Pharmaceutical Biology

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Parathesilactones and Parathesiquinones from

Branches of Parathesis amplifolia.

Pablo N. Solis, Norio Nakamura, Dionisio Olmedo, Masao Hattori & Mahabir
P. Gupta

To cite this article: Pablo N. Solis, Norio Nakamura, Dionisio Olmedo, Masao Hattori & Mahabir
P. Gupta (2006) Parathesilactones and Parathesiquinones from Branches of Parathesis�amplifolia.,
Pharmaceutical Biology, 44:5, 328-335, DOI: 10.1080/13880200600746220

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Published online: 07 Oct 2008.

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Pharmaceutical Biology
2006, Vol. 44, No. 5, pp. 328–335

Parathesilactones and Parathesiquinones from Branches

of Parathesis amplifolia

Pablo N. Solis1, Norio Nakamura2, Dionisio Olmedo1, Masao Hattori2, and Mahabir P. Gupta1
1
Centro de Investigaciones Farmacogn
osticas de la Flora Paname~ na (CIFLORPAN ), Facultad de Farmacia,
Universidad de Panam
a, República de Panam
a; 2Institute of Natural Medicine, Toyama Medical and
a, Panam

Pharmaceutical University, Toyama, Japan

Abstract
Three new lactone derivatives, (3E)-5,6-dihydroxy-3-
(3-hydroxy-4-nonyl-5-oxofuran-2(5H)-ylidene)-7-nonyl-
1-benzofuran-2(3H)-one (1), (3E)-5,6-dihydroxy-3-
(3-hydroxy-4-decyl-5-oxofuran-2(5H)-ylidene)-7-decyl-1-
benzofuran-2(3H)-one (2), and (3E)-5,6-dihydroxy-3-
(3-hydroxy-4-undecyl-5-oxofuran-2(5H)-ylidene)-7-
undecyl-1-benzofuran-2(3H)-one (3), denominated as
parathesilactones A, B, C, respectively, and two new
quinone derivatives, (2,7,8-trihydroxy-3,6-didecyldibenzo
[b,d]furan-1,4-dione (4) and (2,7,8-trihydroxy-3,6-
dinonyldibenzo[b,d]furan-1,4-dione) (5), denominated
as parathesiquinones A, B, respectively, were isolated
from the branches of Parathesis amplifolia Lund.
(Myrsinaceae). In addition, three known triterpenes,
a-amyrin (6), b-amyrin (7), and bauerenol (8), and
four known alkenylresorcinols, 5-pentadec-8-enyl
resorcinol (9), 5-pentadec-10-enyl resorcinol (10),
5-heptadec-8-enyl resorcinol (11), and 5-heptadec-10-enyl
resorcinol (12), were also isolated. The structure
elucidation was achieved by means of MS, GC-MS, IR,
1 General experimental procedures
H, 13C spectroscopy including Heteronuclear Multiple
Quantum Coherence (HMQC), and Heteronuclear
Multiple Bond Correlation (HMBC) techniques.
Keywords: Alkenylresorcinol, lactones, Parathesis ampli-
folia, quinones, triterpenes.
Introduction
Parathesis amplifolia Lund. (Myrsinaceae) is an endemic
tree, 15–20 ft high, with brown inflorescence and brown
leaf underneath (Lundell, 1971; Ricketson, 1997). In our
ongoing study of Panamaniam flora, the chloroform
extract of the branches of Parathesis amplifolia resulted
in the isolation of three novel parathesilactones A–C:
[(3E)-5,6-dihydroxy-3-(3-hydroxy-4-nonyl-5-oxofuran-
2(5H)-ylidene)-7-nonyl-1-benzofuran-2(3H)-one (1), (3E)-
5,6-dihydroxy-3-(3-hydroxy-4-decyl-5-oxofuran-2(5H)-
ylidene)-7-decyl-1-benzofuran-2(3H)-one (2), and (3E)-
5,6-dihydroxy-3-(3-hydroxy-4-undecyl-5-oxofuran-2(5H)-
ylidene)-7-undecyl-1-benzofuran-2(3H)-one (3)], and
two new parathesiquinones A, B [(2,7,8-trihydroxy-3,6-
didecyldibenzo[b,d]furan-1,4-dione (4) and (2,7,8-trihydroxy-
3,6-dinonyldibenzo[b,d]furan-1,4-dione) (5)] (Fig. 1), in
addition to three known triterpenes (6–8) and four
alkenylresorcinols (9–12).
Materials and Methods
IR spectra were recorded in KBr pellets using a Jasco
(Japan) FT=IR-230 spectrometer. NMR spectra were mea-
sured on a Varian (USA) UNITY 500 spectrometer in
CDCl3 or DMSO at 500 MHz and 125 MHz for 13C as
solvent with TMS as internal standard. Mass spectra were
obtained on a Jeol (Japan) JMX-AX 505 HAD at 70 eV.
GC-MS measurements were performed on a Shimadzu
(Japan) 17-A gas chromatograph attached to a Jeol
Automass System II, equipped with a capillary column
(30 m
0.25 mm narrow bore), film 0.25 mm (J&W Scien-
tific (USA)); elution was carried out at the temperatures

