3-(4-Methyl-3-pentenyl)-2(5H)-furanone, alpha,alpha-acariolide and 4-(4-methyl-3-pentenyl)-2(5H)-furanone, alpha,beta-acariolide: new monoterpene lactones from the astigmatid mites, Schwiebea araujoae and Rhizoglyphus sp. (Astigmata: Acaridae).

Article abstract of DOI:10.1271/bbb.66.135

A new monoterpene lactone from the acarid mite, Schwiebea araujoae, was elucidated without its isolation by GC/FT-IR and GC/MS analyses to be 3-(4-methyl-3-pentenyl)-2(5H)-furanone (1) and tentatively named as alpha,alpha-acariolide. The structure of 1 was identified by its synthesis from alpha-bromo-gamma-butyrolactone via 4 reaction steps. The synthesized compound gave the same GC/MS and GC/FT-IR spectra as those of the natural product. The other monoterpene lactone was likewise elucidated from the unidentified Rhizoglyphus mite to be 4-(4-methyl-3-pentenyl)-2(5H)-furanone (2) and named as alpha,beta-acariolide; it was also identified by its synthesis in 5 reaction steps from the same butyrolactone as the starting material. GC/MS and GC/FT-IR spectra of the preparation were identical to those of the natural product.

Full text of DOI:10.1271/bbb.66.135

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3-(4-Methyl-3-pentenyl)-2(5H)-furanone, α,α-
Acariolide and 4-(4-Methyl-3-pentenyl)-2(5H)-
furanone, α,β-Acariolide:
a
a
a
b
a
Hirokazu TARUI , Naoki MORI , Ritsuo NISHIDA , Kimiko OKABE & Yasumasa KUWAHARA
a
Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University
Sakyo-ku, Kyoto 606-8502, Japan
b
Forest Insect Management Laboratory, Forestry and Forest Products Research Institute
Tsukuba Norin Kenkyu Danchi, P.O. Box 16, Ibaraki 305-8687, Japan
Published online: 22 May 2014.
To cite this article: Hirokazu TARUI, Naoki MORI, Ritsuo NISHIDA, Kimiko OKABE & Yasumasa KUWAHARA (2002) 3-
(4-Methyl-3-pentenyl)-2(5H)-furanone, α,α-Acariolide and 4-(4-Methyl-3-pentenyl)-2(5H)-furanone, α,β-Acariolide:,
Bioscience, Biotechnology, and Biochemistry, 66:1, 135-140, DOI: 10.1271/bbb.66.135
To link to this article: http://dx.doi.org/10.1271/bbb.66.135
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Biosci. Biotechnol. Biochem., 66 (1), 135–140, 2002
3
-(4-Methyl-3-pentenyl)-2(5
H
)-furanone,
a
,
a
-Acariolide
-Acariolide:
and 4-(4-Methyl-3-pentenyl)-2(5
H
)-furanone, a, b
New Monoterpene Lactones from the Astigmatid Mites,
Schwiebea araujoae and Rhizoglyphus sp. (Astigmata: Acaridae)†
Hirokazu TARUI, Naoki MORI, Ritsuo NISHIDA, Kimiko OKABE* and Yasumasa KUWAHARA††
Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku,
Kyoto 606-8502, Japan
*
Forest Insect Management Laboratory, Forestry and Forest Products Research Institute, Tsukuba Norin
Kenkyu Danchi, P.O. Box 16, Ibaraki 305-8687, Japan
Received August 6, 2001; Accepted September 25, 2001
A new monoterpene lactone from the acarid mite,
Schwiebea araujoae, was elucidated without its isolation
Several compounds also function as anti fungal sub-
3–5)
stances.
by GC FT-IR and GC MS analyses to be 3-(4-methyl-3-
W
W
In the present study, two monoterpenoids were
newly found from the acarid mite Schwiebea
araujoae, and from an unidentiˆed Rhizoglyphus sp.
