DE2302382C2 - Triphendioxazine fiber-reactive dyes and their use for dyeing cellulosic textile materials - Google Patents

Description

The invention relates to fiber-reactive triphendioxazine dyes according to the above The main claim and the use of these dyes for dyeing cellulose textile materials

SO ₃ H Cl

ίο Hen.

Fiber-reactive dyes that differ from a triphendioxazine chromophore of structure

SO ₃ H

are known, for example from US Pat. No. 2,927,035 (with reactive triazinyl groups), FR-PS 12 66 733 (with reactive dichloropyrimidinyl groups) and NL-OS 2 65 019 (with reactive chloropyridazinyl groups). Surprisingly, it has been shown that the Dyes according to the invention are much better absorbed on cellulose fibers and accordingly tie can achieve more color tones.

The dyes according to the invention preferably have reddish-blue shades, but also red and black shades are possible.

The dyes of the invention can be prepared by adding a diamino compound the formula

(SO ₃ H) ₁

Cl

in which the symbols R, R ¹ , X, Y, m and η have the meanings given above, with 2 mol of a compound of the formula

Z-Cl

(8th)

45

wherein the symbol Z has the meaning given above.

The above process can conveniently be carried out by placing the reactants in an aqueous medium in one of the ways above Reactivity of the compound of formula (8) corresponding temperature, which in the case of cyanuric chloride can be between 0 and S ° C or if Acid chlorides or heterocyclic chloro compounds with low reactivity can be used up Can be 5OC or more. It is usually preferred to add an acid-binding agent during the course of the reaction in order to neutralize the hydrogen chloride formed and the pH between the Keeping limits of 5 and 8. eo

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

NH ₂

65

(9) in which the symbols X and Y have the meanings given in claim 1 and η door is 0 or 1, and the dianilide obtained is heated in oleum to bring about a ring closure. _{Additional SO 3} H groups can be introduced during this process. For example, for diamines of formula (9) that can be used for this purpose are:

4,4'-diaminoazobenzene-2-sulfonic acid, 4,4'-diaminodiphenylurea-2,2'- and

-3,3'-disulfonic acid, l, 2-3is (4'-amino-2'-sulfophenoxy) alhan,

and in particular compounds of the formula

NH

SOjH

NH

(SO ₃ H),

NH ₃

(11)

where ρ stands for 1 or 2, which can easily be obtained by reacting 4-nitrochlorobenzene-2-sulfonic acid with an appropriately substituted phenylenediamine, in particular m- or p-phenylenediamine monosulfonic acid, and reducing the nitro group.

In special cases the compounds of formula (11) can be the following:

4,4'-diaminodiphenylamine-2,3'-

disulfonic acid, 3 ', 4-diaminodiphenylamine-2,4'-

disulfonic acid, 2 ', 4-diaminodiphenylamine-2,5'-

disulfonic acid and 3 ', 4-diaminod ^; 5 / henylamine-2 ', 4', 6'- methyl-2,5'-disulfonic acid.

Examples of compounds of the formula (8) used in Manufacturing processes that can be used are:

2,2,3,3-tetrafluorocyclobutyl

carbonyl chloride, 2,2,3, S-Tetrafiuorocyclobutyl-

acryloyl chloride, 2,3,3-trifluorocyclobut-l-enyl-

carbonyl chloride,

as well as heterocyclic compounds which contain at least 2 nitrogen atoms in the heterocyclic ring and which also contain 2 or more halogen atoms, in particular chlorine atoms, of which at least one of them is in the ortho position to one of the nitrogen atoms present, may contain, such as. B.

l ^ -Dichloro-quinoxaline-S- and

-o-carbonyl chloride, 2,3-dichloro-quinoxaline-S- and

-6-sulfonyl chloride, 2,4-dichloro-quinazoline-6- and

-7-sulfonyl chloride, SAo-trichloro-quinazoline -? - and

-8-suIfonyIchloride, 2,4,7- and 2,4,8-trichloro-quinazoline- 6-sulfonyl chloride,

2,4-dichloro-quinazoline-6-caΓbonyl chloride, l ^ -Dichloro-phthalazine-o-carbonyl chloride, 2,4-dichloro-pyrimidine-5-caΓbonylchloΓid, jJ- (4,5-Dicl.loro-pyridaz-6-onyl-l-)

propionyl chloride, l- {4'-Ch) orocarbonylphenyl) -4,5-dichloro-

6-pyridazon, W-chlorosulfonylphenylM.S-dichloro- 6-pyridazon,

2,4,6-tribiomo- and trichloro-pyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-methylsulfonyl-4,5-dichloro-6-

methylpyrimidine, S-methyl-iAo-trichloropyrimidine,

2,4-dichloropyrimidine-S-carbonyl chloride,

Cyanuric bromide, Cyanuric chloride,

as well as the primary condensation products of cyanuric bromide or cyanuric chloride with ammonia, an alkali metal sulfite or an organic hydroxy compound or an organic primary or secondary amine such as B .:

Methanol,

Ethanol,

Isopropanol,

Phenol,

o-, m- and p-chloroiftbenol,

ο-, m- and o-cresol.,

o-, m- and p-sulfophenol,

Methyl, dimethyl, ethyl, diethyl, n-propyl, isopropyl, Butyl, hexyl and cyclohexylamine, Toluidine,

Ethanolamine, Anilin-2,4-, -2,5- and -3,5-disulfonic acid, Orthanilic, metanilic and sulfanilic acid,

2-, 3- and 4-aminobenzoic acid, 4- and S-SuIfo-2-aminobenzoic acid,

4- and 5-sulfo-o-to! Uidine,

S-amino-2-hydroxybenzoic acid,

2-aminoethanesulfonic acid,

Aminonaphthalene mono- and disulfonic acids and N-methylaminoethanesulfonic acid;

as well as the secondary condensation products of Cyanuric chloride with alkyl metal sulfites. The new dyes in which Z is a monochloro amino or substituted amino-s-triazine radical can also be obtained by reacting the corresponding dye, in which Z Pir is a dichloro-s-triazine group, with ammonia or the corresponding primary or secondary amine.

