CA1161034A - Reactive dyes, processes for their manufacture and use thereof - Google Patents

Abstract

JAN 2 1984 ~
The invention provides reactive dyes of the formula

Description

~ 4 1-11902/=

Reactive dyes, processes for their manufacture and use ~hereof The present invention provides reactive dyes of the formula D - N - C C - N ~ $1) Rl N~ ~N R2 F X
wherein D is the radical of an organic dye which contains sulfo groups, Rl is hydrogen or Cl-C4alkyl, R2 is hydrogen, methyl or ethyl, X is a radical of the formula -S02CH2CH2Cl, -S02CH=C~2, -S02C~l2CH2~S03H, H CH OP0 H or -N(R3)S02CH2CH20S03H, and 3 or ethyl, and the benzene or naphthalene radical can contain further substituents in addition to X.

In the reactive dyes of the formula (1), the radical D is in particular the radical of a dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series.

Preferred reactive dyes are those of formula (1), wherein D is the radical of a mono- or disazo dye.

As alkyl of 1 to 4 carbon atoms, the subst~tuent Rl in formula (1) is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

If the radical bonded through the -N(R~) bridge member to the s-triazine ring is a naphthalene radical, it can be bonded in the a- or ~-position.

In addition to containing one or more sulfo groups, the radical D in formula (1) can contain further substituents, for exam-ple alkyl groups of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups of 1 to 4 carbon ato~sl such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups of 1 to 6 carbon atoms, such as acetylamino, propionylamino and benzoyl-amino, halogen, such as fluorine, chlorine and bromine, nitro7 cyano, trifluoromethyl, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, and sulfomethyl.

In addition to X, the benzene or naphthalene radical in formula (1) can contain-eTg~ the following further substituents:
Cl-C4alkyl, Cl-C4alkoxy, halogen, such as fluorine, chlorine and bro-mine, nitro, hydroxyl, carboxyl and sulfo.

Preferred reactive dyes of the formula (1) are those wherein Rl is hydrogen, methyl or ethyl, and each of R2 and R3 is a hydrogen atom..

An important class of reactive dyes comprises those of the formula HO
A-N=N~ (S03H)m ~ ~ CO~}, ~ C C-~
~C~
~2), F
wherein A is a benaene or naphthalene radical, m is 1 or ~, n is O or 1 and p is O or 1, ~hile the benzene or naphthalene radical A and the benzene radical B can contain further substituents and X is as defi-ned for formula (1).

Further eligible substituents in the benzene or naphthalene radical A and the benzene radical B are the same as those named as possible substituents in the radical D in the definition of formuha (1) .

If the radical D or A contains complex forming groups, such as hydroxyl, carboxy-l, amino and sulfo groups, it is also possible to obtain the heavv metal complexes of the reactive dyes of the formulae (1) and (2).

A valuable reactive dye of the class characterised by formu-la (2) is that of the formula SO H ~N ~ ~
03 ~ ~ C' 502CH2CH20S3 ~3) , The reactive dyes of the formula (1~ are obtained by conden-sing in any order, 2,4,6-trifluoro-s-triazine of the formula ~N~
F - C C - F
N N (4) , ~C' F
an organic dye of the formula D - NH
Rl (5) which contains sulfo groups, or a primary product thereof, and an amine of the formula -3~

HN ~
R2 ~ (6) to produce a reactive dye of the formula (1), and, if primary products are used, converting these latter into the desired end dyes of the for-mula (1).

Organic dyes of the formula (5) which contain sulfo groups are, in particular, those wherein D is the radical of a dye of the mono- or polyazo, metal complex a7-o, anthraquinone, phthalocyanine, formazane, azomethine, ni~roaryl, dioxazine, phenazine or stilbene series.

Preferred starting materials are organic dyes of the formula (5) which contain sulfo groups,in which D is the radical of a mono~ or disazo dye.

As the individual process steps described above can be car~..^.
ried out in varying sequence, and, if desired, in some cases also simultaneously, different variants of the process are possible.

In general, the reaction is carried out stepwise in succes-sion and the sequence of the simple reactions between the individual reaction components of the formulae (4), (5) and (6) can be freely chosen.

Important processes variants for obtaining the reactive dyes of the formula (l) comprise 1) condensing 2,4,6-trifluoro-s-triazine of the formu1a (4) with an organic dye of the formula (5) which contains sulfo groups and conden-sing the primary condensation product with.an amine of the formula (6);
~, . . . . . .. .

3'~

2) condensing 2,4,6-trifluoro-s-triazine of the formula t4) with an amine of the formula (6) and condensing the primary condensation pro-duct with an organic dye of the formula (5) which contains sulfo groups.

In a modification of the above process, the reactive dyes of the formula (1), wherein D is the radical of an organic dye which is composed of t~o or more components ~nd contains sulfo groups, can be ob-tained by condensing one component of the dye of the formula (5) which contains a -~ group~, a- 2,4,6-trifluoro-s-triazineof the formula (4) and an aminobenzene of the formula (6), and, in any step of the process, reacting the condensation product with the o~her component or compo-nents of the dye of the formula (5) to produce a reactive dye of the formula (1).

Exa~ples of such organic dyes which are composed of two or more components are: monoazo, disazo, trisazo, tetraazo, metal com-plex azo,formazane and azomethine dyes, The above described process modification is chiefly of impor-tance for the manufacture of reactive dyes of the formula (1)~ wherein D is the radical of an azo dye which contains sulfo groups. In these dyesl that portion of the azo dyestuff radical to which the s~triazine radical is bonded can be either the radical of the diazo component or the radical of the coupling component. This possibility gives rise to two variants of the above described modification of the process.

The first of these two variants consists in condensing a diazo component which contains a -~ group with 2,~,6-trifluoro-s-triazine of the ormula (4~, diazotising the resulting condensattonproduct and coupling the diazo Gompound to a coupling component, and - reacting the resulting azo compound, before or af~er the coupling, with an amine of the fo~mula (6).

The second variant cansists in condensing a coupling compo-nent which contains a -~1 group with 2,4,6-trifluoro-s-triazine of the formula (4) and coupling a diazotised diazo component to the condensa-tion product and reacting the resulting azo compound, before or after the coupling, with an amine of the formula ~6).

In this process variant, it is possible to obtain reactive dyes of the formula (1) which contain two reactive s-triazine radicals by condensing a diazo componentwhich contains a ~ ~ group with a 2,4,6-trifluoro-s-triazine of the formula (4), and also condensing a coupling component which contains a - ~ group with a 2,4,6~trifluoro-s-~rianzine I
of the for~ula ~4) and diazotising the condensation product of the dia-zo component and coupling the diazonium compound to the condensation product of the coupling component and reacting theresulting azo com-pound, before or after the coupling, with an amine of the formula (6).

Reactive dyes, which contain two or more reactive s-triazine radicals can also be obtained by condensing organic dyes of the for-mula (5) which contain sulfo groups and which contain further - ~

groups in the radical D, with a corresponding amount of the 2,4,6-tri fluoro-s~triazine of the formula (4), so that two or mores-triazine radicals are introduced into the dye molecule.

A preferred embodiment of the process for the manufacture of the reactive dyes of the formula (1) comprises the use of organic dyes of the formula (5) which contain sulfo groups, wherein D is the radical of a mono- or disazo dye, as starting materials, or condensing diazo components and/or coupling components which contain a -N(Rl)H
group with the 2,4,6-trifluoro-s-triazine of the formula (4), and subsequently,or after the further condensation with the .

. .

amine of the formula (6), obtaining the dye by coupling with the other component or other components of the mono- or disazo dye respe~tively.

A further preferred embodiment is that wherein the starting materials are organic dyes of the formula (5) which contain sulfo groups, wherein Rl is hydrogen, methyl or ethy-l, and amines of the formula (6), wherein each of R2 and R3 is a hydrogen atom.

The preferred reactive dyes of the formula (2) are obtained by reacting, in any order, a diazotised amino compound of the formu~a A - NH2 (~) a coupling component of the formula HO

(S03H)~ (8) ~ CO ~ } - ~H ~ ~I

2,4,6-trifluoro-s-triazine of the formula (4) and an amine of the for-muIa 2 ~ (9) by coupling and condensation, to produce a reactive dye of the formula (2).

The most important process variants for obtaining the reac-tive dyes of the formula (2) com~rise 1) coupling a diazotised amino compound of the formula (7) with a cou-pling component of the formula (8) to produce an azo compound of the formula HO
A-~=N ~ (~3H)m (10) ~ ~ } - ~ ~ H

condensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine-of the formula (4) and condensing the primary condensation product wi~h an amine of the formula (9) to produce a reactive dye of the formula (2);
2) condensing a coupling component of the formula (8) with 2,4,6-tri-fluoro-1,3,5-triazine of the formula (4), condensing tbe primary con-densation product with an amine of the formula (9) and coupling the secondary condensation product with a diazotised amino compound of the formula (7) to produce a reactive dye of the formula (2);

3) condensing a coupling component of the formula (8) with 2,4,6-tri-fluoro-1,3,5-triazine of the formula (4), coupling a diazotised amino compound of the formula (7) to the primary condensation product and condensing the resulting azo compound wi-th an amine of the formllla (9) to produce a reactive dye of the formula (2).

If the end reactive dyes of the formula (1) and (2) contain complex forming groups, they can subsequently be reacted with heavy metal donors.

The~particularly valuable reactive dye of the for~ula (3) is preferably obtained by process variant 2) by condensing 1-amino-8~hy-droxynaphthalene-3,6-disulfonic acid with cyanuric fluoride, condensing the primary condensation product with l-aminobenzene-3-~-sulfatoethyl-sulfone, and coupling diazotised 2-aminonaphthalene-1,5-disulfonicacid to the secondary condensation product.

,, ': ' .

.

- 9 ~ 34 As starti.ng materials for the manufacture of the dyes of the formula (1) there may be mentioned:

a) 2,4,6-Trifluoro-s-tria~.ine (cyanuric fluoride) of the formula

(4) b) Organic dyes of the formula (5) which contain sulfo groups 1. Monoazo compounds of the fonmula OH

!dO35 ~ - NHRl (Il) , wherein Dl is an at most bicyclic aryl radical which contains no azo groups and -NHR groups, Rl is hydrogen or Cl-C4 alkyl and the -NHR
group is preferably bonded to the 5-, 6-, 7- or 8-position of the naphthalene nucleus, and which additionally can contain a sulfonic acid group in the 5- or 6-position of the naphthalene nucleus.

Dl can be a radical of the naphthalene or benzene series which does not contain any azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylamlno radical. In this class, attention is also drawn to the related dyes in which the -NHR group, instead of being bonded to the naphthalene nucleus, is bonded to a benzoylamino or anilino group which is bonded to the 5-1 6-, 7- or 8-position of the naphthalene nucleus.

Particularly valuable starting dyes are those. wherein Dl is a sulfonated phenyl or naphthyl radical, especially those which con-tain a -SO3H group in the ortho-position to the azo bond. The phenyl radical can be further substituted, for example by halogen atoms, such as chlorine atoms, alkyl radicals, such as methyl, acylamino groups, such as acetylamino and alkoxy radicals, such as methoxy.

2. Disazo compounds of the formula (11), wherein Dl is a radi-cal of the azobenzene, azonaphthalene or phenylazonaphthalene series A_ . ~
3~

and the naphthalene nucleus is substituted by the -N~Rl group and, if desired, by sulfonic acid, as in class 1.

3, Monoazo compounds of the formula D - N - N ~ ~ N~Rl (12) , wherein Dl is an at most bicyclic aryl radical, as described in class 1, and is preferably a disulfonaphthyl radical or a stilbene radical, Rl is as defined above, and the benzene nucleus can contain further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido and acylamino groups.

4. Monoazo or diazo compounds of the formula H N Dl N (13) Rl , wherein Dl is an arylene radical, for example a radical of the azo-benzene, azonaphthalene or phenylazonaphthalene series or, preferably, an at most bicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or the radical of an enolised or enolisable ketomethylene compound (such as an aceto-acetarylide or a 5-pyrazolone) with the OH group in the ortho-position to ~he azo group, and Rl has the above meaning. Dl represents prefer-ably a radical of the benzene series which contains a sulfonic acid group.

5. Monoazo or diazo compounds of the formula Dl - N = N ~ Kl N~DRl wherein Dl is a radical of the types defined for Dl in classes 1 and 2 abo~e and Kl is the radical of an enolisable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group in the ortho-position to the azo group.

