1952
E. YANASE et al.
Me
N
Me
N
6'
3'
OH
O
OAc
O
4'
10
5'
R
R
4
7
Ac2O - Pyridine
HO
HO
AcO
AcO
O
O
1'
8
9
3
11
2'
OH
OAc
2
6
N
H
N
H
2a: R=Me 87% from 1a
2M HCl
70º 1h
1a: R=Me
1b: R=H
2b: R=Ac 72% from 1b
Methylation
68%
Me
N
R
HO
N
H
3a: R=Me 74% from 1a (bufotenine)
3b: R=H 57% from 1b
Fig. 1. Transformation of Serotonin Analogs 1a and 1b.
amines rather than the free amine. Indeed, 3a and 3b
1
(2H, br.d, J ¼ 5:0, H-10), 3.08 (2H, br.d, J ¼ 5:0,
H-11), 3.48 (1H, t, J ¼ 9:4, H-40), 3.56–3.61 (3H, m,
H-20, 30, 50), 3.74 (1H, dd, J ¼ 6:4, 12.4, H-60), 3.94
(1H, dd, J ¼ 1:8, 12.4, H-60), 5.09 (1H, d, J ¼ 7:8,
H-10), 7.06 (1H, dd, J ¼ 2:3, 9.2, H-6), 7.28 (1H, s,
H-2), 7.37 (1H, d, J ¼ 2:3, H-4), 7.45 (1H, d, J ¼ 8:7,
H-7); 13C-NMR ꢂC (150 MHz, D2O): 25.5 (C-10), 36.3
(N-C), 52.6 (C-11), 63.5 (C-60), 72.4 (C-40), 75.9 (C-20),
78.4 (C-30), 78.9 (C-50), 104.6 (C-10), 108.1 (C-4), 113.4
(C-3), 115.4 (C-7), 116.1 (C-6), 127.9 (C-2), 129.6
(C-8), 135.7 (C-9), 153.3 (C-5); UV ꢃmax (MeOH) nm
afforded H-NMR data similar to those reported in the
literature upon the addition of carbon dioxide or acetic
acid.
The structures of compounds 1a and 1b were
therefore respectively determined to be N,N-dimethyl-
serotonin 5-O-ꢀ-glucoside and N-methylserotonin 5-O-
ꢀ-glucoside. Furthermore, compound 1b could be con-
verted to 1a by N-methylation which proceeded in a
68.2% yield. The respective contents of 1a and 1b in
immature seeds of Z. piperitum were estimated to be
0.29% and 0.15% (w/w) by an HPLC analysis, and
neither of these compounds nor their aglycons 3a and 3b
were detected in the pericarps.
In summary, two serotonin analogs were isolated from
the seeds of Z. piperitum, and their structures were
determined to be N,N-dimethylserotonin 5-O-ꢀ-gluco-
side 1a and N-methylserotonin 5-O-ꢀ-glucoside 1b.
Dimethyl derivative 1a was isolated from Z. piperitum
for the first time together with novel monomethyl
derivative 1b. The levels of 1a and 1b in the seeds were
significantly high enough to suggest that they may have
some unknown important functions in this plant. We are
currently studying the relationship between the growth
stage and endogenous levels of these compounds to
further elucidate their biological significance.
("): 278 (4,700), 220 (21,400); IR ꢄmax (KBr) cmꢁ1
:
2924, 1627, 1483, 1199, 1075, 1042; HR-ESI-MS m=z:
calcd. for C17H25N2O6, 353.1713; found, 353.1719;
25
½ꢁꢂ
ꢁ30.63 (c1.0, H2O).
D
Acknowledgments
We thank Mr. Kazuhiko Naito of Hidasansyo Co.,
Ltd., for providing the Zanthoxylum piperitum seeds.
This work was financially supported by Nagara Science
Co., Ltd.
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phous; 1H-NMR ꢂH (600 MHz, D2O): 2.34 (6H, s,
N-Me), 2.74 (2H, t, J ¼ 7:8, H-10), 2.94 (2H, t, J ¼ 7:8,
H-11), 3.49 (1H, t, J ¼ 9:4, H-40), 3.55–3.66 (3H, m,
H-20, 30, 50), 3.75 (1H, dd, J ¼ 6:0, 12.4, H-60), 3.94
(1H, dd, J ¼ 2:3, 12.4, H-60), 5.07 (1H, d, J ¼ 7:3,
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H-2), 7.37 (1H, d, J ¼ 2:3, H-4), 7.44 (1H, d, J ¼ 8:7,
H-7); 13C-NMR ꢂC (150 MHz, D2O): 24.8 (C-10), 46.4
(N-C), 61.5 (C-11), 63.4 (C-60), 72.3 (C-40), 75.9 (C-20),
78.4 (C-30), 78.9 (C-50), 104.7 (C-10), 108.2 (C-4), 115.3
(C-3), 115.3 (C-7), 116.0 (C-6), 127.1 (C-2), 129.7
(C-8), 135.6 (C-9), 153.2 (C-5); UV ꢃmax (MeOH) nm
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("): 278 (3,680), 220 (16,300); IR ꢄmax (KBr) cmꢁ1
:
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m=z: calcd. for C18H27N2O6, 367.1869; found,
25
367.1873; ½ꢁꢂ
ꢁ32.07 (c1.0, H2O).
D
N-Methylserotonin 5-O-ꢀ-glucoside 1b. Amorphous;
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