DE1964690A1 - Coupling components and azo dyes made with them - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. FINCKE DIPL.-ΙΝβ. H. BOHR ¹ DIPU-INfG. S. STAEQER

Long-distance call: "26 SO 40

S MUNICH S ₁ . MOllerstrasse 31

2 3. DE11969

Folder 22120 - Dr ₀ K ₀ ICI Case D ₀ 2t591 / 22044

IHPEHIAL CHEMICAL IKDUSiPRIES LTD, Londons, UK

as well as azo color produced with it

fabrics

Priorities: December 23, 1968> Jul. 11, 1969, Nov. 7, 1969 - Great Britain

It has been found that products of the formula

C-H,

X.

HO

A c

JlH O

009829/1878

wherein one X is H and the other represents GN, and 2 a chain of atoms, the R 5 form one or 6-membered ring "represents may be characterized srhalten _B that a compound of the formula

(or a tautomer thereof) alone or in a solvent heated, whereby water is evolved and a cyclization takes place,

The resulting products are valuable coupling components. which couple with a wide range of diazonium salts fc ^. "and thereby form azo dyes« If ßer. No dye contains water-soluble maclienden groups, then it can be used as a disperse dye for dyeing, for example, acetate, Nylon or polyester fibers are used «

If the diazo component contains a cellulose-reactive group, vrie Z ₀ B ₀ a mono- or dihalotriazinyl group or a pyrimidylamino or sulfatoethylsulfone group, then the dye can be used as a reactive dye. For a reaction with cellulose it is also preferred that an SO-jH group is also present in the diazo component «

00 9 8 29/187 8

If the diazo component contains a quaternary amino group or a group which can then be converted into a quaternary amino group, then the dye (which therefore contains a quaternary ammonium group) can be used for dyeing and printing acrylic fibers.

Wine also ^d: .e Diassokomponente a hydroxyl or carboxyl group in oitho-St RECOVERY contains the diazonium Dain rc suitierende dye can be prepared by treatment with eiiem metal salt is converted into a Metallkomplexverbindurig ve c to, for example, in a 1: 1 he -Klpf -, 1: 1 ^ nickel, 1: 2 chromium or 1: 2 cobalt complex

The dyes obtained by the coupling process can be represented by the formula (1), where _P has the meaning given, one X is H and the other X is an aromatic radical bonded via the zo group

Coupling components of the formula (2) can be obtained by condensation of acetoacetic ester, cyanoacetic ester and a diamine of the formula HH ₀ -Z-IiH ₂ J where a considerable excess of the latter compound is used.

Ei: ie JECLasse of Heaktivfarb'stOffeii can be dargesttllt (1) by the above Forme L, wherein an X OW and a && other is a group of the formula.

.J> - H- β Η - '3)

there: r represents _F in which D is an aromatic Badika-1, _P which contains at least one acidic water-soluble group and at least one with fibers, reactive oxupps-

009829/187 8 BAD

Examples of groups reactive with fibers should be mentioned become: vinyl sulfone and aliphatic sulfone groups, soft ' a halogen atom or BuIfat ester groups in β-3tposition to the. Sulfur atom contain »for example ß-chloroethyl or fi-Suliatoathylsulfon- and fi-aulfatoäthylsulfonylaminogruppen, ol, ß ~ unsaturated alkyl radicals from aliphatic carboxylic acids » such as acrylic acid, dl-chloroacrylic acid, propiolic acid, Maleic acid and mono- and dichloromaleic acid; as well as that Acyl radicals from acids, which contain a sub-substituent that reacts in the presence of an alkali when the fiber is used, for example c.as radical of a halogenating aliphatic Acid, such as ß.B »chloroacetic acid * ß-chloro- and Q-bromo ^ propionic acid and oC, 6- * I) ichloro and «dibroinopropionic acid ο Other examples of groups reactive with fibers include tetrafluorocycloTSu-tancarbonyl-, trifluorocyclobutenoarbonyl-, Tetrftfluorocyclolsutyläthenyl-carbonyl-, Trifluorocyolobutanäthenyloarbonyl- and heterooyclisohe radicals, the 2 or 3 Nitrogen atoms in the heterocyclic ring and at least one containing reactive substituents on a carbon atom of the ring with fibers.

An example of «for such heterocyclic b & aicals» should be: 2 _! 3-Dicblorü-oMnoxaliii-5- od «r 2,5- ^ Dichloro-3iiijao2iiliii * 5 ~ or oc or -7-

7- or -8-sfulfonyl-, 2,4,7- or

s tmd tasbeaondere «-» friaÄta-S-irl- isnd "PyrifeLSia 2-yl- odeje «4-yl-radifcale, which at isiadeatens one of the

009829/1878

«» 5 - ■■ '-'

remaining 2-, 4- and β-positions a bromine or preferably a chlorine atom, a stilfonic acid group, a thiocyano group, an aryloxy or arylthio group with an electronegative substituent, such as 2 _o B _a SuIf © phenoxy, sulfophenylthio, nitro sulf © phenoxy, Oisulf © phenoxy and StJfonaphthoxy ,, or one. J troop of formula

- S - q J ¹ (4)

wherein R- and R are the same or different and a hydrogen atom or an alkyl, aryl or aryloscy group represent, contain », '

If the pyrimidine ring or the $ riaBin ring is just one of the airtigen reactive ßubstituenten bears,., then ^ the ring " e: ln non-reactive substituents on the remaining Containing carbon atoms

009829/1078

wherein Y represents a group of atoms which form a 5- or 6-membered heterocyclic ring required *

is s which can carry substituents or form part of a condensed ring system, or a quaternary ammonium or I ^ yriäiniumgruppe, or a group of the formula '"■' ■■■ s" R ¹

- S - C -K- ^ (5)

κ ² :

12th

wherein R and R are each the same or different alkyl, Represent cycloalkyl, aryl or aralkyl groups or together with the nitrogen atom a 5- or 6-membered group form a heterocyclic ring, or a group of the formula,

- s - oZ

1984ISO

The term "non-reactive subatituent" means a group which is bonded to the triazine or pyrimidine nucleus by a covalent bond to a carbon atom, this covalent bond not being used under the conditions that are used _: cow application of the reactive dye breaks ο Examples of such substituents are: primarily amino and hydroxyl groups, as well as mono- or disubstituted amino groups, etherified hydroxyl and etherified mercapto groups. In the case of substituted amino groups, this ice includes, for example, mono- and dialkylamino groups, in which the alkyl group is preferred contains a maximum of 4 carbon atoms, and also substituents such as a "B _Q can carry hydroxyl and alkoxy groups, as well as phenylamino and naphthylamino groups, which preferably carry sulfeaic acid substituents." In the case of etherified hydroxyl and mercapto groups, this class includes, for example, alkoxy and alkylthio groups, preferably those with. ei: iem low nolecular weight, therefore those which have up to 2u 4 Kx) carbon atoms, as well as phenoxy, phenylthio, Ha: ohthoxy or naphthylthio groups. Suitable as special examples? All these ELassea should be mentioned: Methylamine-, Ätjiylaiäino-, Dimethylamine-, ß-Hydroxyäthylamino-, Di (B-hydroxyäthyl) amino-, ß-Ghloroäthylamino- p Cyclohexylamino-, Anilino-, Sulfophenylamino-, Disulfophenvlamino- »N- MethylsulLfophenylaminc-, ir-ß-Hydroxyäthylsulfophenylamino-, SiiLf0-o-toluylaE.ino-, Carboxyphenylamiiio- Vaa SuIfocarboxyphonylamino-f methoxy, ethoxy and butoxy, phenoxy * methyl .phonoxy-, Chlorcphenoxy- and phenylthio Ghloratome _0, | od <3r cyano, uritro, carboxy and caroalkoxy groups in the 5-3 position of a pyrimidyl radical fall into the category: '1' e: c non-reactive substituents ₀

00 9829/187

In the above formula (3), the symbol P can represent a radical of the benzene or naphthalene series * which contains the group reactive with aging in some cases directly attached to a nuclear carbon atom, but preferably bonded to a nuclear carbon atom via a connecting amine group., Typical _{B 0} B ₀ radicals are not only phenyl and kaphthyl, but also stilbene, diphenyloxide, diphenylraethane, diphenylurea, diphenoxyethane and diphenyl oak at least one and preferably white

8ulf0Hßä \ 2Tegruppen contained

line related class ym new * dyes are the Metallko ^ pleiazofarbstoffe where a Metallatoa complex to a laetalliBierbareGruppe _s in D in the ortho position to Asogxvppe and "ur hydroxyl or wahrechein less - / ^" N-At eo de '; ^ olieiert en I ^ ridcmkerne is located is. Beia ^ eU for these dyes are the

line Serene urine · from Metallkoaplex reactive dyes Bind C% rome and Koteltkooplexe, which are only a nucleus of an Ass or oWgen Forsöl, which is given a Fwwrn reactive «Gruppe iarfendung» and iron swettea

b? i the e · eich ία «inen unterisoliedlio ^ iia A» of »rb # off acts, egg a sub-colored aehifesf-shed igemdem, which has a group that is reactive with FasurE ^ hAlti ·. Ton beso «a« re> i lateresse are in this Htgss Formeins dye β. - -

-HH - CR ₂ CH ₂ NH Φ

- CH ₂ CH ₂ NHT

where X stands for O or CO ₂ * I stands for a group reactive with fibers and A stands for a benzene or naphthalene amine which contains at least one sulphonic acid group when T does not contain any and which furthermore by a nitro, chlorine or one with fibers © reactive group label be substituted · Di "preferred dyes are those" where ΐ sine Honoehloro-e ~ tr: represents lasinylgruppe "tn of the third carbon atom of the · friazinkerns a sulfoniearues Hienoxy-, or it sulfonated Anilinoradlkal bears" in which the benzene nucleus can optionally be further substituted, for example rturoh Cl “OH ^ ^ ^βΓ MCOCH- _o These dyes

.009829 / 1878

; result in reddish hues with an unusually good one Lightfastness ο

The new dyes according to the invention can be obtained by a wide variety of processes, depending on their constitution. Metal-free dyes can be obtained by coupling a diazotized aromatic amine or a tetrazotized aromatic diamine with a compound of the formula (1) in which one X is H and the other is CN and Z is as defined above. Examples of aromatic amines and diamines for this purpose should be mentioned:
Aminoazobenzene, aono and disulfonic acid, orthanil, hetaail and sulfanilic acid, 2-, 5- and 4-a inobenzioic acid | :

AniliÄ-2,4-, -2,5- and-3,5-disulfonic acid,
4-methoxyaniline 2- and - »3-sulfoiic acid _e
2-metho ^ sraniline <-5-efulfonic acid,
5-Andno-2-hydroay-3r3ulfobenzoic acid,
4- and 5-acetylaminoaniline-2-sulfonic acid,
5-acetylamino-2-aminobenzoic acid »

4- and 5- (2% 4 '»DichlorQ-s-triazin-e'-ylaininoJ-aniline ^ -. sulfonic acid, -.

