Six new anthraquinone glycosides from Lasianthus acuminatissimus Merr.

Article abstract of DOI:10.1080/14786419.2019.1686366

Six new anthraquinones named lasianthuoside F (1), G (2), H (3), I (4), J (5), K (6) were isolated from an acetone extract of the root of Lasianthus acuminatissimus. Their structures were elucidated by physical and chemical evidence and spectral analysis.

Full text of DOI:10.1080/14786419.2019.1686366

Natural Product Research
Formerly Natural Product Letters
ISSN: 1478-6419 (Print) 1478-6427 (Online) Journal homepage: https://www.tandfonline.com/loi/gnpl20
Six new anthraquinone glycosides from Lasianthus
acuminatissimus Merr.
Xingxing Liu, Taoan Li, Yong Liu, Hongdong Liu, Xiaotian Chen, Jianxin Ming,
Xuewen Lai & Bin Li
To cite this article: Xingxing Liu, Taoan Li, Yong Liu, Hongdong Liu, Xiaotian Chen, Jianxin Ming,
Xuewen Lai & Bin Li (2019): Six new anthraquinone glycosides from Lasianthusꢀacuminatissimus
Merr., Natural Product Research, DOI: 10.1080/14786419.2019.1686366
To link to this article: https://doi.org/10.1080/14786419.2019.1686366
View supplementary material
Published online: 08 Nov 2019.
Submit your article to this journal
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
https://www.tandfonline.com/action/journalInformation?journalCode=gnpl20

NATURAL PRODUCT RESEARCH
https://doi.org/10.1080/14786419.2019.1686366
Six new anthraquinone glycosides from Lasianthus
acuminatissimus Merr.
Xingxing Liu, Taoan Li, Yong Liu, Hongdong Liu, Xiaotian Chen, Jianxin Ming,
Xuewen Lai and Bin Li
Academician Workstation, Jiangxi University of Traditional Chinese Medicine, Nanchang, Jiangxi,
P.R. China
ABSTRACT
ARTICLE HISTORY
Received 3 June 2019
Accepted 25 October 2019
Six new anthraquinones named lasianthuoside F (1), G (2), H (3),
I (4), J (5), K (6) were isolated from an acetone extract of the root
of Lasianthus acuminatissimus. Their structures were elucidated by
physical and chemical evidence and spectral analysis.
KEYWORDS
Lasianthus acuminatissimus;
anthraquinone; lasianthuo-
side; acetone extract
1. Introduction
Lasianthus acuminatissimus Merr., a plant of the Rubiaceae family, is used to treat
rheumatoid arthritis in traditional Chinese medicine. The research group have made a
deep chemical study on the plant previously in which 46 compounds have been iso-
lated and identified from the plant (Li et al. 2006a, 2006b, 2006c, 2007; Huang et al.
2017, 2018a, 2018b). The 46 compounds include eight new anthraquinones, a new fur-
fural glycoside and a new sesquiterpene; among them anthraquinones have been
proved to be the bioactive compounds containing anti-inflammatory and anti-tumor
activities. In order to find out other bioactive constituents from the plant, the group
did the current experimental research in which the acetone extract of the roots was
chromatographed. As a result, six new anthraquinone glycosides were isolated and
structurally identified, namely lasianthuoside F (1), G (2), H (3), I (4), J (5), K (6).
CONTACT Bin Li
lbin@jzjt.com
Supplemental data for this article can be accessed at https://doi.org/10.1080/14786419.2019.1686366.
ß 2019 Informa UK Limited, trading as Taylor & Francis Group

2
X. LIU ET AL.
2. Results and discussion
Compound 1 was obtained as an orange, amorphous powder. The molecular formula
of 1 was deduced as C22H22O10 from HR-ESI-MS (m/z 469.1107 [M þ Na]þ, calcd.
469.1111) analysis and its 1H and 13C-NMR evidence, accounting for 12 indices of
hydrogen deficiency. The UV and IR spectrum suggested the presence of a hydroxyan-
1
thraquinone. H NMR spectra of 1 showed one isolated aromatic proton at dH 7.62
(1H, s, H-4), declaring a penta-substituted aromatic ring which was deduced further
from signals in 13C NMR spectra at dC 164.4 (C-1), 121.0 (C-2),164.0 (C-3), 107.3 (C-4),
136.3 (C-4a) and 112.9 (C-9a). Four aromatic protons [dH 8.26 (1H, dd, J ¼ 7.5, 2.0 Hz, H-
5), 7.86 (1H, br t, J ¼ 7.5 Hz, H-6), 7.88 (1H, br t, J ¼ 7.5 Hz, H-7) and 8.32 (1H, dd,
J ¼ 7.5, 2.0 Hz, H-8)] in a symmetrical AA0BB0-type pattern indicated that other aromatic
ring in the anthraquinone was unsubstituted. An AB spin system at dH 4.71 and 4.74
(each H, d, J ¼ 10.8 Hz, H-11), a methoxy proton at dH 3.40 (s), declaring the existence
of a hydroxymethyl and a methoxy. The 13C NMR spectra showed 22 carbon signals,
including two carbonyl carbon atoms (dC 183.2, 188.8), two benzene rings, a methoxy
signals (dC58.6) and one hydroxymethyl (dC62.6), and a glycosyl section.
