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Identification of some L-numbered Lycopodium alkaloids

Article  in  Canadian Journal of Chemistry · February 2011

DOI: 10.1139/v90-200

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 Identification of some L-numbered Lycopodium alkaloids
WILLIAMA. AYER,'LOISM. BROWNE,A. WARRENELGERSMA,
AND PETERP. SINGER
Department of Chemistry, University of Alberta, Edmonton, Alta., Canada T6G 2G2
Received February 22, 1990

WILLIAM A. AYER,LOISM. BROWNE, A . WARREN ELGERSMA, and PETERP. SINGER. Can. J. Chem. 68, 1300 (1990).
The pioneering research on ~ ~ c o ~ o d alkaloids
ium carried out by R. H. F. Manske and L. Marion led to the characterization of
a large number of alkaloids. Many of these alkaloids were designated by numbers preceded by an L (e.g., L1, which has since
been shown to be dihydrolycopodine). While the identity of many of these alkaloids has now been established, several remain
unreported. We have examined samples of alkaloids L15, L 16, L17, L 18, L22, L24, L25, L26, L28, L29, L3 1, and L35,
obtained from Marion's collection, by GC-MS and GC-IR, and report herein the identity of these alkaloids and alkaloid
mixtures. Most of the samples proved to be mixtures of known alkaloids. Acetylannofoline (S), a component of alkaloid L17,
and 5,15-oxidolycopodane (9), a component of alkaloids L28 and L31, are identified for the first time as natural products.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 118.195.65.249 on 06/06/13

A complete listing of the L-numbered alkaloids is provided.

Key words: Lycopodium alkaloids, alkaloids, acetylannofoline, oxidolycopodane.

WILLIAM A. AYER,LOISM. BROWNE, A. WARREN ELGERSMA et PETER P. SINGER. Can. J . Chem. 68, 1300 (1990).
Les travaux de pionniers rCalisCs par R. H. F. Manske et par L. Marion sur les alcaloYdes du Lycopodium ont conduit h la
caractirisation d'un grand nombre d'alcaloi'des. Plusieurs de ces alcaloi'des ont CtC dCsignCs par des chiffres prCcCdCs de la lettre L
(par example, L1; il a depuis CtC ttabli qu'il s'agit de la dihydrolycopodine). MCme si l'identitt de plusieurs de ces alcaloi'des a
maintenant CtC Ctablie, plusieurs n'ont pas CtC rCttudiCs. Faisant appel a la SM/CPG et a l'IR/CPG, on a donc reexamink des
Cchantillons des alcalo'ides L15, L16, L17, L18, L22, L24, L25, L26, L28, L29, L31 et L35 qui ont CtC obtenus de la collection
de Marion et on rapporte ici I'identitC de ces alcalo'ides et de ces melanges d'alcaloides. L'acttylannofoline (S), un composant
de I'alcalo'ide L17, et le 5,15-oxidolycopodane (91, un composant des alcaloides L28 et L31, n'avaient jamais CtC identifiCs
antkrieurement comme produits naturels. On fournit une liste complbte des alcalo'ides dCsignts par L et un numCro.
Mots elks : alcalo'ides du Lycopodium, alcalo'ides, acbtylannofoline, oxidolycopodane.
[Traduit par la revue]
For personal use only.

