Improved synthesis of (3E,7Z)-3,7-tetradecadienyl acetate, the major sex pheromone constituent of the potato pest Symmetrischema tangolias (Gyen)

Article abstract of DOI:10.1021/jf802473m

An efficient six-step synthesis of (3E,7Z)-3,7-tetradecadienyl acetate, the major component of the sex pheromone of the potato pest Symmetrischema tangolias (Gyen), is described, starting from the commercially available dihydropyran. The stereoselective formation of the 7Z double bond is accomplished by a Wittig reaction, while the 3E double bond is formed by a modified Knoevenagel condensation. The overall yield of the synthesis is 28%, giving the final product in high stereochemical purity (95%). The simplicity and the low cost of the herein reported synthesis suggest the potential practical use of the above pheromone in integrated management programs, for this serious insect pest.

Full text of DOI:10.1021/jf802473m

J. Agric. Food Chem. 2008, 56, 11929–11932 11929
Improved Synthesis of (3E,7Z)-3,7-Tetradecadienyl
Acetate, the Major Sex Pheromone Constituent of the
Potato Pest Symmetrischema tangolias (Gyen)
VALENTINE RAGOUSSIS,* STAMATIS PERDIKARIS, ANTONIS KARAMOLEGKOS, AND
KONSTANTINA MAGKIOSI
Laboratory of Organic Chemistry, Department of Chemistry, University of Athens,
Panepistimiopolis Zographou, 157 71 Athens, Greece
An efficient six-step synthesis of (3E,7Z)-3,7-tetradecadienyl acetate, the major component of the
sex pheromone of the potato pest Symmetrischema tangolias (Gyen), is described, starting from the
commercially available dihydropyran. The stereoselective formation of the 7Z double bond is
accomplished by a Wittig reaction, while the 3E double bond is formed by a modified Knoevenagel
condensation. The overall yield of the synthesis is 28%, giving the final product in high stereochemical
purity (95%). The simplicity and the low cost of the herein reported synthesis suggest the potential
practical use of the above pheromone in integrated management programs, for this serious insect
pest.
KEYWORDS: Pheromone synthesis; potato tuber moth; tomato stem borer; Symmetrischema tangolias
(Gyen); (3E,7Z)-3,7-tetradecadienyl acetate; Knoevenagel condensation
INTRODUCTION
tubers, and the environment and development of this insecticide-
resistant pest. Considerable efforts have been made for the
development and evaluation of the efficacy of alternative control
methods (5, 6). The use of an insect’s pheromone by the mass
trapping technique has shown promising results (1, 2, 7).
Griepink et al. isolated and identified the sex pheromone
constituents from the female moth’s gland extract in 1995 (7).
The amounts of the same pheromone constituents were also
measured later by direct pheromone glands introduction into
two-dimensional gas chromatography (GC) (8). The main
constituent of the female-produced pheromone is the (3E,7Z)-
3,7-tetradecadienyl acetate, 1 (Figure 1), which was identified
in the pheromone as a 2:1 mixture with (3E)-tetradecenyl
acetate. In the sex pheromone glands, two additional minor
The potato plant Solanum tuberosum L., an important plant
for human nutrition cultivated extensively in most countries
around the world, is extremely susceptible to various insect
attacks (1). At present, one of the most devastating pest of
potatoes in South America and especially in Andean valleys of
Bolivia, Colombia, and Peru, as well as in Australia, is the tuber
moth Symmetrischema tangolias (Gyen) (Lepidoptera: Gelechi-
idae), (synonym: Symmetrischema plaesiosema, Turner) (2).
Damage is caused by larvae, which burrow into tubers and
stems, making them unsuitable for human consumption or for
seed. A population survey showed that it remains in potato fields
after harvesting, even in the absence of a host plant, threatening
the next crop. Furthermore, this destructive pest became the
most dominant enemy in potato storehouses or in open facilities,
where harvested tubers are commonly stored for up to 4 months
before marketing. The accidental introduction of infested tubers
into stores allows the development and reproduction of tuber
moths. S. tangolias is also reported as a pest of tomatoes
worldwide (3) and that is why it is also known with the
systematic name “tomato stem borer” (4).