~\ ~

6. The metal complex compounds, for example the copper complexes, chromium complexes and cobalt complexes of the formulae (11) to (14), wherein each of Dl, K and Kl has the indicated meaning, and furthermore a metallisable group (for example a hydroxyl, lower alkoxy or carbo-xylic acid group) is present in the ortho-position to the azo group Examples Class 1:
6-amino-l-hydroxy-2-(27-sulfophenylazo)-naphthalene-3-sulfo-nic acid, 6-methylamino-1-hydroxy-2-(4'-acetylamino-2'-sulfophenylazo)-naphthalene-3-sulfonic acid, 8-amino-1-hydroxy-2-(2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2-(4'-chloro-2'.-sulfophenylazo)-naphthalene-3,5-di-sulfonic acid,

7-amino-2-(2',5'-disulfophenylazo)-1-hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2-(2'-sulfophenylazo)-1 hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2-(4'-methoxy-2' sulfophenylazo)-l-hydroxy-naphthalene-3-sulfonic acid, ~-~3'-aminobenzoylamino)-l-hydroxy-2-(2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid,

8-amino-1-hydroxy-2,2'-azonaphthalene-1',3',S',6-tetrasulfonic acid, 8-amino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic acid, 6-amino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic.acid, 6-methylamino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic acid, 7-amino-1-hydroxy-2.,2'-azonaphthalene-1',3-disulfonic acid, 8~amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)-naphthalene-3,6-disulfonic acid and 6-amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylaæo)-naphthalene-3,5-disulfonic acid.

Class 2:
8-amino-1-hydroxy-2-[4'-(2"-sulfophenylazo)-2'-methoxy-S'-methylphenyl-azo]-naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2-~4!-(4" ~ethoxyphenylazo)-2'-carboxyphenylazo]-naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2-[4'-(2"-hydroxy-3",6"-disulfo-1"-naphthylazo)-2'-carboxyphenylazo]-naphthalene-3,6-disulfonic acid, 4,4'-bis-(8"-amino~ hydroxy-3",6"-disulfo-2"-naphthylazo)-3,3'di-methoxydiphenyl and 6-amino-1-hydroxy-2-~4'-(2"-sulfophenylazo)-2'-methoxy-5'-methylphenyl-azo]-naphthalene-3,5-disulfonic acid.

Class 3:
2-(4'-amino-2'-methylp~enylazo)-naphthalene-4,8-disulfonic acid7 2-(4'-amino-2'-acetylaminophenylazo)-naphthalene-5,7-disulfonic acid, 4-nitro-4'-(4"-methylaminophenylazo)-stilbene-2,2'-disulfonic acid, 4-nitro-4'-(4"-amino-2"-methyl-5"-methoxy-phenylazo)-stilbene-2,2'-disulfonic acid, 4-amino-4'-(4"-methoxyphenylazo)-stilbene-2,2'-disulfonic acid, and 4-amino-2-methylazobenzene-2',5'-disulfonic acid.

Class 4:
1-(2',5'-dichloro-4'-sulfophenyl)-3-methyl-4-(3"-amino-4"-sulfophenyl-azo)-5-pyrazolone, 1-(4'-sulfophenyl)-3-carboxy-4-(4'-amino-3"-sulfophenylazo)-5-pyrazo-lone,l-(2'~methyl-5'-sulfophenyl)-3-methyl-4-(4"-amino-3"-sulfophenyl-azo)-5-pyrazolone, 1-(2'-sulfophenyl)-3-methyl-4-(3"-amino-4"-sulfophenylazo)-5-pyrazolo-ne, 4-amino-4' (3"-methyl-1"-phenyl-4"-pyrazol-5"-onylazo)-stilbene-2,2'-disulfonic acid, 4-amino-4'-(2"-hydroxy-3",6"-disulfo-1"-naphthylazo)-stilbene-2,2'-di-sulfonic acid, 8-acetylamino-1-hydroxy-2-(3'-amino-4'-sulfophenylazo~-naphthalene-3,6-disulfonic acid, 7-(3'-sulfophenylamino)-1-hydroxy 2-(4'-amino-2'-carboxyphenylazo)-- 13 ~

naphthalene-3-sulfonic acid, 8-phenylamino-1-hydroxy 2-`(4"-amino-2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid and 6-acetylamino-1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-naphthalene-3-sulfonic acid.

Class 5:
1-(3'-aminophenyl)-3-methyl-4-(2'~5'-disulfophenyl-azo)-S-pyrazolone, 1-(3'-aminophenyl)-3-carboxy-4-(2'-carboxy-4'-sulfophenyl-azo)-5-pyrazolone, 4-amino-4'-[3't-methyl-4"-(2"',5"'-disulfophenylazo)-1"-pyrazol-5"-onyl]-stilbene-2,2'-disulfonic acid and 1-(3'-aminophènyl)-3-carboxy-4-[4"-(2"', 5"'-disulfo~henylazo)-2"-methoxy-5"-methylphenylazo]-5-pyrazolone.

C~ass 6:
The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy-5"-sulfophenyl-azo)-naphthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2-:(2'-hydroxy-5'-sulfophenyl-azo)-naphthalene-3-sulfonic acid, the copper complex of 6-amino-1-hydroxy-2-(2'-hydroxy-5'-sulfophenyl-azo)-naphthalene-3,5-disulfonic acid, the copper complex of 8-amino-1-hydroxy-2(2'-hydroxy-3'-chloro-5'-sulfophenylazo)-naphthalene-3,6-disulfonic acid, the copper complex of 6-methylamino-1-hydroxy-2-(2'-carboxy-S'-sulfo-phenylazo)-naphthalene-3-sulfonic acid, the copper complex of 8-amino-1-hydroxy-2-[4'-~2"-suIfophenylazo)-2'-methoxy-5'-methylphenylazo]-napthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2-[4'-(2",5"-disulfophenyl-azo)-2'-methoxy-S'-methyl~henylazo]-naphthalene-3,5-disulfonic acid, the copper complex of l-(3'-amino-4'-sulfophenyl)-3-methyl-4-~4"~(2"'-5"'-disulfophenylazo)-2"-methoxy-5"-methylphenylazo]-5-pyrazolone, the copper complex of 7-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-~

.

(2"',5"'-disulfophenylazo)-2"-methoxy-5"~methylphenylazo]-naphthalene-3-sulfonic acid, the copper complex of 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-(2"-carboxyphenylazo)-naphthalene-3-sulfonic acid, the 1,2-chromiùm complex of 7-amino-6'-nitro-1,2'-dihydroxy-2,1'-azonaphthalene-3,4-disulfonic acid, the 1,2-chromium complex of 6-amino-1-hydroxy-2-(2'-carboxyphenylazo)-naphthalene-3-sulfonic acid, the 1,2-chromium complex of 8-amino-1-hydroxy-2-(4'-nitro-2'-hydroxy-phenylazo)-naphthalene-3,6-disulfonic acid, the 1,2-cobalt complex of 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-(5"-chloro-2'-hydroxyphenylazo)-naphthalene-3-sulfonic acid, the 1,2-chromium complex of 1~(3'-amino-4'-sulfophenyl)-3-methy1-4-(2"-hydroxy-4"-sulfo-1"-naphthylazo)-5-pyrazolone, the 1,2-chromium complex of 7-(4'-sulfoanilino)-l~hydroxy-2-~4"-amino-2"-carboxyphenylazo)-naphthalene-3-sulfonic acid~

.. . ..
.
Particularly important azo dyes which can be used for the production of thereaction dyes of the formula (1) are the azo dyes of the formulae (S03H)o_3 ,., N = N - K
~ : ~
'i " (15) , ~ _.
)H
H; Ol.H3; i~H-aCYl pH N (Rl )H
(HO3S )0~ N = ~ ~ (S03H) 1-3 and ; 3; CH3; ~H-acyl ,~(Rl)H
(H035) ~ ~ ~ ~ ~ (503H)o 3 (17) H3; NH-acyl wherein K is the radical of a coupling component of the benzene, naphthalene or heterocyclic ser~es, acyl is a low molecular aliphatic ~; acyl ~adical of notmore than 3 carbon atoms or an aromatic radical of ~- not more than 8 carbon a~oms and Rl i5 as defined for formula (1), and the metal complex azo dyes of the formulae A~ Me 9 N ~ (18) )0 3 .~ : 1' .xj N -H~OH, H; Cl; NO2 (S03H)1_3 : and (S03H)0_2 I ,D Cu--,0 = N ~NH2 ( or ~;IH-ac~l ) ~J (S03H)1_3 (19), ~Rl)H

wherein R and acyl are as defined in the formulae (15), (16) and (17) and Me r~presents Cu, Cr or Co.

7. ~nthraquinone compounts which ccntain a group of the formu-la -NHRl~ wherein Rl has the above meaning, bonded to an alkylamino or arylamino group, which is Itself bonded to ~he -position of the anthraquinone nucleus, in particular of the formula (20) ~IH-Z ' ~

wherein theanthraquinonenucleus can contain an additional sulfonic acid group in the 5-, 6-, 7- or 8-position and Z' is a bridge member which is preferably a divalent radical of the benzene series, for example a phenylene~ diphenylene or 4,4'-stilbene or azobenzene radi-cal. Preferably Z' should contain one sulfonic acid graup for each benzene ring present.

Examples l-amino-4-(4'-aminoanilino)-anthraquinone-2,3'-disulfonic acid and the corresponding 2,3', 5-, 2,3', 6- and 2,3', 7-trisulfonic acids, l-amino-4-(4"-amino-4'-benzoylaminoaniline)-anthraquinone-2,3'-disulphonic acid and the corresponding 2,3'5~~risulfonic acid, 1-amino-4-~4-'-(4"-aminophenylazo)-anilino]-anthraquinone-2,2",5-trisulfonic acid, l-amino-4-(4'-amino-3'-carboxyanilino~-anthraquinone-2,5-disulfonic acid~ 1-amino-4-(3'-aminoanilino)-anthraquinone-2,4',5-trisulfonic acid and the corresponding 2,4-disulfonic acid, 1-amino-4-['-(4"-aminophenyl)-anilino]-anthraquinone-2,3",5-erisulfonic acid, l-amino 4-(4'-methyl.--amino)-anilino-anthraquinone~2,3'-disulfonic ~cld and the correspon-ding 2,3',5-trisulfonic acid, 1-amino-4-(4'-n-butylamino)-anilino-anthraquinone-2,3'-disulfonic acid, 1-amino-4-(4'-methylamino-3'-carboxyanilino)-anthraquinone-2-sulfonic acid, 1-amino-4-(3'-~-hydroxyethylamino)-anilinoanthraquinone-2,5-disulfonic acid, 1-(4'-aminoanilino)-anthraquinone-213'-disulfonic acid and 1-amino-4-(4'-amino-2'-methoxyan.ilino)-anthraquinone-2,3'-disulfonic acid.

8. Phthalocyanine compounds of the formula Pc ~ (SO2- ~ ` (21) , ~ ( So2~H- Z ~~ )m wherein Pc denotes a phthalocyanine nucleus., preferably copper phthalo-cyanine,~ is -OH and/or -~H2, Z' is a bridge member9 preferably an aliphatic, cycloaliphatic or aromatic bridge, and each af n and m is 1~ 2 or 3 and can be identical or different, provided that the sum of n ~ m is not greater than 4.

, : ':
' The dye compounds of the phthalocyanine series which can be used as starting materials in the process of the invention are prefera-bly metal-containfng phthalocyanines, such as copper phthalocyanines, which contain at least one waterwsolubilising group, such as a sulfonic acid group, and at least one group of the formula -NHRl, wherein Rl has the above meaning. The -NE~l group or groups can be bonded direct or through a divalent bridge to the benzene rings of the phthalocyan-~ne nucleus,for example through a -phenylen-, -CO-phenylene-, -SO2-phenylene-, -NH phenylene-, -S-phenylene-, -O-phenylene, -CH2S-pheny-lene-, -CH20-phenylene-, -CH2-phenylene-, -SCH2-phenylene-, -SO2CH2-phenylene-, -S02-NR-phenylene-, -CH2-, -S02NR-arylene, -NRCO-phenylene-, -NRS02-phenylene, -S020-phenylene-, -CH2-, CH2NR-phenylene-, -CH2NH-CO-phenylene-, -S02NR-alkylene-, -CH2NR-alkylene-, -CONR-phenylene-, -CONR-arylene-, -SO2- or -CO- bridge. In the above divalent bridge members, R is hydrogen alkyl or cycloalkyl, arylene denotes a divalent aromatic radical which is unsubstituted or substituted, for example by halogen, alkyl or alkoxy, and wherein the terminal bonds may be attached to identical or different nuclei, and alkylene denotes a di-valent aliphatic radical which can include heteroatomss such as ni-:
trogen, in the chain of atoms, for example the radical -CH2CH2-NH-CH2-CH2-.

