DE2944624A1 - MONOAZO CONNECTIONS WITH FIBER REACTIVE REMAIN - Google Patents

Description

- 5 - Case 150-4252

Monoazo compounds with a fiber-reactive radical

The invention relates to monoazo compounds, their diazo component from the sulfo-aniline series and its coupling component from the aniline series free are of substituents ortho to the azo group, with to the amino group the coupling component bonded fiber-reactive radical from the 2,4,6-trihalogen-l, 3,5-triazine series, in which a halogen atom is replaced by an aliphatic or aromatic-carbocyclic amine function containing at least one water-solubilizing group is replaced, as well as their salts and mixtures thereof, processes for the preparation and their use.

The compounds according to the invention preferably correspond to the formula

wherein R is hydrogen, halogen, (l-4C) alkyl or (l-4C) alkoxy, X hydrogen, (1-4C) alkyl, (l-4C) alkoxy or carboxy,

R. and R independently of one another are hydrogen or (1-4C) alkyl, Shark fluorine, chlorine or bromine

and Z is an aliphatic or aromatic carbocyclic radical which contains at least one water-solubilizing group,

mean, and their salts and mixtures of these compounds of the formula I.

R in the meaning of halogen stands for fluorine, chlorine or bromine, preferably for chlorine or bromine, especially for chlorine. Preferred alkyl and alkoxy groups for R .. contain one or two C atoms and are in particular Methyl and hethoxy.

R- stands: preferably for R | as hydrogen, methyl, methoxy or ethoxy;

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more preferably for R ' ¹ as hydrogen, methyl or methoxy; more preferably for R '"as hydrogen or methyl and in particular for hydrogen.

If R _{1 is} hydrogen, the sulfo group is particularly preferably in the 3-position to the azo group; if R has a meaning other than hydrogen, then K and the sulfo group are preferably arranged ortho to one another.

X as alkoxy is preferably methoxy or ethoxy, in particular for Methoxy; X as alkyl is preferably methyl.

X preferably represents X in the meaning of hydrogen, methyl, methoxy, Ethoxy or carboxy; further preferred for X "in the meaning of hydrogen, Methoxy or ethoxy; further preferred for X_ as methoxy or ethoxy and especially for methoxy.

R “preferably denotes Ri as hydrogen or methyl; in particular means R »hydrogen.

R. preferably denotes R 'as hydrogen, methyl or ethyl, more preferably R .. denotes hydrogen or methyl and particularly preferably hydrogen.

Suitable water-solubilizing groups in the radical Z are preferably sulfo and Carboxy; Z is preferably at least in an aromatic-carbocyclic radical a sulfo group is present.

Z as an aromatic radical preferably denotes a phenyl radical which is one or two substituents from the sulfo and carboxy series and one or two substituents from the fluorine, chlorine, bromine and (1-4C) alkyl series or (l-4C) alkoxy may carry; the alkyl and alkoxy substituents preferably contain one or two carbon atoms.

Z as an aliphatic radical preferably denotes a HO S (2-4C) alkyl or HOOC- (2-4C) alkyl radical, the alkyl radicals of which are preferably two or three carbon atoms and in particular contain two carbon atoms.

Z preferably represents Z ₁ in the meaning of a radical of the formula (a),

(a)

R.

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where R, hydrogen, SuIfο or carboxy and R ^ are hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy,

or an HO ₃ S- (2-4C) alkyl or HOOC- (2-4C) alkyl radical; more preferably for Z in the meaning of a radical of the formula (a);

more preferably for Z as a radical of the formula (a), in which R_ is hydrogen, Denotes methyl or methoxy;

more preferably for Z as a radical of the formula (a) in which R is hydrogen or Means methyl;

further preferred for Z as a radical of the formula (a), in which R, sulfo or carboxy and R- are hydrogen or methyl, in particular hydrogen;

Z very particularly preferably represents the disulfophenyl radical.

Here meet for the preferred embodiments of Z in the meaning of a substituted phenyl radical of the formula (a) the following preferred arrangements of the substituents:

If R, and R_ are hydrogen, the sulfo group is in 3- or 4 position.

If R, carboxy and R ^ are hydrogen, the 2-carboxy / 4- or 5-sulfo positions are preferred; mean R, SuIfο and R ₁ . Hydrogen, the two sulfo groups are preferably in the 2,4- or 2,5-, in particular in the 2,5-position.

