1976 23Structures of Eight New Triterpenoids and Isolation of Other Triter-penoids and Epi-ikshusterol from the Stems of Lithocarpus corneaBy (Miss) Wai-Haan Hui * and Man-Moon Li, Department of Chemistry, University of Hong Kong, Hong KongEight new triterpenoids from the light petroleum extract of the stems of Lirhocarpus cornea (Lour.) Rhed. have beenproved to be taraxer-l4-ene-3&29-diol (VI I I ) and its diacetate (VI I ) , 29-hydroxytaraxer-14-en-3-0ne (X) and itsacetate (IX). 14a-hydroxytaraxeran-3-one (XXIX). taraxerane-3~,14a-diol (XXX), 22-hydroxy-21 aH-hopan-3-one(XXIII), and lup-20(29)-ene-3P.27-diol (XXXII). Other triterpenoids isolated from the same extract, besides thosealready reported were lupeol, betulin, and myricadiol ( I ) . The steroid epi-ikshusterol (stigmast-5-ene-3p,7(3-diol) (XXXVII) was also obtained.THE light petroleum extract from the stems of Litho-carpus comea (Fagaceae) has been found to containfriedelin, taraxerone, friedelan-3p-01, taraxerol, sitosterol,and three new pentacyclic triterpenoids designated A,, A,,and A3.1 On repeating the same investigation on a biggerscale, five more new triterpenoids and small quantities oflupeol, betulin, myricadiol (I) ,2 and epi-ikshusterol(stigmas-5-ene-3p,7 p-diol) (XXXVII) have been iso-lated.Compound (XXXVII) has been reported previ-ously only 0nce.3 This paper describes the determina-tion of the structures of the eight new triterpenoids.They all gave a positive Liebermann-Burchardt reaction.The least polar of the eight new compounds isolatedfrom column chromatography of the extract was thediacetate (VII), C,H,,O,.Its i.r. spectrum showed thepresence of two OAc groups and a trisubstituted doublebond, also indicated by n.m.r. signals at S 2.05 (3H,s),2.09 (3H,s), and 5.55 (lH, q). One of the OAc groupswas shown to be primary by a signal at 8 3.80 (2H,s), alsoindicative of the CH,OAc group being in a non-hinderedequatorial position attached to a tertiary carbon atom.The other was proved to be secondary, equatorial, and inthe environment CH,*CH*OH by a signal at 6 4.47 (lH,q, JmSep 7 and Jm,- 10 Hz). Compound (VII) wasidentical with the acetylation product of the diol As1The next to least polar new compound (IX), C,,H,,O,,showed in its i.r. spectrum the presence of one OAcgroup, one carbonyl function, and a trisubstituted doublebond. Its n.m.r.spectrum indicated a non-hinderedequatorial4 CH,*OAc group attached to a tertiary carbonatom [6 3.78 (2H,s) and 2.06 (3H,s)], a CH,-C=O func-tion [6 2.40 (2H, m)], and an olefinic proton (6 5.62).Compound (IX) was identical with the acetate of the ketolA: (X), C~OH&@,. The n.m.r. spectrum of (X) revealeda CH,C=O function [6 2.40 (2H, m)], an olefinic proton(6 5.57), and a non-hindered equatorial CH,OH groupattached to a tertiary carbon atom [S 1.62 (lH, s, D,Oexchangeable) and 3.30 (2H, s)].4Compounds (VI1)-(X) each gave a yellow colour withtetranitromethane. Comparison of their molecular for-mulae and spectroscopic properties, indicated that theywere all probably inter-related.Indeed reduction ofcompound (X) with borohydride gave the diol (VIII).(VIII), C,,H,O,.W. H. Hui, P. D. S. KO, Y. C. Lee, M. M. Li, and H. R.a A. A. Ryabinin and L. G. Matyukhina, Doklady Akad. Nuuk.Arthur, Plzytochemistry, 1975, 14, 1063.S.S.S.R., 1959, 129, 125.The presence of a CH,*OH (or CH,*OAc) group togetherwith seven tertiary Me groups as revealed in the n.m.r.spectrum of each of compounds (VII), (IX), and (X)suggested an oleanane or rearranged oleanane skeleton.The signal due to the olefinic proton in each of com-pounds (VII), (IX), and (X) [(VIII) was too insoluble inCDC13 for its n.m.r. spectrum to be determined] appearedas a well-defined quartet (J 4 and 7 Hz), which indicatedtwo vicinal methylene but no allylic protons.Thisfitted well with a C-14 double bond, as in taraxer-14-enederivatives. Taraxeryl acetate (11), taraxerone (111),epitaraxerol (IV), and myricadiol diacetate (V) givesimilar quartets at S 5.62, 5.62, 5.53, and 5.47, respec-tively. One of the oxygen functions was likely to be atthe usual C-3 position, and this was proved by tosylationof the ketol (X) to give a keto-tosylate (XI), reduction-I+- -of which with lithium aluminium hydride yielded tara-xerol (VI).The mass spectra of compounds (VI1)-(X) confirmedthe above by the presence of the species (a) and (a');S. S. Deshmane and S. Dev, Tetrahedron, 1971, 27, 1109. * A. Gaudemer, M. J. Polonsky, and E. Wenkert, BUZZ. SOC.6 W. H. HuiandM.L. Sung, AustraZ. J . Chem., 1968,21, 3137.chim. France, 1964, 40724 J.C.S. Perkin Ithe second oxygen function appeared in species (b), whichcontained rings D and E. As the fragmentations of (VII)were similar to those of (V) with only slight differences inintensities,6 but the two compounds were not identical,the second oxygen function must be at either C-29 orC-30. Since the n.m.r. spectra showed relatively highfield methylene proton signals for the CH,0R2 group[R2=Ac for (VII) and (IX), and H for (X)] the equa-torial C-29 position was fa~oured.~ Hence the structuresof compounds (VI1)-(X) were deduced.The double bonds in taraxer-14-ene derivatives canbe isomerized readily under mild acidic conditions to givethe corresponding olean-12-enes.Thus, as expected,treatment of compound (VII) with hydrochloric acid-29(VU) R' =WH, P-OAC, R ~ = A C( ~ m ) R'=~-H,P-oH, R ~ = H (1x1 R'=O,R~=AC(XI R'=o,R~=H(XI) R'=O,R~=TSacetic acid gave the diacetate (XII), C,H,O,, 6 4.50(lH, q, J 7 and 10 Hz, axial CHOAc), 3.73 (2H, s, equa-torial CH,OAc group 4), and 5.22 (lH, q, J 3 and 4 Hz,olefinic proton of the olean-12-ene type '). Compound(XII) is not identical with olean-12-ene-3fi,30-diol dia-cetate (XIII),8 the n.m.r. spectrum of which showed atwo-proton singlet at 6 4.029 (axialCH,*OAc), although itsmass spectrum was very similar to that of (XII), withthe base peak at m/e 276 and abundant fragments atm/e 249,216,203, and 189. Compound (XII) is thus thecorresponding 3P,29-diol diacetate, which has not beenreported previously.Like compounds (VII), (IX), and (XII), methylmesembryanthemoidigenate diacetate (methyl 3&29-diacetoxyolean-12-en-28-oate) (XIV) gives a two-protonsinglet at 6 3.80.1° The structure of (XII) was finally6 H.Budzikiewicz, J. M. Wilson, and C. Djerassi, J . Amer.T. Kikuchi, M. Takayama, T. Toyoda, M. Arimoto, and M.C . Djerassi, J. A. Henry, A. J. Lemin, and T. Rios, Chem.R. G. Wilson and D. H. Williams, Tetrahedron, 1969,25, 155.lo B. Tursch, J. Ledercq, and G. Chiurdogiu, Tetmhedronl1 W. H. Hui and C. T. Ho, Austyal. J . Chem.. 1968, 21, 547.Chem. SOC., 1963, 85, 3688.Niwa, Chem. and Pharm. Bull. (Japan), 1973, 21, 2243.and Ind., 1955, 1520.Letters, 1965, 4161.confirmed by partial synthesis from methyl mesembryan-themoidigenate (XVI) ,11 which was first reduced with29 3023 2L(Xn) R'=d-H,P-OAc, R2= R'=Me, R3=CHZ.OAc(XIY) R ' = a - H , P-OAC, R2= C02Me,R3=CH2-OAc,RL=Me(Xm)(XY)R1=Q- H, p-OAc, R2= R3=Me, RL=CH2.0AcR'= 0, R2= R3= RL= MeHO.(xu1111 (XIXI+( X X I )+SCHEMElithium aluminium hydride to give the trio1 (XVII).Controlled tosylation of (XVII) gave a mixture of tosy1976 25lates (XVII1)-(XX), which on reduction (LiAlH,)followed by acetylation yielded a mixture of acetates.Chromatography of this mixture gave p-amyrenylacetate (XXI), then erythrodiol diacetate (XXII), andfinally olean-12-ene-3p,29-dol diacetate, C,H,O,,identical with (XII) (see Scheme).The proposed struc-tures of compounds (VI1)-(X) are thus confirmed.The fifth new compound (XXIII), C,H,O,, whichwas more polar than sitosterol, gave a negative resultin the tetranitromethane test.Its i.r. spectrum showedOH and C=O functions, but no C=C absorption. ACH,*C=O function was indicated in its n.m,r. spectrum[6 2.40 (2 H, m)]. There was no proton signal at 8 >3.0, indicating the absence of olefinic protons and thetertiary nature of the OH group, which was also provedby the resistance of compound (XXIII) to oxidationwith Jones reagent. Eight tertiary Me singlets, two ofwhich occurred at 6 1.20, showed the presence of apentacyclic molecule, probably belonging to the hopaneseries, containing a CMe,OH group. This was alsosupported by strong peaks at m/e 384 (M+ - Me,CO),207, 189, 149, and 59 in the mass spectrum, characteristicof 22-hydroxyhopane derivatives.12 The spectra of(XXIII) and hydroxyhopanone (XXV) differ only in theintensities of the peaks.(XXYrI) R = O(xxvm) R =CC-H,~-OH(XXlY, ( X X Y ) (XXVI)Attempted acetylation of compound (XXIII) withacetic anhydride-pyridine in the cold was unsuccessful ;on boiling, a dehydration product, C,H,O, identicalwith hop-17(21)-en-3-one (XXIV) l3 was obtained.This is again characteristic of 22-hydroxyhopane deriva-tive~.