全 文 :2016
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Vol41,No.7 April,2016
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[
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mݮEF
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Lèéê
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ÇÄæÏQ
TriterpenoidsaponinsfromBupleurummarginatumvarstenophylum
FANGWei1,YANGYinjun1,GUOBaolin1,CENShan2
(1.KeyLaboratoryofBioactiveSubstancesandResourcesUtilizationofChineseHerbalMedicine,MinistryofEducation,Instituteof
MedicinalPlantDevelopment,ChineseAcademyofMedicalSciencesandPekingUnionMedicalColege,Beijing100193,China;
2.InstituteofMedicinalBiotechnology,ChineseAcademyofMedicalSciencesandPekingUnionMedicalColege,Beijing100050,China)
[Abstract] Twelvecompoundswereobtainedbyphytochemicalinvestigationof70% EtOH(containing05%NH3·H2O)extract
oftherootsofBupleurummarginatumvarstenophylumBasedoncomparisonoftheirspectraldata,includingHRESIMS,1H
NMR,13CNMRdata,withthoseoftheliterature,theirstructureswereelucidatedassaikosaponinb2(1),saikosaponina(2),saikosa
poninb1(3),saikosaponind(4),hydroxysaikosaponina(5),saikosaponinb3(6),saikosaponinc(7),saikosaponini(8),saiko
saponinf(9),chikusaikosidesⅡ(10),saikosaponins(11),andsaikosaponinI(12)Alcompoundsbelongtooleantypetriterpe
noidsaponinandcompounds1,3,5,89,11,and12wereisolatedfromthisplantforthefirsttimeAtaconcentrationof20μmol·
L-1,compounds2,4,6,8,11and12showedstronginhibitionactivityagainstinfluenzavirusWSN33withtheinhibitionrateof
913%,886%,534%,613%,773% and574%,respectively
[Keywords] Bupleurummarginatumvarstenophylum;triterpenoidsaponin;oleantype
doi:10.4268/cjcmm20160716
ÎyùÉp>èF±,ëÍD[
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·1521·
2016
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4
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Vol41,No.7 April,2016
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300g
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20%,40%,60%,90%,100%
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(150g)
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TLC
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1(200mg)。
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~100%
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<ä
4
G
(D1~D4),
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HPLC
Ë)
(80%
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<ä_V
2(13mg)。60%
¨ü1í
(120g)
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(200~300
