Journal of the Chinese Chemical Society, 2000, 47, 373-380

373

The Constituents of Lindera glauca

Yuh-Chwen Changa,b (
), Fang-Rong Changb (
) and Yang-Chang Wu*b (
)
Department of Chemical Engineering, Kao Yuan Institute of Technology, Kaohsiung county, Taiwan, R.O.C.
b
Graduate Institute of Natural Products, Kaohsiung Medical University, Kaohsiung, Taiwan, R.O.C.

Twenty-eight com pounds in clud ing seven al ka loids, (+)-3-chloro-N-formylnornantenine (1), (+)-Nformylnornantenine (2), (+)-boldine (3), (+)-norboldine (4), (-)-norboldine (5), lycicamine (6), and tetrahydroberberine (7); four flavonoids, kaempferol (8), kaempferol-3-O-arabinoside (9), quercetin (10), and
quercetin-3-O-rhamnoside (11); one butanolide, akolactone A (12); one p-quinone, 2,6-dimethoxy-p-quinone
(13); one cyclohex-2-en-1-one, blumenol A (14); six benzenoids, methylparaben (15), p-hydroxybenzoic acid
(16), vanillic acid (17), syringic acid (18), 3,4,5-trimethoxybenzoic acid (19), and 3-(3,4-dihydroxyphenyl)
propionic acid (20); one diterpene, phytol (21); one triterpene, squalene (22); six steroids, -sitosterol (23),
-sitostenone (24), stigmasta-4,22-dien-3-one (25), 6 -hydroxy- -sitostenone (26), 6 -hydroxystigmasterone
(27), and -sitosteryl-D-glucoside (28) were isolated from the aerial part of Lindera glauca. These compounds
were characterized and identified by physical and spectral method. All compounds were isolated for the first
time from this plant. Among them, (+)-3-chloro-N-formylnornantenine (1) is a new one.

INTRODUCTION

RESULTS AND DISCUSSION

Lindera glauca Sieb.& Zucc.(Lauraceae) is a small deciduous tree growing in the forests at low altitudes in Japan,
China and Taiwan.1 Previously, three alkaloids, nineteen fatty
ac ids, eight monoterpenes, five sesquiterpenes, two naph thalenes, and eleven butanolides have been reported from this
plant.2-8 As part of our continuing investigation of the phytochemical and bioactive compounds of Formosan Lauraceous
plants, the methanol extract of this plant was subjected to solvent partition and chromatographic separation to characterize
twenty-eight pure compounds. Among them, 1 is a new compound, and known compounds 2~28 were isolated for the first
time from this species. The present paper deals with the isolation and characterization of the isolated components.

A methanolic extract of L. glauca was concentrated to

obtain a residue and then partitioned between CHCl 3 and H2O.
The aqueous layer was partitioned with n-BuOH. Each layer
was concen trated and subjected to chromatography. Fifteen
compounds including five alkaloids, (+)-3-chloro-N-formylnornantenine (1), (+)-N-formylnornantenine9 (2), (+)-nor boldine10 (4), (-)-norboldine11,12 (5), and lysicamine13 (6); one
butanolide, akolactone A (12); one benzenoid, methylparaben 14 (15); one diterpene, phytol (21); one triterpene,
squalene (22); and five ste roids, -sitosterol 13,15 (23), sitostenone13 (24), stigmasta-4,22-dien-3-one13 (25), 6 hydroxy- -sitostenone 13 (26), 6 -hydroxystigmasterone13
(27), and -sitosteryl-D-glucoside13 (28) were obtained from

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Chang et al.

The Constituents of Lindera glauca

the chloroform layer. Thirteen compounds including two alka loids, (+)-boldine11,12 (3) and tetrahydroberberine16 (7);
four flavonoids, kaempferol 17 (8), kaempferol-3-Oarabinoside 18 (9), quercetin 17 (10), and quercetin-3-Orhamnoside 19 (11); one p-quinone, 2,6-dimethoxy-p quinone 20 (13); one cyclohex-2-en-1-one, blumenol A21,22
(14); five benzenoids, p-hydroxybenzoic acid14 (16), vanillic
acid14 (17), syringic acid 14 (18), 3,4,5-trimethoxybenzoic
acid14 (19), and 3-(3,4-dihydroxyphenyl) propionic acid 23
(20) were obtained from the n-Butanol layer. Among them 1 is
a new com pound, and oth ers are known com pounds which
were isolated for the first time from this plant and characterized by com parison of their physical and spectral data (UV,
IR, NMR and MS) with values previously reported in the literature.
The alkaloid 1 was recrystallized from methanol as color less nee dles. Its mo lec u lar for mula was es tab lished as
C 20 H 18 O 5 NCl by HREI mass spec trom e try m/z M + (found
387.0867, calcd 387.0874), with a mp over 300 C. The IR
spectrum with peaks at 1660 and 1620 cm-1, was suggestive of
an amidic functional group. The UV absorptions showed max
at 272sh, 281, 302, and 312sh nm, indicating alkaloid 1 possessed a 1, 2, 3, 9, 10-substituted aporphine 24. EI-MS spec-

