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3 United rates Patent i9 "ice 3,674,925 Patented Jan. 22, 1953 2 1: 3,074,925 AZO ANTHRAQUINONE DYESTUFFS CON TAINING A TRIAZINE Robert Norman Heslop, Blackley, Manchester, England, assignor to Imperial Chemical Industries Limited, Lon don, England, a corporation of Great Britain No Drawing. Filed June 4, 1959, Ser. No. 817,981 Claims priority, application Great Britain Nov. 29, 1954 6 Claims. (Cl. 260-153) 10 This application is a continuation-in-part of application Serial No. 549,176, ?led in the United States Patent Of?ce on November 25, 1955; and of application Serial No. 732,841, ?led May 8, 1958, as a continuation-in-part of application Serial No. 549,160, ?led November 25, 1955, now abandoned, which application Serial No. 732,841, is and l which radicals contain at least one strongly acid solu bilising group. The benzene nuclei in A may also contain now United States Patent 2,892,670, having issued June other substituents, especially chlorine atoms, lower alkyl 30, 1959. groups or lower alkoxy groups, e.g. methyl, methoxy The present invention is concerned with water-soluble dyestuifs of the triazine series. More particularly the 20 and ethoxy groups, without markedly affecting the gen eral properties of the dyestuils. invention is concerned with water-soluble dyestu?s of the The new dyestutfs may be obtained by the condensa tion of cyanuric chloride with about one molecular pro triazine series which contain both an azo chromophore and an anthraquinone chromophore. It is well-known, for example, from British Patents portion of an amino-azoanthraquinone compound which Nos. 466,886 and 554,463, that water-soluble dyestu?fs 25 is represented in the acid form by the formula: of the triazine series may be obtained which contain both an azo chromophore and an anthraquinone chrornophore. In the dyestuffs hitherto described, this has been achieved by condensing an m-aminoanthraquinone compound which contains a reactive amino group and an amino-azo dyestuff containing a reactive amino group with a cyanuric halide, and usually replacing the ?nal halogen atom of 0 II run I -—SOaH 30 (503.11)“ (I) NH-A-NH: the cyanuric halide by reaction with an amine, e.g. aniline. in which A and n have the meanings given above. The We have now found that valuable dyestu?s may be said aminoazo anthraquinone compounds used in this 35 obtained by condensing cyanuric chloride with certain manner are mainly novel but may be obtained by general water-soluble amino compounds which contain both the methods in themselves known from the past, for ex mthraquinone and the azo chromophore in such manner ample, by condensing a diaminoazobenzene which con that two chlorine atoms are left attached to the carbon tains a strongly acid water-solubilising group with a 4 atoms of the triazine ring. The dyestuffs forming the bromo-l-amino-anthraquinone-Z-sulphonic acid or a 5-, subject of the invention may be broadly represented, in 40 6-, 7- or 8-sulphonic acid derivative thereof, or by cou the acid form, by the formula: pling a diazotised aniline containing a strongly acid water-solubilising group with a l-amino-4-(m-amino anilino)anthraquinone-Z-sulphonic acid or a 5-, 6-, 7- or S-sulphonated derivative thereof analogously to the method described in German Patent No. 659,591. The reaction of the said aminoanthraquinone com pound with cyanuric chloride is preferably carried out in aqueous medium at a low temperature, preferably be 50 tween 0 and 10° C. Advantageously the reaction medium is maintained at or about neutrality by the addition of acid-binding agents such as sodium carbonate during the reaction so as to neutralise the hydrochloric acid formed. the azobenzene series which contains at least one strongly If desired, an excess of cyanuric chloride may be used acid water-solubilising group, for example, a sulphonic to allow for hydrolysis. 55 acid group or a carboxylic acid group. In general A will The new dyestuffs so obtained can be isolated from not contain more than two such groups. the medium in which they are produced by the commonly The dyestuffs so de?ned have a similarity of dyeing used methods, for example by salting out the dyestuti in properties as‘hereinafter set out which are determined the alkali-metal salt form and ?ltration or by spray by these broad structural features and which are little the whole reaction mixture. Owing to the pres a?ected by the variations of structure possible within 60 drying ence of the labile chlorine atoms in the molecule it is these de?nitions, or by the presence or absence of non desirable to carry out the drying cautiously, for example solubilizing groups in A. at a moderate temperature such as between 29° C. and wherein n stands for 0 or 1 and A stands for a radical of .Thus, the nitrogen atoms linking the