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One new and several minor
diarylheptanoids from Amomum
muricarpum
a

a

b

Phan Minh Giang , Phan Tong Son , Katsuyoshi Matsunami &
Hideaki Otsuka

b

a

Faculty of Chemistry, College of Natural Science, Vietnam
National University , Hanoi, 19 Le Thanh Tong Street, Hanoi ,
Vietnam
b

Graduate School of Biomedical Sciences, Hiroshima University ,
1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553 , Japan
Published online: 23 Aug 2011.

To cite this article: Phan Minh Giang , Phan Tong Son , Katsuyoshi Matsunami & Hideaki Otsuka
(2012) One new and several minor diarylheptanoids from Amomum muricarpum , Natural Product
Research: Formerly Natural Product Letters, 26:13, 1195-1200, DOI: 10.1080/14786419.2010.545775
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Natural Product Research
Vol. 26, No. 13, July 2012, 1195–1200

One new and several minor diarylheptanoids from Amomum
muricarpum

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Phan Minh Gianga*, Phan Tong Sona, Katsuyoshi Matsunamib
and Hideaki Otsukab
a
Faculty of Chemistry, College of Natural Science, Vietnam National University, Hanoi,
19 Le Thanh Tong Street, Hanoi, Vietnam; bGraduate School of Biomedical Sciences,
Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553, Japan

(Received 30 June 2010; final version received 3 December 2010)
A new natural diarylheptanoid, designated muricarpin, together with four
diarylheptanoids were isolated from the rhizomes of Amomum muricarpum
Elmer (Zingiberaceae) growing in Vietnam. Three known compounds,
1,7-bis(3,4-dihydroxyphenyl)heptan-3-yl acetate, 1-(40 -hydroxyphenyl)-7(300 ,400 -dihydroxyphenyl)heptan-3-yl acetate and 1-(30 ,40 -dihydroxyphenyl)7-(400 -hydroxyphenyl)-heptan-3-one were isolated for the first time from the
genus Amomum, meanwhile (5R)-5-hydroxy-1,7-bis(4-hydroxyphenyl)heptan-3-one was found for the first time in plants. Their structures were
determined using spectroscopic analyses.
Keywords: Amomum
muricarpin

muricarpum;

Zingiberaceae;

diarylheptanoid;

1. Introduction
Within the family Zingiberaceae a number of diarylheptanoids are known to be
biosynthesised by plants of the genera Alpinia (Ali, Tezuka, Awale, Banskota, &
Kadota, 2001), Curcuma (Park & Kim, 2002) and Zingiber (Kikuzaki, Kobayashi, &
Nakatani, 1991). Regarding the genus Amomum, very few reports were published on
the occurrence of diarylheptanoids (Giang, Son, Matsunami, & Otsuka, 2006;
Kikuzaki, Kawai, & Nakatani, 2001; Moon, Cho, & Lee, 2005). Amomum
muricarpum Elmer is a plant of 2–3 m height which is distributed in China,
Philippines and Vietnam (Flora of China, 2010, ).
The rhizomes of A. muricarpum originating in Vietnam have been shown to be a
source of diarylheptanoids and our previous paper (Giang et al., 2006) reported the
isolation of two new diarylheptanoids, muricarpone A and muricarpone B, together
with 1,7-bis(30 ,40 -dihydroxyphenyl)-4-hepten-3-one, 1-(30 ,40 -dihydroxyphenyl)-7(400 -hydroxyphenyl)-4-hepten-3-one, and 1,7-bis(p-hydroxyphenyl)-4-hepten-3-one.
The diarylheptanoid constituents from the Amomum species are of our interest
and further investigation on the minor constituents of A. muricarpum led to the
isolation of a new diarylheptanoid, designated muricarpin (1), together with
*Corresponding author. Email:

ISSN 1478–6419 print/ISSN 1478–6427 online
ß 2012 Taylor & Francis
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1196

P.M. Giang et al.
OH
OH

OH
R2

O
OH
HO

AcO

OH

4 R1 = OH R2 = H
5 R1 = H
R2 = OH

2 R = OH
3 R=H

1

R

R1
OH

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O

OH

Figure 1. HMBC correlations of 1 and structures of compounds 1–5.