Chemical and biological control applications, including the
use of the soil bacterium Bacillus thuringiensis, have been used
by farmers worldwide. However, leaf mining and tuber bur-
rowing, the feeding behavior of S. tangolias, make the use of
insecticides low and inefficient. Moreover, the general utility
of insecticides is limited by high cost, persistence of residue in
Figure 1. Reagents and conditions: (a) HCl/H2O. (b) CH3(CH2)5-
CH2P+(Ph)3Br-; KN[Si(Me)3]2, THF -78 °C. (c) PCC/Celite, CH2Cl2. (d)
CH2(COOH)2, piperidinium acetate, DMSO. (e) Red-Al/ether. (f) Ac2O,
pyridine.
* To whom correspondence should be addressed. Tel: +30 210
7274497. Fax: +30 210 7274761. E-mail: ragousi@chem.uoa.gr.
10.1021/jf802473m CCC: $40.75  2008 American Chemical Society
Published on Web 11/17/2008

11930 J. Agric. Food Chem., Vol. 56, No. 24, 2008
Ragoussis et al.
dropwise over
5
min to
a
suspension of freshly prepared
alkenyl constituents, (7Z) and (5Z)-tetradecenyl acetates, have
been identified but have proved nonsignificant in attractiveness.
The ratio of the above four C14 components in the sex
pheromone gland is (3E,7Z):(3E):(7Z):(5Z) ) 63:31:5:1. To
confirm the structural assignment and to provide samples of
suitable size for laboratory and field bioassay, the above
scientists carried out a stereospecific six-step synthesis of
compound 1 (7). The synthetic active compound was found to
be highly attractive to males in field tests and, applied in traps,
caught large numbers of insects. Therefore, the availability of
high-purity synthetic pheromone, by the development of a
practical chemical synthesis, would aid integrated pest manage-
ment programs in monitoring or control of the above noxious
insect.
(E,Z)-Diene structures are widespread in insect pheromones,
which are responsible for special functions (9), but pose great
challenges for their stereoselective synthesis. The 3,7-dienyl
moiety is not common in Lepidoptera pheromones, other than
S. tangolias. To our knowledge, the only synthetic report found
in the literature (7) for the creation of the 3E,7Z double bond
system of this main component of the pheromone is based on
the partial reduction of suitable acetylenic precursors. However,
this synthesis is lacking in experimental details and structural
description of the intermediates. The reported overall yield is a
few percent; therefore, the method is unsuitable for large-scale
preparation. An alternative approach for the synthesis of the
title compound has therefore been developed in this study.
[Ph3P+CH2(CH2)5CH3]Br- (2.58 g, 5.87 mmol) in dry THF (15 mL)
at 0 °C, under nitrogen. The resulting orange solution was stirred for
1 h at 0 °C and then cooled to -78 °C. A solution of the lactol 3 (0.40
g, 3.92 mmol) in dry THF (9 mL) was added dropwise over 30 min,
maintaining the temperature below -70 °C. The resulting yellow
solution was allowed to warm slowly to room temperature over a period
of 1 h and left overnight. Then, the reaction mixture was quenched
with a saturated solution of NH4Cl (20 mL) and extracted with ether
(3 × 15 mL). The combined organic phases were washed with brine
(15 mL), dried over Na2SO4, and concentrated. The residue was
chromatographed (petroleum ether/diethyl ether 6:1 to 1:1) to give
practically pure 4 (0.52 g, 72%, purity by GC 98%, Z/E 98/2), as a
colorless oil. IR νmax/cm-1: 3640 (w), 3009 (w), 2932 (s), 2861 (s),
1550 (s), 1440 (w). 1H NMR: δ 0.87 (t, 3, J ) 7.2 Hz), 1.21-1.35 (m,
8), 1.41 (qt, 2, J ) 7.2 Hz), 1.57 (qt, 2, J ) 7.2 Hz), 2.00 (qd, 2, J )
6.6 Hz), 2.05 (qd, 2, J ) 7.2 Hz), 3.64 (t, 2, J ) 6.6 Hz), 5.30-5.40
(m, 2). 13C NMR 14.2, 22.8, 26.1, 27.1, 27.4, 29.2, 29.9, 32.0, 32.5,
62.9, 129.5, 130.5. MS m/z (%): 166 (M+ - H2O, 3), 110 (11), 95
(33), 82 (43), 81 (45), 67 (87), 55 (80), 41 (100). The NMR spectra
are in accordance with those reported in the literature (12).
