全 文 ：Rosmarinus officinais L. (Lamiaceae) popularly
known as rosemary, is a shrub widely distributed in
Europe, Asia, and Africa. And one of its elective growing
areas is the Mediterranean basin where spontaneous
plants are diffusely distributed. Rosemary has been
traditionally used as a culinary spice, mainly to modify
or improve food flavors as well as in folk medicine,
being a greatly valuable medicinal herb[1].
Diterpenoids, flavonoids, triterpenoids, essential
oils and phenolic acids are their main constitutents.
热带亚热带植物学报　2015， 23(3)： 310 ~ 316
Journal of Tropical and Subtropical Botany
Received: 2014–07–28　　　　Accepted: 2014–09–16
This study was supported by Program for New Century Excellent Talents in University (NCET-12-1069), Program for Tianjin Innovative Research
Team in University (TD12-5033).
* Corresponding author. E-mail: zhwwxzh@263.net
卢旺达产迷迭香化学成分研究 I
TIWALADE Adegoke Adelakun, 李晓霞, 瞿璐, 陈玥, 王涛, 张祎*
(天津市中药化学与分析重点实验室，天津 300193)
摘要： 为了解迷迭香(Rosmarinus officinais L.)中的化学成分，从其 95% 乙醇提取物中分离得到了 13 种化合物，经波谱分析，分
别鉴定为(Z)-3-hexenyl glucoside (1)，(Z)-3-hexenyl O-β-D-glucopyranosyl-(1′′→6′)-β-D-glucopyranoside (2)，erythritol-1-O-(6-O-
trans-caffeoyl)-β-D-glucopyranoside (3)，2,3,4,5-tetrahydroxyhexyl-6-O-trans-caffeoyl-β-glucopyranoside (4)， 1,2,3,4-tetrahydroxy-
2-methylbutane-4-O-(6-O-trans-caffeoyl)-β-D-glucopyranoside (5)，咖 啡 酸 (6)，迷 迭 香 酸 (7)，methyl rosmarinate (8)，methyl
benzoate-4-β-glucoside (9)，benzyl-β-D-glucopyranoside (10)，benzyl-O-β-D-apiofuranosyl-(1→2)-β-D-glucopyranoside (11)，
1,2-di-O-β-D-glucopranosyl-4-allylbenzene (12)及(+)-syringaresinol-4′-O-β-D-glucopyranoside (13)。其中，化合物 1~5 和 8~13 为
首次从迷迭香属分离得到，并修正了化合物 13 的波谱数据。
关键词： 迷迭香； 化学成分； 酚酸
doi: 10.11926/j.issn.1005–3395.2015.03.012
Chemical Constituents from Rwandan Plant Rosmarinus officinalis L. (I)
TIWALADE Adegoke Adelakun, LI Xiao-xia, QU Lu, CHEN Yue, WANG Tao, ZHANG Yi*
(Key Laboratory of Traditional Chinese Medicinal Chemistry and Analytical Chemistry of Tianjin, Tianjin 300193, China)
Abstract: In order to understand the chemical constituents of Rosmarinus officinalis, 13 compounds were
isolated from its 95% EtOH extract. On the basis of spectral data, their structures were identified as (Z)-3-
hexenyl glucoside (1), (Z)-3-hexenyl O-β-D-glucopyranosyl-(1′′→6′)-β-D-glucopyranoside (2), erythritol-1-O-
(6-O-trans-caffeoyl)-β-D-glucopyranoside (3), 2,3,4,5-tetrahydroxyhexyl-6-O-trans-caffeoyl-β-glucopyranoside
(4), 1,2,3,4-tetrahydroxy-2-methylbutane-4-O-(6-O-trans-caffeoyl)-β-D-glucopyranoside (5), caffeic acid (6),
rosmarinic acid (7), methyl rosmarinate (8), methyl benzoate-4-β-glucoside (9), benzyl-β-D-glucopyranoside (10),
benzyl-O-β-D-apiofuranosyl-(1→2)-β-D-glucopyranoside (11), 1,2-di-O-β-D-glucopranosyl-4-allylbenzene (12)
and (+)-syringaresinol-4′-O-β-D-glucopyranoside (13). Among them, compounds 1–5 and 8–13 were isolated
from the Rosmarinus genus for the first time. For the known ones, the NMR data of compound 13 was corrected.
Key words: Rosmarinus officinalis; Chemical constituent; Phenolic acid
第3期 311
The derived essential oils are mainly used in
local application for their balsamic, antispasmodic and
anti-inflammatory activities[2]. Among them, phenolic
acids are the main antioxidant compounds present in
rosemary[3].
In the course of our study on the constituents of this
plant, thirteen compounds were isolated and identified
from its aerial parts, and their chemical structures
(Fig. 1) were elucidated based on physico-chemical
properties and spectral data.
Fig. 1 Structure of compounds 1–13
1 Materials and methods
1.1 Plant material
The dried aerial parts of Rosmarinus officinais
(Lamiacea) were collected from Butarie, Rwanda and
identified by Dr. LI Tian-xiang. The voucher specimen
(No. 20110910) was deposited at the Academy of
Traditional Chinese Medicine of Tianjin University of
TCM.
1.2 General experimental procedures
Optical rotations were measured on a Rudolph
Autopol® IV automatic polarimeter. IR spectra were
recorded on a Varian 640-IR FT-IR spectrophotometer.