The anomeric signals at dH 5.20 (1H, d, J ¼ 7.5 Hz, H-10) and dC 102.0 (C-10) together
with the characteristic signals at dC 74.8 (C-20), 77.9 (C-30), 71.0 (C-40), 78.5 (C-50) and
62.3 (C-60) were attributed to a glucose group. Acid hydrolysis of 1 afforded a D-glu-
cose, which was determined by GC experiment with an authentic sample. Except for a
methoxymethyl signals (dH 3.40, 4.74 and 4.71; dC 58.6 and 62.6), the left signals at dC
188.8 and 183.2 were assigned to two conjugated carbonyl groups. The presence of
two carbonyl carbons together with two benzenoid moieties also suggested that1 was
a hydroxyanthraquinone. The aforementioned information suggested that 1 was
closely similar to lasianthuoside B (Li et al. 2006c). The only difference between two
compounds was a methoxy in lasianthuoside B while a hydroxy in 1 at C-1. The 14 Da
difference in molecular weight between them is diagnostic for the current assignment.
Furthermore, the HMBC spectrum exhibited correlations from H-11 to C-1 and C-3,
which verified that a methoxymethyl group was positioned at C-2. The anomeric pro-
ton of glucosyl moiety at dH5.20 (1H, d, J ¼ 7.5 Hz, H-10) exhibited an HMBC correlation
with the aromatic carbon at 164.0 (C-3), confirming that the glucose unit was linked at
1
C-3. All the H and 13C NMR data of 1 were unambiguously assigned by means of the
HSQC and HMBC experiments. The glucopyranoside was b-configuration on the
ground of the coupling constant of the anomeric proton. Thus, the structure of 1 was
established as 1,3-dihydroxy-2-methoxymethylanthraquinone 3-O-b-D-glucopyranoside
and named lasianthuoside F.
Compound 2 was isolated as a yellow powder. Its molecular formula C23H24O11 was
deduced from the HR-ESI-MS pseudo-molecular ion at m/z 499.1209 ([M þ Na]þ, calcd.
499.1216). The UV and IR spectrum suggested the presence of a hydroxyanthraqui-
1
none. The H NMR showed four aromatic protons at dH7.87 (1H, s, H-4), 7.73 (1H, br d,
J ¼ 7.5 Hz, H-5), 7.67 (1H, dd, J ¼ 8.3, 7.5 Hz, H-6) and 7.30 (1H, br d, J ¼ 8.3 Hz, H-7),
indicating the existence of a 1,2,3-trisubstituted aromatic ring and an unsubstituted
1
aromatic of the hydroxyanthraquinone. The H and 13C NMR spectra of 2 exhibited
resonances also similar to those of lasianthuoside B (Li et al. 2006c). Comparing to
lasianthuoside B, an additional hydroxy group should be substituted at C-8 in 2, which

NATURAL PRODUCT RESEARCH
3
was supported by the HMBC correlations from H-4 and H-5 to C-10 both, declaring
there was no group substituted at C-5. The 16 Da difference in molecular weight
between them is diagnostic for the current assignment. Therefore, the structure of this
new anthraquinone glycoside was established as 3,8-dihydroxy-1-methyoxy-2-methoxy-
methylanthraquinone3-O-b-D-glucopyranoside and named lasianthuoside G.
Compound 3 was obtained as a yellow gum. The molecular formula of 3 was deter-
mined to be C27H30O14 by HR-ESI-MS at m/z 601.1523 [M þ Na]þ (calcd. 601.1533). The
1
UV and IR spectrum suggested the presence of an anthraquinone. H NMR spectra of
3 showed an isolated aromatic proton at dH 7.62 (1H, s, H-4), four aromatic protons
[dH 8.26 (1H, br d, J ¼ 7.6 Hz, H-5), 7.86 (1H, m, H-6), 7.87 (1H, m, H-7) and 8.31 (1H, br
d, J ¼ 7.6 Hz, H-8)] in a symmetrical AA0BB0-type pattern indicated that one aromatic
ring in the anthraquinone was unsubstituted and the other ring was trisubstituted. A
methoxy proton at dH 3.40 (3H, s) and a hydroxymethyl proton at dH 4.71 and 4.74
(each H, d, J ¼ 10.9 Hz, H-11), declaring the existence of a hydroxymethyl and a
methoxy. The 13C NMR spectra showed 27 carbon signals including two carbonyl car-
bon atoms (dC 183.2, 188.8), two benzene rings, a methoxy signals (dC 58.5) and one
hydroxymethyl (dC 62.6), and two glycosyl sections, which also verified the existence
of a hydroxyanthraquinone.
