346 Short Reports

21), 459 (lH, m, H-3), 5 10 (lH, m, H-20), 542 (lH, m, H-6) REFERENCES
Compound 7, powder. mp 262-265’, EIMS m/i 414
PW,,H,,~dl+ Lg.91 Itokawa, H, Xu, J P and Takeya, K (1987) Chem Pharm
Reductron of 3 wnh NaBH, NaBH, (1 mg) was added to a Bull 35, 4524
soln of 3 (2 mg) m MeOH, and the mixture stlrred for 5 hr at Itokawa, H ,Xu, J P, Takeya, K ,Watanabe, K and ShoJI, J
room temp The reactlon mixture was treated rn the usual way to (1988) Chem Pharm Bull 36, 982
yield 1 (07 mg\ Itokawa, H , Xu, J P and Takeya, K (1988) Phytochemrstry
Acetomdec o/ 1 and 2 Each sample (3 mg) was stirred with p- 27,1173
TsOH (1 mg) m Me,CO (1 ml) for 10 hr at room temp The Itokawa, H ,Xu, J P and Takeya, K (1988) Chem Pharm
reactIon mixture was poured mto H,O and extracted with Et,0 BulI 36. 2084
The Et?0 layer was washed with satd NaHCO, soln, dried with Itokawa, H , Xu, J P and Takeya, K (1988) Chem Pharm
Na,SO, and coned to yield 8 and 9, respectively Compound 8, Bull 36,4441
‘H NMR (CDCI,) S 102 (3H, s, Me-l@, 1 07 (3H, s, Me-19), 1 37, Kasal. R, Sakuma, S, Kawamshl, S and ShoJl. J (1972)
147 [3H x 2, 5, C(Me),], 3 42 (3H, s, OMe), 3 51 (lH, m, H-3), Chum Pharm Bull 20, 1869
354 (2H. m, CH,-21). 4 13 (1H. dd, J=76, 28H~, H-20), 542 Sakuma, S , Ishlzone, H , Kasal, R, Kawamshl, S and Shop, J
(lH, m, H-6) Compound 9, ‘H NMR (CDCI,) j 105 (3H, s, Me- (1971) Chem Pharm Bull 19, 52
18), 1 14 (3H, \, Me-19). 1 37,t 43 (each 3H, 7. C(Me),), 3 38 (3H, Golab, T, Jager. H and Reichstem. T (1963) H&I Chrm
s, OMe), 341 (!H,dd,J=104.8 3 HI. Ha-21), 3 53 (lH,m. H-3), Acra 46, 9
355(1H,dd,./=104,20Hz,Hb-21),416(1H,dd,J=83,20Hz, Yoshu, E , Kolzuml, T, Ikeshlma, H , Ozakl, K and Hayashl,
H-20), 5 16 (1H. m, H-15). 541 (lH, m, H-6) 1 (1975) Chem Pharm Bull 23, 2496

003194??,90$300+000
(‘ 1989Pergdmon
Press
plc

SCORAZANONE, A LAZA-ANTHRAQUTNONE FROM GONZOTHALAMUS

SCORTECHINII

L~ILY BIN DIN.STEWN M COLEGATE* and DZIILKIFLIA RAZAht

Department of Chemistry. Umveraltl Kebangsaan Malaysia, 43600 UKM. Bangl, Malaysia. *School of Vetermary Studies. Murdoch
Umverslty Murdoch. Western Austrahd. 6154. tSchoo1 ofPharmxeutlca1 Science\, IJnwersltl Sams Malaysia. 11800 USM, Mmden,
Malaysld

Kq Word Index Gonrothularnusacorfrchrnu. Annonaceae, scorazanonc. I-ara-anthrdqumone, 2.3-dtmethoxy-4-

hydrouq-ben7o~~g]qumohne-9.lO-dlonr

___.-- -
Abstract- roots of Gorzrorhalarnus scortechum.
The ;l~r dried collected m Malaysia, yielded a new I-aza-anthraqumone,
scoraranone, which was ldentlfied usmg spectroscopic techniques
___-___-