If R, stands for hydrogen and R_ is not equal to hydrogen, then are as positions preferably 2-R ../ 4- or 5-sulfo, in particular 2-R_ / 4-sulfo.

If R stands for sulfo or carboxy and R_ not equal to hydrogen, they are three substituents are preferably arranged in positions 2, 4, 5, with a carboxy group or one of the two sulfo groups present being preferred is in position 2.

Hal preferably means fluorine or chlorine, particularly preferably chlorine.

030022/0607

2SU624

- 8 - Case 150-4252

Preference is given to compounds of the formula T in which

(1) R1 and R2 represent hydrogen;

(2) Z is Z ₁ ;

(3) Z stands for Z, more preferably for Z_ and in particular for Z;

(4) Z for Z ₁ . stands;

(5) those of (1) wherein Z is Z;

(6) those of (2), in which R _{1 represents} R ', in particular R ¹ ";

(7) those in which X is X;

(8) those of (1) wherein Z is Z ₉ ;

(9) those of (1) wherein Z is Z;

(10) those from (1) to (9), in which Hai is fluorine or chlorine, in particular chlorine means;

(11) compounds corresponding to formula Ia,

.. -0 — ßr

NH-Z, _

3 la

Shark '

in which Ha] ¹ denotes fluorine or chlorine and in particular chlorine, and more preferably those in which, in the event that R '"denotes hydrogen, the sulfoivriippe is in the 3-position relative to the azo group, and in the case that dnss Γ.'" Methyl means "R ¹ " and the SuHo group are ortho to one another, as well as their SaI ro;

(12) Pt)] r! Ic vtvi (11), where Γ. '"Stands for Kasserstof i"; u! die Si '] fo ^ ruppc ri cli in I'nr.it Ί cn 3 bt-i'indet;

(13) Mi] Hn \ o;) (I]). vi.; · ί w :: for> iitfhl;

(] / :) f. <i] i1 'Vi t ( ¹ O,''"in>' IHr / -! in 'inrb.'(in'c ri for K ι In:; y; U'lil; (] 'O mi] ·!:' · -:, ι (11) hi :; (K), \ .Mi in ','. For '/. Sees;

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29U624

- 9 - Case 150-4252

(16) those from (11) to (14), in which Z. for Z ₁ . and in particular represents a disulfophenyl radical.

The nature of the cation of the sulfo groups and possibly additionally the presence of carboxy groups is not a critical factor; act not chromophoric cation, for example an alkali metal ion or an unsubstituted or substituted ammonium ipn. Examples of suitable cations are lithium, sodium, potassium, ammonium, Mono-, di-, tri- and tetramethylammonium, triethylammonium, mono-, di- and To mention triethanolannonium and mono-, di- and triisopropanolammonium. Preferred cations are the alkali metal ions including ammonium thereof sodium is particularly preferred.

The compounds of the invention are prepared by adding a cyanuric halide on the one hand with the corresponding monoazo compound (free of reactive groups) or a mixture thereof, on the other hand with an aliphatic or aromatic-carbocyclic substituted amine, the at least one water-solubilizing Contains group, or a mixture thereof reacts, the reaction being independent of the order in which the two components are added, and optionally converted into the salts. Thus, the preferred compounds of formula I are prepared by a cyanuric halide on the one hand with an aminomonoazo compound of the formula

R,

.'Vif Λ \

N -

and on the other hand with the amine component of the formula

HNR ₃ -Z III

reacted, the reaction being independent of the order in which a compound of the ^{formula I was added, and optionally the hereditary 1} .1 l "t: iien compounds of the formula I were converted into their salts.

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The individual condensation steps are carried out according to themselves known methods. The gradual: Replacement of the halogenatorce in the cyanuric halide is preferably carried out in a weakly acidic to weakly alkaline medium, for example, the first chlorine atom is preferably at temperatures from 0 to 5 ° C, the second. Chloratora at elevated temperature, preferably exchanged between room temperature and 65 ° C. Sodium carbonate, sodium bicarbonate or sodium hydroxide, for example, can be used as acid-binding agents.

The isolation of the compounds according to the invention can be carried out in a manner known per se Way to be carried out; E.g. the compounds can be separated from the reaction mixture by the usual salting out with alkali metal salt, filtered off and dried in vacuo.