Accepted: March 14, 2006

Address correspondence to: P. Gupta, Centro de Investigaciones Farmacogn
osticas de la Flora Paname~
na, Facultad de Farmacia,
Universidad de Panam
a, Apartado 10767, Panam
a, República de Panam
a. Tel.: þ507-269-7655; Fax: þ507-264-0789; E-mail:
cytedqff@ancon.up.ac.pa

DOI: 10.1080/13880200600746220 # 2006 Taylor & Francis Group, LLC

 Lactones from Parathesis
Figure 1. Parathesilactone A, B, C (1–3) and parathesiquinone A, B (4–5). Structures of isolated compounds: Triterpenes (6–8) and
Alkenylresorcinols (9–12).
specified and using He as carrier gas at 50 cm=s. For the
analysis of the alkenylresorcinols, the temperature was
set from 200 to 290C, at 3 degrees per min, total time
30 min; and for the analysis of the triterpene mixture,
starting from 150 to 300C, at 10 degrees per min, then
15 min at 300C. Silica gel, glass-backed plates (Merck,
Kieselgel 60 F254 or RP18 F254 S, 0.25-mm thickness) were
used for thin-layer chromatography (TLC), and the com-
pounds were detected by means (254 nm and 365 nm) of
ultraviolet light and were sprayed with anisaldehyde–5%
H2SO4). Silica gel 60 [Fuji Silycia (70–230 mesh)] was used
for column chromatography (CC, Chemglass, USA). Low-
pressure liquid chromatography was carried out on Lobar
columns LiChroprep RP-8 (Merck, size A).
Plant material
Parathesis amplifolia Lund. was collected in Altos de
Campana National Park, Myrsinaceae Trail, on July
18, 1996, a cloud forest 1000 m above sea level, in the
Province of Panama. The taxonomic identification was
established by Prof. Mireya D. Correa, Director of the
Herbarium of the University of Panama (PMA), where
voucher specimens (FLORPAN 2636) are deposited.
Extraction and isolation
The dried powdered branches (234 g) of P. amplifolia
were extracted with CHCl3 by percolation at room
329
temperature, and the extract was filtered and concen-
trated to obtain a residue (6.92 g, 2.95%). The chloro-
form extract was subjected to fractionation by column
chromatography, using silica gel (150 g) and benzene-
acetone (100 to 80:20) as eluent to give five major
fractions. Repeated open column chromatography of
fraction 2 yielded 35.6 mg of compound 1 (fr. 2a)
and 25 mg of a triterpene mixture (6–8) (fr. 2b). From
fraction 3, after repeated Lobar RP-8 column (Merck)
using MeOH-H2O (9:1) as eluent, compound 4 was
obtained. By repeated Lobar RP-8 column (Merck) of
the fraction 5 using MeOH-H2O (9:1) as eluent, two oily
fractions (fr. 5a) and (fr. 5b) were obtained. The GC-MS
(EI-MS) analysis of the dimethyldisalfide derivatives
(DMDS) derivatives of the alkenylresorcinols series was
carried out for resolving the mixture and determining
the homologous long chains and the position of the
double bond in compounds 9, 10 (fr. 5a) and compounds
11, 12 (fr. 5b),respectively.
Preparation of methyl derivatives
Ten milligrams of parathesiquinone B (5) were dissolved
in 2.0 ml of MeOH, and 1 ml of trimethylsilyldiazo-
methane (10% in n-hexane) (TCI) was added and stirred
overnight. The solvent was evaporated and the derivative
purified either by small column chromatography or
pTLC.
330 P.N. Solis et al.