pentenyl)-2(5
H
)-furanone (1) and tentatively named as
a,
a
-acariolide. The structure of 1 was identiˆed by its
synthesis from -bromo- -butyrolactone via 4 reaction
steps. The synthesized compound gave the same GC
a
g
1)
other than those already summarized. Both species
W
collected from organic soil are possible pests of
agricultural crops. In order to elucidate the chemical
structures of the remaining unidentiˆed components,
their opisthonotal gland secretions were reinvestigat-
ed by using a mite extract prepared by dipping mites
in hexane for 3 min, and we could identify the struc-
ture of the two new monoterpenoids as each isomer
based on the mass fragmentation pattern. Both com-
pounds were identiˆed by syntheses.
MS and GC FT-IR spectra as those of the natural
product.
W
The other monoterpene lactone was likewise elucidat-
ed from the unidentiˆed Rhizoglyphus mite to be 4-(4-
methyl-3-pentenyl)-2(5
H )-furanone (2) and named as
a, b
-acariolide; it was also identiˆed by its synthesis in 5
reaction steps from the same butyrolactone as the start-
ing material. GC MS and GC FT-IR spectra of the
W
W
preparation were identical to those of the natural
product.
In the hexane rinse of Schwiebea araujoae females,
a new compound (1,
R
t : 12.34 min) was recognized as
the second major component after heptadecadiene
: 14.88 min) by a GC MS analysis. The following
Key words: Schwiebea araujoae; monoterpene lac-
(
t
R
W
tone;
tenyl)-2(5
4-methyl-3-pentenyl)-2(5
a,a-acariolide; 3-(4-methyl-3-pen-
eight compounds in decreasing order were also ob-
H
)-furanone;
a
H
,
b
-acariolide, 4-
6)
served in the extract: isorobinal
(
(
t
t
R
: 10.99 min),
: 10.06 min),
(
)-furanone
7)
8)
neral
(
t
R
: 9.48 min),
a
-acaridial
R
9
)
10)
robinal
(
t
R
: 12.03 min), dehydrocineole
(
t
R
: 5.62
We are studying the chemical components excreted
from the pair of opisthonotal glands commonly
present among astigmatid mites for as many species
of mites as possible. Parts of these compounds func-
tion as semiochemicals (alarm, aggregation and sex
pheromones) to each corresponding species. At
present, a total of 67 compounds comprising mono-
terpenes, hydrocarbons and aromatics have so far
been identiˆed as the opisthonotal gland components
from 52 species of astigmatid mites belonging to 9
min), heptadecene (
t
R
: 14.95 min) and isopiperite-
1
1)
+
none
(
t
R
: 9.96 min). Compound 1 gave the M ion
) and the base ion at m z 69
at m z 166 (31
z
W
W
(100
z
) together with a characteristic diagnostic ion
at m z 98 (81
z
) (Fig. 1). The base ion at m z 69
W
W
suggested the presence of a 4-methyl-3-pentenyl
moiety in the molecule. The rearranged fragment ion
at m z 98 implies an other part of the molecule,
W
because the sum of m z 69 and m z 98 is m z 166
W
W
W
+
m z 1. The GC FT-IR spectrum of 1 indicated an
„1
W
W
1
)
families. The alarm pheromones have been identi-
ˆed in 16 species, the aggregation pheromones in two
unusually high C
＝
O band at 1791 cm , which is
evidence for the presence of a ˆve-membered con-
jugated lactone moiety (Fig. 2). The putative frag-
1
,2)
species, and the sex pheromones in seven species.
†
Chemical Ecology of Astigmatid Mites LXVI.
To whom correspondence should be addressed. Fax: +81-75-753-6312; E-mail: kuwa34
††
＠
kais.kyoto-u.ac.jp

1
36
H. TARUI et al.
Fig. 1. GC Mass Spectra of the Lactones.