The starting compounds are known or can be used according to or analogously to an knownon methods can be produced from known starting materials.

The compounds of the invention and mixtures thereof in the form of the free ones Acid and especially in saline form are reactive dyes. You own for dyeing and printing organic containing hydroxyl groups and nitrogen Substrates. Leather and textile are to be mentioned as preferred weaves. materials made from natural and synthetic polyai.iidoa, such as wool, Silk or nylon, and in particular made of natural or regenerated cellulose, such as cotton, viscose or wool, consist of or contain them.

The dyes according to the invention can be used in dye liquors or in printing pastes according to all dyeing and printing processes customary for reactive dyes can be used. They are colored and show particularly high Fixation values with fast fixation time.

Dii. The dyeings and prints achieved are noticeable to lightfastness in addition to good general chLln'iten, ζ.Γ .. wet fastnessc-n. like washing, in particular good Mührfach-Kochwaaclu'chLho. i t; Sweat, chlorine bath and llypochlor i tbl ei ehe »lit Heil :.

hl if \ 'ί · ιΊ> ΐ nihiiij.t'i) {', οι ä :::: cV.r Frf inihiii ;;. are also called Ko ⁿ .ili in: iri nis; · Jei ^T \ -i) lo nut Γίτ!) :; 1 of fen; ·, 1ι · i clu'v Kiiisc ( ^r ut ('■' i [ ^r , uft. da. ^c :! <: iiisl'cscndfi'e no c t. '. JyiiC

030022/0607

BATH

- 11 - Case 150-4252

For the dyes according to the invention, their should also be emphasized Padding liquor and printing paste stability soxfie their very good washability both in the block and in the printing process.

In the following examples, parts are parts by weight and percentages Weight percent; the temperatures are given in degrees Celsius.

example 1

92.3 parts of finely powdered 2,4,6-trichloro-1,3,5-triazine are in 500 parts Ice water stirred homogeneously. A neutral solution of 126.5 parts of 1-aminobenzene-2,5-disulfonic acid in 500 parts of water is left with ice-cooling and add the required amount of sodium hydroxide solution within about 5 minutes and then stir for about 3 hours at 0-5 °. By adding 3N sodium carbonate solution the pH is kept at approx. 6. The resulting monocondensation product dissolves.

153.5 parts of 4-aliino-3-methoxy-l, l'-azobenzene-3'-sulfonic acid by coupling 1 equivalent of diazotic 1-ainobenzene-3-sulfonic acid to 1 equivalent of l-Araino-2-methoxybenzene-N-w-methanesulfonic acid and then Cleavage of the W-MethanesulfonsMurerest, are in about 1000 parts of water are stirred and by adding the necessary amount of sodium hydroxide solution dissolved at pH 7. About 75 parts of sodium bicarbonate are added and this mixture is left for about 15 minutes as described above Solution of the monocondensation product o flow. Then you increase the reaction temperature within: about an hour to about 35-40 ° and stir 3-4 hours until the reaction is complete.

The yellow Honochlorlriaziny] dye is obtained by adding sodium chloride filled in, ahl il freezes and dried in vacuo at 100 °. Tj- has the Γοπποί

Sl) Well
^J

0 3 0 fJ 2 2/0 (ί Π 7

bath

2944524

Case 150- ^ 252

On cotton and regenerated cellulose you get it in particular lightfast and washfast, light, greenish yellow dyeings or prints.

According to the information in Example 1, further compounds of the formula 1 getting produced. They correspond to the Forriel

• Ν —Ζ

D-N = N-

Shark

for which the individual variables are listed in the table below and depend on the manufacturing and isolation conditions as sodium salts; however, they can also be replaced by ar. usual Massnahir.cn can be isolated in the form of the free acid. With these dyes can cellulose fibers by one of the known suitable processes be colored and printed. The dyeings and prints show good general characteristics, especially good lightfastness and washfastness. The last column J shows the shade of the dyeing on cotton; it mean where a = yellow and b = reddish yellow.

Tabel

3-Su] phenyl

do.

do.

do.
4-sulfophenyl

do.

do.

do.

