DE2302382A1 - REACTIVE COLORS - Google Patents

Description

DIPL.- "
LI .-! ..-;

- ■■ -..-. 1 B. YES ^ '- ■ - ■ - ■ -

- '■ <■ - <■ - .._ 31

Folder 23C85 - Dr. E.
Case Dd 24648

Imperial Chemical Industries Ltd. London, UK

Reactive dyes

Priority: 1/18/1972 - Great Britain

The invention relates to new reactive dyes and
in particular to new reactive dyes of the triphendioxazine series, which preferably have reddish-blue shades, but which can also have red and black shades.

According to the invention, dyes of the formula

3 09830/1102

ZBH -Y-X

Σ - Y - HH - Z

worm

H and H stand for Cl, CH ,, OCH, or SO ₅ H, where at least

a symbol stands for SO ₅ H,
η stands for 0 to 3,
ei stands for 1 to 4,
Ί. stands for a direct bond or a connecting atom or a connecting group,

Y stands for a benzene or naphthalene nucleus, and Z stands for a radical which is reactive with cellulose has cyclic core that directly / ailfch a CO or SO Linking group is bound to the NH group.

Examples of atoms or groups represented by X are 0, S, CH ₂ , CO, CH = CH, UHCORH, OCH ₂ CH ₂ O, IT = II,

^K \

(X ¹ = C1, OH or

or preferably NH.

The radical Z can be homocyclic, heterocyclic or mixed homocyclic-heterocyclic radical, which is bound directly to the NH group through a CO group and

309830/1102

which has at least one cellulose-reactive substituent bonded to the core. Examples of this are:-

2,2,3,3-tetrafluorocyclobutyl-carbonyl-, 2,3 »3-Trifluorocyclobutenyl-carbonyl-, 2,2,3,3-ietrafluorocyclobutyl-acryloyι-, 2,3-3ichloro-quinoxaline-5- or -6-sulfonyl-, 2,3-dichloro-quinoxaline-5- or -6-carbonyl-, 2,4 ~ dichloro-quinazoline-6- or -7-sulfonyl-, 2,4,6-trichloro-quinazoline-7- or -8-sulfonyl-, 2,4,7- or 2,4,8-1 ^^ 10 ^ -0111 ^ 201 ^ -6-8 ^^ 1 ^ 1-, 2,4-dichloro-quinazoline-e-carbonyl-, 1 ^ -Dichloro-phthalazine-ö-carbonyl-, 4, fj-dichloro-pyridaz-e-on-i-yl-, 2,4-difluoro-5-chloro-pyrimid-6-yl-, 2, ^ - dichloro-pyrimidine ^ -carbonyl-, 2-methyl-sulfonyl-5-chloro-6-methyl-pyrimid-4-yl-, 4 (4, 5'-dichloro-pyridaz-6'-on-1'-yl) benzoyl-, 4- (4 ', 5'-dichloro-pyridaz-6'-on-1'-yl) phenylsulfonyl- and in particular s-triazin-2-yl- and pyrimidin-2-yl- or -4-yl radicals, which at least one of the remaining 2-, 4- and 6-positions contain the following: a bromine or preferably a chlorine atom, a sulfonic acid group, a Thiocyanato group, an aryloxy or arylthio group, the has an electronegative substituent, e.g. Sulfophenoxy, sulfophenylthio, nitrosulfophenoxy, disulfophenoxy and sulfonaphthoxy, or a group of the formula

- S -V V (2)

wherein Y stands for a group of atoms which are necessary for the formation of a 5- or 6-membered heterocyclic ring, which carry substituents or a part of a condensed one

309830/1102

Can form ring system; or a quaternary ammonium or Pyridinium group; or a group of the formula

S ^ R ²
Il ^

-S-G-N (3)

where R and R ^ each represent the same or different alkyl, Cycloalkyl, aryl or aralkyl groups or R and R ^ together with the nitrogen atom form a 5- or 6-membered heterocyclic ring; or a group of the formula

-S-C

wherein R and R ^ can be the same or different and each represent a hydrogen atom or an alkyl, aryl or aralkyl group.

ring
In the case in which the pyrimidine or the triazine ring has only one such reactive substituent, said ring can have a non-reactive substituent on the remaining carbon atoms.

With a "non-reactive substituent" is a group meant that is bound by a covalent bond to a carbon atom of the triazine or pyrimidine nucleus, this covalent bond is not broken under the conditions that are required for the application of the reactive dye be used.

309830/110 2

Examples of such substituents are primary amino and hydroxyl groups as well as mono- or disubstituted amino groups, etherified hydroxyl and etherified ones. Mercapto groups. In the case of substituted amino groups, this class includes, for example, mono- and dialkylamino groups, in which the alkyl groups preferably have at most 4 carbon atoms and which can also contain substituents, such as hydroxyl or alkoxy groups, as well as phenylamino and taphthylamino groups, which preferably contain sulfonic acid groups. In the case of etherified hydroxyl and mercapto groups, this class includes, for example, alkoxy and alkylthio groups, preferably those with a low molecular weight, ie those with up to 4 carbon atoms, and phenoxy, phenylthio, haphthoxy or naphthylthio groups. Specific examples of all of these classes are: methylamino,
Ethylamino,
Dimethylamino,
ß-Hydroxyäthylamino-,
Di- (ß-hydroxyethyl) -amino-,
ß-chloroethylamino,
Cyclohexylamine-,
Anilino,

Sulfophenylamino, disulfophenylamino, K-methylsulfophenylamino-, ϊϊ-3-hydroxyethylsulfophenylamino-, Mono-, di- and tri-sulfonaphthylamino, SuIfo-o-tolylamino-, Carboxyphenylamino and sulfocarboxyphönylamino, H-w-sulfomethylphenylamino-, Methoxy, ethoxy and butoxy, phenoxy, methylphenoxy and chlorophenoxy and Phentylthi ο groups.

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Chlorine atoms and cyano, nitro, carboxy and carbalkoxy groups fall in the 5-position of a pyrimidyl radical also into the category of non-reactive substituents.

Another class of reactive groups is represented by the following formula:

/ \ ¹

C Cj I ^

1 l ^{k 6}

1 l »* ⁶

C C

L I

A ¹ A ¹

A ^{1 represents} Cl, Br or SO ₅ H,

B ^{1 represents} Cl, Br, SO ₅ H, OH ⁷ , HR ⁶ R ⁷ or SR ⁷ , R in each case independently represents H or an optionally

is substituted alkyl group, and R ^{7 is} H or an optionally substituted alkyl or aryl group, and

Q is an alkylene, arylene, or substituted arylene group stands, where the group - N - Q - N - also stands for

E ⁶ E ⁶

1,4-piperazinylene can stand.

Examples of groups represented by Q are:

Ethylene, trimethylene, hexamethylene, propylene, 2-hydroxy- and 2-sulfato-trimethylene, ß-Äthylenaminoäthylen, 1,5- iind 1,4-phenylene, 4-sulfo- and 4,6-disulfo-1, -3- phenylene, 2-sulfo- and 2,5-disulfo-1,4-phenylene, 4,8-disulfo-2,6-naphthylene and also 4 ₉ 4'-divalent radicals such as the following:

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Stilbene-2,2'-disulfonic acid,

Diphenylamine-2-sulfonic acid and -2,2'-disulfonic acid, Biphenyl urea-2,2'- and -3,3'-disulfonic acid, Diphenyl O2tid-2,2 * -disulfonic acid,

Diphenylmethane-3,3'-disulfonic acid, Diphenoxyethane-2,2'-disulfonic acid and Diphenyl-2,2'- and -3i3'-disulfonic acid.

The preferred dyes of the formula 1 are those of Formula:

(SO ^ HV ^{H G} l ^(S / ° 3 ^E) s

ί Ύ W \ \ ^Jmz

W \

fei H ^(S0 3 ^K) Q

where Z has the meaning given above, (p + q) has the value of 2, 3 or 4 and (r + s) has the value of O, 1 or 2.