~* Hence (XXIII) is 2Z-hydroxy-l7~H,Zl~H-hopan-3-one.To determine the stereochemistry at C-17l2 R. E. Corbett and H. Young, J . Chem. Soc. ( C ) , 1966, 1656.l3 H. R. Arthur, W. H. Hui, C. N. Lam, and S. K. Szeto,l4 J. Cerny, A.Vystrcil, and S. Huneck, Chern. Ber., 1963, 90,Austral. J . Chem., 1964, 17, 697.3021.and C-21, dehydration of (XXIII) was carried out undernon-acidic conditions, with phosphoryl chloride in anexcess of pyridine.15 The product was a mixture, whichon chromatography (AgNO,-SiO,) gave hopenone a[hop-21 (22)-en-3-one] (XXVI) and moretenone [21 orH-hop-22(29)-en-3-one] (XXVII),16 the latter being themore polar and minor product. Hence the configura-tions of (XXIII) at C-17 and C-21 must be the same asthose of (XXVII), and (XXIII) is therefore 22-hydroxy-21 aH-hopan-3-one.Finally compound (XXIII) was partially synthesizedfrom (XXVII) by oxymercuriation followed by reductionwith sodium borohydride. The product (XXIII) wasobtained in low yield, together with a large amount ofunchanged (XXVII) and a small quantity of moretenol(XXVIII), formed from the latter during reduction of theintermediate.The sixth new compound isolated, All (XXIX),C,H,,O,, was a ketol which gave no colour with tetra-nitromethane.Its n.m.r. spectrum indicated a CH,COfunction [6 2.40 (2 H, m)]. The presence of a tertiaryOH group and the absence of olefinic protons were shownby the absence of proton signals at 6 > 3.0. Reductionwith borohydride, gave a diol, CmH,,O,, identical with theseventh new compound (XXX). The n.m.r. spectrumof (XXX) revealed a signal at 6 3.26 (lH, q, Jaz,ep 7,Jm,az 9 Hz) showing the presence of an equatorial OHgroup, in the environment CH,-CH*OH. Both (XXIX)and (XXX) showed eight tertiary methyl proton absorp-tions, indicating an oleanane or rearranged oleananeskeleton.Oxidation of compound (XXX) gave the ketol(XXIX); the latter (XXIX) was unchanged on similartreatment.The presence of a tertiary OH group in bothcompounds is thus confirmed, Attempted acetylation of(XXIX) at room temperature was unsuccessful; how-ever at elevated temperature both (XXIX) and (XXX)gave mixtures of dehydration products. From theformer, p-amyrenone (XV) and taraxerone (111), andfrom the latter p-amyrenyl acetate (XXI) and taraxerylacetate (11) were obtained. Hence (XXIX) is either134-hydroxyoleanan-3-one or 14f-hydroxytaraxeran-3-one, and (XXX) is the corresponding 3p-hydroxy-compound. The presence of a taraxerane skeleton ismore probable, as the olean-12-ene skeleton is morestable, and migration of the C-27 methyl group in theformer from C-13 to C-14 to give the latter skeleton iswell known.This was proved when compound (XXIX)was dehydrated under basic conditions with phosphorylchloride in an excess of pyridine to give taraxerone (111)as the sole product.The configuration of the hydroxy-group at C-14 wasfinally shown to be a by partial synthesis of (XXX) from14a,15a-epoxytaraxeran-3~-yl acetate (XXXI), firstprepared by Beaton et aZ.17 by action of perbenzoic acidl5 W. J. Dunstan, H. Fazakerley, T. G. Halsall, and E. R. H.Jones, Croat. Chem. Acta, 1957, 29, 173.16 W. H. Hui and C. T. Ho, Austral. J . Chena., 1968,21, 1675.17 J. M. Beaton, F. S.Spring, K. Stevenson, and J. L. Stewart,J . Chem. SOC., 1955, 213126on taraxeryl acetate (11). We used freshly purified m-chloroperbenzoic acid for epoxidation since it is morestereospecific.18 The epoxide (XXXI) , C32H520,,showed an n.m.r. signal at 6 3.03 (1 H, m) for the C-15methine proton. Treatment of (XXXI) with lithiumaluminium hydride in te trahy dro fur an gave t araxer ane-3p,14a-diol, identical with (XXX). Compound (XXIX)is therefore 14~-hydroxytaraxeran-3-one.(XXIX) R = O(XXX) R =d-H,P-OH(XXXI 1The structures of compounds (XXIX) and (XXX) werefurther confirmed by strong peaks at m/e 424 (basepeak, M+ - H20), 300, 285, and 205 for (XXIX) and426 (base peak, M+ - H,O), 302,287,284,269,207, and189 for (XXX) in their mass spectra, identical with thosegiven bytaraxerone (111) andtaraxerol (VI), respectively.6The eighth new compound (XXXII), C30Hm02, was adiol which gave a yellow colour with tetranitromethane.On acetylation under mild conditions it gave a mixtureof mono- and di-acetates, C3,H5,03 (XXXIII) and CM-HMO4 (XXXIV), respectively, separable by repeatedtecryst allization from chloro f orm-met hanol, the formerbeing less