全 文 ：天然产物研究与开发 Nat Prod ResDev 2006 , 18:238-242
文章编号:1001-6880(2006)02-0238-05
Recieved May 27 , 2005 Accepted June 21 ,2005
＊Conesponding author Tel:86-28-85225401;E-mai l:zhanggl@cib.ac.cn
攀援孔药花化学成分研究
何志恒1 , 2 ,罗应刚1 ,李洪娟1 , 2 ,张国林1＊
(1.中国科学院成都生物研究所 ,成都 610041;2.中国科学院研究生院 , 北京 100039)
摘 要:从攀援孔药花全草 95%乙醇提取物中首次分离得到 19 个化合物 , 通过波谱数据或与已知物对照 ,它们
分别鉴定为:(2S , 3S , 4R)-2-[(2R)-2-羟基-二十一酰胺基] -二十一烷-1 , 3 , 4-三醇(1)、(2S , 3S , 4R)-2 -二十四酰
胺基-十八烷-1 , 3 , 4-三醇(2)、胡萝卜甙(3)、β-谷甾醇(4)、(20S , 22E , 24R)-5α, 8α-表二氧-麦角甾-6 , 22-二烯-3β-醇
(5)、6β-羟基-豆甾-4-烯-3-酮(6)、十六烷酸-1-甘油酯(7)、桦木酸(8)、大黄素(9)、二十二烷酸-1-甘油酯(10)、对羟
基苯甲醛(11)、十七烷酸-1-甘油酯(12)、金色酰胺醇乙酸酯(13)、十九烷酸-1-甘油酯(14)、棕榈酸(15)、(E)-p-香
豆酸(16)、(22E , 24S)-24-甲基-5α-胆甾-7 , 22-二烯-3β , 5α, 6β-三醇(17)、2-去氧-β-蜕皮激素(18)和 auranamide(19)。
关键词:攀援孔药花;甾体;神经酰胺;金色酰胺醇乙酸酯;auranamide;甘油酯
中图分类号:R284.2;Q946.91 文献标识码:A
Chemical Study on Porandra scandens
HE Zhi-heng1 , 2 , LUO Ying-gang1 ,LI Hong-juan1 ,2 ,ZHANG Guo-lin1＊
(1.Chengdu Institute of Biology , Chinese Academy of Sciences , Chengdu 610041 , China;
2.Graduate School of Chinese Academy of Sciences , Beijing 100039 , China)
Abstract:Nineteen compounds were isolated from the 95% EtOH extract of the whole plants of Porandra scandens for the first
time.On the basis of spectral data or by comparison with authentic samples , they were identified as(2S , 3S , 4R)-2-[(2R)-2-
hydroxyheneicosanoylamino] -1 , 3 , 4-cheneicosanetriol(1),(2S , 3S , 4R)-2-tetracosanoylamino-1 , 3 , 4-octadecanetriol(2), dau-
costerol(3), β-sitosterol(4),(20S , 22E , 24R)-5α, 8α-epidioxy-ergosta-6 , 22-diene-3β-ol(5), 6β-hydroxystigmast- 4-en-3-one
(6), 2 , 3-dihydroxypropyl hexadecoate(7), betulinic acid(8), emodin(9), 2 , 3-dihydroxypropyl docosoate(10), p-hydroxyben-
zaldehyde(11), 2 , 3-dihydroxypropyl heptadecoate(12), aurantiamide acetate(13), 2 , 3-dihydroxypropyl nonadecoate(14), pal-
matic acid(15),(E)-p-coumaric acid(16),(22E , 24S)-24-methyl-5α-cholesta-7 , 22-diene-3β , 5α, 6β-triol(17), 2-deoxy-
crustecdysone(18), and auranamide(19).
Key words:porandra scandens;steroids;ceramides;aurantiamide acetate;auranamide;gly ceride
The genus Porandra(Commelinaceae)consists of only
three species.P.scandens is mainly distributed in Yun-
nan Province , China[ 1] .No chemical investigations were
carried out on the genus and relevant genera of this fami-
ly.In this study nineteen compounds were isolated from
the 95% ethanol extract of the plants.On the basis of
spectral evidence or comparison of them with authentic
samples , they were identified as(2S ,3S , 4R)-2-[(2R)-
2-hydroxyheneicosanoylamino ]-1 , 3 , 4-heneicosanetriol
(1), (2S , 3S , 4R)-2-tetracosanoylamino-1 , 3 , 4-octade-
canetriol(2), daucosterol(3), β-sitosterol(4), (20S ,
22E , 24R)-5α, 8α-epidioxy-ergosta-6 , 22-diene-3β-ol
(5), 6β-hydroxystigmast-4-en-3-one(6), 2 , 3-dihydrox-
ypropyl hexadecoate(7), betulinic acid(8), emodin(9),
2 , 3-dihydroxypropyl docosoate (10), p-hydroxyben-
zaldehyde(11), 2 , 3-dihydroxypropyl heptadecoate(12),
aurantiamide acetate(13), 2 , 3-dihydroxypropyl nonade-
coate(14),palmatic acid(15),(E)-p-oumaric acid(16),
(22E , 24S)-24-methyl-5α-cholesta-7 , 22-diene-3β , 5α,
6β-triol(17), 2-deoxycrustecdysone(18)and auranamide
(19).
