Caudatosides A-F: New iridoid glucosides from Citharexylum caudatum

Article abstract of DOI:10.1021/np020211c

Six new iridoid glucosides, caudatosides A-F (2-7), and one known iridoid glucoside, 5-deoxypulchelloside I (1), were isolated from the fruits of Citharexylum caudatum. The structures of these compounds were elucidated by various one- and two-dimensional NMR techniques as well as high-resolution negative-ion ESIMS. Other plant parts were extracted on a small scale, and TLC of these extracts revealed the presence of the same iridoids.

Full text of DOI:10.1021/np020211c

J . Nat. Prod. 2002, 65, 1621-1626
1621
Ca u d a tosid es A-F : New Ir id oid Glu cosid es fr om Cith a r exylu m ca u d a tu m
Sloan Ayers and Albert T. Sneden*
Department of Chemistry, Virginia Commonwealth University, P.O. Box 842006, Richmond, Virginia 23284-2006
Received May 3, 2002
Six new iridoid glucosides, caudatosides A-F (2-7), and one known iridoid glucoside, 5-deoxypulchelloside
I (1), were isolated from the fruits of Citharexylum caudatum. The structures of these compounds were
elucidated by various one- and two-dimensional NMR techniques as well as high-resolution negative-ion
ESIMS. Other plant parts were extracted on a small scale, and TLC of these extracts revealed the presence
of the same iridoids.
Citharexylum caudatum L. (Verbenaceae) is a large
shrub originally found in the Caribbean, Mexico, and
Central America. The plant was later introduced to Hawaii,
1
where it has flourished and is considered a pest plant. C.
caudatum has been used as an emmenagogue, as an
abortifacient, and as a pectoral in traditional medicine. The
fruits have been used by natives to make beverages and
1
are a food source for birds. Recently, extracts of this plant
were screened for activity against leishmania, and an
extract from the fruits showed limited activity.
Iridoids are monoterpenes that are usually glucosylated
2
and are widespread in Verbenaceae. This class of com-
pound has been shown to exhibit a wide range of biological
activities3 and has been found in other members of the
4
,5
Citharexylum genus, in C. fruiticosum
and, more re-
6
cently, in C. quadrangular. C. fruiticosum and C. qua-
drangular are apparently the only members of the genus
that have been chemically investigated. The current work
is the first investigation of C. caudatum and is also
apparently the first investigation of the fruits of any
member of the Verbenaceae family outside of the genus
Vitex.
Resu lts a n d Discu ssion
Dried, ground fruits of C. caudatum (1 kg) were sequen-
tially extracted with petroleum ether, chloroform, acetone,
and 95% ethanol. The acetone extract was fractionated
initially by silica gel column chromatography, and further
separation was carried out by reversed-phase (C18) flash
chromatography to give iridoid glucosides 1-5. Preparative
RP-TLC was used to isolate 6 and 7.
The separation of 2 and 3 from each other, as well as
separation of 6 and 7 from each other, proved difficult,
presumably due to facile acyl transfer of the phenylpro-
panoid ester from the O-6 to the O-7 and vice versa,
especially in aqueous conditions. (Interestingly, this phen-
omenon was not a problem in the separation of 4 and 5
from each other.) These pairs of compounds could not be
separated from each other by normal-phase silica gel
chromatography, except on a small scale by HPLC. Separa-
tion of 2-5 on a large scale was accomplished by rapid
reversed-phase column chromatography to avoid acyl trans-
fer facilitated by the aqueous conditions required for
separation. To separate 6 from 7, preparative RP-TLC was
employed, with the eluting mobile phase modified with
Compound 1 was determined to have the formula
-
C
17
H
26
O
11 from the parent ion at m/z 405.14 [M - H] in
the negative ion low-resolution ESIMS and was determined
to be an iridoid by the presence of diagnostic peaks in the
0
.1% trifluoroacetic acid. To avoid acyl transfer catalyzed
by residual acid, NaHCO was added to the scraped PTLC
bands prior to adding the solvent used to extract the pure
and 7 from the silica gel.
1
H NMR spectrum (Table 1). The structure of 1 was
3
1
confirmed by comparison of the H NMR data to data of
known iridoids and determined to be 5-deoxypulchelloside
6
5
I, first isolated from the leaves of C. fruiticosum.