Preparation of benzoyl derivatives of triterpenoids
Thirty milligrams of a mixture of three triterpenes were
dissolved in 0.5 ml of pyridine, and 0.5 ml of benzoyl
chloride (Nacalai Tesque, Kyoto, Japan) were added
on an ice bath. After the mixture was allowed to stand
at room temperature for 20 h, it was poured on ice-cold
water and 20 ml of diethyl ether was added. The aqueous
layer was further washed with diethyl ether twice
consecutively. The organic fraction was washed with
NaHCO3 1% (3
20 ml) and concentrated in vacuo and
chromatographed on pTLC (0.5 m, 20
20 cm, silica gel
60 F254, Merck) using benzene as eluent. The upper
layer yielded 6.1 mg and showed to be a mixture of
a-and b-benzoyl amyrin, the lower (21 mg) was the third
compound unknown as yet. To 10.0 mg of the latter, 5 ml
of KOH 1 N in MeOH was added and heated at 70C for
2 h. The solvent was removed and the residue partitioned
between water and benzene; the organic layer was dried
to afford 7.03 mg of the bauerenol.
Preparation of DMDS derivatives for alkenylresorcinols
One milligram of each compound was dissolved in 100 ml
of hexane and 100 ml of DMDS (dimethyl disulfide)
(Nacalai Tesque, Kyoto, Japan) and 20 ml of iodine sol-
ution (60 mg of I2 in 1 ml of diethyl ether). The reaction
was carried out in a 2-ml glass tube tightly closed with a
Teflon cap and kept for 18 to 20 h at 50C. Samples were
diluted with 200 ml of Na2S2O3 solution (5% in distilled
water). The organic phase was removed with a Pasteur
pipette and the aqueous layer extracted again with n-
hexane. The sample was applied to a small pTLC
plate (5
5 cm) and developed using benzene-acetone
(98:2) as solvent. The main band was recovered
and extracted with the same solvent. The EIMS of the
residue was obtained to determine the position of the
double bond.
Parathesilactones (A–C) (1, 2, 3) (3E)-5,6-dihydroxy-
3-(3-hydroxy-4-nonyl-5-oxofuran-2(5H)-ylidene)-7-
nonyl-1-benzofuran-2(3H)-one (1), (3E)-5,6-dihydroxy-
3-(3-hydroxy-4-decyl-5-oxofuran-2(5H)-ylidene)-7-decyl-
1-benzofuran-2(3H)-one (2), (3E)-5,6-dihydroxy-3-
(3-hydroxy-4-undecyl-5-oxofuran-2(5H)-ylidene)-7-
undecyl-1-benzofuran-2(3H)-one (3): Red deli-
quescent needles from CHCl 3 35.6 mg, Ir n
(KBr) cm 1 : 3520, 3320, 2840, 2920, 2960, 1760,
1720, 1650, 1625, 1495, 1320, 1020. HRMS: m=z cal-
culated 514.2930 (C 30 H 42 O 7 ) found 514.2906; m=z
calculated 570.3556 (C 34 H 50 O 7 ) found 570.3507;
m=z calculated 542.3244 (C 32 H 46 O 7 ) found
542.3289 EIMS (70 eV): m=z (rel. int. %) 570 (5),
542 (20), 514 (100), 401 (12), 318 (30), 292 (10), 289
(10), 205 (12), 195 (7). 1 H NMR (500 MHz, DMSO):
d 11.81 (1H, s, OH-3 0 ), 9.79 (1H, s, OH-5), 9.44 (1H,
s, OH-6), 7.07 (1H, s, H-4), 2.55 (2H, t, J ¼ 7.5 Hz,
CH 2 -1 00 ), 2.26 (2H, t, J ¼ 7.4, CH 2 -1 000 ), 1.51 (4H,
m, CH 2 -2 0 H, 2 000 ), 1.28–1.24 (24H, br s, 12(CH 2 ),
0.838 (6H, t, J ¼ 6.6, 2CH 3 ). 13 C NMR (125.75,
MHz, DMSO): d 172.97 (C-2), 167.43 (C-5 0 ), 161.76
(C-3 0 ), 148.16 (C-2 0 ), 147.82 (C-6), 146.86 (C-7a),
142.92 (C-5), 113.56 (C-7), 110.81 a (C-3a), 107.62 a
(C-3), 107.61 (CH-4), 106.37 (C-4 0 ), 23.32 (CH 2 -1 00 ),