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(25∶1~0∶1),
TLC
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¶G
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¬ⅡV¬<äGH1(516g),GG¬
GⅢV¬<ä H2(300g)。H1$= MDS
(60% ~90%
¨
)
<ä
5
G
(H1O1~H1
O5)。
Ó$G
H1O4
HPLC
Ë)
(36%
m«
),
<ä_V
3(7mg)
¬_V
4(3mg)。
G
H1O2
HPLC
Ë)
(76%
¨
)
<ä_V
5(6mg)
¬_V
6(12mg)。H2
$=
MDS
(40%~70%
¨
)
<ä
6
G
(H2O1~
H2O6),
G
H2O4
HPLC
Ë)
(31%
m
«
)
<ä_V
7(50mg)、
_V
8(23mg)
¬_V
9(12mg)。
G
H2O2
$=
ODS
<ä
6
,
G
H2O25
HPLC
Ë)
(27%
m
«
)
<ä_V
10(7mg)
¬_V
11(6mg),
G
H2O22
HPLC
Ë)
(22%
m«
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<ä_V
12(5mg)。
3
÷<â
_V
1
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
803[M+Na]+;1HNMR(C5D5N,600MHz)δ:673
(1H,dd,J=102,24Hz,H11),575(1H,d,J=
102Hz,H12),538(1H,d,J=78Hz,H1″),
503(1H,d,J=78Hz,H1′),170(3H,s,H27),
148(3H,d,J=66Hz,H6′),107(3H,s,H26),
103(3H,s,H25),101(3H,s,H29),095(3H,s,
H30),091(3H,s,H24);13CNMR(C5D5N,600
MHz)δ:1366(C13),1335(C18),1268(C12),
1267(C11),1071(C1″),1065(C1′),857(C
3′),822(C3),793(C3″),789(C5″),763(C
2″),727(C4″),724(C4′),721(C2′),715(C
5′),681(C16),652(C28),646(C23),632
(C6″),545(C9),479(C5),458(C17),442
(C4),424(C14),416(C8),395(C19),389
(C1),370(C10),359(C21),331(C20),330
(C15),328(C7),324(C30),267(C2),256
(C29),249(C22),224(C27),194(C6),188
(C25),178(C26,C6′),136(C24)。
a÷=>
·2521·
Oè
:
DEF$Lèéêı«¬
Ñ^
[3]
kÚ±=>[c
,
Ý<â_V
1
E
Féê
b2。
_V
2
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
803[M+Na]+;1HNMR(C5D5N,600MHz)δ:602
(1H,d,J=108Hz,H12),568(1H,dd,J=108,
30Hz,H11),537(1H,d,J=78Hz,H1″),500
(1H,d,J=78Hz,H1′),146(3H,d,J=60Hz,
H6′),142(3H,s,H26),112(3H,s,H27),101
(3H,s,H25),095(3H,s,H29),094(3H,s,H
30),092(3H,s,H24);13CNMR(C5D5N,150
MHz)δ:1326(C11),1316(C12),1072(C1″),
1065(C1′),857(C3′),845(C13),820(C
3),793(C3″),789(C5″),763(C2″),735(C
28),726(C4″),723(C4′),720(C2′),715(C
5′),645(C23),644(C16),632(C6″),536
(C9),526(C18),478(C5),475(C17),461
(C14),442(C4),427(C8),391(C1),382
(C19),367(C10),366(C15),352(C21),
341(C24),320(C7,C20),266(C2),262(C
22),243(C30),213(C27),205(C26),192
(C25),180(C6),177(C6′),135(C24)。
a
÷=>Ñ^
[3]
kÚ±=>[c
,
Ý<â_V
2
EFéê
a。
_V
3
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
803[M+Na]+;1HNMR(C5D5N,600MHz)δ:655
(1H,dd,J=102,24Hz,H11),573(1H,d,J=
102Hz,H12),538(1H,d,J=78Hz,H1″),
502(1H,d,J=78Hz,H1′),148(3H,d,J=66
Hz,H6′),110(3H,s,H27),099(6H,s,H24,H
25),094(3H,s,H26),089(6H,s,H29,H30);
13CNMR(C5D5N,150MHz)δ:1369(C13),1338
(C18),1275(C12),1262(C11),1072(C1″),
1065(C1′),857(C3′),821(C3),793(C3″),
