58976-97-9

Upstream product

• 15910-11-9 1,4-diacetoxy 1,3-butadiene 
• 51287-54-8 3-(phenylsulfanyl)isobenzofuran-1(3H)-one 
• 7474-90-0 5,6,7,8-tetrahydro-1,4-naphthoquinone 
• 476-60-8 leucoquinizarin 
• 638-37-9 butanedial 
• 58976-82-2 Acetic acid 5,6,11,12-tetraoxo-1,4,4a,5,6,11,12,12a-octahydro-naphthacen-1-yl ester 
• 1709-63-3 anthracene-1,4,9,10-tetraone 
• 76641-28-6 11-Hydroxy-6-methoxy-12-oxo-5,7,8,9,10,12-hexahydro-naphthacene-5-carboxylic acid methyl ester 
• 77972-58-8 6-chloro-11-hydroxy-1,4,4a,12a-tetrahydronaphthacene-5,12-dione 
• 58976-96-8 Acetic acid 6,11-dihydroxy-5,12-dioxo-1,2,3,4,4a,5,12,12a-octahydro-naphthacen-1-yl ester 
• 13623-10-4 5,6,7,8-tetrahydronaphthalene-1,4-diol 
• 88-95-9 Phthaloyl dichloride 
• 77972-67-9 6-chloro-11-hydroxy-1,2,3,4,4a,12a-hexahydronaphthacene-5,12-dione 
• 37845-20-8 5,12-diacetoxy-1,2,3,4-tetrahydronaphthacene-6,11-dione 

Downstream Products

• 20494-73-9 1,2,3,4-tetrahydro-1,5,12-trihydroxynaphthacene-6,11-dione 
• 37845-20-8 5,12-diacetoxy-1,2,3,4-tetrahydronaphthacene-6,11-dione 

Relevant academic research and scientific papers

Synthesis, EPR, ENDOR and TRIPLE Resonance Investigations of Anthracycline-Related Semiquinones

The synthesis of five substituted anthraquinones related to anthracyclines is described.One-electron reduction of these compounds yields the corresponding semiquinones, which were characterized by EPR, ENDOR and TRIPLE resonance spectroscopy.The data indicate a rapid conformational interconversion of the cyclohexene moiety (ring A in the anthracyclines).The low-temperature structures could be assigned to half-chair conformers whose splitting constants and torsion angles were obtained by simple calculations.Introduction of substituents in the 4-position, disturbing the symmetry of the anthraquinone, results in remarkable changes in the spin density distribution, in contrast to published results.A reinterpretation and assignment of known anthraquinone radicals is presented.Key Words: Anthracycline semiquinones, EPR, ENDOR, TRIPLE, Conformation

Direct access to 1,4-dihydroxyanthraquinones: The Hauser annulation reexamined with p-quinones

(Chemical Equation Presented) 3-Phenylsulfanylphthalides (e.g. 8a) readily react with p-benzoquinones in the presence of LiOtBu in THF to furnish 1,4-dihydroxyanthraquinones in good yields and one-pot operations.

A NEW METHODOLOGICAL APPROACH TO ANTHRAQUINONE AND ANTHRACYCLINONE SYNTHESIS

A new general methodology for the anthraquinone and anthracyclinone synthesis has been developed.In contrast to the data reported in the previous literature, anthraquinones can be obtained under mild conditions from ortho dicarboxylic acid chlorides and suitable aromatic substrates via a Friedel-Crafts process.In this context the classic Wong synthesis of anthracyclinones has been greatly improved.The study of the reaction mechanism permitted the unexpected results to be rationalized and to account for the "ortho template bisacylation" of the phenol substrates.

METAL TEMPLATE ORTHO-ACYLATION OF PHENOLS; A NEW GENERAL APPROACH TO ANTHRACYCLINONES

Direct and mild synthesis of dihydroxyanthraquinones including 4-demethoxy-7-deoxydaunomycinone 8 from ortho-phthaloyl dichloride and hydroquinone derivatives is described.

Annelation Reactions of Quinone Monoketals. Studies Directed at an Efficient Synthesis of Anthracyclinones

The annelation chemistry of quinone monoketals with dimethyl homophthalate, 7-methoxy-3-(phenylsulfonyl)-1(3H)-isobenzofuranone, and 7-methoxy-3-cyano-1(3H)-isobenzofuranone has been studied.The first two reagents mentioned above allowed the formation of oxygenated tri- and tetracyclic anthrone and anthraquinone systems in 40-50percent yields.While less extensively studied, the 7-methoxy-3-cyano-1(3H)-isobenzofuranone afforded a 75percent yield in an annelation reaction with a highly functionalized monoketal.These reactions, coupled with the unique effect of an allylic methoxylgroup on the regiochemistry of quinone bisketal hydrolysis, allowed a regiospecific preparation of certain tetracyclic anthraquinones.The work reported herein comprises a formal synthesis of racemic daunomycinone and forms a basis for an efficient, practical synthesis of fully functionalized anthracyclinones.

Chemistry of Quinones. Part 7. Synthesis of Anthracyclinone Analogues via Diels-Alder Reactions of 1,4-Anthraquinones

Diels-Alder adducts were formed by reaction of 1,4-anthraquinone with buta-1,3-diene, with 1-acetoxy-, 1-methyl-, 2-methyl-, and 2,3-dimethyl-buta-1,3-diene, and with cyclohexa-1,3-diene.Adducts were also prepared by reaction of 9-chloro-10-hydroxy-1,4-anthraquinone with buta-1,3-diene and with 2-methylbuta-1,3-diene.Some of the linear tetracyclic adducts were transformed to 1,2,3,4-tetrahydro-1,5,12-trihydroxynaphthacene-6,11-quinone (21) and 2-acetyl-1,2,3,4-tetrahydro-2,5,12-trihydroxynaphthacene-6,11-quinone (7).The latter has been converted by other workers into 4-demethoxydaunomycinone (48) and 4-demethoxydaunomycin (8).