Scorazanone (1) was isolated from petrol extracts of roots monoacetate which demonstrated the appropriate mol-
of Gonzothularnus scortechwr and ldentlfied as 2,3-ch- ecular Ion peak at m/z 327
methoxy-4-hydrnxybenzo[g]qumolme-9,lO-dlone on the The 300 MHz ‘H NMR spectrum showed four coupled
basis of Its spectroscopic data. Scorazanone IS readily aromatic protons mdlcatmg the orrho-dlsubstltuted ben-
soluble m aqueous alkalme solution, msoluble m aqueous zene entity The two lower field aromatrc signals
acid solution and Its yellow spot on TLC turns pmk/pur- (68 2--8 4) Indicate that their respective protons are each
pie on exposure to ammoma vapour affected by a prrl carbonyl as shown m partial structure 2
Only 17 ‘-‘CNMR signals were resolved but the There IS ample precedent m the hterature for this asslgn-
WRMS mlphcd a moleculnr formula ofC,,H,,NO, The ment. For example. H-5 and H-8 of clelstophohne (3)
fragmentatron pattern of the EI mass spectra afforded resonate at is8 25 and 8 35 [I] whereas H-5 and H-8 of the
evidence for the methoxyl substnuents and for the qum- acrldone, arbormme, (4) resonate at 6x7 8 and at 8.23
onold entity Acetylatlon of the compound yielded a respectively 121 The ‘%I NMR spectrum supports par-
 Short Reports 347

teal structure 2 m that four methme carbons are observed

at 6135 0, 134 2, 127 8 and 126 6. This chemical shift OMe
pattern IS very stmtlar to that observed for cleistopholine
[l] and for simtlar anthraqumone compounds [3]
The non-eqmvalence of the methoxy substttuents 1s OMe

evident from the difference m their ‘HNMR chemical

shifts (64 05 and 4.22) and their r3C NMR chemical shifts
(654.95 and 60.91) and supports the suggestton that one
methoxy is adjacent to the nitrogen atom The ‘H
resonance srgnal at 64 05 IS m good agreement wrth that
of a stmtlarly placed methoxyl substttuent m the phomaz-
arm-related I-aza-anthraqumone (5) whtch occurs at
fi 3.96 ppm [4]
The hydrogen-bonded relatronshtp of the hydroxyl
substttuent (6 12.5) to one of the carbonyls was imphed by
the IR spectrum whrch clearly shows carbonyl absorp-
ttons at 1690 and 1640 cm- ’ mdrcattve of a free carbonyl 2
and a hydrogen-bonded carbonyl respectively. Thts ob-
servatton, when taken m constderatton with parttal struc-
ture 2, imphes either the l-aza-anthraquinone (1) or the 2-

& \
aza-anthraqumone (6) structure for scorazanone. Sup- Ott
port for structure 1 1sderived from the 13CNMR spec- Ok
trum whtch shows a quaternary carbon srgnal at S 142 48
whrch IS conststent wrth an aromatic ring junction carbon
directly bonded to a mtrogen atom (C-9a). This IS demon- 7 ’ OMe McO

strated by 8-0-methylbostrycotdm (7) and the phomazar- tie

m-related compound (5) m whtch C-9a resonates at 6 125
[S] and 143 7 [6] respecttvely 4
Further support for the 1-aza-anthraqumone structure
(1) ISoffered by the htgh resolution mass measurements of
two fragment Ions m the mass spectrum The ions at m/z
171 0327 and 143 0370 correspond well wrth the expected 0 OR’ OH 0
masses for C,,H,NO, and C,H,NO respectively. Such Me0 Me
OMe
tons can only be reasonably dertved from a l-aza-
anthraqumone structure. The alternative fragment tons
dertved from a 2-aza-anthraqumone structure would be
expected at m/z 171 0446 (C,,H,O,) and 143 0497
(C,,H,O) Thus, based upon spectroscoptc properttes
and compartson of these properttes wtth those of simtlar 6a R’ = H, R’ = Me
7
compounds, scorazanone was assigned the l-aza-anthra- 6b R’ = Me, R’ = ti

qumone structure (1)

