全 文 :2016
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Vol41,No.6 March,2016
[
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TriterpenoidsfromGanodermatheaecolum
LIULiying1,KANGJie1,WUChanghui2,LIYe2,CHENRuoyun1
(1.StateKeyLaboratoryofBioactiveSubstanceandFunctionofNaturalMedicines,InstituteofMateria
Medica,ChineseAcademyofMedicalSciencesandPekingUnionMedicalColege,Beijing100050,China;
2.NationalEdibleFungiprocesingTechnologicalResearchSubCenter,MedicinalFungiCultivationandDeepProcesingofNational
Local,JointEngineeringResearchCenter,FujianXianzhilouBiologicalScienceandTechnologyCo.,Ltd.,Fuzhou350002,China)
[Abstract] FifteenlanostanetriterpenoidswereisolatedfromtheethanolextractofGanodermatheaecolumbymeansofpreparative
HPLC,columnchromatographyoversilicagel,ODSandwereidentifiedaslucidoneC(1),lucidoneD(2),7oxoganodericacidZ2
(3),7oxoganodericacidZ(4),ganoderenicacidH(5),ganoderenicacidB(6),3β,7βdihydroyl11,15,23trioxolanost8,16dien
26oicacid(7),3β,7βdihydroyl11,15,23trioxolanost8,16dien26oicacidmethylester(8),ganolucidicacidB(9),ganolucidate
F(10),methylganoderateC2(11),ganodericacidζ(12),ganodericacidAP3(13),methylganoderateB(14),andganoderolB(15)
Compounds115wereisolatedfromthisspecieforthefirsttime
[Keywords] Ganoderma;Ganodermatheaecolum;triterpenoids
doi:10.4268/cjcmm20160617
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2016
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3
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Vol41,No.6 March,2016
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$ÊKÊ1XDBÃÑ T]
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(12),
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1
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95%
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110g。50%
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=r
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a
10
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。
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FrB
1
(10g)
?wFNKL
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(9∶1~
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a
25
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。FrB8
?wF
NKL
,
iÙö
®7ö
(4∶1)
ß±
,
=r_=
2(45mg)。FrB9
?wFNKL
,
iÙö
®7
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(7∶3)
ß±
,
=r_=
7(25mg),FrB25
?
wFNKL
,
iÙö
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(6∶4)
ß±
,
=r_
=
8(10mg)。FrC
1
(35g)
?wFNKL
,
i
Ùö
®7Â
(9∶1~1∶1)
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,Frs1~36
a
36
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?wFNKL
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(9∶1)
ß±
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=r_=
1(4mg),5(56mg),FrC9
?wFNKL
,
iÙö
®7ö
(4∶1)
ß±
,
=r
_=
11(3mg),9(2mg),10(5mg),FrC21
?
wFNKL
,
iÙö
®7ö
(6∶4)
ß±
,
=r_
=
6(2mg),13(15mg)。FrD
1
(84g)
?w
FNKL
,
i»H
àÊÂ
(30∶1~1∶1)
ß±
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Frs1~55
a
55
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?wFNKL
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(2∶1)
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=r_=
14(1
mg),FrD32
?wFNKL
,
i»H
àÊö
(9∶
1)
ß±
,
=r_=
12(2mg)。70%
²Ê1@ò
wFNKL
,
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(20∶1~1∶1)
ß
±
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=r
FrsA~G
a
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(21g)
?wFNKL
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(135mg),FrA8
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(15
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a
8
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?wFNKL
,
i
»H
àÊö
(6∶4)
ß±
,
=r_=
15(5mg)。
3
<^Vv
_=
1
Kxv§w
。ESIMSm/z
4052[M+H]+。1HNMR(pyridined5,600MHz)δ:
105(3H,s,H18),109(3H,s,H19),127(3H,s,
H29),149(3H,s,H30),157(3H,s,H28),208
(3H,s,H21),350(1H,dd,J=48,66Hz,H3),
·6701·
ûóö
:
j¢Þß$Lkd
496(1H,m,H7),532(1H,dd,J=12,78Hz,H
15);13CNMR(pyridined5,150MHz)Ü1。b$
=.^Þ
[7]
k.
3β,7β,15αtrihydroxy4,4,
14αtrimethyl11,20dioxo5αpregn8ene[÷,IV
v_=
1
ò$ß7
C(lucidoneC)。
Ü
1
_=
1~8
13CNMR
=.