4- and 5- (2 * -Ch: Loro-4 '* aJiitoo-s- ^{triazin-6 l} -yla! Dino) aniliii- ^ sulfonic acid,

4- and 5- (2 ^r -0hloro-4'-metanüiao-s-triazine-ö * -ylamino) -aniline-2-sulfonic acid,

4- and 5- (S'-QKioro ^ ¹ -sulfo-O-toluidino-s-triazin-e'-ylamino) aniline-2-sulfonic acid,
Chloro- and NitroanilinsulfonsäurQ, - '
^: 1-aminonaphthalene- ^{4-5 1} = - * -6- vaaä -7 ~ sulfonic acid ,
2-Aminoiiaphthalin-i-, »» 4 ·· »" -6 · »» .- «-? ♦ - and ~ 8-sulfonic acid,

1964630

1-aminonaphtha: yn-3,6-disulfonic acid _f

2 '= - aminonaphtha: in- _{1,5- s} -3,6-, -4,8-, -5,7- and -6,8-di3ulfonic acid,

1- and 2-an & noraphthalene-trisulfonic acid, 4-nitro-4'-amir ostilbene-2,2'-distilfonic acid, ; 4 ~ and 5-sulfo-2-aininobenzoic acid,

.6-chloro-, 6-N2tro-? and 6-acetylami | ia-2-aminophenol-4 * - .sulfonic acids

2-aminophenol-4- and -5-sulfonic acid and -4, δ ~ disulfonic acid, 3 ~ amino-2 ~ hydroxy-5-sulf © benzoic acid / 4 ~ chloro ~ and 4-liitro-2 ~ aminopüenol-6-sulfonic acid, .1 'amino ^ ^ -hydrcxymptithaläJ sulfonic acid, 6-nitro = -1 -2-amines hydrox5 ^r naphtheLLin-4-sulfonic ₉ 1 s J-Pnenylendiemin · ^, 6-> disulf onsäurev. 1 ρ 4-PB.enylendismin ~ 2, 5 = »disulphonic acid i 4 _i 4 ^f -diaminodiphenyl-2- 'and ~ 3-sulphonic acid _p 4p4'-diaminodiihenyl-2.2 ^l - and -3.3 ^f ° disulphonic acid _p · Spö-Naphthaliiiöiamin-ITS- and -3,7-dü.aulfonic acid, 4 "4 '-Diaminodij henylharnst off-2,2' - ijnd -3,3 '-disulfonic acid, and,.

4 _i , 4 ^I -diamino3til'ben-2,2 ^<l -diaulfonic acid <* -

The MetaH complex dyes © can be obtained by combining a compound of the formula (?), In which one X is H and the other is ON and Z has the meaning given above, with a diazonium metal of an aromatic amine which has a hydrosyl, carboxylic acid or alkoxy group containing in ortho-position to the amino group, coupling and the Azoverfcindung a Wetallisierung obtained subjecting _d a Schwermetallkomplea :, beispielsiiöise a copper ", nickel, chromium * or cobalt complex to produce fier azo compound * the Mefcallisierung example, in an aqueous MeäiuK with a salt of the corresponding metal

9829/1878

196A690

• ti -

be carried out, for example with chromium sulfate, cobalt aoe did, cobalt si; If at, copper sulfate and copper acetate _o In some «cases. at ee prefer, a complex metal salt, which ·· belöpielsweiee in the form of a hetallaramine complex is present, use em, such as Z ₀ B ₀ the copper amine sulfates, those au * copper sulfate and ammonia, pyridine or ethanolamine can be obtained. Other suitable hetullizing agents are those in which the metal is a (file of a complex anlone forms, partially ChTOBicoinplexe of organisohen i

Hydroxycarboxylic acids, for example salicylic acid, or

of copper or cobalt old aliphatic amino *,

or ^ fdroxycarboxylic acids, for example olcolic acid, milk " eAic and tartaric acid.

Oil treatment kit for metallizing agents can be carried out by an known procedures at tree temperature or slightly increased ten Ϊei ^ eraturen be aueeefunrt. When a dealkylation is predicted, then at a temperature

from 50 ~ 120 ° C into an open container under reflux or Worked in a closed container under pressure at a pH suitable for the reaction, examples of this Treatments are acidic copper plating kit or copper sulfate atlrattiene copper plating with Cupraenoniuiafsulfate

Contain nenen dyes and your Bchwermetallkomplexe that ^Gine llerbare group, such as "group one acylated amino ~, in particular a solohe the i'ornel HH (wherein a positive Gst & esahl, vorzugeireise 7 or! Group) or line group, for example a nitro or ⁱ Acetylaainogrupp3 which automatically converted into an acylated amino ~ - can be converted contain, can after treatment, the © for the formation of amino aoylierbaren rforder- "

19646910

lent is converted into a dye reactive with fibers by condensation with the anhydride or halide acid, the acid radical of which has a substituent which is able to react with the fiber to form a chemical bond, or by Condensation with a heterocyclic compound »the one Halogen atom to a carbon atom of the heterocyclic nucleus and also a reactive substituent of those just mentioned Kind, contains »

As examples for acid halides or acid anhydrides or: for heterocyclic compounds that can be used, the following should be mentioned: carbyl sulfate and the anhydrides or acid halides of OC, ß-unsaturated aliphatic acids, such as chloro; nalein anhydride, propiolyl chloride and acrylyl chloride, the acids halogenated aliphatic acids, such as ZcB> chloroacetyl chloride, stilfochloroacetyl chloride, ß-bromo- and ß-chloropropionyl chloride and <X, fi-I) ichloro- and -dibromopropionyl chloride, 2,2,3 »5-tetrailuorocyclobutane carbonyl chloride, ß- (2.2, 3 »I-tetrafluorocyclobutyl acrylyl chloride, 2,3» 3- ^ rif luorocyclobut-1-ene carbonyl chloride, β- (2,3 »3-trifluorocyclobut-1-enyl) acrylyl chloride and heterocyclic clusters which contain at least two nitrogen atoms in the heterocyclic rings which contain two or more halogen, especially chlorine atoms, in the ortho positions to the nitrogen atoms ^ such as z _o B _e 2p3-dichloroquinoxaline ~ 5-tLid -e-carbonylchlorideg 2,3- ^ iShIOrOChInOXaIIn-5- and -6-sulfo: iyl chloride, 2 ₉ 4-33ichl © Γoc! ιinazolin-6- and -7-sulfonyl chloride, as ^ e-irfchloroGhinasolin -? - and ~ 8 ~ eulfonyl chloride,? _f 4.7- and 2.4-8-iPrieM.orochinazolin-6-sulfonylchloriä, 2,4 "> Di-ihloroohinazolin-6-carbonylchlorid _f . ■ 1,4-Dichlorophthalazi'i-S-carbonylchloride, 2,4-Dichloropyriiaidtsi -5-carbonjt2 iilor Ld, ß- (4, S- ^ ichloiOpyridazonyl-1 -) proplonyl-

009829/1878

Chloride, 1- (4 ^l ^ hloroforinylpheayl) -4 »5-öichloro-6-pyridaaon, 1,4 * -chlorosulfonylphenyl * 4,5-diohloro-6-pjridazon, 2,4,6-tribromo and trichloropyrimidine, 2 _t 4r5T6-Ietrachloropyrimid · - in, 5-Methyi-> 2,4,6-trichloropyrimidin _r 5-Nitro-2,4 _t 6-trichloropyrimidinj Z ^ -Dichlorc ^ S ^ nitro-e-methylpyrimidiii, 2,4- Di-. ohloro-5-nitro-pyrimidine, 2,4 _r 6 ~ Trichloro - 5-cy9no ^ pyriiBidiii, -. ^ iithoxycarlKmyl * -2 _t 4 * -dichloropyriinidiii _> 2,4-dichloropyrimiaih-5-earbonyl chloride, gyanur bromide, cyanuric chloride; the primary condensation products of cyanuric bromide or cyanuric chloride with ammonia, an alkaline metal sulf it or thiocyanate or an organic mercaptan, a hydroxy compound or an organic primary or secondary amine, such as methanol, ethanol, isopropanol, phenol, o-, m- and p-Ghloit) phenol, o-, m- and p-cresol, o-, m- and p-Snlfophenol, thiophenol, thioglycolic acid, dimethyldithiocarbaninsaxire, mercaptobenzthiaol, thioacetamide, methyl-, dimethyl-, ethyl- _e dietnyl -, n-propyl, isopropyl, butyl, hexyl and cyclohexylamift, toluidine, piperidine, morpholine, methoxyethylamine, ethanolamine, aminoacetic acid, aniline-2,4 * / -2,5 »and

Orthanilic, Meienilic and Stylfanilic Acid,

2-, 3- and 4-aminobenzoic acid, 4- and S-sulfo-a-aminobenzoic acid, 4- and 5-sulfo-o-toluidine, 5-amino-2-hydroxybenzoic acid., 2 ~ aminoethanesulfonic acid, aminonaphthalene mono * - and - disulfonic acid and K-Methylaminoäthattsulfonsaüre; as well as the secondary condensation products of gyanuric chloride with alkali metal sulfites, alkali metal thiocyanates, phenols and thiophenols which contain an electronegative substituent and compounds of the formula - ^ t \ *

H - S - 0. T ¹ , (9)

009829/181 »

S _Λ
HSCN ^ (10)

H-S-Of (11)

wherein Y, R, R, R ^ and R have the meanings given above own"

Water-insoluble azo dyes of the formula (1), wherein an X for GN and the other for a group of the formula

wherein the symbol D is an aryl or heterocyclic Radical represents which is free of water-solubilizing groups can be obtained by one A compound of the formula (1) in which one X is H and the other is CN represents and Z has the meanings given above, with the Biazoniuanrerbrück an aromatic or heterocyclic Amine, free of water-solubilizing groups, coupled

Examples of such amines should be mentioned in particular are the amines which contain a heterocyclic five-membered ring which has two or three heteroatoms, preferably one nitrogen atom and one or two sulfur or oxygen atoms, as well as aminobenzene compounds the formula.

009829/187 8

wherein a for H _{r is} a halogen atom or an alkyl «alkoxy, nitro, cyano, alkoxy« carbonyl or alkylsulfonyl group,

b for H, a halogen atom or an alkyl, cyano or Trifluoromethyl group stands and. I.

c represents a nitro, cyano, alkoxy-carbonyl or alkyl sulfonyl group Bteth.

All examples of such amines should be mentioned:

2-aminothiazole, 2 <rA »ino-5-nitrothiazole ₉ '2-amino-5-methylsulf © riyl-thiazole, 2-amino-5-eyanothiaeol, -

2-Affiino-4-methyl-5-nitrothiazole _f ,

2-Affiino-4-aiethylthl & Bol, 2-Assino-4-phenylthiazole, 2-amino-4- (4'-chloro) -phenylthiazole _t 2-aaino-4- (4'-nitro) -phenylthiazole, $ »aminopyridine, 3-aainoohinoline, 5-aainopyrazole, ! f-Amino-1-phenylpyraaol, 5-aminoindazole, 5-amino-1 ₉ 2 _f 4-triazole _f

5- (diethyl-, ethyl-, phenyl- and benzyl) - !, 2,4-trias ©!;. O-1- (4'-methoxyphenyl) pyrazole,

2-Asilno ~ 6-methylbenzthiazole β

2-amino-6-metho: cybenzthiazole,

2 ~ amino-6-chlorobenzothiazole _t

2-amino-6-cyanol3enzthiazole,

2-Amino-6-thiocyanato'benzthiazole,

2-amino-6-nitrobenzthiazole ,

2 «Amino-6-ethoxycarbonyn5enztlilazole,

2-amino- (4- and ß-J-methylsulfonylbenzthiazole,

2-amino-i, 5t4 * thiadiazole, m 2-amino-i, 3 r 5-thiadiazole _f

2-Amino-4-phenyl- and -4-methyl-1 _t 3> 5-thiadiazöl _p

2-amino-5-phenyl-1,3,4-thiadiazole,

2-Alino-3-nltΓO-5-πletnylsulfonyl-thiophene,

2-Amino-3 »5-bis (methylstilfonyl) thiophene ,,

5-amino-3-methyl-isothiazole, 2-amino-4-cyano-pyrazole , 2- (4 '-nitrophenyl) - ^ amino ^ -cyanopyrazole , 3- and 4-aminophthalimide, aniline,

p-chloroaniline,

p-bronraaniline,

p-toluidine »
P p-nitroaniline.,.

p-cyanoaniline,

2 _f 5-dicyanoaniline, 4-methylsulfonylaniline, 4-amino-ethylbenzoate, 2,4-dichloroaniline, 2,4-dibromoaniline * 2-methyl-4-chloroaniline, 2-trifluoromethyl-4-chloroaniline, 2-cyano-4- ohloroaniline, 2-methoxycaΓbonyl-4-chloroaniline ₉

0098 29/187

2-1 -Iethoxycarbonyl ~ 4-nitroam JLin _t
2- (ihloro-4-cyanoaniline _F
2 ~ ('chloro-4-nitroaniline,
2- »] 5romo-4 ~ nitroanili ^ i ,.
2- ( ^; chloro-4-ethoxycarbonylaniline _s

2 ~ I .etbylsulfonyl -4-chloroaiiilinji

2, .ι •• dinitro ~ 6 ~ m & thylßiilf ojiylanilin, 2 »i ■ --Dinitro-6- (2 ^J -hydroxyäthylsulf onyl) aniline 2 ιi dinitro-6- (2 '-chioroäthylsulfonyl} aniline _t

2s, ^^ Dicyanoanilia _f
2 * -Cyano "" 4-methyl-3ulfonylaniline _i

2 » i -Dicliloro-4- = oyanoaniline _?
2j £ -Dichloro-4-κi

2-C ys

. il-minolaenssoi-Z-, -3 ~ s "" and -4-bixlfonamid _{i, for} example, the ÜT-Üethyl-, N, ^ dimethyl »and N _B H« diethylanu & _s - · H, f-Isppropyloxypropyl-2 »amino- naphtkalin-6 ~ s-aifonamid. _s An.ilin-2'-, -3- and "-4-SuIfOn-Hj, Y-isopropyloxypropylamldp Λη:) 11η-2 ~ 5, ^ o- wad. *> 4 "Stilfon-N" .lsopropy.lamid _s An.ilin-2 «» _P «-5- '

4- 'C hloroaniline-2-siilf onaaiid »

unc the sulified derivatives thereof , 2-j 5 ~ "and 4 ~ araii: .ophenylsu.lfamic acid _?

