Synthesis of 4E,7Z-tridecadien-1-ylacetate, a component of the Phthorimaea opercucella sex pheromone

Article abstract of DOI:10.1007/s10600-007-0105-2

A new synthetic approach to 4E,7Z-tridecadien-1-ylacetate, a component of the Phthorimaea opercucella (Zeller) potato moth sex pheromone, was developed using a highly stereoselective Claisen rearrangement and Wittig reaction.

Full text of DOI:10.1007/s10600-007-0105-2

Chemistry of Natural Compounds, Vol. 43, No. 3, 2007
SYNTHESIS OF 4 ,7 -TRIDECADIEN-1-YLACETATE,
E Z
A COMPONENT OF THE
SEX PHEROMONE
Phthorimaea opercucella
R. R. Vakhidov and I. N. Musina
UDC 542.91+547.473+639.936.2
Phthorimaea opercucella
E Z
A new synthetic approach to 4 ,7 -tridecadien-1-ylacetate, a component of the
(Zeller)potatomothsexpheromone, wasdevelopedusingahighlystereoselective Claisen rearrangement and
Wittig reaction.
Key words:
, 4 ,7 -tridecadien-1-ylacetate, synthesis.
Phthorimaea opercucella E Z
4 ,7 -Tridecadien-1-ylacetate (1) has been identified as a component of the sex pheromone of the potato moth
E Z
(Zeller), a potato pest [1]. Several syntheses of this compound have been reported [2-14].
Phthorimaea opercucella
The new synthesis of 1 that was developed by us is based on a thermal Claisen rearrangement of secondary allyl
alcohols and is highly recommended as a stereospecific method for constructing a double bond with the ( )-configuration [4].
E
The starting material was acrolein (2), which reacted with the Grignard reagent generated from the tetrahydropyran
ether of 2-bromoethan-1-ol to give the key synthon, alkenic secondary alcohol 3. Thermal Claisen rearrangement occurred
smoothly upon heating of 3 with triethylorthoacetate in the presence of catalytic amounts of propionic acid for 1 h at 138°C.
Removal of the THP protecting group produced unsaturated alcohol 4 with exclusively the -configuration, as confirmed
E
by GC and IR and PMR spectra. In particular, the absorption band of C=C vibrations appeared at 965 cm−1 whereas it was
−1
780 cm
for the analogous compound with the -configuration. Then, 4 was oxidized to aldehyde 5 using pyridinium
Z
chromate. A Wittig reaction of 5 with the phosphorus ylide generated from hexylbromide gave diene ester 6 with the
7 -configuration for the double bond. The final step was hydride reduction of the ester in 6 and acetylation of the resulting
Z
4 ,7 -tridecadien-1-ol (7) to give 1.
E Z
OH
COOEt
COOEt
O
O
THPO
HO
3
2
4
5
COOEt
OR
6
1, 7
1: R = Ac
7: R = H
According to capillary GC, 1 contains at least 99% of the main product, the structure of which was confirmed by IR
and PMR spectroscopy.
EXPERIMENTAL
IR spectra of thin layers were recorded on a Microlab 620 MX (Beckman) instrument. PMR spectra were obtained in
(CD ) CO on a Tesla BS-587A spectrometer (working frequency 80 MHz). Chemical shifts are given on the δ scale with
3 2
Scientific Research Institute of Low-Tonnage Chemicals and Reagents, Russia, Ufa. Translated from Khimiya
Prirodnykh Soedinenii, No. 3, pp. 235-236, May-June, 2007. Original article submitted April 19, 2007.
0009-3130/07/4303-0282 ©2007 Springer Science+Business Media, Inc.
282

