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Triterpenoids from Ganoderma theaecolum

茶病灵芝中三萜类成分研究



全 文 :2016
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TriterpenoidsfromGanodermatheaecolum
LIULiying1,KANGJie1,WUChanghui2,LIYe2,CHENRuoyun1
(1.StateKeyLaboratoryofBioactiveSubstanceandFunctionofNaturalMedicines,InstituteofMateria
Medica,ChineseAcademyofMedicalSciencesandPekingUnionMedicalColege,Beijing100050,China;
2.NationalEdibleFungiprocesingTechnologicalResearchSubCenter,MedicinalFungiCultivationandDeepProcesingofNational
Local,JointEngineeringResearchCenter,FujianXianzhilouBiologicalScienceandTechnologyCo.,Ltd.,Fuzhou350002,China)
[Abstract] FifteenlanostanetriterpenoidswereisolatedfromtheethanolextractofGanodermatheaecolumbymeansofpreparative
HPLC,columnchromatographyoversilicagel,ODSandwereidentifiedaslucidoneC(1),lucidoneD(2),7oxoganodericacidZ2
(3),7oxoganodericacidZ(4),ganoderenicacidH(5),ganoderenicacidB(6),3β,7βdihydroyl11,15,23trioxolanost8,16dien
26oicacid(7),3β,7βdihydroyl11,15,23trioxolanost8,16dien26oicacidmethylester(8),ganolucidicacidB(9),ganolucidate
F(10),methylganoderateC2(11),ganodericacidζ(12),ganodericacidAP3(13),methylganoderateB(14),andganoderolB(15)
Compounds115wereisolatedfromthisspecieforthefirsttime
[Keywords] Ganoderma;Ganodermatheaecolum;triterpenoids
doi:10.4268/cjcmm20160617
  
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4052[M+H]+。1HNMR(pyridined5,600MHz)δ:
105(3H,s,H18),109(3H,s,H19),127(3H,s,
H29),149(3H,s,H30),157(3H,s,H28),208
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=.†^Þ
[7]
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v_=‹

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1 
_=‹
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=.
Table1 13CNMRdataofcompounds18
No 1 2 3 4 5 6 7 8
1 354 336 339 348 361 356 347 347
2 288 274 275 274 344 287 276 276
3 775 775 776 779 770 777 783 783
4 391 391 388 389 460 395 387 387
5 499 510 501 498 486 501 497 497
6 290 362 189 366 369 284 260 260
7 6931990202219911999 667 672 672
8 15991463150613891478159115811581
9 14191517151816491521142814201420
10 393 406 398 397 399 394 391 391
11 199019842023 2361995198119821982
12 515 482 516 301 491 498 444 444
13 475 440 473 449 494 466 516 516
14 548 565 489 477 572 583 587 587
15 7242056 321 3192074215121102110
16 307 348 273 287 374 38712341234
17 567 528 489 489 514 50218891889
18 191 179 168 158 180 193 313 313
19 198 178 175 183 181 187 185 185
20 20762054 360 36215381538 283 283
21 311 312 183 186 214 211 209 209
22 - - 345 34712571254 493 493
23 - - 257 2581992197220622062
24 - - 14501455 413 485 454 454
25 - - 12701266 285 356 347 347
26 - - 172917291812180017981798
27 - - 120 120 164 179 169 169
28 288 279 278 250 284 253 282 282
29 166 155 154 274 224 166 156 156
30 204 219 258 153 181 288 329 329
OMe - - - - - - - 520
_=‹
2 
ËÓKxv­§w
。ESIMSm/z
4012[M+H]+。1HNMR(CDCl3,500MHz)δ:
073(3H,s,H18),088(3H,s,H19),102(3H,s,
H29),126(3H,s,H30),158(3H,s,H28),219
(3H,s,H21),305(1H,d,J=160Hz,H12α),
277(1H,d,J=160Hz,H12β),334(1H,t,J=
175,175Hz,H17),325(1H,dd,J=50,200
Hz,H3);13CNMR(CDCl3,125MHz)Ü1。ìb
=.†^Þ
[8]
k.ƒ
3βhydroxy4,4,14αtrimeth
yl7,11,15,20tetraoxo5αpregn8ene÷,IVv_