The invention also relates to a process for the preparation of the new dyes, which is carried out by a diamino compound of the formula:

Cl

wherein the symbols R, R, X, Y, m and η are those given above Have meanings with 2 moles of a compound of the formula

Z-Cl (8)

3 09830/1102

wherein the symbol Z has the meaning given above.

The above process can conveniently be carried out by thin the reactants. aqueous medium at one of the reactivity of the compound of formula stirred (8) corresponding temperature which may be in the case of cyanuric chloride between O and 5 ° C, or, if acid chlorides or heterocyclic chlorine compounds with low reactivity are used, up to 5O ^C C or more can be. It is usually preferred w ä during the course of the reaction to add an acid-binding agent to neutralize the hydrogen chloride formed and maintain the pH between the limits of 5 and 8 »u.

The compounds of the formula (7) can be prepared by adding 2,3,5,6-tetrachloro-1,4-benzoquinone with 2 mol of a diamine of the formula

(9)

-1

in which the symbols R, R, X, Y, m and η have the meanings given above, and the dianilide obtained is heated in oleum to bring about a ring closure. Additional SO, E groups can be introduced during this process. Examples of diamines of the formula (9) which can be used for this purpose are: benzidine-2,2 ¹ - and -3,3'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4 , 4'-diaminoazobenzene-2-sulfonic acid, 4 _s 4'-diaminodiphenylurea-2,2- and -3,3'-disulfonic acid * 1,2-bis (4'-amino-2-sulfophenoxy) ethane,

309830/1 102

1,2-bis (4'-amino-2'-sulfophenylamino) ethane, 2,4-3is (4'-amino-3'-sulfophenylamino) -6-hydroxy-s-triazine, 2,4-bis (4'-amino-3'-sulfophenylamino) -6-chloro-s-triazine, 2- (4'-aminophenylamino) -4- (3 ^lf -amino-4 "-sulfophenylamino) -6-chloro-s -triazine,

4,4'-Diamino-2'-chlorodiphenylamine-3'-6-disulfonic acid, 4,3 '-Diamino- ^ - chlorodiphenylamiii- ^' -6-disulfonic acid _t 4,2 '-Mamino ^ -chlorodipherLylamin ^', 6-disulfonic acid, 4,4'-diaminodiplenylamine-2-cllloΓO-2 '-mettioxy-6,5-disulfonic acid, 4,4 ^l -diamino-3-ch.lorodiplienylamine-2', 5- disulfonic acid, 4,4'-diamino ^ -clilorodiphenylamine-e-sulfonic acid, 4,4-diamino-3,3'-dichlorodiphenylurea-2,2'-disulfonic acid, 4,4'-diamino-3 »3 '-dimetlioxydiphenylurea -2,2'-disulfonic acid, 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid and in particular compounds of the formula

(10)

and especially the formula

(11)

which can easily be obtained by adding 4-nitrochlorobenzene-2-sulfonic acid with an appropriately substituted phenylenediamine or naphthalenediamine, in particular m- or p-phenylenediamine monosulfonic acid, converts and the Reduced nitro group.

309830/1102

In special cases, the compounds of formulas (10) and (11) can be the following: 4,4'-diaminodiphenylaEiin-2,3'-disulfonic acid, 4,4 '-Diaminodiph.enylaiain-2-sulfonic acid, 3't4-diaminodiphenylamine-2,4'-disulfonic acid, 2 ', 4-Diaminodiph.en7land.n-2,5' -disulfonic acid, 3 ', 4-diaminodip] ienylamine-2', 4 ', 6'-trimethyl-2,5'-disulfonic acid, 2-amino-6- (4'-aminophenylamino) naphthalene-2 ', 4,8-trisulfonic acid, 1-Ämino-5- (4'-aminophenylaiiiino) naplitlialin-2 ', 4,8-trisulfonic acid, -4,4'-Diamino ^ -methoxydiphenylamine ^ '^ 5-disulfonic acid, 4,4 '-Diamino ^ -chlorodiphenylamine- ^', 5-disulfonic acid, 4,4'-diamino-3-bioethoxydiphenylamine-2'-sulfonic acid and 4,4'-Diablino-3-chlorodiplenylamine-2'-sulfonic acid.

Examples of compounds of the formula (8) which can be used in the process according to the invention are: 2.2 _t 3 »3-tetrafluorocyclobutylcarbonyl _{chloride Ϋ 2.2.3} » 3-tetrafluorocyclobutyl acryloyl chloride, 2.5 _i 3-trifluorocyclobut-1-enyl carbonyl chloride, as well as heterocyclic compounds which have at least 2 nitrogen atoms in the heterocyclic ring and which also have 2 or more halogen atoms, in particular chlorine atoms, of / at least one of them in ortho position to one of the nitrogen atoms, such as, for example

2,3-DiChIOrO-QuinOXaIIn -? - and -6-carbonyl chloride, 2,3-dichloro-quino: xaline-5- and -6-sulfonyl chloride, 2,4-dichloro-quinazoline-6- and -7-sulfonyl chloride, 2, iljD-trichloro-quinazoline -? - and -8-sulfonyl chloride, 2,4,7- and 2,4,8-trichloro-quinazoline-6-sulfonyl chloride, 2,4-dichloro-quinazoline-6-carbonyl chloride, 1 ^ -Dichloro-phthalaain-ö-carbonyl chloride, 2,4-Mchlo3X> -pyrimidine-5-carbonyl chloride, β- (4,5-dichloro-pyridaz-6-onyl-1-) propionyl chloride, 1- (4 ^l -chlorocarbonylphenyl ) -4,5-dichloro-6-pyridazon. " • 1 - (4 • -chlorosulfony! Phenyl) -4,5-dichloro-6-pyridazon ^

309 8 30/1102

- and -Trichloro-pyrimidine, 2.4 \ 6-trifluoro -5-ch.loropyriuiidin, 2 j 4,516-tetrachloropyrimidine, 2-methylsulfonyl-4-, 5-dichloro-6-methylpyrimidine, 5-methyl-2,4, 6-triehloropyrimidine, 5-ifit ro-2,4,6-tri chloropyrlmidine, 2,4-dichloro ^ -iutro-e-methyl-pyrimidine, 2,4-dichloro -5-nit ropyriaiidin, 2,4-, 6-iricliloro -5-cyanopyrimidine, 5-lthoxycarbonyl-2 ^ -dicliloropyrimidine, 2,4-Bickloropyrimidin-5-carlDonyl clilorid, Cyanurb rc mid,

Cyanuric chloride,

as well as the primary condensation products of cyanuric bromide or cyanuric chloride with ammonia, an alkali metal sulfite or thiocyanate or an organic mercaptan, one organic hydroxy compound or an organic primary

or secondary amine, such as:

Methanol,

Ethanol,

Isopropanol,

Phenol,

o-, m- and p-chlorophenol, o-, m- and p-cresol,

Or-, m- and p-sulfophenol, Thiophenol,

Thiοglycolic acid,

Biicethyldithiocarbamic acid, Mercaptobenzothiazole,

■ thioacetamide,

Methyl, dimethyl, ethyl, diethyl, n-propyl, isopropyl,

Butyl-, hexyl- and cyclohexylamine, Toluidine,

Piperidine,

. '! orpholin, -

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Methoxy ethylamine,
Ethanolamine,
Aminoacetic acid,

Aniline-2,4-, -2,5- and -3,5-disulfonic acid, Orthanilic, metanilic and suIfanilic acid, 2-, 3- and 4-aminobenzoic acid, 4- and 5-sulpho-2-amino'benzoic acid, 4- and 5-sulpho-o-toluidine, 5-amino-2-hydroxybenoic acid, 2-amino-ethanesulfonic acid, Aminonaphthalene mono- and disulfonic acids and Η-methylaminoethanesulfonic acid;

as well as the secondary condensation products of cyanuric chloride with alkali metal sulfites, alkali metal thiocyanates, phenols and thiophenols that contain an electronegative substituent,
and compounds of the formula

H -S - Cf "Y ¹ (12)

S / R ² W Χ H -SC- Ii (13)

H-S-C

1 2 ^ 4- 5
wherein X, B, R, R and R · ^ have the meanings given above

own.

