DE2103612A1 - - Google Patents

Description

PATENT LAWYERS
DR.-IK6. H. FiMCKE DiPi = IM O. H BOSIÄ DIPL.-Hiö. S. STAOGER MUNICH 5 MOLLERSTR. 31

——C ^

2 6th year 1971

Imperial Chemical Industries Limited Great Britain

Process for the production of Af; of asking open

The invention relates to flavoring dyes that calibrate Suitable for dyeing natural and synthetic textiles.

109848/1677

Genes of the present invention are the Azo dyes are created which is an Eadical of the formula

Al H-R

N-N-

included, with the ring A nocb additional Can carry substituents and the radical R is an optionally substituted aliphatiscb.es Hydrocarbon is radical, and where the Radical of the formula given above from a diaronium compound one in the 2-position substituted 3-A * inoind & r.ole.

t The dyes can wake up the formula

N-H-E

represent, in which the ring A still ruaätrliohe The radical R can carry substituents

- 3 -109848/1677

optionally substituted allphatieches Is hydrocarbon radical and E represents the remainder of a coupling component.

As examples of the additional substituents. which may be bound to the ben? ol ring A can include the following: Halogenatoae, such as * .B. Chlorine or bromine atoms, alkyl radicals, especially lower alkyl radicals, such as 7.B. Methyl radicals, Alkoxy radicals, especially lower alkoxy> via 7..B. Methoxy radicals, nitro groups, cyano groups, Acy! Amino groups, vie * .Β. Acetylamino and Benr.oy laminogruppea, C & rbo-Niederalkoxyradlkale, like r.B. Carbon ethoxy radicals, lower alkyl sulfonyl radicals, such as is. B. Me thy lsulfony! Radicals, arylsulfonyl radicals, like?:. B. p-Toluenesulfonyl radicals, sulfonaaido groups and N-lower alkyl and Ν, Η-di-lower alkyl derivatives thereof, carbonamido groups and N-lower alkyl and N, H-di-lower alkyl derivatives thereof, sulfonanillide groups, Sulfo acid groups, carboxylic acid groups, trifluoromethyl groups, rhodane groups, lower alkylthio groups, Phenyltblo groups, acyl groups such as r.B. Acetyl and benzyl groups, acyl groups, such as r.B. Acetoxy groups, aryloxy groups, such as * .B. Phenoxy groups, as well as arylthio groups, such as 7.B. Phenyl

mercapto groups.

109848/1677

For the purposes of the invention, the expressions "ffiederalkyl", "ffiederalkosy" bsw. "ffiederalkenyl" in each case an alkyl «, alkoxybrw · alkenyl radical with 1 to 4 carbon atoms are understood.

The optionally substituted aliphatic hydrocarbon radicals represented by K are preferably unsubstituted or substituted lower alkyl or lower alkenyl radicals Examples of this include never the alky! .Radical, such as ? .. B · methyl, ethyl, n-propyl and n-butyl radicals, Hiederalkeny! Radical, like r..B. Vinyl radicals, half-alkyl radicals substituted by aryl groups, how?!. B. Benzyl and ß-phenylethyl radicals, as well Lower alkyl radicals formed by hydroxy, cyano, Lower alkoxy, acyloaty, carbo-lower alkoxy, Lower alkyl sulfonyl, lower alkyl carbonyl, Aryloxy », acyl or arylsulfonyl groups are substituted. However, preferably B is a Niederalky! Radical

The represented by S · Best of a coupling component can be the remainder of any coupling component which couples with a diazo component in the adjacent position or in the ortho or para position ffu an ifdroxy or amino group «

As specific examples of such best, Ban Might mention those of the coupling components of the Phenol-, naphthol-, acylacetoarylamid-, 5 «-iyrs- * olone, 5-aminopyra * ol, 2,2 ~ bihydroxypyridine series as well as primary, secondary or tertiary amines of Benzene or naphthalene series.

The radical E can also be a hadical of the formula

N-N-S

be in which the benzene ring B carry substituents may or may form part of an optionally substituted naphthalene ring and £ those above has given meaning.

The radicals of coupling components represented by E can have such substituents (also A * o groups), which are usually present in such components. As examples such substituents can be those which contain a quaternary ammonium group which imparts solubility or those which contain fibers reactive group contain or consist of aolohen groups, mention, one under a with fibers reactive group a group

- 6 -109848/1677

should stand that with Celluloee-Textiletoffen in Can react in the presence of an acid-binding agent, the dye being bound to the cellulose textile via a «covalent bond.

As examples of groups reactive with fibers one can mention the following * Vinylaulfon- and aliphatic «sulfonic groups containing a halogen atom or sulfate ester groups in the ß-position sum Contain sulfur atom, like r..B. ß-chloroethyl sulfone, ß-SulfatoäthylmiLion- and ß-Sulfatoäthylsulfonylaminogruppen ;. α, β-unsaturated acyl radicals of the aliphatic carboxylic acids such as acrylic acid. α-chloroacrylic acid, propiolic acid, shark acid and hono- and dichloromaleic acid; also the acyl radicals of acids that contain a substituent that is reactive with fibers in the presence of an alkali, «.Β. the radical of a halogenated aliphatic acid such as chloroetic acid, ß-chlorine and ß-bromopropionic acid and α, ρ-dichloro and α, ß-dibromopropionic acid. More examples of with Fibers reactive group are Te met luorcyclobutane carbonyl, Trifluorcyclobu-. tencarbonyl, tetrafluorocyclobutylethenylcarbonyl, Trifluorocyclobutanethylcarbonyl groups; and especially heterocyclic radicals, the 2 or

3 nitrogen atoms in heterocyclic ring and at least one reactive with fibers Contain substituents on a carbon atom of the ring.