UV spectra were obtained on a Varian Cary 50 UV-
Vis spectrophotometer. NMR spectra were determined
on a Bruker 500 MHz NMR spectrometer at 500 MHz
for 1H and 125 MHz for 13C NMR, with TMS as an
internal standard. Positive- and Negative-ion HRESI-
TOF-MS were recorded on an Agilent Technologies
6520 Accurate-Mass Q-Tof LC/MS spectrometer.
Column chromatographies were performed on
macroporous resin D101 (Haiguang Chemical Co.,
Ltd., Tianjin, China), Silica gel (48–75 μm, Qingdao
Haiyang Chemical Co., Ltd., Qingdao, China), and
ODS (40–63 μm, YMC Co., Ltd., Tokyo, Japan).
Preparative HPLC (PHPLC) column, Cosmosil 5C18-
MS-II (20 mm i.d.×250 mm, Nakalai Tesque, Inc.,
Tokyo, Japan) were used to purify the constituents.
Pre-coated TLC plates with Silica gel GF254 (Tianjin
Silida Technology Co., Ltd., Tianjin, China) were
used to detect the purity of isolates achieved by spraying
with 10% aqueous H2SO4-EtOH, followed by heating.
1.3 Extraction and isolation
The dried aerial parts of R. officinalis (2.5 kg)
TIWALADE Adegoke Adelakun等：卢旺达产迷迭香化学成分研究 I
312 第23卷热带亚热带植物学报
were refluxed with 95% EtOH. The solvent was
evaporated under reduced pressure to yield the 95%
EtOH extract (455 g). Then, the extract (379 g) was
partitioned in a CHCl3-H2O mixture (1：1, V/V) to
give both CHCl3 (269 g) and H2O (100 g) partitions.
Then, the H2O layer (100 g) was subjected to D101
macroporous resin column chromatography (CC) and
eluted with H2O and 95% EtOH, successively. As a
result, H2O (47 g) and 95% EtOH (45 g) eluted fractions
were obtained.
The EtOH fraction (36 g) was subjected to normal
phase silica gel CC [CHCl3 → CHCl3-MeOH (100：3→
100：5 →100：7, V/V) → CHCl3-MeOH-H2O (10：3：1 →
7：3：1, V/V/V) → MeOH] to yield 11 fractions (Fr. 1–
Fr. 11).
Fraction 6 (0.7 g) was purified by PHPLC [CH3CN-
H2O (17：83, V/V)] into 8 subfractions (Fr. 6-1–Fr. 6-8).
Subfraction 6-7 was identified as (Z)-3-hexenyl
glucoside (1, 14.1 mg). Subfractions 6-5 (52.2 mg)
and 6-8 (243.8 mg) was further purified by PHPLC to
obtain caffeic acid (6, 16.8 mg), (+)-syringaresinol-4′-
O-β-D-glucopyranoside (13, 4.1 mg). Fraction 7 (5.5 g)
was subjected to ODS CC [MeOH-H2O (20：80→30：
70→40：60→50：50→60：40→70：30→100：0, V/V)]
to yield 9 subfractions (Fr. 7-1–Fr. 7-9). Subfraction
7-2 (616.4 mg) was purified by PHPLC to isolate both
(Z)-3-hexenyl β-D-glucopyranoside (1, 8.3 mg) and
rosmarinic acid (7, 126.1 mg). Subfraction 7-5 (1.61 g)
was also purified by PHPLC to offer benzyl-β-D-
glucopyranoside (10, 5.7 mg) and methyl benzoate-4-
β-D-glucopranoside (9, 2.2 mg). Subfractions 7-5-14
(554.6 mg) and 7-5-15 (147.8 mg) were also combined
and further purified by subjecting it to silica gel CC
[CHCl3→CHCl3-MeOH (100：3→100：5→100：7, V/
V)→CHCl3-MeOH-H2O (20：3：1→10：3：1→7：3：
1, V/V/V)→MeOH] to give 14 fractions (Fr. 7-5-14-
1–Fr. 7-5-14-14). Furthermore, subfraction 7-5-14-8
(126.2 mg) was subjected to PHPLC to give methyl
rosmarinate (8, 42.8 mg).
Fraction 9 (10.0 g) was separated by ODS
CC, silica gel CC and PHPLC to offer benzyl-O-β-D-
apiofuranosyl(1→2)-β-D-glucopyranoside (11, 41.4 mg).
Fraction 10 (6.3 g) was subjected to PHPLC through
gradient elution [MeOH-H2O (25：75→40：60→60：
40→80：20→100：0, V/V)] to yield 35 subfractions
(Fr. 10-1–Fr. 10-35). Subfractions 10-14 (73.0 mg),
10-16 (36.4 mg), 10-17 (86.8 mg), and 10-22 (127.5 mg)
were purified by PHPLC respectively to give erythritol-
1-O-(6-O-trans-caffeoyl)-β-D-glucopyranoside (3,
6.3 mg), 2,3,4,5-tetrahydroxyhexyl-6-O-trans-caffeoyl-
β-glucopyranoside (4, 9.9 mg), 1,2,3,4-tetrahydroxy-2-
methylbutane-4-O -(6-O - trans- caffeoyl)-β-D- gluco-
pyranoside (5, 4.6 mg), and (Z)-3-hexenyl O-β-D-gluco-
pyranosyl-(1′′→6′)-β-D-glucopyranoside (2, 9.3 mg)
and 1,2-di-O-β-D-glucopranosyl-4-allylbenzene (12,
36.2 mg).