As examples of such divale~t aromatic radicals, which are referred to as arylene, there may be mentioned:
aromatic nuclei, for example a benzene, naphthalene, acridine and car-bazole nucleus, which can carry further substituents, and radicals o the formula ~ ~ (~2) wherein the benzene rings can carry further substituents and -D- deno-tes a bridging group, for example -CH=CH-~ -NH-, -S-, -O-, -SO2-, -NO-N-, -N~N-, -NH-CO-NH-CO-NH-, -O-CH2CH20- or N N
~ 3) -C C~
, Examples ~ . .
3-(3'-amino-4'-sulfophenyl)-sulfamyl-copper phthalocyanine-tri-3-sulfonic acid, di-4-(3'-amino-4'-sulfophenyl)-sulfamyl-copper phthalocyanine-di-4-sulfonic acid, 3-(3'-aminophenylsulfamyl)-3-sulfamyl-copper phthalocyanine-di-3-sul-fonic acid, copper phthalocyanine-4-N-(4-amino-3~sulfophenyl)-sulfonamide-4',4", 4"'-trisulfon;c acid, cobalt phthalocyanine-4-4'-di-N-(4'-amino-4'-sulfophenyl)-carboxamide-4",4"'-dicarboxylic acid, and copper-4-(4'-amino-3'-sulfobenzoyl)-phthalocyanine.
Mixtures of phthalocyanines~can also be used. For example, a mi~ture of approximately equal parts of copper phthalocyanine-N-(4-amino-3-sulfophenyl)-su~fonamide-tr~sulfonic acid and copper phthalocyanine-di-N-(4-amino-3-sulfophenyl)-sulfonamide-disulfonic acid can be used.

9. Nitro dyes of the formula o2N-D-N-Q (24)1 wherein D is a naphthalene or benzene nucleus which can be further substituted, the nitrogen atom N is in the ortho-position to the nitro group, Z is a hydrogen atom or an unsubstituted or subs-tituted hydrocarbon radical and Q is a hydrogen atom or an organic radical --bonded to the nitrogen through a carbon atom, and wherein Q and Z are not both hydrogen atoms, and Q can be bonded to Z, if Z is a hydro-carbon radical, or can be bonded to D in the ortho-position to the nitrogen atom N to form a heterocyclic ring, and which contain at least one group of the formula -NHRl, wherein Rl has the above meaning, in particular nitro dyes of the formula ~- NH-B-NHR (2~), ~

:' wherein V and B are monocyclic aryl nuclei and the nitro group in V is the ortho-position to the NH group.

Example 4-Amino-2'nitro-diphenylamine-3,4'-disulf~nic acid.

9. Metal complexes of formazane dyes of the formula N=N-A-Yl _ ¦ rRll C~ C / - t ~! l (n = 1 o~ 2) (26) , ~ 8--Y2 n wherein Q is an organic radical~ a nitro or cyano groùp, A and B are radicals of diazo components of the benzene, naphthalene or hetero-cyclic series and each of Yl and Y2 is a substituent which is bound in the ortho-position to the azo group and which is able to form a complex with a heavy metal, and Rl has the indica~ed meaning. The radical Q is especially a radical of the benzene series, such as phe-nyl or sulfophenyl, or a low molecular alkyl group, such as a methyl group, a low molecular alkanoyl group, a low molecular, preferably Cl-C4-carbalkoxy group, a benzoyl group or a heterocyclic radical, and A and B are preferably phenyl radicals which are substituted by sulfo, sulfonamido or alkylsulfonyl groups. Suitable substituents Yl and Y2 are above all the hydroxyl and carboxyl groups. Suitable heavy metals are copper, chromium, cobalt and nickel.

Examples the copper complex of 2'-carboxy-2"-hydroxy-3"-amino-1,3,5-triphenyl-formaæane-4'-5",3"'-trisulfonic acid, the copper complex of 2',2"-dihydroxy-3'-amino-5'-methylsulfonyl-1,3,5-triphenyl-3",5",4"'-trisulfonic acid, the copper complex of 2'-carboxy-4'-amino-2"-hydroxy-1~3,5-triphenyl-formazane-3",5",2"'-trisulfonic acid, , $~ 4 the copper complex of 2'-hydroxy-2"-carboxy-4"'-amino-1,3,5-triphenyl-formazane-4'-4"-disulfonic acid, the copper complex of 2',2"-dihydroxy-S"-amino-l~S-diphenyl-3-methyl-formazane-S',3"-disulfonic acid, the copper complex of 2',2"-dihydroxy-5'-amino-1,3,5-triphenylforma-zane-3'-3"-5"-trisulfonic acid, the copper complex of 2'-carboxy-3'-amino-2"-hydroxy-3"'(1""-phenyl-3""-methyl-pyrazol-S""-onyl-4""-azo)-1,3,5-triphenylformazane-3",5", 2"",5""-tetrasulfonic acld, the nickel complex of 2',2"-~icarboxy-1,5-diphenyl-3-(m-aminobenzoyl)-formazane-4'-4"-disulfonic acid.
~ he following diazo and coupling components are particularly suitable for the manufacture of the prefèrred reactive dyes of the formula (1), wherein D is the radical of an azo dye:
~iazo components:
aminobenzene, l-amino-2-, -3- or -4-methylbenzene, l-amino-2-, -3- or -4-methoxybenzene, l-amino-2-, -3- or -4-chlorobenzene, l-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene l-amino-3-methyl-6-methoxybenzene, l-amino-2-methoxy-4-nitrobenzene, 4-aminodiphenyl, l-aminobenzene-2-, -3- or -4-carboxylic acid, 2-aminodiphenylether, 1-aminobenzene-2-, -3- or -4-sulfonamide~
-N-methylamide, -N-ethylamide, -~,N-dimethylamide or -N,N-diethylamide, dehjdrothio-p-toluidine-sulfonic acid, l-amino-3-trefluoromethyl-6-sulfonic acid,l-amino-3- or -4-nitroben-zene7 1-amino-3- or -4-acetylaminobenzene, l-aminoben~ene-2-, -3- or -4-sulfonic acid, l-aminobenzene-2,4- and -2,5-disulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-amino-2-carboxybenzene-4-sul-fonic acid, l-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or -5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or -4-sulfonic acid, l-amino-3,4-dichlorobenzene-6-sulfonic acid, l-amino-2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-- 21 ~

sulfonic acid, l-amino-4-methyl-5-chlorobenzene~2-sulfonic acid, 1-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, l-amino-4- or -5-metho-xybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or -4-sulfonic acid, l-amino-6-ethoxybenzene-3- or -4-sulfonic acid, 1-amino-2,4-di-methoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfo-nic acid, l-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-ace-tylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid, 2-amino-1-methylbenzene-3,5-disulfonic acid, l-amino-4-methoxybenzene-2,5-disul~onic acid, 1,4-diaminobenzene-2,5-disulfo-nic acid, l-amino-3- or -4-nitrobenzene-6-sulfonic acid, l-aminonaphtha-lene, 2-aminonaphthalene, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid,2-aminonaphthalene-1-, -5-, -6- or-8-sulfonic acid, l-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,ô- or -6,8-disulfonic acid, l-aminonaph-thalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, 3,6,8- or -4,6,8-t~isulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-4,6-disulfonic acid~ 1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, l-hydro-xy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-hydroxy-2-amino-4-methyl-sulfonyl-benzene, l-amino-2-hydroxy-6-nitronaphthalene-4-sul~onic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2',4'-di-sulfonic acid; 3-methoxy-4-amino-6-methylazobenzene-2l,5'-disulfonic acid. --Coupling components-phenol, l-hydroxy-3- or -4-methylbenzene, 1-hydroxybenzene-4-~ulfonic acid, l-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxynaphthalene-6- or -7-sulfonic acid, 2-hydroxynaphthalene-3,6- or -6,3-disulfonic acid, l-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6-or -4,7-disulfonic acid, 1-amino-3-methylbenzene, 1-amino-2 methoxy-5-me~hylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, l-ami-no-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-di~
' aminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-suIfonic acid, l-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaph-:.
thalene-5,7-disulfonic acid,:l-amino-8-hydroxynaphthalene-2,4,6-tri-sulfonic acid, l-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid, l-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxy-naphthalene-7-sulfonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphtha-lene~7-sulfonic acid, 2-(~-acetyl-~-methylamino)-5-hydroxynaphthalene-7-sulfonic acid, 2~acetylamino-S-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxy-naphthalene-6-sul~onic acid, 2-methyl- or -ethylamino-8-hydroxynaphtha-lene-6-sulfonic acid, 2-(N-acetyl-~-methylamino)-8~hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sul~onic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8-hy-droxynaphthalene-3,6-disulfonic acid, l-amino 5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, l-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-di-sulfonic acid, 1-(3'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-(3'-nitrobenzoylamino)-8-hydroxynaphthalenè-3,6- or -4,6-disulfonic acid, 2-(4'-amino-3'-sulfophenylamino)-5-hydroxynaphthalene-7-sulfonic acid, 3-methylpyrazolone-(S), l-phenyl- -3-methyl-5-pyrazolone, 1-(4'-sulfophenyl)-3-methyl-5-pyrazolone, 1-(4'-sulfophenyl)-pyrazolone-(5)-3-carboxylic acid, 1-(3' aminophenyl)-3-methyl-5-pyrazolone, 1-(2',5'-disulfophanyl)-3-methyl-5-pyrazolone, 1-(2'-methyl-4'-sulfophenyl)-5-pyrazolone-3-carboxylic acid, 1-(4'~8'-disulfonaphthyl-[2']-3-methyl-5-pyrazolone, 1-(',7'-disulfonaphthyl-E 2']-3-methyl-5-pyrazolone, 1-(2',5'dichloro-4'-sulfophenyl)-3-methyl-5-pyrazolone, 3-aminocarbonyl 4-methyl-6-hydroxypyridone-2, l-ethyl-3-cynao- or -3-chloro-4-methyl-t-hydroxypyridone-2,1-ethyl-3-sulfo-methyl-4-methyl-6-hydroxypyridone-2, 2,4,6-triamino-3-cyanopyridine, 2-(3'-sulophenylamino~-4,6-diamino-3-cyanop~ridine, 2-(2'-hydroxyethyl-amino-3-cyano-4-methyl-6-aminopyridine, 2,6-bis-(2'-hydroxyethylamino)-3-cyano-4-methylpyridn, 1-ethyl-3-carbamoyl--4-methyl-6-hydroxypyridone~
(2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypridone-(2), N-acetoacetylaminobenzene, l-(N-acetoacetylamino)-2-methoxybenzene-5-sulfonic acid, 4-hydroxyquinolone-(2), 1-amino-8-hydroxy-7-(phenylazo)-naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7-(4'-sulfophenyl-azo)-naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7-(2'5'-disul-ophenylazo)-naphthalene-3,6-disulfonic acid.

Amines of the formula (6) .. . .. .
l-aminobenzene-2-, -3- or -4-~-sulfatoethylsulfone, l-aminobenzene-3-~-phosphatoethylsulfone, 1-amino-4-methylbenzene-3-~-sulfatoethylsulfone, l-aminobenzene-3-~-chloroethylsulfone, l-amino-4-methoxybenzene-3-~-sulfatoethylsulfone, l-aminobenzene-4-~-sulfatoethylsulfone-2-sulfonic acid, l-aminobenzene-5-~-sulfatoethylsuflone-2-sulfonic acid, l-aminobenzene-5-~-sulfatoethyl-sulfone-2,4-disu~fonic acid9 l-aminonaphthalene-4~-suIfatoethylsulfone, l-amino-2,5-dimethoxybenzene-4-~-sulfatoethylsulfone3 l-aminobenzene-4-~-sulfatoethylsulfone-2-carobxylic acid, l-aminobenzene-5-~-sulfatoethylsulfone-2-carboxylic acid, l-amino-2-methoxybenzene-4-~-sulfatoethylsulfone, l-amino-2-chlorobenzene-4-~-sulfatoethylsulfone, l-amino-2-methoxybenzene-5-~-sulfatoethylsulfone, 2-aminonaphthalene-8-~-sulfatoethylsulfone, 2-aminonaphthalene-8-~-sulfatoethylsulfone,6-sulfonic acid, l-amino-2,5-dimethoxybenzene-4-vinylsulfone7 l-amino-2-methoxy-5-methylbenzene-4-~-sulfatoethylsulfone, l-amino-2,5-diethoxybenzene-4-~-sulfatoethylsulfone, l-amino-2-bromobenzene-4-~-sulfatoethylsulfone, l-amino-2-bromobenzene-4 vinylsulfone, l-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, l-aminobenzene-5-~-phosphatoeathylsulfone-2,4-disulfonic acid, 1-2minobenzene-5-~-ch~oroethylsulfone-2,4-disulfonic acid, 2-aminonaphthalene-8-~-phosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid, l-amino-2-methoxy-5-methylbenzene-4-~-chlorethylsulfone~
2-aminophenol-4-~-sulfatoethylsulfone, l~aminobenzene-3- or -4-vinylsulfone, l-amino-2-hydroxybenzene-4-~-sulfatoethylsulfone, l-aminobenzene-S-vinylsulfone-2sulfonic acid, 3-(N-methyl-~-sulfatoethylsulfonylamino)-l-aminobenzene, 3-(N-ethyl-~ sulfatoethylsulfonylamino)-l-aminobenzene, 3 ~-sulfatoethylsulfonylamino-l-aminobenzene.