J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

375

trum showed that one chlorine is bonded to alkaloid 1 with a

spectrum of 3 to 1 ratio at m/z (rel. int %): 387(23, M +)/389;
351(52, [M-Cl]+)/353; 329(100)/331. The molecular ion m/z
387(23, M +)/389, and base peak m/z 329(100)/331 are due to
loss of (CH2-N-CHO+H) from the molecular ion. It followed
that the amidic func tion was in the shape of an N-formyl
group. Moreover, the two species were actually present in solution, due to isomerism about the amidic bond could be immediately derived from the 1H-NMR spectrum. Broad downfield singlets at 8.25 and 8.36 represented the N-formyl proton. The integrals of these peaks in di cated that the iso mers
were present in a ratio of 2:1.
The spectra for the two isomers could be clearly differentiated, even though the two isomers could not be separated.
While the differences in chemical shifts were minimal in the
case of the methoxyl and methylenedioxy signals, they were
clearly noticeable for the aromatic protons, with signals at
6.78 (H-8) and 7.91 (H-11) for the major isomer 1a, and at
6.76 and 7.92 for the mi nor iso mer 1b. The di ver gence between the two iso mers was quite prom i nent in the aliphatic
range. Some of the more salient differences in chemical shifts
occurred in the resonances for the hydrogens bonded to C-5,
C-6a and C-7. For the major isomer 1a, the signals for H-6a

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J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

and H-7 were downfield at 4.91 and 2.97, respectively. On

the other hand, for 1b, these two protons are relatively upfield
at 4.45 and 2.75, respectively. For both isomers, the H-7
signals were characterized by small coupling constants with
H-6a (ca. 4.0 Hz), but the H-7 signals were denoted by large
constants (ca. 14.0 Hz).
The disparity in geometry between the two isomers also
came to the fore when NOESY measurements were obtained.
In par ticular, the prox imity of the formyl pro ton to H-5 (
3.86) in the major isomer and to H-6a ( 4.45) in the minor isomer was clearly ev i dent. With both iso mers, a strong nOe
could be observed between H-7 and H-8 (see Fig. 1). A similar observation for alkaloid 2 has been found in the literature.9
In view of al ka loid 2, the H-3 sig nal dis ap peared in
those of 1. It strongly indicates that the chlorine atom was substituted at 3-position. Since neither chlorine gas nor HCl was
even used during extraction or chromatography, an artifact is
ex cluded. On the ba sis of the re sult men tioned above, the
struc ture was thus de ter mined as (+)-3-chloro-N- formylnornantenine. In ad di tion, the bi o log i cal ac tiv i ties of these
compounds are currently under investigation.

EXPERIMENTAL SECTION
General Methods
Un cor rected melt ing points were de ter mined on a
Mel-Temp II apparatus. Optical rotation was taken on a Jasco
DIP-370 dig i tal polarimeter. Ultra vi o let (UV) and in fra red
(IR) spec tra were obtained us ing a Hitachi U-2000 spectrophotometer and a Hitachi 260-30 spectrophotometer, respectively. NMR spec tra were re corded with a Varian Gem ini
NMR Spectrometer (200 MHz) and a Varian Unity Plus NMR
Spectrometer (400 MHz) using TMS as an internal standard.
Mass Spec tra (MS) were re corded on a JEOL JMS-HX 110
mass spectrometer. Active charcoal (Wako) and silica gel 60
(E. Merck, 230-400 mesh) were used for open column chro-

Fig. 1. NOESY correlations for 1.

Chang et al.