5Z-Dodecenal (5). A 50 mL round-bottom flask, equipped with a
magnetic stirring bar, was charged with pyridinium chlorochromate (0.7
g, 3.25 mmol), Celite (0.7 g), and anhydrous CH2Cl2 (6 mL). The
alcohol 4 (0.4 g, 2.17 mmol) in anhydrous CH2Cl2 (3 mL) was added
to the stirred suspension at room temperature. Progress of the reaction
was monitored by TLC. When the starting material disappeared (2 h),
the mixture was diluted with Et2O (25 mL) and filtered through a pad
of Florisil. The filter cake was washed with Et2O (2 × 8 mL). After
evaporation of the solvent, the crude product was purified by column
chromatography (petroleum ether/diethyl ether 4:1 to 2:1) producing 5
(372 mg, 94%, purity by GC 97%, Z/E ratio 98/2) as a colorless oil.
IR νmax/cm-1: 3011 (w), 2931 (s), 2859 (s), 2718 (w), 1728 (s), 1550
(s), 1460 (w). 1H NMR δ 0.81 (t, 3, J ) 7.2), 1.16-1.30 (m, 8), 1.63
(qt, 2, J ) 7.2 Hz), 1.93 (qd, 2, J ) 7.2 Hz), 2.02 (qd, 2, J ) 7.2 Hz),
2.36 (dt, 2, J1 ) 7.2 Hz, J2 ) 1.8 Hz), 5.24 (dtt, 1, J1 ) 10.8 Hz, J2 )
7.2 Hz, J3 ) 1.2 Hz), 5.35 (dtt, 1, J1 ) 10.8 Hz, J2 ) 7.2 Hz, J3 ) 1.2
Hz), 9.70 (t, 1, J ) 1.8 Hz). 13C NMR δ 14.3, 22.2, 22.8, 26.6, 27.4,
MATERIALS AND METHODS
Spectroscopic data were obtained on the following instruments: 1H
NMR spectra, in CDCl3 solution on a Varian 600 MHz spectrometer;
13C NMR spectra, in CDCl3 solution on a Varian Mercury 200 MHz
spectrometer. IR spectra were obtained in CCl4 solutions (5%) on a
Perkin-Elmer 247 spectrophotometer. Gas chromatography-mass
spectrometric (GC-MS) analyses were carried out with a Hewlett-
Packard 5890-5970 system, equipped with a SPB-1 capillary column
(20 m × 0.25 mm, 0.33 µm film thickness, Supelco, Sigma-Aldrich
Ltd., Greece); carrier gas, helium, 1 mL/min; injector temperature, 230
°C; oven temperature, 50 °C for 5 min isothermal and then raised to
250 °C at a rate of 4 °C/min and then held for 10 min; ion source
temperature, 220 °C; interface temperature, 250 °C; mass range, 40-500
amu; and EI, 70 eV. GC analyses were carried out with Agilent 6890
N chromatograph either in a polar capillary column CP-Wax 52 CB
(30 m × 0.32 mm, 0.25 µm film thickness, Varian Inc., CA) or in a
nonpolar capillary column SPB1 (20 m × 0.32 mm, 1.0 µm film
thickness, Supelco, Sigma-Aldrich Ltd.): carrier gas, helium, 1 mL/
min; injector temperature, 200 °C; oven temperature, 60 °C for 5 min
isothermal and then raised to 250 °C at a rate of 4 °C/min and then
held for 15 min. Thin-layer chromatography (TLC) was performed on
0.25 mm precoated silica gel 60 F254 aluminum sheets and column
chromatography on silica gel 60 (0.063-0.2 mm) as well as silica gel
60 (<0.063 mm Merck & Co., Darmstadt, Germany). All commercial
reagents and solvents were used as supplied. Petroleum ether was the
light fraction bp 40-60 °C. Piperidinium acetate was prepared in situ
by mixing equivalent quantities of piperidine and glacial acetic acid in
dimethyl sulfoxide (DMSO). Red-Al was a solution of sodium bis(2-
methoxyethoxy) aluminum hydride, 65 wt % in toluene (Sigma-Aldrich
Ltd.). KN[Si(Me)3]2 was a solution of potassium bis(trimethylsilyl)-
amide, 0.5 M in toluene (Sigma-Aldrich Ltd.).