The NMR data of compound 3 were found to be similar to those of compound 1.
Except for, the MS fragmentation pattern and the NMR spectra of 3 were more com-
plex and showed the presence of a series of additional signals at dH 4.92, 3.93, 3.76,
1
4.02, 3.65 and 3.68 in the H NMR spectrum and dC 111.1, 78.3, 80.7, 75.2, 66.2 in 13C
NMR signals, which may be contributed to be a pentose moiety. And the pentose was
elucidated as an apiofuranose based on the characteristic chemical shifts, which were
fully assigned by the HSQC and HMBC spectra data and the literature data (Huang
et al. 2018a). Acid hydrolysis of 3 also afforded a D-glucose and a D-apiose, which was
determined by GC with an authentic sample. The configuration of the glycosidic link-
age of D-glucose was b on the base of the coupling constant of the anomeric proton
at dH 5.15 (1H, d, 7.6). The apiose anomeric proton at dH 4.92 (1H, d, J ¼ 1.7 Hz, H-100)
was identified via its HMBC correlation to an oxygenated methylene carbon at dC 68.6
(Glc C-6, Supplemental Figure S1), indicated the presence of a b-D-apiofuranosyl-
(1!6)-b-D-glucopyranosyl moiety. Thus, the structure of compound 3 was established
as 1, 3-dihydroxy-2-Methoxymethylanthraquinone-3-O-b-D-apiofuranosyl-(1!6)-b-D-
glucopyranoside, named lasianthuoside H.
Compound 4 was obtained as a yellow gum. The HR-ESI-MS of compound 4 exhib-
ited a pseudo-molecular ion peak at m/z 655.1988 [M þ Na]þ (calcd. 655.2003), which
was consistent with the molecular formula C31H36O14, indicating 14 degrees of unsat-
uration. The UV and IR spectrum suggested the presence of an anthraquinone. 1H
NMR spectra of 4 showed one isolated aromatic proton at dH 7.81 (1H, s, H-4), declar-
ing a penta-substituted aromatic ring, four aromatic protons [dH 8.20 (1H, br d,
J ¼ 7.6,H-5), 7.78 (1H, br d, J ¼ 7.6 Hz, H-6), 7.83 (1H, br d, J ¼ 7.6 Hz, H-7) and 8.22 (1H,
br d, J ¼ 7.6 Hz, H-8)] in a symmetrical AA0BB0-type pattern indicating the other aro-
matic ring was unsubstituted in the anthraquinone. Two methoxy protons at dH3.94
(s), 3.41 (s), a hydroxymethyl proton at dH 4.69 and 4.71 (each H, d, J ¼ 10.4 Hz, H-12)
declaring the existence of two methoxy and a hydroxymethyl. The 13C NMR spectra

4
X. LIU ET AL.
showed 31 carbon signals including two carbonyl carbon atoms (dC 182.6, 183.8), two
benzene rings, two methoxy signals (dC63.7, 58.6) and a hydroxymethyl (dC 63.5), and
two glycosyl sections.
1
The H and 13C NMR data of 4 assigned with the help of its HSQC spectrum sug-
gesting that it was also an anthraquinone glycoside similar to compound 3. Compared
to the spectra of 3, an additional methoxy signal at dH 3.94 (3H, s) and dC 63.7, as well
as an isopropyl group at dH 1.12 (3H, s), 0.88 (3H, s) and dC113.9, 27.8 and 27.4 were
observed, this was confirmed by the HMBC correlations from the two methyl proton
signals to the ketal carbon at dC 113.9. The attachment of the isopropyl group was
determined to be at C-200 and C-300 by the evidence that in 13C NMR spectrum these
two carbons obviously downfield shifted (dC 87.2 and 93.9) and the presence of an
HMBC correlation (Supplemental Figure S1) from the proton dH 4.23 (1H, br s, H-200) to
C-1000at dC 113.9 in 4. Furthermore, a methoxy signal at dH 3.94 (3H, s) showed HMBC
correlation with C-1 (dC163.4), indicating the placement of this group was at C-1.
According to the above analysis, compound 4 was established as 3-hydroxy-1-
methoxy-2-methoxymethylanthraquinone- 200, 300-isopropyl- 3-O-b-D-apiofuranosyl-
(1!6)-b-D-glucopyranoside, and named as lasianthuoside I.