ò$ß7
D(lucidoneD)。
_=‹
3 
 K§w

àÊ
)。ESIMSm/z
5292[M-H]-。1HNMR(CDCl3,400MHz)δ:080
(3H,s,H18),087(3H,s,H29),092(3H,d,J=
64Hz,H21),100(3H,s,H28),116(3H,s,H
30),129(3H,s,H19),182(3H,s,H27),327
(1H,dd,J=52,112Hz,H3);13CNMR(CDCl3,
100MHz)
Ü
1。
@òzL=.‘›`†^Þ
[8]
=.­,
IVvñ_=‹ò
7oxoganoderic
acidZ2。
_= ‹
4 
  K § w

à Ê
)。ESIMS
m/z5292[M-H]-。1HNMR(CDCl3,400MHz)δ:
065(3H,s,H18),088(3H,s,H29),091(3H,s,
H28),094(3H,d,J=56Hz,H21),099(3H,s,
H30),117(3H,s,H19),183(3H,s,H27),328
(1H,dd,J=44,116Hz,H3);13CNMR(CDCl3,
100MHz)
Ü
1。
@òzL=.‘›`†^Þ
[9]
=.­,
Vvñ_=‹ò
7oxoganodericacidZ。
_=‹
5 
 Kxv­§w
。ESIMSm/z
5113[M-H]-。1HNMR(CDCl3,500MHz)δ:328
(1H,dd,J=50,105Hz,H3),315(1H,dd,J=
70Hz,H25),214(3H,s,H21),155(3H,s,H
30),125(3H,s,H19),120(3H,d,J=70Hz,H
27),104(3H,s,H28),089(3H,s,H29),071
(3H,s,H18);13CNMR(CDCl3,125MHz)Ü 1。
ìb=.†^Þ
[10]
k.ƒ
ganoderenicacidH
[
÷

IVv_=‹

òÞßà]
H。
_=‹
6 
 K
。ESIMSm/z5153[M+
H]+。1HNMR(CDC13,600MHz)δ:106(3H,s,H
18),109(3H,s,H29),125(3H,s,H30),138
(3H,d,J=72Hz,H27),141(3H,s,H19),146
(3H,s,H28),226(3H,s,H21),349(1H,dd,J=
59,102Hz,H3),484(1H,dd,J=87,87Hz,H
7),632(1H,s,H22);13CNMR(CDC13,150MHz)
Ü
1。
†^Þ
[11]
k.ƒ=.[÷

IVv_=
‹

ò
ganoderenicacidB
=.²z

_=‹
7 
¹ËK

àÊ
)。ESIMSm/z
5153[M+H]+。1HNMR(CDCl3,400MHz)δ:
084(3H,s,H29),101(3H,s,H28),110(3H,d,
J=68Hz,H21),118(3H,s,H19),120(3H,d,
·7701·
2016
y

z à
41
áà

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Vol41,No.6 March,2016
J=64Hz,H27),121(3H,s,H18),152(3H,s,
H30),322(1H,dd,J=56,108Hz,H3),478
(1H,dd,J=99,77Hz,H7),573(1H,s,H
16);13CNMR(CDCl3,100MHz)Ü1。@òzL
=.‘›`†^Þ
[12]
=.­,
Vvñ_=‹ò
3β,7βdihydroxy11,15,23trioxolanost8,16dien
26oicacid。
_=‹
8 
 K§w

àÊ
)。ESIMSm/z
5273[M-H]-。1HNMR(CDCl3,500MHz)δ:084
(3H,s),102(3H,s),110(3H,d,J=72Hz),
119(3H,s),118(3H,d,J=64Hz),121(3H,
s),150(3H,s),320(1H,dd,J=56,110Hz),
364(3H,s),478(1H,dd,J=96,80Hz),573
(1H,s)。13CNMR(CDCl3,125MHz)=.Ü 1。
²
1HNMR
$ëú³àÔv< δ364(3H,s);13C
NMR
ˆ$ëδ520ƒtàÔv<。@òzL=.
‘›`†^Þ
[12]
=.­,
Vvñ_=‹ò
3β,
7βdihydroxy11,15,23trioxolanost8,16dien26oic
acidmethylester。
_=‹
9 
 K§w

