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PHENYLETHANOID GLUCOSIDE AND ANTHRAQUINONE COMPOUNDS FROM MORINDA LONGISSIMA Y. Z. RUAN ROOTS
Nguyen Manh Cnong*-*, Pham Quoc Long', Tran Thu Huong', Ninh The Son', Doan Thi Van', Pham Ngoc Khanh', To Dao Cuong', Vu Thi Ha', Nguyen Cong Thuy Tram^
' Department of Bioactive Compounds, Institute of Natural Products Chemistry, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay. Hanoi
' Faculty of Biology and Environmental Science. College of Education Danang 459 Ton Due Thang Lienchieu. Danang, Vietnam
Abstract
In the search for chemical compositions of botanical species in Vietnam, the roots of Morinda longissima Y. Z, Ruan were selected for chemical investigation. Phytochemi(^ analysis of dichloromethane and water fractions of this plant led to the isolation of seven compounds including three phenylethanoid glucosides as acteoside (1), isoacteoside (2), and cistanoside-E (3), three mono-anthraquinones such as morindone-5-methyI ether (4), moiindone-6-methyI ether (5), and l-hydroxy-2-methyl-6-methoxyanthraquinone (6), and a flavonoid quercetin (7). The structures of the natural compounds were determmed from the spectroscopic evidences, including ID-NMR and APCI-MS. Here is the first report described the isolation of phenyl glucosides (acteoside (1), isoacteoside (2), and cistanoside-E (3)) from genus Morinda, &mily Rubiaceae.
Keywords: Morinda longissima Y. Z. Ruan, phenylethanoid glucoside, an^uaquinone.
1. INTRODUCTION
The Rubiaceae family in Vietnam conaprises about 64 genera, several of which are very common and widely distributed throughout fbe country such as Prismatomeris, Xanthophytum, Randia. and Morinda [I]. Previous investigations fiom various plant parts of Morinda species led to the isolation and structural elucidation of mono- antfaraquinones [2], anthraquinone glucosides [3], uidoids [4, 5], flavonoids and flavonoid glycosides [6], and essential oils [7]. The species Morinda longissima Y. 2. Ruan (local name "Nho dong") is used by ethnic minority 'Tay" and "Thai" in Chieng An-Son La province as hepatoprotective herb. The plant was also pronounced as newly taxonomicai plant m 2004 [8].
In previous papers, we reported the isolation of mono anthraquinone derivatives &om Morinda longissima roots [9, 10]. In this study, we describe the isolation and structural elucidation of seven conqraunds, including three phenylethanoid glucosides as acteoside (1); isoacteoside (2);
cistanoside-E (3), three mono-anthraquinones as morindone-5-mefliyl ether (4); morindone-6-methyI ether (5); l-hydroxy-2-methyI-6- methoxyanthraquinone (6). and one flavonoid quercetin (7). The sductures of the natural con^raunds were identified by comparison of the physicochemical and spectroscopic data [ID-NMR
and APCI-MS (+)] with those reported m tbe literature.
2. EXPERIMENT
2.1. General experimental procedures 'H-NMR (500 MHz), '^C NMR (125 MHz);
spectra were measured on a Bruker AVANCE 500]
spectrometer. 'H-NMR (400 MHz), '^C NMR (100 MHz) spectra were obtained on Varian Unity Inova 400 spectrometer. APCI-MS (+) spectra was determined by Agilent 1260 Series Single^
Quadrupole LC/MS systems. Column chromatography (CC) was carried out on silica gelj (Si 60 F2S4, 230-400 mesh, Merck). AU solventsj were distilled before use. Precoated plates of silica^
gel 60 F2J4 were used for analytical purposes.?
Compounds were visualized under UV ratUatioi^
(254, 365 nm) and by spraying plates with 10%j H2SO4 followed by heating with a heat gun. HPLQ was carried out using a Water system with a UV]
detector and an YMC Pak ODS-A column (20 >« 250j mm, 5 /mi particle size. YMC Co.. Ltd., Japan) andj HPLC solvents were from Burdick & Jackson, USA-J
2.2. Plant material ^ The roots of M. longissima were collected in
Son La province, Viehiam and identified bft ethnobotanist Ngo Van Trai (National Institute oS Medicinal Materials, NIMM). A voucher specimew (C-520) was deposited in the herbarium of tbg
H^i thdo khoa hgc ky nigm 40 n&m thdnh lap Vi§n Hdn ISm KH&CN Vi$t Nam Institute of Natural Products Chemistry, VAST,
[{anoi, Vietnam.