ma tog ra phy and precoated sil ica gel plates (E. Merck,
Kieselgel 60 F-254, 0.25 mm) were used for preparative TLC.
Plant Material
L. glauca Sieb. Zucc.(Lauraceae) was col lected from
Taipei county, Taiwan in July 1996. A voucher specimen is on
de posit in the Grad u ate In sti tute of Nat u ral Prod ucts,
Kaohsiung Medical University, Kaohsiung, Taiwan, Republic
of China.
Extraction and Separation
Air-dried, ae rial parts (9.8 Kg) of L. glauca were extracted re peat edly with MeOH at room tem per a ture. The
methanolic ex tracts were con cen trated and par ti tioned between chloroform and water to form a chloroform layer and an
aque ous layer. The chlo ro form layer was con cen trated to
leave a brown ish vis cous res i due (8.8 g). The res i due was
placed on a sil ica gel col umn and eluted with CHCl 3 which
was gradually enriched with MeOH to afford eleven fractions.
Fr.2 (2.1 g) eluted with a gradient of n-hexane/CHCl3/EtOAC
was sep a rated us ing sil ica gel CC and prep. TLC and gave
(+)-3-chloro-N-formylnornantenine (1) (3 mg), (+)-Nformyl nornantenine (2) (5 mg), akolactone A (12) (3 mg),
phytol (21) (20 mg) and squalene (22) (20 mg), respectively.
Fr.5 (1.4 g) eluted with CHCl 3 was isolated using repeatedly
sil ica gel CC and prep. TLC (CHCl 3 ) and gave -sitosterol
(23) (50 mg). (+)-norboldine (4) (10 mg), (-)-norboldine (5) (4
mg) and methylparaben (15) (10 mg) were obtained from Fr.7
(1.3 g) by means of re peat edly sil ica gel CC eluting with
CHCl3-MeOH (20:1). Fr.8 (0.6 g) eluted with CHCl3-MeOH
(15:1) was fur ther sep a rated us ing sil ica gel CC and prep.
TLC and gave lysicamine (6) (5 mg). Fr.10 (0.8 g) eluted with
CHCl 3-MeOH (10:1) was sep arated using sil ica gel CC and
prep. TLC and gave -sitostenone (24) (10 mg), stigmasta4,22-dien-3-one (25) (15 mg), 6 -hydroxy- -sitostenone (26)
(10 mg) and 6 -hydroxystigmasterone (27) (10 mg), respectively. Fr.11(1.1 g) eluted with CHCl3-MeOH (8:1) was fur ther sep a rated us ing sil ica gel CC and gave -sitosterylD-glucoside (28) (30 mg).
The aque ous layer was par ti tioned with n-Butanol to
give a n-Butanol layer and an aqueous layer. The n-Butanol
layer was concentrated (4.8 g) and chromatographed over silica gel us ing CHCl3 /EtOAC/MeOH as an eluent to pro duce
ten fractions. Fr.3 (0.8 g) eluted with CHCl 3 was further purified in silica gel column using the same solvent to obtain compound 2,6-dimethoxy-p-quinone (13) (10 mg). Fr.4 (2.3 g)
eluted with CHCl 3-MeOH (10:1) was further separated using
silica gel CC and prep. TLC and gave kaempferol (8) (10 mg),
quercetin-3-O-rhamnoside (11) (50 mg); blumenol A (14) (30
mg), p-hydroxybenzoic acid (16) (20 mg), vanillic acid (17)

The Constituents of Lindera glauca

J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

377

(10 mg), syringic acid (18) (10 mg), 3,4,5-trimethoxybenzoic

acid (19) (10 mg), (+)-boldine (3) (10 mg), kaempferol-3-Oarabinoside (9) (20 mg) and quercetin (10) (20 mg), respectively. Fr.6 (0.6 g) eluted with CHCl3-MeOH (8:1) was further
separated using silica gel CC and prep. TLC and gave tetrahydroberberine (7) (4 mg) and 3-(3,4-dihydroxyphenyl)
propionic acid (20) (3 mg), respectively.

+85 (c = 0.5, MeOH); UV max/nm 220, 282, 304; IR max/

cm -1 3450; 1 H NMR (CD 3 OD) /ppm 2.56 (3H, s, N-CH 3 ),
3.55 (3H, s, C 1-OCH 3), 3.83 (3H, s, C10-OCH 3), 6.53 (1H, s,
H-3), 6.72 (1H, s, H-8), 7.93 (1H, s, H-11), 2.49~3.15 (7H, m,
H-4a, H-4b, H-5a, H-5b, H-6a, H-7a, H-7b); EI-MS m/z (rel.
int ) 327 (90, M +), 326 (100), 312 (47), 296 (30), 284 (35),
269 (20), 224 (19).

