Grosulfeimin and new related guaianolides from cynara scolymus L.

GROSULFEIMIN ANO NEW RELATEO GUAIANOLlOES FROM CYNARA SCOL YMUS L. P. Ba be i*, l. Chiappini, G. Fa della, G. G andolini * Is i u o di Chimica Fannaceu ica e Tecnica Fannaceu ica Uni e si a di Pe ugia -Via del Liceo 1,06100 Pe ugia -ITALY Abs ac : Th ee new guaianolides 11-H-13- ne hylsul onylg oshei nin 5 (G osul ei nin), 8-deoxy-11, 13-dihyd oxyg osheimin 7 and 8-deoxy- 11-hyd oxy-13-chIo og osheimin 8 ha e been isola ed o n he lea es o Cyna a scolymus L. Besides, 8-epig oshei nin 9 has been isola ed o he s ime o n his sou ce. The s uc u es we e de e nined by spec oscopical ne hods and by che nical co ela ions. Key wo ds: Cyna a scolymus L., sesqui e pene lac ones, sul onyl guaianolides, guaianolides. INTRODUCTION S i nula ed by he g owing in e es in biologica1ly ac i e sesqui e pene lac ones o n Co nposi ae, pa icula ly in hei cy o oxic ac i i ies [1-4], so ne in es iga ions ha e been ca ied ou on Cyna a scolymus L. leading o he isola ion and che nical elucida ion o he ollowing guaianolides: cyna opic in 1, [3,5], 3-dehyd ocyna opic in 2, g oshei nin 3 [3,6-10], cyna olyde [11] and cyna o iol 4 [12]. Mo eo e , so ne analy ical p ocedu es o he quan i a i e de e nina ion o hese lac ones in a ichoke ha e been poi i ed ou [13]. RESULTS AND DISCUSSION In he cou se o ou s udies on he I alian lo a [14-17] we ha e now isola ed o n he lea es o Cyna a scolymus L. h ee new guaianolides, iden i ed as 11-H -13- me hylsul onylg oshei nin 5 in he ne hanol ex ac , 8-deoxy-11-hyd oxy-13- chlo og oshei nin 8 and 8-deoxy-11, 13-dihyd oxyg oshei nin 7 in he chlo o o n 433 ex ac o The known 8-epig osheimin 9, p e iously ob ained om C epis i ens [17], was also isola ed and cha ac e ized. Compound 5, name1y G osul eimin, is o be conside ed an unusual na u al p oduc , being known in he li e a u e he sole case oí he isola ion o he me hylsul onylguaianolide Sul e alin om Helenium au umnale [18,19]. The s uc u es o 5,7 and 8 we e de e mined on he basis o hei elemen al analysis, IR, MS, lH-NMR (200 MHz) and 13C-NMR (50.32 MHz) spec a. These we e con mned, o g osul eimin 5, by chemical co ela ion wi h g osheimin 3 ia ll-H-3-me hylsul ideg osheimin 6 (see scheme) and, o he compounds 7 and 8, by spec oscopical da a o hei pa en compounds ob ained by ace yla ion (7a, 8a) and by ace onyla ion (7b) (see ables 1 and 2). Iden i ica ion o 9 was achie ed by di ec compa ison o an au hen ical sample o 8-epig osheimin om C epis i ens [17]. Repea ed ch oma og aphic sepa a ions o he CHC13-soluble ex ac (29.8 g) and