Synthesis of the four stereoisomers of 3,12-dimethylheptacosane, (Z)-9-pentacosene and (Z)-9-heptacosene, the cuticular hydrocarbons of the ant, Diacamma sp..

Article abstract of DOI:10.1271/bbb.66.1032

All of the four stereoisomers of 3,12-dimethylheptacosane were synthesized from the enantiomers of citronellal. (Z)-9-Pentacosene and (Z)-9-heptacosene were also synthesized. These hydrocarbons are the characteristic components of the cuticular hydrocarbo

Full text of DOI:10.1271/bbb.66.1032

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Synthesis of the Four Stereoisomers of 3,12-
Dimethylheptacosane, (Z)-9-Pentacosene and (Z)-9-
Heptacosene, the Cuticular Hydrocarbons of the Ant,
Diacamma sp.
Yui MASUDAa & Kenji MORIab
a Department of Chemistry, Faculty of Science, Science University of Tokyo Kagurazaka
1-3, Shinjuku-ku, Tokyo 162-8601, Japan
b Present address: Insect Pheromone and Traps Division, Fuji Flavor Co. Ltd. Midorigaoka
3-5-8, Hamura-City, Tokyo 205-8503, Japan
Published online: 22 May 2014.
To cite this article: Yui MASUDA & Kenji MORI (2002) Synthesis of the Four Stereoisomers of 3,12-Dimethylheptacosane,
(Z)-9-Pentacosene and (Z)-9-Heptacosene, the Cuticular Hydrocarbons of the Ant, Diacamma sp., Bioscience,
Biotechnology, and Biochemistry, 66:5, 1032-1038, DOI: 10.1271/bbb.66.1032
To link to this article: http://dx.doi.org/10.1271/bbb.66.1032
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Biosci. Biotechnol. Biochem., 66 (5), 1032–1038, 2002
Synthesis of the Four Stereoisomers of 3,12-Dimethylheptacosane,
(Z )-9-Pentacosene and (Z )-9-Heptacosene, the Cuticular
Hydrocarbons of the Ant, Diacamma sp.†
††
Yui MASUDA and Kenji MORI
Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3,
Shinjuku-ku, Tokyo 162-8601, Japan
Received November 16, 2001; Accepted December 27, 2001
4)
All of the four stereoisomers of 3,12-dimethylhep-
tacosane were synthesized from the enantiomers of
＝
(
R
)-A ( 8). According to the known method, (
citronellal (4, 96.0 e.e.) was converted to ( )-4-
methyl-1-hexanol (5), whose tosylate (
ed with sodium iodide to give iodide (
of (
larly, (
S)-
z
R
citronellal. (
Z
)-9-Pentacosene and (
Z
)-9-heptacosene
R
R
)-6 was treat-
were also synthesized. These hydrocarbons are the char-
acteristic components of the cuticular hydrocarbons of
the queen of the ant, Diacamma sp..
)-7. Coupling
R
)-7 with lithium acetylide aŠorded (
)-citronellal (4, 97.2 e.e.) was converted to
)-8 via )-5, 6, and 7. Another building block,
)-B ( 14), was then prepared from ( )-citronellal
R)-8. Simi-
R
z
(
(
S
S
(S
Key words:
(
Z
)-alkene; cuticular hydrocarbon; Dia-
＝
R
camma sp.; dimethyl-branched alkane;
(4) as shown in Scheme 3. The addition of
tridecylmagnesium bromide to ( )-4 gave alcohol 9.
queen ant
R
The cuticular hydrocarbons of social insects such
as honeybees and ants are known to be important in
their species, colony and queen recognition.1) A GC-
MS analysis by Yamaoka and his co-workers identi-
ˆed the hydrocarbons shown in Fig. 1 as the charac-
teristic components of the cuticular hydrocarbons of
the queen ant of Diacamma sp. (Togeá -oâ hariari in
Japanese), and suggested them to be possible queen
recognition substances.2) To verify this possibility,
however, substantial amounts of these hydrocarbons
must be available for a bioassay. At the request of
Yamaoka, we initiated our project to synthesize all of
the hydrocarbons shown in Fig. 1, and have already
published our synthesis of the enantiomers of A, B,
C, D and E.3) In this paper, we report the synthesis of
the remaining hydrocarbons, i.e., all of the four
stereoisomers of 3,12-dimethylheptacosane (1), (
Z )-
9-pentacosene (2) and (Z)-9-heptacosene (3).
The retrosynthetic analysis of (3R,12S)-3,12-
dimethylheptacosane (1) is shown in Scheme 1. The
carbon skeleton of 1 can be constructed by the alky-
lation of alkyne (
to be derived from (
can be prepared from (S)-citronellal (4). The enan-
R
)-F with iodide (
S)-G. Alkyne F is
R
)-citronellal (4), while iodide G
tiomers of citronellal (96–97
available.
z e.e.) are commercially
Fig. 1. Structures of the Cuticular Hydrocarbons of the Ant,
Dicamma sp.
Scheme 2 summarizes the synthesis of alkyne
†
Pheromone Synthesis, Part 215. For Part 214, see Shibata, C., Furukawa, A., and Mori, K., Biosci. Biotechnol. Biochem., 66, 582–587
(2002)
To whom correspondence should be addressed. Insect Pheromone and Traps Division, Fuji Flavor Co. Ltd., Midorigaoka 3-5-8,
Hamura-City, Tokyo 205-8503, Japan; Fax: 81-42-555-7920
††

Synthesis of the Cuticular Hydrocarbons of the Ant, Diacamma sp.