The reaction can expediently be carried out in an aqueous medium in the presence of an acid-binding medium By means of being executed. An excess of ammonia or amine can also be used, which then acts as an acid-binding agent. A temperature in

Range of 30 to 6OC is usually suitable.

Examples of amines that can be used are:

Methyl, ethyl and dimethylamine, jS-hydroxyethyl and

Di - (/? - hydroxyethyl) -a; nin, Cyclohexylamine, Aniline and Ν-ω-sulfomethylaniline,

o-, m- and p-sulfoaniline, «O 2,4-, 2,5- and 3,5-disulfoaniIin,

m- and p-sulfo-N-methylaniline,

m- and p-sulfo-N-jS-hydroxyethylaniline,

4- and 5-SuIfo-2-methylaniline,

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-l-naphthylamine,

1-, 3-, 5- and 7-sulfo-2-naphthyiamine, so l-naphthylamine-3,6- and -3,7-disulfonic acid,

2-naphthylamine-3.6-, -4.8-, -5.7- and -6,8-disulfonic acid,

l-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-,

-2 6,3- and -4,6,8-trisulfonic acid, 2-naphthylamine-i J, 7-, -1,5,7- and -3,6,8-trisulfonic acid,

as well as amines of the formula N

/ \ H —Dm — C C-B "

(15)

N N

CI

wherein Dm has the meaning given in claim 1 and B "represents an amino group, the radical of a primary or secondary amine or an etherified hydroxyl group, as indicated in claim 1 for E, is. These amines can in turn can be obtained by using a diamine of the formula

(16)

(D, Dm and E ¹ have the meanings given in claim 1)

can also be obtained by mixing 2 moles of a diamine of the formula (16) with 1 mole of the corresponding dye, in which Z is a group of the formula

N D

C C

I Il (is)

NN

N /

n C

(D has the meaning given in claim 1)

As examples of such diamines of the formula (16) ^{stehl and mil 2 Mo! of a} triazine of the formula should be mentioned:

H-Dm-H with a triazine compound of the formula

B "

Cl \ / Λ N C. C.
H / C. '^ i Il
N N Cl /

(17)

Ethylene, trimethylene and Hexamethylenediamine,

2-hydroxy- and 2-sulfato-trimethylenediamine, Propylenediamine, Diethylenetriamine, m- and p-phenylenediamine, 4-sulfo and

4,6-disulfo-1,3-phenylenediamine, 2-sulfo- and

2,5-disulfo-1,4-phenylenediamine, 4,8-disulfo-2,6-diaminonaphthalene, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylamine-2-sulfone and

-2,2'-disulfonic acid, 4,4'-diaminodiphenylurea-2,2'- and -3,3'-disulfonic acid,

4,4'-diaminodiphenyloxide-2,2'-disulfonic acid, 4,4'-diaminodiphenyimethane-3,3'-

disulfonic acid, 4,4'-diaminodiphenoxyethane-2,2'-

disulfonic acid and 4,4'-diaminodiphenyl-2,2'- and

-3,3'-disulfonic acid.

As examples of triazines of the formula (17) are intended be mentioned:

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

and the co-condensation products of cyanuric chloride with ammonia or any of the amines found in penultimate paragraph were mentioned.

The new dyes in which Z is a group of formula

N N

κ ν / ν,

- C C-Dm-C CE ¹

Il I Il I

NN N N (5)

\ f \ f

C C

! I.

D D

(19)

DNE

C C

N N

Λ / c

(D and E have the meanings given in claim 1)

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

The above process can conveniently be carried out in an aqueous medium at a temperature which is in the range from 0 to 60 ^° C and in in some cases can be even higher, according to the reactivity of the diamine of the formula (16) and the triazine of formula (19). In general, it is desirable to add an acid binding agent to the acid set free during the reaction

so neutralize.

The new dyes can be obtained from the medium in which they were produced by conventional means Processes that are used to isolate water-soluble reactive dyes are isolated, both for example by salting out and subsequent filtration and drying or by spray drying the reaction mixture. If necessary, stabilizers, such as B. alkali hydrogen phosphates, or diluents such. B. sodium chloride or urea, added be practiced.

The new dyes can be used as reactive dyes for cellulose textile materials, which in bright reddish-blue or red or black shades with an excellent authenticity Wash and light colors when applied together with an acid-binding agent. she are particularly suitable for an exhaustion coloring. Because of its high coloring power, the amount of dye

which are used to achieve rather animal hues becomes small, which gives relatively economical colorations.

The invention * is illustrated by the following examples explains in more detail where the parts are expressed by weight.

example 1

(A; J.lO-Bis - ^ '- amino-S'-sulfoanilinoJ-o.D-dichlo rotriphendioxazine-4, ll-disulfonic acid

A neutral solution of 7.2 parts of 4,4'-diaminodiphenylamine-2,3'-disulfonic acid and 2.5 parts of 2,3,5,6-tetrachlorobenzo-1,4-quinone in 50 parts of water becomes

IO

Stirred for 6 hours at ^50.degree. 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% sodium chloride solution and dried at 80X.

10 parts of this product are added to 100 parts of 20% oleum and the mixture is 2 st at 2O ⁰ C and then was added to 1000 parts of ice and water was added. The filling is filtered off, washed with saturated brine, and dried at 80 C ^c. The product you receive will likely have the following formula:

^ s. χι Λι r \ yfs. κι

(20)

SO ₃ H

The 4,4'-diaminodiphenylamine-2,3'-disulfonic acid used can be obtained by 4-Nitrochlorobenzene-2-sulfonic acid condensed with 1,4-phenylenedianine-2-sulfonic acid and the obtained Reduced nitroamino compound.

(B) Preparation of the dye

A neutral solution of 8.9 parts of the product from (A) in 150 parts of water becomes a suspension of 4.0 parts of cyanuric chloride in a mixture of 160 parts of water and 40 parts of acetone are added at 0 to 5 ° C, and the mixture is then 4 hours at 0 to 5 ° C stirred, the pH being kept at 6 to 7 by adding sodium hydroxide solution. Then fil- triert. 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 alien in bright reddish blue hues with a good authenticity to light.