1
The H NMR data of the remaining six compounds, 2-7,
*
To whom correspondence should be addressed. Tel: (804) 828-1674.
Fax: (804) 828-2171. E-mail: atsneden@vcu.edu.
were similar to the 1H NMR data of 1 except for the
1
0.1021/np020211c CCC: $22.00
© 2002 American Chemical Society and American Society of Pharmacognosy
Published on Web 09/26/2002

1
622 J ournal of Natural Products, 2002, Vol. 65, No. 11
Ayers and Sneden
Ta ble 1. 1H NMR Data for Compounds 1-7 (300 MHz, chemical shifts in δ, coupling constants in Hz, 1 in D2O, 2-7 in acetone-d6)
proton
1
2
3
4
5
6
7
1
3
5
5.60, d, J 1,9)1.5
7.47, d, J 3,5)0.9
2.90, ddd,
5.58, d, J 1,9)3.3
7.42-7.45
5.61, d, J 1,9)2.1
7.42-7.45
5.58, d, J 1,9)3.0
7.42, d, J 3,5)1.2
5.60, d, J 1,9)2.4
7.44, d, J 3,5)0.6
5.57, d, J 1,9)3.0
7.41, d, J 3,5)1.5
5.59, d, J 1,9)2.1
7.44, d, J 3,5)0.9
3.01, ddd, J 5,3)obsc., 2.96, ddd, J 5,3)obsc. 2.99, ddd, J 5,3)1.2 2.94, ddd J 5,3)0.6 3.00, ddd, J 5,3)1.5 2.94, ddd J 5,3)0.9
J 5,3)0.9
J 5,6)2.4, J 5,9)8.9
J 5,6)1.5, J 5,9)9.0
J 5,6)2.4, J 5,9)9.3 J 5,6)1.6, J 5,9)8.7 J 5,6)2.4, J 5,9)9.3 J 5,6)1.8, J 5,9)9.0
J 5,6)0.9, J 5,9)9.3
6
7
8
9
4.02, dd, J 6,5)0.9 5.40, dd, J 6,5)2.4
4.34, dd, J 6,5)1.5
J 6,7)4.0
4.72, dd, J 7,6)4.0
J 7,8)9.2
5.38, dd, J 6,5)2.4 4.32, dd, J 6,5)1.6 5.37, dd, J 6,5)2.4 4.32, dd, J 6,5)1.8
J 6,7)3.9
3.61, dd, J 7,6)3.9 3.81, dd, J 7,6)4.6
J 7,8)9.3 J 7,8)8.6
J 6,7)4.6
J 6,7)4.3
J 6,7)3.9
J 6,7)4.2
J 6,7)3.6
3.79, dd, J 7,6)4.3 4.70, dd, J 7,6)3.9 3.77, dd, J 7,6)4.2 4.69, dd, J 7,6)3.6
J 7,8)8.6 J 7,8)9.3 J 7,8)8.7 J 7,8)9.0
2.31, ddq, J 8,7)9.3 2.35, ddq, J 8,7)8.6
J 8,9)9.3, J 8,10)7.5 J 8,9)8.9, J 8,10)7.2
2.86, ddd, J 9,1)1.5 2.82, ddd, J 9,1)3.3
J 9,5)9.3, J 9,8)9.3 J 9,5)8.9, J 9,8)8.9
1.07, d, J 10,8)7.5 1.13, d, J 10,8)7.2
4.71, d, J 1′,2′)8.4 4.67, d, J 1′,2′)7.8
3.21, dd, J 2′,1′)8.4 3.21, dd, J 2′,1′)7.8
2.67, ddq, J 8,7)9.2 2.34, ddq, J 8,7)8.6 2.65, ddq, J 8,7)9.3 2.32, ddq, J 8,7)8.7 2.64, ddq, J 8,7)9.0
J 8,9)9.0, J 8,10)7.2
J 8,9)9.3, J 8,10)7.5 J 8,9)8.7, J 8,10)7.2 J 8,9)9.3, J 8,10)7.5 J 8,9)9.0, J 8,10)7.2
2.88, ddd, J 9,1)2.1 2.81, ddd, J 9,1)3.0 2.85, ddd, J 9,1)2.4 2.81, ddd, J 9,1)3.0 2.85, ddd, J 9,1)2.1
J 9,5)9.0, J 9,8)9.0
1.11, d, J 10,8)7.2
4.66, d, J 1′,2′)7.8
3.22, dd, J 2′,1′)7.8
J 2′,3′)9.0
J 9,5)9.3, J 9,8)9.3 J 9,5)8.7, J 9,8)8.7 J 9,5)9.3, J 9,8)9.3 J 9,5)9.0, J 9,8)9.0
1
1
2
0
′
′
1.12, d, J 10,8)7.5
4.66, d, J 1′,2′)7.8
1.10, d, J 10,8)7.2
4.65, d, J 1′,2′)8.1
1.12, d, J 10,8)7.5
4.65, d, J 1′,2′)7.5
1.09, d, J 10,8)7.2
4.65, d, J 1′,2′)8.1
3.20, dd, J 2′,1′)7.8 3.20, dd, J 2′,1′)8.1 3.22, dd, J 2′,1′)7.5 3.22, dd, J 2′,1′)8.1
J 2′,3′)9.3
J 2′,3′)9.0
3.31-3.46
3.88, dd, J 6′a,5′)2.4
J 6′a,6′b)11.7
J 2′,3′)9.3
3.29-3.45
J 2′,3′)9.0
3.30-3.44
J 2′,3′)8.7
3.34-3.43
J 2′,3′)8.7
3.35-3.47
3
6
′,4′,5′ 3.33-3.50
3.31-3.46
′a
3.91, dd,
3.88, dd, J 6′a,5′)2.4 3.88, dd, J 6′a,5′)2.4 3.87, dd, J 6′a,5′)2.4 3.86, dd, J 6′a,5′)2.4 3.86, dd, J 6′a,5′)2.4
J 6′a,5′)2.1
J 6′a,6′b)12.3
J 6′a,6′b)12.0
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
3.67-3.74
6
′b
3.62-3.68
(obscured
by -CO2CH3)
3.64, s
3.62-3.67
(obscured
by -CO2CH3)
3.69, s
3.61-3.67
(obscured
by -CO2CH3)
3.63, s
3.61-3.67
(obscured
by -CO2CH3)
3.68, s
3.65-3.70
(obscured
by -CO2CH3)
3.64, s
3.64-3.70
(obscured
by -CO2CH3)
3.68, s
(obscured
by -CO2CH3)
CO2- 3.74, s
-
CH3
R
6.59, d, J R,â)16.2
7.72, d, J â,R)16.2
7.67-7.71
6.56, d, J R,â)15.9
7.68, d, J â,R)15.9
7.66-7.69
6.37, d, J R,â)15.9 6.36, d, J R,â)15.9 6.31, d, J R,â)15.9 6.28, d, J R,â)16.2
7.64, d, J â,R)15.9 7.60, d, J â,R)15.9 7.57, d, J â,R)15.9 7.53, d, J â,R)16.2
7.55, d, J 2′′,3′′)8.4 7.54, d, J 2′′,3′′)8.4 7.18, d, J 2′′,6′′)2.1 7.17, d, J 2′′,6′′)2.1
6.89, d, J 3′′,2′′)8.4 6.89, d, J 3′′,2′′)8.4
â
2
3
4
5
6
′′
′′
′′
′′
′′
7.42-7.45
7.42-7.45
7.42-7.45
7.42-7.45
7.42-7.45
7.42-7.45
6.89, d, J 5′′,6′′)8.4 6.89, d, J 5′′,6′′)8.4 6.87, d, J 5′′,6′′)7.8 6.86, d, J 5′′,6′′)8.4
7.55, d, J 6′′,5′′)8.4 7.54, d, J 6′′,5′′)8.4 7.01, dd, J 6′′,2′′)2.1 7.01, dd, J 6′′,2′′)2.1
7.67-7.71
7.66-7.69
J 6′′,5′′)7.8
J 6′′,5′′)8.4
presence of new signals in the aromatic region consistent
with a phenylpropanoid moiety, as well as a large downfield
shift of either the H-6 or H-7, indicating esterification of
the phenylpropanoid group at one of these positions.