■ 309830/1102

The new dyes in which Z represents a monochloroamino or substituted amino-s-triazine radical can also be obtained by treating the corresponding dye, in which Z represents a dichloro-s-triazine group, with ammonia or the corresponding primary or secondary Amine converts. The reaction can conveniently be carried out in an aqueous medium in the presence of an acid-binding agent. An excess of ammonia or amine can also be used, which then acts as an acid-binding agent. A temperature in the range from 30 to 60 ^° C. is usually suitable.

Examples of amines that can be used are:

Methyl, ethyl and dirnethylamine, ß-hydroxyethyl and di- (ß-hydroxyethyl) amine, ß-chloroethylamine,

Cyclohexylamine,

Aniline and H-u-sulfomethy! Aniline, o-, m- and p-sulfoaniline, 2,4-, 2,5- and 3,5-disulfoaniline, m- and p-sulfo-K-methylaniline, m- and p-sulfo-N-ß-hydroxyethylaniline, 4- and 5-sulfo-2-methyl aniline, 4- and 5-sulfo-2-methoxyaniline, 4- and 5-sulfo-2-chloroaniline, Anthranilic acid,

4- and 5-sulfo-2-aminobenzoic acid, 4-, 5-, 6-, 7- and 8-sulfo-4-naphthylamine, 1-, 3-, 5- and 7-3ulfo-2-naphthylamine, 1- Naphthylamine-3,6- and -3 * 7-disulfonic acid,

2-naphthylamine-3,6-, -4,8-, -5,7- and -6,8-disulfonic acid, i-naphthylamine-2,4,6-, -2,4,7-, -2, 5.7-, -3.6.8- and -4.6.8-

trisulfonic acid,

2-naphthylamine-1,3,7-, -1,5,7- and -3,6,8-trisulfonic acid,

as well as amines of the formula

309830/1102

^{E E}

Cl

wherein Q and Eg have the meanings given above and B "for an amino group, the radical of a primary or secondary amine or an etherified hydroxyl group. These amines can in turn be obtained by that one is a diamine of the formula

HH-Q-EH I I

(16)

with a triazine compound of the formula

¹ I.

N N

Cl converts.

Examples of such diamines of the formula (16) are intended to be be mentioned:

Ethylene, trimethylene and hexamethylene diamine, 2-hydroxy and 2-sulfato trimethylene diamine, Propylenediamine, Diethy le nt r iaain,

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πι- and p-phenylenediamine,

4-sulfo- and 4,6-disulfo-1,3-pkenylenediamine, 2-sulfo- and 2,5-disulfo-1,4-phenylenediamine, 4,8-disulf o-2,6-diaminonaphthalene, 4,4'-diaminostilbene-2,2'-disulfonic acid i

4,4'-Diaaiinodiphenylamine-2-sulfon- and -2,2'-disulfonic acid, ^, ^ '- Biaminodiphenylurea - ^^' - and -J ^ '- disulfonic acid,

4,4 * -Diaminodiplienyloxid-2,2 '-disulf oic acid, 4,4'-Biaminodiphenylmethan-3,5'-disulfonic acid, 4,4' -Diaminodipiienoxyätiian-2,2 '-dl sulfonic acid and 4.4 ^liters - Diaminodiphenyl-2,2 ^t - and -3,3'-disulfonic acid.

As examples of triazines of the formula ("0 are to be mentioned:

2-methoxy-4,6-dichloro-s-triazine, 2-v-Kethoxypropoxy-4,6-dichloro-s-triazine, 2-Fhenoxy-4 ₁ 6-dictiloro-s-triazine.

and the monocondensation products of cyanuric chloride with Ammonia or any of the amines in the penultimate

Paragraph were mentioned.

The new dyes in which Z is a group of the formula (5) can also be obtained by mixing 2 holes of a diamine of the formula (16) with 1 mol of the corresponding A dye in which Z is a group of the formula

A ¹

ι Ii ⁽¹⁸⁾

N _v N

ceht and with 2 KoI of a triazine of the formula

30 9830/1102

(19)

of which a number of examples above in the compounds the formula Z.Cl was given, condensed.

The above process can expediently be carried out in an aqueous medium at a temperature which can be in the range from 0 to 60 ^° C. and in some cases even higher, in accordance with the reactivity of the diamine of the formula (13) and of the triazine of the formula (19) · In general, it is desirable to add an acid-binding agent in order to neutralize the acid ζλι set free during the reaction.

The new dyes can be obtained from the medium in which they are produced have been, by conventional methods used for the isolation of water-soluble reactive dyes are isolated, for example by salting out and subsequent filtration and drying or by spray drying of the reaction mixture. If necessary, stabilizers, such as alkali hydrogen phosphates, or diluents, such as sodium chloride or urea can be added.

The new dyes can be used as reactive dyes for cellulosic textile materials, 'which they in bright reddish blue or red or black shades with excellent fastness to washing and light color when co-applied with an acid scavenger. They are particularly suitable for a

309830/1 102

Coloration of exhaustion. Because of its high tinting power, the amount of dye needed to achieve fairly deep shades used is small, which results in relatively economical dyeings.

The invention is further illustrated by the following examples in which the parts are expressed by weight.

example 1

(A) 3,10-bis (4 * -amino-3'-sulfoanilino) -6,13-dichlorotriphen dioxazine-4,11-disulfonic acid

A neutral solution of 7/2 parts of ^ -, ^ '2,3'-disulfonic acid and 2.5 parts of 2,3,5,6-tetrachlorobenzo-1,4-quinone in 50 parts of water is stirred for 6 hours at 50 ° C, the pH being kept at 6 to 7 by adding sodium hydroxide solution. The solution is then cooled and then 15 parts of salt are added. The precipitated product is filtered off, washed with 25% brine and dried at 80 ⁰ C.

10 parts of this product are added to 100 parts of 20% oleum and the mixture is stirred for 2 hrs and then added to 1C00 parts of ice and water at 20 ⁰ C. The precipitate is filtered off, washed with saturated brine, and dried at 80 ⁰ C. The product obtained will likely have the following formula:

SO, H

Cl

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(20)

The 4,4'-diaminodiphenylamine-2,3'-disulfonic acid used can be obtained by adding 4-nitrochlorobenzene-2-sulfonic acid condensed with 1,4 ~ phenylenediamine-2-sulfonic acid and reducing the nitroamino compound obtained.

(3) Preparation of the dye

A neutral solution of 8.9 parts of the product from (A) in 150 parts of water is added to a suspension of 4.0 parts of cyanuric chloride in a mixture of 160 parts of water and 40 parts of acetone at 0 to 5 ^C , and the mixture is' then 4 h at 0 to 5 ⁰ C stirred while the pH is maintained by addition of 6 to Hatriumhydroxidlösung. 7 It is then filtered. Then 90 parts of salt are added to the filtrate, and the precipitate is filtered off, washed with 30% saline and dried at room temperature.

The product obtained dyes cellulose textile materials in bright reddish blue shades with good fastness towards light.