Dyes giving similar hues are obtained when the cyanuric chloride used in part (B) is replaced by an equivalent amount of any of the following

40 substances is replaced:

E.g. respondents

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

3 2,3-dichloroquinoxaline-6-sulfonyl chloride

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-j!? - ethoxyethoxy-s-triazine

8 2,4-dichloro-6-methylamino-s-triazine

9 l / J-dichloro-o-N-sulfomethylanilino-s-triazine

10 2,4-dichloro-6- (4 ', 8'-disulfonaphth-2-ylamino) -s-triazine

11 2- (2 ', 4'-dichloro-s-triazinylamino) -4- (2'-chloro-4'-p-sulfoanilino-s-triazinylamino) benzenesulfonic acid

12 2- (2 ', 4'-Dichloro-s-triazinyiamino) -5- [2'-chloro-4' - (2 ", 5" -disulfoanilino) -s-tria2ynylamino] -benzene-1,4-disulfonic acid

Example 13

3 ', 4-diaminodiphenylamine-2,4'-disulfonic acid (produced by the condensation of 4-nitrochlorobenzene 2-sulfonic acid with nvphenylenediamine sulfonic acid and Reduction of the nitro group) is used instead of 4,4'-diaminodiphenylamine-2,3'-disulfonic acid in Example 1

11th

Part A used. The product obtained presumably has the formula:

SO ₃ H Cl

(21)

HO ₃ S

SO ₃ H NH ₂

When condensed with cyanuric chloride in a manner similar to Example IB it becomes a product obtained, which dyes cellulose textile materials in bright reddish blue shades. Similar dyes will be obtained when the cyanuric chloride is replaced by an equivalent amount of one of the following substances:

E.g. respondents

14th
15th
16
17th
18th
19th
20th
21

22nd 23

24

Example 25

2.4-dichloro-6- (m-sulfoanilino) -s-triazine

S ^ -Dichloropyridazine ^ -carbonyl chloride

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

2,4,6-trichloropyrimidine

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

2,4-dichloro-6-n-butoxy-s-triazine

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

2,4-dichloro-6-N-methyl-m-sulfoanilino-s-

triazine

2,4-dichloro-6- (1 \ 5'-disulfonaphth-2'-ylamino) -

s-triazine

2- (2 ', 4'-dichloro-s-triazinylamino) -4- (2'-chloro-

4'-p-sufoanilino-s-triazinylamino) benzene-l, 5-

disulfonic acid

2- (2 ', 4'-dichloro-s-triazinylamino) -5- (2'-chloro-

4 '- (2 ", 5" -disulfoanilino) -s-triazinylamino) -

benzenesulfonic acid

2,4'-Diaminodiphenylamine-2 ', 5-disulfonic acid (manufactured by condensation of 4-nitrochlorobenzene-2-sulfonic acid mi l, 2-diaminobenzene-4-sulfonic acid and

NH ₂

SO ₃ H

NH

Reduction of the nitro group) is used instead of 4,4'-diaminodiphenylamine-2,3'-disulfonic acid used in example 1 part A. The product you receive will likely have the following formula:

SO ₃ H (22)

SO ₃ H

If it is with cyanuric chloride in a similar way as in Example! 1 part B is condensed, then becomes a product obtained, which also dyes cellulose textile materials in bright 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:

E.g. respondents

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

27 2,4-dichloropyrimidine-5-carbonyl chloride

28 2,4-dichloro-G-metho: * y-s-triazine

29 2,3-dichloroquinoxaline-6-carbonyl chloride

30 2.4-dichloro-6-amino-s-triazine

continuation

E.g. reaction trainer

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

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

33 2,4-dichloro-6-o-sulfoanilino-s-triazine

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

35 2,5-Bi5 (2 ', 4'-dichloro-s-triazinylamino) -benzene-1,4-disulfonic acid

36 2- (2 ', 4'-Dichloro-s-triazinylamino) -4- (2'-chloro-4'-amino-s-triazinylamino) benzenesulfonic acid

Example 37

Nitro group) are used instead of 4,4'-diaminediphenyl

5.6 parts of 2,4'-diphenylamine-4-suItonic acid (heramine-2,3'-disulfone: used from Example 1) by condensation of 2-nitro-morobenzene. The product obtained presumably has fol-4-sulfonic acid with p-phenylenediamine and reduction of the following formula:

Cl

HO ₃ S

SO ₁ H

(23)

When condensed with cyanuric chloride in a manner similar to Example 1 Part B, it becomes a product obtained, which also dyes cellulose textile materials in reddish blue, bright shades.

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

E.g. reaction workers

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

39 1 ^ -Dichlorophthalazine-o-carbonyl chloride

40 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-JS-hydroxyethylamino-s-triazine

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

45 2,4-dichloro-6- (3 ', 5'-disulfoanilino) -c-iriaiin

46 .2.4-Dk;: '-. Jiv, -6 - {4'-sulfo-2'-carboxyanilino) -triazine

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

48 2- (2 ', 4'-dich! Or> s-triaz! Nyiamino) -4- (2'-chloro-4'-amino-s-triazinyiamino) benzene-1,5-disulfonic acid

B e i s ρ i e I

8.0 parts 3,4'-Diav?, I "o-2 4..fi-triiTieihyIdipheny] arnir! - 2 ', 5-disulfonic acid (obtained by condensation of 4-nitrochlorobenzo'-2-? Ulfonic acid with' i, j-diamino-

2,4,6-trimeihy! B2n2. "V-5- ·".;'"" Sävire and reduction of the Nii * o group) are added to the 4.4'-Diarninodiphcr »;'^; TcAxi-Ki -uiSülforträure in example 1 part A

15th

turns. The product you receive will likely have the following formula:

NH

CH ₃

CH ₃

SO ₃ H

SO ₁ H

CH ₃

NH ₃ 16

(24)

When condensed with cyanuric chloride in a manner similar to Example 1 Part B, a product is obtained which is cellulosic textile material as well colors in bright reddish blue shades.

