Fe-catalyzed synthesis of (4E)-tridec-4-en-1-yl acetate, sex pheromone of tomato pinworm (Keiferia lycopersicella)

Article abstract of DOI:10.1134/S1070428013050059

Starting with industrially available 1,3-dichloropropene a stereoselective process was developed for the preparation of (4E)-tridec-4-en-1-yl acetate, sex pheromone of tomato pinworm (Keiferia lycopersicella) using in the key stage the Fe-catalyzed cross-coupling of ethyl (4E)-5-chloropent-4-enoate with octylmagnesium bromide.

Full text of DOI:10.1134/S1070428013050059

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 5, pp. 669−671. © Pleiades Publishing, Ltd., 2013.
Original English Text © R.N. Shakhmaev, A.Sh. Sunagatullins, V.V. Zorin, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 5, pp. 687−689.
Fe-Catalyzed Synthesis of (4Е)-Tridec-4-en-1-yl Acetate,
Sex Pheromone of Tomato Pinworm (Keiferia lycopersicella)
R. N. Shakhmaev, A. Sh. Sunagatullina, and V. V. Zorin
Ufa State Oil Engineering University, Ufa, 450062 Russia
e-mail: biochem@rusoil.net
Received September 24, 2012
Abstract—Starting with industrially available 1,3-dichloropropene a stereoselective process was developed for the
preparation of (4Е)-tridec-4-en-1-yl acetate, sex pheromone of tomato pinworm (Keiferia lycopersicella) using in
the key stage the Fe-catalyzed cross-coupling of ethyl (4Е)-5-chloropent-4-enoate with octylmagnesium bromide.
DOI: 10.1134/S1070428013050059
(4Е)-Tridec-4-en-1-yl acetate (I) was identified as the
sex pheromone of tomato pinwarm [1], a dangerous pest
of the nightshade vegetables growing in the Russian Fed-
eration. Several methods of synthesis are known where the
transoid configuration of a double bond is built up using
acetylene intermediates [2–4], Knoevenagel condensation
[5], Claisen rearrangement [6], the opening of a cyclo-
propane [7] or dihydropyran ring [8], the isomerization
of a cis-alkenol in a trans-isomer [9].
available 1,3-dichloropropene, a toxic side product of
propylene chlorination.
The developed protocol of the pheromone synthe-
sis is based on the alkylation of malonic ester II with
(Е)-1,3-dichloropropene (III) [10] to obtain diethyl
[(2Е)-3-chloroprop-2-en-1-yl]propanedioate (IV). Its
subsequent decarboxylation by Krapcho procedure [11]
leads to the formation of ethyl (4Е)-5-chloropent-4-enoate
(V). The Fe-catalyzed cross-coupling of ester V with
octylmagnesium bromide in the presence of N-methyl-
pyrrolidone (NMP) furnishes in a high yield ethyl (4Е)-
We examined the possibility to obtain the tomato
pinwarm pheromone proceeding from the industrially
O
O
O
O
O
O
K2CO3
CH3CN
Cl
Cl
+
O
O
II
III
Cl
IV
O
O
LiCl, H2O
180oC, DMSO
OctMgBr, Fe(acac)3
O
Cl
O
NMP, ТГФ
VI
V
O
AcCl, Py
LiAlH4
HO
O
I
VII
669

