Agricultural and Biological Chemistry

ISSN: 0002-1369 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/tbbb19

Isolation from Nutmeg of Growth Inhibitory

Substances to Silkworm Larvae

Akira Isogai, Shigeo Murakoshi, Akinori Suzuki & Saburo Tamura

To cite this article: Akira Isogai, Shigeo Murakoshi, Akinori Suzuki & Saburo Tamura (1973)
Isolation from Nutmeg of Growth Inhibitory Substances to Silkworm Larvae, Agricultural and
Biological Chemistry, 37:4, 889-895, DOI: 10.1080/00021369.1973.10860739

To link to this article: https://doi.org/10.1080/00021369.1973.10860739

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 Agr. BioI. Chem., 37 (4), 889~895, 1973

Isolation from Nutmeg of Growth Inhibitory Substances to

Silkworm Larvae

Akira ISOGAI, Shigeo MURAKOSHI,* Akinori SUZUKI and Saburo TAMURA

Department of Agricultural Chemistry, The University of Tokyo. Bunkyo-ku. Tokyo

* Kanagawa Prefectural Institute of Sericultural Science, Ebina-shi. Kanagawa-ken
Received November 2, 1972

From nutmeg, a seed of Myristicafragrans Houtt., were isolated thirteen phenylpropanoids.

Among them, seven compounds have been hitherto unknown. Most of the compounds isolated
here revealed growth inhibitory activity to silkworm larvae, Bombvx
. mori L .

During the course of our screening search
for natural products with biological activity
to insects, we examined effects of various
drug plants on the growth and morphogenesis
of silkworm larvae, Bombyx mori L. The
larvae were reared on artificial diets, to which
plant materials were added for oral administra-
tion. Of more than sixty samples tested,
nutmegs, seeds of Myristica fragrans Houtt.
being used as a spice, revealed extremely
interesting activity; the seeds inhibited the
growth of fourth instar larvae resulting in final
death or occasionally made them cause pupa-
tion without the fourth larval molting. From
our provisional trial, it was found that the
biological activity originated from neutral
and phenolic fractions. Then, we attempted
the separation of components causative of the
biological actions. This paper describes the
isolation of thirteen monomeric and dimeric
phenylpropanoids from nutmegs. Among
them, myristicin (V), methyl ether of eugenol
(VI), methyl ether of isoeugenol (VIII)1-3J
and 2,6-dimethoxy-4-allylphenol (XI),4-G) have
been separated earlier from the same plant,
and dehydrodiisoeugenol (X) and dehydro-
dieugenol (XII) have so far been obtained
through synthesis. -6 l2J
A large scale extraction was carried out
according to the procedure illustrated in Fig. I.
At first the plant material was extracted with
methylene chloride, and the extract was
evaporated under reduced pressure. The
residue was added with 95 % ethanol to pre-
cipitate a large amount of triglycerides mainly
composed of trimyristin. 3) After removal
of the precipitates, the filtrate was treated
with the conventional method to separate
neutral and phenolic fractions.
The neutral fraction was subjected to alu-
mina column chromatography, and the column
was eluted with benzene. After evaporation
of the solvent from the eluate, the residual oil
was further chroma to graphed on a silicic
acid column, which was eluted with hexane,
hexane-benzene, benzene, benzene-ethyl acetate
and ethyl acetate, successively. The eluates
with benzene-ethyl acetate and ethyl acetate
alone were combined and evaporated under
reduced pressure. The residue was applied
to thin-layer chromatography (TLC) by use
of silicic acid and alumina in order, and the
plate was developed with benzene-ethyl acetate
in each case to give compounds I, II, III and
IV (Fig. 2).
Since the neutral fraction seemed to contain
several related compounds other than these,
it was alternatively subjected to thorough
examination. The fraction was chromato-
graphed on an alumina column by the suc-
cessive use of hexane, hexane-benzene, ben-
zene, and benzene-ethyl acetate as eluants.
Compounds I and 111- IX were eluted out of
the column and subsequently purified with
preparative TLC using silicic acid and benzene
or benzene-ethyl acetate (Fig. 3). In this
case, compound II was not obtained probably
due to hydrolysis on the alumina column
890 A. ISOGAI, S. MURAKOSHI, A. SUZUKI and S. TAMURA