soluble.The n.m.r. spectrum of (XXXII)showed one equatorial hydroxy-group in the environ-ment CH,*CH*OH [6 3.20 (1 H, q, Jaz,q7, Jaz,az9 Hz)] andthat the other hydroxy-group was primary and probablyaxially orientated [6 3.32 (1 H, d J 11 Hz) and 3.77 (1 H,d, J 11 Hz) 4]. The latter observation was confirmedby the mass spectra of (XXXI1)-(XXXIV) whichshowed strong peaks at m/e 411, (M+ - CH,OH), 453(M+ - CH,OH) and 453 (.W+ - CH,OAc), respectively.These also indicated that monoacetylation had occurredat the secondary hydroxy-group.The n.m.r.spectrum of compound (XXXII) revealedthe presence of five tertiary methyl groups and an iso-propenyl group [6 1.68 (3 H, s), 4.57 (1 H, d), and 4.68la N. N. Schwartz and J. H. Blumbergs, J . Org. Chem., 1964,as W. J. Chin, R. E. Corbett, C. K. Heng, and A. L. Wilkins,29, 1976.J.C.S. PerRin I, 1973, 1437.J.C.S. Perkin I(1 H, d)]. The two olefinic proton signals indicated thatthe isopropenyl group belonged to the lup-20 (29) -eneand not to the hop-22(29)-ene skeleton, which wouldgive a broadened ~ing1et.l~ This supposition was con-b e d by tosylation of (XXXIII) at high temperaturein pyridine (tosylation at 0 "C or room temperature wasunsuccessful) followed by reduction (LiAlH,) to give lupeol(XXXV) as the final product.Compound (XXXII)is thus lup-20(29)-ene-3p,x-diol. The mass spectra ofcompounds (XXXI1)-(XXXIV) indicated that theCH,0R2 function was at either C-27 or C-28 by fragmentsat mle 234 for (XXXII) and (XXXIII) and mle 276 for(XXXIV) comprising rings D and E and part of ring c[species (C)],6 and base peaks at mle 203 for all threecompounds representing loss of CH20R2 from the abovefragments. The 28-position is ruled out as (XXXII) isnot identical with betulin (XXXVI). Hence (XXXII) islup-20(29)-ene-3p,27-diol.(xxxn) R'= R ~ = H(xxxmi R'=AC, R ~ = H(XXXIY) R'=R*=AC27+- C H ~ O R ~ .- m/e 203(XXX17) R2=H, m h 234( X X X m 1( XXXlY 1R2= H, m/e 234R2= Ac, m/e 276The 27-position in lupane derivatives is highly hin-dered; 2o this explains the difficulty in acetylation andtosylation of the CH,=OH group. The location of thisgroup was further supported by a comparison of the*O C. S. Chopra, A. R. H. Cole, K. J. L. Theiberg, D. E. White,and H. R. Arthur, Tetrahedron, 1965, 21, 15291976 27methyl n.m.r. signals of (XXXII) with those of (XXXV)and (XXXVI) (see Experimental section).After the isolation of compound (XXXII), betulin(XXXVI), myricadiol (I), and taraxer-14-ene-3p,29-diol(VIII) were obtained successively, followed by anothercompound (XXXVII), C,H,O,, which was probably asteroid diol with one double bond.The n.m.r. spec-trum revealed a pair of one-proton multiplets at 6 2.20and 2.30 for the C-4 protons and a one-proton multi-plet at 6 3.55 for the C-3 (CHOH) proton, characteristicof a 5-en-3p-01 system. It also showed a low fieldCHOH signal at 6 3.80 together with an olefinic protonsignal at 6 5.57 (1 H, d) suggesting the C=CH-CHOHgrouping. Hence the second hydroxy-group was prob-ably at C-7. The mass spectrum showed prominentpeaks at m/e 289 (M+ - C,oH21), 271 (289 - H,O),H,O), and 211 (247 - 2H,O), characteristic of thestigma-stane skeleton with a saturated side chain, and the twoOH functions in the fragment containing rings A, B, andC. Compound (XXXVII) was thus stigmast-5-ene-3p,7c,diol, and was proved to be the 7p-isomer by the follow-ing reactions.Oxidation of the allylic OH group in (XXXVII) bymanganese dioxide followed by acetylation gave a com-pound identical with 7-oxost igmast-5-en-3p-yl-acet ate253 (289 - ZHZO), 247 (M+ - C,,-,H,1- 42), 229 (247 -(XXX VCI I R' = H , R * = ~ - H , p-OH( X X X Y m l R'=Ac, R 2 = 0(XXXVIII) prepared from sitosteryl acetate.,, Reduc-tion of (XXXVIII) (LiAlH,) yielded stigmast-5-ene-3p,7p-diol (epi-ikshusterol) as the major product, identicalwith (XXXVII).The total number of triterpenoids isolated from thestems of L. cornea in this and our former investigationamounts to fifteen.Of these, nine belong to the tara-xerane, three to the lupane, two to the friedelane, andone to the hopane series.All four types have beenfound to be common to the other nine Hong KongLithocarpus species,l from all of which sitosterol has alsobeen obtained. However, epi-ikshusterol has not beendetected in any other species.EXPERIMENTALMass spectra were recorded with a Hitachi-Perkin-ElmerRMU-6E