DE2751293A1 - FIBER-REACTIVE AZO DYES, THEIR PRODUCTION AND USE - Google Patents

Description

GERMANY - · '*' ^ CV; ,

Fiber-reactive azo dyes, their production and use

The present invention relates to fiber-reactive azo dyes of the formula

CH,

0 V OH
R.

wherein X is sulfomethyl, cyano or carbamoyl, R is hydrogen or C1-alkyl, Y fluorine, chlorine, an alkoxy or alkoxyalkoxy group with 1 to 4 carbon atoms, or an optionally substituted amino group, a Z fluorine or Chlorine, and the other Z is an alkoxy or alkoxyalkoxy group having 1 to 4 carbon atoms, or one optionally substituted amino group.

For R come into consideration as C,, -alkyl: methyl, ethyl, Propyl, isopropyl, butyl, isdbutyl, sec-butyl and tert-butyl. For Y and Z come into consideration as alkoxy or Alkoxyalkoxy group having 1 to 4 carbon atoms or as optionally substituted amino group the remainder of one of the hydroxy or amino compounds mentioned in the description of the process for the preparation of the fiber-reactive azo dyes of the formula (1) mentioned as possible starting materials are.

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- V-

Fiber-reactive azo dyes of the formula (1) are preferred, wherein X is carbamoyl, R is ethyl, Y is chlorine, one Z is chlorine and the other Z is an amino group.

Valuable dyes of the constitution defined above are the fiber-reactive azo dyes of the formula

CH

N = N

Cl

H ₀ N-CO
²

^C 2 ^H 5

The dyes of the formula (1) are fiber-reactive since they can be split off 1 to 2 together in the two s-triazine radicals Contain halogen atoms.

Fiber-reactive compounds are to be understood as meaning those with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides are able to react with the formation of covalent chemical bonds.

The preparation of the fiber-reactive azo dyes of the formula (1) is characterized in that one can use any Order 6-hydroxy-pyridone- (2) of the formula

CH.

where W is hydrogen or carbamoyl,

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with diaminobenzenes of the formulas

XT < ⁵ >

HO ₃ sr ^ '

(6)

and halo-s-triazines of the formulas

YC \ - Y

N N

Z-C C-Z

couples and condenses and optionally a halogen atom Y and / or a halogen atom Z by condensation with an amine or replacing alcohol with an amino, alkoxy or alkoxyalkoxy group. If in 6-hydroxypyridone- (2) of the formula (4) W is carbamoyl and X is not a hydrogen atom, the carbamoyl radical becomes W in the coupling according to the method cleaved.

According to a preferred embodiment - by appropriate choice of starting materials - obtained fiber-reactive azo dyes of the formula (1) in which X is carbamoyl, R is ethyl, Y is chlorine, one Z is chlorine and the other Z is an amino group.

Because the individual process steps specified above which can be carried out in a different order, possibly also partially simultaneously, are different Process variants possible. The starting materials to be used for each partial reaction result from formula (1). in the

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In general, the implementation is carried out one after the other, with the order of the simple reactions between the individual reaction components of the formulas (4) to (8) and any amines to be used or Alcohols can be chosen freely.

Important process variants are characterized by the fact that one

1) a halo-s-triazine of the formula (7) with a diaminobenzene of the formula (5) condensed, the resulting primary condensation product is diazotized and converted to a 6-hydroxypyridone- (2) of the formula (4), the azo compound condenses with a diaminobenzene of the formula (6), the resulting secondary condensation product condensed with a halogen-s-triazine of the formula (8), and finally a halogen atom Z by condensation replaced with an amine by an amino group;

2) a diaminobenzene of the formula (5) is diazotized and coupled to a 6-hydroxypyridone- (2) of the formula (4), the azo compound condensed with a halogen-s-triazine of the formula (7), the monocondensation product with a diaminobenzene of the formula (6) condensed, the secondary condensation product obtained with a halogen-s-triazine of the formula (8) condensed, and a halogen atom in the external s-triazine residue by condensation with an amine through an amino group replaced;

3) a 6-hydroxypyridone (2) of the formula (4), a diaminobenzene of the formula (5) and a halo-s-triazine of the formula (7) coupled and condensed, furthermore a diaminobenzene of the formula (6), a halo-s-triazine of the formula (8) and an amine condensed, and both intermediates condensed with one another;

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A) a 6-hydroxypyridone- (2) of the formula (4), a diaminobenzene of the formula (5), a halo-s-triazine of the formula (7) and a diaminobenzene of the formula (6) couples and condenses the intermediate product obtained with a halo-s-triazine of the formula (8) condensed and this condensed with an amine;

5) a diaminobenzene of the formula (5), wherein one of the two amino groups is acetylated, diazotized and on a 6-hydroxypyridone- (2) of the formula (4) couples, splits off the acetyl radical by saponification and then as described under 2), continue;

6) a diaminobenzene of the formula (6) on the one hand with a halogen-s-triazine of the formula (7) and on the other hand with a Halo-s-triazine of the formula (8) condenses in the resulting Condensation product replaces a halogen atom Z by an amino group by condensation with an amine, and that intermediate product obtained with one prepared according to 2) or 5) (first reaction stage and optionally saponification) Aminoazo compound condensed;

7) performs the coupling as the last reaction step, e.g. by carrying out the partial reactions described under 1) in reverse order, or the bireactive Intermediate product 6) condensed with a diaminobenzene of the formula (5), the condensation product is diazotized and on a 6-hydroxypyridone- (2) of formula (4) couples.

