J. Nat. Prod.

1999, 62, 335-336 335

Nordihydrocapsiate, a New Capsinoid from the Fruits of a Nonpungent Pepper,

Kenji Kobata,*,† Kouzou Sutoh,‡ Tomoko Todo,† Susumu Yazawa,§ Kazuo Iwai,⊥ and Tatsuo Watanabe†
School of Food and Nutritional Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan,
Graduate School of Nutritional and Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan,
Graduate School of Agriculture, Kyoto University, Oiwake-cho, Kitashirakawa, Kyoto 606-8502, Japan,
and Faculty of Home Economics, Kobe Women’s University, Suma-ku, Kobe 654-8585, Japan

Received August 7, 1998

A new capsiate-like substance, named nordihydrocapsiate (1), has been isolated from the fruits of a
nonpungent cultivar, CH-19 Sweet, of pepper (Capsicum annuum). The structure of 1 was determined to
be 4-hydroxy-3-methoxybenzyl 7-methyloctanoate by spectroscopic methods.

The pungent principal of red peppers (Capsicum spp., formula of 1 was found to be C17H26O4 by HRMS. The IR
Solanaceae) is a group of acid amides of vanillylamine and spectrum showed hydroxyl (3450 cm-1) and ester carbonyl
C8 to C13 fatty acids, which are known generally as absorptions (1740 cm-1). The 1H NMR spectrum of 1
capsaicinoids. The major capsaicinoids in red peppers are indicated the typical 1-, 2-, and 4-substituted phenyl group
capsaicin,1 (E)-N-(4-hydroxy-3-methoxybenzyl)-8-methyl-6- by the coupling constants and patterns of three aromatic
nonenamide, and dihydrocapsaicin,2 and the structure of protons (δ 6.90 d, 6.86 dd, and 6.87 d) and showed a
the latter is a 6,7-dihydro analogue of capsaicin. Nordihy- phenolic hydroxyl group (δ 5.62 br s). A methoxyl group (δ
drocapsaicin is recognized as the third major capsaicinoid, 3.90 s and 56.0) and a methylene group (δ 5.03 s and 66.3)
and the structure is a mono-nor homologue of the acyl between the phenyl group and the oxygen were also
residue of dihydrocapsaicin, that is, N-(4-hydroxy-3-meth- observed in the 1H and 13C NMR spectra of 1. These results
oxybenzyl)-7-methyloctanamide.3 More than 10 capsaici- indicated the presence of a vanillyl-oxy moiety in 1.
noids occur in red peppers as minor components.4-6 In the 1H NMR data, characteristic signals for an
Yazawa et al. reported that the fruits of a nonpungent isopropyl group (δ 0.85 d, 0.85 d, and 1.50 m) were
cultivar of Capsicum annuum L., named CH-19 Sweet, indicated. The isopropyl group gave rise to the signals of δ
contains only a small amount of capsaicinoids but has 22.6, 22.6, and 27.9 in the 13C NMR data. Furthermore,
considerable capsaicinoid-like substances (CLSs).7 In our the 13C NMR data showed a carbonyl carbon (δ 173.8) and
previous work, the structures of two major CLSs were five aliphatic methylene carbons (δ 25.0, 27.0, 29.4, 34.4,
determined to be 4-hydroxy-3-methoxybenzyl (E)-8-methyl- and 38.8). From these results, it is obvious that compound
