 parts of fine reticulated polyacrylonitrile flakes, heated to the boil within 30 minutes and dyed 1 1/2 hours at boiling temperature. The colored material is then rinsed well. A level red-yellow dyeing with excellent fastness properties is obtained.

309 8 28 A10 A 2-

Claims (1)

Claims 1. Free from acidic, water-solubilizing groups, basic azo dyes of the formula D - Ή = YY wherein two radicals Z are groups of the formula -NR ¹ R "and one radical Z is a group of the formulas -NR ¹ R", -OR ¹ "or -S-R '", where R ¹ , R "and R ^m each Mean hydrogen, aryl, alkyl, cycloalkyl or an aliphatic radical and R 'and R "can form a ring containing the amine nitrogen and the radicals -NR'R" can be the same or different from one another, Y is a radical of the formula * - CN or -CONHp and D is the radical of an aromatic or heterocyclic diazo component and wherein at least one) radical Z and / or D is a basic, optionally containing cationic group.
2.. Free from acidic, water-solubilizing groups, basic azo dyes according to claim 1 of the formula K, R '. ■ 1 - / 2 N ". 3098 2 8/1042 ciBA-GEiGYAG - 84 - wherein D ^{1 is} the radical of an aromatic or heterocyclic diazo component and Y is a group of the formula -CN or -CONH ₉ and Rj, Rp, R _7. , R ^ and R ₁ - each is hydrogen or an aryl, aralkyl, cycloalkyl radical or mean an aliphatic radical, where R with R_ and R, with R, den
Amine nitrogen-containing ring can form and Q each is a directly or via a bridge bound, optionally quaternized amino, hydrazino, etherified hydroxylamino or pyridine grouping and ρ and q each 1
or 2, wherein when ρ and q are both 1, D 'is a heterocycle having a quaternized ring nitrogen atom, and wherein Z is an oxygen or sulfur atom or an imino group of the formula I ⁶ -N- where R ^ is hydrogen, an aryl, aralkyl, cycloalkyl radical or an aliphatic radical, which with Rj- or with Q can be linked. 3. Azo dyes according to Claims 1 and 2, in which · Y is a cyano group. 4. Azo dyes according to Claims 1 to 3 »worii * D ^{1 is} a radical from the benzene series or a sulfur- and / or nitrogen-containing heterocyclic radical. 5. Azo dyes according to Claims 1 to 3, in which "R ₁ , R ₂ , R-, and R ^, each denote hydrogen. 309828/1042 CIBA-GEIGYAG 6. Azo dyes according to Claims 2 to 4, in which R ₁ and Rg are each hydrogen j radicals of the benzene series, benzyl, cycloalkyl or alkyl radicals with a maximum of 8 carbon atomsj 'which are optionally replaced by oxygen, nitrogen or Sulfur atoms interrupted and optionally with the
mentioned basic radicals can be substituted and which can be linked directly or via an oxygen, sulfur or nitrogen atom to form a ring containing the amine nitrogen. 7. Azo dyes according to Claims 2 to 6, in which Q is a group of the formula. . -H - H ' ^R 2 where R 'and R' are hydrogen or an alkyl, aralkyl or cycloalkyl radical, R 'is hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group mean, and where N with R | and / or R 'and / or R' can form part of a heterocyclic ring, X is an anion and η is 1 or 2. . . ·. 309828/1042 CIBA-QEIGYAG 8. Azo dyes according to Claims 2 to ό, wherein Q a group of the formula ri; ₊ R- X n-1 is, which directly or via a carbonyloxy or Carbonylamino group is bonded to the dye molecule and in which Rj, an alkyl, cycloalkyl or aralkyl radical, X is an anion and η is 1 or 2. 9, azo dyes according to claims 2 to 6, the general formula NH ₂ CN where D ¹ , Q and q are the same as above and Z ^{1 is} a piperidine, morpholine, pyrrolidine, 3-Pi ^GO lyl ^am i ⁿ - or piperazine radical bonded via a ring nitrogen atom, where, when q is 1, either Z ¹ is a 3-Pic ° lylar ⁿ domestic or Piperazinrest-. must be or D ¹ must contain a quaternized nitrogen atom.
