Water-soluble constituents of coriander.

Article abstract of DOI:10.1248/cpb.51.32

From the water-soluble portion of the methanol extract of coriander (fruit of Coriandrum sativum L.), which has been used as a spice and medicine since antiquity, 33 compounds, including two new monoterpenoids, four new monoterpenoid glycosides, two new monoterpenoid glucoside sulfates and two new aromatic compound glycosides were obtained. Their structures, were clarified by spectral investigation.

Full text of DOI:10.1248/cpb.51.32

32
Chem. Pharm. Bull. 51(1) 32—39 (2003)
Vol. 51, No. 1
Water-Soluble Constituents of Coriander
Toru ISHIKAWA, Kyoko KONDO, and Junichi KITAJIMA*
Showa Pharmaceutical University; 3 Higashi-Tamagawagakuen, Machida, Tokyo 194–8543, Japan.
Received July 26, 2002; accepted October 2, 2002
From the water-soluble portion of the methanol extract of coriander (fruit of Coriandrum sativum L.), which
has been used as a spice and medicine since antiquity, 33 compounds, including two new monoterpenoids, four
new monoterpenoid glycosides, two new monoterpenoid glucoside sulfates and two new aromatic compound gly-
cosides were obtained. Their structures, were clarified by spectral investigation.
Key words coriander; Coriandrum sativum fruit; hydroxylinalool; monoterpenoid glycoside; phenylpropanoid glycoside
Coriander (Coriandrum sativum L.; Umbelliferae) is in-
Monoterpenoid glucoside 1 (C H O , an amorphous
16 28 7
2
1
digenous to the Mediterranean region and is now widely cul- powder, [a] ꢀ20°) was identified as (3S,6E)-8-hydroxyli-
D
tivated as a spice. Its culinary and medical uses have been nalool 3-O-b-D-glucopyranoside by comparison with pub-
8)
documented for over 3000 years (Ebers papyrus of 1550 lished data.
BC), it is an essential ingredient in curry powder, and is used
Monoterpenoid glycoside 2 (C H KO S, an amorphous
16 27 10
ꢁ ꢁ
1)
21
in minced meat dishes, sausages, and stews. The fruit is powder, [a] ꢀ12°) showed [2MꢁH] , [MꢁK] , [Mꢁ
D
ꢁ
ꢁ
listed in the British, German, and European pharma- Na] , and [MꢁH] ion peaks at m/z 901, 489, 473, and 451
2
,3)
ꢀ
ꢀ
copoeias
and has been used as a drug for indigestion, in the positive FAB-MS, and [2MꢀK] , [MꢀH] , and
ꢀ
against worms, and as a component of embrocations for [MꢀK] ion peaks at m/z 861, 449, and 411 in the negative
rheumatism and pains in the joints. It contains an essential FAB-MS. Enzymatic hydrolysis of 2 gave (3S,6E)-8-hydrox-
4)
9)
oil (up to 1%) constituted of (3S)-linalool (main, 60—70%), ylinalool (1a) as an aglycone, and the presence of a potas-
other monoterpenoids (citronellol, geraniol, myrcene, a- and sium sulfate group in 2 was suggested by a positive result in
10,11)
g-terpinene, limonene, a- and b-phellandrene, p-cymene, a- the potassium rhodizonate test.
From a comparison of its
H- and C-NMR data with those of 1 (Tables 1, 2), 2 was
oleic, linolenic, and palmitic acids etc.). However, to the concluded to be the potassium sulfate of 1, and the position
1
13
and b-pinene (ꢀ)-borneol, and camphor), and fatty acids
4)
(
best of our knowledge no report has been published on the of the sulfate group was revealed to be C-3 of the glucose
constituents of the water-soluble portion of this fruit. In a moiety by the downfield shift of H-3 (by 1.0 ppm) and C-3
continuation of our studies on the water-soluble constituents (by 6.3 ppm) signals and the upfield shift of C-2 (by 2.0 ppm)
5)
of spices, and to show the relationship between the essential and C-4 (by 1.6 ppm) signals of the glucosyl moiety. From
oil and the water-soluble constituent, we undertook a detailed these results, 2 was determined to be (3S,6E)-8-hydroxyli-
investigation of this fruit. In this paper, we discuss the isola- nalool 3-O-b-D-(3-O-potassium sulfo)glucopyranoside.
tion and structure elucidation of monoterpenoid alcohols and
its glucosides, norcarotenoid glucosides, an aromatic com- powder, [a] ꢀ8°) showed an [MꢁH] ion peak at m/z 335
pound and its glycosides, alkyl glucosides, glucides, uracil, and an [MꢀC H O ꢁH] ion peak at m/z 155 in the posi-
Monoterpenoid glucoside 3 (C H O , an amorphous
16 30 7
ꢁ
2
1
D
ꢁ
6
12
6
and nucleosides.
tive FAB-MS. Enzymatic hydrolysis of 3 gave an aglycone
2
1
Commercial coriander was extracted with 70% methanol, (3a; C H O , an amorphous powder, [a] ꢁ5°) and D-glu-
1
0
20
2
D
and the methanolic extract was suspended in water and suc- cose. Although 3 showed one peak in HPLC, this was sug-
cessively extracted with ether and ethyl acetate. The aqueous gested to be a mixture of two isomeric compounds in a ratio
layer was chromatographed on Amberlite XAD-II to give of 2 : 1 from the NMR data of 3 and 3a (Tables 1, 2). From a
1
13
water and methanol eluate fractions. The methanol eluate comparison of its H- and C-NMR data with those of 1 and
fraction was chromatographed on Sephadex LH-20 and then analysis of the heteronuclear multiple bond connectivity
subjected to a combination of silica gel, Lobar RP-8 column (HMBC) spectrum (see Experimental), the planar structure
chromatography, and HPLC to separate two monoterpenoid of the aglycone of 3 was suggested to be 8-hydroxy-6,7-dihy-
triols (4, 5), seven monoterpenoid glycosides (1 to 3, 6 to 9), drolinalool, and the position of the glucosyl unit was found
12)
three norcarotenoid glucosides (10 to 12), an aromatic com- to be C-3 of the aglycone. In our previous paper, we re-
pound (17), seven aromatic compound glycosides (13 to 16, ported the isolation of (6E)-8-hydroxylinalool 3-O-b-D-glu-
1
3
2
8 to 20), two alkyl glucosides (21, 22), eight glucides (23 to copyranoside (34) which gave an aglycone with negative op-
2
1
0), uracil (31), and two nucleosides (32, 33). Among them, tical rotation (34a; [a] ꢀ12°) contrary to that of 1 (1a;
D
2
1
to 9, 18, and 19 are new. All new glucosides described in [a] ꢁ16°), and 34 was found to have the 3R configuration.