W
A) Synthetic and B) Natural
a,a-Acariolide (1), C) Synthetic
and D) Natural -Acariolide (2).
a, b
Fig. 2. GC FT-IR Spectra of the Lactones.
W
A) Synthetic and B) Natural
a
,
a
-Acariolide (1), C) Synthetic
ment ion of a lactone with a methylene moiety cor-
and D) Natural a, b-Acariolide (2).
responds to m z 97 which actually appeared as the
W
rearranged ion at m z 98, as shown in Fig. 3. If
W
compound 1 is assumed to be an intramolecular
Canizzaro reaction product of a-acaridial present in
the species, the structure of 1 might be either 3-(4-
methyl-3-pentenyl)-2(5 )-furanone or 4-(4-methyl-
-pentenyl)-2(5 )-furanone.
During GC MS analyses of the extracts from an
H
3
H
W
unidentiˆed Rhizoglyphus mite, we found an other
compound (2,
t : 13.44 min) in addition to 1, both as
R
minor compounds as will be indicated later. Com-
pound 2 gave a similar mass spectrum to that of com-
pound 1, but with a diŠerent
R
t value. The species
was characterized from the other Rhizoglyphus spe-
6
)
cies by the presence of eicosadienal (t : 19.97 min,
R
often as the largest component) in the gland secre-
tion, together with the following 16 compounds in
Fig. 3. Putative Fragmentation to Generate Fragment Ions at
m z 98 and 69.
W
1
2)
decreasing order: tridecane
(
t
R
: 10.28 min),
a
-
1) From a,a-Acariolide (1); 2) from a, b-Acariolide (2).
8
)
13)
acaridial (
min), isorobinal (
min), 3-hydroxybenzene-1,2-dicarbaldehyde
t
R
: 10.06 min), neryl formate
(t
R
: 10.01
: 12.03
6
)
9)
t
R
: 10.99 min), robinal (
t
R
1
4)
(
t
R
:
The GC MS spectrum of 2 showed the same sets of
+
W
1
5)
1
0.21 min),
b
-acaridial
(
t
R
: 11.04 min), rhizo-
the following ions as those of 1: m z 166 (M , 8
z
),
, the rearranged
), m z 121 (8 ) and
W
1
6)
6)
glyphinyl formate
(
t
R
: 12.43 min), eicosenal
(
(
(
t
t
t
R
R
R
:
:
:
m z 69 (the base ion), m z 98 (28z
W
W
7
)
2
9
9
0.14 min), geraniol (
t
R
: 9.64 min), geranial
fragment ion), m z 138 (11
z
z
W
W
7
)
+
.90 min), 2, 1, nerol (
t
R
: 9.28 min), neral
: 7.37 min).
m z 109 (8
z
). The relative intensities of the M ion
W
1
7)
.48 min) and perillene
(
t
R
and m z 98 are lower than that of 1, whereas those of
W

a
,
a
-Acariolide and
a,
b
-Acariolide: New Monoterpene Lactones
137
m z 138, 121 and 109 are higher than 1. The GC FT-
W
W
IR spectrum of 2 indicated an unusually high C
＝
O
„
1
band at 1804 cm which also provided evidence for
the presence of a ˆve-membered and conjugated lac-
tone moiety, similar to those of 1. These results imply
a positional diŠerence of the 4-methyl-3-pentenyl
residue. The structure of 2 was, therefore, elucidated
to be an other isomer of 1, either 3-(4-methyl-
-pentenyl)-2(5
pentenyl)-2(5
The synthetic routes to 1 and 2 are shown in
Fig. 4. A mixture of -bromo- -butyrolactone and
dimethylsulˆde (Me S) was re‰uxed to give
methylthio- -butyrolactone (3, 96 ) by following
3
H
)-furanone
or
4-(4-methyl-3-
H
)-furanone.