Compound 5 was also obtained as an orange, amorphous powder. The positive HR-
ESI-MS (m/z 671.1950, [M þ Na]þ, calcd. for C31H36O15Na, 671.1952) gave the molecular
1
formula as C31H36O15, consistent with the complete assignments of H and 13C NMR
data determined through HSQC and HMBC experiments. The UV and IR spectrum sug-
1
gested the presence of a hydroxyanthraquinone. The H NMR showed four aromatic
protons at dH 7.78 (1H, s, H-4), 7.70 (1H, br d, J ¼ 7.5 Hz, H-5), 7.63 (1H, dd, J ¼ 8.3,
7.5 Hz, H-6), and 7.26 (1H, br d, J ¼ 8.3 Hz, H-7), indicating that a 1,2,3-trisubstituted
aromatic ring and an unsubstituted aromatic ring in the hydroxyanthraquinone.
Protons at dH 3.95 (s), 3.42 (s) and dH 4.67, 4.69 (each H, d, J ¼ 10.4 Hz, H-12) declared
the existence of two methoxy groups and a hydroxymethyl, respectively. The 13C NMR
spectrum supported by DEPT experiment revealing 31 carbons, included 11 methines
containing seven oxygenated carbons, four oxygenated methylenes, two methyls, two
methoxy groups, and 12 quaternary carbons consisting of two conjugated carbonyl
groups at dC 188.9 (C-9), 183.1 (C-10), and two glycosyl sections. Proton signals at dH
1.15(3H, s), 0.88(3H, s) and carbon signals at dC 113.9, 27.8, 27.4, declaring an isopropyl
group.
Comparison with the NMR data of 4 suggested that structure of compound 5 was
quite similar to that of 4, except for, there was an unsubstituted ring appearance in
compound 4, while there was an additional hydroxy appearance in 5. In the HMBC
spectrum, the protons at dH 7.78 (1H, s, H-4) and 7.70 (1H, br d, J ¼ 7.5 Hz, H-5) were
associated with dC 183.1 (C-10), confirming that a hydroxy group should be
substituted at C-8. Accordingly, the structure of 5 was established as 3, 8- dihydroxy-
1-methoxy-2-methoxymethylanthraquinone-200,
300-isopropyl-3-O-b-D-apiofuranosyl-
(1!6)-b-D-glucopyranoside, named lasianthuoside J.
Compound 6 was isolated as a yellow powder. The HR-ESI-MS of 6 showed a
molecular ion peak at m/z 657.1782 [M þ Na]þ (calcd. 657.1795) in accordance with a
1
molecular formula of C30H34O15. The H NMR showed four aromatic protons at dH 7.69
(1H, s, H-4), 7.61 (1H, br d, J ¼ 7.0 Hz), 7.70 (1H, dd, J ¼ 7.6, 7.0 Hz) and 7.31 (1H, br d,

NATURAL PRODUCT RESEARCH
5
J ¼ 7.6 Hz), indicating that one aromatic ring was trisubstituted and the other aromatic
ring was three unsubstituted. Proton signals at dH 3.88 (3H, s) and dH 4.67, 4.69 (each
H, d, J ¼ 10.4 Hz, H-12) declared the existence of a methoxy and a hydroxymethyl,
respectively. The 13C NMR spectrum showed 30 carbon signals including two carbonyl
carbon atoms (dC 186.8, 181.5), two benzene rings, one methoxy(dC 62.8) and one
hydroxymethyl (dC51.8), these signals further indicated the presence of a hydroxyan-
thraquinone containing a methoxy, a hydroxymethyl and two phenolic hydroxyls.
Proton signals at dH 1.13(3H, s), 0.98(3H, s) and Carbon signals at dC 111.7, 27.4, 26.9,
declaring the existence of an isopropyl group.
The NMR spectroscopic data of 6 were very similar to those of 5 although meas-
ured in different solvents. The only difference was that a methoxy signal (dH 3.42, dC
58.7 in 5) disappeared in 6, suggesting that in compound 6 a hydroxymethyl was
replaced from a methoxymethyl moiety in 5. The hydroxymethyl carbon signal shifted
obviously upfield approximately 11 ppm, also indicated of the absence of the methoxy
group. Thus, the structure of compound 6 was established as 3, 8- dihydroxy-1-
methoxy-2-hydroxymethylanthraquinone-200, 300-isopropyl-3-O-b-D-apiofuranosyl-(1!6)-
b-D-glucopyranoside, namely lasianthuoside K.
3. Experimental
3.1. General procedures
The optical rotations were taken with a MCP 500 high precision digital rotation. The
UV spectra were obtained using a Shimadzu UV-2550 spectrophotometer. The IR spec-
tra were measured on a Perkin Elmer Spectrum Two infra-red spectrometer. The NMR
spectra were carried out on a Bruker AVANCE III 600 spectrometer (Bruker BioSpin
GmbH, Rheinstetten, Germany). Chemical shifs (d) were expressed in ppm with refer-
ence to the solvent signals. The HR-ESI-MS were recorded on an Agilent 1100 series
LC/MSD Triple TOF5600 þ spectrometer. The Preparative HPLC was performed on an
ODS column (250 mm ꢀ 20 mm, i.d., YMC) with a UV detector (Waters 2489). The GC
was conducted using an Agilent7890A instrument. Column chromatography was per-
formed with HPD750 macroporous resin (Cangzhou Baoen Absorption Materials
Technology Co. Ltd., Hebei, China), silica gel (200–300 mesh, Qingdao Marine
Chemical, Inc, Qingdao, China), Sephadex LH-20 (20–100 lM, Pharmacia), and ODS
(50 lM, YMC, Japan). TLC was performed with silica gel GF254 (Qingdao Marine
Chemical Industry Factory).
