The Danaine Butterfly, Idea Leuconoe
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Agric. Biol. Chem., 55 (7), 1787-1792, 1991 1787 Ideamine A^Oxides: Pyrrolizidine Alkaloids Sequestered by the Danaine Butterfly, Idea leuconoe Ritsuo Nishida, Chul-Sa Kim, Hiroshi Fukami and Ryozo Irie* Pesticide Research Institute, Faculty of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606, Japan . * Department of Agricultural Chemistry, Shinshu University, Kamiina-gun, Nagano 399-45, Japan Received January 8, 1991 Twonew pyrrolizidine alkaloids, ideamines A and B, together with other analogs (lycopsamine and parsonsine) were isolated in the TV-oxide forms from adult bodies of the Apocynaceae-feeding danaine butterfly, Idea leuconoe. Ideamine A was characterized as a homolog of lycopsamine, in which the viridifloric acid moiety was replaced by a 2-ethyl-2,3-dihydroxybutanoic moiety. Likewise, ideamine Bwas identified as a nor-derivative of parsonsine, in whichthe trachelanthic acid moiety was replaced by a 2-ethyl-2,3-dihydroxybutanoic moiety diastereomeric to the necic acid from ideamine A. Idea leuconoe Erichson is a large danaine Four alkaloid components (1-4) were butterfly whose larvae feed exclusively on the isolated from an extract of laboratory-reared plant, Parsonsia laevigata Alston (Apocyna- /. leuconoe adults by reverse-phase liquid ceae), in the Ryukyu Islands of Japan. Wehave chromatography.1} The molecular weights of isolated four pyrrolizidine alkaloids, both from compounds 1^1 were determined to be 301, the insect (adult bodies and eggs) and from the 315, 441 and 455, respectively, from the host plant, demonstrating the acquisition of secondary ion mass spectra (SIMS). the alkaloids directly from the larval host in Compound2 was identified as lycopsamine this species.1} These alkaloids were found TV-oxide, since 2 yielded lycopsamine (2a, predominantly as TV-oxides in the insect tissues C15H25NO5, [a]D +4.2°; lit. [a]D +3.3°,2> as well as in the plants. We report here the [a]D +4.8o3)) when treated with zinc dust in identification of the alkaloid components, diluted sulfuric acid. The identity of 2a was which were isolated from the bodies of /. confirmed from its diagnostic 1H- and leuconoe, including two new analogs, ideamine 13C-NMRspectra,3) and by alkaline hydrolysis A and B JV-oxides. of 2a to (-)-viridifloric acid (5) and (+)- 1788 R. Nishida et al. retronecine (6). dihydroxybutanoic acid. The 1H-NMR spec- Compound4 was identified as parsonsine trum of la exhibited AB-type doublet signals TV-oxide, since the ^-NMR signals of its by C-9 methylene protons at £4.75 and 4.87 Zn-reduced product 4a (C22H33NO8, [a]D (.7= 13Hz), indicating the acyl moiety to be +15°) coincided with those reported for attached to the C-9 position.3) Thus, the parsonsine (lit. [a]D + 19.8°).4) Further confir- structure of ideamine ATV-oxide was given as mation was provided by alkaline hydrolysis that shown in formula 1. The 1H- and of the macrocyclic ester 4a to ( + )-retronecine 13C-NMRassignments of 1 are listed in Tables (6), trachelanthic acid (7) and a-isopropylmalic I and II in comparison with 2, which were given acid (8). with the help of two-dimensional NMR Compound 1 was reduced to free alkaloid analyses (H-H COSY and C-H COSY la ([a]D +4.0°), the molecular formula of spectra). which was determined to be C14H23NO5. Compound 3 yielded free alkaloid 3a Compound la gave (+)-retronecine (6) and (C21H31NO8, [a]D +21°) by Zn reduction. esterifying acid 9 ([a]D -5.9°). The ^-NMR Upon alkaline hydrolysis, 3a gave (+)-6 and spectrum of9 exhibited a methyl triplet (3 0.86) two necic acids (8 and 10). Dioic acid 8 showed coupled to a methylene quartet at 51.79 a negative optical rotation ([a]D -17°), and (/=7.4Hz), and a methyl doublet ((51.15) thereby C-2" should possess an S-configura- coupled to a methine quartet at 53.93 tion.5) The XH- and 13C-NMR and mass (/=6.6Hz). Combined with 13C-NMR and spectra for 10 gave very similar patterns to mass spectrometric data (see the experimental those for 9. The ^-NMRspectrum of 10, section), 9 was identified as 2-ethyl-2,3- however, gave a methyl triplet (S O.S3) coupled