SU340182A1 - - Google Patents

Description

This invention relates to a process for the preparation of new triazine active dyes, which can be used to dye cellulosic materials.

A known method for producing A1 active dyes of a triazine series of the general formula

/

NH -X- NH-C

I I A

i il N N RR N N

V cl

Cl r

where D-X is the radical of the water-soluble dye; X is alkylene, phenylene, di4) enylene.

The method of obtaining "x based on the condensation of cyanuric acid chloride with the azo-dye residue, followed by condensation of a two-molecular derivative with a diamine.

A method of obtaining generic dyes of the general formula

R -

Where

hydrogen or ALHll; X -

hydrogen, methyl, chlorine; D-N - Radium Cal soluble in water dye, nazmeyushchey rpyniny -NHR, for example, measures derived fec; 1lazonirazolo) 1a, 2- {4amdano-2-metllfe.ch "lazo) - naphthalene-4,8-disulfonic acids.

The amino groups of the benzene rings in the above formula can be found both in meta- and so-so in relation to each other, and the SOsH group can be in any remaining position of the benzene ring. However, it is desirable that the NH groups are in a-polol pairs and relative to each other and that the sulfonic acid group (OOSI) is in ortho-position with respect to the NH-CO-NH group.

Takim o.brazom, the most preferred class of dyes is a class in which the linking group is before. The 4,4-di-4-di-4-di-1-di-2-2-disulphacid odonic acid and D-NR is a radical of the phenylazopyrazolone compound containing an NHR group and a sub-solution of my groups in water.

The method of obtaining new active dyes consists in the co-condensation of cytochloric acid chloride with 1 g mol of solution HiMoro in water of a dye that has an optical base of D – NHR, where D, R and the indicated values, and with 0.5 g mol of dianyl diphenyl omericyl sulfide. which may include CH 3 or C 1 as substituents in each M benzene ring.

The above process can be carried out with chickpeas mixed with cyanuric acid chloride in an aqueous medium with a dye at a temperature O-20 ° C until one chlorine anhydride and cyalurum atom is replaced. the acid radical of this dye, the subsequent addition of diam. and the continuation of the reaction at a slightly higher temperature, usually in the range of 30 to 50 ° C, until the second atol: halogen, which is at the heart of triazine, reacts with each amino group,

Cyanuric chloride can react first with diamino1m at a lower temperature, o.dis a bisdichlorotriazine derivative, and then with a dye at a higher temperature. Condensation reactions and usually proceed at a pH of from 4 to 7 with the addition of an acid binding agent in order to neutralize the hydrochloric acid released during the reaction in the free state. When this reaction is complete, new active dyes can be isolated using the usual method adopted for extracting active water-soluble dyes, for example, by salting out crystals and solution by filtration, or by drying (and spray) a reaction mixture in which This dye was formed. It is possible to add stabilizers, alkaline acid phosphate salts of alkali metals.

As dnamimodiphenyl. CsvevinodSULPHONOVYY acids it is possible IONOLZOVA TL.

Blowing: 4,4-dia1Mnodife: -gilmschev1-2,2disulfonic acid; and 4,4-cdaci110 diphepilmochevino-3, 3-disuliphenic acid; 3,3-diamI1NodiphenylMochevino-4, 4-disulfonic acid and 3.3 dio. Mono-diphenyLgoneE (-6.6-disulfonic acid; 2,2-, di.methyl-3,3-diaminodinfenplMochevino-5, 5-Disulfo, acid-4.4 diamino-2,2d. chloride-urea-6.6-disulfonic acid.

