免费文献传递   相关文献

Iridoids from stem bark of Syringa pinnatifolia

羽叶丁香茎皮中环烯醚萜类成分



全 文 :2016
y

z ³
41
ų

}
Vol41,No.7 April,2016
·
j^
·

”•)(
] 20151220

–—˜R
] 
ì(81473426);
‘%ö™W™åjk
(BJGJ1536)

™x?š
] 
¬­y

€

•–—˜èéêëìtí)îï£$$€
,Tel/Fax:(010)64286350,Email:xingyunchai@
yeahnet
=®>?@A$MBCèĖ—
O ¡¢
2,
 £
1,3,
¤¥¦
1,3,

1,3,
¨©
1,3,
ª`«
1,
¬­y
1
(1.
}~!#$‘% !$ÈU€!t

}~
100029;
2.
ðñògóôõñ##q

ðñò góôõö÷
750300;
3.
}~!#$‘% !$%q

}~
100102)

›
] 
@¸(眝¦W,–(,ŠÒW?rŽ˜=®>?±@A$—ä

¥±¬

î±MBCè

Ӝ÷Þç

%”ôçè—à

ÊÑ^”=>€ñì<â

_V˜

쮕ÒW?èê
A(alashanidoidA)。5
î–——`•
(8E)
³X
ïê
(2),
Õ³Xê
(3),3′OβD·¸£³Xê(4),10‚1³Xê(5),y¢Yꀇ(6),Ó$3~5•>?Ç8HºkÚ,2
¬

•98HºkÚ

_V˜
1~6

RAW2647
Za$
NO
–¬
HepG2
Zah±ðµ:;

}¥hiúh±9Ëðµ


œž
] 
ÒW?

W,

MBCè

ÒW?èê

IridoidsfromstembarkofSyringapinnatifolia
CHENSuyile2,SUGuozhu1,3,BAIRuifeng1,3,YINXu1,3,CAOYuan1,3,TUPengfei1,CHAIXingyun1
(1.ModernResearchCenterforTraditionalChineseMedicine,BeijingUniversityofChineseMedicine,Beijing100029,China;
2.AlashanLeagueMongolianMedicineHospital,Alashan750300,China;
3.SchoolofChineseMateriaMedica,BeijingUniversityofChineseMedicine,Beijing100102,China)
[Abstract] Onenewiridoid,namedalashanidoidA,andfiveknownanalogues,wereisolatedfromthestembarkofSyringapinnati
foliabyvariouschromatographicmethodsTheirstructuresweredeterminedonthebasisofMSandNMRspectroscopicdataanalyses,
andcomparisonwiththoseinliteratureAmongthem,compounds35wereisolatedfromthisgenusforthefirsttime,and2and6were
isolatedfromthespeciesforthefirsttimeTheseisolatesweretestedfortheirinvitroantiinflammatoryactivitiesagainstNOproduction
inlipopolysaccharide(LPS)inducedRAW2647macrophagesinmiceandcytotoxicityofHepG2celline,however,noobviousactivi
tywasobservedattheconcentrationof40μmol·L-1
[Keywords] Syringapinnatifolia;Mongolianfolkmedicine;iridoid;alashanidoidA
doi:10.4268/cjcmm20160715
  
=®>?
SyringapinnatifoliaHemsl
Z®‚á
Ò>?

•y¢&
Oleaceae
>?ǎ˜

É»%>?
ǖB¤

L/—‹¿»%8W



ùÉ

ö
H

tK

A èF

Ó$a8W¬#«A“±‚á
ÒFJò•È$
[1]。
=®>?%A±Ø

Ø@Ê
ð

É[–(W,Š
———
ÒW?

W,®


Ù
·
KZ›
”,
-B9[·

ª«

0üè¥É

L$
S

W

¢µè\ü

[·µSˆ



L;[·


WAžÓ$ˆW]WB

S—é¢èS#Ü
O

ˆÉh·
[1]。
•Ö[ÍÎúÒW?ôS—颱,ɘÞ1
i¬/—nž’[dT±W,Ë>

9“pž
C57BL/6
:Rå^²¶;œÒ~ÓôS—é¢
Éæ

m±ÒW?m¨#֘-Bh·±deé¢
·6421·
yn·$è

=®>?@A$MBCèĖ—
µS—ƒ„±0ž
[2]。
¦Oì¥&O,ž±@A
Ön_«¬

a}•ÒW?,É1í±_*+
#GìH¤

pž?