1033
Scheme 3. Synthesis of the Enantiomers of 14.
Scheme 1. Retrosynthetic Analysis of (3R, 12S)-1.
Reagents: (a) CH3(CH2)12MgBr, THF (97
z
). (b) MsCl,
C5H5N, CH2Cl2. (c) LiB(C2H5)3H, THF (99
z
, 2 steps). (d) 1)
, 2 steps).
, 2
O3, hexane, MeOH, CH2Cl2 (1:2:1). 2) NaBH4 (65
(e) TsCl, C5H5N, CH2Cl2. (f) NaI, DMF, Me2CO (88
steps).
z
z
Scheme 2. Synthesis of the Enantiomers of 8.
Reagents: (a) TsCl, C5H5N, CH2Cl2. (b) NaI, DMF, Me2CO
(81 , 2 steps). (c) LiC CH H2N(CH2)2NH2, DMSO (60 ).
z
ø
・
z
Corresponding mesylate 10 was reduced with lithium
triethylborohydride (Super-Hydride}) to furnish
alkene (S)-11. Ozonolysis of 11 and subsequent
reductive workup with sodium borohydride gave al-
cohol ( )-12. Corresponding tosylate ( )-13 yielded
iodide ( )-14 ( B) upon the Finkelstein reaction
with sodium iodide. Similarly, ( )-14 was prepared
from ( )-citronellal (4).
S
S
S
＝
R
S
Finally, the two building blocks, 8 and 14, were
coupled and further manipulated as summarized in
Scheme 4 to give target hydrocarbon 1. Alkylation of
Scheme 4. Synthesis of the Stereoisomers of 1.
alkyne (
(3 ,12
platinum oxide to give (3
ting-point solid. The overall yield of (3
based on citronellal (4) was 42 via )-5 (5 steps) or
48 via )-9 (9 steps). Similarly, the remaining
R
)-8 with iodide (
)-15, which was hydrogenated over Adams'
,12 )-(„)-1 as a low-mel-
,12 )-1
S)-14 furnished new alkyne
Reagents: (a) 8+
n
-BuLi, THF, HMPA; then 14 (88
).
z). (b)
R
S
H2, PtO2, hexane (99
z
R
S
R
S
z
(R
z
(R

1034
Y. MASUDA and K. MORI
data were measured with an Atago DMT-1 refrac-
tometer.
(R)-4-Methylhexyl tosylate [(R)-
and ice-cooled solution of ( )-5 (15.0 g, 129 mmol)
in dichloromethane (250 ml) and dry pyridine (30 ml)
was added -toluenesulfonyl chloride (24.6 g,
155 mmol) at 0 C. The solution was stirred for 12 h
at 4 C. It was then poured into water, and extracted
with Et2O. The ethereal extract was successively
6]. To a stirred
R
p
9
9
washed with water, 1
M
HCl, a saturated aqueous
NaHCO3 solution and brine, dried with MgSO4, and
concentrated in vacuo to give 35.1 g (quant.) of crude
(R
)-6. IR nmax (ˆlm) cm„1: 1600 (m, Ar), 1500 (w,
Scheme 5. Synthesis of 2 and 3.
Reagents: (a) 10+
for 18; 87 for 20). (b) H2, 5
(73 for 2; 78 for 3).
n
-BuLi, THF, HMPA; then 17 or 19 (71
z
Ar), 1360 (s, SO2), 1190 (s, SO2), 1180 (s), 965 (m),
920 (m), 780 (m). NMR dH (90 MHz, CDCl3):
0.54–0.94 (6 H, m, 6-H3, 4-Me), 1.01–1.86 (7 H, m,
z
z
Pd-BaSO4, quinoline, hexane
z
z
4-H, 2-, 3-, 5-H2), 2.45 (3 H, s, Ar-C
H
3), 4.01 (2 H,
8.3 Hz, Ar), 7.80
8.3 Hz, Ar). This compound was em-
ployed in the next step without further puriˆcation.
＝ ＝
7.2 Hz, 1-H), 7.34 (2 H, d, J
t,
J
three isomers, (3
(3 ,12 )-(„)-1, were also synthesized by employing
)- or ( )-8 and ( )- or ( )-14. The IR, NMR and
mass spectra of these four stereoisomers of 1 sup-
ported their structures. The signs and magnitudes of
the speciˆc rotation values of these four isomers indi-
cate that the chirality at C-3 of 1 contributed greatly
to determining their chiroptical properties.
S
,12
R
)-(+)-1, (3
S
,12
S
)-(+)-1 and
(2 H, d, J
＝
R
R
R
(
S
R
S
(S)-4-Methylhexyl tosylate [(S)-
6
]. In the same
)-5 (10.5 g,
manner as that just described,
(S
90.3 mmol) was converted into 24.4 g (quant.) of
1
(
S
)-6 as a colorless oil. Its IR and H-NMR spectra
were identical with those of (R)-6. This compound
Scheme 5 shows the synthesis of (
(2) and ( )-9-heptacosene (3). Alkylation of 1-de-
cyne (16) with pentadecyl bromide (17) furnished 18,
whose semi-hydrogenation gave 2 in a 52 yield
Z
)-9-pentacosene
was employed in the next step without further puriˆ-
cation.