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

E.g. respondents

50 2,4-dichloro-6-methoxy-s-triazine

51 l-M'-chlorocarbonylphenylMJ-dichloro-opyridazone

52 2,4-dichloro-b- (m-sulfoanilino) -s-triazine

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

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

55 2,4-dichloro-6-p-sulfophenoxy-r »-triazine

56 2,4-dichloro-6-di - (/? - hydroxyethyl) amino-striazine

57 2,4-dichloro-6- (2'-methyl-5'-sulfoanilino) -triazine

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

59 2- (2 ', 4'-Dichloro-s-triaziriylamino) -5- <2'-chloro-4'-m-sulfoanilino-s-triazinylamino) benzenesulfonic acid

60 2- (2 ', 4'-dichloro-s-triazinylamino) -5- (2'-chloro-4'-aminos-triazinyiamino) benzene sulfonic acid

B e ι s ρ ι e 1 61 reduction of the nitro group) instead of the 4,4'-

5.6 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid diaminodiphenylamine * 2,3'-disulfonic acid from

(produced by condensation of 4-nitrochloro- '· Example 1, part A used. The product obtained

benzoI-2-sulfonic acid with p-phenylenediamine and probably has the following formula:

SO ₃ H

NH

NH ₃ (25)

SO, H

When mixed with cyanuric chloride in a similar manner Similar dyes are obtained when the cyano-

as in Example 1 Part B is condensed, then a nitrate chloride is replaced by an equivalent amount of one of the following

Get a product that replaces cellulose in luminous substances:

tint blue shades (i.e., greener than in Example 1). * "

E.g. respondents

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

63 2,4,6-tribromopyrimidine

64 2,4-dichloro-6-methoxy-s-triazine

262/104

17th

continuation E.g. recipients of actions

65 2-methylsulfonyl-4,5-dichloro-6-methyl-pyrimidine

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

67 2,4-dichloro-fr ^ -OS'-hydroxyäthylaminoJäthylamino-s-triazine

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

69 2,4-Dichloro-6- (N-methyl-p-sulfoanilino) -striazine

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

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

72 2- (2 ', 4'-Dichloro-s-triazinylamino) -5- (2'-chloro-4'-amino-s-triazinyiamino) benzene-1,4-disulfonic acid

example

5.8 parts of 4,4'-diaminobenzene-2-sulfonic acid become instead of 4,4'-diaminodiphenylamine-2,3'-disulfone

acid used in Example 1 Part A The product obtained presumably has you. Formula:

NH,

(26)

SOjH

It is obtained with cyanuric chloride in a manner similar to that in Similar dyes are obtained when the cyano- Example 1 Part B condensed, wherein a dye-permanent chloride by an equivalent amount of one of the following

the cellulose textile materials are replaced in black * o ing fabrics: Color shades Dyes.

E.g. respondents

74 2,4-dichloro-6-methoxy-s-iriazine

75 2,4-dichloroquinazoline-6-carbonyl chloride

76 2,4-dichloro-6-amino-s-triazine

77 S-methyl ^ .o-trichloropyrimidine

78 2,4-dichloro-6-m-sulfoanilino-s-triazine

79 2,4-dichloro-6-p-chloropheiioxy * s-triazine

80 2,4-dichloro-6-> sulfatoethylamino-s-triazine

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

82 2,4-Dichloro-6- {2'-carboxy-5'-sulfoanilino) -striazine

83 2- (2 ', 4'-dichloro-s-triazinylamino) -4- (2 "chloro-4'-m-sulfoanilino-s-triazinylamino) benzenesulfonic acid

84 2,5-bis- (2 ', 4'-dichloro-s-triazinylamino) benzoisulfonic acid

example

8.0 parts of 4,4'-diaminodiphenylurea-2,2'-disulfonic acid are used instead of 4,4'-diaminodiphenyl

amine-2,3'-disulfonic acid in Example 1 Part A used. The product obtained presumably has the formula:

19th

SOjH

co

SOjH Cl

NH ₂

(27)

It is treated with cyanuric chloride in a manner similar to that in m Example 1 Part B condenses to give a dye which turns cellulosic fabrics into reddish blue Shades of color

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

E.g. respondents

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

87 2,4-dichloroquinazoline-6-sulfonyl chloride

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

89 ^ - {4,5-dichloropyridaz-o-on- i -yi) propionyl chloride

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

91 2,4-dichloro-6-m-sulfophenoxy-s-tria2ine

92 l ^ -Dichloro-o-N-methyl-jS-sulfatoethylamino-striazine

93 2,4-Dichloro-6- (2 ^/ , 5'-disulfoaniHno) -s-triazine

94 2,4-dichloro-6- (tn-carboxyanilino) -s-triazine

95 2- (2 ', 4'-Dichloro-s-triazinylamino) -4- (2'-chloro-4'-m-sulfoaniIino-s-triazinylamino) benzene-1,5-disulfonic acid

96 2.4-ßis- (2 ', 4'-dichloro-s-triazinylamino) benzenesulfonic acid

Example 97

8.0 parts 1,2-bis (4'-amino-2'-suIfophenylamino} ithan (obtained by condensation of 2 moles of 4-nitrochlorobenzene-2-sulfonic acid with ethylenediamine and reduction of the nitro groups) are used instead of 4,4'-DiaminodiphenyIamin-2,3'-disulfo ^r \ acid in examples * ·> Game 1 Part A. The product obtained presumably has the formula:

SO, H

SOjH

NH ₂

CH ₁ CH;

NH,

CH ₂ CH ₂

ⁿ nh

SOjH

SOjH

(28)

It is made with cyanuric chloride in a manner similar to that in Example 1 Part A condenses, producing a dye which turns cellulosic textile materials into reddish blue Shades of color.