4 ~ ρ ~ 5 ^m '.-Nd ~ 6- »meth.ylphenylatO.faminsäar ©. _J)

009829/187 8

2 ~ A nino-5-yne thiioxy-phenylcuf "amic acid, 3-A-αχηο-β-οΜοχΌ ;: -honylstilf pynic acid, 3-" A: iino ~ 2 _s a «diaii '" or ophenylsilfamic acid _r and

4-Αηίηοαζο ^Γ 22ηεϋ1 compounds "used as a ^ diazo component"

who Jen can ,, ίτ ". 'ΐά ζ-, Β, .4-Aninoasobsnsol,. 3,2' · dimethyl - 4 · -aminoazobensols, 2-Mt; thyl-5 - -es tho jiy - ^ - aJirL 4 ~ Αί] ino-2 "nitroae] · foenzene _;

2 = M {thyl-4 '«metiic :: y-4-aißlnoazobenzol ₈ 3s, 4' i.ö-Srimetlaoxjf- 4-arainoa.üöüenzoij, 4 ^ = C 3aloro = 4-amincazoberi3Ol, 2'- and 3 ' -Chlore ^ -aminoagobensoi _s 3 ~ Hi tro-4 ~ aaiino ~ 2 "', 4' -diohloroazobenzol and 4-« Ab inoa2oben2ol-4 * ^ sulfonamid ₀

Aside from all of the above, other diazo components can also be used, which are free from groups that make money and which contain a group that is reactive with a group ₃ such as, for example,. s-iriaainylradilcalej which have 1 or 2 chloro- or bromate or: 5 am iriaainl & rn »-Pyrimid.ylraclikalische ?. the one or two chlorine atoms or one or two acrylsulfonyl or alkanesulfonyl groups . Pyrisiidiiiring aJ-fweise ₉ Mono = or bis- {Y ^ -halogeno - .. ": - = hydrozypropyl j --aminognippen _P ß- Hälogenoäthy Lsulfamylradiiale _p ß = _{HalogenoätiiO35ygruppen s} S-Halogeno · - äthy Jjnercaptogruppan _s 2-ChIoro- bsssthiasolyl-ß-azo benz fchiazolyl-6-ainino _t l ^ Halogen-iS-hyd ChIo -Oacetylamj.no- _s ^ "ß-DibromoprapionyX ·

BATH ORiGiNAL 009829/187 8

^ 9 -

Examples of such a diazo component !! should be mentioned rerdenr

I. _r ß-Ghlproäthyl ~ 3- ^o öhlorO '»4-amiiiO" -ben2o3 - stilfonamidChydrochloride .), ■■ - ,; ■

l ·, ß ^ Moroäthyl-4 ~ aininoTDenaol-8ulf OBamld (hydrochloride.) j, 1-Bromo-4-ainlxLO - ^) - chloroacetoplienoiip 1 " _t TT-GlLi.oro-'ß-hydroxypropyl-4-aminoben2Ol ~ sulfonamide -,. I, ß-Chloroethyl «1 -amino« ~ 4 ~ naphthylsulfonaraid, I, ß-chloroethyl-1-amino-3y5-dichloro-bei) solst2lfonamid tmd 4 ~ ("jr-chloro-β-hydroxy-proposy )-aniline"

£ ine ireitere class of valuable dyes are etallk the ^: ^ omplexa .ofarbstoffe _ί containing a half atom of chromium or cobalt 3e mole of compound of formula (1) in which Z has the above mentioned Bedeutimg "a X for GN and the other for

D - N β N- (3)

is where D is. Benzene radical, which is a carboxylate Contains hydroxyl group ortho to the azo group and what other substituents apart from Sulfonic acid substituents in any positions or Carboxylic acid in positions other than the ortho position to the Aaogruppe may contain

These Forbötoff e can dadui'ch -sierden .. that a compound of the formula (I) ₁ wherein "one X for H and the other for CN and 3 has the meaning given above, with the diazonium as an o-hydroxy odero-Garboxyamins of the benzene series, which freely couples τοη SOJi or other to COpH-G groups ist ₉ , and di = i-ssultiere'nd "Aaonietall5.siertr.

0098 29/187 8

Examples of amines that can be used are o-hydroxy and o-carbocyanine compounds that can be substituted, for example by halogen (Z ₀ B ₅ chlorine), alkyl (e.g. methyl) , Alkoxy- (e.g. iüethoxy-), nitro- *. -CO-alkyl- (e.g. -CO-CH-), acylamino- (ζ _ο Β _β aoetylamino-). Sulfonyl (ζ, B ₀ -SOg-CH-), arylazo and • preferably sulfonamide groups that contain an N-substituent (z _o B _e -SÖ ^ NH-CBL or -SO ₂ M-CgH ₅ ). As examples of amines of this type should be mentioned 2- »aminophenol,

^ Phenylazo ^ -aininophenox, ·

4-methyl-2 ~ aminophenol, - ■ -

4-Hetho2y * 2-amiriophenol, "*.

4-chloro-2-iminophenol,.

4- and 5-nitro-2-aminophenol, 4-metho ^ -5-chloro-2-alπinophenol, e-Acetylamino ^ -chloro and -4-nitΓo = -2-aninophenol,

5- and e-

3-Amino-4-hydro-aeetophenone, 6-HitΓO-4-acetylaminO-2-aminophβnol, 5- ^ itΓo-3-amino · -4-hydroxy-acetophenone, 2-amine-phenol-4-cexbonsunld »4,6 -Dinitro-2-aminophenol, 4 _s 6-dichloro-2-aminophenol, 3,4, e-Trichloro ^ -aiainophenol, 4-Hitro-6-chloro-2-aininophenol, 6-Hitro- and 6-Chloro- ^: -2-aminophenol-4-sulfonamide,

4-nitro- and 4-chloro-2-aiöiJio-phenol-5- and -6-ßulfonamid, 2-i \ minophenol-4- and -5-sulfonamide and the corresponding -K-methyl-, -N-ethyl-, Üi-ß-hydrozyäthyl-, N, y-methO3cy-

009829/1878

1964890

and -äthoxjrpropyl ^ r -lSf - diaie; thyl-- _i , ^ SI-phenylamidei as well as the corresponding morpholii and piperidide as well as 2-aminopnenol ~ 4- \ and ^ 5 ~ sulfon "S _? 5 ⁱ -si ^ fonanddopheny3 _r amid. and 5 ^β ~> Sul, fainyl-5

Examples of o-carbo ^ aminobenzene compounds that should be mentioned are 4- and 5-chloro-2 ^ ainiaoben2ioesäure _Ä 4- and S-nitro ^ -aminobenzoic acid and tothranilsäuresulfonamides, for example ^ -Mdnobenzoeaäure ^ - and -5-suf onamideo

The coupling of the compound of formula 1 were carried out with the compound Diazonium. lcann by ordinary methods, for example, in a weak or alkaline medium 2s _e Bo acidic alkali metal carbonates or hydroxides enthä3.to

When the EJapplung is finished _fr then the dye from the Eupplungsgemischt tion can be isolated easily by filtration before the Metalli. In some cases it is possible to carry out the metallization directly without isolation from the coupling metal _{or the like}

The metallization can be carried out by treating the azo compound with a chromium or cobalt releasing agent, for example by treatment in an aqueous "medium with a salt of the metal or with a chromium or cobalt complex of an aliphatic dicarboxylic acid or hydroxycarboxylic acid> for example oxalic acid _e lactic acid, glycolic acid, Citric acid or vialic acid, or an aromatic o-hydroxycarboxylic acid, e.g. salicylic acid. The treatment is preferably carried out hot or under reflux, and in some cases it is preferred that the

1364690

Treatment in the presence of organic solubilisers Means * to carry out e.g. E-Xthoxyäthanoiy *

The metallization can be carried out with a single azo dye or with a mixture "which contains this dye and a further metallizable dye, in which case a mixed complex of the two dyes is obtained". These mixed cornpleate can alternatively be obtained by that you first prepare a 1: 1 complex with one of the dyes and then convert this into a 1: 2 complex by reaction with the second dye _o

Another class of. Valuable dyes are those that have an externally bonded quaternizable nitrogen atom and do not contain acidic groups, which for example can produce undesirable betaine structures and which in a reaction with an alkylating agent a quaternized Form dye. This quaternizable IT atom is bound to the radical of the diazo component, and in particular to the radical of an aromatic diazo component of the benzene or naphthalene series odes to one at most bicyclic heterocyclic diazo component.-, the a quaternizable amino, hydrazino or etherified one Contains hydrozylamino group attached to a carbon atom. is bonded, which can form a part of a ring or a low molecular weight aliphatic radical «,

As examples of such dyes, mention should be made of the dyes of the class of the formula (1) in which Z is the. has given meaning and one X for GN and the other © ^l for a group of the formula

009 829 / t878

- ζ.

N * H -

where A ^ is a benzene nucleus » Z ^ © is a direct link or a bridge member, for example -0-, -NR ¹ -, -CO-, -HR ¹ GO- or -NR ¹ SOg-, where EH or a lower alkyl group means _p -X- for a FeSilenstoff * chain with a maximum of 6 carbon atoms stands ₉ dl © is optionally interrupted by a heteroatom and which can be bonded to Rc and / or Rg, so that an oyoliache system arises, Re and SgΉ or a alkyl or ₂ lralkyl- Cycloalkyiradifcal t3ödea.t®% 9 H ^ S _s a © alkyl, aralkyl, cycloalkyl, or mixte ÄiÄSigrappe: means nteCtfcijria. H, Rg ", Rg and R» together aia ®i @ r can form several Rin ^ ® and X stands for an anion _β

These dyes can be obtained by amidation or ®sndei3satioa, coupling or quaternization, txm production by amidation or condensation is © in dye, which the group

X ₂ - 2 _t > A ₁ -Ϊ «Ä - {φ

contains, wherein A ₁ and Z ^ have the meanings given above and Tg is a carbon chain Ton at most 6 carbon atoms, which can be interrupted by a Hateroatom j, which can carry a reactive atom or a reactive group, for example Cl, -0 SOJH or an aryl or alkylsulfonylozygruppe, reacted with an amine, Rydryzla or an irerätherten Hydrozylamin.