spectrometer, n.m.r. spectra (solvent CDCl,) with a*1 W. J. S. Lockley, D. P. Roberts, H. H. Rees, and T. W.Goodwin, Tetrahedron Letters, 1974, 3773.Hitachi R-20 (60 MHz) instrument, i.r. spectra (KBr discs)with a Perkin-Elmer 337 spectrophotometer, U.V. spectrum(solvent 95% ethanol) with a Unicam SP 8000 spectrophoto-meter, and optical rotations (solvent CHC1,) with a Belling-ham and Stanley Pepol 60 spectropolarimeter. Alumina(B.D.H. activity 11) was used for column and silica gel G(Merck) for thin-layer chromatography.Light petroleumhad b.p. 60-80". Where compounds are stated to beidentical, they were shown to be so by mixed m.p., i.r.,n.m.r., and mass spectral comparisons with authenticsamples.Extraction and Isolation of Comfiounds.-Milled air-driedstems (43.5 kg) of Lithocarpus cornea were extracted twicewith light petroleum a t room temperature for 10 days, andthe combined concentrated extracts were chromatographedon alumina (3 kg). Light petroleum eluted in successionfriedelin (3.0 g ) , m.p. 261--263", taraxerone (111) (0.02 g),m.p. 249-251°, compound (VII), plates (from light petrol-eum) (5 mg), friedelan-3P-01 (0.20 g), m.p. 285-287", andlupeol (XXXV) (0.02 g), m.p.209-211". Light petrol-eum-benzene (1: 1) eluted taraxerol (VI) (2.0 g), m.p.287-289", then a semi-crystalline mass, which after re-peated recrystallization from chloroform-methanol affordedneedles of compound (IX) (0.02 g), followed by sitosterol(0.80 g), m.p. 139-140", and finally a gummy material,which after washing with light petroleum and recrystalliza-tion from methanol yielded prisms of compound (XXIII)(0.08 8). Benzene eluted compound All (XXIX) (0.20 g)as prisms (from benzene), compound A,l (X) (0.10 g) asprisms (from methanol), compound (XXX) (0.08 g ) asplates (from chloroform-methanol), compound (XXXII)(0.04 g) as needles (from methanol), and betulin (XXXVI)(0.07 g), m.p. 253-256". Benzene-chloroform (1 : 1) elutedmyricadiol (I) (0.02 g), m.p.271-273" (frommethanol), [& +8.0" (c 0.8), M+ 442, vm,. 3 370 (OH), 3 060, 1 645, and 818cm-l (C=CH) [diacetate, m.p. 256-257", M+ 526, vmx. 1 748,1260 (OAc), 3 070, 1 640, and 820 cm-l (CzCH)], and com-pound A31 (VIII) (0.04 g) as fine needles (from chloroform-methanol). Chloroform eluted epi-ikshusterol (XXXVII)as plates (0.028 g), m.p. 221-223", [aID -20.8' (c 0.7) (lit.,3and 840 cm-l (CXH).211-214", [a]D -20.5°),3 m+ 430, Vmx. 3 410 (OH), 1670,Compownd (VII) .-Taraxer-14-ene-3P, 29-diol diacetate hadC&&4 requires M , 526), v,, 1 740, 1 730, 1 250 (2 x OAc),C,4H,40, requires M , 5263, vmx 1740, 1730, 1250(2 x OAc) 3 055, 1 650, and 820 cm-1 (eCH).Compound (VIII) . -Taraxer- 14-ene- 3p, 29-diol had m.p .298-299" (formerly reported 1 as 295-297"), [a]D +23.5"(c 0.10) (Found: M+ 442. C3,H5,0, requires M , 442), vmx.3 380 (OH), 3 056, 1 650, and 818 cm-1 (C=CH) ; diacetate,m.p.271-272" (Found: C, 77.4; H, 10.3Oj,; M , 526.Calc. for C3~H5404: C, 77.5; H, 10.3%; M, 5261, identicalwith compound (VII) .Compound (I X) .-3-Oxotaraxer- 14-en-29-yl acetate hadm.p. 198-20O0, [.ID +11.3" (c 1.2) (Found: M+, 482.C32H,,0, requires M, 482), vmx 1745, 1250 (OAc), 1715(GO), 3 055, 1 648, and 820 cm-l (C=CH).Comfiound (X) .-2 9-Hydroxytaraxer- 14-en-3-one had m.p.263-264" (formerly reported as 238-242"), [aID + 38.0"(c 0.8) (Found: M+, 440. C3,H4,0, requires M , 440), vmaX.3 550 (OH), 1 700 (GO), 3 050,l 645, and 810 cm-l (C=CH) ;acetate, m.p.197-199" (Found: C, 79.4; H, 10.4%; M ,22 R. A. Abramovitch and R. G. Micetich, Canad. J. Chem.,m.p. 271-272", [a]D +39.0° (C 0.40) [Found: M+ 526.1962, 40, 2017J.C.S. Perkin I482. Calc. for C32H5003: C, 79.6; H, 10.4%; M , 482),identical with compound (IX).Reduction of Compound (X).-Compound (X) (0.025 g)was refluxed with sodium borohydride (0.05 g) in propan-2-01(30 ml) for 2 h. The product was recrystallized frommethanol to give fine needles (0.02 g), m.p. 297-299", identi-cal with compound (VIII) [diacetate, m.p. 270-272",identical with compound (VII)].Tosylation of Compound (X).-Compound (X) (0.03 g) inpyridine (10 ml) was treated with toluene-P-sulphonylchloride (0.5 g) a t 0 "C for 24 h. The product was re-crystallized from chloroform-methanol to give plates of thetosylate (XI) (0.04 g), n1.p.201-203", v,,, 1720 (GO),1 605, 1480, 1460, 1 370, 1 170, 840, 820 (tosylate), 3 070,1650, and 820 cm-1 (C=CH); 6 7.80 (2 H, d, J 9 Hz), 7.33(2 H, d, J 9 Hz), 3.67 (2 H, s), and 2.42 (3 H, s).Reduction of the Tosylate (XI) .