In the following examples, the preparation of the intermediates is not described in all cases, they however, it follows without further ado from what has been said above. :

As starting materials that can be used for the preparation of the fiber-reactive azo dyes of the formula (1), are mentioned:

6-hydroxypyridone- (2) of formula (4)

l-ethyl-S-carbamoyl ^ -methyl-ö-hydroxy-pyridon- (2), l ^ -Dimethyl-S-carbamoyl-e-hydroxy-pyridon- (2), 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2),

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3-SuIfemethy1-4-methy1-2,6-dihydricxypyridine, 3-cyano-4-methylamine-2,6-dihydroxypyridine, 1-ethyl-S-cyano-A-methyl-G-hydroxy-pyridon- (2), 3-carbamoyl-4-methyl-2,6-dihydroxypyridine,

1-ethyl-3-sulfomethy1-4-methy1-5-carbamoy1-6-hydroxy-pyridon- (2), 3-SuIfomethy1-4-toethyl-5-carbamoy1-2,6-dihydroxypyridine, 1-Ethyl-3-cyano-4-methy1-5-carbamoy1-6-hydroxypyridone- (2).

Diaminobenzenes of the formulas (5) and (6)

1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid.

Halo-s-triazines of the formulas (7) and (8)

2,4,6-trifluoro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine,

2,4-Difluoro (chlorine) -6-amino (alkoxy, alkoxyalkoxy) -l, 3,5-triazine, wherein the amino, alkoxy or alkoxyalkoxy substituent is, for example, the radical of one of the amines mentioned below or alcohols. However, as described above, these connections can also be subsequently connected to the Azo dye-bound dihalo-s-triazine residue is condensed, for the purpose of replacing a halogen atom in the mono- or Dihalo-s-triazine radical with an amino, alkoxy or alkoxyalkoxy substituent.

As examples of the amino and hydroxy compounds mentioned above are mentioned:

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, ibutylamine, isobutylamine, sec-butylamine, tert-butylamine, hexylamine, methoxyethylamine, Ethoxyethylamine, methoxypropylamine, chloroethylamine, Hydroxyh'thylaniin, üihydroxya'thylamin, Hydroxypropylamin, Aminoäthansul fonsäure, ß-sulfatoiithylamine, benzylamine, cyclohexylamine, Aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethy] aniline, o-, m- and p-chloroaniline, N-methylani.iin, N-Aethylnnilin, 3- or 4-Acctylami noanilin, o-, in- and

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p-nitroaniline, ο-, m- and p-aminophonol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitro-aniline, 2-nitro-4-methyl-aniline, 3-nitro-4-methyl-aniline, o-, m- and p-phenylenediamine, 3-ainino-4-methyl-aniline, 4-amino-3-methyl-aniline, 2-amino-4-methyl-aniline, ο-, m- and p-anisidine, ο-, m- and p-phenetidine, naphthylamine- (1), caphthylamine- (2 ), 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2-amino-l-hydroxy-naphthalene, l-amino-4-hydroxy-naphthalene, l-amino-8-hydroxy-naphthalene, 1-amino-2-hydroxy-naphthalene, l-amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, Sulphanil, aniline-2,4-disulphonic acid, aniline-2,5-disulphonic acid, Anthranilic acid, m- and p-aminobenzoeseiurc, 2-aminotoluene-4-sulfonic acid, 2-AmInOtOlUoI-S-SuIfOnSaUrP., P-Aminosalicylic acid, l-amino-4-carboxy-benzene-3-sulfonic acid, 1-amino-2-carboxy-benzene-5-sulfonic acid, l-Amino-5-carboxybenzene-2-sulfonic acid, l-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-: sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, l-naphthylamine-2,4-, -2,5-, -2,7-, -2,8-, -3.5-, -3.6-, -3.7-, -3.8-, -4.6-, -4.7-, -4.8- and -5.8-disulfonic acid, 2-naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and -6,8-disulfonic acid, 1-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine, 2-ainobenzothiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, Morpholine, piperidine, piperazine, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ß-methoxyethanol, 0-ethoxyethanol, γ-methoxy propanol.

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The diaminobenzenes of the formula (5) are generally diazotized by the action of nitrous acid in aqueous-mineral acid solution at low temperature, the coupling to the 6-hydroxypyridone- (2) of the formula (4) weakly acidic, neutral to weakly alkaline pH values.

