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Journal of Chinese Pharmaceutical Sciences 2001, 10 (4) 169

The Chemical Constituents from the Bulbs of Ornithogalum caudatum

Tang Yuping, Yu Biao*, Hu Jie, Wu Tao and Hui Yongzheng

State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032

Received August 8, 2001; Accepted October 29, 2001

Abstract A new natural product (1) together with 26 know compounds were isolated from the Bulbs of
Ornithogalum caudatum. Their structures were established on the basis of spectral analyses as n-butyl pyroglutamate
(1), nonadecyl alcohol(2), eicosanol(3), behenic acid(4), b-sitosterol(5), stigmasterol(6), glycerol 1-monocerotate(7),
pyrocatechol(8), p-ethoxybenzoic acid(9), p-coumarinic acid(10), protocatechuric acid(11), ursolic acid(12), betulinic
acid(13), fumaric acid(14), succinic acid(15), uracil(16), xanthine(17), quercetin(18), kaempferol (19), isorham-
netin(20), adenosine(21), daucosterol(22), stigmasterol 3-O-b-D-glucopyranoside(23), quercetin 3-O-b-D-glucopyra-
noside(24), kaempferol 3-O-b-D-glucopyranoside(25), rutin(26), and kaempferol 3-O-b-rutinoside(27). All of them,
except compound 5, were isolated from this plant for the first time.

Key words Ornithogalum caudatum; Bulb; Chemical constituent

Introduction

Ornithogalum caudatum Ait. (Liliaceae), an annual
herb distributed in southern Africa, and introduced to
ancient China, is known in Chinese folk medicine
exhibiting anticancer, antimicrobial, and antiinflam-
matory activities and has been used for the treatment of
hepatitis, parotitis, and some kinds of tumor in northern
China[1,2]. In previous work, we reported the isolation
and structure elucidation of three new homoisoflavanone
glycosides from the bulbs of O. caudatum[3]. In a
continuation of chemical examination of this plant, a
new natural product, n-butyl pyroglumate(1), and 26
known compounds were isolated. Their structures were
determined on the basis of chemical and spectral
analyses.





Fig. 1. The chemical structure of compound 1.

Results and Discussion

The molecular formula of compound 1, a colorless
oil, was inferred from HRFABMS ([M+H]+ m/z
186.1144), to be C9H15O3N. It is supported by 13C NMR
and DEPT spectra, which showed 9 resonance lines
consisting of one methyl, five methylenes, one methine,
and two quaternary carbons. The IR spectrum of
compound 1 exhibited absorption bands at 3190~3080
(NH), 1730(C=O, ester), and 1700(C=O, lactam). The 1H
NMR spectrum of compound 1 revealed signals for one
n-butoxyl group at d 0.88(3H, t, J=7.4 Hz), 1.32(2H, d,
J=7.4 Hz), 1.56(2H, q, J=7.4 Hz) and 4.08(2H, t, J=7.4
Hz), one cyclic methylene [d 2.00(1H, m) and d 2.35(1H,
m)], one methylene [d 2.15(2H, m)] linked to an car-
bonyl moiety, one methine [d 4.16(1H, m)] linked to a
carbonyl group and having a function group containing
nitrogen, and one proton [d 7.97(1H, brs)] linked to a
nitrogen atom. Furthermore, the 13C NMR was featured
by two carbonyl carbon signals at d 173.04 and 177.30.
Thus, compound 1 was supposed to be n-butyl
pyroglutamate (Fig. 1). 2D NMR allowed the assignment
of all 1H and 13C NMR signals of compound 1 (Table 1).
In HMBC spectrum, the proton signal at d 4.08 was
correlated to ester carbonyl carbon signal at d 173.04.
Therefore, the butoxyl group was attached to a carbonyl
carbon rather than to the cyclic. Comparison of spectral
data of compound 1 with corresponding compounds[4,5]
also supported our assumption. All of these data
demonstrated that compound 1 was n-butyl pyro-
glutamate.

Table 1. The NMR data of compound 1 in DMSO-d6 (d )
Position 13C 1H DEPT H-H COSY
1 7.97(1H, brs)
2 177.30 s
3 30.21 2.15(1H, m) t 2.00, 2.35
4 29.01
2.00(1H, m)
2.35(1H, m)
t
2.15, 2.35, 4.16
2.00, 2.15, 4.16
5 54.92 4.16(1H, m) d 2.00, 2.35
6 173.04 s
1¢ 64.48 4.08(2H, t, J = 7.4 Hz) t 1.56
2¢ 24.67 1.56(2H, q, J = 7.4 Hz) t 1.32, 4.08
3¢ 18.62 1.32(2H, d, J = 7.4 Hz) t 0.88, 1.56
4¢ 13.61 0.88(3H, t, J = 7.4 Hz) q 1.32
*To whom correspondence should be addressed. Tel: (021) 64163300-1407. Fax: (021)64166128. E-mail:byu@pub.sioc.ac.cn.
6
5
43
2
3
4
2
1
N
O
O
O
H