3.2. Plant material
The roots of Lasianthus acuminatissimus Merr. were collected from Yushan County of
Jiangxi Province in China, during September, 2017. The plant material was identified
by Professor Yong Liu (Jiangxi University of Traditional Chinese Medicine). It (voucher
specimen number 001703) has been deposited in Herbarium of Jiangxi University of
Traditional Chinese Medicine.

6
X. LIU ET AL.
3.3. Extraction and isolation
Air-dried and powdered roots of the plants (85.0 kg) were refluxed with 95% EtOH
three times, and The EtOH extract was concentrated under reduced pressure to yield
895.0 g of the extract. The total extract (895.0 g) was applied on silica gel CC (2700.0 g)
eluting with chloroform, ethyl acetate, acetone, n-butanol, and methanol respectively.
The acetone fraction (50.0 g) was applied to a HPD 750 chromatography column and
eluted successively with a gradient of C2H5OH/H2O. The 50% Ethanol fraction(10 g)
was subjected to a Polyamide column chromatography and eluted with C2H5OH/H2O
to give 4 fractions (A1–A4). Fraction A1 (3.0 g) was separated by a ODS eluting with
MeOH/H2O to give six subfractions (A1-1–A1-6). Compound 1 (2 mg) and compound 2
(4 mg) were obtained from subfraction A1-2 (110 mg) by preparative HPLC, eluting
with 60% Methanol on a YMC-Pack ODS-A column (250 ꢀ 20 mm, 5 lm) at a flow rate
of 5 mL/min and UV detection at 264 nm. Subfraction A1-5 (500 mg) was further frac-
tionated to a Sephadex LH-20 (Methanol) chromatography to give seven subfractions
(A1-5-1–A1-5-7). Subfraction A1-5-3 (280 mg) was purified by a preparative HPLC and
eluted with 60% Methanol at a flow rate of 5 mL/min (264 nm) to obtain compound 3
(10.9 mg), 4 (49.5 mg), 5 (30.1 mg), 6 (4 mg).
3.4. Acid hydrolysis and sugar analysis
Compounds 1 (1 mg), 3 (1 mg) were refluxed with 2 mL of 7% HCl for 2 h to obtain a
brown material. The residual material was dissolved in 1.0 mL of pyridine (containing
2.5 g/mL hydroxylaminehydrochloride) and 1.0 mL of TMCS and then reacted for 1 h at
80 ꢁC. Then the derivatives were analysed by GC, and the retentiontimes (tR) were as
follows: D-apiose(12.03 min), L-apiose(12.45 min), D-glucose (13.62 min) and L-glucose
(13.93 min), (Huang et al. 2018a). The monosaccharides obtained from the acid
hydrolysis of compounds 1and 3were treated in a similar manner to the authentic
monosaccharide samples and were identified as D-apiose (12.03 min) and D-glucose
(13.62 min), which were matched to the standard D-apiose and D-glucose.
3.4.1. Lasianthurin F (1)
20
An orange amorphous powder; ½aꢂD -54.0 (c0.001 in MeOH); UV(MeOH) kmaxnm: 264;
IR(KBr) cmꢃ1:3354, 2920, 1628, 1586, 1482, 1367, 1272; HR-ESI-MS at m/z
469.1108[M þ Na]þ(calcd For C22H22O10469.1111). 1H NMR (600 MHz,CD3OD) dH: 7.62
(1H, s, H-4), 8.26 (1H, dd, J ¼ 7.5, 2.0 Hz, H-5), 7.86 (1H, brt, J ¼ 7.5 Hz, H-6) , 7.88 (1H,
brt, J ¼ 7.5 Hz, H-7),8.32 (1H, dd, J ¼ 7.5, 2.0 Hz, H-8), 4.71, 4.74 (2H, d, J ¼ 10.8 Hz, H-
11), 3.40 (3H, s, H-11-OMe), 5.20 (1H, d, J ¼ 7.5 Hz, H-10), 3.58 (1H, m, H-20), 3.53 (1H, t,
J ¼ 9.1 Hz, H-30), 3.47 (1H, t, J ¼ 9.1 Hz, H-40), 3.58 (1H, m, H-50), 3.75, 3.91 (1H, dd,
J ¼ 12.3, 5.2, Hz, H-60); 13C NMR (150 MHz, CD3OD) dC: 164.4 (C-1), 121.0 (C-2), 164.0 (C-
3), 107.3 (C-4), 136.3 (C-4a), 128.2 (C-5), 135.7 (C-6), 135.6 (C-7), 127.9 (C-8), 134.7 (C-
8a), 188.8 (C-9), 112.9 (C-9a), 183.2 (C-10), 134.6 (C-10a), 62.6 (C-11), 58.6 (C-11-OMe),
102.0 (C-10), 74.8 (C-20), 77.9 (C-30), 71.0 (C-40), 78.5 (C-50), 62.3 (C-60).