29.2, 29.8, 31.9, 43.5, 128.4, 131.6, 202.8. MS m/z (%): 164 (M+
-
H2O, 3), 138 (13), 110 (13), 98 (23), 81 (25), 67 (52), 55 (61), 41
(100). The NMR spectra of 5 are consistent with the literature (12).
The IR and mass spectra of 5 matched those of the literature (13).
(3E,7Z)-3,7-Tetradecadienoic Acid (6). To a stirred solution of
piperidine (0.033 mmol) and AcOH (0.033 mmol) (one drop from each
one) in DMSO (3 mL) was added malonic acid (0.4 g, 3.85 mmol). To
the resulting clear solution, the aldehyde 5 (0.35 g, 1.92 mmol) was
added, and the mixture was stirred at room temperature for 30 min.
Then, it was heated at 85 °C under stirring, until the evolution of CO2
had stopped (2-3 h). The mixture was poured into H2O (10 mL) and
extracted with Et2O (3 × 8 mL). The combined organic phases were
dried over Na2SO4, and the solvent was concentrated under vacuum.
Column chromatography (petroleum ether/diethyl ether 8:1 to 3:1) gave
acid 6 (320 mg, 75%, purity by GC 97%) as a colorless oil. IR νmax
/
cm-1: 3011 (w), 2931 (s), 2860 (s), 1712 (s), 1548 (s), 969 (m). H
NMR: δ 0.87 (t, 3, J ) 6.6 Hz), 1.20-1.35 (m, 8), 2.00 (qt, 2, J ) 7.2
Hz), 2.09 (m, 4), 3.07 (d, 2, J ) 6.6 Hz), 5.32 (dt, 1, J1 ) 10.8 Hz, J2
) 7.2 Hz), 5.37 (dt, 1, J1 ) 10.8 Hz, J2 ) 7.2 Hz), 5.52 (dt, 1, J1 )
15.0 Hz, J2 ) 6.6 Hz), 5.60 (dt, 1, J1 ) 15.6 Hz, J2 ) 6.0 Hz). 13C
NMR: δ 14.3, 22.9, 27.3, 27.5, 29.2, 29.8, 32.0, 32.8, 38.0, 121.3, 128.8,
130.9, 135.1, 179.1. MS m/z (%): 224 (M+, 1), 164 (10), 112 (8), 100
(10), 84 (45), 69 (92), 55 (100), 41 (80). Anal. calcd for C14H24O2: C,
74.94; H, 10.79. Found: C, 74.60; H, 10.67.
1
(3E,7Z)-3,7-Tetradecadienol (7). To a cold (0-4 °C) stirred solution
of Red-Al (1 mL, 3.21 mmol, 65 wt % in toluene) in anhydrous diethyl
ether (5 mL), a solution of 6 (0.3 g, 1.34 mmol) in diethyl ether (2
mL) was added dropwise under nitrogen. Stirring was continued for
1 h at the same temperature, and then, the solution was left overnight
at room temperature. The end of the reaction was checked by TLC.
The reaction mixture was hydrolyzed by dropwise addition of cold
solution of 5% HCl (10 mL), under inert atmosphere, and then diluted
with water and extracted with diethyl ether (3 × 10 mL). The organic
5-Hydroxytetrahydropyran (3). This lactol was prepared in 85%
yield from 1,3-dihydropyran (2), according to a literature procedure
(10). After the workup of the reaction mixture, the product was directly
used for the Wittig reaction without further purification.
