Gossypidien, a lignan from stems of Jatropha gossypifollia

Article abstract of DOI:10.1016/S0031-9422(98)00727-4

A new lignan, gossypidien, has been isolated from the stems of Jatropha gossypifolia. The structure of the compound was deduced from its spectral data, as well as from its synthesis.

Full text of DOI:10.1016/S0031-9422(98)00727-4

\
PERGAMON
Phytochemistry 40 "0888# 004Ð006
0
Gossypidien\ a lignan from stems of Jatropha `ossypifollia
Biswanath Dasꢀ\ G[ Anjani
Organic Chemistry Division!I\ Indian Institute of Chemical Technology\ Hyderabad\ 499 996\ India
Received 16 October 0887
Abstract
A new lignan\ gossypidien\ has been isolated from the stems of Jatropha `ossypifolia[ The structure of the compound was deduced
from its spectral data\ as well as from its synthesis[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
Keywords] Jatropha gossypifolia^ Euphorbiaceae^ Stems^ Lignan^ Gossypidien
0[ Introduction
"d 6[71\ s\ H!6 and H!6?# and six aromatic protons "d
[96!5[88\ m\ H!1\ H!4\ H!5\ H!1?\ H!4? and H!5?#\ along
6
Jatropha `ossypifolia\ a small shrub\ grows wild in
di}erent parts of India "Sastri\ 0848#[ This plant exhibits
various important medicinal "Sastri\ 0848^ Das + Das\
883# and pesticidal properties "Sastri\ 0848^ Chatterjee\
Das\ Adityachaudhury\ + Debkirtaniya\ 0879#[ Previous
workers reported several diterpenoids "jatraphone
Kupchan et al[\ 0869^ Kupchan\ Sigel\ Matz\ Gilmore\
Bryan\ 0865# and its analogues "Taylor et al[\ 0872#\
jatropholones A and B "Purushothaman et al[\ 0868#
and jatrophatrione "Rahman\ Ismail\ + Yin\ 0889## and
lignans "jatrophan "Chatterjee\ Das\ Pascard\ + Prange\
with two methylenedioxy "d 4[87\ 3H\ s#[ The deshielded
ole_nic protons "H!6 and H!6?# indicated "Chatterjee et
al[\ 0870^ Banerji et al[\ 0873# the trans "E# con_guration
0
2
0
for two double bonds at C!6\ C!7 and C!6?\ C!7?[ The C
NMR spectrum showed the signals for only 00 carbons
present in the half portion of the molecule[ These signals
revealed the presence of six aromatic carbons\ one tri!
substituted double bond\ one methylenedioxy and one
carbomethoxyl group "vide Section 2#[ Structure 0 incor!
porates all the spectral features of the new lignan\
gossypidien[
"
+
0
0
870#\ gadain "Banerji\ Das\ Chatterjee\ + Schoolery\
873# and their analogues "Chatterjee et al[\ 0877## as
The structure of gossypidien "0# was settled unam!
biguously by synthesis starting from piperonal "1#
"Scheme#[ Stobbe condensation of 1 with dime!
thylsuccinate in the presence of sodium methoxide in
methanol\ a}orded compound 2[ Its H NMR spectrum
showed the presence of a deshielded vinylic proton at d
its major constituents[ We have recently isolated a new
lignan\ gossypidien "0# from the stems of this species[ The
structural elucidation and synthesis of the compound are
reported here[
0
6
0
[61 indicating "Chatterjee et al[\ 0870^ Banerji et al[\
873# the trans "E# con_guration of the ole_nic double
1
[ Results and discussion
bond[ Compound 2 was methylated with diazomethane
to form the diester 3[ A second Stobbe condensation of
Gossypidien was isolated as pale yellow crystals[ Its
3
with piperonal produced compound 4[ The trans "E#
¦
mass spectrum showed the ðMŁ at m:z 309 in accordance
with the molecular formula C H O [ The molecule pos!
sesses no optical activity[ The IR spectrum "nmax\ cm
con_guration of both the ole_nic double bonds present
in 4 was evident "Chatterjee et al[\ 0870^ Banerji et al[\
1
1
07
7
KBr
−0
]
0
873# from the appearance of two deshielded vinylic pro!
0691\ 0599 and 0378# indicated it to be an aromatic com!
0
tons at d 6[70 and 6[68 in its H NMR spectrum[ Com!
pound 4 was _nally methylated to form a diester\ which
was found to be identical to the naturally occurring gos!
pound containing an a\b!unsaturated ester moiety[ The
0
H NMR spectrum showed the presence of two ole_nic
0
sypidien "0# in all its physical and spectral "IR\ H NMR
an mass spectrum# properties[
0
Part 18 in the series Studies on Phytochemicals[ For Part 17 see
Gossypidien "0# is the second compound representing
an intermediate in the biosynthetic scheme for the for!
mation of lignans of Blears + Haworth "0874#[ The _rst
Das\ B[\ + Venkataiah\ B[ "0887#[ Biochem[ Syst[ Ecol[\ in press[ IICT
Communication No[ 3037[
ꢀ
Corresponding author[
9
920!8311:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[
PII] S9920!8311 "87#99616!3

