DE2708441A1 - 2-Amino-5-thiocyanato-thiadiazole - prepd. from corresp. 5-mercapto cpd. and useful for azo dyes mfr. - Google Patents

Abstract

New 2-amino-5-thiocyanato-thiadiazole-(1,3,4) (I) is used in the mfr. of new azo dyes having formula (II): (where Y is a coupling component gp.). (II) are used in dyeing and printing hydrophobic-, acid-modified- and natural or synthetic polyamide fibre materials, and also in heat transfer printing. (I) can be prepd. by reacting 2-amino-5-mercapto-thiadiazole-1,3,4 with CICN in a water/ice/isopropanol mixt., with addn. of NaOH.

Description

2-Amino-5-thiocyanato-thiadiazole- (1.3.4). its creation and Ver

Use for the synthesis of azo dyes The invention relates to the compound of the formula It is already known (cf. Arch. Pharmaz. 300, p. 590 (1967)) that when 2-amino-5-mercapto-thiadiazole- (1,3,4) is reacted with nascent cyanogen bromide in KBr-saturated Methanol, a substance of the above formula with a melting point of 176 - 1780C, is to be created.

If one works, however, the manufacturing method given in this reference after, a compound with this melting point is obtained, but it is based on the exact elemental analysis, the IR and NMR spectra and the mixed melting point with an authentic comparator preparation produced independently (cf.

Chem Ber. , 2108) does not have the formula given above, but represents 2-amino-5-methylmercapto-thiadiazole- (1.3.4).

The invention is 2-amino-5-thiocyanato-thiadiazole- (1.3.4) therefore new.

This compound is obtained, for example, by adding 2-amino-5-mercapto-thiadiazole- (1.3.4) in water or an organic solvent which is indifferent to the reactants with halocyan in the presence of an acid-binding agent such as an alkali metal hydroxide or a tertiary organic amine according to the information in DT-AS 1 195 743.

Compared to the 2-amino-5-methylmercapto-thiadiazole- (1.3.4) draws the new compound is characterized by an SCN band in the IR spectrum at 2170 / cm.

The present invention also relates to azo dyes of the formula where K is the remainder of a coupling component.

Suitable radicals K are, for example, radicals of coupling components of the benzene, Naphthalene, pyrazole, acylacetic acid amide, pyrimidine, pyridine, thiazole, indole, Imidazole, indazole and quinoline series as well as residues of enolizable aliphatic Ketones, residues of the aminobenzene series being particularly suitable.

Preferred dyes of the formula II are those which are not water-soluble making cruppen included.

Particularly preferred dyes correspond to the formula where R1 is hydrogen, alkyl, O-alkyl, halogen, CF3, NQ1, COQ5, NQ1-SO2Q2, NQ1Co2Q2 or NHCONQ1Q5 R2 is hydrogen, alkyl, -OQ2, halogen or CO2Qe R5 is hydrogen, alkyl, alkenyl, aralkyl or alkyl subst. by halogen, -CN, OH, Aryl or a group (-O-CH2-CH2) -Q4 with n = 1 - 8, R4 aryl or R5 or R2 + R3 or r3 + R4 members of a 5- or 6-membered heterocyclic ring, Q1 hydrogen or alkyl ( H is preferred), Qe alkyl, alkenyl, aralkyl or aryl, Q5 hydrogen or Qe Q4 -OH, -Cl, -OQ2, -CN or -COOH, where the alkyl radicals mentioned above in any context preferably have 1-4 carbon atoms and the alkenyl radicals preferably have 3-5 carbon atoms and the aryl radicals are preferably phenyl radicals, which are preferably 1-3 times through Alkyl, O-alkyl or halogen can be substituted, "halogen" (in the context of this invention) preferably being understood as meaning bromine and especially chlorine.

Preferred alkyl radicals are methyl, ethyl and propyl. Preferred aryl radical is phenyl. "Bulky" residues (e.g. t-butyl) are preferably located in such Positions where they do not cause steric hindrance (e.g. in the m- or p-position a phenyl radical).

In the context of the dyes of the formula III, those types are preferred where R1 is H, Ch3, NHCO-alkyl, NH-C00-alkyl or NH-SO2-alkyl.

