CA1063600A - Fibre-reactive dyes, their manufacture and use - Google Patents

Abstract

Abstract of the Disclosure Fibre-reactive dyes of the formula

Description

~ -`
~OG36610 The present inventi~n provides fibre-reactive dyes of the formula Al 7 1 11 1 B ~ 2 (1) ~

~ F
.
wherein Al is the radical of a chromophore which contains sulpho groups, A2 is hydrogen or an organic radical, B is an-alkylene or arylene radical and each of ~lj R2, R3 and R~
independently is hydrogen or alkyl.
The radical of a chromophoré Al can be the radical of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series. The organic radical A2 can be a radical that does not impart colour or also the radical of a . .
chromophore. ~ .-:
. ~ Possible radicals A2 that do not impart col.our are, for example, besides hydrogen: alkyl groups, such as methyl, : ethyl, propyl, isopropyl, butyl, methoxyethyl, methoxypropyl, `
:~ ethoxyethyl,.cyanoethyl, hydroxyethyl, cyclohexyl, methyl-. ;
:~ ~ cyclohexyl; aryl groups, such as phenyl, which is unsubstituted .~ .
~i or s~bstituted by alkyl groups, for examp:le methyl,ethyl, : -~ : . propyl, isopropyl, butyl, alkoxy groups, for example, methoxy, - ethoxy, isopropoxy? ~ethoxyethoxy, isopropoxypropoxy, acyl :
groups, or example acetyl, acetylamino or benzoylamino, the ~:.
~ureido, Garboy~y and sulpho group, and by halogen atoms~ for. ~ . ~

" ~
36~ -example chlorine or bromine; naphthyl, sulphonaphthyl;
heterocyclic radicals, such as pyridyl, benæthiazolyl, oxazolyl, thiazolyl, quinolyl. In addition, A2 can also be part of a he~erocyclic radical through A2 and R~ in formula (1) being closed to form a ring, so that this is attached direct to the s-triazine radical through the nitrogen atom to which A2 and A4 are attached. Examp].es of such heterocyclic radicals are piperidyl and morpholyl. Above all, A2 is a the radical of a chromophore. Like Al, this can be the radical of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series. In addition, A2 and Al are preferably the same radicals.
The alkylene or arylene radical B is derived from an aliphatic or aroma~ic diarnine. Thus B can be a long~chain (for example containing 10 or more carbon atoms) or short-chain, a straight-chain or branched alkylene radical. A
suitable alkylene radical is in particular one o~ 1 to 6 - ~ . , ~ ,, . :
~ carbon atomsj for example ethylene, propylene, butylene, ~-:
~hexylene or cyclohexylene. Preferably B is an aromatic radical, for example a naphthylene radical, the radical of a diphenyl or stilbene, or in particular .
a phenylene radical. This radical can contain ~ ~
~urther substituents, for example halogen atoms, low molecular -alkyl and alkoxy groups, carboxy and sulpho groups. Where B is an alkylene radical, R2 and R3 also form a closed ~ 3 - ~ ;

636~0 aliphatic chain, so that the bridge member.

. -N B-N-

2 3 is a heterocyclic ring containing two ring nitrogen atoms, for example 1,4-p;perazinylene, Preerably ~ a phenylene radical. . . .
~esides hydrogen, Rl, R~ R3 and R4 can also be ~l~yl radicals of 1 to .6 carbon atoms, for example methyl, ethyl,.propyl, isopropyl, butyl or cy~loheYyl. Preferably ;.
Rl, R2, R3 and R~ are hydrogen atoms. . . :~
Preferred fibre-reactive dyes are those of the formula (l) in which A2 is the radical of a chromophore, .
and Al,B, Rl, R2, R3 and ~4 are as defined in formula (1). - - ~
Particularly preferred fibre-reactive dyes ara I .:
. ,: .
those of the.formula ~1) wherein Al and A2 are the same . . -.
.chromophore:of the anthraquinone, azo, phthalocyanine or :nitroaryl series, B is a phenylene radical and each of Rl, R~, R3 and R4 is a hydrogen atom.
: A preferred.embodiment o~ the fib.re-reactive . .dyes o~ the formula (1), wherein A2 is a colourless organic : -.~ radical, are those of the formula (2): . .

Al--NH_~i'N`ICl - ~H--13 ?IE~ Ni14~9 (2), ~C,N ~N~C'N X
1- 'I
-~
.

: . _ 4 _ . :.. . ~

636i~0 ~ ~ .
wherein Al and B are as deflned in fo,:mula (1)~ X is hydrogen, alkyl, alkoxy, carbo~y or sulpho, and the ben~ene ring ~ can .
contain further subs~ituents, in par~icular a furtiler sul~ onic acid group The presence of t~o remov2ble fluorine a~oms a~
.1 .
both s-tria~ine rings of the dyes of formula (1) means tha~
these dyes are fibre-(bi) reactive.
By fibre-reactive co~lpounds are meant those compounds ~hich are able to react ~ith the hydro~l groups o~ cellulose or with the amino groups of natural or synth~tic polyamides to form covalent chemical bonds.
The fibre-reactive dyes of the formula (1) are obtained by reactin4 a dye of the formula Al- I H
1~1 - a compound of the formula Hl A2 (4) ~ . . -an alkylenediamine or arylenediamine of the formula ~
, ' : ~-. .~::
` ~ :HN B NH (5) R
; ~ 2 3 and trifluoro-s-triazine of the formula -:
:, .
:
. - , - .
~ S ~ ` . :.

;36(~0 ~`
'' "N I F
N~,N (6) ~. . .

' . ... ' "
with each other in such a way that a fibre-reactive dye of the formula (1) is formed, it being possible to choose the ::
sequence of the partial reactions freely, taking into account the starting compounds to be reacted, and Al, A2, B, Rl, R2, R3 and R~ in the formulae (3), (4~ and (5) being as defined . .
in formula (1). ~.
As starting materials it is preferable to use compounds of the formula (4), wherein A2 is the radical of a chromophore and R4 is hydrogen or alkyl, and furthermore compounds of the formulae (3) and (5), wherein Al, Rl, B, R2 and R3 are as defined in formula (1). : ~.. : .
.
The preferred fibre~reactive dyes of ~he form~lla (l)`,~
: ~wherein Al and A2 are the same chromophore of the anthraquinone, ~; : aæo, phthalocyanine:or nitroaryl series, B is a phenylene . :
radical~and each of RI, R2, R3 and R4 is a~hydrogen atom, are obtained~by~acylating a dye o~f the- formula . . . . .
.
2) ~2 (7) with trifluoro-s-triaæine to give a compound of the formala :~

' ' .. " ' ' ' ' . ". ' ' '. , ' . " ': '' ' ' .

a 10~360~3 A~l ( 2 ) ~L C ~ ~ ~ 8 ) N~iijjC~N ~ ' "
. . . I .
:E ' and condensing this compound in ~he molar ratio 2:1 wi~h a phenylenediamine of the formula H~N B NH2 ( ) An important modification of the process for .
obtaining the fibre-reactive dyes of the formula (1) comprises reacting a dye of the for~lula (3), an alkylenediamine or . - , -.
arylenediamine of the formula (5) and trifluoro-s triazine-o the formula (6) together in such a manner tha~ a fibre~
reactive dye of the formula :

T--B--~ F : (10) . . ~: :
: R~ R2 R3 (~N

. . '' ' . . "~., is formed, it:beLng possible to choose the sequence of the partial reactions freely, taking into account the starting compounds to be reacted, and condensing the dye of the formula (10) with a compound of the formula (4j, with Al, A2, B, Rl, ~ . .
R2, R3 and R4 in the formulae (3), ~4), (5) and (10) being . :
as defined in formula (l).

- 7 ~ - ~ :

,. : .

`~ 36 Thus, Lor eY.ample, the fibre-reactive dyes of the formula (1), w~erein Al and A2 are the same chromophores of the anthraquinone, azo, pht.halocyanine or nitroaryl series, B is a phenylene radical and each ~ Rl, R2, R3 and R4 is a hydrogen atom, are obtained by condensing a phenyl~nediamlne of the formula ~9) in the mol.ar ratio 1:2 with trifluoro-s-triazine of the :E~rmula (6) to give a compound of the or~ll1a F~ N`C - NH- B - ~H- C~N`C - F (11) M~C~N N~c, -: :. .

and condensing this compound with a dye of tll~ formula (7) in the molar ratio 1:2. .
.
As compound of the formula (4) in this modi~ication :~
of the process as just described, in which a fibre-reactive dye of the formula (10) is condensed with a compound of the ~ -,. ~... . .
formula (4), there is used advantageously an aminobenzene o~

the formula : ::
. .
.
~ H2N ~ (12) , ;; :.--X :. . .
..
. .
..
. .

wherein X is hydrogen, halogen, alkyl, alkoxy, carbonxy or - sulpho, and the ben~ene ring D can contain ~urther substitu~nts, ...
in par~icular a further sulphonic acid group, ..
. -- 8 ~
- i , : .,,.. :
.. .

' :'.: ' , : ' : ' ,: :~, .,, '.' . ~.:, - ' , :.. , . ,', '';, . , .,.. - ' ~ :, - 10 ~3~
In another method of carrying out the process, the fibre-reactive dyes of the formula ~2) are ob~ained by acyl.a.tin~ a dye of the formula .