Journal of Chinese Pharmaceutical Sciences 2001, 10 (4) 170
Twenty-two of the known compounds, were identi-
fied by comparing their physical and spectral data with
literature values, namely, nonadecyl alcohol[6], eicosa-
nol[6], behenic acid[6], b-sitosterol[7], stigmasterol[8], pyro-
catechol[9], p-ethoxybenzoic acid[6], protocatechuric
acid[9], ursolic acid[10,11], betulinic acid[12,13], fumaric acid
[14], suc cinic acid[15,16], quercetin[17,18], kaempferol[17,18],
isorhamnetin[17,18], adenosine[19,20], daucosterol[17,21], stig-
masterol 3-O-b-D-glucopyranoside[22], quercetin
3-O-b-D-glucopyranoside[23,24], kaempferol
3-O-b-D-glucopyranoside[23,24], rutin[23,34], and
kaempferol 3-O-b-rutinoside[23,24]. In addition, four
known substances were identified by comparison of
spectral data with those of authentic samples: glycerol
1-monocerotate, p-coumarinic acid, uracil, and xanthine.

Experimental

General experimental procedures
Melting points were determined on a Kofler instru-
ment and uncorrected. Optical rotations were recorded
with a Perkin-Elmer model 241 polarimeter. UV and IR
spectra were measured on a Shimadzu UV-1601 instru-
ment and on a Perkin-Elmer 983 spectrometer, respec-
tively. All NMR spectra were run on a Bruker DRX-400
instrument operating at 400 MHz for 1H and 100 MHz
for 13C, using standard pulse sequences. Chemical shifts
were reported on the d scale in parts per million, down-
field from TMS. Carbon multiplicities were determined
from DEPT-135 and DEPT-90 experiments. All 2D
NMR spectra were recorded using pulsed field gradients.
1H-1H correlations were observed in double quantum
filtered (DQF) COSY and TOCSY experiments.
One-bond 13C-1H correlations were observed in an
HMQC experiment. Long-range 13C-1H correlations
were observed in HMBC experiments. FABMS spectra
were obtained on a JEOL JMS DX-303HF mass
spectrometer. Column chromatography was performed
on Si gel (Marine Chemical Factory, Qingdao, People’s
Republic of China), Sephadex LH-20 (Pharmacia), and
RP-18 (Shimadzu).

Plant material
The bulbs of O. caudatum Ait. were collected from
Jilin Province, People’s Republic of China, and the plant
was identified by Dr. Wu Tao. After collection, the bulbs
were allowed to dry at ambient temperature for about
one week, and were then crushed and immediately ex-
tracted. A voucher specimen was deposited in the State
Key Laboratory of Bio-organic and Natural Products
Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai, People’s Re-
public of China.

Extraction and isolation
The dried and crushed bulbs of O. caudatum (7.8 kg)
were extracted three times with 95% EtOH under reflux
for 3 h each time, with the solvent removed under re-
duced pressure, and the residue was dissolved in hot
water. This residue was left in the refrigerator overnight
and filtered. The filtrate was partitioned with CH2Cl2 and
n-BuOH, successively. The CH2Cl2 extract (760.2 g) was
concentrated and subjected to Si gel column chromatog-
raphy eluting with petroleum ether-EtOAc (100:1) fol-
lowed by stepwise adding EtOAc to yield 12 fractions.
Each fraction was purified by Si gel column chromatog-
raphy to give 1 (17 mg), 2 (41 mg), 3 (15 mg), 4 (18 mg),
5 (68 mg), 6 (2 g), 7 (30 mg), 8 (10 mg), 9 (10 mg), 10
(10 mg), 11 (8 mg), 12 (8 mg), 13 (9 mg), 14 (10 mg), 15
(80 mg), 16 (22 mg), and 17 (14 mg), respectively. The
n-BuOH extract (352.2 g) was concentrated and sub-
jected to Si gel column chromatography eluting with
CHCl3-MeOH (30:1) followed by stepwise adding
MeOH to yield 13 fractions. Each fraction was subjected
to Si gel, and was purified by Sephadex LH-20 (MeOH)
chromatography to give 18 (8 mg), 19 (7 mg), and 20 (5
mg), 21 (20 mg), 22 (700 mg), 23 (75 mg), 24 (10 mg),
25 (10 mg), 26 (10 mg), and 27 (12 mg), respectively.
n-Butyl pyroglutamate (1) Colorless oil. IR nmaw
(cm-1): 3190~3080(NH), 1730(C=O, ester), 1700(C=O,
lactam), 1240(C-O). 1H NMR (DMSO-d6, 400 MHz) and
13C NMR (DMSO-d6, 75 MHz), see Table 1. HRFABMS
m/z 186.1144 [M+H]+ (calcd for C9H16O3N, 186.1148).

