5626. Lycorine

Nomenclature

CAS number: 476-28-8
(1α,2β)-3,12-Didehydro-9,10-[methylenebis(oxy)]galanthan-1,2-diol; 3,3a-didehydrolycoran-1α,2β-diol; 2,4,5,7,12b,12c-hexahydro-1H-[1,3]dioxolo[4,5-j]pyrrolo[3,2,1-de]phenanthridine-1,2-diol; amarylline; belamarine; narcissine; galanthidine.
C16H17NO4; mol wt 287.31.
C 66.89%, H 5.96%, N 4.88%, O 22.27%.

Description and references

Alkaloid isolated from the bulbs of Lycoris radiata L., Narcissus pseudonarcissus L., N. tazetta L., from Buphane disticha Herb., in Crinum spp., Amaryllis belladonna L., Clivia miniata Regel and other Amaryllidaceae. Extraction procedure: Cook, Loudon in Manske-Holmes, Alkaloids vol. II (Academic Press, 1952) p 336. Identity of lycorine and galanthidine: Proskurnina, Dokl. Akad. Nauk SSSR 90, 565 (1953), C.A. 49, 12500c (1955). Structure: Takeda et al., J. Am. Chem. Soc. 80, 2562 (1958). Stereochemistry: Nakagawa, Uyeo, J. Chem. Soc. 1959, 3736; K. Kotera et al., Tetrahedron Lett. 1966, 2009. Crystal structure: R. Roques, Acta Crystallogr. 30B, 296 (1974). Attempted synthesis: Dyke et al., Tetrahedron 29, 213 (1973). Synthesis: Y. Tsuda et al., Chem. Commun. 1975, 933; eidem, J. Chem. Soc. Perkin Trans. 1 1979, 1358; T. Sano et al., Heterocycles 14, 1097 (1980); S. F. Martin, C. Tu, J. Org. Chem. 46, 3763 (1981). Biosynthesis: Archer et al., Proc. Chem. Soc. London 1963, 168; Fugati, Mazza, Chem. Commun. 1972, 936. Review: W. C. Wildman in The Alkaloids vol. XI, R. H. F. Manske, Ed. (Academic Press, New York, 1968) pp 307-400.

Chemical structure

Properties

Stout prisms from alcohol, mp 275-280° (dec). [α]D16 -129° (c = 0.16 in 98% alc). Alkaline reaction to litmus; salts hydrolyze easily. Sparingly sol in alcohol, chloroform, petr ether. Sol in dilute acids. Practically insol in water, alkalies.

Derivative

Hydrochloride.
C16H17NO4.HCl; mol wt 323.77.
C 59.35%, H 5.60%, N 4.33%, O 19.77%, Cl 10.95%.

Properties

Long needles from water, mp 217° (dec with slight preliminary sintering). [α]D20 +43°.

Derivative

Hydrochloride monohydrate.

Properties

Elongated prisms from water, mp 206°. Soluble in 20 parts water.

Derivative

Methiodide.
C16H17NO4.CH3I; mol wt 429.25.
C 47.57%, H 4.70%, N 3.26%, O 14.91%, I 29.56%.

Properties

Two forms exist which may be stereoisomeric about the nitrogen atom. α- Form: polyhedra from alc, dec 247°. [α]D20 -46° (c = 1.52). Freely sol in water; sparingly sol in hot alcohol. β-Form: prisms contg 1H2O from water, dec 198°, after recryst from alcohol, dec 281°. [α]D20 +123° (c = 2.44). Freely sol in water and hot alcohol.