IS. Extraction and isolation
Dried powdered roots of Morinda longissima [2.5 kg) were extracted with EtOH 96 "C for 5 days jt room ten^rature and concentrated under reduced pressure to yield a black crude EtOH extract (50.0 B)-
g The crude EtOH extract was then suspended in
^eOH-water (1:1, v/v)) and successively partitioned with dichloromethane (j)CM). The resulting fraction was concentrated under decreased pressure to give the corresponding solvent-soluble fraction DCM (16.6 g).
I The DCM fraction (16.6 g) was fibromatographed on a silica gel column, using gradient of n-hexane-acetone (3:1, 1:1, v/v, each 1.0 L) to afford 5 sub-firactions (Dl to D5). The sub- fiaction D3 (4.0 g) was rechiomatographed on a silica gel column, eluting with (24:1, 15:1, 9:1, v/v, each 500 mL) to yield conipoimd 6 (3.5 mg) and sub-fraction D3.4, which was further purified on a siUca gel colimrn eluting with CHCh-EtOAc (15/1, jl.O L) to get compound 4 (5.0 mg). In the same nanner, the sub-fraction D4 (2.8 g) was separated by CC on silica gel, eluting wifli CHClj: EtOAc (100:0, 9:1, v/v each 500 mL) to give compound 5 (20 mg).
Dried powdered roots of Morinda longissima (1.5 kg) were decocted in hot water (2.5 L) and concentrated under reduced pressure to get black 'crude aqueous extract. The extract (100.0 g) was subjected to chromatography on a Diaion HP-20 column, eluting vrith HaO-McOH (1:0, 3:1, 1:1, 0:1, v/v, each 1.5 L), to give four fractions (Wl to W4).
The W3 fraction (8.2 g) was chromatographed in a RP-18 sihca gel column, using MeOH - H2O (1:3, 1:1,5:1, v/v, each 500 mL) as mobile phase to afford
|12 sub-fractions (W3.1 to W3.12). The sub-fraction W3.1 was fiHther purified by semi-preparative 'HPLC [YMC Pack ODS-A column; mobile phase
^HeOH/ItO (25:75 -» 50:50); flow rate 5 mL/min;
VS. minutes; W detection at 210 nm] to yield Bmpounds 1 (30 mg), 2 (15 mg), 3 (10 mg), and 7 t& mg), respectively.
2.4. Spectral and physical data
F Acteoside (l):C2»Hj<iOis(M = 624); pale yeUow powder; 'H-NMR (400 MHz) and "C-NMR (100
^ ) (CD3OD-A, S ppm): see table 1.
1 Isoateoside (2): CZPHMOIS ( M = 624); pale bUow powder; 'H-NMR (400 MHz) and "C-NMR (100 MHz) (CDsOD-tk, S ppm): see table 1.
Cistanoside-E (3): CziHiaOu (M - 476); white powder; 'H-NMR (400 MHz) and "C-NMR (100 MHz) (CDjOD-A, S ppm); see table 1.
Morindonc-5-methyI ether (4): CieHnOs (M = 284); yeUow red powder; APCI-MS (+): 285 [M-m]*; 'H-NMR (500 MHz, CDCb, S ppm): 13.01 (IH, s, 1-OH), 8.14 (IH, d, 8.5 Hz, H-8), 7.69 (IH, d, 7.5 Hz, H-4), 7.51 (IH, d, 7.5 Hz, H-3), 7.34 (IH, d, 8.5 Hz, H-7), 4.03 (3H, s, 5-OCH3), 2.37 (3H, s, 2-CHj); "C-NMR (125 MHz, CDClj, S ppm): 187.9 (s, C-9), 182.0 (s, C-10), 160.7 (s, C-l), 156.0 (s, C- 6), 146.9 (s, C-8a), 136.9 (d, C-3), 1345 (s, C-9a), 132.4 (s, C-4a), 127.1 (s, C-5), 126.0 (s, C-lOa), 125.5 (d, C-8), 120.0 (d, C-7), 118.9 (d, C-4), 134.7 (s, C-2), 62.3 (q, 5-OCHj), 16.0 (s, 2-CH3).