1.4 Structural elucidation
(Z)-3-Hexenyl β-D-glucopyranoside (1)　　
White powder. Negative-ion mode m/z: 297.1078
[M + Cl]– (calcd for C12H22O6Cl 297.1110).
1H NMR
(CD3OD, 500 MHz): δ [3.56 (1H, dt, J = 7.0, 9.5 Hz),
3.87 (1H, m, overlapped), H2-1], 2.39 (2H, dt, J =
7.0, 7.0 Hz, H2-2), 5.38 (1H, m, H-3), 5.46 (1H, m,
H-4), 2.08 (2H, m, H2-5), 0.97 (3H, t, J = 7.0 Hz,
H3-6), 4.30 (1H, d, J = 8.0 Hz, H-1′), 3.20 (1H, dd,
J = 8.0, 9.0 Hz, H-2′), 3.38 (1H, dd, J = 9.0, 9.0 Hz,
H-3′), 3.30 (2H, m, overlapped, H-4′ and 5′), [3.69
(1H, dd, J = 5.0, 12.0 Hz), 3.87 (1H, m, overlapped),
H2-6′];
13C NMR (CD3OD, 125 MHz): δ 70.6 (C-1),
28.7 (C-2), 125.7 (C-3), 134.6 (C-4), 21.5 (C-5), 14.6
(C-6), 104.2 (C-1′), 75.0 (C-2′), 78.0 (C-3′), 71.6 (C-
4′), 77.8 (C-5′), 62.6 (C-6′). The NOE correlations
between δH 2.08 (H2-2) and δH 1.92 (H2-5) observed
in the NOESY spectrum indicated the configuration
in △3,4 was Z. On the basis of above mentioned and
by comparing the 1H and 13C NMR data of it with the
reported data[4], the structure of 1 was identified as
(Z)-3-hexenyl β-D-glucopyranoside.
(Z)-3-Hexenyl O-β-D-glucopyranosyl-(1′′→6′)-
β-D-glucopyranoside (2)　　White powder. Negative-
ion mode m/z: 459.1623 [M + Cl]– (calcd for C18H32O11Cl
459.1639). 1H NMR (C5D5N, 500 MHz): δ [3.60 (1H,
dt, J = 7.0, 9.5 Hz), 4.11 (1H, m, overlapped), H2-1],
2.39 (2H, dt, J = 7.0, 7.0 Hz, H2-2), 5.44 (1H, m, H-3),
5.36 (1H, m, H-4), 1.92 (2H, m, H2-5), 0.82 (3H, t, J =
第3期 313
7.0 Hz, H3-6), 4.72 (1H, d, J = 7.5 Hz, H-1′), 3.91 (1H,
dd, J = 7.5, 9.0 Hz, H-2′), 4.16 (1H, dd, J = 9.0, 9.0 Hz,
H-3′), 4.10 (1H, dd, J = 9.0, 9.0 Hz, H-4′), 3.99 (1H,
m, H-5′), [4.27 (1H, dd, J = 5.5, 11.0 Hz), 4.77 (1H,
dd, J = 2.0, 11.0 Hz), H2-6′], 5.03 (1H, d, J = 8.0 Hz,
H-1′′), 3.98 (1H, dd, J = 8.0, 9.0 Hz, H-2′′), 4.13 (1H,
dd, J = 9.0, 9.0 Hz, H-3′′), 4.18 (1H, dd, J = 9.0, 9.0 Hz,
H-4′′), 3.86 (1H, m, H-5′′), [4.31 (1H, dd, J = 4.5,
11.5 Hz), 4.45 (1H, br. d, ca. J = 12 Hz), H2-6′′];
13C NMR (C5D5N, 125 MHz): δ 69.4 (C-1), 28.3 (C-
2), 125.6 (C-3), 133.4 (C-4), 20.8 (C-5), 14.4 (C-6),
104.5 (C-1′), 75.0 (C-2′), 78.4 (C-3′), 71.5 (C-4′), 77.2
(C-5′), 70.1 (C-6′), 105.5 (C-1′′), 75.1 (C-2′′), 78.4
(C-3′′), 71.6 (C-4′′), 78.4 (C-5′′), 62.7 (C-6′′). The
NOE correlations between δH 2.39 (H2-2) and δH 1.92
(H2-5) were observed in the NOESY spectrum, which
indicated that the configuration in △3,4 was Z. Finally,
the compound 2 was identified as (Z)-3-hexenyl O-β-
D-glucopyranosyl-(1′′→6′)-β-D-glucopyranoside by
comparison of the physical, 1H and 13C NMR data
with the reported data[5].
Erythritol-1-O-(6-O-trans-caffeoyl)-β-D-glucopy-
ranoside (3)　　White powder. Negative-ion mode
m/z: 445.1380 [M – H]– (calcd for C19H25O12 445.1351).