The condensations of 2,4-difluoro (chlorine) -6-amino- (alkoxy or alkoxyalkoxy) -s-triazines or 2,4,6-trifluoro (Chlor) -s-triazines with the diaminobenzenes of the formulas (5) and (6) and optionally amines or alcohols take place preferably in aqueous solution or suspension, at low temperature and weakly acidic, neutral to slightly alkaline pH value. The fluoride or hydrogen chloride released during the condensation is advantageous continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

The fiber-reactive azo dyes of the formula (1) are characterized by high reactivity and a high degree of fixation.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, super polyamide fibers and super-polyurethanes, but especially cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable for the exhaust process as well as for dyeing after the padding process, after which the goods with aqueous and possibly also salt-containing dye solutions is impregnated, and the dyes after an alkali treatment or in the presence of alkali, if appropriate be fixed under the action of heat.

They are also suitable for printing, in particular on cotton, but also for printing on nitrogen-containing materials Fibers, e.g. from wool, silk or blended fabrics containing wool.

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away

It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if necessary with the addition of a dispersing agent. ^T irkenden and subject to the diffusion of the unfixed portions promoting agent.

More important in the following examples; the parts Gevjichtsteile, and the temperatures are in degrees Celsius specified.

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example 1

To a neutral aqueous solution containing 35.8 parts of the sodium salt of 2- (3'-aminophenyl) -amino-4,6-dichloro-1,3,5-triazine-4'-sulfonic acid contains 25 parts by volume of an anhydrous sodium nitrite solution, cools through, adding ice to 0 and pour 25 parts by volume of concentrated hydrochloric acid at once. When the diazotization is complete, a small one is destroyed Excess of nitrous acid by adding sulfamic acid. It is poured into the suspension of the diazo compound now an aqueous neutral solution of 19.6 parts of 1-ethyl-4-methyl-6-oxy-2-pyridone-3-carboxamide. By adding sodium hydroxide solution, it is initially set to p "4, after about Stir for 3 hours at p "7. You now give a neutral

rl

aqueous solution of 21 parts of the sodium salt of 1,4-phenylenediamine-2-sulfonic acid. One condenses at 20 to 25, the p “value being added dropwise with sodium hydroxide solution the solution is held at 6 to 7. When the condensation has ended, the mixture is cooled to 0 and a solution is added of 18.5 parts of cyanuric chloride in 50 parts of acetone. The condensation is carried out at 0 to 5, and by adding dropwise Sodium hydroxide solution keeps the p “value at 6 to 7. After finished Condensation is added to 25 parts by volume of a 20% strength ammonia solution and the mixture is stirred at 40 ° for 3 hours. By adding Sodium chloride becomes the color of the formula

^CH · 'ι j

HD ^ NN N

¹ I ⁵ I.

^CH 2 ^CH 3 Cl Cl

salted out, then filtered off and dried. It dyes cellulose fibers in real, greenish yellow tones.

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Further similar examples are summarized in the following table 1: The dyes, which one by Diazotizing 2- (3'-aminophenyl) -amino-4,6-dichloro-1,3,5-triazine-A'-sulfosMure, Coupling onto the pyridone from column II, condensing with the phenylenediaminesulfonic acid from column III, Further condensation with cyanuric chloride and finally with the amine obtained from column IV, colors cotton in the in Column V indicated nuances.

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Q) W)

W) • Η

O • Η 4J (O

O O

48

CM

00 • Η 43

U • rl

4-1

CO

00

cd γ-ι

4-1 0) (O W)

CM

CM

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49

V OO

V 00

M) τ!

χ: ο

(O

OO

CM CO

(U 00

CO

NO OO

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co co ro

I. 9 II III IV V 10 CH ₀ 0
i 3 ti
HOg S-CH ₂ - ^ N-CNH ₂
KO ^ N ^ OH H ₂ N- / ~ \ - NH ₂ ^ ^CH 3
(^ NH ₂
HO ₃ S ^- ^ greenish yellow 11 CH ₃
HO ^ N ^ OH /
If (T) -NH ₂ yellow 12th ! " H ₀ N- ^. .NH ₀
v ^ ii
SOoH CH ₃ OZ ^) - NH ₂ yellow 13th H ₂ NC- ^ J
O ^ N ^ H
CH ₃ Η ₂ ΝΗζ \ -ΝΗ ₂
SO ₃ H CH ₃
CH ₃ ^ greenish yellow CH ₃
HO ₃ S-CH ₂ - ^ S
O ^ N ^ OH
CH ₂ CH ₃ ti HIGH «CH-
^ ^Z ^ NH
HIGH ₂ CH ₂ ^ strong greenish cast
yellow

ro cn fo

•
> very greenish cast
yellow >
M. CM
I O
CM III CM
I el
iif ^W
55
CM M.
M. cn
δ
CM
§ δ
cn j / cm
δ °
I.
co
cn
O M. l-t

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One can proceed in such a way that the diazo component from Example 1 with the pyridone of column II of Table 2 couples the coupling product with the phenylenediamino sulfonic acid condensed from column III and then further condensed with the substituted triazine from column IV. The dyes obtained in this way dye cellulose materials in the nuances indicated in column V.