Nutmeg (1 kg)
Extd. with CH 2Cb
_ _ _ _ _ _--c_ _ _ _ _ _ _ _ _ _

I I
Residue Filtrate
Evapd. in vaCllO;
Added with 95 % EtOH;
Kept at O°C
I I
Precipitates Filtrate
Evapd. in vaCllO;
Dissolved in ether;
Washed with 5% HCI
and 5~';:; NaHCO:l
---------
I I
Aq. Layer Organic Layer
I, Extd. with 5 ~,~ NaOH
I I
Aq. Layer Organic Layer
Extd. with Dried over
I ether at pH 3 anhyd. Na2S04;
I -~-- I Evapd. in vacuo
Aq. Layer Ether Layer Neutral fraction
I
Dried over
anhyd. Na 2SO,;
, Evapd. ill vacuo
Phenolic fraction

FIG. I. Separation Procedure of Neutral and Phenolic Fractions from Nutmeg.

Neutral fraction (5 g)
I
AL03 column chromatography;
Eluted with benzene

I
Eluate

Evapd. ill vacuo

i

Crude oil

I, SiO z column chromatography

- - - - - - , - - - - ----,--------------c------,
I I I I I
Hexane Hexane-Benzene Benzene Benzene-Et acetate Et acetate
I_-----c-_ _ _ _ I
Si0 2 preparative TLC
(Benzene-Et acetate, 5: I)

Ab03 preparative TLC

(Benzene-Et acetate, 5: 1)
- - - --.-------"'-------,----------,-
I I I I
I II III IV
(14 mg) (321 mg) (95 mg) (108 mg)

FIG. 2. Isolation Procedure of Compounds I~IV from Neutral Fraction of Nutmeg.

 Growth Inhibitory Substances to Silkworm Larvae from Nutmeg 891

Neutral fraction (I6 g)

Alz03 column chromatography

I------~ I~------'" ~---- 1--------0
1
Hexane Hexane-Benzene Benzene Benzene-Et acetate
______ 1 _ _- ,

'8 1 ?) , 1 1 1 ---~ 1
( :- (7: 3) (6: 4) (4: 6) (2: 8)
1 1 1 1 1
Preparative Si0 2 TLC
1 1 1 1 1
V VI VII VIII IX 1 1
(3.5 g) (300 mg) (70 mg) (364 mg) (150 mg) III IV
(930 mg) (300 mg)
I
(15 mg)

FIG. 3. Isolation Procedure of Compounds I and III~IX from Neutral Fraction of Nutmeg.

Phenolic fraction (8 g)

SiO z column chromatography

-------
1
c- -----~·~-----.I

Benzene Benzene-Et acetate Benzene-Et acetate

(97:3) (90:10)
Benzene-Et acetate
(94: 6)
----'------ I
i 1
I

(Fr. No. 40 - 55) (Fr. No. 56 -72)

. I \
(Fr. No. 88-91)
. Cystn.
(Fr. No. 115-131)
Mother liq. ,,
XII
!
1 (50 mg)
X I
(350 mg) XIII
I Preparative (530 mg)
, SiO z TLC
(Benzene-Et acetate)
1
XI
(60 mg)

FIG. 4. Isolation Procedure of Compounds X - XIII from Phenolic Fraction of Nutmeg.

