Photooxidative transformations of anthrone, bianthronyl, and bianthrone in acid solution

Filipescu, Nicolae; Avram, Eliza; Welk, Katherine D.

doi:10.1021/jo00423a024

Cited by 8 publications

(5 citation statements)

References 7 publications

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“…7,10,29 On the other hand, the ratios of III/IV for naturallyoccurring chrysophanol-physcion bianthrone (15), chrysophanol-isophyscion bianthrone (16), and physcion-emodin bianthrone (17) need to be conrmed by calculations (Table 1), which may be taken as valuable references for their analogues. As a result, the cis diastereomer originally assigned for 17 should be trans.…”

Section: Heterobianthrone Differentiationmentioning

confidence: 99%

“…Thus, the original differentiation of 22 is unacceptable, 7 and bianthrone A2a (18) from Psorospermum tenuifolium and (+)-crinemodin-rhodoptilometrin from Himerometra magnipinna are deduced to feature the trans and cis H-10/ 10 0 , respectively, by comparison with their analogues (6b/c and 2a). 7,10,29 On the other hand, the ratios of III/IV for naturallyoccurring chrysophanol-physcion bianthrone (15), chrysophanol-isophyscion bianthrone (16), and physcion-emodin bianthrone (17) need to be conrmed by calculations (Table 1), which may be taken as valuable references for their analogues. As a result, the cis diastereomer originally assigned for 17 should be trans.…”

Section: Heterobianthrone Differentiationmentioning

confidence: 99%

“…2,4,8 Additionally, the epimerization and photooxidation under acidic conditions preclude hydrolyses and derivations by some chemical methods. 6,16 Thus, the congurations for most of the substituted bianthrones have been assigned almost in chaos so far due to the meso, racemic, and axisrotating phenomena, which may restrict the application and development of these molecules to some extent. Based on the calculations by the Dreiding force eld in MarvinSketch 17 and density function theory (DFT) in Gaussian 09 (ref.…”

Section: Introductionmentioning

confidence: 99%

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A rule to distinguish diastereomeric bianthrones by 1H NMR

Liang

Sun

et al. 2014

RSC Adv.

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Section: Heterobianthrone Differentiationmentioning

confidence: 99%

Section: Heterobianthrone Differentiationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A rule to distinguish diastereomeric bianthrones by 1H NMR

Liang

Sun

et al. 2014

RSC Adv.

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“…Dianthrylethylene 113f, for which electronic absorption and emission spectra, as well as X-ray diffraction data indicate enhanced intramolecular interaction of the two 124 125 The photochemical geometrical isomerization of Intramolecular photochemical dehydrocyclizations of anthracene-related compounds are well known for bianthrone and similar stilbene-like anthrone derivatives. [267][268][269][270][271] In recent years, several examples of styrylsubstituted anthracenes undergoing photochemical dehydrocyclization have been reported. Irradiation of styryl-substituted anthracene 129 in xylene for 60 h gave 130 in 15% yield.…”

Section: A Geometrical Isomerization and Cycloaddltlon Reactionsmentioning

confidence: 99%

Unimolecular photochemistry of anthracenes

Becker¹

1993

Chem. Rev.

387

273

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“…The formation of bianthronyl could then occur by the previously established photo-oxidation of anthrone (7). This photo-oxidation reaction is little affected by the presence of OAO and its hydroxy derivatives in the irradiated acid solution, because anthrone absorbs in the 350 nm region, where the other compounds are relatively transparent.…”

Section: Forrnariorl Of Anthrone and Biarzthrorlylmentioning

confidence: 99%

The photochemistry of 9,10-anthracenedione in sulfuric acid solution. The dependence of product yields on reaction conditions

Broadbent¹,

Stewart²

1983

Can. J. Chem.

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I965 (1983). Irrz~diation of a sulfuric acitl solution of 9,IO-anthraccnctlionc with ncar-uv light gcncratcd 2-l1ydroxy-9,lO-anth1~accncdionc as thc major product. In addition. thc I-hydroxy and polyhydroxy dcl.ivntivcs and thc rcduction products anthronc and bianthronyl wcrc also formcd. Thc yiclds of thcsc minor products wcrc markcdly influcncctl by thc concentrations of water and oxygcn in thc sulfuric acid. At low light intcnsitics, oxygcn qucnchctl thc cfficicnt formation of thc hydroxyanthraccncdioncs and also oxidiscd thc initial quinonc rcduction products. Photorctluction of thc anthraccncdionc and photooxidation of anthronc occurrcd si~nultancously in thc solution. l'hc rcaction mechanism is morc cornplcx than prcvious studics indicatcd.A. DOUGL.AS BROADBENT ct JOHN M . STEWART. Can. J. Chcm. 61, 1965 (1983. L'irradiation dc I'anthrackncdionc-9.10. cn solution dans I'acidc sulfuriquc avcc unc lumikrc clu prochc uv conduit i la formation dc I'hydroxy-2 anthrackncdionc-9.10 commc produit mqjoritairc. Dc plus, il sc formc dgalcmcnt I'hydroxy-I, Ics ddrivds polyhydroxy ct lcs produits de In rdduction dc l'anthronc et du bi~unthrony Ic. Lcs I-cndcmcnts dc ccs produits sccondaircs sont fortcmcnt influcncCs par la concentration cn cau ct en oxygknc dans I'acidc sulfuriquc. Lorsqu'on utilisc unc lurnikrc dc faiblc intcnsitd, l'oxygknc bloquc la formation cfficacc des hydroxyanthrackncdioncs ct oxydc dgalcmcnt Ics produits initiaux dc la rdduction dc la quinonc. La photorCduction dc I'anthrackncdionc ct la photoxydation de I'anthronc sc produiscnt simultanCrncnt cn solution. LC n~dcanisn~e dc la rdnction cst plus complcxc quc nc I'indiqucnt Ics dtudcs antdricurcs.[Traduit par Ic journal] Introduction Although sulfuric acid is a widely used and excellent solvent for 9,IO-anthracenedione and its derivatives ( I), little is known about photochemical reactions of these compounds in this solvent. lrradiation of a 100% sulfuric acid solution of 9,10-anthracenedione-2-sulfonate, with near-uv light, has been reported to produce only 2-hydroxy-9.10-anthracenedione sulfonates, with no I-hydroxy derivatives (2). Total regioselectivity was also found in the similar photochemical reaction of the unsubstiti~ted 9.10-anthracenedione (OAO). which was claimed to yield 2-hydroxy-9,lO-anthracenedione (2-HO-OAO) as the sole product (3). Observation of well-defined isosbestic points in a series of uv spectra of a progressively irradiated solution indicated a clean, efficient reaction. No differences in reaction rate were noted between preparative experiments using nitrogen or air bubbling. The lack of oxygen influence on the photochemical reaction of O A O in sulfuric acid was apparently confirmed by subsequent studies (4), in which I-hydroxy-(I-HO-OAO) and 1,4-dihydroxy-9,lOanthracenedione (quinizarin) were also isolated in addition to the major 2-HO-OAO.Changes in the product distribution during the reaction suggested that the initially formed I-HO-OAO underwent a subsequent photochemical hydroxylation reaction yielding quinizari...

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Photooxidative transformations of anthrone, bianthronyl, and bianthrone in acid solution

Cited by 8 publications

References 7 publications

A rule to distinguish diastereomeric bianthrones by 1H NMR

A rule to distinguish diastereomeric bianthrones by 1H NMR

Unimolecular photochemistry of anthracenes

The photochemistry of 9,10-anthracenedione in sulfuric acid solution. The dependence of product yields on reaction conditions

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