2013

NPC Natural Product Communications Vol. 8

No. 10
Guaiol - A Naturally Occurring Insecticidal Sesquiterpene 1353 - 1354
Tao Liua, Chun-Juan Wangb, Hui-Qin Xieb* and Qing Mua*
a
School of Pharmacy, Fudan University, Shanghai 201203, China
b
Department of Plant Protection, Agricultural College of Shihezi University, Xinjiang 832000, China

muqing2200@gmail.com (Dr Q Mu and HQ Xie)

Received: February 26th, 2013; Accepted: July 22nd, 2013

The dichloromethane fraction of Ferula ferulaeoides was analyzed by GC and GC-MS, and thirty-four compounds were identified. The main component in the
1 13
fraction, guaiol (37.0%) was separated by chromatographic methods and identified from spectroscopic data, including H and C NMR, and X-ray
crystallographic diffraction. Guaiol showed significant inhibition of aphids at a concentration of 70 mg/L. It also showed good contact activities against the
4th instar larvae of Mythimna separate and 3rd instar larvae of Plutella xylostella, with LD50 values of 0.07 and 8.9 mg/larva, as well as fumigation activity against
the
4th instar larvae of M. separata and adult Musca domestica, with LC50values of 3.5 µL/L and 16.9 µL/L,
respectively.

Keywords: Ferula ferulaeoides, Guaiol, GC-MS, X-ray, Insecticidal activity.

The wide use of chemical insecticides has resulted in the higher than 2.5% are presented in Table 1. The major constituent
development of insect resistance. Scientists throughout the world (37.0%) was isolated and its structure determined by 1H and 13C
have concentrated on searching active natural products from plants NMR, MS and X-ray crystallographic analysis. The compound was
as ecologically safe alternatives [1]. These products possess natural identified as guaiol, 2-[(3S,5R,8S)-3,8-dimethyl-1,2,3,4,5,6,7,8-
degradation pathways so they cannot lead to environmental octahydroazulen-5-yl]-propan-2-ol (Figure 1).
pollution. The genus Ferula (Apiaceae) includes about 150 species
grown in a wide geographical region and 26 species are distributed Table 1: Key Composition of F. ferulaeoides analyzed by GC-MS.
in China. As a traditional herb, species of Ferula were used in the SN N a me Area%
treatment of digestive disorders and arthritis [2]. Their chemical
compositions have been widely studied and shown to include
sesquiterpenes and their derivatives [3]. In pharmacological
research, Ferula species have been found to possess biological
effects including antiviral [4,5], anti-inflammatory [6], anticancer
[7], and antibacterial [8] activities.

The dichloromethane extract of the root of F. ferulaeoides (Steud.)

Korov. was found to possess strong insecticidal activity against
common agricultural insects. Using GC-MS, thirty-four compounds
were identified and compounds representing their concentration
 Figure 2: Insecticidal activity of guaiol against aphids.

HO 3' 3

5
4
2 350 mg/L, the mortality rate was nearly 100% (Figure 2). Guaiol
1'
2' showed significant contact activity against the 4th instar larvae of
1
6 Mythimna separate and 3rd instar larvaeof Plutella xylostella with
7 8 LD50 values of 0.07 and 8.9 mg/larva, respectively. Significant
fumigation activity was observed against the 4th instar larvae of
Figure 1: Structure and X-ray crystallography ORTEP of guaiol. M. separate and adult Musca domestica at LC50 of 3.5 µL/L
and
16.9 µL/L, respectively.

Crystal data and Structure was measured using Bruker SMART

Guaiol, a hydroxyl sesquiterpene having the guaiane skeleton, exists
in essential oil of many medicinal plants [9]. It is a key metabolite
in the biogenesis of a large number of guaiane natural products [10].
The insecticidal activity of guaiol was evaluated on aphids. Results
observed at 24 and 48 h after administration were almost the same.
They show aphid killing activity at a concentration of 70 mg/L. At
APEX-II single-crystal diffraction. GC-MS, Thermo Focus DSQ
with a mass-selective detector with electron impact ionization.
Plant material: Roots of Ferula ferulaeoides were collected in
Xinjiang Province, China. A voucher specimen (No. FF-1) was
deposited at the School of Pharmacy, Fudan University. The plant
was identified by Xie Hui-Qin, Associate Professor in the
Department of Plant Protection, Shihezi University, China.