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- 17 -

Q)
r-ί
dd

bO • Η Xi υ

• Η 4J (O

U (ο

(U o

ο =

Q) OO

J3 U • Η 4Y (O

V4

60

CM

CM

CO CO

CM

-2-154293

(U (»Ο

CO CO

K ff!

U O

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I. II III IV V yellow 5 CH ₃
NHC - [^ Sj
O ^ N ^ OH
CH ₂ CH ₃ H ₂ N - / ^) NH ₂
SO ₃ H Cl
N ^ Si
Cl ^1N OCH ₂ CH ₂ CH ₂ OCH ₃ greenish yellow 6th CH ₃
H ₂ N-COfS
O ^ N ^ OH
CH ₂ CH ₃ It Cl
N ^ Si
crS ^ oo < _ru ³ greenish yellow 7th It Cl
N ^ Sjf O
C1 "^ N ^ NHCNH ₂ strong greenish cast
yellow 8th CH ₃ O
HO ₃ S-OT ₂ - [^ IpCNH ₂
■ j O ^ N ^ OH
CH ₂ CH ₃ K It

as

Example 2

39.5 parts of 1-ethyl - ^ - methyl-S- (5'-amino-2'-sulfophenylazo) -6-oxy-2-pyridone-3-carboxamide are brought into solution in water with concentrated sodium hydroxide solution at p .. 7. After cooling to 2 °, a solution of 18.5 parts is obtained Cyanuric chloride, dissolved in 50 parts of acetone, is poured in. During the condensation, the p "is added by further addition kept at 4 to 5 by sodium hydroxide solution. After condensation, a neutral solution of 21 parts of the Sodium salt of 1,4-phenylenediamine-2-sulfonic acid is added, the solution is warmed to 40 and the p "value held at 6 to 7 with sodium hydroxide solution during the 2nd condensation. If no more diamine can be detected, will the solution is cooled to 5 ° and a solution of 18.5 parts of cyanuric chloride in 50 parts of acetone is added. It is condensed at 0 to 5 °, the p n value being kept at 6 to 7 by adding sodium hydroxide solution dropwise. is the condensation has ended, 25 parts of concentrated aqueous ammonia solution are added and the mixture is stirred at 40 ° for 4 hours. By adding sodium chloride, filtering and drying, the same dye is of similar quality as in Example 1 isolated.

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If the procedure is exactly as indicated in Example 2, but instead of the aqueous ammonia solution used for Finally, an equivalent of one of the amines listed in Table 3 below, the acid being released is neutralized with further sodium hydroxide solution, so you get dyes, the cotton in the same shade and in dye fastness properties similar to that described in Example 2.

Table 3

I. II 1
2 CH ₃ CH ₂ NH ₂ 3 ^CH 3 / ^NH 2 4th Q-NH ₂ NHCNH ₀
Il ^
O 5 f V-NH ₀
V = / 2 NHCCH ₀
M J
O 6th ^ Xl * J V ^ V / il r \ V> H Λ INIlΛ 7th HO ₃ S-CH ₂ CH ₂ NH ₂ 8th
ι HOOC-CH ₂ NH ₂ 8098 2 1 / ÜÖ7S

I. II B ₂ CH ₂ CH ₂ CH ₂ KH ₂ 9 HO ₃ SO-CH ₂ CH ₂ NH ₂ -O. 10 CH ₃ - 11 HO ₃ S 12th HOOC 13th -Q - "* 14th CH ₃ 15th NH ₂ 16 ^ O ₃ H SO ₃ H Cl-CH ₂ CH ₂ NH ₂ CH _{3 >>} o, ₃ c

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Example 3

An aqueous neutral solution of 113 parts of the sodium salt of l-ethyl-4-methyl-5- [5 '- (4 ", 6" -dichlorl ", 3", 5 "-triazin-2 ^l -yl) -amino- 2'-sulfophenylazo] -6-oxy-2-pyridone-3-carboxatnids v; ird with a neutral solution of 34 parts of 2-amino-4- (4'-amino-3'-sulfo-an lino) -6- Chlorine-1,3,5-triazine sodium salt is mixed in water. It is heated to 40 ° and the pH is kept constant at 6.5 to 7.5 by adding sodium hydroxide solution. When the condensation is complete, it is salted out, filtered off with suction and dried Dye that is of the formula

hß-Cf VN = N-TVNH-C ^ -c_NH- <r> - _Ii HC * ν ^ ₂ ■ Ν ^ H HO S ^ ¹ Vj ^ O ₀ ⁿ ^ c ^{/ N}

