SU657048A1 - Polyazo dyes of triazine series for polyvinyl chloride and rubber materials cellulose, protein and polyamide fibres - Google Patents

Description

(54) TRIAZINE RANGE POLYAZOROUS DIAGNOSES FOR POLYVINYL CHLORIDE AND RUBBER MATERIALS, CELLULOSE PROTEIN AND POLYAMIDE FIBERS that improves the environmental conditions for the production of triazine dyes. According to the proposed method, new azo dyes of the formula § are obtained using as diasomatrons of amino-substituted 2,4,6-tris (arylmethylamino) -1,3,5-triazine (III), which can be obtained by the interaction of K, S, N -trimetrolmelamine with an aromatic amine of the general formula AHj, where A is arylene. In molecules of such diazo compounds and azo dyes, generally formula 11, derived from them, arylene A is directly associated with the methylene group in the amino group of the melamine residue, which: provides dyes of different shades as compared to those which can be obtained by the well-known J2 method. Amines III are easily diazotized using conventional methods, and the resulting trisdiazo compounds easily enter into azo combination with the same or different azo compounds, including those containing azo groups. Example 1. 1.26 g of melamine, 2.32 g of formaldehyde in the form of a 40% solution and 10 ml of water are heated by stirring in a water bath at 60 ° C until complete dissolution of the melamine. The clear solution of trimethylol melamine formed is rapidly cooled until it is stirred. 3.72 g of aniline is added, heated to 65-75 seconds and stirred at this temperature for 2 hours. The precipitated resinous precipitate is dissolved in 98% acetic acid, adding 20% sodium hydroxide solution to 20% 5-6 are planted slightly yellowish precipitate, which is filtered, washed with water, then ethanol and dried in a vacuum. mind-desiccator over caustic soda. 3.96 g (90%) of 2,4,6-tris (aminobenzylamino) -1,3,5-triazine are obtained, m.p. 132134 0, it is difficult to dissolve in benzene, ether is acetone, it is highly soluble in chloroform, carbon tetrachloride, acetic acid, hydrochloric acid, dimethylformamide. Found the equivalent by the method of diazotization: 147.5 € 24Н27 OIL, H N (NHn),. The equivalent is calculated: 147,17. Example 2. About 66 g of 2,4,6-tris (aminobenzylamino) -1,3,5-triazine are dissolved in 20 ml of E8% acetic acid, 5 ml of concentrated hydrochloric acid and 20 ml of water are added , solution stirring tide 30% aqueous g.,. ,, „„ „„ „„ „„ „sodium nitrite solution (0.31 g sodium nitrite). At the end of the diazotization, the excess of nitrous acid is removed by urea. 0.72 g of 2-naphthol is dissolved at 60 ° C in 50 ppm. 2% aqueous solution of caustic soda and cooled to. pH of the solution is 11-12. 5 g of soda ash are added to the naphthol solution. ice until the temperature is reached and with good stirring the diazo-solution, previously neutralized with soda to pH 5-6 and cooled to, is gradually added. Having finished „„. . . prisalenie diazo solution, continue stirring until the end of the combination, then filtered, washed and dried with a red pigment corresponding to the formula

CNB Weight 1.24 g (92%). The pigment is insoluble in water, soluble in acetone, benzene, ether, chloroform. Y; LA01x 480 N Alax 21480 (in dioxane). The molecular weight (cryoscopically, in benzene) J 867 is found. -54 3 The molecular weight is calculated: 907. Example - 3. 0.8 g of 1-phenyl-3-methylpyrazolone-5 is dissolved in 50 ml of 2% sodium hydroxide solution, the solution is cooled until 5 g of soda ash is added to the solution in 50 ml of water and the tris-diazo compound obtained is obtained by diazotization 0.66 g 2,4,6-tris (aminobenzylamino) -, 3,5-triazine (see example 2). During the combination process, the temperature is maintained no higher than the medium — alkaline with brilliant yellow paper. The resulting yellow pigment of the formula

dHj-nn-U N

N

(MgMN-g nsn.2

kn

filtered off, washed with water and dried at 60 ° C. Weight 1.43 g (96%). The pigment is insoluble in water, highly soluble in organic diluents Ld, h, 398-nm, dd, from 2240 (in dioxane). Example 4. 0.8 g of acetoacetic acid anilide is dissolved in 50 ml of 0.5 n. soda, add acetic acid until acidic by litmus, cool before and

with ".co 1 (

I

f

inso

/

Weight 1.33 g (89%). The pigment is not grown in water, it is readily soluble in organic solvents. L / waKc 376 250 s dioxane).

