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362 热带亚热带植物 学报 第 l0卷
II．And in the same way，the CHCI3-soluble portion gave compound HI，IV and V．
Compoun d I．was obtained as yellow acicular crysta1．Its C NM R an d H NMR spectra
(Table l and 2)showed the characteristic signals of kaempferol，two rhamnosyl residues and
an acetyl(Ac)group．From both the spliting characters of H NMR spectrum and the COSY
sign als betw een the carbon an d hydrogen atoms ofthe rhamnosyl in HM BC，the H NMR sign al
ofthe ll H-rhamnosyl were assigned to 0．78(3H，d，J-6 Hz，Me-6”)，1．21(3H，d，J-6 Hz，
Me-6”’)，2．08(3H，s，Ac)，3．27(IH，m，H-5”)，3．46(IH，t，j_-10 Hz，H-4⋯)，3．60(IH，m，
H-3”’)，3．818(IH，t，j-10 Hz，H-5⋯)，3．824(IH，t，j_-10 Hz，H-3”)，4．02(IH，br s H-2⋯)，
4．2l(IH，br s，H-2”)，5．5l(IH，br s，H-l”)，5．55(IH，br s，H-l⋯)．The -rhamnosyl can also
be confirmed．Th e sign al ofthe other H-4 ofrhamnosyl was hiden in the signal ofwater according
to a correlation of one C-rhamnosyl an d the H-H20 in the HM BC spectrum． Th e sign als betw een
H-lm an d C-7， H-l”an d C-3，an d C-Ac an d H-4”were strong， an d sign als of the COSY
between H-l”and C-2”，5”，C-I”and H-6，H-8，H-I⋯and C-3⋯，C-7 were weaker(Fig．1)．
Therefore，the Ac was attached to the C-4”which belonged to the rhamnosyl attaching to C-3，
an d the other rhamnosyl was attached to C-7． Th e attachment of Ac to C-4”made the C
NMR an d H NM R sign als of C-4”downfield shift an d those of neighbouring C-atoms upfield
shift．By what has been discussed above．compoun d 1 was confirmed as kaempferol 3-O- -L-
f4-O-acety1)rhamnopyranoside-7-O-or．-L-rhamnopyranoside．
Th e data of1 was conflict with a previous reportt 】ofa compoun d that had had the same
structure as I， an d an other previous research had reported a compoun d named kaempferol
3-O-or．-L-(3-O-acety1)rhamnopyranoside-7-O-or．-L-rhamnopyranoside【 】，which had the sanle H
NMR an d C NMR da ta as compoun d I． but there were no explicit sign al of the attachm ent
ofthe Ac an d the rhamnose in the NOSEY，by which all carbon atoms ofthat compoun d were
assign ed．
Compoun d II，was obtained as yellow acicular cry sta1．Its C NMR an d H NMR spectra
(Table 2、 showed the characteristic signals of kaempferol and two rhamnosyl residues． Two
carbon sign als assign ed to the C·7 an d C·3 ofthe aglycone were shifted to the C·7 an d C·3 of
kaempferol themselves 【 ． an d were accordant with those of I． Th ese findings supported the
fact that the two rhanmoses were attached to C-3 and C-7，respectively．Accordingly,compound
11 was considered to be kaempferol 3-O-or．-L-rhamnopyran oside-7-O-a-L-rhamnopyran oside．
Compound HI ，obtained as white powder，had a molecular weight 456(ESI)．Th e C
NMR an d DEPT spectra showed that there were six methyl gr oups， eleven methene groups，
six methyne groups，four quaternary carbon atoms，a carboxyl，an d an ethenyl unit in all ofthe
thirty carbons． Th e carbon signal at 866．7 was attached to hydroxy．Th e molecular form ula
was C3oi-I4803． Th e six single peaks of methyne in the H NM R showed that each methyne
group was attached to a qua tern ary carbon atom ．According to the degree of unsaturation，th e
other nineteen carbon atoms were assign ed to a six-ring-terpene unit．Tlle EI spectrum showed
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第 4期 栾欣等：狗脊化学成分研究 363
Ⅱ c0珈 ction of也e siX methyne groups，the carboxyl，the ethenyl unit and the terpene unit【6】
Fr0m what had been discussed above，compound II1 was identified as woodwardinic acid·