Moriildone-6-methyl ether (S): CuilizOs (M = 284); yeUow red powder, APCI-MS (+): 285 [M+H]*; 'H-NMR (500 MHz, DMSO-*, S ppm):
13.07 (IH, s, 1-OH), 13.00 (IH, s, 5-OH), 7.81 (IH, d, 8.5 Hz, H-8), 7.71 (IH, d, 7.5 Hz, H-4), 7.68 (IH, d, 7.5 Hz, H-3), 7.45 (IH, d, 8.5 Hz, H-7), 3.98 (3H, s, 6-OCH)), 2.33 (3H, s, 2-CH,). "C-NMR (125 MHz, DMSO-is, 5 ppm): 187.5 (s, C-10), 186.7 (s, C-9), 160.0 (s, C-l), 154.1 (s, C-6), 152.1 (s, C-5), 136.7 (d, C-3), 134.7 (s, C-2), 130.7 (s, C^a), 124.0 (s, C-8a), 120.5 (d, C-8), 118.3 (d, C-4), 116.7 (d, C- 7), 115.4 (s, C-lOa), 114.8 (s, C-9a), 56.1 (q, 6- OCHj), 15.2(q,2-CH3).
l-Hydroxy-2-methyl-6-methoxy
anthraquinone (6): Ci(Hi204 (M = 268); yellow powder, APCI-MS (+): 269 [M+H]*; 'H-NMR (500 MHz, CDjOD-ii, S ppm): 8.28 (IH, d, 9.0 Hz, H-8), 7.71 (IH, d, 2.5 Hz, H-5), 7.70 (IH, d, 7.5 Hz, H-4), 7.60 (IH, d, 7.5 Hz, H-3), 7.39 (IH, dd, 9.0; 2.5 Hz, H-7), 4.02 (3H, s, 6-OCH3), 2.37 (3H, s, 2-CHj),
"C-NMR (125 MHz, CDjOD-A + DMSO-A, S ppm): 189.4 (s, C-9), 183.6 (s, C-10), 166.6 (s, C-6), 161.9 (s, C-l), 137.9 (d, C-3), 136.2 (s, C-lOa), 135.4 (s, C-2), 133.0 (s, C-4a), 130.6 (d, C-8), 127.9 (s, C-8a), 121.6 (d, C-7), 120.1 (d, C-4), 116.4 (s, C- 9a), 111.9 (d. C-5), 56.7 (q, 6-OCHj), 15.9 (q, 2- CH3).
Quercetin (7): CijHioOr (M = 302); yellow powder; 'H-NMR (500 MHz, DMSO-*, S ppm):
12.48 (IH, s, 5-OH), 7.67 (IH, s, H-2'), 7.54 (IH, d, / = 8.0 Hz, H-eO, 6.88 (IH, d, 8.0 Hz, H-5'), 6.40 (IH, s, H-8), 6.18 (IH, s, H-6). "C-NMR (125 MHz, DMSO^ii, Sifpm): 175.8 (s, CA), 98.2 (d, C-6), 163.8 (s, C-7), 160.6 (s, C-5), 156.1 (s, C-8a), 147.6 (s, H-4'), 146.7 (s, C-2), 145.0 (s, C-3'), 135.7 (s, C- 3), 122.0 (s, C-O, 120.0 (d, C-6'), 115.5 (s, C-5'), 115.0 (d, C-2'), 102.9 (s, C-4a), 93.3 (d, C-8).
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3. RESULTS AND DISCUSSION
Repeated column chromatography of the dichloromethane fraction and water extract of M.
longissima resulted in the isolation of seven known compoimds (1-7) including acteoside (1), isoacteoside (2), cistanoside-E (3). morindone-5- methyl ether {4), morindone-6-
methyl ether (5). l-hydroxy-2-methyl-6.
methoxyanthraquinone (6), and quercetin (7) and (Fig.l). The structures of the natural compounds were identified by conqiarison of the physicochemical and spectroscopic data [ID-NMR and APCI-MS (+)] with those reported in the literature.