ր_`¬
SephadexLH20
è(ç()¦ÒW?@A$—ž<âD

MBC
èĖ—

Ӝ÷Vç()ÊÑ^”=>ñò<
â

RS

¥±MBCè

⮕ÒW?èê

(alashanidoidA,1),
¬

îÄ˜
(8E)
³X
ïê
(2)[3],
Õ³Xê
(3)[4],3′OβD·¸£³

(4)[5],10
‚1³Xê
(5)[6],
y¢Yꀇ

(6)[78],
_V˜
3~5
•>?Ç8HºkÚ
,2
¬

•98HºkÚ

1 
ŠÌ
VarianInova500
Q%”ô“

{9÷àÝÉ
¤€

žïM

únOþÞç“

‘%hÚ`
Autopol
IV
Ó3“
;SephadexLH20(
…˜
AmershanBiosci
ences);Waters2535
Ë)¤€

‘%
Waters);

) ( ç ”
Shimpack PREPODS(H) C18
(20mm×250mm,5μm)。ODS(40~63μm,\%
Merck);
”(çž_`
(200~300
À

Êaû(çž
GF254
_`kËT

u•ö÷H€_gjÂã


¬—ž$bž_Ãu•—à‹

23_gj
);
hiÛq•23˜()BCDEã¤
;SANYO
MCO18AIC
Za4½Z
;MoticAE2000
L23h
Ó¯
;ESCOOptiMair
Õ°g0Ã

…n
TECAN
M1000
Q•¥{q“
;DMEM
4½1
(Hyclone,
‘
%
);
†í¢ª
(Gibco,
‘%
);
[t_>‚áé

bH˘()BCDE
);
™µìH•òAە
‘%
Sigma
DEã¤

ýʊcZa
RAW2647
¬‚ˆZa
HepG2
ߕ÷HZab

=®>?
2013
y

zp•8WÛK­Ù‚á
ÒFJ

K­ÙdWAA>yn·$<â•
S
pinnatifolia,
Õ®‚áÒ>?
Spinnatifoliavar
alashanensisYCMa&SQZhou[1],
)Ö@A

a
ej©

NŠÂ9;Ÿ23$A,…$,±
P«¬$S
(SP201307B)。
2 
#Öїž
ÒW?@A
(13kg),
·ºž
95%
¬
80%
±m
¨–G#Ö

º


25L,

15h。
#Ö¤&
=Åb325g。
pž?€_`”(ç

·ºž
ûf

‡¨
(20∶1~0∶1)
œü<ä

G—
(A~I)。
E(106g)
¬
F(82g)
V¬pž?€_`”(ç

am¼m

‡¨
(10∶1~0∶1)
œü<ä

G—
(EF1~EF8)。EF1(12g)
Ö€_`—ž‡¨

¢
(1∶2~1∶0)
ϟ
,SephadexLH20
”(燨œ
ü

‹_<ä_V˜
3(35mg)
¬
4(65mg),
Óá
1—@¸
HPLC
Ë)¤€
(30mL·min-1,


¢
18∶82)
<ä_V˜
1(tR =245min,65mg)¬ 6
(tR=273min,102mg)。EF3(25g)HPLCË
)¤€

‡¨

¢
,40∶60)
‹_<ä_V˜
2(tR =
333min,5005mg)
¬
5(tR=435min,2001mg)。
_V˜
1~6
œ÷ó]q
1。
q
1 
_V˜
1~6
±œ÷ó¬

±‘
HMBC
v<
Fig1 Structuresof16andkeyHMBCcorelationsof1
3 
ô0¬‚ˆZah:;
Öì=ÂË}±
RAW2647
Za

©|&
2×105
Za=zŸ
96
&T$
,24h
YÅO
50μL¥¦
ž±U°_V˜
,2h

50μLLPS(1mg·L-1)

24h,
Å
MTT,
·Ó
4h,570nm
@áZa
A,
a
630nm
0•n?VË

ÖZa÷ª
50μL,pž
Griess
áâ[t_>
(NO)
±ëß

Öì=ÂË}
±
HepG2
Za

©
5×104
Za=zŸ
96
&$

·
Ó
24h
5ºYÅO
100μL¥¦Å¾±U°_V˜,

24h,
Å
MTT,
·Ó
4h,570nm
@áZa
A,
a
630nm
0•n?VË

9ˇ©H@óx-


‡
=(A
PQ
-A
~,
)/A
PQ
×100%。
·7421·
2016
y

z ³
41
ų

}
Vol41,No.7 April,2016
4 
œ÷<â
_V˜
1 
¨(£o²
,[α]25D -974(c01,
MeOH);UV(MeOH)λmax(logε):277(308),226
(396),202(384)nm;IR(KBr)vmax:3132,
1630,1516,1400,1309,1158,1078cm-1;HR
ESIMSm/z7092326[M +Na]+(
x-ۓѕ
Þß
7092324,C31H42O17Na),œVӝ%=>î
â—ïó•
C31H42O17,¥m¬¾11。
1HNMR(CD3OD,500MHz)=>]* 1,œV
HSQC
qç—àhi