reSUlting in the formation of III. On the
basis of physicochemical data, compounds
V, VI and VII were identified as myristicin, and
methyl ethers of eugenol and isoeugenol.
The phenolic fraction was applied to a
silicic acid column. The column was eluted
with benzene and benzene-ethyl acetate in-
creasing stepwise the content of ethyl acetate
to give compounds X- XIII (Fig. 4). Com-
pounds X, XI and XII were identified as
dehydrodiisoeugenol, 2,6 - dimethoxy - 4 - allyl-
phenol and dehydrodieugenol based on the
chemical and spectrometric evidences. Com-
pound X, C 2o H n 0 4, was converted into methyl
ether, p-nitrobenzoyl ester and dihydroderi-
vative, whose physicochemical properties
showed complete identity with those reported
for the corresponding derivatives of dehyd-
6 9 121
rodiisoeugenoI. - •
Compound XI, C ll H 14 0 3 , gave elemicine 2 !
on treatment with dimethyl sulfate and sodium
hydroxide. Benzoyl ester of XI melted at
7S-76°C showing its identity with the
corresponding ester of 2,6-dimethoxy-4-
ally Iphenol. 4.51
The NMR spectrum of compound XII,
892 A. ISOGAI, S. MURAKOSHI, A. SUZUKI and S. TAMURA

C2oH2204, revealed an ABCXAype signal Compounds I~IV, VIII, IX and XIII

(4H, br d, (5 3.39; 4H, m, (5 4.9~5.3; 2H, m, isolated in this experiment have been con-
(5 5. 7 ~6.4) which is ascribable to two allyl firmed to be phenylpropanoids hitherto un-
groups attached to aromatic rings. Through known. Details of the results leading to
catalytic hydrogenation to a tetrahydroderiva- structure elucidation will be reported elsewhere
tive followed by acetylation to a diacetyl- in the near future.
tetrahydroderivative (XIIb), compound XII As for the biological activity of the phenyl-
6 9 1
was established as dehydrodieugenoI. • - 1} propanoids tested, compound VIII showed
most striking action causing the death in all
fourth instar larvae of silkworm 3 days after oral
R, administration at a dosage of 300 ppm in the
diet. Interestingly, compound IV revealed
Rz antifeeding effect on the larvae at 50 ppm
resulting in the inhibition of their growth. As
Compd. R, R2 a sole exception, dehydrodiisoeugenol (X)
VIII O-CH2-0 hardly showed any efficacy even at 500 ppm.
IX O-CHz--O The result of bioassay will be described in the
X OCH3 OH
succeeding paper in detail.