Experimental
Melting points were recorded on an X-6 apparatus and are
uncorrected.Optical rotations were measured with a
Perkin-Elmer 341 automatic polarimeter.IR spectra were
recorded on a Perkin-Elmer Spectrum One spectrometer.
NMR spectrawere obtained on a Bruker Avance 600 spec-
trometer(1H:600 MHz , 13C:150 MHz).Chemical shifts
(δ)are given in ppm relative to tetramethylsilane(TMS)as
internal standard and coupling constants in Hertz(Hz).
MS spectra were carried on a Finnigan LCQDECA mass
spectrometer(ESIMS)and on a VG 7070E(70 eV)mass
spectrometer(EIMS).Silica gel H(when not mentioned ,
silica gel with 200 ～ 300 mesh was used.),MCI gel(330
mL), sephadex LH-20 and silica gel 60 were used for col-
umn chromatography(CC).Silica gel GF254(0 ～ 40 μm)
was used for thin layer chromatography(TLC)plates ,
which were activated at 110 ℃ for 2 hours.Spots on TLC
plates were visualized by spraying 8% phosphomolybdic
acid-ethanol solution followed by heating.
Fig.1 Compounds isolated from P.scandens
The whole plants of P .scandens were collected in
September 2001 from Xishuangbanna , Yunnan Province ,
China and identified by Prof.Jing-yun Cui at Xishangban-
na Tropical Botanical Garden , the Chinese Academy of
Sciences(CAS).A voucher specimen(GF-31)is deposited
at the Herbarium of Chengdu Institute of Biology , CAS ,
Chengdu 610041 ,China.
The air-dried and powdered whole plants of P.scandens
(4.9 kg)were soaked with 95%ethanol(25 L×3 , each 7
days)at room temperature.The solvents were removed un-
der reduced pressure to give 198 g residue , which was
suspended in water(2 L)and extracted successively with
ethyl acetate(2 L×4)and n-butanol(2 L×4)to give frac-
tion A(71.5 g)and fraction B(15 g), respectively.
Fraction A was divided into 14 fractions(A1-14)by CC on
silica gel(160 ～ 200 mesh , 1 kg)eluted with petroleum
ether-acetone(100:1 , 50:1 , 40;1 , 30:1 , 20:1 , 10:1 , 4:
1 ,2:1 , 0:1 , each 5000 mL)and then eluted with chloro-
form-methanol(10:1 , 5:1 , 3:1 , 2:1 , 0:1 , each 5000
mL).1(60 mg),2(10 mg)and 3(80mg)were precipitated
from A8 ,A6 and A11 , respectively.A3 was subjected to
CC on MCI gel eluted with methanol-water(4:1)to yield
A3A.4(100 mg), 5(5 mg)and 6(15 mg)were obtained
from A3A separated by CC on silica gel(300 g)eluted
with petroleum ether-acetone(20:1 , 10:1 , 3:1).A4 was
subjected to CC on MCI gel eluted with methanol-water
(7:3 ,8:2 , 9:1 , 15:1)to yield A4A-C.Using petroleum
ether-acetone(10:1)as solvents , A4A was separated by
CC on silica gel(10 g)to give 7(15 mg)and 8(2 mg).
