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Studies on flavonoids from Cirsium setosum

小蓟中黄酮类化学成分的研究



全 文 :2016
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Vol41,No.5 March,2016
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StudiesonflavonoidsfromCirsiumsetosum
MAQinge1,WEIRongrui2,LIUWenmin1,SANGZhipei1,ZHANGSu3,WANGQuanqin4,
FENGZhanwen5,LILujun1,LIYaping1
(1ColegeofChemistryandPharmaceuticalEngineering,NanyangNormalUniversity,Nanyang473061,China;
2ColegeofPharmacy,ChinaPharmaceuticalUniversity,Nanjing210009,China;
3WuyangWeisenBiologicalMedicineCo.,Ltd.,Wuyang462400,China;
4HenanQuanyuPharmaceuticalCo.,Ltd.,Neixiang474350,China;
5HenanFusenPharmaceuticalCo.,Ltd.,Xichuan474450,China)
[Abstract] ToinvestigatethechemicalconstituentsofethylacetatefromCirsiumsetosum,fifteenflavonoidswereobtainedbycolumn
chromatographyonsilicagel,MCI,SephadexLH20,andpreparativeHPLCTheirstructureswereidentifiedas4′,5,6trihydroxy7
methoxyflavone(1),4′,5dihydroxy7,8dimethoxyflavone(2),sorbifolin6Oβglucopyranoside(3),kaempferol7OαLrhamno
side(4),kaempferol(5),quercetin3OβDglucosyl7OαLrhamnoside(6),myricetin(7),myricetin3OβDglucoside(8),5,
7dihydroxy3′,4′dimethoxyflavone(9),3′,4′,5trihydroxy3,7dimethoxyflavone(10),3′,3,4′,5tetrahydroxy7methoxyflavone
(11),3′hydroxy4′,5,7trimethoxyflavone(12),7hydroxy3′,4′,5trimethoxyflavone(13),4′,5dihydroxy2′,3′,7,8tetramethox
·868·
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ylflavone(14),and5hydroxy2′,3′,7,8tetramethoxylflavone(15)byspectroscopicdataanalysisAlcompoundswereisolatedfrom
thisplantforthefirsttimeCompounds(115)wereevaluatedfortheirhypoglycemicactivitiesbyPTP1BenzymemodelAmongthem,
compounds2,12,and14showedsignificantPTP1BinhibitoryactivitieswithIC50 valuesof254,185,211μmol·L
-1,
respectively
[Keywords] Cirsiumsetosum;flavonoids;chemicalconstituents;hypoglycemicactivities
doi:10.4268/cjcmm20160518
  
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1 
Û>Èö
,mp2336~2345℃,
ESIMSm/z3231[M+Na]+,3357[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:682(1H,s,H3),
690(1H,s,H8),795(2H,d,J=88Hz,H2′,H
6′),694(2H,d,J=88Hz,H3′,H5′),1265(5
OH),875(6OH),390(3H,s,7OCH3),1039(4′
OH)。13CNMR(DMSOd6,100MHz)δ:1638(C
2),1026(C3),1823(C4),1461(C5),1298
(C6),1545(C7),564(7OCH3),914(C8),
1499(C9),1051(C10),1215(C1′),1285(C
2′),1161(C3′),1612(C4′),1161(C5′),
1285(C6′)。
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2 
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,mp2541~2560℃,
ESIMSm/z3372[M+Na]+,3496[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:680(1H,s,H3),
·968·
2016
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41
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}
Vol41,No.5 March,2016
687(1H,s,H8),794(2H,d,J=88Hz,H2′,
H6′),692(2H,d,J=88Hz,H3′,H5′),1290
(5OH),373(3H,s,6OCH3),391(3H,s,7
OCH3),1042(4′OH)。
13CNMR(DMSOd6,100
MHz)δ:1637(C2),1031(C3),1818(C4),
1522(C5),1315(C6),557(6OCH3),1580
(C7),596(7OCH3),1015(C8),1515(C9),
1046(C10),1208(C1′),1287(C2′),1157
(C3′),1607(C4′),1157(C5′),1287(C6′)。
2¼=‰ª^•
[3]
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3 
DÛ>ö
,mp2675~2686℃,
ESIMSm/z4853[M+Na]+,4978[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:686(1H,s,H3),
694(1H,s,H8),797(2H,d,J=88Hz,H2′,
H6′),693(2H,d,J=88Hz,H3′,H5′),1305
(5OH),391(3H,s,7OCH3),1044(4′OH),495
(1H,d,J=52Hz,H1″),515(1H,m,H2″),506
(1H,m,H3″),504(1H,m,H4″),434(1H,m,
H5″),413(1H,dd,J=50,100Hz,H6″a),360
(1H,dd,J=45,110Hz,H6″b)。13CNMR(DMSO
d6,100MHz)δ:1641(C2),1022(C3),1822
(C4),1517(C5),1282(C6),1585(C7),568
(7OCH3),919(C8),1525(C9),1048(C10),
1212(C1′),1285(C2′),1161(C3′),1614
(C4′),1161(C5′),1285(C6′),1028(C1″),
744(C2″),775(C3″),700(C4″),765(C5″),
610(C6″)。
2¼=‰ª^•
[3]
±Ä£4[Q

