300 PH’r TO< HtMfC AL Rt POR JS

TRITERPENOID AND OTHER CONSTITUENTS OF X,4N THORHlZA Sf MPLf Cf SSf MA

JOSE A LOPFZ, DAVII> J SLATKIN, MICHA THEINFR,” PAUL L SCHIFI-, JR

and JOSEPH E KNAPP

Department of Pharmacognosy School of Pharmacy Umverz~ty ot Pittsburgh Plttsbur& P4 15261 L’S A

Key Word Index- Xunthorhm srnzp/~~~~trrnu Rdnuncu~acede, feruhc dcld fdtt! duds ursohc xld +dlkdne\, alto\terol campesterol stlgmasterol cholesterol, palmatme

Plunt Xanthorhm slrnpllclwmu Marsh Sourer S B Pemck and Co, New York Lot No X14-BKM-1 liwt Has been used as ‘1 medlclnal in the Umted StdteS ’ P~r~ouc work On rhizomes ‘tnd root\ ls3

Pf ewjtt pork The dried, ground rhizomes dnd roots (10 kg) were extr‘lcted by percoln- tlon with EtOH After removal of the solvent 112 I-UCLW dt 40 . the residue (1 2 kg) &as partl- tloned between 2”;, dq cltrlc acid and Et,0 to gate d bdslc ‘md non-bdslc fraction The non-basic fraction wns frdctiondted by standard methods into neutIa1 (55 g), acidic (40 g) dnd phenohc (9 g) fractions

Phe~~ol~cfiac.t~otz Chromdtography over slllc~c dcid dnd elution alth CHCI, gdvc d frac- tion which, when re-chromntogrdphed over sillcic dad and eluted with CHCl,-MeOH (4 I ) afforded fenrl~ izcln (60 mg) m p 165 5 166 5’ (hght petrol ) I:::‘” 216 nm (log E

4 72) 234 (4 17), 295 (4 23). 320 (4 35) I~~~; 3460, 1670. 1600, 1510 ,ind 1170 cm- ’ MS M’ nl;r 194(100:;,), 179 (24), 177 (10) 150 (14) Direct compdnson (m p m nip Lc,V IR and MS) with dn duthenbc sample confirmed the IdentIty

AC&C frattoll Chromatography over slllclc acid and elutlon with light petrol -C,H, (4 1) gdve n fatty acid fraction whrch crystalhzed from MeOH (200 mg), m p 70--71 \1’1: 2940,2860, 1700 1460, 1300 and 720 cm-’ GLC of the methyl esters on n 160 cm column of0 8”; OV-I 7 on Gas Chrom Q (X0-100 mesh) showed the mixture to be composed of Czr (24’>$), CJ3 (15), C,, (46), CZj (8) and CZh (6) saturated straight fatty ‘tclds The Identltj was confirmed by GC- MS

Elutlon with C,H,-CHCI, (1 3)gave ursolrc aczd (150 mg), m p 1142-243 (hght pct101 MeOH) (lit” 224-244” [ether] 260- 280” [EtOH] 2%281 [Et,Gllght petrol]) $,~: 3450, 2950, 2890, 1685. 1450 1030 dnd 990cm-‘, [r];” + 70- (< 04 CHCI,) MS M r 456 (3?;), 248 (100) Treatment with acetlc dnhydnde~pyridme gave 0-acc~r~lur~lrc LKI~ m p 268-270’ (hght petrol ) v$y: 1735, 1690 and 1234 cm-‘, [Y];” + 53 7 (c 0 7 CHCl,) Direct compdrlson (m p, m m p, IR, MS) with an ‘iuthentlc sample of the compound ,md derivative confirmed the IdentIty

* Depdrtment of Blocheml\tr, School of Dent,11 Mcdwne I’nlwrsltj of Pltt\burgh Plttshurgh P4 I531 CJ s A