5Z-Dodecenol (4). (a) The n-heptylphosphonium bromide was
prepared in 75% yield (mp 172-174 °C) from 1-bromoheptane and
triphenylphosphine, by a previously described procedure (11), using
toluene as the solvent instead of xylene. (b) Potassium bis(trimethyl-
silyl)amide (11.7 mL, 5.87 mmol, 0.5 M solution in toluene) was added

Synthesis of (3E,7Z)-3,7-Tetradecadienyl Acetate
J. Agric. Food Chem., Vol. 56, No. 24, 2008 11931
phase was dried over anhydrous Na2SO4, and the solvent was evaporated
under vacuum. The resultant crude product was purified by column
chromatography, over silica gel, to give (3E,7Z)-tetradecadienol (7)
by column chromatography, gave the (3E,7Z)-tetradecadienoic
acid (6) in 75% yield. This procedure provides higher than 97%
configurational purity of the 3E bond. The regio- and stereo-
selectivity of the product 6 were unambiguously confirmed by
values of chemical shifts and coupling constants in the 1H NNR,
which exhibited resonances attributable to vinyl hydrogens on
two different double bonds. The presence of a coupling constant
of 15.0 Hz at 5.52 ppm and another one of 15.6 Hz at 5.60
ppm revealed two trans olefinic protons at C4 and C3,
respectively. A second vinyl resonance coupling constant of 10.8
Hz, at both 5.32 and 5.37 ppm, confirmed the presence of two
cis olefinic protons at C8 and C7, respectively. The transforma-
tion of (3E,7Z)-3,7-tetradecadienoic acid (6) into the target
compound was done by reduction to the corresponding alcohol
7 and subsequent acetylation to the final acetate 1. The reduction
of the acid 6 to (3E,7Z)-3,7-alkadienol (7) was effected in 71%
yield, with an excess of Red-Al in ether (20), without affecting
the double bonds. The acetylation was carried out in 92% yield,
under standard conditions by acetic anhydride in pyridine
solution to give the final product (3E,7Z)-tetradecadienyl acetate
(1) in high purity (95%) (21). The system of the olefinic protons
appears as follows: one doublet of triplet at 5.46 ppm (J1 )
15.6) attributed to C3 proton and one multiplet at 5.24-5.36
ppm, attributed to C4, C7, and C8 protons, respectively.
Although the complexity of the second vinyl resonance did not
allow measurement of a coupling constant, the described
conditions of reduction and acetylation do not affect the
geometry of the system of the double bonds, which remain
unchanged as in the precursors 5 and 6. The values of chemical
(200 mg, 71%, purity by GC 95%) as a viscous oil. IR νmax/cm-1
:
3640 (w), 3010 (w), 2930 (s), 2860 (s), 1550 (s), 972 (m). 1H NMR δ
0.82 (t, 3, J ) 7.2 Hz), 1.15-1.30 (m, 8), 1.94 (qd, 2, J ) 6.6 Hz),
2.03 (qt, 4, J ) 6.6 Hz), 2.19 (qd, 2, J ) 6.6 Hz), 3.56 (t, 2, J ) 6.6
Hz), 5.26 (dt, 1, J1 ) 10.8 Hz, J2 ) 6.6 Hz), 5.29-5.36 (m, 2), 5.49
(dt, 1, J1 ) 15.6 Hz, J2 ) 6.6 Hz). 13C NMR δ 14.3, 22.9, 27.3, 27.5,
29.2, 29.9, 32.0, 33.0, 36.1, 62.1, 126.4, 129.1, 130.7, 133.7. MS (m/
z) 210 (M+, 1), 192 (2), 124 (5), 95 (10), 83 (32), 69 (60), 55 (100),
41 (72).
(3E,7Z)-3,7-Tetradecadienyl Acetate (1). To a solution of acetic
anhydride (1.0 mL, 10 mmol) in pyridine (4.0 mL), at 0-4 °C, the
dienol 7 (0.25 g, 1.19 mmol) was added under stirring. The reaction
was maintained at the same temperature for 1 h and then was brought
to room temperature and monitored by TLC. When the reaction was
finished (5 h), the mixture was poured in cold water (20 mL) and was
extracted with diethyl ether (2 × 10 mL). The organic phase
was washed by dilute 5% HCl, then by saturated NaHCO3, and finally
dried over anhydrous Na2SO4. The solvent was removed under vacuum,
and the crude product was purified by column chromatography over
silica gel to give 1 (275 mg, 92%, purity by GC 95%) as a viscous
liquid. IR νmax/cm-1: 3008 (w), 2931 (s), 2859 (s), 1741 (s), 1550 (s),
1239 (s), 972 (m). 1H NMR: δ 0.82 (t, 3, J ) 6.6 Hz), 1.15-1.30 (m,
8), 1.97 (s, 3), 1.92-2.04 (m, 6), 2.24 (qd, 2, J ) 7.2 Hz), 3.99 (t, 2,
J ) 7.2 Hz), 5.24-5.36 (m, 3), 5.46 (dt, 1, J1 ) 15.6 Hz, J2 ) 6.6
Hz). 13C NMR: δ 14.3, 21.1, 22.8, 27.3, 27.5, 29.2, 29.9, 32.0, 32.1,
32.9, 64.3, 125.6, 129.0, 130.6, 133.1, 171.2. MS m/z (%): 192 (M+
-
60, 3), 149 (3), 135 (4), 121 (12), 83 (17), 67 (69), 55 (28), 43 (100).