three known compounds 1,7-bis(3,4-dihydroxyphenyl)heptan-3-yl acetate (2),
1-(40 -hydroxyphenyl)-7-(300 ,400 -dihydroxyphenyl)heptan-3-yl acetate (3) and 1-(30 ,40 dihydroxyphenyl)-7-(400 -hydroxyphenyl)-heptan-3-one (4) (Figure 1). 5-Hydroxy-1,7bis(4-hydroxyphenyl)-heptan-3-one was previously synthesised as a racemic mixture
(Bratt & Sunnerheim, 1999); its 5S enantiomer (platyphyllonol) was isolated from
Betula platyphylla Sukatch. var. japonica Hara (Terazawa, Koga, Okuyama, &
Miyake, 1973) or semi-synthesised (Park et al., 2010); therefore compound 5
(5R form) was isolated for the first time from plants.

2. Results and discussion
The dried rhizomes of A. muricarpum were extracted with MeOH and the resulting
MeOH extract was sequentially fractionated using solvents of increasing polarities to
give n-hexane-, CH2Cl2-, EtOAc- and 1-BuOH-soluble fractions. The diarylheptanoids were isolated from the CH2Cl2- and EtOAc-soluble fractions by a sequential
fractionation using silica gel and octadecyl silica (ODS) gel open-column chromatography (CC) and purification by repeated preparative reversed-phase HPLC.
Compound 1 was isolated as a syrup. Its molecular formula was deduced to be
C19H22O4 ([M–H]– m/z 313.1404) by negative-ion HR-FABMS. The IR spectrum
showed the presence of hydroxyl (3345 cm–1), ketone (1698 cm–1) and aromatic ring
(1609, 1514 and 1445 cm–1) absorptions. The 1H and 13C NMR spectroscopic data of
1 showed the presence of a diaryl-3-heptanone (C 213.6, C-3) (Kiuchi, Shibuya, &
Sankawa, 1982; Itokawa, Morita, Midorikawa, Aiyama, & Morita, 1985). Two
aromatic moieties were determined to be 3,4-dihydroxyphenyl [H 6.64 (1H, d, J ¼ 8.0
Hz), 6.58 (1H, d, J ¼ 2.0 Hz) and 6.45 (1H, dd, J ¼ 8.0 Hz, 2.0 Hz)] and
4-hydroxyphenyl [H 6.97 (2H, d, J ¼ 8.8 Hz) and 6.67 (2H, d, J ¼ 8.8 Hz)] on the
basis of 1H NMR coupling patterns. HMBC correlations between the methylene
protons at H 2.67 (H2-2) and C-100 (C 133.3), between H-20 /H-60 (H 6.97) and C-1
(C 30.2), between H2-7 (H 2.39) and C-100 (C 135.3), C-200 (C 116.6), and C-600
(C 120.7), between H-200 (H 6.58) and C-7 (C 35.9) and between H-600 (H 6.45) and
C-7 indicated the locations of the 4-hydroxyphenyl and 3,4-dihydroxyphenyl rings at
C-1 and C-7, respectively. Thus the structure of 1 was determined to be

1-(40 -hydroxyphenyl)-7-(300 ,400 -dihydroxyphenyl)-heptan-3-one, which was named
muricarpin.


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Compounds 2–4 were found in MEGxp Catalog (Collection of pure natural
products from plants) of AnalytiCon Discovery GmbH under code numbers
NP-003624, NP-012941 and NP-012940, respectively (AnalytiCon Discovery GmbH,
2010, ). However, no references and data on these
compounds were available and therefore the physico-chemical and spectroscopic
data of 2–4 were reported in this article.
Compound 5 was isolated as a syrup, []25
D þ51.8. The IR spectrum showed the
presence of hydroxyl (3400 cm–1), ketone (1699 cm–1) and aromatic ring (1611, 1513
and 1450 cm–1) absorptions. The 1H NMR spectroscopic data of 5 showed the planar
structure of 5 as 5-hydroxy-1,7-bis(4-hydroxyphenyl)-heptan-3-one. Recently, its 5S
enantiomer platyphyllonol, which possessed a negative optical rotation ([]25
D –1.8),
was semi-synthesised from its glucoside platyphylloside (Park et al., 2010). Since the
1
H NMR of 5 was in good agreement with that of platyphyllonol its positive optical
rotation decided the absolute stereochemistry 5R of the hydroxyl group at C-5 of 5.
In conclusion, this study and the previous one (Giang et al., 2006) showed that
linear diarylheptanoids are the main type of secondary metabolites of
A. muricarpum. The structures of these diarylheptanoids appeared to be biogenetically-related; while the aryl moieties were 4-hydroxyphenyl or 3,4-dihydroxyphenyl