22.19 (CH 2 -1 000 ), 14.03 (CH 3 -9 00 , 9 000 ), 31.36, 29.05,
28.98, 28.93, 28.80, 28.77, 28.68, 28.41, 26.96,
21.44, 21.30 signals for the side chain as CH 2 .
Carbon signal may be interchangeable. HMQC and
HMBC were used to confirm these assignments.
Parathesiquinone A (2,7,8-trihydroxy-3,6-didecyl-
dibenzo[b,d]furan-1,4-dione) (4): 10 mg, dark red gum.
HRMS: m=z calculated 498.2981 (C30H42O6) found
498.2594. EIMS (70 eV): m=z (rel. int. %) 498 (100),
442 (30), 441 (80), 386 (35), 300 (20), 273 (75), 232
(60), 135 (40), 91 (100). 1H NMR (500 MHz, CDCl3): d
7.3 (1H, s, H-9), 2.90 (2H, br s, H-100 ), 2.52 (2H, br s,
H-1000 ), 1.25 (24H, br s, side chain), 0.87 (6H, t, CH3).
1
H NMR (500 MHz, D6MSO): d 10.79 (1H, s, OH-C-
2), 10.03 (1H, s, OH C-7), 9.07 (1H, s, OH-C-8), 7.17
(1H, s, H-9), 2.78 (2H, t, H-100 ), 2.50 (4H, br s, H-200 ,
H-2000 ), 2.35 (2H, t, H-1000 ), 1.28–1.19 (24H, br s,
side chain), 0.826 (6H, t, CH3). 13C NMR (125.75,
MHz, D6MSO): d 179.58 (C-1), 177.11 (C-3), 154.27
(C-2), 151.37 (C-4a), 150.06 (C-5a), 145.87 (C-8),
145.66 (C-7), 119.25a (C-1a), 118.80 (C-3), 113.29a
(C-9a), 112.53 (C-6), 102.17 (C-9), 32.16, 29.94, 29.91,
29.85, 29.74, 29.624, 29.41, 28.698, 22.96, 14.42 (side
chains).
Parathesiquinone B (2,7,8-trihydroxy-3,6-dinonyldi-
benzo[b,d]furan-1,4-dione) (5): 3 mg, dark red gum.
HRMS: m=z calculated 526.3294 (C32H46O6) found
526.3211. EIMS (70 eV): m=z (rel. int. %) 526 (100),
414 (30), 386 (25), 273 (15). NMR (500 MHz, CDCl3):
d 7.28 (1H, s, H-9), 2.90 (2H, br s, H-100 ), 2.52 (2H, br s,
H-1000 ), 1.25 (28H, br s, side chain), 0.87 (6H, t, CH3).
Carbon signal may be interchangeable. HMBC was used
to confirm these assignments.
Methylparathesiquinone B (5a): Orange gum. NMR
(500 MHz, CDCl3): d7.36 (1H, s), 4.10 (3H, s), 3.96
(3H,s), 3.89 (3H, s), 2.92 (2H, t, J ¼ 7.8), 2.52 (2H, t,
J ¼ 7.7), 1.678–1.647(4H, m), 1.25 (24H, br s), 0.876
(6H, m).
Triterpene mixture (6, 7, 8): a, and b-Amyrin (6, 7)
and bauerenol (8) mixture. 25 mg, colorless needles from
CHCl3=MeOH. Ir t(KBr) cm 1: 3400, 2950, 1460, 1380,
1030. EIMS (70 eV): m=z (rel. int. %) 426 (50), 411 (25),
247 (60), 218 (100). 1H NMR (500 MHz, CDCl3): d 5.43–
5.407 (1H, m, H-7 bauerenol), 5.19–5.18 (1H, m, H-11b-
amyrin), 5.13–5.12 (1H, m, H-11a-amyrin).
Bauerenol (8): 7.03 mg, white solid. [a]D (CHCl3,
C ¼ 3.51 mg=ml)  20.2. EIMS (70 eV): m=z (rel. int. %)
 Lactones from Parathesis
426 (60), 247 (90), 229 (50), 218 (30), 205 (25). 1H NMR
(500 MHz, CDCl3): d 5.42 (1H, dd, J ¼ 2.8, 6.8, H-7),
3.27–3.23 (1H, m, H-3), 1.03, 0.99, 0.97, 0.94, 0.86, 0.74
(3H each, s, CH3), 1.05, (3H, d, J ¼ 6.8, CH3), 0.95 (3H,
d, J ¼ 5.8, CH3). 13C NMR (125, CDCl3): d 145.34,
116.42, 79.25, 54.86, 50.39, 48.20, 41.22, 38.87, 37.99,
37.71, 37.67, 36.86, 35.31, 35.19, 32.39, 32.03, 31.50,
29.21, 28.85, 27.67, 27.53, 25.63, 24.14, 23.65, 22.65,
22.56, 16.79, 14.66, 12.98.
Benzoylbauerenol (8a): 21 mg, white solid. EIMS
(70 eV): m=z (rel. int. %) 530 (75), 351 (100), 229 (70),
105 (100). 1H NMR (500 MHz, CDCl3): d 8.05 (2H,
dd, J ¼ 0.86, 7.48, H-20 ), 7.55 (1H, t, J ¼ 7.7, H-40 ),
7.45 (2H, t, J ¼ 7.7, H-30 ), 5.44–5.43 (1H, m, H-7),