In the manufacture o~ the preferred reactive dyes of the formula (1), wherein D is the radical of an azo dye which contains sulfo groups, in particular of a mono- or disazo dye, the diazotisa-tion of the intermediates which contain a diazotisable amino group is usually effected by treatment with nitrous acid in an aqueo~s solution of a mineral acid at low te~perature, and the coupling is carried out at weakly acid or neutral to weakly alkaline pH values.

The condensation reactions of the 2,~,6-trifluoro-s triazine of the formula (4) with the organic dyes of the for~ula (5) which contain sulfo groups, or with the primary products thereof which contain a -N(Rl)H group, and the amines of the formula ~6),are pre-ferably carried out in aqueous solution or suspension, at low tempera-ture ancl at weakly acid or neutral to weakly alkaline p~ value, and such that a fluorine atom remains as remova61e radical in the end of the formula (1). The hydrogen fluoride which is liberated during the condensation is advantageously neutralisedcontinously by the addition of aqueous alkali hydroxides, carbonates or bicarbonates.

If the reactive dyes of the formula (1), wherein D is the radical of an azo dye which contains sulfo groups~ contains complex forming groups in the o,o'-position to the azo group, e.g. hydroxyl or carboxyl groups, it is also possible to obtain metal complexes of the a~o dyes of the formula (1) by treating the azo compounds which contain complex forming groups in the o,o'-position t~ the a~o g~oup, before, or optionally also after, the condensation with the 2,4,6-trifluoro-s-triaæine of the formula (4), with metal donors.

Copper complexes of azo dyes of the formula (1) are of parti-cular interest. A suitable method of metallation, in addition to that described above, is also that of dealkylati~g metallation and, for the production of copper complexes, oxidative coppering.

The dyes of the formula tl) are fibre-reactive, as they con-tain a removablP fluorine atom in the s-triazine radical.

By fibre-reactive compounds are meant those compounds which react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form ~ovalent cbemical bonds.

The dyes of the formula (1) are new. They are distinguished by high reactivity and produce dyeings having go~d wet- and lightfast-ness properties. They have in addition good fixation properties and produce dyeings of notably high tinctorial strength. The good build-up of the red azo dyes of the formula (1), in particular of those of the formula (2), on bleached cotton yarn, is to be singled out for special mention.

The reactive dyes of the formula (1) are suitable for dyeing and printing a very wide variety of materials, snch as silk9 leather, wool, polyamide fibres and polyurethanes, but especially cellulosic materials of Eibrous structure, such as linen, cellulose, regenerated cellulose, and especially cotton. They are suitable both for dyeing by the exhaust method and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous and9 if desired, also with salt containing dye solutions, and the dyes are fixed after treatment with alkali or in the presence of alkali, with or without the application of heat.

They are also suitable for printing, in particular on cotton, and also for printing nitrogen-containing fibres, for example wool, silk or blends containing wool.

It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if appropriate with the addition of an agent which acts as a dispersant and promotes the diffusion of non-fixed dye.

The manufacture of the mono- or disazo intermediates is not described in ev~ry case in the Examples, but it can be readily inferred from the foregoing description.

In the following Examples, the parts and percentages are by weight.

Exa~ple 1: 24.5 parts of the dye of the formula 03SCH2 ~ ~ - N ~ 1 L o OH ~H2 _¦ 2 Na (3 _ . .
are dissolved neutral in 400 parts of water. The solution is cooled with ice to 0-5C and then, at this temperature, 7.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise in the course of 15 min-utes, whilst keeping the reaction mixture at pH 5-6 with the simultane-ous addition of sodium hydroxide solution. As soon as no more starting dye can be detected by chromatographyJ 14.8 parts of 1-aminobenzene 3-~-sulfatoethylsulfone are added. A pH of 6 to 6.5 is maintained by continuously neutralising the liberated hydrogen fluoride with 2N sodium h~droxide solution and raising the ~emperature to 20C.
When the reaction is complete, the reactive dye is salted QUt with sodium chloride, collectad by filtration, washed and dried in vacuo.
It is a yellow powder and dyes cotton and regenerated cellulose in clear yellow shades.

Dyes with similar properties are-obtained by condensing the amino dyes of column 2 in Table 1 with equlvalent parts of 2,4,6-trifluoro-1,3,5-triazine and immediately thereafter with the amines of column 3 in accordance with the particulars of this Example.

__ ._ _ CO ~I ~ ~ ~ ~ ~ ,_ o _ _ _ ID
I I I I I I I ~ i I I ~-p r~ P ~ ~ P Y ~
C O 'C O 'd O ~ O ~ O ~ O O O C O ~ O
t P ~-- ~ Y ~ P 1-- P X P ~ P
P~ P p~ J p.) (D P~
~t p ~' p 5 ~ ~' ~ p~ r p. ~
~ 0 5 0 ~ J :~ O ~r r ~5' 0 :J
p N P N P P P N P~3 P::1 N ::1 ~D p ~ ~ ~ p ~D p~
Jl O1-- t--ID Y
`' CO ~ ~
CL~ N P~ ~ ~ t '~
Y~ ~' P
O
~:: C ~:: 5 ~ C ~ C C P.
~q ~ p ~0 pO p p ~ p pO ~D
n n n n n n n n n n n n n n n n n n l l l l l l l l l a ~ a ~ ~ ~ a 1 P P P P P P P ~ P
' 0l 0l 0l 0l 0l 0l 0l 0l _ _ ~ I C I ~ I ~ I ~ I
t~ Yp~ O
a . ~ p. ~ . p, .
O O O O O O P~ O O O ~-C ~ O
~ ~ :S' p ~ p~1~ P 0 5 P
O O O ~ N ~ N ~ Nrl N . ~ N
. . . ~ ~ ) ta ~ p ~
C ~ C ~ C ~ ._ I~ h O I O I O I~' I O
P ~:a P ~ ~ ~ P
I (D (D I p I ~ I

_ _ _ _ ~ P.
0 1- ~ O 1- 0 0 0 0 ~ ~ P
~ . ' O 1' On P

_ _ , ~ _ ~
' ~ 1~ ~ P
~n ~ ~~ ~ O ~ O
_ _ . . . I
I I ~ II 'q I I ~ I ~I I I I I ~ I I
~ ~ P~t ~I) pt~ tD P~S ~D ~P P t~ p ~1 ~ p~
p ~ 31~ ~ 3 ~ rr 31~ 3 5E3E~ E3 r~
O `- p' o ~ p' 0~ ~,<5 p' o~ ,~ ~,, p' ~ ~ p~ ~ . . P
~ ~nO p !--o ~ o ~ Po o o o o P o o rr o _ I t~) II rD I I ID I 3~ P P I P 1-- ~ ~ 1.-.
Zl I ~ I ~1.~) 1 ~ ~ I ~ 1-'~ P~ N 1'~ rD P P :~
~ . p 1~ I p ~ I p ~ I o s CJ' ~ ~ '1 ) p~
,~ n n ~ 3n --' C n `-- C 5 ~ rr ~
n ~^ . ,~
--~~ ~ ~ prt ~.nIt) rt ~n l-h ,~ ,Q~ N 1~ P I P P O
~ o~ O~C I O ~ I O W ~ (D ~ 3 Y U~ P
~n ~P ~ 3 p ~D ~ _~
p,1 3 o ~t 3 l t rt 3 J~ p C~ CJ 5 1 ~ ~ 5 1 1 ~ I O I 1 O _ P j,, o ::~ o ~ p o ~ ~ P a~
~ I ~ ~ C
)'' ~ p 3 ~ ~ 3, ~ I ~ I Pw ~I P Y `~ ~,, N ~_ ~ N ~ 3 NCl. 3 1~ h I O
o ~ o ::1 o rt ~D ~D fD ~ a~ 5 1~ 1'' ~:
p a~ 5 a~ p Y a~ ~-- a O C
'q I~C I ~ I I I p p p ~ ~_ ~~ C I :: p I C I n~ n, n p oh ~, 0 I ~ CS~ p ~ P
p p 1 ~
~ o 5 o ~ O. O ~ n n P n n 3 P ~ P ~' tt P ~ O ~ ~
p, O Y~ O ~ P. P P P
rt nIt n ~, X n X P n ~-- n o P X ~ I P I ~P~
n I n n i I ~ ~
~ ~ ~ ~ (D
~ ` .
1- w 1~
C I I I ~ I
~h 3 , ~ ~h P3 .
.,~ o o C o o o O O p P ~ O O
1~
cq p ~ rt ca p C ' ,~ ~5 C ' æ
@ ' C p P ' tPD
P

. ~ . .

~5 ~ C
~ ' ~D
I ~ ~ O O
O
~ P. ~ O O ~- P
o o o ~ ~ rr o .~ _,,,,_ _ __ ~
.

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

.

~ ~3 ~ ~~ O ~ C~ O cr~ -__ !--~ I~D
O )'~ O ~` ~I'~ N ~ N ~ _ ~. O ~ --~
~ ~, P ~ P ''CO P 3 o E. ~ P ~ ~ o g :r N ~ N1 N ' I 1~ O P~ ~' rt ~ r~ C
5i O ~ D J' (DC ~D P~
p, ~ ' ~ n ~ p, p ~ 3. ~ P
~ . ~ I-h P ~ P P P
_~ p P ~0 ~ P
~ ~ n a ~h O ~h ~D I N 11) p N~ N ~ N ~
' I n' I n ~ I ~:
o ~ ~
E. ~ C ~ ~ ~ I I n I ~C c ~ I
n ~ ~oh E ~ ~ ~ c ~ cPN~ 1-- ~ C
P~ I P P~ (D ~h CJ' I-h O l-h ~ Hl n ~ n- ~ ~ P ` I ~I n ~ n ~ O ~
E ~ P' P PE' E ' ~ ~ ' , _ _ . .
~, ~
o ~ ~
P. P~ ~ P. ~ ~ rr ~D
O O O O O O ~ p C, P' ~D

~ o ~ ~ ~ P. ~
o p, o o o . P
.__ _ l6;939~

- -~, W ~ ~ ~3 o ~ cO ~ n ~ ~ O
,. . . , ~ ~
~ p, ~,_ ~ p ,_ ~ ~ ~ ~ ~ ,_ .~, ~ ~ ~ Pl ~ ~
~ ,~ ~P ~ ~ 3 b~ ~ b b~ ~ b ~ b ~
l ' O ~ ~ O n I P O O Po' O E ~ o E ~ o ~ o ô
I ~ J X I I I ~ ~ ~ . I P
o ~ 1 I N ~q N p~ ~~. 3 3 ~ t~ 3 rc~ c ~ P ~I P ~ O ~ o ::J' O ~ P~
-- P ~ I tD O ~I) ~t ~ 1~ ~ I P~ I P~ X P~ rl O -- Co I ~ 1 5 O O O ~1 y ~.11 ~ ~ )_ 1., a I ~ X ~ p ~ o ~D ~ v P I ~D ~ P G ~ fD _ :J ~ I ~ C P tD P~ (D ~ I P~ I ~ I
I ~: ~ G ~ 1--Il) p ~ P It 1-- ~t W r~ ~-- .
: ~ O ~- ~ I-h I N ~ N O v O V ~ -~ 0 ~ p ~" p ~ V~n ~ J 1- 1 ~
p~ p ~ ~ I'~ D P ~ ~ ".
n ,c I ,~ ~P
J' ~- p ~ I P
~ ,~ ~ I n o ~o (D ~n r~ ~ rr 1'.
P~ ~ n ~ 1~ p ~ q ~ ca I ~ ~d ,~ ~ v ~ ~. Y ~I ~ P C P~ C ~ ~D
~D ~ p) ~ r~ ~ ~ ~ C P
n I o D I P o~ ~ ~ ~ ~ p ~ ~ p p p Op ~h n Y I O~ 1- 1 ~- p p~
c I P. o o ~ n ~I n ~ n .
~- ~n v ~ P P I I n a~ ~ ~ o~ ~ ~' n n ~h ~ I P I
I O Y~ P p~
p u~ ~ n ~ n n o po ~ C _ , ~
p P' O ~ ~ ~ P' n ~ ~ n p, . ~ p ~ ~ P~
c~ 'I o ~ ~ n ~' I 1, ~
P~ . .
3' ._ ._ __ _ __. _. __ ._.. _ .
~ I
p, p. a D cr ~D
O C O O O O O ~ P
. . . ~ . . .
CP
~1 _ . _ . .

