全 文 ：·化学·
Hernsubanine E，a new hasubanan alkaloid from Stephania hernandifolia
ZHANG Nan1，2，TANG Li-jia2，DENG Lu-lu2，GUAN Huan-yu2，
ZHANG Jian-xin2，HAO Xiao-jiang2，ZHANG Yuan-hu2*
(1. School of Chemistry and Material Science，Guizhou Normal University，Guiyang 550001，China;
2. The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences，Guiyang 550002，China)
［Abstract］ A new hasubanan alkaloid，hernsubanine E(1) ，as well as two known compounds p-hydroxybenzaldehyde(2)and
(－)-syringaresinol(3)have been isolated from the whole plants of Stephania hernandifolia by various column chromatographic meth-
ods. Their structures were identified by physicochemical properties and spectral analyses. Compounds 2 and 3 were isolated from the
genus of Stephania for the first time.
［Key words］ hasubanan alkaloid;hernsubanine E;Menispermaceae;Stephania hernandifolia
［Ｒeceived date］ 2013-12-25
［Foundation item］ Science and Technology Commission of China
(2012CB722601) ;National Major Scientific Instruments Development
Project(2011YQ12003506)
［Corresponding author］ * ZHANG Yuan-hu，Tel: (0851)3806114，
E-mail:zhangyuanhu@ 263. net
［First author］ ZHANG Nan，Tel:18708502985，E-mail:zhangxiao-
nan0512@ 163. com
Stephania hernandifolia (Willd. ) Walp.
(Menispermaceae)is a perennial twining vine distribu-
ted mainly in the southwest area of China，and used as
a folk medicine for the treatment of rheumatoid arthri-
tis，heatstroke，dysentery，mumps，sore throat，stomati-
tis，analgesia and paralysis［1］． The previous studies of
this plant led to the isolation of some isoquinoline alka-
loids，such as hernandine［2-4］． Ｒecently，in the course
of our continue investigation on the alkaloids in this
plant［5-8］，a new hasubanan alkaloid，hernsubanine E
(1) (Fig. 1) ，and two known compounds were isolated
from the whole plants of S. hernandifolia． These
known compounds were identified as p-hydroxybenzal-
dehyde(2)［9］and(－)-syringaresinol(3)［10］ by com-
parison of their MS，1H-，and 13C-NMＲ spectroscopic
data with those reported and isolated from the genus of
Stephania for the first time． This paper mainly de-
scribes the isolation and structural elucidation of this
new alkaloid.
Fig. 1 Structures of compound 1 and hernsubanine A
1 Materials and methods
1. 1 General
All solvents used for the extraction and isolation
were distilled prior to use． The petroleum ether used for
the chromatography had a b. p． ranging from 60-90 ℃．
For the column chromatography(CC) ，silica gel(SiO2，
300-400 mesh， SiO2 H10-40 μm，Qingdao Marine
Chemical，China) ，MCI gel CHP20P(75-150 μm，Mit-
subishi Chemical Industries Company，Japan) ，Ｒp-18
gel(50 μm，YMC，Japan) ，and Sephadex LH-20(40-
70 μm;Amersham Pharmacia Biotech AB，Sweden)
were used． TLC was performed on precoated silica gel
plates(GF254，Qingdao Marine Chemical，China)and
spots were visualized by spraying the Dragendorffs rea-
gent． M. p.:X-4 melting-point apparatus． Optical rota-
tions:Ｒudolph Autopol 1 digital polarimeter(2. 5-cm
cell)． UV Spectra:Shimadzu UV-2401 PC UV/VIS
spectrophotometer，λmax(logε)in nm． IＲ Spectra:Bruk-
er Tensor 27 FT-IＲ spectrometer，KBr disks，ν in cm －1 ．
1D-and 2D-NMＲ Spectra:Bruker DPX-400 NMＲ spec-
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trometer，δ in ppm rel． to Me4Si as internal standard，J in
Hz． HＲ-EI-MS:VG Auto Spec-3000 mass spectrometer.
1. 2 Plant material
The whole plant material of S． hernandifolia was
collected in Luodian (Guizhou，China) in August
2008，and identified by Prof． LI An-ren，Institute of
Botany，the Chinese Academy of Sciences． A voucher
specimen(No． Zhang20080813)has been deposited in
the Key Laboratory of Chemistry for Natural Products of
Guizhou Province and Chinese Academy of Sciences.
