CS255194B1 - S-Amino-6-arylazo-1,10-phenanthrolines and a process for their preparation - Google Patents

Abstract

5-amino-6-arylazo-1,10-phenanthrolines of the general formula II, where R denotes hydrogen, methyl, fluorine, chlorine, bromine, iodine and methoxy groups, can be used for dyeing wool, silk and leather. The method of preparing azo dyes of formula II consists in the reduction of 5-nitro-1,10-phenanthroline with ammonium sulfide to 5-amino-1,10-phenanthroline of formula I, which was coupled with a solution of the corresponding diazonium salt in aqueous acetic acid in the presence of sodium acetate.

Description

The invention relates to 5-amino-6-arylazo-l, 10-phenanthrolines of the general formula II, wherein R is hydrogen, methyl, fluorine, chlorine, bromine, iodine and methoxy and a process for their preparation.

Said substances belong to the group of basic azo dyes having in addition complex-forming properties.

The preparation of azo dyes of the formula IX, wherein R is as defined above, consists in coupling the corresponding cations of the diazonium salts of the formula III in which R is hydrogen, methyl, fluorine, chlorine, bromine, iodine or methoxy in a weakly acidic medium at pH 4 to 6 s. 5-amino-l, 10-phenanthroline of formula I, prepared by reduction of 5-nitro-l, 10-phenanthroline with ammonium sulfide.

The preparation of compounds of formulas I and II is illustrated in the following examples.

Example 1

5-amino-1, 10-phenanthroline (I)

A mixture of 9.52 g (42.27 mmol) of 5-nitro-9,10-phenanthroline, 210 ml of ethanol and 30 ml of a 25% aqueous ammonia solution was stirred with hydrogen sulfide under stirring and left in a closed flask at room temperature for 7 days with occasional shaking. . The reaction mixture was then heated at 60 ° C on a water bath under reflux for 1 h and finally evaporated. The residue was then extracted with 360 mL of 2% hydrochloric acid, the extract was filtered and basified by adding an excess of 26% aqueous solution. The precipitated crystalline solid was filtered off with suction, washed with water and dried. Yield 7.57 g (92.70%). After recrystallization from propanol, m.p. 258 DEG-260 DEG.

For C ₁₂ H ₈ N ₃ (195.22) calculated: 73.83% C, 4.65% H, 21.53% N found: 73.71% C, 4.69% H, 21.32% N

Example 2

5-Amino-6-phenylazo-1, 10-phenanthroline (Ha)

A solution of diazonium salt prepared from a solution of 260 mg (2.01 mmol) of aniline hydrochloride in a mixture of 2.0 mL of 37% HCl and 8 mL of water by diazotizing with a solution of 138 mg (2.00 mmol) of NaNO3 in 3 mL of water at 0-5 ° C was added portionwise to a solution of 400 mg (2.05 mmol) of compound I and 3.0 g of CH 3 COON in a mixture of 6 ml of acetic acid and 30 ml of water at this temperature with stirring and cooling. The precipitated HCl hydrochloride precipitate was aspirated after 48 h and suspended in 50 ml of 3% NH _3. The free base Ha was aspirated after 48 h, washed with water and dried at 120 ° C. Yield: 565 mg (94.4%) Mp 283-285 ° C after recrystallization from ethanol.

For C ₁₈ H ₁₃ N ₅ (299.32) calculated: 72.22% C 4.38% H 23.40% N Found: 71.98% C, 4.34% H, 23.31% N

The following azo dyes were prepared analogously and in corresponding yields: 5-amino-6- (4-tolylazo) -1,10-phenanthroline (IIb), m.p. 265 DEG-267 DEG.

For C ₁₉ H ₁₅ N ₅ (313.35) calculated: 72.83% C 4.83% H 22.35% N Found: 72.87% C, 4.86% H, 22.44% N

5-amino-6- (4-fluorophenylazo) -1,10-phenanthroline (IIc), m.p. Mp 289-291 ° C.

For C ₁₈ H ₁₂ N ₂ P (317.10) calculated: 68.07% C, 3.81% H, 22.09% N Found: 67.95% C, 3.94% H, 21.93% N

5-amino-6- (4-chlorophenylazo) -1,10-phenanthroline (IId), m.p. 297-299 ° C.

25.5194

For C ₁₈ H ₁₂ N ₂ Cl (333.79, calculated: 64.77 C, 3.62 H, 20.98%. Found: C 64.62, H 3.71, 20.85 % N

5-amino-6- (4-bromophenylazo) -1,10-phenanthroline (Ile), m.p. Mp 295-297 ° C.

For C ₁₈ H ₁₂ N ₅ Br (378.25) calculated: 57.16% C, 3.20% H, 18.52% N found: 57.03% C, 3.28% H, 18.33% N

5-amino-6- (4-iodophenylazo) -1,10-phenanthroline (Uf), m.p. Mp 279-281 ° C.

For C ₁₈ H ₁₂ N ₅ I (425.25) calculated: 50.84% C, 2.84% H, 16.47% N found: 50.69% C, 2.75% H, 16.28% N

5-amino-6- (4-methoxyphenylazo) -1,10-phenanthroline (lig), m.p. Mp 247-249 ° C.

For C ₁₉ H ₁₅ N ₅ O (329.35) calculated: 69.28% C 4.59% H 21.27% N Found: 69.35% C, 4.66% H, 21.12% N

In the IR spectrum of a solution of compound IXa in CH 2 Cl 2, the most intense band at 1600 cm ^-1 , which, together with the less intense band at 3,472 cm ^-1 , corresponds to the 5-imino-6-phenylhydrazono-5,6-di hydrotautomer. Electron spectrum 5xl0 ^- ^ M ethanolic solution of compound Ha \ IAX ° ^ ^® ε ^/! 3232 ^nm ( ^{2 * 4} ' ⁵ ') '257 nm (4.31), 287 nm (4.27), 439 nm (4.24). All said azo dyes stain both protein and cellulose fibers as well as the skin.

Claims (3)

SUBJECT OF THE INVENTION CLAIMS 1. 5-Amino-6-arylazo-1, 10-phenanthrolines of the general formula II, in which R represents hydrogen, methyl, fluorine, chlorine, bromine, iodine and methoxy. 2. A process for the preparation of a compound according to claim 1, wherein: 5-Amino-l, 10-phenanthroline of formula I, prepared by reduction of 5-nitro-l, 10-phenanthroline with ammonium sulfide, is coupled with cations of diazonium salts of formula III wherein R is hydrogen, methyl, fluoro, chloro, bromo, iodo and methoxyl, at an ambient pH of 4 to 6.