R,,- EXPERIMENTAL

All melting points are uncorrected. UV spectra

were determined on a Cary spectrophotometer Model
Compd. R, R2 R3 R4
14. IR spectra were recorded on a JASCO Model
V
VI
CH,-CH~CH,
-
CH2-CH~CH2
- O-CH2-0
OCH3 OCH3
OCH 3
H IR-S infrared spectrophotometer. NMR spectra
VII CH~CH-CH3 OCH3 OCH 3 H were measured with a JEOL JNM-MH-60 NMR
Xl CH2-CH~CH2 OCH3 OH OCH 3 spectrometer and a JEOL JNM-4H-lOO NMR spectro-
meter. Chemical shifts are given in 0 values from tetra-
R, methyl silane as an internal standard. Mass spectra
I H were obtained with a Hitachi RMU-6 mass spectro-
R"O- -C-C-CH
H I 3 meter, and high resolution mass spectra were determin-
o ed with a Hitachi RMH-2 mass spectrometer equipped
HFO OCH3 with a Hitachi Datalizer-002. Gas chromatography
was performed with a Hitachi K53 gas chromatograph
equipped with a FlD detector. Thin-layer chromato-
graphy (TLC) was carried out using silicic acid GF254
(Merck) or alumina GF 254 (Merck). For preparative
Hz TLC these materials were used as plates of 0.5 mm
Compd. R, thickness. Spots were detected with a UV lamp and
R2 R3
I H CH 3 OCH3 an h-bath. Column chromatography was performed
II OAc CH3 H using aluminum oxide (Merck) or silicic acid (Mallin-
III OH CH3 H ckrodt).
IV OH CH, OCH3
XIII OH H H Plant material. Nutmeg is a dried seed kernel of
AJyristica fragrans Houtt. The material used in this
CH z CH z
II 1/ experiment was a powdery matter supplied from Fuji-
CH CH sawa Pharmaceutical Co., Ltd.
I I
CH z CH 2
Bioassay. During the fractionation of active
components from nutmeg, bioassay was carried out in
the following way. An appropriate amount of the
sample to be tested was dissolved in a small amount
OH OH
of a suitable solvent (distilled water, acetone or
XII methanol) and added to the mixture composed of
 Growth Inhibitory Substances to Silkworm Larvae from Nutmeg
mulberry leaf powder (50~~), defatted soybean meal
(24 %), cellulose powder (15 %), agar powder (5 %),
citric acid (4 ~Io), L-ascorbic acid (1.5 %) and sorbic acid
(0.5 %). Then, the mixture was added with distilled
water at a ratio of 2.5 ml/g solid and was steamed at
Q
80-85 C for 15 min. Fourth or fifth instar larvae of
silkworm (Bombyx mori L.) were reared on the artificial
diet thus prepared, and their growth was compared
with that of the control insects fed on the diet lacking
the test sample.
Separation of neutral and phenolic fractions from nutmeg
The procedure of separation is illustrated in Fig. 1.
The powdery material (1 kg) was extracted with three
3 liter-portions of CH 2CIz. After filtration the ex-
tracts were combined and evaporated under reduced
pressure. The residual oil was added with 600 ml of
95 % ethanol and kept at O°C overnight. Precipitates
of triglycerides were rapidly filtered by use of a Buchner
funnel and were washed with a small volume of cold
95 % ethanol. The filtrate was evaporated under
reduced pressure, and the residual brown oil was
dissolved in 500 ml of ether. The ether solution was
successively shaken with each three 150 ml-portions of
5~~ NaHC03, 5% HCI and 5/~ NaOH. After drying
over anhyd. Na 2SO" the ether layer was evaporated
under reduced pressure to give a neutral fraction as
a brownish yellow oil (21 g). The NaOH solution
separated from the ether layer was acidified to pH 3
with dil. H Cl and extracted with three 150 ml-portions
of ethyl acetate. The combined extracts were dried
over anhyd. Na 2SO, and evaporated under reduced