Table1 13CNMRdataofcompounds18
No 1 2 3 4 5 6 7 8
1 354 336 339 348 361 356 347 347
2 288 274 275 274 344 287 276 276
3 775 775 776 779 770 777 783 783
4 391 391 388 389 460 395 387 387
5 499 510 501 498 486 501 497 497
6 290 362 189 366 369 284 260 260
7 6931990202219911999 667 672 672
8 15991463150613891478159115811581
9 14191517151816491521142814201420
10 393 406 398 397 399 394 391 391
11 199019842023 2361995198119821982
12 515 482 516 301 491 498 444 444
13 475 440 473 449 494 466 516 516
14 548 565 489 477 572 583 587 587
15 7242056 321 3192074215121102110
16 307 348 273 287 374 38712341234
17 567 528 489 489 514 50218891889
18 191 179 168 158 180 193 313 313
19 198 178 175 183 181 187 185 185
20 20762054 360 36215381538 283 283
21 311 312 183 186 214 211 209 209
22 - - 345 34712571254 493 493
23 - - 257 2581992197220622062
24 - - 14501455 413 485 454 454
25 - - 12701266 285 356 347 347
26 - - 172917291812180017981798
27 - - 120 120 164 179 169 169
28 288 279 278 250 284 253 282 282
29 166 155 154 274 224 166 156 156
30 204 219 258 153 181 288 329 329
OMe - - - - - - - 520
_=
2
ËÓKxv§w
。ESIMSm/z
4012[M+H]+。1HNMR(CDCl3,500MHz)δ:
073(3H,s,H18),088(3H,s,H19),102(3H,s,
H29),126(3H,s,H30),158(3H,s,H28),219
(3H,s,H21),305(1H,d,J=160Hz,H12α),
277(1H,d,J=160Hz,H12β),334(1H,t,J=
175,175Hz,H17),325(1H,dd,J=50,200
Hz,H3);13CNMR(CDCl3,125MHz)Ü1。ìb
=.^Þ
[8]
k.
3βhydroxy4,4,14αtrimeth
yl7,11,15,20tetraoxo5αpregn8ene÷,IVv_
=
2
ò$ß7
D(lucidoneD)。
_=
3
K§w
(
àÊ
)。ESIMSm/z
5292[M-H]-。1HNMR(CDCl3,400MHz)δ:080
(3H,s,H18),087(3H,s,H29),092(3H,d,J=
64Hz,H21),100(3H,s,H28),116(3H,s,H
30),129(3H,s,H19),182(3H,s,H27),327
(1H,dd,J=52,112Hz,H3);13CNMR(CDCl3,
100MHz)
Ü
1。
@òzL=.`^Þ
[8]
=.,
IVvñ_=ò
7oxoganoderic
acidZ2。
_=
4
K § w
(
à Ê
)。ESIMS
m/z5292[M-H]-。1HNMR(CDCl3,400MHz)δ:
065(3H,s,H18),088(3H,s,H29),091(3H,s,
H28),094(3H,d,J=56Hz,H21),099(3H,s,
H30),117(3H,s,H19),183(3H,s,H27),328
(1H,dd,J=44,116Hz,H3);13CNMR(CDCl3,
100MHz)
Ü
1。
@òzL=.`^Þ
[9]
=.,
Vvñ_=ò
7oxoganodericacidZ。
_=
5
Kxv§w
。ESIMSm/z
5113[M-H]-。1HNMR(CDCl3,500MHz)δ:328
(1H,dd,J=50,105Hz,H3),315(1H,dd,J=
70Hz,H25),214(3H,s,H21),155(3H,s,H
30),125(3H,s,H19),120(3H,d,J=70Hz,H
27),104(3H,s,H28),089(3H,s,H29),071
(3H,s,H18);13CNMR(CDCl3,125MHz)Ü 1。
ìb=.^Þ
[10]
k.