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

E.g. respondents

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

99 2,4-dichloroquinazoin-o-sulfonyl chloride

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

101 2,4,6-trichloropyrimidine

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

103 2,4-dichloro-6v9-methoxyethoxy-s-triazine

104 2,4-dichloro-6-cyclohexylamino-s-triazine

21

continuation

E.g. respondents

105 2,4-dichloro-6- (2 ', 4'-disulfoanHino) -s-triaz! N

106 2,4-dichloro-6-iin- _: / S-su! Iaioätnylsulfonylanilino) -s-triazine

107 2- (2 ', 4'-Dichloro-s-triazinylaniino) -4- [2'-chloro-4' - {2 ", 5" -disulfoanilino) -s-triazinylamino] benzene sulfonic acid

108 2 (2 ', 4'-dichloro-s-triazinylamino) -5- {2'-chloro-4'-p-sulfoanilino-s-triazinylamino) benzenesulfonic acid

example

8.0 parts 1,2-bis (4'-amino-2 "-sulfonphenoxy) ethane are instead of 4,4'-diaminodiphenylamine-2,3'-

NH ₂

CH ₂ CH

disulfonic acid used in Example 1 Part A. The product obtained presumably has the formula:

CH ₂ CH

SO ₃ H SO ₃ H

(29)

It is obtained with cyanuric chloride in a manner similar to that in FIG. 30. Similar dyes are obtained when the Cy example 1 Part A condenses, with a dye containing an- anuric chloride by an equivalent amount of one of the foils replacing cellulosic textile materials with reddish fabrics: Shades of color

E.g. respondents

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

111 2,2,3,3-tetrafluorocyclobutyl acryloyl chloride

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

113 2,4,6-trichloropyrimidine

114 2,4-D: chloro-6-m-sulfoanilino-s-triazine

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

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

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

118 2,4-Dichloro-6- (5'-sulfonaphth-l-ylamino) -striazine

119 2- (2 ', 4'-Dichloro-s-triazinylamino) -4- [2'-chloro-4' - (2 ", 5" -disulfoanilino) -s-triazinylamino] -benzene-1,5-disulfonic acid

120 2 (2 ', 4'-Dichloro-s-triazinylamino) -5- (2'-chloro-4'-p-sulfoanilino-s-triai: inyiarnino) benzene-1,4-disulfonic acid

example

Example 1 is repeated, but the addition in place of salt for precipitation of FarbstofTs is a neutralized solution of 4.0 parts of m-aminobenzenesulfonic acid in 50 parts of water was added and the mixture 4 h at 30 to 35 ⁰ C quilted, wherein the pH is kept at 6 to 7 by adding sodium bicarbonate solution.

The product obtained is similar to that of both

65 game 2 identical.

The table below describes a number of dyes from earlier examples which can be obtained in a similar manner if the diamino-triphendioxazine in column 2 is first treated with cyanuric chloride and then ammonia or an amine, as indicated in column 3 , implements.

24

example

Triphendioxazine of the formula ammonia / amine

According to example no.

Ammonia 6

Methylamine 8

N- (sulfomethyl) aniline 9

2-naphthylamine-4,8-disulfonic acid 10

2-Amino-4- (2 '- <_ hIoro-4'-p-sulfoanilino-s-triazinylamino) benzene-11 sulfonic acid

2-Amino-5- [2'-chloro-4 '- (2 ", 5" -disulfoanilino) -s-triazinylamino] - 12

benzene-1,4-disulfonic acid

m-aminobenzenesulfonic acid 14

Ammonia 18

Dimethylamine 20

M-Meihyi-m-aminobenzoi-sulfonic acid 2 i

2-naphthylamine-1,5-disulfonic acid 22

2-Amino-4- (2'-chloro-4'-p-sulfoanilino-s-triazinylamino) benzene-23

1,5-disulfonic acid

2-Amino-5- [2'-chloro-4 '- (2 ", 5" -disulfoanilino) -s-triazinyl- 24

amino benzene sulfonic acid

m-aminobenzenesulfonic acid 26

Ammonia 30

Ethylamine 32

o-aminobenzenesulfonic acid 33

2-naphthylamine-3,6,8-trisulfonic acid 34

2-Amino-5- (2 ', 4'-dichloro-s-triazinylamino) benzene-1,4-di-35 sulfonic acid

2-Amino-4- (2'-chloro-4'-amino-s-triazinylamino) benzene-36 sulfonic acid

Ammonaik 38

m-aminobenzenesulfonic acid 40

Ethanolamine 43

Aniline-3,5-disulfonic acid 45

5-sulfo-2-aminobenzoic acid 46

2-Amino-4- (2 ', 4'-dichloro-s-triazinylamino) benzoI-l, 5-di-47 sulfonic acid

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

m-aminobenzenesulfonic acid 52

Ammonia 54

Di - (/? - hydroxyethyl) amine 56

4-sulfo-2-aminotoluene 57

l-naphthylamine-3,6-disulfonic acid 58

2-Amino-5- (2'-chloro-4'-m-sulfoanilino-s-triazinyiamino) benzene-59 sulfonic acid

2-Amino-5- (2'-chloro-4'-amino-s-triazinyiamino) benzene-60 sulfonic acid

m-aminobenzenesulfonic acid 62

Ammonia 66

^ -Hydroxyethyl-ethylenediamine 67

N-methyl-p-aminobenzenesulfonic acid 67

Anthranilic acid 70

2-Arnino-5- (2'-chloro-4'-m-sulfoani !! no-s-triaz! Ny! 3rnino) benzo! - 71 1,4-disulfonic acid

2-Amino-5- {2'-chloro-4'-ainsno-s-triazinylamino) benzene-1,4-di-72 sulfonic acid

121/1 20th 121/2 20th 121/3 20th 121/4 20th 121/5 20th 121/6 20th 121/7 21 121/8 21 121/9 21 121/10 21 121/11 21 121/12 21 121/13 21 121/14 22nd 121/15 22nd 121/16 22nd 121/17 22nd 121/18 22nd 121/19 22nd 121/20 22nd 121/21 23 121/22 23 121/23 23 121/24 23 121/25 23 121/26 23 121/27 23 121/28 24 121/29 24 121/30 24 121/31 24 121/32 24 121/33 24 121/34 24 121/35 25th 121/36 25th 121/37 25th 121/38 25th 121/39 25th 121/40 25th

121/41

25th

continuation example

Triphendioxazine the formula

Ammonia / amine

According to example no.

