Phenanthrene 3:4:8-trimethoxy

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). 

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]. 

Hofmann degradation of N-methylthebenine dimethyl ether methiodide or methomethylsulphate, which result from the complete methylation of thebenine, affords 3 4 8-trimethoxy-5-vinylphenan-threne [vn], the 4-methoxyl group of which is so readily hydrolysed that boiling with acetic acid or alcoholic hydrogen chloride results in formation of methebenol and bromination in formation of bromo-methebenol [8], 3 4 8-Trimethoxy-5-vinylphenanthrene can be reduced to 3 4 8-trimethoxy-5-ethylphenanthrene, identical with a specimen prepared from 2-nitroveratric aldehyde and 2-methoxy-5-ethylphenyl-acetic acid by the Pschorr phenanthrene synthesis [11]. 

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],... 

Trimethoxy-5-vinylphenanthrene. Thebenine [lxxxv, R = H], itself a fully aromatic phenanthrene derivative, can be degraded to 3 4 8-trimethoxy-5-vinylphenanthrene [lxxxvi] [91-92],... 

Diels-Alder condensation of 3,4-dihydro-5,6,7-trimethoxy-l-vinylnaphth-l-ol (299) with methyl acrylate afforded the isomeric hexahydro-6,7,8-trimethoxy-phenanthrene-2a-carboxylic acids (300) and (301). The acid (300) was readily... 

V-Methyllaurotetanine, C20H23O4N, was obtained from the tertiary phenolic fraction of the alkaloids from L. citrata by Spath and Suominen (28). The alkaloid and its derivatives were amorphous for the greater part. However, the 0-ethyl ether was exhaustively degraded to a nitrogen-free compound which proved to be 3,4,6-trimethoxy-7-ethoxy-l-vinyl-phenanthrene (m.p. 140-141°), identical with a specimen already prepared from laurotetanine (27). The structure of this alkaloid is therefore XV. 

The oxidation of the unsaturated compound II gives, in addition to the acid HI already mentioned, a small amount of a monobasic acid, C17H14O7 (m.p. 304° methyl ester, m.p. 252°), which is regarded as 2,3,8-trimethoxy-xanthone-5-carboxylic acid (VI). Its formation was considered to be analogous to the formation of fluorenone in the oxidation of phenanthrene... 

Methoxy 4 -acetozy sti1ben 3 1498. 1.2.7 Trimethoxy anthracen 3 II llOl. 1.5.3 Trimethozy-phenanthren 6, 1140,... 

S-meth -benzoeeiuie] 10 u 135. 3-Acetoxy.diphenyl.dicarbona5ure.(4.4 )-dimethyieater 10 1 263. 8.0xy-3.4.6-trimethoxy-phenanthren-canx>nstture.(9) 10 1 282. f.Biscumailnafture 10II400. Biscumarmsiure 10II400. 

---