294 PH\MCHI UICAI. RI PORTS

LABD-13-EN-8-OL-15OIC ACID IN THE TRUNK RESIN OF AMAZONIAN

HYMENAEA COC’RBARIL

ALAN CIJYNI~GHAM, SUSAN S MARTIN and JFA? H LAVX~HHCIM

Dlvwon of Ndtuirll Sclencea Umvetslty of C&fornu Santa Crur CA 95064 II SA

(RWII~ 12 Jww 1973 ,4<teptrd 9 5~1) 1971)

Key Word Index--Wynwntm cow hul rl, Legummosae ream acid dlterpene

Plant and source Hymrrzuea courharzl L trunk resm (J H Langenhelm No 5621) was collected dt the Pdlhiio Reserve near Santerim, Par& Brazil (central Amazomdn region) Upon conclusion of a detalled study of the genus Hymrnaea now In progress, specimens documentmg this collection will be deposlted m the herbdrlum of the University of Cahfor- ma, Berkeley Crres Trunk resm has been used m the manufacture of vdrnish Plecrou<

work On other species of Hq~mcnaea ’ A On Iesm chenustry m the genus 4 “ On the che- rmstry of the trunk resm of H coulha?~l 5 Plarlt part eamln~~d Hardened trunk iesln secreted by cells m the cambldl zone ‘md collected In lyslgenous cavltlec produced bq the breakdown of resin secretory cells Upon natural or man-mdde Injury to the bdrk the resm may exude to the exterior of the tree where it eventually forms hardened masses lo ’ ’

L~?~-~~-P~-~-o~-I~-ozc ac ld (1) has been isoldted ds d major component of the hdrdened trunk resin of H courha~zi This dlterpene has been synthesized from scldreol’ ‘2m14 and 1s enantiomeric to the series of dlterpene dclds prevlousiy lsoldted from N (r~harrl and other species m the genus ’ ’ Labdane skeleton dl terpene dclds of the “1101 mdl’ stereoche- mlcal type have been reported from other genera of the tribe Detdnede, to which Hymumea belongs ” 1 ’

’ LANGEYHEIM, J H (1973) m -1‘roprcal Forest Ecoq&ems 111 4frxa and South Ame~r~a 4 Comparatrw Reneu (MEGGERS, B J AY~NSL E S dnd DLCKWORTH W D eds) pp 89 104 Smlthsomdn Instltutlon Press Washmgton D C

’ LAPIGEYHEIM. J H LFF, Y T and MAK~N S S (1970) Am J Botanv57,754 3 LIE, Y T (1973) Ph D Dlssertatlon, Umv of Callforma Santa Cruz 4 LA~GFNHTIU J H Lrt, Y T and MAKTI~~, S S (1973) Actu -Im~nmta HI press ’ NAKAVO T dnd DJERASSI, C (1961) J Orq Chum 26, 167 ’ MARTIN S S LAUGFNHEIM J H and ZAVARIN, F (1972) Ph~tochr~trw~ 1 I, 3049 ’ CUNNYGHAM A MARTIN, S S md LA\G~~H~J~ J H (1973) Ph~to<hemrct~ 1 12, 633 ’ MARTIN S S LANGE~HEIU J H and ZAVARIN E (1973) Btochrrn Swemat~~ 5 1, 35 !a MARTIN S S (1973) Ph D Dlssertdtlon, Umv of Cahforma Sant.1 CIrw

‘” LANGE~H~IM J H (1967) .I Arrzold Arho~ 48, 203 ” LA~GFNHIIM, J H (1969) Scre~c 163, 1157 ’ ’ L~~ERER E (1960) Frame Ses Pmfum 3, 28 l3 BORY, ‘3 dnd LFDERER, E (1957) Croat Clzern Act0 29, 157 I4 BURY S, FETUON M and LAS~LO, P (1963) Bull SOL C&m Fr 2310 ” BPVA~ C W L, EKOUG D E U and OK~GU~~ J I (1968) J Chem Sor 1067 lb Ztrss, H H and GRAYT F W (1957) J Am Chrm Sot 79, 1201

PHYTOCHEMKAL REPORTS 295

(1) R =H (2) R = Me

EXPERIMENTAL

NMR spectra were obtained at 60 MHz m CDCl, with TMS as an Internal standard lsolatzon The Et,0 soluble fraction of a powdered trunk ream sample was partitioned with saturated Ll,CO,

and the aqueous phase was adJusted to pH 3 with HOAc Extractlon of the aqueous phase with Et10 followed by evaporation of the Et,0 ylelded 31% resm acids The acids were methylated (CH,N,) and separated by TLC (slhca gel_AgNO,)

Methyl lab&13-en-S-ol-15-oate (2) UV 122” 222 nm, log E 4 1 (ht’ np’.“,” 222 nm, log E 4 11),

Cffl gHc’J + 43” (c 06) (ht I2 I3 [a]gHc’3 + 42”) viz; 3410, 1720 (ester), 1651 (olefin) 1265, 1151 (ester) cm-‘, NMR 6 0 80 (s, 6H), 0 88 (s, 3H), 1 16 (s, 3H), 2 18 (d, J 1 5 Hz, 3H, C-13 Me trawl4 to C-14 H), 3 70 (s, 3H), 5 73 (m 1H) MS m/e 336 (M+), 318,205,204,114 (100%) [ht 5 318,205,204, 114 (lOO%)]

Acknowledgements-We thank Mr Hehomar Magnago of SUDAM m Santarem, Para, Brazil, for assistance to J H Langenhelm in collectmg the resms Appreeatlon 1s also expressed to Dr A C Oehlschlager, Department of Chermstry, Simon Fraser Umverslty, Burnaby, B C, Canada, and Dr Phllhp Crews, Board of Stu&es m Che- rmstry, Umverslty of Cahforma at Santa Cruz, for helpful suggestions on lsolahon procedures and interpretation of data Grateful acknowledgement also IS made for funds to support this study through National Science Foun- dation grant GB-13659

Phytochemlstry 1974 Vol 13 pp 295 to 297 Pergamon Press Pnnted m England

FLAVONOIDS OF BRACKENRIDGEA ZANGUEBARZCA*

E BOMBARDELLI, A BONA~, B GABETTA and G MUS~CH

Laboratorlo Rlcerche Chlmlche, Inverm della Beffa, Via Rlpamontl, 99-Mllano. Itaha

(Recezved 5 July 1973 Accepted 17 August 1973)

Key Word Index-Brackenrzdgea zanguebarzca, Ochnaceae, flavonolds, Isoorlentm, sequoJaflavone, vitexm, vltexm 2”-0-acetyl7-O-methyl ether

From the cold methanohc extract of the leaves of Brackenrzdgea zanguebarzca Ohv (Ochnaceae) we isolated 4 flavonolds by column chromatographles over s~hc acid Three of them were identified as vltexm (OOSl’?), lsoorlentm (0 066%) and sequojaflavone (7-O-methylamentoflavone) (0 052%) by NMR spectra exammatlon of the respective acetates I-’

* Part IV m the series “Plants of Mozambique’ For Part III see GABETTA, B, MARTINELLI, E and MUSTKH, G (1973) Fztoterapza 44, 55

1 HILLIS, W E dnd HORN, D H S (1965) Australzan J Chem 18, 531 * EADE, R A, HILLIS, W E, HORN, D H S and SIME~, J J H (1965) Australzan J Chem 18,715 3 GENTILI, B and HOROWITZ, R M (1968) J Org Chem 33,157l 4 MIURA, H , KIHARA, T and KAWANO, N (1968) Tetrahedron Letters 2339