Caudatoside A (2) was shown to have the molecular for-
Caudatoside B (3) was shown to have the same molecular
formula as 2, C26 12, by analysis of the negative ion
32
H O
-
1
high-resolution ESIMS (m/z 571.1522 [M + Cl] ). The H
1
NMR data of 3 (Table 1) were similar to the H NMR data
of 2 except for the large upfield shift of H-6 and the
downfield shift of H-7, indicating esterification at the O-7
instead of O-6. The aromatic regions of 2 and 3 were
essentially identical. After acetylation of 3 to give 10, the
mula C26
32
H O12 by analysis of the negative ion high-res-
-
1
olution ESIMS (m/z 571.1492 [M + Cl] ). The H NMR data
of 2 (Table 1) were very similar to the H NMR data of 1
1
1
except for new signals in the aromatic region and the large
downfield shift of H-6 to δ 5.40, indicating esterification of
O-6. The signals in the aromatic region are typical of a
cinnamoyl ester, which was sited at C-6, due to the down-
field shift of H-6. The glycosyl moiety at C-1 was confirmed
as a glucopyranosyl moiety from the coupling constant data
of the pentaacetate 9 (Table 2) prepared from 2.
H NMR spectrum of 10 (Table 2) again confirmed that the
C-1 glycosyl moiety was a glucopyranosyl group. The
stereochemistry of 3 was confirmed as described for 2. From
these data, compound 3 was determined to be 7-cinnamoyl-
5-deoxypulchelloside I, named caudatoside B.
Caudatoside C (4) was shown to have the molecular
formula C26
H
32
O
13 by analysis of the negative ion high-
-
The stereochemistry of 2 was determined by comparison
of chemical shifts and coupling constants to literature data
and by analysis of the ROESY spectrum. The relationship
of H-5 to H-9 was determined to be cis from the coupling
constant (8.9 Hz), which is larger in trans-fused iridoids
resolution ESIMS (m/z 551.1723 [M - H] , 587.1544 [M +
-
1
Cl] ). The H NMR data of 4 (Table 1) were essentially
1
identical to the H NMR data of 2 except for the aromatic
region. The signals in the aromatic region clearly indicate
the presence of a p-substituted phenylpropanoid. The
HMBC spectrum showed a correlation between the methyl
proton signal at δ 3.63 and the carbonyl carbon signal at δ
166.87, confirming that the methyl group was part of a
methyl ester at C-4. Thus, the phenylpropanoid moiety was
shown to be a p-coumaryl ester and not a p-methoxycin-
namoyl ester. This ester was sited at C-6, on the basis of
7
,8
(
1
∼12-13 Hz). In most iridoids, the configuration of the
-glucose, H-5, and H-9 is â, and the 13C NMR chemical
shifts of C-1 and C-1′ are typically δ 93-98 and 97-101,
respectively. When the configuration at these three posi-
tions is R, the shifts of C-1 and C-1′ are, on average, 5-6
ppm further downfield.9 The C NMR data for all seven
compounds reported here (Table 3) indicate the normal â
stereochemistry for the 1-glucose, H-5, and H-9.
,10
13
1
the chemical shift of H-6 (δ 5.38) in the H NMR spectrum
(Table 1). The glucopyranosyl moiety at C-1 was confirmed
as described for 2 and 3, as was the stereochemistry. From
these data, compound 4 was determined to be 6-p-cou-
maryl-5-deoxypulchelloside I, named caudatoside C.
Caudatoside D (5) was shown to have the same molec-
The stereochemistry at C-6, C-7, and C-8 was determined
from the ROESY spectrum. Correlations (Figure 1) from
the H-1 to CH -10, from CH -10 to H-7, and from H-7 to
3 3
H-6 indicate that these protons are all on the same face of
the molecule. The H-8 and H-9 correlate to one another,
but H-8 did not correlate to H-7, indicating that H-8 and
H-9 were on the opposite face of the molecule from H-1,
ular formula as 4, C26
H
32
O
13, by analysis of the negative
-
ion high-resolution ESIMS (m/z 551.1797 [M - H] ,
-
1
587.1612 [M + Cl] ). The H NMR data of 5 (Table 1) were
1
H-6, H-7, and CH
3
-10. The H-6 did not correlate to H-5,
essentially identical to the H NMR data of 3 except for
confirming that H-5 is on the same face as H-8 and H-9.
From these data, compound 2 was determined to be
the aromatic region, indicating substitution at O-7. The
resonances in the aromatic region were identical to those
of 4, confirming the presence of a p-coumaryl group. The
6
-cinnamoyl-5-deoxypulchelloside I, named caudatoside A.

New Iridoid Glucosides from Citharexylum
J ournal of Natural Products, 2002, Vol. 65, No. 11 1623
Ta ble 2. 1H NMR Data for Acetates 8-14 (300 MHz, chemical shifts in δ, coupling constants in Hz, CDCl3)
proton
8
9
10
11
12
13
14
1
3
5.37, d, J 1,9)1.8
7.40, d, J 3,5)0.6
5.41, d, J 1,9)1.8 5.41, d, J 1,9)1.5
7.43, d, J 3,5)0.9 7.43, d, J 3,5)<0.6
5.41, d, J 1,9)1.8
7.43, d, J 3,5)1.2
5.40, d, J 1,9)1.2
7.42, d, J 3,5)0.9
5.41, d, J 1,9)1.8
5.40, d, J 1,9)1.2
7.44, d, (obscured 7.42, d, J 3,5)<0.6
by 2′′)
5
2.96, ddd, J 5,3)0.6 3.08, ddd,
J 5,3)0.9
3.02, ddd, J 5,3)<0.6 3.07, ddd, J 5,3)1.2 3.01, ddd, J 5,3)0.6 3.07, ddd, J 5,3)1.5 3.01, ddd, J 5,3)0.9
J 5,6)1.2, J 5,9)9.3 J 5,6)2.0,
J 5,9)9.3
J 5,6)2.0, J 5,9)9.3
5.48, dd, J 6,5)2.0
J 5,6)1.8, J 5,9)9.3 J 5,6)1.8, J 5,9)9.3
5.53, dd, J 6,5)1.8 5.47, dd, J 6,5)1.8
J 5,6)2.1, J 5,9)9.3 J 5,6)1.8, J 5,9)9.3
5.52, dd, J 6,5)2.1 5.47, dd, J 6,5)1.8
6
7
8
5.39, dd, J 6,5)1.2 5.53, dd,
J 6,5)2.0
J 6,7)2.7
J 6,7)4.1
J 6,7)4.1
4.98, dd, J 7,6)4.1
J 6,7)3.9
J 6,7)4.2
J 6,7)3.9
J 6,7)4.2
4.80, dd, J 7,6)2.7 4.88, dd,
J 7,6)4.1
J 7,8)8.9
4.88, dd, J 7,6)3.9 4.97, dd, J 7,6)4.2
4.88, dd, J 7,6)3.9 4.96, dd, J 7,6)4.2
J 7,8)8.7
J 7,8)obsc.
