Lycopodium Alkaloids: Xii. Flabelliformine

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The mass spectra of a number of Lycofiodium alkaloids are recorded and schemes proposed for their fragmentation. The loss of the bridge dominates the fragmentation process in the structural types examined.The Lycopodium alkaloids have been the subject of many studies in the past few years, but there are still many alkaloids of unknown constitution. Those alkaloids whose structures have been elucidated are, for the most part, the most abundant while those whose structure still await solution have been found in smaller quantity. The mass spectrometric method, which has been used in many recent investigations, is particularly well suited to structural studies on substances available in small a m o~n t .~ I t was of interest, therefore, to record the spectra of the Lycopodium alkaloids of known structure and t o study their fragmentation in order that the information so obtained might be applied t o the study of those alkaloids whose structures are yet unresolved and to those alkaloids yet to be isolated.The Lycopodium alkaloids which are now known may be conveniently classified for the purposes of this discussion into four groups: those related in skeletal structure to lycopodine ( 2 ) , by far the largest group; those related in skeletal structure to lycodine (3, 4),

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Lycopodium Alkaloids Xiii. Mass Spectra of Representative Alkaloids

MacLean¹

1963

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“…Thus Young (6) has reported the isolation of two new alltaloids, flabelliformine and flabelline, t o each of which a structure has been assigned (7,8). Alam (9) has found four alkaloids of ltnown structure (clavolonine, lycodine, annotinine, and des-N-methyl-a-obscurine) and a new base hydroxy-des-N-methyl-a-obscurine, the structure of which is discussed in this paper.…”

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confidence: 94%

Lycopodium Alkaloids: Xv. Structure and Mass Spectra of Some Minor Alkaloids of L. Flabelliforme

Alam¹,

Adams²,

MacLean³

1964

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Hydroxy-des-N-methyl-a-obscurine, C I~H~~O ?~\ T ? , has been isolated froin L . fEabelliforme and a structure assigned to it on the basis of physical evidence. A s t r i l c t~~r e is assigned t o Lycopodium allraloid L.5, which we have named flabellidine, on the basis of physical evidence and its chemical derivation from lycodine. The mass spectra of hydroxy-des-N-methy1-aobscurine, flabellidine, and flabelline are discussed.The alltaloids of L. flabelliforme were first investigated by i\/Ianslte and Marion ( I ) , who isolated lycopodine (the major alkaloid), nicotine, and six bases, which they designated by number only. Alkaloid L.1 is now ltnown t o be dihydrolycopodine (2), L.2 t o be acetyldihydrolycopodine (3), and L.6 t o be a mixture of a-and P-obscurine (4). The structures of lycopodine and its derivatives (2) and of a-and p-obscurine (5) are now known. The structure of alkaloid L.5, t o which we have assigned the trivial name flabellidine, is discussed in this paper, leaving alkaloids L.3 and L.4 of the original six still uninvestigated.By using chromatographic and countercurrent distribution methods, an additional seven alltaloids have been isolated from L.flabell.iforme in this laboratory. Thus Young (6) has reported the isolation of two new alltaloids, flabelliformine and flabelline, t o each of which a structure has been assigned (7,8). Alam (9) has found four alkaloids of ltnown structure (clavolonine, lycodine, annotinine, and des-N-methyl-a-obscurine) and a new base hydroxy-des-N-methyl-a-obscurine, the structure of which is discussed in this paper.The structure assigned t o hydroxy-des-N-methyl-a-obscurine I rests on physical evidence as insufficient material was available t o investigate its chemistry.The presence of a hydroxyl group in I is inferred from its infrared spectrum, which, in Nujol and in chloroform, shows a pealt a t 3510 cm-l. The position of this peak in chloroform solution is not shifted upon dilution, thereby indicating that the hydroxyl group is intrainolecularly hydrogen bonded. Aside from the pealt in the hydroxyl region, the spectrum of this compound is remarkably similar t o that of a-obscurine (11) and des-Nmethyl-a-obscurine (111). The spectra of the three are reproduced in Fig. 1 for the region 3600-1500 cm-I.The ultraviolet spectrum of I (l:f:;OH 255 mp, log E = 3.78) is almost identical with that of I1 (~::i~~ 255 mp, log E = 3.75) and I11 (l:f:{OH 255 mp, log E = 3.81). From the spectral evidence i t appears that I must have the same chromophoric system as I1 and 111.The mass spectrum of the hydroxy compound shows a molecular weight of 276, corresponding t o the molecular formula C16H2402b?2. This formula differs in colnposition from I11 (C16H240N2) by one oxygen atom, suggesting t h a t the new base may be a simple hydroxy derivative of the latter. T h e fragmentation pattern of I , discussed later, is in agreement with this proposition.The nuclear magnetic resonance (n.m.r.) spectrum of I shows a three proton doublet For personal use only.