-Compound (XI) (0.035 g)in dry tetrahydrofuran (35 ml) was refluxed with lithiumaluminium hydride for 3 days. The product (0.02 g),m.p. 283-286" (from chloroform), [a], ZtO.0" (c 0.80),M+ 426, vmX. 3 500 (OH), 3 070, 1 650, and 820 cm-l (C=CH),was identical with taraxerol (VI) ; acetate, m.p. 301-302",vmX. 3 070, 1 735, 1 650, 1 250, and 820 cm-l, identical withtaraxeryl acetate (11).Isomerization of Cowpound (VII) in A cid.-Compound(VII) (0.025 g) was suspended in glacial acetic acid (10 ml)a t 90 "C and concentrated hydrochloric acid (0.5 ml) wasadded dropwise.The mixture was heated on a steam-bathfor 15 min. The solid gradually dissolved, and M-sodiumhydroxide was immediately added. The precipitate formedwas recrystallized from light petroleum to give fine needlesof olean-12-ene-3P,29-diol diacetate (XII) (0.02 g), m.p.207-209", [a], +51.0° (c 0.63) (Found: C, 77.65; H, 10.0%;M+, 526. C34H5404 requires C, 77.5; H, 10.3%; M , 526),vm, 1 750, 1 745, 1 250 (2 x OA4c), 3 050, 1 650, and 812cm-l (C=CH).Reduction of Methyl .Mesenabryanthemoidigenate (XVI) .-Compound (XVI) (0.10 g) was treated with lithium alu-minium hydride in ether. The product was recrystallizedfrom methanol to give plates of olean-12-ene-3P,28,29-triol(XVII) (0.08 g), (Found: A!!+, 458.Calc. for C3,H5,0,: M ,458), m.p. 288-289", [.ID $43.1" (c. 0.62), (lit.,,3 m.p.cm-1 (GCH).Partial Synthesis of the Diol Diacetate (XII) from the Trio1(XVII).-Compound (XVII) (0.07 g) in pyridine (20 ml) wastreated with toluene-9-sulphonyl chloride (0.50 g) at 0 "C for30 min. The dried oily product (0.12 g) in tetrahydrofuran(30 ml) was refluxed with lithium aluminium hydride(0.10 g) for 3 days to give a mixture of hydroxy-compounds287-289", [a]D $47.6"), V,. 3 350 (OH), 1 655, and 820Tertiary inethyl resonances (6 values) *Compound C-23 C-24 C-33 C-26 C-25 C-281).89 0.89 0.91 1 . 1 0 0.96 0.83( * I ) 0.87 ().xi ( i . ! f 2 l.llfi 0.32[TrI) 0.88 (1.88 0.91 1.10 U.!r7 0.881.1:: O.!U 1 .0 7 1.Oi 1.05 0.85(Ix) 1.1.3 11.93 1.0: 1.07 1.07 0.85 (x) 1.10 0.!)1 1.04 1.06 1.06 0.83 !$:\) 0.83 0.85 0.93 0.S6 1.11 0.83* Interpretation according lo Corbett ct al.24 and Tursch etai.26c-29 c-a00.!)1 0.960.91 u.920.9i0.960.9311.810.96(0.055 g), 3 300 cn-l, which showed 3 spots on t.1.c.This was acetylated, and the product mixture was chromato-graphed on silica gel (8 g) in light petroleum to give first23 S. Rangaswami and S. Sarangan, Tetuahdvoiz, 1969, 25, 3701.a4 R. E. Corbett, S. L). Cumming, and E. V. Whitehcad, J.C.S.Pevkiit I , 1973, 2827.P-aniyrenyl acetate (XXI) (0.025 g), m.p. 241--242*, M+468, vmx. 1745, 1655, 1250, and 812 cm-l, followed byerythrodiol diacetate (XXII) (0.012 g), m.p.185-186",M+ 626, v,, 1 750, 1 650, 1 250, and 830 cm-l, and finallyolean-l2-ene-3@,29-diol diacetate as needles (8 mg) , m.p.206-208", M + 526, v,, 1 750, 1 745, 1 650, 1 250, and 812cm-l, identical with compound (XII) .Compound (XXIII) .-22-Hydroxy-2 1aH-hopan-3-one(XXIII) had m.p. 214-215", [a], +50.0° (c 1.1) (Found: C,81.3; H, 11.3%; M+, 442. C30H500a requires C, 81.4; H,11.4%; M , 442), v,, 3 470 (OH) and 1 700 cni-1 (GO).Attempted Oxidation of the Hopanone (XXIII) .-Com-pound (XXIII) (0.015 g) was treated with Jones reagent atroom temperature. Unchanged (XXIII) (0.013 g), m.p.214-215", M+ 442, vma, 3 470 and 1 700 cm-l, was isolated.Attempted Acetylatzon of the Hopanone (XXIII) .-(a)Compound (XXIII) (0.01 g) was kept in cold acetic anhy-dride and pyridine for 3 days.The product (8 mg), m.p.214-215", was unchanged (XXIII).(b) Compound (XXIII) (0.018 g) was refluxed with aceticanhydride and pyridine for 4 h. The product affordedprisms (0.015 g), m.p. 197-199" (from methanol), [a],+83.0" (G 0.50), Mf 424, v,, 1 720 (GO) and 1 675 cm-1(GC), identical with hop-17(21)-en-3-one (XXIV).l3Dehydration of the Hopanone (XXIII) .-A solution ofcompound (XXIII) (0.04 g) in pyridine (10 ml) was treatedwith phosphoryl chloride (1 ml) a t room temperature for24 h. The product (0.035 g) showed two spots on t.1.c.