0
05
B[ Das\ G[ Anjani : Phytochemistry 40 "0888# 004Ð006
Scheme 0[ Synthesis of gossypidien "0#[
compound\ jatrodien "Das\ Rao\ Srinivas\ + Das\ 0885#\
was also reported from the same species\ J[ `ossypifolia[
These two compounds possibly act as intermediates for
the biosynthetic formation of the lignan constituents of
the plant[
097[3 "C!1 and C!1?#\ 091[9 "1× ÐOCH OÐ#\ 42[9 "1×
ÐCOOMe#[ MS m:z "rel[ int[#] 309 ðMŁ "31#\ 249 "03#\
208 "22#\ 181 "04#\ 146 "39#\ 038 "87#\ 024 "099#[
1
¦
2[3[ Synthesis of gossypidien "0#
2
[3[0[ Stobbe condensation of piperonal with dimethyl!
succinate
Piperonal "0 g# and dimethylsuccinate "09 ml\ d]0[3 g
2[ Experimental
−
0
2[0[ General
ml # were added to a soln of NaOMe "9[4 g# in MeOH
49 ml#[ The reaction mixt[ was re~uxed for 1 h\ cooled
"
Mps uncorr[ CC] silica gel "BDH\ 099Ð199 mesh#[
TLC] silica gel G[ TLC spots visualized by exposure of
and acidi_ed with HCl "0 N#[ The mixt[ was extracted
with Et O "2×49 ml#[ The Et O fr[ was reextracted with
1
1
plates to I vapor[
aq[ NaHCO soln "2×49 ml#[ Acidi_cation of the aq[
1
2
NaHCO extract with conc[ HCl "01 N# produced an oily
2
2[1[ Plant material
layer which was again extracted with CH Cl "2×49 ml#[
1
1
The extract was washed with H O "2×49 ml#\ dried and
concd to produce a yellow solid\ which was recrystallized
1
Stems of J[ `ossypifolia L[ were collected from West
Bengal\ India\ in August\ 0886\ and identi_ed botanically[
A voucher specimen "No[ JG!St# is preserved in our lab!
oratory[ Another voucher specimen "JG!St# is preserved
in IICT herbarium[
from EtOH to produce the compound 2\ 544 mg[ Mp
031Ð032>\ IR nmax cm ] 2399\ 0694\ 0508\ 0491[ H NMR
KBr
−0
0
"199 MHz\ CDCl #] d 6[61 "0H\ s\ vinylic!H#\ 5[86Ð5[64
2
"2H\ m\ Ar!H#\ 5[93 "1H\ s\ ÐOCH OÐ#\ 2[75 "2H\ s\
1
ÐCOOMe#\ 2[48 "1H\ s\ ÐCH ÐCOOH#[ MS m:z "rel[ int[#]
153 "34#\ 119 "37#\ 078 "7#\ 054 "8#\ 059 "099#[
1
2[2[ Extraction and isolation
Air!dried stems "0 kg# were powdered and extracted
2[3[1[ Methylation of 2 with diazomethane
with hexane in a Soxhlet apparatus for 019 h[ The extract
was _ltered and concd by rotary evapn[ The thick brown
residue obtained was chromatographed over silica gel
and the column eluted with solvents of increasing polarity
using hexane and EtOAc[ The frs eluted with hexaneÐ
EtOAc "1]2# were mixed\ concd and rechromatographed[
Early frs from hexaneÐEtOAc "1]2# a}orded a solid which
was recrystallized from EtOH to produce gossypidien "0#\
A soln 2 "499 mg# in MeOH "09 ml# was added to an
ice!cold soln of CH N ÐEt O[ The mixt[ was kept for 01
h\ _ltered and then concd[ The residue was recrystallized
1
1
1
from EtOH to yield the diester 3\ 349 mg[ Mp 73Ð74>[
KBr
−0
0
IR nmax cm ] 0691X\ 0543\ 0497[ H NMR "199 MHz\
CDCl #] d 6[64 "0H\ s\ vinylic!H#\ 6[89Ð5[55 "2H\ m\ Ar!
2
H#\ 4[85 "1H\ s\ ÐOCH OÐ#\ 2[65 and 2[69 "2H each\ s\
1
1× ÐCOOMe#\ 2[35 "1H\ s\ ÐCH ÐCOOMe#[ MS m:z
1
1
4
as pale yellow crystals\ 20 mg\ mp 079Ð070>[ ðaŁ 29>
"rel[ int[#] 167 "27#\ 107 "09#\ 078 "11#\ 054 "19#\ 094 "099#[
D
0
2
"
"
MeOH\ c 9[6705#[ C NMR "49 MHz\ CDCl #] d 056[4
2
C!8 and C!8?# 031[3 "C!6 and C!6?#\ 038[9 "C!3 and C!
2[3[2[ Stobbe condensation of 3 with piperonal
3
5
?#\ 036[8 "C!2 and C!2?#\ 017[7 "C!0 and C!0?#\ 014[6 "C!
and C!5?#\ 013[8 "C!7 and C!7?#\ 097[6 "C!4 and C!4?#\
Compound 3 "399 mg# underwent Stobbe con!
densation "following the above mentioned procedure#