Fig. 4. Synthetic Procedure for
Acariolide (2).
a,a-Acariolide (1) and a, b-
a
g
2
a-
a: Me
2
W W
S, re‰ux; b: LDA HMPA; c: OXONE MeOH; d: tol-
g
z
uene, re‰ux; e: DIBAL Et
2
W
2 2
O; f: PDC CH Cl
W
1
8)
the reported method. Butyrolactone 3 was then
reacted with 5-iodo-2-methyl-2-pentene dissolved in
hexamethylphosphoramide (HMPA) by using
lithium diisopropylamide (LDA) to give
-pentenyl)- -methylthio- -butyrolactone (4, 57
Oxidation of by 2KHSO
(OXONE) as reported gave
methyl-3-pentenyl)- -methylsulfonyl- -butyrolac-
tone (5, 50 ). Butyrolactone 5 was re‰uxed in tol-
). Reduction of
with diisobutylaluminum hydride (DIBAL) gave
-(4-methyl-3-pentenyl)-2-methylthio-1,4-butanediol
). Diol 6 was reacted with OXONE to give
-(4-methyl-3-pentenyl)-2-methylsulfonyl-1,4-
), and subsequent oxidation of 7
a-(4-methyl-
3
a
g
z)
1
9)
as reported.
KHSO SO
4
5
・
2
0)
4
K
2
4
a-(4-
a
g
z
Fig. 5. Co-relationships of Protons in Synthetic Compounds 1
uene to give target compound 1 (87
z
1
1
and 2 by H– H COSY Experimments.
4
2
1
1
(
6, 96
z
H– H COSY experiment is summarized in Fig. 5.
2
The GC MS and GC FT-IR spectra of synthetic 2
W
W
butanediol (7, 27
z
were identical to those of the natural product from
with pyridinium dichromate (PDC) gave target com-
Rhizoglyphus sp. (Figs. 1 and 2).
pound 2 (30
z
).
A similar monoterpene lactone, (E )-2-(4-methyl-
1
13
H-NMR together with C-NMR of synthetic 1
3-pentenylidene)-4-butanolide, has been identiˆed
demonstrated the presence of a prenyl group; two
from the mold mite, Tyrophagus putrescentiae, and
2
1)
methyls at
proton at
protons at
d
H
H
1.61 (3H, s) and 1.69 (3H, s), a vinyl
5.10 (1H, br.qn) and two methylene
2.24–2.33 (4H, m), together with a
named as b-acariolide in relation to b-acaridial.
d
The present identiˆcation of 1 and 2 provide the se-
cond and third examples of lactones being found
among astigmatid mites.
d
H
2
dimethyl-substituted sp carbon at
d
C
133.9. All the
7.15 (1H,
1.70 Hz) and an oxygen-substituted methy-
4.77 (2H, q, 1.70 Hz). These observa-
other protons observed were a vinyl at
qn,
lene at
d
H
In conclusion, 3-(4-methyl-3-pentenyl)-2(5
furanone (1) and 4-(4-methyl-3-pentenyl)-2(5
H
H
)-
)-
J
＝
d
H
J
＝
furanone (2) were identiˆed as new compounds
from the acarid mites, Schwiebea araujoae and
Rhizoglyphus sp., respectively. Compound 1 was
tions suggested that the lactone carbonyl must be en-
docyclically conjugated with the other double bond
1
1
in the molecule. The H– H COSY experiment also
tentatively named as
acariolide, correlating the ˆrst double bond to
acaridial [(
a
,
a
-acariolide, and 2 as
a
,
b
a
-
-
supported the structure of synthetic 1 (Fig. 5). The
GC MS and GC FT-IR spectra of synthetic 1 were
E
)-2-(4-methyl-3-pentenyl)-butenedial]
W
W
conˆrmed to be identical to those of the natural
product from Schwiebea araujoae females (Figs. 1
and 2).
and the alkenyl substituted position of the lactone
ring. Trial exposure of mites to each of synthetic
compounds 1 and 2 in stock cultures evoked no
remarked eŠect on either species, so their biological
functions remain obscure at present.