1-a1 Mino-4- (4-methylmeyshoanilino) - anthraquinone-2, 3-disulfonic acid;

l-aiMHHO-4- (3-aiMi HO -2,4,6-tri-metlanilino) anthraquinone-2,5-disulfonic acid;

6-aMino-1-hydroxy-2- (2-sulfophenyl1-alazo) -naphthalene-3-sulfonic acid, b-amino -1-hydroxy-2- (2 sulfofenylazo) -zaphtali “-3,6-disulfonic acid; 7-a: Mino-2- (2,5-disulfophenylazo) - l-hydroxynaphalia-3-sulfoxy acid;

7- | Methylamino-2- (2-sulfophenylazo) -1-oxine a f t and Lin-3 - s l lf aqs lot;

7-methyl.mino-2- (4-methoxy -2-sulfophenylazo) -1-O1 Xynaphthalene-3-sulfonic acid;

8- (3-am.I1NO: benzoyl 1I | HO) -1-entrac-2- (2-sulfophenylazo) -naphthalene-3,6-d. And Sulfonic acid; 8-amino-1-ox-1-2,2-azonaphthalene -1,3,5,6-tetrasulfonic acid; 6-a. Mio-1-hydroxy -2- (4-acetyl-2-sulfophenylazo) - naphthalene-3 sulfonic acid;

b-methylamino -1-hydroxy-2- (4-1methoxy-2-sulfophenylazo) naphthalene-3-1 sulfonic acid; 8-amino-1ox-2-phenylazonaphthalene-3,6-disulfonic acid;

8-al1ino-1-hydroxy -2,2-azonaphthalene -1,3,6-trisulfo acid;

6-amyio-1-OXI-2- (4-, methoxy -2-sulfofiielazo) naphthalene-3-sulfonic acid; 8-amino-1-hydroxy-2,2-azonaphthalene-G, 3,5-tris u lu f ok from the lot;

6-a.m.-1-hydroxy-2,2-aza-naphthalene-G, 3,5-trnsulphonic acid;

6-methyl. Mino -1-0 KCi-2,2-azoiaphthalene-G, 3,

5-trisulfonic acid;

7-a.mino-1-ox1Ci-2,2-azaphthalene-1,3-disulfonic acid;

8-al1ino-1-oxI-2- (4-O1XI-3-carbox-phenylazo) naphthal “n-3,6-di Sulfonic acid; 6-amino -1-hydroxy-2- (4-hydroxy-3-carboxyphenylazo) n-naphthalene-3,6-disulfonic acid;

8-am-no-1-hydroxy-2- 4- (2-sulfophenylazo) -2-methoxy-5-methylphenylazo-naphthalene. 3,6-disulfonic acid;

4,4-bis- (alsno-G- o "si-3, disulfo-2 naphtalazo) -3,3-dnmethoxydiphenyl;

D) -amino -1-hydroxy-2- 4- (sulfophenylazo) -2 methoxy-5-methylphenyllazo-1 phthala: 1-3,5 disulfonic acid; 2- (4-amino-2-1.met1Ilphenylazo) -naphthalene4, 8- disulfonic acid; 2- (4-amIno-2-acetyllamphenylazo) - naphthalene-5,7- disulfonic acid;

2- (4-a1-amino-2-ureidophenylazo) naphthalene 3, 6,8-trisulfonic acid;

4-ntro-4- (4 -1met1adi-jofe1nilazo) -stilben-2, 2-disulfonic acid;

4-nitro (amino-2 (Methyl-5-methoxy-1plus-eye) -stilbn-2,2-disulfonic acid; 2- (4-amino-2 -petilaminophenylazo) -naphthal1 H-4, 8-dnsulfox1-Acid;