Introduction
The presence of alkaloids in the genus Lycopodium (family
Lycopodiaceae) was first noted in 1881. An extensive investiga-
tion of these compounds did not commence until the 1940's,
and it was not until the late 1950's and early 1960's that the
structures of these alkaloids began to be clarified. In Canada
the study of the chemistry of the Lycopodium alkaloids was
pioneered by R. H. F. Manske and L. Marion, who isolated and
characterized a large number of alkaloids from various species
of the club moss. Since that time the structures of about 100
alkaloids classified into 16 structure types have been established
and their chemistry has been the subject of several reviews
(1-4). However, the structures of a number of alkaloids origin-
ally characterized by Manske and Marion remain unreported
(4). In the past few years we have been fortunate to come into
possession of many of the original Lycopodium samples of
Manske and Marion. Several of the alkaloids that were isolated
over 40 years ago and whose structure or identity remain to
be resolved were found in their sample collection. We have
reexamined the samples of alkaloids L15 (L. tristachyum), L16
and L17 (L. obscurum), L18 (L. clavatum), L22, L24, and L25
(L. lucidulum), L26 (L. sabinaefolium), L28, L29, and L31
(L. annotinum), and L35 (L. densum) and report herein their
identity.
Results and discussion
The alkaloid identification was based on GC/MS (5) exami-
nation coupled with GC/IR (6) examination of the sample to
rapidly establish the structure. A reference library of MS and IR
spectra of known alkaloids was prepared from over 35 authentic
samples available to us. In each GC/MS and GC/IR analysis a
library search algorithm program was used to search the sample
' ~ u t h o rto whom correspondence may be addressed.
spectrum against the data base to find the best match to a sample
spectrum. When the sample was found to be a mixture of
alkaloids and sufficient sample was available, the components
were separated and the identity of the alkaloids was verified by
spectral analysis including high resolution MS and NMR and
by comparison with authentic samples.
In the early 1940's Marion and Manske began their chemical
investigation of the genus Lycopodium with the hypothesis that
similarities of alkaloid constituents were indicative of botanical
similarities and that this information could form the basis of
a chemotaxonomical classification of the genus. Accordingly,
several Lycopodium species were investigated,. their alkaloids
isolated, characterized, and designated with an L number. In
early 1944 examination of the alkaloids of L. tristachyum Pursh
led to the isolation of nicotine, lycopodine, L13 (later found
to be identical with lycopodine), L14 (subsequently identified
as anhydrodihydrolycopodine (7)), and L15. Alkaloid L15
(reported as C20H31N04)(8) was analyzed by GC/MS and
found to comprise one major and one minor component with
molecular ions of m/z 247 and 263, respectively. Analysis of
the sample by GC/IR confirmed the presence of two compo-
nents and identified lycopodine (1) as the major alkaloid in the
mixture. Since the components of the mixture eluted almost
simultaneously from the GC column, it was not possible to
identify unambiguously the minor alkaloid of L 15. Thus alkaloid
L15 was separated by chromatography into its components. The
least polar compound from the mixture was found to be identical
with an authentic sample of lycopodine. The more polar
compound was identified as flabelliformine (2) (9) by spectral
analysis and by comparison with an authentic sample.
The chemical investigation in 1944 of the alkaloids of
L. obscurum var. dendroideum (10) yielded lycopodine, L13,
obscurine, and two new alkaloids: L16 and L17. Alkaloid L16
(C16H2SNO)was reported by these authors to be isomeric with
 AYER ET AL
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For personal use only.
lycopodine and L13. Analysis of alkaloid L16 by GC/MS
revealed that it is a 1:l mixture of two compounds with
molecular ions of m/z 247 and 231. Subsequent examination
of L16 by GC/IR confirmed the presence of two alkaloids and
identified these as lycopodine (1) and anhydrodihydrolyco-
podine (3). Alkaloid L17 was examined by GC/MS and GC/IR
and found to be a 2:l mixture of alkaloids. The minor
component was identical with acetylacrifoline (4) (11). The
major alkaloid was shown to be acetylannofoline (5) (12).
Later in 1944 L. clavatum L. of North American origin
was examined and found to contain nicotine, lycopodine, L19
(subsequently found to be identical with L34 and shown to be
clavolonine) (13, 14), and L18 (reported as CIIH19N0and
isolated as its picrate) (15). Alkaloid L18 was examined by
GC/MS and found to contain two alkaloids (ratio 3: 1) each with
a molecular ion at m/z 278 (C18H34N2,HRMS) and with very
similar fragmentation patterns. GC/IR confirmed that alkaloid
L18 was a mixture and that each of the component alkaloids
contained N-methyl functionality (2780 cm-'). Attempted
separation of the sample by chromatography was unsuccessful.
Analysis of the 'H NMR spectrum of the mixture revealed
the structural similarity of each component. Each component
contains two N-methyl groups (6 2.16, 2.28 (major); 2.25,
2.26 (minor)) and a secondary methyl (6 0.84 (major); 0.92
(minor)). The spectral properties of the minor component are
identical with those of N,N-dimethylphlegmarine2 (6) (16). We
believe that the major component is an isomer of this compound.
2 ~ thank
e Dr. J. C. Braekman for copies of the spectra of this
compound.
A total of nine alkaloids were isolated from L. lucidulum
Michx. by Manske and Marion in 1946 (17). Besides nicotine,
lycopodine, and L13, the remaining alkaloids include L20 (18),
L21 (later shown to be luciduline) (19), L22 (reported as
Cl6HZ7NO),L23 (subsequently found to be isolycodoline (7))
(20), L24 (reported as CI6Hz5NO), and L25 (reported as
C16H25N02). We examined alkaloid L22 by GC/MS and
GC/IR. Each analysis revealed that it was a mixture of two
alkaloids (ratio 3:2), one of which was lycopodine (1). The
other component of the mixture shows a molecular ion at m/z
263 (C16H25N02)and was found to closely match isolyco-
podine (7) in the GC/IR library. Separation of the sample
by chromatography led to the isolation of lycopodine and
isolycopodine, identical in all respects with authentic samples.
Analysis of alkaloids L24 and L25 by GC/MS and GC/IR
revealed that each was a single compound. Alkaloid L24 was
identified as lycopodine (1) while alkaloid L25 was found to be
identical with isolycopodine (7) (L23).
In a continuation of their studies, Manske and Marion
reported that L. sabinaefolium Willd. contained four alkaloids:
nicotine, lycopodine, alkaloid L13, and alkaloid L26 (reported
as Cl5Hz5NO)(21). Alkaloid L26 was analyzed by GC/MS and
GC/IR. It was found to be a pure compound with a molecular
formula of CI6Hz7NO (HRMS) and its IR spectrum matched
perfectly with that of dihydrolycopodine (22) from the library
of known alkaloids. Further analysis of the sample was not
undertaken due to the small sample size.
In 1947 it was reported that L. annotinum var. acrifolium
contained a different alkaloid spectrum than other varieties of L.
annotinum. In addition to annotinine and acrifoline (L27), four
 CAN. J . CHEM. VOL. 68, 1990