Al--NH _ I~N~ _~T~ - B - N~I2 (1~) 'N~C,N . , , - . , with a phenylamino-difluoro~s-triazine of the formula ::

N ~ -N. ~ ~ (14) N ~ --r ~:
, . ~li-- ' X ' ' ' ' ~'' '.'' ,, - ' ., If the dye radical Al or A2 is composed of several .::
components (as in azo or formaæane dyes3, then the fibre- ~ -reactive dyes of the formula (1) can also be obtained by synthesising them from components Al and A2, one of ~hicll -~
contains the.~ibre-reactive halogeno-s-triazine radical. :
,: . , . :.: .
~The procedure is that components of the dye o~ the ~:; formula (3) which contains an amino group of the formula : -N~l (15) : R~
., or components of the compound of the fonnula (~) which contains an amino group o the formula :

~: g _ . : -: , ~ . : . ~ .

06~6(;~a~

HN (16) R~

are acylated with trifluoro~s~triazine of the formula (6), and the resultant acyla~ion products are combined ~ith further components and alkylenediamines or arylenediamines c;f the formula (5), the sequence of the partial reactions being optional, to give fibre-reactive dyes of the formula (1).
Preferably, starting materîals are used which ;~1'`'' .
contain water-solubilising groups.
The reactions of the difluoro~ or trifluoro-s~
triazines with the compounds or dyes which contain amino groups, or the components thereof, is advantageously carried out using acid acceptors, for e~ample sodiunl carbonat-e or `~
sodium hydroxide, and in organic solvents, or at relatively low temperatures~in aqueous medium. These reactions must be carried out in such a manner that one replaceable fluorine atom per s-triaæine ring still remains in the finished product.
~ As the formula (1) shows, the clyes to be reacted with the trifluoro-s-triazines of the formula ~6) must :
contain at leaat one acylatable amino group of tXe formula -NHRl or -NHR4, wherein Rl and R~ are hydrogen or alkyl. ~;
The dyestuff compounds of the azo series, containing-at least one -NHR group, which are used as starting materials ~ ;
can be obtained in accordance with various processes.
~' .' ., ,, - 10 -: . . ~ ~ ~ . : .

636(~

One process is to diazotise an aromatic primary amine and to couple the diazonium compour,d thus obtained ~7ith a couplin~
componen-t containing a -NHR group. As examples of aromatic primary amines whic~l can be used in this ~lay to give aminoazo compounds there may be mentioned: aniline, o-, m- ~-,~ , .
and p-toluidines, o-, m- and p~anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, ~- and ~-naphthylam.ine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl~
aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3^- or 4-aminobenzenesulphonamide or -sulphoinono- :~-methylamide or -sulphoethylamide or -sulphodimethylamide or -sulphodiethylamide, dehydrothio-p-toluidinemonosulphonic acid or dehydrothïo-p-toluidinedisulphonic acid, anil.ine-2-, . - . .

-3- and -4-sulphonic acids, aniline-2,~$- or -2,5-disu~phonic -: .acid, 2,4-dimethylaniline-6-sulphonic acid, 3-aminobenzo~ ~-trifluoride-4-sulphonic acid, 4-chloro~5-methylaniline-2-sulphonic acid, 5-chloro-4-methylaniline-2-sulphonic acid, sulfoanthranilic acid, 3-acetylaminoaniline-6-sulphonic ~ " `
.;
acid, 4-acetylaminoaniline-2-sulphonlc acid, 4-chloro- -aniline-2-sulp~onic acid, 3,~-dichloroaniline-6-sulphonic acid, 4-methylaniline-2-sulphonic acid, 3-methyl--aniline-6-sulphonic acld, 2,4-dimethoxyaniline-6-sulphonlc acid, 4-metho*yaniline-2-sulphonic acid and 5-methoxyaniline-2-sulphonic acid, 2,5-dichloroaniline-4-sulphcnic acid, 2 naphthylamine-4,8- and -6,8-disulphonic acid, 1 naphthylamine~
2-J -4-, -5-, -6- or 7-monosulphonic acid, l-naphthylamine-- . ' :- ~: .

.. . .. , ,... , ,, , . ,~. , . . ., ... ~ . ,, .. .. , ., . . ,, " , ~ . .

l(~636~10 : ~;
3,6-disulphonic acid, 2-naphthylamine-1-sulfonic acid, 2-naphthyla~line-1,5-, 3,6- and -5,7-disulphonic acid, :~
2-nap~thyla-,nine-3,6,8-~risulphonic acid, m- and p-nitroanili.ne, 4-nitroaniline-2-sulphonic acid, 3~nitro-anili.ne-6~sulphonic acid, m or p-aminoacetanilide and 4 amino-2 acetylami.notoluene-5-sulphonic acid The follo~ing may be men-tioned as examples of cou-~)ling components which can be used: 2-amino- and 2-methylamlino-5-naphthol-7-sulphonic acid 2 2-~nino- and 2-me-thylarnino-8 naphthol-6-sulphonic acid, l-amino- and l-ethyl~nino-S-naphthol-6-sulphonic acid and correspondirlg 3,6- and 4,6-disulphonic acids, 1-(3l- or 4'-aminobenzoylamino)-8-naphthol-3,6 and`-4,6-disulphonic acid, aniline, o- and m- ;:~
anisidinej o- and m-toluidine, 2,5-dimethylaniline, 3-a-nino-methoxytoluene~ 2,5-dimethoxyaniline, ~-methylaniline, N-ethyl-o-toluidine, N-methyl-m-anisidine, 3-methylamino-4-methoxytoluene, 1-(3'-aminophenyl)-3-methyl-, -carboxy- and - :
carboetho~y-5-pyrazolone, 1-(4'-aminophenyl)-3-methyl-, -carboxy- and -carboethoxy~5-pyrazolone and 1-(4'-amino-3'- ~ -carboxyphenyl)-3 methyl-5-pyrazoloine, 3-~minoacet~nilide, , 3-aminophenylurea.
- The aminoazo compounds to be used in the process according to the inventlon are not restricted to cornpounds containing merely one azo group. For exarnple, disazo compounds can be obtained by tetrazotisation o~ an arom.atic diarnin~ containing two primary amino groups and coupling the .

' ' ' ' : ' ' ' ' '. . ! ., . . ~ .

3~U
,. . . ; .
tetrazo ccmpound, thus obtalned, with 2 molar proportions o one of the coupling components defined abovc or with 1 molar proportion o* each of two of the coupling components defined above or ~ith 1 molar proportion of one o~ the coupling col~-ponents defined above a~ ith l molar proportion of a couplin~
componen-t not containing an ~nino gro~p. The follo~ling may be mentioned as examples of such aromatic diamines:
benzidine, '3,3l-di~ethoxybenzidine, benzidine-2,2~-disulphon-ic acid, benzidine 3,3'-dicarboxylic aci~, benzidine-~,3'-diglycollic acid and 4,4'-diaminostilbene-~,2'-disulphonic acid. Furthermore, disazo or polyazo compounds can be obtained by the use of primary aromatic amines or diamines containing azo groups. The ~ollowing may be mentioned .
as examples of such primary aromatic amines or diamin~s con '' taining azo groups: 4-aminoazobenzene-4'-sulphonic acid, ' .

4'-amino-2'-methylphenylazo-3-naphthalene-4,8-disulphonic -~ ' : . . .
acid and 4-amino-5-methoxy 2-methyl-4'-nltro-21-sulphoazo- ' -'benzene. ~ t Instead o~ starting from amines free from -I~HR groups, it Ls also possible to couple a coupling com~onent which ' ~' optionally not contains a -NHR group wi~h a diazonium compound '~
. ~
containing a -~nHR group. Such diazonium compounds can be obtained in accordanse with kno~m processes by diazotisation o~ primary aroMatic amines which contain a second amino ~; group or a monosubstituted amino group. As examples o~
sùch pri~lary aromatic amines there may be mentioned:~ p- ' ~ 1 S

636E~00 . .
phenylenediamine, 1,4-phenylenedia.rnine-2-sulphonic acid, 1,4- -phenylenediamine-2-carboxylic acid and 1,4-diaminona~hthal-ene-2-sulphonic acid. As examp].es of coupling components whicn can be used in this ~ay the.re may be mentioned the coupling components lis-t;ed above and also ~-naphthol, 2-naphthol-6- or -7-sulphonic acid, 2-naphthol-3,6- or -6,8-di-sulphonic acid, l-naphthol-4-sulphonic aci~, 1-phenyl-3-methyl-5-p~Jrazolone, 1--(4'-sulphophenyl)-3-me~hyl-5-pyrazoloIle, 1-(2~,5~-dichloro-4~-sulphophnyl)-3-methyI 5-pyrazolone, 2-benzoyli~mino~5 naphthol-7-sulphonic acid, 1-benzoy~.amino-8-naphthol-3,6- or -4,6-disulphonic acid, phenol, p-cresol, acetoacetanilide and ace-toacet-2-methoxyaniline-5-sulphonic acid. ~ ;
3-aminocarbonyl-4-methyl-6-hydroxypyridone-2, ~;
l-ethyI-3-cyano- or 3-chloro-4-methyl-6-hydroxypyridone-2, 1-ethyl-3-sulphomethyl-4-met'nyl-6-hydroxypyridone-2, 2,4,6--triamino-3-cyano-pyridine, 2-(3'-sulphophenylamino~-4,6-diamino-3-cyano-pyridine, 2-(2'~-hydroxyethylamino~-3-cyano-4 methyl-6-amino-pyridine, 2,6-bis-(2~-hydrox~ethylamino)-3-cyano-4-methylpyrîdine.
: ~
~ urther processes for the manufacture of the dyes-tuff compounds of the azo series which contain a -NHR group and ; which can be used in the process according to the inven-~ion comprise reducing a dyes-tuff containing nitro groups or treating an azo or polyazo compound which contains at least one acylamino group with aqueous acid or aqueous alkali in :~
;. . '. "
- 14 - ~ ~
.:- :, . ..
~,: , .. . , . , .. ; . .. .. ; .. . . , , . . ~, . . . . . ... .