6-nonenoate and 4-hydroxy-3-methoxybenzyl 8-methyl- 1 has a 7-methyloctanoyl moiety as an acyl residue.
nonanoate, and the two novel compounds were named Although the IR and UV spectra of 1 were similar to
capsiate and dihydrocapsiate, respectively.8 The acyl resi- those of capsiate and dihydrocapsiate, the molecular
dues of capsiate and dihydrocapsiate were the same as formula of 1 indicated the lack of one carbon and two
those of capsaicin and dihydrocapsaicin, respectively, protons in comparison with that of dihydrocapsiate.8
although their aromatic portions were not vanillylamine
Furthermore, the 1H and 13C NMR spectra of 1 were
such as capsaicinoids but vanillyl alcohol. They had no
extremely similar to those of dihydrocapsiate except for the
pungency upon our oral tasting. The present paper de-
lack of a signal of a methylene group.8
scribes the isolation of a new substance, nordihydrocapsiate
(1), from the fruits of C. annuum L. cv. CH-19 Sweet as Therefore, we concluded the structure of 1 to be a mono-
the third major component, and the structure of 1 was nor homologue of the acyl residue of dihydrocapsiate, that
determined to be 4-hydroxy-3-methoxybenzyl 7-methyloc- is, 4-hydroxy-3-methoxybenzyl 7-methyloctanoate. The new
tanoate by spectroscopic methods. compound 1 was named nordihydrocapsiate. Like capsiate
and dihydrocapsiate, nordihydrocapsiate had no pungency
upon our oral tasting.
Nordihydrocapsiate (1) was isolated as the third major
component after capsiate and dihydrocapsiate from the
fruits of C. annuum L. cv. CH-19 Sweet, and the structure
of 1 was determined to be an ester of vanillyl alcohol and
7-methyloctanoic acid. The acyl residue of 1 was the same
as that of nordihydrocapsaicin. Considering our previous
An oleoresin from the fruits of cv. CH-19 Sweet was
results,8 the content ratio of capsiate, dihydrocapsiate, and
chromatographed successively on Si gel and reversed-phase
1 in cv. CH-19 Sweet was approximately [Link]. This value
Si gel, followed by reversed-phase HPLC purification with
was similar to that of capsaicin, dihydrocapsaicin, and
silver nitrate eluent to afford compound 1. The molecular
nordihydrocapsaicin in several varieties of Capsicum spe-
cies.9 The acyl residues of capsaicinoids are biosynthesized
* To whom correspondence should be addressed. Tel.: +81 54 264 5544.
Fax: +81 54 264 5099. E-mail kobata@[Link]). from L-valine, L-leucine, and L-isoleucine,10,11 and the
† School of Food and Nutritional Sciences.
‡ Graduate School of Nutritonal and Environmental Sciences.
vanillylamine moiety is biosynthesized from L-phenylala-
§ Kyoto University. nine via cinnamic, caffeic, and ferulic acids.4,6,10 We specu-
⊥ Kobe Women’s University. late that the biosynthetic pathway of the three compounds
10.1021/np9803373 CCC: $18.00 © 1999 American Chemical Society and American Society of Pharmacognosy
Published on Web 12/10/1998
336 Journal of Natural Products, 1999, Vol. 62, No. 2 Notes