10. Azo dyes according to Claims 2 to 6, wherein D ' 309828/1042 Cl BA-GEIGY AG a heterocyclic radical of the formula ι V Λ where R is an alkyl, cycloalkyl or aralkyl radical means' and X "" is an anion. · 11. Azo dyes according to Claims 7, 8 and 1Q " wherein R 'R ^, R' Rj ^ and YL · alkyl radicals with 1 to k C atoms, preferably methyl radicals. 12. Cationic azo dyes according to Claims 1 to 11, the anions of which are derived from hydrogen halide acids, nitric, sulfuric, phosphoric acids, benzenesulfonic acids, benzoic acid] !, aliphatic carboxylic and sulfonic acids with 1 to 4 carbon atoms each, alkylsulfuric acid half-esters with 1 to 4 carbon atoms or as double salts with zinc and cadmium halides. 15. Azo dyes according to claims 1 to 12, wherein D or D 'is a heterocyclic radical of the thiazole, benzthiazole, thiophene, imidazole, pyridine, indazole, pyrazole, triazole, benzotriazole, thiadiazole, isothiazole - or benzisothiazole series.
14. Azo dyes according to Claims 1 to 12, in which 309828/1042 D or D 'is a residue of the benzene series, which is unsubstituted or by halogen atoms, nitro, cyano, thiocyano, trifluoromothyl, alkyl, alkoxy, Aryloxy, alkyl mercapto, aryl mercapto, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, alkylsulfonyl, aminosulfonyloxy, Sulfonamide, carboxamide, acyl, acylamino radicals and phenylazo groups in which the phenyl nucleus contains chlorine atoms and cyano, nitro, alkyl, alkoxy, alkoxycarbonyl and may carry sulfonamide groups, is substituted. 15. Process for the production of azo dyes !! * which are free of acidic water-solubilizing groups and of the formula ^ Z ₅ Y where two radicals Z are groups of the formula -NR'R "and one radical Z is a group of the formulas -NR'R", -OR ¹ "or -SR" ¹ , where R ', R "and R ¹ " each is hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical and R ¹ and R "can form a ring containing the amine nitrogen and the radicals -NR'R" can be the same or different from one another, Y is a radical of the formulas -CN or -CONHp, and D is the remainder of an aromatic or heterocyclic diazo component, by coupling, quaternization or condensation, where appropriate 309828/1042 CIBA-GEIGYAG when Y = CU, the cyano group in concentrated sulfuric acid converts to -CONHp group. l6. . »Process according to claim I5 for the production of basic azo dyes of the formula where D 'is the residue of an aromatic or heterocyclic one Diazo component and Y is a group of the formula - CN or - CONHg and R _n j R ", R ,, R ,. and R "each is hydrogen or one, 12345 Aryl, aralkyl, cycloalkyl radical or an aliphatic radical, where R, with R and R, with Rj, can form a ring containing the amine nitrogen and Q each is an optionally quaternized amino, hydrazino, etherified hydroxylamino or pyridine grouping and ρ and q are each 1 or, where if ρ and q are both 1 * D ^? is a heterocycle having a quaternized ring nitrogen atom, and wherein Z is an oxygen or sulfur atom or an imino group of the formula is where Rg is hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical, which with R, - or with 309828/1042 CIBA-GEIGYAG. _ vJG _ Q can be linked, characterized in that a) a diazotized amino compound of the formula (Q) -D'-NH _p
