9,10-Dihydroxy phenanthrene

Diacyl-biphenyle4 gehcn bei der Reduktion in 9,10-Dihydroxy-9,10-di-hydro-phenanthrene (70—90% d. Th, c/s/tram-Gcmische) iiber3 4 ... 

Biological. Catechol is the central metabolite in the bacterial degradation of phenanthrene. Intermediate by-products include l-hydroxy-2-naphthoic acid, 1,2-dihydroxynaphthalene, and salicylic acid (Chapman, 1972 Hou, 1982). It was reported that Beijerinckia, under aerobic conditions, degraded phenanthrene to as-3,4-dihydroxy-3,4-dihydrophenanthracene (Kobayashi and Rittman, 1982). 

Bezalel et al. (1996) reported that the white rot fungus Pleurotus ostreatus, grown in basidiomycetes rich medium, metabolized 94% of the phenanthrene added. Approximately 52% was converted to /rans-9,10-dihydroxy-9,10-dihydrophenanthrene (28%), 2,2 -diphenic acid (17%), and unidentified metabolites (17%). In addition, 3% was mineralized to carlaon dioxide. Sack et al. (1997) reported that phenanthrene was degraded by an Aspergillus niger sixain isolated from a mineral oil-contaminated soil in La Plata, Argentina. The major metabolite was identified via GC/MS as 1-methoxyphenanthrene. Two minor metabolites identified were 1- and 2-phenanthrol. 

Lithium aluminum hydride reduced p-benzoquinone to hydroquinone (yield 70%) [576] and anthraquinone to anthrahydroquinone in 95% yield [576]. Tin reduced p-benzoquinone to hydroquinone in 88% yield [174] Procedure 35, p. 214). Stannous chloride converted tetrahydroxy-p-benzoquinone to hexa-hydroxybenzene in 70-77% yield [929], and 1,4-naphthoquinone to 1,4-di-hydroxynaphthalene in 96% yield [180]. Other reagents suitable for reduction of quinones are titanium trichloride [930], chromous chloride [187], hydrogen sulfide [248], sulfur dioxide [250] and others. Yields are usually good to excellent. Some of the reagents reduce the quinones selectively in the presence of other reducible functions. Thus hydrogen sulfide converted 2,7-dinitro-phenanthrene quinone to 9,10-dihydroxy-2,7-dinitrophenanthrene in 90% yield [248]. 

The major phytotoxic principles (Fig. 3) from M. densa, were shown to be the phenanthrene derivatives erianthridin (17 9,10-dihydro-2,7-dihydroxy-3,4-dimethoxyphenanthrene) and gymnopusin (18 2,7-dihydroxy-3,4,9 -trimethoxyphenan threne). ... 

Phenanthrene is transformed to trans-9,10- (major), trans-1,2- (minor), and trans-3,4-dihydrodiol (minor) metabolites via monooxygenase-catalyzed formation of arene oxides, followed by epoxide hydrolase-catalyzed hydration in mammalian liver systems.219-221 In bacterial cultures, phenanthrene is converted to cis-3,4- (major) and cis-1,2- dihydrodiols (minor) through the action of dioxygenase enzymes and molecular oxygen.221,222 Recently, Boyd et al.10 have prepared trons-3,4-dihydroxy-1,2,3,4-tetrahydrophenanthrene (359) and cis-3,4-dihydroxy-1,2,3,4-tetrahydrophenanthrene (360) in optically pure forms. These compounds have made possible the determination of the configurations of the trans- and cis-3,4-dihydrodiol metabolites of phenanthrene (361 and 362) as (-)-(3R,4R) and ( + )-(3S,4R), respectively. 

Calculations at the 4-31G level of theory found that the 1,2-bis-carboxonium ion (72) is significantly more stable than the carbenium-carboxonium dication (73). Thus, when compared with the 1,1-dihydroxylie structure 73, the 1,2-dihydroxy lie structure 72 is more effective at stabilizing the 1,2-ethylene dication. This effect leads to the stabilization of dication 71 (eq 16), and not to phenanthrene cyclization. 

Silver oxide and sodium sulfate are frequently used to oxidize 1,2-dihydroxy aromatic compounds to orf/io-quinones. Phenanthrene furnishes, after being shaken for 15 s with the mixture in ether at room temperature, a 65% yield of 3,4-phenanthrenequinone [171]. Another oxidant used to prepare orfho-quinones is sodium iodate (equation 321) [754],... 