Acknowledgement This work was supported by the Ministry of Science and Technology of China (96-901-05-266).

References

[1] Liu DY, Wang KY, Zhang H, Chen WH and Chen ZL. [J] Chin Tradit Herb Drugs, 1998, 29: 443
[2] Xu TH, Xu YJ, Liu DY and Xu DM. [J] Acta Pharm Sin, 2000, 35: 32
[3] Tang YP, Yu B, Hu J, Wu T and Hui YZ. [J] J Nat Prod, to be published
[4] Brennan JJ, Imondi AR, Westmoreland DG and Williamson MJ. [J] J Pharm Sci, 1982, 71: 1199
[5] Rigo B, Lespagnol Ch and Pauly M. [J] J Hetercycl Chem, 1988, 25: 49
[6] Tang YP, Lou FC and Wang JH. [J] Nat Prod Res Dev, 2001, 13: 5
[7] Zheng WP, Tang YP, Lou FC and Zhi F. [J] J China Pharm Univ, 2000, 31: 5





Journal of Chinese Pharmaceutical Sciences 2001, 10 (4) 171
[8] Bai YL, Lou W and Liu YL. [J] Chin Tradit Herb Drugs, 1985, 16: 530
[9] Lou FC, Wang GY and Guo YL. [J] J China Pharm Univ, 1998, 29: 316
[10] Lin G, Xu XD, Liu D, Ju JH and Yang JS. [J] Chin Pharm J, 2000, 35: 298
[11] Yang SC, Fang JM and Cheng YS. [J] J Chin Chem Soc (Taipei), 1995, 42: 573
[12] Ikuta A and Itokawa H. [J] Phytochemistry, 1988, 27: 2813
[13] Kamiya K, Yoshioka K, Saiki Y, Ikuta A and Satake T. [J] Phytochemistry, 1997, 44: 141
[14] Sadtler Research Laboratories, Inc. Sadtler standard proton NMR Spectra [M], 1969, vol 7, 4407
[15] Sadtler Research Laboratories, Inc. Sadtler standard proton NMR Spectra [M], 1969, vol 7, 4531
[16] Zhou FX and Liang PY. [J] Chin Tradit Herb Drugs, 1980, 11: 523
[17] Tang YP, Lou FC, Wang JH and Li YF. [J] Chin Pharm J, 2001, 36: 231
[18] Tang YP, Wang JH, Li YF, Lou FC and Ma W. [J] Acta Phytoecol Geobot Sin, 2001, 10: 59
[19] Coburn WC, Thorpe MC, Montgomery JA and Hewson. [J] J Org Chem, 1965, 30: 1114
[20] Akhren AA, Mikhailopulo IA and Abranmov AF. [J] Org Magn Resonamce, 1979, 12: 247
[21] Jares EA, Tettamanzi MC and Pomilio AB. [J] Phytochemistry, 1990, 29: 340
[22] Lou FC, Ma QY and Du FL. [J] J China Pharm Univ, 1989, 20: 37
[23] Tang YP, Wang Y, Lou FC, Li YF and Wang JH. [J] Acta Pharm Sin, 2000, 35: 363
[24] Markham KR, Ternai B, Stanley R, Geiger H and Mabry TJ. [J] Tetrahedron, 1978, 34: 1389










虎眼万年青球茎中的化学成分

唐于平 俞 飚 胡 杰 吴 弢 惠永正

中国科学院上海有机化学研究所生命有机化学国家重点实验室，上海 200032


摘 要 从虎眼万年青 (Ornithogalum caudatum) 的球茎中，用色谱方法分离得到 1个新天然产物 1和 26个已知化合物
2~27，它们的结构经波谱法和化学方法确定为 n-butyl pyroglumate(1), 十九醇(2), 二十醇(3), 二十二烷酸(4)，b-谷甾醇(5)，
豆甾醇(6)，二十六烷酸 1-甘油酯(7)，儿茶酚(8)，对乙氧基苯甲酸(9)，p-香豆酸 (10)，原儿茶酸(11)，熊果酸(12)，白桦脂酸
(13)，富马酸(14)，琥珀酸(15)，尿嘧啶(16)，黄嘌呤(17)，槲皮素(18)，山柰酚(19)，异鼠李素(20)，腺嘌呤核苷(21)，胡萝卜
甙(22)，豆甾醇 3-O-b-D-葡萄糖甙(23)，槲皮素 3-O-b-D-葡萄糖甙(24)，山柰酚 3-O-b-D-葡萄糖甙(25)，芦丁(26)，山柰酚 3-O-b-
芸香糖甙(27)。其中除化合物 5外，其它成分均首次从虎眼万年青属植物中分离得到。

关键词 虎眼万年青；球茎；化学成分