~ ;3f~
order to hydrolyse off the acylamino group or groups. Such azo or polyazo cor~1~0unds can be ob-tained from primary a-rom-atic amine~ and/or coupling components ~Ihich contain acyl-amino groups. - As examples of such priLnar~J aromatic amines there may be mentioned: monoacetylben~.idine, 4-amino~
~-acetylarninonaphthalene-6-sulphonic acid, ~-amino-4'--acety1-~aminodiphen~Jl-3-sulphonic acid, 4-amino-3-sulphoacetanilide, 3-aMino-l~-sul~hoacetanllide and 4-ami.no-4l-acetylamino5-'il-bene-2,2~-disulphonic acid, and as exa~ples of such coupling eomponents there rnay be men-cioned 2-acetylamino-5-naphthol-7 sulphonic acid, 2-N-acetyl-N-methylamino-5-naphthol-7-sulphonic acid, 2-acetylamino- and 2-I~-acetyl-N~methylarnlno--8-naphthol-6-sulphonic acids and l~acetylamino-~ naph-thol-3,6-and -4,6-disulphonie acids. ~ -~
As examples o~ dyestuf`f eompounds of the anthre~lu~_ n~ series, w}lich can be used~ as starting products in the proeess aeeording to the invention, there may be men-cioned:
anthraquinone compounds ~7hieh contain a group o~ the Iorrnula -N~R, defined above, bonded to an all~ylamino or arylamino -~;
group, which is i~se~f bonded to ~he a-position of the anthra~uinone nucleus. As examples of` sueh anthra-quinone compounds there may be mentioned: l-amino-4-(4-~-aminoaniline)-anthraquinone-2,3'-disulphonic acid and -the , corresponding 2,3',5-, 2,3'96- and 2,3'7-trisulphonie aeids, l-amino-4-(4"-amino-4 t -benzoylaminoaniline)-anthraquinone-:
2,3'-disulphonic acid and the corresponding -2,3',5-tri~
sulphonie aeid, l-amino-4-[4'-(4"-aminophenylazo) anilino]~

-- 10636(~0 anthraquinone-2,2",5-trisulphonic acid, 1-amino-4-(~ ar.~ino-3'-carboxyanil.ino)-an-thraquinone_2,5-disulphonic acid, 1- ~ :
amino-4-(3l-aminoanilino)-an-thraquinone-2,4',5-trisulphonic acid and the corresponding 2~L~-disulphonic aci.cl, 1-amino-4-[~'-(4"-aminoph~nyl)-anilino~-anthraquinone~293",5-trisulph-onic acid, l-arninol~-(4'-me-thylamino)-anilinoanthraqllinon ~,3'-disulphon.ic acid and the corresponding 2,~',5--~ri.sulph-onic acid, l-arni.no-4-(4'-n-butylamino)_anilinoan-thraqui~one-2,3'-disulphonic acid, 1-arnino-4-(4'-methylamino-3'~carboxy~
anilino)-anthraquillone-2-sulphollic acid, 1-amino-4--(3'-~
hydroxyetn~,tlarnino)- anilinoan-thraquinone-2,5-disulpllonic acid, 1-(4 t -aminoanilino)~c~nthraquinone-2,3!~disulphonlc acid and l-amino-4-(4'-amino-2'-methoxyanilino)-anthraquinon~-2,3 t _ disulphonic acid;
- Such dyestuff compounds of the anthraquinone series `~
oan themseLves be obtalned from ~nthraqulnone compounds irhich contain a halogen atom or a nitro group bonded to the corres-~ .ponding a-position of the anthraquinone nucleus, or ~rom the ~ ~ .
~ leuco-derivative of a 1,4-dihydroxy-, 1,4-diamino or ~ ,, S ' - ", , aminohydroxyanthraquinone by reaction of the corresponding anthraqulnone compound with at least one molar proportlon of an aliphatic or aromatic-diamine.
Dyestuff~compounds o~ the ~o~ rhich can be used in the process according to the~invention are : :
~ ~ pre~erably metal-containing phthalocyanines such~as copper : . . . . . ... .
phthalocyanines, ~Jhich contain at least one group which oon-fers solubility in water, suoh as a sulphonic acid group, and .
~ ~ . . . : . , , . . ~ . , l0~36a~
at least one group of the formula ~ ~, as defined a~o~e.
The ~ roup or groups can be-bonded to the benzene rings `~
of the phthalooyanine nucleus direc~ly or via a divalent :
bridge, for exa~ple via a -phenylene-, -CO-~-phenylene-, -S0 phenyl~ne~ I-ph~nylene-, -S-phenylene-, -O-phenylene, -G~I2S-phenylene-, -CH20-phenylene-, -CH2-phenylene-, ~SCH2- ` `
phenylene-~ -S02C~I2-phenylene-~ -$2~l-Phenylene-~ -C~2-~
-S02NRl-arylene-, -NRlCO-phenylene-, -NRlS02-phenylene-, . . . .
-S020-phenylene-, -CH2-, -CH2NRl-phenylene-, -CH2NH~CO-phenylene-, -S02NRl-alkylene-, -CH2MRl-alkylene-, -C~~
phenylene-, -COI~l-arylene-, -S02- or a -CO- bridge. In ~he abovementioned divalent bridge members, R~ denotes . :.
hydrogen, alkyl or cycloalkyl, arylene.de~otes a dlvalent: ~
: aromatic radical ~hlch is~:optionally substituted,~ ~or:e~ample ; ~ `. -by halogen,: alkyl or alkoxy, and~whereln~the terminal bonds ~ :
~ay be bonded to ldentlcal or~different nuclel,~ and:a].kyl.ene . ..
: :denotes a~divalentaliphatic radical~which may include netero~
~` atoms~ such:as;nitrogen, in ~he.atom~ chain, for example he~radlcal~:-cH2cH2-N~I-cH2cH2 The;~following~may be~mentioned~as examples of such~
di~alent~aromatic~radic~als~rhi~ch~are~`designated as~arylene~
aromatic:nuclei :~for example:~a benzene~,~ naphthalene:,:acridine: : . -d~-oarbazole nucleus,~.whioh~ca ~carry ~ her substi ~ ents, : ~ ... ;-and rà;dicals of.~:the ~ormula: ~

~::

106~36~0 ~ : :
herein the benzene rings can carry further subs~ituents and -~- denotes a bridging group, for example -CH=CH-, ~ H-, -S-, '' :
-O-, -S02-, -N0=N-, -N=N-, -l~I-C0-NH-C0-NH-, -0-CH2CH20- or ' N~ - N ' . .

O
, The following may be mentloned as particular examples '.
o~ dyestu~L compounds of the ph-thalocyanine serles which can be used in the process according to the invention: copper phthalocyanine-4-N-(4-amino~3-sulphophenyl)-sulphonamide-4, , 4~t-trisulphonic acid, cobalt p~thalocyanine-4,4'-di~N-(~' '~, :'.. ;, amino-4'-sulphophenyl)-carboxylic acid amide-4",4"'-~icar-; '~
boxylic acid and copper-4-(4'-amlno-3'-sulphobenzoyl)~
phthalocyanlne, Mixtures':of~aminoph-thalocyc~nines can also be used. .,: ' .
~For~example, a~mixture of appro~imat:ely equal parts of copper ' ~ ,:
phthaIocyanine-N-(4-àmino-3-sulphophenyl)~sulphonamide-tri-'.
sulphonic acid~and:eopper-phthalocyanine-di-N-(4-amino-3 s ~phophè~yl)-sulphonamlde-dlsulphonic~acld:~c n be~used.~
e~aminophthal:oc~yanines~eontaining:~a sulphonic acid : ~:
:group~ean~be~obtained~either.by~su~lphonation of kno~m phthalo-oyenlnes~containing primary,:or~;~seeondary~amino groups or by :~
s ~ thesi~:from~mixturea~ of.phthali~c~acid~derivatives cnd~s~ - ,' :
phonàted phthali~e;~ac~1d~derivatl~es.~ Examples of:~sulphonatln~ ' ,:''.
agents used~are~ole m~ or~:e le~a~20 -~st eng~:solut on~o~~
ulphur:~:trioxide in:~sulphuri:e::acid.~ mey ca~ also~:be ~: ~ ::. - ..
obtalnèd"~by~ ~:jointly~warming~suitàble derivativ2's~0~