00982971878

Al .s examples of amines _v hydrazines and hydroxylamines which can be reacted with a dyestuff containing a group of the formula (13) are to be selected; Armonia, methylamine, ethylamine * Isopra-pylamine _P Methoxyä ^ hylamin ,, Meti.oxypropylamin _f Dimethylaoin * Diethylamine _r N _{-Methylaniline f} ET-Äthylanilin, Chlorfeth; rlaymln »Äthsoiplamin,, diethanoiaminj? ropanolamine _f Benzylamln- Oyclohexylsjnj..n _i N- methylcycloheisylamine ,, morpholine ₉ pyrrolidine ^ - piperidine ,, pjperazine, trimethylamine triethylamine _$ triethanolamine _r DimethylbenzylaiaiiJif, diethylamine. _f l'yridiru P: Lcolin ₈ Lt.tidin _f Njli-dimethylcyclohexylamine; H-Jiethylpiperidiii. " N-Methylpiperas.in, Ii-Metliylmorpholin _f Quinolln * Pyrimidin ur d 1,4-Diazabioyolo (2 _r 2 «2) -ootane _g N-Hq -"; hylhydrazine _R ίΤ _? 1ί-DjmethyJUbydrazine »NjITpir '.- Trimethylhydraiiin, ^ Η Ν, Ν ', ¹ * Ιϊ Tetramethylhydriizin _N-f ^ Arainopiperidrln If-Aminopyrrolidinj i, -5 ~ diazabicyclo- _(0.5? 5) octane _p. N- (metho :: y) -methylaminp N-.iÄthoxyJmethyläthylamJJif iii ~ (^ f Benzylöi dimethylamine '.Cetrahydroisooxazol ,, N ~ methyl tetrahydro -. 1 ₉ 2-oxazin _p Ji "(Cyelohexyloxyjclimethylamin, li (methoxy) -? cyolohexylamin _F K (ÄthO3 y) * -IF ethyl-ß -ohloroätliylamin. VNC ß-CUER-Iiethyl-H "me bhoxy) propion2 ^r lchlorid _f.

The implementation of the dye, which is a rc active atom or ej ie reactive Cr? ^# ^ Uppe contains the / ixiin ₉ hydrazine or etherified HydroxylaEiin _r λ eclanäßiger manner .in? Jj3 a neutral solvent ausga ^ Jart, for example Chiprobenaol _t ^ ethanol aqueous ethanol or dimethyl "fο rmamidj and z ?? ar preferably at a r increased temperature and possibly in the presence of a catalyst, t wi5 ZoB ₀ sodium iodide.

009829/1878

.D; e preparation by clutch is unt * r using a Vc rMndung the ormejL Ä * CO wherein a 1 'H w A .or the Amier fir GET is _f as a coupling component tt;? .d untex Verwezidung ejnes amine of formula ~.

Il -

BL ..

HH,

ίηϊ

a3s Diazokompor> mte carried outο It is "preferred ;, one
löjaso component of the formula

Alkylene - CO.

(1.5).

zx. use «, ¹ ä) rin Σ _Ρ IU _P ^ g? ^S 7 ¹ ^ ¹¹⁰ - ^A 'äia oaen indicated
⁷ OC- ^ eIi have meanings. As examples of such ver
03 indications should: ι be mentioned:

4- Amino-oC "(H-Ohloro-JSr ^ li _? N = trimethyl ~

inethoxyamino) '- acetophenone _P

4- Ainitto - c ^ - {Nc} iloro-W _l iF _s ] I-trlätlQrl-

ai hO2tyamino) -actitoplienoia

4 ~ Amino = o4 '- (ii' - ciilox'0-'l! T-iüetliyl · = · and -S-yunthoxy-piperidlno) -acetophenone »

4-Am: aio-3 «methyl» o («· (IT-chloro-l _t ET- _s N-friethyl- and -K" K-

diethy3.-H ~ metho>: yam ± no) »acetophenon j, ^

4- Amino ~ 3 »-metho: - ^ ~ <^ ~ (N-ch3.oro ™ H _r N / u-tL '':, äthanol" and -Ν ,, Η-di äthano3.-ITf-äthoxyamino) -acetophenone,

4- * 4fflijiQ-3 "Chloro" - (7 ^ ~ (N »ch; Loro ~ Ii ₈ N-dimet} iylhydraslno) ~ a

pt © non j.

009829/187 8

plenon ^

4- Amno ~ 2-c! IlDxo ~ £ rt. - "CN-oliloro-ίΓ, ΙΙ, ίΤ ¹ - ■ trijaethylhydrasino) -» acetophenon *

4-Amino ~ 2 _f 5-climothyl = oC = -> (H-chloro-Ii - = - aminopiperidino) -aeeto-

4- Amäjao-ß- (IT-cKLoro-iT-methoiHf-piperiaino) ~ propiophencn ₉

3- Amino- CL »- ( IT-o 'iloro ->' i _f ff-dimsthyl — K-ine thox, y amino) -ac e ΐ ο— α ρΙβηοη _Β mid"

4- Amino "c ^" {H-'fe-Omo-K-ethyl-If-benzyl-IJ-nethoxyaniino) - »aceto ~

Tuck Dia.sokoiapi> n.ea.teti can ütircb. an üieh belcaiinto fshren hergeste ^ i-li; ϊ? βΓά.βη _? bsIspielsVsine dadurca .. claJ3 nian acetanilide with t ^; 'Chloroacet, y3chlarid or chloropropionyl chloride T2ffis the resultant product with a tertiary ami2i _r K _? ii ~ disul> sti '& ttierön hyäranin or il-ii-dxs'ab— substituted trerated hydroxylamine reacted and the acetaminogroup liyd :: olyzed ,.

Another EHitsse v <m suitable Biaabkoaponeziten sa tease the formula -

wcrin. ¥ a Ki "ro- _f illkylstilionyl ^ c- which represents an optionally substituted Snlfonaioiclgrappe, W an aweiwertig € S Badifcal. for example -O- or» 3 * -, or a direct bond represents \ t and Y _,? S _fr ß _rr; Rg road S _17, the above reasonable

08 0

003829/1878

^ have level meanings,

Examples of such biazo components: en should .eri-fätar * ·· verden:

-liit: ro-2-ß- (K-chloro ~ N _t li ^ imetliylhydrazino) ethoxyanil 3Ji " ι -Methylstafonyl-2-» ß- = (H - = - t »ensyl) Si-li" Ciim3 thyl-H-methyl - iitilfonato) ethoxyaniline,

.o-4 ^l - (K "ChlorQ-H ₅ N _f I ^ tri ^ ethyllaminoacetyl, - c iphenylfrfcher _Q *»

There are other illasses of suitable biaxo components cieJenigen the formula

Ir - τ, ._ z, -Q— ^tiH 2 ■]

torin the symbols X _p R ^, Rg, IU, Y ₁ unei Z. _{have the above atige- £; flat operating rings ", such as ζ, Β- Φ-β ^ ίΚ ^ ηΙοΓΟ-Β, Ν-cimethyl-N- äthoxyajnino) äthylsi0.fainylmailin and 4- (H-Cal.oro f, H "-dimetliyl-H« l) enjsylaminc) acetyloxyanxlin,

/ are other suitable se ^ iazole components? 2-AminonaphtlialiJa-6-γ5 "(Η, H, K-trine tliyl-lT-methylsulfons toamino} propyleulf qn-

raphthalene _r 4 - "mino-4 '- (U-chloro-iT, f: sN-trimethylaminoaee LyI) ■ ezobenzene and 4- (3' ^ Äinophenyllainincca: 'l2onyl) -F ~ chloro-II-ir ethylisoquinoline.

009829/1878

AZb heterocyclic diazo component !! should be the compounds of the formula

.BL

HH-

(18)

can be detected, in which X, R ^ , Rg, H_, Y. and Z * have the meanings given above and A «denotes an aromatic radical which contains a 5- or 6-membered heterocyclic ring which has 1-3 heteroatoms, of which at least one is nitrogen ₀ Ale Examples of such compounds should be mentioned: 2-AiiLinobenzthiaaol-6- (N-chloro-N _f N, N-trimethylamino-propyl) sitLf onaraid,

2-aminobenzthiaaol-6-carbon- (N-bromo-N, H, N-triethylaminoethyl) amide,

2-Amino-6 ~ ( Ή- methylsulfonate oN, N, Nt i-ime thyl-aminomethyl) ~ benzthiazole,

= 5-. Amino-3- (4 ° »If-'Chloro-NsN ^ lJ-trimethylainino-methyliph.enyl-" 1,2,4-thiadiasol,

2-amino-5- (N-bromo-N, II, N «trimethylaraino) methyl-1,3,4-thiav-. diazo !, and '

2-Amino-5- (4 '-N-chloro-ii, II, N-trimethylaminomethyl) phenyl-1 _t 3,4-thiadiazoI _B

Dia diazotization of the above diazo components can be used, for example Treatment with a mineral acid, in particular and HatriuEanitrite or by treatment with a solution of nitrösylsulfuric acid in concentrated sulfuric acid

009829/1878

■ - 29
executed

The coupling can be carried out in a neutral or Söhwaöh acidic solution, if necessary in the presence of Hatriümaeetat or similar buffers or catalysts, such as s _o B _rt Pyridia *

The production through qyatemization can thereby

Forinel (1), |

* röi "in 2 has the 'meaning given above ' * an X for

CN tmd öass others for a group of the formula "■

t.

" ¹ ^ m - Y. * 2. -" ft ,, - '»β ar- * (19)

> a with a connection of the formula

Examples of combinations of the formula S «■■» X Often, you will get food from starin mineral acids or organic sulfonic acids, for example _{ethyl sulfate 9} diethyl sulfate *. Alkylhariogenide ,, like ζ ₀ Β «KtethylehlOfid * Kethyrbro and Meth | rl« did _t Ar ^ kylhalogenide, like ζ .E ₀ Benaylf solder ^ ön niediaöleiaÄär ^ n Alfeaftsmifenaaurett /, -wri «οϊ * Βρ Hethylest © ?? of ifethän- * Äthaa * · and ButanQulfea * re V && Ister ton Beiizoi ^ tilfönsäuren scfitie their core-

t ^ ftie SoBo die iiethyl ^ Ithyl ~ ELlsulfong ^ öre ρ -ron 2- * ijnd 1 « roa ^ Qhlorofcen ^ olsT ^ fonsgw ^ e uni ifön 3«

C0

Dyes f which contain a group of the 3? onasl (19) ,, = 'can be obtained by adding a compound of the formula (1') v wherein Z has the meaning given above j. one X is H and the other is CK, with the diazonium salt of an amine of the formula

_A Ni - J ₁ - Z ₁ «A - EIH, (20)

R ^ _t Rg, T ^, Z ^ and A ^ the above Matters gen have _t. implements _o A favored pale amines of this formula are üxirah the

^ K- Älkylön GO * Ä _f M ₅ {21}

^a «. ■■■

shown

"ErnSimt should be used as examples of such Ämkie
4-Aniiao-ot-amino-acetoph © noa »l

imd -chloro-öC-arnnno-acetophenon »
fiminopropiophenone and also compounds that give them that
.'Siminoacetyl radical mono * · or dialkjlieri; or else is aralkylated »for example 4

amiiioacetophenone, 4

ainiiio-aoetophijnoni

on, 4-amino-2-chloro'-a ^ 3Sf »methylliydrasi3ioaeetophenön

003629/1878

These diazo components can be obtained by processes known per se, for example by reacting aaetanilide with chloroacetyl chloride or chloropropionyl chloride _t the resulting product with a primary or secondary amin ₁ . Hydrazine or an N-substituted hydrazine or a fused hydroxylamine or an N-substituted hydroxylamine and hydrolysis of the acetylamide group can follow.

Another class of suitable egg co-components are Amines of the formula

(22)

wherein V, W _f Y _1. , R ₁ - and Hg have the meanings given above. Examples of such amines should be mentioned who

4-Witro-2- (ß-H-methylhydraainoätlioxy) aniline _t ^ methanesuli'onyl-Z-iß-benzylaniinoethoxyJaniliii, 4-nitro-2- (ß-tetrahydroisoxazol-N-ylethoxy) aniline, and 4- "nitro-2 - (p-dine thylaminoace tophenöxy) aniline c

Another class of suitable diazo components are the amines of the formula

009829/187 8 bad ORlGlNAS.

'-' ■■ - 32 - ■ '

wherein Z ₁ , Y., R ₅ and Rg have the meanings given above «■ '"■'

Examples of such amines that should be mentioned are x ^/ p-Ainobenzyldiniethylamin, ^ "

p-aminobenzyl ~ iT ~ methyl-hydrazine _t
p ~ ß ~ DimethylaminoäthylsTiLfonyl ~ aniline _r p-ß- (N-ethyl- = W-ethoxyamino) ethyl sulfamyl-aniline, p-amino-ß- (N-methylhydrazino) ethyl benzoate _f '

p-aminophenyl-dimethylamihoacetate, and - ^ ¹ -dimethylaminoacetyl-dipheijyl.