Dyes giving similar hues are obtained when the cyanuric chloride used in part (B) is replaced by a equivalent amount of one of the following substances is replaced:

E.g. respondents

2 2,4-dichloro-6- (m-sulfoanilino) -s-triazine

3 2,3-dichloroquinoxaline-6-sulfonylchloria

4 2,4-dichloro-6-methoxy-s-triazine

5 2,4,5,6-tetrachloropyrimidine

6 · 2,4-dichloro-6-amino-s-triazine

7 2,4-dichloro-6-ß-ethoxyethoxy-s-triazine

8 2 ^ -Dichloro-ö-methylamino-s-triazine

9 2,4-dichloro-6-N-sulfomethylanilino-s-triazine

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Respondents

-G- (A - ', 8'-disulfonaphth-2-ylamino) -striazine

2- (2 ', 4 · -Dichloro-s-triazinylamino) -4- (2'-chloro-4 · p -silfoanilino-s-triazinylamino) benzenesulfonic acid 2- (2', 4'-dichloro-s-triazinylamino ) -5- \ Z '-chloro-4' - (2 ", 5" - ^ iSuIfoanilino) -s-triazinylamineq] benzene-1,4-disulfuric acid

Example 1 $

3 ', 4-diaminoaiphenylamine-2,4'-disulfonic acid (manufactured by Condensation of 4-nitrochlorobenzene-2-sulfonic acid with m-phenylenedianiinsulfonic acid and reduction of the nitro group) is used instead of 4,4'-diaminodiphenylamine-2,3-disulfonic acid used in example 1 part A. The product obtained presumably has the formula:

SO, H

(21)

If done in a similar manner to Example 1B with cyanuric chloride is condensed, then a product is obtained, the cellulosic fabrics in bright reddish blue Shades of color. Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the the following substances are replaced:

309830/1 102

E.g. respondents

14-2,4-dichloro-6- (m-sulfoanilino) -s-triazine

15 3 "e-dichloropyridazine - ^ - carbonyl chloride

16 2,4-dichloro-6-methoxy-s-triazine

17 '2,4-, 6-trichloropyrimidine

18 ■ 2,4- dichloro-6-amino-s-triazine

19 2 ^ -Dichloro-e-n-butoxy-s-triazine

20 2,4-dichloro-6-dimethylamino-s-triazine

21 2,4-dichloro-6-IT-methyl-m-sulfoanilino-s-triazine

22 2,4-DiChIOrO-G- (1 ', 5'-disulfonaphth-2'-yalmino) -s-triazine

23 2- (2 ^'iJ _y - ^{l -I)} iciiloro-s-triazinylamino) -4- (2 ^{l -chloro-4-1} -p-sulf oanilino-s-triazinylamino) benzene-1,5-disulf onsäizre

24 · 2- (2 ', 4- ^f -Dichloro-s-triazinylamino) -5- (2 ¹ -chloro-4 ·' - (2 ", 5" -disulfoanilino) -s-triazinylamino) benzenesulfonic acid

example

2,4 · '-Diaminodiphenylamine-2', 5-disulfonic acid (produced by condensation of 4-nitrochlorobenzene-2-sulfonic acid with 1 ^ -diaminobenzene- ^ - sulfonic acid and reduction of the nitro group) is used instead of ^ j ^ '- diaminodiphenylamine ^ ^ ¹ -disulfonic acid used in Example 1 Part A. The product obtained will likely have the following formula:

EEL

309830/1102

Venn it with cyanuric chloride in a similar manner to Example 1 Part B is condensed, then a product is obtained, the cellulosic textile materials also in bright reddish blue Shades of color. Similar dyes are obtained when the cyanuric grid is replaced by an equivalent amount of any of the following Substances is replaced;

E.g. action participants

26 2,4-dichloro-6- (m-sulfoanilino) -s-triazine

27 2,4-dichloropyriinidine-5-carbonyl chloride

28 2 ^ -Dichloro-ö-methoxy-s-triazine

29 2,3-dichloroquinoxaline-6-carbonyl chloride

30 2,4-dichloro-6-aniino-s-triazine

31 2,4-dichloro-6-isopropoxy-s-triazine

32 2,4-dichloro-6-ethylamino-s-triazine

33 2,4-DiChIOrO-G-O-SuIfoanilino-s-triazine

34 2,4-dichloro-6- (3 ', 6', 8'-trisulfonaphth-2'-ylamino) -s-triazine

35 2,5-bis (2'4 · dichloro-s-triazinylamino) -benzene-1,4-disulfonic acid

36 2- (2 ', 4 ^L -Dichloro-s-triazinylamino) -4- (2 ^L - • chloro-4 ^f -amino-s-triazinylamino) benzenesulfonic acid

Example 37

5.6 parts of 2,4'-diphenylamine-4-sulfonic acid (manufactured by Condensation of 2-nitrochlorobenzene-4-sulfonic acid with p-phenylenediamine and reduction of the nitro group) are used instead of 4,4'-diaminodiphenylamine - ^, 3'-disulfonic acid from Example 1 part A used. The product obtained will likely have the following formula:

309830/1102

<■ »

If it is condensed with cyanuric chloride in a similar manner as in Example ^Λ - Part B, then a product is obtained which also dyes cellulosic textile materials in reddish blue, bright shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances will:

For example, participants in the seaction

38 2,4-dichloro-6-amino-s-triazine

39 1,4-dichlorophthalazine-e-carbonyl chloride 4-0 2,4-dichloro-6-m-sulfoanilino-s-triazine

41 2,4,6-trichloro-5-cyanopyrimidine

42 2,4-dichloro-6-methoxy-s-triazine

43 2,4-dichloro-6 ~ ß-hydroxyäthylaaino-s-triazine

44 2,4-dichloro-6-phenoxy-s-triazine

45 2,4-dichloro-6- (3 ', 5'-disulfoanilino) -s-triazine

46 2,4-dichloro-6- (4'-sulfo-2 ^l -carboxyanilino) -triazine

47 2,4-bis (2 ', 4 ^l -dichloro-s-triazinylamino) benzene-1,5-disulfonic acid

48 2- (2 ', 4'-Dichloro-s-triazinylamino) -4- (2 ^L -chloro-4'-amino-s-triazinylamino) benzene-1,5-disulfonic acid

309830/1102

Example 4-9

δ, O parts of 3,4'-diamino ^, 4,6-trimethyldiphenylamine-2 ^! , 5-disulfonic acid (obtained by condensation of 4-liitrochlorobenzene-2-sulfonic acid with 1,3-diamino-2,4-, 6-trimethylbenzene-5-sulfonic acid and reduction of the nitro group) are used instead of the 4-, 4'-diaainodiphenylamine -2,3'-disulfonic acid used in Example Ί Part A. The product obtained will likely have the following formula:

CH

SO ₂ H i 3

ΛΛΛ

If it is with cyanuric chloride in a similar manner as in example 1 part B is condensed, then a product is obtained, the cellulose textile materials also in luminous colors reddish blue shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances will:

Respondents

2, ^ -Dichloro-S-methoxy-s-triazine

1- (4'-Chlorocarbonylphenyl) - ^ ·, ^ - 2,4 ~ dichloro-6- (m-sulfoanilino) -s-triazine

309830/1 102

E.g. Heaction participants

53 2 ₁ 4,6-trifluoro-5-chloropyrimidine

54 2,4-dichloro-6-amino-s-triazine

55 2,4-dichloro-6-p-sulfophenoxy-s-triazine

56 2,4-dichloro-6-ai- (β-hydroxyethyl) amino-s-triazine

57. 2,4-DichloiO-6- (2 ^L -methyl-5 ^L -sulfoanilino) -s-triazine

58 2,4-dichloro-6- (3 ', 6'-disulfonaphth-1'-ylamino) -s-triazine

59 2- (2 ', 4'-DicGloro-s-triazinylamino) -5- (2 ^L -chloro-4 · ¹ -m-sulfoanilino-s-triazinylamino) benzenesulfonic acid

60 2- (2 ^! _I 4 ^l -Dichloro-s-triazinylamino) -5- (2'-chloro-4- ¹ -amino-s-triazinylamino) benzene sulfonic acid

Example 61

.5.6 parts 4,4'-diaminodiphenylamine-2-sulfonic acid (manufactured by condensation of 4-nitrochlorobenzene-2 ^ sulfonic acid with p-phenylenediamine and reduction of the nitro group) are used instead the 4,4'-diaminodiphenylamine ^^ '- disulfonic acid of Example 1 part A used. The product obtained will likely have the following formula:

(25)

309830/1102

When treated with cyanuric chloride in a manner similar to in Example 1 Part B is condensed, then a product is obtained which cellulose in bright medium blue shades (i.e. greener than in Example 1).