D
1
this paper were b-D-glucopyranosides as shown by their H- Thus the absolute configuration at C-3 of 3 was indicated to
and C-NMR data (Tables 1, 2), which was confirmed by hy- be S. As the glycosylation shift values of C-2, C-3, C-4, and
drolysis yielding D-glucose and/or the comparison of the C-10 of 3 showed identical values to those of 1 which has the
1
3
6,7)
[M] values with those of their aglycones. Their molecular 3S configuration [C-2 (3, ꢀ2.6; 1, ꢀ2.5), C-3 (3, ꢁ7.8; 1,
D
formulae were suggested from the accurate mass number of ꢁ7.7), C-4 (3, ꢀ1.1; 1, ꢀ1.1), C-10 (3, ꢀ5.0 and ꢀ4.9; 1,
ꢁ
ꢁ
ꢁ
the [MꢁH] or [MꢁNa] or [MꢁK] ion peak in the high- ꢀ4.9)], and the glycosylation shift values of C-4 and C-10 of
resolution positive FAB-MS. 3 showed an obvious difference between the values of 34
∗
To whom correspondence should be addressed. e-mail: Kitajima@ac.shoyaku.ac.jp
© 2003 Pharmaceutical Society of Japan

January 2003
33
2
1
which has the 3R configuration [C-4 (3, ꢀ1.1; 34, ꢀ2.4), C- ꢀ27°) and 7 (C H O , an amorphous powder, [a] ꢁ6°)
1
6
30
8
D
1
13
1
0 (3, ꢀ5.0 and ꢀ4.9; 34, ꢀ4.3)], the absolute configuration also showed similar H- and C-NMR spectral features (Ta-
ꢁ ꢁ
6
at C-3 of 3 was concluded to be S. Therfore, 3 was character- bles 1, 2) and revealed [MꢁH] and [MꢀC H O ꢁH] ion
12
6
ized as an epimeric mixture of (3S)-8-hydroxy-6,7-dihydroli- peaks at m/z 351 and 171, respectively, in the positive FAB-
nalool 3-O-b-D-glucopyranoside at C-7. MS. Both glucosides were hydrolyzed with hesperidinase
Monoterpenoid triols 4 (C H O , an amorphous powder, and 4 and D-glucose from 6, and 5 and D-glucose from 7
1
0
20
3
2
1
21
D
[
ꢁ
a] ꢀ15°) and 5 (C H O , an amorphous powder, [a]
were obtained from the hydrolyzed mixtures. Consequently, 6
D
10 20
3
ꢁ
24°) showed [MꢁH] ion peaks at m/z 189 in the positive and 7 are monoglucosides of 4 and 5. The position of the b-
1 13
FAB-MS. They revealed similar H- and C-NMR spectral glucosyl unit of both glucosides was confirmed to be C-3
features (Tables 1, 2) and have three tert-methyls, two meth- from the HMBC correlation of glucosyl H-1/C-3 in the
ylenes, one oxygenated methine, two oxygenated quaternary HMBC spectrum of 6. Previously, we reported the isolation
carbons, and one vinyl group. From the results of the HMBC of 6,7-dihydroxy-6,7-dihydrolinalool 3-O-b-D-glucopyra-
experiment of 4 (see Experimental), they were suggested to noside (35), which has the same planar structure as 6 and
13)
23
D
be 6,7-dihydroxy-6,7-dihydrolinalool, respectively. Monoter- 7. Glucoside 35 gave an aglycone (35a; [a] ꢀ22°),
2
1
1
13
penoid glucoside 6 (C H O , an amorphous powder, [a]
which had identical H- and C-NMR spectra and the oppo-
1
6
30
8
D
1
Table 1. H-NMR Chemical Shifts of 1—9, 1a, and 9a (in Pyridine-d , 500 MHz)
5
1
1a
2
3
H-1a
b
H-2
5.22 1H, dd (1.5, 11.0)
5.39 1H, dd (1.5, 17.5)
6.30 1H, dd (11.0, 17.5)
1.81 2H, m
5.17 1H, dd (2.0, 11.0)
5.58 1H, dd (2.0, 17.0)
6.18 1H, dd (11.0, 17.0)
1.81 2H, m
5.25 1H, br d (11.0)
5.35 1H, br d (17.5)
6.24 1H, dd (11.0, 17.5)
1.76 2H, m
5.20 1H, dd (1.5, 11.0)
5.37 1H, dd (1.5, 17.5)
6.28 1H, dd (11.0, 17.5)
1.74 2H, m
H -4
2
H -5
H-6a
b
2.36 2H, m
5.69 1H, dd (7.0, 7.0)
—
2.45 2H, m
5.78 1H, dd (7.0, 7.0)
—
2.30 2H, m
5.65 1H, dd (7.0, 7.0)
—
1.60—1.71 2H, m
1.19 1H, m
1.61 1H, m
2
H-7
—
—
—
1.78 1H, m
H -8
4.27 2H, br s
—
1.76 3H, s
4.31 2H, d (5.0)
—
1.81 3H, s
1.48 3H, s
—
4.26 2H, br s
—
1.75 3H, s
1.51 3H, s
4.91 1H, d (8.0)
5.24 1H, dd (8.0, 8.0)
3.63 1H, dd (7.0, 9.5)
3.72 1H, dd (7.0, 9.5)
1.028 3H, d (7.0) [1.033 3H, d (7.0)]
1.58 3H, s
4.99 1H, d (7.5)
4.24 1H, dd (8.0, 8.0)
2
H -9
3
H -10 1.59 3H, s
3
Glc H-1 4.98 1H, d (7.5)
Glc H-3 4.24 1H, dd (8.0, 8.0)
—
4
5
6
7
H-1a
b
5.13 1H, dd (2.0, 11.0)
5.59 1H, dd (2.0, 17.5)
5.14 1H, dd (2.0, 10.5)
5.59 1H, dd (2.0, 17.0)
5.16 1H, br d (11.0)
5.39 1H, br d (17.5)
5.16 1H, dd (2.0, 11.0)
5.41 1H, dd (2.0, 17.5)
H-2
H-4a
b
6.21 1H, dd (11.0, 17.5)
1.97 1H, ddd (3.5, 13.0, 13.0)
2.43 1H, ddd (3.5, 13.0, 13.0)
6.21 1H, dd (10.5, 17.0)
1.99 1H, ddd (4.5, 13.0, 13.0)
2.42 1H, ddd (4.5, 13.0, 13.0)
6.33 1H, dd (11.0, 17.5)
1.99 1H, ddd (3.5, 13.0, 13.0)
2.51 1H, ddd (3.5, 13.0, 13.0)
6.30 1H, dd (11.0, 17.5)
1.90 1H, ddd (4.0, 13.0, 13.0)
2.56 1H, ddd (4.0, 13.0, 13.0)
H-5a
b
1.94 1H, dddd (3.5, 9.5, 13.0, 13.0) 1.94 1H, dddd (4.5, 10.0, 13.0, 13.0) 1.92 1H, dddd (3.5, 8.5, 13.0, 13,0) 2.04 1H, dddd (4.0, 9.5, 13.0, 13,0)
2.20 1H, dddd (2.0, 3.5, 13.0, 13.0) 2.20 1H, dddd (2.0, 4.5, 13.0, 13.0) 2.28 1H, dddd (3.5, 6.0, 13.0, 13.0) 2.20 1H, dddd (4.0, 4.0, 13.0, 13.0)
H-6
3.79 1H, dd (2.0, 9.5)
3.78 1H, dd (2.0, 10.0)
3.77 1H, dd (6.0, 8.5)
3.73 1H, dd (4.0, 9.5)
a)
a)
a)
a)
H -8
1.48 3H, s
1.50 3H, s
1.46 3H, s
1.46 3H, s
3
a)
a)
a)
a)
H -9
1.51 3H, s
1.51 3H, s
1.50 3H, s
1.49 3H, s
3
H -10 1.51 3H, s
1.48 3H, s
1.62 3H, s
1.62 3H, s
3
Glc H-1 —
Glc H-3 —
—
—
5.04 1H, d (8.0)
4.22 1H, dd (8.0, 8.0)
5.06 1H, d (8.5)
4.24 1H, dd (8.0, 8.0)
8
9
9a
H-1a
b
H-2
H-4a
b
H-5a
b
H-6
5.15 1H, dd (1.5, 11.0)
5.36 1H, dd (1.5, 17.5)
6.29 1H, dd (11.0, 17.5)
H-3endo
exo
H-4
H-5endo
exo
H-6exo
2.02 1H, br d (18.0)
1.98 1H, br d (18.0)
2.32 1H, ddd (4.0, 4.0, 18.0)
1.92 1H, br dd (4.0, 4.0)
1.92 1H, br dd (4.0, 13.5)
2.67 1H, dddd (4.0, 4.0, 9.0, 13.5) 2.49 1H, dddd (3.5, 4.5, 10.0, 14.0)
4.37 1H, br d (9.0)
0.85 3H, s
0.68 3H, s
1.20 3H, s
4.78 1H, d (7.5)
5.81 1H, d (2.5)
2.33 1H, ddd (3.5, 4.5, 18.0)
1.90 1H, br dd (4.5, 4.5)
1.85 1H, br dd (3.0, 14.0)
1.91 1H, ddd (3.5, 13.0, 13.0)
2.51 1H, ddd (3.5, 13.0, 13.0)
1.99 1H, dddd (3.5, 8.5, 13.0, 13.0)
2.20 1H, dddd (3.5, 8.5, 13.0, 13.0)
3.74 1H, dd (3.5, 8.5)
4.39 1H, dd (3.0, 10.0)
0.82 3H, s
0.70 3H, s
1.22 3H, s
4.84 1H, d (8.0)
—
H -8
3
H -9
3
a)
H -8
1.46 3H, s
H -10
3
3
a)
H -9
1.48 3H, s
Glc H-1
Api H-1
3
H -10 1.53 3H, s
3
Glc H-1 5.00 1H, d (7.5)
Glc H-3 5.26 1H, dd (9.0, 9.0)
d in ppm from TMS [coupling constants (J) in Hz are given in parentheses]. Minor stereoisomeric components are given in brackets. a) Assignments may be interchanged
in each column.