groups the heptane chain contained 3-oxygenated or 3,5-dioxygenated pattern.
3. Experimental
3.1. General experimental procedures
Optical rotation was measured on a JASCO P-1030 digital polarimeter. FT-IR
spectra were recorded on a Horiba FT-710 spectrophotometer. 1H (400 MHz) and
13
C NMR (100 MHz) spectra were recorded using a JEOL JNM- 400 NMR
spectrometer with TMS as an internal standard. Negative-ion HR-FABMS spectra
were measured on a JEOL SX-102 mass spectrometer with PEG-400 as a calibration
matrix. HPLC was carried out with a JASCO PU-1580 pump and an UV-2075 Plus
detector (set at 254 nm) on ODS (YMC, Japan) analytical (150 Â 4.6 mm i.d.) and
preparative (150 Â 20 mm i.d.) columns at the corresponding flow rates of 0.5 and
5 ml/min. Silica gel 60 (0.063–0.200 mm, Merck, Germany) and ODS gel (YMC,
Japan) were used for open-column chromatography. TLC was carried out on glass
TLC plates (silica gel 60 F254, Merck, Germany) and detected by spraying with 10%
H2SO4 in 50% EtOH, followed by heating on a hot plate at 200oC.
3.2. Plant material
The rhizomes of A. muricarpum were collected from Tam Dao, province Vinh Phuc,
Vietnam, and identified by Mr Nguyen Quoc Binh, a botanical taxonomist of the
Institute of Ecology and Biological Resources, Vietnam Academy of Science and
Technology, Hanoi, Vietnam, in October 2003. A voucher specimen (no. VN 1199)
has been deposited at the Institute of Ecology and Biological Resources.

3.3. Extraction and isolation
The fresh rhizomes of A. muricarpum (7.3 kg) were oven-dried at 40oC and the dried
material (0.84 kg) was powdered and then extracted with MeOH at room


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P.M. Giang et al.