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances will:

E.g. respondents

62 2,4-dichloro-6- (m-sulfoanilino) -s-triazine

63 2,4,6-tribromopyrimidine

64 2:, 4-dichloro-6-ynethoxy-s-triazine

65 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine

66 2,4-dichloro-6-amino-s-triazine

67 2,4-dichloro-6-ß- (ß-hydroxyethylamino) ethylamino-s-triazine

68 2,4-dichloro-6-ethoxy-s-triazine

69 2,4-DichloIΌ-6- (l r-methyl-p-sulfoanilino) -s-triazine

70 2,4-dichloro-6- (o-carboxyanilino) -s-triazine

71 2- (2 ', 4'-Dichloro-s-triazinylamino) -5- (2'-chloro-4-m-sulfoanilino-s-triazinylamino) benzene-1,4-disulfonic acid

72 2- (2 ', 4 ^f -Dichloro-s-triazinylamino) -5- (2'-chloro-

4 · -amino-s-triazinylamino) benzene-1,4-disulfonic acid.

309830/1102

example

5.8 parts of 4,4'-diaminoazobenzene-2-sulfonic acid are used instead of 4,4'-diaminodiphenylamine-2,5'-disulfonic acid in Example 1 Part A used. The product obtained presumably has the formula:

rHH,

/ S \

N = N

/ y SO ₃ H

(26)

It is condensed with cyanuric chloride in a manner similar to Example 1 Part B to give a dye which Dyes cellulosic textile materials in black shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances will:

Respondents

2,4-dichloro-6-methoxy-s-triazine 2,4-dichloroquinazoline-6-carbonyl chloride 2,4-dichloro-6-amino-s-triazine 5-methyl-2,4,6-trichloropyrimidine 2,4-Dichloro-6-m-sulfoanilino-s-triazine 2 ^ -Dichloro-6-p-chlorophenoxy-s-triazine 2,4-dichloro-6-ß-sulfatoethylamino-s-triazine

309830/1

For example, “respondents

81 2,4-dichloro-6-p-sulfoanilino-s-triazine

S2 2,4 - Mchloro-6- (2 ^l -carboxy-5'-sulfoanilino) ~ s-triazine

83 2- (2 ', 4 -'-dichloro-s-triazinylamino) - ⁱ {- (2 ^I --chloro-

4- '-m-sulfoanilino-s-triazinylamino) benzenesulfonic acid

84- 2,5-bis- (2 ', ^' - dichloro-s-triazinylauaino ^ lbenzene-

sulfonic acids

example 85

8.0 parts ^^ '- diaminodiphenylurea ^^' - disulfonic acid verden instead of the 4,4 -'-diaminodiplienylamine-2 ₁ 3 ^f -disulfonic acid in Example 1 part A used. The product obtained "probably has the formula:

SO ₃ H

(27)

Ss is made with cyanuric chloride in a manner similar to Example Part B condenses to give a dye which dyes cellulosic fabrics in reddish blue shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances is replaced:

309830/110 2

E.g. reaction participants

86 2,4-dichloro-6-amino-s-triazine

87 2,4-dichloroquinazoline-δ-sulfonyl chloride

88 2,4-dichloro-6-m-sulfoanilino-s-triazine

89 β- (4-, 5-dichloropyridaz-6-on-1-yl) propionyl chloride

90 2,4-dichloro-6-methoxy-s-triazine

91 2,4-dichloro-ö-m-sulfophenoxy-s-triazine

92 2,4-dichloro-6-li-methyl-β-sulfatoethylamino-rs-triazine

93 2,4-Dichloro-6- (2 · _i 5'-disulfoanilino) -s-triazine 94-2,4-DiChIOrO-S- (m-carboxyanilino) -s-triazine

95 2- (2 ', 4- ^l -Dichloro-s-triazinylamino) -4- (2'-chloro-4 -'- m-sulfoanilino-s-triazinylamino) benzene-1,5-di su if onic acid

96 2,4-bis- (2 ·, 4'-dichloro-s-triazinylamino) benzenesulfonic acid

Example 97

8.0 parts of 1 _{l of} 2-bis (4- ^l -amino-2'-sulfophenylamino) ethane (obtained by condensation of 2 moles of 4-Mtrochlorobenzene-2-sulfonic acid with ethylenediamine and reduction of the nitro groups) are used instead of the 4,4 '-DiaminodiphenylaBiin-2,3-disulfonic acid used in Example 1 Part A. The product obtained presumably has the formula;

CH ₂ CE ^ γ ^ -tf f γ r ί _{gH CH}

SO ₅ H

(28)
30 9 830/1102

Ss is treated with cyanuric chloride in a similar manner to Example 1 Part A condenses ", producing a dye" of the cellulosic textile materials colors in reddish blue shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances will:

E.g. respondents

98 2,4-dichloro-6-m-sulfoanilino-s-triazine

99 2,4-dichloroquinazoline-6-sulfonyl chloride

100 2,4-dichloro-6-methoxy-s-triazine

101 2,4,6-trichloropyrimidine

102 2,4-dichloro-6-amino-s-triazine.

103 2, A-- dichloro-6-ß-methoxyethoxy-s-triazine

104 2, ^ - dichloro-ö-cyclohexylamino-s-triazine

105 2,4-dichloro-6- (2 ', 4 -'-disulfoanilino) -s-triazine

106 2,4-dichloro-6- (m-ß-sulfatoethylsulfonylanilino) -s-triazine

10? 2- (2 ', 4 ^l -Dichloro-s-triazinylamino) -4-g ^l -chloro-4 · -

(2 ", 5" -disulfoanilino) -s-triazinylaBiinq] benzenesulfonic acid

103 2- (2 ', 4 ^l -Dichloro-s-triazinylamino) -5- (2 ^I -chloro-4 ¹ -

p-sulfoanilino-s-triazinylamino) benzene sulfonic acid

109

S, 0 parts of 1,2-bis (4 ^f -amino-2'-sulfophenoxy) ethane are used instead of the ^, V-diaminodiphenylamine ^^ '- disulfonic acid in Example 1, part A. The product obtained presumably has the formula:

309830/1102

SO, H

, Ov

CH ₂ CH ₂

S0, H

(29)

Condense with cyanuric chloride in a manner similar to Example 1 Part A to give a dye which Dyes cellulose textile materials in reddish shades.

Similar dyes are obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances:

Respondents

110 2,4-Diehloro-6-methoxy-s-triazine

111 2,2,3,3- ^ etrafluorocyclobutyl acryloyl chloride

112 2,4-dichloro-6-amino-s-triazine

113 2,4,6-trichloropyrimidine

114 2,4-dichloro-6-m-sulfoanilino-s-triazine

115 2,4-dichloro-6-isobutoxy-s-triazine

116 2,4-Mchloro-6-n-butylamino-s-triazine

117 2,4-dichloro-6-anilino-s-triazine

118 2,4-Dichloro-6- (5'-sulfonaphth-1-yiamino) -s-triazine

119 2- (2 ', 4 ^l -Dichloro-s-triazinylamino) -4-f2 ^I -chloro-4 ^l - (2 ", 5" -disulfoanilino) -s-triazinylajnino ~) benzene-1,5-disulfonic acid

120 2- (2 ^f , 4 ^f -Dichloro-s-triazinylamino) -5- (2'-chloro-4'-p-sulfoanilino-s-triazinylamino) benzene-1,4-disulfonic acid

309830/1 102

Example 121

Example 1 is repeated, but instead of adding salt a neutralized solution of 4.0 parts of m-aminobenzenesulfonic acid in 50 parts of water is used to precipitate the dye added, and the mixture is stirred for 4 hours at 30 to 35 ° C, the pH by adding sodium carbonate solution to B to is held.