Compound 1 was isolated as pale yellow powder (CzgHseOis. M = 624). The 'H NMR spectrum of compound 1 showed signals characteristic for the presence of two 1,3,4- trisubstihited benzenes at 5H 6.57 (IH, dd,J= 8.0;
2.0 Hz, H-6), 6.68 (IH, d, J= 8.0 Hz, H-5) and 6.70 (IH, d, / = 2.0 Hz, H-2) and $B 6.79 (IH, d, / = 8.0 Hz, H-5'), 6.95 (IH, dd, 7 = 8.0; 2.0 Hz. US') and 7.06 (IH, d. 2.0, H-2') (Table 1). A froftr-double bond was assignable at 3H 6.27 (IH, d, / = 16.0 Hz, H-8') and 7.59 (IH, d, 7 = 16.0 Hz, H-7'), together with the aromatic resonance protons of a 3',4'- dihydroxy phenyl ring indicated the presence of a cafreoyl moiety. An AA'BB' pattern of an ethylene group observed at da 2.79 (IH, t, / = 6.8 Hz. H-7), 3.72 (IH, m Hb-8) / 4.05 (IH, m, H,-8), along with other aromatic resonance protons of 3,4-dihydroxy phenyl ring revealed the presence of a phenylethyl moiety. Characteristic resonances of a methyl group at SH 1.09 (3H, d, 6.4 Hz, S'-'-CHj) and of an anomeric proton at Sa 5.19 (IH, d, 1.6 Hz, H-l'") suggested the presence of a a-L-rhamnopyranosyl moiety. The proton signal belonging to an anomeric proton observed as doublet at Sa 4.37 (IH, d, H-l") with J = 8.0 Hz suggested for the presence of of a glucopyranosyl moiety in ^D-configuratioiL The
"C NMR spectrum of compound 1 contained 29
Fig.l. Structures of isolated compounds (1-7)
148.1)] conjugated to carbonyl carbon Sc 168.4 (C- 9'), a vicinal ethyl group [C-7 {Sc 36.7) and C-8 {5c 72.5)], an a-L-rhanmopyranosyl moiety with 6 signals at Sc 18.6-103.2, and a p-D-glucopyranosyl moiety with 6 carbon signals at Sc 62.3-104.3 (Table 1). Based on the above analysis, flic stmchire of confound 1 was elucidated as 3.4- dihydroxyphenethyl-O-a-L-rhanmopyranosyl- (r"-»-3")-4"-0-caffeoyl-^D-glucopyranoside, namely acteoside. Acteoside was isolated from several families such as Gesneraiaceae, Acanthaceae, Scrophylariaceae etc. [11, 12]. Here is the fust report described the isolation of Mteoside from family Rubiaceae. genus Morinda.
Compound 2 was isolated as pale yellow powder (C29H360i5, M = 624). Analysis of the 'H and '^C NMR spectra of 2 revealed the presence of two sugar moieties in similarity to those of 1. but it was slightly different from 1 in the substituted position of caffeoyl moiety. In compound 2. the caflfeoyl group located at oxygenated carbon C-6' (5c 64.7) of p-D-glucopyranosyl moiety (Table !)•
Based on ihe above analysis, the structure O' con^und 2 was elucidated as 3,4- dihydroxyphenefli^-O-a-L-rhamnopyranos^- (1 '"_,.3")-6"-0-c^eoyl-^D-glucopyran(Bide, named isoacteoside. Uke couqraund 1, the isolation carbon signals also confirmed for the presence of of compound 2 from Morinda genus, Rubiac*
two 1,3,4-trisubstituted benzenes with 12 aromatic family was reported also for the first time [U, 12].