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3¯ sorbifolin6Oβglucopyranoside。
_ñ.
4 
DÛ>ö
,mp2294~2308℃,
ESIMSm/z4554[M+Na]+,4677[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:642(1H,d,J=
20Hz,H6),683(1H,d,J=20Hz,H8),953
(3OH),1248(5OH),809(2H,d,J=88Hz,H
2′,H6′),693(2H,d,J=88Hz,H3′,H5′),
1015(4′OH),555(1H,d,J=18Hz,H1″),352
(1H,m,H2″),379(1H,m,H3″),340(1H,m,H
4″),382(1H,m,H5″),121(3H,d,J=60Hz,
H6″)。13CNMR(DMSOd6,100MHz)δ:1472(C
2),1360(C3),1761(C4),1604(C5),988(C
6),1614(C7),944(C8),1559(C9),1048
(C10),1217(C1′),1297(C2′),1155(C3′),
1595(C4′),1155(C5′),1297(C6′),986
(C1″),701(C2″),703(C3″),716(C4″),701
(C5″),182(C6″)。
2¼=‰ª^•
[4]
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4¯
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7OαLx±gÄ。
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5 
Û>ö
,mp2746~2758℃,
ESIMSm/z3092[M+Na]+,3217[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:622(1H,d,J=
20Hz,H6),640(1H,d,J=20Hz,H8),955
(3OH),1249(5OH),1072(4′OH),805(1H,
d,J=70Hz,H2′,H6′),693(1H,d,J=70Hz,
H3′,H5′)。13CNMR(DMSOd6,100MHz)δ:1468
(C2),1356(C3),1758(C4),1606(C5),982
(C6),1638(C7),934(C8),1562(C9),1031
(C10),1217(C1′),1295(C2′),1154(C3′),
1592(C4′),1154(C5′),1295(C6′)。
2¼=
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[5]
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6 
Û>ö
,mp2581~2594℃,
ESIMSm/z6432[M+Na]+,6558[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:642(1H,d,J=
20Hz,H6),682(1H,d,J=20Hz,H8),1263
(5OH),935(3′OH),928(4′OH),758(1H,d,
J=14Hz,H2′),688(1H,d,J=80Hz,H5′),
768(1H,dd,J=80,14Hz,H6′),546(1H,d,
J=75Hz,H1″),476(1H,m,H2″),496(1H,m,
H3″),435(1H,m,H4″),483(1H,m,H5″),420
(1H,dd,J=25,110Hz,H6″a),394(1H,dd,J=
50,110Hz,H6″b),555(1H,d,J=18Hz,H
1),356(1H,m,H2),382(1H,m,H3),352
(1H,m,H4),376(1H,m,H5),113(3H,d,
J=60Hz,H6)。13CNMR(DMSOd6,100MHz)
δ:1558(C2),1335(C3),1778(C4),1571
(C5),994(C6),1624(C7),945(C8),1593
(C9),1058(C10),1221(C1′),1154(C2′),
1456(C3′),1487(C4′),1161(C5′),1210(C
6′),1013(C1″),746(C2″),768(C3″),705
(C4″),781(C5″),612(C6″),997(C1),702
(C2),704(C3),716(C4),696(C5),
178(C6)。2¼=‰ª^• [6]±Ä£4[Q,
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,mp2570~2586℃,
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::$Û9•_‡Ž˜™
ESIMSm/z3413[M+Na]+,3536[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:1264(5OH),
1082(7OH),619(1H,d,J=20Hz,H6),638
(1H,d,J=20Hz,H8),719(2H,s,H2′,H6′),
913(2H,s,3′,5′OH),889(1H,s,4′OH)。13C
NMR(DMSOd6,100MHz)δ:1561(C2),1376
(C3),1781(C4),1616(C5),987(C6),1662
(C7),939(C8),1568(C9),1042(C10),
1208(C1′),1079(C2′),1460(C3′),1368(C
4′),1462(C5′),1091(C6′)。
2¼=‰ª^•
[7]
±Ä£4[Q