4.77 (1H, dd, J ¼ 4.4,11.6, H-3), 1.09, 1.04, 1.012, 0.97,
0.93, 0.82 (6H=each, s, CH3), 1.05 (3H, d, J ¼ 7.0,
CH3), 0.91 (3H, d, J ¼ 5.7, CH3).
5-Pentadecenylresorcinol (9, 10): 30.0 mg, colorless
oil. EIMS (70 eV): m=z (rel. int. %) 318 (90), 222 (38),
205 (15), 191 (23), 163 (23), 137 (50), 125 (40), 124
(100), 123 (70). 1H NMR (500 MHz, CDCl3): d 6.23
(2H, s, H-4,6), 6.17 (1H, s, H-2), 5.36–5.33 (2H, m, H-
80 ,90 ), 2.47 (2H, t, J ¼ 7.7, H-10 ), 2.02–1.99 (4H, m, H-
70 , 100 ) 1.57–1.53 (2H, m, H-20 ), 1.29 (16H, br s, H-on
side chain), 0.88 (3H, t, J ¼ 7.1, 3.8, H-15 ¼ ). 13C
NMR (125.75, MHz, CDCl3): d 156.58 (C-1), 100.28
(C-2), 156.58 (C-3), 108.14 (C-4), 146.17 (C-5), 108.14
(C-6), 36.09 (C-10 ), 27.47 (C-70 ), 129.92 (C-80 ), 130.06
(C-90 ), 27.50 (C-100 ), 14.42 (Me), 32.05, 31.32, 30.03,
29.67, 29.58, 29.53, 29.50, 29.28, 22.95.
DMDS-5-Pentadecenylresorcinol (9, 10) EIMS (70 eV):
m=z (rel. int. %) 458 (90), 341 (40), 313 (100), 170 (25), 145
(60), 117 (20), 123 (20).
5-Heptadecenylresorcinol (11, 12): 12.0 mg, colorless
oil. EIMS (70 eV): m=z (rel. int. %) 346 (100), 250 (30),
205 (15), 166 (23), 163 (20), 137 (50), 125 (25), 124
(100), 123 (70). 1H NMR (500 MHz, CDCl3): d 6.23
(2H, s, H-4,6), 6.17 (1H, s, H-2), 5.36–5.33 (2H, m,
H-80 ,90 ), 2.47(2H, t, J ¼ 7.7, H-10 ), 2.02–1.98 (4H, m,
H-70 , 100 ) 1.56–1.51 (2H, m, H-20 ), 1.29 (20H, br s,
H-on side chain), 0.88 (3H, t, J ¼ 7.1, 6.0, H-150 ).
13
C NMR (125.75, MHz, CDCl3): d 156.58 (C-1),
100.28 (C-2), 156.58 (C-3), 108.14 (C-4), 146.17
(C-5), 108.14 (C-6), 36.09 (C-10 ), 27.47 (C-90 ), 129.92
(C-100 ), 130.06 (C-110 ), 27.50 (C-120 ), 14.42 (Me),
32.05, 31.32, 30.03, 29.67, 29.58, 29.53, 29.50, 29.28,
22.95.
DMDS-5-Heptadecenylresorcinol (11, 12): EIMS
(70 eV): m=z (rel. int. %) 486 (60), 341 (60), 313
(100), 173 (35), 170 (50), 145 (35), 123 (20).
Results and Discussion
A mixture of three novel lactone derivatives (1–3) and a
mixture of two novel quinone derivatives (4, 5); a mixture
331
of three triterpenes a and b-amyrin (6, 7), bauerenol (8),
and a mixture of four alkenylresorcinols [5-pentadec-
8-enyl resorcinol (9), 5-pentadec-10-enyl resorcinol (10),
5-heptadec-8-enyl resorcinol (11), and 5-heptadec-8-enyl
resorcinol (12)] were isolated and characterized as
described earlier.
The IR spectrum of compound 1 showed absorption
bands typical of C ¼ O 1760, 1720 cm 1 of five-
membered lactone ring. The HR mass spectrum showed
a [M] þ peak at m=z 514.2906 corresponding with the
molecular formula C30H42O7. The 1H NMR spectrum
(DMSO, 500 MHz) showed signals for three OH groups
at d 11.81, 9.79, and 9.44. A one-proton signal in the
aromatic region (d 7.07) was assigned to the C-4 proton,
while the triplets integrating for 2 protons at d 2.55
and 2.26 were assigned to the protons on the C-100 and
C-1000 in the side chains. A four proton multiplet at d
1.51 (4H) was assigned to the C-200 and C-2000 protons,
the broad singlet (d 1.28–1.24) was assigned to the
protons on the side chain, and, a triplet integrating
for 6 protons at d 0.838 was assigned to the methyl
groups at the end of the side chains. 13C NMR spectrum
showed 12 carbons in the aromatic region, of which