Z
z
(R)-1-Iodo-4-methylhexane [(R)-
7]. To a solution
based on 17 (2 steps). Similarly, alkylation of 16 with
heptadecyl bromide (19) aŠorded 20, which fur-
of crude ( )-6 (ca. 35 g) in dry acetone (300 ml) and
R
DMF (80 ml) was added sodium iodide (25.1 g,
168 mmol) at room temperature. The mixture was
stirred and heated under re‰ux for 7 h. To this mix-
ture was added a saturated aqueous Na2S2O3 solu-
tion, and acetone was removed in vacuo. The residue
was poured into water and extracted with Et2O. The
ethereal extract was successively washed with water
and brine, dried with MgSO4, and concentrated in
vacuo. The residue was chromatographed on silica
gel (100 g, hexane) and distilled to give 23.7 g [2
nished 3 in a 68
z overall yield based on 19 (2 steps).
In conclusion, the three cuticular hydrocarbons, 1,
2 and 3, characteristic of the ant queen of Diacamma
sp. were synthesized. In the case of dimethyl-bran-
ched hydrocarbon 1, all of its four stereoisomers
were also prepared. These six hydrocarbons, together
with ten previous samples will be bioassayed by Prof.
Yamaoka. This biological study will hopefully clarify
the chemical basis of queen recognition in Diacamma
sp.
steps, 81
Bp 105–107
1.05, hexane). IR
z
based on (
R
)-5] of (
R
)-7 as a colorless oil.
24
9
C at 40 Torr. n2D4 1.4981. [
a
]
„11.1 (
c
D
n
max (ˆlm) cm„1: 2960 (s), 2870 (s),
Experimental
1460 (s), 1175 (s). NMR dH (90 MHz, CDCl3):
0.62–1.01 (6 H, m, 4-Me, 6-H3), 1.06–1.62 (5 H, m,
4-H, 3-, 5-H2) 1.62–2.00 (2 H, m, 2-H2), 3.18 (2 H, t,
＝
Boiling point (bp) data are uncorrected. Melting
point (mp) data were measured with a Yanaco MP-S3
instrument and are uncorrected. IR data were
J
6.8 Hz, 1-H2). HRMS m z (M+): calcd. for
W
measured with Jasco A-102 and Jasco FT IR-410
C7H15I, 226.0218; found, 226.0218.
W
1
spectrometers. H-NMR data were measured with
Due to the volatility of 7, no satisfactory combustion
analytical data could be obtained.
Jeol JNM-EX90A (90 MHz), Jeol JNM-LA400
(400 MHz) and Jeol JNM-LA500 (500 MHz) spec-
＝
＝
trometers (TMS at dH 0.00 or CHCl3 at dH 7.26
(S)-1-Iodo-4-methylhexane [(S)-
manner as that just described, ( )-6 (ca. 24 g) was
converted into 16.2 g [2 steps, 80 based on ( )-5]
7]. In the same
was used as the internal standard). Optical rotation
data were measured with
S
a
Jasco DIP-1000
z
S
polarimeter, and MS data were measured with a Jeol
JMS-AX 505 HA spectrometer. Refractive index (nD
of (
S
)-7 as a colorless oil. Bp 98–99
9
C at 42 Torr. n2D1
24
D
1
)
1.4900. [
a
]
+10.6 (
c
1.00, hexane). Its IR and H-

Synthesis of the Cuticular Hydrocarbons of the Ant, Diacamma sp.
1035
NMR spectra were identical with those of (
R
)-6.
(6S,8RS)-2,6-Dimethyl-2-henicosen-8-ol [(S)-
9
]. In
HRMS m z (M+): calcd. for C7H15I, 226.0218;
the same manner as that just described, (S)-4 (2.00 g,
W
found, 226.0221.
13.3 mmol) was converted into 3.37 g (79
z
) of (
S
)-9
as a colorless solid. Mp ca. 25
9C. [
a
]
22 +2.5 (
c
1.07,
D
1
(R)-6-Methyl-1-octyne [(R)-
cooled solution of ( )-7 (23.2 g, 105 mmol) in dry
DMSO (200 ml) was added a lithium acetylide
ethylenediamine complex (21.4 g, 209 mmol) at 10
under argon. The mixture was stirred for 30 min at
10 C and was then allowed to warm to room temper-
8
]. To a stirred and ice-
hexane). Its IR and H-NMR spectra were identical
R
with those of (
R)-9. Anal. Found: C, 81.65; H,
13.94 . Calcd. for C23H46O: C, 81.58; H, 13.69
z
z.
9
C
(6R,8RS)-8-Methanesulfonyloxy-2,6-dimethyl-2-
9
henicosene [(R)-10]. To a stirred and ice-cooled solu-
ature over 12 h. The reaction was quenched with
water, and the mixture was extracted with hexane.
The organic phase was successively washed with
water and brine, dried with MgSO4, and concentrated
in vacuo. The residure was puriˆed by distillation to
tion of (R)-9 (3.00 g, 9.29 mmol) in dichloromethane
(100 ml) and dry pyridine (10 ml) was added
methanesulfonyl chloride (1.43 ml, 18.5 mmol) at
0
9
C. After stirring for 12 h at 4
9C, the mixture was
poured into water and extracted with hexane. The
give 7.72 g (60
z
) of (
R
)-8 as a colorless oil. Bp
organic phase was successively washed with 0.5
M
118–120
9
C. n2D1 1.4550. [
a
]2D6„12.6 (
c
1.01, hexane).
HCl, water, a saturated aqueous NaHCO3 solution
IR nmax (ˆlm) cm„1: 3315 (s) 2120 (m). NMR dH
(90 MHz, CDCl3): 0.60–1.00 (6 H, m, 6-Me, 8-H3),
1.00–1.70 (7 H, m, 6-H, 4-, 5-, 7-H2), 1.94 (1 H, t,
and brine, dried with MgSO4, and concentrated in
vacuo to give 3.73 g (quant.) of crude (R)-10. IR nmax
(ˆlm) cm„1: 1360 (s, SO2), 1185 (s, SO2), 910 (s).