CH CH I I

2 3 Cl Cl

corresponds, cellulose really dyes in brilliant green cast yellow shade,

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as

Example 4

21 parts of l, 3-phenylenediamine-4-sulfonic acid as a neutral solution present in water, cooling to 0 ⁰ C, with 18.5 parts of cyanuric chloride, dissolved in 50 parts of acetone, and enable by gradually adding 50 parts of 2N sodium hydroxide solution at Condense pH 4.5. Acidify with 25 parts of concentrated hydrochloric acid and diazotize with 25 parts of 4 normal sodium nitrite solution. After stirring for a short time, remove any excess nitrite with sulfamic acid and add a neutral, aqueous solution of 29 parts of 1-ethyl-3-sulfomethyl-4-methyl-6-oxy-2-pyridone-5-carboxamide. First set to pH 4 with sodium hydroxide solution and after about 3 hours of stirring and warming to room temperature to pH 7. Add a neutral aqueous solution of 21 parts of 1,4-phenylenediamine-2-sulfonic acid, warm to 40 ° C. and add 50 parts dropwise Condense 2 normal sodium hydroxide solution at pH 6-7. After the condensation has ended, ^{cool again to 0 °} C. and add a solution of 18.5 parts of cyanuric chloride in 50 parts of acetone. At 0-5 ⁰ C and pH 6-7 with 50 parts of 2N sodium hydroxide solution condense, after fill in 25 parts of a 20% ammonia solution and stirred for 3 hours at 40 ° C. By adding sodium chloride the dye of the formula

CH ₂ CH ₃

salt out, filter off, dry and grind. He dyes cellulose fibers very real in strong greenish yellow tones.

Similar dyes are obtained if the procedure described in Example 4 is followed, but those described in Table 4 Converts materials in the order of the columns in the table.

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3 * -

• Η O) -U W) w cd W)

^ 4C W) U

ro

CO

CM

3d

CM

CO

O

CO. ( CM

3d / = \ 3d

ir

CM 3d

co

(U W)

CM

CM

3d

co O

CM

rc

co

CM

Ϊ5

-L

CM W)

3d

co O

CM

3d

CM

3d

3d

co

2ZS4 ^ 93

• rl Q) 4J W) CO

W) υ

co

O = O

CO CO

δ ο ν

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I. II III SO ₃ H H ₂ NC IV H ₂ N V VI t-l VII VIII 5 Cl
N ^ Si
_c jA _N A _cl CH ₂ CH ₃ ^ SO-H
0
NH ₂ Cl
Cl ¹ ^ cI Cl ^N OCH ₃ Η, Ν- ^) greenish
yellow Cl HO ₃ SCH ₂ -T
<y CH ₃₀ ; 6th it cMnH N = C-
O'' ^K N ^ OH
CH ₂ CH ₃ H ₂ N ti It H ₂ NCH ₂ CH ₂ OH strong green
st ichig
yellow 7th dd ß
ciMni ^ 0 CVt
^ "^ ΟΗ
CH ₂ CH ₃ NH,
Mon ₃ H ti yellow Cl CH δ It ώοΗ If not applicable yellow

CO Ca »

60 co CM X 60 CO co
δ O
rl Xi CO ₌ SJ l-l
r-l • rl X CM CO •H Pc r-l O ^ ι x: pc ο I X! SJ O Q) υ CM u β ο χι CO <O CM \} C O Xl co O cm 60 δ CU ti Ή rl CM ^ 3-H rH te / - \ pc
C _) _ / [3 - (J) CM U Lj AJ Q) Lj 4J Q) 1— ^ δ W 60 W 60 60 W 60 I O 4Y OiU r I r-l υ M. 4J r-l CM Μ C M CO > (U 4-1 O • X CM δ CO CO
! U PC ο
CM
X \ ι 4m X
U I. I-I CO CM > O PC CM > M. r— (
M.
r-l r-l
M. M.

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Example 5

34.7 parts of the diazonium salt prepared in Example 1 from 2- (3'-aminophenyl) -ainino-4,6-dichloro-1,3,5-triazine-4'-sulfonic acid are to 17.8 Te'.le l-ethyl-3-cyano-4-methyl-6-oxy-2-pyridone coupled. Danac. it is first condensed with 21 parts of the sodium salt of 1,4-phenylenediamine-2-sulfonic acid at 40, the p n value being kept constant from 6 to with sodium hydroxide solution. After finished Condensation is then cooled and at 0 ° and a p .. value from 4 to 5 further condensed with 18.4 parts of cyanuric chloride using sodium hydroxide solution. Then after adding of 20 parts of concentrated ammonia solution for 4 hours at 40 °, then it is salted out, filtered and dried. The dye of the formula

K = C— γ \ N = N (^ y-NH-C ^ C — HH — C3 — NH — C ^ C-

ι Il

^CH 2 ^CH 3 Cl Cl

stains cellulose with a brilliant yellow color of very good fastness.