34
Vol. 51, No. 1
site optical rotation to 5. Consequently, 5 and 35a were both (3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool 3-O-b-D-glucopy-
enantiomers. The absolute configuration at C-3 of 4 to 7 was ranoside, respectively.
determined by comparison of the glycosylation shift values
Monoterpenoid glycoside 8 (C H KO S, an amorphous
16 29 11
ꢁ ꢁ
2
2
of the a- and b-carbon between 1, 3, 6, 7, 34, and 35. The powder, [a] ꢀ14°) showed [MꢁK] and [MꢁNa] ion
D
glycosylation shift values of C-2, C-3, C-4, and C-10 of 6 peaks at m/z 507 and 491 in the positive FAB-MS, and
ꢀ
ꢀ
and 7 showed identical values to those of 1 which has the 3S [MꢀH] and [MꢀK] ion peaks at m/z 467 and 429 in the
configuration (Table 2), and the glycosylation shift values of negative FAB-MS. Enzymatic hydrolysis of 8 gave 5 as an
C-4 of 6 and 7 showed an obvious difference between the aglycone, and the presence of a potassium sulfate group in
values of 34 and 35 which have the 3R configuration (6, 8 was suggested in the same manner as in 2. From a compari-
15)
1
13
ꢀ
1.6; 7, ꢀ1.3; 34, ꢀ2.4; 35, ꢀ3.7). Then the absolute con- son of its H- and C-NMR data with those of 2 and 7 (Ta-
figuration at C-3 of 4 to 7 was concluded to be S. It has been bles 1, 2), 8 was suggested to be (3S,6R)-6,7-dihydroxy-6,7-
reported that the (3R,6R)- and (3R,6S)-forms of 6,7-dihy- dihydrolinalool 3-O-b-D-(3-O-potassium sulfo)glucopyra-
2
0
droxy-6,7-dihydrolinalool show positive {[a]
ꢁ25.5° noside.
D
2
0
(
CHCl )} and negative {[a] ꢀ15.9° (CHCl )} optical rota-
Monoterpenoid glycoside 9 (C H O , an amorphous
21 34 11
ꢁ
3
D
3
14)
21
tion, respectively. Because 4 and 5 showed negative and powder, [a]D ꢀ73°) showed an [MꢁH] ion peak at m/z
ꢁ
ꢁ
positive optical rotations, respectively, 4 and 5 should be the 463, and [MꢀC H O ꢁH] and [MꢀC H O ꢁH] ion
5
8
4
11 20 10
1
(
3S,6S)- and (3S,6R)-forms. Therefore 4, 5, 6, and 7 were peaks at m/z 331 and 151 in the positive FAB-MS. The H-
characterized as (3S,6S)-6,7-dihydroxy-6,7-dihydrolinalool, and C-NMR spectral data (Tables 1, 2) showed the presence
1
3
16)
(
3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool, (3S,6S)-6,7-dihy- of one b-apiofuranosyl-(1→6)-b-glucopyranosyl,
three
droxy-6,7-dihydrolinalool 3-O-b-D-glucopyranoside, and tert-methyls, two methylenes, two methines (one of which
13
Table 2.
C-NMR Chemical Shifts of 1—9, 1a, 3a, and 9a (in Pyridine-d , 125 MHz)
5
1
2
1a
3
3a
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
114.79
115.11
111.27
147.04
72.32
43.11
22.95
125.11
136.24
68.11
13.88
28.45
114.62
[114.59]
111.04 [111.01]
147.37 [147.42]
72.46 [ 72.45]
43.73 [ 43.71]
22.09 [ 22.07]
34.50 [ 34.50]
36.70 [ 36.70]
67.61 [ 67.59]
17.34 [ 17.37]
28.48 [ 28.38]
144.50 (ꢀ2.5)
79.99 (ꢁ7.7)
41.97 (ꢀ1.1)
22.62
124.88
136.36
68.08
13.94
23.58 (ꢀ4.9)
99.79
75.38
143.97 (ꢀ3.1)
80.22 (ꢁ7.9)
41.89 (ꢀ1.2)
22.49
124.78
136.28
68.01
13.87
23.44 (ꢀ5.0)
99.10
73.59
144.80 (ꢀ2.6) [144.80] (ꢀ2.6)
80.24 (ꢁ7.8) [ 80.24] (ꢁ7.8)
42.67 (ꢀ1.1) [ 42.61] (ꢀ1.1)
21.73
34.34
36.54
67.53
17.36
[ 21.79]
[ 34.34]
[ 36.54]
[ 67.48]
[ 17.40]
C-9
C-10
Glc-1
Glc-2
Glc-3
Glc-4
Glc-5
Glc-6
23.48 (ꢀ5.0) [ 23.48] (ꢀ4.9)
99.60
75.38
78.88
71.77
78.20
62.89
[ 99.60]
[ 75.38]
[ 78.88]
[ 71.77]
[ 78.20]
[ 62.89]
78.85
71.83
78.11
62.96
85.12
70.23
77.13
62.20
4
5
6
7
8
9
9a
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
111.11
147.44
72.60
41.17
27.03
79.65
72.77
25.87
26.16
28.75
111.19
147.49
72.58
41.14
26.91
79.78
72.78
25.92
26.07
28.67
114.25
144.91 (ꢀ2.5)
80.33 (ꢁ7.7)
39.59 (ꢀ1.6)
26.55
79.53
72.82
25.67
26.44
24.18 (ꢀ4.6)
99.60
75.38
78.88
71.77
104.06
114.19
63.36
215.19
43.50
41.88
37.10
84.63
47.76
19.86
20.22
8.28
106.41
75.03
78.44
71.63
77.24
68.87
111.13
77.88
80.51
75.05
65.65
63.42
215.39
43.49
41.83
36.90
84.60
47.85
19.82
20.20
8.31
106.48
75.23
78.42
71.44
78.52
62.85
145.09 (ꢀ2.4)
80.21 (ꢁ7.6)
39.80 (ꢀ1.3)
26.54
79.61
72.81
25.99
25.99
24.30 (ꢀ4.4)
99.59
75.40
144.73 (ꢀ2.8)
80.30 (ꢁ7.7)
38.68 (ꢀ2.5)
26.16
79.34
72.86
26.01
26.38
24.50 (ꢀ4.2)
99.02
73.47
a)
a)
a)
a)
a)
a)
a)
a)
C-9
C-10
Glc-1
Glc-2
Glc-3
Glc-4
Glc-5
Glc-6
Api-1
Api-2
Api-3
Api-4
Api-5
78.86
71.93
78.44
63.18
84.08
70.33
77.53
62.35
78.20
62.89
d in ppm from TMS. Dd (d glucosideꢀd aglycone) are given in parentheses. Minor stereoisomeric components are given in brackets. a) Assignments may be interchanged
in each column.

January 2003
35
1
Table 3. H-NMR Chemical Shifts of 17—19 and 19a (in Pyridine-d , 500 MHz)
5
1
7
18
19
7.04 1H, s
—
—
7.04 1H, s
4.87 1H, dd (6.0, 7.0)
1.96 2H, m
—
1.11 3H, t (7.0)
3.78 6H, s
5.75 1H, d (7.0)
19a
7.08 1H, s
—
—
7.08 1H, s
4.91 1H, dd (6.5, 6.5)
2.04 2H, m
—
1.15 3H, t (7.0)
3.81 6H, s
—
H-2
H-3
H-5
H-6
H-1ꢃ
7.70 1H, d (8.5)
7.25 1H, d (8.5)
7.25 1H, d (8.5)
7.70 1H, d (8.5)
5.28 1H, t (6.0)
4.20 2H, br d (6.0)
7.59 1H, d (8.0)
7.20 1H, d (8.0)
7.20 1H, d (8.0)
7.59 1H, d (8.0)
5.33 1H, dd (3.0, 8.5)
4.05 1H, dd (8.5, 10.5)
4.41 1H, dd (3.0, 10.5)
—
H -2ꢃ
2
—
—
—
—
—
H -3ꢃ
3
3,5-OCH3
—
Glc H-1
Api H-1
5.01 1H, d (7.5)
5.77 1H, d (2.5)
1
3
was oxygenated), two quaternary carbons, and one carbonyl Table 4. C-NMR Chemical Shifts of 17—19 and 19a (in Pyridine-d5,
125 MHz)
group. From the analysis of HMBC spectral data (see Experi-
mental), 9 was suggested to be a glycoside of 6-hydroxycam-
phor, and partial hydrolysis of 9 with 0.5 N H SO afforded
1
7
18
133.35
128.39
116.06
158.28
73.31 (ꢀ1.9)
77.20 (ꢁ7.8)
19
19a
2
4
(
1R,4S,6S)-6-hydroxycamphor b-D-glucopyranoside (9a,
C-1
134.85
128.40
116.00
158.17
75.25
143.46 (ꢁ5.9)
104.80
153.61 (ꢁ4.6)
134.90 (ꢀ1.6)
75.08
137.52
104.51
149.04
136.47
75.38
2
3
C H O , an amorphous powder, [a] ꢀ66°), which was re-
ported to be a biotransformation product from a cell suspen-
sion culture of Eucalyptus prerriniana following administra-
C-2,6
C-3,5
C-4
C-1ꢃ
C-2ꢃ
C-3ꢃ
1
6
26
7
D
17)
tion of (ꢁ)-camphor and apiose. By comparison of the
M] value between 9 and 9a ([M] value of 9ꢀ[M] value
69.41
33.18
33.33
[
10.81
10.92
D
D
D
6
,7,18)
of 9aꢂꢀ119°),
apiose was confirmed to be the D-form.