ganoderenicacidH
[
÷
,
IVv_=
5
òÞßà]
H。
_=
6
K
。ESIMSm/z5153[M+
H]+。1HNMR(CDC13,600MHz)δ:106(3H,s,H
18),109(3H,s,H29),125(3H,s,H30),138
(3H,d,J=72Hz,H27),141(3H,s,H19),146
(3H,s,H28),226(3H,s,H21),349(1H,dd,J=
59,102Hz,H3),484(1H,dd,J=87,87Hz,H
7),632(1H,s,H22);13CNMR(CDC13,150MHz)
Ü
1。
^Þ
[11]
k.=.[÷
,
IVv_=
6
ò
ganoderenicacidB
=.²z
。
_=
7
¹ËK
(
àÊ
)。ESIMSm/z
5153[M+H]+。1HNMR(CDCl3,400MHz)δ:
084(3H,s,H29),101(3H,s,H28),110(3H,d,
J=68Hz,H21),118(3H,s,H19),120(3H,d,
·7701·
2016
y
3
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41
áà
6
}
Vol41,No.6 March,2016
J=64Hz,H27),121(3H,s,H18),152(3H,s,
H30),322(1H,dd,J=56,108Hz,H3),478
(1H,dd,J=99,77Hz,H7),573(1H,s,H
16);13CNMR(CDCl3,100MHz)Ü1。@òzL
=.`^Þ
[12]
=.,
Vvñ_=ò
3β,7βdihydroxy11,15,23trioxolanost8,16dien
26oicacid。
_=
8
K§w
(
àÊ
)。ESIMSm/z
5273[M-H]-。1HNMR(CDCl3,500MHz)δ:084
(3H,s),102(3H,s),110(3H,d,J=72Hz),
119(3H,s),118(3H,d,J=64Hz),121(3H,
s),150(3H,s),320(1H,dd,J=56,110Hz),
364(3H,s),478(1H,dd,J=96,80Hz),573
(1H,s)。13CNMR(CDCl3,125MHz)=.Ü 1。
²
1HNMR
$ëú³àÔv< δ364(3H,s);13C
NMR
$ëδ520tàÔv<。@òzL=.
`^Þ
[12]
=.,
Vvñ_=ò
3β,
7βdihydroxy11,15,23trioxolanost8,16dien26oic
acidmethylester。
_=
9
K§w
(
àÊ
)。ESIMSm/z
5013[M-H]-。1HNMR(pyridined5,600MHz)δ:
095(3H,d,J=60Hz,H21),097(3H,s,H29),
109(3H,s,H18),134(3H,d,J=72Hz,H27),
136(3H,s,H30),147(3H,s,H19),184(3H,s,
H28),351(1H,dd,J=48,66Hz,H3),464
(1H,dd,J=60,36Hz,H15);13CNMR(pyridine
d5,150MHz)δ:2083(C23),1973(C11),1761
(C26),1636(C8),1388(C9),769(C3),710
(C15),531(C14),517(C12),513(C5),489
(C22),481(C17),464(C13),460(C24),
387(C4),382(C16),373(C10),348(C25),
342(C1),320(C20),298(C7),279(C2),
279(C30),187(C21),185(C28),184(C
19),169(C6),167(C27),161(C18),157(C
29)。
@òzL=.`^Þ
[13]
=.,
Vvñ_=ò
ganolucidicacidB。
_=
10
K§w
(
àÊ
)。ESIMSm/z
5013[M-H]-。1HNMR(pyridined5,500MHz)δ:
093(3H,s,H18),109(3H,s,H29),110(3H,d,
J=62Hz,H21),124(3H,s,H28),136(3H,s,
H19),147(3H,s,H30),215(3H,s,H27),351
(1H,m,H3),460(1H,dd,J=92,59Hz,H15),
499(1H,dt,J=81,60Hz,H23);13CNMR(pyri
dined5,125MHz)δ:1983(C11),1706(C26),
1645(C8),1452(C24),1396(C9),1285(C
25),777(C3),719(C15),667(C23),539(C
14),527(C12),522(C5),497(C17),472(C
13),442(C22),395(C4),394(C16),381(C
10),351(C1),342(C20),307(C6),288(C
2),287(C28),197(C21),195(C30),192(C
19),177(C7),168(C18),165(C29),133(C
27)。
@òzL=.`^Þ
[14]
=.,
Vvñ_=ò
3β,15α,23trihydroxy11oxo5αla
nosta8,24dien26oicacid(ganolucidateF)。
_=
11
K
(
àÊ
)。ESIMSm/z
5333[M+H]+。1HNMR(CDCl3,400MHz)δ:
088(3H,s,H18),102(3H,s,H30),085(3H,d,
J=60Hz,H21),118(3H,d,J=70Hz,H27),
102(3H,s,H28),085(3H,s,H29),127(3H,s,
H19),332(1H,m,H3),455(1H,dd,J=102,
72Hz,H7),469(1H,m,H15),239(1H,m,H
22α),224(1H,m,H22β);13CNMR(CDCl3,100
MHz)δ:2098(C23),1995(C11),1740(C26),
1575(C8),1421(C9),782(C3),725(C15),
696(C7),539(C14),524(C12),519(C31),
491(C5),481(C17),471(C13),454(C24),
420(C22),386(C4),386(C10),364(C16),
346(C1),346(C25),323(C20),284(C6),
282(C28),278(C2),198(C19),195(C21),
194(C30),171(C27),157(C18),97(C29)。
²
1HNMR
$ëú³àÔv< δ376(3H,s);13C
NMR
$ëδ519tàÔv<。ìb=.^
Þ
[15]
k.