A4B was separated by CC on silica gel 60(20 g)eluted
with petroleum ether-acetone(10:1)to give 9(5 mg)and
10(7 mg).A5 was subjected to CC on MCI gel eluted
with methanol-water(7:3 , 8:2 ,9:1)to yield A5A-C.11
(10 mg)was obtained from A5A separated by CC on silica
gel(40 g)eluted with petroleum ether-acetone(5:1).A5B
was separated by CC on 50 g of silica gel eluted with
petroleum ether-acetone(5:1)to give 12(5 mg)and 13(8
mg).Using petroleum ether-acetone(5:1)as solvents ,
A5C was separated by CC on silica gel(24 g)to give 14(4
mg).A6 was subjected to CC on MCI gel eluted with
239Vol.18 HE Zhi-heng et al:Chemical Study on Porandra scandens
methanol-water(7:3 ,8:2 ,9:1)to yield A6A-C.A6A was
separated by CC on silica gel(45 g)eluted with petroleum
ether-acetone(5:1)to give 15(8 mg).A7was subjected to
CC on MCI gel eluted with methanol-water(7:3 , 8:2 , 9:
1 ,19:1)to yield A7A-D.16(15 mg)was obtained from
A7A separated by CC on sephadex LH-20(100 mL)eluted
with methanol.17(5 mg)was obtained from A7D separated
by CC on silica gel(18 g)eluted with petroleum ether-ace-
tone(3:1).A12was subjected to CC on CI gel eluted with
methanol-water(7:3 ,8:2 , 9:1 , 19:1)to yield A12A-B.
A12A was then subjected to CC on silica gel(17 g)eluted
with petroleum ether-acetone(2:1)to give 18(80 mg).
Using CHCl3-CH3OH(15:1)as solvents ,A12B was sepa-
rated by CC on silica gel(120 g)to give 19(6 mg).
Compounds Identification
(2S , 3S , 4R)-2-[(2R)-2-Hydroxyheneicosanoyl
amino] -1 , 3 , 4-heneicosanetriol(1)White amorphous
powder(acetone);[ α] 28D +15.3°(c 0.20 , pyridine),mp.
127 ～ 129 ℃;ESI-MS(negative mode)m/z:682 [ M-
H] -;IRυKBrmax cm-1:3340 , 2918 , 2850 , 1620 , 1552 , 1467 ,
1071 ,722;1H NMR(C5D5N):δ8.57(1H , d , J =8.8
Hz ,-NHCO),5.10(1H ,m ,H-2),4.60(1H ,dd , J =7.1 ,
3.5 Hz ,H-2′),4.50(1H ,dd , J =10.6 , 4.2 Hz ,H-1a),
4.41(1H ,dd , J =10.6 ,4.5 Hz ,H-1b),4.34(1H ,m ,H-
3), 4.27(1H , m , H-4), 2.20 ～ 2.24(2H , m), 2.00 ～
2.02(1H ,m),1.89 ～ 1.93(2H ,m), 1.75(1H ,m), 1.66
～ 1.70(2H ,m),1.42(1H ,m),1.21 ～ 1.26(about 59H ,
methylene),0.82(6H , t , J =6.7 Hz ,H-21 and H-21′);
13C NMR(C5D5N):δ175.0(C-1′),76.5(C-3),72.8(C-
4), 62.0(C-1), 53.0(C-2), 36.0(C-5), 34.0(C-3′),
32.0(C-6 and C-4′), 29.4-30.1(C-7-C-18 and C-5′-C-
18′), 26.4(C-19), 25.6(C-19′), 22.7(C-20 and C-
20′),14.0(C-21 and C-21′).The [ α] D , mp., IR and
NMR data were in accordance with those reported[ 2] .
(2S ,3S ,4R)-2-Tetracosanoylamino-1 ,3 ,4-octadec-
anetriol(2)White powder(acetone);[ α] 28D +25.0°(c
0.16 ,MeOH),mp.111 ～ 112 ℃;ESI-MS(positive mode)
m/z:690 [ M +Na] +;IRυKBrmax cm-1:3435 , 2919 , 2851 ,
1642 ,1544 ,1471;1H NMR(C5D5N):δ8.55(1H ,d , J =
8.4 Hz ,-NHCO), 5.11(1H , m , H-2), 4.50(2H , m , H-
1), 4.41(1H ,m ,H-3), 4.30(1H , m ,H-4), 2.46(2H , t ,
J =7.4 ,H-2′), 2.24(1H ,m ,H-5a),1.68 ～ 1.98(5H ,
m , H-5b , H-6 and H-3′), 1.24 ～ 1.29(about 62H ,
methylene),0.84(6H , t , J =6.9 Hz ,H-18 and H-24′);
13
C NMR(C5D5N):δ174.2(C-1′),77.6(C-3),74.0(C-
4), 63.0(C-1), 54.7(C-2), 37.7(C-2′), 34.9(C-5),
33.0(C-16 and C-22′), 30.8 ～ 30.9(methylenes), 27.6
(C-6),27.3(C-3′), 23.8(C-17 and C-23′), 15.2(C-18
and C-24′).The[ α] D , mp., IR and NMR data were in
consistent with those of(2S , 3S , 4R)-2-tetracosanoyla-
mino-1 ,3 ,4-octadecanetriol[ 3] .