1~i3600 :~
. .
sulphonated ph~halic a~id and substituted phthalic aci~s in accordance ~Jith the generally kno~ processes, for example by -.
jointly wa~ming a mixture of 4-~sulphophthalic anh~dride and l~-p-nitrobenzoylphthalic ~ydridej? urea, copper~
chlnride and ammonium molybdate i~ o-dichlorobenzene at al~ou~
150C. Ph-thalocyanines ~lhich are us~d as startin~ mater~
ials can also be manufactured by sulphonation of the corres-ponding primary and secondary amines or by reaction of a pri~
mary (or secondary N-alkyl- or N-cycloall~yl-) nitroanili.ne =~
~ith a ph-thalocyanine wh1ch conta1ns c~lloromethyl groups a~ad .~
sulphonic acid groups or carboxylic acid groups. Further- :
. more, such aminophthalocyanines`can`also be manufactured~by reacting a phthalocyanine ~/hich contains chlorosulphonyl groups, with a monoacety1alkylened1am1ne or an amino-N-benzyl~
acetam1de 1n the presence~of ~at~r,~and treatiDg ~ ~ the pro-.duct~thus obtained (which contains~both su~phonamide and sul-phon1c ac1d:groups) w1th;aqu~ous alkali to hydrolyse the àcetylamino group,.or by ~react~in~ ~ a phtha10cyanine, w~ii^h contains~ohloromethyl;~and sulphonic ac1d:or carboxylic acid groups~ Jith a~monoacety1alliiylenedi2m1ne~and~:treating ~he~
product~thus~obtained::with.aqueous alkali~to`~hydrolyse;:~the ~:;
acet~1àm}no~groups.~ Furthermore:,they~can~be~obtained b-direct~su1pllonation~or~by~warming~a;mixture~ of ~
:suitable~carboxy-:or sulpho-phthalic::acid:derivatives wi~h :
substituted~phthalic;~:acid derivatives,~for example~by warining .. :.
thè~anhydrîdes~with urea~and~a~cata1yst, 1n an organic~sol~ent, and; reducing~ the~ nitrophtha10~cyanine-sulphon1c~ac1d or~

~L06360~
-carboxylic acid thus obtained, or hydrolysing the acyl~
aminophthalocynine-slllphonic acid or -carbo~ylic acid thus .. ~ - .
obtained, or by reacting a phthalocyanine compound ~nicc contains carboxylic acid chloride groups, with a diamino~ --benzene-su]phonic acid or -carboxylic acid, an aminobenzene- :
sulphonic acid or an aminobenzoic acid, ~Jhich also contains a ~ ..
nitro group, and reduction of the ni-tro corn~r~ound thus obtained, or finally by reacting a phthaloc~Janine compound which contains carboxylic acid chloride groups with a N- -. . .
aminobenzylacetamide and subsequently hydrolysing the ~:
~.. .. .. ..
. resultant produc~ with aqueous alkali.
Dyestuff compounds of the nit.ro seri.es which can be ~.
. . .
used in the process according to.the inventi.on are preferably those o~ the formula ~ . . .
(19) N0 -D-N-Q . . .

~; ~ ;wherein~D denotes a naphthalene:or benzene nucleus~hich can .
be~ further~ substitute~d, the nitrogen atom N is in the ortho-~ .
position~to the.nitro ~roup, Z den~tes hydro~en or an opti.o~
ally~substituted hydrocarbon:radlcal~and~Q~denotes hydrogen.or ; ; :
an~orgànic radLcal bonded`to:the~nitrogen:by a carbon~atom,~
and~Q~and:Z are~not both hydrogen,~and Q:can be bonded to Z, if.~Z~is~a:~hydrocarbon~radlcal, or;~can;~be~bonded to D in the~
ortho-position~to~-the~nitrogen atom N:,~to:~form a heterocyclic ~ . . ..~ .
ring,~ and:~Jhlch~contain~at l~east~one group of the formula ;~
NHR~ as~ defined above.
The compounds of~the follo~nng categories~may~be~

1(Jt63606~ :
~entioned as particular exa~pl~s of dyestu~f compounds ~.hich contain at ].east one -~R group and whi.ch can be used as .' starting mat~rial~. in the process according to the invcntion: . .
l. Monoazo compounds of the.formula ~ - -OH

,, D~ N~ ) ; "~'' ~03S

wherein Dl d~notes an at most bicyclic aryl rad]cal free îrom ~zo groups and -~IR groups3 and the ~DR group is preîerabl~
bonded to ~he 6-, 7- or 8-position ol -the napht-halene nucl~us, ; and which can contain a sulphonic acid group in the 5- or 6~
, : position of the naphthalene nucleus.~
. :' Dl can h~re denote a radical of the~naphthalene. or . .
benzene series which does no-t contain any azo subst1tuents,~
, ~ or example a stilbene, diphenyl, benzthi.azol~l-phenyl or :
: ~ diphenylamine radical. :In this category, xegard should - .:
also'be g1ven to~the related dyestuffs in;~which the~-~ :.' group-,~instead~of~being bonded~to~the~naphth.alene nucleus,;
is~bonded~to a benzoylam1no~or an1l1no~group wh1ch~is bonded .
';to~the~6-,~7-~or;:8-posit1on of the;naphthalene nucleus. ~
'Particularly useful~ ;start1ng dyes~:are those :~''.':'.' herein:D'~ denotes~:a:suIphonated phenyl or naphthyl;radical ::
especially~thosé~which oonta1n;a~-503H~group in~the ortho~
`posi:t1on~to~.'the~azo bond; :the phenyl~radical ma~ be fu~ther~
ùbs ff tuted~ for example by halogen atoms~ suoh~ as .chlorin~,~alkyl rc~dicals,~such~as:;~me~hyl,~ac~ mino;grou~s, :.-.: '' -~-'` 1063G~V
. :
such as acetylamino, and alkoxy radicals, such as metho,;~
2. Disa~o compoullds of'th~ formula (22), wherein nl , ' ,:.
denotes a radical of the azobenzene~ azonaphthalene or phenyl~ ,. ......
azonaph~halene series and the naphthal~ne nuc1eus is SU~Sti~
ted by the -~I~R group and, i~ desired, by sulphonic acid, as ~ '' j in ca~egory 1. ' ' , 3. Mono~zo compounds of the formula . '- . "
, Dl-N=~ ~ ~IIR (21) '~ ' ;

wherein Dl denotes an at most bicyclic aryl radical, such as ., ~.
'described in cate30ry 1, and preferably a disulphonaphthyl or stilbene radical, and the benzene nucleus,can contain furthe substi-tuents, such as halogen atoms or all;yl, alkoxy, car~
boxylic~acid~and acylamino groups.~
: ' 4. Monoazo or disazo compounds of the formu~a '' -N-Dl-N=N~ (22) ` ' ;~

: ~ wherein~Dl~denotes an~arylene radical, such as a radlcal of ,. .' .. : .
the~àzob~nzene, azonaphthalene or ~ phenylazonaphthalene ~ series~
or~prefèrably an~at most bicycllc~arylene~radical of the;~ben~ "',: ."~.
zené~ or naphthalene;seri:es:,:~and ~:denotes~the radical of a ;naphtho ~ phonic aci;d~or~the radlcal~o~f:an'enolised or~enol~
isablq ketom~e`thy~lene~c;ompo ~ d~(such~as~a ~:acetoace-tary;lide or~ ,.:,'~',... . .
;a~5-pyrazolone:)~ with the~OE~group~ln,:the ortho-positlon,to ~:,..''. ...
the azo~ roup.~ Dl preferably~denotes;~a radi Gal oI;the ben~
zene~series which~contains~;~a;sulphonlc acid~group.
.:5.~ Mo~oazo:or disazo:compounds~:of the formula~

-- ~06360~) Dl-N=N-~C2 NHR (23~ ' herein Dl denotes a radical of the types d~fined for Dl in categories 1 and 2 above an~ K2 denotes the radical o~ an enolisable ketomethylene compound ( such as acetoacetarylide or a 5-pyrazolone) wi-th the OH group in the oriho-position to the azo group. . ~ ' .
6. l'he metal complex compounds, for e~ample the copper, chromium and cobalt complexes, of the dyes of the indicated ~ormulae (22~ ~nd (23), wher~in Dl, K and K2 have their respective indicated meanin-~s and furthermore ~. .
a~metallisable group (or example a hydroxyl, lower alkoxy '. .' or carboxylic acid group) is present in the ortho-position ';`
to:the azo group in Dl. .'- . .
. .
7. Anthraquinone compounds of -the formula ".' - ~ CO ~ (2~) ' ' ';"'' 33~

NH -Zl-NHR

herein'the anthraquinone nucleus can contain an additional ~ .~'. ~.' ' sulphoni~c~acid~group :in~the 5-, 6-;, 7- or ~--position and Z' '~
denotes~a~bridge:~member~which is preferably~a divalent radi~
cal~of~the~benzene series, for example a phenylene~,~diphen~
ene,~4,4'-stl}bene~or 4~,4i-azobenzene:radical. ;Preferably, Z' should:contain:aii:sulphonic acid group in each~b~nzene ring~present,;~