NATURAL PRODUCT RESEARCH
7
3.4.2. Lasianthurin G (2)
20
Yellow powder; ½aꢂD -141.6 (c 0.001 in MeOH); UV (MeOH) kmax nm:267; IR (KBr)
cmꢃ1:3379, 1666, 1578, 1475, 1347, 1275; HR-ESI-MS at m/z 499.1209 [M þ Na]þ(calcd
1
For C23H24O11499.1216). H NMR (600 MHz,CD3OD) dH: 7.87 (1H, s, H-4), 7.73 (1H, brd,
J ¼ 7.5 Hz, H-5), 7.67 (1H, dd, J ¼ 8.3, 7.5 Hz, H-6) , 7.30 (1H, brd, J ¼ 8.3 Hz, H-7), 4.68,
4.70 (2H, d, J ¼ 10.2 Hz, H-11), 3.96 (3H, s, H-1-OMe), 3.42 (3H, s, H-11-OMe), 5.21 (1H,
d, J ¼ 7.5 Hz, H-10), 3.58 (1H, m, H-20), 3.53 (1H, t, J ¼ 9.1 Hz, H-30), 3.47 (1H, t, J ¼ 9.1 Hz,
H-40), 3.58 (1H, m, H-50), 3.75, 3.91 (1H, dd, J ¼ 12.3, 5.2 Hz, H-60); 13C NMR (150 MHz,
CD3OD) dC: 163.8 (C-1), 129.5 (C-2), 163.2 (C-3),110.7 (C-4), 138.2 (C-4a),119.9 (C-5),
137.1 (C-6), 125.7 (C-7), 163.6 (C-8), 118.0 (C-8a), 188.8 (C-9), 121.5 (C-9a), 183.2 (C-10),
134.1 (C-10a), 63.6 (C-11), 63.9 (C-1-OMe), 58.8 (C-11-OMe), 102.1 (C-10), 74.8 (C-20),
77.9 (C-30), 71.0 (C-40), 78.5 (C-50), 62.3 (C-60).
3.4.3. Lasianthurin H (3)
20
Yellow gum; ½aꢂD -86.9 (c0.002in MeOH); UV(MeOH) kmax nm: 267; IR(KBr) cmꢃ1: 3356,
2925, 1632, 1589, 1482, 1367, 1297; HR-ESI-MS at m/z 601.1523 [M þ Na]þ (calcd For
C27H30O14 601.1533). 1H NMR (600 MHz,CD3OD) dH: 7.62 (1H, s, H-4), 8.26 (1H, brd,
J ¼ 7.6 Hz, H-5), 7.86 (1H, m, H-6) , 7.87 (1H, m, H-7), 8.31 (1H, brd, J ¼ 7.6 Hz, H-8),
4.71, 4.74 (2H, d, J ¼ 10.9 Hz, H-11), 3.40 (3H, s, H-11-OMe), 5.15 (1H, d, J ¼ 7.6 Hz, H-10),
3.57 (1H, m, H-20), 3.52 (1H, t, J ¼ 9.2 Hz, H-30), 3.37 (1H, t, J ¼ 9.2 Hz, H-40), 3.73 (1H, m,
H-50), 3.59, 4.06 (1H, dd, J ¼ 11.2, 6.9 Hz, H-60), 4.92 (1H, d, J ¼ 1.7 Hz, H-100), 3.93 (1H, d,
J ¼ 1.7 Hz, H-200), 3.76, 4.02 (1H, d, J ¼ 9.7 Hz,H-400), 3.65, 3.68 (2H, d, J ¼ 11.5 Hz, H-
500);13C NMR (150 MHz, CD3OD) dC: 164.4 (C-1), 121.0 (C-2), 164.0 (C-3), 107.5 (C-4),
136.3 (C-4a), 127.8 (C-5), 135.6 (C-6), 135.7 (C-7), 128.3 (C-8), 134.7 (C-8a), 188.8 (C-
9),113.0 (C-9a), 183.3 (C-10), 134.6 (C-10a), 62.6 (C-11), 58.5 (C-11-OMe), 101.9 (C-10),
74.8 (C-20), 77.9 (C-30), 71.5 (C-40), 77.5 (C-50), 68.6 (C-60), 111.1 (C-100), 78.3 (C-200), 80.7
(C-300), 75.2 (C-400), 66.2 (C-500).