Compounds of the formula III are very particularly preferred in which a) R1 is methyl, R2 = H and Ri and R4 have the meaning mentioned or b) R1 is C1-C4-alkylcarbonylamino or C1-C4-alkoxycarbonylamino, R2 is hydrogen, methyl, Chlorine, methoxycarbonyl or ethoxycarbonyl, Ra C2-C4-alkyl or C2-C4-alkyl subst. by C1-C4-alkoxy, CN, OH, phenoxy or phenyl and R4 are hydrogen or RS.

The water-insoluble dyes listed above are suitable Excellent for dyeing hydrophobic fiber materials, especially those made from aromatic polyesters, cellulose triacetate or polyamide, according to the types of fiber used for these types of fibers customary dyeing methods using aqueous or non-aqueous dye liquors.

The fibers are thereby in strong yellow to purple hues colored with good general fastness properties. Those with the dyes should be emphasized the formula III achievable clear red colorations, as they have so far only with the, however less abundant inthraquinone dyes were obtained.

The very particularly preferred dyes of the formula III a + b draw good aftertaste, sublimation and lightfastness as well as good drawability the end.

The dyes of the formula III a can moreover be used with good success be used in heat transfer printing.

In addition to the aforementioned types of dyes, there are also such dyes of formula II of particular interest which has a cationic coupling component exhibit. Such dyes are particularly suitable for coloring acidic modified ones Fiber materials, especially those made from acrylonitrile polymers and polyesters.

Preferred types correspond to the formula where T1 is hydrogen, methyl or chlorine, T2 is hydrogen, methyl, chlorine, methoxy or xthoxy, T3 is hydrogen, benzyl, phenylethyl, C1-C4 alkyl, C2-C4-alkyl subst.

by OH, C1-C4-alkoxy CN or -NT5T0T7, T4 C2-C6-alkylene, T5 / T6 / T7 Allyl or T3 or together with N a heterocycle, preferably pyridine, form, and An # is an anion (preferably Cl-, ZnCl3 #, BF4 # or methosulfate).

Finally, the new diazo component is also suitable for building up "Acid" dyes, especially those containing carboxyl groups or sulfonic acid groups Dyes whose preferred field of application is the dyeing of natural and synthetic Polyamides is.

Particularly preferred dyes of this type correspond to the formula where V1 is hydrogen, halogen, alkyl, alkyl or alkylcarbonylamino, V2 is hydrogen, alkyl or alkyl, V3 is hydrogen, alkyl, hydroxyalkyl, cyanoalkyl or -V4-V5-SO2H, V4 is Cl-C4-alkylene and y5 is oxygen, phenyl or a direct bond mean, where "alkyl" and "halogen" are as defined above.

V6 SO3H or are very particularly preferred in the context of formula V those dyes in which V1 is hydrogen, methyl or acetylamino, V2 is hydrogen, Methyl, methoxy or ethoxy, V3 C2 -C4-alkyl, hydroxyethyl, cyanoethyl or sulfonethyl, V4 -CH2- and V; Phenyl and V6 are SO3H, the sulfo group preferably in the m-position stands.

The new dyes are produced according to known methods Methods by reacting the diazonium salt or the N-nitroso compound of 2-amino-5-thiocyanato-thiadiazole with a coupling component of the formula KH and isolation of the resulting Dye by conventional methods such as precipitation, salting out and the like.

The conversion of the N-nitroso compound is expediently carried out according to the information in DT-OS 1906838 (corresponds to GB-PS 1254727), d. H.

in a weakly acidic medium.

The diazotization of II can be carried out in a manner known per se in aqueous, organic or aqueous / organic media in the presence of inorganic or organic Acids with inorganic or organic nitrites (nitrous acid esters) or nitrosyl compounds such as nitrosyl chloride or nitrosyl sulfuric acid can be carried out.

The coupling to KE also takes place in a manner known per se in aqueous, organic or organic / aqueous medium, optionally with the addition of acid-binding Means to increase the pH in order to achieve an optimal reaction rate and often associated with achieving an optimal dye yield.