azobenzene radical A to the anthraquinone and triazine nuclei may be at 40° C. and, if desired, under reduced pressure. The ad dition of certain buffers aids the stabilisation of these tached to the same or diiferent benzene nuclei, so that A 65 labile chlorine atoms especially valuable being mixtures may represent such radicals as for example: of alkali metal hydrogen phosphates and mixtures of the free acids and alkali metal salts of dialkylarylamine sulphonic acids (e.g. diethylmetanilic acid) in which the 70 alkyl groups contain 2 or more carbon atoms. The new dyestutfs are suitable for dyeing or printing a wide variety of material, for example wool, silk and 3,074,925 3 4 polyamide materials, and are especially valuble for use on cellulose textile materials such as linen, viscose rayon These dyestuffs have the formulae: O and cotton when dyed in the presence of an a kali or when NH: H the dyed material is after-treated with an alkali. On these | S0311 materials they give olive-green shades which are very 6 fast to washing and to light. They are especially suit able for dyeing cellulose at or about room temperature in an aqueous alkaline both which contains a salt, and may also be ?xed on cellulose by padding or textile print ing methods incorporating a treatment with an alkali, 10 and if desired, a short heat treatment. , ferred those in which A represents a radical of the /C\ ‘It H038 c“) 11IH®N=N~©~NH~o \ % 0-01 A 0:13: N and The preferred dyestuffs of the invention are those in which A of the general formula represents a 4:4’-radical of the azobenzene series containing a sulphonic acid group or a carboxylic acid group, and above all are pre (In O NH: H I S0311 15 Z1 formula: / \ . 20 If ‘I Hot 0 liIHON=N— ml.\ % $-01 SOaH N 02H wherein A1 stands for a ‘1:4-monocyclic radical of the benzene series. The invention is illustrated but not limited by the ‘following examples in which parts are by weight: respectively. In place of the trisodium salt of 1-amino~4-[4'-(4" amino) phenylazo] anilinoanthraquinone - 2:2":5 - trisul 25 phonic acid used in the above example there is used an equal weight of 1-amino‘4-[4'-(4”-amino)phenylazo] anilinoanthraquinone-2z2”:S-trisulphonic acid, a dyestuif Example 1 A solution of 4.06 parts of cyanuric chloride in 20 parts of acetone is added gradually to a stirred mixture 30 of 50 parts of water and 100 parts of crushed ice. To the stirred suspension of cyanuric chloride thus obtained there is added at 0° to 4° C. during 1 hour a solution in 250 parts of water of 14.8 parts of the trisodium salt of 1-amino-4-[4’-(4"-aminophenylazo)~aniline]-anthra 35 quinone-ZzZ":S-trisulphonic acid, which may be prepared of the formula: 11038 g‘) NH: S0111 01 \ I I 0 NH N/ \III N=N NH-ii 0-01 % by condensing 4-bromo_l-aminoanthraquinone-Z:5-disul~ SOaH phonic acid with 4:4'-diamiuoazobenzene-2-sulphonic acid is obtained. It dyes in shades slightly bluer than the in alkaline medium. The mixture is stirred for a further 40 minutes at 0°—4° C. and then sufficient 2 N sodium 40 dyestutfs of the formulae indicated above. carbonate solution is added gradually during 30 minutes Example 2 A solution of 0.93 part of cyanuric chloride in 16 parts of acetone is added gradually to 100 parts of water stirred at 0° to 2° C. To the stirred suspension of cyanuric chlo— to render the reaction mixture neutral to litmus. A solu tion of 11.4 parts of disodium hydrogen phosphate and 7.2 parts of potassium dihydrogen phosphate in 100 parts of water is added, the mixture is stirred for 10 minutes and then su?icient sodium chloride to give a concentra 45 ride so obtained a solution of 3.37 parts of 1-amino-4~(3' amino - 4’ - phenylazo)anilinoanthraquinone - 2:2”:5” tion of 50 grams per litre is added and the mixture is stirred for 3 hours when separation of the dyestuff is com plete. The mixture is ?ltered, and the solid on the ?lter is washed with a solution of 25 parts of sodium chloride, 11.4 parts of disodium hydrogen phosphate and 7.2 parts 50 of potassium dihydrogen phosphate in 500 parts of water, and ?nally dried at atmospheric temperature. The prod not so obtained has the formula: 0 H NH: l -SOaH maintained at 5° to 10° C. and the pH at between 5.5 and 6.5 by the addition of 2 N sodium carbonate solution. After stirring for one hour longer, a mixture of 0.5 part of disodium hydrogen phosphate and 1.0 part of potassium dihydrogen phosphate is added. When these have dis solved, the reaction mixture is ?ltered, sodium chloride is 55 added to the ?ltrates and the dyestuli so precipitated is ?ltered and washed on the ?lter with a solution of 40 parts or N trisulphonic acid in 200 parts of water is added during about 1 hour the temperature of the reaction mixture being /C\N 5. of sodium chloride, 1.35 parts of disodium hydrogen phos phate and 2.7 parts of potassium dihydrogen phosphate in 200 parts of water and ?nally dried at room-temperature. 