Compounds 3 , 4 and 5 were identified as daucosterol , β-
sitosterol and(20S , 22E , 24R)-5α, 8α-epidioxy-ergosta-
6 , 22-diene-3β-ol[ 4] by comparing them with authentic
samples on TLC and by co-mp..
6β-Hydroxystigmast-4-en-3-one(6)Flaky crystal(ace-
tone);[ α] 20D +32.2°(c 0.10 , CHCl3), mp.204 ～ 206
℃;IRυKBrmax cm-1:3475 , 2956 , 1692 , 1629 , 1465 , 1384 ,
1253 ,1036 ,880;1H NMR(CDCl3):δ5.83(1H , s ,H-4),
4.37(1H ,brs ,H-6), 2.38(1H , m , H-2a),2.52(1H , m ,
H-2b), 2.04(1H , m , H-1a), 1.86(1H , m ,H-1b), 2.04
(1H ,m ,H-12a), 1.15(1H ,m ,H-12b),1.98(1H , m ,H-
8),1.68(2H ,m ,H-28), 1.52(2H ,m ,H-11), 1.38(3H ,
s ,H-19),1.29(1H ,m ,H-25), 1.25(7H , m , H-7), 1.15
(1H , m , H-23), 1.10(1H , m , H-17), 1.03(1H , m , H-
14), 0.92(2H , d , J =6.5 Hz , H-21), 0.90(1H , m ,H-
9),0.85(3H , d , J =6.6 Hz , H-26), 0.81(3H , d , J =
6.6 Hz ,H-27),0.81(3H , t ,H-29), 0.74(3H , s ,H-18);
13C NMR(CDCl3):δ200.4(C-3), 168.4(C-5), 126.3(C-4),73.3(C-6), 56.0(C-17), 55.9(C-14), 53.6(C-
9),45.9(C-24),42.5(C-13),39.6(C-12),38.6(C-7),
38.0(C-10),37.1(C-1),36.1(C-20),34.3(C-2),33.9
(C-22),29.7(C-8),29.2(C-25),28.2(C-16), 26.1(C-
23), 24.2(C-15), 23.1(C-28), 21.1(C-11), 19.8(C-
26),19.5(C-19),19.0(C-27), 18.7(C-21), 12.0(C-18
and C-29).The mp., IR and NMR data were identical to
those reported[ 5] .
2 , 3-Dihydroxypropyl hexadecoate(7)White powder
(acetone);EI-MS m/z(%):330 [ M+] (0.12), 299
(11.4),270(6.4),239(36.2),134(44.3),112(26.4),
98(79.4), 43(100.0);IRυKBrmax cm-1:3431 , 2919 , 2852 ,
1731 ,1634 , 1107 , 799;1H NMR(CDCl3):δ4.21(1H ,
dd , J =11.5 ,6.1 Hz , H-1′a), 4.15(1H , dd , J =11.5 ,
6.1Hz ,H-1′b),3.94(1H , m ,H-2′), 3.70(1H , dd , J =
11.2 ,3.6 Hz , H-3′a),3.60(1H ,dd , J =11.3 , 6.0 Hz ,
H-3′b), 2.45(1H , brs , 2′-OH), 2.35(2 H , t , J =7.4
Hz ,H-2), 2.01(1H , brs , 3′-OH), 1.65(2H , m , H-3),
1.30(24H ,m ,H-4-H-15), 0.90(3H , t , J =6.8 Hz ,H-
16);13C NMR(CDCl3):δ174.4(C-1), 70.2(C-2′),
65.2(C-1′),63.3(C-3′),34.2(C-2),32.0(C-14),29.7
～ 29.1(C-4-C-13), 24.9(C-3), 22.7(C-15), 14.1(C-
16).The IR ,EIMS and NMR data were identical to those
of 2 ,3-dihydroxypropyl hexadecoate[ 6] .