1H NMR (CD3OD, 500 MHz): δ [3.67 (1H, dd, J = 6.5,
11.0 Hz), 4.09 (1H, dd, J = 2.5, 11.0 Hz), H2-1], 3.76
(1H, ddd, J = 2.5, 6.5, 14.0 Hz, H-2), 3.60 (1H, ddd,
J = 2.0, 6.0, 14.0 Hz, H-3), [3.58 (1H, dd, J = 6.0,
11.0 Hz), 3.74 (1H, dd, J = 2.0, 11.0 Hz), H2-4], 4.35
(1H, d, J = 8.0 Hz, H-1′), 3.26 (1H, dd, J = 8.0, 9.0 Hz,
H-2′), 3.40 (1H, dd, J = 9.0, 9.0 Hz, H-3′), 3.36 (1H,
dd, J = 9.0, 9.0 Hz, H-4′), 3.55 (1H, m, H-5′), [4.30 (1H,
dd, J = 5.5, 12.0 Hz), 4.51 (1H, dd, J = 2.0, 12.0 Hz),
H2-6′], 7.05 (1H, d, J = 2.0 Hz, H-2′′), 6.78 (1H, d, J =
8.5 Hz, H-5′′), 6.95 (1H, dd, J = 2.0, 8.5 Hz, H-6′′),
7.57 (1H, d, J = 16.0 Hz, H-7′′), 6.29 (1H, d, J = 16.0 Hz,
H-8′′). Compound 3 was identified as erythritol-1-O-
(6-O-trans-caffeoyl)-β-D-glucopyranoside by comparison
of the physical, 1H and 13C NMR (Table 1) data with
the reported data[6].
2,3,4,5-Tetrahydroxyhexyl-6-O-trans-caffeoyl-
β-glucopyranoside (4)　　White powder. Negative-
ion mode m/z: 489.1609 [M – H]– (calcd for C21H29O13
489.1614). 1H NMR (CD3OD, 500 MHz): δ [3.73 (1H,
dd, J = 6.5, 10.5 Hz), 4.11 (1H, dd, J = 2.5, 10.5 Hz),
H2-1], 3.83 (1H, ddd, J = 2.5, 6.5, 15.0 Hz, H-2),
3.59 (1H, m, H-3), 3.57 (1H, m, H-4), 3.86 (1H, m,
H-5), 1.18 (3H, d, J = 6.5 Hz, H3-6), 4.35 (1H, d, J =
7.5 Hz, H-1′), 3.27 (1H, dd, J = 7.5, 9.0 Hz, H-2′),
3.41 (1H, dd, J = 9.0, 9.0 Hz, H-3′), 3.37 (1H, dd, J =
9.0, 9.0 Hz, H-4′), 3.54 (1H, m, H-5′), [4.30 (1H, dd,
J = 6.0, 12.0 Hz), 4.52 (1H, dd, J = 2.0, 11.0 Hz),
H2-6′], 7.05 (1H, d, J = 2.0 Hz, H-2′′), 6.77 (1H,
d, J = 8.0 Hz, H-5′′), 6.94 (1H, dd, J = 2.0, 8.0 Hz,
H-6′′), 7.58 (1H, d, J = 16.0 Hz, H-7′′), 6.29 (1H,
d, J = 16.0 Hz, H-8′′). Compound 4 was identified
as 2,3,4,5-tetrahydroxyhexyl-6-O-trans-caffeoyl-β-
glucopyranoside according to the 1H, 13C NMR (Table
1) and 2D-NMR experiments.
1,2,3,4-tetrahydroxy-2-methylbutane-4-O-(6-
O-trans-caffeoyl)-β-D-glucopyranoside (5)　　White
powder. Negative-ion mode m/z: 459.1509 [M – H]–
(calcd for C20H27O12 459.1508).
1H NMR (C5D5N,
500 MHz): δ [4.06 (1H, d, J = 11.0 Hz), 4.16 (1H, d, J =
11.0 Hz), H2-1], 4.58 (1H, dd, J = 3.0, 8.0 Hz, H-3),
[4.33 (1H, dd, J = 3.0, 10.5 Hz), 4.89 (1H, dd, J = 8.0,
10.5 Hz), H2-4], 1.60 (3H, s, 2-CH3), 5.03 (1H, d, J =
8.0 Hz, H-1′), 4.05 (1H, dd, J = 8.0, 8.5 Hz, H-2′), 4.20
(1H, dd, J = 8.5, 9.0 Hz, H-3′), 4.12 (1H, dd, J = 9.0,
9.0 Hz, H-4′), 4.03 (1H, m, H-5′), [4.88 (1H, dd, J =
5.5, 12.0 Hz), 5.04 (1H, dd, J = 2.0, 11.0 Hz), H2-6′],
7.53 (1H, d, J = 2.0 Hz, H-2′′), 7.17 (1H, d, J = 8.0 Hz,
H-5′′), 7.08 (1H, dd, J = 2.0, 8.0 Hz, H-6′′), 7.92 (1H,
d, J = 16.0 Hz, H-7′′), 6.58 (1H, d, J = 16.0 Hz, H-8′′);
1H NMR (CD3OD, 500 MHz): δ [3.43 (1H, d, J =
11.0 Hz), 3.53 (1H, d, J = 11.0 Hz), H2-1], 3.81 (1H, dd,
J = 2.5, 8.5 Hz, H-3), [3.39 (1H, dd, J = 2.5, 10.5 Hz),
3.56 (1H, dd, J = 8.5, 10.5 Hz), H2-4], 1.10 (3H, s,
2-CH3), 4.35 (1H, d, J = 8.0 Hz, H-1′), 3.26 (1H, dd,
J = 8.0, 9.0 Hz, H-2), 3.41 (1H, dd, J = 9.0, 9.0 Hz,
H-3′), 3.37 (1H, dd, J = 9.0, 9.0 Hz, H-4′), 3.53 (1H,
m, H-5′), [4.32 (1H, dd, J = 6.0, 12.0 Hz), 4.51 (1H,
dd, J = 2.0, 12.0 Hz), H2-6′], 7.05 (1H, d, J = 2.0 Hz,
H-2′′), 6.77 (1H, d, J = 8.0 Hz, H-5′′), 6.94 (1H, d,
J = 2.0, 8.0 Hz, H-6′′), 7.58 (1H, d, J = 16.0 Hz, H-7′′),
6.29 (1H, d, J = 16.0 Hz, H-8′′). Compound 5 was
TIWALADE Adegoke Adelakun等：卢旺达产迷迭香化学成分研究 I
314 第23卷热带亚热带植物学报
identified as 1,2,3,4-tetrahydroxy-2-methylbutane-4-
O-(6-O-trans-caffeoyl)-β-D-glucopyranoside by com-
parison of the physical, 1H and 13C (Table 1) NMR
data with the reported data[6].