_V˜

$ëB
AA′BB′

?Þï
[δH705(2H,d,J=80Hz,H2″,6″),668
(2H,d,J=80Hz,H3″,5″)],2
BÞï δH751
(1H,brs,H3),610(1H,brq,J=70Hz,H8),1
‡t1δH371(3H,s)¬1‡1δH176(3H,d,
J=70Hz),2
¹1Þï δH479(1H,d,J=75
Hz,H1′),δH435(1H,d,J=80Hz,H1)Ê£÷
ÓâÞïv<
。13CNMR(CD3OD,125MHz)]*2,
hi
31
!v<

RS

g1 δC1729(C7)
¬
1689(C11),4
ñ! δC1568(C4″),1306
(C1″),1305(C9),1093(C4),2
B! δC
1553(C3),1251(C8),4
±?! δC1309×2,
1161×2,1
Át! δC722(Cα),3m¬! δC
363(Cβ),316(C5),407(C6),1‡t1 δC
519,1
‡1δC137,aÊ2£÷!v<。÷g
•Ç¬œV€Z±
HMBC
—àMaúî_V˜

$ëB

ì‚1ƒm¨-¨

§åÊ
H1ä Cα
±
HMBC
€hiƒm¨-¨ÑÓ$

£€Á

Ó↣ýð±
NMR
=>—àMaÿ—ï$
¿[MBCèœ÷

€Z±
HMBC
Å]q
1。
[[£¹1v<
H1′
Ñ
C1
€

#iMBCè
¿
C1
í–ê

÷g—àhi

_V˜

Ñî_

(8E)
³Xïê
(2)[3]
¬Õ³Xê
(3)[4]
œ÷
vwÎ

€ZñòÓ
13CNMR
=>m±

†
C2
[ΔδC-(14~19)],C3[ΔδC+(15~34)],
C4[ΔδC-(08~32)],C5[ΔδC+(19~26
)]
±_íymÂD[â _ð