Ò×_ñ.
7¯
*íì

_ñ.
8 
ñÛ>ö
,mp2983~2995℃,
ESIMSm/z5034[M+Na]+,5157[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:1265(5OH),
1081(7OH),618(1H,d,J=20Hz,H6),636
(1H,d,J=20Hz,H8),915(2H,s,3′,5′OH),
888(1H,s,4′OH),717(2H,s,H2′,H6′),545
(1H,d,J=75Hz,H1″),465(1H,m,H2″),481
(1H,m,H3″),426(1H,m,H4″),475(1H,m,H
5″),418(1H,dd,J=25,110Hz,H6″a),398
(1H,dd,J=50,110Hz,H6″b)。13CNMR(DMSO
d6,100MHz)δ:1562(C2),1336(C3),1778
(C4),1614(C5),986(C6),1651(C7),936
(C8),1565(C9),1054(C10),1202(C1′),
1087(C2′),1455(C3′),1363(C4′),1455(C
5′),1087(C6′),1012(C1″),767(C2″),778
(C3″),700(C4″),738(C5″),614(C6″)。
2
¼=‰ª^
[8]
±Ä£4[Q

Ò×µ_ñ.

¯
*íì
3OβDûügÄ。
_ñ.
9 
Û>ö
,mp2335~2358℃,
ESIMSm/z3373[M+Na]+,3496[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:1296(5OH),
1004(7OH),682(1H,s,H3),635(1H,d,J=
20Hz,H6),676(1H,d,J=20Hz,H8),718
(1H,d,J=18Hz,H2′),696(1H,d,J=80Hz,
H5′),726(1H,dd,J=80,18Hz,H6′),392
(6H,s,3′,4′OCH3)。
13CNMR(DMSOd6,100MHz)
δ:1638(C2),1041(C3),1816(C4),1613(C
5),980(C6),1653(C7),931(C8),1570(C
9),1048(C10),1203(C1′),1107(C2′),1482
(C3′),1507(C4′),1161(C5′),1212(C6′),
561(3′OCH3),563(4′OCH3)。2¼=‰ª^•
[9]
±Ä£4[Q

Ò×_ñ.
9¯ 5,7
<`£
3′,
4′
<ë^£Û9

_ñ.
10 
Û>ö
,mp2326~2345℃,
ESIMSm/z3531[M+Na]+,3656[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:1270(5OH),
937(3′OH),979(4′OH),637(1H,d,J=20
Hz,H6),672(1H,d,J=20Hz,H8),758(1H,
d,J=20Hz,H2′),693(1H,d,J=80Hz,
H5′),748(1H,dd,J=80,20Hz,H6′),381
(3H,s,3OCH3),385(3H,s,7OCH3)。
13CNMR
(DMSOd6,100MHz)δ:1561(C2),1378(C3),
1781(C4),1612(C5),979(C6),1653(C7),
923(C8),1562(C9),1053(C10),1208(C
1′),1160(C2′),1451(C3′),1486(C4′),
1156(C5′),1208(C6′),561(3OCH3),565
(7OCH3)。2¼=‰ª^• [10]±Ä£4[Q,
Ò×_ñ.
10
¯
3′,4′,5
L`£
3,7
<ë^£
Û9

_ñ.
11 
Û>ö
,mp2782~2796℃,
ESIMSm/z3392[M+Na]+,3517[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:945(3OH),
1249(5OH),636(1H,d,J=20Hz,H6),671
(1H,d,J=20Hz,H8),773(1H,d,J=20Hz,H
2′),691(1H,d,J=80Hz,H5′),759(1H,dd,
J=80,20Hz,H6′),927(3′OH),960(4′
OH),386(3H,s,7OCH3)。
13CNMR(DMSOd6,100
MHz)δ:1472(C2),1357(C3),1757(C4),
1605(C5),975(C6),1646(C7),918(C8),
1602(C9),1041(C10),1216(C1′),1159
(C2′),1453(C3′),1476(C4′),1153(C5′),
1201(C6′),560(7OCH3)。2¼=‰ª^•
[10]
±Ä£4[Q

