全 文 ： 2011 年 3 月 第 9 卷 第 2 期 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 115

Chinese Journal of Natural Medicines 2011, 9(2): 0115−0119
doi: 10.3724/SP.J.1009.2011.00115
Chinese
Journal of
Natural
Medicines







Chemical Constituents of Toona ciliata var. pubescens
LIU Yu-Bo1, CHENG Xiang-Rong1, QIN Jiang-Jiang1, YAN Shi-Kai1,
JIN Hui-Zi1*, ZHANG Wei-Dong1, 2*
1School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China;
2Department of Phytochemistry, Second Military Medical University, Shanghai 200433, China
Available online Mar. 2011
[ABSTRACT] AIM: To study the chemical constituents of the leaves and stems of Toona ciliata var. pubescens. METHOD: Silica gel
column chromatography, Sephadex LH−20 gel column chromatography and preparative HPLC were employed for the isolation and
purfication. The structures were identified on the basis of spectroscopic data and chemical evidence. RESULTS: 23 Compounds were
isolated from the 95% ethanol extract of the leaves and stems of T. ciliata var. pubescens, and their structures were identified as siderin
(1), 4, 6, 7-trimethoxy-5-methylcoumarin (2), isoscopoletin (3), scopoletin (4), 6, 7-dimethoxycoumarin (5), 7-hydroxy-6, 8-dime-
thoxycoumarin (6), dehydrodiconiferyl alcohol (7), (−)-lariciresinol (8), thero-2, 3-bis-(4-hydroxy-3-methoxypheyl)-3-methoxy-propa-
nol (9), cycloeucalenol (10), 8(14), 15-isopimaradiene-2, 3, 19-triol (11), 3S, 5R-dihydroxy-6R, 7-megstigmadien-9-one (12), (−)-lolio-
lide (13), (+)-catechin (14), dimethyl malate (15), diisobutyl phthalate (16), dibutyl phthalate (17), 1, 3, 5-trimethoxybenzene (18),
syringic acid (19), syringaldehyde (20), vanillic acid (21), vanillin (22), and 3, 3′, 5, 5′-tetra-tert-butyl-2, 2′-dihydroxybiphenyl (23).
CONCLUSION: All compounds were isolated from this plant for the first time.
[KEY WORDS] Meliaceae; Toona ciliata; Chemical constituents; Coumarin
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)02-0115-05

1 Introduction
Toona ciliata Roem. var. pubescens belongs to the fam-
ily Meliaceae which is widely distributed in the tropical areas
of Asia such as India, Malaysia, Indonisia, and southern
China[1]. Previous investigations on Meliaceae revealed the
presence of coumarin, terpenoids, and campesterol [2]. However,
no phytochemical investigations have been reported on this
plant. In this paper, we described the isolation and structure
elucidation of 23 compounds.
2 Apparatus and Reagents
ESI-MS spectra were recorded on Varian MAT-212 mass
spectrometer and a preparative column (Shimadzu PRC-ODS
EV0233) was used for preparative HPLC (Shimadzu

[Received on] 15-Nov.-2010
[Research Funding] This project was supported by the Scientific
Foundation of Shanghai Committee of Science and Technology (No.
09DZ1972200).
[*Corresponding author] ZHANG Wei-Dong：Prof., Tel/Fax: 86-
021-34205989, E-mail: wdzhangy@hotmail.com; JIN Hui-Zi：Prof.,
kimhz@sjtu.edu.cn
These authors have no any conflict of interest to declare.
LC-6AD). 1H and 13C NMR spectra were recorded on Bruker
DRX-500 spectrometers at 500 and 125 MHz, respectively.
All solvents used were of analytical grade (Shanghai Chemi-
cal Company, Ltd.). Silica gel (Yantai, China) and Sephadex
LH-20 (Pharmacia Co., Ltd.) were used for column chroma-
tography, and precoated silica GF254 plates were used for
TLC (Yantai, China).
3 Plant Material
The leaves and stems of T. ciliata Roem. var. pubescens.
were collected in Xiushui, Jiangxi Province, PR China, in
September 2008. The plants were authenticated by Professor
Zhang Han-Ming, Department of Pharmacognosy, School of
Pharmacy, Second Military Medical University. A voucher
specimen was deposited at School of Pharmacy, Shanghai
Jiao Tong University.