~06360V
. . .
8. Phthalocyanine co~pounds of the formula (SO~ a)n Pc / (25) \ (S02NH-Z ~NHR)m wherein Pc ~enotes a phthalocyanine nucleus, preferab].y copper ph-thalocyc~li.ne, w denotes -OH and/or -NH2, 7.' denotes a bridge me~ber~ preferably an aliphatic? cycloalipha~i.c or aromatic brid~e~ and n and m each denote 1, 2 or 3 and cc~n be identical.or di~f~rent, provided that n ~ m does not exceed 4.
- ,.,, :. . .,:
~9.~Nitro dyes-tu~fs of the forrnula V-NH-B-~R
, (26) ~

wherein~V and B denote monocycl~lc aryl nuclei and the~nitro~
group~in~ is in~the~ortho-posltlon~to;the NH group.
e~following~are~examplss o~possible starting~
dy~es ` in~the;~dyest~ f ca gorles~mentioned~

6~ r;o-}hydroxy-2-~2'-sulphophe ~yla~o)-naph--elene, honic àcid, m 1 no-l-h 2 ~(4'~-ac~e 1 no-~he azo)=n~aph alenq-3-su~ honic acl~d~,~8-a ln~o~
h~ he lazo)-naphthalene-3,6-dîs~phonlc~
a¢id,~8-amino- ~hydroxy-2-(~4'~-chloro-2~'-s~ phophenylazo)-~
' ~ htha~iène-3,5-disulphonlc~acid,:7-amino-2-(2',5'-dlsulpho-~
phenylazo)~ hydroxynaph le 3 1 h ino-2-(2'-sulphophen ~ azo)-l-hydrox ~aphthalenè-3-~

~ - \
~ 360~

sulphonic acid, 7-me-t~lylamino~2-(41-me-thoxy-2'-sulphophenyl -azo)-l-hydroxynaphthalene-3-sulphonic aci(l, 8-(3'-as~ino-benzoylamino)-l-hydroxy-2-(2l-sulphophenylazo)-na~hthalene-3,6-dIsulphonic acid, 8-amino-l~hydroxy-2,21-azonaphtha..ene-l',3 ,5',6-tetrasulphonic acid, 8-amino-l-hydroxy-2.,2'-azo~
naphl;halene-l',3,5'-trisulphonic acid, 6-amino-1-hydrox~
. 2,2'-aæonaphthalene-l',3,5'-t-risulphonic acid, 6-me-thy] a~mino-l-~hydroxy-2,21~azonaphthalene-l',3,5'-trisulphonic acld, 7-amino-l-hydroxy-2,2'-azonaphthalene-l',3-disulphonlc acid, ..
8-amino-l-hydroxy-2-(41-hydroxy-3'~carbo~yphenylazo)-n~ph-.. , ~. , .
thalene-3j6-disulphonic acid and 6-amlno-l-hydroxy-2-(4'~
hydroxy-3'-carboxyphenylazo)-naphthalene-3,5-disulphonic acid. . ~ :
In category 2: . . `
- 8-amino-l-hydro}~y-2~[4'-(2"-sulphOphenylazo~~2'~
;me.thoxy-5'-me-l;hylphenylaz~o]-napht-.halene-3,6-disulphonic ~ci~, .,.: ~ .' ~8-amLno-l-hydroxy-2-[4'-(4"-methoxyphenylazo)-2'-carboxy- . -- : ~` phenylazo]-naphthalene-3,6-disulphonic acid,~ 8-amino-l~
hydroxy-2-[4'-(~Z"~-hydroxy-3'',6"-disulpho-l"-naph-thylazoj-2'- ;. .:; -. .
carbox~phenylazo~-naphthalene-3,6-disulphonlc acld, 4,4' bis~ ramlno~ hydroxy-3",6'i-disulpho-2"-naphthylazo)~
3,3'-dlmèthoxydiphenyl ~and~ 6~ no-l-hydroxy-2-C4'-~2"-sulpho~
phenylaæ~o):-2~'~-methoY.y-5'-methylphenylazo]~naphthalene-3:,5 disu;Lphonio~àcld.
In~: oateeory 3 2-(4'~amlno-2'~methylphenylazo)-naph~halene-4,8 di~sulphonio~àc~ld,:~ 2-(4'-amino-2'-aoetylaminophenylazo)~
naphthalene-5~,7-disulphonic:~:acid,~ 4-nitro~4'-(4"-me:thylamino- ::~

~3600 ~ .:
phenyla~zo)-stil~en~ - 2,2'-disulI~honic acid, ~nitro~ (4"- .
amino 2"-methyl-5"-methoxy-phenylazo)~stilbene-2,2'--disul- :
phonic acid, 4-amlno-4'-~4"-methoxyphenylazo)-stilbene-2,2'-disul.phonic acid aI~d 4-amino-2-methylazobenzene-2',5'-disul- . : .
phoni.c acid. . .
In ca-tegory L~
1-(2',5l-di.chloro-4'-sulphophenyl)-3-methyl-4-~3"-amino-6"-sulphophenylazo)-5-pyrazolone, 1-(4'-su:l~hophenyl)-3- . .:
carl~oxy~4-(4"-arnino-2"-sulphophenylazo)-5~pyrazolone, 1-(2'-- ~
. . ~ - ~ .
methyl-5'-su].pllophenyl)-3-methyl-4-(4"-amino-2"-sulphopheny].
. azo)-5-pyrazol~one, 1-(2'-sulphophenyl)-3-methyl-4-(3:'-aJnino- ...
6"-sulphophenylazo)-5-pyrazolone, 4-amino-4'-(3"-methyl-1~
: .. .. ..
phenyl-4"-pyrazol-5"-onylazo)-stLlbene-2,2'-disulphonic acid, ..
4-amino-4'-(2"-hydroxy-3",6"-disulpho~ naphthylazo)-stlI- ... . :
bene-2,2!-disulphonlc acld, B-ace~tylamino-l-hydroxy-2-(3'- .. .. :.
amino-6'-sulphophenylazo) naphthalene-3,6-dlsulphonlc acid, 7-(3'-:sulphophenylamino):-1-hydroxy-2-(4:' amino-2'~-carboxy~
phenylazo)-naphthalene-3-sulphonic ;acid,~ 8-pheny~.amlno~
hydroxy 2-~(4'-am~no-2'-sulphophenyl.azo)-naph-thalene-3,6-:~
disulphonic acid~:and~6-~acetylamino-1-hydroxy-2-(5'-amino-2'~- :: .
sulphophenylazo):-naphthalene-3-sulphonic acid.
category~5 (3~ aminophenyl)-3-methyl-4-(2~'~,5'._disulphophenyl- ~: ` .
azo)-5-pyrazolone,~ 3'-aminophenyl~ 3-~carboxy-4-(2'~
oarboxy-4~ sulpho henylazo)-5-pyrazolone~,~ 4-amino-4'-~[3"~
ie~hyl-~4"~-~(2"'~, 5 ~ -disulphophenyl~a~o)-1"-pyrazol-5~ onyl]~ ~ ;
:stilbene-2,2'-disulphonic~acid and~1-(3'-aminophenyl)~

~06360~ .
carboxy-4-[~ (2"',5"'-disulphophenylazo)-2"-rnethoxy-5"-.. . . .
methylphen~ zo]~5-pyrazolone.
In category 6:
The copper complex OI 8~~mino~l-hydroxy-2~ (2'~1nydrox~

5"-sulphophenyla~o)~naphthalene~3,6~clisu].phonic acid, the .
copper complex of 6~amino-l-hydroxy-2-(2'-hydroxy-5'-sulpho- `~
phenylazo)-rlaphth~.lene-3-sulphonic aci.d, t;he copper comple~: o.