60 The dyestuli so obtained has the formula: i’ re SOZH which yields olive-green shades on cotton and viscose. By replacing the above trisodium salt of Lamina-4 65 [4'-(4"-amino)phenylazo] anilinoanthraquinone - 2:2":5 . trisulphonic acid with equal parts of the trisodium salt of l-amino - 4 - [4'-(4"-amino)phenylazo]anilinoanthra quinone-Z13":5-trisulphonic acid, a dyestuft‘ almost iden tical in shade and properties is obtained. Also by sub 70 stituting the above trisodium sulphonate with 14.1 parts of the trisodium salt of l-amino-4-[4’-(4"-amino-3" carboxy) phenylazo] anilinoauthraquinone-Z:5‘disulphonic acid a dyestuff very similar in shade and properties is obtained. 75 as ('i NH~QN=N 1%IH 0 80311 3,074,925 6 5 2:2":5-trisulphonic acid used in the above example, a It possesses very good solubility in water and yields fast olive-green shades on cotton, bluer than the dyestu?s of similar dyestuif having the formula: Example 1. 0 Example 3 5 sonar A solution of 1.94 parts of cyanuric chloride in 20 parts of acetone is added gradually to 80 parts of water stirred at 0° to 2° C. To the stirred suspension of cyanuric chloride so obtained a solution of 7.53 parts of the tri sodium salt of 1-amino-4-[4’-(4"-aminophenylazo)-3'~ NH, I or L 01 I 11“ \Ir' 10 H038 ii rim- methyl]anilinoanthraquinone-Z:2":5-trisu1phonic acid in / CH3 N=NONH-o \ / b-ol a 1 N “$03K 200 parts of water is added during 30 minutes the tem is obtained. perature of the reaction mixture being maintained at less 1 What I claim is: than 5 ° C. and the pH between 5 and 6 by the addition of l. The dyestuffs represented, in the acid form, by the 2 N sodium carbonate solution. After stirring for 30 5 formula: minutes longer, sodium chloride is added and the dyestu? 0 Nm so precipitated is ?ltered off, washed on the ?lter with a II solution of 4 parts of sodium chloride, 1.5 parts of disodi um hydrogen phosphate and 3 parts of potassium dihydro 20 30:11 gen phosphate in 200 parts of water and ?nally dried at room temperature. The dyestu? so obtained has the formula: 0 II \ . NH--A——NH-C . t/ \“JC-Cl 0 0 % N 1 (51 wherein n is 1 and A represents an azobenzene radical which contains from 1 to 2 strongly acid water-solubilising groups selected from the class consisting of sulfonic acid and carboxylic acid groups, the other substituents on the \ 1103s C 25 N112 son: . H t/ ‘t N=N-®C 0-01 \N_% CH: NH It has good solubility in water and yields fast olive green carbon atoms of A being selected from the group con sisting of hydrogen, chlorine, lower alkyl and lower alkoxy. 35 2. The dyestuif of the formula: t ‘is shades on cotton. $01K Example 4 A solution of 1.95 parts of cyanuric chloride in 20 parts of acetone is added gradually to 80 parts of water at 0° to 2° C. To the stirred suspension of cyanuric chlo ‘° . .l noas 0 ('21 /O\ t‘ \t' NH—C>N=N ride so obtained a solution of 7.83 parts of the trisodium 30 minutes, the temperature of the reaction mixture being $02K (in 50 ‘K n o um chloride, 1.5 parts of disodium hydrogen phosphate and 3 parts of potassium dihydrogen phosphate in 200 It ‘.1C-Cl —NI-I-G NH-C>—N:N— \ 4 N parts of water and is ?nally dried at room temperature. 55 The dyestuti so obtained has the formula: 30311 4. The dyestuif of the formula: 0 II NH: NE: 50:13: 30:31 a. 3. The dyestul’f of the formula: off washed on the ?lter with a solution of 4 parts of sodi N NH-C \ v% C-Cl H0313 (l) IIIH: 200 parts of water and 30 parts of acetone is added during maintained at from 5° to 10° C. and the pH at between S and 6. After stirring for 30 minutes longer sodium chloride is added and the dyestu? so precipitated is ?ltered , $0311 salt of 1-amino~4-[4'-(4”-aminophenylazo)-5'-methyl-2' 45 methoxy] anilinoanthraquinone-Z : 2" : S-trisulphonic acid in 0 ([11 (30311)“ 01 ('31 C Hoag | 5. The dyestutf of the formula: 0 CH3 (|) NH: It posssesses good solubility in water and yields fast SOaH olive green shades on cotton. 70 By substituting 8.04 parts of the trisodium salt of 1 (I, amino - 4 — [5' - chloro _ 2' - methoxy - 4’ - (4" - amino) phenylazo]anilinoanthraquinone-Z:2":5-trisulphonic acid Hols for the trisodium salt of 1-amino-4-[4’-(4"-aminophenyl azo) - 5’ - methyl - 2' - methoxy]anilinoanthraquinone 75 Cl l 0 on \ | ‘ NH- N/ \N Nn-d (‘J-Cl N=N 0cm dour N/ 3,074,925 6, Thedyesm? of the formula: 0 ' NH, ' References Cited in the ?le of this patent ' UNITED STATES PATENTS ' 50811 C1 ('31 HOalS 3 NH cmo 5 Haller et a1 ____________ __ Nov. 8, 1932' 2,108,126 Honold et a1 __________ .._ Feb. 15, 1938 ' 2,145,954 Semple et a1 ____________ __ Feb. 7, 1939 N% \N 2,892,670 Alsberg et a1 __________ .__ June 30, 1959 MMGNHJ, 403E _ 1,886,480 11,, §N/ OTHER REFERENCES 1 Sommer: “American Dyestuff Reporter," v01. 47, No. 1° 25, Dec. 15, 1958, pp. 895-899.