pressure to give a phenolic fraction as a brown oil
(14 g).
Isolation of compollnds I ~ IX from neutral fraction
A. The neutral fraction (5 g) was dissolved in 10 ml
of benzene and applied onto an alumina column
(200 g, 35 i 250 mm), which was then eluted with 1.1
liter of benzene. After evaporation of the solvent
from the eluate, the residual oil (2.3 g) was dissolved
in 5 ml of hexane-benzene (2: I) and placed on a silicic
acid column (200 g, 35, 450 mm). The column was
successively eluted with hexane-benzene (2: 1,3.0 liter;
1: 1, 2.5 liter; 2: 3, 2.0 liter; 1: 3, 2.4 liter), benzene
(1.1 liter), benzene-ethyl acetate (98: 2, 1.5 liter; 95: 5,
2.0 liter; 90: 10, 2.1 liter; 80: 20, 2.2 liter; 75: 25,
2.3 liter; 50: 50, 2.0 liter) and ethyl acetate (2.0 liter).
The eluates with benzene-ethyl acetate and ethyl
acetate, both showing biological activity, were combin-
ed and evaporated under reduced pressure. The
residue was applied to preparative TLC by successive
use of silicic acid and alumina, and the plate was
developed with benzene-ethyl acetate (5: I) in each
case. Thus, compounds I and II were obtained as
oils (14 mg and 321 mg), while compounds III and IV
as crystals (95 mg and 108 mg). Recrystallization of
893
III and IV from hexane-benzene afforded colorless
prisms melting at 65.0~ 66.0'C and 65.5 ~ 66.5 °c,
respectively.
Rf values of the compounds on silicic acid TLC:
I, 0.44; II, 0.39; III, 0.33; IV, 0.33. On alumina
TLC: 1,0.65; II, 0.56; Ill, 0.40; IV, 0.33.
B. The neutral fraction (16 g) was dissolved in 20 ml
of hexane and applied onto an alumina column (1600 g,
60 x 630 mm). The column was successively eluted
with hexane (5.0 liter), hexane-benzene (8: 2, 3.0 liter;
7: 3, 3.0 liter; 6: 4,4.0 liter; 5: 5,4.0 liter; 4: 6,4.5
liter; 3: 7, 3.6 liter; 2: 8, 2.0 liter; 1: 9, 3.0 liter),
benzene (4.5 liter), benzene-ethyl acetate (99: I, 3.0
liter; 98: 2, 3.0 liter; 95: 5, 6.0 liter, 90: 10, 3.0 liter;
80: 20, 5.0 liter) and ethyl acetate (2.0 liter). As
illustrated in Fig. 3, elution with hexane-benzene
mixtures followed by preparative silicic acid TLC
using benzene afforded compounds V (oil, 3.5 g), VI
(oil, 300 mg), VII (oil, 70 mg), VIII (364 mg, prisms
from hexane-benzene, mp 92.0~ 92.5°C), and IX
(oil, 150 mg). On a similar treatment, the eluate with
benzene alone gave compound I (15 mg), and the eluate
with benzene-ethyl acetate (97: 3) gave compounds
III and IV (930 mg and 300 mg).
Identification of compounds V, VI and VII
Compounds V, VI and VII were identified as my-
risticin, methyl ether of eugenol and methyl ether of
isoeugenol, respectively, in comparison of their IR
and NMR spectra and gas chromatograms with those
of authentic samples.
Compound V. Colorless oil. IR ~~,i,1;, cm- 1 : 1630,
1500, 1426, 1320, 1193, 1134, 1093, 1044. NMR (in
CCl,) ,i: 3.23 (2H, br d, J=6.0 Hz), 3.85 (3H, s),
4.9~5.3 (2H, m), 5.6~6.3 (lH, m), 5.88 (2H, s), 6.28
(2H, br s).
Compound VI. Colorless oil. IR ~;;;~~ cm- l : 1635,
1590, 1510, 1265, 1235, 1155, 1140, 1030. NMR
(in CCLd rJ: 3.28 (2H, br d, J = 6.0 Hz), 3.76 (6H, s),
4.9~5.3 (2H, m), 5.6~6.3 (IH, m), 6.6~6.7 (3H, m).
Compound VII. Colorless oil. lR ));;;l~ cm- 1 : 1605,
1585, 1512, 1270, 1235, 1158, 1140, 1020, 961.
NMR (in CCl,) rJ: 1.84 (3H, d, J=5.2 Hz), 3.80 (6H, s),
6.02 (1 H, dq, J = 15.0, 5.2 Hz), 6.26 (1 H, d, J = 15.0 Hz),
6.6-6.9 (3H, m).
Gas chromatography. Column: PEG 20M (3 ~{
v
on Chromosorb W); 1 m; 130 C. Carrier gas: N2