4-aMino -2-methylazobenzene-2,5-disulfonic acid; d.metilfepilazo -1 -naphnlamln-7-sulfonic acid; 4- 4- {2, o, tr sulfonaph-1-ylazo) -naft1-ylaz-1-aphthalamy1H-3-sulphonic acid; (sulfofenlazo) - 2-sulfophenyl} 1-lazo -1-naphthylMi. n-6-sulfo; Acid; 1- (2,5-dichloro-4-sulfophen, yl) -3-methyl-4 (3-alshNO-4 sulfofe1H1Ilazo) -5-pyrazolo; 1 - (4-sufofe: nil) -3-1kar (boksi-4- (4 -amyne, o3: sulfofeniliso) -5 n and | rasolon; 1-1 (2 -meta l -5-sulfophenyl) -3 -methyl-4 - (4 amy1NO-3 -sulfoF & n11lazo) -5- (pyrazolone; 1- (2- | Sulfophenyl) -3-methyl-4- (3 -am, and "o-4 sulfofiNIlazo") 5-pi | razol1n; 4-aiMHiH 0-4- (3 methyl-G-phenyl-4-lirazol-5a Nylazo) -ST1ILBe 11-2,2-disulfonic acid; 4-aiMHHO-4- (2 -OKCH-3 , 6 - disulfo - G-naphthylazo) -stilben-2,2-disulfonic acid; 8-acetylamino - 1-hydroxy-2- (3-amino-4-sulfophenylazo) -naphthalene-3,6-disulfonic acid; 7- (3 -sulfophenylamino) -1 - hydroxy-2- (4-amino2-carboxyphenylazo) naphthalene-3-sulfonic 8-phenyl II-OH-hydroxy -2- (4-am, E11U-2-sulfophene lazo) naphthal "n-3,6-disulfonic acid; 6-acetylamino-1-ox-2- (5-amino-2-sulfophenylazo) -naphthalene-3-sulfonic acid; b-ureido - 1-hydroxy-2 (5 -amino-2-sulfophenylazo) naphthalene-3,6-disulfonate; 1- (4,8-disulfonaph-2-yl) -3-methyl-4- (5 amino-2-sulfofennlazo) -5-nerazolone; 1 - (2-sulfophenyl) -3-carboxy-4- (5-amino 2-sulfophenylazo) -5-pyrazolone; 1- (2.5-dnO (p-4-sulfophenyl)) - 3-methyl-4 (.mino- 2-sulfofenilazo) -5-lirazolone; 1 - (3-aminophenyl) -3-methyl-4- (2,5-disulfophenylazo) -o-pyrazolone; 1- (3-amiofeiyl) -3-carboxy-4- {2-carboxy-4-sulfophenyl1-ylazo) -5-irazolone; 4-ash-4-3 -methyl - (2,5-disulfophenylazo) - -pyrazole - 5 -onyl-stilbene-2,2-disulfonic acid; 1- (3-aminophenyl.) -3 - carboxy - (2,5 disulfophenylazo) -2-methoxy - 5-methylphenylazo-5-pyrazolone; comilex compound with copper 8-amnno-1oxn-2 - (2-scs-5-sulfophenylazo) -naphthalene-3, 6-disulfonic acids; a complex compound with copper b-alpsho-1 oxn-2- (2-hydroxy - 5-sulfophenylazo) - naphtha li-3-sulfonic acid; a complex compound with copper 6-amino-1 hydroxy-2- (2 coco-o-sulfofennlazo) - naphtha li-3,5-disulfonic acid; complex compound with copper 8-amio-1 hydroxy-2- (2-hydroxy-3-chloro-5-sulfophenylazo) naphthalium-3,6-disulfonic acids; complex compound with copper 8-amino-1 oxen-2-4-2-sulfophenylazo) -2-methoxy-5 methylphennlazo-naphthalene-3,6-disulfonic complex with copper 1- (3-amino4-sulfophenyl) -3 - methyl 4-4- (2,5-disulophenylazo) -2-methoxy-5-methylphene, ylazo-5pyrazolone; Complex compound with copper 7- (4-am-11-O3-sulfoanilino) - - hydroxy-2-4 - (2.5-disuliphenylazo) -2-methoxy - 5-metnlphenylazo aftalin-3-sulphonic acid; Complex compound with copper 6- (4-amino3-sulfoanilino) -1 - hydroxy-2- (2-carboxyfe1ylazo) naphthalene-3-sulphonic acid; - (3-amino-4-sulfophenyl) -sulfamyl or phthalocyanine-3-sulfonic acid; - (3-Amino-4-sulfophenyl) -sulfamyl copper stoltsiannn-3,4-sulfonic acids; 3- (3- or 4-aminophenyl) -sulfamyl copper phthalocyanine-3-sulfonamide-di-3-sulfonic acid; 4-amino-2-pitrodiphenylamino - 3,4-d "sulfonic acid. Newly active pssetelle represented the south of value for dyeing textile textile. OV, including materials based on natural or regenerated cotton. These new dyes can be applied in the technique of printing processes, but mainly in dyeing processes. In the outfitting of textiles based on cellulose BOvioKH, they are used in combination with treatment with agents that bind Acid, such as caustic soda, as well as carbonate phosphate, slipcate, sodium