Ò×_ñ.
11
¯
3,3′,4′5
@

7
ë^£Û9

_ñ.
12 
Û>ö
,mp2076~2091℃,
ESIMSm/z3511[M+Na]+,3638[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:653(1H,s,H3),
646(1H,d,J=20Hz,H6),677(1H,d,J=20
Hz,H8),738(1H,d,J=18Hz,H2′),683(1H,
d,J=85Hz,H5′),748(1H,dd,J=85,18Hz,
H6′),952(3′OH),383(3H,s,5OCH3),385
(3H,s,7OCH3),386(3H,s,4′OCH3)。
13CNMR
(DMSOd6,100MHz)δ:1596(C2),1056(C3),
·178·
2016
y

z ©
41
ª©

}
Vol41,No.5 March,2016
1756(C4),1602(C5),963(C6),1635(C7),
932(C8),1603(C9),1082(C10),1233
(C1′),1121(C2′),1465(C3′),1504(C4′),
1123(C5′),1180(C6′),559(5OCH3),561
(7OCH3),563(4′OCH3)。2¼=‰ª^• [11]
±Ä£4[Q

Ò×_ñ.
12¯ 3′`
£
4′,5,7
L
ë^£Û9

_ñ.
13 
Û>ö
,mp2332~2350℃,
ESIMSm/z3513[M+Na]+,3636[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:666(1H,s,H3),
636(1H,d,J=20Hz,H6),659(1H,d,J=20
Hz,H8),1083(7OH),746(1H,d,J=18Hz,H
2′),688(1H,d,J=85Hz,H5′),758(1H,dd,
J=85,18Hz,H6′),380(3H,s,5OCH3),383
(3H,s,3′OCH3),387(3H,s,4′OCH3)。
13CNMR
(DMSOd6,100MHz)δ:1598(C2),1070(C3),
1761(C4),1608(C5),967(C6),1625(C7),
956(C8),1597(C9),1078(C10),1234
(C1′),1092(C2′),1492(C3′),1517(C4′),
1118(C5′),1195(C6′),558(5OCH3),561
(3′OCH3),560(4′OCH3)。2¼=‰ª^•
[11]
±Ä£4[Q

Ò×_ñ.
13
¯
7`
£
3′,
4′,5
Lë^£Û9

_ñ.
14 
Û>ö
,mp2368~2376℃,
ESIMSm/z3972[M+Na]+,4096[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:674(1H,s,H3),
655(1H,s,H6),1249(5OH),926(4′OH),
668(1H,d,J=90Hz,H5′),746(1H,d,J=90
Hz,H6′),391(3H,s,7OCH3),379(3H,s,
8OCH3),385(3H,s,2′OCH3),379(3H,s,
3′OCH3)。
13CNMR(DMSOd6,100MHz)δ:1625
(C2),1056(C3),1812(C4),1591(C5),957
(C6),1568(C7),1312(C8),1489(C9),
1135(C10),1134(C1′),1534(C2′),1419(C
3′),1565(C4′),1037(C5′),1231(C6′),604
(7OCH3),565(8OCH3),603(2′OCH3),598
(3′OCH3)。2¼=‰ª^•[12]±Ä£4[Q,Ò
×_ñ.
14
¯
4′,5
<`£
2′,3′,7,8
@ë^£
Û9

_ñ.
15 
Û>ö
,mp1512~1531℃,
ESIMSm/z3812[M+Na]+,3937[M+Cl]-。
1HNMR(DMSOd6,400MHz)δ:671(1H,s,H3),
654(1H,s,H6),1248(5OH),731(1H,dd,J=
78,18Hz,H4′),727(1H,t,J=78Hz,H5′),
736(1H,dd,J=78,18Hz,H6′),391(3H,s,
7OCH3),385(3H,s,8OCH3),389(3H,s,
2′OCH3),377(3H,s,3′OCH3)。
13CNMR(DMSO
d6,100MHz)δ:1624(C2),1102(C3),1823
(C4),1582(C5),968(C6),1588(C7),1255
(C8),1496(C9),1047(C10),1102(C1′),
1536(C2′),1478(C3′),1162(C4′),1253(C
5′),1207(C6′),613(7OCH3),569(8OCH3),
610(2′OCH3),566(3′OCH3)。2¼=‰ª^•
[12]
±Ä£4[Q

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[3] GloriaIHB,LuisWTT,RosaMP,etalAntigiardialactivity
offlavonoidsfromleavesofAphelandrascabra[J]RevBras
Farmacogn,2015,25:233
[4] 
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[5] MarkhamKR,TerablB,StanleyR,etalCarbon13NMRstudies
offlavonoidsⅢ,naturalyoccuringflavonidglycosidesandtheir
acylatedderivatives[J]Tetrahedron,1978,34:1389
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