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Example 6

66.7 parts of 2- (4'-amino-3'-sulfo-anilino) -4- (3 "- [2 ^ΙΜ , 6"'dioxy-3"' - carbonamido-4"'- methyl-pyridine-5 "'-ylazo] -4" -sulfoanilino) -6-chloro-1,3,5-triazine are dissolved in water with the addition of sodium hydroxide solution at p "6 to 7, cooled to 0 and mixed with a solution of 18.4 parts Cyanuric chloride in acetone was added. By adding caustic soda, condensation takes place at p "4. Then 25 parts of concentrated ammonia solution are added and the mixture is stirred at 40 for about 3 hours. The dye of the formula

O ι ^X 3

-NH-

I Il ^ Y I Il

I I

Cl Cl

is salted out, filtered and dried. He dyes cellulosic materials in brilliant yellow tones of good authenticity.

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Example 7

15.8 parts of 1-ethyl - ^ - methyl-S- (5'-amino-2'-sulfophenylazo) -6-oxy-2-pyridone-3-carboxamide are dissolved in water with concentrated sodium hydroxide solution at p "7. To

Cooling to 0, 5.67 parts of cyanuric fluoride are added dropwise and at the same time the p "by adding sodium hydroxide solution to 6.5 held. If the p "remains constant, a neutral solution of 7.5 parts of 1,4-phenylenediamine-2-sulfonic acid becomes admitted. It is then heated to 40 and at the same time the p "is kept at 7.5 by adding more sodium hydroxide solution. After the end of the 2nd condensation, the mixture is cooled again to 0, 5.94 parts of cyanuric fluoride are added dropwise and the p " kept at 6.5 by the simultaneous addition of sodium hydroxide solution. If the p. Is constant again, 44 parts of in-ammonia solution will be obtained added and the p "by adding another drop of soda

kept lye at 7.5. It is warmed up to 30 to 40. By adding sodium chloride, the dye becomes the formula

Yjcr **

O ^ H ⁷ N) H HO, «« ^^, _Qn "

ι t> ^ Cr SO-H υ '

CH CH i I

Cj I Jl

pleases. After suctioning off, drying and grinding, one obtains a yellow powder that dyes cotton in genuine, brilliant, bright yellow tones.

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Proceeding as in Example 7, but using the azo dye described in column II of Table 5 as starting material, condensed first with cyanuric fluoride, then with the diamine from column III, then again with cyanuric fluoride and finally with the amine from column IV, one obtains further dyes, the cotton in the specified Dyeing shades with very good fastness properties.

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Table 5

II

S-

HO

CH ₂ CH ₃

0 H ₂ NC

CH,

N-N β HO

CH ₂ CH ₃

NSC

NN ^IH HO

CH ₂ CH ₃

CH ₂ CH ₃

III

H ₂ N,

SO ₃ H

NH,

Il

H ₂ N.

NH ₂ SO ₃ H

SO ₃ H

IV

NH,

H ₂ N

CH,

H ₂ N

SO ₃ H

H ₂ NCH ₂ CH ₂ SO ₃ H

strong greenish yellow

greenish yellow

yellow

greenish yellow

Example 8

The same dye as described in Example 3, in just as good yield and quality, can also be used as follows produce:

Dissolve 19 parts of cyanuric chloride in 50 parts of hot acetone and pour it onto 120 parts of ice and 30 parts of water fail again. At 5 to 10 ° C and pH 8 to 8.5 add a 5N ammonia solution in water until no more Ammonia is consumed more. A neutral solution of 18 parts of 1,4-phenylenediamine-2-sulfonic acid in 100 parts of water allow to drip into the suspension, while increasing the temperature to 25 ° C. and adjusting the pH by simultaneously metering in Keep 2N sodium hydroxide solution constant at 6.5. In the meantime prepare a suspension of 19 parts of cyanuric chloride as above, and let the suspension of the dicondensate run in. Keep the temperature at 5 ° C by adding ice and the pH with further sodium hydroxide solution to 7. After the condensation has ended, a neutral solution of 19 parts of 1,3-phenylenediamino-4-sulfonic acid pour in 100 parts of water. Warm to 30-40 ° C while still maintaining the pH at 7. if no more sodium hydroxide solution is taken up, cool to 0 °, add 25 parts of 4N sodium nitrite solution and Diazotize by toppling 25 parts of concentrated hydrochloric acid. After destroying a small excess of nitrite with a neutral solution of 19.6 parts of 1-ethyl-4-methyl-6-oxy-2-pyridone-3-carboxamide add 50 parts of water and adjust the pH to 4. After 4 hours of stirring up Set pH 7 and precipitate the dye by adding sodium chloride, filter off, dry and grind.

809821/0875

Color regulation 1

2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water at 20 to 50 ° with the addition of 5 to 20 parts of urea and 2 parts of calcined soda. A cotton fabric is impregnated with the resulting solution, so that it increases by 60 to 80% of its weight, and then dried. Thereafter it is heat-set for \ to 5 minutes at 140 to 210, then soaped for a quarter of an hour in a 0.1% boiling solution of an ion-free detergent, rinsed and dried.