Example 5. A solution of diazo compound from O. 66 g 2,4,6-tris (aminobenzylamino) -1, 3,5-triazine (see Example 2). poured to a solution of 0.5 g of resorcinol in 50 ml of 2% sodium hydroxide solution cooled to 0 ° C.

a solution of a diazo derivative obtained by diazotization of 0.66 g of 2,4,6- (aminobenzylamino) -1,3,5-triazine (see Example 2) is poured. During the combination, the medium should be kept acidic in a litmus neutral in the Congo red by adding a 25-30% solution of sodium acetate. Temperature - not higher than 15 ° C. At the end of the combination, they are filtered, washed with water and the yellow pigment of formula

COCHs

k-bn CONH

COGH,

 Cosh

to which a solution of 5 g of soda ash in 50 ml of water is previously added. The temperature in the combination process is maintained not higher than 10 ° C, the medium is alkaline over brilliant yellow paper. The resulting light brown pigment is filtered, washed with water and dried at. Weight 1.13 g (94%.). The structure corresponds to the formula

HE.

he

to

The pigment is insoluble in water, highly soluble in organic solvents. Kc390 nm, 14470 (in dioxane).

Example b. A diazo compound solution of 0.66 g of 2,4,6-tris- (aminobenzylamino) -1,3, 5-triazine (see Example 2) is added to the solution of Al-acid prepared by dissolving 1.5 g of the monosodium salt of Al- acids

: and 5 g of stocked soda in 80 ml of water and pre-cooled to. The temperature during the combination process is maintained no higher than 10. ° C.

Wednesday is sour over congo. At the end of the combination, the dye is salted out by adding 30 g of sodium chloride, filtered off, washed with 10% sodium chloride solution and dried at 60 ° C. Get 1.93 g (87%) of the dye of the formula

NH2

SNGK JJ wsng

 GU

Ozn

SH he

$ oh

V

NH, OH.

one

CH

The dye is well soluble in water and dyes wool / silk and nylon in brick-red color. I, „„, 425 nm. / VXd KS / (in water. Example 7. A solution of diazo compound, prepared as in example 2 and previously neutralized with v.1. - - - - J-CH2 is poured by adding 30 g of common salt, filtered, washed with 10% saline and dried at 60 ° C. Weight 2.1 g (95%). The dye is highly soluble in water and dyes wool, silk and caprone in the color of burgundy. I llaks 495 nm {in water), HE is salted out by adding 30 g of salt , filtered, washed with 10% sodium chloride solution and dried at 60 ° C. Weight 1.61 g (90%), the dye is highly soluble in water and dyes wool, silk and caprone in orange color. Lddo, 438 nm (in water Example 9. A solution of the diazo compound, prepared as in Example 2, CH? NH- | #. H with soda to pH 5-6, is poured into a solution cooled to Ash-acid, | prepared as in Example b. The temperature is not higher than 10 ° C, the medium is alkaline on a brilliant yellow piece of paper (adding soda). At the end of the combination, the dye of the formula OH (H. It is Example 8. The solution of the diao compound obtained as in Example 2 is poured into the solution cooled to the I-acid prepared by dissolving 1 g of I-acid and 5 g of soda ash in 50 ml of water. At the end of the combination The diluent of formula NHCHj is poured into a solution of 1 g of naphthionic acid and 5 g of soda ash in 50 ml of water cooled to Q ° C. After the completion of the combination, they are salted out with the addition of 30 g of sodium chloride, filtered, washed with 10% sodium chloride solution and dried at 60 ®C dye of formula

Weight 1.59 g (93%) IMAX 464 nm (in water). The dye dyes wool, silk and nylon in a light cherry color,

Example 10 The solution of the diazo compound, prepared as in Example 2, is poured into a solution of cooled saline of 0.62 g of salicylic acid and 5 g of soda ash in 50 ml of water.

 l J-dHaNHY Y ™ Weight 1.21 g (91%), Yaddo, s367 nm (in. genus). Dye paints wool, silk and capron in yellow. Example 11. 0.43 g of 2-naphthol is dissolved in 50 ml of a 2% sodium hydroxide solution (pH of the solution is 11-12), cooled to the OC immediately poured to the cooled to the solution of the diazo compound, prepared as in example 2, to which soda is previously added before the alkaline reaction. Reaction of the medium during CoCrHjNH-j CH

N

Bee 1.23 g (88%, counting on the diazo component). The pigment is insoluble. in water, well soluble in organic solvents h.Lddo, 380 nm, max 12420 nm,, 5130 (in dioxane) ...

Example 12. 1.54 g of Al-acid is dissolved in 100 ml of water, added with soda until the acid is completely dissolved. The solution, which should have a weakly acidic reaction by litmus, is cooled to 10–12 ° C by adding ice and added dropwise for 1 h with good stirring to a P-nitrobenzene diazonium solution prepared by diazotization of 0/62 g p-nitroaniline in 50 ml of water and 5 Concentration ml. The combination process is supported by adding soda to an alkaline medium in brilliant yellow paper. At the end of the combination, salted out with the addition of 30 g of sodium chloride, filtered off, washed with 10% solution of salt and dried at 60 ° C.