789(C5″),771(C16),763(C2″),727(C4″),
723(C4′),721(C2′),715(C5′),645(C23,
C28),632(C6″),550(C9),478(C5),449
(C17),448(C14),442(C4),410(C8),389
(C19),388(C1),370(C10),356(C21),354
(C15),331(C20),329(C7),328(C30),304
(C22),266(C2),253(C29),224(C27),193
(C25),187(C6),178(C6′),175(C26),136
(C24)。
a÷=>Ñ^
[3]
kÚ±=>[c
,
Ý
<â_V
3
EFéê
b1。
_V
4
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
803[M+Na]+;1HNMR(C5D5N,600MHz)δ:606
(1H,d,J=102Hz,H12),572(1H,dd,J=102,
30Hz,H11),536(1H,d,J=78Hz,H1″),500
(1H,d,J=78Hz,H1′),165(3H,s,H27),146
(3H,d,J=60Hz,H6′),138(3H,s,H26),105
(6H,s,H25,H29),098(3H,s,H30),096(3H,
s,H24);13CNMR(C5D5N,150MHz)δ:1325(C
11),1324(C12),1072(C1″),1065(C1′),857
(C3′),854(C13),822(C3),793(C3″),789
(C5″),783(C28),776(C16),763(C2″),
727(C4′),723(C2′),720(C4″),715(C5′),
646(C23),632(C6″),535(C9),519(C18),
479(C5),458(C17),442(C4),441(C14),
424(C8),392(C1),389(C19),373(C21),
368(C10),360(C15),343(C29),324(C
20),320(C7),318(C22),266(C2),249(C
30),201(C26),193(C25),186(C27),181
(C6),178(C6′),136(C24)。
a÷=>Ñ^
[3]
kÚ±=>[c
,
Ý<â_V
4
EF
éê
d。
_V
5
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
821[M+Na]+;1HNMR(C5D5N,600MHz)δ:561
(1H,d,J=36Hz,H12),540(1H,brs,H11),
536(1H,d,J=78Hz,H1″),499(1H,d,J=78
Hz,H1′),142(3H,d,J=60Hz,H6′),145,
124,117,101,096,086(
x
3H,s,6×CH3);
13CNMR(C5D5N,150MHz)δ:1456(C13),1286
(C12),1072(C1″),1065(C1′),858(C3′),
822(C3),793(C5″),789(C3″),763(C2″),
727(C4″),724(C4′),720(C2′),715(C5′),
692(C28),673(C11),669(C16),648(C
23),632(C6″),562(C9),483(C5),470(C
19),445(C4),444(C17),443(C18),442(C
14),420(C8),415(C1),387(C10),373(C
15),347(C7),340(C21),338(C29),315(C
20),273(C27),271(C2),265(C22),244(C
·3521·
2016
y
4
z ³
41
ų
7
}
Vol41,No.7 April,2016
30),188(C6),187(C26),183(C6′),177(C
25),142(C24)。
a÷=>Ñ^
[4]
kÚ±=>
[c
,
Ý<â_V
5
hydroxysaikosaponina。
_V
6
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
835[M+Na]+;1HNMR(C5D5N,600MHz)δ:586
(1H,brs,H11),555(1H,d,J=30Hz,H12),
536(1H,d,J=78Hz,H1″),500(1H,d,J=78
Hz,H1′),325(3H,s,OCH3),143(3H,d,J=66
Hz,H6′),142(3H,s,H26),113(6H,s,H27),
109(3H,s,H25),102(3H,s,H29),098(3H,
s,H30),091(3H,s,H24);13CNMR(C5D5N,150
MHz)δ:1488(C13),1230(C12),1072(C1″),
1065(C1′),858(C3′),822(C3),793(C5″),
789(C3″),764(C11),763(C2″),727(C4″),
723(C4′),721(C2′),715(C5′),690(C28),
667(C16),647(C23),632(C6″),545(
OCH3),526(C9),481(C5),475(C19),445
(C14),444(C18),443(C17),441(C4),415
(C8),406(C1),386(C10),373(C15),347
(C21),338(C7),337(C29),316(C20),270
(C27),268(C2),264(C22),245(C30),189
(C6),188(C26),184(C25),177(C6′),142
