(Tosyloxy)anthraquinones. Versatile synthons for the preparation of various aminoanthraquinones

Abstract

Various aminoanthraquinones can be easily prepared from (tosy1oxy)anthraquinone precursors. Unsymmetrical 1,4diaminoanthraquinones are prepared via the intermediate monoamino mono(tosy1oxy)anthraquinones derived from 1,4-bis(tosyloxy)anthraquinone. The ability to remove tosylate groups sequentially is controlled by the proper selection of solvent and temperature. Hindered 1,4-diamino and 1-aminoanthraquinones are prepared from their corresponding tosyl derivatives, and the amount of steric hindrance present can be successfully correlated with spectral and color data. The methods described offer advantages over the literature preparations of these compounds.

Synthesis and solid state structure of fluorous probe molecules for fluorous separation applications

“…Several 1,4-bis-alkylamino-anthraquinones, such as Sudan Blue II (1,4-bis-butylamino-anthraquinone), are commercial dye products; however, the laboratory synthesis and characterization of only a few 1,4-bis-alkylamino-anthraquinones has been reported, primarily as part of studies of their solubility in supercritical carbon dioxide 20-22. One general approach to alkylamino-anthraquinones is the nucleophilic displacement of chloride, fluoride or other leaving groups from appropriately functionalized anthraquinone precursors, an approach that has been employed for the synthesis of a variety of symmetrical and unsymmetrical 1,4-bis-alkylamino-anthraquinones 23-25. Alternatively, symmetrical 1,4-bis-alkylamino-anthraquinones can be synthesized directly by the reaction of an alkyl amine with 1,4-dihydroxy-anthraquinone 26…”

9,10-Dioxoanthracene-1,4-diyl bis(4-methylbenzenesulfonate)

“…1,4-Bis(hydroxy)anthraquinone is one of an important anthraquinone starting materials for preparation the various anthraquinone dyes and pigments (Zielske, 1987). In this work, we report the intermediate of an anthraquinone dye with the two symmetric tosylate substituents.…”

“…Additionally, 1 H of 1,4-bis(tosyloxy)anthraquinone were recorded in CDCl 3 solution on a Varian Mercury Plus 400 spectrometer. 1 H NMR spectrum (δ, ppm): 7.94-8.02 (2H,m); 7.69-7.91 (6H,m); 7.45 (2H,s); 7.24-7.33 (4H,m); 2.35 (6H,s) (Zielske et al, 1987).…”

“…For background to the structures of anthraquinones and their biological activity, see: Zielske (1987); Yatsenko et al (2000); Huang et al (2004); Meng et al (2005); García-Sosa et al (2006); Cho et al (2006); Carland et al (2010). For related structures, see: Swaminathan & Nigam (1967); Cao et al (2007).…”

1,8-Bis(tosyloxy)-9,10-anthraquinone

“…The tosyl group is a very good leaving group, commonly used in organic synthesis in nucleophilic substitution reaction. This phenomenon is applicable to prepare the various aminoanthraquinone from (tosy1oxy)anthraquinone precursors (Zielske, 1987). The 1,8-Bis(tosyloxy)-9,10-anthraquinone is a very convenient and often used precursor to obtain the 1,8-diaminoanthraquinones derivatives (Dzierzbicka et al, 2006).…”