J 7,8)8.7 J 7,8)obsc.
J 7,8)8.7 J 7,8)obsc.
2.48, ddq, J 8,7)8.7 2.57, ddq,
J 8,7)8.9
2.58, ddq, J 8,7)obsc. 2.56, ddq, J 8,7)8.7 2.58, ddq, J 8,7)obsc. 2.54, ddq, J 8,7)8.7 2.57, ddq, J 8,7)obsc.
J 8,9)9.6, J 8,10)7.5 J 8,9)9.3,
J 8,10)7.2
J 8,9)9.3, J 8,10)7.2
J 8,9)9.6, J 8,10)7.2 J 8,9)9.3, J 8,10)7.2
J 8,9)9.3, J 8,10)7.2 J 8,9)9.3, J 8,10)7.5
9
2.91, ddd, J 9,1)1.8 3.00, ddd,
J 9,1)1.8
2.97, ddd, J 9,1)1.5 2.99, ddd, J 9,1)1.8 2.97, ddd, J 9,1)1.2 2.98, ddd, J 9,1)1.8 2.97, ddd, J 9,1)1.2
J 9,5)9.3, J 9,8)9.6 J 9,5)9.3,
J 9,8)9.3
J 9,5)9.3, J 9,8)9.3
1.11, d, J 10,8)7.2
4.84, d, J 1′,2′)8.4
4.98, dd, J 2′,1′)8.4
J 9,5)9.3, J 9,8)9.6 J 9,5)9.3, J 9,8)9.3
J 9,5)9.3, J 9,8)9.3 J 9,5)9.3, J 9,8)9.3
1
1
2
0
′
1.05, d, J 10,8)7.5
1.09, d,
1.09, d, J 10,8)7.2
4.83, d, J 1′,2′)8.4
1.10, d, J 10,8)7.2
4.83, d, J 1′,2′)8.4
1.09, d, J 10,8)7.2
4.83, d, J 1′,2′)8.4
1.10, d, J 10,8)7.5
4.83, d, J 1′,2′)8.4
J 10,8)7.2
4.80, d, J 1′,2′)8.4
4.83, d,
J 1′,2′)8.4
′
4.95, dd, J 2′,1′)8.4 4.97, dd,
J 2′,1′)8.4
J 2′,3′)9.6
5.20, dd, J 3′,2′)9.6 5.22, dd,
J 3′,2′)9.6
J 3′,4′)9.6
5.08, dd, J 4′,3′)9.6 5.10, dd,
J 4′,3′)9.6
J 4′,5′)9.6
4.97, dd, J 2′,1′)8.4 4.98, dd, J 2′,1′)8.4
4.98, dd, J 2′,1′)8.4 4.98, dd, J 2′,1′)8.4
J 2′,3′)9.6
J 2′,3′)obsc.
J 2′,3′)9.6 J 2′,3′)obsc.
J 2′,3′)9.6 J 2′,3′)obsc.
3
4
5
′
′
′
5.22, dd, J 3′,2′)9.6
5.22, dd, J 3′,2′)9.6 5.22, dd, J 3′,2′)9.6
J 3′,4′)9.6 J 3′,4′)9.6
5.22, dd, J 3′,2′)9.6 5.22, dd, J 3′,2′)9.6
J 3′,4′)9.6 J 3′,4′)9.6
J 3′,4′)9.6
J 3′,4′)9.6
5.10, dd, J 4′,3′)9.6
5.10, dd, J 4′,3′)9.6 5.10, dd, J 4′,3′)9.6
5.10, dd, J 4′,3′)9.6 5.10, dd, J 4′,3′)9.6
J 4′,5′)9.6
J 4′,5′)9.6
J 4′,5′)9.6 J 4′,5′)9.6
J 4′,5′)9.6 J 4′,5′)9.6
3.74, ddd, J 5′,4′)9.6 3.76, ddd,
J 5′,4′)9.6
3.76, ddd, J 5′,4′)9.6 3.76, ddd, J 5′,4′)9.6 3.76, ddd, J 5′,4′)9.6 3.77, ddd, J 5′,4′)9.6 3.76, ddd, J 5′,4′)9.6
J 5′,6′a)2.4,
J 5′,6′b)4.5
J 5′,6′a)2.1,
J 5′,6′b)4.2
J 5′,6′a)2.1,
J 5′,6′b)4.4
J 5′,6′a)2.1,
J 5′,6′b)4.4
J 5′,6′a)2.1,
J 5′,6′b)4.5
J 5′,6′a)1.8,
J 5′,6′b)4.5
J 5′,6′a)1.8,
J 5′,6′b)4.2
6
6
′a
′b
4.14, dd, J 6′a,5′)2.4 4.16, dd,
4.15, dd, J 6′a,5′)2.1 4.16, dd, J 6′a,5′)2.1 4.15, dd, J 6′a,5′)2.1 4.16, dd, J 6′a,5′)1.8 4.15, dd, J 6′a,5′)1.8
J 6′a,5′)2.1
J 6′a,6′b)12.3
4.29, dd, J 6′b,5′)4.5 4.30, dd,
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
J 6′a,6′b)12.3
4.30, dd, J 6′b,5′)4.4 4.30, dd, J 6′b,5′)4.4 4.30, dd, J 6′b,5′)4.5 4.31, dd, J 6′b,5′)4.5 4.30, dd, J 6′b,5′)4.2
J 6′b,5′)4.2
J 6′b,6′a)12.3
CO2- 3.70, s
CH3
J 6′b,6′a)12.3
J 6′b,6′a)12.3
3.71, s
J 6′b,6′a)12.3
3.71, s
J 6′b,6′a)12.3
3.71, s
J 6′b,6′a)12.3
3.71, s
J 6′b,6′a)12.3
3.71, s
-
a
3.71, s
6.44, d,
J R,â)15.9
7.68, d,
J â,R)15.9
7.52-7.56
7.38-7.40
7.38-7.40
7.38-7.40
7.52-7.56
6.38, d, J R,â)15.9
7.65, d, J â,R)15.9
6.39, d, J R,â)15.9 6.33, d, J R,â)15.9
7.66, d, J â,R)15.9 7.62, d, J â,R)15.9
6.39, d, J R,â)15.9 6.32, d, J R,â)15.9
7.62, d, J â,R)15.9 7.58, d, J â,R)15.9
7.38, d, J 2′′,6′′)2.1 7.35, d, J 2′′,6′′)2.1
b
2
3
4
5
6
′′
7.50-7.53
7.37-7.40
7.37-7.40
7.37-7.40
7.37-7.53
7.55, d, J 2′′,3′′)8.4 7.53, d, J 2′′,3′′)8.4
7.13, d, J 3′′,2′′)8.4 7.12, d, J 3′′,2′′)8.4
′′
′′
′′
′′
7.13, d, J 5′′,6′′)8.4 7.12, d, J 5′′,6′′)8.4
7.55, d, J 6′′,5′′)8.4 7.53, d, J 6′′,5′′)8.4
7.24, d, J 5′′,6′′)8.4 7.22, d, J 5′′,6′′)8.4
7.42, dd, J 6′′,2′′)2.1 7.40, dd, J 6′′,2′′)2.1
J 6′′,5′′)8.4
1.90, 1.99
J 6′′,5′′)8.4
1.90, 2.01
ace-
tates
1.88, 1.99
1.90, 1.99
1.90, 2.00
1.90, 1.99
1.90, 2.00
1
2
.99, 2.02
.06, 2.09
2.00, 2.03
2.11
2.03, 2.07
2.10
2.00, 2.04
2.11, 2.32
2.03, 2.06
2.10, 2.31
2.01, 2.04
2.11, 2.31
2.04, 2.06
2.10, 2.30
2.31
2
.32
glucopyranosyl moiety at C-1 was confirmed as described
for 2 and 3, as was the stereochemistry. Compound 5 was
therefore determined to be 7-p-coumaryl-5-deoxypulchel-
loside I, named caudatoside D.
Caudatoside F (7) was shown to have the same molecular
formula as 6, C26 14, by analysis of the negative ion
32
H O
-
1
high-resolution ESIMS (m/z 567.1464 [M - H] ). The H
1
NMR data of 7 were very similar to the H NMR data of 5
(
7
Table 1) except for the aromatic region, again indicating
-substitution. The presence of a caffeoyl group was proven
Caudatoside E (6) was shown to have the molecular
formula C26
32
H O14 by analysis of the negative ion high-
-
1
as for 6. The glucopyranosyl moiety at C-1 was confirmed
as described for 2 and 3, as was the stereochemistry. From