(C24)。
a÷=>Ñ^
[3]
kÚ±=>[c
,
Ý
<â_V
6
EFéê
b3。
_V
7
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
949[M+Na]+;1HNMR(C5D5N,600MHz)δ:594
(1H,d,J=102Hz,H12),567(1H,dd,J=102,
30Hz,H11),497(1H,d,J=78Hz,4′rhaH
1″),483(1H,d,J=78Hz,3gluH1′),476(1H,
brs,6′gluH1),168(3H,d,J=66Hz,4′rhaH
6″),137(3H,s,H26),132(3H,s,H23),117
(3H,s,H27),100(3H,s,H25),099(3H,s,H
29),094(3H,s,H30),088(3H,s,H24);13C
NMR(C5D5N,150MHz)δ:1326(C11),1316(C
12),896(C3),845(C13),735(C28),646
(C16),557(C5),533(C9),527(C18),475
(C17),461(C14),427(C8),402(C4),390
(C1),383(C19),368(C10),366(C15),352
(C21),342(C29),323(C7),321(C20),284
(C23),270(C2),263(C22),243(C30),214
(C27),205(C26),190(C25),187(C6),169
(C24);3glu,δ:1072(C1′),757(C2′),773(C
3′),803(C4′),761(C5′),696(C6′);4′rha,
δ:1035(C1″),730(C2″),732(C3″),743(C
4″),711(C5″),184(C6″);6′glu,δ:1056(C
1),753(C2),790(C3),719(C4),789
(C5),631(C6)。a÷=>Ñ^[3]kÚ±
=>[c
,
Ý<â_V
7
EFéê
c。
_V
8
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
949[M+Na]+;1HNMR(C5D5N,600MHz)δ:568
(1H,d,J=54Hz,H11),563(1H,d,J=54Hz,
H12),498(1H,d,J=78Hz,4′rhaH1″),481
(1H,d,J=78Hz,3gluH1′),477(1H,brs,6′
gluH1),168(3H,d,J=60Hz,4′rhaH6″),
135,129,127,115,104,103,094(
x
3H,s,
7×CH3);
13CNMR(C5D5N,150MHz)δ:1553(C
9),1458(C13),1216(C12),1167(C11),893
(C3),695(C28),672(C16),523(C5),475
(C19),437(C8),436(C14),431(C18),411
(C17),401(C4),392(C10),379(C1),366
(C15),346(C21),337(C29),329(C7),315
(C20),288(C23),277(C2),266(C22),259
(C27),245(C30),217(C26),215(C25),
190(C6),176(C24);3glu,δ:1071(C1′),
755(C2′),773(C3′),802(C4′),760(C5′),
697(C6′);4′rha,δ:1035(C1″),730(C2″),
732(C3″),743(C4″),710(C5″),190(C
6″);6′glu,δ:1057(C1),753(C2),789(C
3),718(C4),790(C5),630(C6)。a÷
=>Ñ^
[5]
kÚ±=>[c
,
Ý<â_V
8
EFéê
i。
_V
9
}(ãå
(MeOH),Liebermannbur
chard
ÖÛÜ (
,molish
Öµ
。ESIMSm/z
951[M+Na]+;1HNMR(C5D5N,600MHz)δ:584
(1H,d,J=60Hz,H12),498(1H,d,J=78Hz,
4′rhaH1″),483(1H,d,J=78Hz,3gluH1′),
475(1H,brs,6′gluH1),168(3H,d,J=54
Hz,4′rhaH6″),137(3H,s,H26),132(3H,s,H
23),104(3H,s,H27),103(3H,s,H29),101
(3H,s,H25),097(3H,s,H30),085(3H,s,H
24);13CNMR(C5D5N,150MHz)δ:1444(C13),
·4521·
Oè
:
DEF$Lèéêı«¬
1231(C12),896(C3),693(C28),671(C
16),562(C5),476(C19),475(C9),449(C
18),443(C14),416(C17),406(C8),400(C
4),393(C1),373(C15),372(C10),348(C
21),339(C7),334(C29),316(C20),287(C
23),277(C27),271(C2),267(C22),246(C
30),244(C11),190(C6),175(C24),174
(C26),162(C25);3glu,δ:1072(C1′),757
(C2′),773(C3′),803(C4′),761(C5′),696
(C6′);4′rha,δ:1035(C1″),730(C2″),732
(C3″),743(C4″),711(C5″),189(C6″);6′
glu,δ:1056(C1),753(C2),790(C3),719
