Studies on the Acid Anthraquinone Dyes, I-II

Abstract

In the Previous papers, we have reported on a manufacturing method of Na-monochloro-, and -1, 4-dichloroanthraquinone-7-sulfonates from Na-anthraquinone-sulfonate (Silver salt).In the present papers, we report on the synthesis of some acid anthraquinone dyes, from Na-1, 4-dichloroanthraquinone-7-sulfonate (I).1). Condensation of I with 2 moles of aniline, to obtain Na-1, 4-dianilino anthraquinone-7-sulfonate. 5g. I, 60g. aniline, and 2g. NaOAc. were stirred at 183-5°, for 8hr. The product was greenish black powder. Yield, 6.3g.(96.9% of the calc. amount). It showed no mp., and dyed wool, as well as nylon, bluish green hue of excellent light fastness. Dyeing and testing methods are outlined. In water solution, absorption maxima were found at 200mg, and 640mμ2). Amination of condensation product of I with 1 mole of aniline, to obtain Na-amino-anilino-anthraquinone-sulfonate. A mixture of 40g. I, 38.4g. aniline, 18g. Na2CO3 and 440cc. water was stirred at 95°, in the presence of freshly prepared cuprous oxide, for 4hr., until the condensation was complete (reaction end point was detected by paper chromatographical method). The product (11) was reddish violet powder. Yield, 38-40g.(83-86% of calc. amount). It showed no mp., and dyed wool bluish red. In water solution, absorption maxima were found at 259.0mμ., 332.5mμ., and 535mμ.Amination of II.5g. II (as Na salt), 180cc. 28% ammonia, and 2g. p-toluene sulfamide were taken in an autoclave, and heated at 125° and 20 atm. for 4hr. The product was deep blue powder. It showed no mp. Yield, 2.9-3.0g.(64-66% of calc. amount). It dyed wool navy blue of excellent light fastness. In water solution, absorption maxima were found at 255mμ., 550mμ., and 590mμ. The presence of amino group in the dye was identified by its diazotisation and coupling with β-naphtol, to obtain a brown acid azo dye.3). Condensation of I, with 1 mole of monomethylamine, and 1 mole of aniline, to obtain Na-methylamino-anilino-anthraquinone-sulfonate. 5g. I and 3g. Na2CO3 were dissolved in 150cc. water at 95°. To the solution, 0.9g. CH3NH2·HCl, dissolved in 20cc. water, was added, and stirred at 95° for 4-5hr. The product was reddish violet powder (III). Yield, 4.6g.(93.5% of calc. amount). It showed no mp., and dyed wool clear bluish red hue, but of little value as dye. In water solution, absorption maxima were found at 255.5mμ., and 535mμ.Condensation of III with 1 mole of aniline. 4 g. III (as Na salt), 50g. aniline, and 2g NaOAc were stirred at 183-5° for 25hr. The product was greenish black powder. Yield, 4.1g.(89.1% of calc. amount). It showed no mp., and dyed wool blue-black hue, similar to Acid Blue Black. 10 B.(C. I. 246). Dyeing and fastness properties were studied in details (See Table 3-5). In water solution. absorption maxima were found at 254mμ. and 620mμ.