The following can be mentioned as examples of such heterocyclic radicals: 2 _% 3-dichloroquinoxaline * 5- or -6-sulfonyl-, 2, J-dichloroquinoxaline -; * - or • 6-cexbonyl-, 2 _l 4-dichloroquinoxaline -6- or «7-eulfonyl-, 2,4,6-trichloroquina * olin-7 · - or -8-sulfonyl-, 2,4,7- or 2,4,8-trichloroquina?; Olin-6- eulfonyl-, 2 _t ^ -Dichlorchinar, olin-6-carbonyl, 1 ^ -Dichlorphthalarin-e-carbonyl, 4-, 5-Dichlorpyrida "on-1-yl _t 2 ^ -Dichlorpyriaidin-ö-carbonyl 1-,

1- (Fheny 1-4-stilfony 1) - *, 5-dichlorpyridawoxi- 'and in particular 1-, 3 _t 5-Tria * in-2-yl- and -I ^ rrimidin-2-yl- or -4- yl radicals which at one of the remaining 2-, 4- and 6-positions contain a bron-, fluorine "or preferably chlorato" or one of the following groups: a sulfo acid group, a rhodan group, "!" aryloxy- or arylthio group with electronegative substituents such as sulfophenoxy, sulfophenyltnio, hitrosulfophenoxy, disulfophenoxy and sulfonapb ^ hjcjgrpen, also a group of the formula

109848 / 1B77

-S-C

wherein X represents a group of atoms like them are necessary for the formation of a 5- or 6-membered heterocyclic binge, the substituents can carry or can form part of a condensed ring system, also a quaternary Ammonium or xfyridinium group, or a group of the formula

S. -S-C-N

wherein R and B ^, which are the same or different can, in each case mean an alkyl, cycloalkyl, aryl or aralkyl group or with the neighboring group Nitrogen atom members of a 5- or 5-membered member represent heterocyclic rings, or a group of the formula

HR ⁵ -8 - C

109848/1677

wherein R * and R ^ are the same or different can and each have a hydrogen atom or «ine Represent alkyl »aryl or aralkyl group.

If the lyrimidine ring or tri-ring is just one carries such reactive substituents, the ring in question may be a non-reactive Carry substituents on the remaining carbon atom or atoms.

Under an unresponsive b * w. A group is to be understood as meaning non-reactive substituents attached to a carbon atom of the triaxial or lyrimidine nuclei via a covalent bond is bound, which is not dissolved under the conditions of application of the reactive dye will. The following can be mentioned as examples of such substituents: primary amino and Hydroxyl groups, also mono- or dl-substituted amino groups, etherified hydroxyl groups and etherified mercapto groups; the substituted amino groups are * .B. to mono and Dialky! Amino groups in which the alkyl groups are preferably at most 4 carbon atoms contain and also substituents, * .B. hydroxyl or alkoxy groups, as well as phenyl

- 10 -

"? 098Λ8 / 7 R ₇₇

amino and haphthy! amino groups, preferably with sulfonic acid groups as substituents; the etherified hydroxyl and mercapto groups are * .B. around alkoxy and alkylthio groups, preferably with a low molecular weight, ie with bin * u 4 carbon atoms in the molecule, as well as phenoxy, phenylthio, haphthoxy or haphtbylthio groups; the following can be mentioned as specific examples of this range of substituents: !! ethylamino-, ethylamino-, dimethylamine-, P-hydroxyethylamine; , SuIfophenylamino-, Biaalfophenylamino-, N-Methyleulfophenylamino «, N- (α-Ιξτdr <a & äthy 1) sulfophenylamino-sulfo-o-tolylamino-, carboxyphenylamino, ßulfocarboxyphenylamino-, ßulfocarboxyphenylamino- and methoxy-, phenylamino- and methoxy-, Methylphenoxy, chlorophenoary and phenylthio groups, chlorine atoms or cyano, nitro, carboxy and carboalkoxy groups in the 5-position of an iyrieldy! Radical are also regarded as non-reactive substituents.

According to a further feature of the invention, a process is used to prepare the azo dyes proposed according to the invention, which consists in that an amine of the formula I

dia * otlert and the received DiaKo connection a with a coupling component of the formula H-S is coupled, where A, E and R have the meanings given above.

The inventive method leads to "wake up" Realize massively by the fact that sodium nitrate KU a solution or suspension of the amine in a inorganic acid r.ugeset * t with water if necessary and the resulting solution b * w. suspension Clay of the diazo component * u of a solution of the Coupling component is added, the pH of the resulting mixture * ur relief the coupling reaction is stopped. The dye thus obtained is then used in the usual Way isolated.

The amines of the formula I can be prepared in this way be that the corresponding amine of the formula IX

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109 8 48/1677

Al HH II

a is treated with a reagent that represents the HH group converting the heterocyclic rings to the NR group, which K.B. by treating with a Dialkyl sulfate in Hitrobenr.ol can happen at elevated temperature. You amines of the formula II can be prepared in that the corresponding benronitrile of the formula

wherein W is a Hethoxygruppe or a chlorine or Is bromine atom, is reacted with a hydrazine, whereupon the thus obtained, corresponding 2 "Cyanopheny! Hydrazine of the formula

109848/1677

~ 13 -

by heating in an aqueous hydrochloric acid « solution is cyclized.

The following can be mentioned as specific examples of amines of the formula I: 2-methyl-5-amino-5-nitroinda oil, 2-methyl-3-amino-5,7-dinitroindaeol, 2-methyl-3-aminoindaeol, 2 -Xthy1-3-aminoindazole, 2-methyl-3-amino-5-nitro- "7-cbiorinda9? Ol _t 2-methyl ~ 3 * -axaino-5-nitro-7-bromindaK oil, 2-methy 1-3 -amino-

nitroinda?: ol _t 2-methyl-3-amino-5,7-dibromo-6-methy 1 indar.ol and 2- (ß ~ ethoayethyl) -3-amino-5,7-dinitroinda?! ol.

The azo dyes according to the invention tilt d «v formula

N-E

where A, R, B 'and E have the above meanings, can be obtained by making a dia * over bond of an amine of the formula I with an amine of Formula III

- 14 -

109848/1677

III

or coupled with the corresponding sulfamic acid, if appropriate, the sulfamic acid group is split off by hydrolysis, the product is diarotated again and with a coupling component of the Formula E-H is coupled.