q-1 with a coupling component of the formula p-1 converts, where D ', γ, R ₁ , R ₃ , R, R ^, R, Z, q, ρ and Q have the same meanings as above or that one b) an azo dye of the formula (V) -D'-N = N- ^ r> -Ζ-R ₅ - (V) q-1 where D ', Y, R ₁ , R _gJ R ^, R ^, R, p, q and Z have the meaning given, but ρ + q must be at least 3 and V is a reactive atom or a reactive one 309828/1042 CIBA-GEIGYAG Group is _: with an amine, hydrazine, etherified hydroxylamine, an optionally quaternary aminocarboxylic acid chloride or pyridine carboxylic acid chloride or that one c) an azo dye of the formula (Q) -D'-N = BT- <C> —Z — R_-fQ) where D- ¹ . Y * R ₁ ^ R ~ * R-? * Ri.j> ^r c ^un <3. Z has the meaning given • Λ <d ^ 4 9 have and at least 1 residue Q or D 'a non-quaternized Contain nitrogen atom, quaternized by treatment with alkylating agents or that one d) in the event that D 'is a nitrogen-containing heterocycle bonded in the vicinity of the nitrogen atom • means a hydrazone of the B'brmel \ C = N-NH ₂ ^ - -N ■ Rr, 309828/1042 CIBA-GEIGYAG - with one of the coupling components indicated under a) in the presence of oxidizing agents and where one optionally, when Y = CN, converts the cyano group in concentrated sulfuric acid to the -CONH group. 17 'Method according to claims 15 and 16, thereby characterized in that one starts from compounds in which Y is a cyano group. l8. Process according to Claims 15 to IJ, characterized in that amines of the benzene series or amines of sulfur- and / or nitrogen-containing heterocycles are used as the diazo component. 19 · The method according to claims I5 to 18, thereby characterized in that one starts from coupling components of the formula given in which R ,, Rp, R and R ^ each Mean hydrogen. 20. The method according to claims 15 to 19 *, characterized in that one starts from coupling components of the formula given in which R _R and R, - each hydrogen, radicals of the benzene series, benzyl, cycloalkyl or ■ alkyl radicals with at most 8 carbon atoms are, which can optionally be interrupted by oxygen, nitrogen or sulfur atoms and optionally substituted by the basic radicals mentioned and which can be linked directly or via an oxygen, sulfur or nitrogen atom to form a ring containing the amine nitrogen. 309828/1042 CIDA-GEIGYAG 21. The method according to claims 15 to 2C) for the preparation of azo dyes ^ of the formula given, wherein Q is a group of the formula -Ν — RA ^J nl where R 'and JlI are hydrogen or an alkyl, aralkyl or cycloalkyl radical, R' is hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an Annncgruppe, and v / orin N with R 'and / or R 'and / or R ^ can form part of a heterocyclic ring, X is an anion and η is 1 or 2, characterized in that, ... that one a) diazotized amines and coupling components are used, at least one component being a radical Q of above formula contains or that one b) a dye of the "formula R ₁ R ₉ - ' NY \ ^R 4 309828/1042 CIBA-GÜIGYAG _ ^ _ wherein D ¹ , Y, R, R, R, R ^, Rp-, ρ, q and Z have the meaning given, but ρ 4- q must be at least 3, and V is a halogen atom, a Alkylsulfonates-, arylsulfonato-, especially benzenesulf is onato, alkylsulfato, hydroxyl or amino group, with a compound of the formula R / R / I, ι ■ HNR 'or Cl-CO-CH ₀ -NR' I "5 ^? ~ 1 3 converts, wherein R, ', R ^ -', R ₇ , ¹ , X and η mean the same as above , or that one. ' c) azo dyes in which Q is a group of the formula -NR, ¹ IvI is with. an alkylating agent of the formula Rp X quaternized, where R 'R' and R 'the same as above and X 'are chlorine, bromine, iodine, a low molecular weight alkyl sulfonate benzene sulfonate, where the benzene ring optionally carries further substituents, or denotes an alkyl sulfate group having 1 to 4 carbon atoms, and that if necessary, the process can be retrofitted introduced anion replaced by another. 