Caffeic acid (6)　　White powder. Positive-
ion mode m/z: 181.0504 [M + H]+ (calcd for C9H9O4
181.0495). 1H NMR (CD3OD, 500 MHz): δ 7.04 (1H,
br. s, H-2), 6.78 (1H, d, J = 8.0 Hz, H-5), 6.93 (1H, br.
Table 1 13C NMR (125 MHz, δ) data of compounds 3–5
Position 3a 4a 5b 5a 3a 4a 5b 5a
1 73.1 73.2 68.7 68.5 5′ 75.6 75.5 75.5 75.5
2 72.6 71.7 74.1 74.5 6′ 64.7 64.5 64.5 64.5
3 73.6 72.7 74.6 74.7 1′′ 127.8 127.6 126.9 127.6
4 64.7 74.7 72.9 72.4 2′′ 115.3 115.1 115.9 115.1
5 70.3 3′′ 146.9 146.8 147.6 146.8
6 19.5 4′′ 149.7 149.6 150.4 149.6
2-CH3 20.7 19.6 5′′ 116.6 116.4 116.6 116.5
1′ 105.1 104.9 105.7 104.9 6′′ 123.1 123.0 122.1 123.0
2′ 75.2 75.1 75.3 75.2 7′′ 147.3 147.2 146.0 147.2
3′ 77.8 77.6 78.3 77.7 8′′ 114.9 114.7 114.9 114.8
4′ 71.7 71.6 71.4 71.6 9′′ 169.2 169.0 167.6 169.1
a: CD3OD; b: C5D5N
d, ca. J = 8 Hz, H-6), 7.52 (1H, d, J = 16.0 Hz, H-7),
6.23 (1H, d, J = 16.0 Hz, H-8); 13C NMR (CD3OD,
125 MHz): δ 128.0 (C-1), 115.1 (C-2), 146.8 (C-3),
149.4 (C-4), 116.5 (C-5), 122.8 (C-6), 146.7 (C-7),
116.1 (C-8), 171.6 (C-9). Compound 6 was identified
as caffeic acid by comparison of the physical, 1H and
13C NMR data with the reported data[7].
Rosmarinic acid (7)　　White powder. [α]D
25
+ 37.7° (c 0.78, in MeOH). Negative-ion mode m/z:
359.0786 [M – H]– (calcd for C18H15O8 359.0772).
1H
NMR (CD3OD, 500 MHz): δ 6.76 (1H, d, J = 2.0 Hz,
H-2), 6.70 (1H, d, J = 8.0 Hz, H-5), 6.62 (1H, dd, J =
2.0, 8.0 Hz, H-6), [3.00 (1H, dd, J = 8.5, 14.0 Hz),
3.10 (1H, both dd, J = 3.0, 14.0 Hz), H2-7], 5.18 (1H,
dd, J = 3.0, 8.5 Hz, H-8), 7.04 (1H, d, J = 1.5 Hz,
H-2′), 6.77 (1H, d, J = 8.0 Hz, H-5′), 6.94 (1H, dd, J =
1.5, 8.0 Hz, H-6′), 7.54 (1H, d, J = 16.0 Hz, H-7′), 6.26
(1H, d, J = 16.0 Hz, H-8′); 13C NMR (CD3OD, 125 MHz):
δ 129.5 (C-1), 117.6 (C-2), 146.2 (C-3), 145.2 (C-
4), 116.3 (C-5), 121.8 (C-6), 38.1 (C-7), 75.3 (C-8),
173.7 (C-9), 127.7 (C-1′), 115.2 (C-2′), 146.8 (C-3′),
149.7 (C-4′), 116.5 (C-5′), 123.1 (C-6′), 147.6 (C-7′),
114.6 (C-8′), 168.6 (C-9′). Compound 7 was identified
as rosmarinic acid by comparison of the physical, and
1H NMR data with the reported data[8].
Methyl rosmarinate (8)　　White powder, [α]D
25
+ 31.6° (c 0.93, in MeOH). Negative-ion mode m/z:
373.0919 [M – H]– (calcd for C19H17O8 373.0929).