NMR dH (90 MHz, CDCl3): 0.72–1.00 (6 H, m,
6-Me, 21-H3), 1.10–1.40 (29 H, m, 6-H, 5-, 7-,
＝
J
2.7 Hz, 1-H), 2.00–2.26 (2 H, m, 3-H2). HRMS
m z (M+): calcd. for C9H16, 124.1252; found,
W
＝
124.1258. Due to the volatility of 8, no satisfactory
9
¿
20-H2), 1.61 (3 H, br.s, C
H
3-C C), 1.68 (3 H,
3-C C), 1.80–2.18 (2 H, m, 4-H2), 2.99
(3 H, s, C 3SO2), 4.60–4.80 (1 H, br.m, 8-H),
＝
combustion analytical data could be obtained.
br.s, CH
H
(S)-6-Methyl-1-octyne [(S)-
as that just described, ( )-7 (16.1 g, 71.4 mmol) was
converted into 3.71 g (42 ) of ( )-8 as a colorless
oil. Bp 115–117
C. n2D1 1.4553. [
8
]. In the same manner
4.95–5.20 (1 H, br.m, 3-H). This compound was em-
ployed in the next step without further puriˆcation.
S
z
S
26
9
a
]
+12.7 (
c
1.05,
(6S,8RS)-8-Methanesulfonyloxy-2,6-dimethyl-2-
henicosene [(S)-10]. In the same manner as that just
D
1
hexane). Its IR and H-NMR spectra were identical
with those of (
R
)-8. HRMS m z (M+): calcd. for
described, (
into 4.10 g (quant.) of crude (
NMR spectra were identical with those of (
S)-9 (3.30 g, 10.2 mmol) was converted
W
1
C9H16, 124.1252; found, 124.1257.
S
)-10. Its IR and H-
)-10.
R
(6R,8RS)-2,6-Dimethyl-2-henicosen-8-ol [(R)-
To a stirred and ice-cooled solution of (R)-4 (594 mg,
9
].
This compound was employed in the next step
without further puriˆcation.
3.80 mmol) in dry THF (5 ml) was added a solution
of the Grignard reagent prepared from 1-bromotride-
cane (4.00 g, 15.20 mmol) and magnesium (406 mg,
(S)-2,6-Dimethyl-2-henicosene [(S)-11]. To a solu-
tion of crude (R)-10 (ca. 3.7 g) in dry THF (10 ml)
16.72 mmol) in THF (15 ml) at 0
9C under argon. The
was added Super-Hydride} (a 1.0
180 ml, 180 mmol) at 0 C under argon. After stirring
M
solution in THF,
mixture was allowed to warm to room temperature
over 4 h. The reaction was then quenched with a satu-
rated aqueous NH4Cl solution, and the mixture was
extracted with Et2O. The organic phase was succes-
sively washed with water, a saturated aqueous NH4Cl
solution and brine, dried with MgSO4, and concen-
trated in vacuo. The residue was chromatographed
9
for 18 h at room temperature, the mixture was
poured into water and extracted with hexane. The or-
ganic phase was successively washed with a saturated
aqueous NH4Cl solution, water, a saturated aqueous
NaHCO3 solution and brine, dried with MgSO4, and
concentrated in vacuo. The residue was chro-
matographed on silica gel (60 g; hexane) to give 2.8 g
on silica gel (30 g; hexane ethyl acetate, 30:1) to give
W
1.19 g (97
z
) of (
R
)-9 as a colorless solid. Mp ca
.
[2 steps, 99
z
based on (
R
)-9] of (
S
)-11 as a colorless
22
22
25
9
C. [
a
]
„2.9 (
c
1.10, hexane). IR nmax (KBr)
oil. n2D3 1.4564. [
a
]
„2.0 (c 1.10, hexane). IR nmax
D
D
cm„1: 3350 (s, O-H). NMR dH (90 MHz, CDCl3):
(ˆlm) cm„1: 1465 (m), 1375 (m), 830 (w), 720 (m,
CH2). NMR dH (90 MHz, CDCl3): 0.75–1.00 (6 H,
m, 6-Me, 21-H3), 1.05–1.18 (31 H, m, 6-H, 5-, 7-, 8-,
9-, 10-, 11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-,
0.85–0.95 (6 H, m, 6-Me, 21-H3), 1.15–1.53 (30 H,
m, 6-H, 5-, 7-, 9
3-C C), 1.69 (3 H, br.s, C
(2 H, br.q, 4-H2), 3.65 (1 H, br.m, 8-H), 5.10 (1 H,
br.t, 3-H). Anal. Found: C, 81.63; H, 13.82
Calcd. for C23H46O: C, 81.58; H, 13.69
¿
20-H2, 8-OH), 1.60 (3 H, br.s,
C
H
＝
H
3-C C), 1.85–2.07
＝
＝
20-H2), 1.60 (3 H, br.s, C
H
3„C C), 1.69 (3 H,
3„C C), 1.85–2.05 (2 H, br.t, 4-H2), 5.10
(1 H, br.t, 3-H). Anal. Found: C, 85.61; H, 14.52
Calcd. for C23H46: C, 85.63; H, 14.37
＝
z
.
br.s, CH
z
.
z
.
z.

1036
Y. MASUDA and K. MORI
(R)-2,6-Dimethyl-2-henicosene [(R)-11]. In the
same manner as that just described, ( )-10 (ca. 4.0 g)
puriˆcation.