3,5-OCH
56.57
56.35
3
Glc-1
Glc-2
Glc-3
Glc-4
Glc-5
Glc-6
Api-1
Api-2
Api-3
Api-4
Api-5
105.53
75.26
78.47
71.76
77.18
68.91
111.13
77.79
80.45
75.04
65.56
105.25
76.10
78.37
71.58
78.67
62.61
Therefore 9 was characterized as (1R,4S,6S)-6-hydroxycam-
phor b-D-apiofuranosyl-(1→6)-b-D-glucopyranoside.
Norcarotenoid glucosides 10 (C H O , an amorphous
1
9
30
8
2
3
powder, [a] ꢀ117°), 11 (C H O , an amorphous powder,
D
19 30
8
2
3
25
[
a] ꢀ51°), 12 (C H O , mp 173—174 °C, [a] ꢀ100°),
D
19 30 18
D
aromatic compound glycosides 13 (C H O , mp 120—
1
3
8
6
2
1
21
D
1
ꢀ
(
21 °C, [a] ꢀ53°), 14 (C H O , mp 133—135 °C, [a]
D
18 26 10
2
D
3
98°), 15 (C H O , mp 232—234 °C, [a] ꢀ21°), 16
1
4
20
9
21
D
C H O , mp 175—177 °C, [a] ꢀ21°) and 20 (C H O ,
1
5
22
9
19 28 10
25
an amorphous powder, [a] ꢀ86°) were identified as citro-
D
d in ppm from TMS [coupling constants (J) in Hz are given in parentheses]. Dd (d
glucosideꢀd aglycone) are given in parentheses.
1
9)
19)
20)
side A, citroside B, and icariside B , benzyl b-D-glu-
2
2
1)
21,22)
23)
copyranoside, icariside F2,
leonuriside A, 4-hydroxy-
21)
3
,5-dimethoxybenzyl alcohol 4-O-b-D-glucopyranoside,
22)
1
13
and icariside D , respectively, by comparison with authen- FAB-MS. The H- and C-NMR data for 19 (Tables 3, 4)
1
tic compounds or published physical and spectral data.
showed the presence of one b-glucopyranosyl, one 1,2,4,5-
2
4
Aromatic compound 17 (C H O , mp 128—132 °C, [a]
tetrasubstituted benzene, one ethyl group, one hydroxylated
8
10
3
D
ꢁ
10°) was identified as 1ꢃ-(4-hydroxyphenyl)ethane-1ꢃ,2ꢃ- methine, and two methoxyl groups. Enzymatic hydrolysis of
diol, which was reported to be isolated from whole plants of 19 gave an aglycone (19a; C H O , an amorphous powder,
1
1
16
4
2
4)
22
D
C. sativum. Aromatic compound glycosides 18 (C H O , [a] ꢁ5°) and D-glucose. From the analysis of the HMBC
1
9
28 12
2
2
an amorphous powder, [a] ꢀ38°) gave 17, D-glucose, anꢁd spectrum (see Experimental), the aglycone of 19 was indi-
D
D-apiose upon enzymatic hydrolysis and showed an [MꢁH]
cated to be 1ꢃ-(4-hydroxy-3,5-dimethoxyphenyl)propan-1ꢃ-
ion peak at m/z 449 in the positive FAB-MS. Glycoside 18 ol, and the position of the glucosyl unit was C-4. As 19a
was suggested to be a b-apiofuranosyl-(1→6)-b-glucopyra- showed a positive optical rotation value that was the same as
1
13
26,27)
noside of 17 based on the H- and C-NMR spectral data that of (1R)-1-phenyl-1-propanol,
the absolute configura-
(
Tables 1, 2), and the position of the sugar unit was indicated tion at C-1ꢃ of 19 was suggested to be R. Therefore 19 was
to be C-2ꢃ by the HMBC correlation of glucosyl H-1/C-2ꢃ in represented as (1ꢃR)-1ꢃ-(4-hydroxy-3,5-dimethoxyl)propan-
the HMBC spectrum. Thus 18 was characterized as 1ꢃ-(4-hy- 1ꢃ-ol 4-O-b-D-glucopyranoside.
2
1
droxyphenyl)ethane-1ꢃ,2ꢃ-diol 2ꢃ-O-b-D-apiofuranosyl-(1→
Alkyl glucosides 21 (an amorphous powder, [a] ꢀ8°)
D
21
6
)-b-D-glucopyranoside. As 17 showed a positive optical ro- and 22 (an amorphous powder, [a] ꢀ20°), glucides 23 (an
D
2
1
tation value that was the same as that of synthetic (1ꢃS)-1ꢃ- amorphous powder, [a] ꢀ7°), 24 (an amorphous powder,
D
25)
21
D
21
D
phenylethane-1ꢃ,2ꢃ-diol, the absolute configuration at C-1ꢃ [a] ꢀ72°), 25 [an amorphous powder, [a] ꢄ0° (H O)],
2
2
2
of 17 and 18 was considered to be S.
Aromatic compound glycoside 19 (C H O , an amor- syrup, [a] ꢀ93° (H O)], 28 (a colorless syrup, [a]
26 [mp 168—169 °C, [a] ꢀ30° (pyridine)], 27 [a colorless
D
2
2
22
D
1
7
26
9
D
2
2
3
ꢁ
22
D
phous powder, [a] ꢀ10°) showed [MꢁK] and [Mꢀ ꢀ33°), 29 [mp 80—83 °C, [a] ꢁ49° (H O)], and 30 [an
D
2
ꢁ
22
C H O ꢁH] ion peaks at m/z 413 and 195 in the positive amorphous powder, [a]D ꢁ66° (H O)], and nucleosides 32
6
12
6
2

36
Vol. 51, No. 1
Fig. 1. Structures of 1—9
Fig. 2. Structures of 10—20
2
3
(
[
1
mp 164—166 °C, [a] ꢁ4°) and 33 [mp 233—235 °C,
D
21
a] ꢀ62° (H O)] were identified as (2S)-propane-1,2-diol
D
2
28)
-O-b-D-glucopyranoside,
butane-2,3-diol 2-O-b-D-glu-
2
8)
29)
copyranoside, D-arabinitol, methyl a-L-arabinofuranoside,
glycerol, D-mannitol, D-fructose, methyl b-D-fructofura-
30)
noside, D-glucose, sucrose, uridine, and adenosine, respec-
tively.
The ingredient relationship between the essential oil and
the water-soluble constituent was confirmed by the isolation
of glucosides of (3S)-linalool derivatives from the polar frac-
tions.