1H
NMR (CD3OD, 500 MHz): δ 6.72 (1H, d, J = 2.0 Hz,
H-2), 6.70 (1H, d, J = 8.0 Hz, H-5), 6.57 (1H, dd, J =
2.0, 8.0 Hz, H-6), 3.03 (2H, m, H2-7), 5.20 (1H, dd, J =
5.0, 7.5 Hz, H-8), 3.69 (3H, s, 9-OCH3), 7.05 (1H,
d, J = 2.0 Hz, H-2′), 6.79 (1H, d, J = 8.0 Hz, H-5′),
6.95 (1H, dd, J = 2.0, 8.0 Hz, H-6′), 7.56 (1H, d, J =
16.0 Hz, H-7′), 6.26 (1H, d, J = 16.0 Hz, H-8′); 13C
NMR (CD3OD, 125 MHz): δ 128.7 (C-1), 117.5 (C-
2), 146.1 (C-3), 145.3 (C-4), 116.3 (C-5), 121.8 (C-6),
37.9 (C-7), 74.6 (C-8), 172.1 (C-9), 52.6 (9-OCH3),
127.5 (C-1′), 115.2 (C-2′), 146.7 (C-3′), 149.7 (C-4′),
116.5 (C-5′), 123.2 (C-6′), 147.9 (C-7′), 114.1 (C-8′),
168.3 (C-9′). Compound 8 was identified as methyl
rosmarinate by comparison of the physical, 1H and 13C
NMR data with the reported data[9].
Methyl benzoate-4-β-D-glucopyranoside (9)
　　White powder. Positive-ion mode m/z: 337.0911
[M + Na]+ (calcd for C14H18O8Na 337.0894).
1H
第3期 315
NMR (CD3OD, 500 MHz): δ 7.97 (2H, d, J = 9.0 Hz,
H-2,6), 7.15 (2H, d, J = 9.0 Hz, H-3,5), 3.87 (3H, s,
1-COOCH3), 5.01 (1H, d, J = 7.0 Hz, H-1′), 3.47 (2H,
m, H-2′ and 3′), 3.35 (1H, dd, J = 9.0, 9.0 Hz, H-4′),
3.48 (1H, m, H-5′), [3.71 (1H, dd, J = 5.5, 12.0 Hz),
3.91 (1H, dd, J = 2.0, 12.0 Hz), H2-6′];
13C NMR
(CD3OD, 125 MHz): δ 125.1 (C-1), 132.5 (C-2,6),
117.3 (C-3,5), 163.0 (C-4), 168.3 (1-COOCH3), 52.5
(1-COOCH3), 101.7 (C-1′), 74.8 (C-2′), 78.0 (C-3′),
71.3 (C-4′), 78.3 (C-5′), 62.5 (C-6′). Compound 9 was
identified as methyl benzoate-4-β-D-glucopyranoside
according to the 1H, 13C, and 2D-NMR experiments.
Benzyl-β-D-glucopyranoside (10)　　White
powder. Negative-ion mode m/z: 305.0768 [M + Cl]–
(calcd for C13H18O6Cl 305.0797).
1H NMR (CD3OD,
500 MHz): δ 7.42 (2H, m, H-2,6), 7.32 (2H, m, H-3,5),
7.26 (1H, m, H-4), 4.67, 4.93 (1H each, both d, J =
11.0 Hz, H2-7), 4.36 (1H, d, J = 7.5 Hz, H-1′), 3.28
(1H, dd, J = 7.5, 9.0 Hz, H-2′), 3.35 (1H, dd, J = 9.0,
9.0 Hz, H-3′), 3.31 (1H, dd, J = 9.0, 9.0 Hz, H-4′),
3.30 (1H, m, overlapped, H-5′), [3.69 (1H, dd, J = 5.5,
11.5 Hz), 3.89 (1H, dd, J = 2.0, 11.5 Hz), H2-6′];
13C
NMR (CD3OD, 125 MHz): δ 139.1 (C-1), 129.3 (C-
2,6), 129.2 (C-3,5), 128.7 (C-4), 71.8 (C-7), 103.3 (C-
1′), 75.1 (C-1′), 78.1 (C-3′), 71.7 (C-4′), 78.0 (C-5′),
62.8 (C-6′). Compound 10 was identified as benzyl-
β-D-glucopyranoside by comparison of the physical,
1H and 13C NMR data with the reported data[10] and
2D-NMR determination.
Benzyl-O-β-D-apiofuranosyl(1→2)-β-D-gluco-
pyranoside (11)　　White powder. Negative-ion mode
m/z: 401.1456 [M – H]– (calcd for C18H25O10 401.1452).