NMR and MS spectra of 1 were in agreement with those described in
the literature (7).
1
shifts in the H NNR and those of 13C NMR of the synthetic
acetate 1 were consistent with those reported for the isolated
natural product and also with the reported synthetic compound
(7).
RESULTS AND DISCUSSION
The main pheromone component 1 of the potato tuber moth
S. tangolias was synthesized by an unambiguous stereoselective
route, as outlined in Figure 1. This method involves the
following six steps: Hydration of the 2,3-dihydropyran (2) in
wet acid according to the literature (10) afforded 2-hyroxytet-
rahydropyran (3) in 85% yield. The carbonyl olefination of the
lactol 3 with phosphorus ylids is a general method for the
preparation of 5Z-alkenols (14). To ensure cis selectivity of this
Wittig olefination, potassium bis(trimethylsilyl)amide was cho-
sen as the base. The ylide, prepared from heptyltriphenylphos-
phonium bromide (11) by reaction with potassium bis(trime-
thylsilyl)amide as the base (15), in a stoichiometric ratio of
reagents, reacted with 3 in THF at -78 °C to give the alkenol
4. Pure 5Z-dodecenol (4) was isolated from the reaction mixture
by column chromatography in good yield (72%) and excellent
purity (98%, Z/E ratio 98/2). Oxidation of 4 with pyridinium
chlorochromate/Celite in dichloromethane (16) afforded the
required 5Z-dodecenal (5), which was purified by column
chromatography. The yield was 94%, and the Z geometry of
the double bond of 5 was confirmed by the vicinal vinyl
hydrogen coupling constant J ) 10.8 Hz. It must be mentioned
here that the 5Z-dodecenol (4) and 5Z-dodecenal (5) are found
as components in the chemical communication system of various
species. For example, these compounds are major volatile
constituents in the sex pheromone glands of females of the lappet
moth Gastropacha quercifolia (Lepidoptera: Lasiocampidae)
(17) and of other species in the genus Dendrolimus (18). The
5Z-dodecenal (5) was also identified in the anal gland of the
male wild rabbit (13).
In conclusion, (3E,7Z)-3,7-tetradecadienyl acetate (1), the
main pheromone component of the potato tuber moth S.
tangolias (Gyen), was prepared in six experimentally simple
steps and an overall yield of 28% from commercially available
2,3-dihydropyran (2). The products can be easily purified in
sufficient quantities by rapid column chromatography, and no
efforts have been made to optimize the yields. The simplicity
of the operation along with the high regio- and stereoselectivity
obtained, the low cost of reagents, and the easily scalable
procedure suggest the potential practical use of the above
pheromone for the development of alternative environmentally
safe control methods for this serious insect pest.
ACKNOWLEDGMENT
We acknowledge IOPC (Athens, Greece) for providing its
NMR facilities and also Dr. H. Bardouki (Vioryl S.A) for
running the mass spectra as well for her helpful suggestions.
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(21) The acid 6, the alcohol 7, and the final product (3E, 7Z)-3,7-
tetradecadienyl acetate 1 were homogeneous in GC analysis with
a capillary nonpolar column. The acid 6 and the alcohol 7 were
also homogeneous in GC analysis with a polar capillary column.
Only the analysis of the final product 1, in a polar capillary
column, showed the presence of a less polar geometrical isomer
(1.0%), giving exactly the same mass spectrum and a more polar
isomer (1.1%), probably the (2E, 7Z)-2,7-tetradecadienyl acetate
according to the fragmentation of the mass spectrum.
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Received for review August 8, 2008. Revised manuscript received
October 13, 2008. Accepted October 16, 2008.
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