6-amino-l-hydroxy-2-~2'-hydroxy-5'-su]phophenylazo)-naphthal~
ene-3,5-disulphonic acid, the copper complex o:~ 8-amlno-l-hydroxy-2-(2'-hydroxy-3'-chloro-5I-sulphophenylazo)-naphtha~
ene-3,6-disulphonic acid, the copper complex of 6~Metllylamino~
l-hydroxy-2-(2~~carboxy-5'-sulphophenylazo)-naphthalene-3- . ','.'.,.
.: .
sulphonic acid, the copper compiex o~ 8-amino-l-hydro.;~-2-C4'- ` ~
(2"-sulphophenylazo)-2'-methoxy-5'-methylphenylazo]-na~hthal- :':.~ ,"-'.' ene-3,6-disulphonic~ acld, the copper~complex of 6-amino~
~hydroYy-2-[4t-(2",~5"-disulphophenylazo)-2'-methoxy-5'-methylphenylazo~-nàphthalene-3,5-dlsulphonlc acid,~ the copper~
complex of l-~(3'~-amlno-4'-sulphophenyl)-3-methyl-4-[4"-(2"~
5"'-disulphophenylazo)-2"-me-thoxy-5"~-methylphenylazo]-5- 4 pyrazol;one~, the ~copp`er~ oomplex OI 7-(~4'-amlno-3'-sulpho-anilino~)-l-hydroxy-2-[4"-(2"',5'~ disulphopllenylazo)-2 methoxy-5~ methylphenylazo]-naphthalene-~3-sulphonlo~:acldJ the coppèr complex of~ 6-;(4'-amino-3'-sulphoanilino3-l-hyclroxy-2-2~"-carboxyphenylazo~)-naphth~alene-3-~sulphonlo acid,~the 1,2-chroml~ ~oomplex~of 7-~mlno-6'-ni~ro-1~,2'-dihydroxy 2,1'-azo-- ~ . naphthalene-3~,4'-d;isulphonio acid,~the 1,2-ohromiu l complex~o~
6-amin~o-1-hydroY.y-2'-:(2~-carboxyphenylazo)-naphthalcene-3--~ 10~i3~0~ .
sulphonic acid, the 1,2-chromi~l cornpl~x of 8-al~ino-1-hydro~
. .: : .. .
2-(4'-nitro-2~-hydro~.yphenyl.azo)-naphthalene-3,6-disulphcnlc ..
acid, the 1,2-cobal.t comple~ of 6-(4'-amino-3'-sulphoa~i.lino)- ...:
l-hydroxy-2-(5"-chloro-2"-hyàroxyphenylazo)-naphthalene-3- .
sulphonic acid~ the 1,2-chrornium cornplex of 1-(3'-amino-sulphophen~l)-3-rrlethyl-4-(2"-hydroxy-4"-sulpho-1"-naph~nyl- `~ ;
a~o)-5-pyrazolone,t~e 1,2-chromium comp3.ex of 7-(4'-sulpilo-anilino)-l-hydroxy-2-(4"-amino-2"-carboxyphenylazo)-naphthal- ..
en~-3-sulpnonic acid and the 1,2-chromium complex of 1-(~
aminophenyl)-3--methyl-4-(4"-nitro-2"-carboxyphenylazo)-5 pyrazolone. :~
In category 7: ~ : .s~ :
l-amino-4-(3'-amino-4'-sulphoanilino)-anthraquinone-2- .: .:
sulphonic:~acidj l-amino-4-(4'-amlno~3'-sulphoanilino~-anthra- :
:
quinone-2J5-disulphonic acid, 1-amino-~-(4'~(4"-arnino-3'- - ~:
su1phophenyl)-an}lino]-anthraqulnone-2,5-disulphonic acid, ~.
amino-4-~[4'-~(4"-amino-2"-sulphophenylazo)-anilino]-an.thra-quinone-2,5-disulphonic acid:and I-amino-4-(4'-m~thylarr.jno-~
sulphoanilino)-anthraqulnone-2-sulphonlc acld. .
In~.c~a~e`gory 8~
3-~(3~ amino-4~-sulphophenyl):-sulphamyl-copper phtha~lc-cyànine-tri-3-sulphonic~acid,~di-(4-~(3'~-amino-4'-sulphoph~nyl)-: :-~sulphamyl-oopper:~phthalocyanine-di-4-sulphcnic.acid~and 3-(3'~
amLnophenylsulphàmyl)-3-sulpllamyl-copper phthalocyanine-di-3- ::~',~ ',' sulphonic~:acid~
In~category~9~
:4-~mino-2.'-nitro-dlphenylàmino-3,4'-disulphonic acid.

`- ~063600 The dyes of the present invention can be isolated and -converted into useful dry dyeing preparations. They are preferably isolated at as a lo~ a temperature as possible by salting out and filtration. The filtered dyes can be dried, if ~ ;
appropriate, after the addition of extenders and/or buffers, ~ i for example after adding a mixture of equal parts of mono-sodium phosphate and disodium phosphate; preferably, the drying is carried out at temperatures which are not too high, ~-~
and ~mder reduced pressure. By spray drying the entire reaction~
.. ..
mixture, the dry prepara ions according to the invention carl `
in some cases be manufactured directly, that is to say without ., .
first isolating the dyes. ;
The dyes are suitable for dyeing and printing a -wide range of materials, such as silk, leather, wool poLyamid~e~ fibres and~polyurethanes,~;but especially~celluLosic matérials~ of fibrous~structure~, such as linen~, cellulose, ~`
regenerated cellulose and, above e.l~ cotton They~are~
paxticularly~suitable;~or dyeing~by~the exhaustion;~process rom~a~dilute liquor, fro~m an~alkallne aqueous bath~which optionally~contains~a~large;amount~of saLt, and by the~pad~
dyeing~process,~`in~which;the~goods~are~impr~ègnat.ed~with aqueous~dyes~tuff~solutions which~optionally~also contai.n salt~
and~the~dyestufs~are fixed after~ an alkali treatment or in the~presence~of~aikali~,~if appropr~iate with~heat ~reat~ment.
The~dyes are~also`~suitable~for printing, especi-ally~on cotton,~but~also for printing~nitrogen-contain;ng~

a~ - 106360~ ~ ~
fibres, for example wo~l, silk or blends which containing ~ ' :
wool. '~': ' - The dyes are charact~rised by high reactivity, .
so that dyeings can be obtained at a lower temperature, or with a sllorker fixing time, than'are usually employed for con~
parable dyestuffs.
Furtl~er advantageous properties are good affini~y and hence a high degree of fixation, good stability of the bond bet- :
' ' ween the dye and the fibre., ease with which non-~i.xed dye can be removed, and good build-up..The dyeings and prints obtained are very strong and have good fastness to light and very good wet astness properties, for e~ampIe good fastness;to washin~
- - To improve the wet fastness properties it is .":.
advisable to rince dyeings and prints thoroughly with cold ~ :
and hot water, if~appropriate with the addition of~an agent ;`
which;has~a dispersing action and 2s~ists the diffusion of non-fixed dye.
In:the examples which follow, the parts and ....
percent2g2s are~by weight, unless otherwise indicated. Parts '.
by~weight~and~.parts:by~;volume~bear~the same~relationship ~
to~one~another as that of the:gram to~the cubic centimetre. ' i~.~.''''-~' :

Example 1 . . .
30.5 parts of the dye of th~ formula ' L f)3S~ C~
.'..
are dissolved in 600 parts by volume of water, and the solution is condensed with 7 parts of 2,4.,6-trifluoro-1,3,5-triaæine. After no further diazotisahle amino groups are detectable, an aqueous solution containing 3.1 parts of 2,4-diaminotoluene is added to the dyestuf solution at 0 to -.. .. .
5C at pH 4"5. The pH of the reaction mixture is now increased to 7.5 by adding sodium carbonate and the , .
temperature is s]owly raised to 25C. When the condensation is complete, the dye of the formula ~ .
. .

~ ~ r ~3S SO~ MHCON~I2 - ~ 1 - - L ~ 2 ~..... .
is precipitated with sodium chloride after the addition of buffer salts, and is then filtered, washed and dried. -~
. . .
~, . . .

- 31 - ~

lL0636~

The dye is in the form of an orange powcler and dyes cotton in golden yellow shades.
, Further dyes having similar properties are obtained by conclensing the aminoazo dyes listed in the following Table I with equivalent parts of 2,4~6-trifl.uoro-1,3,5-triazine, and i~necl:iately afterwards condensing the resultillg products ~i.th the diamines listed in the said Table in accordance with the particulars of Example 1. ~ .
. . ' , .

.

~ . " ' ~ . -.. ~ '.'.~,., .
.. , . : .

: . .
..
. .
:

': : ' . ' ' : . ~ . , . . :. :
- ,' ', ' , , . .. . .
:. ' , , . ':' ,' : ' -- . -... ~ .:
~ , . .
,:
32 ~
, : ,. .: . ~
: ~ ; ; . . . ~

~ 3~C~Q : ~ ~

_ V
o t, . . ,,, O ~ d 'C) ,~
O ~~ r-~
~1 ~ d t~ h h ,Q
a~ ~ u `~
~, o u~
.~ . . ..
V~
_ ~

r ~ .r ~ rl .
~
~d O ~ O 'd O
v q) v q) ~ : . .
S:~ ~ o C~ O ~ ~ O ' rl ~ a s~ ~ 7 E3 r '~ ~d . .. : .
. ~ ~t ~ ~ ~ '~ '. :
~ r. ~ ~ r-l .' _ ~
r 1 rl O ~ I . ':
I I ~ l O
~1 .. _ V I 'd I .~ -P~ I I O .~ ~1 1 r~ I O t) a~
,t~ ) N Q~ ~ O t~ rl r-l I t~ .C td ~ R~
a) N~ r-l C~ ~1 C C~l ~ ~ O-rl U~
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c~ O .~ rl~ r~ ~ I V S ~
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:1 O ~ tO t ' ,~ I ~~ I C~l ~~ I S~ ~d . : :: ~ .:
,~ ~1 rl .~ q~ ~-~ o o X ~I o ~ ~ ~ o I ~
,i~ ~ I~ $ 1 .C O u~ X u~ o .
~J I I C~ CLI ,C~ I ~ V O I ,~ IJ
~1 : Ut ~ O C~ ~~' ,C~.Ci ~ :~ .G . ^ rl O I Ll~i : h rl - ~ Il) 1 I t~ V I O Cl~ ~: e ~ ~ t - o e U~i rl e~ t.. ~ N t~

r~ u~ _ .~ ~, I o I oI r, I o~! c~ ^ r i ~ :. . .:
;,- ~ I C~lir~ I _ ~ -- .GO I ~ .C~Q) I ~ rl ., ~ 0 1 L~ 1 ~ V ~ U~ ~ V,CI 00 C~l d C) . ~h O I rl ~ CJ`~ .C~r~ I ~' .S ' O I ~ aJ ru :.. . .:
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: ~ E~ O -- ~ O ~ O I dr-( N I ~ E~ N I O ~r~i :.
:: C.l ~d ~ l I ~ O ,C~ O I~ t~ O I tlli t~l O d ~
.~ I I O~ ~ O~ CLi ~ .G r~ r~i O
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. ~ I I ~ I ~U :~ I I I N I ,C~, I N I .~
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.~ ~