S
was converted into 3.9 g [2 steps, 98
z
based on
(R)-4-Methylnonadecyl tosylate [(R)-13]. In the
same manner as that just described, ( )-12 (895 mg,
3.10 mmol) was converted into 1.36 g (quant.) of
)-13 as a colorless oil. Its IR and 1H-NMR spectra
were identical with those of ( )-13. This compound
(
S
)-9] of (
+1.9 (
were identical with those of (
85.32; H, 14.64 . Calcd. for C23H46: C, 85.63; H,
14.37
R
)-11 as a colorless oil. nD24 1.4560. [
a
]
R
24
D
1
c
0.99, hexane). Its IR and H-NMR spectra
S
)-11. Anal. Found: C,
(R
z
S
z
.
was employed in the next step without further puriˆ-
cation.
(S)-4-Methylnonadecan-1-ol [(S)-12]. Ozone was
bubbled into a stirred solution of ( )-11 (983 mg,
3.25 mmol) in methanol (15 ml), dichloromethane
(30 ml) and hexane (15 ml) for 1.5 h at „45 C. After
‰ashing oŠ the excess O3 with O2 gas, to the stirred
mixture was slowly added NaBH4 (540 mg,
S
(S)-1-Iodo-4-methylnonadecane [(S)-14]. To a so-
lution of crude (S)-13 (ca. 1.6 g) in DMF (20 ml) was
9
added sodium iodide (1.04 g, 6.94 mmol). The mix-
ture was stirred and heated under re‰ux for 7 h. To
this mixture was added a saturated aqueous Na2S2O3
solution. The residue was poured into water and ex-
tracted with Et2O. The ethereal extract was succes-
sively washed with water and brine, dried with
MgSO4, and concentrated in vacuo. The residue was
chromatographed on silica gel (20 g, hexane) to give
3.57 mmol) at „45
warm to 0 C over 6 h before being quenched with
1.0 HCl and extracted with Et2O. The organic
9
C. The mixture was allowed to
9
M
phase was successively washed with water, a saturat-
ed aqueous NaHCO3 solution and brine, dried with
MgSO4, and concentrated in vacuo. The residue was
1.19 g [2 steps, 88
z
based on (
S
)-12] of (
S)-14 as a
26
chromatographed on silica gel (50 g; hexane ethyl
colorless oil. n2D6 1.4788. [
a
]
+2.5 ( 1.00, hexane).
c
D
W
acetate, 30:1) to give 604 mg (65
z
) of (
D
S
)-12 as a
IR nmax (ˆlm) cm„1: 2950 (m), 2900 (m), 1470 (m).
NMR dH (90 MHz, CDCl3): 0.71–1.05 (6 H, m,
4-Me, 19-H3) 1.05–1.60 (31 H, m, 4-H, 3-,
20
colorless solid. Mp ca. 28–30
hexane). IR
9C. [a] „1.1 (c 0.50,
n
max (ˆlm) cm„1: 3350 (br.m, O-H), 1060
(br.m, C-O). NMR dH (90 MHz, CDCl3): 0.78–1.00
5
J
¿
18-H2), 1.80–2.02 (2 H, m, 2-H2), 3.27 (2 H, t,
＝
(6 H, m, 4-Me, 19-H3), 1.00–1.80 (34 H, m, 4-H, 2-,
6.3 Hz, 1-H2). Anal. Found: C, 58.59; H,
3-, 5
¿
18-H2, 1-OH), 3.62 (2 H, t,
J
＝
6.5 Hz, 1-H2).
z. Calcd. for
10.29
z
. Calcd. for C20H41I: C, 58.81; H, 10.12
z
.
Anal. Found: C, 80.26; H, 14.24
C20H42O: C, 80.46; H, 14.18
z
.
(R)-1-Iodo-4-methylnonadecane [(R)-14]. In the
same manner as that just described, ( )-13 (1.36 g,
3.32 mmol) was converted into 1.19 g [2 steps, 88
R
(R)-4-Methylnonadecan-1-ol [(R)-12]. In the same
manner as that just described, ( )-11 (1.79 g,
) of
z
R
based on (
R
)-12] of (R)-14 as a colorless oil. nD22
22
1
5.85 mmol) was converted into 688 mg (40
z
9
C. [
1.4776. [
a
]
„2.5 (
c
0.50, hexane). Its IR and H-
D
20
(
R
)-12 as a colorless solid. Mp ca. 28–30
a
]
NMR spectra were identical with those of (
S
)-14.
D
1
+1.4 (
c
1.15, hexane). Its IR and H-NMR spectra
Anal. Found: C, 59.00; H, 10.25
C20H41I: C, 58.81; H, 10.12
z
. Calcd. for
were identical with those of (
80.66; H, 14.30 . Calcd. for C20H42O: C, 80.46; H,
14.18
R
)-12. Anal. Found: C,
z.
z
z.