Diazotization and coupling do not have to be spatially separated from one another occur. It is often possible to use a mixture of thiadiazole II, the coupling component KH and an inorganic or organic acid - in adaptation on the reaction rate of the diazotization and coupling - that of the diazotization necessary derivative of nitrous acid (see above) to add and thus the dye synthesis to make a one-pot reaction in a cost-saving manner.

The preparation of the nitroso compound III and its implementation with KH in the presence of a proton-donating substance also take place in a per se known way, e.g. B. by adding an alkali metal nitrite to the solution or suspension of II in an organic acid or a mixture of organic acids such as formic acid, Acetic acid, propionic acid, possibly with the addition of chlorine, dichloro, trichloroacetic acid or sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

The reaction with the coupling component KH can be carried out in the same a chemically related or a chemically different medium such as e.g. B. a Alcohol or water may take place with an increase in temperature.

Inorganic acids such as 10-85 are preferred as diazotization media sige phosphoric acid, 5-100% sulfuric acid, acetic acid, propionic acid, in particular Mixtures, e.g. B. Mixtures of acetic acid with phosphoric acid, sulfuric acid or Propionic acid.

The following diazotizing agents are recommended: blkalinitrites such as sodium, Potassium or lithium nitrite, nitrosyl chloride, nitrosyl sulfuric acid, nitrous acid ester of alcohols or ether alcohols, especially if the corresponding alcohols or ether alcohols play a role as reaction medium in dye synthesis.

In addition to water, alcohols are particularly suitable as coupling media such as methanol, ethanol, propanol and isopropanol, as well as ethylene glycol, methyl glycol, Ethyl glycol, propyl glycol, as well as Aosetsun4sprodukte of propylene with C1 - C3 - alcohols. But also DMF, acetonitrile, sulfolane, ß-methosypropionitrile, B-hydroxypropioni tri 1 often cause a particularly favorable course of the reaction and thus a high dye yield Diazotization and coupling are advantageous carried out in the temperature range between -100C and + 100C. For the implementation of the Nitroso compound III with the coupling components KH is often an increase in temperature at 40 - 90 "C particularly advantageous.

Suitable coupling components for building up water-insoluble dyes of formula II are those as they are, for. B. in British Patents 1,125,683 (Page 5) and 1,349,727 (pages 4-6) and U.S. Patent 3,862,117 (columns 11-13) are.

Suitable coupling components for building up cationic dyes are such as In U.S. Patent 2,972,508 (claim 1 and columns 5-8) or in U.S. Patent 3,862,117 (columns 37, 38, 39, 40, 41).

Suitable coupling components for building up acidic dyes are such as they z. B. in GB-PS 1 265 283 (pages 2 and 3), 1 272 884 (table), 1,343,543 (tables) and 1,372,527 (pages 3-5 and tables) and in U.S. Patent 3,635 939 (Example 1) and U.S. Patent 3,624,068 (Example 1).

2-Amino-5-thiocyanato-thiadiazole- (1.3.4): a) To a suspension of 133 g of 2-amino-5-mercapto-thiadiazole- (1,3,4) in 500 ml of carbon tetrachloride 106 g of cyanogen bromide are added at 0-5 "C.

Then, drop by drop with stirring in 1 - 2 hours.

138 ml of triethylamine are added and the temperature is increased by cooling with air kept below 100C. The mixture is stirred for a further hour at 0-10 ° C. and the Then increase the temperature to 20 - 250C.

The precipitate is filtered off with suction, washed with water and removed for removal unreacted mercarpto compound in water and stirred with soda to pH 8-9 posed. The precipitate is isolated, washed first with acetone and then with water and dried in vacuo at 500C.

Yield: 110 g (70% of theory) of a slightly yellowish powder.

b) 133 g of 2-amino-5-mercapto-thiadiazole- (1,3,4) and 61.5 g of cyanogen chloride are successively in a mixture of 400 ml of water, 400 g of ice and 10 ml of isopropanol registered. A solution is added dropwise to this at 0-5 ° C. in about 2 hours while stirring of 40 g of NaOH in 400 ml of water.

After stirring overnight at room temperature, the pH is adjusted with soda solution to pH 9, stirred for one hour, then filtered the precipitate and washes it neutral with water.