ÓâíL=>1
9d+[c

1Ÿ£1_ì€Õ!_íy±ò
ó

¬Ñ^”$
itosidesC
¬
F[9]
$€± _‹š
€ù

Q¸îâ
C3íÑ C7g1€Á,îâD
_V˜

œ÷x-¨±Ázw™

£±ÄQq¢
7Y—àîâ

-°q0›@


DMSO
˜7±_

1(095mg)
ÑèÞß±hiÛq[¦ÅOm
¼m¼ÌyÕ»˜¤$
(pH45,20mL)。
¯V˜
¤¿¶¾
40℃
:L
12h
YÑè°2±m¼m¯
V



ô$

Ö@û¢¤Åb

Ñ·¸£ÂȤ
TLC
ÊÓ3=>ñì

<╠βD·¸£。÷û˜
¤ÅbY


LCMS
—àîâì‚1ƒm¨¬M
BCèê~

*
1 
_V˜
1~6
±
1HNMR(CD3OD,500MHz)%=>(J,Hz)
Table1 1HNMR(500MHz)datafor16inCD3OD,JinHz
NO 1 2 3 4 5 6
1 595(brs) 586(brs) 597(brs) 591(brs) 594(brs) 591(brs)
3 751(brs) 746(brs) 752(brs) 750(brs) 751(brs) 751(brs)
5 399(m) 394(m) 402a 396(dd,40,90) 392(dd,40,95) 399(dd,40,90)
6 271(m) 269(dd,50,145)
243(dd,90,145)
286(d,40)
257(dd,100,150)
242(dd,90,140)
269(dd,45,90)
248(dd,95,150)
271(dd,40,150)
244(dd,95,140)
274(dd,45,140)
8 610(brq,70) 604(brq,70) 613(brq,65) 605(brq,70) 613(brt,70) 610(brq,70)
10 176(d,70) 167(dd,10,70) 175(dd,10,70) 163(dd,10,70) 425,410(m) 172(dd,10,70)
7OMe 363(s)
11OMe 371(s) 363(s) 371(s) 370(s) 369(s) 370(s)
1′ 479(d,75) 476a 478(d,80) 485a 480(d,75) 479(d,80)
2′ 332a 340a 340a 352(dd,90,120) 333a 333a
3′ 340a 330a 350(t) 360a 333a 333a
4′ 338a 330a 467(brt) 343(brt,85) 333a 333a
5′ 336a 333a 340a 320~340a 340(brt,85) 340(brt,85)
6′ 389(d,120)
364a
365(m)
384(d,105)
387(m)
367(m)
389a
362a
390(m)
365(dd,60,120)
386(m)
366(m)
α1 400(m) 391(m) 402a 422(m) 420(m)
α2 369(m) 367(m) 370a 411(m) 414(m)
β 282(m) 278(brt,70) 283(m) 282(brt,70) 281(brt,70)
·8421·
yn·$è

=®>?@A$MBCèĖ—
,*

NO 1 2 3 4 5 6
2″,6″ 705(d,80) 700(d,80) 705(d,80) 705(d,85) 703(d,80)
3″,5″ 668(d,80) 664(d,85) 668(d,85) 672(d,85) 670(d,80)
1 435(d,80) 426(d,75) 430(d,80 457(d,80)
2 327(d,90) 316(brt,85) 330a 320~340a
3 488(d,95) 340a 340a 320~340a
4 343a 330a 332a 320~340a
5 332a 340a 335a 320~340a
6 364

382(d,120)
429(dd,15,115)
416(dd,60,115)
355(d,10)
340(m)
389a
362a
  
å
:a.
v(signalsoverlapped)。
*
2 
_V˜
1~6
±
13C(CD3OD,125MHz)%=>
Table2 13CNMR(CD3OD,125MHz)datafor16
No 1 2 3 4 5 6
C1 956 951 955 951 946 951
C3 1553 1551 1554 1551 1550 1551
C4 1093 1093 1093 1094 1092 1093
C5 316 317 316 318 323 318
C6 407 412 408 412 412 410
C7 1729 1730 1724 1731 1730 1735
C8 1251 1249 1254 1249 1294 1248
C9 1305 1304 1305 1300 1299 1305
C10 137 137 138 138 592 135
C11 1689 1686 1686 1686 1684 1686
11OMe 519 520 519 519 519 519
C1′ 1009 1008 1012 1005 1009 1009
C2′ 747 749 747 741 748 747
C3′ 779 778 779 876 785 784
C4′ 716 714 712 699 715 714
C5′ 784 782 783 782 779 779
C6′ 628 626 625 626 628 627
Cα 722 721 722 669 669
Cβ 363 363 363 352 352
C1″ 1306 1306 1307 1304 1310
C2″,6″ 1309 1309 1309 1310 1310
C3″,5″ 1161 1161 1161 1163 1163
C4″ 1568 1567 1568 1571 1571
C1 1043 1043 1043 1052
C2 732 746 751 755
C3 793 778 759 778
C4 697 715 729 716
C5 776 750 757 781
C6 623 649 625 626
7OMe 522
  
¿
ROSEY
ç$Ma½ä
H1
Ñ
H6
€

*
ú
H1
Ñ
H5
Ց
;H10
Ñ
H5
€Mÿü‘÷


÷Q

Ö[͜VÓ3=>ÊÑ^”ñ
ì
[3],
îâ_V˜

±€ì÷Q—`•
H1α¬
H5β,Q¸<âD_V˜1±œ÷, SciFinder=
>•‚j•[bœ÷

⮕ÒW?èê
A(alas
hanidoidA)。
_V˜
2 
}(ãå
,[α]25D -1023(c017,
MeOH);HRESIMSm/z6852321[M-H]-,
—ï
ó
C31H42O17,
1H
¬
13CNMR
=>—`]*
1,2。
a
÷=>Ñ^”
[3]
kÚ[c

Ý<â•
(8E)
³Xï
ê
[(8E)nüzhenide]。
_V˜
3 
À(ãå
,[α]25D -916(c002,
MeOH);HRESIMSm/z6852321[M-H]-,
—ï
ó
C31H42O17,
1H
¬
13CNMR
=>—`]*
1,2。
a
÷=>Ñ^”
[4]
kÚ[c