Venn the Hing B ¹ and the residue of a coupling component represented by E each represent a group which can be metalized, such as * »B. contain a hydroxyl, methoxy, amino or carboxylic acid group, in the ortho position or in the adjacent position ru of the A group connecting the radicals B and E, then such dyes can contain metal complexes, * .B. Copper, cobalt or chromium complexes can be reacted by heating with a solution of a metallizing agent. Such metallized dyes are also within the scope of the invention

As examples of the amines of the formula III brw. the corresponding sulfamic acids can be mentioned as follows $ 2-methyl - ^ - methoaty aniline, 2,5-dimethoxyaniline, m-toluidine, α-haphthylamine

- 15 -

109848/1677

- 15 - and 1 "-Haphthylamine-6- or -7-sulfoic acid.

AIb ücatiiamte examples of the coupling component of the Porael E-H can be mentioned as follows: Phenols, such as?, B. Phenol itself and o-, a- and p-cresol, resorcinol, 4-phenylaT.o-1 ₁ 5-dihydroxylDen9: ol and 5-acetylejiinophenol; Naphthols, vie * .Β · 1- or 2-haphthol, 6-broa-2-naphthol, 4-hethoxyi-naphthol, S-haphthol-e-sulfonamide, 2-amino «5-naphthol-7-sxilfoBäiire, 2- MethylalRillo-5-naphthol-7-bulfonic acid, 2-amino-8-naphthol-6-8ulfonic acid, 2-ethyl aino-8-naphthol-6-8ulfonic acid, 1-amino-8-naphthol - ^ - sulf ossätire, 1 -Amino-2- (4'-nitropnenylar.o) -8-iiaphthol-3,6-di3ulfonic acid _l 1 ~ Ajaino-8-naphthol-3,6- or -4-, 6-disulfonic acid and the H-lower alkyl derivatives thereof , 2-Aaino-5-naphthol-1,7-di8ulphonic acid, 1-acetylino-8-naphthol-3,6-diaulphonic acid, 1-haphthol 4-, -5-, -6- or -7- or -e-sulfoic acid, 2-kaphthol-6-, -7- or -8-sulfonic acid, 1 ~ haphthol <-6, & - disulfonic acid, 1-aaphthol-3.6 _t 8-trisulfonic acid, 2-haphthol-6, 8-disulfonic acid, i-haphthylaatino-6- or -7-eulfonic acid, 1-Benr.oylafflino-8-naphthol-3,6-di-sulfonic acid, 1- (4 ^f , 6 -dicloro-1 ', 3', 5 · -Tria * in-2 ♦ -yla «ino) -8-naphthol-3,6-disulfoeaure, 1-Aeino-2 - (* · - (4 ^B , 6" -Dichlor-1 ", 3", 5 ⁿ -tria * in-2 "-ylamino) phenylaip) -8-

- 16 -

109848/1677

naphthol-3,6-dlßulfoic acid, 1- (4-chloro-6 * -aetboxy-1 ^f * 3 ', 5 ^f -triasin-2' -ylamine O-S-naphthol ^ e-di-sulfoic acid, 1- (4 ⁵ ~ chloro-6'-sulfoanilino-i ^l , 3 ⁱ , 5 ^t -tria * in-2 '-ylamino ^ e-naphthol ^ .e-disulfoic acid, 2- (4 *, 6'-dichloro-1 », 3 ·, 5 ^f -tria * in-2'-ylamino) -5-naphthol-7-siafonic acid, 1 - <* * - (4 ^π , 6 "-DiChIOr-I" ^ ", 5" -tria ?: iii-2 ⁿ -ylamino) anlllno) -8-naphthol-3,6-diaulfonic acid; 1- (di- or frichlorpypisidylamino) -8-naphthol-'3t6-

^ dleulfosätire iwid 1 ~ (5 ^l -Qyano «* dichlorpyrlaldylaaino) -

8 ~ naphthol-3,6-disulfonic acid j Acylacetarylaaide, like wB, Acetacetanilid, Acetacet ^ -chloranilid and Acetacet-2-, -3- or -4 - (methyl ~ or -methoxy) -anilid} 5-Amiaopyra ?; ole how
5-aminopyrar, ol and i-

pyra? iol; 2,6-Dihydro3typyridines, such as * .B · methy1-2 _f β-dlhydroay pyridin _t 1-Ithy1-3-cyano -4- metayl-6-hydroxypyrid-2-one _f 1- (Y-dimethylaminopropyl) «3 -cyano-4- ■ methyl-6-hydΓoχypyrid-2-one hydrochloride and

w 1- (5 '-iTriaethylaiBiaoni uaphenyl) - ^ - cyano - ^ - nethy 1-6-

hydro2ypyrid-2-one-chloridi 5-iyra9: olone _f like r. , B. 1,3-dimethyl-5-pyra? Iolone, 1-phenyl-3 ~ (carboalkosy -, -cai'boaiaido- or -methyl) -5-pyra?: Olone, 1- (2 * - _t
-3'- or-4 '- (nitro, amino, chlorine, bromine,
-SaIfo-, -Carboxy-, -Methyl- or -Metho3Qr) phenyl) -ΐ-5-ΡΡ * α * ο1οη, 1- (3 ^$ - or - ^ '- (4 ", 6" -Di- ", 3 "f 5 ^w ~ tria * in-2 ^M -ylamino) phenyl) -3-methyl ~

5-pyrasolon and I-C ^ '- trimethylammoniaimacetylphenyl) ^ -metbyl - ^ - pyrasolon chloride; primary, secondary or tertiary amines of the aromatic series which couple in the para position * ur amino group, such as * .B « 1-naphthylamine and N- (ß-hydro: ^ äthyl) -1-naphthylamine, and especially amines of the formula