TABLE
1. Lycopodium alkaloids: the " L numbers
Molecular Molecular
L no. weight formula Name (reference)

L1 249 CI6Hz7NO Dihydrolycopodine (complanatine, L26) (22)

L2 29 1 C18H31N02 0-Acetyldihydrolycopodine(1)
L3 29 1 C18H3,NO2 0-Acetyldihydrolycopodine(1)
LA 23 1 CI~HZ~N Anhydrodihydrolycopodine (7)"
L5 288 ClBHz8N20 Flabellidine (30)
L6 Mixture: m- and P-obscurine (31)
L7 275 CI6H2,No3 Annotinine (32)
L8 263 C16H25N02 Lycodoline (L30) (24)
L9 Mixture: lycopodine and acetyllofoline
LlO Structure not reported and sample unavailable
L11 288 C16H21N03 Annotine (33)
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L12 305 C18H25N03 0-Acetylacrifoline (1 1)

L13 247 C16H25N0 ~~co~odine~
L14 23 1 c16H25N Anhydrodihydrolycopodine (7)"
L15* Mixture: lycopodine and flabelliformine (9)
L16* Mixture: lycopodine and anhydrodihydrolycopodine (7)
L17* Mixture: acetylannofoline (12) and acetylacrifoline (33)
L18* Mixture: N, N-dimethylphlegmarine and isomer
L19 263 Cl6HZ5No2 (L34), clavolonine (13, 14)
L20 263 C16H25N02 6a-Hydroxylycopodine (18)
L2 1 207 C13H21N0 Luciduline ( 1 9)
L22* Mixture: lycopodine and isolycodoline (L23) (20)
L23 26 3 C16H25N02 Isolycodoline (epilycodoline, pseudoselagine) (20)
L24* 247 C16H25N0 Lycopodine
L25* 263 C16H25N02 Isolycodoline (epilycodoline, pseudoselagine) (20)
For personal use only.

L26* 249 CI6Hz7NO Dihydrolycopodine (Ll) (22)

L27 26 1 C16H23N02 Acrifoline (26, 27)
L28* Mixture: lycopodine and oxidolycopodane (I)
L29* 26 1 C 16H23N02 Acrifoline (26, 27)'
L30 263 C16H25N02 Lycodoline (L8) (24)
L31* Mixture: 0-acetyllofoline and oxidolycopodane (1)
L32 262 CI6Hz6N20 Cernlline (34)
L3 3 27 8 C16H26N202 Lycocernuine (34)
L34 263 Cl6HZ5No2 Clavolonine (L19) (13, 14)
L35* Mixture: lycopodine, flabelliformine (9), and lycodoline (24)

*Alkaloids identified recently in this or other studies in our laboratories.