these data, compound 7 was determined to be 7-caffeoyl-
resolution ESIMS (m/z 567.1683 [M - H] ). The H NMR
data of 6 (Table 1) were similar to the H NMR data of 2
1
and 4 except for the aromatic region, which clearly showed
the presence of either a caffeoyl or a feruloyl phenylpro-
panoid group sited at the O-6. HMBC was used to show
that the methyl signal at δ 3.64 was due to a methyl ester
at C-4, as described above for 4, thus making the phenyl-
propanoid moiety a caffeoyl group. The glucopyranosyl
moiety at C-1 was confirmed as described for 2 and 3, as
was the stereochemistry. From these data, compound 6 was
determined to be 6-caffeoyl-5-deoxypulchelloside I, named
caudatoside E.
5
-deoxypulchelloside I, named caudatoside F.
Other plant parts of C. caudatum were collected along
with the fruits. All parts were collected from Hawaii except
one sample of stemwood, which was collected from Panama.
Other Hawaiian samples include stems, stemwood, fruits/
inflorescence, and leaves. These five samples were ex-
tracted separately on a small scale with 95% ethanol for
24 h. These extracts were subjected to silica gel TLC as
well as RP-TLC (C18) along with the pure iridoids that were

1
624 J ournal of Natural Products, 2002, Vol. 65, No. 11
Ayers and Sneden
Ta ble 3. 13C NMR Data for Compounds 1-14a (75 MHz, chemical shifts in δ, 1 in D2O, 2-7 in Acetone-d6, and 8-14 in CDCl3)
carbon
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1
3
4
5
6
7
8
9
1
1
2
3
4
5
6
-
-
-
a
b
1
2
95.52 94.96 94.96 94.96 94.96 94.94 94.95 93.72
153.04 152.90 152.86 152.84 152.81 152.89 152.81 151.69
109.92 109.66 110.17 109.76 110.25 109.74 110.26 109.56
36.79 36.75 39.02 36.75 39.04 36.65 38.98 35.10
76.15 78.76 74.62 78.50 74.69 78.51 74.69 75.48
78.34 78.14 81.64 78.23 81.38 78.22 81.34 78.04
36.94 39.76 36.24 39.76 36.26 39.68 36.24 35.66
38.78 40.00 39.24 40.01 39.30 39.95 39.28 38.45
12.82 13.99 13.88 14.01 13.89 13.98 13.89 13.09
98.34 99.18 99.25 99.18 99.30 99.14 99.28 95.43
72.66 74.33 74.21 74.34 74.29 74.22 74.19 70.41
76.42 77.78 77.61 77.64 77.69 77.49 77.56 72.32
69.67 71.41 71.28 71.43 71.38 71.30 71.28 67.98
75.67 77.62 77.69 77.78 77.76 77.79 77.79 72.12
60.80 62.82 62.69 62.84 62.76 62.66 62.63 61.56
52.07 51.29 51.40 51.28 51.36 51.31 51.35 51.52
169.29 166.86 167.45 166.87 167.40 166.92 167.42 166.03
166.00 166.64 166.44 167.00 166.60 167.04
93.80
151.67
109.52
35.39
75.64
78.12
35.88
38.59
13.22
95.48
70.43
72.35
68.02
72.15
61.62
51.62
165.93
165.34
117.56
145.03
134.15
128.02
93.80
151.46
109.74
35.26
75.70
78.23
36.51
38.77
13.32
95.44
70.44
72.35
68.02
72.15
61.60
51.56
165.97
165.97
117.27
145.25
134.09
128.05
93.79
151.65
109.51
35.39
75.71
78.12
35.91
38.60
13.22
95.48
70.44
72.36
68.03
72.16
61.62
51.62
165.93
165.23
117.74
143.89
131.90
129.16
93.80
151.46
109.74
35.25
75.70
78.30
36.51
38.78
13.32
95.44
70.44
72.36
68.02
72.16
61.60
51.57
165.97
165.84
117.46
144.10
131.84
129.19
93.76
151.68
109.44
35.35
75.80
78.06
35.90
38.57
13.22
95.45
70.41
72.34
67.98
72.13
61.60
51.65
165.92
164.96
118.74
143.08
133.04
122.72
93.75
151.47
109.70
35.19
75.63
78.40
36.44
38.72
13.31
95.40
70.40
72.32
67.96
72.12
61.57
51.58
165.95
165.57
118.48
143.25
132.97
122.68
0
′
′
′
′
′
′
CO
CO
2
2
CH
CH
3
3
OCOAcyl
119.39 118.93 115.96 115.52 115.68 115.30
144.70 144.95 144.82 145.04 145.40 145.55
′′
′′
135.29 135.12 126.90 126.78 127.27 127.18
128.73 128.76 130.64 130.69 115.04 115.12
6
.02
3
4
5
6
′′
′′
′′
′′
129.56 129.55 116.47 116.49 146.24 146.24
130.82 130.90 160.17 160.25 148.73 148.79
129.56 129.55 116.47 116.49 116.30 116.33
128.73 128.76 130.64 130.69 122.19 122.21
20.08
128.78
130.27
128.78
128.02
20.19
128.75
130.30
128.75
128.05
20.19
122.05
151.97
122.05
129.16
20.19
122.02
151.99
122.02
129.19
20.19
142.26
143.38
123.85
126.37
20.20
142.22
143.38
123.81
126.41
20.19
-
OCOCH
3
3
2
2
2
0.57(2) 20.67(2) 20.67(2) 20.67(2) 20.67(2) 20.69(2) 20.68(2)
0.75(2) 20.83
0.86
20.83
20.97
20.84
20.88
20.83
20.96
21.22
20.73
20.77
20.86
20.71
20.75
20.84
20.98
167.82
167.92
168.93
169.22
169.35
169.99
170.44
20.89
2
1.23
2
0.89
-
OCOCH
169.04
168.91
169.21
169.97
170.21
170.42
168.92
169.21
169.34
169.97
170.42
168.91
168.97
169.21
169.97
170.19
170.43
168.92
168.95
169.21
169.34
169.97
170.42
167.85
167.95
168.92
169.23
170.00
170.22
