Anthraquinones and Related Compounds

Most of the previously identified 25 chlorinated anthraquinones are found in lichen and fungi (1). The newly discovered examples have a wider range of sources. Studies of the lichen Nephroma laevigatum from the British Columbia coast have identified the new anthraquinone, 7-chloro-l-O-methyl-co-hydroxy-emodin (2157), and the two novel hypericins, 7,7 -dichlorohypericin (2158) and 2,2, 7,7 -tetrachlorohypericin (2159) (1931), as well as 5-chloroemodin (2160), 5-c h I oro -1 - (9 - m e t h v I - o - h yd ro x ye m od i n (2161), and 5-chloro-co-hydroxyemodin (2162) (1932). In addition to containing several known chlorinated anthraquinones, the Scandinavian fungus Dermocybe sanguinea has afforded the new 5,7-dichloroendocrocin (2163) (1933). The novel tetracyclic anthraquinones 

The Streptomyces strain that produces celastramycin A (1212) has also yielded celastramycin B (2166) (1225). Another Streptomyces sp. has afforded bischloro-anthrabenzoxocinone ((-)-BABX) (2167), which has antibacterial activity and inhibits ligand-binding activity of liver X receptors (1937). An example of a rare chlorinated anthraquinone is anthrasesamone C (2168), which was characterized in the Japanese plant Sesamum indicum (1938). The angucycline-type marmycin B 

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Several types of woods that contain anthraquinones and related compounds are highly resistant to attack by marine borers (Southwell and Bultman, 1971). 2-Methyl- (57), 2-hydroxymethyl- (75) and 2-formylanthraquinones in the heartwood of teak (Tectona grandis, Verbenaceae) are effec-... 

Inoue, K., Y. Shiobara, H. Nayeshiro, H. Inouye, G. Wilson, and M. H. Zenk, Biosynthesis of anthraquinones and related compounds in Galium mollugo cell suspension cultures. Phytochemistry, 23, 307-311 (1984). 

Singh, R. Geetanjali. Isolation and synthesis of anthraquinones and related compounds of Rubia cordifolia. J. Serb. Chem. Soc. 2005, 70, 937-942. 

WILSON, M.H. ZENK. 1984. Biosynthesis of anthraquinones and related compounds in Galium mollugo cell suspension cultures. Phytochemistry 23 307-311. 

Brown, J.P. (1980). A review of the genetic effects of naturally occurring flavonoids, anthraquinones and related compounds. Mutat. Res. 2i 243-277. 

Richtol, H.H., Fitch, B.R., Triplet state acidity constants for hydroxy and amino substituted anthraquinones and related compounds. Anal. Chem. 46 1860-1863. 

Anthraquinone-a,a -disulfonic acids and Related Compounds. Anthraquinone-a,a -disulfonic acids and their derivatives are important intermediates for manufacturing disperse blue dyes (via 1,5-, or 1,8-dihydroxyanthraquinone, or 1,5-dichloroanthraquinone) and vat dyes (via... 

Many naturally occurring substituted anthraquinones [including morindaparvin-A (60) and -B (61)] and naphthoquinones (including psychorubin and related compounds) possess cytotoxic antileukemic activities.55-57 In the former compounds, removing the hydroxy substituents retained or increased cytotoxicity for example, 62 lacks one hydroxyl (R4 = H) found in 61 (R4 = OH), and is more active in the KB cell line (ID50 61, 4.0 mg/kg 62, 0.09 mg/kg). 

Bemanthrone and Related Compounds. Benzanthrune is prepared by the reaction of anthraquinone with glycerol, sulfuric acid, and a reducing agent such as iron. Benzanchrone is an important intermediate for manufacturing vat dyes. 

Bis(2-diethylaminoethoxy) fluoren-9-one or tilorone dihydrochloride and related compounds e.g. - fluorenone ethers - fluorenone esters - fluorene ketones - fluorenone ketones - dibenzofuran ketones - xanthone ethers - anthraquinone ethers - anthraquinone sulfonamides - fluoranthene esters 2. Thiazine and acridine derivatives - Thiazine derivatives in vivo (mice, rats) Late 85-91)... 

From the viewpoint of organic synthesis, nature provides us with a number of target molecules, which have novel structures and a variety of biological activities. As already shown in Section II.A, electrochemical oxidation of phenols has been applied successfully to natural products synthesis. Hypervalent (diacyloxyiodo)benzenes have also been proved to be effective for natural products synthesis. Generally, oxidation of o- and p-methoxyphenols in MeOH provides the corresponding o- and p-quinone monoketals, respectively. They are utilized as promising synthons for natural products and related bioactive compounds, as demonstrated by Swenton . Recently, these quinone monoketals have been utilized for syntheses of terpenoids, neolignans, anthraquinones, alkaloids and related compounds. 