ρ
in which the benzene ring B can carry substituents and J. and X each represent a water atom or an optionally substituted hydrocarbon radical, in particular an optionally substituted lower alkyl radical. The following can be mentioned as specific examples of such coupling components: N, N-Dimethylaniline, H ", H-Di- (ß-carbomethoxyätbyl) -m-toMdin, H- (Y-Hethoa ^ ypropyl) -3-acetylaminoaniline, H, N-Di (ß-hydro3-ethyl) -2,5-dimethoxyaniline, diphenylanine, N ~ ethyl-N- (ßyanoethyl) aniline, N, N-di (ß-acetoatyethyl) -mtoluidine, 2-methoxy-5- »acetylamino -Ni ß- (β '-methoay-PthO3Q5rcarbonyl) ethyl) aniline, ß- (KJEthyl-M-phenyl- © aino) ethylpyrinium chloride, ß ~ ((li-iEthyl-H- (3' methyl ) phenylamino) ethylpyridinium chloride _t ß- (H-

- 18 -

1 [J 9 3 4 8/1 P 7 1

β -Cfranoäthyl-H-phenylamino) äthy lpyridinium-KShlorid, ß-Hydro: xy-Y- (H-äthyl-H-phenylamino) propylpyridiniumchlorid, p- {ß- (H-äthyl-H-phenylajndj ^) etho: "Y) ph« ayltrimethylamaonium chloride, ß- (H-ethyl-H-phenylaiiino) -äthyltrlmethylamaonium-chloride, ß- (n-ethyl-H-phenylamino) ethyldlmethylhydra * inlum-chloride, ß-f m- { H, H-diethylamino) phenylsulfoi ^ lamlno) ethylpyridinium chloride, β- (m- (Hl% enyl-H ~ ethylaminomethyl) - phei ^ 18ulfonylamino) ethylpyridinium chloride and ß- (m- (H ₁ H dietby laaino) pheny lcarbamoy 1) ethylpyridiniuia chloride

Genäse becomes a further feature of the invention Another process for the preparation of the azo dyes according to the invention, one with pasers contain reactive group proposed, which consists in that an Ar.ofarerstoff after the Invention, which contains an acylatable group, in particular an acylatable amino group, * ur reaction is brought about with a Anhydride or halide of an acid in which the acid residue is a group reactive with fibers contains, or with a heterocyclic compound having a hydrogen atom bonded to a carbon atom of the heterocyclic nucleus and also an atom reactive with fibers brw. a · with

Contains fibers reactive group,

- 19 -

I 0 9 β Λ 8/1 β 7 "

Dior? Reaction can be measured by this perform that the acylatable group-containing A ?. © dye together with the anhydride b * w. Halide is stirred in water or in an organic solvent (mixture), if necessary an acid binding agent is added. The dye having a group reactive with fibers thus obtained can be used in a conventional manner Be isolated.

As examples of halides bxw. Anhydride of acids or of heterocyclic compounds which may be used may be the following mention: b carbyl sulfate and anhydrides * w, acid halides of ct _t ß-ungeaättigtsn aliphatic acids, such as chloromaleic, propiolyl-cblorid and AeryIy1-chloridj the acid chlorides of halogenislerten aliphatic Acids such as r-.B. Chlor ace ty 1-chloride, sulfochloroacetyl chloride, ß-Ba? Om and ß-Ghlorpropionylchlorid and α, β-Biehlor- and et, p-DibroiBpropionylchlorid, 2,2,3,3-Setrafluorcyclobutanarbonyl-chloride, ß- ( 2 _f 2,3,3-tetrafluorocyclobutyl) acrylic 1-chloride, 2,3,3-trifluorocyclobut-i-enecarbony1-chloride and β- ( _{2.3 t} 3-trifluorocyclobut-1-ayl) acrylyl -chloride; and heterocyclic compounds having at least 2 nitrogen atoms in the heterocyclic ring and

- 20 109848/1677

~ 20 -

with 2 or more halogen, especially Ohloratoraen in the ortho positions ψλχ the nitrogen atoms, such as r ... B. 2,3-dichloroquinoxaline-5- or -6-carbonyl chloride, 2,3-dichloroquinoxaline-5- or -6-sulfonyl chloride, 2,4-dichloroquinoxaline-6- or -7-eulfonyl chloride, 2, 4,6 Trichlorchina ^ olin -? - or -8-aulfonylchlorid, 2,4-DichloΓ-2-chlna9'.oXin-6-cal ^ bonyl-chlOΓid ₉ ^ i ^ -Dichlorphthalawin-e-carbonyl-chloride, 2, 4-Di * chlorpyriBidin-6-carbonyl-chloride, β- (4,5-dicblorpyriday.onyl-i) -propionyl-chloride _t 1- (4'-chloroformylphenyl) - ^, 5-dichloro-6-pyridav; on , 1- (4 '-Chlorsulf ony phenyl) -4, 5-dichlorH5-pyrida: one, 2,4,6-Trlbrom- or -trichlorpyrieidin, 2 _t 4, i »* 5- £ etrachlorpyriaidin, 5 ~ Methyl-2,4,6-trichloropyrimidine, 5-nitro-2,4,6-trichloropyrimidine, 2,4-dichloro-5-nitro-6- »ethyl pyrimidine, 5-jethoxycarbonyl-2,4-dichloropyrimidine, 2 , 4-dichloropyrilnidine-5-carbonyl chloride, cyanuric bromide, cyanuric chloridej the primary condensation products of cyanuric bromide or cyanuric chloride and ammonia, an alkali metal sulfite or rhodanate or an organic mercaptan, a hydroxy compound or an organic pri maren or eefeiMdär Amin, «, B. Methanol, ethanol, isopropanol _t phenol, o-, m- or p-chlorophenol, o-, m- or p-eresol, o-, m- or p-sulfophenol, thiophenol,

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109848/1677

Thioglycolic acid, dimethyldithiocarbamic acid, mercaptobenzethasol, thioacetamide, methyl, dimethyl, ethyl, diethyl, n-propyl, ieopropyl, butyl, acyl or cyclohexylamines, toluidine, piperidine, morpholine, methoxyethylamine, ethylamine, ethanolamine, -2,4-, -2,5- or -3,5-diolfoic acid, quathanilic acid, metanilic acid, sulfanilic acid, 2-, 3- or 4- aminobes?: Acidic, 4- or 5-sulfo-2-aminobes! , 4- or 5-sulfo-o-toluidine, 5-amino-2-hydroxybenzoic acid, 2-aminoethfinesulfonic acid, aminonaphthalene-mono- or disulfonic acid waA N-methylaminoethanaulfoic acid; also the secondary condensation products of cyanuric chloride with alkali metal sulfites, alkali metal rhodanates, phenols and thiophenols with electronegative substituents and compounds of the formulas

HSC Ί

S η - s - σ -> ν

and

Ί Λ ~ J2. ^ i it-

wherein Y ₉ R, R% Br and R have the meanings given above.