àÊ
)。ESIMSm/z
5013[M-H]-。1HNMR(pyridined5,600MHz)δ:
095(3H,d,J=60Hz,H21),097(3H,s,H29),
109(3H,s,H18),134(3H,d,J=72Hz,H27),
136(3H,s,H30),147(3H,s,H19),184(3H,s,
H28),351(1H,dd,J=48,66Hz,H3),464
(1H,dd,J=60,36Hz,H15);13CNMR(pyridine
d5,150MHz)δ:2083(C23),1973(C11),1761
(C26),1636(C8),1388(C9),769(C3),710
(C15),531(C14),517(C12),513(C5),489
(C22),481(C17),464(C13),460(C24),
387(C4),382(C16),373(C10),348(C25),
342(C1),320(C20),298(C7),279(C2),
279(C30),187(C21),185(C28),184(C
19),169(C6),167(C27),161(C18),157(C
29)。
@òzL=.‘›`†^Þ
[13]
=.­,
Vvñ_=‹ò
ganolucidicacidB。
_=‹
10 
 K§w

àÊ
)。ESIMSm/z
5013[M-H]-。1HNMR(pyridined5,500MHz)δ:
093(3H,s,H18),109(3H,s,H29),110(3H,d,
J=62Hz,H21),124(3H,s,H28),136(3H,s,
H19),147(3H,s,H30),215(3H,s,H27),351
(1H,m,H3),460(1H,dd,J=92,59Hz,H15),
499(1H,dt,J=81,60Hz,H23);13CNMR(pyri
dined5,125MHz)δ:1983(C11),1706(C26),
1645(C8),1452(C24),1396(C9),1285(C
25),777(C3),719(C15),667(C23),539(C
14),527(C12),522(C5),497(C17),472(C
13),442(C22),395(C4),394(C16),381(C
10),351(C1),342(C20),307(C6),288(C
2),287(C28),197(C21),195(C30),192(C
19),177(C7),168(C18),165(C29),133(C
27)。
@òzL=.‘›`†^Þ
[14]
=.­,
Vvñ_=‹ò
3β,15α,23trihydroxy11oxo5αla
nosta8,24dien26oicacid(ganolucidateF)。
_=‹
11 
 K

àÊ
)。ESIMSm/z
5333[M+H]+。1HNMR(CDCl3,400MHz)δ:
088(3H,s,H18),102(3H,s,H30),085(3H,d,
J=60Hz,H21),118(3H,d,J=70Hz,H27),
102(3H,s,H28),085(3H,s,H29),127(3H,s,
H19),332(1H,m,H3),455(1H,dd,J=102,
72Hz,H7),469(1H,m,H15),239(1H,m,H
22α),224(1H,m,H22β);13CNMR(CDCl3,100
MHz)δ:2098(C23),1995(C11),1740(C26),
1575(C8),1421(C9),782(C3),725(C15),
696(C7),539(C14),524(C12),519(C31),
491(C5),481(C17),471(C13),454(C24),
420(C22),386(C4),386(C10),364(C16),
346(C1),346(C25),323(C20),284(C6),
282(C28),278(C2),198(C19),195(C21),
194(C30),171(C27),157(C18),97(C29)。
²
1HNMR
$ëú³àÔv< δ376(3H,s);13C
NMR
ˆ$ëδ519ƒtàÔv<。ìb=.†^
Þ
[15]
k.ƒ
methylganoderateC2[÷,IVv_