EXPERIMENTAL

The 300 MHz ‘H and 20.1 MHz 13CNMR spectra were C,,H,NO, reqtnres 171 0320, C,H,NO reqmres 143 0371 and
recorded at the Orgamc Chemistry Department of the Umver- C,H,O reqmres 129 0340 13C NMR (CDCI,) 6 189 0 (s, qumon-
slty of Western Austraha Low and high resolution mass spectra old C-9 and C-lo), 161 3 (s, C-2), 158 9 (s, C-3 and C-4), 142 5 (s,
were recorded at the Department of Chemistry of the Australian C-9a), 135 1 (d, C-6 or C-7), I34 2 (d, C-7 or C-6), 133 1 (s, C-8a or
Natlonal Umverslty Kleselgel 60 G (Merck) was used as the C-lOa), 132 3 (7, C-1Oa or C-8a), 127 8 (d, C-5 or C-8), 126 7 (d, C-
adsorbent for TLC and for radial chromatography. Slhca gel 8 or C-5), 60 9 (4, C-2-OMe), 54.9 (q, C-3-OMe). ‘HNMR
7734 (7&230 mesh ASTM) was used as the adsorbent for CC (CDCI,) S 12 47, I-H, s (C-4-OH), 8 29-8 34 (lH, m, H-5 or H-8,
M p corr. GanX&&m~. V0&?crhmI%was c&X&d at !&d&I m 8 U-8 28 (1% m, H-8 or H-5), 7 79-7 87 (2H, 5 H-6 and H-7>
northern Malaysia and the roots were air-dried before ex- 4 22 (3H, s, C-2-OMe), 4 05 (3H, s, C-3-OMe) EIMS, m/z 285 (M,
tractlon A voucher specimen of the plant was deposlted at the lOO%), 284 (26), 270 (37), 267 (I), 257 (4), 256 (22), 254 (16), 242
Herbarmm, School of Blologlcal Sciences, Umversltl Sams Mal- (19), 238 (16), 226 (9), 171 (24), 143 (3), 129 (9), 115 (12), 114 (9).
aysla, I 1800 Penang, Malaysia Petrol used for chromatography IR vKBr 1693 (m), 1644 (s), 1589 (m), 1556 (m), 1476 (m), 1351 (s),
and for extractlons refers to the fraction 4&6Q 1301 (s) Acetylatlon of scorazanone, with Ac,O and pyndme,
Exrractron of%omothalamus scortechmn. The air-dried roots ylefded a monoacetate as a pale yellow oil. ‘HNMR (CDCY,)
of G scortech~nrr (340 g) were extracted m a Soxhlet with petrol 8.25-830 (lH, m, H-5 or H-8), 8 16821 (lH, m, H-8 or H-
for 72 hr Evaporation of the petrol extract afforded a waxy, 5),7 70-7 80 (2H, m, H-6 and H-7), 4 26 (3H, s, C-2-OMe), 4.01
brown gum (3 4 g) CC, usmg petrol and EtOAc mixtures as the (3H. F, C-3-OMe); 2 55 (3H, AC). EIMS, m/z 327 (M, 1 6%), 285
eluent, yielded a yellow sohd (10 mg) which was further purified (100). 284 (20). 270 (40). 256 (25), 239 (28), 226 (12), 171 (22).
usmg radial chromatography with petrol-CHCl, mixtures as the
eluent. Recrystalhzatlon from Et,0 yielded yellow needles Acknowledgements-The authors wish to thank Dr L Byrne
(6 mg) mp 205 5-206 5” HRMS found m/z 285 0638. 1710327, (Umverslty of Western Austraha) for recordmg the NMR spectra
143.0370 and 129 0340 C, ,H, ,NO, reqmres 285.0637, and Dr J MacLeod (Austrahan Natlonal Umverwty) for the
348 Short Reports

mash spectra Identlficatlon of the plant was done by Dr A Latiff 2 Pakrashl. S C and Roy, S K (1961) Chm fnd, 464
(Botany Department, Um\ersltl Kebangsaan, Malaysta) This 3 Berger, Y and Castonguay. A (197X)Or</ M~lcjn Rmm 11.
work waq supported by the Network for Blologlcally Important 375
Natural Products 4 Birch, A J, Butler, D N , Effenberger, R , RIckaIds R W ‘tnd
Simpson, T J (1979) J Chem Sot PerLm I, 807

5 Steyn, P S and Wessels, P L (19791 fetrczhcciron 35. IS51

REFERFVCES
6 Birch, A J and Sampson T J (1979) .I (‘hem So<, PwLm I.
1 Waterman, P G and Muhammad, I (1985) Phytothrmrstr) 816
24, 523

A DIHYDROBENZOFURAN LIGNAN FROM CROTON ERYTHROCHILC'S

Lee A c’ PIETFRS. DIRK A VANDEN BERCHE and ARNOLII J VmrlhcK

Department of Pharmaceutical Sciences. I;ntcerslty of Antwerp (UIA). Unlverstteltsplem I, B-2610 Antwcrp Bclg~uu