1
1
1
1
1
69.35
69.62
70.11
70.31
70.56
1
70.46
a
Assignments were confirmed by HSQC and HMBC spectra at 300 MHz.
films on a NaCl disk. NMR spectra were obtained on a Varian
Mercury 300 MHz spectrometer equipped with a Sun Micro-
systems Ultra 5 processor and VNMR version 5.1b software.
UV spectra were run on a Hewlett-Packard 8453 UV-visible
spectrophotometer with data obtained via Hewlett-Packard
UV-visible ChemStation software. Low- and high-resolution
mass spectra were conducted in the negative ion mode on a
Micromass (Beverly, MA) quadrupole time-of-flight (Q-ToF2)
mass spectrometer with a modified dual micro-electrospray
source for internal calibration. All high-resolution spectra were
calibrated with poly(ethylene glycol) with an average mass of
F igu r e 1. ROESY correlations observed for compound 2.
isolated as described above. All samples of C. caudatum
showed the presence of these iridoids. The leaf and fruit/
inflorescence samples showed particularly strong bands
corresponding to caudatosides A and B, and the Hawaiian
stemwood sample showed a very strong band corresponding
to 5-deoxypulchelloside I.
6
00 Da. Samples 1-7 were electrosprayed from 1:1 methanol/
water, and samples 8-14 were electrosprayed from 9:1
methanol/chloroform (first dissolved in chloroform). Column
chromatography was performed with 60-200 mesh silica gel
(J .T. Baker), and flash reversed-phase column chromatography
Caudatosides A-F are very similar to iridoids isolated
from N. arbortristis. The basic N. arbortristis iridoid
was performed with 40 µm C18 adsorbent (J .T. Baker). Pre-
parative TLC was performed on J .T. Baker Si-C F reversed-
18
structure has the opposite stereochemistry at the 8-position
phase TLC plates (20 × 20 cm, 200 µm thickness). The
compounds were visualized on TLC plates by short (254 nm)
and long (366 nm) wavelength UV light and by spraying with
and sometimes includes a hydroxyl on C-10.1
1-17
N. arbor-
tristis extracts have been shown to exhibit many types of
biological activity.1
8-24
2 4
1% vanillin/H SO followed by heating on a hot plate for 5 min.
The acetone extract of C. caudatum
Solvents were reagent grade and used as purchased. Screens
for activity against Leishmania amastigotes were conducted
at the Walter Reed Army Institute of Research.
showed weak activity against a cutaneous Leishmania
axenic amastigote screen, but the chloroform extract
showed somewhat better activity, suggesting that any
antileishmanial activity may not be due to the iridoids.
However, the pure iridoids have not yet been screened.
P la n t Ma ter ia l. Samples of Citharexylum caudatum L.
were collected in Maui, Hawaii, in 1970 by Dr. Yoneo Sagawa
of the University of Hawaii at Manoa, where voucher speci-
mens (UH-619) are kept.
Exp er im en ta l Section
E xt r a ct ion a n d Isola t ion . Dried, ground fruits of C.
caudatum (1 kg) were extracted three times with petroleum
ether (4 L each extraction), then three times with chloroform
(4 L each), followed by four extractions with acetone (4 L each)
and 95% ethanol (4 L each). The combined acetone extracts
were concentrated in vacuo to give a light brown powder (56.1
Gen er a l Exp er im en ta l P r oced u r es. Melting points were
obtained on a Fisher-J ohn melting point apparatus and are
uncorrected. Specific rotations were measured on a J asco DIP-
1
000 digital polarimeter using a Na lamp at 28 °C. IR spectra
were obtained on a Nicolet Nexus 670 FT-IR spectrometer as

New Iridoid Glucosides from Citharexylum
J ournal of Natural Products, 2002, Vol. 65, No. 11 1625
g). This extract was subjected to column chromatography on
Ca u d a tosid e F (7): light tan solid (46 mg); mp 76-79 °C;
D
[R]2
CH
(4.12); IR (film, NaCl), νmax 3388 (OH), 2939, 1686, 1636, 1602,
8
silica gel using CH
MeOH in CH Cl . Eighteen fractions were collected. Fractions
0 and 11 were combined (3.4 g, eluting with 12.5-15% MeOH
in CH Cl ), fractions 12 and 13 were combined (18.4 g, eluting
with 15-17.5% MeOH in CH Cl ), and fractions 14 and 15
were combined (17.8 g, eluting with 17.5-20% MeOH in CH
Cl ). Combined fractions 10/11 were subjected to flash RP-CC
using a gradient from 85:7.5:7.5 H O/MeOH/AcCN to 0:50:50
O/MeOH/AcCN. This column yielded 2 (477 mg, eluting with
0:25:25 H O/MeOH/AcCN) and 3 (644 mg, eluting with 40:
0:30 H O/MeOH/AcCN).