A preferred class of azo dyes according to of the invention consists of the water-insoluble aroma dyes, which are free from sulfonic acid, carboxylic acid and quaternary anaonium groups and the formula

MR

C ^. _Y 1

I ft Λ V Λ.

H · H

have, where A, B, R, X and X have the meanings given above to have.

Its second preferred class of flavoring color according to the invention consists of the water-soluble » Dyes of the formula reactive with fibers.

MR

HH - Z

Ο'π Η's

where A and H have the meanings ο.a, p is 1 or 2 and 2> a group capable of reacting with fibers, in particular a mono- or dichloro-1,3,5-triazinyl, dichloropyrimidyl or trichloropyrisidy Ig: nippe , means.

A third preferred class of azo dyes according to the invention consists of the water-soluble dyes of the formula

where A, B ^ and X have the meanings given above and X " one substituted by a quaternary amoniuss group Means alkyl radical.

It is further preferred that the subatituents possibly present on the benzene ring A chlorine or Are bromatones or nitro groups.

The azo dyes according to the invention are suitable for coloring natural and synthetic

109848/1677

Vf

Textile fabrics. So are those azo dyes according to the invention, which are not water-soluble Groups (i.e. sulfonic acid, carboxylic acid or quaternary ammonium groups), suitable for dyeing synthetic textiles, * .B. Cellulose acetate ^ and cellulose triacetate fabrics, Polyamide fabrics such as ".Β. Fabrics made from Polyhexaraethylene adipamide, polyacrylonitrile textile fabrics, and preferably aromatic polyester fabrics, 9? .B. Polyethylene terephthalate fabrics. Such fabrics can be in the form of threads, yarns, woven or knitted fabrics. she can also be mixed with other textile materials, KeB · al «? Blends of polyester fabrics with Cellulo.ja or full textile fabrics are present.

Such *} extil8toffe can be ^ weckmässig with the water-insoluble Ar.ofarbstoffen according to the above definition color characterized in that the textile fabric is immersed in a Farbebad _f which consists of an aqueous dispersion of one or more of the dyes, and preferably a non-ionic, cationic and / or contains all surface-active agent, WO3-auf ü & e dyebath is heated to a suitable temperature for an appropriate time. in the

- 24 -

1Q9848 / 1R77

In the case of secondary cellulose acetate textile fabrics, the dyeing process is preferably carried out at a temperature between 60 and 85 ° C .; In the case of cellulose triacetate or polyamide fabrics, dyeing is preferably carried out at 95 to 100 ° C .; in fabric en of aromatic polyesters can dyeing, either at 90 to 100 ⁰ C, preferably in the presence of a carrier, * .B _e diphenyl or o-Bydroxydiphenyl performed or preferably effected over 100 ⁰ C, at 120 to 140 ⁰ C at atmospheric pressure will.

Hau can also proceed in such a way that an aqueous dispersion of the azo dyes is applied to the textile fabric by a pad * or printing process, after which the textile fabric is heated to a temperature of up to τη 250 ° C depending on. Kind of heated or steamed. In such methods, the aqueous dispersion of the dye preferably contains a thickening agent such as * _β Β. Tragacanth, gum arabic or sodium alginate.

At the end of the dyeing process, the fabric is dyed preferably rinsed with water or course * with Treated with soapy water before drying * Used for fabrics made from aromatic polyesters

- 25 -

1 0 9 B 4 8/1 B 7 1

the dyed fabric is preferably one Subjected to treatment with an alkaline aqueous sodium hydrosulfite solution before being atLt Soapy water is treated, including sebtraeb. adhering dye from the surface of the Remove textile fabric ru

May be the novel water-Arofarb- ^ materials have excellent affinity and build-up in terms of synthetic textiles, especially textile materials of aromatic polyesters "so that deep shades received" The dyeings have good fastness to light, Naasbebandlungen and above all TrcGkenwärmebehandlungen _t as r 'B »Pleating can be carried out at holien temperatures.

If desired, the water-insoluble azo dyes according to the invention can be used with other disperse dyes when they are applied to the synthetic textile fabric , as they are * «B. in British patents 606 37i, 835 819i 840 903, 8 *? 175, 852 396, 852 493 »859 899 * 865 328, 872 204, 894 012, 908 656, 909 843, 910 306, 913 856, 919 424,

- 26 -

Hi 9 8 4 8 / I fi 7 1

Vf

513, W 722, 953 887, 959 816, 960 235, 961 412, 976 218, 993 162 and 998 858 are described,

Those azo dyes according to the invention which are water-soluble due to the presence of quaternary ammonium groups are suitable as basic dyes for dyeing fabrics made of polyacrylonitrile or polyamide and polyester fabrics which contain acidic groups and can thus be dyed with basic dyes Dyes can be applied to the textile fabrics mentioned from acidic, neutral or weakly alkaline liquors, the pH of the liquor preferably in the range from 3 to 8 at temperatures between 40 and 120 ^° C., preferably between 80 and 120 ^° C. , is held. They can also be used in the printing process, a thickened printing paste containing one or more of the dyes being used.

