~) Pergamon Plh S0031-9422(97)00233-1 Phylochemisto,. Vol.46. No. 3, pp. 555 558. 1997 i 1997 Elsevier ScienceLtd. All rightsreserved Printed in Great Britain 0031 9422/97 $t7.00 M).00 TETRANORTRITERPENOIDS FROM AZADIRACHTA INDICA CONSOLACION Y. RAGASA,* ZENAIDA D. NACPIL, GAUDENCIO M. NATIVIDAD, MASARU TADA,'t" JOHN C. COLL+ + and JOHN A. RIDEOUT~. Chemistry Department, De La Salle University, 2401 Taft Avenue, Manila, 1004 Philippines; ?Chemistry Department. Waseda University, Tokyo, 169 Japan; ++Chemistry Department, Central Queensland University, Rockhampton 4702. Queensland, Australia (Received in revisedJbrm 25 January 1997) Key Word lndex--Azadirachta indica; Meliaceae; neem tree; tetranortriterpenoid" aza- dirachtolide; deoxyazadirachtolide. Abstract- Azadirachta indica afforded two novel tetranortriterpenoids by gravity column chromatography. Their structures were elucidated by extensive 1D and 2D NMR techniques. ~, 1997 Elsevier Science Ltd INTRODUCTION Azadirachta indica is used as an anti-malarial, anti- inflammatory, anti-pyretic, antitumour and anthel- mintic, a febrifuge, and an astringent. It is also used for the treatment of ulcers and skin diseases. The plant is known for its insecticidal and pesticidal properties [1-2]. Earlier studies reported on the isolation of tetranortriterpenoids and triterpenoids [3-24] from the plant which are of relevance to our present report. We now report two additional tetranortriterpenoids (1-2) from the same species. RESULTS AND DISCUSSION The CHC13 extract of the air-dried leaves of A. &dica afforded compounds 1 and 2. The structures of which were elucidated by NMR and FT-IR spectro- scopy and mass spectrometry. The mass spectrum of 1 contained a [M] + peak at m/z 570 which corresponds to a molecular formula of C33H4608. The ~ H NM R spectrum showed resonances for a senecioyloxy substituent [6 1.88 (3H, d, J = 1.2 Hz), 6 2.20 (3H, d, d = 1.2 Hz), 6 5.70 (1H, s, br)] [25], an acetate [6 1.96 (3H, s)], four additional methyl singlets (6 0.97, 6 1.0, 6 1.05, 6 1.19), two olefinic hydrogens [6 5.50 (dd, J = 1.74, 3.0 Hz), 5.70 (s, br)], methylene hydrogens bonded to oxygenated carbons [6 4.4 (1H, t, d = 7.7 Hz), 6 3.95 (1H, t, J = 7.7 Hz), 6 3.63 (1H, d. J = 7.6 Hz), 6 3.56 (1H, d, J = 7.6 Hz)], and methine hydrogens bonded to oxygenated carbons [6 4.12 (1H, dd, J = 3.3, 12 Hz), 6 4.14 (1H, s. br), 6 4.70 (1H, t, J = 3.0 Hz), 6 4.90 (1H, t, J = 3.0 * Author to whom correspondence should be addressed. o o 21 2~ CH3~ /C=CHCOO/, ~ I" 30 '"1 ~"1 CH3 ~ 151 + 1 o R 21 2~ _ . \ oo, ,9 AcO\XW ~ "Itl OH 1 R==O 2 R=H Hz)] (Table 1). The ~3C and DEPT NMR spectra gave the following functionalities: a carbonyl of a lactone at 6 176.0, a carbonyl of an acetate at 6 171.0, a carbonyl of a conjugated ester at 6 166.0, four oxy- genated methine carbons at 6 74.0, 72.8, 71.8 and 71.2, two oxygenated methylene carbons at 6 77.9 and 72.4, two non-protonated olefins at 6 157.4 and 160.0, two 555