B[ Das\ G[ Anjani : Phytochemistry 40 "0888# 004Ð006
006
with piperonal "249 mg# to produce a solid which was
recrystallized from EtOH to yield 4 as light!yellow crys!
References
KBr
−0
Banerji\ J[\ Das\ B[\ Chatterjee\ A[\ Shoolery\ J[ N[ "0873#[ Phyto!
chemistry\ 12 1212[
Blears\ J[ G[ + Haworth\ R[ D[ "0874#[ J[ Chem[ Soc[ 0847[
Chatterjee\ A[\ Das\ B[\ Adityachaudhury\ N[\ Debkirtaniya\ S[ "0879#[
Indian J[ Agri[ Sci[\ 49\ 526[
tals\ mp 095Ð096>[ IR n cm ] 2337\ 0699\ 0562\ 0508[
max
0
H NMR "199 MHz\ CDCl #] d 6[70 and 6[68 "0H each\
2
s\ 1× vinylic!H#\ 6[94Ð5[85 "2H\ m\ Ar!H#\ 5[79Ð5[56
"
2H\ m\ Ar!H#\ 4[83 "3H\ s\ 1× ÐOCH OÐ#\ 2[62 "2H\
1
Chatterjee\ A[\ Das\ B[\ Pascard\ C[\ Prange\ T[ "0870#[ Phytochemistry\
s\ ÐCOOMe#[ MS m:z "rel[ int[#] 285 "01#\ 253 "099#\ 181
54#\ 132 "49#\ 054 "84#[
1
9\ 1936[
"
Chatterjee\ A[\ Das\ B[\ Chakrabarti\ R[\ Bose\ P[\ Banerji\ J[\ Banerji\
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chemistry\ 30\ 874[
3
[2[4[ Methylation of 4 with CH N
1
1
Compound 4 "199 mg# in Et O "19 ml# was methylated
1
Kupchan\ S[ M[\ Sigel\ C[ W[\ Matz\ M[ J[\ Renauld\ J[ A[ S[\
Haltiwanger\ R[C[\ Bryan\ R[F[ "0869#[ J[ Am[ Chem[ Soc[\ 81\ 3365[
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R[ F[ "0865#[ J[ Am[ Chem[ Soc[\ 87\ 1184[
Purushothaman\ K[ K[\ Chandrasekharan\ S[\ Cameron\ A[ F[\
Connoly\ J[ D[\ Labbe\ C[\ Maltz\ A[ + Rycroft\ D[ S[ "0868#[
Tetrahedron Lett[ 868[
with CH N ÐEt O "following the above mentioned pro!
1
1
1
cedure# and the resulting solid was recrystallized from
EtOH to obtain a product as light!yellow crystals\ 076
mg\ mp 068Ð079>\ which was found to be identical to the
naturally occurring gossypidien "0# in all respects "R \ IR\
f
0
H NMR and MS#[
Rahman\ M[\ Ismail\ M[ H[\ Yin\ L[ T[ "0889#[ Pertanika\ 02\ 394
ð"0880# Chem[ Abst[ 004\ 19229yŁ[
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p[ 148#[ New Delhi] CSIR[
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C[A[\ Cordell\ G[ A[\ Farnsworth\ N[ R[\ Kupchan\ S[ M[\ Uchida\
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Chem[ Soc[\ 094\ 2066[
Acknowledgements
The authors thank CSIR and DST "New Delhi# for
_nancial assistance[