(AgN03-SiO, ; CHCl,) . The mixture was chromatographedon an AgN03-SiO, column. Elution with light petroleum-benzene (4 : 1) gave needles (0.025 g), m.p. 189-190" (fromlight petroleum), [a], +63.5" (c 0.82), LW+ 424.v,, 1 700(GO) and 1650 cm-l (C=C), identified as hopenone-a(0.025 g) (XXVI) (lit.,16 m.p. 189-193", [a], +67.0°).Elution with light petroleum-benzene (2 : 3) yielded plates(0.012 g), n1.p. 204-205" (from methanol), [a], +59.3" (c0.30), M+ 424, vmZ 1 710 (GO), 3 080, 1 645, and 880 cni-l(C=CH,) identical with inoretenone (XXVII) .Hydration of Moretenone (XXVII) ; Partial Synthesis ofthe Hopanone (XXIII) .-A solution of compound (XXVII)(0.20 g) in tetrahydrofuran (40 ml) was added with stirringto a solution of mercury(I1) acetate (0.20 g) in aqueoustetrahydrofuran (1 : 1) (80 ml). The mixture was stirred at0 "C for 5 h, then at room temperature for 16 h. A solutionof sodium borohydride (0.04 g) in 3hl-sodium hydroxide(40 ml) was then added with stirring. The precipitatedmercury was filtered off and the mother liquor was satur-ated with sodium chloride.The tetrahydrofuran layer wasevaporated to dryness to yield a solid (0.18 g), which waschromatographed on alumina (10 g) in light petroleum togive unchanged (XXVII) (0.15 g). Elution with lightpetroleum-benzene (1 : 1) gave first inoretenol (XXVIII)(0.010 g), m.p. 234-236" (from methanol), [m], t30.5" (c0.30), Mi 426, vmx. 3 400 (OH), 3 080, 1 645, and 892 cm-l(CXH,), then prisms (0.012 g), n1.p. 213-215" (from meth-anol), [a], t51.0" (c 0.40), M+ 442, vmX 3 470 (OH) and1 700 cm-1 ( G O ) , identical with compound (XXIII).Methyl resoiiances (6 values)(XXIII) 1.09 1.0; (1.93 ].(I3 0.!6 0.70 1.20 1.20Compound C-22 C-24 C-23 C-?6 C-?i C-28 C-29 C-30(XXV) 7.I)H 1.02 0.93 1.02 0 .N 0.78 1.20 1.20(XXIV) 1.06 1.01 0.93 1.01 0.93 0.83 1.01 * 1.01 *(XXVII) 1.08 7.02 0.94 1.02 0.94 0.68 1.66 tPri (d, J 6 Hz). CH,=CMe.25 B. Tursch, R. Savoi, R. Ottinger, and G. Chiurdoglu,TetvaJiedifoia Letters, 1967, 5391976 29Compound (XXIX) .-14a-Hydroxytarn-3-one hadm.p. 259-261' (formerly reported as 254-256"), [aID-43.0' (c 1.1) (Found: C, 81.3; H, 11.55%; M+, 442.C30H5002 requires C, 81.4; H, 11.4%; M , 442), vmx. 3 480(OH) and 1 700 cm-l (GO).Compound (XXX) .-Taraxerane-3fi, 14a-diol had m.p.269-270", [a], -58.0" (c 0.3) (Found: C, 78.0; H, 11.7%;M f , 444. C3,H5,02*H20 requires C, 77.9; H, 11.8%; M ,444), vmx.3 450 cm-l (OH).Tertiary methyl resonances (6 values)Compound C-23 C-24 C-25 C-26 C-27 C-28 C-29 C-30(XXIX) 1.08 1.08 1.08 1.18 1.18 0.83 0.94 1.02(XXX) 0.96 0.76 0.83 1.17 1.17 0.83 0.94 1.04Reduction of the Hydroxy-ketone (XXIX) to the Diol (XXX).--Compound (XXIX) (0.05 g) was stirred with a solution ofsodium borohydride (0.05 g) in propan-2-01 (25 ml) for 4 h.The product (0.045 g) had m.p. 268-270" (from methanol),[a], -53.0" (c 0.3), v,, 3 450 cm-l, and was identical withAttempted Oxidation of the Hydroxy-ketone (XXIX) .-Compound (XXIX) (0.01 g) was treated with Jones reagentat room temperature. The product, m.p. 259-261", vmX.3 480, 1 700 cm-l, was unchanged (XXIX).Oxidation of the DioE (XXX) .-A solution of compound(XXX) (0.03 g) in pyridine (50 ml) was stirred with a sus-pension of chromium trioxide (0.10 g) in pyridine (2 ml)at O°C for 3 h, then at room temperature for 12 h.Theproduct was extracted into benzene and recrystallized fromchloroform-methanol to give prisms of the hydroxy-ketone(XXIX) (0.02 g), m.p. 258-260", [a], -41.0" (c l.O), vmx.3 480 and 1 700 crn-l.Attempted Acetylation of the Hydroxy-ketone (XXIX) .-(a) Compound (XXIX) was kept a t room temperature inacetic anhydride and pyridine for 2 days. The product,m.p. 258-260", was unchanged (XXIX). (b) Compound(XXIX) (0.05 g) was refluxed with acetic anhydride andpyridine for 3 h. The product was separated by preparativet.1.c. [AgNO,-SiO,; C,H,-CHC1, (1 : 3)] into fi-amyrenone(XV) (0.25 g), m.p.179-181", M+ 424, v,,, 1720 (GO),1 660, and 818 cm-l (C=CH), and taraxerone (111) (0.013 g),m.p. 248-250", M f 424, vmax 1 720 (GO), 3 055, 1 645, and820 cni-1 (C=CH).Attempted Acetylation of the Diol (XXX) .-Compound(XXX) (0.03 g) was refluxed with acetic anhydride and pyri-dine for 3 h. The product was separated by preparativet.1.c. (AgN0,-50,; C6H6) into P-amyrenyl acetate (0.015g ) , m.p. 240-241", M+ 468, umx. 1 740, 1255 (OAc), 1660,and 820 cm-l (C=CH), and taraxeryl acetate (11) (8 mg),m.p. 303-304", Air+ 468, vmX 1740, 1255 (OAc) 3 060,1 645, and 820 cm-l (C=CH).Dehydration of the Hydroxy-ketone (XXIX) to Taraxerone(III).