Betulinic acid(8)White amorphous powder(acetone);
[ α] 20D +6.5°(c 0.20 ,CHCl3),mp.277 ～ 280 ℃;ESI-MS
(negative mode)m/z:455[ M-H]-;IRυKBrmax cm-1:3436 ,
2928 ,2869 , 1687 , 1640 , 883;1H NMR(CDCl3):δ4.74(1H , s ,H-29a),4.60(1H , s ,H-29b),3.19(1H , dd , J =
11.6 ,4.7 Hz , H-3α), 2.99(1H , ddd , J =11.0 , 11.0 ,
4.6 Hz ,H-19),1.68(3H , s ,H-30), 0.97(3H , s ,H-27),
0.96(3H , s ,H-26),0.93(3H , s ,H-23),0.82(3H , s ,H-
240 Nat Prod ResDev Vol.18
25),0.75(3H , s ,H-24);13C NMR(CDCl3):δ179.2(C-
28),150.4(C-20), 109.7(C-29), 79.0(C-3),56.2(C-
17),55.3(C-5),50.5(C-9), 49.3(C-19),46.9(C-18),
42.4(C-14),40.7(C-8), 38.8(C-4),38.7(C-1), 38.4
(C-13), 37.2(C-10),37.0(C-22),34.3(C-7),32.1(C-
16), 30.5(C-15), 29.7(C-21), 27.9(C-23), 27.4(C-
2),25.5(C-12),20.8(C-11),19.4(C-30), 18.3(C-6),
16.1(C-26), 16.0(C-25), 15.3(C-24), 14.7(C-27).
The [ α] D , mp., IR and NMR data were in accordance
with those of betulinic acid[ 7] .
Emodin(9)Orange powder(acetone);ESI-MS(negative
mode)m/z:269[M-H]-;IRυKBrmaxcm-1:3435 , 2957 , 2872 ,
1697 ,1631 , 1524 , 1456 ,1416 ,1344 , 698;1H NMR(DM-
SO-d6):δ12.1(1H , s ,1-OH),12.0(1H , s ,8-OH), 7.52(1H , s , H-4), 7.20(1H , s ,H-2), 7.13(1H , d , J =2.0
Hz ,H-5), 6.61(1H , d , J =2.0 Hz ,H-7),2.42(3H , s ,
CH3-3);13C NMR(DMSO-d6):δ190.2(C-9),182.0(C-
10),166.1(C-6),165.0(C-8),161.9(C-1),148.8(C-
3),135.6(C-10a), 133.3(C-4a), 124.6(C-2), 121.0
(C-4),114.0(C-9a),109.5(C-8a), 109.3(C-5), 108.4
(C-7), 22.0(C-3-CH3).The IR and NMR data were
identical to those of emodin[ 8] .
2 , 3-Dihydroxypropyl docosoate(10)White powder
(acetone);EI-MS m/ z (%):383 [ M-CH2OH ] +(0.81),355(11.6),326(6.8),296(30.2), 134(55.0),
112(33.5), 98(97.2), 57(100.0), 43(100.0);IRυKBrmax
cm-1:3430 ,2918 , 2851 , 1730 , 1633 , 1048;1H NMR(CD-
Cl3)δ4.21(1H , dd , J =11.5 , 6.1 Hz , H-1′a), 4.15
(1H , dd , J =11.5 , 6.1 Hz , H-1′b), 3.94(1H , m , H-
2′),3.70(1H ,dd , J =11.2 ,3.6 Hz ,H-3′a), 3.60(1H ,
dd , J =11.3 , 6.0 Hz , H-3′b), 2.48(1H , brs , 2′-OH),
2.35(2 H , t , J =7.4 Hz ,H-2),2.05(1H ,brs , 3′-OH),
1.63(2H , m , H-3), 1.30(36H , m , H-4-H-21), 0.90
(3H , t , J =6.8 Hz ,H-22).The EIMS , IR and 1H NMR
data were in consistent with those of 2 , 3-dihydroxypropyl
docosoate[ 9] .
p-Hydroxybenzaldehyde(11)White amorphous powder
(acetone);ESI-MS(negative mode)m/z:121 [ M-H] -;
IRυKBrmaxcm-1:3171 , 1668 , 1648 , 1599 , 1518 , 1454 , 1287 ,
1161;1H NMR(CDCl3):δ9.87(1H , s ,-CHO), 7.81(2H ,d , J =8.6 Hz ,H-2 and H-6),6.98(2H ,d , J =8.6
Hz , H-3 and H-5), 6.48(1H , s ,-OH);The IR and 1H
NMR data were identical to those reported[ 10] .
