Diamino-9,10-anthraquinone

A representative plot of AA vs pH is shown in Figure 4. However, whereever such intramolecular stabilisation effect is not present, the pK(l) value goes up, e.g. 9,10-anthraquinone-l,5-disulphonate l,4-diamino-9,10- anthraquinone 1-amino-4-hydroxy-9,10-anthraquinone 5,12-naphthacene quinone, etc. 

In the case of 2,6-diamino-9,10-anthraquinone having a lower value, the initial extent of P700 and the extent of the slow decay phase were low (Fig. 1). This may reflect incomplete reduction of this quinone by Aq". This quinone seems to belong to A type (Fig. 2), in which the E of the quinone is comparable or lower than that of Aq. 

Various more complex dyes of industrial significance contain more than one carbazole system. For example, Cl Vat Orange 11 (6.86) contains two carbazole components and a central unit derived from 1,5-diaminoanthraquinone. This dye is prepared by carbazolisation of the trianthrimide produced when two moles of 1-chloroanthraquinone react with one mole of 1,5-diaminoanthraquinone. The equivalent isomeric dye obtained from 1,4-diamino-anthraquinone is reddish brown (6.87 Cl Vat Brown 1). The interesting, symmetrically-substituted tetracarbazole dye Cl Vat Green 8 (6.88) was first synthesised in 1911 by Hepp from 1,4,5,8-tetrachloroanthraquinone. Not surprisingly, the product (C70H28N4Oio relative molecular mass 1084) is of very low solubility. The structure was confirmed in 1957 by Jayaraman, who found no evidence of uncyclised anthrimides in the UV spectrum of the dye solution in concentrated sulphuric acid [32]. 

SYNS 9,10-ANTHRACENEDIONE, 2,6-DIAMINO- ANTHRAQUINONE, 2,6-DIAMINO- 2,6-DIAMINO-ANTHRACHINON 2,6-DIAMINOANTHRA-QLTNONE... 

Several quinones are used clinically in the chemotherapy of cancer [61,62]. Some examples are adriamycin (doxorubicin), daunomycin (daunorubicin), mitomycin C and more recent diaziridinyl benzoquinones and diamino anthraquinones [5]. Physiological enzyme based reduction of these quinones caused by xanthine oxidase, cytochrome P450 reductase etc.[63], leads to the formation of semiquinone and hydroquinone forms. Pulse radiolysis can generate and characterise these intermediates and products [10]. 

Semi permanent. A long list of dyes may be used, i.e. 4-nitro-2-phenylene diamine, 2-amino-3-nitrophenol, 1,4 diamino anthraquinone... 

There are only a few publications in the field of TLC of disperse dyes, although this method provides better resolution and is more time-economical than PC. WoiJiENWEBEB [84] has separated Celliton Fast Red Violet RN (C. I. 61100), CelHton Fast Pink B (C. I. 60710) and qumizarin (C. I. 58050) through TLC on acetyl-ceUulose powder of 10% acetyl content he used the solvent ethyl acetate-tetrahydrofuran-water (6 + 35 + 47) which is suitable also for PC-separations on acetyl-paper (43). Many azo- and anthraquinone disperse dyes have been separated by Rettie and Haynes [61] with the help of TLC on the same adsorbent, using tetrahydrofuran-water-4N acetic acid (80 + 54 + 0.05) and mixtures of similar composition. Better separations of disperse dyes of the anthraquinone class can be obtained by TLC on silica gel 6, using chloroform-acetone (90+ 10) [61] 1-Amino-, 2-amino-, 1,2-diamino- and 1,4-diamino-anthraquinones could be thus separated. 

Anthraquinone Blue B (Acid Blue 45, l,5-diamino-4,8-dihydroxy-9,10-anthraquinone-3,7-disulfonic acid di-Na salt) [2861-02-1] M 474.3, m >300°, Cl 63010, X.max 595nm, pKesi(1) <0, pKEst(2) 2, pKEst(3) 9. Purified by salting out three times with sodium acetate, followed by repeated extraction with EtOH [McGrew and Schneider 7 Am Chem Soc 72 2547 1950]. 

Sometimes decomposition reactions can be avoided by carrying out diazotizations in concentrated sulfuric acid. By this method Law et al. (1991) obtained the 1,5-bisdiazonium salt (incorrectly called tetrazonium salt) of l,5-diamino-4,8-dihy-droxy-anthraquinone, which is deprotonated to 2.28. The structure was verified by cross-polarization magic angle spinning (CPMAS) 13C NMR spectroscopy. 

Derivatives of diaminoanthrarufin (3.77 X = Y = H) and its 1,8-dihydroxy-4,5-diamino isomer (diaminochrysazin) have been among the most widely used anthraquinone dyes for ester fibres. For example, methylation of diaminoanthrarufin gives Cl Disperse Blue 26, a mixture of several components. Study of the pure N-alkylated derivatives from the base confirmed that monosubstitution (3.77 X = H, Y = alkyl) gives mid-blue dyes with excellent dyeing properties and acceptable fastness on polyester, but the bis-alkyl dyes (3.77 X = Y = alkyl) are greener and inferior in application properties. Mixtures of the unsubstituted base with alkylated components, as obtained industrially, were especially advantageous for build-up to heavy depths, however [93]. 

Gasparutto D, Ravanat J-L, GerotO, Cadet J (1999) Characterization and chemical stability of photo-oxidized oligonucleotides that contain 2,2-diamino-4-[(2-deoxy-(1-D-eryfhro-pentofuranosyl)-amino]-5(2FI)-oxazolone. J Am Chem Soc 120 10283-10286 Geimer J, Beckert D (1998) Study of radical pairs generated by photoreduction of anthraquinone-2,6-disulfonic add with thymine by Fourier transform electron paramagnetic resonance. Chem Phys Lett 288 449-458... 

Acylation of 1-amino- or 1,5-diaminoanthraquinones yields yellow vat dyes and affords red to ruby colored dyes when 1,4-diaminoanthraquinones are used. Use of 4,8-diamino-l,5-dihydroxy-anthraquinones gives violet to blue dyes. The relatively low lightfastness of the yellow acylaminoanthraquinones may be improved greatly by using azodiphenyl-4,4 -dicarboxv 1 ic acid. Acylaminoanthraquinones are relatively sensitive to atmospheric conditions. 

Ethidium bromide (= 2,7-Diamino- 10-ethyl-9-phenyl-phenanthridinium bromide)] (phenanthridinium) [Heliquinomycin] (glycosylated rubromvcin) [4 -Hydroxymethyl-4,5, 8-trimethylpsoralen =HMT] (furanocoumarin) [Mitoxantrone] [anthraquinone]... 

Figure 3.20 Isomeric structures of a diamino-substituted anthraquinone dye.

SYNS ANTHRAQUINONE, 2-BROMO-l,5-DIAMINO-4,8-DIHYDROXY- MODR OSTACETOVA LR... 

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