(+)-3-Chloro-N-formylnornantenine (1)
Colorless needles (CHCl3); mp 300 C; [ ]24D +165 (c
= 0.1, MeOH); UV max/nm 272sh, 281, 302, 312sh; IR
max/cm -1 1660, 1620, 1030, 930; 1 H NMR (CDCl 3 ) /ppm
(1a) major isomer (Z-form): 2.69 (1H, m, H-7 ), 2.76 (1H, m,
H-4 ), 2.91 (1H, m, H-4 ), 2.97 (1H, dd, J = 14.0, 4.4 Hz,
H-7 ), 3.36 (1H, m, H-5 ), 3.86 (1H, m, H-5 ), 3.75 (3H, s,
C1-OCH3), 3.95 (3H, s, C 2-OCH3), 4.91 (1H, dd, J = 14.0, 4.4
Hz, H-6a), 5.99, 5.98 (each 1H, d, J = 1.4 Hz, OCH2O ), 6.78
(1H, s, H-8), 7.91 (1H, s, H-11), 8.25 (1H, s, NCHO); (1b) minor isomer (E-form): 2.75 (1H, m, H-7 ), 2.77 (1H, m, H-4 ),
2.82 (1H, m, H-4 ), 3.04 (1H, dd, J = 14.0, 3.8 Hz, H-7 ), 3.16
(1H, m, H-5 ), 3.75 (3H, s, C1-OCH3), 3.95 (3H, s, C2-OCH3),
4.42 (1H, m, H-5 ), 4.45 (1H, dd, J = 14.0, 4.0 Hz, H-6a),
6.00, 6.01 (each 1H, d, J = 1.3 Hz, OCH2O), 6.76 (1H, s, H-8),
7.92 (1H, s, H-11), 8.36 (1H, s, NCHO); EI-MS m/z (rel. int
) 389 (8), 387 (23, M + ), 353 (13), 351 (52, [M-Cl] + ), 331
(30), 329 (100).

(+)-Norboldine (4)
Brown solid (MeOH); mp 113~115 C; [ ]24D +77 (c =
0.5, MeOH); UV max /nm 220, 283, 305; IR max/cm -1
3550, 3300, 1600; 1 H NMR (CD 3 OD) /ppm 3.61 (3H, s,
C1 -OCH 3), 3.88 (3H, s, C 10-OCH 3 ), 6.65 (1H, s, H-3), 6.76
(1H, s, H-8), 8.02 (1H, s, H-11), 4.14 (1H, dd, J = 14.0, 4.4 Hz,
H-6a), 2.77~3.80 (6H, m, H-4a, H-4b, H-5a, H-5b, H-7a,
H-7b); EI-MS m/z (rel. int ) 313 (36, M+), 312 (72), 298 (11)
, 284 (5), 282 (15), 255 (3), 239 (3), 43 (100).

(+)-N-Formylnornantenine (2)
Col or less nee dles (CHCl 3 ); mp 229~231 C; [ ] 24 D
+290 (c = 0.1, MeOH); UV max/nm 220, 280, 310, 320; IR
max/cm -1 1660, 1030, 930; 1H NMR (CDCl 3 ) /ppm (2a)
major isomer (Z-form): 2.70 (1H, dd, J = 14.0, 3.8 Hz, H-7 ),
2.76 (1H, m, H-4 ), 2.91 (1H, m, H-4 ), 3.01 (1H, dd, J =
14.0, 3.8 Hz, H-7 ), 3.40 (1H, m, H-5 ), 3.82 (1H, m, H-5 ),
3.67 (3H, s, C1-OCH3), 3.89 (3H, s, C2-OCH 3), 4.88 (1H, dd, J
= 14.0, 4.0 Hz, H-6a), 5.97, 5.99 (each 1H, d, J = 1.4 Hz,
OCH 2O ), 6.62 (1H, s, H-3), 6.78 (1H, s, H-8), 7.98 (1H, s,
H-11), 8.25 (1H, s, NCHO); (2b) minor isomer (E-form): 2.70
(1H, dd, J = 14.0, 3.8 Hz, H-7 ), 2.77 (1H, m, H-4 ), 2.82
(1H, m, H-4 ), 3.04 (1H, dd, J = 14.0, 3.8 Hz, H-7 ), 3.16
(1H, m, H-5 ), 3.67 (3H, s, C1-OCH3), 3.89 (3H, s, C2-OCH3),
4.42 (1H, m, H-5 ), 4.45 (1H, dd, J=14.0, 4.0 Hz, H-6a), 6.00,
6.01 (each 1H, d, J = 1.3 Hz, OCH2O ), 6.65 (1H, s, H-3), 6.75
(1H, s, H-8), 7.99 (1H, s, H-11), 8.37 (1H, s, NCHO); EI-MS
m/z (rel. int ) 353 (64, M+), 308 (10), 295 (100), 281 (23),
251 (14).
(+)-Boldine (3)
Amor phous nee dles (MeOH); mp 160~162 C; [ ] 24 D