at 1.0 kg/cm2. Retention times: V, 7.4 min; VI, 2.9
min; VII, 5.8 min.
Isolatioll of compounds X XIII from phenolic fraction
The phenolic fraction (8 g) was dissolved in 10 ml
of benzene and placed on a silicic acid column (650 g,
894 A. ISOGAI, S. MURAKOSHI, A. SUZUKI and S. TAMURA
60 >; 480 mm). The column was successively eluted
with benzene (10 liter) and benzene-ethyl acetate
(97: 3, 6 liter; 94: 6, 3 liter; 90: 10, 4 liter), fractions
being collected by 150 ml each (Fig. 4). The eluates
with benzene alone (Fraction No. 40~ 55) gave com-
pound X, which was recrystallized from hexane-benzene
to afford colorless needles (350 mg). The mother
liquor from the recrystallization was combined with
the eluates with benzene (Fraction No. 56~72) and
evaporated under reduced pressure. The residue was
subjected to preparative silicic acid TLC by use of
benzene-ethyl acetate to give compound XI as an oil
(60 mg). The eluates with benzene-ethyl acetate
(97: 3) (Fraction No. 88~91) gave compound XII as
crystals (50 mg). Recrystallization of XII from
benzene afforded colorless plates. From the eluates
with benzene-ethyl acetate (94: 6) was obtained com-
pound XIII, which was recrystallized from hexane-
benzene to yield colorless rods (530 mg).
ldellfification of compound X
Compound X was identified as dehydrodiisoeugenol
based on the following experiments.
Compound X. Mp 133~134°C(Lit.61 133~134°C).
Ms m/e: 326 (M+). Anal Found: C, 73.69; H, 6.76.
Calcd. for C 2o H 22 0,: C, 73.60; H, 6.79 ~~. UV
A~;;l~13 mi' (log E): 278 (4.34), 298 (shoulder). IR !i::'l~j~'1
cm- I : 3450, 1610, 1515, 1495, 1280, 1220, 1145, 1128,
1031,960. NMR (in CDCb) iJ: 1.37 (3H, d, J=7.0 Hz),
1.85 (3H, d, J = 5.5 Hz), 3.43 (lH, m), 3.86 (3H, s),
3.89 (3H, s), 5.12 (lH, d, J=9.0 Hz), 5.72 OH, s),
6.18 (1 H, q d, J = 5.5, 14.0 Hz), 6.37 (1 H, d, J = 14.0
Hz), 6.82 (2H, br s), 6.92~6.99 (3H, m).
Methyl ether of X. Treatment of X with dimethyl
sulfate and NaOH in ethanol gave the corresponding
methyl ether. Colorless needles from hexane-benzene.
Mp 119.5~120.5'C (Lit 61 126°C). MS m/e 340
(M). C 2I H,,04. IR ,,;;,,~j,ol cm- I : 1600, 1515, 1495,
1420, 1272, 1243, 1223, 1166, 1148, 1127, 1020, 960.
p-Nitrophenzoyl ester of X. X (30 mg) was treated
with 30 mg of p-nitrobenzoyl chloride in I ml of py-
ridine. After shaking overnight the reaction mixture
was poured into ice water containing HCI. The
aqueous solution was extracted with ethyl acetate. The
extract was successively washed with 5 % HCI and
5 /~ NaHCO:) and dried over anhyd. Na 2SO,. After
evaporation of the solvent, the residual oil (20 mg)
was subjected to preparative silicic acid TLC by use of
benzene-ethyl acetate. The solid thus obtained was
recrystallized from methanol to give orange needles
(5 mg). Mp 155~156°C (Lit,121 155~157°C).
C 27H2S07N. MS m/e: 475 (M+). IR !i::'~.~l cm- I :
1740, 1605, 1510, 1492, 1270, 1166, 1149, 1134, 1080,
1032, 964.
Hydrogenation of X. Hydrogenation of X in metha-
nol over 5 %Pd-C afforded a dihydro derivative. Color-
less needles from hexane-benzene. Mp 94~95°C.
C2oH2404. MS m/e: 328 (M+). IR !i::'~j,;'l cm- 1 :
3470, 1610, 1515, 1495, 1332, 1283, 1220, 1171, 1146,
1130, 1035, 955. NMR (in CDCh) 0: 0.96 (3H, t,
J=7.0 Hz), 1.36 (3H, d, J=7.0 Hz), 1.64 (2H, m),
2.55 (2H, t, J=7.2 Hz), 3.42 (lH, q d, J=9.5, 7.0 Hz),
3.87 (6H, s), 5.07 (lH, d, J=9.5 Hz), 5.61 (lH, s),
6.59 (2H, br s), 6.88~6.98 (3H, m).
Identification of compound XI