carbons, a double bond [C-8' {Sc 115.5) and C-7' {Sc
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Table l . ' H
Fosltton
and '*C-NMR data (400 MHz, CDjOD) of Acteoside (1) and Isoacteoside (2) and Cistanoside-E (3)
&
Phenylethyl moiety I 2 3 4 5 6 7 8 3-OCHj
I3I.6.S U 7 . 1 , d 146.2, a 144.8, s 116.4, d 121.4, d 36.7, t 72.5, t
Caffeoyl moiety 2' r
3' 4' 5' 6' 7' 8' 9'
127.8, s 114.8, d 146.9, s 149.9, s 116.6, d 123.3, d 148.1, d 115.3, d 168.4, s p-D-GlDcosyl moiety
1"
2"
3"
4"
5"
6"
104.3, d 76.3, d 81.7, d 70.6, d 76.2, d 62.3, t a-L-Rtaanmosyl moiety
1- 2"' 3 "
4 "
5'"
5--CH3 103.2, d 72.3, d 72.2, d 73.9, d 70.7, d 18.6, q
1
& ( 7 i n H z )
6.70 (d, 2.0)
6.68 (d, 8.0) 6.57 (dd, 8.0; 2.0) 2.79 (t, 6.8) 4.05 (m) 3.72 (m)
7.06 (d, 2.0)
6.79 (d, 8.0) 6.95 (dd, 8.0;2.0) 7.59 (d, 16.0) 6 2 7 (d, 16.0)
4.37 (d, 8.0) 3.97 (m) 3.82 (t, 9.2) 4.93 (t, 9.6) 3.52-3.64 (m) 3.52-3.64 (m) 5.19 (d, 1.6) 3.93 (m) 3.52-3.64 (m) 3.31 (m) 3.52-3.64 (m) 1.09 Cd, 6.4)
*
131.5, s 117.1, d 146.9, s 144.7. s 116.5, d 121.4, d 36.8, t 72.4, t
127.8, s U4.9,d 146.2, s 149.7, s 116.6, d 123.3, d 147.4, d 115.2, d 169.3, s 1045, d 75.8, d 84.1, d 70.1, d 75.5, d 64.7, t
102.8, d 72.5, d 72.3, d 74.1, d 70.5, d 18.0, q
2 Af/inHz)
6.68 (d, 1.6)
6.64 (d, 8.0) 6.53 (dd, 8.0; 1.6) 2.78 (t, 7.6) 4.03 (m) 3.72 (m)
7.04 (d, 1.6)
6.77 (d, 8.4) 690 (dd, 8.4; 1.6) 7.56 (d, 15.6) 629 (d, 15.6)
4.37 (d, 7.0) 3.31-3.44 (m) 3.54 (m) 3.31-3.44 (m) 3.54 (m) 4.49 (brd, 10.8) 4 3 5 (br d, 8.0) 5.19 (s) 3.95 (m) 3.31-3.44(01) 3.31-3.44 (m) 3.99 (m) 1.25 (d, 6.0)
&
131.6, s 116.3, d 146.2, s 144.7, s 117.2, d 121.3, d 36.7, t 72.3,1 55.3, q
104.3, d 75.7, d 84.6, d 70.2, d 78.0, d 62.8, t
102.9, d 72.2, d 73.4, d 74.1, d 70.3, d 18.0, q
3 iik(/inHz)
6.65 (d, 2.0)
6.63 (d, 8.4) 6.52 (dd, 8.0; 2.0) 2.76 (m) 3.98 (m) 3.94 (s)
4.26 (d, 7.6) 3.22-3.48 (m) 3.22-3.48 (m) 3.22-3.48 (m) 3.22-3.48 (m) 3.83 (brd, 14.5) 3.66 (m) 5.13 (s) 3.92 (m) 3.22-3.48 (m) 3.22-3.48 (m) 3.96 (m) 1.21 (d, 6.4) Compound 3 was isolated as white powder.
(CiiHaiOH, M = 476). The 'H- and '^C-NMR of the compound is similar to those of 1 and 2 except for the presence of a methoxy group at Sa 3.94 (s, 3- OCH3) and the absence of the caffeoyl moiety (Table 1). Based on the above analysis, flie shTichire of conqwund 3 was elucidated as 3-methoxy-4- liydroxyphenethyl-C?-a-L-rhamnopyranosyl- (l"'r-*3").^D-glucopyranoside, named cistanoside-
|1|13]. This is the first report described the presence Sf this compound m Morinda genus, Rubiaceae (amily.
Con^und 4 was obtained as yellow red [lowder. The molecular formula of 4 is CisHuOj as ieduced from pseudo-molecular ion peak at m/z 285
[M+H]* m APCI-MS (+) spectroscopy. The 'H NMR spectrum of 4 showed two pairs of ortho- coupled proton signals at [Sa 7.34 (d, 7 = 8.5 Hz. H- 7) / da 8.14 (d, / = 8.5 Hz, H-8] and at [^H 7.51 (d.