309828 / .10-4 2 - CIBA-GEIGYAG. _ ~ » 22. The method according to claims 15 to 20 for the preparation of azo dyes, wherein Q is a group of Formula. . is, plural marriage directly or through a carbonyloxy or Carbonylamino group bound to the dye ir.ol ekül and where Rj is an alkyl, cycloalkyl or aralkyl radical, X is an anion and η is 1 or 2 ^ characterized in that that he a) starting from diazotized amines and coupling components, at least one component having a radical Q of the specified Formula contains, or that one b) azo dyes in which the radical Q is a non-quaternized pyridine radical; cLh. n = l, quaternized with alkylating agents of the formula Rj, ¹ X *, in which R ^, ^{1 has} the meaning given and X ^{1 is the} same as in claim 21, and that the introduced anion is optionally subsequently replaced by another or that c) azo dyes which contain an amino or hydroxyl group instead of a radical Q of the formula given, with pyridinecarboxylic acid chlorides of the formula.,. · .., _Λ '., .., 30982871042 ci-co- implements and, if necessary, treated further as under b). 23. The method according to claims 15 to 20, characterized in that one of coupling components of the formula —Ζ NH ₂ CN where Z ^{1 is} a piperidine, morpholine, pyrrolidine, 3-picolylamine or piperazine radical bonded via a ring nitrogen atom, where, if the diazo component does not contain any basic groups, Z * is a ^ -? \ Q, o \ ^ \ 3m \ Vi or a piperazine residue. 24. A process for the preparation of azo dyes according to claims 15 to 20, wherein D ^{1 is} a heterocyclic radical of the formula , —J RV rj Λ 309828/1042 CIBA-GEIGYAG where R is an -alkyl, cycloalkyl or aralkyl radical 7 _ means and X ~ is an anion, characterized in that one a) of diazotized amines of the formula ■ -i- ^NH 2 I R X "7 where R and X ^- "have the meaning given, goes out, 7 · 'or that one b) an azo dye of the formula ι
V wherein R, R ₂ , R, R ^, RY and Z have the meaning given with a compound of the formula RX ^! quaternized, .7 where R and X ^{1 have} the meaning given and that if necessary, the anion introduced according to the method is subsequently replaced by another, or that man ■ ■ c) in the event that the specified radical D ^f is bonded in the position adjacent to the nitrogen atom, a hydrazone of the formula 309828/1042 CIBA-GEIGYAG R. ■
7th couples in the presence of oxidizing agents with one of the specified coupling components. 25. The method according to claims 21 ,. 22 and 24> characterized in that one starts from compounds in which R ', R ₂ ', R. ', R ^ ¹ and R are alkyl radicals with 1 to 4 carbon atoms, preferably methyl radicals. 26. The method according to claims 15 to 25, characterized characterized in that cationic azo dyes are prepared whose anions are derived from hydrogen halide acids, nitric, sulfuric, phosphoric acid ^, Benzol sul fön acids, Ber.zoe acidic., Aliphatic Carfcori- and sulfonic acids with 1 to 4 carbon atoms each, alkylsulfuric acid half-esters with 1 to 4 carbon atoms or as double salts with zinc and cadmium halides. Present. ■ 27 · Process according to claims 15 to 26, characterized in that that diazotized amines of the thiazole, thiophene, imidazole, pyridine, indazole, pyrazole, triazole, Benztriazole, benzthiazole, thiadiazole, isothiazole or Benzisothiazolrelhe proceeds. 309828/1 0 A 2 CIBA-GEIGY AG 93 28. "Process according to claims 15 to 26, characterized by dadurph, that one starts from diazotized amines of the benzene series., In which the benzene ring has one or more halogen atoms Nitro, cyano, thiocyano, trifluoromethyl, alkyl, Alkoxy, aryloxy, alkyl mercapto, aryl mercapto, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, Aryloxycarbonyloxy, alkoxysulfonyl, aminosulfonyloxy, sulfonamide, carboxamide, acyl and acylamino radicals as well as phenylazo groups, the phenyl nucleus with cyano, chlorine, nitro, alkoxycarbonyl, sulfonamide, Alkyl and alkoxy groups can be substituted. 29 · Process for dyeing and printing polymers or copolymers of acrylonitrile, asymmetrical dicyanethylene, anionically modified polyester, and polyamide, characterized by the use of those defined according to claims 1 to 14 or 15 to 28 obtained Dyes 30. The obtained according to claim 29, colored or printed material. · ------ 309828 / 1-042