is closely related to that of capsaicinoids except for a part by a characteristic peak was collected. The eluent was parti-
of the pathway for the aromatic portion. tioned with CHCl3 three times; the CHCl3 fractions were dried
Our preliminary work indicated the existence of several using anhydrous Na2SO4 and then filtered. The filtrate was
evaporated under reduced pressure to afford compound 1 (25.5
capsiate-like substances as minor components in cv. CH- mg).
19 Sweet (data not shown). They may be analogues and
Compound 1 (nordihydrocapsiate): colorless oil; HRE-
homologues of the acyl residues of these compounds, and IMS m/z 294.1872 (calcd for C17H26O4, 294.1831); EIMS (70
they may also be several analogues and homologues eV) m/z 294 [M+] (10), 252 (5), 236 (3), 154 (27), 137 (46), 107
involving the acyl residues. Yazawa et al. reported that (14), 73 (47), 44 (100), 40 (90); IR (film) νmax 3450, 1740, 1615,
CLSs occur in several cultivars of C. annuum.7 We propose 1610, 1520, 1470, 1435, 1275, 1160, 1120, 1035, 970, 850, 815,
that the compound group of capsiate-like substances that 795, 560 cm-1; UV(MeOH) λmax () 281 (2400), 231 (6800) nm;
1H NMR (CDCl , 399.65 MHz) δ 6.90 (1H, d, J ) 8.3 Hz, H-5′),
are esters of vanillyl alcohol and fatty acids be named 3
capsinoid(s). 6.87 (1H, d, J ) 1.5 Hz, H-2′), 6.86 (1H, dd, J ) 8.3, 1.5 Hz,
H-6′), 5.62 (1H, bs, OH), 5.03 (2H, s, H-7′), 3.90 (3H, s, OCH3),
2.33 (2H, t, J ) 7.6 Hz, H-2), 1.63 (2H, quint, J ) 7.6 Hz, H-3),
Experimental Section
1.50 (1H, m, J ) 6.8 Hz, H-7), 1.25 (2H, m, H-4), 1.25 (2H, m,
General Experimental Procedures. 1H and 13C NMR H-5), 1.14 (2H, q, J ) 6.8 Hz, H-6), 0.85 (3H, d, J ) 6.8 Hz,
spectra (TMS as the internal standard) were recorded on a H-8), 0.85 (3H, d, J ) 6.8 Hz, H-9); 13C NMR (CDCl3, 100.40
JEOL R-400 instrument at 399.65 and 100.40 MHz, respec- MHz) δ 173.8 (C-1), 146.5 (C-3′), 145.8 (C-4′), 128.1 (C-1′), 122.0
tively. IR spectra were recorded on a Hitachi 270-50 IR (C-6′), 114.4 (C-5′), 111.3 (C-2′), 66.3 (C-7′), 56.0 (OCH3), 38.8
spectrophotometer, and UV spectra were recorded on a JASCO (C-6), 34.4 (C-2), 29.4 (C-4), 27.9 (C-7), 27.0 (C-5), 25.0 (C-3),
Uvidec 660 spectrophotometer. HRMS and EIMS measure- 22.6 (C-8), 22.6 (C-9).
ments were carried out on a JEOL JMS-AX500 apparatus. Si
Acknowledgment. We express our thanks to Mr. Yasu-
gel 60 was purchased from Merck (Darmstadt, Germany), and
fumi Morita of Toyama National College of Technology for
reversed-phase Si gel, Wakosil 25C18, was from Wako Pure
measuring the HRMS and EIMS data.
Chem. Ind., Ltd. (Osaka, Japan). The packed column for
HPLC, J’sphere ODS-H80 (20 × 150 mm), was purchased
References and Notes
from YMC Co., Ltd. (Kyoto, Japan).
Plant Material. Fruits of cv. CH-19 Sweet (C. annuum L.) (1) Nelson, E. K.; Dawson, L. E. J. Am. Chem. Soc. 1923, 45, 2179-
2181.
were grown at the experimental farm of Kyoto University. The (2) Kosuge, S.; Inagaki, Y.; Okumura, H. Nippon Nogei Kagaku Kaishi
CH-19 Sweet is a nonpungent cultivar that was selected and 1961, 35, 923-927; Chem. Abstr. 1964, 60, 9827g.
cultivated from a pungent cultivar, CH-19, of pepper obtained (3) Kosuge, S.; Furuta, M. Agric. Biol. Chem. 1970, 34, 248-256.
(4) Bennett, D. J.; Kirby, G. W. J. Chem. Soc. (C) 1968, 442-446.
from Thailand.7 (5) Maillard, M.-N.; Giampaoli, P.; Richard, H. M. J. Flavour Fragrance
Isolation of 1. An oleoresin (7.3 g) from fresh fruits (1.00 J. 1997, 12, 409-413.
kg) of cv. CH-19 Sweet was obtained by our previously (6) Suzuki, T.; Iwai, K. In The Alkaloids: Chemistry and Pharmacology;
Brossi, A., Ed.; Academic: Orlando, 1984; Vol. 23, Chapter 4, pp 227-
described method.8 The oleoresin was chromatographed on Si 299.
gel (36 × 200 mm) with stepwise elution of n-hexane and (7) Yazawa, S.; Suetome, N.; Okamoto, K.; Namiki, T. J. Jpn. Soc. Hortic.
EtOAc. The fraction eluted with n-hexane-EtOAc (80:20) was Sci. 1989, 58, 601-607.
rechromatographed on reversed-phase Si gel (20 × 90 mm) (8) Kobata, K.; Todo, T.; Yazawa, S.; Iwai, K.; Watanabe, T. J. Agric.
Food Chem. 1998, 46, 1695-1697.
with 75% MeOH eluent, and a mixture containing 1 was (9) Jurenitsch, J.; Kubelka, W.; Jentzsch, K. Planta Med. 1979, 35, 174-
obtained. The mixture was purified by a preparative HPLC 183.
system. HPLC conditions were as follows; column: J’sphere (10) Leete, E.; Louden, M. C. L. J. Am. Chem. Soc. 1968, 90, 6837-6841.
ODS-H80 (20 × 150 mm); eluent: 80% MeOH containing 0.05 (11) Fujiwake, H.; Suzuki, T.; Iwai, K. Agric. Biol. Chem. 1982, 46,
2591-2592.
M AgNO3; flow rate: 8.0 mL/min; detection: fluorescence,
Excitation 280 nm, Emission 320 nm. The fraction represented NP9803373