Table 1 C NMR Data of compound I
Assigned by HMBC experiments
Run at 500 MHzin MeOH—d4．
1：R=Ac
lI：
Fig．1 HM BC correlations of compound I
Table 2 tH NMR spectrum data of compound I and lI
Assignm~atsof Ibased onHMBC,IIbased on HJH COSY；Run at 500MHzin M eOH-d4
Compound IV，obtained as white powder,having melting point at 134—135~C，was identified
as B．sitosterol compared with authorized compound in TLC using both CHC13／MeOH and
PE／EtOAc systems．
Compoun d V，obtained as white powder，had melting point at 27 1—273~C．The EI spec’
mlm showcd the characteristic signals of sitosterolt71．Compound V WaS considered to be dauc0s-
terol c0mpared with authorized compound in TLC using CHC13／M eOH system·
2 Experiments
PlIant material W0odwardia japonica was colected at Baoshan District， Yunnan
Province，China，an d identified by Prof．Zhan g Xian ·chun，Institute of Botany，the Chinese
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热 带亚热 带植物 学报 第 10卷
Academy of Sciences．
Extraction and isolation Dried plant(1．4 kg)was extracted three times with 95％EtOH．
After concentration，the combined extract(200 g)was suspended in H2O，and extracted、Ⅳith
CHCl3 and EtOAc successively．The CHCl3 layer(27．3 g)was subjected repeatedly to CC on
silica gel with CHCl3 to give IV (588 mg)，CHCl3-MeOH (100：1)，to give Eli (214 mg)，
CHCl3一MeOH(100：3)to give V (29 mg)．The EtOAc layer(13．9 g)was subjected to CC on
silica gel Witl CHC13一MeOH(100：10)to give I(42 mg)and II(50 mg)．
Compound I Yelow acicular crystal(MeOH)：Uv (max)(MeOH)265，315(sh)，
345；IR 1J m。‘：3422，2922，2852，1723，1656，1603，1492，1376，135l，1257，1209，l178，
ll 14，1058，1024，973；EI m／z 286(100)[kaempfero1] ，285(25)[kaempferol-l】+，258(1O)
[kaempferol—l8】 ，257(10)[kaempferol-29] ，153(4)[C7H4O4+l】+，124(12)[C7H4O4—281 ，134
(4)【C8H6O】 ，121(25)[C7H502] ，93(8)【c7H5Oz一281 ，129(1 1)；。 C NMR and‘H NMR see
Table l an d 2．
Compound I Yelow acicular crystal(MeOH)：IR 1)l2854，1656， 1604， 1515，1491， 1478，135l，1260， 1208，l179， l137， ll17，1097， 1060，
1024，994，973；EI m／z 286(100)[kaempfero1] ，285(25)[kaempferol—l】 ，258(10)[kaempferol—
l8】+，257(12)[kaempferol一29] ，153(6)[C7H4O4+l】+，124(12)[c7H4O4—28] ，134(5)[C8H6O】+，
121(20)[C7H5O2】 ，93(8)[C7H5O2—281 ，129(11)；‘H NMR see Table 2；”C NMR(500 MHz，
MeOH—d4)8l7．7(C一6”)，l8．1(C一6⋯)，71．3，71．7，71．9，72．1，72．1，72．2，73．3，73．7
(Rham一2”-5”，2”’-5”’)，95．7(C一8)，99．9(C-1”’)，100．6(C-6)，103．6(C一10)，107．6(C—l”)，
ll6．6(C一3’，5’)，122．5(C—l’)，132．0(C-2’，6’)，136．5(C-3)，158．1(C-9)，159．8(C一2)，161．7
(C一4 )，163．0(C一5)，163．6(C一7)，179．8(C一4)．
Compound m White powder；IR 1)l135l，1332，1292，1254，l 171，l 128，1092，1076，l022，994，884，837，735，663；ESI m／z 456
[M】 ，438[M—H2O】+，41l[M—COOH] ；EI m／z 456[M】+，l89(100)，237(40)，219(10)，175
(30)，218(15)；‘H NMR(500 lVlHz，Pyridine)80，73(3H，s，Me)，0．92(3H，s，Me)，1．02(3H，
s，Me)，1．45(3H，s，Me)，1．71(3H，s，Me)，1．85(3H，s，Me)，4．89(2H，s，H-30)；‘ C NMR
(500 MHz，Pyridine，assigned by DEPT)816．4(C—Me)，16．8(C—Me)，16．9(C—Me)，19．2
(C—Me)，20．1(C—Me)，25．1(Me一24)，66．7(c一3)，llO．6(c一22)，148．7(C一30)，181．7(C一23)．
Acknowledgements We are indebted to Dr．Tu Guang—zhong， Analyt ical Center，
Bei Jing Inst itute of Microchemi stry for NMR measurement s，He Wei，Inst itute of
Botany， the Ch inese Academy of Sc iences for MS measurement s， and Prof． Zhang
Xian-chun，Institute of Botany， the Chinese Academy of Sciences for identification
of the plant．
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第 4期 栾欣 等：狗脊化 学成分研 究 365
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