The chemical shifts of two methyls [
and 1.70 (3H, d, 1.40 Hz)], a vinyl [
6.95, 1.40 Hz)] and two methylenes [
2H, dt, 7.14, 6.95 Hz) and 2.45 (2H, t,
7.14 Hz)] in synthetic 2 indicated the presence of
d
H
1.62 (3H, s)
5.07 (1H,
2.29
J
＝
d
H
thp,
J
＝
d
H
(
J
＝
Experimental
J
＝
a prenyl group in the molecule, together with a
The astigmatid mite Schwiebea araujoae, was
collected from organic soil behind our laboratory
at Kyoto University. The other unidentiˆed
Rhizoglyphus sp. was collected from Kochinda in
Okinawa. Cultures of both species were maintained
2
dimethyl-substituted sp carbon at
other protons observed for synthetic 2 were a vinyl at
5.84 (1H, qn, 1.71 Hz) and an oxygen-substi-
tuted methylene at 4.73 (2H, d, 1.71 Hz). The
d
C
133.8. The
d
H
J
＝
d
H
J
＝

1
38
H. TARUI et al.
at 20
9
C under high humidity by feeding dried yeast.
puriˆed in a silica gel column by eluting with a mix-
GC MS was carried out by a Hewlett Packard
ture of hexane and ether to give 4 as a colorless oil
W
1
HP-5890 series II Plus gas chromatograph mass
(7.4 g, 57
(3H, s, CH
1.69 (3H, s, CH
2.08 (1H, ddd,
O–CH –), 2.11 (3H, s, CH
–C CH CH ), 2.42 (1H, ddd,
8.75 Hz, O–CH –), 4.34 (1H, dt,
1.34, O–CH –), 4.43 (1H, ddd, 10.83, 8.75, 6.08,
O–CH –) and 5.12 (1H, m, –CH
(75 MHz, CDCl : 11.4 (CH –S), 17.6 (–CH
22.9 (–CH –), 25.6 (–CH ), 32.8 (ring, –CH –), 34.9
–), 48.6 (ring, –C–), 65.1 (ring, O–CH –),
) and 175.4 (CO). GC MS:
z
). H-NMR (300 MHz, CDCl
3
)
d
H
: 1.63
W
spectrometer operated at 70 eV in the split-less mode,
3
C
＝
), 1.68 (1H, m, –C
H
2
CH
2
CH
CH
＝
＝
),
),
using an HP-5MS capillary column (0.25 mm ID
×
3
C
＝
), 1.95 (2H, m, –CH
2
3
0 m
ture was programmed from 60
C at the rate of 10 C min, using helium as the carri-
er gas at 1.20 ml min. GC FT-IR spectra were
×
0.25
m
m in ˆlm thickness). The oven tempera-
J
＝
13.65, 6.08, 1.34 Hz,
–S), 2.26 (1H, m,
13.65, 10.83,
8.75, 8.75,
9
C (2-min hold) to 290
2
C
H
2
3
9
9
H
2
2
＝
J
＝
W
2
C
H
2
J
＝
W
W
recorded by a Bio-Rad FT-IRD instrument coupled
with the foregoing GC apparatus and column under
the stated conditions.
2
J
＝
1
3
2
＝
). C-NMR
),
3
)
d
C
3
3
1
13
H- and C-NMR spectra were obtained by a
2
3
2
1
13
Bruker AC300 instrument ( H: 300 MHz, C:
(–CH
2
2
1
1
7
5 MHz) in CDCl
3
. H– H COSY analyses were car-
122.8 (CH
＝
), 132.7 (C
＝
W
W
+
ried out to conˆrm the structure of the synthetic
M
at m z 214 (21
z
) and the base ion at m z 132
W
1
compounds by a Bruker ARX500 instrument ( H:
with GC
t 14.88 min.