(3R,12S)-3,12-Dimethyl-7-heptacosyne [(3R,12S)-
15]. To stirred solution of )-8 (508 mg,
4.10 mmol) in dry THF (5 ml) and dry hexamethyl-
phosphoric triamide (HMPA, 1 ml) was added
butyllithium in hexane (1.6 , 2.5 ml, 3.9 mmol) at
„40 C under argon. The solution was stirred at 0
for 5 h and then cooled to „40 C. A solution of
)-14 (816 mg, 2.05 mmol) in dry THF (10 ml) was
added dropwise to the mixture at „40 C. The mix-
a
(R
(S)-4-Methylnonadecyl tosylate [(S)-13]. To
stirred and ice-cooled solution of ( )-12 (1.00 g,
3.47 mmol) in dichloromethane (10 ml) and dry pyri-
a
S
n-
M
dine (2 ml) was added
(728 mg, 3.81 mmol) at 0
p
-toluenesulfonyl chloride
9
9C
9
C. The solution was stirred
9
for 12 h at 4
9
C, before being poured into water and
(S
extracted with diethyl ether. The ethereal extract was
9
successively washed with water, 1
M
HCl, a saturated
ture was stirred at ambient temperature for 12 h be-
fore being poured into a saturated aqueous NH4Cl
solution at 09C and extracted with hexane. The ex-
tract was successively washed with water and brine,
dried with MgSO4, and concentrated in vacuo. The
residue was chromatographed on silica gel (20 g,
aqueous NaHCO3 solution and brine, dried with
MgSO4, and concentrated in vacuo to give 1.64 g
(quant.) of crude (
S
)-13. IR nmax (ˆlm) cm„1: 1590
(m, Ar), 1480 (m, Ar), 1365 (s, SO2), 1190 (s, SO2),
1180 (s), 965 (m). NMR dH (90 MHz, CDCl3):
0.70–0.90 (6 H, m, 4-Me, 19-H3), 1.10–1.60 (33 H,
hexane) to give 711 mg (88
z
„3.2 (
) of (3
R
,12
S)-15 as a
20
m, 4-H, 2-, 3-, 5
¿
18-H2), 2.45 (3 H, s, Ar-C
H
3),
colorless oil. n2D6 1.4650. [
a
]
c
1.04, hexane).
D
4.07 (2 H, t,
J
6.4 Hz, 1-H2), 7.43 (2 H, d,
J
IR nmax (ˆlm) cm„1: 2925 (s), 2855 (s), 1460 (s), 1375
(m), 720 (m). NMR dH (90 MHz, CDCl3): 0.75–1.00
(12 H, m, 1-H3, 3-Me, 12-Me, 27-H3), 1.05–1.35
＝
＝
＝
8.4 Hz, Ar), 7.79 (2 H, d,
pound was employed in the next step without further
J
8.4 Hz, Ar). This com-

Synthesis of the Cuticular Hydrocarbons of the Ant, Diacamma sp.
1037
(40 H, m, 3-H, 12-H, 2-, 4-, 5-, 10-, 11-, 13
2.00–2.25 (4 H, m, 6-H2, 9-H2). Anal. Found: C,
85.81; H, 13.70 . Calcd. for C29H56: C, 86.05; H,
13.95
¿
26-H2),
(3S,12R)-3,12-Dimethylheptacosane [(3S,12R)-
In the same manner as that just described, (3
12 )-15 (290 mg, 0.730 mmol) was converted into
281 mg (99 ) of (3 ,12 )-1 as a colorless solid. Mp
ca. 26 C [
]2D1 +4.4 ( 1.00, hexane). Its IR, 1H-NMR
and 13C-NMR spectra were identical with those of
1].
S
,
z
R
z.
z
a
S
c
R
9
(3S,12R)-3,12-Dimethyl-7-heptacosyne [(3S,12R)-
15]. In the same manner as that just described, ( )-8
(285 mg, 2.30 mmol) and ( )-14 (608 mg, 1.53
) of (3
0.97, hexane). Its
S
(3R,12S)-1. HRMS m z (relative intensity): 408
W
R
(M+, 5.0), 238 (24.0), 197 (20.0), 99 (23.0), 85 (49.0),
71 (68.0), 57 (100), 43 (50.0); calcd. for C29H60,
408.4695; found, 408.4708. Anal. Found: C, 85.38;
mmol) were converted into 427 mg (70
z
S,
20
12
R
)-15. n2D6 1.4656. [
a
]
+2.8 (
c
D
1
IR and H-NMR spectra were identical with those of
R,12S)-15. Anal. Found: C, 85.85; H, 14.18z.
H, 14.81
z. Calcd. for C29H56: C, 85.21; H,14.79
z.
(3
Calcd. for C29H56: C, 86.05; H,13.95
z
.
(3S,12S)-3,12-Dimethylheptacosane [(3S,12S)-
1
].
In the same manner as that just described, (3
S
,
(3S,12S)-3,12-Dimethyl-7-heptacosyne [(3S,12S)-
15]. In the same manner as that just described, ( )-8
(260 mg, 2.09 mmol) and ( )-14 (694 mg, 1.74 mmol)
were converted into 406 mg (59 ) of (3 ,12 )-15.
0.90, hexane). IR max (ˆlm)
12
S
)-15 (180 mg, 0.450 mmol) was converted into
S
179 mg (99
z
) of (3S,12S
)-1 as a colorless oil. nD21
26
S
1.4537. [
a
]
+4.2 (c 1.00, hexane). IR nmax (KBr)
D
z
S
n
S
cm„1: 2925 (s), 2855 (s), 1465 (s), 1370 (m), 720 (m).
NMR dH (500 MHz, CDCl3): 0.82–0.90 (12 H, m,
1-H3, 3-Me, 12-Me, 27-H3), 1.04–1.18 (4 H, m, 2-H2 ,
n2D0 1.4678. [
a
]
20 +6.4 (
c
D
cm„1: 2950 (s), 2900 (s), 1480 (s), 1390 (m), 740 (m).