121/42 26th 121/43 26th 121/44 26th 121/45 26th 121/46 26th 121/47 26th 121/48 26th 121/49 27 121/50 27 121/51 27 121/52 27 121/53 27 121/54 27 121/55 27 121/56 28 121/57 28 12-58 28 121/59 28 121/60 28 121/61 28 121/62 28 121/63 29 121/64 29 121/65 29 121/66 29 121/67 29 121/68 29

121/69

29

Ammonia 76

m-aminobenzenesulfonic acid 78

jS-sulfatoethylamine 80

p-aminobenzenesulfonic acid 81

4-sulfo-2-aminobenzoic acid 82

2-Amino-4- (2'-chloro-4'-m-sulfoanilino-s-triazinylamino) - 83 benzene sulfonic acid

2-Amino-5- (2 ', 4'-dichloro-s-triazinyl-amino) benzene-84 sulfonic acid

Ammonia 86

m-aminobenzenesulfonic acid 88

N-methyl-jS-sulfatoethylamine 92 Aniline-2,5-disulfonic acid 93

m-aminobenzoic acid 94

2-Amino-4- (2'-chloro-4'-m-sulfoanilino-s-triazinylamino) - 95 benzene-1,5-disulfonic acid

2-Amino-4- (2 ', 4'-dichlorotriazinylamino) benzoI-sulfonic acid 96

m-aminobenzenesulfonic acid 98

Ammonia 102

Cyclohexylamine 104 Aniline-2,4-disulfonic acid 105

m-jS-sulfatoethylsulfonylaniline 106

2-Amino-4- [2'-chloro-4 '- (2 ", 5" -disulfoanilino-s-triazinyl-107 amino) benzene sulfonic acid

2-Amino-5- (2'-chloro-4'-p-sulfoanilino-s-triazinylamino) - 108 benzene sulfonic acid

Ammonia 112

m-aminobenzenesulfonic acid 114

n-butylamine 116

Aniline 117

1-naphthylamine-5-sulfonic acid 118

2-Amino-4- [2'-chloro-4 '- (2 ", 5" -disulfoanilino) -s-triazinyl-119 amino] benzene-l, 5-disulfonic acid

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

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 l, 4-phenylenediamine-2,5-disulfonic acid in 40 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 40 ⁰ C, the pH by the addition is maintained at 6 to 6.5 by sodium hydroxide solution. Then will

Salt is added to precipitate the dye, which is then filtered off and dried.

The product dyes cellulose textile materials in bright reddish blue shades. It is identical to that of Example 12.

The following table lists a number of other dyes from earlier examples or isomers of the same. give, which can be obtained in a similar manner if one of the diaminotriphendioxazine from column 2 reacts with cyanuric chloride, the product with the phenylenediamine mono- or disulfonic acid from column 3 converts, and the product with the triazine from column 4 implements

Triphendioxazine the formula

Diamine

Triazine According to example 2-chloro-4-p-suIfoanilino 1I ₁ (isomer) 2-chloro-4-amino 36 (isomer) 2-chloro-4-m-sulfoanilino 83 (isomer) Cyanuric chloride 96 (isomer) 2-chloro-4- (2 ', 5'-disulfo- 107 (isomer) anilino) 2-chloro-4- (2 ', 5'-disuiro- 24 (isomer) anilino) 2-chloro-4-sulfoanilino 59 (isomer) 2-chloro-4-amino 60 (isomer) CyaiiuiChiuiid 84 (! Süfiici) 2-chloro-4-p-sulfoanilino 108 (isomer) 2-chloro-4-p-sulfoanilino 23 Cyanuric chloride 47 2-chloro-4-amino 48 2-chloro-4-m-sulfoanilino 95 2-chloro-4- (2 ', 5'-disulfo- 119 anilino) Cyanuric chloride 35 2-chloro-4-m-sulfoanilino 71 2-chloro-4-amino 72 2-chloro-4-p-sulfoanilino 120

122/1 122/2 122/3 122/4 122/5

122/7 122/8 i 2 2/9

122/10 122/11 122/12 122/13 122/14 122/15

122/16 122/17 122/18 122/19

20th 22nd 26th 27 28

21

24 24 26th 28 21 23 23 27 29

22nd 25th 25th 29

1,3-phenylenediamine-4 · 1 ^ -phenylenediamine, 3-phenylenediamine-4 1,3-Phenylenediamine-4 · 1,3-Phenylenediamine-4 ·

• sulfonic acid sulfonic acid sulfonic acid sulfonic acid ■ sulfonic acid

1,4-phenylenediamine-2-sulfonic acid

1,4-phenylenediamine-2-sulfonic acid

1,4-phenylenediamine-2-sulfonic acid

i, 4-phenylenediamine-2-sulfonic acid

1,4-phenylenediamine-2-sulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,4-Phenylenediamine-2,5-disulfonic acid 1,4-Phenylenediamine-2,5-disulfonic acid 1,4-Phenylenediamine-2,5-disulfonic acid 1,4-Phenylenediamine-2,5-disulfonic acid

Example 123

340 parts (0.947 mole) of 4,4'-diaminodiphenylamine-2,3'-disulfonic acid are added to a Aufchlämmung of 145 parts (360 MOI) magnesium oxide in 2400 parts of water at 40 ⁰ C and then stirred for 5 min tvi 40 ° C. Then 119.5 parts (0.486 mol) of chloranil are added together with 50 parts of ethanol. The mixture is stirred for 1 1/2 hours at 50 ° C. and then filtered and then salted out with potassium chloride up to 20% (w / v). Then 70 parts of 36% hydrochloric acid are added and the precipitate is filtered off, washed with saturated potassium chloride solution and im vacuum dried at 70 ⁰ C. The product is 2n with 4000 parts of hydrochloric acid 3 st stirred and then filtered, washed with 2N hydrochloric acid and 1000 parts of dried at 8O ⁰ C.

6.24 parts of this product are added 34.7% oleum to 46.5 parts, whereby the temperature is maintained below 20 ⁰ C, after which the mixture is stirred vigorously for 30 min at 40 ± 1 ° C. The mixture is poured into 300 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 up to 30% (w / v) was added and the product is filtered off, washed with acetone and dried at 6O ⁰ C Elemental analysis of the product gave: C 27.1%, N 6.1%, Cl 5.9 %, S 9.3%. Taking into account a moisture content of 21.2%, the theoretical values for C ₃₀ H ₁₆ O ₁₄ N ₆ S ₄ CI ₂ K _{4 are} : C 27.3%, N 6.4%, a 5.4%, S 9.7% .