Color requirement 2

2 parts of the dye obtained in Example 1 are dissolved in 2000 parts of water with the addition of 120 parts Table salt or calcined Glauber's salt dissolved at 75 °. You go into this with 100 parts of a cotton fabric Dye bath and keep the temperature constant for 30 to 60 minutes. After that, 10 parts of calcined soda and 4 ml Sodium hydroxide solution (36 ° B6) was added. The temperature is held at 75 to 80 ° for a further 45 to 60 minutes, then during Soaped, rinsed and dried in a 0.1% boiling solution of an ion-free detergent for 15 minutes.

Staining instruction 3

2 parts of the dye obtained in Example 6 are added with 0.5 part of m-nitrobenzenesulfonic acid Sodium dissolved in 100 parts of water. A cotton fabric is impregnated with the resulting solution so that it is around 75% of its weight increases, and then dried.

Then the fabric is impregnated with a 20 ° warm solution containing 5 grams of sodium hydroxide and per liter

809821/0875

Containing 300 grams of sodium chloride, squeezes to 75% weight gain off, the coloration attenuates for 30 seconds at 100 to 101 °, rinses, soaps for a quarter of an hour in a 0.37 ° boiling solution of an ion-free detergent, rinses and dries.

Dyeing instructions i 'ift 4

2 parts of the dye obtainable according to Example 6 are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water 60 parts of sodium chloride and goes with 100 parts of one Cotton fabric into this dye bath.

The temperature is increased to 60 °, after 30 minutes 40 parts of calcined soda and another 60 parts Sodium chloride can be added. The temperature is kept at 60 ° for 30 minutes, and the dyeing is then rinsed and soaped during 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinses and dries.

Printing specification

2 parts of the dye prepared according to Example 1 are mixed with rapid stirring in 100 parts of a stock thickening, containing 45 parts of 57o sodium alginate thickener, 32 parts of water, 20 parts of urea, 1 part of m-nitrobenzenesulfonic acid Sodium and 2 parts of sodium carbonate sprinkled in.

The printing paste obtained in this way is used to print a cotton fabric on a roller printing machine and steam the obtained printed fabric 4 to 8 minutes at 100 ° in saturated steam. The printed fabric is then in cold and rinsed thoroughly with hot water, which is not Remove chemically fixed parts from the fiber very easily and then dry them.

809821/0875

Dyeing instruction 5

100 parts of a cotton fabric are placed in 600 parts of water. The bath is heated to 40 ° C. and 20 parts of table salt are added. After 5 minutes, 1.2 parts of an antioxidant and 0.25 part of a wetting agent dissolved in water are added; after a further 5 minutes, 2 parts of dye no. 1 from Table 2, dissolved in water, was added. It is now allowed to draw out for 10 minutes at 40 ° C., then 2 ml of sodium hydroxide solution (36 ° Be) are slowly allowed to flow in. The bath is heated within 30 minutes to 70 ° C, then allowed to fix for 30 minutes at 70 ⁰ C. Thereafter, the dyed fabric is rinsed 5 times with cold water, rinsed for 10 minutes with 80 ⁰ C hot water, soaped at the boil for 20 minutes with a solution containing 2 g / l of an ion-free detergent, optionally rinsed hot for 10 minutes, and then rinsed again with cold water and finally dried. The result is a strongly greenish yellow coloration with good fastness properties.

809821 / 087S

Claims (20)