Other suitable bio-components are:

2-amino-6 ~ dimethylaminopropylsulf if-amyl-naphthalene, i-amino-4-äiinetliylaminoacetyl-naphthalene, 4-amino-4-amino ~ ^s -dimethylaminomethylazobenzolr 4 4 ^l -dimethylaminoacetylazobenzol _(t and ß-picolinoyl-m-phenylene aiamin.

The Asailne ' formula are used as heterocyclic diazo components. '■ ■. - -'ϊΏ ^ γ ^

H- Y ₁ - Z ₁ - ~ A ₂ - IiH ₂ (24)

preferred, in which R ^ f Rg »Y« »Z ₁ and A« have the meanings given above. Examples of such amines should be mentioned;

BATH ORIGINAL

00 9829/187 8

2-iüninobenztMazol-6 «(N _t lI-dijnethylaminoprop2rl) sulfonaniid 2 ~ amino-6» ß ~ (dimethylamine) ethoxycarbonylbenzthiazole , 2 ~ affiinobenzthiazol ~ 6 ~ earhon-M,

ä-Amino-ijHmorpholinQmeiihylthiazöl,

5-Δπι1ηο-3 ^β (4 **, ti-dimethylaia ± nomethyl) phenyl ~ 1,2,4-tMadi-

aso2. _a

2 <-Aminö-5 ~ (4 ^f -M ^ H-dimethylafliiiiomethyl) phenyl «»! "J>4-thia"

-t- (4yyp

J »and

The oMgen biazo components can be "for example" treated, treated with oil "Hineral acid, especially HGl _f imd ufatriia imitrite or with a ¥ 03a hit: rosyi8 sulphuric acid in concentrated sulfuric acid, can in acidic or weakly acidic coupling -Rerden » xm & although if necessary in Amresenfeteit voa Katrituoacetat or similar buffers or ^v / iie ZoB» Pyridine »

With alky / l ± er »ng of the azo dyes with & en endings of the formula B« rX can be made out »by heating the reaction participants in örgamaohen solvents»

in EöMentmsseratoffen * Terfle © «, B» Benzene ₉ % lol | in Haiogenated Eoalenwaöserstoffen »like

,, .-. λ ßAD ORIGINAL

ζ. «Β _β Carbon tetrachloride, tetrachloroethane, chlorobenzene and o — dichlorobenaolj in nitro hydrocarbons, like zoBo nitromethane, nitrobenzene and nitro naphthalene; may anhydrides ,, amides and nitrites, such as acetic anhydride, Dlmethylforraamid, acetonitrile and dimethyl sulfoxide "Instead of an inert organisohen solvent to use a large excess of the alkylating agent, but you have to make sure the mixture _p not to overheat because usually an exothermic fieaktion proceeds more ο in some cases, the alkylation of ¹ can be used in the medium or in -wäßrigem be performed G-egenwart an alcohol. to give nachhilft optionally by using a small amount KaliungodHd _o

The novel dyes »the acidic lösliehmaehende groups ent ~ keep to the dyeing mod printing a large number of materials are used, such as _Q B _{o Silk's} wool> Super polyamides Polyhydrbsjysiatarialien with Fä-3erstruIctus? EnV""for example, regenerated cellulose _e as Viskoserayons _s and natural cellulose such as cotton and linen ₃ "Many of the dyes are look for dyeing nitrogen-containing materials * particular wool from an acid bath _a

The new dyestuffs _3, which contain sulfonic acid groups and a group reactive with fibers, are of value in the dyeing and printing of cellulose textile materials, with which they react in the presence of an alkali and, if necessary, by using poor substances »

The new dyes _? free of complex HetaHgri * pp®ß and sulfonic acid groups can be used as _g ßispersionsfarbstoiT®

00982 $ ^: / tft78

. "'55; - ■ ■

: η presence of dispersing agents <r- rwe'nt .; _; -h ; erdeii _r ί "B, sulfitiet '; e cellulose or synthe-; ± sche o" be :: \ f.lat

ective agent or a combination au: '· a AEFE-zmitte.T ■ ind a "Disrergierinittelp l ÜR dieson Zweclr -is eil: ^{l'c:. T} l" · - £ toffpräparat used _t that a üispa: gierml -ircsZ um * contains the dye in a finely divided state; " These.

I arbetoffpräpa: "ate can be borrowed in the usual way.

1an, for example by I1alu.3i. of the dye in g

Presence of dispersant _r and 3; They can be used for the treatment of cellulose acetate and polyethylene etc. by conventional methods, depending on the case, tan at 100 ° C or above or in the form of a carrier such as salicylic acid , which represents I'Loi oi, ₁ 0- or p-hydroxy diphenyl ~, or by a heat-setting gaverfa3rcen _f bsi TejctilstpAi by a dispersion dye as c-get Lotzt is un he then ^f i a short Oc IVemperatur \ 3ϊί 18O 2tO ° G ..the possible vraiso - treated even higher

deep chromium and cobalt compounds , which are free from sulfonic acid and carboxylic acid, can be dispersed in water and wax-acid baths xsxi can be used for dyeing (

tid di-bridges vo-.i animal fibers, wi ^ _o ZCB silk, leather _r υ id lnsbesoadcire V / ol, tmd how r of some synthetic Katelialieiif, .B "Super polyamides and => iperpolyiirethane _r eowie rendet of Polyoropylen ver ^ weröei . For that svrecfc 1? Can they be brought from weakly acidic, neutral or weakly alkaline baths, and in particular from a Kss5% acid bath?

E Le. Dyes which have a quaternary ainr onium gnippe, contain an aniori of a strongest acidic. like z »Bv Sulfuric acid "one of the hardest esters of the same, or"

009829/1878 BAD

1984690

Aiylsulfonsäure- or a chloride ion _or this anion can dt raw. the anior. Another acid can be replaced by the anion iron Piiospho: 'acid or an oiganic acid, "for example formic acid _p lactic acid ocer tartaric acid-, In certain lallen ksrai the free base can be obtained The Salae can be in it Double salts are transferred "" for example with the Ha. '. Ogenides of the elements of the second group of the periodic table ^ in particular zinc chloride or cadmium chloride

The dyes _P which contain a quaterenary km nium group can be used for dyeing or printing real, synthetic fibers. be, iTie z “B. _o furethanen PGL of P <lyvinyl.ch3.orid, polyamides, _f Polyäthylente rephthalaten and in3besoMere polyacrylonitrile and Polyv.ij ylidencyanidfasern ₀ Un; he "rn-PolyacrylnitrilfafK" Ausdr.ick the incident range of polymers * the melxr than 80 ^c / _»f examples as 80-95Ji Acrylnitr.'il-containing, where di 's remaining 5 Ispielsweiee be ims vinyl acetate Vinylpjriidin, Väjiylchlorid _e iylidenchlori Vi (i _t Acrylaäure, asters acrylic acid, or Metbi Efethacrylsäure} ^ rylsäureesteriri Besteher _o This can dyes sinä usually schvjach gege over Electrolyte em3> insensitive and partially show the auegesprochen good LöMlichkeit in l ^r ater. or polarized Lösungemittelno Da.i dyeing can be alisgeführt in an aqueous neutral or weakly acid medium, and afar preferably at Sindepunkt and under atmospheric Dxu3k or at higher temperature and higher pressure.

The invention is explained in more detail by the following examples In the examples, the parts are weighted in terms of

009B29 / 187

■ 3Τ-

IE Ine Iföaimg of 3y83 file 1. _P 3
s lure la ieilen 50 mi + water pH "tone is 6.5 abgofcwhli to O '5 ⁰ G;" üforäuf 1 part -einer Sr-.sponsion-, iaigig WIrA ₉ die dtarek dissolving -stob, 2 ₉ 65 share Ciranm-öblörid eats. 2) Steep acetone xmä addition over so erlis Iteaeii I solution 2Pa ei, nea? Mieoinmg aua Z5 Seilten Bi ^; taid · 2f 'ϊοϋκο. Water ■ e. »Haiten ■ wöx'desii is _o " The .Gemisek is ο-aim iV2 iM-Oiiden at GS ⁰ C geruiirtf xfolaei the pH dtordb. Gegsg rmtlic'ae addition 2: 4 iTatrlOmearbonatlösmig sof 5 * · 6 gsiiaTvl en is,>

Am © liösting of 2 _B 5 ropes MetaBllsir ^ e Jn 50 ropes of water ErJj a pH Ten 6 _f S ^ ilrd darai atsa H'3iif-sionsgemiseii: "bm ma die Iiofnang becomes 1 Steacle l> ei % -35 ^Q G & tv pH held by g '-; legent3.iciie i & ugabe ψοη Za Nat 1) Siang e & £ 6-7

IKe liöBimg is then to 0-5 ⁰ G a, b bgeMSIü Imae 4 'rush S: ULagäud e- (36 ° IV) The acidified Lösnüg wii (i AAIM dxxrdh tropxeKweisen £ asatz a Iiösmig το:!?! Α 1 ieil ^ aöriiasßitril; -ii? Divide VJa ^ aer cliasotiert ₉ bio a scnwäöJaer over finally a 1 nitrous acid consist Meibt ■:

B Le according to the above :: -? Original script, iijivä clemxi zn "own Suapeütsiön τοη S ₈ 5 fisilen eriner ö ;; ng der 3?

(25) O

■ itt)

009829/1878

BATH ORIGINAL

ii 200 parts of water, 4 parts of a 2nd solution eon

raid 100 parts acetone ssagßgßherxc 10 parts Hatriwmt werc.en dem üeadacfc. added., mid dia suspension. is cooled to 10 ⁰ G, the eaisch tii.cd 2 Btinulen "bsi K) ⁰ O and gutm '<5 hours jböi IlaLuiitemperatixr stirred _£ , the Ii () Siing is filtered off _? imd äaa Pil-fcrat is with einar n solution iron Ealiuinaoete.t atisg © saf.s "äo the unusual one

is filtered off, in 500 toil ^ n ethyl alcohol on <gi'Solüäinmt ;, Filtrierö of ethyl alcohol xmd at 40 ° G im Vi lamb dried,

Analysis is being carried out, öass- der S'afbstofa? 0.9 atoms drolyzable ?! Chlorine per molecule

If the! Dye axrC cellulose on ^ eb! 'Eight w.t-rd «da-in er it gives greenish-yellow hues; the "opposite Irieht = · and en corners si

■ Me Tei-'blnd'.mg Ίατ foviae'Än (25 = · ο) wirrt <; riialtea,

Hours ir> ethylene glycol, .- attf his'Scäa-ilapunki; odex heated to 2CO ⁰ O ^ i

■ Eia G-ealscb. from 26.9 ^f feij. an 2-Aiaisioplic3äol ~ 4. _i 6 <»ilisulphonic acid in 20 parts hydrochloric acid (3 ° Tw) in 250 parts. Viassäar is stirred at 0 "5 ⁰ _{G s} ^ sA ss is eäiie löeiing iroB. 6 _? 9 files: Naferiuraöltpit in 50 reile.-Water laisgsfm augsge'oen« The biaao solution is then sti a S ^ Bpenai <η iron 18 * 4 Parts of cyslized 2 "hydroxy" 3-cyano: -4 ^ methyl - 1-ß ~ an? Ijioätmyl-- · pyeia-6 ~ one (prepared as in Example 1) 33i 200 parts water and 50 ropes of pyridine, di © Stirred at 5 ° ΰ

zv given. The mixture is then 5 minutes at. 5- »10 ° C

(70 ° Tv) made alkaline rl'hrt and then by adding 20 m itetrins part lc solution, Hgch a 1 stüneilgeji Rihren "at 5-1C ⁰ C the pH of the _LbVan; r by gradual Zx would 8al of ?. 3äure ( "56 ° Tw) is set to 6 _r O, and the Asofarbstöff is by the addition of 5C0 g / l potassium chloride precipitated * the dye is t abfiltriox and geeattigter with 500 parts Kaliumchloridlösurig ^ ewaßcheji- the precipitate -is Daxin in 300 parts of Waese-r {? Erickt _P filtr: lert _i | Washed with 100 parts of Viasaer and dried ^{toi 6O 0 C}

