1
43
W[ G[ MA et al[
re~uxed in 09 ml 0 N HCl for 29 min[ The mixt[ was
EXPERIMENTAL
cooled and then extracted with n!BuOH[ The organic
layer was evapd[ to dryness and then dissolved in
MeOH[ The aq[ layer was treated as described above[
From the organic layer\ compound 6 was detected
and from the aq[ layer glucose was identi_ed by direct
TLC comparison with authentic samples ðCHCl2Ð
MeOHÐH O\ 03 ] 5 ] 0 for glucose "R 9[05# ^ CHCl Ð
General
Mps ] uncorr[ NMR ] JEOL EX!169 and Brucker!
AM!499 spectrometers[ Optical rotations ] MeOH[
IR ] KBr[ TLC ] Merck HPTLC RP!07 WF143 plates ^
saccharide identi_cation was carried out on Merck
silica gel TLC plates[
1
f
2
MeOH\ 8 ] 0 for aglycone "R 9[34#Ł[
f
Acknowled`ements*The authors are grateful to Dr
Eri Fukushi and Mr Kenji Watanabe "GC!MS and
NMR Laboratory\ Faculty of Agriculture\ Hokkaido
University# for the measurement of 1D NMR and
MS[
Extraction and isolation
Powdered air!dried roots of E[ tuberosum were
extracted successively with CH Cl and MeOH as
described in Ref[ ð0Ł[ The n!BuOH!soluble fr[ "1[4 g#
from the MeOH extract was submitted to MPLC on
RP!07 "14Ð39 mm\ Merck# and eluting with a MeOHÐ
1
1
REFERENCES
H O stepwise gradient 0 ] 8Ð8 ] 0 a}orded _ve sub!frs[
1
Sub!fr[ 1 was analysed by Lobar RP!07 CC with
0[ Ma\ W[ G[\ Fuzzati\ N[\ Li\ Q[ S[\ Yang\ C[ R[\
Stooeckli!Evans\ H[ and Hostettmann\ K[\ Phyto!
chemistry\ 0884\ 28\ 0938[
MeOHÐH O "2 ] 6#\ followed by separation on Lobar
1
Diol CC and repeated gel _ltration on Sephadex LH!
1
2
9 with MeOH to give compound 0 "12 mg#[ Sub!fr\[
was separated by Lobar Diol CC using CHCl2Ð
1[ Ma\ W[ G[\ Fuzzati\ N[\ Xue\ Y[\ Yang\ C[ R[
and Hostettmann\ K[\ Phytochemistry\ 0885\ 30\
0176[
MeOH "8 ] 0 : 6 ] 2#\ followed by gel _ltration on
Sephadex LH!19 with MeOH\ to provide compounds
2[ Ma\ W[ G[\ Fuzzati\ N[\ Lu\ S[ L[\ Gu\ D[ S[ and
Hostettmann\ K[\ Phytochemistry\ 0885\ 32\ 0228[
3[ Tahara\ S[\ Hashidoko\ Y[\ Ingham\ J[ and
Mizutani\ J[\ A`ricultural and Biolo`ical Chem!
istry\ 0875\ 49\ 0798[
1
"09 mg#\ 2 "49 mg#\ 3 "59 mg# and 4 "1[9 mg#[ Sub!
fr[ 0 was repeatedly separated by Sephadex LH!19 CC
eluting with MeOH followed by silica gel CC "CHCl2Ð
MeOH\ 8 ] 0# to provide compounds 5 "09 mg# and 6
"
04 mg#[
4[ Mabry\ T[ J[\ Markham\ K[ R[ and Thomas\ M[
B[\ The Systematic Identi_cation of Flavonoids\
0869\ Springer\ Berlin[
Compound 0 "4!O!methylgenistein 6!O!b!D!apio!
furanosyl!"0 : 5#!O!b!D!glucopyranoside#[ Yellowish
amorphous powder\ mp 059Ð052>[ HPTLC RP!07
5[ Pelter\ A[\ Ward\ R[ S[ and Gray\ T[ I[\ Journal
of Chemical Society\ Perkin Transactions 0\ 0865\
1364[
6[ Wenkert\ E[ and Gottlieb\ H[ E[\ Phytochemistry\
0866\ 05\ 0700[
7[ Kitagawa\ I[\ Hori\ K[\ Sakagami\ M[\ Hashiuchi\
F[\ Yoshikawa\ M[ and Ren\ J[\ Chemical and
Pharmaceutical Bulletin\ 0882\ 30\ 0249[
8[ Snyder\ J[ R[ and Serianni\ A[ S[\ Carbohydrate
Research\ 0876\ 055\ 74[
10
"
MeOHÐH O\ 0 ] 0# R 9[50[ ðaŁ −66[6> "c 9[15\
1 f D
MeOH#[ UV lmax "MeOH# nm "log o# ] 146 "3[38#\ 174
sh "2[80#\ 219 sh "2[61# ^ ¦NaOMe\ 141 sh "3[03#\ 162
"
¦
3[26#\ 298 sh "3[02# ^ ¦AlCl \ 146 "3[38#\ 208 sh "2[73# ^
NaOAc\ 146\ 208 sh[ IR "KBr# nmax cm 2223\ 0527\
2
−0
0
406\ 0348\ 0148\ 0972\ 861[ FD!MS m:z 468
¦
¦
¦
ðM¦HŁ \ 336 ðM−021¦HŁ \ 335 ðM−021Ł \ 173
ðM−021−051Ł \ 022 ð021"apiose#¦HŁ \ 052
ð051"glucose#¦HŁ [ H and C NMR ] Table 0[
¦
¦
¦
0
02
Hydrolysis of 0[ Compound 0 "4[4 mg# was re~uxed 09[ Breytenbach\ J[ C[\ Journal of Natural Products\
in 09 ml 9[0 N H SO for 19 min[ The mixt[ was cooled
0875\ 38\ 0992[
and 09 ml H O added[ The aq[ layer was extracted with 00[ Southon\ I[ W[\ Bisby\ F[ A[\ Buckingham\ J[\
1
3
1
n!BuOH\ then neutralized with NaHCO followed by
freeze!drying[ The residue obtained was dissolved in
Harborne\ J[ B[\ Zarucchi\ J[ L[\ Polhill\ R[ M[\
Adams\ B[ R[\ Lock\ J[ M[\ White\ R[ J[\ Bowes\
I[\ Hollis\ S[ and Heald\ J[\ Phytochemical Dic!
tionary of the Le`uminosae\ Vols 0 and 1\
Chapman and Hall\ London\ 0883[
2
0
ml MeOH\ _ltered and concd[ to 9[4 ml[ Comparison
on TLC with authentic samples gave apiose from the
MeOH fr and compound 2 from BuOH extract[ "In
CHCl ÐMeOHÐH O\ 03 ] 5 ] 0 ^ R s[ ] 9[27 for apiose\ 01[ Rodriguez\ D[ J[ D[\ Chulia\ J[\ Simoes\ C[ M[
2
1
f
9
[57 for 2[#
O[\ Amoros\ M[\ Mariotte\ A[ M[ and Girre\ L[\
Hydrolysis of 0 with HCl[ Compound 0 "1 mg# was
Planta Medica\ 0889\ 45\ 48[