HMDS internal standard. GC was carried out on a Chrom-5 instrument with a flame-ionization detector, 3500 × 3 mm
column, SE-30 (5%) stationary phase on Chromaton N-AW-DMCS (0.16-0.20 mm), working temperature 50-250°C,
He carrier gas (30 mL/min). Compounds 1, 4, and 7 were analyzed on a Carlo Erba instrument with a glass capillary column
(20 m × 0.2 mm) and working temperature 50-200°C. TLC was performed on Silufol plates with a fixed layer of SiO .
2
1-(Tetrahydropyran-2-yl)hydroxypent-4-en-3-ol (3). The Grignard reagent prepared from the THP ether of
2-bromoethan-1-ol (6.27 g, 30.0 mmol), Mg (0.80 g, 33 mmol), and dry diethylether (100 mL) was cooled; treated dropwise
with acrolein (1.68 g, 30 mmol) in absolute diethylether (20 mL); stirred for 1 h; and treated with cold water (20 mL). The
aqueous layer was separated and extracted with diethylether (3 × 20 mL). The combined organic layer was dried over Na SO .
2
4
The solvent was evaporated. The residue was chromatographed over silica gel to afford 3 (4.53 g, 81%).
IR spectrum (ν, cm−1): 3500 (OH), 1640 and 970 (CH=CH ).
2
PMR spectrum (δ, ppm): 1.2-1.5 (8H, m, CH ), 3.6-4.2 (5H, m, CH –O, CH–O), 4.84 (1H, m, O–CH–O), 5.1-5.4 (2H,
2
2
m, CH =C), 5.6-5.9 (1H, m, CH=C).
2
Ethyl-7-hydroxyhept-4E-enoate (4). A mixture of 3 (3.73 g, 20.0 mmol), triethylorthoacetate (9.68 g, 6.0 mmol),
and propionic acid (0.02 g) was heated on an oil bath at 138°C for 1 h. The ethanol that was formed was removed through a
fractionating condenser. The mixture was cooled, treated with diethylether (100mL), washedwith saturatedNaHCO and NaCl
3
solutions, dried over Na SO , and evaporated. Unreacted triethylorthoacetate was distilled offin vacuo. Theresiduewas diluted
2
4
with diethylether (100 mL), treated with TsOH (0.2 g), stirred at room temperature for 24 h (TLC monitoring), treated with
saturated NaHCO and NaCl solutions, dried over Na SO , and evaporated. The residue was chromatographed over silica gel
3
2
4
to afford 4 (19.3 g, 56%).
IR spectrum (ν, cm−1): 3500 (OH), 1740 (C=O), 1650 and 965 (E-CH=CH).
PMR spectrum (δ, ppm, J/Hz): 1.12 (3H, t, J = 6, CH ), 1.8-2.1 (6H, m, CH C=CH , CH COO), 3.6-4.1 (5H, m,
3
2
2
2
CH –O, O–H), 5.2-5.5 (2H, m, CH=CH).
2
Ethyl-7-oxo-4E-heptenoate (5). A suspension of pyridinium chromate (16.45 g, 9.21 mmol) in dry CHCl (100 mL)
3
was treated dropwise with 4 (1.70 g, 7.86 mmol) over 5 min, stirred for another 30 min, diluted with diethylether (100 mL),
passed over a column of silica gel (15 cm layer), washed successively with NaHCO and NaCl solutions, dried over Na SO ,
3
2
4
and evaporated. The residue was chromatographed over silica gel to afford 5 (0.83 g, 62%).
IR spectrum (ν, cm−1): 1740 (C=O), 1650 and 965 (E-CH=CH).
PMR spectrum (δ, ppm, J/Hz): 1.12 (3H, t, J = 6, CH ), 1.8-2.2 (4H, m, CH C=C, CH COO), 3.6-4.3 (4H, m, CH O,
3
2
2
2
C=C–CH –C=O), 5.2-5.5 (2H, m, CH=CH), 9.3 (1H, s, CH=O).
2
Ethyl-4E,7Z-tridecadienoate (6). Hexylbromide (0.69 g, 4.18 mmol) and PPh (1.10 g, 4.18 mmol) in a flask under
3
Ar were heated at 160°C for 8 h, cooled to -20°C, and treated with absolute THF (50 mL). t-BuOK (0.46 g, 4.18 mmol) was
carefully added at -20°C. The mixture was stirred for 30 min, cooled to -70°C, treated with 5 (0.71 g, 4.18 mmol), stirred at
-70°C for 2 h, left overnight, diluted with hexane (50 mL), filtered through a Schott filter to remove Ph PO, evaporated, and
3
chromatographed over a column of silica gel to afford 6 (0.63 g, 64%). IR and PMR spectra were analogous to those
published [12].
4E,7Z-Tridecadien-1-ol (7) and 4E,10Z-tridecadien-1-ylacetate (1) were synthesized and characterized as
before [12].
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