A solution νου 6 _f i6 parts Kobaltsul.fa; heptahydrati.u ix. 75 parts Viaisser is UTiter a RUokflußfciihler miter stirring and under nitrogen 10 minutes cooked "Sine Lösunf; ve η 4.9 parts of triethylenetetramine in 10 parts. Water is then added "and the vegetables are boiled under nitrogen for a further 10 minutes." The solution then errs when cooled to 40 ° C «. A mixture of 10 _s 6 parts of azo dyes prepared as above with 250 parts of water and 15 parts of 2r sodium carbonate solution is poured and the oil mixture is stirred at 20-3O ° C. for 1 hour. The cobalt formed kcmples i is from £ _r iltriert with 300 parts V / ater washed Urd dried at 60 ° U _o

A solution of 4 _S 6 parts of aniline ~ 2.5 ~ ä: .sülfonsaure in 1CD parts Viassor from pH 6.5 a Suspsiision of 3 parts A Cyanurchloiüd in 20 divider Aoetcn and 100 parts of water at a Q su ⁰ C was added = the GejrAsoh is gerlihi't 3 hours at 5 ° C _p-r wherein the pH durct gi? legentliche Ztigabe 2n HatriumciirbonatlÖBung is maintained at 6-7 »

1984110

This solubility is then added to a suspension of 10.5 parts of the cobalt complexa in 200 parts of water and the mixture is stirred for ^{3 hours at 35-4O 0} C, the. The pH is kept at 7.5-8 "5" by the occasional addition of 2N sodium carbonate solution. The mixture is then stirred and filtered for 16 hours at 20 ° C., and the dye is precipitated from the filtrate by adding 50 g / l potassium acetate. De: dye is filtered off »in 600 parts of ethyl alcohol m slurried and filtered» and the precipitate is dried at 40 ⁰ O, the dried dye is slurried in 300 parts of ethyl alcohol, filtered and dried at 40 ⁰ C. By analyzing Found- "Dafi this product contains 0" 85 atoms of chlorine per mole of dye hydrolyeierbares ._ ^v. _ ^. ■ '■■ * .. ■ _: __''

If the dye is applied to cellulose, then it results in bluish-red shades that are opposite to washing and Light real sindo

Other examples of the invention were carried out "in a similar manner as in Example 2" can be found in the following w Talselle I. The diazo component in column II is coupled with the cyclized 2-Hydw ^ -3-cyario-4HBethyl-t-ß-amino- · ätliylpyrid-6-one »converted into the 1: 1 cobalt complex and finally with trietbylenetetramine and then mi"i; indicated in column III heterocyclic Verbin "· dung umgesetztο the hue * _t is obtained when the dye is applied to cellulose, is given in column IV.

Further examples according to the invention performed in a similar manner can be carried out in Example 1 »are given in Table II

009829/1878

to find. Here, the biamin from column II is first condensed with 1 equivalent of the heterocyclic compound or the aoylating agent from column III, and the condensation product is then diazotized and coupled with the coupling component used in example 1 _β

009829/187 8

00

{Ο

-j 00

II Table I. III 'IV I. Diazo component Heterocyclic compound hue at
game 2 ~ aminophenol-4,6-disulfonic acid Zt 4-dichloro ~ 6- (3 * -sulfophenyl) -
amino-a-triazine bluish-
Red 3 dt © 2,4-diohloro-6- (4'-sulfophenyl-
ΟΤΏλΤΪΟγ ⁸ * f? ** vZ * X € t? a XT dto 4th dto 2,4-Diehloro-6- (2'-methyl-5-
sulfophenylamino) -s-triazine dto 5 dto 2,4-dichloro-6- (2'-oarboxy-4'-
sulfophenylamino) -a ~ triazine dto 6th 2-AndBophenol-4-8ulfonic acid 2,4-Bichloro ~ 6- (2 ^l , 5 * -disulfo-
phenylaraino) -s-triazine dto ^7th dto 2,4-dichloro-6- (3 ' , 5' »disulfo-
pfflinyl ηηι JüTin) -n-tri a «AlJ dto. θ dto 2,4-dichloro-6- (4 '-sulfophenoxj ^ -
s-triaain dto 9 6-chloro-2-
aminophenol-4-sulfonic acid 2,4-Bichloro-6 * - (2 ', 5' -disulf o-
phenylamino) -s-trlazine dtOo 10 2-carboxy ~ 4-sulfo-1-
aminobenzene 2,4-dichloro-6- (3'-sulfpphenyl-
anjinö) -s-triazine orange
Brown 11th 6-Hitro-2-aminophenpl-4-
sulfonic acid 2, 4 ^ dichlbro-6- (2 ', 5 ■ · -rdisulf o-
phenylamino) -s-triazine reddish-
violeti; 12th ■ '': ■ '■■■' ■ ^dt0 . '■ ■ ^: ■ ■ "ζ. ¹ 2,4-dichloro-6- (3 ', 5 ^ disulfo-
phenylajniho) -s-triazine dto

IVJ I

gate * Ig I ■■■,,:, ■ ■■■ "ι ^1;. , '. '. '■ TIl ■. ■ '· / ■■. .- '■■.'. ■ ':'. hue :: ■ ?: ■■ ■■■; .: ■ ■ .. · ■■. ν · ι ο *, ■. "■: ■■ - · ■. ·. ·,. ,,. Aoylation Agents bi-sharkfe- at
game Diazo component 2j4 — l ^ iohloiO — 6 — F— -ffulfoeethytfl «* - 14th 2 ~ aminophenol ^ r6 ^ iaulfanoic acid lino-e-triazine : ■, ■; : _V dto> ..: *, _v CatfblealfÄ * 15th ^: · Dto ■.,, ■; - ■ ■ 2,4-diohloro-6- (3 ^l -ß-sulfatoethyl- ■, ■■ '■■.,.: 16 ,, ■ dto ' ^: ■.' ■ - ^; · Cyaimr chloride ¹ ■ ■ ■ ■ ',' ■ ' 17th ¹ ■■■ ■ ■ · ■ .dto :. ^: ,. ■ ·. ■■ ".. '■ ·: ■ - Sulfonyl pyrimidine ". ^; " dto ^:;: »'" 18th ., ■; ■, ■, ■■ :, dto .. ■■■■; ■ ;. 2,4,5,6-tetrahaloropyrimidine 19th f '\' ■ ' ■ .. ·.' ■ ■ dto - "■ ■ '■■. ■■■ chloride dto 20th dto fl- (4flS-dichloropyridazon-I-yl) -
propionyl chloride dto 21 dto 2,4 1 6-Tr ichloropyriinldiii . dto 22nd dto Acryloylochloride braua 23 dto 2,4-Dichloro ^ w (2 ^l , V -disulföaiiili ^ dto? . ;.; ■ »■: acid , ' ^v : ■. ".' ■ ■■■■■. ''" ^: '"'■'. 25th 2-amino-1-naphthol-4,8-
dlsulfonic acid

Table

... I Π dto III I? at Diandn ■ ■■■ ';'dto'; ^: ' Heterocyclic or hue game ■■ '■■. .dto ■; ■ '■. ■ Acylating compound 26th 1, 3-Phenylendiaiiiiii ^ _r 6-disvil- 2 »4 -]) ichloro-6-metho3cy-s-tria2ine greenish fonsätare dto J, ■ ', ■' ^ "■■ yellow I- ■ ■
27 Cyantrehlorid dto 28 dt © Acryloyl chloride dto 29 4 »5-dichloro-6-methyl-2-methylsul- dto dto fonylpyrimidine 30th 2 5-Bt cWO ^ OnM ΤΪΟ * »Τ 1 n-fi-.r» n? * Hpr »y1„ dto dte chloride 31 ß- (415-dichloopyridezon-i-yl) - dto dto propionyl chloride 32 2,4,6-trlehloropyrimidi R. dte 33 2,4,5 $ 6 ~ Tetraebloropyriinid ± n dto 34 2, 4 * -Diohlorö-6- (p-pulf oanilino) - ¹ · - s-triassin. dto 35 2,4 * Diohloro-6- (5 * -0wlf o * -2 · -methyl- dto

■ labile 1

ο ο co

I. II III IV I at
game Biamin , Heterocyclic or
AcylationB compound hue 36
37
- ■ 38th ■
39 ·. ' 1,5-phenylenedianiine <«4,6-
disulfonic acid
dto
¹
, '; ■. · '. 'dto'"■'■■■.
1 »4« Phenylenediamia ~ 2, .5-
disulfonic acid 2,4-dichloro-6- (3 ', 5'-disulfoanili-
no) -s-triazine ■
4,4 '-Bis- (2 " _f 4"-' dichloro-s «triazine-
6 "-ylajainLO) -aiphenylurea f-2 ₉ 2 '-
disulfonic acidi
4 ^ 4 '* bis- (2 ", 4" -dichloro-s-triazine-
6 "-ylamino-diphenoxyethane-2 _f 2'- ■
disulfonic acid
Cyanogen chloride
chloride. '"■.. _t .
■ Rill ^ 1 T> ^ft ) - R ^ triazine. greenish
yellow
dto
dto
reddish
yellow
dto
dto

dto

2,4-Diciaöro-6- (3 ¹ , 5 '-disulfo aiailino) ^ tii

Example 44

A solution of 18.5 parts of the monoazo dyes .hergestellten in Example I au is in a mixture 3500 parts of water and ι, stirred in 8 parts of trimethylamine for 30 mewed "The pH of the solution is then adjusted to 7» Q with 2N hydrochloric acid, followed the dye is precipitated with sodium chloride .. The quaternized dye is filtered off and dried ", When applied to cellulose materials, it gives greenish-yellow tones that give a? have good fastness to washing and light ,, '

Beis Tiel 45

25 parts of the dye prepared in Example 2 are stirred into a mixture of 200 parts of water and 2.5 parts of byyridine. A solution of 3.5 parts of sodium sulfite in 50 parts of water is then added, and the mixture is then added hey 60 0 stirred ρ until the sulfation is over LSt ₁ , which can be determined by an increase in the chloride ion _{content in the solution o} The solution is counted to 20 ⁰ O, and the sullfiti €; rte dye is precipitated by the addition of K? 2iuxnacetat ο The dye is filtered off, washed well with ethyl alcohol and dried.

If he is consumed on ZeHulosematerials, he surrenders bluish-red shades that are real compared to wascien and light

Beisidel 46 ^.

A suspension of 11.5 parts of j-amiilo- ^ aulfoacetanilide in? 300 parts of water and 20 parts! Hydrochloric acid (36 ° Tw) with 0 »Ö · 5 ° is dissolved ater allmäM.iche by adding 3" 45 parts of sodium nitrate., The ^f in 25 parts of V, Diazo yaws "

009829/1878

The diazonium chloride formed in this way then becomes:? Suspension vim% 6 parts cyeliaiert on 2-hydroxy-3-cyano-4-meih5rl-1-ß-aminoäthjlpyrid-6-one in 300 1 rush of water, 150 parts Aoetonund 20 SeilenNatriumcarbonat added ^ Bas Genisoh 20 Stundenbeil5 ⁰ O -gerfSbrt «; Padded: .and / getrook ^ net. The monoaso dye obtained is ground down until it passes through a sieve with a size of O _f 25 mm, and boiled with 1000 parts of hydrochloric acid under a liquid cooler with 1000 parts of hydrochloric acid for A hours. Bas mixture is then abgelrtihlt to 2O ⁰ and G ^ ausgesalsstj with 100 parts of sodium chloride, you mnd ^ ausgeiallene AmihOäzoiarbßtoff% rird abfütriert and ge trocloaet-. . '. "..;. · ■; ■ - ■■. :: ■ - .. '' ;: ■ -. '■ -._. ■

Bine Misohtmg from 10 * Q parts 2,4-iöhloro-6- (2,5 ^l -disulfoanil5jao) -5-tria2sin and 9 '. "» 35 parts of the above aminoazo color- • töffsvird in 500 parts water at 35- ⁰ 40 G for 4 hours, "wherein the pH is maintained by occasional addition of 2N Natriumoarbonatlösung to 6-7 _o the solution then filtered vird" 20 ⁰ O abgekühlt. and the Farbetoff is polished by. Zxigabe of Ealixunohlorid and dried .