R
5
00 MHz). All the solvents used for syntheses were
dried and freshly distilled. Wako-gel C-200 was used
for column chromatography with the indicated sol-
vents. HRMS data were obtained by a Jeol JMS HX
HX 110A spectrometer.
a
-(4-Methyl-3-pentenyl)-
butyrolactone ( . A solution of OXONE, (1.4 g,
2.3 mmol) in water (30 ml) was added to a mixture of
methanol (15 ml) and 4 (500 mg, 2.3 mmol) at 0 C,
a-methylsulfonyl-g-
5
)
W
9
and the resulting cloudy slurry was kept for 6 hrs
while stirring. After the temperature has been raised
to r.t. while stirring and the mixture kept over night,
the product was extracted three times with ether. The
combined organic layers were successively washed
a
-Methylthio-
g
-butyrolactone (
3
)
. A mixture of
a
2
-
bromo- -butyrolactone (25 g, 150 mmol) and Me
g
S
(
50 ml, 680 mmol) was re‰uxed for 40 hrs in an N
2
atmosphere. After cooling to r.t., the precipitated
trimethylsulfonium bromide was removed by ˆltra-
tion, and the resulting residue was washed with ether.
The combined ˆltrate and washings were concentrat-
ed in vacuo to give a pale yellow oil which was puri-
ˆed in a silica gel column. The product (3) as an oil
with satd. NaHCO
Na SO . Oily yellowish product 5 (290 mg, 50
obtained after concentrating the extract. H-NMR
(300 MHz, CDCl : 1.62 (3H, s, CH ), 1.70
(3H, s, CH ), 2.08 (4H, m, –C CH–), 2.52
(1H, dt, 14.84, 8.70 Hz, O–CH –), 3.04 (1H,
ddd, 14.84, 8.70, 3.51 Hz, O–CH –), 3.09
(3H, s, CH SO –), 4.36 (1H, dt,
O–CH –), 4.51 (1H, q, 8.70, O–CH
(1H, br.t, –CH
17.6 (–CH ), 22.9 (ring –CH
(CH –S), 32.1 (–CH –), 36.0 (–CH
(O–CH –), 70.6 (ring C), 121.1 (–CH ), 134.4 (C+
and 172.8 (CO). GC : 16.97 min. GC MS: M at
m z 246 (8 ) and the base ion at m z 82.
3
and brine, and dried over
2
4
z) was
1
3
)
d
H
3
C
＝
3
C
＝
H
2
2
C
H
2
2
(
19.1 g, 96
with a mixture of hexane and ether. H-NMR
300 MHz, CDCl : 2.10–2.20 (1H, m, ring
CH(SMe)–), 2.29 (3H, s, S–CH ),
CH(SMe)–), 3.44
9.45, 4.69 Hz, ring CO–CH(SMe)–),
8.95, 8.06, 4.54 Hz, ring
–), 4.44 (1H, dt, 8.95, 7.52 Hz, ring
–). C-NMR (75 MHz, CDCl : 14.5
–), 40.8 (– H(SMe)–CO, 66.8
z
) was obtained in the fraction eluted
J
＝
＝
C
H
1
J
2
C
＝
H
2
(
3
)
d
H
3
2
J
8.70, 3.51,
O–CH
2
C
H
2
3
2
J
＝
2
–) and 5.06
1
3
2
.61–2.73 (1H, m, ring O–CH
2
C
H
2
＝
). C-NMR (75 MHz, CDCl
–), 25.1 (–CH ), 25.6
–), 66.5
3
)
d :
C
(
1H, dd,
J
＝
3
2
3
4
.33 (1H, ddd,
J
＝
3
2
2
O–C
O–C
H
H
2
CH
CH
2
J
＝
2
＝
＝
)
1
3
2
2
3
)
d
C
t
R
W
(
(
(
S–CH
–CH
82 ) and the base ion at m z 86 with
3
), 29.7 (–CH
2
C
z
W
W
+
2
–O), and 175.2 (CO). GC MS: M at m z 132
W
W
z
t
R
8.96 min.
