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Grosulfeimin and new related guaianolides from cynara scolymus L.

Barbetti, P.,Chiappini, I.,Fardella, G.,Grandolini, G. · 1991

Abstract

Three new guaianolides 11-H-13-rnethylsulfonylgrosheirnin 5 (Grosulfeirnin), 8-deoxy-11, 13-dihydroxygrosheimin 7 and 8-deoxy-11-hydroxy-13-chlorogrosheimin 8 have been isolated from the leaves of Cynara scolymus L. Besides, 8-epigrosheirnin 9 has been isolated for the ftrst time frorn this source. The structures were deterrnined by spectroscopical rnethods and by chernical correlations.

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Grosulfeimin and new related guaianolides from cynara scolymus L.

Author: Barbetti, P.,Chiappini, I.,Fardella, G.,Grandolini, G.
Publisher: Universidad de Granada, Facultad de Farmacia.
Year: 1991
Source: https://digibug.ugr.es/bitstream/10481/83584/1/Ars%20Pharm.%201992%3b33%281-2-3-4%29_433-439.pdf
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 . Cos an ino Mo iconi o his echnical assis ance.
This wo k was suppo ed by he Minis e o della Rice ca Scien i ica e Tecnologica
(M.U.R.S.T.) o I aly.
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