bicarbonate, which can be applied to textiles based on cellulose fibers. during, after or before the dye is applied to them. The dyes applied in this manner chemically react with cellulose, li impart color to the fabric, so that it is very high in washing. The invention of illiteraution (but not limited by W1I1C) is an example in which all the pieces of information are given on weight. Example 1. A solution of 3.7 parts of cyanuric acid chloride in 30 parts of acetone is added to an ice-cold: 11.4 part of a three-salt 1- (4-sulfophenyl 11l) 3-: carboxy-4- (sulfate-5-a) salt of 1L sulfate ) 5-: pyrazolone in 200 parts of water. Then 20 parts of normal p. Are added: - StBras rashy hydroxy sodium hydrate to neutralize the resulting acid. A solution of 4.5 parts of disodium salt was added to 4.4 liters of M: a1SMD; phenyl1 Urea-2, 2-Disulfo: xyloids in 100 parts of water 1 the mixture was heated for one and a half hours at 35 ° C; at the same time 20 parts of 1 n are added to the reaction mixture. sodium hydroxide solution so that the solution is neutral. Then 100 parts of potassium chloride are added and the black precipitate is filtered off and dried at 50 ° C. gaios dye and textile materials on ociHo Be cellulose in the presence of a binder. X that slot agents, it turns out a greenish-yellow dye with high strength to light and moisture. The fixation (fixing) of the above Kraoitels is carried out on cotton and cotton cellulose materials with a ratio of a skin solution to a material equal to about 5: 1 and 20: 1, with a temperature of 80 ° C as follows. The dye in 1klichiste, corresponding to 1 to 2000 g mol, is dissolved in water and the corresponding ratios are prepared at a staining of 5: 1 to 20 :. The salt of the salt was added to this solution in an amount of 60 g / l and then heated to a temperature of 80 ° C. These materials are added (in the form of a skein, 5 g in the case of dyeing cotton at a ratio of 20: 1, and, 8 cuks of material and dried for 30 days at a temperature of 80 ° C. After that, the material is removed from the plastic solution and washed in water (the ratio of the dye solution to the material is 20: 1) at a temperature of 80 ° C for 30 minutes. The relative amounts of the dye in the new dye solution, the amount of the extracted edge of the strong solution The amount of the washing water measured with an adsorption | Spectrum The photophotometer shows the following e degree of fixation "(%). The ratio of dyeing solution to .ma5: 120: 1 material. Cotton 7675 PIcKyccTBeHHoe - cellulose fiber 9187 AN and a logical acre axil ai and using Kraoitel in an amount corresponding to 1/600 g mole and salts in the amount of 100 g / l, show: next: -1e ste: py hyf41cation (%). OTF-fGLLeiiiHe dye; Whose solution to the material Cotton Art. naeo cellulose fiber you: Juice the degree of fixation of these dyes is observed also for use: use them when printing AI. For example, when using printing pastes containing sodium carbonate, the degree of consolidation is 85% liter higher, the resultant Oppressions have high strength (with filling paint: ni) when they are treated with water. Example 2–37. -3 -carboxy-4 (2-sulfo-5-am-inofeni) -5-pyrazol1; a, used in the product, an equivalent amount of the specified chemicals. The table shows the colors obtained in a x when these dyes are applied to textile materials based on cellulose fibers in the presence of an OTU binding agent. Dye Tre. sodium salt of 2- (4-am sho-2ureidophenylazo) -naphthalene-3, 