The product obtained is identical to that of Example 2.

In ά? Τ following table, a number are described dyes previous examples which can be obtained in a similar manner, if one diamino-triphendioxazine the column first with cyanuric chloride and then with ammonia or an amine, as indicated in column 3, implements.

309830/1102

Example triphendioxazine of the formula

20th

Ammonia / amine

according to example no,

121/1 121/2 121/5 121/4 309 121/5 8 30 / 12.1 / 6 _i
CD 121/7 N » 121/8 121/9 121/10 121/11 121/12

Ammonia 6

Methylamine 8

N- (sulfomethyl) aniline 9

2-naphthylamine ~ 4, 8-disulfonic acid 10

2-amino-4- (2 ^l -chloro-4 ^< p ~ 8ulfo ~ 11

anilino-s-triazinylamino) benzene

sulfonic acid

2-Amino-5- [2'-chloro-4 '- (2 ", 5" -di-12 sulfoanilino) -s-triazinylamino ^ benzene-1,4-disulfonic acid

m-aminobenzene sulfonic acid ammonia

Dimethylamine

.14 18 20

N-methyl-m-aminobenzenesulfonic acid 21 2-naphthylamine-1,5-disulfonic acid 22 2-amino-4- (2'-chloro-4'-p-sulfo-23

anilino-s-tria.zinylamino) benzene-

1,5-disulfonic acid

Example triphendioxazine of the formula ammonia / amine

O CO OO CO O

121/15

121/14 121/15 121/16 121/17 121/18 121/19

121/20

121/21 121/22 121/25 121/24 121/25 according to example no.

21

22nd

25 2-Amino-5- [2 · --chloro-4 '- (2 ", 5" -

disulfoanilino) -s ~ triazinylamino] -

benzene sulfonic acid m-aminobenzenesulfonic acid

ammonia

Ethylamine o-aminobenzenesulfonic acid 2-naphthylamine-5,6,8-trisulfonic acid 2-amino-5- (2 ', 4'-dichloro-s-triazinylamino) benzene-1,4-disulfonic acid 2 ~ Amino-4- (2'-chloro-4'-aminotriazinylamino) benzenesulfonic acid

Ammonia m-aminobenzenesulfonic acid

Ethanolamine aniline-5 »5-disulfonic acid 5-sulfo-2-aminobenzoic acid

24

26th 1
- V) J
VYY
[ 50 52 55
54 55 56 58 40 2302382 45 45 46

Example triphendioxazine of the formula ammonia / amine

O
CO
OO
CO
O

121/26 121/27

121/28 121/29 121/30 121/31 121/32 121/33

121/34

121/35 121/36 121/37

23

24

It

2-Amino-4- (2 ', 4'-dichloro-striazinylamino) benzene-1,5-disulfonic acid

2-Amino-4- (2 '~ chloro-4 ^l -amino-striaziny! Amino) benzene-1,5-disulfonic acid

m-aminobenzenesulfonic acid

Ammonia di- (ß-hydroxyethyl) amine

4-sulfo-2-aminotoluene

1-naphthylamine-3 »6-disulfonic acid

2-Amino-5- (2 · -chloro-4'-m-sulfoanilino-s-triazinylamino) benzenesulfonic acid

2-Amino-5- (2'-chloro-V-aminotriazinylamino) benzene sulfonic acid

m-aminobenzenesulfonic acid

ammonia

ß-hydroxyethyl ethylenediamine

according to example no.

47 48

52 54 56

59

60

62 66

67

O NJ CO OO K)

Example triphendioxazine of the formula ammonia / amine according to example no.

CO
O
CD
CO
CO
O

121/58 121/59. 121/40

121/41

121/42 121/45 121/44 121/45 121/46 121/47

121/48 121/49

26th

27 N-methyl-p-aminobenzene-sulphonic acid Anthranilic acid

2-Amino-5- (2 ¹ -chloro-4'-m-sulfo * anilino ~ s-triazinylamino) benzene-1,4-disulfonic acid

2-Amino-5- (2 ^L -chloro-4'-amino- * striazinylamino) benzene-1,4-disulfonic acid

Ammonia m-aminobenzo1-sulfonic acid ß-sulfato ethylamine

p-Aminobenzenesulfonic acid 4-sulfo-2-aminobenzoic acid

2-Amino-4- (2 ^f ~ chloro-4'-m-sulfoanilino-s-triazinylamino) benzene sulfonic acid

2-Amino-5- (2 ', 4 · ~ dichloro-s ~ triazi ~ nyl-amino) benzene ~ sulfonic acid

ammonia

67 70 71

72

76 VM
Vn 78 I. 80 81 82 85 84 86 2302382

Example! Friphendioxazine of the formula ammonia / amine

121/50 121/51 121/52 121/53 121/54 309830 / 121/55
121/56 1 102 121/57
121/58 121/59 121/60 121/61

27

28 m-amine Qbea & oi-sulfonic acid
N-methyl-ß-sulfatoethylamine
Aniline-2,5-4isulfoic acid
m ~ amlnoben ζ oe acid

2-Amino-4- (2 · -cliloro-Λ ■ · -m-sulfoanilino-s-triazinylamino) benzene-1,5-cLisulf oic acid

according to example no.

88 92 93

95

2-Amino-4 ~ (2 · ^ '- dichlorotriazinylamino) benzene sulfonic acid

96

nn-aminobenzenesulfonic acid 98 2302382 ammonia 102 Cycloexylamine 104 Aniline-2,4-disulfonic acid 105 m-ß-sulfatoethylsulfonylaniline 106 2-amino-4- [2 '-chloro-4 · - (2 ^11, 5 "-
disulfoanilino ~ s-triazinylamino)
benzene sulfonic acid 107 -

Example triphendioxazine of the formula ammonia / amine 121/62

30983 121/63 • ο 121/64 121/65 121/66
121/67 121/68

121/69

28

29

M It 2-amino-5- (2 ^l -cnloro -4'-p-sulfoanilino-s-triazinylamino) benzene sulfonic acid

Ammonia m-aminobenzenesulfonic acid

n-butylamine

Aniline 1-naphthylamine-5-sulfonic acid

according to example no.

.108

112 114 116 117 118

2-Amino-4-C2 ^l -chloro ~ 4 ^l - (2 "5" -disul- 119 foanilino) -s-triazinylaminojbenzene-

1 _t 5-disulfonic acid 2-amino-5- (2'-chloro-4'-p-sulfoani- 120 lino-s-triazinylamino) benzene-1 _t 4-disulfonic acid

OJ CD K> GO OO N)

Example 122

Example 1 is repeated, but instead of a salting-out to precipitate of the dye is a neutralized solution of 5.4 parts of 1 ^ -Phenylendiamine, 5-disulfonic acid in 4-0 parts of water was added, and the mixture 4 h at 35 to 40 ⁰ C. stirred, the pH being kept at 6 to 7 by adding sodium carbonate solution.

Then a solution of 8.5 parts, 2,4-dichloro-6- (2,5-disulfoanilino) -s-triazine was added in 100 parts of water, and the mixture is then stirred at 4O ⁰ C, wherein the pH by the addition is kept at 6 to 6.5 by sodium hydroxide solution. Salt is then added to precipitate the dye, which is then filtered off and dried.

The product colors cellulose textile materials in bright reddish blue shades. It is identical to that of example.

In the following table a number of other dyes of earlier examples or isomers thereof are given, which can be obtained in a similar manner by reacting the diaminotriphendioxazine from column 2 with cyanuric chloride, reacting the product with the phenylenediamine mono- or disulfonic acid from column 3, and the product reacts with the triazine from column 4.