~S ~D
p~ O
O O ~D O n o o P ~

n ~ o ~ z ~ ~
~ -- l--CI ~ 5 C I ~ P P~
IEll ~ 1 3 ~ I ~ ~ ~ ~ N
gP' ~ ~ P' ~ g ~ P- o P' ~ P' P' ~ ~ P o ~ O O :1 o o 3 1-- 0 3 0 0 0 0 1-~ ~ O
I X ~ I X ~ ~ X ~ P P
co 'q 1~ co ~ ~ 3 ~ ~- ~n ~ y ~ P' r~
~ X ~ ~ X o; ~ X ~ g O ~ p~
rt @~ P~ r~
o ~- o ~ o ~ ~ ~-O 'd Po~ O ~ Po P' 0 3' P P
p ~ P ~ J P cr ~
~ P ~ P ~0 P ~ ~ ~D p ~ I
:J' N p~ N X N:S' N I N O `' ~ ~ p ~p p~. p ~
p~ I C I P~ ~' ~?
~1) :1~ Il~ ~ ~ ~ ~D ~ ~ 1~ ~ U~ 3 p _ p _ ~- P ~ h I ~ C o~
p~ ~ ~ 1~ ,1~ _1 p.~ 1'- ~-- ,~ O
- n u~ o p ~ tn O ~ ~
P n tD
' nn' ~D
U~ OV~ O I O O O ~ ~ I~
~ P C P ~n p p p p, ,, ~.
Y ~ ~ n oh n oh n ~ n n n C ~' P P~ P Pl o P~ I
Y~ n 1~ n P n n n n u~
n ~' n ~ In ~ ~ ~ 3 ~ ~ C 1~

~ 1~ ~ ~ '`
I o .1 ~ ~ ~ G 1- n ~
c I ~ 1 5 I C
1-- ~ 5 ~
~h 3 `q N 3 0 3 0~ oP C P o o o o 0~ 5 ~ 0~ P 0~ 5 P
. ~: N P 1~ 3 Y w . ~c N
~3 p tn ~t C O ~ P
C ~ ~-- I'h 1 1~ P ._.
H7 ~ ~ ~ O ~ H~
pO I p~ ~ p I O
~D 0~

__ ___ ._ _ ~ U~
P .
0~ o~ 0~ ~ ~ ~ ~
~ rg~
~ P .
, .

, Y ~3 t~ ~ o ~ ~o ~ O P~
. . ~
~ 1~ 1-- ~ 1-- ~ ~-- ~ 1-- Y ~ --- ~ , c~ I I n I (D I ~ I ~7 c ~ ~ . ~ ~ ~ 5 q ~ ~ ~ ~ 5 ~_ n ~ . n ~ n P. ~.
O p ~ ~ p ~ P ~ O ~ ~ P ~ O
3 0 0 ~ ~ O P. I O ~h I O El I O O O
I I ~ C P
tD ~ ~ ~ 3 ~ ~ tD 3 y ~ rr, ~ 3~ n 5 ~ C 3 ~ ~ 5 ~ P
`~ D O ~ I O ~ o I _~ OI ~q I t ~c ~ I ~ n I ~ ~ I P~ ~
~ O CO ~ 0 3 ^ ~ ~ r 3 3 c ~ 3 ~ ~ p ~ ~ o 3 po PY~ ~
P P I o. I ~ ~ I o ~cl. I o ~
p~ P~ n ~ ~ X rS cr~ 3 ~ 5~ P ~ ~ p (D
5 5 El ~ ~ 3 ~ j 1 5 N
5 ~ rt pr~ X P ~ D 5 P 2 ~ ~ ~: ~ O ~ 0 ~1 ~ ~ ?:
fD ~ r' P 5 P~ 1~ D ~ P .i P !PD5 ~ 5 !~ ~ t5` O
I I P~ - I I P.
r1~ t1~ P 1-' p ~ PA ~
a~ co P ~ P ~P C~p `' I'~ ~D ., ~ 1~ I P I P P~ ~--1~ ~ p N~ p ~ N ~ N Y ~ l-h U~ O
~:: C ~ I ~I ~ P ~ P c P
n o o I ~ - ~ o E. E. ,t 1- c ,- c I C I P P~
n ~ h Yc ~ c n O~ O ~h O ~ h P~ ~ C O O P O ~h O r n n 1~ P 1~ PO P O O
n ~ n ~ PY~ P
o n pp, p, n n ~ n ~ n n1~ n ~ n ~ n P) n Y~ n . _ . _ u~ ~--c I
~ p.

O . ~ N @~
C P~ P' P~l ,.

. - . --- . . ... .. . _ _ ___ ._~ _ _ P~
C' C ~D
~ ~ ~ ~ C~ O' O
O O O O ~ 1- P
. . . . ~D ~) , P

, .. , _ .. . _ _. _ .. ... .__ . , . , " . ,~ .. , ,, , ., ... , _ . ~,.:. , _, . _, ~,, .. ,.. _ .. , _.. , , ~ _ ~ ., .. ,, ", . _.. . , _.. . .. .

~ a~ Z ~3 co ~ O O P~

C 3 1 ~ :1 3 P g P 3 ~:: 3 ~ g C ~ - 3 I~ O 1'` 0 ~ O 1'~
p p ~ p ~ p ~ P ~h P~h:1 ~ p ~
O O ~ O ~ O ~ O~D O O O O O O O _ O O
P 1 5 1 1 1 1 1 1 I P I P I ~ I I I ~5 n I oh I ~ I ~ I n I n I n I It I P
p~ p ~ W p~ n n ~ n _ I - n - n n _ c ~ P~
n I ~ I - I p. I ~ I ~
g ~. 3 P~ 3 ~ ~ ~ 3 ~ O' n ~P ~ P
P ~ P ~ P ~5 1-- :~ P ~ P ~ P
O P. O ~'~ O C~h ~ O O O ~ O
A n ~ ~3D ~ I p , ~ ~ ~ p, r n ::~
n n ~n :s o - n - ta n n ~ ~D
~ ,-- o ~ P II P P P
o~ ~ P. I n g~ ~ ~ ~ ~ ~
x x P ~ ~~ P 3 P3~ 3 2?
n oo ~ Y ~ ~
n ;:~~. II p p p ~ ,~.
P? ~ ~ ~ ~ ~ O O O O P
3 ~3 ~ p, :r~ I I I I o Po o ~ P P ~
P ~ ~ 3 ~ (D
r~ P
J 5 p o o C C :: C
,Q ~ ~ I I O O O O
C ~ p p p p p p ~ D
P P 5 ~ I l l I
o O It It ~ ~ ~
~ I
_ _ . .
.
.~ ~ C I C
~ P
1'' 0 g O o C ~D ~ ~ ~ ~p, ~ ~ P O o oo o o O ::~ p p ~ N ~ ' ~ W
n C tD c P~ p I p I
~ ~D I rD I

PP.
~ 3 ~, p. C O
O O C ~DO O O O C P
ID @ ~ ~D O

P

. ~ . .

.. . .

~ o ~
. ' _ _ CT
Y P~1~ ~ Y P~
3 1 3 1 .
P' EP~ C P~ p' ~} p' 3 ~_ o ~ Y~ O t~ O ~-~ O
P P P ~ ~h p,~ 3 ~ p_~ p O
O ~ O O O ~ O,Q O I O I O I O C
C I P I C I C I pP I p I ~ I P
n I P I P ~ l ~
~n ~ O ~ ~ O ~ O ~ ~ ,_:r p ~ p~ ~ C
n ~ . P~
I I I ~ I I I I I,~ I "~ I ,~ I rt po ~? ~ a ~ g~ P
n g C ~ o ~ Po ~ oPo o Po o P Po _, ~ I oh p~ I oh 3 oh rD ~ I I ~ I ~ . .
~ p ~ p ,~ ~ _ ~ _ ~ _ ~ I ~ 5 ~ I I
~ O ~n ~ n ~: ~ 3 3 ~1 O p~ I p~p7 I p~ i ~ r~ ~ rr1~ r~ ~
3n, ~ n, ~ 0~ ~ 0~ ~ O ~ !3, ~ ~ ~ o ~ Y. I E. I E. I o ~P ~ ~ o o n n n n n n o ~ p ~ ~ P' ~ ' P ~ ~, n _~ p rt~ ~ r~ o ~ o ~ o I O ~1-- 1-- ~ ::1' ~ ~ ~ 3 - p p- p o I I I
I ~
-~ o~
C ~h 3 ~ c I
p, ~ .
~ r~ p ~ rt P
P (OD ~r C (D cr oP' n 5 ~ 0~0~ 0~ 0~ 0~I-h ~ P
~ N ~ O ~ W
n ~ ~ E. u~ P ~i c I n C tD P ..
P I n ~ I
. _ Çl' ~ ~ ~ P. ~ ~ ~ ~
o o o o o o o c n . . . . . . . rD o P

_ _ . _ _ _ ~ Z
O ~ O cr~
_, _ . (D
W Z: ~ ~ Z ~ ,_ p, _ I ~ I P I Y
P 3. ~ . r~
o t~ P P ~ ~ o P~ 3 3 P~ ~ o ~ o P
O It ~ o rS I I ~ I r~
5 ,~ p W P' 1, , Y _ ~D _ i~' oh ~ oh C: 'S 3 ~ 3 P
~ h 5 ~h ~' o ~ ~
P ~ ~ I P ~ ..
,_ p ~ n OP .
~ I ~
Z ~ Z 3 ,~ ~
~ 0 ~ ~:
~ _ ~ _ '~ ~ ~
; ~ G 3 5 a ~
w o w o ~t o .~ P ~ p ~ ~ I
~ :
.~ . --~

u, ~ O ~r 1 C~ n' a~
.~ o~ P
~ ~ W ~ ~ I ~
: P I ~ I ., ~ I ~

: ~ ~, ~~ r.~
''~ . ,o o ~ o :
P
_ _ _ CO ~ ~3 ,_ o G
~ ~_ u~ ~ Q æ ~ ~ Z ~ ~ ~ ~ P. æ ~ ~ Z _ ID
5 ~ 1 0 - I
~ ~ ~ ~ q ~ ~ 7 ' ~ 5 ~ ~ q ~ 1-~C I o I n ~ I n ~ I n ~-- I n)~ I
O ~h 5 o ~ ~ o ~h n o~h n N ~- n n 3 P~ p ~ O P. ~ O It ~o ~n O ~: O ~D ~ O (D ~ O ~tD O ~ ~ O :~ O ~-Y X ~: ~ X ~ X ~~ X ~ ~ X
P 'd `-- ~ ~q ~ ~ ~ c~ p W I I I ~ q I p.
~ W _~ ~n ~ ~ I ~ ~ r~
I ~ I n ~ 3 CF:~ ~ 3 C E~ pO
o~ 1' tD o ~ oI Po ~ ~oh ~ o ~ I o _, C ~: I - ~~ I - ~ - ~ X
S \~ I S I S `' :
a ~o ~ ~-a ~ c ~-a C a ~a ~ ~ ~ ~ P ~ ~ ~ P ~ ~ ~ ~ ~ ~
`~ h O ~ h O --~ O --' O _' Y~
I P NO ~ IO O ~ I ~ I r~ I P
~h ~ P~ S Z~ ~ ~ S Z O Z O
O1-- P S ~D - S S
~ Ipp a I a I ~ ' ~
æ: ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ I
N
I ~ ~ S
~7~ O ~ I~ ~ O ~
- O - ~04 0 - B ~ ~ ~ O P.
`~ B I E3 ~ O El ~ ~a ~ ~ ~ ~ p 0 3 ~ N ~ P O S O
C~ ~ N X P~ ~ P
n I ~ ~ N _ p C
- O I -~
~C ~0~ p~, _ _ . _ .
C ~
O O
1~ Cr ~ ~ ~ ~ P~ ~ ~ P
O O O O O O 'C
~ I

.
, .
_ ~
~q P~
n ~D
P, ~ ~ ~ P, ~ ~. cr Op o o C ~ o~ o ::
. . (D ~ g c~ r~
I_ ~ r~
. ~ ~CC po . _ _ _ ~ Co Co ~ l . . . .. . 1~

C
n ~ ~o ~ W W ~ ~
~ 1~ ~
~ cn ~ O u~ O o c~ o c~ cn O _ ~
o o ~ ~ ~ ~ ~ C~ ~ ~ o ¢~ 3.`

O . . ~ N ~ : .
~'1 ._ : :
~ ___ ~
P~
O
o o o ~ o .. _. _ . _ ,, , 3~

. W ~ w ~o~: P~
~ W O C
. _ _ . _ _ _ "

:~ W 4 ~ 4 W P
; ~ ~ 1- 1 1 1 1 1 -~ ~' ~ D ~ 3 ZOD ~3 ~ w N N ~

. `'~ , W
.' .
`~ . _ C~

O O O ~ ~ ~ ~' , . C ~ ~D , ., OI ~
.