4 Extraction and Isolation
Air-dried leaves and stems of T. ciliata Roem. var. pu-
bescens (10.0 kg) were chopped and percolated with 95%
ethanol for three times at room temperature. The ethanolic
extract was partitioned with petroleum ether (PE), CH2Cl2,
EtOAc, and n-BuOH, respectively. The petroleum ether (PE)
fraction (79.5 g) was given to column chromatography using
LIU Yu-Bo, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 115−119
116 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 2011 年 3 月 第 9 卷 第 2 期

silica gel, eluting with petroleum ether (PE)-EtOAc (100% to
50%) to give eleven subfractions. Then the subfractions were
subjected to a series of chromatographic techniques, such as
silica gel column, SephadexLH-20 and preparative HPLC,
yielding compounds 1 (24.3 mg), 2 (15.2 mg), 10 (11.3 mg).
And compounds 3 (51.9 mg), 4 (5.9 mg), 5 (2.4 mg), 6 (2.7
mg), 7 (10.1 mg), 8 (3.3 mg), 9 (10.2 mg), 11 (9.2 mg), 12
(9.8 mg), 13 (3.2 mg), 14 (66.2 mg), 15 (12.3 mg), 16 (3.4
mg), 17 (2.5 mg), 18 (3.0 mg), 19 (3.7 mg), 20 (3.1 mg), 21
(18.8 mg), 22 (7.2 mg), and 23 (3.4 mg) were obtained from
the CH2Cl2 fraction with the forementioned method.
5 Identification
Compound 1 C12H12O4, white needles, mp 196 - 197
°C, ESI-MS m/z 243 [M + Na]+, 463 [2M + Na]+. 1H NMR
(CDCl3, 500 MHz) δ: 6.67 (1H, d, J = 2.5 Hz, H-8), 6.61 (1H,
d, J = 2.5 Hz, H-6), 5.53 (1H, s, H-3), 3.93, 3.83 (each 3H, s,
2 × OCH3), 2.61 (3H, s, CH3); 13C NMR (CDCl3, 125 MHz) δ:
163.2 (C-2), 87.6 (C-3), 169.8 (C-4), 138.5 (C-5), 115.7
(C-6), 161.9 (C-7), 98.7 (C-8), 156.7 (C-9), 107.9 (C-10),
55.9, 55.5 (2 × OCH3), 23.5 (CH3). The physical and spectral
data were in accordance with those reported in the literature[3],
and 1was identified as siderin.
Compound 2 C13H14O5, white needles, mp 209 - 210
°C, ESI-MS m/z 273 [M + Na]+. 523 [2M + Na]+. 1H NMR
(CDCl3, 500 MHz) δ: 6.72 (1H, s, H-8), 5.56 (1H, s, H-3),
3.94, 3.91, 3.75 (each 3H, s, 3 × OCH3),2.58 (3H, s, CH3);
13C NMR (CDCl3, 125 MHz) δ: 163.1 (C-2), 88.0 (C-3),
169.9 (C-4), 130.0 (C-5), 144.3 (C-6), 156.2 (C-7), 98.4
(C-8), 152.3 (C-9), 107.7 (C-10), 60.6, 56.0, 55.5 (3 × OCH3),
14.0 (CH3). The physical and spectral data were in accor-
dance with those reported in the literature [4], and 2 was iden-
tified as 4, 6, 7-trimethoxy-5-methylcoumarin.
Compound 3 C10H8O4, yellow needles, mp 152 - 153
°C, ESI-MS m/z 215 [M + Na]+, 407 [2M + Na]+, 191 [M
− H]−. 1H NMR (CD3OD, 500 MHz) δ: 7.84 (1H, d, J = 9.5
Hz, H-4), 7.10 (1H, s, H-8), 6.76 (1H, s, H-5), 6.19 (1H, d, J
= 9.5 Hz, H-3), 3.90 (3H, s, OCH3); 13C NMR (CD3OD, 125
MHz) δ: 164.1 (C-2), 109.9 (C-3), 146.1 (C-4), 112.5 (C-5),
147.1 (C-6), 153.1 (C-7), 104.0 (C-8), 151.5 (C-9), 112.6
(C-10), 56.8 (OCH3). The physical and spectral data were in
accordance with those reported in the literature [5], and 3 was
identified as isoscopoletin.