"Identical with L14, identified as anhydrodihydrolycopodine by Marion and Manske (Dr. Marion's laboratory
notebook 698, p. 15). This identity was confirmed by GC/MS and GC/IR.
bIdentified as lycopodine by Marion and Manske (Dr. Marion's laboratory notebook 698, p. 57). Eleven samples
of L13 isolated from several Lycopodium species were found to be composed mainly of lycopodine by GC/MS
and GC/IR.
'We thank T. Chua, Alberta Heritage Undergraduate Summer Research Assistant, 1986, for this identification.

previously unreported alkaloids were isolated and designated
numbers L28-L3 1 (23). Subsequent investigations revealed
that L30 was identical with L8, which has been shown to
possess structure 8 and has been named lycodoline (24). The
structures of L28, L29, and L31 have not been reported to date.
L28 (reported as C17H27N02)was analyzed by GC/MS. It was
shown to be a mixture of two compounds, each of which has a
molecular weight of 247 with similar but not identical mass
spectral fragmentation patterns. Analysis by GC/IR confirmed
the presence of two components and revealed that one of the
components was lycopodine (1). The mixture was separated
by chromatography over alumina. The less polar component,
L28-1, was identified as lycopodine by comparison of its
spectral properties with those of an authentic sample. The more
polar component, L28-2, was isolated as an optically active,
air-sensitive oil. The HRMS confirmed its molecular weight as
m/z 247 and established the molecular formula as C16H25N0.
The base peak at m/z 174 (M+ - C4H90) is consistent with
oxygen functionality on the "bridge atoms" (C-8, C-14, C-15).
Examination of the IR spectrum of L28-2 revealed the absence
of hydroxyl or carbonyl functional groups and thus the oxygen
of L28-2 must be present as an ether. This was corroborated by
its I3C NMR spectrum, which showed oxygenated carbons at
6 74.3 (CH) and 72.3 (C). The 'H NMR spectrum of L28-2
revealed a methyl singlet (6 1.15) and this suggested that L28-2
may have structure 9. 5,15-Oxidolycopodane (9) has not been
isolated previously from natural sources although it has been
prepared synthetically in a series of reactions from lycopodine
(25). To confirm the identity of 9, we oxidized dihydrolyco-
podine with lead tetraacetate. The oxidation product obtained
was identical in all respects (MS, IR, 'H and 13C NMR) with
L28-2. In earlier studies in these laboratories alkaloid L29 was
identified as acrifoline (26, 27) by comparison (TLC, IR, MS)
with an authentic sample.
Another unidentified alkaloid isolated from L. annotinum,
L31 (reported as C20H29N04),was also found to be a mixture
of two components by GC/MS: C16H25N0 (m/z 247) and
C20H31N04(m/z 359). The presence of two components in
 AYER ET AL. 1303

TABLE2. Compounds in the GC/MS and GC/IR library*

Molecular Molecular Molecular Molecular

weight formula Name weight formula Name

207 CI3H2,NO Luciduline 274 C17H26~2 Dihydroobscurinine

23 1 C16H2sN Anhydrodihydrolycopodine* 274 C17H26N20 Sauroxine
242 C16HZ2N2 Lycodine 275 CI6HZINo3 Annotine
242 Cl5HI8N2O Huperzine A (selagine) 275 CI6HZ1No3 Annotinine
245 C1aZ3NO Fawcettidine 278 C16H26N202 Lycocemuine
247 C16H25N0 Lycopodine 279 C16H25N03 Alopecuridine
248 CL6H28N2 Dihydrodeoxycemuine 29 1 C18H29N03 Clavine
249 C16H27N0 Dihydrolycopodine 29 1 CI7Hz5NO3 Lyconnotine
258 CI6Hz2N2O Des-N-methyl-P-obscurine 303 CL8H25N03 Acetylacrifoline
260 CI6Hz4N2O Des-N-methyl-a-obscurine 305 CI8H27NO3 Acetylannofoline*
26 1 CI6H23NO2 Acrifoline 305 C18H27N03 Dehydro-a-lofoline
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26 1 C16H23N02 Serratidine 305 C18H27N03 Dehydrofawcettiine