(-)-Norboldine (5)
Brown solid (MeOH); mp 113~115 C; [ ]24D -154 (c =
0.5, MeOH); UV max/nm 216, 280, 304; IR max/cm -1
3550, 3300, 1600; 1 H NMR (CD 3 OD) /ppm 3.60 (3H, s,
C1 -OCH 3), 3.87 (3H, s, C 10-OCH 3 ), 6.61 (1H, s, H-3), 6.74
(1H, s, H-8), 8.01 (1H, s, H-11), 3.95 (1H, dd, J = 14.0, 4.8 Hz,
H-6a), 2.68~3.78 (6H, m, H-4a, H-4b, H-5a, H-5b, H-7a,
H-7b); EI-MS m/z (rel. int ) 313 (40, M + ), 312 (80), 298
(54), 284 (30), 282 (35), 255 (26), 239 (8), 43 (100).
Lysicamine (6)
Yellow needles (CHCl3); mp 185~187 C; UV max/
nm 256, 282, 334; IR max/cm -1 1650; 1 H NMR (CDCl 3 )
/ppm 4.09 (3H, s, C 1-OCH3 ), 4.18 (3H, s, C 2 -OCH 3 ), 7.27
(1H, s, H-3), 7.63 (1H, td, J = 8.0, 1.1 Hz, H-9), 7.83 (1H, td, J
= 8.0, 1.4 Hz, H-10), 7.88 (1H, d, J = 5.2 Hz, H-4), 8.60 (1H,
dd, J = 8.0, 1.4 Hz,H-8), 8.98 (1H, d, J = 5.2 Hz, H-5), 9.19
(1H, dd, J = 8.0, 1.1 Hz, H-11); EI-MS m/z (rel. int ) 291 (99,
M+), 248 (100), 233 (17), 219 (5), 188 (14), 177 (30), 163 (9),
150 (16).
Tetrahydroberberine (7)
Colorless needles (MeOH); mp 201~203 C; UV max/
nm 220, 295; IR max/cm -1 1040, 935; 1 H NMR (CD 3OD)
/ppm 2.63 (2H, m, H-5a & H-6a), 3.05 (1H, m, H-5b), 3.10
(1H, m, H-6b), 2.78 (1H, dd, J = 16.0, 12.0 Hz, H-13), 3.34
(1H, dd, J = 16.0, 4.8 Hz,H-13), 3.55 (1H, dd, J = 12.0, 4.8 Hz,
H-13a), 3.50 (1H, d, J = 16.0 Hz, H-8a), 4.20 (1H, d, J = 16.0
Hz, H-8b), 5.90 (2H, t, J = 1.6 Hz, OOCH2), 6.60 (1H, s, H-4),
6.82 (1H, s, H-1), 6.89 (1H, d, J = 8.4 Hz, H-11), 6.93 (1H, d, J
= 8.4 Hz, H-12); EI-MS m/z (rel. int ) 339 (57, M + ), 176

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J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

(32), 174 (100), 164 (35), 150 (30), 149 (43), 135 (54).
Kaempferol (8)
Yel low nee dles (CHCl 3); mp 267~269 C; UV max/
nm 210, 265, 362; IR max/cm-1 3400, 1643, 1590; 1H NMR
(CD3OD) /ppm 6.17 (1H, d, J = 1.6 Hz, H-6), 6.38 (1H, d, J =
1.6 Hz, H-8), 6.90 (2H, d, J = 8.8 Hz, H-3' & H-5'), 8.08 (2H,
d, J = 8.8 Hz, H-2' & H-6'); EI-MS m/z (rel. int ) 286 (100,
M+), 258 (12), 257 (13), 121 (91), 108 (30).
Kaempferol-3-O-arabinoside (9)
Yellow nee dles (MeOH); mp 217~219 C; UV max/
nm 266, 300, 350; IR max/cm-1 3400, 1643, 1590; 1H NMR
(Pyridine-D 5 ) /ppm 4.11~5.23 (5H, H-5a", H-5b", H-3",
H-2", H-4"), 6.53 (1H, d, J = 1.6 Hz, H-6), 6.73 (1H, d, J = 2.0
Hz, H-1"), 6.74 (1H, d, J=1.6 Hz, H-8), 7.25 (2H, dd, J = 8.8,
2.0 Hz, H-3', H-5'), 8.38 (2H, dd, J = 8.8, 2.0 Hz, H-2', H-6');
13
C NMR (50 MHz, Pyridine-D5 ) /ppm 157.6 (s, C-2), 135.1
(s, C-3), 179.1 (s, C-4), 157.7 (s, C-5), 99.7 (d, C-6), 165.9 (s,
C-7), 94.6 (d, C-8), 162.8 (s, C-9), 123.5 (s, C-1'), 134.7 (d,
C-2'), 122.0 (d, C-3'), 161.6 (s, C-4'), 121.9 (d, C-5'), 134.7 (d,
C-6'), 109.9 (d, C-1
(d, C-2
(d, C-3
(d,
C-4 ), 62.4 (t, C-5 EI-MS m/z (rel. int ) 287 (16), 286
(100, [M-arabinose]+), 285 (37), 258 (9), 257 (11), 121 (46).
Quercetin (10)
Yellow nee dles (MeOH); mp 279~281 C; UV max/
nm 210, 254, 370; IR max/cm-1 3400, 1643, 1590; 1H NMR
(CD3OD) /ppm 6.18 (1H, d, J = 2.0 Hz, H-6), 6.39 (1H, d, J =
2.0 Hz, H-8), 6.88 (1H, d, J = 8.4 Hz, H-5'), 7.63 (1H, dd, J =
8.4, 2.0 Hz, H-6'), 7.74 (1H, d, J = 2.0 Hz, H-2'); EI-MS m/z
(rel. int ) 302 (100, M+), 301 (31), 273 (10), 229 (10), 228
(9), 153 (18), 137 (28), 128 (19), 69 (35).
Quercetin-3-O-rhamnoside (11)
Yellow needles (MeOH); mp 298~300 C; [ ]24D -105
(c = 0.5, CHCl3); UV max/nm 256, 293, 375; IR max/cm-1
3300, 1650, 1600; 1H NMR (CD3OD) /ppm 0.94 (3H, d, J =
5.8 Hz, CH 3), 3.29-4.24 (4H, m, H-2 H-3 H-4 and H-5
d J = 1.7 Hz, H-1
d J = 2.0 Hz, H-6),
6.35 (1H, d, J = 2.0 Hz, H-8), 6.90 (1H, d, J = 8.4 Hz,H-5
dd J = 8.4, 2.0 Hz, H-6 ), 7.33 (1H, d, J = 2.0 Hz,
H-2 ); EI-MS m/z (rel. int ) 302 (100, [M-rhamnosyl] +) , 358
(3), 273 (11), 228 (15), 153 (20).
Akalactone A (12)
Col or less oil (CHCl 3 ); UV
max/nm 210; IR
max/cm-1 1750, 1660; 1H NMR (CDCl 3) /ppm 0.89 (3H, t, J =
6.8 Hz, H-19), 1.26 (18H, brs. H-10~18), 1.43 (3H, d, J = 6.8