Yield: 144 g (approx. 90% of theory) decomposes on rapid heating the connection at 1470C.

IR spectrum: SCN band at 2170 / cm C3H2N4S2 (158): Ber. C = 22.8 H = 1.3 N = 35.4; S = 40.5 Fd. C = 22.9; H = 1.4; N = 35.3g S = 40.7 Example 1 6.9 g of 2-amino-5-thiosyanato-thiadiazole- (1,3,4) are added to a mixture of 60 ml of glacial acetic acid and 20 ml of propionic acid at 0-100C Stir interspersed. At about 0 ° C., 7.5 ml of 41.2 goat nitrosylsulfuric acid are added dropwise in about 30 minutes and the mixture is then stirred at about 0 ° C. for 3 hours. Then 0.5 g of urea is added and kept at OOC for a further 30 minutes. A solution of 8 g of N-ethyl-N- (β-cyanoethyl) -aniline in 30 ml of glacial acetic acid is allowed to run into the diazo solution thus obtained at 0-50 ° C. in 30 minutes. After a further 30 minutes, the reaction mixture is added with stirring to 200 g of ice water, the dye of the formula separates out as a red precipitate. It is diluted with water to a volume of 600 ml, the dye is filtered off with suction and washed neutral with water. It dyes polyester and polyamide fibers in clear, red shades with good general fastness properties, in particular good sublimation fastness of the polyester dyeing.