1. 3 Extraction and isolation
The dried and powdered whole plant(22. 0 kg)of
S． hernandifolia was refluxed extracted with 95%
EtOH(100 L × 4)for four times，and three hours for
each time． After removing the solvent under reduced
pressure，the residue(1 020 g)was partitioned between
petroleum ether and 5% HCl． The aqueous phase was
adjusted to pH 7 with saturated NH3-H2O and extrac-
ted with CHCl3 to give crude alkaloids(502 g)． The
crude alkaloids(496 g)were subjected to silica gel
column chromatography(CC)and eluted with CHCl3-
MeOH(100∶ 0-0∶ 100)to yield twelve fractions(Frs． A-
L). Fr． B(57. 0 g) (CHCl3-MeOH 100∶ 2)was isolated
by MCI gel CC with MeOH-H2O(30∶ 100-100∶ 0)to af-
ford four fractions(Subfrs． B1-B4)． Subfrs． B3(1. 1 g)
(MeOH-H2O 70 ∶ 100)was further separated by silica
gel CC using CHCl3-MeOH(100∶ 0-0∶ 100)and petrole-
um ether-acetone(100 ∶ 0-0 ∶ 100)to give compound 2
(24 mg)． Subfrs． B4(0. 7 g) (MeOH-H2 O 90 ∶ 100)
was further isolated by Ｒp-18，Sephadex LH-20，and sili-
ca gel CC using MeOH-H2 O(30 ∶ 100-100 ∶ 0) ，CHCl3-
MeOH(1∶ 1) ，and CHCl3-AcOEt(100∶ 0-0∶ 100)to give
compound 1(13 mg)and 3(14 mg).
2 Ｒesults and discussion
Hernsubanine E {(6β，7β，8β，10β)-8，10-epoxy-
7，8-dimethoxy-2，3-［methyl-enebis(oxy) ］-hasubanan-
6-cinnamate; 1 } (Fig． 1 )． Colorless crystals
(MeOH)． Mp 202-204 ℃ ． ［α］13. 6D 8. 6(c 1. 30，
CHCl3)． UV(CHCl3)λmax:283(2. 88) ，485(1. 47) ，
498(1. 57)． IＲ(KBr)νmax:3 451，2 923，2 853，
1 598，1 484，1 464，1 262，1 112，1 036，804 cm －1 ．
EI-MS m/z 491(M +·) ，213，131． HＲ-EI-MS m/z
491. 193 1(M +·) ，(C28H29NO7;calc． 491. 194 4)．
Hernsubanine E(1)was obtained as colorless crys-
tals． Its molecular formula was assigned as C28H29 NO7
by HＲ-EI-MS m/z 491. 193 1 (M +· ) ，(calc．
491. 194 4) ，with fifteen degrees of unsaturation． The
UV absorptions recorded at λmax 283 (2. 88) ，485
(1. 47) ，498(1. 57)implied the presence of a highly
conjugated system in 1． The IＲ spectrum of 1 suggested
the absorption bands of NH(3 451 cm －1) ，and aryl
group(1 598，1 484，1 464 cm －1)． The 13C-NMＲ spec-
trum consisted of 28 signals corresponding to two MeO，
five methylenes(four saturated and one methylened-
ioxy) ，twelve methines(seven aromatic，three oxygenated
and two olefinic)groups，and nine quaternary carbons
(one C O，five aromatic and three saturated)． Com-
bined with the typical EI-MS fragmentation ions at m / z
213 and 131，13C-NMＲ data at δ 101. 6(s)and 77. 2
(d) ，1 was deduced to be a hasubanan-type alkaloid
with a ketal ether bridge between C-8 and C-10［11］．
The 1H-1H COSY and HMQC spectra revealed the
presence of a methylenedioxy group and isolated
-CH2CHOＲCHOＲ-，-CH2CHOＲ-，-CH2CH2- fragments
(Fig． 2)． Further examination of the 1H-，13C-，and 2D-
NMＲ data and the degrees of unsaturation of compound
1 suggested that 1 was similar to the known alkaloid
hernsubanine A(Fig． 1)［7］ except for the substituent
groups at C-6． In 1，the ester group was determined to
be a cinnamate group as judged by the 1H- and
13C-NMＲ data(table 1) ，and confirmed by HMBC corre-
lations of H-7 with C-1，2，6，8，9，H-2 with C-1，
3，4，7(Fig． 2)． Therefore，1 was identified as(6β，
7β，8β，10β)-8，10-epoxy-7，8-dimethoxy-2，3-［methyle-
nebis(oxy) ］-hasubanan-6-cinnamate and confirmed by
the HSQC，HMBC，and 1H-1H COSY spectra．
Fig. 2 1H-1H COSY(－)and key HMBC(H→C)correlations
of compound 1
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Table 1 The NMＲ data of compound 1(δ in ppm，J in Hz)
No.