A portion of combined fractions 12/13 (1.8 g) was subjected
2
Cl
2
followed by increasing amounts of
3 3 3
-57.3° (c 0.0084, 4:1 CH CN/CH OH); UV (4:1 CH CN/
2
2
3
OH) λmax (log ꢀ) 222 (4.19), 235 (4.19), 298 (4.04), 324 nm
1
-
1
1
2
2
1524, 1442, 1374, 1287, 1184, 1077, 989 cm
(acetone-d
, 300 MHz) (Table 1); 13C NMR (acetone-d
(Table 3); high-resolution ESIMS m/z 603.1353 [M + Cl]
;
H NMR
2
2
6
6
, 75 MHz)
-
2
-
-
2
(calcd for C26
32
H O14+Cl 603.1481); 567.1464 [M - H] (calcd
2
for C26 14, 567.1713).
31
H O
H
2
Acetyla tion of Com p ou n d s 1-7. Compounds 1-7 (20 mg,
5
3
2
except compound 6, 13 mg) were each treated with Ac O (1
2
2
mL) and pyridine (1 mL) at room temperature for 24 h. The
reaction mixture was suspended in 10 mL of H O, then
2
to flash RP-CC using the same gradient as for combined
fractions 10/11. This column yielded 4 (521 mg, eluting with
subsequently extracted three times with CHCl (10 mL each).
3
The combined CHCl layers were extracted twice with 1 N HCl
3
6
5
5:17.5:17.5 H
5:22.5:22.5 H
2
O/MeOH/AcCN) and 5 (725 mg, eluting with
O/MeOH/AcCN).
(10 mL each), once with 5% NaHCO (10 mL), and finally once
3
2
with saturated NaCl (10 mL). Each CHCl layer was dried over
3
A portion of combined fractions 14/15 (2.0 g) was subjected
to flash RP-CC using a gradient from 93:7 H O/MeOH to 100%
Na SO and filtered to give compounds 8-14, respectively.
2
4
2
5
-Deoxyp u lch ellosid e I h exa a ceta te (8): colorless amor-
MeOH. This column yielded 1 (1.34 g, nonretained) and a
mixture of 6 and 7 (484 mg, eluting from 19% to 60% MeOH).
A portion of this mixture of 6 and 7 (103 mg) was subjected to
phous solid (29 mg); UV (CH
2 2
Cl ) λmax (log ꢀ) 233 (4.06), 281
nm (2.99); IR (film, NaCl), νmax 2955, 1751, 1713, 1643, 1437,
-1
1
1
369, 1228, 1080, 1040, 910, 733 cm ; H NMR (CDCl
3
, 300
preparative RP-TLC using 60:25:15:0.1 H
2
O/MeOH/AcCN/
13
MHz) (Table 2); C NMR (CDCl
3
, 75 MHz) (Table 3); low-
trifluoroacetic acid. The bands were immediately marked and
scraped after development and transferred into a flask con-
-
resolution ESIMS m/z 693.25 [M + Cl] .
Ca u d a tosid e A p en ta a ceta te (9): colorless amorphous
taining acetonitrile, a small amount of NaHCO
drous Na SO to avoid acyl transfer. After filtration and
evaporation of the relevant fractions, pure 6 (29 mg) and 7
46 mg) were obtained.
-Deoxyp u lch ellosid e I (1): white crystalline solid (1.34
3
, and anhy-
solid (27 mg); UV (CH
2 2
Cl ) λmax (log ꢀ) 281 nm (4.16); IR (film,
2
4
NaCl), νmax 2954, 1757, 1715, 1639, 1368, 1229, 1166, 1078,
-1
1
1
039, 912, 732 cm ; H NMR (CDCl
3
, 300 MHz) (Table 2);
(
13
C NMR (CDCl
3
, 75 MHz) (Table 3); ESIMS m/z 781.31 [M +
5
-
Cl] .
Ca u d a tosid e B p en ta a ceta te (10): colorless amorphous
solid (29 mg); UV (CH Cl ) λmax (log ꢀ) 281 nm (4.09); IR (film,
NaCl), νmax 2954, 1755, 1714, 1639, 1368, 1229, 1165, 1078,
2
8
g); mp 94-97 °C; [R]
D
-112.7° (c 0.0116, 4:1 CH
OH) λmax (log ꢀ): 237 (4.41), 328 nm (3.21); IR
film, NaCl), νmax 3372 (OH), 2921, 1693, 1640, 1440, 1303,
3 3
CN/CH -
OH); UV (CH
3
2
2
(
1
-
1
1
13
184, 1076 cm ; H NMR (D
2
O, 300 MHz) (Table 1); C NMR
-
1
1
1
040, 913, 733 cm ; H NMR (CDCl
3
, 300 MHz) (Table 2);
(
D
2
O, 75 MHz) (Table 3); low-resolution ESIMS m/z 441.10
1
3
C NMR (CDCl
3
, 75 MHz) (Table 3); ESIMS m/z 781.31 [M +
-
[M + Cl] .
-
Cl] .
Ca u d a tosid e C h exa a ceta te (11): colorless amorphous
solid (25 mg); UV (CH Cl ) λmax (log ꢀ) 285 nm (3.98); IR (film,
NaCl), νmax 2954, 1758, 1715, 1640, 1508, 1369, 1228, 1165,
Ca u d a tosid e A (2): tan solid (477 mg); mp 105-108 °C;
2
8
[
(
R]
D
3 3 3
-75.2° (c 0.0108, 4:1 CH CN/CH OH); UV (CH OH) λmax
2
2
log ꢀ) 278 nm (4.27); IR (film, NaCl), νmax 3385 (OH), 2949,
-
1
1
704, 1637, 1450, 1440, 1364, 1310, 1287, 1184, 1075 cm ;
H NMR (acetone-d
-
1 1
1
13
1079, 1039, 912, 733 cm ; H NMR (CDCl
3
, 300 MHz) (Table
6
, 300 MHz) (Table 1); C NMR (acetone-
1
3
2
); C NMR (CDCl , 75 MHz) (Table 3); ESIMS m/z 839.31
3
d
6
, 75 MHz) (Table 3); high-resolution ESIMS m/z 571.1492
-
-
[M + Cl] .