Only three phenanthrene glucosides have been identified so far. 2,4,6-Trihydroxyphenanthrene-2-O-glucoside (318) was isolated from a commereial Riesling wine [32] 3,4,6-trihydroxyphenanthrene-3- O-b-D-glucopyranoside (319) was isolated from the rhizome of Dioscorea opposite [163] and denchryside A (336), from the herbs of Dendrobium chrysanthum, a diglycoside identified as 2,6-dihydroxy-1,5,7- trimethoxy-phenanthrene-2-0-[a-L-rhamnopyranosyl-( 1 6)]-Z)-D-glucopyranoside [173]. The new phenanthrene structures have been shown in Fig. (16). 

Methoxy-3,4,7-trihydroxy-phenanthrene (312) and 4-methoxy-2,5-dihydroxy-phenanthrene suppressed HL-60 and SMMC-7721 cells. Synergistic inhibition of the two phenanthrenes with puerarin was observed against HL-60 [159]. 

Some phenanthrenes, 2,5-dihydroxy-3,4-dimethoxyphenanthrene (324), fimbriol-A, nudol, gymnopusin and erianthridin, from Maxillaria densa provoked inhibition of the spontaneous contractions in the rat ileum. Their activity however did not involve a direct nitrergic or antihistaminergic mode of action or an interference with calcium influx into the smooth muscle cells [520]. 

The morphine alkaloids were shown by Vongerichten and Pschorr to bo derivatives of 3 6-dihydroxy-4 5-phenanthrylene oxide [ix] by i.lie conversion of morphenol [x] (obtained as methyl ether by the exhaustive methylation of codeine[30]) on fusion with potassium hydrox-ido at 250° C. to [xi], identified by methylation to 3 4 5-trimethoxy-phenanthrene [31] and comparison of the latter with an authentic spocimen [32]. 

Diacetoxy-3-methoxyphenanthrene and triacetylisothebenine are obtained by the acetolysis of sinomenine hydrate and the 1-bromo-derivatives of these can be prepared in the same way from 1-bromosinomeninone. Catalytic reduction of both triacetylisothebenine and its 1-bromo-derivative affords triacetyl-9 10-dihydroisothebenine [55], believed by Schopf, Pfeiffer, and Hirsch [64] to be triacetylisothebenine when the same sequence of reactions was carried out on (—)-l-bromo-sinomeninone. /sothebenine is probably 4 6-dihydroxy-3-methoxy-5-(/3-methylaminoethyl)-phenanthrene [lxxxh], or the 4 7-dihydroxy-isomer [64], On heating with sodium hydroxide and methyl alcohol at 80° C., 1-bromotriacetyKsothebenine yields a compound C2oH2004NBr in 7 per cent, yield this is probably 1 -bromo-N-acetylisothebenine [55] (see also Chap. XXV). 

Methoxy-4 6-diacetoxyphenanthrene [nr] is formed when codeinone [lii] [68] and sinomenine hydrate [un] [69] axe heated with acetic anhydride and sodium acetate a second product in the degradation of [lih] is triacetyh sothebenine [liv ]. The 1-bromo-derivative can be obtained in like manner from the antipodes of 1-bromosino-meninone [69-70] and reduced catalytically to [li]. Hydrolysis of [li] affords the corresponding 4 6-dihydroxy-compound, which results from heating codeinone methiodide with ethanol at 160° C. [71] both compounds have been identified by conversion to 3 4 6-trimethoxy-phenanthrene [68],... 

Human recombinant AKRs have been shown to catalyze identical reactions for bay region trans-dihydrodiols (phenanthrene, chrysene, B[a]P, benz[a]anthracene), methylated bay region trarcs-dihydrodiols (5-methylchrysene and 7,12-DMBA), and fjord region trans-dihydrodiols (B[g]C) [18-20], Thus far, no human AKR has been show to be an efficient catalyst of the oxidation of the potent proximate carcinogen HR,12R-dihydroxy-dihydro-DB[a,l]P. Interestingly, this metabolic pathway of... 

Laryea, A., Cosman, M., Lin, J.M., Liu, T., Agarwal, R., Smirnov, S, Amin, S Harvey, R.G., Dipple, A., and Geacin-tov, N.E. (1995) Direct synthesis and characterization of site-specific adenosyl adducts derived from the binding of a 3,4-dihydroxy-1, 2-epoxybenzo[c] phenanthrene stereoisomer to an 11-mer oligodeoxyribonudeotide. 

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