Synthesis of (Z/E)-11-tetradecen-1-ol, a component of Ostrinia nubilalis sex pheromone

Article abstract of DOI:10.1007/s10600-008-9020-4

11-Tetradecen-1-ol acetate is a mixture of geometric isomers with the Z/E-conformations in a 94:6 ratio that is used as an attractant to trap corn pests. It has a powerful attractive action similar to that of an isomeric mixture of 11-tetradecenyl acetate with the Z/E-conformation in a 95:5 ratio that was extracted from the peritoneal cavity of male Ostrinia nubilalis Hubner in Xinjing (PRC).

Full text of DOI:10.1007/s10600-008-9020-4

Chemistry of Natural Compounds, Vol. 44, No. 2, 2008
SYNTHESIS OF (Z/E)-11-TETRADECEN-1-OL, A COMPONENT
OF Ostrinia nubilalis SEX PHEROMONE
J.-M. Li,1,2 J.-P. Yong,1,2 and H. A. Aisa1*
UDC 547.632
1
1-Tetradecen-1-ol acetate is a mixture of geometric isomers with the Z/E-conformations in a 94:6 ratio that
is used as an attractant to trap corn pests. It has a powerful attractive action similar to that of an isomeric
mixture of 11-tetradecenyl acetate with the Z/E-conformation in a 95:5 ratio that was extracted from the
peritoneal cavity of male Ostrinia nubilalis Hubner in Xinjing (PRC).
Key words: Ostrinia nubilalis Hubner, sex pheromone, (Z/E)-11-tetradecen-1-ol acetate, synthesis.
Herein we report a cheaper and simpler synthetic method for 11-tetradecen-1-ol acetate in 34.8% overall yield. The
European corn borer (Ostrinia nubilalis Hubner) is a common pest that is widely distributed in Europe and the Far East and
decreases grain production. The goal of our work was to find a suitable agent for controlling corn pests. For this reason, we
synthesized the sex pheromone of the European corn borer.
Several synthetic methods for the sex pheromone of the Asian corn borer have been reported [1-4]. However, little
information is available on the synthesis of pheromones of the European corn borer [5-6]. The reported methods produced
pheromones in low yields from expensive reagents. Thus, the goal of our work was to find an economical and convenient
synthetic method for the sex pheromones of O. nubilalis Hubner.
We report the synthesis of the sex pheromone of the European corn borer (1 and 2) in 34.8% overall yield. The starting
compound was a cheap 11-undecanoic acid, reduction of which with LiAlH produced bromhydrin 3. Then, reaction of 3 with
4
triphenylphosphine gave (11-hydroxyundecyl)triphenylphosphonium bromide4. A double bond was constructed using a Wittig
reaction. Propionaldehyde and (11-hydroxyundecyl)triphenylphosphonium bromide reacted to give a mixture of geometric
isomers (Z/E)-11-tetradecen-1-ols 5 and 6, acetylation of which gave theZ-isomer with an impurityoftheE-isomer (94:6 ratio).
Et O, LiAlH , 0°C
2
4
Ph P, CH CN
3
3
Br CH (CH ) COOH
2 9
HO CH (CH ) CH Br
Ph PCH (CH ) CH OHBr
3 2 2 9 2
2
2
2 9
2
reflux
4
3
O
O
OH
OH
O
CH CH CHO
pyridine, Ac2O
r, t
1
3
2
5
THF, BuLi
O
2
6
1
) Xinjing Technical Institute of Physics and Chemistry, Academy of Sciences of the People's Republic of China,
Urumchi, 830011, PRC, e-mail: haji@ms.xjb.ac.cn; 2) Graduate School of the Chinese Academy of Sciences, Beijing, 100039,
PRC. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 177-178, March-April, 2008. Original article submitted
January 24, 2008.
©
0
009-3130/08/4402-0224 2008 Springer Science+Business Media, Inc.
2
24