Experimental
Fig. 3. Structures of 21—23 and 31—33
Melting points were determined on a Yanagimoto micromelting point ap-
paratus and are uncorrected. Optical rotations were measured on a JASCO
DIP-370 digital polarimeter. FAB-MS were recorded with a JEOL HX-110
spectrometer using glycerol as matrix. H- and C-NMR spectra were column (Merck), and Amberlite XAD-II (Organo). TLC was performed on
recorded on JEOL A-500 spectrometers with tetramethylsilane as an internal
silica gel (Merck 5721), and spots were detected with p-anisalde-
1
13
standard, and chemical shifts were recorded in d values. Column chromatog- hyde–H SO reagent. HPLC separation was carried out on Symmetryprep
2
4
raphy was carried out under TLC monitoring using Kieselgel 60 (70—230
mesh, Merck), Sephadex LH-20 (25—100 mm, Pharmacia), a Lobar RP-8
C18 7 mm [Waters, column size, 7.8ꢅ300 mm, ODS] and carbohydrate
analysis [Waters; column size 3.9ꢅ300 mm, CHA] columns. Acetylation

January 2003
37
was done in the usual way using Ac O and pyridine. No acetoxyl group was described in Tables 1 and 2), citroside A (10), citroside B (11), icariside B2
2
detected by NMR spectral analysis of the materials prior to acetylation.
Extraction and Separation Commercial coriander (the fruit of C.
sativum L., purchased from Asaoka Spices Ltd., lot no. 99012001, 7.0 kg)
(12), benzyl b-D-glucopyranoside (13), icariside F (14), leonuriside A (15),
2
4-hydroxy-3,5-dimethoxybenzyl alcohol 4-O-b-D-glucopyranoside (16),
1
13
(1S)-1ꢃ-(4-hydroxyphenyl)ethane-1ꢃ,2ꢃ-diol (17, the H- and C-NMR spec-
was extracted with 70% methanol (10 lꢅ4) for 2 weeks, and the extract tral data are described in Tables 1 and 2), icariside D (20), (2S)-propane-
1
(
363.6 g) was partitioned into ether–water and ethyl acetate–water, respec-
1,2-diol 1-O-b-D-glucopyranoside (21), butane-2,3-diol 2-O-b-D-glucopyra-
noside (22), D-arabinitol (23), methyl a-L-arabinofuranoside (24), glycerol
(25), D-mannitol (26), D-fructose (27), methyl b-D-fructofuranoside (28), D-
glucose (29), sucrose (30), uracil (31), uridine (32), and adenosine (33).
Enzymatic Hydrolysis of 1 A mixture of 1 (10 mg) and b-glucosidase
(5 mg, TOYOBO Co. Ltd., lot 93240) in water (5 ml) was shaken in a water
tively. The aqueous portion (278.1 g) was chromatographed over Amberlite
XAD-II (H O→MeOH) to give water eluate (238.1 g) and methanol eluate
2
(40.0 g) fractions.
The methanol fraction was subjected to Sephadex LH-20 [MeOH–H O
2
(9 : 1)] to give seven fractions (frs. A—G). Fraction C (30.0 g) was chro-
matographed over silica gel [CHCl –MeOH–H O (17 : 3 : 0.2→4 : 1 : bath at 37 °C for 5 d. The mixture was concentrated in vacuo to dryness and
3
2
0
.1→7 : 3 : 0.5)→MeOH] to give 14 fractions (frs. C —C ). Fraction C
the residue was chromatographed over silica gel [CHCl –MeOH (9 : 1)] to
1
14
2
3
(1.54 g) was passed through a Lobar RP-8 column [MeOH–H O (1 : 1)] to
afford the aglycone 1a (3 mg).
2
21
give 12 fractions (frs. C2-1—C2-12), and fr. C2-5 was subjected to HPLC
(3S,6E)-8-Hydroxylinalool (1a) An amorphous powder, [a] ꢁ17°
D
21 1
[
[
(
ODS, MeOH–H O (1 : 1)] and silica gel column chromatography
CHCl –MeOH (14 : 1)→MeOH] to give 4 (6 mg) and 5 (8 mg). Fraction C
0.83 g) was passed through a Lobar RP-8 column [MeOH–H O (1 : 1)] to
(cꢂ0.4, CHCl ), [a] ꢁ16° (cꢂ0.4, MeOH). H-NMR (pyridine-d , 500
3 D 5
13
2
MHz): Table 1. C-NMR (pyridine-d , 125 MHz): Table 2.
5
3
3
(3S,6E)-8-Hydroxylinalool 3-O-b-D-(3-O-Potassium sulfo)glucopyra-
2
21
give 10 fractions (frs. C3-1—C3-10), and fr. C3-2 was subjected to HPLC
noside (2) An amorphous powder, [a] ꢀ12° (cꢂ0.9, MeOH). Positive
D
ꢁ ꢁ
[ODS, MeOH–H O (1 : 19)] to give 17 (10 mg). Fraction C was subjected FAB-MS m/z: 901 [2MꢁH] , 489.0602 [MꢁK] (Calcd for C H K O S:
2
3-6
16 27
2
10
ꢁ
to HPLC [ODS, MeOH–H O (3 : 7)] and silica gel column chromatography
489.0600), 473.0874 [MꢁNa] (Calcd for C H KNaO S: 473.0860),
16 27 10
ꢁ
2
[
CHCl –MeOH (15 : 1)] to give 12 (36 mg). Fraction C (1.03 g) was passed 451.1021 [MꢁH] (base, Calcd for C H KO S: 451.1041), 433 [Mꢀ
3 4 16 28 10
ꢁ ꢀ ꢀ
through a Lobar RP-8 column [MeCN–H O (3 : 17)] to give 12 fractions
H OꢁH] . Negative FAB-MS m/z: 861 [2MꢀK] , 449 [MꢀH] , 411 [Mꢀ
2
ꢀ
2
1
13
(frs. C4-1—C4-12), and fr. C4-7 was subjected to HPLC [CHA, MeCN–H O K] (base). H-NMR (pyridine-d , 500 MHz): Table 1. C-NMR (pyridine-
2
5
(
19 : 1)] to give 13 (79 mg). Fraction C (0.57 g) was subjected to a Lobar d5, 125 MHz): Table 2.
5
RP-8 column [MeCN–H O (3 : 17)] and HPLC [CHA, MeCN–H O (97 : 3)]
Enzymatic Hydrolysis of 2 A mixture of 2 (6 mg) and cellulase (5 mg;
2
2
to give 19 (12 mg). Fraction C (0.85 g) was passed through a Lobar RP-8
Tokyo Kasei Kogyo Co. Ltd., lot FGG01) in water (5 ml) was shaken in a
6
column [MeCN–H O (3 : 17)] to give 15 fractions (frs. C6-1—C6-15), and fr. water bath at 37 °C for 14 d. The mixture was treated in the same way as de-
2
C6-10 was subjected to HPLC [ODS, MeCN–H O (1 : 7)] and silica gel col-
scribed for 1 to afford the aglycone 1a (1 mg).
2
umn chromatography [CHCl –MeOH–H O (7 : 3 : 0.5)] to give 1 (80 mg).
Detection of the Sulfate Group in 2 and 8 A solution of 2 and 8 (2 mg
of each) in aqueous 2 N HCl (1 ml) was heated for 2 h, neutralized with di-
luted NaOH, and evaporated to dryness under reduced pressure. The residue
was subjected to paper partition chromatography and developed with a
3
2
Fraction C6-11 was subjected to HPLC [ODS, MeCN–H O (3 : 17)] to give 3
2
(7 mg). Fraction C7 (2.00 g) was passed through a Lobar RP-8 column
[
MeCN–H O (3 : 17)] to give 15 fractions (frs. C7-1—C7-15), and fr. C7-3 was
2
subjected to HPLC [CHA, MeCN–H O (19 : 1)] to give 16 (16 mg) and 15 MeOH–H O (9 : 1) mixture. After drying in air, the paper was sprayed with a
2
2
(25 mg). Fraction C7-7 and fr. C7-9 were subjected to HPLC [CHA,
solution of BaCl (20 mg) in 70% methanol (10 ml) and dried again in air.
2
MeCN–H O (19 : 1)] to give 10 (58 mg) from fr. C7-7, and 11 (7 mg) and 9 The paper was then sprayed with a solution of potassium rhodizonate (5 mg)
2
(
8 mg) from fr. C7-9. Fraction C (2.57 g) was passed through a Lobar RP-8
in 50% methanol (25 ml) to develop the positive coloration (yellow).