11
òÞß]
C2à³。
_=‹
12 
 K
。ESIMSm/z5153
[M+H]+。1HNMR(pyridined5,600MHz)δ:091
(3H,s,H18),104(3H,s,H29),113(3H,s,H
28),115(3H,d,J=54Hz,H21),136(3H,s,H
19),174(3H,s,H30),215(3H,s,H27),343
(1H,dd,J=48,66Hz,H3),484(1H,dd,J=
87,87Hz,H23),737(1H,d,J=84Hz,H
24);13CNMR(pyridined5,150MHz)δ:2081(C
15),2004(C11),1999(C7),1708(C26),
1518(C9),1472(C8),1428(C24),1288(C
·8701·
ûóö

j¢Þß$Lkd‘„…
25),768(C3),667(C23),577(C14),517(C
5),499(C12),461(C16),447(C13),438(C
17),410(C10),410(C22),398(C4),370(C
6),342(C1),340(C20),284(C28),282(C
2),215(C30),201(C21),181(C19),163(C
18),162(C29),135(C27)。
†^Þ
[16]
k.ƒ
ganodericacidζ=.²z。
_=‹
13 
 K§w

àÊ
)。ESIMSm/z
5292[M-H]-。1HNMR(pyridined5,600MHz)δ:
101(3H,s,H18),112(3H,s,H29),131(3H,d,
J=72Hz,H27),135(3H,s,H28),139(3H,s,
H30),178(3H,s,H19),184(3H,s,H21),435
(1H,dd,J=96,66Hz,H15);13CNMR(pyridine
d5,150MHz)δ:2154(C3),2112(C23),2046
(C7),2012(C11),1778(C26),1523(C9),
1504(C8),733(C20),720(C15),528(C
14),525(C22),521(C12),509(C17),490
(C5),478(C13),477(C24),464(C4),391
(C10),368(C6),350(C1),345(C25),339
(C2),302(C16),272(C28),266(C21),206
(C30),202(C29),189(C18),175(C19),
170(C27)。
@òzL=.‘›`†^Þ
[17]
=
.­,
Vvñ_=‹ò
ganodericacidAP3。
_=‹
14 
 K~
。EIMSm/z530[M]+·,
512[M-H2O]
+。1HNMR(CDCl3,600MHz)δ:086
(3H,s,H18),102(3H,d,J=60Hz,H21),109
(3H,d,J=72Hz,H27),122(3H,s,H29),125
(3H,s,H19),135(3H,s,H21),217(3H,s,H
28),321(1H,dd,J=48,66Hz,H3),481(1H,
dd,J=60,84Hz,H7);13CNMR(CDCl3,150
MHz)δ:2172(C23),2094(C15),1977(C11),
1743(C27),1568(C8),1427(C9),783(C
3),668(C7),585(C14),519(C31),503(C
12),491(C22),490(C17),467(C24),456
(C5),450(C10),409(C16),388(C13),386
(C4),348(C1),347(C25),315(C20),281
(C2),277(C6),266(C26),244(C29),198
(C21),184(C28),174(C19),170(C18),
154(C30)。
²
1HNMR
qL$$ëú³àÔv<
δ376(3H,s);13CNMRˆ$ë δ519ƒtàÔv
<

†^Þk
[18]

methylganoderateB
=.²
z

IVv_=‹
14
òÞß]

à³

_=‹
15 
 K§w

àÊ
)。ESIMSm/z
5292[M-H]-。1HNMR(CDCl3,400MHz)δ:057
(3H,s,H18),088(6H,s,H28
¨
H30),092
(3H,d,J=64Hz,H21),098(3H,s,H29),101
(3H,s,H19),167(3H,s,H27),324(1H,dd,J=
44,108Hz,H3),399(2H,s,H26),532(1H,
d,J=60Hz,H7),540(1H,d,J=64Hz,H24),
547(1H,d,J=60Hz,H11)。13CNMR(CDCl3,
150MHz)δ:1459(C9),1427(C8),1343(C
25),1270(C24),1202(C7),1163(C11),789
(C3),691(C26),509(C17),503(C5),491
(C14),438(C13),387(C4),378(C12),374
(C10),361(C20),359(C22),357(C1),315
(C16),281(C2),279(C15),278(C29),256
(C28),245(C23),230(C6),227(C19),184
(C21),158(C30),157(C18),136(C27)。
@
òzL=.‘›`†^Þ
[19]
=.­,
Vvñ_
=‹òÞßÊ
B。
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·9701·
2016
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41
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Vol41,No.6 March,2016

yg?z

[1] 
£…Ì

°¸u

ÞßLk_‘„…—‡
[J].
,
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[20] 
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