temperature (three times, each time for three days). After filtration and concentration under reduced pressure, the resulting MeOH extract (80 g) was successively
partitioned between H2O and n-hexane, CH2Cl2, ethyl acetate and 1-BuOH. The
CH2Cl2-soluble fraction (12.5 g) was chromatographed on silica gel using a gradient
of CHCl3 and CHCl3/MeOH (9 : 1) to give four fractions on the basis of TLC
analyses. Fraction 4 (3.9 g) was further subjected to silica gel CC using n-hexane/
acetone 3 : 2 to give four subfractions. Subfraction 4 (0.83 g) was purified by
reversed-phase HPLC using MeOH/H2O (1 : 1) to afford 2 (12.8 mg). The EtOAcsoluble fraction (25.7 g) was subjected to silica gel CC and eluted under gradient
conditions with CHCl3 and CHCl3/MeOH (4 : 1, 3 : 2, 2 : 3 and 1 : 4) to afford six
fractions. Fraction 1 (1.0 g) was purified by reversed-phase HPLC using MeOH/H2O
(1 : 1), yielding 5 (1.1 mg). Fraction 2 (21.7 g) was chromatographed on a silica gel
column with n-hexane/acetone (gradient 3 : 2 and 1 : 1) to afford six subfractions.
Subfraction 1 (1.0 g) was further purified by reversed-phase HPLC using
MeOH/H2O (1 : 1) to yield 1 (10.8 mg) and 4 (7.6 mg). Subfraction 3 (2.4 g) was
sequentially chromatographed on an ODS column eluting with a gradient of
MeOH/H2O (3 : 1 and 2 : 3) and reversed-phase HPLC using MeOH/H2O (1 : 1) to
give 3 (8.0 mg).
Muricarpin (1): Syrup; IR (film) max cmÀ1: 3345, 1698, 1609, 1514, 1445, 1232; 1H
NMR (CD3OD):  1.49 (4H, m, H2-5, H2-6), 2.37 (2H, t, J ¼ 6.8 Hz, H2-4), 2.39
(2H, t, J ¼ 6.8 Hz, H2-7), 2.67 (2H, m, H2-2), 2.73 (2H, m, H2-1), 6.45 (1H, dd,
J ¼ 8.0 Hz, 2.0 Hz, H-600 ), 6.58 (1H, d, J ¼ 2.0 Hz, H-200 ), 6.64 (1H, d, J ¼ 8.0 Hz,
H-500 ), 6.67 (2H, d, J ¼ 8.8 Hz, H-30 , H-50 ) and 6.97 (2H, d, J ¼ 8.8 Hz, H-20 , H-60 );
13
C NMR (CD3OD):  24.3 (C-6), 30.2 (C-1), 32.2 (C-5), 35.9 (C-7), 43.7 (C-4), 45.4
(C-2), 116.2 (C-30 , C-50 ), 116.3 (C-500 ), 116.6 (C-200 ), 120.7 (C-600 ), 130.2 (C-20 , C-60 ),
133.3 (C-10 ), 135.3 (C-100 ), 144.2 (C-400 ), 146.1 (C-300 ), 156.6 (C-40 ) and 213.6 (C-3);
Negative-ion HR-FABMS: m/z 313.1404 (Calcd for C19H21O4, [M–H]–, 313.1440).

1,7-Bis(3,4-dihydroxyphenyl)heptan-3-yl acetate (2): Syrup; []25
D –10.2 (c ¼ 1.28,
MeOH); IR (film) max cmÀ1 : 3367, 1730, 1606, 1522, 1445, 1375, 1281, 1113; 1H
NMR (CD3OD):  1.28 (2H, m, H2-5), 1.52 (2H, m, H2-6), 1.56 (2H, m, H2-4), 1.75
(2H, m, H2-2), 1.97 (3H, s, 3-OAc), 2.42 (2H, m, H2-7), 2.44 (2H, m, H2-1), 4.83 (1H,
quint., J ¼ 6.1 Hz, H-3), 6.45 (2H, dd, J ¼ 8.0 Hz, 1.6 Hz, H-60 , H-600 ), 6.58 (2H, d,
J ¼ 1.6 Hz, H-20 , H-200 ), 6.64 (1H, d, J ¼ 8.0 Hz, H-500 ) and 6.65 (1H, d, J ¼ 8.0 Hz,
H-50 ); 13C NMR (CD3OD):  25.6 (C-5), 32.1 (C-1), 32.4 (C-6), 34.9 (C-4), 35.9 (C-7),
37.1 (C-2), 75.3 (C-3), 116.2 (C-500 ), 116.4 (C-50 ), 116.5 (C-200 ), 116.6 (C-20 ), 120.6
(C-600 ), 120.7 (C-60 ), 134.6 (C-100 ), 135.4 (C-10 ), 144.1 (C-400 ), 144.3 (C-40 ), 146.0
(C-300 ), 146.1 (C-30 ) and 172.9/21.1 (3-OAc); Negative-ion HR-FABMS: m/z
373.1634 (Calcd for C21H25O6, [M–H]–, 373.1651).
1-(40 -Hydroxyphenyl)-7-(300 ,400 -dihydroxyphenyl)heptan-3-yl acetate (3): Syrup; []25
D –
4.4 (c ¼ 0.8, MeOH); IR (film) max cmÀ1: 3382, 1730, 1609, 1515, 1448, 1375, 1272,
1113; 1H NMR (CD3OD):  1.28 (2H, m, H2-5), 1.54 (2H, m, H2-6), 1.57 (2H, m,
H2-4), 1.75 (2H, m, H2-2), 1.97 (3H, s, 3-OAc), 2.42 (2H, t, J ¼ 6.8 Hz, H2-7), 2.5
(2H, m, H2-1), 4.82 (1H, quint., J ¼ 6.4 Hz, H-3), 6.45 (1H, dd, J ¼ 8.0 Hz, 2.0 Hz,
H-600 ), 6.58 (1H, d, J ¼ 2.0 Hz, H-200 ), 6.64 (1H, d, J ¼ 8.0 Hz, H-500 ), 6.67 (1H, d,
J ¼ 8.6 Hz, H-30 , H-50 ) and 6.95 (1H, d, J ¼ 8.6 Hz, H-20 , H-60 ); 13C NMR (CD3OD):
 25.6 (C-5), 31.9 (C-1), 32.4 (C-6), 34.9 (C-4), 35.9 (C-7), 37.2 (C-2), 75.3 (C-3),