262 C16H26N20 Cemuine 305 Cl8HZ7No3 Dihydro-0-acetylacrifoline
263 C1azSNO2 Clavolonine 307 CI8H2$io3 a-Lofoline
263 CI6Hz5No2 Flabelliformine 307 C18H29N03 Fawcettiine (P-lofoline)
263 C1a2SN02 Isolycodoline 307 C18H29N03 Lycoclavine
263 CI6HzsNo2 Lucidioline 320 CI8Hz8N2O3 Acetyllycocemuine*
263 C16H25N02 Lycodoline 32 1 CI8HZ8N04 N-Acetylalopecuridine
263 C16H25N02 Lycofoline 323 C18H29N04 Lycofawcine
264 C16Hz8N20 Dihydrodeoxylycocemuine 333 C19H27N05 Acetylannopodine
265 C16H27N03 Dihydroclavolonine 349 CZOH31NO4 Acetyllofoline
272 C17H24N2 Isoobscurinine* 349 C20H31N04 Acetylfawcettiine
272 CI7Hz4N2 Obscurinine 349 C2~31N04 Acetyllycoclavine
274 Cl6HZ6N2O a-Obscurine 367 C23H29N03 Alopecurine
For personal use only.

*Alkaloids not present in the GC/MS library.

L31 was confirmed by GC/IR analysis, which indicated the
presence of compound 9 and acetyllofoline. The components
were separated by chromatography over alumina to give L3 1- 1,
identified as oxidolycopodane (9) by comparison with an
authentic sample, and L31-2, identified as acetyllofoline (10)
by comparison with an authentic sample (28).
The last species of Lycopodium investigated by these workers
was a species indigenous to New Zealand, L. densum Labill.
This plant, which has a lower than usual total alkaloid content,
contains lycopodine, L34 (identified as clavolonine) (12, 13),
and alkaloid L35 (reported as C14HZ1N02)(29). GC/MS
analysis revealed that alkaloid L35 is a mixture of three compo-
nents (ratio 5: 1:2) with molecular ions of m/z 247 (C16H25NO),
263 (C16H25N02),and 263 (C16H25N02). Examination of
the mixture by GC/IR indicated that these alkaloids were
lycopodine (I), flabelliformine (2) (9), and lycodoline (L8) (8)
(24), respectively. Alkaloid L35 was separated by chromatog-
raphy. Comparison of the spectral data of each compound
isolated with those of authentic samples confirmed their
identity.
The Lycopodium alkaloids have proven to be a rich source
of chemically interesting compounds. In total there were 35
alkaloids designated with an L number by Manske and Marion.
The structures or identity of the majority of these alkaloids were
determined previously. Table 1 presents a complete list of all
of the L-numbered alkaloids. They are presented in order of
increasing L number, and the table includes their molecular
weight, molecular formula, name, and reference to their
structure determination.
Experimental
Materials and methods
The alkaloids used in compiling the library of spectra are listed in
order of increasing molecular weight in Table 2.
GC/MS and GC/IR
Alkaloid samples were prescreened by GC using the conditions
described below. Initially retention indices were calculated with
respect to lycopodine. Over the time period for this study, however, the
retention index of some standards changed enough to warrant this
data unacceptable for identification purposes. Analysis of the alkaloid
sample by GC/MS was performed on a HP5985 MS system using an
HP5840A gas chromatograph with a 18835 spliiless capillary inlet.
The samples (1-2 kL, c = 1 mg/mL) were injected onto a fused
silica capillary column (12 m X 0.32 rnrn i.d.) coated with an SE-54
equivalent. (Conditions: flow rate 4 mL/min; camer gas He; tempera-
tures: injector 280°C, detector 300°C, oven 80°C (1 min), 80-300°C at
20°/min, 300°C (5 rnin).) The gas chromatograph was connected to the
mass spectrometer by an open split interface (MS: positive ion mode;
ionizing beam 70 eV; temperatures: source 200"C, transfer line 300°C;
mass range 35-500; 50 scans/min). The MS of authentic samples of
alkaloids were entered into a GC/MS library and test samples identified
by computer match when possible (5). Analysis of the alkaloids by
GC/IR was performed on a HP5965A IRD system. The samples
(1-2 kL, c = 1 mg/mL) were injected onto an Ultra2 capillary column
(conditions: carrier gas He; temperature: injector 200°C, oven 80°C
(1 min), 80-290°C at 20°/min, 290°C (5 min)). The gas phase IR
spectra of known alkaloids were entered into the GC/IR library. The
gas phase IR spectra of the unknown alkaloids were compared to
library spectra by computer using a library search algorithm. The
spectrum search parameters were developed and the accuracy of the
match between the sample spectrum and known spectrum was assessed
and a match quality number assigned. Match quality numbers greater
than 950 (maximum 1000) were considered to be identical with
an authentic sample. The best match was visually inspected for
confirmation of identity.
5.15-Oxidolycopodane (9)
Alkaloid L28 (L. annotinum) was chromatographed over alumina
(eluant: CH2C12-CH30H (2%) gradient) to give two compounds. The
less polar constituent was identified as lycopodine by comparison with
an authentic sample. The more polar component was identified as
 1304 CAN. 1. CHEM. VOL. 68, 1990