Ý<â•Õ³Xê
(isonüezhenide)。
_V˜
4 
}(ãå
,[α]25D -720(c01,
MeOH);HRESIMSm/z6852312[M-H]-,
—ï
ó
C31H42O17,
1H
¬
13CNMR
=>—`]*
1,2。
a
÷=>Ñ^”
[5]
kÚ[c

Ý<â•
3′OβD·
¸£³Xê
(3′OβDglucopyranosyligustroside)。
_V˜
5 
À(£o²
,[α]25D -1360(c007,
MeOH);HRESIMSm/z5631638[M +Na]+,
—
ïó
C25H32O13,
1H
¬
13CNMR
=>—`]*
1,2。
a÷=>Ñ^”
[6]
kÚ[c

Ý<â•
10
‚1³

(10hydroxyligustroside)。
_V˜
6 
À(£o²
,[α]25D -1840(c
0082,MeOH);HRESIMSm/z4631452[M +
HCOO]-,
—ïó•
C18H26O11,
1H
¬
13CNMR
=>
—`]*
1,2。
a÷=>Ñ^”
[78]
kÚ[c

Ý
<â•y¢Yꀇ
(oleosidedimethylester)。
_V˜
1~6
¿
40μmol·L-1žì LPS\]
RAW2647
Za
NO
–

òAە™µìH

¬
HepG2
Zahu¥hi9Ë0ž

·9421·
2016
y

z ³
41
ų

}
Vol41,No.7 April,2016
5 
œæÑÚs
>?ǎ˜±_–—L/•MBCèÄ

y
%ÛÄ

ƒm¨ÊƒˆÛÄ
[10],
§=®>?%A±
@¬Ø$±L/–—•y%Û
[1],
ïí[6ƒBM
BCè±kÚ

9«¬Hºì=®>?@AÖnD
_–—«¬

¦$—ž<â

MBCèÄ

RS

¥±¬

îÄ˜

«¬œæ8•=®>
?ѦÇÓ⎘±—Ä#GD_—Ä·>

ç¿[â¹¾÷ŠúDMBCèāêãŸ=®
>?±@y

§Ž•¿€Ap®$

’píю˜n
žïĘÞ2ijkGHèÂߥ{€
[11],
¦
OçµiMBCèĖ—¥ÉÒW?ôS—颱
,ɘÞ


„q=

[1] 
n%”



?I

è

W,ÒW?±_–—¬,Sðµ
«¬Ö×
[J].
$%$,-.
,2015,40(20):4333.
[2] CaoY,WangJ,SuG,etal.Antimyocardialischemiaefectof
SyringapinnatifoliaHemsl.byinhibitingexpressionofcyclooxy
genase1and2inmyocardialtissuesofmice[J].JEthnophar
macol,2016,doi:10.1016/j.jep.2016.04.039.
[3] MachidaK,KanekoA,HosogaiT,etal.Studiesontheconstit
uentsofSyringaspecies.X.fivenewiridoidglycosidesfromthe
leavesofSyringareticulata(Blume)Hara[J].ChemPharm
Bul,2002,50:493.
[4] FekuyamaY,KoshinoK,HasegawaT,etal.Newsecoiridoid
glucosidesfromLigustrumjaponicum[J].PlantaMed,1987,53
(5):427.
[5] SakamotoS,MachidaK,KikuchiM.Secoiridoiddiglycosides
fromOsmanthusilicifolius[J].Heterocycles,2009,77(1):
557.
[6] ShenYC,LinCY,ChenCH,SecoiridoidglucosidesfromJas
minummultiflorum[J].Phytochemistry,1990,29:2905.
[7] GaoBB,SheGM,SheDM.Chemicalconstituentsandbiolog
icalactivitiesofplantsfrom thegenusLigutrum[J].Chem
Biodivers,2013,10(1):96.
[8] 
yyú

lO



è

€Ÿ9œ#֘_–—±«
¬
[J].
$,
,2011,42(3):447.
[9] ChaiXY,XuZR,RenHY,etal.ItosidesAI,newphenolic
glycosidesfromItoaorientalis[J].HelvChimActa,2007,90
(11):2176.
[10] SuGZ,CaoY,LiC,etal.Phytochemicalandpharmacological
progressonthegenusSyringa[J].ChemCentJ,2015,9:2.
[11] GhisalbertiEL.Biologicalandpharmacologicalactivityofnatu
ralyoccuringiridoidsandsecoiridoids[J].Phytomedicine,
1998,5(2):147.

€-0
 
¦§¨

·0521·