NMR dH (90 MHz, CDCl3): 0.69–1.00 (12 H, m,
1-H3, 3-Me, 12-Me, 27-H3), 1.05–1.60 (40 H, m, 3-H,
26-H2), 1.20–1.40 (44 H, m, 3-H, 12-H, 4
¿11-H2,
13 25-H2). NMR C (125 MHz, CDCl3): 11.4, 14.1,
¿
d
12-H, 2-, 4-, 5-, 10-, 11
6-H2, 9-H2). Anal. Found: C, 85.82; H, 14.11
Calcd. for C29H56: C, 86.05; H, 13.95
¿
26-H2), 2.00–2.25 (4 H, m,
19.2, 19.7, 22.7, 27.05, 27.08, 29.3, 29.5, 29.63,
29.67, 29.7, 30.0, 31.9, 32.7, 34.4, 36.6, 37.1. HRMS
z
.
z
.
m z (relative intensity): 408 (M+, 4.0), 238 (24.0),
W
197 (20.0), 99 (23.0), 85 (50.0), 71 (68.0), 57 (100), 43
(50.0); calcd. for C29H60, 408.4695; found, 408.4681.
(3R,12R)-3,12-Dimethyl-7-heptacosyne [(3R,12R)-
15]. In the same manner as that just described, ( )-8
(861 mg, 6.94 mmol) and ( )-14 (1.10 g, 2.78 mmol)
were converted into 587 mg (54 ) of (3 ,12 )-15.
n2D0 1.4656. [ ]2D0 „6.3 ( 0.98, hexane). Its IR and 1H-
NMR spectra were identical with those of (3
12 )-15. Anal. Found: C, 86.32; H, 14.29 . Calcd.
for C29H56: C, 86.05; H, 13.95
R
Anal. Found: C, 85.38; H, 14.81
C29H56: C, 85.21; H, 14.79
z
. Calcd. for
R
z.
z
R
R
a
c
(3R,12R)-3,12-Dimethylheptacosane [(3R,12R)-
1].
S
,
In the same manner as that just described, (3R,
S
z
12R)-15 (20 mg, 0.050 mmol) was converted into
z.
19.8 mg (99
z
„4.1 (
) of (3
R
,12
R
)-1 as a colorless oil. n2D1
26
1
1.4565. [
a
]
c
1.25, hexane). Its IR, H-NMR
D
(3R,12S)-3,12-Dimethylheptacosane [(3R,12S)-
1
].
and 13C-NMR spectra were identical with those of
A solution of (3 ,12 )-15 (595 mg, 1.50 mmol) in
R
S
(3
S
,12
S
)-1. HRMS m z (relative intensity): 408 (M+,
W
hexane (5 ml) was hydrogenated with hydrogen gas in
the presence of platinum oxide (40 mg) at atmospher-
ic pressure. The reaction mixture was then stirred for
12 h at room temperature, before the mixture was
4.0), 238 (33.0), 197 (25.0), 99 (23.0), 85 (55.0), 71
(75.0), 57 (100), 43 (50.0); calcd. for C29H60,
408.4695; found, 408.4697. Anal. Found: C, 85.10;
H, 14.85
z z
. Calcd. for C29H56: C, 85.21; H, 14.79 .
ˆltered, and the ˆltrate was concentrated in vacuo
The residue was chromatographed on silica gel (10 g,
hexane) to give 592 mg (99 ) of (3 ,12 )-1 as a
„4.2 ( 0.98,
.
9-Pentacosyne [18]. To a stirred and cooled solu-
tion of 16 (1.00 g, 7.23 mmol) in dry THF (10 ml)
z
9
C. [
R
S
21
colorless solid. Mp ca. 26
a
]
c
and HMPA (5 ml) was added
hexane (1.60 , 4.55 ml, 7.23 mmol) at „40
argon. The solution was stirred at „20 C for 2 h and
then cooled to „40 C. A solution of 17 (2.01 g,
7.23 mmol) in dry THF (20 ml) was added dropwise
to the mixture at „40 C. The mixture was stirred at
ambient temperature for 12 h, before being poured
into a saturated aqueous NH4Cl solution at 0 C and
n
-butyllithium in
D
hexane). IR nmax (KBr) cm„1: 2960 (s), 2920 (s), 2850
(s), 1465 (s), 1375 (m), 1150 (w), 720 (m). NMR dH
(500 MHz, CDCl3): 0.70–0.80 (12 H, m, 1-H3, 3-Me,
12-Me, 27-H3), 1.03–1.18 (4 H, m, 2-H2, 26-H2),
M
9
C under
9
9
1.20–1.40 (44 H, m, 3-H, 12-H,
4
¿
11-H2,
9
13 25-H2). NMR C (125 MHz, CDCl3): 11.4, 14.1,
¿
d
19.2, 19.7, 22.7, 27.1, 29.4, 29.5, 29.66, 29.70, 29.74,
9
30.0, 31.9, 32.7, 34.4, 36.7, 37.1. HRMS m z (rela-
extracted with hexane. The extract was successively
washed with water and brine, dried with MgSO4, and
concentrated in vacuo. The residue was chro-
matographed on silica gel (40 g, hexane) to give
W
tive intensity): 408 (M+, 4.0), 238 (27.0), 197 (23.0),
99 (23.0), 85 (52.0), 71 (72.0), 57 (100), 43 (50.0);
calcd. for C29H60, 408.4695; found, 408.4689. Anal
Found: C, 85.17; H, 14.77 . Calcd. for C29H56: C,
85.21; H, 14.79
.
z
1.82 g (71
z) of 18 as a colorless solid. Mp ca. 289C.
z
.