SHAKHMAEV et al.
670
tridec-4-enoate (VI). The subsequent reduction of ester
VI with lithium aluminum hydride and the acetylation
of the formed alcohol VII affords the target pheromone
I containing over 99% of the (E)-isomer.
(2СН2О), 120.04 (=СHCl), 129.06 (=СHCH2), 168.25
(2С=О). Mass spectrum, m/z (Irel, %): 199 (17), 161 (13),
160 (16), 143 (18), 133 (14), 125 (100), 115 (15), 97 (88),
81 (19), 77 (11), 75(29), 69 (11), 55 (12), 53 (24), 51 (12).
The stereochemical homogeneity and the configuration
of the substituents at the double bond of the obtained
pheromone were proved by GLC on a capillary column
and by NMR spectra. In the 13С NMR spectrum of the
synthesized (4Е)-tridec-4-en-1-yl acetate (I) the allyl
carbon atoms give rise to the signals at δ 28.79 (С3) and
32.51 (С6), whereas in the spectrum of its cis-analog they
are shifted upfield by 5 ppm. Similar characteristic shift of
the allyl carbon signals has been observed several times
[12], and it may serve as a proof of the spatial arrangement
of unsaturated compounds.
Ethyl (4Е)-5-chloropent-4-enoate (V). A mixture
of 10.08 g (0.0429 mol) of compound IV, 1.54 g
(0.0856 mol) of Н2О, 3.64 g (0.0856 mol) of LiCl, and
16 ml of DMSO was stirred at boiling for 18 h. Then it
was diluted with 30 ml of water and 30 ml of hexane,
the organic layer was separated, the water layer was ex-
tracted with hexane (2 × 30 ml). The combined organic
solutions were washed with water, dried with Na2SO4,
and concentrated. The reaction product was isolated
by column chromatography. Yield 5.32 g (76%), oily
substance. IR spectrum, cm–1: 2982, 2932, 1732, 1634,
1445, 1373, 1350, 1300, 1240, 1192, 1161, 1096, 1036,
935, 856. 1H NMR spectrum, δ, ppm: 1.26 t (3Н, СН3,
J 7 Hz), 2.34–2.44 m (4Н, 2СН2), 4.11 q (2Н, СН2О,
J 7.1 Hz), 5.86–5.95 m (1Н, =С4Н), 6.03 d (1Н, =С5Н,
Jtrans 13.3 Hz). 13С NMR spectrum, δ, ppm: 14.04 (СН3),
26.07 (С3), 33.34 (С2), 60.39 (СН2О), 118.30 (С5), 131.67
(С4), 172.27 (С1). Mass spectrum, m/z (Irel, %): 127 (86),
117 (27), 99 (100), 91 (24), 89 (40), 88 (31), 75 (27), 53
(46), 43 (15).
EXPERIMENTAL
IR spectra were recorded on a Fourier spectropho-
1
tometer IRPrestige-21 Shimadzu from thin films. Н
and 13С NMR spectra were registered in CDCl3 on a
spectrometer Bruker АM-300 (operating frequencies
300 and 75.47 MHz), internal reference TMS. GC-MS
measurements were carried out on an instrument GCMS-
QP2010S Shimadzu (EI, 70 eV, range of detected masses
33–500 Da), capillary column HP-1MS (30 m × 0.25 mm
Ч 0.25 μm), vaporizer temperature 280°C, ion source
temperature 200°C., ramp from 50 to 280°С at a rate 10
deg/min, carrier gas helium (1.1 ml/min).
Ethyl (4Е)-tridec-4-enoate (VI). To a solution of
0.507 g (3.12 mmol) of compound V, 1.5% (14.5 mg)
of Fe(acac)3 in a mixture of 3 ml of THF and 3 ml of
N-methylpyrrolidone in an argon atmosphere was added
dropwise within 5 min at 0 °С 3.6 ml (3.6 mmol) of 1 M
solution of octylmagnesium bromide in THF. The mix-
ture was stirred for 30 min at room temperature, then it
was diluted with 10 ml of 5% aqueous HCl and 10 ml of
hexane, the organic layer was separated, the water layer
was extracted with hexane (2 × 10 ml). The combined
organic solutions were washed with saturated solution
of NaHCO3, dried with Na2SO4, and concentrated. The
reaction product was isolated by column chromatogra-
phy. Yield 0.540 g (72%), oily substance. IR spectrum,
cm–1: 2924, 2853, 1735, 1470, 1371, 1344, 1300, 1248,
1177, 1161, 1040, 968. 1H NMR spectrum, δ, ppm: 0.88 t
(3H, C13H3, J 7 Hz), 1 .23–1.36 m (15Н, СН3CH2O,
6 СН2), 1.96 q (2Н, С3Н2, J 6.7 Hz), 2.27–2.39 m (4Н,
С2Н2, С6Н2), 4.13 q (2Н, СН2О, J 7 Hz), 5.34–5.51 m
(2Н, =С4Н, =С5Н). 13С NMR spectrum, δ, ppm: 14.03
(С13), 14.18 (СН3CH2O), 22.63 (С12), 27.90 (С3), 29.10
(СH2), 29.25 (СH2), 29.43 (СH2), 29.67 (СH2), 31.85
(С11), 32.45 (С6), 34.47 (С2), 60.13 (СН2О), 127.87 (С5),
131.79 (С4), 173.22 (С1). Mass spectrum, m/z (Irel, %):
Diethyl [(2Е)-3-chloroprop-2-en-1-yl ]propanedio-
ate (IV). A mixture of 10.00 g (0.062 mol) of malonic
ester, 8.31 g (0.075 mol) of (Е)-1,3-dichloropropene,
0.33 g (1.25 mmol) of 18-crown-6, 15.27 g (0.11 mol)
of K2CO3, and 25 ml of acetonitrile was stirred at boiling
for 4 h. Then it was diluted with 50 ml of water and 50
ml of hexane, the organic layer was separated, the water
layer was extracted with hexane (2 × 50 ml). The com-
bined organic solutions were washed with water and dried
with Na2SO4. The reaction product was isolated from the
mixture by vacuum distillation, bp 90–92°C (2 mm Hg).
Yield 10.08 g (69%), oily substance. IR spectrum, cm–1:
2982, 2938, 2907, 1748, 1732, 1699, 1634, 1464, 1445,
1393, 1369, 1337, 1281, 1221, 1153, 1096, 1032, 978,
1
937. H NMR spectrum, δ, ppm: 1.27 t (6Н, 2СН3,
J 7 Hz), 2.63 t.d (2Н, =CHСН2, J 7.3, 1.2 Hz), 3.40 t
(1Н, СНC=O, J 7.3 Hz), 4.21 q (4Н, 2СН2О, J 7 Hz),
5.88 d.t (1Н, =CHCH2, Jtrans 13.2, 7.3 Hz), 6.09 d.t (1Н,
=CHCl, Jtrans 13.2, 1.2 Hz). 13С NMR spectrum, δ, ppm:
13.89 (2СН3), 29.84 (=CHCH2), 51.15 (СHC=O), 61.44
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013