Claims 1. Fiber-reactive azo dyes of the formula NH-C C-NH- < J ^ N _n NH-C C-Z SO, H N N wherein X sulfomethyl, cyano or carbamoyl, R hydrogen or C 1, -alkyl, Y fluorine, chlorine, an alkoxy or alkoxyalkoxy group with 1 to 4 carbon atoms, or an optionally substituted one Amino group, one Z is fluorine or chlorine, and the other Z is an alkoxy or alkoxyalkoxy group with 1 to 4 carbon atoms, or an optionally substituted amino group. 2. A fiber-reactive azo dye according to claim 1, wherein X is carbamoyl, R is ethyl, Y is chlorine, one Z is chlorine and the other Z is an amino group. 3. The fiber-reactive azo dye according to claim 1 of the formula H = H ^ ^C 2 ^H 5 Cl Cl 4. The fiber-reactive azo dye according to claim 1 of the formula H ₉ K-CO Jv I Il N ^ N ^C 2 ^H 5 Cl Cl 809821/0875 ORIGINAL INSPECTED 5. The fiber-reactive azo dye according to claim 1 of formula > —Im — c ^ o-Kl · I! J ¹ SO ₅ H 6. Process for the production of fiber-reactive azo dyes according to claim 1, characterized in that one in any Order 6-hydroxy-pyridone- (2) of the formula wherein W is hydrogen or carbamoyl, with diaminobenzenes of the formulas HO ₃ S NlL and NH, SO ₃ H and halo-s-triazines of the formulas Y- C C I Il N _n ^ N - Υ and (5) (6) (7) 809821/0875 Z-C C-Z I Il / ON NN ⁽⁸⁾ couples and condenses and optionally a halogen atom Y and / or a halogen atom Z by condensation with a Amine or alcohol through an amino, alkoxy or alkoxyalkoxy group replaced. 7. The method according to claim 6, characterized in that compounds of the formulas (4), (7) and (8) in which X is carbamoyl, R is ethyl, Y is chlorine and Z is chlorine, and an amine as starting materials used. 8. The method according to claim 6, characterized in that a halo-s-triazine of the formula (7) with a diaminobenzene of the formula (5) condensed, the resulting primary condensation product is diazotized and converted to a 6-hydroxypyridone- (2) of the formula (4), the azo compound condenses with a diaminobenzene of the formula (6), the resulting secondary condensation product condensed with a halogen-s-triazine of the formula (8), and finally a halogen atom Z by condensation replaced with an amine by an amino group. 9. The method according to claim 6, characterized in that a halo-s-triazine of the formula (8) with an amine and condensed a diaminobenzene of the formula (6), the secondary condensation product obtained with a halogen-s-triazine of Formula (7) condenses, the bireactive intermediate product condenses with a diaminobenzene of the formula (5), the condensation product diazotized and on a 6-hydroxy-pyridon- (2) the formula (4) couples. 809821/0875 - yf- 10. The method according to claim 6, for the production of a fiber-reactive Azo dye, characterized in that the by condensation of 1, S-diaminobenzene ^ -sulfonic acid 2- (3'-aminophenyl) -amino-4, 6-dichloro-1,3,5-triazine-4'-sulfonic acid obtained with cyanuric chloride diazotized and coupled to 1-ethyl.3-carbamoyl-4-methyl-6-hydroxy-2-pyridone, the monoazo compound monocondensed with 1, A-diaminobenzene-2-sulfonic acid , the secondary condensation product obtained monocondensed with cyanuric chloride, and in the resulting 4,6-dichloro-1,3 , 5-triazin- (2) -yl radical a chlorine atom is replaced by an H-N group by reaction with ammonia, so that the fiber-reactive Azo dye of the formula Γ ³ n n-co-j ^]) - Ii - :; ■ / yiiii-c ^ifK ' ^v c-KH- <I> -hh- I I ^C 2 »ii Cl Cl is obtained. 11. The method according to claim 6, for the preparation of a fiber-reactive azo dye, characterized in that cyanuric chloride is condensed with ammonia and then with 1,4-diaminobenzene-2-sulfonic acid, the resulting 2-amino-4- (4 ¹ -amino-3 '-sulfophenyl-aminoi-o-chloro-s-triazine is condensed with cyanuric chloride, the condensation product is condensed with 1,3-diaminobenzene-4-sulfonic acid, the secondary condensation product formed is diazotized and converted to l-ethyl-3-carbamoyl-4-methyl- 6-hydroxy-pyridon- (2) couples, so that the fiber-reactive dye of the formula C received wii "d. 80982 1/0875 12. The method according to claim 6, for the preparation of a fiber-reactive azo dye, characterized in that l-amino-S-acetylaminobenzene-o-sulfonic acid is diazotized and l-ethyl-S-carbamoyl ^ -methyl-o-hydroxypyridone- ( 2) couples, the acetyl group is split off by saponification, the monoazo compound obtained is condensed with cyanuric fluoride, the primary condensation product is monocondensed with 1,4-diaminobenzene-2-sulfonic acid, the secondary condensation product obtained is monocondensed with cyanuric fluoride, and the resulting 4,6-dif luene -s-triazin- (2) -yl radical replaced a Fluoratotn by an H _O N group, so that the fiber-reactive azo dye formula CH., JL ^ * ^N n / - \ Λ H ₀ N-CO -r ^ t \ N = N ΓΤ ~ NH-C C-NH- <V-NH-C C-NH ₀ IH IJ IH \ / .IM ^ ~ sr ^ ν ν ι ν ν O.H * C I J I F F is obtained. 13. The fiber-reactive obtained according to the examples Azo dyes. 14. Procedure according to the examples given. 15. The fiber-reactive ones obtainable according to claims 6 to 12 Azo dyes. 16. Process according to the dyeing or printing examples. 17. Use of the fiber-reactive azo dyes according to claims 1 to 5 or those according to claims 6 to 12 obtained fiber-reactive azo dyes for dyeing and printing 18. A process for dyeing and printing using the fiber-reactive azo dyes according to claim 1. 809821/0875 19. Procedure according to; Claim 18 for coloring cellulose fibers. 20. Fä'rbe- und Druckpräparate, the fiber-reactive azo dyes according to claims 1 to 5 obtained. 809821/0875