IR nmax (KBr) cm„1: 2955 (s), 2850 (s), 1470 (s), 715

1038
Y. MASUDA and K. MORI
(m). NMR dH (90 MHz, CDCl3): 0.70–1.06 (6 H, m,
1-H3, 25-H3), 1.10–1.45 (38 H, m, 7-H2,
12 24-H2), 2.00–2.25 (4 H, m, 8-H2, 11-H2). Anal
Found: C, 86.17; H, 14.00 . Calcd. for C29H56: C,
86.12; H, 13.88
2.65 mmol) was converted into 783 mg (78z) of 3 as
2
¿
a colorless oil. n2D1 1.4652. IR nmax (ˆlm) cm„1: 2925
(s), 2855 (s), 1465 (s), 720 (m). NMR dH (500 MHz,
¿
.
＝
z
CDCl3): 0.88 (6 H, t,
1.20–1.38 (42 H, m, 2 7-H2, 12
6.7, 5.8 Hz 8-H2, 11-H), 5.30–5.40 (2 H, m,
9-H, 10-H). NMR C (125 MHz, CDCl3): 14.1, 22.7,
J
6.7 Hz, 1-H3, 27-H3),
z
.
¿
¿
26-H2), 2.01 (4 H,
＝
J
dt,
(Z)-9-Pentacosene [
1.58 mmol) and quinoline (0.5 ml) in hexane (5 ml)
was treated with hydrogen gas in the presence of 5
2
]. A solution of 18 (550 mg,
d
27.2, 29.32, 29.37, 29.53, 29.57, 29.66, 29.70, 29.78,
z
31.92, 31.93, 129.9. HRMS m z (relative intensity):
W
Pd-BaSO4 (30 mg) at atmospheric pressure. The mix-
ture was stirred for 2 h at room temperature, before
the mixture was ˆltered, and the ˆltrate was concen-
trated in vacuo. The residue was chromatographed
378 (M+, 37.0), 139 (20.0), 125 (36.0), 111 (60.0), 97
(100), 83 (93.0), 57 (98.0), 55 (76.0), 43 (77.0), 41
(37.5); calcd. for C27H54, 378.4226; found, 378.4233.
Anal. Found: C, 85.52; H, 14.54
C29H56: C, 85.63; H, 14.37z.
z
. Calcd. for
on silica gel (100 g, hexane) to give 393 mg (73
as a colorless oil. n2D1 1.4566. IR max (ˆlm) cm„1: 2925
(s), 2855 (s), 1455 (s), 720 (m). NMR dH (400 MHz,
z) of 2
n
Acknowledgments
＝
CDCl3): 0.88 (6 H, t,
1.20–1.38 (38 H, m, 2 7-H2, 12
6.6, 5.6 Hz, 8-H2, 11-H2), 5.30–5.40 (2 H, m,
9-H, 10-H). NMR C (125 MHz, CDCl3): 14.1, 22.7,
J
6.4 Hz, 1-H3, 25-H3),
¿
¿
24-H2), 2.01 (4 H,
We thank Prof. R. Yamaoka (Kyoto Institute of
Technology) for his suggestion to undertake the
present work. We are grateful to Takasago Interna-
tional Corporation for presenting the enantiomers of
citronellal and also for providing research funding.
＝
J
dt,
d
27.2, 29.3, 29.4, 29.52, 29.56, 29.65, 29.70, 29.8,
31.91, 31.92, 129.9. HRMS m z (relative intensity):
W
350 (M+, 37.0), 125 (36.0), 111 (60.0), 97 (100), 83
(95.0), 57 (100), 55 (85.0),43 (85.0); calcd. for C25H50,
350.3922; found, 350.3913. Anal. Found: C, 85.53;
References
1) Francke, W., Pheromones. In ``Comprehensive Natur-
al Products Chemistry,'' Vol. 8, ed. Mori, K., Elsevi-
er, Oxford, pp. 247–249 (1999).
2) Yamaoka, R., Personal communication to K. M.
dated June 28, 1999.
3) Marukawa, K., Takikawa, H., and Mori, K., Phero-
mone synthesis, 207. Synthesis of the enantiomers of
some methyl-branched cuticular hydrocarbons of the
ant, Diacamma sp. Biosci. Biotechnol. Biochem., 65,
305–314 (2001).
H, 14.40
z z
. Calcd. for C29H50: C, 85.63; H, 14.37 .
9-Heptacosyne [20]. In the same manner as that
described for the conversion of 16 to 18, 16 (1.04 g,
7.51 mmol) and 19 (2.00 g, 6.26 mmol) were convert-
ed into 2.07 g (87
28 C. IR
max (KBr) cm„1: 2955 (s), 2850 (s), 1470 (s),
715 (m). NMR H (90 MHz, CDCl3): 0.88 (6 H, t,
6.3 Hz, 1-H3, 27-H3), 1.08–1.52 (42 H, m, 2 7-H2,
12 26-H2), 2.00–2.25 (4 H, m, 8-H2, 11-H2). Anal
Found: C, 85.80; H, 14.08 . Calcd. for C29H56: C,
86.09; H, 13.91
z
) of 20 as a colorless solid. Mp ca.
9
n
d
J
＝
¿
4) Mori, K., Suguro, T., and Uchida, M., Pheromone
synthesis, 23. Synthesis of optically active forms of
¿
.
z
(Z )-14-methylhexadec-8-enal, the pheromone of fe-
z.
male dermestid beetle. Tetrahedron, 34, 3119–3123
(1978).
(Z)-9-Heptacosene [
3]. In the same manner as that
described for the conversion of 18 to 2, 20 (1.00 g,