33 ~

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? ~ I ~r~ ~rl ~ I rl ~ O p~
O ~d rC r I ~ C ~ ~a ~ r~ I I I O tl5 . N ~ ~ ~~1 o I o ~ ~ ~ -,1 _ _ rC
1 . . t~ V ,~ ~ ~ J s~ d c~ l Q~ Cl rQ r~ o~ O

.~ rc~ rC ~ rSC~l r ~ d ~ ~ d r~
i~ ~ Q~ ri I CLI I ~ I I I I - ~ rC ~ ~I) O a) O O a ~~ ~ ~ O~ O O O a) ~ rC~
i E~ I~3 0 ~ T--I rci E3 N O I I r~ r O

N a~ ~rC ~c~ I I N _S:
r-l a) ~ _~ C O r~ ~ O ~ I O Q~ rC O ~ ~ ~ ~ ~ ~ rC .~ rC ~ s .~ ~,a ~, o ~ ~ ~ ~ do ~ ~ ,v ~ ~ ~ ~ ~ N
rl t~ ~ ~ ri r~ 1 rc~ _1 0~ rC .,dl ~ .d ~ ,~1 ~
rC ~ ai ~ u~ r-l h~ O hi O ai a c~l d C~ d ~ Q~ rc~ n rci ~-1 ~ u~ ~ hi ~ r!J t~
¢ :~ a~ o r~

,; _ ~I ~
' ~: . ~ : 34 ~636 _ ~
,:. ': ' ' g . ~
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r ~- ~
. . .
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.~
_ .
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.
. . O
d E ~:
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~ . ....
C~l . ".
_ _ .', ,~ , ~ . ~.
.,~` . . , ~ . . ' '' ' ,' . ' ,,,, , . ~
,,.,.`,~, . .~ . ' , :' ' . ' .~

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. .~d~_1 ,., ;"` ~, ' ~: - ~ S-l ~ C~ I ~

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~ . - - 36 :.: ~

... .

~ 63ti~ ~
::
Example 2 :... ~. .
30.5 parts of the dye of the formula ..
' ..::
r S03- . ~ . .

O S/(~' C f }~I2 ., . ~ C0i~ 2 are dissolved in 600 parts by volu~e of water, and the solution is condensed with 7.4 parts of 2,~,6-trifluoLo~
.~ ..
1,3,5-triazine at 0 to 2C and pH 4.5 in accordance with :.... .
the preceding Examples. ~hen the acylation is complete, :.- ~: .
.. . .
130 parts by volume of an aqueous solu~ion con~aining 10.5 .
. parts of 1,3-diaminobenzene-4-sulphoDic acid (Na salt) are i . added to the dye solution, and the temperature is subsequently ..
~ . . . . .allowed to rise to 20C. The pH of the reaction solution ~ ... .
, .... . .
:. is kept at 4l5 with sodium carbonate solution. When the . . .:.
reaction is complete, the dye is precipitated with sodium ~
~ ~. chloride,~ filtered, and, while still moist, dissolved in 1500 parts by volume of water at pH 5.5. After renewed . ~ ~^... - ~ : . .
condensation with 7.4 parts of 2,4,6-trifluoro-1,3,5- ~ .
triazine at~0 to 2C and pH 4.5, 5.4 parts of 2-methyl- .
.aniline are added to the reaction mixture. ~ .

.~ - . .
.~.. ~ . .

~ 37 _ . :

~ 636~

The pH is kept at 7.5 ~uring condensation by the drop~ise addition of sodlum carbonate solution and tlle temperature is raised to ~0C. When the reaction i.s complete, the dye of the formula :
,~

~i~ ~C--N~ So.~ a~3 3 S03 ~HCONH2 ~T~ MH--cl~N~e--~h~
. . F - N~C' : ; ~

. is precipitated with sodium chloride after the addition of ~ .
. buffer salts and is then filtered and washed. After drying~
:` ' the product is in ~he form of an orange powder which dyes : cotton in golden yellow shades.
~' Useful dyes which dye cotton in golden yellow shades are .. also obtained by using equivalent amounts of a~nonia, ., .
`~ methylamine, N-methylpropylamine, cyclollexylamine, ~-methoxy- ~ .
ir~ ~
`~ aniline, ~acetylaminoaniline, 4-aminobenzoic acid, 2-chloro-,. .
;`. : aniline, aniline-3-sulphonic acid, aniline-4-sulphonic acid, 2-amino-5-sulphobenzoic acid, 1-naphthyl.amino-5-sulphonic acid or I-naph~hylamino-4,7-disulphonic acid, instead of !,'`'`- ~ : 2-methylaniline. .
. ` Further dyes are obtained by condensing the chromophores ~; . .
Al-N-Hj the diamines H-~-B-N-H and the amines H-N-~2, listed ~ .
~ Rl R2 3 ~ 4 .`,':~: ~ . ,, ~ - 38 - : . ..

~3~

in Table II, in the ~ en sequence with 2,4,6-trifluoro~
1,3,5-triazine in accordance with the procedure described in this ~xalnple.
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:i '.. .: :: ' ' ' . ', ''; .' : ,.:, 1. . . ' :' ' , . '' ' ' . '', ;' `. ' ' . '' .' :: ` '.' ' . ' '.. '' : :- . ' . ' . ': ' ' . ' .

1g~6361~30 Examp]e 3 8.65 parts of 2-aminobenzenesul~honic acid are dissolved in water at pH 7 ~ith the addition of sodium hydroxide solution. To tl~is solution are then added S parts of sodium bicarbonate. The temperature is lowered to 0C and 7.4 par~s ~^
o~ 2,4,6-trifluoro-1,3,5-triazine are subsequently added dropwise When the condensation is complete, an aqueo~ts solution o~ 10.5 parts of the sodium salt of 1,4-phenylene-diamine-2~sulphonlc acid i5 added and condensation is carried out at S co 10C, with the hydrogen fluoride formed during condensation being continuously neutralised by the dropwise addition of 2N sodiurn hydroxide solution. When the condensation , is complete, the temperature is again lowered to oC ancl a ~ -further 7 parts of 2,4,6-trifluoro-1,3,5-triazine are then ;~
added dxopwise at a pH-value o~ 6 to 7. An aqueous solution -of 25.4 parts of the dye of the ormula _ ~03_ N=~ ~ ~E2 2 Na~ ; ;

, ' SO - ~

is inally added and the solution is heated to 20C. The .~, . ..
hydrogen ~luoride which is liberated during condensation is continuously neutralised by the addition of sodium hydroxide solution. When the condensation is complete, , . ~, .
, ''~

, ' . `', :

` ' ' ', ' . i . , . '` .'.1'` ` . '' ' " ' / ' ' . . ' . ' "'1' , , ` ~'.. ', :,. "` . ; :; . . '" '; . '` " i :' ', "' ' ' : . ' '' ' '.' ' , .

~ 36~CI

the dye is prccipitated by adding sodium chloride; it is filtered off and dried after the addition o~ buffer salts.
~t dye-s cotton in fas~ yellow shades.

A dye having very simi].ar properties is obta:ined by replaclng 1,4-phenylenediamine~ su].phonic acid witl the same amount of 1,3-phenylenediamine-4--sulp'nonic acid.

Further use~ul dyes are obtained by using, instead ~ :
of the given aminoazo dye, the chromophores containing amino groups ~hich are listed ln Example 2 and in the .:
.
Table following Example 2. The shades obtainable on cellulose ibres are also indicated in Exarnple 20 ~ ~

. ~.' ' ~ . ' , E~ample 4 : .
, 14.3 parts of the dye of the formula ~ :
'' . :' ., .' '.
¦ H2 ~ S03 3 . N=N ¦ CH2S3 2 Na~
. HO' N . . .~
I ' . ."
C2H5 :- :

are dissolved in water. The solution ls cooled to 0C and - ~ 4~1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, with the pH of the reaction mix~ure being ~:.
kept at 6 by the simultaneous~addition of sodium hydroxide solution. An aqueous solution o~ 6.3 parts of the sodiurll ' -.:
. - 45 ~

.
' 10~36~(~
:
salt of 1,3-phenylenediamine-4-sulphonic acid is then added, and stirring is continued at 5 to 10C at pII 6~5 unti] condensation is complete. The reaction mixture is again cooled to 0C and at pE~ 6 to 6.5 a further 4.1 parts 2,4~G-trifluoro-1,3,5-triaæine are added dropwise. Fin~l]y, 17.5 parts oI the dye containing amino groups, o the formula _ _ .'~' :' ' .

3S ~ ~o~~ 3 iJa~
0 NH ~ ~2 . CO~~ .
. _ _ ,~
are added in the form of an aqueous solution.
The temperature is raised to 20 to 25C, and the hydrogen `fluoride which is liberated during condensation is continuously neutralised by the addition of sodium carbonate solution at pH 7. The dye is precipitated as sodium salt from thç green dye solution by adding sodium chloride, th~n filtered off and dried. It dyes cotton in green shades fast to wet processing.
A green dye is also obtained by using an equivalent amount of the blue copper complex of l-amino-7-(2'-hydro~y , amino-4'-sulphonaphth-1-ylazo)-8-naphthol-2,4-disulphonic ; acid instead of the anthraquinone dye.
'"

:' ., ~;' .. .. . . . ..