Baughman, G. L., E. J. Weber and M. S. Brewer. 1992. Sediment reduction of anthraquinone dyes and related compounds anthrone formation. Presented at the American Chemical Symposium on the Oxidation-Reduction Transformations of Inorganic and Organic Species in the Environment, San Francisco, CA, April 5-10, 1992. 

Anthraquinone Vat Dyes. Many of the best vat dyes are derivatives of anthraquinone or related compounds. A relatively simple dye of this class is Vat Yellow 3, which is made by benzoylation of 1,5-diaminoanthraquinone. It is a yellow pigment that is used as such when properly ground and dried. As a vat dye, it usually is supplied as an aqueous paste. Reduction with sodium hydrosulfite in caustic soda solution gives the alkali-soluble anthra-hydroquinone, which has affinity for cellulosic fibers. After application to the fiber, the insoluble dye is re-formed by oxidation, as described earlier under Vat Dyes. ... 

Anthracene and Related Compounds. The formation of anthracene by elimination of hydride from 9,10-dihydroanthracene has been reported in the preceding section. An improved high-yield synthesis of 7,12-dimethylbenz-[ajanthracene (336), a compound of biological interest, utilizes the reaction of 7,12-benz[a]anthraquinone with MeLi. Subsequent reaction with dry HCl in ethyl acetate produces 7-(chloromethyl)-12-methylbenz[a]anthracene, reduction of which gives (336). 

Engchpedia articles oa specific chemical types of dyes ate Azinedyes Azo dyes Cyanine dyes Dyes, anthraquinone Phthalocyanine compounds POLYTffiTHINE dyes StILBENE DYES SULFURDYES ThIAZOLE DYES TrIPHENYLT THANE AND RELATED DYES XaNTTIENE DYES. 

Carmine belongs to the anthraquinone class of compounds and several other chemically closely related compounds are also used as colorants.25 Kermes is a well known colorant in Europe. It is obtained from the insects, Kermes ilicis or Kermococcus vermilis, which grow on oak trees. It contains kermisic acid, the aglycone of carminic acid, and its isomer ceroalbolinic acid. Its properties are very similar to carmine. Lac is a red colorant obtained from the insect Laccifera lacca which is found on several families of trees in India and Malaysia. The lac insects are better known for their production of shellac. They contain a complex mixture of anthraquinones. Alkanet is a red pigment from the roots of Alkanna tinctoria Taush and Alchusa tinctoria Lom. All three have been cleared for food use in Europe but not in the US. 

Endophytic Penicilliumjanthinellum from the fruits oiMelia d2Mdarach in Brazil yielded known anthraquinones, emodin, citreorosein, and a related compound, citrinin, as well as a novel anthraquinone, janthinone... 

The autoxidation mechanism by which 9,10-dihydroanthra-cene is converted to anthraquinone and anthracene in a basic medium was studied. Pyridine was the solvent, and benzyl-trimethylammonium hydroxide was the catalyst. The effects of temperature, base concentration, solvent system, and oxygen concentration were determined. A carbanion-initi-ated free-radical chain mechanism that involves a singleelectron transfer from the carbanion to oxygen is outlined. An intramolecular hydrogen abstraction step is proposed that appears to be more consistent with experimental observations than previously reported mechanisms that had postulated anthrone as an intermediate in the oxidation. Oxidations of several other compounds that are structurally related to 9,10-dihydroanthracene are also reported. 

Oxidation of Related Compounds. Several other compounds related to dihydroanthracene in structure were oxidized in pyridine solvent (Table VI). No attempt was made to optimize the yields in any instance except with dihydroanthracene. It was surprising that anthrone reacted much more slowly than dihydroanthracene and that only a 40% yield of anthraquinone was obtained. 

A variety of plant substances with planar, polycyclic, aromatic structures can intercalate with DNA, examples being the quinoline alkaloid camptothecin and the furanocoumarin phenolic psoralen (Table 12.1). A variety of plant-derived anthraquinones and naphthoquinones bind to DNA and it is notable that the structurally related anthraquinones mitox-antrone and adriamycin are clinically employed as anticancer drugs (Table 12.1). DNA-binding compounds that interfere with DNA repair, DNA replication and gene expression are cytotoxic and have potential as anticancer agents (see Chapter 9). 

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