Kej Word Index---Cm/on et vrhroclt~h, Euphorblaceae, Sangre de Drago, dlhydrobcnlofuran hgndn 4-O-
mcthyldlhydrodehydrod~comferyl alcohol, 3’,4-0-dlmethylcedrusm, 2-(3’,4’-dtmethoxyphenyll-?-h!dr~~,xqmethyI-
2,3-dlhydro-7-methoxybenzofuran-j-n-prupnnol

AbstractmmmAnew dlhydrobenzofuran hgnan, 4-U-methyldlhydrodehydrodlcomferyl alcohol, 3’,4-O-dlmethylccdrusln

or 2-(3’,4’-d~methoxyphenyl)-3-hydroxymethyl-2,3-d~hydro-7-methoxybenzofuran-~-~~-prop~~n~~l, was Isolated from
Sangre de Drago, prepared from Croton evJthrochl/us
_~____ ---.- ~~. --.-.- __~_~.~

‘Sangre de Drago’ or ‘Sungue de Drago’, a blood-red latex doublet at ii5 57 (J = 7 8 Hz) The H-8 multlplet occurs at
produced by different plants, mcludmg Croton snlutur~s, 6 3 62, and the two proton signal of the hydrox ymcthg lene
D~LIUKW~ dram, Croton erJ~throchllus and Croton dracon- group (H-9) at 3 94 These values arc characterlrtlc for a
o&s, also known as Croton palanost~ymu, IS largely used trnns H-7. H-8 stereochemlstry of dlhydrobenLufuran
m tradItIona medlcme for wound heahng [l, 21 A hgnans The presence of a 9-hydroxymethyl group and
‘Sangre de Drago’ preparation from C er~~throchrlus, a the truns-stereochemistry are confirmed b\i the character-
native of Peru, 15 marketed m that country Because istic ‘%NMR slenals of C-7 (nX7 71, C-d (53 7) and C-9
plants beloigrng to the genus Croton (Euphorblaceae) are (63 9) The ‘“C NbR signals of C-7’. C-X’ and c-0’ of the
known to contain co-carcinogenic dlterpene esters [3], n-propanol side chain occur at 1534h. .31 0 and 62 3.
this commerclnl prep‘lratlon was mvestlgated No dlter- respectively Taking a half-&au conformatlon for the
pene esters were found. but a new dlhydrobenzofuran dlhydrobentofuran moiety Into conslderdtlon, the con-
hgnan, 4-O-methyldlhydrodehydrodlcomferyl alcohol, former with both the aryl and the h!dro\ymethyl groups
3’.4-O-dlmethylcedrusm or 2-(3’.4’-dlmethoxyphenyl)-3- m dn equatorial orlentatlon IS preferred over the ccln-
hydroxymethyl-2.3-dlhydro-7-methoxy~benzofuran-5-n- former with an axial orlentatlon [7 Y] The proposed
propanol (l), was Isolated and identified This compound structure was confirmed bl mass spectrometry BeaIdes
hds not been reported before as a natural product the molecular Ion, Important fragment Ions wcrc found
Dlhydrodehydrodlcomferyl alcohol, cedrusm and their 4- by losses of OH, H,O. CH,O. HZ0 t Mc and H,O
0-glucosldes were isolated prevrously from Cedrus de- + OMe neutral fragments The LTV specttum M~S m
odtrrrr (or PUUIS dcodara) [4], and cedrusln-4-O-glucoslde agreement with pubhshed d,~ta for cedruqm L4] The
from PUIU, ~yl~atns [S] and Pn2u.s contorta [S] blologlcal actlvlty of this new dlhydrobenzoful,+n hgn,m
The ‘H and ’ 3C NMR spectra of 4-O-methyldlhydro- 1s under mvestlgatlon
dehydrodlcomferyl alcohol are very slmllar to those of
dlhydrocarmatmol, which has a 8’,9’-double bond The
EXPERIMEhTAI
‘H NMR spectrum of our compound revealed the pres-
ence of five aryl protons, three methoxy groups, and an n- ‘Sangre de Drago’ was purchd\ed In Lm~a. Peru f‘recrc-
propanol stde chain. The H-7 produces a charactertstlc drymg of 272 5 g Sangrr de Drago >Iclded -!Og of rc\tnou\