~6~6C~) Dy~ ,Exan-.ples -- . .
A. 20 parts oE the yellow dye of the Example 1 are dissolved in 1000 ~ rts by volume of water. Thiis dye sol.ution is used to slop-pad a cotton abric, which is subseq~erltly squee~ed out to 80% liquor pick-u~. After it has been dri.ed first at 50C, the dyeing is treated with a solution of 200 parts of sodium chloride and 10 parts by volume of 30% sodium hydroxide solution in 1000 par-s by volume of water, and afterw~rds steani~ed at 100 for 15 seconds. A full greenish-yellow dyeing which is fast ~;
to washing is obtained after rinsing.
An almost equally strong dyeing is obtained by storing at room temperature for 2 minutes instead of . ~ ..
st~.aming.
B. 3 parts of the blue dye No. 8 in Table I are dissolved in 100 parts of water. A cotton cloth is padded with this solution at the usual temperature, and then dried at 50C. The coloured article obtained is subsequently immersed for 10 seconds in a solution at 30 consisting of 250 parts of sodium chloride and 30 parts by volume of sodium hydroxide solution in 1000 parts by volume of water, an~d then rinsed with cold water and with hot water.
A strong blue dyeing which is fast to washing and light is obtained.

, . ` ' ~. ''" ~ .

~0 S3 ~0 ~

C. A cotton fabric is impregnated ~ith a solution of 25 parts of the or~nge dye No. 3 in Table I, 20 parts of sodium carbona~e anc~ 30 parts of sodium sulphate in 1000 parts by volume o water, and subsequently squeezed out to 70% increase itl weight. The impr~gnated r fabric is then stored for 4 hours in the moist condition at: 25C and ater~ards ~ell rinsed. An orange, washfast dyeing is obtained.

D. 1 part of the reddish-ye]low dyestuff No. 1 in Table 1 and 30 parts of sodium chloride are dissolved in 1000 parts by volume of water. 50 parts of moistened cotton fabric are then introduced into this bath at 40C, and dyeing is performed for 30 minutes with continuous agitation of the fabric. After 15 minutes' dyeing time, a further 30 parts of sodium ch]oride are added Then 20 parts of anhydrous sodium carbonate are added and dyeing is continued for a further 60 minutes at 40C. The resu]tant dyeing is rinsed cold and hot, centrifuged and dried. A strong golden yellow dyeing of excellent fastness properties is obtained. ;~

E. A padding liquor is prepared from 3 parts of the dyestuff No. 8 in Table I, 10 parts of urea, 5 parts o sodium bicarbonate and 82 parts of water. This padding liquor is used to impregnate a fabric made from mercerised cotton. The material is afterwards squeezed out and .
~ 8 ~- ~

. .. , , , .. , - ., , . , . ;., . ~.. ,. . :.: . , ., . , .. ,, ..... ; ..

~L~6360~:P

subsequently heated for 60 seconds at 160C~ A brillian~ blue dyeing is obtained after rinsing. ~:

Pr;ntin~ E~_a~
50 parts of the dye No. 2 of the Table are sprinl~led into and dissolved in a printing-paste thickenlng con~istlng of 730 parts of a 3% aqueous alginate solution, 200 parts of urea and 19 parts of sodium bicarbonate. A cotton fabric is printed with this printing paste and subsequently driec~
The printing is fixed by steaming for two minutes at 100C
and then ~ashed. A strong greenish-yellow printing is obtained.
~ Instead of being fixed by steamin~, the printing can also be fixed, with the same dye yield, by immersion for lO seconds at 90C in a bath containing 250 par~s of sodium chloride and 30 parts of 30% sodium hydroxide solution in lOOO parts of ~ater.

.

-: ' ' ' . ,' " ' .
. . . ' ,., ,' ."

. .
_ ~g _ :.' '' .
b -

Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Fibre-reactive dyes of the formula (1) , wherein A1 is the radical of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series which contains sulpho groups, A2 is hydrogen, an alkyl, aryl or heterocyclic radical or the radical of a chromophore which contains sulpho groups, B is an alkylene or arylene radical and each of R1, R2, R3 and R4 independently is hydrogen or alkyl.

2. Fibre-reactive dyes according to claim 1, wherein A2 is the radi-cal of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series, and A1, B, R1, R2, R3 and R4 are as defined in claim 1.

3. Fibre reactive dyes according to claim 2 of the formula (1), wherein A1 and A2 are the same chromophores of the anthraquinone, phthalo-cyanine or nitroaryl series, B is a phenylene radical and each of R1, R2, R3 and R4 is a hydrogen atom.

4. Fibre-reactive dyes according to claim 1 of the formula (2) , wherein A1 and B are as defined in claim 1, X is hydrogen, halogen, alkyl, alkoxy, acetylamino, carboxy or sulpho, and the benzene ring D can contain an additional sulphonic acid group.

5. A fibre-reactive dye according to claim 1 of the formula

6. A process for the manufacture of fibre-reactive dyes of the formula (1), wherein A1 is the radical of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series which contains sulpho groups, A2 is hydrogen, an alkyl, aryl or heterocyclic radical or the radical of a chromo-phore which contains sulpho groups, B is an alkylene or arylene radical and each of R1, R2, R3 and R4 independently is hydrogen or alkyl, which process comprises reacting together a dye of the formula (3), a compound of the formula (4), an alkylenediamine or arylenediamine of the formula (5) and trifluoro-s-triazine of the formula (6) in such a way that a fibre-reactive dye of the formula (1) is formed, it being possible to choose the sequence of the partial reactions freely, taking into account the starting compounds to be reacted, and with A1, A2, B, R1, R2, R3 and R4 in formulae (3), (4) and (5) being as defined in formula (1).

7. A process according to claim 6, wherein compounds of the formula (4), in which A2 is the radical of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series, and R4 is hydrogen or alkyl, and further-more compounds of the formulae (3) and (5), in which A1, R1, B, R2 and R3 are as defined in claim 6, are used as starting materials.

8. A process according to claim 6 for the manufacture of fibre-reactive dyes of the formula (1), wherein A1 and A2 are the same chromo-phores of the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and each of R1, R2, R3 and R4 is a hydrogen atom, wherein a dye of the formula (7) is acylated with trifluoro-s-triazine to give a compound of the formula (8) and this compound is condensed in the molar ratio 2:1 with a phenylenediamine of the formula H2N-B-NH2 (9)

9. A process according to claim 6 for the manufacture of fibre-reactive dyes of the formula (1), wherein a dye of the formula (3), an alkyl-enediamine or arylenediamine of the formula (5) and trifluoro-s-triazine of the formula (6) are reacted together in such a way that a fibre-reactive dye of the formula (10) is formed, it being possible to choose the sequence of the partial reactions freely, taking into account the starting compounds to be reacted, and the dye of the formula (10) is condensed with a compound of the formula (4), with A1, A2, B, R1, R2, R3 and R4 in the formulae (3), (4), (5) and (10) being as defined in formula (1).

10. A process according to claim 6 for the manufacture of fibre-reactive dyes of the formula (1), wherein A1 and A2 are the same chromophores of the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenyl-ene radical and each of R1, R2, R3 and R4 is a hydrogen atom, wherein a phenylenediamine of the formula (9) H2N-B-NH2 (9) is condensed in the molar ratio 1:2 with trifluoro-s-triazine of the formula (6) to give a compound of the formula (11) and this compound is condensed with a dye of the formula (7) (7) in the molar ratio 1:2.

11. A process according to claim 9, wherein an amino benzene of the formula (12), in which X is hydrogen, halogen, alkyl, alkoxy, acetylamino, carboxy or sulpho, and the benzene ring D can contain a further sulphonic acid group, is used as compound of the formula (4).

12. A process according to claim 6 for the manufacture of fibre-reactive dyes of the formula (2), wherein A1 and B are as defined in claim 6, X is hydrogen, halogen, alkyl, alkoxy, acetylamino, carboxy or sulpho, and the benzene ring can contain a further sulphonic acid group, wherein trifluoro-s-triazine of the formula (6) is condensed with a dye of the formula (7) and an alkylenediamine or arylene-diamine of the formula (9) to give a dye of the formula (13) and wherein trifluoro-s-triazine of the formula (6) is condensed with an aminobenzene of the formula (12) (12) a phenylamino-difluoro-s-triazine of the formula (14) and the dye of the formula (13) is acylated with the phenylamino-difluoro-s-triazine of the formula (14).

13. A process for the manufacture of fibre-reactive dyes of the formula (1) (1), wherein components of the dye of the formula (3) (3) which contains an amino group of the formula (15) or components of the compound of the formula (4) (4), which contains an amino group of the formula (16) are acylated with trifluoro-s-triazine of the formula (6) (6) and the acylation products obtained are combined with further components and alkylenediamines or arylenediamines of the formula (5) (5) the sequence of the partial reactions being optional, to give fibre reactive dyes of the formula (1)

14. A process according to claim 8 for the manufacture of the fibre-reactive dye of the formula wherein the dye of the formula is condensed with trifluoro-s-triazine and the resultant condensation product is condensed with 2,4-diaminotoluene in the molar ratio 1:2.

15. A process according to claim 6, wherein the reactions with di-fluoro- or trifluoro-s-triazines are carried out in aqueous solution.

16. A process for dyeing and printing cellulose fibres which com-prises use of fibre-reactive dyes as claimed in claim 1.

17. The dyed or printed material obtained by a process as claimed in claim 16.