Compound 4 C10H8O4, yellow needles, mp 184 - 186
°C, ESI-MS m/z 215 [M + Na]+, 407 [2M + Na]+, 191 [M −
H]−. 1H NMR (CD3OD, 500 MHz) δ: 7.82 (1H, d, J = 9.5 Hz,
H-4), 7.06 (1H, s, H-8), 6.72 (1H, s, H-5), 6.15 (1H, d, J =
9.5 Hz, H-3), 3.89 (3H, s, OCH3); 13C NMR (CD3OD, 125
MHz) δ: 164.6 (C-2), 112.1 (C-3), 146.5 (C-4), 110.0 (C-5),
147.9 (C-6), 152 (C-7), 104.4 (C-8), 154.7 (C-9), 112.3
(C-10), 57.0 (OCH3). The physical and spectral data were in
accordance with those reported in the literature [6], and 4 was
identified as scopoletin.
Compound 5 C11H10O4, white needles, mp 140 - 142
°C, ESI-MS m/z 229 [M + Na]+, 435 [2M + Na]+. 1H NMR
(CD3OD, 500 MHz) δ: 7.88 (1H, d, J = 9.5 Hz, H-4),7.13
(1H, s, H-5), 6.98 (1H, s, H-8), 6.26 (1H, d, J = 9.5 Hz, H-3),
3.92, 3.87 (each 3H, s, 2 × OCH3). The physical and spectral
data were in accordance with those reported in the literature[7],
and 5 was identified as 6, 7-dimethoxycoumarin.
Compound 6 C11H10O5, yellow needles, mp 146 - 148
°C, ESI-MS m/z 245 [M + Na]+, 467 [2M + Na]+, 221 [M −
H]−. 1H NMR (CDCl3, 500 MHz) δ: 7.61 (1H, d, J = 9.5 Hz,
H-4), 6.66 (1H, s, H-5), 6.26 (1H, d, J = 9.5 Hz, H-3), 4.07,
3.93 (each 3H, s, 2 × OCH3); 13C NMR (CDCl3, 125 MHz) δ:
160.6 (C-2), 113.5 (C-3), 143.8 (C-4), 103.2 (C-5), 144.6
(C-6), 134.5 (C-7), 143.1 (C-8), 140.7 (C-9), 113.3 (C-10),
61.6, 56.5 (2 × OCH3). The physical and spectral data were in
accordance with those reported in the literature [8], and 6 was
identified as 7-hydroxy-6, 8-dimethoxycoumarin.
Compound 7 C21H24O6, white amorphous powder, mp
123 - 125 °C, ESI-MS m/z 395 [M + Na]+, 371 [M − H]− . 1H
NMR (CD3OD, 500 MHz) δ: 6.97 (1H, s, H-6), 6.94 (2H, s,
H-2, 2′), 6.82 (1H, dd, J = 8.1, 1.7 Hz, H-6′), 6.76 (1H, d, J =
8.1 Hz, H-5′), 6.56 (1H, d, J = 15.8 Hz, H-7), 6.16 (1H, dt, J
= 15.8, 6.3 Hz, H-8), 5.52 (1H, d, J = 6.2 Hz, H-7′), 4.05 (2H,
dd, J = 6.2, 1.2 Hz, H-9), 3.49 (1H, dd, J = 12.4, 6.2 Hz,
H-8′ ), 3.80 (3H, s, 3′-OCH3), 3.81 (2H, m, H-9′), 3.87 (3H, s,
3-OCH3), 3.35 (3H, s, 9-OCH3); 13C NMR (CD3OD, 125
MHz) δ: 132.5 (C-1), 112.5 (C-2), 145.8 (C-3), 149.8 (C-4),
130.7 (C-5), 117.0 (C-6), 134.7 (C-7), 124.5 (C-8), 74.6(C-9),
134.8 (C-1′), 110.9 (C-2′), 149.4 (C-3′), 147.9 (C-4′), 116.5
(C-5′), 120.1 (C-6′), 89.6 (C-7′), 55.4 (C-8′), 65.2 (C-9′), 56.7
(3′-OCH3), 57.1 (3-OCH3), 58.3 (9-OCH3). The physical and
spectral data were in accordance with those reported in the
literature [9-10], and 7 was identified as dehydrodiconiferyl
alcohol.