Chang et al.

Hz, C5-CH3), 1.57 (2H, m, H-9), 2.16 (2H, q, J = 6.8 Hz, H-8),
5.03 (1H, qd, J = 6.8, 1.6 Hz, H-4), 6.11 (1H, d, J = 16 Hz,
H-6), 6.80 (1H, dt, J = 16.0, 6.8 Hz, H-7), 7.03 (1H, d, J = 1.6
Hz, H-3); EI-MS m/z (rel. int ) 292 (12, M +), 137 (82), 95
(100), 93 (94).
2,6-Dimethoxy-p-quinone (13)
Yel low nee dles (CHCl 3); mp 249~251 C; UV max/
nm 285; IR max/cm -1 1695, 1645, 1590, 1260, 1100; 1 H
NMR (CDCl 3) /ppm 3.81 (6H, s, C2-OCH3 & C 6-OCH3), 5.84
(2H, s, H-3 & H-5); EI-MS m/z (rel. int ) 168 (57, M +), 138
(21), 125 (14), 80 (31), 69 (100), 53 (20).
Blumenol A (14)
White powder (CHCl3); mp 114~116 C; [ ]24D -86 (c =
0.2, CHCl3); UV max/nm 237; IR max/cm-1 3400, 1685;
1
H NMR (CD3OD) /ppm 1.02 (3H, s, CH3-11), 1.04 (3H, s,
CH3-12), 1.24 (3H, d, J = 6.8 Hz, CH3-10), 1.91 (3H, d, J = 1.2
Hz, CH3-13), 2.16 (1H, d, J = 16.4 Hz, H-2a), 2.48 (1H, d, J =
16.4 Hz, H-2b), 4.32 (1H, dq, J = 6.4, 6.4 Hz, H-9), 5.79 (1H,
d, J = 16.0 Hz, H-7), 5.80 (1H, dd, J = 16.0, 6.4 Hz, H-8), 5.88
(1H, q, J = 1.4 Hz, H-4); 13C NMR (50 MHz, CD 3OD) /ppm
42.1 (s, C-1), 50.4 (t, C-2), 200.8 (s, C-3), 126.8 (d, C-4),
167.1 (s, C-5), 80.0 (s, C-6), 129.6 (d, C-7), 136.6 (d, C-8),
68.3 (d, C-9), 19.2 (q, C-10), 24.2 (q, C-11), 23.5 (q, C-12),
23.1 (q, C-13); EI-MS m/z (rel. int ) 206 (5, M-18 +), 168
(24), 150 (21), 135 (21), 125 (45), 124 (100), 122(32).
Methylparaben (15)
Colorless needles (MeOH); mp 129~131 C; UV max/
nm 225, 257, 310; IR max/cm -1 3400, 2960, 2850, 1695,
1610, 1590; 1H NMR (CD3OD) /ppm 3.85 (3H, s, COOCH3),
6.82 (2H, d, J =8 .7 Hz, H-3 & H-5), 7.86 (2H, d, J = 8.7 Hz,
H-2 & H-6); EI-MS m/z (rel. int ) 135 (100, M +), 121 (35),
93 (23), 77 (20).
p-Hydroxybenzoic acid (16)
Colorless oil (MeOH); UV max/nm 252, 285, 290; IR
max/cm-1 3400, 1650, 1590, 1500, 840; 1H NMR (CD3OD)
/ppm 6.79 (2H, d, J = 8.8 Hz, H-3 & H-5), 7.85 (2H, d, J = 8.8
Hz, H-2 & H-6); EI-MS m/z (rel. int ) 138 (100, M + ), 121
(35), 93 (23), 77 (20).
Vanillic acid (17)
Colorless needles (MeOH); mp 210~212 C; UV max/
nm 220, 264, 300; IR max/cm -1 3600, 3400, 1680, 1590,
1500; 1H NMR (CD 3OD) /ppm 3.88 (3H, s, C3-OCH3), 6.83
(1H, d, J = 8.8 Hz, H-5), 7.54 (1H, dd, J = 8.8, 1.8 Hz, H-6),
7.56 (1H, d, J = 1.8 Hz, H-2); EI-MS m/z (rel. int ) 168 (100,