8
column [MeCN–H O (3 : 17)] to give 17 fractions (frs. C8-1—C8-17). Fraction
(3S)-8-Hydroxy-6,7-dihydrolinallol 3-O-b-D-Glucopyranoside (3) An
2
2
1
C8-3 was subjected to HPLC [CHA, MeCN–H O (24 : 1)] to give 33 (32 mg),
amorphous powder, [a] ꢀ8° (cꢂ0.5, MeOH). Positive FAB-MS m/z: 669
D
ꢁ ꢁ
2
and fr. C8-11 was subjected to HPLC [CHA, MeCN–H O (19 : 1)] to give 20 [2MꢁH] , 357.1897 [MꢁNa] (Calcd for C H NaO : 357.1890), 317
2
16 30
7
ꢁ
ꢁ
1
(
[
(
[
150 mg). Fraction C9 (0.48 g) was subjected to a Lobar RP-8 column
[MꢀH OꢁH] , 155 [MꢀC H O ꢁH] (base). H-NMR (pyridine-d5,
500 MHz): Table 1. C-NMR (pyridine-d , 125 MHz): Table 2. HMBC Cor-
2 6 12 6
1
3
MeCN–H O (3 : 17)] and HPLC [ODS, MeCN–H O (1 : 9)] to give 14
2
2
5
370 mg). Fraction C10 (0.89 g) was passed through a Lobar RP-8 column
relations: H -1/C-2, C-3; H-2/C-3, C-4, C-10; H -4/C-2, C-3, C-5, C-6, C-
2
2
MeCN–H O (3 : 17)] to give 12 fractions (frs. C10-1—C10-12), and fr. C10-5
10; H -5/C-3, C-4, C-6; H -6/C-4, C-5, C-7, C-8, C-9; H -8/C-6, C-7, C-9;
2
2
2
2
was subjected to HPLC [ODS, MeCN–H O (1 : 9)], silica gel column chro-
H -9/C-6, C-7, C-8; H -10/C-2, C-3, C-4; Glc H-1/C-3.
3 3
2
matography [CHCl –MeOH–H O (3 : 1 : 0.1)] and HPLC [CHA, MeCN–
Enzymatic Hydrolysis of 3 A mixture of 3 (5 mg) and hespiridinase
(5 mg; ICN Biomedicals Inc., lot 72635) in water (5 ml) was shaken in a
water bath at 37 °C for 3 d. The mixture was concentrated in vacuo to dry-
ness and the residue was chromatographed over silica gel [CHCl3–
3
2
H O (19 : 1)], to give 7 (8 mg) and 6 (13 mg), respectively. Fraction C
2
12
(
1.33 g) was passed through a Lobar RP-8 column [MeCN–H O (3 : 17)] to
2
give 12 fractions (frs. C12-1—C12-12), and fr. C12-5 was subjected to HPLC
[
ODS, MeCN–H O (1 : 39)] to give 18 (9 mg). Fraction C12-8 (146 mg) was MeOH–H O (9 : 1 : 0.1 and 1 : 1 : 0.1)] to afford 3a (1 mg) and a sugar frac-
2
2
suggested to be rich in the sulfate of 1 by NMR spectra, and the sulfate frac-
tion. The sugar fraction was passed through Sephadex LH-20 (MeOH) to
tion thus obtained was purified by silica gel column chromatography give a syrup, and HPLC [carbohydrate analysis (Waters); detector, JASCO
[
CHCl –MeOH–H O (3 : 1 : 0.1)] and HPLC [ODS, MeCN–H O (1 : 9)] to
RI-930 detector and JASCO OR-990 chiral detector; solvent, MeCN–H O
3
2
2
2
give 2 (44 mg). Fraction C13 (3.31 g) was subjected to a Lobar RP-8 column
MeCN–H O (3 : 17)] to give a fraction of the sulfate of 7 (120 mg), and the
(17 : 3), 2 ml/min; tR 4.50 min (same location as that of D-glucose)] showed
[
the presence of D-glucose.
2
21
sulfate fraction thus-obtained was purified by silica gel column chromatog-
raphy [CHCl –MeOH–H O (7 : 3 : 0.2)], HPLC [CHA, MeCN–H O (9 : 1),
(3S)-8-Hydroxy-6,7-dihydrolinalool (3a) An amorphous powder, [a]D
1
ꢁ5° (cꢂ0.1, MeOH). H-NMR (pyridine-d , 500 MHz) d: 6.171 (1H, dd,
3
2
2
5
and ODS, MeCN–H O (1 : 39)] to give 8 (10 mg). A part of the water eluate Jꢂ11.0, 17.5 Hz, H-2), [6.174 (1H, dd, Jꢂ11.0, 17.5 Hz, H-2)], 5.56 (1H,
2
fraction (45.0 g) was subjected to Sephadex LH-20 (80% MeOH) to give dd, Jꢂ2.0, 17.5 Hz, H-1b), 5.14 (1H, dd, Jꢂ2.0, 11.0 Hz, H-1a), 3.76 (1H,
three fractions (frs. H—J). Fraction I (38.7 g) was chromatographed over sil- dd, Jꢂ6.0, 10.0 Hz, H-8b), 1.84 (1H, m, H-7), 1.59—1.80 (5H, m, H-4a,
ica gel [CHCl –MeOH–H O (17 : 3 : 0.2→4 : 1 : 0.1→7 : 3 : 0.5)→MeOH] to
-4b, -5a, -5b, -6b), 1.46 (3H, s, H-10), 1.28 (1H, m, H-6a), 1.082 (3H, d,
3
2
give 24 fractions (frs. I —I ). Fraction I (0.06 g) was subjected to a Lobar
Jꢂ7.0 Hz, H-9), [1.076 (3H, d, Jꢂ7.0 Hz, H-9)], minor stereoisomeric com-
1
24
2
1
3
RP-8 column (H O), silica gel column chromatography [CHCl3–
ponent is given in brackets. C-NMR (pyridine-d , 125 MHz): Table 2.
2
5
MeOH–H O (17 : 3 : 0.2)], and HPLC [CHA, MeCN–H O (49 : 1)] to give
Enzymatic Hydrolysis of 34 A mixture of 34 [(6E)-8-hydroxylinallol
3-O-b-D-glucopyranoside, the H- and C-NMR spectral data are described
in Tables 1 and 2; 13 mg] and b-glucosidase (5 mg) in water (5 ml) was
2
2
1
13
3
1 (2 mg) and 24 (17 mg). Fraction I (3.14 g) was passed through a Lobar
9
RP-8 column (H O) and HPLC [CHA, MeCN–H O (49 : 1) and (19 : 1)] to
2
2
give 25 (115 mg), 28 (130 mg), 32 (47 mg), 22 (9 mg), and 21 (3 mg). Frac- shaken in a water bath at 37 °C for 7 d. The mixture was treated in the same
tion I14 (0.93 g) was passed through a Lobar RP-8 column (H O) and HPLC
way as described for 1 to afford the aglycone 34a (6 mg).
(3R,6E)-8-Hydroxylinalool (34a) An amorphous powder, [a] ꢀ14°
2
2
1
[
CHA, MeCN–H O (19 : 1)] to give 23 (76 mg), 27 (82 mg), 29 (20 mg), and
2
D
2
1
1
13
26 (11 mg). Fraction I23 (5.96 g) was passed through a Lobar RP-8 column
(cꢂ0.5, CHCl ), [a] ꢀ12° (cꢂ0.5, MeOH). H- and C-NMR spectral
3 D
(
H O) and HPLC [CHA, MeCN–H O (3 : 1)] to give 30 (225 mg).
data were identical to those of 1a.
2
2
The following compounds were identified by comparison with authentic
(3S,6S)-6,7-Dihydroxy-6,7-dihydrolinalool (4) An amorphous powder,
2
1
21
compounds or published physical and spectral data. (3S,6E)-8-hydroxyli- [a] ꢀ29° (cꢂ0.3, CHCl ), [a] ꢀ15° (cꢂ0.3, MeOH). Positive FAB-MS
D
3
D
1
13
ꢁ
ꢁ
nalool 3-O-b-D-glucopyranoside (1, the H- and C-NMR spectral data are
m/z: 377 [2MꢁH] , 227.1041 [MꢁK] (Calcd for C H KO : 227.1049),
10 21 3

38
Vol. 51, No. 1
ꢁ
ꢁ
2
[
11 [MꢁNa] , 189.1487 [MꢁH] (Calcd for C H O : 189.1490), 171 [CHCl –MeOH–H O (7 : 3 : 0.5)] to show the presence of apiose (Rf 0.29).