Ca u d a tosid e D h exa a ceta te (12): colorless amorphous
solid (25 mg); UV (CH Cl ) λmax (log ꢀ) 285 nm (3.99); IR (film,
NaCl), νmax 2953, 1755, 1714, 1639, 1508, 1370, 1228, 1164,
[M + Cl] (calcd for C26
32
H O12+Cl, 571.1583).
Ca u d a tosid e B (3): tan solid (644 mg); mp 112-115 °C;
2
8
2
2
[
(
R]
D
-80.4° (c 0.0108, 4:1 CH
3 3 3
CN/CH OH); UV (CH OH) λmax
log ꢀ) 278 nm (4.21); IR (film, NaCl), νmax 3388 (OH), 2936,
-
1 1
-
1
1
1079, 1040, 913, 733 cm ; H NMR (CDCl
3
, 300 MHz) (Table
1
d
3
702, 1638, 1440, 1286, 1182, 1075 cm ; H NMR (acetone-
2); 13C NMR (CDCl
, 75 MHz) (Table 3); ESIMS m/z 839.31
, 300 MHz) (Table 1); 1 C NMR (acetone-d
); high-resolution ESIMS m/z 571.1522 [M + Cl] (calcd for
12+Cl, 571.1583).
Ca u d a tosid e C (4): light tan solid (521 mg); mp 111-114
3
3
6
6
, 75 MHz) (Table
-
-
[M + Cl] .
C
26
H
32
O
Ca u d a tosid e E h ep ta a ceta te (13): colorless amorphous
solid (15 mg); UV (CH Cl ) λmax (log ꢀ) 284 nm (4.07); IR (film,
NaCl), νmax 2956, 1756, 1714, 1641, 1505, 1435, 1371, 1228,
2
2
2
8
°
C; [R]
D
-88.7° (c 0.0096, 4:1 CH
3 3 3
CN/CH OH); UV (CH OH)
-
1
1
λ
max (log ꢀ) 233 (4.08), 313 nm (4.22); IR (film, NaCl), νmax 3377
1180, 1040, 991, 906, 735 cm ; H NMR (CDCl
(Table 2); 13C NMR (CDCl
, 75 MHz) (Table 3); ESIMS m/z
897.34 [M + Cl]
Ca u d a tosid e F h ep ta a ceta te (14): colorless amorphous
solid (24 mg); UV (CH Cl ) λmax (log ꢀ) 282 nm (4.18); IR (film,
NaCl), νmax 2954, 1756, 1714, 1640, 1505, 1436, 1371, 1218,
3
, 300 MHz)
(
OH), 2951, 1697, 1635, 1605, 1515, 1440, 1366, 1290, 1170,
3
-1
1
13
-
.
1
075 cm ; H NMR (acetone-d
6
, 300 MHz) (Table 1); C NMR
(
5
acetone-d
6
, 75 MHz) (Table 3); high-resolution ESIMS m/z
-
87.1544 [M + Cl] (calcd for C26
H
32
O
13+Cl, 587.1532); 551.1723
13, 551.1765).
Ca u d a tosid e D (5): light tan solid (725 mg); mp 124-127
2
2
-
31
[M - H] (calcd for C26H O
-
1 1
3
1180, 1111, 1078, 1040, 991, 905, 872 cm ; H NMR (CDCl ,
300 MHz) (Table 2); C NMR (CDCl
ESIMS m/z 897.31 [M + Cl] .
2
8
13
°
λ
(
C; [R]
max (log ꢀ) 232 (4.05), 314 nm (4.22); IR (film, NaCl), νmax 3377
OH), 2951, 1696, 1635, 1605, 1515, 1440, 1367, 1289, 1170,
D
-74.1° (c 0.0096, 4:1 CH
3
CN/CH
3
OH); UV (CH
3
OH)
3
, 75 MHz) (Table 3);
-
-
1
1
13
1
075 cm ; H NMR (acetone-d
6
, 300 MHz) (Table 1); C NMR
Ack n ow led gm en t. This work was supported by a grant
from the Thomas F. J effress and Kate Miller J effress Memorial
Trust, and the Department of Chemistry at VCU. We would
like to gratefully acknowledge J ason Flora and Dr. David
Muddiman of the VCU Mass Spectrometry Resource Center
for obtaining the mass spectrometry data. D.S.A. wishes to
acknowledge a grant from the VCU School of Graduate Studies
Graduate Student Grant-In-Aid Program.
(
5
acetone-d
6
, 75 MHz) (Table 3); high-resolution ESIMS m/z
-
87.1612 [M + Cl] (calcd for C26
H
32
O
13+Cl, 587.1532); 551.1797
13, 551.1765).
Ca u d a tosid e E (6): light tan solid (29 mg); mp 72-75 °C;
-
31
[M - H] (calcd for C26H O
2
8
[
R]
D
-41.6° (c 0.0084, 4:1 CH
OH) λmax (log ꢀ) 221 (4.16), 235 (4.15), 297 (4.00), 325 nm
4.06); IR (film, NaCl), νmax 3381 (OH), 2938, 1689, 1636, 1601,
3 3 3
CN/CH OH); UV (4:1 CH CN/
CH
(
1
3
-
1
1
525, 1442, 1376, 1288, 1185, 1076, 988 cm
;
H NMR
, 75 MHz)
1
3
(
(
(
acetone-d
6
, 300 MHz) (Table 1); C NMR (acetone-d
6
Refer en ces a n d Notes
-
Table 3); high-resolution ESIMS m/z 603.1373 [M + Cl]
calcd for C26
(
(
1) Moldenke, H. N. Phytologia 1958, 6 (5), 262-310.
-
32
H O14+Cl, 603.1481); 567.1683 [M - H] (calcd
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for C26
H
31
O
14, 567.1714).
(3) Ghisalberti, E. L. Phytomedicine 1998, 5 (2), 147-163.

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(
1
NP020211C