Compound 8 C20H24O6, colorless oil, ESI-MS m/z 383
[M + Na]+, 359 [M − H]−. 1H NMR (CD3OD, 500 MHz) δ:
6.64 (1H, dd, J = 8.0, 2.0 Hz, H-6), 6.72 (1H, d, J = 8.0 Hz,
H-5), 6.79 (1H, d, J = 2.0 Hz, H-2), 2.49 (1H, dd, J = 13.2,
11.0 Hz, H-7α), 2.92 (1H, dd, J = 13.2, 4.8 Hz, H-7β), 2.73
(1H, m, H-8), 3.63(1H, dd, J = 11.0, 7.5 Hz, H-9a), 3.83 (1H,
dd, J = 11.0, 4.8 Hz, H-9b), 6.77 (1H, dd, J = 8.0, 1.9 Hz,
H-6′), 6.90 (1H, d, J = 1.9 Hz, H-2′), 6.79 (1H, d, J = 8.0 Hz,
H-5′), 4.74 (1H, d, J = 6.9 Hz, H-7′), 2.37 (1H, m, H-8′), 3.71
(1H, dd, J = 8.4, 6.0 Hz, H-9′a), 3.98 (1H, dd, J = 8.4, 6.0 Hz,
H-9′b), 3.84, 3.82 (each 3H, s, 2 × OCH3); 13C NMR
(CD3OD, 125 MHz) δ: 133.8 (C-1), 113.7 (C-2), 149.3(C-3),
147.4 (C-4), 116.5 (C-5), 122.5 (C-6), 34.0 (C-7), 44.2 (C-8),
73.8 (C-9), 136.0 (C-1′), 111.0 (C-2′), 149.3 (C-3′), 146.2
(C-4′), 116.3 (C-5′), 120.1 (C-6′), 84.4 (C-7′), 54.4 (C-8′),
60.8 (C-9′), 56.7 (2 × OCH3). The physical and spectral data
were in accordance with those reported in the literature [11],
and 8 was identified as (−)-lariciresinol.
Compound 9 C18H22O6, yellow oil, ESI-MS m/z 357
[M + Na]+, 333 [M − H]−. 1H NMR (CD3OD, 500 MHz)
LIU Yu-Bo, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 115−119
2011 年 3 月 第 9 卷 第 2 期 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 117

δ: 6.49-6.72 (6H, m, Ar-H), 4.48 (1H, d, J = 5.0 Hz, H-7),
3.68 (2H, d, J = 5.0 Hz ,H-9), 2.86 (1H, m, H-8), 3.75, 3.67,
3.16 (each 3H, s, 3, 3′, 7-OCH3); 13C NMR (CD3OD, 125
MHz) δ:132.3 (C-1), 115.6 (C-2), 148.7 (C-3), 146.9 (C-4),
114.4 (C-5), 123.2 (C-6), 84.9 (C-7), 57.0 (C-8), 64.4 (C-9),
132.2 ( C-1′), 115.5 (C-2′), 148.3 (C-3′), 146.2 (C-4′), 111.8
(C-5′), 121.3 (C-6′), 56.5, 56.4, 56.2 (3, 3′, 7-OCH3). The
physical and spectral data were in accordance with those
reported in the literature [12], and 9 was identified as thero-2,
3-bis-(4-hydroxy-3-methoxypheyl)-3-methoxy-propanol.