3.4.4. Lasianthurin I (4)
20
Yellow gum; ½aꢂD -129.4 (c0.001 in MeOH); UV(MeOH) kmax nm: 267; IR(KBr) cmꢃ1:3419,
1668, 1575, 1455, 1311,1282; HR-ESI-MS at m/z 655.1991 [M þ Na]þ (calcd For
C31H36O14 655.2003).1H NMR (600 MHz,CD3OD) dH: 7.81 (1H, s, H-4), 8.20 (1H, brd,
J ¼ 7.6 Hz, H-5), 7.78 (1H, brt, J ¼ 7.6 Hz, H-6) , 7.83 (1H, brt, J ¼ 7.6 Hz, H-7), 8.22 (1H,
brd, J ¼ 7.6, Hz, H-8), 4.69, 4.71 (2H, d, J ¼ 10.4 Hz, H-11), 3.94 (3H, s, H-1-OMe), 3.41
(3H, s, H-11-OMe), 5.24 (1H, d, J ¼ 7.5 Hz, H-10), 3.58 (1H, m, H-20), 3.54 (1H, t, J ¼ 9.2 Hz,
H-30), 3.28 (1H, t, J ¼ 9.2 Hz, H-40), 3.77 (1H, m, H-50), 3.57, 3.96 (1H, brd, J ¼ 12.0 Hz, H-
60), 4.91 (1H, brs, H-100), 4.23 (1H, brs, H-200), 3.76, 3.83 (1H, d, J ¼ 10.0 Hz, H-400), 3.72
(2H, s, H-500), 1.12 (3H, s, H-2000), 0.88 (3H, s, H-3000); 13C NMR (150 MHz, CD3OD) dC:
163.4 (C-1), 128.9 (C-2),162.1 (C-3), 110.1 (C-4), 138.3 (C-4a), 127.8 (C-5), 134.6 (C-6),
135.6 (C-7), 128.0 (C-8), 136.1 (C-8a), 182.6 (C-9), 121.8 (C-9a), 183.8 (C-10), 134.0 (C-
10a), 63.5 (C-11), 63.7 (C-1-OMe), 58.6 (C-11-OMe), 101.0 (C-10), 74.7 (C-20), 77.9 (C-30),
71.9 (C-40), 78.5 (C-50), 66.9 (C-60), 108.9 (C-100), 87.2 (C-200), 93.9 (C-300), 75.3 (C-400), 65.7
(C-500), 113.9 (C-1000), 27.8 (C-2000), 27.4 (C-3000).

8
X. LIU ET AL.
3.4.5. Lasianthurin J (5)
20
An orange amorphous powder; ½aꢂD -126.7 (c 0.006 in MeOH); UV(MeOH) kmaxnm: 264;
IR (KBr) cmꢃ1: 3565, 2987,1671, 1579, 1455,1308, 1233; HR-ESI-MS at m/z 671.1952
[M þ Na]þ (calcd For C31H36O15Na 671.1952). H NMR (600 MHz,CD3OD) dH: 7.78 (1H, s,
1
H-4), 7.70 (1H, brd, J ¼ 7.5 Hz, H-5), 7.63 (1H, dd, J ¼ 8.3, 7.5 Hz, H-6) , 7.26 (1H, brd,
J ¼ 8.3 Hz, H-7), 4.67, 4.69 (2H, d, J ¼ 10.4 Hz, H-11), 3.95 (3H, s, H-1-OMe), 3.42 (3H, s,
H-11-OMe), 5.23 (1H, d, J ¼ 7.5 Hz, H-10), 3.59 (1H, m, H-20), 3.54 (1H, t, J ¼ 9.2 Hz, H-30),
3.28 (1H, t, J ¼ 9.2 Hz, H-40), 3.76 (1H, m, H-50), 3.57, 3.96 (1H, dd, J ¼ 11.8, 1.7 Hz, H-60),
4.90 (1H, brs, H-100), 4.22 (1H, brs, H-200), 3.76, 3.83 (1H, d, J ¼ 10.0 Hz, H-400), 3.72 (2H, s,
H-500), 1.15 (3H, s, H-2000), 0.95 (3H, s, H-3000); 13C NMR (150 MHz, CD3OD) dC: 163.8 (C-1),
129.3 (C-2), 162.7 (C-3), 110.4 (C-4), 138.3 (C-4a), 119.9 (C-5), 137.1 (C-6), 125.6 (C-7),
163.6 (C-8), 118.0 (C-8a),188.9 (C-9),121.3 (C-9a), 183.1 (C-10), 134.2 (C-10a), 63.5 (C-11),
63.9 (C-1-OMe), 58.7 (C-11-OMe), 101.0 (C-10), 74.7 (C-20), 77.9 (C-30), 71.8 (C-40), 78.4 (C-
50),66.9 (C-60), 108.9 (C-100), 87.2 (C-200), 93.9 (C-300), 75.3 (C-400), 65.8 (C-500), 113.9 (C-1000),
27.8 (C-2000), 27.4 (C-3000).