11 were quaternary, based and HMQC and HMBC
correlations, a CH signal at d 107.61 was assigned to
C-4. The signals at d 172.97 and 167.76 were assigned
to carbonyl group C-2 and C-50 , respectively. While
signals at 161.76, 148.16, 147.82, 146.86, and 142.92
corresponded with aromatic carbons bearing oxygens,
there were signals for the CH2 and methyl groups of the
side chain.
Comparison of the 13C NMR of 1 with that of embe-
line reported by Kiuchi et al. (1998a, 1998b) and the
resorcinols series with the same nucleus but without the
side chains reported by Cirigottis et al. (1974), together
with the HMBC correlations allowed us to establish
the structure as parathesilactone A (3E)-5,6-dihydroxy-
3-(3-hydroxy-4-nonyl-5-oxofuran-2(5H)-ylidene)-7-
nonyl-1-benzofuran-2(3H)-one) (1), unequivocally
(Fig. 2). In addition to the peak at [M] þ 514.2906, the
EIMS showed two peaks at 542.3289 and 570.3507 corre-
sponding with the formula C32H46O7 and C34H50O7,
respectively. This data suggests that 1 is a mixture of
three homologous compounds differing in the length of
the side chain, because cleavage of two CH2 is not
observed in long side chains. Therefore, parathesilactone
B (3E)-5,6-dihydroxy-3-(3-hydroxy-4-decyl-5-oxofuran-
2(5H)-ylidene)-7-decyl-1-benzofuran-2(3H)-one) (2) and
parathesilactone C (3E)-5,6-dihydroxy-3-(3-hydroxy-4-
undecyl-5-oxofuran-2(5H)-ylidene)-7-undecyl-1-benzo-
furan-2(3H)-one) (3) have two side chains of 10 and 11
carbons, respectively.
The HR mass spectra of 4 showed a [M] þ peak at m=z
526.3211 corresponding with the formula C32H46O6. 1H
NMRshowed a broad signal at d10.79 assigned to the
332 P.N. Solis et al.
Figure 2. HMBC, MS, and 1H NMR % parathesilactone A (1).
OH on C-2 and two singlets at d10.03 and 9.07 were
assigned to OH bound to C-7 and C-8, respectively.
The singlet at d 7.17 for an isolated aromatic proton
was assigned to proton on C-9, which showed correlation
with the signal at d102.17 (C-9) In the HMQC spectrum,
two triplets, integrating for two protons, at d 2.78 and
2.35 were assigned to the protons on C-100 and C-1000 in
the side chain. A broad singlet, integrating for 4 protons
(d 2.50), was assigned to the protons on the second car-
bon in each of the two side chains. There were signals
for the protons in the side chains (d 1.28–1.19) and for
the methyl terminal of the side chains as triplet at d
0.826. 13C NMR showed 12 carbon signals in the aro-
matic region, 11 being quaternary carbons. The signals
at d 179.58 and 177.11, corresponding with a quinone
system, were assigned to C-1 and C-4, respectively.
Signals occurred at 154.27 (C-2), 151.37 (C-4a), 150.06
(C-5a), 145.87 (C-8), 145.66 (C-7), indicating aromatic
carbons bearing oxygen. There were signals for the
CH2 and methyl groups of the side chain. The 13C
NMR was compared with a synthetic compound with
the same nucleus but without side chains together
with its own HMBC correlations. Comparison of
the13C NMR of 4 with the resorcinols series reported
for Cirigottis et al. (1974) and by comparison with
embeline reported by Kiuchi et al. (1998a, 1998b)
established the structure of parathesiquinone A