PHYTOCHEMICAL REPORTS 301

Neutralfiactlon Chromatography over s~hac acid and elutlon with light petrol gave an alkane fraction which crystalhzed from MeOH (75 mg), m p 65-65 5”, vzfi 2930,2860, 1460,725 and 715 cm-’ GLC on a 160 cm column of 0 8% OV-17 on Gas Chrom Q (80- 100 mesh) showed the rmxture to be composed primarily of C,, to Ca5 n-alkanes, Cz5 (lx),

CX (2), C,, (6)> C2s (4), CZ~ (20), COO (5), CJ~ (25), C32 (4), C33 (19), C34 (2), C,, (1) The identity was confirmed by GC-MS Elutlon with light petrol-&H, (2 3) gave a sterol rmxture which crystalhzed from MeOH (400 mg), m p 136-137” vkfi 3450, 2960, 1460, 1375 and 1060 cm-’ GLC on a 160 cm column of 0 8% OV-17 on Gas Chrom Q (SO-100 mesh) showed the rmxture to be composed of sltosterol(55’A), campesterol(32), stlgmasterol (9) and cholesterol (4) The identity was confirmed by GC-MS The spectra were consistent with those of authentic samples

Baslcfvactlon Refrigeration of the acidic solution gave an alkaloidal preclpltate (157 g) Chromatography over slhclc acid and elutlon with CHCl,-MeOH afforded an alkaloid fraction (1 2 g) Treatment with saturated methanohc KI gave palmatme lodlde (60 mg), mp 228-229” $$,‘x”” 227 nm (loge 4 58), 270 (4 42), 350 (4 41) and 439 (3 71) vkti 1600, 1360,127O and 1020 cm-’ MS M’ m/e 352 (8x), 351 (17), 337 (95) and 142 (100) Reduc- tion with NaBH, gave tetrahydropalmatme m p 142” (MeOH) &$zH 209 (log E 4 02) and 282 (3 78) MS M+ 355 (40x), 339 (40), 164 (100) and 149 (50) Direct comparison (m p, m m p , IR, MS) with an authentic sample of the compound and derivative confirmed the identity The previously isolated compounds,Jatrorrhlzzne,2 oxyacanthzne3 and obamegme3 were re-isolated and identified by m p , m m p , IR, MS and optical rotation

Acknowledgements-The authors are grateful to Professor Jack L Beal, Dlvlslon of Pharmacognosy and Natural Products, College of Pharmacy, The Ohlo State Umverslty for the gift of the plant material and authentic samples of palmatme, Jatrorrhizine, obamegme and oxyacanthme, Professor H H S Fong, Department of Pharmacog- nosy and Pharmacology, College of Pharmacy, Umverslty of Ilhnols at the Me&al Center, for the sample of ursohc aad, Mr John NdWOrdl, Graduate School of Public Health, Umverslty of Pittsburgh for determmlng the MS Tlus mvesttgatlon was supported m part by Research Grant 5SOIRR05455-10 from the National Instl- tutes of Health, Education and Welfare, Bethesda, MD 20014, U S A The mass spectrometer facility was sup- ported by Research Grant RR-00273 to the Umverslty of Pittsburgh from the Natlonal Institutes of Health

Phytochemlstry 1974 Vol 13 pp 301 lo 302 Pergamon Press Prmted !n England

ALCALOIDES DE BAUERELLA BAUERZ

MARYSE BERT, MICHEL KOCH et MICHEL PLAT

Laboratolre des maheres pretmeres et medlcaments naturels, U E R des Sciences Pharmdceutlques, 1 rue Vaubenard, 14000~Caen-F et Laboratone de Pharmacte Galemque, U E R de Chmue Therapeutlque,

4, Ave de l’observatolre, 75006-Parts-F, France

(Regu le 22judkt 1973 Accepte le 20 aotit 1973)

Key Word Index-Bauerelfa bauerl, Rutaceae, acrldones, acronycme, mehcoptdme

La plante Baurella bauerl (Schott) Engler Cette espkce a kti: r&colt&e le 10 septembre 1968 ?t Pouembout (Nouvelle Cal&dome) par Sevenet et McKee Elle fait encore l’obJet