“…Flabelliformi~le, a hydroxy derivative of lycopodine, was recently isolated from this plant, and its structure elucidated (6).…”

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confidence: 99%

“…They reported the isolation of lycopodine, the bases L1 to LG, and nicotine. Base L l has since been shown to be dihydrolycopodine (2), L2 to be acetyldihydrolycopodine (3), and LG to be a mixture of two compounds, a-and P-obscurine (4).T h e structures of lycopodine and its derivatives (2) and the obscurines ( 5 ) are now kllown.Flabelliformi~le, a hydroxy derivative of lycopodine, was recently isolated from this plant, and its structure elucidated (6).In this coinmunication we wish to report the isolation and structural elucidation of flabelline, another ininor alkaloid of L. j?abellzforme. The separation procedure used in working up the alkaloids is given in some detail since some fractions are still being investigated and v,rill be reported up011 in a subsequent paper.…”

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Lycopodium Alkaloids: Xiv. Flabelline

Young¹,

MacLean²

1963

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A new alkaloid, ClsH2sOSn, designated flabelline, has been isolated by countercurrent distribution from the extract of Lycopodium$abellifoovme. The structure and stereochemistry of flabelline have been established by its conversion to and preparation from lycopodine.The investigatio~l of the alkaloids of Lycopodiumflebellifo~rne was undertaken by nfanske and 1Iarion in 1942 (1). They reported the isolation of lycopodine, the bases L1 to LG, and nicotine. Base L l has since been shown to be dihydrolycopodine (2), L2 to be acetyldihydrolycopodine (3), and LG to be a mixture of two compounds, a-and P-obscurine (4).T h e structures of lycopodine and its derivatives (2) and the obscurines ( 5 ) are now kllown.Flabelliformi~le, a hydroxy derivative of lycopodine, was recently isolated from this plant, and its structure elucidated (6).In this coinmunication we wish to report the isolation and structural elucidation of flabelline, another ininor alkaloid of L. j?abellzforme. The separation procedure used in working up the alkaloids is given in some detail since some fractions are still being investigated and v,rill be reported up011 in a subsequent paper.The alkaloid was extracted according to the procedure of llanslie and Rlarion ( I ) and the bulk of the lycopodine separated by the method of Barclay and lIacLean (7). The residual alkaloids from a number of extractions collected over a period of several years were conlbined and subjected to a preliminary purification as described in the experimental section. The bases were then subjected, on a large scale, to column chromatography on alumina and divided into three fractions-those eluted with chloroform, those eluted with 27, methanol in chloroform, and a residue eluted wit11 5yo methanol in chloroform. Froin the chloroform fraction, flabelliforinine containing some dihydrolycopodine separated upon treatment with ether. The nlother liquor fro111 the separation of flabelliforrnine was concentrated and the residual bases distributed between chloroform and pH 6.0 citratephosphate buffer in a 12-funnel distribution. The distribution was carried out on a large scale and served merely to separate the weak from the strong b'tses. I\/Iany more transfers with a much smaller amount of base would have been necessary to achieve discrete separation of individual bases.Fractions 1 and 2 from the distribution were allnost pure dihydrolycopodine; fractions 3 and 4, a mixture of dihydrolycopodine and flabelline; and fraction 5, a mixture of