(C4),789(C5),631(C6)。a÷=>Ñ^
[3]
kÚ±=>[c
,
Ý<â_V
9
EFéê
f。
_V
10
}(ãå
(MeOH),Liebermann
burchard
ÖÛÜ (
,molish
Öµ
。ESIMS
m/z965[M+Na]+;1HNMR(C5D5N,600MHz)δ:
596(1H,d,J=102Hz,H12),566(1H,dd,J=
102,30Hz,H11),502(1H,d,J=78Hz,4′rha
H1″),494(1H,d,J=78Hz,3gluH1′),473
(1H,brs,6′gluH1),166(3H,d,J=60Hz,4′
rhaH6″),140(3H,s,H26),109(3H,s,H27),
096(6H,s,H29,H25),094(3H,s,H30),091
(3H,s,H24);13CNMR(C5D5N,150MHz)δ:1327
(C11),1316(C12),845(C13),825(C3),
735(C28),647(C23),645(C16),535(C
9),526(C18),478(C5),475(C17),461(C
14),441(C4),427(C8),389(C1),382(C
19),367(C10),366(C15),352(C21),341
(C29),321(C7),320(C20),264(C2),262
(C22),243(C30),213(C27),205(C26),
192(C25),180(C6),135(C24);3glu,δ:
1063(C1′),756(C2′),773(C3′),801(C
4′),760(C5′),693(C6′);4′rha,δ:1034(C
1″),730(C2″),731(C3″),743(C4″),711(C
5″),190(C6″);6′glu,δ:1056(C1),752(C
2),788(C3),718(C4),790(C5),630
(C6)。a÷=>Ñ^[6]kÚ±=>[c,Ý
<â_V
10
chikusaikosideⅡ。
_V
11
}(ãå
(MeOH),Liebermann
burchard
ÖÛÜ (
,molish
Öµ
。ESIMS
m/z965[M+Na]+;1HNMR(C5D5N,600MHz)δ:
669(1H,brd,J=108Hz,H11),569(1H,d,J=
108Hz,H12),496(1H,d,J=78Hz,4′rhaH
1″),484(1H,brs,3gluH1′),474(1H,brs,6′
gluH1),167(3H,d,J=66Hz,4′rhaH6″),
166(3H,s,H27),107(3H,s,H26),101(3H,s,
H25),099(3H,s,H29),097(3H,s,H30),089
(3H,s,H24);13CNMR(C5D5N,150MHz)δ:1365
(C13),1335(C18),1267(C12),1266(C11),
825(C3),681(C16),652(C28),648(C23),
544(C9),478(C5),458(C17),441(C4),
424(C14),416(C8),395(C19),388(C1),
370(C10),359(C21),331(C20),330(C
15),328(C7),324(C30),265(C2),256(C
29),249(C22),224(C27),194(C6),190(C
25),177(C26),137(C24);3glu,δ:1063(C
1′),756(C2′),773(C3′),802(C4′),760(C
5′),693(C6′);4′rha,δ:1035(C1″),730(C
2″),731(C3″),743(C4″),711(C5″),187(C
6″);6′glu,δ:1056(C1),752(C2),789(C
3),719(C4),790(C5),630(C6)。a÷
=>Ñ^
[7]
kÚ±=>[c
,
Ý<â_V
11
EFéê
s。
_V
12
}(ãå
(MeOH),Liebermann
burchard
ÖÛÜ (
,molish
Öµ
。ESIMS
m/z819[M+Na]+;1HNMR(C5D5N,600MHz)δ:
680(1H,brd,J=108Hz,H11),572(1H,d,J=
108Hz,H12),538(1H,d,J=78Hz,H1″),
503(1H,d,J=78Hz,H1′),148(3H,d,J=66
Hz,H6′),174,127,102,094,092(
x
3H,s,
5×CH3);
13CNMR(C5D5N,150MHz)δ:1368(C
13),1334(C18),1269(C12),1266(C11),
1073(C1″),1066(C1′),858(C3′),821(C
3),794(C5″),789(C3″),763(C2″),739(C
30),727(C4″),723(C2′),720(C4′),715(C
5′),683(C16),655(C28),645(C23),632
(C6″),545(C9),478(C5),463(C17),442
(C4),424(C14),416(C8),389(C1),387
(C20),370(C10),345(C19),328(C15),
324(C7),307(C21),267(C2),246(C22),
224(C27),216(C29),194(C25),188(C6),
178(C26,C6′),136(C24)。
a÷=>Ñ^
[8]
kÚ±=>[c
,
Ý<â_V
12
·5521·
2016
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