5 (5Z)- 2,6,10-Trimethyl-1,5,9-undecatriene 13.7

15 ±-trans-Nerolidol 7.9 Experimental
18 Guaiol 37.0
19 ζ-Eudesmol 3.0 General: Optical rotations, JASCO P-1020 polarimeter; Melting
20 Eudesmol-4(14)-en-11-ol 2.6 point, X-4 micromelting point apparatus. 1H and 13C NMR, Varian
31 (13S)-Labda-8(20)-14-dien-13-ol 2.8
Mercury Plus 400; EIMS, Agilent 5973N MSD spectrometer.
33 3,7,11,15-Tetramethyl-2,6,10,14-hexadecatetren-1-ol 11.1
1354 Natural Product Communications Vol. 8 (10) 2013 Liu et al.

Insect: Aphids were obtained from the Laboratory of Agricultural
College, Shihezi University. Mythimna separate Walker, Plutella
xylostella Linnaeus and adult Musca domestica Linnaeus were
offered by Harmless Insecticides Research and Service Center of
Northwest Agriculture and Forest Science and Technology
University.
Extraction, isolation and identification: Air-dried and powdered
roots of F. ferulaeoides (2.0 kg) were extracted at 45°C with 95%
ethanol (3 × 5 L, 12 h each) to afford the total extract. This was
extracted with dichloromethane (3 × 500 mL) to afford the lipid-
soluble fraction FF (400 g). This was subjected to silica gel CC
(10-20 μm, 10× 75 cm), eluting with a gradient from light petroleum
to ethyl acetate (100:0 and 0:100, v/v; flow rate 30 mL/min) to
afford 15 fractions of different polarity. Fraction Ⅳ (4.5 g) was
re-chromatographed on a silica gel column (30 -40 µm, 2.8 × 40
cm)
eluting with petroleum-acetone (98:2) to yield pure guaiol (2.6 g).
X-ray chrysallography: A single colorless crystalwith approximate
dimensions of 0.22 mm × 0.15 mm × 0.12 mm was used for
analysis. The complete structure of the compound and the crystal
data are summarized as follows: C15H26O, molecular weight 222.36,
trigonal, space group P 32, a = 13.0877(19) A, b = 13.0877(19) A,
c = 7.1857(14) A, Z = 3, Dc =1.039 mg/m3. F(000)=372, μ(CuKα)
= 0.470 mm−1. The structure was solved by the direct method
2
SHELXS-97 and refined with full-matrix least-squares on F using
SHELEXL-97. A total of 6146 reflections (2420 unique, R(int)
= 0.0214) were collected from 3.90 to 67.24 in θ and index ranges:
-15<=h<=15, -15<=k<=15, -8<=l<=8. Final discrepancy indices of
R1 = 0.0354, wR2 = 0.0988 and GOF = 1.058 for observed data. The
final difference electron density map contains maximum and
minimum peak heights of 0.128 and -0.147 eÅ−3.
Biological activity assay: The spray supplied sample, at the
required concentration, was applied to the test insects on the surface
of the leaf, while the same amount of solvent was used as a control.
Then the test insects were fed in an insectary [T = 28-30°C, RH =
75%±5%]. The numbers of dead insects were observed at 24 and
48 h. Twenty insects were used as one treatment and each treatment
was repeated 3 times.
Contact poisoning was monitored by a topical application method.
Different concentrations of sample were sprayed onto the pronotum
of the tested insects while the same amount of solvent was used as a
control. The test insects were fed in an insectary [T= (25±1)°C,
RH=75%±5%, D/L=12 h/12 h]. Dead insects were recorded at 24 h.
Ten insects were used for each treatment and each treatment was
repeated 3 times to calculate the mortality and corrected mortality.
Fumigation activity was tested by the fumigation method. The
sample was diluted to the required concentration and dropped on the
filter paper, and the sample loaded paper was sealed in a container
with tested insects. The number of dead insects was recorded at
12 h. Ten insects were used for each treatment and each treatment
was repeated 3 times to calculate the mortality and corrected
mortality. Aprobit analysis method was used to measure the toxicity
curves and LD50/LC50 of the compound for the tested insects.
Acknowledgments - This work was supported by Medical Mingdao
Project (MDJH201210) of Fudan University and the NSFC grant
21172041 of China.