OCH ₃ H

CH ₃

OCIL ₁ do. H

or: "Η,

H H H H H H H

Hal

Cl

Cl

Cl

Cl

Cl

Cl

II H H H II H H H

Z J 2,5-disulfophenyl a do. a do. a do. a do. b do. b do. b OO . b

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2344624

Case 150-4252

Table (continued)

E.g.
No. D. X ^R 2 Hal ^U 3 Z J 10 3-sulfophenyl OCH ₃ H Cl H 2,5-disulfo-4-inc ethylpheny 1 a 11 do. OC ₂ H ₅ H Cl H do. a 12th 4-sulfophenyl OCH ₃ H Cl H do. b 13th do. do. H Cl H 4-sulfophenyl b 14th 3-sulfophenyl do. H Cl H 2-carboxy-4-sulfophenyl a 15th do. do. H Cl H -CH ₂ CH ₂ SO ₃ Na a 16 do. do. H Cl CH ₃ do. a 17th do. do. H F. H do. a 18th do. do. CH ₃ Cl H 2,5-disulfophenyl a 19th 4-methoxy-3-
sulfophenyl H H Cl H do. b 20th 4-ethoxy-3-
sulfophynyl H H Cl H do. b 21st 3-methyl-4-
sulfophenyl OCH ₃ H Cl H do. b 22nd do. ^0C 2 ^H 5 H Cl H do. b 23 3-methoxy-4-
sulfophenyl H H Cl H do. b 24 do. OCH ₃ H Cl H do. b 25th 4-sulfophenyl COONa H Cl H 4-sulfophenyl b 26th do. do. H F. H do. b 27 do. do. H Cl II 3-sulfophenyl b 28 do. do. H Cl H 2-methy1-4-sulfophenyl b 29 3-sulfophenyl do. H Cl H do. a 30th do. do. H Cl H 2-carboxy-4-sulfophenyl a 31 4-sulfophenyl do. H Cl H do. b 32 do. do. H Cl H 2-carboxy-5-sulfophenyl b

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294452A

Case 15Ü-4252

Table (continued)

E.g.
No. D. X ^R 2 Hal ^R 3 Z J 33 4 - SuIfophenyl COONa H Cl H 2,5-disulfophenyl b 34 3-sulfophenyl do. H Cl H do. a 35 do. do. H P. H do. a

Possible applications of the reactive dyes according to the invention are described in illustrated by the following rules.

Dye vo r font Λ

2 parts of the dye from Example 1 are in 100 parts of warm water (approx. 40 °), to which 10 parts of urea were added, dissolved. A further 30 parts of a 10% strength sodium carbonate solution and 0.5 part of 1-nitrobenzene-3-sulfonic acid are added Sodium too. With this solution, a cellulose fabric is impregnated in such a way that that it absorbs 75% of its dry weight in dye solution. After drying, the fabric is steamed for 5 to 10 minutes at 102 °, then rinsed and soaped at the boil for 15 minutes. Receives after drying one a neutral yellow; Coloring with good light and wet fastness properties.

Dyeing instruction B

2 parts of the dye according to Example 6 are dissolved with 50 parts of water and 20 parts of urea at 20 °. After adding 15 parts of 10% strength sodium carbonate solution, the dye solution is made up to 100 parts by volume. The solution obtained is padded onto 20 parts of Bauinvo 11 fabric so that the liquor pick-up of the fabric is 80% of its dry weight. The padded fabric is first dried in between, then steamed for 10 minutes at 103 °. The dye is rinsed, soaped at the boil , rinsed again and then dried. A reddish yellow dyeing with a good level of fastness is obtained.

030Ü22 / 0607

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Pressure regulation

Mercerized BauiraiolIsatin is made with a printing paste of the following composition

25 parts of the dye from Example 1 10 parts of urea
440 parts of water
400 parts of a 4% sodium rhinate thickener

10 parts of 1-nitrobenzene-3-sulfonic acid sodium

25 parts of sodium carbonate

printed according to the usual method.

The printed textile material is steamed for 4-8 minutes at 102-104 ° and then cold and rinsed warm. After the hot soaping with subsequent rinsing again and drying gives a neutral yellow print with good light and light Wet fastness properties.

These dyeing and printing instructions with the dyes mentioned are representative for the other representatives listed in the example section.