309830/1102 i

E.g. Triphendioxazine
the formula Diamine 122/1 20th 1,3-phenylenediamine
4-sulfonic acid 122/2 22nd Il 122/3 26th Il 122/4 27 Il · 309 8 30/1 122/5
122/6
122/7 28
21
24 •1
1,4-phenylenediamine
2-sulfonic acid
ti 102 122/8
122/9 24
26th Il
Il 122/10 28 Il 122/11 21 1,3-phenylenediamine
4,6-disulfonic acid 122/12 25th Il 122/13 23 Il

Triazine

according to the example

2-chloro-4-p-sulfoanilino 11 (isomer)

2-0hloro-4 ~ amino 36 "

2-chloro-4-m - sulfoanilino 83 "

Cyanuric chloride 96 "

2-chloro-4- (2 ^t _t 5 '"- dis- 107 sulfoanilino)

«24"

2-0hloro-4-m-sulfoanilino 59 "

2-chloro-4-amino 60 "

Cyanuric chloride 84 "

2-chloro-4-p-sulfoanilino 108 "

23

Cyanuric chloride
2-ghloro-4-amino

47

48

N) Ca)

O N) GO OO ΝΪ

Bap. Triphendioxazine the! formula

σ co oo co σ

122/14 122/15 122/16

122/17 122/18 122/19

2? 29 22

25 25 29

Diäffiin

, 3-ptoenylenediaiiiin-, 6-di sulfonic acid

1,4-Phexylenediamine-2,5-disulfonic acid Triezin

2-Cüloro-4 - (2 ', 5' -di sulfoanilino)

Cyanuric chloride

2-chloro-4-m-sulfoanilino 2-chloro-4-amino

2-Ghlö: po-4-p-suifoanilino

95

119

35

71

72

120

Example 125

540 parts (0.94 to 7 mole) of 4,4'-diaminodiphenylamine-2,5-disulfonic acid ^l are added to a slurry of 145 parts (560 mol) of magnesium in 2400 parts of water at 40 ⁰ C and then for 5 min at 40 ⁰ C stirred. Then 119.5 parts (0.486 mol) of chloranil are added together with 50 parts of ethanol. The mixture is st at 50 ⁰ C for 1 1/2 and then filtered, and then salted out with potassium chloride to 20% (G / Y). Then 70 parts of 56% hydrochloric acid was added and the precipitate is filtered off, washed with saturated Kaiinmchloridlösung and dried in vacuo at 70 ⁰ C. The product is st stirred with 4000 parts of 2N hydrochloric acid, 5, and then filtered, washed with 2N hydrochloric acid and 1000 parts of dried at 8O ⁰ C.

6.24 Parts of the product are added to 46.5 parts of 54.7% oleum igeai ', wherein the temperature is maintained below 20 ⁰ C, after which the mixture is stirred vigorously for 50 min at 40 + 1 ° C. The mixture is poured into 500 parts of ice and then salted out with potassium chloride up to 7% (w / v). The precipitate is filtered off and washed free of acid with saturated potassium chloride. The cake is slurried in saturated potassium chloride, filtered off, and slurried again in ethanol. Water is added up to 20% (G / 7), and the product is filtered, washed with acetone and dried at 6O ⁰ C. An elemental analysis of the product gives: C 27.1%, Ii 6.1%, Cl 5.9%, S 9.5%. Taking into account a moisture content of 21.2%, the theoretical values for ' ^G 50 ^H 16 ° 14 ^N 6 ^S 4 ^Cl 2 ^K 4 ^{: C 2} ?> 3%, N 6.4%, Cl 5.4% S. 9.7%.

A neutral solution of 4.0 parts (0.005 moles) of this product in 80 parts of water becomes a suspension

3098 30/1102

of 1.4 parts (0.0076 moles) of cyanuric chloride in a mixture from 30 parts of acetone and 100 parts of water below 5 ° C. were added. The pH is adjusted by adding 2N sodium carbonate solution held at 6.0 to 7> 0. The stirring will continued for 4 hours under these conditions. Excess Cyanuric chloride is filtered off and up to 30% (w / v) salted out. The precipitate is filtered off and saturated with Washed brine and then dried in vacuo at room temperature.

The product obtained dyes cellulose textile materials in bright blue shades with good fastness to it Licht and Vaschen.

Dyes with a similar hue are obtained when the cyanuric chloride used is replaced by an equivalent amount one of the following reactants is replaced, the temperature being adjusted so that the reaction during 4 at expires.

example

123/1 2,2,313-tetrafluorocyclobutyl carbonyl chloride

123/2 ß- (2 ^f , 2 ', 3', 3'-tetrafluorocyclobutyl) acryloyl chloride

123/3 4-Chloro-6-methyl-2-methylsulfonyl-pyrimidine

123/4 4,5-dichloro-6-methyl-2-methylsulfonyl-pyrimidine

123/5 - 2,3-dichloroquinoxaline-6-carbonyl chloride 123/6 β- (4,5-dichloropyridazon-6-yl) -1-propionyl chloride

123/7 6-Methyl-2,4-bis (methylsulfonyl) pyrimidine

123/8 5-Chloro-6-Biethyl-2,4-bis (methyl sulfonyl) pyrimidine

123/9 2,4,5,6-tetrachloropyrimidine

123/10 2,4,6-trichloropyrimidine 123/11 2,4,6-trifluoro-5-chloropyrimidine 123/12 2,4-dichloropyrimidine-5-carbonyl chloride

309 830/1102

example

123/15 2, .4-DiClIlOEO-O- (N-sulfomethylanilino) -s-triazine

1 23/14 2,4-PiClIlCIrO-S- (N-sulfomethyl-ai-toluidino) -s-triazine

123/15 2,4-dichloro-6- (N-sulfomethyl-o-anisidino) -s ^ triazine

123/16 2,4-DiChIOrO-S- (N-sulfomethyl-o-phenetidino) -s-triazine

12 * 3/17 2,4-DiChIOrO-O- (N-sulfomethyl-p-anisidino) -s-triazine

123/18 2,4-DiChIOrO-S- (m-sulfoanilino) -s-triazine

123/19 2,3-dichloroquinoxaline-6-sulfonyl chloride

123/20 2,4-dichloro-6-methoxy-s-triazine

123/21 2,4-Diehloro-6- (ß-ethoxyethoxy) -s-triazine

123/22 2,4-dichloro-6- (4 ', 8'-disulfonaphth-2-ylamino) -s-tria ζ in

123/23 2,4-dichloro-6- (3 ', 5'-disulfoanilino) -s-triazine

123/24 2,4-dichloro-6- (2 ', 5 ^l -disulfoanilino) -s-triazine

123/25 2,4-dichloro-6- (3 ', 6', 8'-trisulfonaphth-1-ylamino) -s-triazine

Participants of the type:

4-Γ2 »-Chloro-4 '- (A) -s-triazin-6'-ylaainoj -2- (2 ·, 4 ¹ -dichloro-

s-triazin-6'-ylamino) benzene sulfonic acid

example

123/26 3 ^M sulfoanilino 123/27 (2 ", 5" -DiSuIfoanilino) 123/28 Methoxy 123/29 (4 ^H -sulfophenoxy) 123/30 4'-phenoxy 123/31 4 · amino 123/32 (3 ⁿ , 5 "-disulfoanilino) 123/33 (4 "-SuIfoanilino) 309830/1 102

example H.