11)
δH δC
1 6. 52(s) 106. 4(d)
2 － 147. 7(s)
3 － 144. 9(s)
4 6. 66(s) 107. 0(d)
5 2. 27(dd，J =2. 4，14. 8 Hz)，2. 44-2. 45(m) 35. 8(t)
6 5. 34-5. 37(m) 67. 5(d)
7 3. 84(d，J =4. 0 Hz) 80. 9(d)
8 － 101. 6(s)
9 1. 93(d，J =10. 4 Hz)，2. 41-2. 42(m) 38. 1(t)
10 4. 88(d，J =6. 0 Hz) 77. 2(d)
11 － 136. 3(s)
12 － 133. 2(s)
13 － 47. 3(s)
14 － 73. 6(s)
15 2. 01-2. 07(m) 38. 7(t)
16 3. 20-3. 24(m) 41. 3(t)
1 － 134. 4(s)
2 7. 35-7. 43(5H，m) 127. 9(d)
3 128. 7(s)
4 130. 0(s)
5 128. 7(d)
6 127. 9(d)
7 7. 33(d，J =16. 0 Hz) 143. 4(d)
8 5. 73(d，J =16. 0 Hz) 118. 0(d)
9 － 166. 8(s)
7-OMe 3. 40(s) 57. 0(q)
8-OMe 3. 58(s) 52. 0(q)
3-OMe － －
4-OMe － －
-OCH2O- 4. 83，5. 59(2d，J =1. 6 Hz) 100. 8(t)
Note:1)1H-and 13C-NMＲ were measured in CDCl3 at 400 and 100 MHz.
Compound 2 White crystals;EI-MS m/z 122
(M +·) ，93，65;1H-NMＲ(DMSO-d6，400 MHz)δ:9. 77
(1H，s，-CHO) ，7. 76(2H，d，J = 6. 8 Hz，H-2，6) ，6. 93
(2H，d，J = 6. 8 Hz，H-3，5) ;13C-NMＲ(DMSO-d6，
100MHz)δ:128. 5(C-1) ，132. 2(C-2，6) ，115. 9(C-3，
5) ，163. 4(C-4) ，191. 1(-CHO)． All the spectral data
were consistent with p-hydroxybenzaldehyde［9］．
Compound 3 White crystals; ［α］13D － 0. 75(c
1. 33，CHCl3)． EI-MS m / z 418(M
+·) ，210，181，
167，155;1H-NMＲ(CDCl3，400 MHz)δ:6. 59(4H，s，
H-2，2″，6，6″) ，5. 54(2H，s，4，4″-OH) ，4. 73(2H，
d，J = 3. 6 Hz，H-2，6) ，4. 29(2H，dd，J = 6. 4，8. 4
Hz，H-4，8) ，3. 91(12H，s，3，5，3″，5″-OCH3) ，3. 09
(2H，m，H-1，5) ;13C-NMＲ(CDCl3，100 MHz)δ:
54. 3(C-1，5) ，85. 9(C-2，6) ，71. 8(C-4，8) ，131. 9
(C-1，1″) ，102. 6(C-2，2″，6，6″) ，147. 1(C-3，3″，
5，5″) ，134. 2(C-4，4″) ，56. 2(-OCH3)． All the
spectral data were consistent with (－ )-syringares-
inol［10］.
［Acknowledgments］ Thank the Key Laboratory of
Chemistry for Natural Products of Guizhou Province and Chinese
Academy of Sciences，and the Kunming Institute of Botany，Chi-
nese Academy of Sciences for the measurement of NMＲ and HＲ-
EI-MS data.
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桐叶千金藤中的一个新莲花烷型生物碱
张楠1，2，唐丽佳2，邓璐璐2，关焕玉2，张建新2，郝小江2，张援虎2*
( 1. 贵州师范大学 化学与材料科学学院，贵州 贵阳 550001;
2. 贵州省中国科学院 天然产物化学重点实验室，贵州 贵阳 550002)
［摘要］ 采用多种柱色谱方法从桐叶千金藤 Stephania hernandifolia Walp 中分离得到 1 个新的莲花烷型生物碱—桐叶莲
花碱 E(1)和 2 个已知化合物—对羟基苯甲醛(2)和(－)-丁香树脂酚(3)。通过光谱学数据分析鉴定了这些化合物的结构。
其中，化合物 2 和 3 为首次从该属植物中分离鉴定。
［关键词］ 莲花烷型生物碱;桐叶莲花碱 E;防己科;桐叶千金藤
doi:10． 4268 /cjcmm20140613
［责任编辑 孔晶晶］
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2014 年 3 月
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