6, 8 trisulfonic acid. The three-sodium salt of 6- (G, 5-dp of Krasios-sulfoiaft-2-ylazo) -2-methylamino-orio-5-naphthol-7-sulfonic acids. chewed disodium salt of 1- (2,5-d11HLORZelenova4-sulfophenyl) - 4- (am1ChO-2, that is yellow sulfophenylazo-3-methyl-5-iirazolone. Disodium salt of 7-phenylazo-1-amino-8-naphthol -3.6- disulfonate. Three-sodium salt of 7- (2-sulfoTo same phenylazo) -1-amnno -3-paphol-3, 6-D 1 sulphonic acid. sulfonic acids. Purple three-sodium salt of copper comilex compound 7nen 7- (2-hydroxy-3 chloro-5-sulfophenylazo) -1-amino8-naphthol-3, 6-disulfonic acids. Rubium trihydrogen salt of copper Komi 6- (2-oKCii-3, j 5 -disulfophenylazo) -2-methylamino-5-naphthol-7-sulfonic acid lexane compound. Quaternary salt of complexRubine blue copper compound 6- (2-hydroxy3,5-disulfophenylazo) -2-amino -5 naphthol-1, 7-disulfonate. Two-amide salt of 1-amipo-4- (4-green-blue amino-anaplino) -anthracine-2,3-dpsulphonic acid. Two tri-salt of 1-amio-4- (4) styrene and anophenyl-anthraquinone Dglatrisna so.ch. 1-ami | g - L. Jaminoanplpno) - pitrakhinon -2,4-di-. Suly1) g. 11sloty. I Dvuyatrieva salt 1-am11o-4- (3KrasR .oiaamino -2.4.6-timethylaiilino) - a-to-sipprahioion-2.5-D sulfonic acid.j Lvunatrpeva salt 0-amino-1-hydroxy : Orange 2- (-sulfophenylazo) -haftal1I-3sulfonic acid .I Three-sodium salt of 6-amyio--1 ox1 (2.5-disulfophenylazo) -: us-3-sulfide, hydroxyacid | Disodium salt b-metitampio orange 1-hydroxy -2- (2-sulfoxybenzo) -aphthalium-3-sulphonic acid. -3-sulfonic acids. Three-sodium ol O-3-aa h no Cine-Krasbenzoyl-amino) -2- (2-sulfophenine lazo) - 1-naphthol-3i6-disulfoK11Sloty. The dye Tre.hiatriev salt 8-am11NO-, 1oxy -2,2-azonaphthann -1,3,6 -trisulfoxplota. Two-sodium salt of 6-amino-2- (4methoxy-2-sulfophenylazo) -1-naphthol-3-sulfonic acid. Disodium salt of b-methylamino-2- (4-methoxy -2-sulfophenylazo) -1 naphthol-3-sulfonic acid. Three-sodium salt-6-amnno-1-ok si-2,2-azo-naphthal 11i-G, 3,5-trnsulphonic acid. Three-sodium salt of 7-aMiii o-l hydroxy-2,2 - azonaphtaln-1,3,5-three sulfonic acids. The three-sodium salt of 1- (2-sstil-3-amino-5-sulfophenyl) -3-carG) ox11-4 2 -sulfophenylazo1-5-1; 1ra:, ola. The three-sodium salt of the copper complex Compound b-amnio 2,2oxn-5-sulfophenyl; .o) -l nafs 3,5-dnsul (|) oxlots. The three-sodium salt of the copper complex / tex compound 6-methi.1a.1nno-2 | 4- (2, disulfophenyl; o) -2 metho; ch-5-methylpheylazo -1-11 naphthol-3 sulfonic acids. The three-sodium salt of the copper complex of the south compound of 8-a.nno-1,2-dnox11-G, 2-azonaphthann-3,4,6 -trisulfonic acid. The four-sodium salt of the copper complex compound B-ampno1, 1-dioxy-2.2-azaphthalene-2,4,6,8 tetrasulphoxy acids. Three-salt salt of the copper complex of the compound 8-amino-2- (2-hydroxy-3-sulfo-5-amiophennlazo) -1 naphthol-5, 7-di sulfonic acids. The three-salt salt of the copper complex compound 8-am11no-2- (2-ochen-4-sulfo-6-algnonaph-1-nla30) -1 -11ac () tol-5, .1fo acid. The three-salt salt of the copper complex compound 6-1-1-4; 1-3-sulfophenylamino) -2- | 2 () x-3 nigro-5-sulfophen: 1ilazo-1-nfgol-sulfonic acid. Disodium salt of 4-am11io-2-1P Trod || phenyl: but -3,4-disulfo acid. P Tipatrneza salt of 8-amino-7- (2, 5-dnsulfofe: p1lazo) -2 - (.mino, eulfofef1N1lazo) -1-naphthol-3,6D11SuLofOK1 SLOTS. Trietriam salt 2-am | 1NO-1- (4 | amyl -2.5-dnsulfofennlazo) - 8i naphthol-6-sulfoxyls. Four-sodium salt of 3- (3-am 111o-4-sulfophenyl) -sulfanln copper phthalocyanne-sulfonic acid.