Those azo dyes according to the invention which are water-soluble due to the presence of acidic water-solubilizing groups are suitable for coloring natural or synthetic polyamide fabric, such as solid, silk or

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109848/1677

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Polyhexamethylene adipamide. Such dyes can on these fabrics from aqueous liquors, the pH of which is preferably kept between 4 and 9 will be applied.

Those azo dyes according to the invention that have acidic water-solubilizing groups as well Fibers contain reactive groups, are suitable for dyeing Celluloae textiles, these dyes being applied to such fabrics in connection with a treatment with an acid-binding agent. The dyes can be done by dyeing, padding or printing are applied, the liquors b * w. Printing pastes contain the usual additives used when using reactive dyes can. The resulting dyeings have excellent washfastness.

The invention is explained in more detail below purely by way of example with the aid of exemplary embodiments, where the ropes and percentages are based on de8 weight are related.

1.92 parts of 2-methyl-3-amino-5-nitro-Indas'.ol (Her

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1 09848 / St.

19th

position according to the Journal of the Chemical Society, 19591 ^ß ° 2363-5) are dissolved in 50 parts of phosphoric acid (80%) at 0 ⁰ C; 0.7 parts of sodium nitrite are then slowly added over the course of 1 hour, after which the mixture is stirred at 0 ° C. for 2 hours. The resulting mixture is then a solution of 3 »10 parts of 2-methoxy-5-acetyl *» ino-H- (β- (β'-methoxyethoxycarbonyl) ethyl) aniline in a mixture of 60 parts of an O, 2N salt? 5 acid solution in water and 60 parts of acetone, the temperature of the mixture obtained being kept at 5 ° C. by adding egg. The mixture is stirred for 1 hour at 5 ° C, whereupon the precipitated dye is filtered off, washed with water and then dried «

A solution of the dyestuff in chloroform has ^ _max 577 »An aqueous dispersion of the dyestuff gives more excellent shades of red-blue when dyeing textiles made from aromatic polyesters

Authenticity.

The procedure is as in Example 1, with the difference that instead of 1 _ton, 92 parts of 2-methyl-3-amino-5 "nitrolnda * ol 2.37 parts of 2-methyl-3-emino-

5,7-dinitroinda * ol can be used.

The dye thus obtained has ^ _max 625 in solution in chloroform. An aqueous dispersion of this dye gives blue-green shades of excellent fastness when dyeing textiles made from aromatic polyesters.

Example 3

Se is worked as in Example 1, with the Deviation that instead of 1.92 parts of 2-methyl-3-amino-5-nitroinda * ol 2.37 parts of 2-methyl-3-amino-5,7-dinitroinda7ol and instead of 3 * 10 parts the coupling component used there 2.06 parts of 3-acetylamino-N, N ~ diethylaniline or 2.72 parts of 2-methoxy-5-acetylamino ~ H, lf-di- · (n-psropyl) aniline can be used.

Solutions of the dyes obtained in chloroform have ^ _max 610 or 662. Aqueous dispersions of the dyes produce green-blue bsw when dyeing textiles made from aromatic polyesters. green tints.

The 2-ethyl-3-aialno-5 _t 7-dinltroLnda?: Ol used as starting material in Examples 2 and 3 was prepared as follows}. · _ ^ ₀

7 * 0 ropes of a 60% aqueous solution of Ifcrdra ^ in hydrate were ?, U a solution of 15 * 0 parts of 2 ^ ethosy-3, 5-dinitroben * onitrile in 230 parts of ethanol with stirring while boiling under reflux added over 30 minutes. The mixture was then stirred at the boiling point for 15 minutes and then cooled to 20 ° 0. The excreted 2-cyano-4,6-dinitrophenylhydray.in was filtered off. This solid was stirred with 115 parts of a boiling aqueous 2N hydrochloric acid solution for 30 minutes. Bann was added a solution of 36 parts krlstallförmlgem Hatriumacetat in 15O parts of water, and the mixture was boiled under 10 Hinuten ents Bückf and then cooled to 20 ⁰ C. The 3-amino- »5,7-dlnitroindar.ol which had separated out was filtered off.

7.0 parts of dimethyl sulfate were added ru ol a mixture of 10 parts of 3-amino-5,7-dinitroinda * ol and 150 parts Äitroben? At 180 ⁰ C with stirring. That was emißch ^ 1 hour at 180 ⁰ C stirred Uncl dam at 30 ⁰ C cooled. 200 parts of diethyl ether were added and the solid residue separated from the liquid. The residue was recrystallized from acetone. Thus ol _t Fp to give 2-methyl-3-amino-5 '7-dinitroinda *. 325 ⁰ C.

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109848/1677

Example 4-

0.7 parts of sodium nitrite are v> u a solution of 1.92 parts of 2-methyl-3-amino-5-ol * nitroinda acidic phosphorus in parts (80 # strength) were added at 0 ⁰ G during 1 hour and the The mixture is stirred for 2 hours at 0 ⁰ G. The resulting solution is then * u a solution of 2.65 parts of NJEthyl-N- (P-pyridiniua-ethyl) aniline chloride in a mixture of 6.2 parts of water and 6.2 parts of acetic acid were added. The mixture is stirred at 0 to 5 ° C. for 16 hours. Then 100 parts of a saturated aqueous solution of sodium chloride are added, and the precipitated dye is filtered off, washed with 150 parts of a 10% aqueous sodium chloride solution and then dried «

If this dye is applied to textiles made of polyacrylonitrile from a neutral or weakly acidic liquor, the result is blue-red shades with excellent fastness.

Example ^

Ee is worked as in example H- with the

109848/1677

-ιέ-Si

Deviation that instead of 2.65 parts of N-ethyl-H- (ß-pyridinium-ethyl) aniline-chloride 2.8 parts N-Ü [thyl-N ~ (ß-pyridiniumethyl) -m-toluidine chloride be used. This gives a dye that is useful when dyeing textiles made of polyacrylonitrile gives violet shades with excellent fastness.