3.4.6. Lasianthurin K (6)
20
Yellow powder; ½aꢂD -78.4 (c 0.001 in MeOH); UV(MeOH)kmax nm: 264; IR(KBr) cmꢃ1: 3355,
2920,1632, 1578, 1455, 1308, 1233; HR-ESI-MS at m/z 657.1779 [M þ Na]þ (calcd For
C30H34O15 657.1795). 1H NMR (600 MHz,DMSO-d6) dH: 7.69 (1H, s, H-4), 7.61 (1H, brd,
J¼ 7.0 Hz, H-5), 7.70 (1H, dd, J¼ 7.6, 7.0 Hz, H-6) , 7.31 (1H, brd, J¼ 7.6 Hz, H-7),4.58, 4.64
(2H, brd, J¼ 11.0Hz, H-11), 3.88 (3H, s, H-1-OMe), 5.15 (1H, d, J¼ 7.2 Hz, H-10), 3.40 (1H, dd,
J¼ 9.2, 7.2 Hz, H-20), 3.37 (1H, t, J¼ 9.2 Hz, H-30), 3.11 (1H, t, J¼ 9.2 Hz, H-40), 3.64 (1H, br
dd, J¼ 9.2, 8.1 Hz, H-50), 3.45, 3.83 (1H, dd, J¼ 11.8, 8.1 Hz, H-60), 4.88 (1H, brs, H-100), 4.18
(1H, brs, H-200), 3.69, 3.76 (1H, d, J¼ 10.0 Hz, H-400), 3.58 (2H, s, H-500), 1.13 (3H, s, H-2000),
0.98 (3H, s, H-3000); 13C NMR (150 MHz, DMSO-d6) dC: 161.1 (C-1), 131.5 (C-2), 160.8 (C-3),
108.9 (C-4), 135.8 (C-4a), 117.8 (C-5), 135.9 (C-6), 124.9 (C-7), 162.2 (C-8), 116.8 (C-8a), 186.8
(C-9), 120.0 (C-9a), 181.5 (C-10), 132.7 (C-10a), 51.8 (C-11), 62.8 (C-1-OMe), 100.0 (C-10), 73.1
(C-20), 75.8 (C-30), 70.1 (C-40), 76.6 (C-50), 65.9 (C-60), 107.0 (C-100), 85.3 (C-200), 92.5 (C-300),
73.8 (C-400), 63.8 (C-500), 111.7 (C-1000), 27.4 (C-2000), 26.9 (C-3000).
4. Conclusions
From an aqueous extract of Lasianthus acuminatissimus Merr., six new anthraquinones
named lasianthurin F (1), G (2), H (3), I (4), J (5), K (6) were isolated and their structures
were elucidated on the basis of the spectroscopic evidence.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by Chinese National Natural Scientific Fund [grant number 20262003,
20662006]. Jiangxi University of Traditional Chinese Medicine Pharmacy college for measuring
the IR, UV, NMR, MS spectra.

NATURAL PRODUCT RESEARCH
9
References
Huang T, Pan LL, Wu YF, Wan N, Li F, Zhou X, Li B. 2017. Review of the studies on chemical con-
stituents and biological activities of Lasianthus. J Jiangxi Univ TCM. 29:54–57.
Huang T, Ming JX, Zhong JL, Zhong YQ, Wu HQ, Liu HD, Li B. 2018a. Three new anthraquinones,
one new benzochromene and one new furfural glycoside from Lasianthus acuminatissimus.
Nat Prod Res.
Huang T, Pan LL, Wu YF, Wan N, Li F, Zhou X, Li B. 2018b. Chemical constituents from root of
Lasianthus acuminatissimus Merr II. Chin Tradit Herb Drugs. 49:801–805.
Li B, Lai XW, Xu XH, Yu BW, Zhu Y. 2007. A new anthraquinone from the root of Lasianthus acu-
minatissimus. Acta Pharm Sin. 42:2–4.
Li B, Zhang DM, Luo YM. 2006a. Chemical constituents from root of Lasianthus acuminatissimus
Merr. Chem Pharm Bull. 31:133–135.
Li B, Zhang DM, Luo YM, 2006b. A new sesquiterpene lacton from the roots of Lasianthus acumi-
natissimus. Acta Pharm Sin. 4:426–430.
Li B, Zhang DM, Luo YM, Chen XG. 2006c. Three new and antitumor anthraquinone glycosides
from Lasianthus acuminatissimus MERR. Chem Pharm Bull. 54(3):297–300.