EXPERIMENTAL
IR spectra were recorded on a Perkin—Elmer 983 spectrophotometer; PMR spectra, on a Varian Inova-400
spectrometer (TMS internal standard, CDCl solvent). Melting points were determined on an XT-4 instrument and are
3
uncorrected. Commercially available reagents were used without further purification. Dichloromethane, ether, and pyridine
were freshly distilled. THF was distilled over sodium and benzophenone before use.
Synthesis of11-Bromoundecan-1-ol (3). Athree-neckedflask (250 mL) was charged with LiAlH (3.416 g, 0.09 mol)
4
and anhydrous ether (35 mL). The mixture was stirred under N for 30 min at -10°C [7], cooled below -10°C, treated dropwise
2
with 11-bromoundecanoic acid (19.89 g, 0.075 mol) in absolute ether (145 mL) under N and then at room temperature for
2
3
0 min, refluxed for 1 h, cooled to room temperature, and treated with aqueous NaOH solution (15 mL, 5%) until the gray
precipitate turned white. The precipitate was filtered off and washed with ether (3 × 10 mL). The organic layers were combined
and dried over MgSO . Ether was removed to produce a white solid that was crystallized repeatedly from ethanol to afford 3
4
-
1
(
16.5 g). Colorless crystals, 81.4% yield, mp 43-46°C. IR spectrum (nmax, cm ): 3429, 2923, 2852, 1466, 1057, 725, 645.
PMR spectrum (d, ppm, J/Hz): 3.58 (2H, t, J = 6, CH OH), 3.37 (2H, t, J = 6.3, BrCH ), 2.50-2.51 (1H, s, OH), 1.76-
2
2
1
.81 (2H, m, 10-CH ), 1.35-1.41 (2H, m, 2-CH ), 1.25 (12H, m, 6CH ).
2
2
2
Synthesis of (11-Hydroxyundecyl)triphenylphosphonium Bromide (4). Compound 3 (16.00 g, 0.064 mol),
triphenylphosphine (19.67 g, 0.075 mol), and CH CN (265 mL) were stirred in a three-necked round-bottomed flask (500 mL)
3
equipped with a reflux condenser for 24 h [8]. The solvent was replaced by ether (80 mL). The mixture was stirred at room
temperature. A white precipitate quickly formed and was filtered off and washed with ether three times. Solvent was removed
-
1
to afford 4 (28.4 g). White solid, 87.4% yield, mp 89-92°C. IR spectrum (nmax, cm ): 3273, 3016, 2924, 2853, 1437, 1113,
106, 1059, 749, 692.
PMR spectrum (d, ppm, J/Hz): 7.69-7.87 (15H, m, 3C H ), 3.77 (2H, t, J = 8, CH O), 2.17 (1H, s, OH), 1.52-1.63 (2H,
1
6
5
2
m, 2-CH ), 1.29-1.32 (2H, m, 11-CH ), 1.20-1.25 (14H, m, 7CH ).
2
2
2
Synthesis of (Z/E)-11-Tetradecen-1-ols 5 and 6. A suspension of 4 (28.0 g, 0.055 mol) in dry THF (150 mL) was
treated with n-butyllithium in hexane (2.5 M, 24 mL, 0.060 mol). The mixture was stirred at -15°C under N for 2 h [9, 10],
2
treated dropwise with propionaldehyde (3.77 g, 0.065 mol) in dry THF (10 mL), stirred at -15°C for 2 h and overnight at room
temperature, treated with saturated NH Cl solution (20 mL), stirred for 30 min, and filtered. The organic layer was washed
4
successively with water and saturated NaCl solution, dried over anhydrous Na SO , and evaporated in vacuo. The product was
2
4
purified byflash chromatographyover a column ofsilica gel (100-200 mesh) with elution bypetroleum ether-ethylacetate (10:1)
to afford 5 and 6 (6.165 g of the mixture) in 52.8% yield. GC showed a purity >98% and Z:E = 94:6.
-
1
IR spectrum (nmax, cm ): 3347, 3007, 2926, 2855, 1462, 1057, 722.
PMR spectrum (d, ppm, J/Hz): 5.31-5.45 (2H, m, CH=CH), 3.55 (2H, t, J = 6.4, –CH –O), 1.99-2.02 (2H, m,
2
CH –CH=CH), 1.95-1.98 (2H, m, 10-CH ), 1.44-1.52(2H, m, 2-CH ), 1.32-1.35 (2H, m, 9-CH ), 1.27-1.32 [12H, m, –(CH ) ],
2
2
2
2
2 6
0
.96 (3H, t, J = 8, CH3).
Synthesis of (Z/E)-11-Tetradecen-1-ol Acetates 1 and 2. A mixture of 5 and 6 (6.000 g, 0.028 mol) was acetylated
for 15 h by acetic anhydride (6 mL, 0.063 mol) in the presence of pyridine (15 mL) [11, 12] with stirring at room temperature,
poured into icewater (50 mL), and extracted with ether. The organic layer was washed with water (20 mL) and saturated NaCl
solution (20 mL), dried over anhydrous Na SO , and evaporated in vacuo. The products were purified byflash chromatography
2
4
over a column of silica gel (100-200 mesh) with elution by petroleum ether-ethylacetate (30:1) to afford a mixture of 1 and 2
(
6.60 g, 92.7%) as a colorless oil. GC showed a purity >98% with Z:E = 94:6.
-
1
IR spectrum (nmax, cm ): 3005, 2961, 2926, 1743, 1464, 1365, 1238, 1037, 972 (s, trans-C=C), 731 (cis-C=C).
PMR spectrum (d, ppm, J/Hz): 5.31-5.45 (2H, m, CH=CH), 4.05 (2H, t, J = 7.4, CH –O), 2.01-2.06 (3H, s, O=C–CH ),
2
3
1
.96-1.99 (4H, m, –CH –C=C–CH –), 1.59-1.64 (2H, m, 2-CH ), 1.27-1.33 (16H, m, 8CH ), 0.96 (3H, t, J = 8, CH ).
2
2
2
2
3
1
3
C NMR spectrum (CD COCD , d): 171.18 (O–C=O), 131.46, 129.25 (C11, C12), 66.42 (C1), 35.55 (C13), 33.36
3
3
(
C10), 30.43, 30.33, 30.15, 29.91, 29.82, 28.63, 27.45, 26.58 (C2-C9), 17.28 (O=CCH ), 14.35 (C14).
3
225

ACKNOWLEDGMENT
The work was supported financially by the program for development and research of high technologies in Xinjiang,
Project (O539161401).
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