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116.2 (C-30 , C-50 ), 116.3 (C-500 ), 116.6 (C-200 ), 120.7 (C-600 ), 130.2 (C-20 , C-60 ), 135.4

(C-100 ), 133.8 (C-10 ), 144.1 (C-400 ), 146.0 (C-300 ), 156.4 (C-40 ) and 173.0/21.1 (3-OAc);
Negative-ion HR-FABMS: m/z 357.1710 (Calcd for C21H25O5, [M–H]–, 357.1702).
1-(30 ,40 -Hydroxyphenyl)-7-(400 -hydroxyphenyl)-heptan-3-one (4): Syrup; IR (film) max
cmÀ1: 3278, 1698, 1609, 1514, 1446, 1234, 1111; 1H NMR (CD3OD):  1.49 (4H, m,
H2-5, H2-6), 2.34 (4H, m, H2-4, H2-7), 2.69 (4H, m, H2-1, H2-2), 6.47 (1H, dd, J ¼ 8.8
Hz, 1.6 Hz, H-60 ), 6.59 (1H, br s, H-20 ), 6.64 (1H, d, J ¼ 8.8 Hz, H-50 ), 6.66 (2H, d,
J ¼ 8.4 Hz, H-300 , H-500 ) and 6.94 (2H, d, J ¼ 8.4 Hz, H-200 , H-600 ); 13C NMR
(CD3OD):  24.3 (C-6), 32.3 (C-5), 30.4 (C-1), 35.7 (C-7), 43.7 (C-4), 45.4 (C-2), 116.1
(C-300 , C-500 ), 116.4 (C-50 ), 116.5 (C-20 ), 120.5 (C-60 ), 130.2 (C-200 , C-600 ), 134.1 (C-10 ),
134.4 (C-100 ), 144.5 (C-40 ), 146.2 (C-30 ), 156.3 (C-400 ) and 213.6 (C-3); Negative-ion
HR-FABMS: m/z 313.1443 (Calcd for C19H21O4, [M–H]–, 313.1440).
(5R)-5-Hydroxy-1,7-bis(4-hydroxyphenyl)-3-heptanone (5): Syrup; []25
þ51.8
D
(c ¼ 0.11, MeOH); IR (film) max cmÀ1: 3400, 1699, 1611, 1513, 1450, 1368, 1229;
1
H NMR (CD3OD):  1.65 (2H, q br, J ¼ 6.4 Hz, H2-6), 2.47 (3H, m, H-4a, H2-7),
2.76 (5H, m, H2-1, H2-2, H-4b), 3.97 (1H, quint., J ¼ 6.4 Hz, H-5), 6.67 (2H, d,
J ¼ 8.4 Hz, H-300 , H-500 ), 6.68 (2H, d, J ¼ 8.4 Hz, H-30 , H-50 ) and 6.98 (4H, d, J ¼ 8.4
Hz, H-20 , H-60 , H-200 , H-600 ).

Acknowledgements
The authors are grateful to the National Foundation for Science and Technology
Development (NAFOSTED, Hanoi, Vietnam) and Vietnam National University, Hanoi
(Hanoi, Vietnam) for the support in this work.

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