O, IDp O O O O
. . . . ~ g _~ 3 ~

I

~ 4 ~' C~ ~
~ ., ~ ~' c~ cn ~ o o o U~

~ , ~, , C P~
~CDI- ~

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

Example 2: 22 parts of 2,4-difluoro-6-(4'-~-sulfatoethylsulfonyl-phenylamino)-s-triazine are added at 20C to a neutral solution in 500 parts of water of 30.5 parts of the trisodium salt of the amino-azo dye obtained by coupling diazotised 2-aminonaphthalene-3,6,8-tri-sulfonic acid with 3-aminophenylurea in acetic acid medium, whilst keeping a pH value of 6 to 6.5 by the constant addition of 2N sodium hydroxide solution. The condensation is continued until no more starting dye can be detected by chromatography. The dye of the formula .~ \./ ~./ N \ / NH ~ ~ - N~--\ /--S02CH2CH20S03H
H0 S/ ~-/ \-~ \S0 H 2 is:salted out with sodium chloride, collected with suction, washed and dried. It dyes cellulose materials in very fast reddish yellow shades.

Table 2 lists further dyes which are obtained in analogous manner by reaction of the amino dyes in column 2 with the primary condenbat~
ion products of 2,4,6-trifluoro-1,3,5~triazine and amine in column 3.

.. . , . . . ... . . , . ... , .. ~ . ,.. .... . ~ .. .. ., , ... . . ~ .. .. ............ ..... .............. . ...... . . . . . .
.. .. . . .. .... .

-~ ...... ... . ~
CO _- ~ ~ ~' ~ ~ ~ o ~ _ P~ CT' p ~ ~ 2 3 ~D n I c a n I n I I 1 3 1 1 I p~ I I I _, I~
CL. 5 ~ 3 ~h ~ ~ 3 P. 3 IP3 ~ 3 3 ~ 3 3 3 3 tD `~: ~ O ~D ,`'` I'(D 1' rr ~ ~ Y~ O
I_ P ;:~ P P prr p5 ~ :1 p :S ~ p p r_ I O 1~1~ ~D P o5 0 ~ O O O O O O O 5' U~ I ~ f W \ ~ ~ ~ ~ W P~ W P~ W
P ~ I p~ ~ ~ ~ 3 ~ I ~:s I ro I ~
~ ~ P~ n 5 5 3 5 ~'~ ~ 3 ~ 3 5 3 5 O P. !- n ~ ~ , ~ rr p r~
P ~ I ID 1:~ 1 5 1 ~ p 5 0 5 rt S ~ 5 rt 5 X ~ ~ P3 P ~ P ~ ~ ~ P 5 P ~ P ~5 P
(~ ~ P? P P P P P I P N ,~ ~ p I p ~ p 3, l ~ C I a~ I ~ I N ~JI 3 ~ N I--~:LI O O I ~. p ~. 5 `. ` ~D`~ (D ~ fD '.
OIQ D' P 3 ~n N Ci~ ~ 00 CO p ~
P1:: rD p ~ ~I) `- 1~ 1 1 ~D 1 5 I rD
' P ~ r~ ~ P ~o ~ P ~ ~ O 1~
I ~ N 5:S' I (D I p ~ .
E ::~ 5 ~ t N C ~:: C ~ C C
I ~ p l-h l h ~ p ~h ~ ~ ~ p 3 C CIt~pO O O N O O
n ~ P ~
P~ I C I ~ o o n n n ~D n n g ,P~. E.
po ~ n n E. E. I' In, _ _ = ._ . . ~ _ _ n Y n ~ n P I t' I C ~ o -- P3 t r1 D~ ~ p r~ 3 ~h 3 t O 1'~ 0 ~ O !'~ I'' ~'' tD
_ P P X P ~ P P
t~ O O ~ O ~ O ~ O ~ O C~
~tD ~ ~tD1' ~ tD n t n ~ rt 3 P n p n P tD p t P O

tDtD tD tD tD tD IJ ~ tD Y ~ tD ;:1 rt p n P n ~ t~ Pt~ P ~
~ I E I,~ I I I o ~ ' ' ' ,~ ,' ' ' , tD I I I O O I I rt ptll O~ U~ . .ca ~
N C S C C t O
P ~ h :~
Irt rt rt rt rt r O O O O O
ItD tD tD tD tD
C ~ ~5 "~ 3, rt O
I-h C C C C~: rt rt ~ -h r O O O O O O D~
fD p p p p p C`l rttD t'D tD tDt~D
~q, ~ ~1`~ I~D tD
l l l l l ~
. t~
_ ~ CO
tD tD tD 3' fDt~A ~ tD t . tD tD
o 5 5 0 o 5 0 t~

~ ~ ~ rr ~ ~ ot .~ -- __ . . ~
_ . _.

,~ o ~
Y o ~ ,, . f' , . _ _ tD
~ ~ _~ ~ o, ~ 1-- ~ P Y ~ P~1-- 3 pt-- D.
c I l I c I I ~ n I ~: n I ~D n I 3 P~ r~ P 1~ P P~ P It Y~ p , 3 c ~ , 3 ~ 3 ~ ~ 3 P ~ ~ 5 ~ 3 ~
po ~ ~- p^ po ~ ~ I P' o ~. ~ P' o n ~ ~ o o ~ o~ ~q o ~ O ,_ o I o o n I I P I ~n Y c I I o I a~
P~ p rD g~ r ~ P ~ , ~ I~ r ~ ~ rl P 3 I n n ~p~ 3 ~ ~ I r,D I :~ l ~D ~
n1~ 3 n :~n 1~ N rt p I P~ ~: ,D P
n ~ ~ ~' O ~ ~ I n ~ ~ n c I ~ ~ D ~ ~ r.~ ~ ~ rt O ~ ~ r,~
O ~r,~ n Y~
3 t3 ~ I ~ ~ ~ o ~7~ ~ P rJ P ~J~ 0~ ~ 3 A r,q 3 ~ 1~ 3 1:1 ; L~tD rn O I ~ r~ I N ~ C1'~ .
~ p P I1-- 0 1~ ~ O I ~ 1'' ~ P
N"I Ul ~- p O1-~ Yr~O O ~h O r~ I O
~ q I'~rJ E- ~ tD P ~ tD
:1 rD ~ ~r~ 1'~ P 1-'rD C P ~h 3 PtD 1'~
D~ h P.1~ tD p~ 1~ 1 ~ N1~'~tD N I . P N
ra ~ ~ O ~I-h rD rD P rD ~ O tD
~ I rD oC --~ 5 P ~n o P r~ ~ P ~ n ~
rt r~r ~ ~ ~ r t1~ ~' p tD ~I~rD ~ ,U rD
~ r~ ~ ~h ~r~p7 1 _, p~ ~_P O ,~ ~ ~ r~ ;' 1~ D rA 5 I~) I rA O
p ~~ o p In ~ ~CD ~ A ' ,~3 A
rD ~rt tD ~ O ~I~ r,D 1-- O !--,~ n --~ l~ I o ~s o l~ ~ o I ~ ~h P ~ P H~ I p r ~ rD rD rD I n rD n .
1~ Iri I r~ ~ I I r~'~
cn ~ h 3 3 1~ C~
1~ 0 1' ~ 0t~ tD
tt~ pp p p p P P ~
Op OrD q rD O' O o rD
iJ~tD ~ ~ '"~ tD rt n P tD ID rr ~ pND
1'~rD oJ 05 i~ l O
~ C J` rD ~ t_ I rD rD O l n rD ~ P N rn ,_ rD ~ND p ~ , o ~-h p P fD !~h P rD rD I rr rt o l.n ~n I O 1.~.
rD I I ~ rt 51 c C ~C o r~ 1-- Y ~ ~n O
C ~ h P C t ~_ p ~ r t 1-- r1 ~h ~ rt o ~h 1 P rD tD rD P rN
rD jr rt ~ tD ;
~ rD
I I I r, t~
o rl rPD
. P~i ~n O ~ r~
U r L, rD ,~ r ~ i-- rD
o P O O 1~ O
r r ~D O P
o ____ ___ ,~ ~ _ , .

-- --:' . . _ , o ~3 o ~ Co ~I ~ ~ 5~
.. , ~ ~ , _ ~ ~ ~ p ~_ p ~ ~ D
O I a~
, r' C ~ ~ 3 ~3 ~ ~1, 3 ~' n rr o ~ , o :r p ~ rt 5 p 5 I P ~h ~ n 3 P~ ~ o o ~ o o oP~,-- op~ P o o ~ o ~ o 1-- ~ I p I~C ~ Xt~ , ~ p ~ p ~ P
fD p p~ 3 I n ` , ~ p ~P~ p ~ p~, p, p, ~ rr X ~ ~tD O N n:5~
P IP~ ~ I ~ I rt Icr~ ~Dp~ ~ ~ C
r~ ~ P. n O ~ r . o ~ co ~ t ~ ~ N I ~P~ 1-- 1- .
~C I p 1~ P I O h~ ,3 (D O
~ ~ 3' 0 P O ~ O pP~ p P
y. ~ ~ ~ ~r~ O ~ ~ C ~ P a) _ C P I o N ~ P ~ C 3 p, p, ~ i .
Y~ n Xr3 n ~ tD ~h o~ ~ p ~n o I ~n O P? rr ~ ~ ~ O ~ p o ~ I o o :: p ~
P a ~t 3:~(D a ~ tD ~ p ~ ,_ ,~-~ P P Y ~ ' ~D X ~ a" ~ "
P~ I ~ X ~ ~o X ~ G~
co 5 ~-- 5 ~ I n o ~ ~ @ ~ oh 5 ~' ~' I E. ~ o~ ~ ~ P
P~ Y ~ P r~ C ^ I n ^ X ~ ~ n ~ ~ Y ~ :r' It ~ ~ r~
OP I n P~ n I ~ P~
' X~D ~ ~ O ~ P. ~ P. p~ ~) n P E. n ~0 si Cn n ~' I I 1'~ tD ~ tD ,~} (D ~ ~ P
~ I ~ ~
. _ _ - . 4 _ ~'I I I C I C I O
C ~ O ~' p ~' ~
OO O O Y~ O ~' O Oq pcr~ ~ ~ n ~ n G P~
' P P ~ P c~ p rr.
N N N n N n N O
p~ ID
n P ~ P ~ P ~ P _, ~ D fD ~
~' l l l l l ~
C C C C ~ ~ O

ot O ot O O~ ~1 t3 a~ 'D
rr rr C

C C C C C O
h P ~ ~ ~ P
I ~ 1 1 ~' '~ I I ~

___ _ ___ ~ 5 '. ~ ~
~' ~0 Po' ~ ~ f~) tD ~ C ~D ~ ~
n o :L

, _, _ __ _ _ o ~ ~ ~ ~ V' _ _ _ ~
~ n I Ga N n I ~D p n n I u~ P~ C I
C 1~ (1) I N 1~ ~ ~ 5 Hl ~
~ p ~I P p ~ p~ po ~ p ~ o n O O O ~ ~ O ~ ~ ~D O ~ Y~ O P~ O
P ~ I ~h ~ I1-- C I ~ n X ~: P
1~ 5 ~ ~ 5 n n I rD rt I ~ ~, ~ 5 P~o~ Op 3 ~ I n I C~
n ~ P~
-- n P~ 5 ~ ~ 3 rr N ~ ~C P E~ , ~ I I , ~ :~1 P