2 , 3-Dihydroxypropyl heptadecoate(12)White powder
(acetone);ES-IMS(positive mode)m/z:367 [ M +
Na] +;IRυKBrmax cm-1:3230 , 3320 , 2910 , 2850 , 1725;1H
NMR(CDCl3):δ4.21(1H , dd , J =11.5 , 6.1 Hz , H-1′
a),41.5(1H , dd , J =11.5 , 6.1 Hz ,H-1′b), 3.94(1H ,
m ,H-2′),3.70(1H ,dd , J =11.2 ,3.6 Hz ,H-3′a), 3.60
(1H , dd , J =11.3 , 6.0 Hz , H-3′b), 2.48(1H , brs , 2′-
OH),2.35(2 H , t , J =7.4 Hz ,H-2),2.05(1H ,brs ,3′-
OH),1.63(2H ,m ,H-3),1.30(26H ,m ,H-4 ～ 16),0.90
(3H , t , J =6.8 Hz ,H-17).The IR and 1H NMR data
were in accordance with those of its homologue(2 ,3-dihy-
droxypropyl pentacosoate)[ 11] .
Aurantiamide acetate(13)White needles(acetone);
[α] 30D-41.0°(c 0.05 ,CHCl3),mp.185 ～ 188 ℃;ES-IMS
(positive mode)m/z:467[M +Na] +;IRυKBrmaxcm-1:3435 ,
1727 ,1661 , 1633 , 1534 , 1454 , 699;1H NMR(CDCl3)δ
7.71(1H , d , J =7.4 Hz , H-2a), 7.54(1H , t , J =7.6
Hz ,H-4a),7.44(2H , t , J =7.7 Hz ,H-3a),7.30(2H ,m
H-3c),7.26(2H , m , H-2c), 7.24(1H , m ,H-4c), 7.17
(2H ,m ,H-3b), 7.15(1H , m , H-4b), 7.08(1H , d , J =
7.0Hz , H-2b), 6.80(1H , d , J =7.7 Hz , H-d), 6.00
(1H ,d , J =8.3 Hz , H-e), 4.78(1H , dd , J =14.3 , 8.2
Hz ,H-3), 4.36(1H ,m ,H-1), 3.92(1H , dd , J =11.3 ,
4.9Hz ,H-2α),3.82(1H ,dd , J =11.3 ,4.1 Hz ,H-2β),
3.23(1H ,dd , J =13.7 ,5.9 Hz ,H-8a),3.06(1H , dd , J
=13.7 ,8.6 Hz ,H-8b), 2.77(2H , m , H-9), 2.03(3H ,
s ,H-7);13C NMR(CDCl3):δ170.8(C-6),170.2(C-4),
167.1(C-5), 136.7(C-1c), 136.6(C-1b), 133.6(C-
1a), 131.9(C-4a), 129.3(C-2c), 129.1(C-2b), 128.8
(C-3c), 128.6(C-3a), 128.5(C-3b), 127.1(C-4c),
127.0(C-1a), 126.7(C-4b), 64.6(C-2), 54.9(C-3),
49.5(C-1), 38.4(C-8), 37.4(C-9), 20.8(C-7).The
mp., [α] D , IR and NMR data were identical to those of
aurantiamide acetate[ 12] .
2 , 3-Dihydroxypropyl nonadecoate(14)White powder
(acetone);IRυKBrmaxcm-1:3240 , 3324 , 2915 , 2850 ,1730;1H
NMR(CDCl3)δ4.21(1H ,dd , J =11.5 ,6.1 Hz ,H-1′a),
4.15(1H , dd , J =11.5 ,6.1 Hz , H-1′b),3.94(1H , m ,
H-2′), 3.70(1H , dd , J =11.2 , 3.6 Hz , H-3′a), 3.60
(1H ,dd , J =11.3 , 6.0 Hz ,H-3′b), 2.48(1H , brs , 2′-
OH),2.35(2 H , t , J =7.4 Hz , H-2), 2.05(1H , brs , 3′-
OH), 1.63(2H , m , H-3), 1.30(26H , m , H-4-H-18),
0.90(3H , t , J =6.8 Hz , H-19).The IR and 1H NMR
was equal to those of 2 , 3-dihydroxypropyl nonade-
coate[ 13] .
Palmatic acid(15)White amorphous powder(acetone);
mp.50 ～ 52 ℃;IRυKBrmaxcm-1:3433(br), 2918 ,2850 ,1699 ,
1295;1H NMR(CDCl3):δ2.35(2H , t , J =7.7 Hz ,H-
2),1.63(2H ,m ,H-3), 1.25(24H , br ,H-4-H-15), 0.88
(3H , t , J =6.7 Hz ,H-16);The mp., IR and 1H NMR
data resembled to those of palmatic acid
[ 14] .