Compound 10 C30H50O, colorless needles, mp: 115-
116 °C, ESI-MS m/z 449 [M + Na]+, 425 [M − H]−. 1H NMR
(CDCl3, 500 MHz) δ: 4.72 (1H, brs, H-31a), 4.67 (1H, brs,
H-31b), 3.22 (1H, m, H-3) , 1.03 (6H, d, J = 6.8 Hz, 26,
27-CH3), 0.98 (3H, d, J = 5.9 Hz, 29-CH3), 0.97 (3H, s,
18-CH3), 0.91 (3H, brs, 21-CH3 ), 0.89 (3H, s, 30-CH3), 0.39
(1H, d, J = 3.8 Hz, H-19a), 0.14 (1H, d, J = 3.8 Hz, H-19b);
13C NMR (CDCl3, 125 MHz) δ: 30.8 (C-1), 34.8 (C-2), 76.6
(C-3), 44.6 (C-4), 43.3 (C-5), 24.7 (C-6), 28.1 (C-7), 46.9
(C-8), 23.5 (C-9), 29.5 (C-10), 25.2 (C-11), 35.3 (C-12), 45.3
(C-13), 48.9 (C-14), 32.9 (C-15), 27.0 (C-16), 52.2 (C-17),
17.8 (C-18), 27.2 (C-19), 36.1 (C-20), 18.3 (C-21), 35.0
(C-22), 31.3 (C-23), 156.9 (C-24), 33.8 (C-25), 22.0 (C-26),
21.9 (C-27), 14.4 (C-28), 19.1 (C-29), 105.9 (C-31). The
physical and spectral data were in accordance with those
reported in the literature [13], and 10 was identified as cyclo-
eucalenol.
Compound 11 C20H32O3, colorless needles, mp 207 -
209 °C, ESI-MS m/z 343 [M + Na]+, 319 [M − H]−. 1H NMR
(CDCl3, 500 MHz) δ: 5.74 (1H, dd, J = 17.0, 10.0 Hz, H-16b),
5.22 (1H, s, H-14), 4.90 (1H, dd, J = 17.0, 1.4 Hz, H-16a ),
4.86 (1H, dd, J = 10.0, 1.4 Hz, H-15), 3.89 (1H, ddd, J = 7.5,
4.2, 1.8 Hz, H-2), 3.79 (1H, d, J = 2.4 Hz, H-3), 3.70 (1H, d,
J = 11.2 Hz, H-19a), 3.39 (1H, d, J = 11.2 Hz, H-19b), 2.27
(1H, dd, J = 14.4, 3.0 Hz, H-7β), 2.03 (1H, dt, J = 14.4, 5.3
Hz, H-7α), 1.56 (1H, overlap, H-5), 1.53-1.64 (2H, m, H-1),
1.52-1.57 (2H, m, H-7), 1.81 (1H, t, J = 7.8 Hz, H-9),
1.51-1.55 (2H, m, H-11), 1.35-1.38 (1H, m, H-12α),
1.44-1.49 (1H, m, H-12β), 1.08, 1.02, 1.82 (each 3H, s,
3×CH3); 13C NMR (CDCl3, 125 MHz) δ: 41.2 (C-1), 67.4
(C-2), 74.7 (C-3), 45.6 (C-4), 49.8 (C-5), 23.2 (C-6), 37.4
(C-7),138.0 (C-8), 51.9 (C-9), 40.1 (C-10), 20.3 (C-11), 35.9
(C-12), 38.6 (C-13), 130.5 (C-14) ,150.2 (C-15), 110.8
(C-16), 26.6 (C-17), 23.3 (C-18), 65.9 (C-19), 17.5 (C-20).
The physical and spectral data were in accordance with those
reported in the literature [14], and 11 was identified as 8(14),
15-isopimaradiene-2, 3, 19-triol.
Compound 12 C13H20O3, white amorphous powder,
mp 134 - 136 °C, ESI-MS m/z 247 [M + Na]+, 223 [M − H]−.
1H NMR (CD3OD, 500 MHz) δ: 5.83 (1H, s, H-8), 4.21 (1H,
m, H-3), 2.17 (1H, ddd, J = 11.2, 4.0, 2.0 Hz, H-4a), 1.93 (1H,
ddd, J = 11.2, 4.0, 2.0 Hz, H-2a), 1.39 (1H, dd, J = 14.0, 11.2
Hz, H-2b), 1.38 (1H, dd, J = 14.0, 11.2 Hz, H-4b), 2.19, 1.40,
1.40, 1.15 (each 3H, 4 × CH3); 13C NMR (CD3OD, 125 MHz)
δ: 37.0 (C-1), 49.9 (C-2), 64.4 (C-3), 49.7 (C-4), 72.4 (C-5),
120.0 (C-6), 200.9 (C-7), 101.1 (C-8), 211.6 (C-9), 32.3
(C-10), 26.5(C-11), 29.3 (C-12), 30.8 (C-13). The physical
and spectral data were in accordance with those reported in
the literature [15], and 12 was identified as 3S, 5R-dihydroxy-
6R, 7-megstigmadien-9-one.