Q CO :3 0~ ~ N ~ 1'1 1 1 . .
,~ l 3 o ~
D n ~ n ~ ~ p o~ ~ ~ o I ~ I
P~ N C ~1 N ~ ~ g(~) lo-h 0 ID ~ p ~ P tDP. ~ ~tl p CO P~
p ~ ~ I n ~
I ~ a~ ~ p ul ~ ~n C ~ !~ C P~ C~ C;~
;:~ 0 3 N
O C~~:J O rr `'I P I ~D
n' 'd ~ I n' ~
I n ~ I .
_ _ __ _ _ 1 . o~ c~
I C I I O
p ~ ' P~ :1 CJ' n C p P
n :~ ~ P ~ ~.
Ul N n N :~ O
~ ' P 5 ~5 3'D.' (D~ (~1 Il) ~ I I I o P P~ P It ~
J-O O
~, C ~ ~ O
~ Y~
O I I 1: N

P P~
~ .~ ~ ~
C C C n r~
." ~ O

,.
Example 3: 16 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved neutral in 400 parts of water. The reaction solution is adjusted to pH 4.5 and, with good stirring, 7 parts of 2,4,6-tri-fluoro-1,3,5-triazine are added dropwise at 0 to 3C. The liberated hydrogen fluoride is neutralised by the metered addition of 2N sodi-um hydroxide solution. As soon as no more free l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid can be detected, 10.6 parts of l-aminobenzene-3-~-sulfatoethylsulfone in 50 parts of water are ad-ded. The ~emperature is allowed to rise to 20-25QC and the pH of the reaction solution is kept at 4 to 4.5. When the condensati~n is complete, the dyestuff intermediate is coupled at 0 to 10C with 15 parts of diazotised 2-aminonaphthalene-1,5-disulfonic acid. At a final pH of 6.5 to 7, the dye of the formula . ~ 3H H~ ~H ~ - NH~
i, I t il i ~ \s02CH2CH20So3H
H03S ~ S03H

is salted out with sodium chloride, collected by filtration, washed and dried in vacuo. It is a dark red powder and dyes cotton and regenerated cellulose in bluish red shades of good wetfastness and good fastness to rubbing and light.

Diazo components whose coupling energy is sufficient for coupling in a pH range from 4 to 5.5 can be coupled to the primary condensation product obtained from coupling component and 2,4,6-trifluoro-1,3,5-triazine. The reaction with the amine then follows in the final step.

Table 3 lists further dyes which are obtained by reaction of 2,4,6-trifluoro-1,3,5-triazine with the coupling components of column 2, then with the amines of column 3, and finally by coupling with the diazo components of column 4.-_ , - , _ CO ~I ~ ~ ~ W ~ ~_ Z ~3 I~ I g ~D

~D O tD 0~ ~ O ~ O ~ P P w O O O 1~ J~ 5 1~- 5 n ~ El ~ rt n ~ ~-h `< p ~ p~q~ X P
P' ~ n' I n ~ ~ P' ~
_ ~ - .. 1-- 1 . I_ _ ~ n P~ a ~ a ~ ~ ~ p ~ ~ C ~ ~D p C O
oh g ~ ~ Ho~ oh ~ oh p o P !~
~ p N C 5 P N P N ~ 5 P N ~ N 1~-O 11~ D p(D p U~ 5 p g P
~ P 1' 1 ~

C

. C 1 0I p, . .~
o I n I I I n I cI I tf , O ~ ~

3- r~ P ~P I N ~p3 ~ rP~

~ ~ N P 1--`' I C C ~D P :~
n i I n C pO n n ~ n I . n n P
c~ ~ n . - ~ ~
o o o o o o o ~ ~

- 5~

26.8 parts of 1,4-diamino-2,5-dlsulfonic acid are dissolved neutral in 250 parts of water with the addi~ion of sodium hydroxide.
After addition of 2,8 g of disodium phosphate, 13.6 parts of 2,4,6-tri-fluoro-1,3,5-triazine are added dropwise at 0C in the course of 5 minutes while keeping the pH of the reaction mixture at 6 with 2N
sodium hydroxide solutiou. When the condensation is completP, a solution of 28 parts of 1-aminobenzene-3~-sulfatoethylsulfone in 100 parts of water is added and the pH is kept at 6.5 by the simul-taneous dropwise addition of 2~ sodium hydroxide solution. The tem-perature is allowed to rise gradually to 20C. Then 7 parts of solid sodium nitrite are added and, after this has dissolved completely, the reaction mixture is poured onto a mixture of 25 parts by volume of 10~ hydrochloric acid and 100 parts of crushed ice. A neutralised solution of l-ethyl-3-sulfomethyl-4-methyl~6-hydroxypyridone-(2)-5-carboxamide in 100 parts of water is then poured into the diazo solution. The pH is adjusted to 6.5 and the reaction mixture is stir-red at this pH value until the coupling is comple~e. The dye of the formula OH ~ N ~

is precipitated with sodium chloride and then isolated, dried and ground, affording an orange powder which dyes cotton from an aqueous bath in strong, slightly reddish yellow shades.

Table 4 lists further valuable dyes which dye cellulose in the indicated shades and which are obtained by using the amines of column 2 instead of l-aminoben7ene-3-~-sulfatoethylsulfone and the coupling components of column 3 instead of 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone-(2)-5-carboxamide after the condensation of 2,4,6-. .

trifluoro-1,3,5-triazine with 1,4~diaminobenzene-2,5-disulfonic acid.
Dyes with similar properties, but which produce more hy~sochromic shades on cellulose material, are obtained by using 1,3-diaminobenz-ene-4,6-disulfonic acid instead of 1,4-diamino-2,5-disulfonic acid.

, :, ' : . ' 3~

_ _ . _ , Z P~
. ,. __. . ___ _ . .. _. _ . _ _ . ~
t , 3, ~ , , rD
3, ~ ,3. o~ 3 N N 3 I N 3 ~ N N ~ N
P P' I ~ P
~ I Cpr ~ ~1 p ~ I O O I ~1 0 1 P
~ ~N p~ ;) N l-h ~ ~ ~ .
~ D 0,~ C ~ C
~ 3 ~ ~ ~
O O O ~- fD C ~0 0 ~ 5 h ~ ;. O
C C ~~ ~ ~ C ~ ~
o o I o l-h ~h ~ ~ pO , P 0~ ~0 __. _ . . .. _ _ ... ___ _____ _ ~ ~ o~ o o o 8 ~ ,_ Y co ~ ~n c ~
3 ~ o - ~ ~
, tutotU rc~ ~ ~ 3 ^ t I_ O ~ J ~ ~ t ~ o ~ n C ~ D
3' ~ ~ Co ~ O ~ t ~ 1 0 ~ aq I tu P t tU t I ta 1 I g (D ~ U l-h ~It P '~ i I El n 0 3 1 1 1 ~ ~ s N 3 ~

'~h C ~::1 ~ ~ ~ 5 ~ ..
~D Y h~ o ~, ~ ~ ~3 P
P tl~ :I tD Y I ~¦ ~ o n~ tD I Y
t~ t L

O O' ~~

. - .. _ .
C t~ ~ ::~
~ . ~ ~ ~
& n t~ t~ tl~ 5 ~ ~ ~0 ~D ,0~ O
_I_ rr , . ~ .. ___. - . - ~---; ' 1~ O' V`
~ 10 - P P P .
cl 5 ~ ~ P
tO (~ P~ r P p ~ ~_~

W O W r~ O ~ P- C
~ tD :~
C ~ I .. : .
P~ P' 5 O ,_ tD
~ ~ o~
o~
It~
pO ~h ,1 (D P
g~ E., P-, E ~ ~ n c p, W ~ ~

,1 o ~ ~ ~ 5 o cn , ~ o 11 ~ o o W~

; I ~ W ., ~ I'' ''' C

~ ICJ ~
t pO
c ~ c-. n . ~
., ~ .

. .

3~
~!-.
P' ~P' , ~ T
. ~ ~o ~o = ~

.

q33~

Example 5: 51.5 parts of aminophenylnaphthotriazole o the formula / ` ~\ N~32 are dissolved in 90O parts of water at pH 5. Then 13.6 parts of2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0C and the pH
is kept constant with 2N sodium hydroxide solution. When the reaction is complete, a solution of 7 parts of sodium nitrite in 50 parts of watèr is added to the reaction mixture,-which is poured onto 25 parts by volume of 10N hydrochloric acid and 100 parts of crushed ice. Any excess nitrous acid is destroyed after an hour with amidosulfonic acid.
To the diazo suspension are added 25.4 parts of 1-(4'-sulfophenyl)-3-me~hylpyrazolone ~5) and the pH is kept cons~ant at 5 with 2N sodium hydroxide solution. When the coupling is complete, 28 parts of 1-aminobenzene-3-~-sulfatoethylsulfone in 100 parts of water are added.
The pH is raised to 6.5 and the temperature is allowed to rise ~radually .. ...
to 20C, When the reaction is complete, the dye of the formula 3 ~ ~ ~ ~N~y,~r~ S03H
W~

NH ~

is salted out and isolated by filtration and dried. It is a yellowish orange powder which dissolves in water to give a yellow solution and dyes cotton in yellow shades.

The dyes listed in Table 5 are obtained in analogous manner -by diazotising the compounds of column 2 after treatment with the reac~ive component, reacting further with a coupling component of column 3 and finally condensing with the amine of column 4.

.. . . . - -- - :

3g~

_ .. . . ~_ ....
Cl~ Z P~
.... _ ~ _ ~D

O O O O O ~ a, . ~ ~ P
~U~ ..
3~
~ ;
~ . .
3 ~ c ~: C ~ C) O ~`
P' ~ I o I ~o o O p~ O fD n P~ ~ _ ~ ~ ~ :1 I-- O N ¦ ~ N 1` ~ O .
~n P ~ rt ~_ ~11 o N I ~.n O I ~ ~
~ _~ 5 ~ C Z ~ ~5 I I . . .! ... - -- . .. _ o o 8 ~ i:

Z ~

O s ~5 (D
I ~~~
_ .. ___ e~~ . ~ . __ Z ~ Z z ~ Z n S

~ _ ~

. . . _ .

'~ o ~ ~ P~
... ~ ~ ._ n ~ I N 5~ N 11 ~ . ~ ~cn n o ~ 1 o oo o o ~ ~ ~

. I-h3 Ih O-P 'd~ O . P

. _.. ,, _ , ,, _. _._.. . ....
3 ~ W ~ O
N -- ~:r ~Q. ~- ~'- _ ~ _ ~r - 1--O C ~ J C 'C ~ P
P ~ ~ I ~ ~ n ~ ~ @~ ~ p, PN~ ~ ~ N O ~ ~ 3 5 rt ~ O n o 5 1-- p N I rp a ~ n P~ ~` (D p p o po I~ O l_ I P C ~

E~ p P ~ 5 ~ I ~ p~
~ L . ._ _ .
W I ~: I C I ~ .

~ O O O O 1: ~D
, . ~ 1 .
C C C
O o O
~ 3 - __~
O :~
~ 0~ ~ ~

, .i ~ _ , .

..... ._ _ ~ ~3 ~ . ~n ~ O
_ _.__ _ ~

. N ( n C
P

.. . --` _.
P~ ~ I P P ~ g ~ ~ C:
P~ o ~ ~:S
,~ ~ I Iq ,: ': ~ ~ p'~ ~
~ O O l~h O
~ ~ ~, I (D I iD P
O~ ~ U~ ~ ~ ~
~ lot p~ I
~ ~X ~ _ ~ .

C~
.. O O O

tD S'S 'd O ~
P~ ~ ~
~ P~
. . O ~ ~ _ .~ . : ~
:~

_ - ~9 ~

E~ample 6: 28.1 parts of 1-aminobenzene-4-~-sulfatoethylsul~one are dissolved in 200 par-ts of water at pH 5. Then 13.6 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0C in the course of 5 minutes while adding 2N sodium hydroxide solution to ensure that the pH does not rise above 6. When the condensation is complete, a solution of 21 parts of the sodium salt of 1,3~diaminobenzene-4-sulfonic acid is added to the solution of the monocondensate.
Condensation is carried out at pH 5 until no more diamine can be detected, and the temperature is allowed to rise to 20C. The con-densation product, which still contains a diazotisable amino group, is then diazotised in accordance with the particulars of Example 4.
To the solution of the diazo compound are added 40.5 pa~ts of the disodium salt of l-acetylamino~8~ hydroxynaphthalene-3,6-disulfonic acid and coupling is subsequently carried out at pH 6 to 6.5. The dye of the formula C~3 ~ N = ~ ~ ~ F

H03S S03H NH ~ S02CH2CH20503H

is precipitated with potassium chloride, isolated and dried. It is a red powder which dyes cotton in brilliant red shades.