-Compound (XXIX) (0.05 g) was refluxed with phos-phoryl chloride (0.2 ml) and pyridine (25 ml) for 2 h.Theproduct on recrystallization from light petroleum affordedprisms of taraxerone (111) (0.035 g), m.p. 248-249", M+ 424,vmx 3 055, 1 720, 1 646, and 820 cm-l.1 4 ~ , 155r-~poxytaraxeran-3p-yZ Acetate (XXXI) .--Tara-xeryl acetate (11) (0.08 g) in chloroform (30 ml) was treatedwith freshly purified zn-chloroperbenzoic acid (0.11 g) a t 0 "Cfor 18 h. The product on recrystallization from chloro-form-methanol yielded needles of 14a, 15a-epoxytaraxeran-3fi-yl acetate (XXXI) (0.065 g), m.p. 254-257", [a], +43.0(c 0.92) (lit.,17 m.p. 257-260", [a], +47'), iMf 484, v,,1 740, 1 250 (OAc), 890, and 870 cm-l (epoxide ring).(XXX).RedzLction of the Epoxide (XXXI) .-Compound (XXXI)(0.05 g) was refluxed with lithium aluminium hydride(0.03 g ) in tetrahydrofuran (25 ml) for 3 days.The producton recrystallization from methanol gave prisms of tara-xerane-3[3,14a-diol (0.03 g), m.p. 268-269', M+ 444,vmx. 3 450 cm-l (OH), identical with (XXX).Compound (XXXII) .-Lup-20 (29)-ene-3/3,2 7-diol hadm.p. 214-215", [a], +67.0° (c 0.52) (Found: C, 78.5; H,11.4%; M+, 442. C,,H5OO2, H,O requires C, 78.2; H,11.4%; M , 442), v- 3 500 (OH), 3 075, 1 650, and 885cm-1 (CZH,).Tertiary methyl signals (6 values)Compound C-23 C-24 C-26 C-26 C-27 C-28 C-30(XXXII) 0.97 0.77 0.85 1.05 0.80 1.68\XXV) 0.97 0.77 0.84 1.05 0.97 0.80 1.68XXXVI) 0.98 0.77 0.83 1.02 0.98 1.68Acetylation of the DioE (XXXII) .-Compound (XXXII)(0.03 g) was treated with acetic anhydride and pyridine atroom temperature for 7 days.The product on t.1.c. gavetwo spots. It was fractionally recrystallized from chloro-form-methanol t o give the major product in the less solublefractions as plates of the 3-monoacetate (XXXIII) (0.019 g),m.p. 287-289", [a], +93.0" (c 0.4) (Found: Mf, 484.c3$&203 requires M , 484), vmx. 3 575 (OH), 1740, 1250(OAc), 3 050, 1 660, and 890 cm-l (CzCH,). The filtrates onconcentration deposited a solid which on repeated re-crystallization from light petroleum afforded needles of thediacetute (XXXIV) (5 mg), m.p. 249-250", [a], +73.0' (c0.20) (Found: M+, 526. C34H5404 requires M , 526), vmX1 750, 1 745, 1250 (2 x OAc), 3 080, 1 645, and 892 cm-1(C=CH,).LupeoE (XXXV) from the Monoacetate (XXXIII) .-Com-pound (XXXIII) (0.015 g) in pyridine (20 ml) was refluxedwith toluene-p-sulphonyl chloride (0.02 g) for 24 h.Thedried oily product (0.023 g) was then refluxed with lithiumaluminium hydride (0.05 g) in tetrahydrofuran (20 ml) for3 days. The purified product (0.01 g), m.p. 205-207', M+428, v,, 3 360 (OH), 3 080, 1 640, and 880 cm-l (C=CH,),was lupeol (XXXV) ; acetate, m.p. 219-220', vmx. 3 080,1 740, 1 645, 1 250, and 880 cm-l.Oxidation of Stigmast-5-ene-3p,7p-cliol (XXXVII) withManganese Dioxide followed by Acety1ation.-Compound(XXXVII) (0.02 g) was stirred a t room temperature with asuspension of manganese dioxide (0.50 g) in chloroform(25 ml) for 2 days. The oily product was treated with aceticanhydride and pyridine at room temperature for 2 days t ogive needles of the ketone (XXXVIII) (0.013 g), m.p.(C=C-C=O), 1735, and 1270 cm-l (OAc), A,, 240 nm( ~ 1 4 000).7-Oxostig~nast-5-en-3/3-yl Acetate (XXXVIII) from Sitos-teryl Acetate.-Sitosteryl acetate (0.2 g) in glacial aceticacid (10 ml) containing sodium acetate (0.2 g) was warmedt o 60 "C, and chromium trioxide (0.2 g) in glacial aceticacid (10 ml) was added. The mixture was kept a t 60 "C for5 h. The product (0.2 g) was chromatographed on alu-mina (20 g) t o give unchanged sitosteryl acetate (0.08 g),m.p. 126-128", followed by 7-oxostigmast-5-en-3[3-y1acetate (0.09 g), m.p. 175-176", iW+ 470, vmx. 1 680, 1 640(C=C-C=O), 1 735, and 1270 cm-l (OAc), identical withReduction of the Ketone (XXXVIII) .-Compound(XXXVIII) (0.05 g) was refluxed with lithium aluminium174-176", [a], -10.6" (C 0.72), M+ 470, vmS. 1680, 1640(XXXVIII)30 J.C.S. Perkin Ihydride in ether for 3 h. The product was purified by pre- We thank Dr. L. G. Matyukhina, Leningrad State Uni-parative t.1.c. (SiO,) to give the major product (0.026 g), versity, for authentic samples of myricadiol and its diace-m.p. 220-222" (from chloroform-methanol) , [a], - 20.8" tate, and the Committee on Higher Degrees and Research(G 0.70) vmx. 3 410, 1 670, and 840 cm-l, identical with Grants, University of Hong Kong, for financial assistance.(XXXVII) . [6/1098 Received, 6th June, 1976