1
0
21
3
3
2
ꢁ
ꢁ
1
MꢀH OꢁH] , 153 [Mꢀ2H OꢁH] (base). H-NMR (pyridine-d , 500
(1R,4S,6S)-6-Hydroxycamphor b-D-Glucopyranoside (9a) An amor-
2
2
5
13
23
MHz): Table 1. C-NMR (pyridine-d , 125 MHz): Table 2. HMBC correla- phous powder, [a] ꢀ66° (cꢂ0.4, MeOH). Positive FAB-MS m/z: 661
tions: H-1a/C-3; H-1b/C-2, C-3; H-2/C-3, C-4, C-10; H -4/C-2, C-3, C-5, C-
, C-10; H -5/C-3, C-4, C-6, C-7; H-6/C-4, C-5, C-8, C-9; H -8/C-6, C-7, C-
; H -9/C-6, C-7, C-8; H -10/C-2, C-3, C-4.
5
D
ꢁ
ꢁ
ꢁ
ꢁ
[2MꢁH] , 369 [MꢁK] , 353 [MꢁNa] , 331 [MꢁH] , 151
ꢁ
2
1
13
6
9
[MꢀC H O ꢁH] (base). H-NMR (pyridine-d , 500 MHz): Table 1. C-
2
3
6
1
2
6
5
NMR (pyridine-d , 125 MHz): Table 2.
5
3
3
(
3S,6R)-6,7-Dihydroxy-6,7-dihydrolinalool (5) An amorphous powder,
(1ꢀS)-1ꢀ-(4-Hydroxyphenyl)ethane-1ꢀ,2ꢀ-diol 2ꢀ-O-b-D-Apiofuranosyl-
21
21
22
[
a] ꢁ22° (cꢂ0.1, CHCl ), [a] ꢁ24° (cꢂ0.2, MeOH). Positive FAB-MS
(1→6)-b-D-glucopyranoside (18) An amorphous powder, [a]D ꢀ38°
D
3
D
ꢁ
ꢁ
ꢁ
m/z: 377 [2MꢁH] , 227.1040 [MꢁK] (Calcd for C H KO : 227.1049), (cꢂ0.5, MeOH). Positive FAB-MS m/z: 471.1481 [MꢁNa] (base, Calcd
1
0
21
3
ꢁ
ꢁ
ꢁ
ꢁ 1
2
[
11 [MꢁNa] , 189.1482 [MꢁH] (Calcd for C H O : 189.1490), 171 for C H NaO : 471.1478), 449 [MꢁH] , 431 [MꢀH OꢁH] . H-NMR
10 21 3
19 28 12 2
ꢁ ꢁ
13
1
MꢀH OꢁH] , 153 [Mꢀ2H OꢁH] (base). H-NMR (pyridine-d , 500
MHz): Table 1. C-NMR (pyridine-d , 125 MHz): Table 2.
(pyridine-d , 500 MHz): Table 1. C-NMR (pyridine-d , 125 MHz): Table 2.
5 5
2
2
5
13
HMBC correlations: H-2/C-4, C-6, C-1ꢃ; H-3/C-1, C-4, C-5; H-5/C-1, C-3,
5
(
3S,6S)-6,7-Dihydroxy-6,7-dihydrolinalool 3-O-b-D-Glucopyranoside
C-4; H-6/C-2, C-4, C-1ꢃ; H-1ꢃ/C-1, C-2, C-6, C-2ꢃ; H -2ꢃ/Glc C-1, Glc H-
2
2
1
(
6) An amorphous powder, [a] ꢀ27° (cꢂ1.0, MeOH). Positive FAB-MS 1/C-2; Glc H -6/Api C-1.
D
2
ꢁ
ꢁ
ꢁ
m/z: 701 [2MꢁH] , 389 [MꢁK] (base), 373 [MꢁNa] , 351.2022
Enzymatic Hydrolysis of 18 A mixture of 18 (5 mg) and b-glucosidase
(5 mg) in water (5 ml) was shaken in a water bath at 37 °C for 7 d. The mix-
ture was treated in the same way as described for 3 to afford the aglycone 17
ꢁ
ꢁ
[
[
MꢁH] (Calcd for C H O : 351.2019), 333 [MꢀH OꢁH] , 171
1
6
31
8
2
ꢁ
1
13
MꢀC H O ꢁH] (base). H-NMR (pyridine-d , 500 MHz): Table 1. C-
6
12
6
5
NMR (pyridine-d , 125 MHz): Table 2. HMBC correlations: H -1/C-2, C-3;
(2 mg) and a sugar fraction. D-Glucose and D-apiose (t 7.95 min; same loca-
5
2
R
H-2/C-3, C-4, C-10; H -4/C-2, C-3, C-5, C-6, C-10; H-5a/C-3, C-4, C-6; H-
tion as that of D-apiose) were detected from the sugar fraction in the same
way as described for 3.
2
5
b/C-4; H-6/C-4, C-5, C-7, C-8, C-9; H -8/C-6, C-7, C-9; H -9/C-6, C-7, C-
2
3
8
; H -10/C-2, C-3, C-4; Glc H-1/C-3.
(1ꢀR)-1ꢀ-(4-Hydroxy-3,5-dimethoxyphenyl)propan-1ꢀ-ol 4-O-b-D-Glu-
3
2
3
Enzymatic Hydrolysis of 6 A mixture of 6 (6 mg) and hesperidinase
5 mg) in water (5 ml) was shaken in a water bath at 37 °C for 5 d. The mix- Positive FAB-MS m/z: 413 [MꢁK] , 397.1473 [MꢁNa] (Calcd for
copyranoside (19) An amorphous powder, [a] ꢀ10° (cꢂ1.0, MeOH).
D
ꢁ ꢁ
(
ꢁ
1
ture was treated in the same way as described for 3 to afford the aglycone 4 C H NaO : 397.1475), 195 [MꢀC H O ꢁH] (base). H-NMR (pyridine-
1
7
26
9
6
12
6
1
3
(
2 mg) and a sugar fraction. D-Glucose was detected from the sugar fraction
as described for 3.
3S,6R)-6,7-Dihydroxy-6,7-dihydrolinalool 3-O-b-D-Glucopyranoside
d5, 500 MHz): Table 3. C-NMR (pyridine-d , 125 MHz): Table 4. HMBC
5
correlations: H-2/C-1, C-3, C-4, C-6, C-1ꢃ; H-6/C-1, C-2, C-4, C-5, C-1ꢃ; H-
1ꢃ/C-2, C-6, C-2ꢃ, C-3ꢃ; H -2ꢃ/C-1ꢃ, C-3ꢃ; H -3ꢃ/C-1ꢃ, C-2ꢃ; 3-O-CH /C-3;
(
2
3
3
2
1
(
7) An amorphous powder, [a] ꢁ6° (cꢂ0.1, MeOH). Positive FAB-MS 5-O-CH /C-5; Glc H-1/C-4.
D
ꢁ ꢁ ꢁ
3
m/z: 701 [2MꢁH] , 389 [MꢁK] (base), 373 [MꢁNa] , 351.2024
Enzymatic Hydrolysis of 19 A mixture of 19 (10 mg) and naringinase
MꢁH] (Calcd for C H O : 351.2019), 333 [MꢀH OꢁH] , 171 (5 mg) in water (5 ml) was shaken in a water bath at 37 °C for 15 d. The mix-
ꢁ
ꢁ
[
[
1
6
31
8
2
ꢁ
1
13
MꢀC H O ꢁH] (base). H-NMR (pyridine-d , 500 MHz): Table 1. C-
ture was treated in the same way as described for 3 to afford the aglycone
19a (5 mg) and a sugar fraction. D-Glucose was detected from the sugar frac-
tion as described for 3.
6
12
6
5
NMR (pyridine-d , 125 MHz): Table 2.
5
Enzymatic Hydrolysis of 7 A mixture of 7 (3 mg) and hesperidinase
(
3 mg) in water (5 ml) was shaken in a water bath at 37 °C for 10 d. The mix-
(1ꢀR)-1ꢀ-(4-Hydroxy-3,5-dimethoxyphenyl)propan-1ꢀ-ol (19a) An
2
2
1
ture was treated in the same way as described for 3 to afford an aglycone 4 amorphous powder, [a] ꢁ5° (cꢂ0.4, CHCl3). H-NMR (pyridine-d5,
D
1
3
(2 mg) and a sugar fraction. D-Glucose was indicated from the sugar fraction
500 MHz): Table 3. C-NMR (pyridine-d , 125 MHz): Table 4.
5
by HPLC [carbohydrate analysis (Waters), detector; JASCO RI-930 detec-
tor] analysis.