Compound 13 C11H16O3, white amorphous powder,
mp 149 - 152 °C, ESI-MS m/z 219 [M + Na]+, 195 [M − H]−.
1H NMR (CD3OD, 500 MHz) δ: 5.74 (1H, s, H-7), 4.20 (1H,
m, H-3), 2.41 (1H, ddd, J = 13.7, 5.1, 2.5 Hz, H-4b), 1.74
(1H, dd, J = 12.9, 4.1 Hz, H-4a), 1.52 (1H, dd, J = 14.4, 3.7
Hz, H-2a), 1.98 (1H, ddd, J = 14.4, 5.3, 3.0 Hz, H-2b), 1.75,
1.46, 1.26 (each 3H, s, 3 × OCH3); 13C NMR (CDCl3, 125
MHz) δ: 37.2 (C-1), 47.9 (C-2), 67.2 (C-3), 46.5 (C-4), 88.9
(C-5), 185.7 (C-6), 113.3 (C-7), 174.4 (C-8), 31.0, 27.4, 26.9
(3 × OCH3). The physical and spectral data were in accor-
dance with those reported in the literature [16], and 13 was
identified as (−)-loliolide.
Compound 14 C15H14O6, white needles, mp 93 - 95
°C, ESI-MS m/z 313 [M + Na]+, 289[M − H]−.1H NMR
(CD3OD, 500 MHz) δ: 5.95 (1H, d, J = 2.2 Hz, H-8), 5.88
(1H, d, J = 2.2 Hz, H-6), 4.56 (1H, d, J = 7.6 Hz, H-2), 3.99
(1H, ddd, J = 8.0, 7.6, 5.4 Hz, H-3), 2.85 (1 H, dd, J = 16.2,
5.4 Hz, H-4a), 2.51 (1H, dd, J = 16.2, 8.0 Hz, H-4b), 6.84(1H,
d, J = 1.6 Hz, H-2′), 6.77 (1H, d, J = 8.2 Hz, H-5′), 6.72(1H,
dd, J = 8.2, 1.6 Hz, H-6′); 13C-NMR (CD3OD,125 MHz) δ:
83.0 (C-2), 69.0 (C-3), 28.6 (C-4), 157.9 (C-5), 96.6 (C-6),
157.7 (C-7), 95.8 (C-8), 157.1 (C-9), 100.1 (C-10), 132.4
(C-1′), 116.4 (C-2′), 146.4 (C-3′), 146.4 (c-4′), 115.5 (C-5′),
120.3 (C-6′). The physical and spectral data were in accor-
dance with those reported in the literature [17], and identified
14 as (+)-catechin.
Compound 15 C6H10O5, white oil, ESI-MS m/z 185
[M + Na]+, 147 [M − H]−. 1H NMR (CD3OD, 500 MHz) δ:
4.51 (1H, dd, J = 7.2, 4.8 Hz, H-2), 2.80 (1H, dd, J = 15.9,
4.8 Hz, H-3a), 2.71 (1H, dd, J = 15.9, 7.2 Hz, H-3b), 3.74,
3.68 (each 3H, s, 2 × OCH3); 13C NMR (CD3OD, 125 MHz)
δ: 175.2 (C-1), 68.8 (C-2), 40.1 (C-3), 172.8 (C-4), 53.0, 52.6
(2×OCH3). The physical and spectral data were in accordance
with those reported in the literature [18], and 15 was identified
as dimethyl malate.