The dyes of the general formula III are obtained in an analogous manner if the coupling components used in this example are replaced by those listed in the table below: They dye polyester or polyamide fibers in the specified shades: E.g. R1 LH R4 color 2 CE5 CH CH-CH2-CN Red CB, OCHS H CEi-CEi-CN Red 4 CH3 I CH H II CE8-CE; -OH Red 5 H C1 H CEi-CH2-CN scarlet 6 HH C2 CH2-CH2-O-CO-CE; Scarlet fever 7 H 11 H C4 CH2-CH2-CN scarlet 8 HH C-C'6-0H CH2-CEi-CN scarlet 9 HH C2Hs CE; -CHOH-CEi-C1 scarlet 10 HH CH * -CE; -O-CsH7 CH2-CE; -O-C3 H7 scarlet 11 HH CE2-CE2-C1 CB2-CHi-Cl scarlet 12 HH CH2-CE; -C1 CEz-CEi t scarlet 13 HH CH2-CE-OH Cz2 t scarlet 14 CEi H C4E; B, ca, -CB, CH2-CEi-O-CO-CEi red 15 cis H 02115 C2Ez Red 16 CEi H C & 115 CH2-CE-O-CO-O-CEg Red 17 CEi H C115 CE; -CE-O-CO-NH-C4E; Red 18 for H CE-CH2-OC 0115-0115-0-0115 red 19 CEi H CH2-CH2-O-C4 0115C1150-04115 Red 20 0115 H CE-CEz-Cl CEi-CEi 4 red 21 C115 H 0115-0115-0-0 C115 4 Red 22 0115 H 0a115 CEi-CEkOCO-H 4 red 23 CB, B CEi H C4Eg CEi-CEi-covo-cE (cEi) Bot Beep R1 R2 115 R4 color 24 CE5 H C2 Hs C115-0115- red 25 CE5 H C3 ca, 0115-0115-0-0-0115 red 26 CH3 H C2 Cg, -C - O - C1 Red 27 CH H C2 0115-0115-0-G'-o 'Red 28 CH g H 0115-0115-0-oQ'-01 0115-0115-0-0-01 Red 29 CEI H Cæ Hs CH2 -I2 -CH2 -CE12 -O- CO-CEI; Red 30 0115 0115 H 0115-0115-0 "Red 31 CH "0115 H 0115-0115.0Q-01 Red 32 0115 H C4 c-ca ,, nC "CaL H;» 0 red red 33 0115 H C2 Cg, -CB, -O-CO-H-CIHo red 34 NH-S02-0115 H C2 02115 Red 35 NH-S02-0115 H Ca 02115 Red 36 NH-SO2 -CEi 1 CH2 -CE12 -O-C4 H 011501150-04115 Red 37 NH-SO2 t H C4 E; C4 E; Red NH-S02 -C4, 38 ca, H 02115 C2 E; Red C1-CB, -CB, 39 JII-COOCEi H C2 H Cs 1I6 Red 40 NH-0000115 HE; C4 Eg red 41 NH00002115 H Cs E16 CEi t3 Red 42 NH00002115 CH, 5 CI H CE; -CEi t red H-C00-CES1 11500-0115 44 N1-00-N115 H 0115-0115-0-02115 -CEL -O-Ct red 45 NH-CO- PH H7 H7 red C q NH-C0-M 46 (CEi) s H 04115 C115 Red (0115> 1 Beep R1 Rs R4 ~ concrete 47 NH-CO.C115 115 H: HB -CB, -OH red 48 NH-CO-CEi 115 HE; -CHOH-CEi-C1 red 49 NH-CO-NH- (CH2) aOCE5 CEi H 5Ei ot 50 NHCOCHa H C115-C'Lt-O-02115 Lt-C115-0-02115 Bot 51 NHCOCEi-C1 H C115C'Lt-C-04115 AEi -CEi -O-C4 H; Red 52 NH-COC115OH H 02115 Red Red 53 NH-COC2Hs H ca, CEg red 54 NH-CO-CB, H C'LtC115COOC115 C2E6 Red 55 NHCO t H CH2-CH2-O-CH-CH2-CN 02115 Red 56 NH-CO- t -OCEi H C'Lt-C'Lt-O-COC115 CH2-CH8-O-COCEi Red 57 NH-CO-Q'-C115 H 115C115 C'Lt C115 000C115 115 C115 C115 Red OCOC115 ot 58 NH-CO-0'.Cl CHs H Lt-CH-C115C'LtC115C C2Eu Ro tot 9 59 NH-CC-CH-C4 115 Ob115 1 CEi-CH8-CN Red C2115 60 NHCOCH8 CE5 COOC2 Hs H C2 Egg Red 61 NHCOCE; 5 CN C 02115 red 62 N-COCES C1 H CE; C'Lt -COOCE red c24 63 NH-SO2 4 CEla H Geh C115 H -CI CB, C $ Rot 64 NHCOOC115 CE5 CE5 red-violet / 65 N / ca, 1 02115 02115 red C'Lt-C'Lt 66 (r) 4 1 Ca EL7 02 ", red N (C'Lt) 4 67 N1-SO2-C115 H C4 1 E ;, c4 E; Red 68 H-SO, -CIh Crh CII, Cg Cl H C2 Ei C2 El6 Red 69 tc r 1 Et 02115 red 4 00 5 / Ot06 Bhp. R1 R shade 7o NH-COCEi OC2 Elw H C2 Ei CEt2 CEi OCOC2 1% red 71 NEtCHO H C2 4 C2 E16 red 72 NHCHO HH (3 red 73 NHCOC8 Ei H C'Lt t Rot 74 NHCOCEL8 H C85 OC115 Red 75 NHCOCEta CHS CHe -CBL, -CB, -CB, red 76 NlCOC115 H 02115 C2 Egg Red 77 NHCOC115 H C4 04115 Red 78 NHCOCH- CEI8 H 02115 02115 Ro t 79 NHCO- IC = CEi H c115-C'Lt-OI CEL2 CX OH red I. 80 NH-CO-CHBr-CH2 Br C'Lt CE18 -CBP -OH H Red 81 NH- CO- CEI8 -Br H c -ca, -ca, -cEh red 82 N'Lt-C0-C'Lt e c115-CiioR-C'Lt-C1 Red 83 N1-CO (: 115 - (: 115 - (: OOI Ca Ek cyg, red 84 Cl 1 CEL2 CEL ¢ OH CEi CEt, OEt Red 85 (: FH C2 02115 Red 86 C004 116 H C2 02 115 Red 87 CB, -CE -COOC, B, H C2 Hs C2 4 Red 88 ca, -CBL -CB H (: 4115 Etb Rot 89 11EtCOCHo 1 CH2 -CI = C115 (: 115 - CH = CX red 90 NlICOOCEi H (: 115 -CH = C115 CX 4D Red 91 IlHCOOCs H6 H Ca H7 C 43 Red Red 92 NHCOOCIi H 1 CtE4s 02115 -CE (: Lt. (: 115-0-Ö '- (: 1 Red 0.05 g of the dye obtained in Example 18 and 0.05 g of the dye obtained in Example 19 are carried in well-dispersed form at 40 ° C. in 1 liter.