/ = 7.5 Hz, H-3) / Sa 7.69 (d, / = 7.5 Hz, H-4)], assigned to two 1,2,3,4-tetrasubstihited phenyl groups. The 'H-NMR spectrum also showed the presence of one methoxy group Sa 4.03 (5-OCHj) and a hydroxy! group at Sa 13.01 (1-OH). The "C NMR spectrum indicated 16 carbon signals, including twelve aromatic carbons {Sc 160.7-114.8).
two carbonyl carbons [182.0 (C-10) and Sc 187.9 (C-9)], a methyl carbon at 5c 16.0 (2-CH3) and a methoxy carbon at Sc 62.3 (5-OCH3). The data led to identify the structure of compound 4 as 1,6-
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benzene ring at 6.88 ( I H , d, / = 8.0 Hz. H-5'); 7.54 ( I H , d, 7 = 8.0, H-6'); Sa 7.67 ( I H . s, H-2'). The '^C N M R spectrum indicated 15 carbon signalg 'i including one carbonyl carbon [5c 175.8 (C-4)], nine ' quaternary carbon signal and five methine carbon signals. The data led us to conclude diat con^iouad 7 \ is 2-(3'.4'-dihydroxyphenyl)-3,5.7-trihydroxy-4H^' chromen-4-one, named quercetin [17].
4. CONCLUSION
Phytochemical analysis of dichloromethane and water fractions of medicinal plant Morinda longissima Y. Z. Ruan led to the isolation of seven compounds mcluding three phenylethanoid glucosides as acteoside (1), isoacteoside (2), and cistanoside-E (3), three mono-anthraquinones such as morindone-5-methyl ether (4). morin(k)ne-6- methyl ether (5), and l-hydroxy-2-meaiyI-6- methoxyanthraquinone (6), and a flavonoid | quercetin (7). H i e structures of the natural compoimds were determined from die spectroscopic evidences, including I D - N M R and APCI-MS. Here is die first report described the isolation of acteoside (1), isoacteoside (2), and cistanoside-E (3) from genus Morinda, family Rubiaceae.
dihydroxy-5-methoxy-2-methyIanairaquinone, named morindone-5-mettiyl e&er [14].
C o n ^ u n d 5 was obtained as yellow red powder, "nie molecular formula of 5 was determined as CisHizOs base on APCI-MS (+) spectroscopy with pseudo-molecular ion peak at m/z 285 [M+H]"^.
The 'H and '^C N M R spectra of 5 were similar to 4 except the reversed substituted petitions of the methoxy group at Sa 3.98 (6-OCH3) and the hydroxyl groiq) Sa 13.00 (5-OH). Based on the above analysis, the structure of conqiound 5 was elucidated as a isomer of 4, named morindone-6- mefliyl ether [15].
Compound 6 was obtained as yellow powder.
The molecular formula of 6 is Ci6Hi204 as deduced from the data of its APCI-MS (+) at m/z 269 [M+H]*. The 'H and " C N M R spectea of 6 were similar to 5 except the presence of a methine at Sa 7.71 (IH, d. 2.5 H z H-5). Based on the above analysis, the stmcture of compound 6 was elucidated as I-hydroxy-2-methyl-6-methoxyanthraquinone [16].
C o n ^ u n d 7 was obtained as yellow powder (C15H10O7, M=302). The ' H N M R spectmm of 7 revealed the presence of a tetra-substituted benzopyrone at Sa 6.18 ( I H . s. H-6); 6.40 ( I H , s, H- 8) and a 1,3,4-tiisubstitiited
Acknowledgement: The authors acknowledge financial support fi-om national science and technology research programs KC.10/11-15project (KC.10.45).
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Hdi thdo khoa hgc ky niem 40 n&m thdnh lap Vign Hdn Idm KH&CN ViStNam
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Zorresponding author. Assoc. Prof. Dr. Ng;uyen M a n h C u o n g fristitute of Natural Products Chemistry,
Vietnam Academy of Science and Technology IH Buitdmg, 18 Hoang Quoc Viet, Cau Giay Ha Noi, Vietnam
Bmail: nmcuonp@inpc.vast.vn
