Pergamon 0031-9422(94)00639-3 Phytochemistry, Vol. 38, No. 2, pp. 549-551, 1995
Copyright © 1995 Elsevier Science Ltd
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ALKALOIDS FROM NARCISSUS TORTUOSUS*
JAUME BASTIDA,JUAN MARCOS FERNANDEZ, FRANCESC VILADOMAT,CARLESCODINA and GABRIELDE LA FUENTE~:
Departament de Productes Naturals, Facultat de Farmficia, Universitat de Barcelona, E-08028 Barcelona, Spain; tInstituto de
Productos Naturales y Agrobiologia, CPNO 'Antonio Gonzfilez', CSIC-Universidad de La Laguna, La Laguna, Tenerife, Spain
(Received 7 March 1994)
Key Word Index--Narcissus tortuosus; Amaryllidaceae; alkaloids; tortuosine; lycorine; 2DNMR
spectroscopy.
Abstract--Whole plants of Narcissus tortuosus were found to contain tortuosine and lycorine. Tortuosirm is reported
for the first time and its structure was established by spectroscopic methods.
INTRODUCTION
Narcissus tortuosus, a species belonging to the Pseudonar-
cissus section, is notable for its pale and beautifully
symmetrical flowers, regularly twisted. Morphologically,
it is separable from N. moschatus by its stronger growth
and broader foliage, and by its larger and less concolo-
rous flowers 1"21.Histological and caryological studies of
N. tortuosus have been made recently I-3,4]. In the
present paper, we describe the isolation and character-
ization of tortuosine (1) and lycorine (2) from whole
plants of this species.
OMe
2
,o I,o 114
7 6
11
12
RESULTS AND DISCUSSION
The alkaloids were extracted by routine acid-base
work-up procedures and after CC (see Experimental) 1
was isolated as yellow crystals. Its HR mass spectrum
([M] + m/z 296.1292) indicated the molecular formula
ClsH~sNO 3 which was consistent with a phenantridin-
ium structure. Support for this assumption was obtained
by comparison with spectroscopic data of the anhydroly-
corinium ion, one of the biosynthetic products of Amaryl-
lis belladonna most inhibitory to murine 3PS leukaemia
[51, and vasconine, a quaternary alkaloid isolated from
N. vasconicus [61.
The ~H and ~3CNMR spectra were assigned taking
into account the correlations observed in 1HCOSY,
HMQC [71, HMBC 181 and ROESY [91 experiments.
The most characteristic signals of the ~H NMR spectrum
(Table 1) were a one proton doublet at 58.13 (J = 1.4 Hz)
assigned to H-1 and one broad singlet at 57.59 assigned
to H-3, since they showed scalar coupling in the
1H COSY spectrum. Also, the ROESY showed a spacial
correlation between H-1 and the one-proton signal at
*Part 21 in the series 'Narcissus alkaloids'. For Part 20 see ref.
[1].
PRY 38-2-5
OH
HO...~
2
68.34, and between H-1 and the methoxy group at 54.20,
allowing us to assign those signals to H-10 and H-2',
respectively. Moreover, in the 1H COSY spectrum, the H-
10 signal showed zig-zag coupling to H-6 at 69.55 1"101
and a NOE contour with the methoxy group at 34.33 (H-
9') in the ROESY spectrum. After that, the signals at
549