oxidolycopodane (9) (25): [a],51" ( c 0.019, CH30H); FTIR: 2964, 4. D. B. MACLEAN. In The alkaloids. Vol. 16. Edited by A. Brossi.
2925,2860, 1442, 1132, 1110 cm-'; 'H NMR (360 MHz, CDC13) 6: Academic Press, New York. 1985.
3.63 (lH, m, H-5), 3.36 (lH, td, J = 3.5, 14.5 Hz, H-le), 3.19 5. R. V. GERARD and D. B. MACLEAN.Phytochemistry, 25, 1143
(lH, td, J = 3.5, 12.0Hz, H-9e), 2.64 (lH, dd, J = 2.0, 12.0 Hz, (1986).
H-14a), 2.53 (lH, dm, J = 2.0, 12.5 Hz, H-la), 2.05 (lH, m, H-41, 6. W. HERRES.In HRGC-FTIR: capillary gas chromatography -
1.97 (IH, m, H-2a), 1.89 (2H, m, H-3a, H-6a), 1.78 (lH, m, H-lOe), Fourier transform infrared spectroscopy. Huthig, New York.
1.73 (IH, ddd, J = 2.5, 2.5, 12.0 Hz, H-11), 1.70 (2H, m), 1.67 1987. p. 1.
(lH, m, H-lo), 1.63 (lH, m), 1.60 (lH, m), 1.55 (lH, ddd, J = 2.0, 7. F. A. L. ANET.Tetrahedron Lett. No. 20, 13 (1960).
4.0,12.0Hz, H-8a), 1.47 (lH, m,H-3e), 1,40(1H,m), 1.27 (lH, dm, 8. L. MARIONand R. H. F. MANSKE. Can. J. Res. 22B, 1 (1944).
J = 13 Hz, H-2a), 1.15 (3H, s, H-16), 1.06 (lH, d, J = 12.0 Hz, 9. M. CURCUMELLI-RODOSTAMO and D. B. MACLEAN.Can. J.
H-14e); I3C NMR (75.5 MHz, CDC13) 6: 74.3 (d, C-5), 72.3 (s, Chem. 40, 1068 (1962).
C-15), 54.3 (s, C-13), 46.8 (d, C-12), 47.4 (t, C-9), 47.0 (t, C-l), 10. R. H. F. MANSKE andL. MARION. Can. J. Res. 22B, 53 (1944).
43.9 (t, C-14), 42.1 (t, C-8), 33.9 (d, C-7), 31.4 (d, C-41, 3 1.0 11. G. S. PERRYand D. B. MACLEAN.Can. J. Chem. 34, 1189
(t, C-6), 29.2 (q, C-16), 26.5 (t, C-lo), 25.6 (t, C-11), 24.6 (t, C-3), (1956).
18.6 (t, C-2); HREIMS (probe) 70 eV, m / z (rel. int.) calcd. for 12. G. C. KASITU.Ph.D. Thesis, University of Alberta, Edmonton,
C1825NO: 247.1936; found: 247.1944; (47), 191 (lo), 190 (60), Alberta. 1988. pp. 90-97.
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176 (lo), 175 (15), 174 (ClzHl6N, loo), 163 (17), 146 (10). 13. R. H. BURNELL and D. R. TAYLOR. Tetrahedron, 15,173 (1961).
14. R. H. BURNELL and D. R. TAYLOR. Chem. Ind. (London), 1239
Transformation of dihydrolycopodine to compound 9
(1960).
Pb(OA)4 (100 mg) and 1 2 (catalytic amount) were added to a solution and R. H. F, MANSKE, Can. J. Res. 22B, 137 (1944).
15, L,
of d i h ~ d r o l ~ c o ~ o d(26
i n emg) in CH2C12 (5 mL). The reaction mixture
16, L, NYEMBO, A. GOFFIN,C, HOOTELE,and J. C. BRAEKMAN,
was irradiated for 16 h using a 75-W light bulb. H 2 0 (10 mL) was
Can. J. Chem. 56, 851 (1978).
added and the layers separated. The aqueous fraction was extracted Can. J. Res. 24B, 57 (1946).
17. R. H. F. MANsKE and L,
several times with CH2C12, then basified (aq. NH3) and extracted 18. W. A. AYER,J. A. BEREZOWSKY, andD. A. LAW.Can. J , Chem,
exhaustively with CH2C12.The CH2C12layer was subjected to acid- 41, 649 (1963).
base work-UP in the usual way. The resultant CH2C12 fraction was
lg. W. A, AYER,N , MASAKI, and D. S. NKUNIKA. Can, J. Chem. 46,
concentrated to give an oil (14.5 mg) that was shown to be a mixture
363 1 (1968).
of components (TLC). Chromatogra~h~ Over A1203 gave dih~dro-
20. W. A. AYER,B. ALTENKIRK, R. H. BURNELL, and M. MOINAS.
lycopodine (5.4 mg) and 5,15-oxidolycopodane (8.0 mg). The third Can. J. Chem. 47, 449 (1969).
component decomposed before it was fully characterized. 21. L. MARION and R. H. F. MANSKE.Can. J. Res. 24B. 63 (1946).
22. W. A. HARRISON, M. CURCUMELLI-RODOSTAMO, D. F.CARSON,
For personal use only.