123/34 2,4-bis- (2 ·, 4 ^f -diciiloro-s-triazine-6 · -ylamina) - "benzene-sulfonic acid e

123/35 2,5-bis- (2 ·, 4'-dichlpro-s-triazin-6'-ylamino) -benzene-sulfonic acid

123/36 2,4-bis- (2 \ 4 ^l -dichloro-s-triazine-6 ^l -ylamino) -benzene-1,5-disulfonic acid

123/37 2,5-bis- (2 ^f , 4'-dichloro-s-triazine-e-ylamino) -benzene-1,4-disulfonic acid

Reaction participant of the type:

5-J2'-chloro-4 '- (A) -s-triazine-6 ^f -ylamino ^ -2- (2', 4'-dichloros-triazin-6'-ylamino) benzene sulfonic acid

example A. 123/38 3 ⁿ -sulfoanilino. 123/39 (4 ^W sulfoanilino) 123/40 (2 ⁿ , 5 ^M -disulfoanilino) 123/41 Hetkoxy 123/42 (4 ^W sulfophenoxy) 123/43 Phenoxy 123/44 Amino 123/45 ■ (3 ^M , 5 "-disulfoanilino)

Respondents of the type:

5- (2'-Chloro-4 · -A-s-triazine-6 · -ylamino) -2- (2'4 · -dichloro-striazin-6'-ylamino) benzene-1,4-disulf onic acid

Example A.
123/46 3 "sulfoanilino
123/47 4 "suIfoanilino

. 3 0 9 8 3 U / 1102

- ⁴ J-ρ -

example A. 123/48 2 ", 5" disulfoanilino 123Α9 Methoxy 123/50 4 ^ft -Sulfophenoxy - 123/51 Phenoxy 123/52 Amino 123/53 3 ", 5 ⁿ -disulfoanilino

Respondents of the type:

4- (2'-Chloro-4'-As-triazinylamino) -2- (2 ', 4'-dichloro-striazine-6 ¹ -ylamino) benzene-1,5-disulfonic acid

Example A

123/54 3 "suIfoanilino

123/55 4 "suIfoanilino

123/56 2 ^M , 5 "disulfoanilino

123/57 methoxy

123/58 4 "sulfophenoxy

123/59 phenoxy

123/60 amino

123/61 3 "» 5 "-disulfoanilino

Respondents of the type:

N- (2'-Chloro-4 · -B-s-triazin-6'-yl) -N '- (2', 4 · -dichloro-striazin-6'-yl) -1,2-diaminoethane

Example B.

123/62 2 ^f , 5'-disulfoanilino

123/63 3 ', 5'-disulfoanilino

123/64 3 ', 6', 8'-tri-sulfonaphth-1'-ylamino

• 309830/1

Reaction participants of the type:

H- (2'-Cliloro-4 · -B-s-triazin-6'-yl) -N '- (2', 4 · -dichloro-striazin-6'-yl) -1,3-diamino-2-sulfatopropane

Example B.

123/65 2 ', 5'-DiSuIfOaXIiIiIiO

123/66 3 ', 5'-disulfoanilino

123/67 3 ', 6', 8 ^f -Trisulfonaphth-1'-ylamino

Alternatively, the reaction product obtained with cyanuric chloride can be mixed with ammonia or the amine in Examples 121 and 121/1 to 121/69 or with the diamines and other triazine compounds described in Examples 122 and 122/1 to 122/19 are given, with a number of dyes with a similar hue and with similar fastness properties is obtained.

Example 124

5.0 parts of sodium acetate are 4,3'-diaminodiphenylamine-2,4-disulfonic acid ^I added to a neutral solution of 21.9 parts (0.061 koi) in 500 parts of water. 7.45 parts (0.030 mol) of chloranil and 80 parts of ethanol are then added, whereupon the mixture is ^{stirred at 65 to 70 °} C. for 1 1/2 hours. The mixture is cooled to room temperature and then 40 parts of hydrochloric acid (SG 1.18) are added, followed by the addition of 400 parts of ethanol. The product is filtered off and then washed well with ethanol and with acetone and then dried at 80 ⁰ C.

5.0 parts of this product becomes 134 parts of 20% Oleum added over 5 min, the temperature below

309830 / 110'2

20 ⁰ C is held. The mixture is stirred for 2 1/2 hours at 20 to 25 ° C. and then poured into 400 parts of water. 50 parts of potassium chloride are then added, and the precipitate is filtered off and washed with saturated potassium chloride solution. The filter cake is dissolved in 350 parts of water with pH 7.0 and filtered. Then 500 parts of saturated potassium acetate solution are added and the precipitate is then filtered off. The cake is slurried with ethanol to, filtered and dried at 80 ⁰ G.getrocknet.

Elemental analysis of the product gives C * 24.8; N «5 * 85; Cl = 4.9; S = 11.95%. Taking into account a moisture content of 17 »0%, the theoretical values for ^C 30 ^H 16 ° 18.2 ^H 6 ^S 5.4 ^Cl 2 ^K 5.4 ^{: C} = ²⁴ ' ⁸ *' ^H » 5.8; Cl »4.9;

s = 11.9%.

4.36 g of this product are reacted with cyanuric chloride in a manner similar to Example 123. The product colors Cellulose textile materials in bright blue shades, that go a little more red. They have similar lightfastness properties and are slightly ^ less washable than the product of example 123

Replacement of the cyanuric chloride in the above example by the reactants listed under 123/1 to 123/67 result in a number of dyes, all of which are similar Have shade and similar fastness properties.

Alternatively, the reaction product obtained with cyanuric chloride can be mixed with ammonia or those in Examples 121 and 121/1 to 121/69 listed amines or with the diamines

3098 30/1 1 0 * 2

and other triazine compounds used in the examples 122 and 122/1 to 122/19 are indicated, using a series of dyes with similar hues, was obtained.

309830/11 0 * 2

Claims (8)

Claims O) R and R stand for Cl, CH _x , OCH, or SO _x H, where at least one of the symbols stands for SO ^ H,
η stands for 0 to 3,
m stands for 1 to 4,
Σ for a direct bond or a bridge atom or a Bridge group stands,
Y stands for a benzene or naphtha left, and Z stands for a radical that is reactive with cellulose or cyclic core, which is directly / via a CO or SO ₂ - bridging group is bound to the NH group. 2. "Dyes according to claim 1, characterized in that Z stands for a heterocyclic radical which has at least has a cellulose reactive substituent attached to the core. 3 dyes according to claim 2, characterized in that that the heterocyclic radical is an s-triazine radical, 309830/1102 which a Chloratoai to at least one of the remaining 2, 4 and 6 positions. 4-, dyestuffs according to claim 3 »characterized in that that the heterocyclic radical is the 2, ^ - dichloro-s-triazin-G-yl radical is. 5- dyes according to any one of claims 1 to 4-, characterized characterized by having the formula (SO _x H) ₁ ZHH • -ff-ISHZ (HO ₅ S) ₁ , (6) where Z has the meaning given above, (p + q) denotes 2, 3 or 4 and (r + s) has the value of Has 0, 1 or 2. 6. Process for the preparation of the dyes according to Claim -1, characterized in that a diamino compound is used the formula (R) (7) 309830/1102 1
■ in which the symbols R, R, X, Y, m and η have the meanings given in claim 1, with 2 KoI a compound of the formula Z-Cl, in which the symbol Z is the. has the meaning given in claim 1, converts. 7. A process for the preparation of those dyes according to claim 1, wherein Z is an s-triazine nucleus, which is substituted by a chlorine atom and an amino or substituted amino group, characterized in that a dye according to claim 1, wherein Z is the dichloro-s-triazine group is, reacts with ammonia or an amine. 8. A process for the preparation of those dyes according to claim 1, in which Z is a group of the formula 0 C-H-Q-H-O Il I Il I ₆ I ₆ I Il (5) ₆ I ₆ ^{E E} i ¹ means in which
A ^{1 stands} for Cl, Br or SO, H,
B ^{1 represents} Cl, Br, SO ₅ H, OR ⁷ , HR ⁶ R ⁷ or SR ⁷ , R each independently represents H or an alkyl group which may be substituted,
R 'represents H or an alkyl or aryl group that substitutes can be, stands, Q is an alkylene, arylene, or substituted arylene group stands, where the group - N - Q - N - also 1,4-piperazinylene E ⁶ E ⁶ 309830/1 10'2 can mean »characterized in that you have 2 moles of one Biamin's formula (16) with Λ Hol of a dye according to claim 1 »wherein Z is a group of the formula I J A ¹ stands and lait 2 fetch of a triazine of the formula? 9 · Verwenäting the dyes according to claim 1 together with a satirical agent for coloring cellulose 3OS830 / 11O2