Water, which also contains 0.2 g of a condensation product of naphthalene, Contains formaldehyde and sulfuric acid and 0.3 g of methyl cresotinate. In this Bath you go with 20 g of a fabric made of polyethylene terephthalate, increases the Temperature to 1000C within approx. 20 minutes and colors at this temperature 60-90 minutes.

A strong, clear red coloration with good aftertaste, sublimation and coloration is obtained Lightfastness.

0.1 g of the dye from Example 47 are in a well dispersed form at 40-450C in 1 liter of water, which also contains 0.5 g of a sulfite cellulose degradation product contains. This bath is filled with 20 g of poly-caprolactan yarn, raised the temperature in about 20 minutes to 95-1000C and colors 1 hour. After rinsing and drying results in a clear, bluish red coloration with good wet and dry properties Lightfastness.

Example 93 12.4 g of 2-amino-5-thiocyanato-thiadiazole- (1.3.4) become stirred in 50 ml of glacial acetic acid and 25 ml of 85 pointer formic acid and turned to OOC.

At 0-5 ° C., 5 g of powdered sodium nitrite are sprinkled in portions in about 30 minutes while stirring and the mixture is stirred for a further hour at 0-50 ° C., 12.5 g of 1-phenyl-3-methyl-5-aminopyrazole are added to 50 ml of glacial acetic acid dissolved and added to the suspension of the 2-nitrosamino-5-thiocyanato-thiadiazoles (1.3.4) prepared above. The mixture is stirred at room temperature until no more nitrosamino compounds can be seen in the thin-layer chromatogram. After cooling, the dye is precipitated with water, filtered off and dried. It dyes polyester fibers, cellulose triacetate and perlon in clear, yellow tones with good aftertaste, lightfastness and sublimation fastness and has the formula Further dyes with a very clear shade with good sublimation and lightfastness are obtained if the 1-phenyl-3-methyl-5-aminopyrazole in the above example is replaced by the compounds listed in the table below. No connection hue 94 l-phenyl-3-methyl-pyrazolone- (5) yellow 95 3-methyl-pyrazolone- (5) yellow 96 1- (ß-Hydroxyethyl) -3-methyl-pyrazolone- (5) yellow 97 3-CJran-4-methyl-6-hydroxypyridon- (2) yellow 98 l-methyl-3-cyano-4-methyl-6-hydroxypyridone- (2) yellow 99 l-Methyl-3-methylaminocarbonyl-4,6-dihydroxypyridone- (2) yellow 100 1-methyl-2-phenyl-indole yellow 101 2-Hydroxy-diphenyl yellow 102 p-cresol yellow 103 2-Hydroxy-naphthalene-3-carboxylic acid ethyl ester orange 104 N-Benzyl-2.2.4-trimethyl-1.2.3.4-tetrahydroquinoline red 105 1-methyl-4-hydroxy-quinolone- (2) yellow 106 3.7-dihydroxy-1.2.3.4-tetrahydro-benzo (h) quinoline blue 107 5-amino-1-hydroxy-quinoline blue 108 2-Diethylamino-4-methyl-thiazole- (1.3) red 109 2-Henzylamino-3-cyano-4-methyl-6- (ß-hydroxyethyl, orange pyridine 110 carbazole red 111 2.6-Di- (3'-methoxypropylamino) -3-cyano-4-methyl-pyridine orange 112 N- (3'-methoxypropylamino) -4-hydroxy-naphthalimide red 113 2-Benzylamino-3-cyano-4. 6-bis-methylamino-pyridine orange 114 2.4.6-Tris- (3'-methoxypropylamino) -3-cyano-pyridine orange Example 115: 6.9 g of 2-amino-5-thiocyanato- (1.3.4) are introduced at 0-100 ° C. into a mixture of 35 ml of glacial acetic acid and 15 ml of 48% strength sulfuric acid. 7.5 ml of 41.2% strength nitrosylsulfuric acid are added dropwise at -5 to 0 ° C. and the mixture is stirred for a further hour at this temperature.