Acknowledgements L. R. C. BARCLAY, andD. B. MACLEAN. Can. J. Chem. 39,2086

We thank T. Chua (Alberta Heritage Undergraduate Summer (1961).
Research Assistant) for the earlier identification of alkaloid 23. R. H. F. MANSKE and L. MARION. J. Am. Chem. Soc. 60,2126
(1947).
L29, Dr. J. C. Braekman for spectra of N,N-dimethyl- 24. W. A. AYERand G. IVERACH. Can. J. Chem. 42, 2514 (1964).
phlegmarine, J. Hoyle for the GC/IR analyses, and the Natural 25. W. A. AYERand K. PIERS.Chem. Commun. 541 (1965).
Sciences and Engineering Research Council of Canada for 26. W. N. FRENCHand D. B. MACLEAN. Chem. Ind. (London), 658
financial support. Special thanks are due to Dr. 0. E. Edwards, (1960).
formerly of the National Research Council, Ottawa, for 27. W. N. FRENCHand D. B. MACLEAN.Can. J. Chem. 39, 2100
providing us with Dr. Marion's collection of Lycopodium (1961).
alkaloids and the lab books describing their isolation, and 28. W. A. AYER,A. N. HOGG,and A. C. SOPER.Can. J. Chem. 42,
Prof. D. B. MacLean for providing many reference samples 949 (1964).
over the years. 29. R. H. F. MANSKE.Can. J. Chem. 31, 894 (1953).
30. S. N. ALAM,K. A. H. ADAMS,and D. B. MACLEAN.Can. J.
Chem. 42, 2456 (1964).
1. D. B. MACLEAN. In The alkaloids. Vol. 10. Edited by R. H. F. 31. W. A. AYERand G. G. IVERACH. Can. J. Chem. 38,1823 (1960).
Manske. Academic Press, New York. 1968. 32. K. WIESNER,W. A. AYER,L. R. FOWLER,and Z. VALENTA.
2. W. A. AYER.In MTP international review of science. Series 1, Chem. Ind. (London), 564 (1957).
Vol. 9. Edited by D. H. Hey and K. F. Wiesner. University Park 33. W. A. SZAREK, K. A. H. ADAMS,M. CURCUMELLI-RODOSTAMO
Press, Baltimore. 1973. p. 1. and D. B. MACLEAN. Can. J. Chem. 42,2584 (1964).
3. D. B. MACLEAN. In The alkaloids. Vol. 14. Edited by R. H. F. 34. W. A. AYER,J. K. JENKINS,S. VALVERDE-LOPEZ, and R. H.
Manske. Academic Press, New York. 1973. BURNELL.Tetrahedron Lett. 2201 (1964).

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