Further examples according to the invention, in which after the in
The procedure described in Example 46 is carried out _f are given in Table 3 "Uas Aminder column II" is coupled with cyolisierl; em 2-hydroxy-3-oyano-4 * methyl-1-β-aminoethylpyrid-6-one, . "- the! product is then hydrolyzed with the corresponding alkanoazo compound" which then -not with the heterocyclic see, or the aoyl compound from column III is condensed. If cyanuric chloride is used "then the product is reacted with one equivalent of a" compound which is also in ■ Column III is used ^

009829/1878

■. ■■ V 'V' ^: '' .V. "'"XX'. .., V '.: / ..;. ■., ■ "in. . ■ ■, .. ,, ■■ VI ^ eteyocyclisohes- or aoyl- Color OE 4-Aminoaoetanilid-2 »5-disul £ on- (1) Cyanurohiorid (2) BTatriuiBsals reddish- acid # '■.' ■: '■: ■ ■' ■. ■. ■; ^·:.: ■ ;, by Hereapto- yellow benzthiazole '. · ■■' ■ '■: ■'. '.'. ■■■ '■■ dt ©. V .'V. ■■. (1) dto (2) Natritmdi ^ dto . ■. '■ ■ ■. ■ '. . "' ethyl dithior. oarbamate 5 ^ ßA ^ O3.CG iÄG ^ AXicL "· ^» O ^^ CtiStllfOÄ · * (V) dto (2) dto greenish ■ ', acid. ^! ,. ₍ ■. '«:., ■.'.;" ■ '■';' ■ ■ .. ', ■. ■ <■■■' ■. . ■, yellow ' ■■■; '■■■■■ ■■ ":'"'■:& * ·' ■■: ■ ■■ " ^: . '_;' (1) Ditto (2) Katritus salt by Heroapto- • benzthiassol dto ^: . ■. '. '' dto. ■ '^{; :} ■■ 2,4-J> ichloro-6- (4 '-ß-stilfatoethyl- ι. , ', ■'',''^; snlf opyi at) il, jf.no/R—triazln dto ■, ', ■.,
4-Aininoacetaiii3, id-3 ~ suLfon- reddish
yellow 3-amino aoetanilide-4,6-disulfone 2,2,3,5-tetrafluorocyclobutane greenish . eäiare '·· ;,. ·. ■■ ■ ■ '. ■■ ■ ^l · ', ^; : ' carbonyl chloride yellow ■ ■ ',' '. ■. ■ 2 * 5 * 3-2! RifluorocyclöbiLt -. 1 -en-
carbonylchloria. dto ■ '". ■." V ■,.' äto "■ ',.' . ■ ■: a- (2 _t 2,3,3-iettafluoroöyclobutyl) «· dto aoryloyl chloride ¹ '', '■■■■■ ** »; ■ ■. .: ':. ■' · ^: ß- ( 2.3 t 5-trifluorocyclobut «· 1» enyl) - dto acryloyl chloride I. At-
game 47 48 49 50 51 52 54 55 $ 6 57 ^r

Example 58

A solution of 6 _ß 27 parts of ß- (4Mtfnino with ^^^ äthyl; 3yridiniuBichlorid in a mixture of 75 parts of water and 10 parts of 10N hydrochloric acid is diazobized at a temperature of less than 10 ⁰ C by adding 10 parts of 2n ^ atriuEHaitritelösung

The resulting solution is then rapidly converted into a stirred solution of 3.68 parts of cyclized 2-hydroxy-3-Cjanor4 ~ iethyl- * 1 ~ ß »amine ethylpyrid ~ 6 ** oix ~ 20 parts of pyridine and 60 parts of water introduced at 5 ³ C ο 14 parts of © i0n JJatriunihj droxydlösung are then added, and the equipment is geriliirto 5 Miaiteno 15 parts of 10η ΗΪ1 are then added, whereupon the addition of. Zinc, chloride solution for the precipitation of the dye ε and 40 parts of HatriJünchlorid,

The filling is filtered, washed with 200 parts The above 1 brine and dried _ö The Eexbstoff Polyacirylaitrilmaterialien colors. from acidic and neutral color baths in reddish-yellow shades "

The following table describes the color shades of a number of "further dyes according to the invention" which are obtained in a manner similar to that obtained in Example 58, but with the diazocomponent replaced by the A-mn _{given in column XI ^ o}

example AmIn hue 59 , .Λ. ,,. “. .vT h _% * " ^Γ - '- -, V"' .ϊ - * J 'τ "- -« - V ^ r ^^ i ^ i ^ W / WWW OVj ^ ** OAiOU J. w U-JuXWxI-- yellow 60 (4-aminophenylaminocarbonyl) methylpyridine ± tunofcloride orange . 61 Ύ * - (4-aminophenylsulfonylamino) propyltrimethy! Ammonium «· reddish chloride yellow 62 1- (3'-Affiinpbenzyi) pyTidinium chloride dto 63 3-aminphenyl-trimethylaiiunoniuia-öhloria dto 64 3- (4'-Aminobenzoylamino) phenyltrimethylammonium chloride dto 65 3- (4'-Amino-2 ^! -Methylphenylaso Jphenyl-trimethylaaimoniuni.
chloride orange 66 4 ~ AjBino-c ( ₍ (N-chloro-li, Ji-dimethylhydraziao) acetophenone reddish- geUa 6? 4-amino- (S-chloro-S, S-diethy! Mercapto) aoetanilide dto * 68 (4 * -Aminophenoxyäthyl) dimethyl-methoxy-ammonituQ-chloride dto 69 N- (4-Aiainöben3oyloxyäthyl) pyridinium chloride dto 70 ^ -Aminophenacyl ^ isothiouroniuni-chiorid dto

"Tl f" ~ ι

Example 71

A suspension of 2.8 files o-Nitranilift in 5 parts of 36 # hydrochloric acid and 15 parts of water is carried out at 0- ^ ⁰ C. gradually before adding 10 parts; -i4 & ger Natritimnitritiesuiig ^ diaesotieirto

The diazo solution then slowly becomes 2u of a stirred solution of 3.8 parts of cyclieiitem 2-Hydro ^ ~ j «cya ^ ιω1ηο ^ & γΙίϊ ^ ί4-6-όη (Εβϊ? ^ 9ΐβ3 ^

Share tasser _# 25 ieileii lyridiii toad 5 parts of 40 # sodium hydroxide solution at a temperature between 0 and 5 ° C. After stirring for 1 hour, the precipitated dye is collected by filtration, washed with water-tmd dried <> -

III the following table eißd further examples of erfindungsgeaÄßen Dispersionafaxbatoffen indicated, obtained by i ■ - a & k lagät the ill the ssweiten column of the table is-amines diaeotiert to output the resulting Diasoverbiniit oyolisierteiBi 2 * ÖyÄro3cy-'5-oyano-4-methyl-1 -fl-apainoättylpyrid - 6-one coupling. In the fourth column, the shade of the coloration obtained is given. I.

009 8 29/1878

example . Diazo component Parbtoa 72 44 * em ^ -2-nitroimilin , .... '■ -; ■ orange 73 4-chloroaniline reddish- 74 4-aniside. '■ -. ·. orange 75 1-naphthylamine orange 76 Ethyl 4-aminobenzoate reddish-: yellow 77 ß-Ethoxyethyl 4-aminobeazoate dto 78 p-Ajoinobenzoi-aulf ohamid dto 79 p-AndLno-benzöl-Btdfon-H-ethylamide dtp 80 3-aminopb.enyl * .K _f N-dimethylstilfainate dto 81 N- (p-aminophonyl) ph-fchpH fn1 d Red 82 p-aminoacetanilide Red' 83 N,! I-Diethyl-p-phenyleneaianiine vlolettj 84 ride '.. 85 4-Amino-4 '-nteti ^ rlazobenzene Red 86 rubln

009 829/187

1984690

example 86

A solution of 3 »5 parts of 5-benzoylaminoaniline-2-suifonaätrre in 10 parts of 2N sodium carbonate solution and 100 parts of tfasser is' acidified with 6 parts of 36 # hydrochloric acid, to 0-5 ° 0, cooled and by adding a solution of 0.7 parts of sodium nitride in 5 parts of water diazotized to the Pia3osu3pension is then eyclized to a stirred solution of 1 »75 parts 2-Hyäroxy ~ 3-cyano-4-methyl "t-ß" aiöiro (manufactured

as in Example 1) in 100 parts of water and 40 parts of pyridine at 0-5 ° 0. "The pH of the suspension is raised to A ₈ O by adding 8 parts of 2N sodium hydroxide solution." After stirring for 1 hour, the solution becomes the same Adjusted to 6.0 by adding hydrochloric acid. 20 parts of sodium chloride are added and the precipitated dye is filled, washed with Seiger saline solution and dried

The dye dyes bulked nylon fabric from a neutral bathroom in greenish-yellow colors with a good one Fastness to wet treatments;

The following table gives further examples of dyes according to the invention which are obtained by _: dai3 ffiah the diaspcomponents given in the second column with the cyclized 2-hydro ^ -3-cyano-4 "methyl-i ^ ß- 'amino · -. - .. äthylgyrid-öiron kuppelt, In "the third column ,, the color tones are given, which are obtained * when the dyes are applied to in» ■:

009821/1876

example Diazo component hue 87
88
89
90
9t
92
95
94
95 Aniline-5-sulfonanilide-2-sulfonic acid
Aniline-S-sulfone-N-ethylanilide ^ -sulfone-
acid
5-acetylaminoaniline-2-sulfonic acid
4-benzoylaminoaniline-2-sulfonic acid
2,5'-dichloroaniline-4-sulfonic acid
4-aminoazo-benzene-4'-sulfonic acid
2-methyl-5-methO3y-4-aminoazobensol-
3'-SuIfOnSaUTe
1-amino ^ -phenylazomphthalin ^ '-sul
hair dryer greenish
yellow
dto
dto
yellow
reddish-
yellow
orange
Red
ruby
greenish
yellow

Example 96

100 parts Viskoserayongarn be in a solution of 1! Eil bsi of the dyestuff of Example 1 in 500 parts of water 50 ⁰ C ο introduced After 10 Minutsn 25 ropes of sodium chloride are added over a period of 20 minutes, and then 7.5 parts of sodium carbonate ( anhydrous) added. After a further 10 minutes, the dyebath is heated to 85 ° 0 and held at this temperature for 60 minutes. The yarn is then removed, rinsed in water, washed for 15 minutes in a boiling 0.3 # detergent, rinsed again and dried

A greenish-yellow color is obtained.

Example 97

A printing paste is produced, which removes the following

009829/1878

5 parts Jmßifäa ^ ipitfB of Example 2 jö parts itoBifoflt ■ - 35 parts 4 # iger iMriy ^^^ töiiidiöke

1 part sodium nitrobenzenesulfonate 1.1.5 parts 49.5 parts 100 parts

The paste is printed by an orphan onto a merged cotton fabric, and the fabric is dried, steamed for 10 minutes at 10 ° -102 °, then for 15 minutes Washed in a boiling detergent solution above, rinsed in Waaear and dried. Be becomes a reddish-blue print obtain"

Example ^ 8

50 parts of polyacrylonitrile are introduced into a solution of 1 part of the dye vtm Example 58 in 1500 parts of water "which acid 0.8% & Basige and contains 1 ^ Hatriumaoetat, BO that a calibrated pH 4.5 yöo results. The bath will take 1 hour

heated, the Qarn wii ^ i denonanen, rinsed and dried. ^^^ Uob ^ gell ^ farH geffirW; and confirmed a preliminary authenticity to washing and light *

example <i9

100 parts of a woven aromatic polyester textile material are immersed in a Förbebed * which contains a dispersion of 2 parts of the dye from Example 71 in 3000 parts of water containing 2 parts of oleyl sodium sulfate. Bas Farbebad is then heated under überatmosphSriechem bridge wShrend 30 minutes 130 ⁰ C and held for another hour at the temperature, DaB dyed textile material is then

009829/1878

taken from the PSrbebad, in water gtspü.l ^ _# 11 read to. _; 'Contains a väßrige solution containing 5O ⁰ C, the $ 0.2 ITatr.ttJöihydroxjrdi oyajS Nöttriianhydroßtilfit υπώ 0,19ε Cetyltrimethylai moniumbroraid immersed _β The textile material is precipitated with water. rinsed, then immersed for 15 minutes in a warm terdiiniite aqueous solution of a synthetic detergent, rinsed again in water and finally dried

Ok The aromatic polyester textile material is dyed in a reddish yellow shade, which has excellent fastness to light, to wet treatments and to "dry färme treatment".