A neutral solution of 4.0 parts (0.003 mol) of this product in 80 parts of water becomes a suspension of 1.4 parts (0.0076 mol) of cyanuric chloride in a Mixture of 30 parts of acetone and 100 parts of water added below 5 ^° C. The pH is kept at 6.0 to 7.0 by adding 2N sodium carbonate solution. Stirring is continued for 4 Λ under these conditions. Excess cyanuric chloride is filtered off and up to 30% (w / v) salted out. The precipitation will

•> 5 filtered off and washed with saturated sodium chloride solution and then at room temperature in vacuo dried.

The product obtained dyes cellulosic textile materials in bright blue shades with a good one

w authenticity to light and washing.

Dyes with a similar hue are obtained if the cyanuric chloride used is through an equivalent amount of one of the following reactants is replaced, the temperature being is that the reaction proceeds for 4 hours

example

µ 123/1 2,2,3,3-TetrafluoroeycIobutyS-carbonyIchloride

123/2 X2 ^/ , 2 ' _r 3' _r 3'-TetrafluorocycIobutyi} äc ₁ ? Iyl chloride

123/3 ^ chloro-o-methyl ^ -methylsulfonyl-

pyrimidine 123/4 4.5-01 ^^ 0-6-1 ^ 11 ^ 1-2-1 ^ 111x15 ^ 50 ^ 1-

pyrimidine 123/5 2,3-dichloroquinoxaline-6-carbonyl chloride

30th

continuation

example

Respondents of the type:

5- [2'-Chloro-4 '- (A) -s-triazin-6'-ylamino] -2- (2', 4'-dichloro-s-triazin-6'-ylaminio) benzene sulfonic acid

123/6 jff- (4.5-dichloropyridazon-6-yI) -l-propionyl chloride

123/7 6-methyl-2,4-bis (methylsulfonyl) pyrimidine 123/8 5-chloro-6-methyl-2,4-bis (methylsulfonyl) pyrimidine

123/9 2,4,5,6-tetrachloropyrifiiidine 123/10 2,4,6-trichloropyrimidine 123/11 2,4,6-trifluoro-5-chloropyrimidine 123/12 2,4-dichloropyrimidine-5-carbonyl chloride

123/13 2,4-dichloro-6- (N-sulfomethylanilino) -s-triazine

123/14 2,4-dichloro-6- (N-sulfomethyl-m-toluidino) -s-triane> n

123/15 2, <dichloro-o-CN-sulfomethyl-o-cnisidino) -s-triazine

123/16 2,4-dichloro-6- (N-sulfomethyl-o-phenetidino) -s-triazine ^<

123/17 2,4-dichloro-6- (N-sulfomethyl-p-anisidino) -s-triazine

123/18 2,4-dichloro-6- (m-sulfoanilino) -s-triazine

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

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

123/21 2,4-dichloro-6-0S-ethoxyethoxy) -s-triazine

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

123/23 2,4-dichloro-6- (3 ', 5'-disulfoanilino) -s-triazine 123/24 2,4-dichloro-6- (2 ', 5'-disulfoanilino) -s-triazine 123/25 2,4-dichloro-6- (3', 6 ', 8'-trisulfonaphth-1-ylamino ) -s-triazine

Respondents of the type:

4- [2'-Chloro-4 '- (A) -s-triazine-6'-ylamino] -2- (2', 4'-dichloro-s-triazine-6'-ylamino) benzene sulfonic acid

Example A.

123/26 3 "sulfoanilino

123/27 (2 ", 5" -disulfoanilino)

123/28 methoxy

123/29 (4 "sulfophenoxy)

123/30 4-phenoxy

123/31 4'-amino

123/32 (3 ", 5" -disulfoanilino)

123/33 (4 "sulfoanilino)

123/34 2,4-bis (2 ', 4'-dichloro-s-triazin-6'-ylamino> benzenesulfonic acid

123/35 2,5-bis-i2'.4'-dichioio-s-tiiarin-6 ^! -yiaminoV benzene sulfonic acid

123/36 2,4-bis (2 ', 4'H3ichloro-s-triazin-6'-ylamino> -

benzene-l, 5-disulphonic acid 23/37 2,5-bis - {? -, 4 ^r -dichi ^ r!>s-triazin-6'-ylamino) -benzene-l, 4-disulphonic acid c

123/38 123/39 123/40 123/41 123/42 123/43 123/44 123/45

3 "suifoanilino

(4 "sulfoanilino)

(2 ", 5" -disulfoanilino)

Methoxy

(4 "-Sulfophenoxy)

Phenoxy

Amino

(3 ", 5" -disulfoanilino)

Reaction participants of the type:

5- (2'-Chlo: o-4'-As-tnazin-6'-ylamino) -2- (2 ', 4'-dichloro-s-triazin-6'-ylamir> o) benzene-1,4 -disulfonic acid

■ , <

Example A.

123/46 123/47 123/48 123/49 123/50 123/51 123/52 123/53

3 "sulfoanilino

4 "sulfoanilino

2 ", 5" disulfoanilino

Methoxy

4 "sulfophenoxy

Phenoxy

Amino

3 ", 5" disulfoanilino

Respondents of the type:

4 - (2 '- Chloro - 4' - A - s - triazinylamino) - 2 - (2 ', 4' - dichloro-s-triazine-ö'-ylaminoibenzene-1S-disulfonic acid

example

123/54 123/55 123/56 123/57 123/58 123/59 123/60 123/61

3 "sulfoanilino

4 "sulfoanilino

2 ", 5" disulfoanilino

Methoxy

4 "sulfophenoxy

Phenoxy

Amino

3 ", 5" disulfoanilino

Respondents of the type:

N - (2 '- chloro - 4' - B - s - triazine - 6 '- y!) - N' - (2 ', 4' - di chloro-s-triazin-6'-yl) -l , 2-diaminoethane

Example!

123/62 123/63

\ 3 ', 5'-Tue ¹ ZuIföennrno

arhth Γ-ylamino

Respondents of the type:

N - (2 '- chlorine - 4' - B - s - triazin - 6 '- yl) - N' - f.2 ', 4 ¹ - di -chloro-s-triazin-6'-yl) -l, 3-diamino-2-sulfatopropane

Example B.