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 Natural Product Communications Vol. 8 (10) 2013
Published online (www.naturalproduct.us)

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 Natural Product Communications
2013
Volume 8, Number 10
Contents
Original Paper Page

Guaiol - A Naturally Occurring Insecticidal Sesquiterpene

Tao Liu, Chun-Juan Wang, Hui-Qin Xie and Qing Mu 1353
3-Oxoabolene and 1-Oxocurcuphenol, Aromatic Bisabolanes from the Sponge Myrmekioderma sp.
Afsaneh Yegdaneh, Sumaitt Putchakarn, Supreeya Yuenyongsawad, Alireza Ghannadi and Anuchit Plubrukarn 1355
Acanthoic Acid Inhibits Melanogenesis through Tyrosinase Down-regulation and Melanogenic Gene Expression in
B16 Melanoma Cells
Weon-Jong Yoon, Young-Min Ham, Hun Seok Yoon, Wook-Jae Lee, Nam Ho Lee and Chang-Gu Hyun 1359
Cembranoids from the Cultured Soft Coral Sinularia gibberosa
Hsiu-Fen Lin, Huey-Jen Su, Nai-Lun Lee and Jui-Hsin Su 1363
Major Constituents of Boswellia carteri Resin Exhibit Cyclooxygenase Enzyme Inhibition and Antiproliferative Activity
Sami I. Ali, Chuan-Rui Zhang, Amal A. Mohamed, Farouk K. EL-Baz, Ahmad K. Hegazy, Maimona A. Kord and Muraleedharan G. Nair 1365
Cucurbitane-type Triterpenes from Citrullus lanatus (Watermelon) Seeds
Takashi Kikuchi, Rina Okada, Yu Harada, Kenji Ikushima, Takahiro Yamakawa, Takeshi Yamada and Reiko Tanaka 1367
A New Taraxerol Derivative from the Roots of Microcos tomentosa
Sutin Kaennakam, Jirapast Sichaem, Suttira Khumkratok, Pongpun Siripong and Santi Tip-pyang 1371
Two New Triterpenoids from Gelsemium elegans and Aglaia odorata
Bing Liu, Lin Yang, You-Kai Xu, Shang-Gao Liao, Huai-Rong Luo and Zhi Na 1373
Inhibition of Tumor Cells Multidrug Resistance by Cucumarioside A2-2, Frondoside А and their Complexes with Cholesterol
Ekaterina S. Menchinskaya, Dmitry L. Aminin, Sergey A. Avilov, Aleksandra S. Silchenko, Pelageya V. Andryjashchenko,
Vladimir I. Kalinin and Valentin A. Stonik 1377
Anticholinesterase and Antioxidant Activities of Fucoxanthin Purified from the Microalga Phaeodactylum tricornutum
Arthitaya Kawee-ai, Ampin Kuntiya and Sang Moo Kim 1381
Impact of Ploidy Change on Secondary Metabolites and Photochemical Efficiency in Solanum bulbocastanum
Immacolata Caruso, Fabrizio Dal Piaz, Nicola Malafronte, Nunziatina De Tommasi, Riccardo Aversano, Cristian Wulff Zottele,
Maria-Teresa Scarano and Domenico Carputo 1387
Alkaloids from an Endophytic Streptomyces sp. YIM66017
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Novel Decaturin Alkaloids from the Marine-Derived Fungus Penicillium oxalicum
Pei-le Wang, Dan-yi Li, Lei-rui Xie, Xin Wu, Hui-ming Hua and Zhan-lin Li 1397
Monanchomycalin C, a New Pentacyclic Guanidine Alkaloid from the Far-Eastern Marine Sponge Monanchora pulchra
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Tatyana N. Makarieva 1399
Antiinflammatory and Antioxidant Flavonoids from Helichrysum kraussii and H. odoratissimum Flowers
Percival B. Legoale, Mahlori J. Mashimbye and Teunis van Ree 1403
Antiproliferative Effect of Flavonoids from the Halophyte Vitex rotundifolia on Human Cancer Cells
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Continued inside backcover

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