(E)-p-Coumaric acid(16)Yellow needles(acetone);
ES-IMS(negative model)m/ z:163[M-H]-;IRυKBrmax cm-1:
3409 ,1671 ,1602 ,1512 ,1449 , 1314.1H NMR(CD3OD):δ7.61(1H ,d , J =15.8 Hz ,H-2),7.50(2H , d , J =8.6
Hz ,H-5 and H-9),6.82(2H ,d , J =8.6 Hz ,H-6 and H-
8),6.30(1H ,d , J =15.8 Hz ,H-3);13C NMR(CD3OD):δ169.6(C-1), 159.8(C-2), 145.2(C-3), 129.7(C-5
and C-9),125.8(C-4), 115.4(C-6 and C-8),114.2(C-
241Vol.18 HE Zhi-heng et al:Chemical Study on Porandra scandens
7).The NMR data were in good accordance with those of
(E)-p-coumaric acid[ 15] .
(22E , 24S)-24-Methyl-5α-cholesta-7 , 22-diene-3β ,
5α,6β-triol(17)White needles(acetone);[α] 25D-31.7(c
0.05 , CHCl3), mp.244 ～ 245 ℃;IRυKBrmax cm-1:3439 ,
2956 ,2863 ,1634;1H NMR(CDCl3):δ5.35(1H , d , J =
5.5 Hz ,H-7), 5.20(1H , dd , J =14.8 , 7.6 Hz ,H-23),
5.16(1H ,dd , J =14.8 ,8.3 Hz ,H-22),4.08(1H ,m ,H-
3),3.63(1H ,brs ,H-6),2.14(1H ,m ,H-4a),1.78(1H ,
dd , J =11.7 , 3.4 Hz ,H-4b),1.08(3H , s ,H-19), 1.02
(3H ,d , J =6.6 Hz ,H-21),0.91(3H ,d , J =6.8 Hz ,H-
28), 0.84 and 0.82(each 3H , d , J =6.8 Hz ,H-26 and
H-27),0.59(3H , s ,H-18);13C NMR(CDCl3):δ144.0(C-8), 135.4(C-22), 132.2(C-23),117.5(C-7), 76.0
(C-5), 73.7(C-6), 67.7(C-3), 56.0(C-17), 54.8(C-
14), 43.8(C-13), 43.5(C-9), 42.8(C-24), 40.4(C-
20), 39.5(C-4), 39.2(C-12), 37.1(C-10), 33.1(C-
25),33.0(C-1),30.9(C-2), 27.9(C-16),22.9(C-11),
22.1(C-15), 21.1(C-21), 20.0(C-26), 19.7(C-27),
18.9(C-19), 17.6(C-28),12.4(C-18).The [α] D ,mp ,
and 1H NMR data were identical to those reported[ 16] .
2-Deoxycrustecdysone(18)White needles(MeOH);
[α] 25D +50.2°(c 0.20 ,MeOH),mp.250 ～ 252 ℃;ES-
IMS(positive mode)m/z :503[ M +K] +;IRυKBrmax cm-1:
3435 ,1635 ,1055;1H NMR(C5D5N):δ6.41(1H , s , 14-
OH),6.29(1H , s ,H-7),4.26(1H ,brs ,H-3), 3.89(1H ,
d , J =10.1 Hz ,H-22), 3.62(1H , t , J =8.7 Hz ,H-9),
3.03(1H , t , J =9.3 Hz , H-17), 1.62(3H , s , H-21),
1.39(6H , s ,H-26 and H-27), 1.25(3H , s ,H-18), 1.09
(3H , s ,H-19);13C NMR(C5D5N):δ203.2(C-6), 165.9(C-8),121.4(C-7),84.0(C-14), 77.3(C-22),76.6(C-
20),69.3(C-25),67.9(C-3),51.2(C-5),47.9(C-13),
49.9(C-17), 42.4(C-24), 37.8(C-10), 34.2(C-4),
32.2(C-15), 31.5(C-12), 29.7-29.9(C-1 , 2 , 26 , and
27),27.2(C-23), 24.2(C-19),21.5(C-11 and C-16),
21.3(C-21), 17.7(C-18).The mp., [α] D , IR and NMR
data were in accordance with those of 2-deoxy-
crustecdysone[ 17] .