Table I. ^-NMRSpectral Assignments of Compounds 1, 2, 3 and 4 (Chemical Shifts, Multiplicity and /-Values in Hz) Compound1 Compound2 Compound3 Compound4 2 5.86br.s 5.87br.s 5.96 br.s 6.03 br.s 3a 4.50d (16) 4.48d (16) 4.68d (16) 4.66d (16) 3b 4.40d (16) 4.39 (16) 4.45 (16) 4.45 (16) 5a 4.24dd (8.7, ll.5) 4.17dd (8.3, ll.5) 3.7-3.8m 3.7-3.8 m 5b 3.76dt (5.5, ll.5) 3.78dt (5.9, ll.5) 6a 2.61m 2.61m 3.19m 3.04m 6b 2.07m 2.06m 2.16dd (5.5, 13.6) 2.17dd (5.9, ll.5) 7 4.68 br.s 4.67br.s 5.98m 5.94br.t (3) 4.68 br.s 4.67 br.s 5.24m 5.01m 4.90d (13.5) 4.90d (14.5) 4.90d (14) 4.96d (13.5) 4.76d (13.5) 4.76d (14.5) 4.84d (14) 4.76d (13.5) 3' 3.83q (6.5) 3.96q (6.6) 5.23q (6.4) 5.43q (6.3) 4' 1.21d (6.5) 1.27d (6.6) 1.24d (6.4) 1.25d (6.3) 5'a 1.85dq (14.4, 7.2) 2.18 septet (6.7) 1.5-1.8m 1.89 septet (7) 5'b 1.72dq (14.4, 7.2) 6'a 0.91 1 (7.2) 0.94d (6.7) 0.891 (7.4) 1.01 d (7) 6'b 0.88d (6.7) 0.96d (7) 3"a 2.87d (16.5) 2.87d (16.5) 3"b 2.60d (16.5) 2.58d (16.5) 5" 1.69 septet (6.7) 1.71 septet (6.7) 6"a 0.97d (6.7) 0.97d (6.7) 6"b 0.83d (6.7) 0.83d (6.7) Compounds 1 and 2weremeasuredin CDC13+CD3OD(9 : 1), andcompounds 3 and4weremeasured in CDC13. Ideamine TV-Oxides from Danaine Butterfly 1789 Table II. 13C-NMRSpectral Assignments of Compounds 1, 2, 3 and 4 Compound1 Compound2 Compound3 Compound4 1 132.26 132.31 130.14 130.01 2 122.80 122.95 125.31 126.97 3 78.02 78.12 80.50 80.34 5 69.10 69.17 70.28 70.38 6 34.55 34.55 32.78 32.91 7 69.71 69.70 75.47 75.78 8 95.79 95.89 95.67 96.29 9 61.49 61.51 60.39 60.53 r 173.80 173.91 173.22 172.49 2' 81.81 84.20 79.90 82.12 3' 72.71 71.81 76.36 74.95 4' 17.45 17.06 13.22 12.98 5' 28.36 32.36 28.85 33.96 6'a 7.83 15.68 8.06 17.23 6'b 17.80 17.31 1" 174.63 175.07 2" 76.14 76.35 3" 43.08 42.79 4" 168.ll 167.57 5" 36.57 36.21 6"a 16.12 16.17 6"b 17.21 17.14 Compounds 1 and 2weremeasuredin CDC13+ CD3OD(9 : 1), andcompounds 3 and4weremeasuredin CDC13. to a methylene multiplet at around 51.6 as the pyrrolizidine alkaloid components (/-7.4Hz), and a methyl doublet (51.15) incorporated by /. leuconoe. Ideamine TV-oxides coupled to a methine quartet at 53.98 (1 and 3) were the homologs of 2 and 4, (/=6.5Hz). These data indicate that com- respectively, lacking one carbon unit from the pound 10 was a diastereoisomer of 9. The hydroxybutanoic moiety. It should be noted 2D-NMR analyses (H-H COSY and C-H that the necic acids (9 and 5) contained in COSY) of compound 3 exhibited parallel monoesters 1 and 2 were diastereomeric to the correlations to those found for compound4, corresponding necic acids (10 and 7) in- except for the C-2' alkyl portions, suggesting corporated in cyclic esters 3 and 4, respectively, the same14-memberedmacrocyclic structure although the absolute configuration at C-2' and for 3. Conclusive evidence for the arrangement C-3' of the ideamines remains to be clarified. of the ester linkages was obtained by the Several analogs of parsonsine have been COLOC (correlation spectroscopy via long- reported from two species of Parsonsia (P. range coupling) spectrum of 3, in which heterophylla and P. spiralis).^ Although a correlation was observed between H-7 (5 5.98) number of macrocyclic pyrrolizidine esters are and C-l" (5 174.63), and between H-9ab (54.84 known from various plants in the family and 4.90) and C-l' (5173.22). Further, a Compositae and Leguminoseae, the 14-mem- significant NOE correlation was observed bered ring system seems to be characteristic of between the H-3' methine (55.23) and H-3" the genus Parsonsia.6) A monoester, parsonine methylene (52.60 and 2.87) in the NOESY (the 5,6-dihydro-7-oxopyrrolizine derivative of spectrum. Thus, the structure of ideamine B (-)-viridifloric ester), which is analogous to TV-oxide was given as that shown in formula 3. 2a, has been isolated from stems of P. Twomonoesters (1 and 2) and two cyclic laevigata. 1) triesters (3 and 4) have been characterized here Lycopsamine (2a) has been found in the 1790 R. Nishida et al. adult bodies of various danaine butterflies represent (broad) singlet, (double) doublet, triplet, quartet together with other types of pyrrolizidine and multiplet, respectively, and coupling constants are given in Hz.