The Constituents of Lindera glauca

M+), 153 (55), 116 (17), 88 (12), 79 (9).
Syringic acid (18)
Pale brown nee dles (MeOH); mp 204~206 C; UV
max/nm 216, 238, 305; IR max/cm -1 3400, 1680, 1590,
1490; 1 H NMR (CD 3 OD) /ppm 3.89 (6H, s, C 3 -OCH 3 &
C5 -OCH 3), 7.33 (2H, s, H-2 & H-6); EI-MS m/z (rel. int )
198 (100, M +), 183 (46), 168 (17), 137 (26), 97 (15).
3, 4, 5-Trimethoxybenzoic acid (19)
Pale brown pow der (MeOH); mp 169~171 C; UV
max/nm 210, 248, 307; IR max/cm -1 3400, 1665, 1590,
1490; 1 H NMR (CD 3 OD) /ppm 3.89 (9H, s, C 3 -OCH 3 ,
C4-OCH3 & C5-OCH3), 7.33 (2H, s, H-2 & H-6); EI-MS m/z
(rel. int ) 212 (98, M+), 181 (100), 170 (13), 137 (19), 111
(9), 95 (21).
3-(3,4-Dihydroxyphenyl) propionic acid (20)
Amorphous powder (MeOH); UV max/nm 210, 250,
305; IR max/cm -1 3600, 3400, 2980, 2870, 1680, 1590,
1500; 1H NMR (CD3OD) /ppm 2.64 (2H, t, J = 8.0 Hz, H-2'),
3.66 (2H, t, J = 8.0 Hz, H-1'), 6.52 (1H, dd, J = 8.0, 2.0 Hz,
H-6), 6.65 (1H, d, J = 2.0 Hz, H-2), 6.67 (1H, d, J = 8.0 Hz,
H-5); EI-MS m/z (rel. int ) 182 (100, M + ), 154 (21), 123
(95), 93 (33).
Phytol (21)
Col or less oil (CHCl 3 ); UV max/nm 210, 235 ; IR
max/cm -1 3500, 2980, 2870, 1650, 1590; 1H NMR (CDCl 3)
/ppm 0.82~0.87 (12H, m, CH3-16, 18, 19 & 20), 1.66 (3H, s,
CH3-17), 1.98 (2H, t, J = 2.8 Hz, H-4), 4.14 (2H, d, J = 7.0 Hz,
H-1), 5.41 (1H, dd, J = 2.0 Hz, H-2); EI-MS m/z (rel. int )
296 (3, M +), 279 (17), 149 (100).
Squalene (22)
Colorless oil (CHCl 3); UV max/nm 335, 480, 510 ; IR
max/cm-1 1660, 1600; 1H NMR (CDCl 3) /ppm 1.60 (18H, s,
CH 3 -1, 24, 25, 26, 29, 30), 1.68 (6H, s, CH 3 -27, 28), 2.01
(20H, m, CH2-4, 5, 8, 9, 12, 13, 16, 17, 20, 21), 5.11 (6H, m,
H-3, 7, 11, 14, 18, 22); EI-MS m/z (rel. int ) 410 (3, M+), 341
(13), 277 (8), 137 (28), 109 (11), 81 (94), 69 (100).
-Sitosterol (23)
White needles (CHCl3); mp 139~141 C; [ ]24D -26 (c =
0.2, CHCl 3); UV max/nm 207; IR max/cm-1 3400, 2960,
2870, 1660, 1450, 1380; 1H NMR (CDCl 3) /ppm 0.67, 1.00
(each 3H, s, CH3-18 & 19), 0.81, 0.83 (each 3H, d, J = 6.8 Hz,
CH3-27 & 26), 0.86 (3H, d, J = 7.2 Hz, CH3-29), 0.91 (3H, d, J
= 6.4 Hz, CH 3-21), 3.49 (1H, m, H-3), 5.34 (1H, dd, J = 5.0,