1H NMR (CD3OD, 500 MHz): δ 7.42 (2H, m, H-2,6),
7.33 (2H, m, H-3,5), 7.26 (1H, m, H-4), 4.63, 4.91
(1H each, both d, J = 11.5 Hz, H2-7), 4.42 (1H, d,
J = 7.5 Hz, H-1′), 3.42 (1H, dd, J = 7.5, 9.0 Hz,
H-2′), 3.48 (1H, dd, J = 9.0, 9.0 Hz, H-3′), 3.33 (1H,
dd, J = 9.0, 9.0 Hz, H-4′), 3.25 (1H, m, overlapped,
H-5′), [3.69 (1H, dd, J = 5.5, 12.0 Hz), 3.89 (1H, dd,
J = 2.5, 12.0 Hz), H2-6′], 5.38 (1H, d, J = 1.5 Hz, H-1′′),
3.95 (1H, d, J = 1.5 Hz, H-2′′), 3.64, 3.93 (1H each,
both d, J = 9.5 Hz, H2-4′′), 3.50, 3.57 (1H each, both
d, J = 11.5 Hz, H2-5′′);
13C NMR (CD3OD, 125 MHz):
δ 138.9 (C-1), 129.30 (C-2,6), 129.26 (C-3,5), 128.7
(C-4), 71.8 (C-7), 102.1 (C-1′), 78.9 (C-2′), 78.6 (C-
3′), 71.7 (C-4′), 77.8 (C-5′), 62.8 (C-6′), 110.6 (C-
1′′), 77.9 (C-2′′), 80.6 (C-3′′), 75.3 (C-4′′), 66.0 (C-
5′′). Compound 11 was identified as benzyl-O-β-D-
apiofuranosyl-(1→2)-β-D-glucopyranoside according
to the 1H, 13C and 2D-NMR experiments. The NMR
data of it in CD3OD was reported, firstly. And the
configurations of the glycosides were determined by
comparison of the 1H and 13C NMR data with those
of 3,4-dimethoxyphenyl-1-O-β-D-apiofuranosyl (1→
2)-β-D-glucopyranoside[11].
1,2-Di-O-β-D-glucopranosyl-4-allylbenzene (12)
　　White powder. Negative-ion mode m/z: 509.1425
[M + Cl]– (calcd for C21H30O12Cl 509.1431).
1H NMR
(CD3OD, 500 MHz): δ 7.10 (1H, d, J = 2.0 Hz, H-2),
7.17 (1H, d, J = 8.5 Hz, H-5), 6.84 (1H, dd, J = 2.0,
8.5 Hz, H-6), 3.34 (2H, m, H2-7), 5.94 (1H, m, H-8),
5.04 (2H, m, H2-9), 4.84 (1H, d, J = 8.0 Hz, H-1′),
3.49 (2H, m, H-2′ and 2′′), 3.46 (2H, m, H-3′ and 3′′),
3.41 (2H, m, H-4′ and 4′′), 3.35 (2H, m, H-5′ and 5′′),
3.71, 3.86 (2H each, both m, H2-6′ and 6′′);
13C NMR
(CD3OD, 125 MHz): δ 137.4 (C-1), 121.0 (C-2 and
5), 149.2 (C-3), 147.5 (C-4), 124.8 (C-6), 40.6 (C-7),
138.7 (C-8), 116.0 (C-9), 104.1 (C-1′), 75.1 (C-2′ and
2′′), 77.7 (C-3′ and 3′′), 71.3 (C-4′ and 4′′), 78.2 (C-5′
and 5′′), 62.4 (C-6′ and 6′′), 104.3 (C-1′′). Compound
12 was identified as 1,2-di-O-β-D-glucopranosyl-4-
allylbenzene by comparison of the physical, 1H and
13C NMR data with the reported data[12].
(+)-Syringaresinol-4′-O-β-D-glucopyranoside
(13)　　White powder. [α]D
25 –13.7° (c 0.19, in
MeOH). Negative-ion mode m/z: 579.2057 [M – H]–
(calcd for C28H35O13 579.2083).
1H NMR (CD3OD,
500 MHz): δ 6.72 (2H, s, H-2,6), 4.76 (1H, d, J =
4.0 Hz, H-7), 3.13 (2H, m, H-8,8′), 4.28 (2H, dd, J =
6.0, 9.0 Hz, Ha-9, 9′), 3.91 (2H, dd, J = 3.5, 9.0 Hz, Hb-
9,9′), 3.86 (6H, s, 3,5-OCH3), 6.65 (2H, s, H-2′,6′),
4.72 (1H, d, J = 4.5 Hz, H-7′), 3.84 (6H, s, 3′,5′-
OCH3), 4.82 (1H, d, J = 7.5 Hz, H-1′′), 3.48 (1H, dd,
J = 7.5, 9.0 Hz, H-2′′), 3.20 (1H, m, H-3′′), 3.41 (2H, m,
H-3′′ and 5′′), 4.82 ( 1H, d, J = 7.5 Hz, H-1′′), [3.67
(1H, dd, J = 5.0, 12.0 Hz), 3.77 (1H, dd, J = 2.5,
TIWALADE Adegoke Adelakun等：卢旺达产迷迭香化学成分研究 I
316 第23卷热带亚热带植物学报
12.0 Hz), H2-6′′];
13C NMR (CD3OD, 125 MHz): δ
135.7 (C-1), 104.9 (C-2,6), 154.4 (C-3,5), 139.6 (C-
4), 87.2 (C-7), 55.7 (C-8)*, 72.9 (C-9 and 9′), 57.1
(3,5-OCH3), 133.0 (C-1′), 104.6 (C-2′,6′), 149.4 (C-
3′,5′), 136.3 (C-4′), 87.6 (C-7′), 55.5 (C-8′)*, 56.8
(3′,5′-OCH3), 105.4 (C-1′′), 75.7 (C-2′′), 77.8 (C-3′′),
71.3 (C-4′′), 78.3 (C-5′′), 62.6 (C-6′′). Compound
13 was identified as (+)-syringaresinol-4′-O-β-D-
glucopyranoside by comparison of the physical, 1H
and 13C NMR data with the reported data[13]. And the
13C NMR data of 2, 6, 2′, 6′, 1′′, 7, and 7′-position [δ
105.4 (C-2,6), 104.9 (C-2′,6′), 104.6 (C-1′′), 87.6 (C-
7), 87.2 (C-7′) in reference] were corrected according
to the 2D NMR experiments. On the other hand, the data
of C-8 and C-8′ could be exchanged with each other.
