Hasubanonine

Mass Spectral Data for Hasubanan Alkaloids of Hasubanonine-Type Cleavage... 

Table VII gives a survey of alkaloids that exhibit the hasubanonine-type cleavage. The characteristic fragmentation pattern of this group, possessing an a,/ -unsaturated carbonyl group in ring C, is significantly different from other groups. In the case of hasubanonine (5) (3), the most abundant and nitrogen-free ion peak was observed at m/z 315, which is important for structure elucidation of this group (2,73).

Potassium borohydride reduction of runanine (17) yielded dihydro-runanine (24), the H-NMR spectrum of which (Table II) exhibited a triplet (64.25), the proton bearing the hydroxyl group coupling with those of C-5 (35). The optical activity of runanine (17), [a]D —400°, was similar to that of hasubanonine (5), [a]D —214° (3) therefore, it was concluded that the ethylamine linkage must have the same configuration as hasubanonine [C-13 (R) and C-14 (S)]. From these results, structure 17 was proposed for runanine (35) however, no application of mass spectral data to the structure elucidation was presented (35). 

During the period 1976-1986, biosynthetic studies on hasubanan alkaloids were carried out by Battersby et al. (81-84) for hasubanonine (5) together with protostephanine (57). The two alkaloids, isolated from Stephania japonica, arise from the same precursor, and their unusual structures are of biosynthetic interest, namely, the vicinally trioxygenated ring C in 5 and the unique natural example of a dibenz d,f ] azonine skeleton in 57. 

Stephania hemendifolia (Willd.) Walp. Qian Jin Teng (root) dl-tetrandrine, fangchinoline, 4-dementhyl-hasubanonine, isochondrodendrine, hemandine, stephisoferuline, hemandoline, hemandolinol, 3-O-demethylhemandifoline.33 Treat nephritic edema, urinary tract infection, rheumatic arthritis, sciatic neuralgia. 

Protostephanine and Hasubanonine.—The unravelling of the biosynthesis of pro-tostephanine (36) and hasubanonine (37), both produced by Stephania japonica,... 

Morphine alkaloids are a subgroup of isoquinoline alkaloids and are derived biogenetically from laudanosine bases by oxidative phenolic coupling/6,7 Alkaloids of the opposite enantiomorphic group occur in several Japanese Sinomenium and Stephania species, the most important compounds being sinomenine, hasubanonine, metaphenin, and protometaphenine. 

In an investigation of the point of attachment of the nitrogen in the alkaloid hasubanonine from Stephania japonica, the base 254 was prepared from 14-bromocodeinone.<384)... 

Sinomenine, discovered by Ishiwari in Smomenium diversifolius [97], has been shown by the researches of Kondo [98] and particularly of Goto and his co-workers [99-100] to have the structure [nxvn] and to be the optical antipode of 7-methoxythebainone. It is readily converted into antipodes of substances obtainable from thebaine and codeine (see Chap. XXVI). Hasubanonine, an alkaloid isolated from Stephania japonica, is believed to be of the morphine type [101] (see Chap. XXVI). 

Hasubanonine, which is best isolated as its nitrate, is present to the extent of about 0-04 per cent, of the dried plant shortly after collection, but the amount decreases with time and reaches 0 per cent, after about one year [90]. 

Hasubanonine has the composition C H OgN, is non-phenolic, contains one carbonyl group and four methoxyl groups. On distillation with zinc-dust it gives phenanthrene, and on oxidation it yields hemipinic acid [90]. 

Only a limited number of formulae are possible for hasubanonine. The aromatic nucleus in the basic morphine skeleton must have methoxyl groups at positions 3 and 4, or (less likely) 2 and 1 it seems probable that the methine base is not a true phenol but contains a readily enolized carbonyl group (this would account for the fact that the methine does not show the expected intense diazo-reaction characteristic of phenols). 

Hasubanonine could therefore have the structure [cxvi] which could suffer loss of the 6-methoxyl group during the Hofmann degradation to give the methine [cxvn] the structure [cxvm] for the methine is untenable as acetolysis, hydrolysis, and methylation of this would give dimethylsinomenol. Alternatively hasubanonine could be [cxix] and the methine [cxx]. Further speculations, however, are pointless until the chemistry of the alkaloid has been more fully investigated. 

A new alkaloid, hasubanonine, believed to be of the morphine type has recently been isolated and studied. It can be degraded to a methine base, the acetolysis of which gives a trimethoxyacetoxyphenanthrene, which has been converted to the corresponding trimethoxyhydroxy- and tetramethoxyphenanthrenes. The structure of these compounds is not yet known [117], but the properties of the tetramethoxyphenanthrene differ from those of dimethylsinomenol [xcvn]. 

Halocorticoids, 361 em-HalofluorocycIopropanes, 424 Haloform reaction, 283 Hasubanonine, 284 Helium, 204... 

Hasubanonine, Protostephanine, and Laurifinine. — Full papers on the biosynthesis of hasubanonine (31) and protostephanine (32), which are most interesting benzylisoquinoline variants, have been published an epic piece of research. (Preliminary accounts ... 

Hasubanonine (115) has been subjected to acetolysis, aromatis-ation, hydrolysis,and 0-methylation to give 1,2,3,5,6-pentamethoxy-... 

Thornber compared the presence of 11 benzylisoquinoline alkaloids in the plants of the Papaveraceae, Menispermaceae, Berberidaceae, Magnol-iaceae, Ranunculaceae, Tutaceae, Monimiaceae, Annonaceae, Aristolo-chiaceae, Lauraceae, and Nymphaceae, and he concluded that the alkaloids cularine and morphine (including codeine and thebaine) are present only in the genera Corydalis and Dicentra (alkaloid cularine) and in the genus Papaver (morphinane alkaloids) the hasubanonine and bisben-zylisoquinoline alkaloids do not occur in Papaver plants (838). 

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