Example 100 .

2 parts of the dyestuff of Example 86 are dissolved in 5000 parts of water, and 100 parts of soaked wool in the Färbetiad, -Which a - =% mperature having from 4O-5Q ^Q Q introduced ο 3 parts Amnioniumacetat are added and the bath is heated to the boil for T hour _o The wool is rinsed in cold water and dried. It is colored in a greenish-yellow shade with excellent fastness to washing and light

009829/1878

Claims (1)

wherein one X v for CN and the other for H or one by one Azo group-bound aromatic radical and Z represents a Chain of atoms that forms a 5- or 6-membered ring, standsο ·. 2o connection according to claim 1, characterized ge k e η η ζ calibrated, that one X for GlT and the other for a group of formula D - N _Ä N-. stands where D is an aromatic radical> which contains at least one SO ~ H group * Jo connection according to claim 2, characterized in that D contains _{a cellulose-reactive group a} 4 ρ compound according to claim 3 »characterized in that the cellulose-reactive group is a mono- or dihalo-s-triazinylamino, pyrimifiylamino or Sulphatoethylsulphone group is " 009829/1878 196A690 5. A compound according to any one of claims 2 to 4, characterized in that it contains a metal atom, in particular Cu, Co, Cr or Ni, in a complex bonded to a metallizable group in D ^; namely in the ortho position "to the azo group and to the hydroxyl group or to the N atom of the cyclized pyridone nucleus. 6 ο connection according to one of claims 2 or 3, characterized characterized as being a chromium or cobalt atom complex to one mole of a compound according to any one of claims 2, 3 or 4 and to one mole of a second ligand bound contains " 7 ο connection according to spoke 6, thereby g e k e η η ae i c h net that the second ligand is a multi-dentate color clearer Is a ligand containing a group reactive with fibers, 8 ο connection according to claim 7, thereby g e k e η η ζ ei c h net that they have the formula CH, - CHo NH T (7) 00 9 829/18? * ISB4690 GH ₂ OH ₂ ΪΙΗΐ (θ) CU. "Uf shows, MOTiXi X fttr O or COu eteth, T stands for a group reactive with fibers and Ä stands for a benzene or naphthalene kera which contains at least one sulphonic acid group / if T does not contain such a group" and the further by a nitro. Chlorine or a group reactive with fibers lert no can. 9, compound according to claim 8, characterized in that T stands for e | ^ e MoÄOohlöro-e-triaBiJoylgruppe, in which the third carbon atom of the JCriaainkems carries a sulfonated phenoxy or sulfonated anilino radical, in Wloheitt der Beneol nucleus can optionally be further substituted ββΐη. . ^: " * _- ^: ~" ~. _: . _: '_'- . ", '■ - _: 1O ₉ Compound NaOH claim 1, characterized geke η η ζ e ic h -η et: that one X is CN and the other ^ε represents a group of formula D is -4IeN- 'wherein D' is an aromatic radical homooyclisohes or heterocyolisohes »That is free from water-soluble groups. 009829/1878 196 λ If _n compound according to claim 10, characterized in that -D ^{1 contains} a heterocyclic five-membered ring _f . which contains two or three heteroatoms. 12o compound according to claim 10, characterized in that D 'is a radical of the formula -a. means in which a for H or a halogen atom, an alkyl, Alkoxy, nitro, cyano, alkoxy, carbonyl or. Alkylsulfonyl group stands, b represents H or a halogen atom, an alkyl, cyano or trifluoromethyl group and c stands for a nitro *, cyano, Alkoxy-aHSarbonyl or alkylsulfonyl group « 13 ο compound according to claim 10, characterized geke η η - is characterized in that it contains a Co or Cr atom complexed to D 9, the bond being via a -0- or a ~ CQ ₂ group, which is in ortho-position cure azo group is located. 14 ο connection r-aeh claim 1, characterized in that one X for CN and the other for one 2 2 G group of the formula D - N »N -, in which D is a radical the benzene or naphthalene series or a. at most bicyelic is a heterocyclic radical which is a quaternized Amino, hydrozino or etherified hydroxylarain group contains = BATH 0 09 829/1878 15 »Connection according to claim 14? thereby g e k e η η - ρ
records that D-KsI- is a group of the formula X " ET (12) represents ₉ wherein A ^ stands for a benzene nucleus, 2 stands for a direct bond or a link ", - as z _o 'B _o for ~ O ~, -HR ¹ - _f -CO-, -KR ¹ CO-, or ^{-NR 1} SO ₂ - (where R is H or a lower alkyl group) * Y, "stands for a carbon chain of at most 6 carbon atoms, which is optionally interrupted by a _{hetero atom and which can be bonded to R c} and / or Rg, ao that a cyclic system is formed, R ₁ -. and Rg stand for H or an alkyl ~ _s ~ aralkjrl- or cycloalkyl radical, R ^ for H _v an alkyl, aralkyl «=, cycloalkyl · ^ or amino group and where Ιί, -ίΙκ » ^ß g uncL Rrj can optionally form one or more rings, and X stands for an anion« 16. A compound according to claim 15, characterized in that g e k a η η draws represents " > that B is a group of the formula R ^ R ₆ »u ^ alkylene - CO A ₁ .- ■""■ o7 17 "Process for the preparation of new compounds. Which are useful as coupling components, thereby geke η η 2.ei without t that one is a compound of the formula 009829/1878 Z-HH ₂ - where Z for a Badikal with a chain iron 2 Ms 3 atoms between the nitrogen atoms is at oil temperature heated, during which water is developed and a cyclization takes place «, 18, A method, characterized for the preparation of azo dyes ^ _ge-s indicates that the erbinätmg öiazoniumsals an aromatic Aiains with a ¥ of formula GH ^J X ■ ι HO - C "Cc" ^ \ O ■ - C- \ (D wherein 4-one X is H and the other is CN, couples. 19 "A method according to claim 18 * characterized ge ke η η ζ e h ic net j, dal3 the product further a metallizing obtained by coupling tsnterworfen« nd / or i: o. a dye reactive with fibers is converted " BAD ORIGINAL Ö09829 / 187a 20 _{o The} method according to claim 19 r characterized in that a uyanuric halide, in particular cyanuric chloride, with an aminoazo compound of the formula NH ₂ -AH = N - J! i HO \ "/ ^" NH ₀ -A- H = N- C where A is an iladical of the benzene or naphthalene series, which contains at least one sulfonic acid group ^ converts <, Method according to Claim 20, characterized in that g e k β η η draws that the Cyanurolilorid, before or after the Reaction with the aminoaso compound, also with ammonia, an alcohol or a phenol, a mercaptan and especially with a primary or secondary compound is reacted » 22 ο Method according to claim 18, characterized in that a compound which contains a pyrimidii group reactive with fibers _t with an aminoazo compound of the formula 00 9 829/1878 A-N = N- I! I. HO ι CH- I ³ A-N = N-Q C O « 1 1 is implemented, 25o The method according to claim 18, characterized in that g e k e η η - ■ ζ ei c h η e t that the aromatic amine. at least one water-solubilizing group contains " 24- The method according to claim 23 »thereby g e k en η ζ e i η e t that the water-solubilizing group is one SO _V H group is _c 25 ο Method according to Claim 24 »characterized in that the aromatic amine also contains a group reactive with fibers _{0 s} 26 ... Method according to claim 25, characterized in that g e k e η η ζ e i c h η e t ρ that the reactive group with Pasern a 00 9829/1878 Chlor © «= or Br ^ mo ^ s-trlazlnyl ^ j, chloro- or a chloro »or bromoproplonylf? ^ a chloro odei» bromo » acryloyl «g a Fluoroeyelobutanecarbonyl-j" a chlorine © = » <öhinoxal.lncarbc "iyi ~ or a methanaulfonylpyrimidyl group 1st ο ".'..- ■ ■ 27 © method according to claim 2j5 _s characterized by the fact that the 'water-solubilizing group "^, a quaternler "o amino", hydrazine © "or etherified Λ HydroxylamlnocrΛρρβ 1st _o 28 _o method η I claim 18 _S thereby geke η η · = κ s 1 ch η et “. that the aromatlscho amine lst free of water solubilizing group 5n _e. 29 ο method _{according to claim 2B 9} thereby ge Ie e η η = ·· sa 1 ch η et ₉ that the aromatic amin belongs to the benzolodene assobenzene or is a mono- or dicycllseries hefcerocy.c llsches aromatic ΐχιίη _o 3oo method n-i-l8 claim _s characterized ke re π η = _"s records that the roduct l'obtained by Behänd-" lu.n £ - with a ^ uatei'nlsierunnsinltte :. is received * 31 ο method n.tch one of claims 18 or $ 30, characterized ä E ke η η% e 1 ch η Qt ₃ that an aromatic Am .n we used as a diazo component and _a wel'.ehos a quaternl "sl-srbare Ακι1η- - ₈ Hydraslno- or vev & i forth te hydroxy lawin "gr'appe enthüit ₈ and the Azofar obtained by working bstoff ^j 'ha: ndlunR with el-IEM (§ & iatern.lslorüng.sini.tte-l quafcernisiert 009829/1878 32 Verwentfurig s liier VerLinduap after -iiter.'t de * ⁷ -ineprilche 2 '- Äs ίβ sun: PIi: ben oder Bedru3lcsn von ^ sxtilir-ateri · - al; .en .. 33 c Usage ¹ '. e drive according to claim 52 _s thereby r, e ~ kc η η ζ e 1 ο: · η et ₉ that! full- ₃ silk- ο 3er polyamide · fibers under ¥ er -iendunp a connection according to one of the claims 2 OIs 1 or 13 can be colored, - by s : iö In a corpse sau "& η ₅ neutral or schi-meh alkaline bath heated ί; is in _o 3 ^i! o Vervrendusiprsv irfahrep according to claim 3'- _a thereby -ge <knew: lc ί η e c «that CslIuloLetuxtllmaterlalien with a connection naeii one of the Ar sp."tlöhe; 5 to 5 or T to 9 in C &ge> iart? on Alkali and riotip, if necessary, under heating pressure: or be gafgr & t, 35 ο Use: ds r connections' after eiii. », - ra. of claims 10 to 12 st an · PI?;: hen or Fiedriiriksn ve η ₅ ynthetl3 «bea fibers ₉ in particular gellyiosis acetate« or polyester fibers, 3β _ο Ve-rv; end «.ng of the connections according to one-in dar * claims: i ^j5 i Hs l6 to Bec'-ruckea or P! ^; rben von Eynthetinchen Fad5-e PoXyaci ylnitrS.! included Compound ηε 2h claim I ₀ thereby ;; eke η η Ic h η · ■! t _z that they have the formula 00 9 8 29/1878 _n NH t ■ I CH ₂ -CH 67 196A690 Cli has ₉ where an X for H and the ζηά: νβ for CH Btciifc, 38 Connection: according to claim 2 * in that ρ eke π η a -ϊ i ch η et _a that it has the formula CII ^. CIu '■ * iS CH CIi. has- «, v / orln.sin-X for CIl and the inner for 3 Group of the form 1 ί ■ = .π Cl bo-, r r PAIENTANWXITE WU-INQ-H-FINCKJ ₁ DIFl-ING-H-BOH * DIPLINGSSTAEeEiI 009829/1878 _0B , _G1 NAt-