Example 6

A solution of 1.95 parts of sodium metanilate in 20 parts of water is added to a suspension of 1.9 parts of cyanuric chloride in a mixture of 15 parts of acetone and 80 parts of ice water, the pH being adjusted by the slow addition of a 10% aqueous solution Sodium carbonate solution is kept between 5 uxul 7. After the condensation has taken place, a solution of 3.5 parts of the disodium salt of 1-amino-8-naphthol-3,6-disulfonic acid in 25 parts of water is added, and the mixture is stirred at 35 to 40 ° C until the condensation is complete, the pH of the mixture being kept between 3.5 and 4.0 by adding a 10% aqueous sodium carbonate solution. The mixture is cooled to O ⁹ G by adding ice, and a solution of the dialiuasal * e8 of

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109848 / 1R77

2.6 parts of 2-methyl-3-amino-5 »7-dinitroinda * ol in 80 parts phosphoric acid (80%) (representation according to Example 3) is gradually added, with the temperature of the mixture between 0 and 5 ° C is maintained by external cooling and the pH value by simultaneous addition of a 3G # aqueous solution Solution of sodium hydroxide adjusted to 6 to 7 will. The mixture is stirred at 5 ° C. for 2 hours, after which sodium chloride is added to make the To precipitate dye. The dye is then filtered off and dried.

The analysis found that the dye had one hydrolyzable chlorine atom per azo group contains.

When dyeing cellulose, this dye results in * Textiles in connection with a treatment with of an acid-binding agent, green-blue shades with excellent fastness to light.

A dye with a similar hue and smoother Authenticity is preserved if the Diazoniuasal * from

2-methyl-3-amino-5,7-dinitroinda * ol by the

of 2 ~ methyl-3-ami * K> -5-iiitroanda * ol

is replaced.

• 34 -

109848/167 7

The table below lists further examples of dispersion dyes according to the invention, which are obtained by diarotating the amines indicated in the 2nd column of the table and coupling the diaro compounds formed with the coupling components indicated in the 3rd column of the table , the procedure vegetable example 1 being applied. In the 4-. Column of the table shows the hues that are obtained when dyeing polyester textiles old with the respective dyes.

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109848 / T677

example

Amine

Clutch component

hue

8th dinitroind & ttol 9 dto. 10 dto. 11 dto. 12th
15th dto. 1098 15th dto.
dto * * »■
03
-ν.
-j> 16 dto.
dto. 17th dto. 18th dinitr oinda * ol 2-n-butyl ~ 3-amino-5,7
dinitroindarol

Bf, H ~ di- (ß-hydroxyethyl) -ia-aminoacetanilide blue

N, K * -Di-i ß- (β-cyanoethoxy) ätbyl) -m-toluidine dto.

H, lT * -diethyl-m-toluidine dto.

H, ISKDi- (ß-acetoxyethyl) -m-toluidine Rofblau

!!, K'-diethyl-m-aminoacetanilide green blue N, IT-Di- (ß-carbomethoacyätbyl) -m-aminoacetanilide blue N-ethyl-N- (ß-carbomethoxyethyl) aniline dto.

Ν, Η-dietbylaniline dto.

N-ethyl-N- (ß-aoetoxyethyl) -m-toluidine dto.

HjN-dimethylaniline. dto.

2-Meth03? Y-5-acetylamino-lir- (ß- (β'-methoxy «blue-green äthoatyearbonyl) äthyl) aniline

dto. dto.

example

Amine coupling component

hue

§ 19th 2-methyl-3-amino-5
nitroinda ^ ol 5 20th dto. Γ " 21st dto. 22nd dto. O
to
00 23
24 dto.
dto. OO 25th dto. S. 26th dto. 27 dto. 28 dto. 29 dto. 30th dto. 31 dto. 32 dto. .... dd dto.

N-ethyl-N- (ß-cyanoethyl) aniline

N- (β-cyanoethyl) -N * (β «methoxy ethyl) -m-toluidine N ~ ethyl ~ N- (ß-acetylethyl) aniline

N-ethyl-N- (α-acety laminopropyl) aniline N-n-Butyl-ϊϊ "{ß-oy anoätbyl) -m-toluidine U-ethyl-ϊΤ-- (ß-chlorätayl) aniline

N- (ß-Cy anoätiay 1) -N- {ß-phenoay ethyl) aniline

N- (ß-Cyanomethyl) -N- {ß- (β-acetoxyethoxycarbonyl) ethyl) aniline

N-Xthyl-N-i ß- (cyanomethoaycarbonyl) ethyl) aniline N- (ß-cyanoethyl) -N- (ß ~ acetO3qfäthyl) aniline Diphenylamine

N, N-di- (ß-hydroxyäthy1) -m-chloroaniline N- (ß-hydroxyethyl) -a-naphthylamine α-naphthylamine

2-methyl-5-metho: xyaniline

scarlet

Hot

dto. blue-red dto.

Red

Scarlet ^ at ..

Hot

dto.

dto.

dto.

Navy blue red blue ruby red

CD GO CT)

Example amine coupling component shade

3 * 2-Metby 1-3-8JaInO-J- 2 ₁ 5-Dimethoxy aniline red-violet

nitroindawol

35 Ditto 2,5-dimethylaniline blue-red

36 dto. 2-Metboxy-5-acetylamino-Bf _t Ii-di (ß-acetoxy-navy blue

ethyl) aniline

37 2-Metbyl-3-aminoindar.ol l ^ N-Diethylaniline Eotorange

38 2-Metbyl-3-8Jaino-5-nitro-2-metho ^ -5-acetylamino-N, N-di (β-acetoxy- green blue

g 7-cblorinda'Ol äthyl) aniline '

S 39 2-methyl-3-amino-5-nitro- dto. Dto. I »* ^

J ^ 7-brominda "-ol

σ co cn

The 2 "ethyl-3-smi.m> inda * ol was obtained by reacting J-Aiüinoiö & a ^ ol with dimethyl sulfate in hi-tr oho

The 2-methyl-3-amino-5-nitro-7-chloro ~ b ^ w. -brominda * ol was made from 2,3-dichloro- b7.w. 2,3-dibromo-5-nitrobensionitrile by reaction with hydra ^ id hydrate in ethanol with subsequent cyclization and subsequent treatment with dimethyl sulfate in JTitroben ^ ol obtained.