Compound 16 C16H22O4, yellow oil, ESI-MS m/z 301
[M + Na]+, 579 [2M + Na]+. 1H NMR (CDCl3, 500 MHz) δ:
7.74 (2H, dd , J = 6.0, 3.6 Hz, H-3, 6), 7.63 (2H, dd, J = 6.0,
3.6 Hz, H-4, 5), 4.07 (2H, d, J = 6.5 Hz, H-1′, 1′′), 2.02 (1H,
m, H-2′, 2′′ ), 0 .99 (12H, m, H-3′, 3′′,4′, 4′′); 13C NMR
(CDCl3, 125 MHz) δ: 133.6 (C-1, 2), 129.9 (C-3, 6), 132.4
(C-4, 5), 72.9 (C1′, 1′′), 29.0 (C2′, 2′′), 19.5 (C3′, 3′′, 4′, 4′′),
169.3 (C=O). The physical and spectral data were in accor-
dance with those reported in the literature[19], and 16 was
identified as diisobutyl phthalate.
Compound 17 C16H22O4, yellow oil, ESI-MS m/z 301
[M + Na]+, 579 [2M + Na]+. 1H NMR (CD3OD, 500
LIU Yu-Bo, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 115−119
118 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 2011 年 3 月 第 9 卷 第 2 期


Fig. 1 Structures of compounds 1-23
MHz) δ: 7.71 (2H, dd, J = 5.7, 3.3 Hz, H-3, 6), 7.61 (2H, dd,
J = 5.7, 3.3 Hz, H-4, 5), 4.29 (4H, t, J = 6.6 Hz, H-1′, 1′′),
1.72 (4H, m, H-2′, 2′′), 1.45 (4H, m, H-3′, 3′′), 0.98 (6H, t, J
= 7.4 Hz, H-4′, 4′′); 13C NMR (CD3OD, 125 MHz) δ: 132.3
(C-1, 2), 129.9 (C-3, 6), 133.6 (C-4, 5), 66.7(C-1′, 1′′), 31.7
(C-2′, 2′′), 20.3 (C-3′, 3′′), 14.0 (C-4′, 4′′), 169.3 (C=O). The
physical and spectral data were in accordance with those
reported in the literature [20], and 17 was identified as dibutyl
phthalate.
Compound 18 C9H12O3, yellow needles, mp 50 - 53
°C, ESI-MS m/z 191 [M + Na]+ , 359 [2M + Na]+. 1H NMR
(CDCl3, 500 MHz) δ: 5.86 (3H, s, H-2 ,4, 6), 3.82 (9H, s, 3 ×
OCH3), 13C NMR (CDCl3, 125MHz) δ: 157.6 (C-1, 3, 5),
107.7 (C-2, 4, 6), 56.8 (3 × OCH3). The physical and spectral
data were in accordance with those reported in the literature
[21], and 18 was identified as 1, 3, 5-trimethoxybenzene.
Compound 19 C9H10O5, white needles, mp 212 - 213
°C, ESI-MS m/z 221 [M + Na]+, 197 [M − H]−. 1H NMR
(CD3OD, 500 MHz) δ: 7.32 (2H, s, H-2, 6), 3.87 (6H, s,
3×OCH3); 13C NMR (CD3OD, 125 MHz) δ: 122.9 (C-1),
108.3 (C-2, 6), 148.8 (C-3, 5), 141.4 (C-4), 170.7 (COOH),
56.8 (2 × OCH3). The physical and spectral data were in ac-
cordance with those reported in the literature [22], and 19 was
identified as syringic acid.
Compound 20 C9H10O4, yellow needles, mp 113-115
°C, ESI-MS m/z 205 [M + Na]+, 181 [M − H]+. 1H NMR
(CD3OD, 500 MHz) δ: 9.68 (1H, s, CHO), 7.20 (2H, s, H-2,
6), 3.89 (6H, s, 2 × OCH3). The physical and spectral data
were in accordance with those reported in the literature [23],
and 20 was identified as springaldehyde.
Compound 21 C8H8O4, white needles, mp 208 - 210
°C, ESI-MS m/z 191 [M + Na]+, 167 [M − H]−. 1H NMR
(CD3OD, 500 MHz) δ: 7.58 (1H, dd, J = 9.0, 1.6 Hz, H-6),
7.57 (1H, d, J = 1.6 Hz, H-2), 6.85 (1H, d, J = 9.0 Hz, H-5),
3.90 (3H, s, OCH3); 13C NMR (CD3OD, 125 MHz) δ: 123.0
(C-1), 113.8 (C-2), 152.7 (C-3), 148.6 (C-4), 115.8 (C-5),
125.3 (C-6), 170.0 (COOH), 56.4 (OCH3). The physical and
spectral data were in accordance with those reported in the
literature [24], and 21 was identified as vanillic acid.