methylganoderateC2[÷,IVv_
=
11
òÞß]
C2à³。
_=
12
K
。ESIMSm/z5153
[M+H]+。1HNMR(pyridined5,600MHz)δ:091
(3H,s,H18),104(3H,s,H29),113(3H,s,H
28),115(3H,d,J=54Hz,H21),136(3H,s,H
19),174(3H,s,H30),215(3H,s,H27),343
(1H,dd,J=48,66Hz,H3),484(1H,dd,J=
87,87Hz,H23),737(1H,d,J=84Hz,H
24);13CNMR(pyridined5,150MHz)δ:2081(C
15),2004(C11),1999(C7),1708(C26),
1518(C9),1472(C8),1428(C24),1288(C
·8701·
ûóö
:
j¢Þß$Lkd
25),768(C3),667(C23),577(C14),517(C
5),499(C12),461(C16),447(C13),438(C
17),410(C10),410(C22),398(C4),370(C
6),342(C1),340(C20),284(C28),282(C
2),215(C30),201(C21),181(C19),163(C
18),162(C29),135(C27)。
^Þ
[16]
k.
ganodericacidζ=.²z。
_=
13
K§w
(
àÊ
)。ESIMSm/z
5292[M-H]-。1HNMR(pyridined5,600MHz)δ:
101(3H,s,H18),112(3H,s,H29),131(3H,d,
J=72Hz,H27),135(3H,s,H28),139(3H,s,
H30),178(3H,s,H19),184(3H,s,H21),435
(1H,dd,J=96,66Hz,H15);13CNMR(pyridine
d5,150MHz)δ:2154(C3),2112(C23),2046
(C7),2012(C11),1778(C26),1523(C9),
1504(C8),733(C20),720(C15),528(C
14),525(C22),521(C12),509(C17),490
(C5),478(C13),477(C24),464(C4),391
(C10),368(C6),350(C1),345(C25),339
(C2),302(C16),272(C28),266(C21),206
(C30),202(C29),189(C18),175(C19),
170(C27)。
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=
.,
Vvñ_=ò
ganodericacidAP3。
_=
14
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512[M-H2O]
+。1HNMR(CDCl3,600MHz)δ:086
(3H,s,H18),102(3H,d,J=60Hz,H21),109
(3H,d,J=72Hz,H27),122(3H,s,H29),125
(3H,s,H19),135(3H,s,H21),217(3H,s,H
28),321(1H,dd,J=48,66Hz,H3),481(1H,
dd,J=60,84Hz,H7);13CNMR(CDCl3,150
MHz)δ:2172(C23),2094(C15),1977(C11),
1743(C27),1568(C8),1427(C9),783(C
3),668(C7),585(C14),519(C31),503(C
12),491(C22),490(C17),467(C24),456
(C5),450(C10),409(C16),388(C13),386
(C4),348(C1),347(C25),315(C20),281
(C2),277(C6),266(C26),244(C29),198
(C21),184(C28),174(C19),170(C18),
154(C30)。
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15
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5292[M-H]-。1HNMR(CDCl3,400MHz)δ:057
(3H,s,H18),088(6H,s,H28
¨
H30),092
(3H,d,J=64Hz,H21),098(3H,s,H29),101
(3H,s,H19),167(3H,s,H27),324(1H,dd,J=
44,108Hz,H3),399(2H,s,H26),532(1H,
d,J=60Hz,H7),540(1H,d,J=64Hz,H24),
547(1H,d,J=60Hz,H11)。13CNMR(CDCl3,
150MHz)δ:1459(C9),1427(C8),1343(C
25),1270(C24),1202(C7),1163(C11),789
(C3),691(C26),509(C17),503(C5),491
(C14),438(C13),387(C4),378(C12),374
(C10),361(C20),359(C22),357(C1),315
(C16),281(C2),279(C15),278(C29),256
(C28),245(C23),230(C6),227(C19),184
(C21),158(C30),157(C18),136(C27)。
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·9701·
2016
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3
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41
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6
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Vol41,No.6 March,2016
[
yg?z
]
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