(2,7,8-trihydroxy-3,6-didecyldibenzo[b,d]furan-1,4-dione)
(4), unequivocally (Fig. 3). In addition to the peak at
[M] þ 526.3211, the EIMS showed a peak at m=z
498.2594 corresponding with the formula C30H42O6.
This suggests that 4 is a mixture of two homologous
 Lactones from Parathesis
13
Figure 3. HMBC and C NMR of parathesiquinone A (4).
compounds differing in the length of the side chain,
because cleavage of two CH2 is not observed in long side
chains. Therefore, parathesiquinone B (2,7,8-trihydroxy-
3,6-dinonyldibenzo[b,d]furan-1,4-dione) (5) has two side
chains of 9 carbons each.
It has been proposed by Kiuchi et al. (1998a, 1998b)
that this series of lactones is formed during the extrac-
tion procedure, as demonstrated in the decoction of
Embelia ribes, which contains embelin-type benzoqui-
nones. Nevertheless, the parent compound in our sam-
ple was not detected. However, a homologue (13, 14,
and 15 carbons in the side chain) mixture was found
in high concentration in the extract from the stembark
of P. amplifolia, obtained in the similar manner by per-
colating with chloroform at low temperature. Determi-
nations of lactone were carried out by extracting, on
ice, small amounts of freshly collected plant material
and injecting into a HPLC-MS; the compound was
detected in high quantities, establishing its natural
occurrence.
333
Fraction 2a, which on TLC showed a single
spot, turned out to be an unresolved mixture of three
triterpenes. On GC-MS, it showed the presence of
a and b amyrin, 6 and 7, by comparison with the
authentic samples. However, the third compound could
not be identified by this method. For this, the mixture
was benzoylated, the components were isolated by
pTLC, then hydrolyzed to obtain the parent compound.
EIMS, 1H and 13C NMR data confirmed its structure as
bauerenol 8, a very well-known triterpene (Meksuriyen
et al., 1986).
Fractions 5a and 5b are very well-known 5-alkenylre-
sorcinols, having a side chain of 15 and 17 carbons,
respectively. Nevertheless, the fraction 5a is an isomeric
mixture of 5-pentadec-8-enyl-resorcinol (9) and 5-penta-
dec-10-enyl-resorcinol (10) (Occolowitz & Wright,
1962; Cirigottis et al., 1974; Tyman & Colenut 1981),
in accordance with the EIMS fragmentation pattern of
the DMDS derivative. The fragmentation for the
5-pentadecenylresorcinols appears in Figure 4. Also,
334 P.N. Solis et al.

Figure 4. Putative mass fragmentation of DMDS-5-pentadecenylresorcinol.

fraction 5b proved to be a mixture of two isomeric
known compounds, 5-heptadec-8-enyl-resorcinol (11)
and 5-heptadec-10-enyl-resorcinol (12) (Cirigottis et al.,
1974; Itokawa, et al., 1987).
Acknowledgments
We thank the International Foundation for Science for
funding a project (grant no. #F=1081-2) (P.N.S) and
the International Matsumae Foundation of Japan for
the postdoctoral fellowship grant to P.N.S. Thanks
are also due to Prof. Mireya D. Correa for the taxonomic
identification of the plant, to Carlos Guerra and
Alex Espinosa for their help in plant collection, and to
the Organization of American States for supporting
CIFLORPAN.
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