The 2-ethyl b ^ w. 2-n-butyl-3-amino-5,7-dinitroinda?! Ol was obtained by treating 3-Ajnino-5,7-dinitroinda * ol with 3) iät hy! sulfate b ^ w. Di-n-butyl sulfate in nitrobene sol obtain.

example

0.7 parts of sodium nitrite are in a solution of 2 _f 37 parts of 2-methyl-3-amino-5,7-dinitroinda?: Ol in 25 parts of phosphoric acid (80%) at ⁰ ° C for 1 hour. ugesetf-t. The mixture is stirred for 2 hours at 0 ° C and then added * u a solution of 2.5 parts of Natriunsalr.es the i-naphthylamine-6-sulfcsäure in 200 parts of water at ^{0 °} C.

The mixture is stirred for 4 hours at 0 ^° C., and that

109848/1677

BAD ORKaINAL

precipitated product is filtered and dried . The Pilterejut is dissolved in iqq parts of water and 100 parts of acetone at 0 ⁰ C, vjorauf 5 parts of a 14 -% - aqueous Itet ^ iumnitritlößung and then 4 parts of a 36% aqueous Salrsäurelösung are added. The mixture is stirred for 1 hour at 0 ⁰ C _t then sulfamic acid is f.ur destruction of excess nitrous acid * was added, and the mixture is ^r / u a solution of 4.5 parts of Dinatriumsal * ·· '/ EO de ?? 2- (V-Amino-J '~ sulfoanilino) ~ 5-aaplithol-7-sulphonic acid: added in 100 parts of water, the pH value of Hinchuriy being kept between 5% by adding iatritic carbonate . After the coupling has ended: i; r ^; ir <'. Natriuachlorid added _t precipitate the A / overbiiiCung that UUD filtered therein is dried "

The solid \ FIRD in 200 ¹ Soll ^ n ^ SiE Raeser goilöst, "and a solution of 1.85 parts of C / annrciblorid in 25 parts of acetone \ * ird to? _T ugegebea wherein the pH value of the mixture '' wipe 5 wnä 7 by Su ^ abe from ITatriuK carbonate is maintained. After condensation, a solution of 4.8 parts of ^f is I? rinatriuH "sa3.zes the i-Naphthylaifiin-3? 6 _t 8 ~ e ^{trisulfosäui%} in 50 parts of water added and the Mi.schuti ·;? vird stirred 2 hours at 40 ⁰ C _t where the pH value is maintained by the addition of sodium carbonate is between 5 u d. 7

109848 / 1G77 "

io.icl is used to precipitate the dye

d «?: · αβϊιϊλ is filtered off and dried

At do: ·. » Analysis of the dye reveals that it contains one hydrolyzable chloratoxa per dye molecule. The dyeing of cellulose Tesrfcllstoffen in conjunction with a treatment an acid-binding Hittel Aife enters this! Blue brown dye! Asehecb.theit hues bit excellent ¥.

In the following table are further examples of fm? given "basic dyes of the invention, characterized dia örhaltea \ e: cd © n _t that dis in the 2nd column en: i specified table Affiiae dia ^ be otiart and öjitstsieiiräexi Dia ^ overbiXiilungen ö""Eils ait the Xi? -. the 3 "3 column of the table angogebaner-n coupling koia ^ onentsii ^ ykuppält v.ar-döJi, where di.s Yerfahren-ΐ-eiR« p; ö, ii ^ ss Soi «pio3 ^ -% u: j, r ) '7a £; dt wiM. In öe: c ^. SjitiJ.ii? Fler table nlu & di ^ hues indicated, which are exthalfcen,: -.- ^ i; m die üöt ^ öffemieri dyestuffs «um Färvm of i 'oi: tilie.ii ε.ν. & polyacrylonitrile used

1098A8 / 1B77

BAD ORK31NAL

example

Amine coupling component

hue

41

42

οο 44 co

2-methyl-3-amino-5 ~ nitroindazole

2-methyl-3-amino-5,7 dinitroindazole

ditto ditto.. ß (m ~ (K, Η diet ny lamino) phenyleul S carbonylamino) · ethylpyridinium chloride

II-ethyl-li (β «pyridiniumethyl) aniline chloride

Si-ethyl-IT- ((3-pyridiniumethyl) -m-toluidine chloride

p-i ß- (N-hienyl-IT-ethylamino) «ethO3Ey) phyltrimethylemmonlum chloride

Bluish red blue

dto.

dto.

ro

O CO Q)

Claims (1)

Claims 1 »Process s <ur production of asso dyes that a radical of the formula • NO H «N - contain, in which the Hing A still 7UBat / borrowed substituents and H is an optionally substituted aliphatic hydrogen radical means, characterized in that an amine the formula where A and R have the meanings given above, diazotized and the resulting diaso compound u ± ^J o is coupled to a coupling component. 2- The method of claim 1, characterized in _t that a clutch componente a compound of the formula 1 0984Θ / 167? HH wherein the benzene ring B ¹ can contain substituents or can form part of an optionally substituted naphthalene ring, is used, and that the compound obtained is diarotated again and a coupling component is coupled. 3. Process for the production of flavorings containing a radical of the formula wherein A and B have the meanings given in claim 1 and also one which is reactive with fibers Contain group, characterized in that an azo dyes according to the method according to Claim 1 or 2 is obtained and contains an acylatable amino group with an anhydride or halide an acid, the acid residue of which contains a group reactive with fibers, or or with a heterocyclic compound which is attached to a carbon atom 1098A8 / 1677 - ORIGINAL i ^ SPICTED of the heterocyclic nucleus bonded halogen atom and oil atom reactive with fibers tmw · contains a group reactive with fibers, is treated » PATlNTANWXlTf DR.-ING.H. FIN-Kt, DtPt.-ΙΝΘ.Η.ΙΟΗ « ORIGINAL INSPECTED