Table 6 lists further dyes of this invention which can be obtained by condensing, according to the procedure of this Example, 2,4,6~trifluoro 1,3,5-triazine firstly with an amine of column 2 and then with adiaminobenzenesulfonic acid of column 3. Diazotisation of the secondary condensation product and coupling of the diazo com-pound to the coupling component of column 4 yields reactive dyes which dye cotton in the light- and wetfast shades indicated in column 5.

. ~

~ 60 --_ _ _ . ___ _ _ , _ ~3 I~ O ~o co ~I a~ ~n ~ . ~ ~ ~_ O P~
. _ ............. . ~_ C, C
~' cr~
P~ . ~D
r~ P ~ ~
~~ o o ~ ~ ~ ~ o o o o o ~ p o o o o oo ' ~ W ' ' ' ~ W
~ ~D Y ~
C ~, ~ P~
~h ~ ~h ~
. ~ I ~ol .
.
. .. ,__ ~ ~ ~ 1-- U~ t~
C ~ C ~ C l' oh I ~ , oh i,~
O tl~ ~, P P
. ~ n ~ ' ~J
O O O ~ O O O O O O 1'~
~, ~o ~ ~o P' W
(D . P~ ~D ~ P
N N
o P :
_ I I
, . ,- _ Y~ 1 5 1 I C 1 1 1 ~ I ~: 1 11) 1 1 1 O
C tD ~h Pn~ n 5 ~ w w 1-- 0 0 ID !:L~ O,3 1'~ 1' N ~ 1--ttl N p l't It p~D O O O ~ O ~ I I
' ~ ;~ n' ~ ~ P n I lo - ~ - C C P
n p, ~ ~ ~ p, ~ P' ~ I I ~ I ~C I ~ ~h n 3 n ~ ~ n Ps 3- 3~ ~ tO I Y- ~ ~- o o O
' ~' O :1' ~' g ~ ~, I C ~n C O S ~ ~ O
I ~n ~ O 1~ Y I O ~h O O O ~ P
0~ D n n 3 o p r~ ~C ~ n (D p 0~ r~
P ~ I I C ::~
~ -o ~
,~ ~ C 3 1~: c ~ ~D
p p~ h ~ 3 ~ ~ .
p~ ~ ~ p rw O ~D n ~ O ~ '<:
~ E` ~ ~ ~, , C ~ ~ ~ D
~ p, ,_.~ o ~ l ~ ' p ,_ ~ ~ p D~ I ~ ~ P' ~ O~, ~ n I ~ '~ 3~ PN~
P (I~ b 5'(D I O O
' n P ~ ~ o t _1 ~D n ~:J I ~
n' I ~ . rOS ~: ~d p~
X I P~ I
I ~ ~ O ~JI
_ _ . ~;, . _ r~ O U~ O O ~ n co n It n rs It ~D o O 0~ g 0~ 0 oP' 0~ 1- rt ~ ~o ~o ' . P
.
. , ~ . _ .

0;3 L ~ o ~3 .
,.. C~
s~ ~ ~ o o o o e P

_ _ C ~ C~-P ~ ~ ~
oP~ ~ n t . p, p . P~ P
n o ~ N
Y` V' 1-` ~D
P. p ~ P
Pl O ~ ~ t ~ C
or~ F~ ~ c n ~
N ~- ~ I_~
5 0~ ~ p 'q P
~ Y~ p~
_, o I ~ n ~ ~t~ I O
C C ~ r~
~h ~h 11 ~ 3 ~D ~D I
~ ~ ~ .
, ~, ~
F~ i ~

,.. , ......... __ ., ~ O
(D ,_ ~ ~r P' ~1 Dyeing Procedure 1 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water while adding 0.5 part of sodium n-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting solution to a liquor pick-up of 75% and then dried.

The fabric is then impregnated with a warm solution of 20C
whi~h contains9 per litre9 5 g of sodium hydroxide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 ~o 101C, rinsed, soaped for a quarter of an hour in a 0,3% boiling solution of a non-ionic detergent, rinsed and dried.

Dyeing Procedure 2 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put into this dyebath. The temperature is raised to 40C and 40 parts of calcined sodium carbonate and another 60~parts of sodium chloride are added after 30 minutes. The tempera-ture is kept for 30 minutes at 40C. The-dyeing is rinsed and then soaped for 15 minutes in a 0.3% boiling solution o' a non-ionic detergent, rinsed and dried.

.

Claims (28)

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

1. A reactive dye of the formula (1) wherein D is the radical of an organic dye which contains sulfo groups, R1 is hydrogen or C1-C4 alkyl, R2 is hydrogen, methyl or ethyl, X is a radical of the formula -SO2CH2Ch2C1, -SO2CH=CH2, -SO2CH2CH2OSO3H, -SO2CH2CH2OPO3H or -N(R3)SO2-CH2CH2OSO3H, and R3 is hydrogen, methyl or ethyl, and the benzene or naphthalene radical can contain as further substituents in addition to X, Cl-4-alkyl, C1-4-alkoxy, halogen, nitro, hydroxyl, carboxyl or sulfo.

2. A reactive dye according to claim 1, wherein D is the radical of a dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, forma-zane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series.

3. A reactive dye according to claim 2, wherein D is the radical of a mono- or disazo dye.

4. A reactive dye according to claim 3, wherein R1 is hydrogen, methyl or ethyl, and each of R1 and R2 is a hydrogen atom.

5. A reactive dye according to claim 4 of the formula wherein A is a benzene or naphthalene radical, m is 1 or 2, n is O or 1 and P is O or 1, while the benzene or naphthalene radical ~ and the benzene radical ~ can contain as further substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, benzoyl-amino, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo, and X is as defined in claim 1.

6. A heavy metal complex of a reactive dye according to claim 1.

7. The reactive dye of the formula

8. A process for the manufacture of a reactive dye of the formula (1) wherein D is the radical of an organic dye which contains sulfo groups, Rl is hydrogen or Cl-C4 alkyl, R2 is hydrogen, methyl or ethyl, X is a radical of the formula -So2CH2CH2Cl, -S02CH=CH2, -SO2CH2CH2OSO3H, -SO2CH2CH2OPO3H or -N(R3)SO2-CH2CH20SO3H, and R3 is hydrogen, methyl or ethyl, and the benzene or naphthalene radical can contain as further substituents in addition to X C1 4-alkyl, C1 4-alkoxy, halogen, nitro, hydroxyl, carboxyl or sulfo, which comprises condensing, in any order, 2,4,6-trifluoro-s-triazine of the formula an organic dye of the formula which contains sulfo groups, or a primary product thereof, and an amine of the formula (6) to produce a reactive dye of the formula (1), and, if primary products are used, converting these latter into the desired end dyes of the formula (1).

9. A process according to claim 8, which comprises the use of organic dyes of the formula (5) which contain sulfo groups, wherein D is the radical of a DYE
of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, forma-zane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series.

10. A process according to claim 9, wherein the starting materials are organic dyes of the formula (5) which contain sulfo groups, wherein D is the rad-ical of a mono- or disazo dye, or which comprises condensing diazo components and/or coupling components which contain a -N(Rl)H group with the 2,4,6-trifluo-ro-s-triazine of the formula (4), and subssequently or after the further conden-sation with the amine of the formula (6), obtaining the dye by coupling with the other component or other components of the mono- or disazo dye respectively

11. A process according to claim 10, wherein the starting materials are organic dyes of the formula (5) which contain sulfo groups, wherein R1 is hydro-gen, methyl or ethyl, and amines of the formula (6), wherein each of R2 and R3 is a hydrogen atom.

12. A process according to claim 11 for the manufacture of a reactive dye of the formula (2), wherein A is a benzene or naphthalene radical, m is l or 2, n is O or 1 and P is O or l, while the benzene or naphthalene radical A and the benzene radical B can contain as further substituents alkyl groups of 1 to ~ carbon atoms, alkoxy groups of l to 4 carbon atoms, acylamino groups of l to 6 carbon atoms, benzoyl-amino, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo, and X is as defined in claim 8, which comprises reacting, in any order, a diazotised amino compound of the formula 2 (7) a coupling component of the formula 2,4,6-trifluoro-s-triazine of the formula (4) and an amine of the formula by coupling and condensation, to produce a reactive dye of the formula (2).

13. A process for the manufacture of a heavy metal complex of a reactive dye of the formula (1), which comprises reacting a reactive dye obtained accord-ing to claim 8 with a heavy metal donor.

14. A process according to claim 8, which comprises condensing 2,4,6-tri-fluoro-s-triazine of the formula (4) with an organic dye of the formula (5) which contains sulfo groups and condensing the primary condensation product with an amine of the formula (6).

15. A process according to claim 8, which comprises condensing 2,4,6-trifluoro-s-triazine of the formula (4) with an amine of the formula (6) and condensing the primary condensation product with an organic dye of the formula (5) which contains sulfo groups.

16. A process according to claim 8 for the manufacture of a reactive dye of the formula (1), wherein D is the radical of an organic dye which is composed of two or more components and contains sulfo groups which comprises condensing one component of the dye of the formula (S) which contains a -NH group, a 2,4,6-trifluoro-s-triazine of the formula (4) and an aminobenzene of the formula (6), and, in any step of the process, reacting the condensation product with the other component or components of the dye of the formula (5) to produce a reactive dye of the formula (1).

17. A process according to claim 16, which comprises con-densing a diazo component which contains a - ~ group with 2,4,6-trifluoro-s-triazine of the formula (4), diazitising the resulting condensation product and coupling the diazo compound to a coupling component, and reacting the resulting azo compound, before or after the coupling, with an amine of the formula (6).

18. A process according to claim 16, which comprises con-densing a coupling component which contains a - ~ group with 2,4,6-trifluoro-s-triazine of the formula (4) and coupling a diazotised diazo component to the condensation product and reacting the resulting azo compound, before or after the coupling, with an amine of the formula (6).

19. A process according to claim 16, which comprises con-densing a diazo component which contains a -NH group with a 2,4,6-trifluoro-s-triazine of the formula (4), and also condensing a coupling component which contains a - ~ group with a 2,4,6-triflouro-s-triazine of the formula (4) and diazotising the condensation product of the diazo component and coupling the diazonium compound to the condensation product of the coupling component and reacting the resulting azo compound, before or after the coupling, with an amine of the formula (6).

20. A process according to claim 8, which comprises condensing organic dyes of the formula (5) which contain sulfo groups and which contain further -?H groups in the radical D, with a corres-ponding amount of the 2,4,6-trifluoro-s-triazine of the formula (4), so that two or more s-triazine radicals are introduced into the dye molecule.

21. A process according to claim 12, which comprises coupling a diazotised amino compound of the formula (7) with a coupling compouent of the formula (~) to produce an azo compound of the formula (10) condensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and condensing the primary condensation product with an amine of the formula (9~ to produce a reactive dye of the formula (2).

22. A process according to claim 12, which comprises condensing a coupling component of the formula (8) with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) condensing the primary condensation product with an amine of -the formula (9) and coupling the secondary condensation product with a diazotised amino compound of the formula (7) to produce a reactive dye of the formula (2).

23. A process according to claim 12, which comprises condensing a coupling component of the formula (8) with 2,4,6-trifluoro-1,3,5-triazine of the formula (4), coupling a diazotised amino compound of the formula (7) to the primary con-densation product and condensing the resulting azo compound with an amine of the formula (9) to produce a reactive dye of the formula (2).

24. A process according to claim 22 for the manufacture of the reactive dye of the formula which comprises condensing l-amino-8-hydroxynaphthalene-3,6-disulfonic acid with cyanuric fluoride, condensing the primary condensation product with l-aminoben-zene-3-.beta.-sulfatoethylsulfone, and coupling diazotised 2-aminonaphthalene-1,5-disulfonic acid to the secondary condensation product.

25. A process for dyeing and printing which comprises the use of a reactive dye according to claim 1.

26. A process according to claim 9 for dyeing cellulose fibres.

27. A dyeing or printing preparation which contains a reactive dye accord-ing to claim 1.

28. The material, especially textile material, dyed or printed according to either of claims 25 or 26.