Shortly before the coupling, excess nitrosylsulfuric acid is destroyed by adding 0.5 g of sulfamic acid. At O-5, a solution of [2- (N-ethyl-N-phenyl-amino) -ethyl] -benzyldimethyl ammonium chloride in 30 ml of glacial acetic acid is slowly added and, after 30 minutes, the mixture is poured onto 200 g of ice with stirring. It is gradually diluted with about 500 ml of ice water, the solution is adjusted to pH 4-5 by adding sodium hydroxide solution and the resulting red dye of the formula below is salted out with sodium chloride.

0.5 g of the product obtained are added with 3 ml of 30% strength Acetic acid dissolved in 3 l of water. In this bath you go at 40-500C with 100 g of polyacrylonitrile yarn a, increases the temperature of the dyebath to 1000C within approx. 40 minutes and stains at this temperature for 1 hour. A clear red color results with excellent lightfastness.

Dyes with similar properties are obtained when the in Diazonium salt prepared in this example with those in column A of the following The coupling components listed in the table are combined.

The nuances of the dyeings obtained on polyacrylonitrile fibers are given in column B. No. A 116 Näc02115c: <115 R / ClQ red t \ CE-CEi-N (CEi) S C1 117 GÖN% Cj'Ltcnt.e Cl red Red 118 X / CEi e ICHw red \ -c't -N-c115 -CI = C c $ I clg b AB 119 g CEi-CE2-N (CEi) S Cl o Cl orange 120 E2N u yellow C. IN N115 10 121 HE t> NEi yellow 122 110¼Qi {c yellow B aY (yellow C115 t3N (c2a) 2 Trot 1 c-ca, cle O 124 2 NOi too red CO-CEi-NtCEi 0 4 @O C1 J yellow CE, 126pos yellow 0 8 CEi -CEi-CE-J (CH) s SO, e No. AB X> \ CH-CH- 9 -CBs! Red C10 Example 128: 6.9 g of 2-amino-5-thiocyanato-thiadiazole- (1.3.4) are stirred up in 20 ml of β-hydroxypropionitrile. With external cooling, 7.5 ml of 41.2% nitrosylachulfuric acid are added dropwise over about 45 minutes at 0-50 ° C. and the mixture is stirred at this temperature for a further 2 hours. The solution obtained is added at 100 ° C. to a mixture of 6.3 g of 2-hydroxynaphthalene, 5 g of magnesium oxide in 200 ml of methanol. After the coupling has ended, it is diluted with water and the orange-colored dye of the formula vacuumed and dried.

1 g of the product obtained, 1 g of a condensation product Naphthalene, formaldehyde and sulfuric acid and 15 ml of water are placed in a ball mill Grind for approx. 24 hours. The dough obtained is made with the addition of 5 g of urea, 4 g ammonium sulfate, 2.5 g sodium calcine and 75 ml water processed into a printing paste. This is used to print fabric made of nickel-modified polypropylene, dry and steam 30 minutes, rinses and soaps. A blue print with good general fastness properties is obtained.

Example 129: 11.4 g of 2-amino-5-thiocyanato-thiadiazole- (1.3.4), 21.2 g of N-ethyl-N- (3'-sulfobenzyl) -aniline and 7.7 ml of 30% hydrochloric acid are mixed in 50 ml of water and 25 ml of ethanol and 30 ml of 10% sodium nitrite solution are added dropwise over 3-4 hours at approx. 100C. After stirring overnight, the resulting dye is of the formula isolated. It dyes fibers made from natural and synthetic polyamides in clear red tones with good light and wet fastness properties.