a
,
a
-Acariolide (
290 mg) was re‰uxed for 7 hrs. After puriˆcation in
a silica gel column eluted with a mixture of hexane
and ether, the target compound (1, 170 mg, 87
1). A toluene (60 ml) solution of 5
W
(
a
-(4-Methyl-3-pentenyl)-
tone ( . A solution of 3 (8.0 g, 60 mmol) in THF
20 ml) was slowly added to a mixed solution of LDA
a-methylthio-g-butyrolac-
4
)
z)
1
(
was obtained as a colorless oil. H-NMR (300 MHz,
CDCl : 1.61 (3H, s, C–CH ), 1.69 (3H, s,
C–CH ), 2.24–2.33 (4H, m, CC CH ),
4.77 (2H, q, 1.70 Hz, –CH O–), 5.10 (1H, br.qn,
–CH C(Me) ) and 7.15 (1H, qn, 1.70 Hz,
O–CH ; 17.7
(–CH ), 25.4 (–CH ), 25.7 (–CH –),
), 133.0 (C ), 133.9
) and 174.4 (CO). GC
in heptane THF ethyl benzene (2
M
, 40 ml) and THF
3
)
d
3
H
＝
3
W
W
(
30 ml) at „78
9
C while stirring. After 1 hr of stir-
＝
＝
H
2
C
H
2
＝
ring, a solution of 5-iodo-2-methyl-2-pentene (12.6 g,
J
＝
2
6
0 mmol) in HMPA (10.7 g, 60 mmol) was slowly
2
C
2
H
＝
H
2
J
＝
3
1
3
added, and the mixture stirred for 3 hrs at „78 C.
9
C
＝
). C-NMR (75 MHz, CDCl
–), 25.6 (–CH
–), 122.7 (–CH
), 144.3 (ring –CH
)
d
C
The temperature was then raised to r.t. while stirring
3
2
3
2
and the mixture kept over night. After adding satd.
70.1 (O–CH
(ring C
2
＝
＝
aq. NH
times with ether , washed with brine and dried over
Na SO . After concentration, the crude product was
4
Cl, the reaction mixture was extracted three
＝
＝
W
+
MS: M at m z 166 (17
together with m z 98 (82 ) and m z 41 (54 ). GC
z z
z) and the base ion at m z 69
W
W
2
4
W
W

a
,
a
-Acariolide and
a,
b
-Acariolide: New Monoterpene Lactones
139
+
t
R
:
10
12.34 min. HRMS m z (M ): calcd. for
a
,
b
-Acariolide (
2
)
. To a CH
2
Cl
2
(20 ml) solution
W
C
H
14
O
2
, 166.0994; found, 166.0999.