P m and m 38.

A solution of 3.7 parts of cyanuric acid chloride in 30 parts of acetone dO | is added to a cooled: open solution of 4.5 parts of disodium salt of 4,4-diaminodiphenylurea-3,3-disilfo acid in 100 parts of water. Then, 20 parts of IIH are added to this mixture. sodium hydroxide solution in order to neutralize the resulting acid. A solution of 9.3 parts of 2- (4-amino-2-methyl-phenylavo) -naphthalene-4,8-disulfonic acid disodium salt is added in 200 parts of water and the mixture is heated for 20 hours at a temperature of 35 ° C.

The subject invention

The method of obtaining the active dyes of the general formula:

N TYAN ,,, OzCh, v, C / C

D-N-C / V L / Y VV) -D with mixing and at the same time adding 1 n to it. Nati hydroxide solution to keep the solution neutral. Then, 100 parts of potassium chloride are added to the operation mixture and the resulting precipitate is filtered off; they are dried and dried: 50 ° C. The dye obtained in this way is a yellow rosé, when applied to textiles. The basis of cellulose fibers in the presence of bent acid agents is a yellow c-veta stain, which has good durability to light and wet treatments. . Below are other examples of dyes, dyui, their yellow color, which can be obtained by replacing 4.5 parts of 4,4-diaminodiffeia1; mo-3,3-disulfonic acid, used in Example 38, equivalent to the amounts indicated in compounds. Example 39. H, 3-Dia1minod. Mpil1il: urea; -: ;; - 4, 4-di.sulfa: SLOT. Example 40. 3,3-D; ia.minodife "iLMochevino-6, 6-disulfs" and slots. P and Measure 41. A solution of 3.7 parts of acid cyanuric acid in 30 parts of acetome is added to an ice-cooled solution of 11.4 parts of 1- (4-: sulfophenyl) -3-carboxy-4 triacetate - (2 sulfo-5-amInophenylazo) -5-pyrazoloia in 200 parts of water. Then add 20 p. 1 and. a solution of sodium hydroxide and sodium hydroxide to neutralize the formed acid. Next, a solution of 4.75 parts of disodium / 2,2-dimethyl-3,3-diai P nodiphenylmochie is added: BIlio5, 5-disulfonic acids in 100 parts of water and the mixture is heated for 3.5 hours at 35 ° C, when orepremein is added, sodium hydroxide solution (20 hours) to keep the solution neutral. Next, 500 parts of potassium chloride are added and the resulting dye precipitate is filtered off. And dried at 50 ° C. The dye obtained in this way is a yellow powder. When applying the dye and textile materials based on cellulosic fibers in the presence of an acid binding agent, a greenish-yellow guania color is obtained, which is highly durable to light and moisture. And where R is hydrogen or alkyl; X is hydrogen, L1etnl, hl chlor; D - N is the radical of the water-soluble I R5 edge, and the -NHR group, for example, phen-ylazopyrazolone derivative, 2- (4amio-2-methylphenylazo) -naphthalene-4,8-diI 12 sulfonic acid, characterized by that the cyanuric acid chloride acid chloride is subjected to condensation with one I1M. mole of the D-NHR sig nal, where D, R have the indicated indications and with the polar moth diarymdiphenylurea and disulfonic acid with the subsequent isolation of the target product by a known technique.