Acknowledgments The authors thank Mr. Y. Takase and Dr. H. Suzuki
Enzymatic Hydrolysis of 35 A mixture of 35 [(3R,6S)-6,7-dihydroxy- of the Analytical Center of our university for NMR and MS measurements.
1
13
6
,7-dihydrolinalool 3-O-b-D-glucopyranoside for which the H- and C-
NMR spectral data are described in Tables 1 and 2, 3 mg] and hesperidinase References and Notes
in water (5 ml) was shaken in a water bath at 37 °C for 5 d. The mixture was
1) Norman J., “The Complete Book of Spices,” Dorling Kindersley, 1990,
treated in the same way as described for 1 to afford the aglycone 35a (1 mg).
p. 32.
(
3R,6S)-6,7-Dihydroxy-6,7-dihydrolinalool (35a): An amorphous powder,
2) British Pharmacopoeia 1, The Stationery Office, 1999, pp. 466—467.
3) European Pharmacopoeia, 3rd edition, Council of Europe Publishing,
1997, p. 672.
23
1
13
[
a] ꢀ22° (cꢂ0.5, MeOH). H- and C-NMR spectral data were identical
to those of 5.
D
(
3S,6R)-6,7-Dihydroxy-6,7-dihydrolinalool 3-O-b-
D
2
-(3-O-Potassium sulfo)
-
4) “Herbal Drugs and Phytopharmaceuticals,” ed. by Wichtl M., CRC
Press, Stuttgart, 1994, pp. 159—160.
5) Ishikawa T., Kudo M., Kitajima J., Chem. Pharm. Bull., 50, 501—507
(2002).
6) Klyne W., “Determination of Organic Structure by Physical Methods,”
ed. by Braude E. A., Nachod F. C., Academic Press, New York, 1975,
p. 73.
2
glucopyranoside (8) An amorphous powder, [a] ꢀ14° (cꢂ0.3, MeOH).
D
ꢁ
Positive FAB-MS m/z: 507.0697 [MꢁK] (Calcd for C H K O S:
1
6
29
2
11
ꢁ
5
4
07.0705), 491.0982 [MꢁNa]
(base, Calcd for C H KNaO S:
16 29 11
ꢀ ꢀ
1
91.0966). Negative FAB-MS m/z: 467 [MꢀH] 429 [MꢀK] (base). H-
NMR (pyridine-d , 500 MHz): Table 1. C-NMR (pyridine-d , 125 MHz):
1
3
5
5
Table 2.
Enzymatic Hydrolysis of 8 A mixture of 8 (4 mg) and naringinase (5
mg; ICN Biomedicals Inc., lot 2421C) in water (5 ml) was shaken in a water
bath at 37 °C for 14 d. The mixture was treated in the same way as described
for 1 to afford the aglycone 5 (1 mg).
7) Klyne W., Biochem. J., 47, XIi—XIii (1950).
8) Uchiyama T., Miyase T., Ueno A., Usmanghani K., Phytochemistry,
28, 3369—3372 (1989).
9) Enzymatic hydrolysis of 2 proceeded with cellulase, but 2 was not hy-
drolyzed with b-glucosidase, hesperidinase, and naringinase.
(
1R,4S,6S)-6-Hydroxycamphor b-
D
-Apiofuranosyl-(1→6)-b-
D-glucopy-
2
1
ranoside (9) An amorphous powder, [a] ꢀ73° (cꢂ0.5, MeOH). Positive 10) Kitagawa I., Kobayashi M., Sugawara T., Chem. Pharm. Bull., 26,
1582—1863 (1978).
C H NaO : 485.1999), 463 [MꢁH] , 331 [MꢀC H O ꢁH] , 151 [Mꢀ 11) Schneider J. J., Lewbart M. L., J. Biol. Chem., 222, 787—794 (1966).
D
ꢁ
ꢁ
ꢁ
FAB-MS m/z: 925 [2MꢁK] , 501 [MꢁK] , 485.2002 [MꢁNa] (Calcd for
ꢁ
ꢁ
2
1
34
11
5
8
4
ꢁ
1
13
C H O ꢁH] (base). H-NMR (pyridine-d , 500 MHz): Table 1. C- 12) Kitajima J., Tanaka Y., Chem. Pharm. Bull., 41, 1667—1669 (1993).
11
20 10
5
NMR (pyridine-d , 125 MHz): Table 2. HMBC correlations: H-3endo/C-1, 13) Kitajima J., Aoki Y., Ishikawa T., Tanaka Y., Chem. Pharm. Bull., 47,
5
C-2, C-4, C-5, C-7; H-3exo/C-2, C-4, C-5; H-4/C-1, C-2, C-3, C-6, C-7, C-
639—642 (1993).
8
8
, C-9; H -5/C-1, C-3, C-4, C-6; H-6/C-1, C-2, C-4, C-5, C-10, Glc C-1; H - 14) Vidari G., Giori A., Dapiaggi A., Lanfranchi G., Tetrahedron Lett.,
2
3
/C-1, C-4, C-7, C-9; H -9/C-1, C-4, C-7, C-8; H -10/C-1, C-2, C-6, C-7;
1993, 6925—6928 (1993).
3
3
Glc H-1/C-6; Api H-1/Glc C-6.
Partial Acid Hydrolysis of 9 Glycoside 9 (5 mg) was dissolved in
15) Enzymatic hydrolysis of 8 proceeded with naringinase, but 8 was not
hydrolyzed with b-glucosidase, hesperidinase, and cellulase.
16) Kitajima J., Okamura C., Ishikawa T., Tanaka Y., Chem. Pharm. Bull.,
46, 1404—1407 (1998).
aqueous 0.5 N H SO and heated at 55 °C for 2 h. The reaction mixture of the
2
4
hydrolysate was neutralized with NaHCO , the salt was filtered off, and the
3
filtrate passed through Sephadex LH-20 (MeOH) to afford a monoglucoside 17) Orihara Y., Noguchi T., Furuya T., Phytochemistry, 35, 941—945
fraction and a sugar fraction. The monoglucoside fraction was chro-
matographed on silica gel [CHCl –MeOH–H O (4 : 1 : 0.1 and 1 : 1 : 0.1)] to
(1994).
18) Hulyalkar R. K., Jones J. K. N., Perry M. B., Can. J. Chem., 43,
3
2
afford 9a (3 mg). The sugar fraction was subjected to silica gel TLC
2085—2091 (1965).

January 2003
39
1
2
2
2
2
2
9) Umehara K., Hattori I., Miyase T., Ueno A., Hara S., Kageyama C.,
istry, 42, 843—846 (1996).
25) Commercial (R)-1ꢃ-phenylethane-1ꢃ,2ꢃ-diol (purchased from Aldrich
Chem. Pharm. Bull., 36, 5004—5008 (1988).
0) Miyase T., Ueno A., Takizawa N., Kobayashi H., Karasawa H., Chem.
Pharm. Bull., 35, 1109—1117 (1987).
1) Kitajima J., Ishikawa T., Tanaka Y., Ono M., Ito Y., Nohara T., Chem.
Pharm. Bull., 46, 1587—1590 (1998).
2) Miyase T., Ueno A., Takizawa N., Kobayashi H., Oguchi H., Chem. 27) Zoorob H. H., Ind. J. Chem., 24B, 1218—1220 (1985).
Pharm. Bull., 35, 3713—3719 (1987).
3) Otsuka H., Takeuchi M., Inoshiri S., Sato T., Yamasaki K., Phytochem-
istry, 28, 883—886 (1989).
2
2
Chemical Co.) showed positive optical rotation ([a] ꢁ45° (MeOH)
D
22
for the S-form; [a]D ꢀ45° (MeOH) for the R-form).
26) Landor S. R., Miller B. J., Tatchell A. R., J. Chem. Soc., 2280—2282
(1966).
28) Kitajima J., Ishikawa T., Tanaka Y., Chem. Pharm. Bull., 46, 1643—
1646 (1998).
29) Green J. W., Pacsu E., J. Am. Chem. Soc., 60, 2056—2057 (1938).
4) Taniguchi M., Yanai M., Xiao Y. Q., Kido T., Baba K., Phytochem- 30) Agrawal P. K., Phytochemistry, 31, 3307—3330 (1992).