NH- tH

N N

OH Jf N

r

NHCHj

hydrochloric acid bath with a solution of 0.31 g of sodium nitrite in 80 ml of water. The temperature during the combination process is maintained not higher than 6-8 ° C.

The solution of the diazo compound, prepared as in Example 2 and previously neutralized by soda until the Congo has disappeared, is poured into the resulting monoazoric neutralizer solution neutralized with soda until the acidic reaction to the Congo disappears, with good stirring. During the combination process, the temperature is maintained at a temperature not higher than and the medium is alkaline with brilliant yellow paper. At the end of the combination, the dye must be all the time alkaline with brilliant yellow paper. The combination ends in 1520 minutes. The reaction mass is poured to a solution of 0.27 g of 1-phenyl-3-methylpyrazolone-5 in 30 ml of 2% sodium hydroxide solution, maintaining the temperature not above and the medium is alkaline with brilliant yellow paper. At the end of the combination, it is filtered, washed with water and dried with an orange pigment of the formula INH / iTTCH NH-J V salted with 30 g of sodium chloride, from) is filtered, washed with 10% (sodium chloride solution and dried at. 2.7 weight (90 %, based on trisaminobenzylaminotriazine) max 540 nm (in water). Dye dye; sews wool, silk and nylon in a dark blue color. Example 13. 6.3 g of melamine are added to a pre-neutralized 1N solution of sodium hydroxide to pH 7 , 5-8 40% formaldehyde solution containing 13.2 g of formaldehyde is heated at 60-70 ° C and stirred until completely dissolved (1520 min) and cooled, placing the vessel in an ice bath and adding crushed ice to the reaction mass. Next, add 10 ml of water, filter the precipitate, rinse with COLD water until the filtrate is neutral, and dry in a vacuum desiccator over sulfuric acid, 8.9 g (82.4%) of trimethylolmelamine is obtained as a white powder, soluble in hot water, alcohol acidified with mineral acid, acetic acid, dimethyl formamide. The product is purified by precipitating chloroform from dimethylformamide. T. l-300 ° C. Found,%: C 30.12; H 6.18; N 34.23. SbN-12 b ° 31 2 ° Calculated,%: C 29.63; H 6.21; N 34.55. IR spectrum (in tablets with KBG); 810, 1000, 1385, 2960, 3350 cmP-p and mep 14. 5.9 g of 1-naphthylamine are dissolved with vigorous stirring and external cooling in 30 ml of 93% sulfuric acid; The temperature should not rise higher. After complete dissolution with stirring and cooling for 1 hour, 2.7 g of trimethylolmelamine is added, stirred for 10 hours at and left at room temperature for 15 hours. Then the reaction mass is poured onto ice at a rate such that no noticeable heating occurs. and tar tar pr 657048 OH “HZ duct. The precipitation is filtered off, suspended in 300 ml of water, the suspension is neutralized with 20% sodium hydroxide solution to pH 7-8, the precipitate is filtered, washed with hot water, alcohol and dried in a vacuum desiccator over sodium hydroxide. 6.62 (89.5%) of 2, 4,6-tris (1-aminonaphthyl-4-methylamino) -1,3,5-triazine are obtained, which is insoluble in water, hardly soluble in benzene, alcohol, chloroform, acetone, soluble in dilute sulfuric acid, dimethylformamide, worse in acetic and dilute hydrochloric acid. Found,%: C 66.28; H 6.26; N 19.22. Szezdzzdzn about. Calculated,%: C, 66.95; H 6.09; N 19.52. IR spectrum; 810.1385, 3350cm An equivalent was found (by titration with sodium nitrite in a hydrochloric acid medium) 199.9. SzbI27 "b (MN ,,) e. The equivalent of 197.3 is calculated. Example 15. 0.71 g of 2,4,6-tris (1-aminonaphthyl-4-methylamino) -1, 3,5-triazine is dissolved in 20 ml of 98% acetic acid, 5 ml of concentrated hydrochloric acid is added. acid and 20 ml of water, cooled to, the solution is poured with stirring; 0.26 g of sodium nitrite in 30 ml of water. At the end of the diazotization, the excess urea nitrite is removed. 0.6 g, 2-naphthol dissolved in 50 ml of a 2% sodium hydroxide solution, cooled, wait, 5 g of soda is added and the ice to reach the temperature with good stirring gradually pours the diazo solution, previously neutralized with soda to pH 5- 6 and cooled to 0-5 ° C. During the whole process of azo combination, the medium should be alkaline with a brilliant yellow piece of paper, and the sample spilled on the filter paper should not give staining with Ash-acid. At the end of the combination, the dye of the formula