Auranamide(19)Colourless needles(CHCl3);[ α] 20D-
24.5°(c 0.10 ,CHCl3), mp.216-217 ℃;ES-IMS(posi-
tive mode)m/z:529 [ M +Na] +;IRυKBrmax cm-1:3322 ,
1755 , 1635 , 1601 , 1578 , 745 , 696;1H NMR(CDCl3)δ
7.71(1H , d , J =8.2 Hz , H-2a), 7.66(1H , d , J =8.2
Hz ,H-2b),7.51(1H , t , J =7.4 Hz ,H-4b),7.45(1H , t ,
J =7.4 Hz , H-4a), 7.40(1H , t , J =7.7 Hz , H-3b),
7.31(1H ,d , J =13.4 ,7.4 Hz ,H-3a),7.23(1H , d , J =
10.1 Hz ,H-2c), 6.70(1H , d , J =8.9 Hz , H-f), 6.60
(1H ,d , J =6.2 Hz ,H-e),4.92(1H , dd , J =12.8 ,6.8
Hz ,H-4), 4.64(1H , m , H-2), 4.56(1H , dd , J =11.3 ,
3.1 Hz ,H-1a),4.03(1H ,dd , J =11.3 ,4.3 Hz ,H-1b),
3.30(1H ,dd , J =13.8 ,6.4 Hz ,H-6a),3.23(1H , dd , J
=13.8 , 7.0 Hz , H-6b), 3.00(1H , dd , J =13.7 , 6.4
Hz ,H-7a),2.90(1H ,dd , J =13.7 , 8.5 Hz ,H-7b).The
mp., [ α] D , IR and 1H NMR data were consistent with
those of auranamide[ 18].
References
1 Institue of Botany Chinese Academy of Sciences , Flora Reipub-
licae Popularis Sinicae , Vol 13 , part III.Beijing:Science Pub-
lishing House , 1997.72-76.
2 Huang Q , Tezuka Y ,Hatanaka Y , et al.Studies on metabolites
of mycoparasitic fungi , new sesquiterpene alcohol from Tricho-
derma koningii.Chem Pharm Bull , 1995 , 43:1035-1038.
3 Su BN ,Misico R, Park EJ , et al.Isolation and characterization
of bioactive principles of the leaves and stems of Physalis
philadelphica.Tetrahedron , 2000 , 58:3453-3466.
4 Ishizuka T , Yaoita Y , Kikuchi M.Sterols from the fruit body of
Grifola frondosa.Chem Pharm Bull , 1997 , 45:1756-1760.
5 Greca MD , Monaco P , Previtera L.Stigmasterols from Typha
latifolia.J Nat Prod , 1990 , 53:1430-1435.
6 Du ZZ , Shen YM , Li BJ , et al.The chemicalconstituents of
pericarp of Trewia Nudiflora.Natural Product Research and
Develop ment , 2002 , 14(2):9-10.
7 Siddiqui S ,Hafeez F , Begum S , et al.Oleanderol , a new penta-
cyclic triterpene from the leaves of Nerium oleander.J Nat
Prod , 1988 , 51:229-233.
8 Cohen PA , Towers GHN.The anthraquinones of Heterodermia
obscurata.Phytochemistry , 1995 , 40:911-915.
9 Li YS , Chen JJ , Liao XR , et al.Studies on chemical con-
stituents of Hedysarum sikkimense var.rigidum.Chin Tradit
Herb Drugs , 2001 , 32:489-490.
10 Han GX ,Wang LX , Zhang WD , et al.Study on chemical con-
stituents of Bletilla striata.Acad J Sec Mil Med Univ , 2002 ,
23:443-445.
11 Hu WY, Luo SD, Cai JX.Studies on the chemical components
of Daguoyoumateng(Mucuna macrocarpa).Chin Tradit Herb
Drugs , 1994 , 25(2):59-60.
12 Wang MY , Lu WG , Zeng LM , et al.The chemical constituents
of the marine sponge Sigmadocia cymiformis Esper.Chin J Appl
Chem , 2002 , 19:1-3.
13 Yuan Y, ChenWS , Zheng SQ , et al.Studies on chemical con-
stituents in root of Rumex patientia L..China Journal of Chi-
nese Materia Medica , 2001 , 26:256-258.
14 Shu RG , Xu CR , Liu QH.Studies on the chemical constituents
of Cyclocarya paiivrvs(Batal.)Iljinsk..China Journal of Chi-
nese Materia Medica , 1995 , 20:680-681.
15 Sadtler Research Laboratories.Sadtler Standard NMR Spectra.
USA:Sadtler Research Laboratories , 1978.27122.
16 Piccialli V , Sica D.Four new trihydroxylated sterols from the
sponge Spongionella gracilis.J Nat Prod , 1987 , 50:915-920.
17 Zhu WM , Yang XS ,He HP , et al.Phytoecdysones from Porana
discifera.Acta Bot Yunnan , 2000 , 22:351-357.
18 Banerji A , Ray R.Auranamide , a new phenylalanine derivative
isolated from Piper aurantiacum.Wall Ind J Chem , 1981 , 20b:
597-598.
242 Nat Prod ResDev Vol.18