2 Discussion
In the course of our studies on the constituents
of this plant by using chromatographies such as D101
resin, silica gel, ODS, Sephadex LH-20 and HPLC
column chromatogaraphies, 13 compounds were
isolated from its aerial parts, including phenolic acids,
phenylpropyl glycosides, including (Z)-3-hexenyl
glucoside (1), (Z)-3-hexenyl O-β-D-glucopyranosyl-
(1′′→6′)-β-D-glucopyranoside (2), erythritol-1-O-(6-O-
trans-caffeoyl)-β-D-glucopyranoside (3), 2,3,4,5-tetrahy-
droxyhexyl-6-O-trans-caffeoyl-β-glucopyranoside (4),
1,2,3,4-tetrahydroxy-2-methyl-butane-4-O-(6-O-trans-
caffeoyl)-β-D-glucopyranoside (5), caffeic acid (6),
rosmarinic acid (7), methyl rosmarinate (8), methyl
benzoate-4-β-glucoside (9), benzyl-β-D-glucopyranoside
(10), benzyl-O-β-D-apiofuranosyl-(1→2)-β-D-gluco-
pyranoside (11), 1,2-di-O-β-D-glucopranosyl-4-allyl-
benzene (12) and (+)-syringaresinol-4′-O-β-D-gluco-
pyranoside (13). Among them, Compounds 1–5, 8–13
were isolated from the Rosmarinus genus firstly. For
the known ones, the NMR data of 13 were corrected.
Nowadays, various pharmacological activities,
such as hepatoprotective, antibacterial, antithrombotic,
antiulcerogenic, anti-inflammatory, and antioxidant
were found for R. officinalis. This is closely related
to its containing phenolic compounds. The result will
provide bases for further studies in R. officinalis.
References
[1]　 Borrás L I, Arráez-Román D, Herrero M, et al. Comparison of
different extraction procedures for the comprehensive characterization
of bioactive phenolic compounds in Rosmarinus officinalis by
reversed-phase high-performance liquid chromatography with
diode array detection coupled to electrospray time-of-flight mass
spectrometry [J]. J Chromatogr A, 2011, 1218(42): 7682–7690.
[2]　 Escop M. The Scientific Foundation for Herbal Medicinal Products
[M]. German: Thieme Medical Publishers (German Medical and
Science Publisher in the Thieme Publishing Group), 2003: 429–
436.
[3]　 Cuvelier M E, Berset C, Richard H. Antioxidant constituents in
sage (Salvia officinalis) [J]. J Agric Food Chem, 1994, 42(3):
665–669.
[4]　 Miyase T, Ueno A, Takizawa N, et al. Studies on the glycosides of
Epimedium grandiflorum Morr. var. thunbergianum (Miq.) Nakai.
III [J]. Chem Pharm Bull, 1988, 36(7): 2475–2484.
[5]　 Song S J, Li L Z, Gao P Y, et al. Terpenoids and hexenes from the
leaves of Crataegus pinnatifida [J]. Food Chem, 2011, 129(3):
933–939.
[6]　 Matsuda N, Kikuchi M. Studies on the constituents of Lonicera
species. VII. Three new polyhydric alcohol glycosides from the
leaves of Lonicera gracilipes var. glandulosa Maxim. [J]. Chem
Pharm Bull, 1995, 43(6): 1049–1051.
[7]　 Zhao X H, Chen D H, Si J Y, et al. Studies on the phenolic acid
constituents from Chinese medicine “Sheng-Ma”, rhizome of
Cimicifuga foetida L. [J]. Acta Pharm Sin, 2002, 37(7): 535–538.
[8]　 Fukui H, Yazaki K, Tabata M. Two phenolic acids from Litho-
spermum erythrorhizon cell suspension cultures [J]. Phytochemistry,
1984, 23(10): 2398–2399.
[9]　 Kuo Y H, Lee S M, Lai J S. Constituents of the whole herb of
Clinoponium laxiflorum [J]. J Chin Chem Soc (Taipei), 2000,
47(1): 241–246.
[10]　 De Rosa S, De Gliulio A, Tommonaro G. Aliphatic and aromatic
glycosides from the cell cultures of Lycopersicon esculentum [J].
Phytochemistry, 1996, 42(4): 1031–1034.
[11]　 Ferrari F, Monache F D. A new phenolic glycoside from Sorocea
ilicifolia stem bark [J]. Fitoterapia, 2004, 75(3): 417–419.
[12]　 Ly T N, Yamauchi R, Shimoyamada M, et al. Isolation and
structural elucidation of some glycosides from the rhizomes of
smaller galanga (Alpinia officinarum Hance) [J]. J Agric Food
Chem, 2002, 50(17): 4919–4924.
[13]　 Yan L H, Xu L Z, Lin J, et al. Studies on lignan constituents of
Clematis parviloba [J]. China J Chin Mat Med, 2008, 33(15):
1839–1843. (in Chinese)