J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

379

1.4 Hz, H-6); 13C NMR (50 MHz, CDCl3) /ppm 37.1 (t, C-1),
31.5 (t, C-2), 71.6 (d, C-3), 42.8 (t, C-4), 140.1 (s, C-5), 122.0
(d, C-6), 31.6 (t, C-7), 31.6 (d, C-8), 50.3(d, C-9), 36.3(s,
C-10), 21.3(t, C-11), 39.5 (t, C-12), 42.1 (s, C-13), 56.9 (d,
C-14), 24.5 (t, C-15),28.3 (t, C-16), 56.3 (d, C-17), 12.0 (q,
C-18), 19.5 (q, C-19), 36.3 (d, C-20), 18.9 (q, C-21), 34.1 (t,
C-22), 26.3 (t, C-23), 46.0 (d, C-24), 29.4 (d, C-25), 18.9 (q,
C-26), 19.2 (q, C-27), 23.2 (t, C-28), 12.0 (q, C-29); EI-MS
m/z (rel. int ) 414 (100, M +), 396 (81), 381 (71), 303 (72),
213 (72), 159 (81), 145 (100).
-Sitostenone (24) & Stigmasta-4,22-dien-3-one (25)
White needles (CHCl3); mp 84~86 C; [ ]24D +86 (c =
0.05, CHCl 3); UV max/nm 227, 331; IR max/cm -1 1670,
1660, 1600; 1H NMR (CDCl3) /ppm 0.67 (3H, s, CH3-18),
0.81 (3H, d, J = 6.8 Hz, CH3-26), 0.85 (3H, s, CH 3-27), 0.87
(3H, t, J = 7.4 Hz, CH3-29), 0.94 (3H, d, J = 6.4 Hz, CH3-21),
1.02 (3H, s, CH3-19), 5.04 (1H, dd, J = 16.0, 8.4 Hz, H-22),
5.13 (1H, dd, J = 16.0, 8.4 Hz, H-23), 5.72 (1H, d, J = 1.4 Hz,
H-3); EI-MS m/z (rel. int ) 412 (100, M + ), 398 (43), 370
(31), 299 (38), 229 (72), 187 (9), 159 (82), 124 (85).
6 -Hydroxy- -Sitostenone (26) and 6 Hydroxystigmasterone (27)
White needles (MeOH); mp 204~206 C; [ ]24D +16 (c
= 0.1, CHCl 3); UV max/nm 225, 330; IR max/cm-1 3500,
1680, 1660, 1600; 1 H NMR (CDCl 3 ) /ppm 0.74 (3H, s,
CH3-18), 0.86 (3H, d, J = 6.4 Hz, CH3-26), 0.83 (3H, d, J = 6.4
Hz, CH3-27), 0.86 (3H, t, J = 6.8 Hz, CH 3-29), 0.93 (3H, d, J =
6.4 Hz, CH3-21), 4.35 (1H, t, J = 2.8 Hz, H-6), 5.11 (2H, m,
H-22 & 23), 5.81 (1H, m, H-4); EI-MS m/z (rel. int ) 428
(100, M +), 414 (53), 227 (36), 152 (82).
-Sitosteryl-D-glucoside (28)
White needles (MeOH); mp 276~278 C; [ ]24D -50 (c
= 0.2, MeOH); IR max/cm-1 3400, 2980, 2870, 1450, 1380;
1
H NMR (pyridine-D5) /ppm 0.67 (3H, s, CH3-18), 0.86 (3H,
s, CH 3 -26), 0.88 (3H, s, CH 3 -27), 0.92 (3H, d, J = 6.4 Hz,
CH 3 -21), 0.94 (3H, t, J = 7.4 Hz, CH 3 -29), 1.01 (3H, s,
CH3-19), 3.98 (1H, m, H-3), 4.05~4.60 (6H, m, sugar moiety
H), 5.06 (1H, d, J = 6.8 Hz, anomeric H), 5.36 (1H, br. d, H-6);
EI-MS m/z (rel. int ) 396 (96, M-180 +), 381 (10, M-33 +),
329 (2, [M-18-67]+).

ACKNOWLEDGMENT
This in ves ti ga tion was sup ported by a grant from the
National Science Council of the Republic of China (NSC-87-

380

J. Chin. Chem. Soc., Vol. 47, No. 2, 2000

2113-M-037-009)

Received August 4, 1999.

Key Words
Lindera glauca; Alkaloids; Flavonoids;
Benzenoids; Diterpenes; Triterpens; Steroids;
(+)-3-Chloro-N-formylnornantenine.

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