Compound 22 C8H8O3, white needles, mp 147 - 148
°C, ESI-MS m/z 175 [M + Na]+, 151 [M − H]−. 1H NMR
(CD3OD, 500 MHz) δ: 9.74 (1H, s, CHO), 7.42 (2H, m, H-2,
6), 6.93 (1H, d, J = 7.9 Hz, H-5), 3.92 (3H, s, OCH3); 13C
NMR (CD3OD, 125 MHz) δ: 127.9 (C-1), 111.3 (C-2), 149.7
(C-3), 154.9 (C-4), 116.4 (C-5), 127.9 (C-6), 192.9 (CHO),
56.4 (OCH3). The physical and spectral data were in accor-
dance with those reported in the literature [25], and 22 was
identified as vanillin.
Compound 23 C28H42O2, white amorphous powder,
mp 164 - 165 °C, ESI-MS m/z 433 [M + Na]+, 409 [M − H]−.
1H NMR (CDCl3, 500 MHz) δ: 7.39 (2H, d, J = 2.3 Hz, 2 ×
Ar-H), 7.12 (2H, d, J = 2.3 Hz, 2 × Ar-H), 1.45 (18H, s, 2 ×
t-Bu), 1.32 (18H, s, 2 × t-Bu); 13C NMR (CDCl3, 150 MHz) δ:
124.8 (C-1, 1′), 149.8 (C-2, 2′), 136.3 (C-3, 3′), 122.4 (C-4,
LIU Yu-Bo, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 115−119
2011 年 3 月 第 9 卷 第 2 期 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 119

4′), 143.0 (C-5, 5′), 125.3 (C-6, 6′), 31.7 (3 × CH3), 29.7 (3 ×
CH3). The physical and spectral data were in accordance with
those reported in the literature [26], and 23 was identified as 3,
3′, 5, 5′-tetra-tert-butyl-2, 2′-dihydroxybiphenyl.
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毛红椿的化学成分
刘玉波 1, 成向荣 1, 覃江江 1, 严诗楷 1, 金慧子 1 *, 张卫东 1, 2 *
1上海交通大学药学院, 上海 200240;
2第二军医大学药学院, 上海 200433
【摘 要】 目的：研究毛红椿茎叶中的化学成分。方法：运用硅胶柱色谱, Sephadex LH-20 柱色谱, 以及高效液相制备色谱
等手段分离和纯化化合物, 再通过光谱学的方法,结合化合物的理化性质鉴定它们的结构。结果：从毛红椿茎叶的 95%乙醇提取
物中分离得到 23 个化合物, 分别鉴定为 4, 7-二甲氧基-5-甲基香豆素(1)、4, 6, 7-三甲氧基-5-甲基香豆素(2)、异莨菪亭(3)、莨菪
亭(4)、6, 7-二甲氧基香豆素(5)、7-羟基-6, 8-二甲氧基香豆素(6)、dehydrodiconiferyl alcohol(7)、(−)−落叶松脂素(8)、thero-2,
3-bis-(4-hydroxy-3-methoxypheyl)-3-methoxy-propanol(9)、环桉烯醇(10)、8(14), 15-isopimaradiene-2, 3, 19-triol(11)、3S, 5R-dihy-
droxy-6R, 7-megstigmadien-9-one(12)、黑麦草内酯(13)、(+)−儿茶素(14)、苹果酸二甲酯(15)、邻苯二甲酸二异丁酯(16)、邻苯二
甲酸二丁酯(17)、1, 3, 5-三甲氧基苯(18)、丁香酸(19)、丁香醛 (20)、香兰酸(21)、香草醛(22)、3, 3′, 5, 5′-四叔丁基-2, 2′-二羟基
苯(23)。结论：所有化合物均为首次从毛红椿中分离得到。
【关键词】 香椿属; 毛红椿; 化学成分; 香豆素

【基金项目】 上海市科委基金项目(No. 09DZ1972200).