Other valuable dyes are obtained when the coupling component used in this example is replaced by the compounds listed in column A of the table below. The color shade of the dyeings achieved on Perlon is listed in column B. No. s B. 2115 130 1 9 | Red 131io (c, | red C115ON-C-SI No. ALB OH 132 red-violet SOzH 133 to / CE; Red \ CEi-CE-SC * H C115 134 H <yellow 1) 031 C'Lt 135 t CEz-SC * H yellow H'O I. 503 H. H 137 H red . 138 2), red CO-CE; -CE-SC * H No. A 3 139 red liH-co-c -c COOH 140 / c, H6 02115 140 Hb C'Lt C'Lt -COOI red \ cg Cg, -COOH C115 141 NgNH-CEi CE52 -COOB red ICB3 C115 142 ct§NH-CE2 CEL2 COOH red CE5 143 GgN (C2Eii) 2 red -COOH / 2 dtC t: OOH 144 COOH 1 yellow Hd O C115 COOH 145 Hv yellow HO 146 X 3 (approx. 146 yellow - - e

Claims (1)

Claims 1) Compound of the formula 2) Process for the preparation of the compound of claim 1, characterized in that 2-lmino-5-mercapto-thiadiazole (1.3.4) is reacted in water or an organic solvent which is indifferent to the reactants with cyanogen halide in the presence of an acid-binding agent. 3) azo dyes of the formula where K is the remainder of a coupling component. 4) azo dyes according to claim 3 of the formula wherein R1 is hydrogen, alkyl, alkyl, halogen, CF3, NQ1, COO6, NQ1-SO2Q21, NQ1CO2Q2 or NHCONQ1Q2 R2 is hydrogen, alkyl, -0e, halogen or CC * Ce R2 is hydrogen, alkyl, alkenyl, aralkyl or alkyl subst. by halogen, -CN, OH, COOH, aryl or a group (-O-CH2-CH2) n-Q4 ilt n = 1-8, R4 aryl or R3 or R2 + R3 or R3 + R4 members of a 5- or 6-membered heterocyclic ring Q1 hydrogen or Alkyl (H is preferred) Q2 alkyl, alkenyl, aralkyl or aryl q5 hydrogen or Q Q4 -Cl, -OH, -OQ2, -CN or -COOH where said alkyl radicals preferably have 1-4 carbon atoms and the alkenyl radicals preferably have 3-5 carbon atoms and the aryl radicals are preferably phenyl radicals, which are preferably 1-3 times by alkyl, alkyl or halogen can be substituted. 5) azo dyes according to claim 4 wherein R1 is hydrogen or methyl and R2 are hydrogen and the other radicals have the meaning mentioned. 6) Azo dyes according to claim 4 wherein R1 is C1-C4-alkylcarbonylamino or C1-C4-alkoxycarbonylamino, R2 is hydrogen, methyl, chlorine, methoxycarbonyl or ethoxycarbonyl, Rs is C2-C4-alkyl or C2-C4-alkyl subst. by Cl-C4-alkoxy, CN, OH, phenoxy or phenyl and R4 denotes hydrogen or R6. 7) methods of dyeing and printing hydrophobic fiber materials, characterized in that dyes of claims 3-6 are used. 8) azo dyes of the formula where T1 is hydrogen, methyl or chlorine, T2 is hydrogen, methyl, chlorine, methoxy or ethoxy, T5 is hydrogen, benzyl, phenylethyl, C1-C4-alkyl, C2-C4-alkyl subst. by OH, C1-C4-alkoxy CN or -NT5T6T7 T4 C2-C-alkylene, T5 / T6 / T7 allyl or T3 or together with N form a heterocycle and Q An is an anion. 9) Process for dyeing and printing eauer-modified fiber materials, characterized in that dyes according to Claim 8 are used. 10) azo dyes of the formula where V1 is hydrogen, halogen, alkyl, alkyl or alkylcarbonylamino, V2 is hydrogen, alkyl or O-alkyl, V3 is hydrogen, alkyl, hydroxyalkyl, cyanoalkyl or -V4-V3-SO3H, V4 is C1-C4-alkylene and V5 is oxygen, phenyl or a mean direct bond, where "alkyl" has the meaning given in claim 4. V6 SOaH or COOH 11) Process for dyeing and printing natural and synthetic polyamides, characterized in that dyes are used Claim 10 used. 12) Verfahrn for the production of dyes according to claim 1, characterized characterized in that the diazonium salt or the N-nitroso compound of 2-amino-5-thiocyanato-thiadiazole with a coupling component of the formula KIT. 13) Use of dyes of claim 5 for the exercise of heat transfer printing.