o he MeOH-soluble ex ac (10.8 g) om he lea es o Cyna a scolymus L. we e ca ied ou on silica gel columns by means o no mal andlo lash ch oma og aphy echniques using he eluen s: CHC13 ---> CHC13/MeOH=70/30, and moni o ing by TLC (silica gel pIa es), eluen s: CHC13/MeOH=95/5 ---> 70/30, phosphomolibdic eagen and H2S04 10% as sp ay de ec o s. I �o o l'Me 434 14 C�o R, I RZ 1 OH H I O o CO llXIo R, I RZ R3 R4 RS I R6 � O H OH =CH2 i OH H H H OH CHZOH 4a OAc H H H OAc CHZOAc � O H OH H CHZSOZCH3 §. O H OH H CHZSCH3 I O H H OH CH20H la O H H OAc CHZOAC lb O H H OoC(CH3)200 � O H H OH CHZ Cl 8a O H H OAc CHZCl .? O OH H =CHZ 435 Table 1 H1 H6 H8 H13 8 H14 H15 o he s· �. b 3.19 4.00 6.31d(2) 5.11 s 1.17 1 d(8) d(10) 3.92 m d(8) -------- d(8) d(10) 6.38d(2) 4.87 s d(2) 4.28 3.89 5.04 s 1.12 i 3.15 ID d(10) 4.10 ID d(4) d(7) 3.20 s d(10) 3.94 4.86 s . d(4) 3.45 4.30 d(3) 5.10 s � 3.20 ID d(10) 4.03 m d(9) 1.20 2.15 s d(10) 3.69 4.75 s d(7) . d(3) d(9) 4.35 3.58b s 4.98 s I 3.15 m d(10) 2.1·2.2 m 1.18 ======== d(10) 3.58b s 4.70 s d(7) 4.15 4.38b d(5) 5.12 s 2.05 s 78 3.25 m d(10) 2.2·2.3 m 1.20 d(10) 4.44b d(5) 4.88 s d(7) 2.12 s + 4.17 3.3Od(4) 5.10 s 1.36 s+- 7b 3.30 m d(10) 2.1·2.2 m 1.22 d(10) 3.26d(4) 4.87 s d(8) 1.59 s ... 4.20 3.64b s 5.06 s ª 3.25 m d(10) 2.1·2.2 m 1.23 =======.=== d(10) 3.64b s 4.69 s d(7) 4.18 3.89b d(5) 5.09 s 8a 3.30 m d(9) 2.3·2.4 m 1.21 2.08 s � d(9) 3.78b d(5) 4.80 s d(8) 4.57 6.40 s 5.08 s ! 3.25 m d(10) 4.08 m 1.27 ===:::===== d(10) 5.67 s 4.85 s d(6) lH•NMR o c� i. � L lJ!. 1!!, ª' � ! a 200 MHz, C""". 1 a 400 MHz. Sol en CDCl3• In pa en heses cQ<4)l ing cons an s in Hz. 436 Table 2 }[18J 48[12J eOlll'. 1 � I � § � i e· 15 15.0 q 18.0 q 15.2 q 14.7 q 14.8 q 14.2 q 14.1 q 15.9 q 16.2 q e·8 73.2 d 27.5 72.6 d 73.0 d 33.3 31.6 30.5 32.7 71. 6 d .¡::.. <..J 00 e·6 83.3 d 79.9 d 63.5 d 84.0 d 82.8 d 82.5 d e·14 114.4 113.1 115.1 114.7 116. S 115.3 e·13 124.5 62.7 48.0 26.3 61.9 65.4 e·11 138.7 S 79.7 s 49.1 d 48.5 d 78.1 s 81.4 s e·10 14S.4 S 148.7 S 145.6 s 146.2 s 147.0 s 148.1 s 169.1 S 165.7 S eH3' O :::===:= 164.4 S ------ - ----- ------ 170.9 S 169.9 S e ·12 170.3 s 171.7 s 170.4 S 171.3 s 173.2 s 175.0 s C·3 218.7 s 84.4 d 218.9 S 218.4 s 215.8 S 216.4 s 13C'NMR (50.32) o c�und. !!.[12]. � � L lJ!, l!., !!i!., � ;n COCl3, CClll'p. 1[18] ;n Py oS' 82.3 d 83.0 d 83.6 d 112.9 114.2 116.0 52.7 54.8 122.S 76.8 s 82.3 s 144.0 s 148.3 s 149.2 S 136.4 S . ------ 168.3 S ====== 175.8 s 176.6 s 170.8 s 218.3 s 218.0 s 220.S s ACKNOWLEDGEMENTS: The au ho s a e g a e ul o M . 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