123/65 123/66 123/67

2 ', 5'-disulfbanuino 3 ', 5-disulfoanilino 3 ', 6', 8-trisulforiaphth-r-ylainino

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 that are described in is Examples 122 and 122/1 to 122/19 are given, using a number of dyes with a similar hue and with similar Fastness properties is obtained.

Example 124 ^M.

5.0 parts of sodium acetate are added to a neutral solution of 21.9 parts (0.061 mol) of 4,3'-diaminodipenylamine-2,4'-disulfonic acid in 500 parts of water. Then, 7.45 parts (0.030 mol) of chloranil and 80 parts of ethanol are added and the mixture st 1 ¹ A at 65 to 70 ⁰ C is stirred. 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 washed well with ethanol and then with acetone and then dried ^{at 80 ° C.}

5.0 parts of this product are added to 134 parts of 20% oleum over 5 minutes, the Temperature is kept below 20 ⁰ C. The mixture is A 2 ¹ st at 20 to 25 ⁰ C and then stirred ate in 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, filtered off and dried at 80.degree

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 Hi ₆ O ₁₈₁₂ N ₆ Ss ₄ Cl ₂ K _{54 are} : C = 24.8; N = 5.8; Cl = 4.9; S = 11.9%.

4.36 g of this product are mixed with cyanuric chloride in implemented in a similar manner as in Example 123. The product dyes cellulosic textile materials in bright blue Shades that go a little more red. You own similar lightfastness properties and are slightly less washfast 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 results in a number of dyes, all of them have a similar hue and fastness properties.

Alternatively, the reaction product obtained with cyanuric chloride can be mixed with ammonia or the amines listed in Examples 121 and 121/1 to 121/69 or with the diamines and other triazine compounds in Examples 122 and 122/1 to 122/19 are given, are reacted, with a number of dyes obtained with similar hues became.

230 262/104

Claims (2)

Patent claims: 1. Fiber-reactive triphendioxazine dyes of the formula Cl (HO ₃ S), ZNH-YX (SO ₃ H) ₁ Χ — Υ — NH-Z (D (/ ■ + s) stands for 0, 1 or 2; X for NH, NHCONH, NHCH ₂ CH ₂ NH, OCH ₂ CH ₂ O or N = N; each Y independently of one another for sulfophenylene, Disulfophenylene or trimethylsulfophenylene; and Z stands for one of the following groups reactive with cellulose: 2,2,3,3-tetrafluorocyclobutylcarbonyl, 2,3,3-trifluorocyclobutenyicarbonyl, 2,2,3,3-tetralluorocyclobutylacryloyI, 2,3-dichloro-quinoxaline-S- or -6-sulfonyl, 2,3-dichloro-quinoxaline-5- or 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-trichloro-quinazoline- 6-sulfonyl, 2,4-dichloro-quinazoline-6-carbonyl, 1 / t-dichlorophthalazine-o-carbonyl, 4 ^ -Dichloro-pyridaz-6-on-l-yl, S.o-dichloropyridazine ^ -carbonyl, 2,4-difluoro-5-chloro-pyrimid-6-yl, 2,4-dichloropyrimidine-S-carbonyl, 2-methylenesulfonyl-5-chloro-6- methylpyrimid-4-yl, 4- {4 ', 5'-dichloro-pyridaz-6'-on-r-yl) · zoyl, jJ- (4 ', 5'-dichloro-pyridaz-6'-on-r-yl) - propionyl. 4- {4.5'-dichloro-pyridaz-6'-one-r-yl) - phenylsulfonyl, dichloropyrimidyl, dibromopyrimidyl, Trichloropyrimidyl, 5-methyldichloropyrimidyl, 5-cyanodichloropyrimidyl and triazinyl of the formula is where D 25th 30th 35 ben- 50 55 / \ -C CD I I N N N / 60 65 stands for Cl, Br or SO ₃ H and for Cl, Br, SO ₃ H, methylamino, ethylamino, butylamino, dimethylamine), ß- hydroxyethylamino, di-08-hydrp ^ yethyl) -amino, ß- OiJ-hydroxyethylamino) - ! ^! - amino, ß- chloroethylamino, ß- sulfatoethylamino and N-methyl-jS-suiratoethylamino, cyclohexyiamino, aniiino, suiibphenylamino, disulfophenylamino, N-methylsulfophenylamino, N-j8-hydroxyethylsulfophenylamino. Mono-, di- and trisulfonaphthyla.mino, sulfotolylamino, carboxyphenylamino, sulfocarboxy- phenylamino, sulfatoethylsulfonylphenylamino, Ν-ω-sulfomethylphenylamino, Methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, sulfophenoxy, chlorophenoxy, methoxyethoxy or a Group of formula D _n , -C CD i N stands, in which E ^{1 stands} for a group or an atom as defined above for E, and D _{n stands} for Ν, Ν'-diradical of one of the following diamines: ethylene, trimethylene and Hexamethylenediamine, 2-hydroxy and 2-sulfato-trimethylene-diamine, Propylenediamine, Dieth / Ientriamine, m- and p-phenylenediamine, 4-sulfo and 4,6-disulfo-1,3-phenylenediamine, 2-sulfo and 2,5-disulfo-1,4-phenylene-diamine, 4,8-disulfo-2,6-diaminonaphthalene, 4,4'-difaminostilbene-2,2'-disulfonic acid, 4 _i 4'-diamine-diphenylamine-2 -sulfone-and 2,2'-disulfonic acid, 4,4'-Diaminodiphenylurea T-2,2'- and 3,3'-disulfonic acid, 4,4'-diaminodiphenyl oxide-2,2'- disulfonic acid, 4,4'-diaminodiphenylmethane-3,3'- disulfonic acid. 4,4'-diaminodiphenoxyethane-2,2'- disulfonic acid and 4,4'-diaminodiphenyl-2,2- and 3,3'-disulfonic acid. 2. Use of the dyes according to claim 1 together with an acid-binding agent for Dyeing of cellulosic textile materials.