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Claims (21)

Monoazo compounds with a fiber-reactive radical Patent claims 1. Monoazo compounds whose diazo component from the SuIfo-aniline series and whose coupling component from the aniline series are free from for Azo group ortho substituents with a fiber-reactive radical from the 2,4,6-trihalo-1,3,5-triazine series bonded to the amino group of the coupling component, in which a halogen atom is replaced by an aliphatic or aromatic carbocyclic amine function containing at least one water-solubilizing group , and mixtures of these compounds as well their salts. 2. Compounds according to claim 1 or mixtures thereof, those of the formula N = N Shark N-Z correspond to where R and R Hai Z and Hydrogen, halogen, (l-4C) alkyl or (l-4C) alkoxy, hydrogen, (1-4C) alkyl, (1-4C) alkoxy or carboxy, independently of one another hydrogen or (1-4C) alkyl, fluorine, chlorine or bromine an aliphatic or aromatic carbocyclic radical which contains at least one water-solubilizing group, and their salts. 030022/0607 ORIGINAL INSPECTED - 2 - Case 150-4252 3. Compounds according to claim 2, wherein Z represents Z in the meaning of a radical of the formula (a) SO-H (a) R.
^R 5 wherein R, hydrogen, sulfo or carboxy. and R ₁ . Mean hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy, or in the meaning of a HO-S- (2-AC) alkyl or HOOC- (2-4C) / \ lkylrestes stands. 4. Compounds according to claim 2 or 3, wherein R. for R '"is hydrogen or methyl. 5. Compounds according to any one of claims 2, 3 or 4, wherein R _? and R_ both represent hydrogen. 6. Compounds according to any one of claims 2-5, wherein Z is Z_ as The remainder of the formula (a) is as defined in claim 3. 7. Compounds according to any one of claims 2-6, wherein Z is Z- as A radical of the formula (a) in which R- is hydrogen, methyl or methoxy. 8. Compounds according to any one of claims 2-7, wherein X represents X ₁ as hydrogen, methyl, methoxy, ethoxy or carboxy. 9. Compounds according to any one of claims 2-8 or mixtures thereof, that of the formula .H RV ' -H = N- SO ₃ H \ 030022/0607 29A4624 - 3 - Case 150-4252 in which R '"is as defined in claim 4, X as in claim 8 and Z_ as defined in claim 7 and Hal' is fluorine or chlorine and in which, when R '" is hydrogen, the sulfo group is in the 3-position to Azo group, and in which, when R ¹ "is methyl, the two groups are ortho to one another, and their salts. 10. Compounds according to claim 9, wherein Z_ is Z- as a radical of the formula (A), in which R, SuIfο or carboxy and R_ signify hydrogen or methyl. 11. Compounds according to claim 9 or 10, wherein Hai 'is chlorine. 12. Compounds according to claim 9, 10 or 11, wherein Z is disulfophenyl means. 13. Process for the preparation of compounds according to claim 1 or of mixtures thereof, characterized in that a cyanuric halide on the one hand with the corresponding monoazo compound which is free of one fiber-reactive group, or a mixture thereof, on the other hand with an aliphatic or aromatic-carbocyclic substituted amine, which at least contains a water-solubilizing group, or a mixture thereof, the reaction being independent of the order of addition of the two components, and optionally the compounds obtained, are converted into the salts. 14. Process for the preparation of compounds of the formula I defined in claim 2 or mixtures thereof according to claim 13, characterized in that a cyanuric halide on the one hand with a compound of formula and on the other hand with the amine component of the formula IR ₃ -Z 030022/0607 HNR ₃ -Z III - 4 -. Case 150-4252 converts, the reaction being independent of the order of addition a compound of the formula II or III, and optionally those obtained Compounds of the formula I converted into their salts. 15. Use of the compounds according to one of the preceding claims 1-12 or mixtures thereof for dyeing or printing hydroxyl-containing and / or nitrogen-containing organic substrates. 16. Use according to claim 15 for dyeing or printing textile materials, which consist of or contain natural or synthetic polyamides or natural or regenerated cellulose. 17. Use according to claim 15 for. Dyeing or printing of leather. 18. A method for dyeing or printing hydroxyl-containing and / or nitrogen-containing organic substrates, characterized in that for this purpose, dye liquors, padding liquors or printing pastes containing a compound according to any one of the preceding claims 1-12 or mixtures thereof can be used. 19. The method according to claim 18 for dyeing or printing textile materials, which consist of or contain natural or synthetic polyamides or natural or regenerated cellulose. 20. The method according to claim 18 for dyeing or printing leather. 21. The materials dyed or printed according to claims 18-20. 030022/0607