Compound XI was identified as 2,6-dimethoxy-4-
allyl phenol based on the following experiments.
Compound XI. Colorless oil. MS m/e: 194.0948
(M"'). Calcd. for C ll HII03: 194.0942. IR !i~l~ cm- I :
3530,1610,1512,1422,1330,1232,1213,1117. NMR
(in CCl,) 0: 3.28 (2H, br d, J=6.5 Hz), 5.6~6.3 OH,
m), 4.9~ 5.3 (2H, m), 6.34 (2H, s), 3.85 (6H, s).
Methyl ether of XI. Treatment of XI with dimethyl
sulfate and NaOH in methanol afforded the correspond-
ing methyl ether. MS m/e: 208 (M+). C I2 HlS03.
IR !i~:,;~ cm- I : 1638, 1589, 1500, 1415, 1332, 1240,
1130, 1040. NMR (in CCI 4) (j: 3.30 (2H, br d, J =
6.5 Hz), 3.72 (3H, s), 3.81 (6H, s), 5.6~6.3 (tH, m),
4.9 ~ 5.3 (2H, m), 6.34 (2H, s). NMR (in CsDs) a:
3.26 (2H, br d, J=7.0 Hz), 3.50 (6H, s), 3.86 (3H, s),
4.9~5.3 (2H, m), 5.6~6.3 (tH, m), 6.41 (2H, s). Rf
value on silicic acid TLC by use of benzene: 0.28.
These data were completely identical with those of
an authentic sam;Jle of elemicine,21 which was supplied
from Dr. K. Hayashi.
Benzoyl ester of XI. XI (20 mg) and benzoyl
chloride (100 mg) was treated in the similar manner as
that for the p-nitrobenzoylation of X. The crude
product was purified through alumina column chroma-
tography using benzene followed by recrystallization
from hexane-benzene to give colorless prisms (6 mg).
Mp 75~76°C (Lit." 76~77CC). MS m/e: 298 (M+).
C 18H 1s0 4 • IR !i~,'~.~J cm- I : 1742, 1635, 1602, 1505,
1418, 1262, 1203, 1136, 1083, 1068, 1028.
Identification of compound XII.
Compound XII was identified as dehydrodieugenol
based on the following experiments.
Compound XII. Mp 106.0~ 106.5°C (Lit,10' 104
~ 105°C). MS l11/e: 326.1525 (M+). Calcd. for
C 2oH 22 0,,: 326.1517. UV A~!~13 ml' (log 0): 290 (3.82).
IR ))::'~.~1 cm- 1 : 3360, 3220, 1638, 1598, 1488, 1420,
1262, 1226, 1146, 1046, 855. NMR (in CDCla) 0:
3.39 (4H, br d, J=6.0 Hz), 3.91 (6H, s), 4.9~5.3
(4H, m), 5.7 ~6.4 (2H, m), 6.09 (2H, br s), 6.89 (4H,
br s).
 Growth Inhibitory Substances to Silkworm Larvae from Nutmeg
Hydrogenation of XII. Hydrogenation of XII in l. Tomita and Miss T. Tadokoro of the Institute for
methanol over Pt02 afforded a tetrahydro derivative. their technical assistance.
Colorless prisms from benzene. Mp 151.0-152.5'C
(Lit. ) 150~ 152'Cj. MS l11/e: 330 (M+). C 2o H2 60".
IO
IR ~~,';,~l cm- 1: 3350, 3260, 1600, 1490, 1420, 1265,
1228, 1148, 1050, 855.
I)
AcetylctiJn oftetrahydro derivative. The tetrahydro
derivative of XII was treated with acetic anhydride in 2)
pyridine to give an oily diacetate. IO ) MS m/e: 414 3)
(M+). C 24 H3006. IR ~~{1~' cm- 1 : 1770, 1592, 1485,
1410, 1278, 1195, 1I42, 1050. NMR (in CDC!,) ri: 4)
0.94 (6H, t, J=7.0 Hz), 1.66 (4H, m), 2.08 (6H, s),
2.60 (4H, t, J=7.2 Hz), 3.84 (6H, s), 6.70 (2H, d, 5)
J=2.0 Hz), 6.80 (2H, d, J=2.0 Hz).
6)
Acknowledgement. We wish to express our thanks 7)
to Fujisawa Pharmaceutical Company, Ltd. for pro-
viding nutmeg, and to Dr. K. Hayashi of T. Hasegawa
Company, Ltd. for supplying authentic samples of 8)
elemicine and myristicin. We are grateful to Professor
J. Nakano, Department of Forestry Products, The 9)
University of Tokyo, for his valuable suggestions. We
also wish to thank Mr. K. Aizawa and his colleagues of 10)
the Analytical Laboratory of our Department for II)
spectral measurements and elemental analysis. We 12)
thank Mr. K. Morii of Kanagawa Prefectural Institute
of Sericultural Science for his encouragement, and Mr.
895
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