of 7 (170 mg, 0.7 mmol), PDC (3.4 g, 9 mmol) was
added in several portions while stirring at r.t., and
the mixture was stirred for 2 days. After ˆltration,
the ˆltrate was chromatographed in a Florisil
column, and the product was eluted with ether. After
evaporating the solvent, the crude product was fur-
ther puriˆed in a silica gel column, and the product
2
-(4-Methyl-3-pentenyl)-2-methylthio-1,4-
butanediol ( . To a solution of -(4-methyl-3-
pentenyl)- -methylthio- -butyrolactone (4, 1.07 g,
mmol) in ether (10 ml), DIBAL (2 ml, 11 mmol)
was slowly added at 0 C and the mixture stirred for
hr at r.t. After adding satd. aq. NH Cl (10 ml) at
C, the product was obtained as the ˆltrate through
6
)
a
a
g
5
9
1
0
4
was eluted with ethylacetate and benzene to give 2
1
9
(30
: 1.62 (3H, s, CH
CH ), 2.29 (2H, d,t,
CH ), 2.45 (2H, t,
CH–CH ), 4.73 (2H, d,
C–CH –O), 5.07 (1H, tq,
C(Me) ) and 5.84 (1H, qn,
). C-NMR (75 MHz, CDCl
), 25.6 (–CH ), 25.7 (–CH –), 28.6 (–CH
73.1 (O–CH –), 115.5 (–C(O)– ), 121.9 (CH
133.8 (C ), 170.2 (ring C ) and 174.1 (CO). GC
z
) as a colorless oil. H-NMR (300 MHz, CDCl
3
)
Celite, and dried over Na
2
SO
4
. After evaporating the
d
H
3
C ), 1.70 (3H, d, J 1.40 Hz,
＝ ＝
solvent, the crude product was chromatographed on
3
C
＝
J
＝
7.14, 6.95 Hz
＝
7.14 Hz,
1.71 Hz,
silica gel, eluting with hexane and ether to give 6 as a
CH–C
H
2
2
C
＝
H C
2
＝
J
J
＝
＝
1
colorless oil (1.04 g, 95
CDCl
1
1
CH
(
(
C–CH
C(Me)
(
3
(
(
z
). H-NMR (300 MHz,
＝
＝
2
C
3
)
d
H
: 1.46–1.59 (2H, m, C–C
.62 (3H, s, CH ), 1.69 (3H, s, CH
.76–1.89 (2H, m, C–C CH
–S), 2.02–2.17 (2H, m, C–CH
2H, br s, –OH), 3.52 (2H, s, –C–CH
1H, m, C–CH –O), 3.83–3.91 (1H, m,
H
2
CH
2
CH
3
＝
＝
),
),
2
J
＝
6.95, 1.40 Hz,
1.71 Hz,
: 17.7
–),
),
3
C
＝
C
–CH
–C(O)–CH
(–CH
2
C
H
＝
＝
2
J
＝
3
1
3
H
2
2
–O), 1.95 (3H, s,
CH ), 3.01
–O), 3.70–3.78
)
d
C
3
2
C
H
2
＝
3
3
2
2
2
2
C
H
＝
＝
2
C
H
2
＝
＝
t
R
:
,
+
2
C
).
H
2
–O) and 5.08–5.12 (1H, m, –CH
2
C
H
＝
13.44 min. HRMS m z (M ): calcd. for C10
166.0994; found, 166.0998.
H
14
O
2
W
1
3
2
C-NMR (75 MHz, CDCl
), 22.1 (–CH
–), 52.5 (C), 58.7
–), 123.7 ( CH) and 132.2
) and the base
), 140
), 82 (63 ),
3
)
d
C
:
9.6
S–CH
3.8 (–CH
O–CH
＝
3
), 17.7 (–CH
3
2
–), 25.7 (–CH
3
),
2
–), 37.4 (–CH
2
Acknowledgments
2
–), 65.5 (O–CH
2
＝
z
+
C). GC MS: M at m z 218 (9
This study was partly supported by a grant-aid for
scientiˆc research from Ministry of Education,
Science, Sports and Culture of Japan (nos. 08406010,
09556010, 09876091 and 8956), and also by research
funding from Daily Foods Corporation (Tokyo). We
thank Dr. N. Akimoto of Faculty of Pharmaceutical
Sciences at Kyoto University for measuring the
HRMS data.
W
W
ion at m z 69 together with m z 152 (36
z
W
W
(
5
13
5 (30
z
), 121 (44
z
z
), 107 (29
z
z
), 95 (48
z
z
), and m z 41 (67
). GC
R
t : 16.34 min.
W
2
-(Methyl-3-pentenyl)-2-methylsulfonyl-1,4-
. To a methanolic (20 ml) solution of 6
940 mg, 4.3 mmol), a solution of OXONE, (2.6 g,
.3 mmol) in water (20 ml) was added at 0 9C . The
resulting cloudy slurry was kept for 2 hrs at 0
butanediol (
(
4
7
)
9
C
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