Fe-CATALYZED SYNTHESIS OF (4Е)-TRIDEC-4-EN-1-YL ACETATE
671
152 (44), 110 (41), 109 (21), 101 (29), 98 (28), 97 (46),
95 (38), 88 (83), 84 (46), 83 (38), 82 (32), 81 (47), 71
(38), 70 (46), 69 (51), 68 (36), 67 (69), 61 (25), 60 (20),
57 (30), 55 (85), 54 (35), 43 (73), 41 (100).
chromatography. Yield 0.270 g (93%), oily substance.
IR spectrum, cm–1: 3020, 2924, 2850, 1743, 1450, 1375,
1240, 1051, 965. 1H NMR spectrum, δ, ppm: 0.88 t (3Н,
С13Н3, J 7 Hz), 1.24–1.34 m (12Н, 6СН2), 1.68 quintet
(2Н, С2Н2, J 7 Hz), 1.97 q (2Н, С6Н2, J 6.9 Hz), 2.03–
2.07 m (5Н, С3Н2, СН3С=О), 4.06 t (2Н, С1Н2, J 6.7 Hz),
5.34–5.47 m (2Н, =С4Н, =С5Н). 13С NMR spectrum, δ,
ppm: 14.05 (С13), 20.95 (СН3С=О), 22.62 (С12), 28.44
(С2), 28.79 (С3), 29.12 (СH2), 29.24 (СH2), 29.42 (СH2),
29.48 (СH2), 31.85 (С11), 32.51 (С6), 63.97 (С1), 128.56
(С5), 131.59 (С4), 171.16 (СН3С=О). Mass spectrum, m/z
(Irel, %): 96 (20), 95 (17), 82 (39), 81 (48), 79 (16), 69
(19), 68 (87), 67 (63), 55 (37), 54 (32), 43 (100), 41 (49).
(4Е)-Tridec-4-en-1-ol (VII). To a solution of 0.54 g
(2.2 mmol) of compound VI in 20 ml of anhydrous ether
was added 0.08 g (1.5 mmol) of LiAlH4 at 0°С in an argon
atmosphere. The mixture was stirred at room temperature
for 3 h till the complete conversion of ester VI (GLC
monitoring). Then the mixture was diluted with 10 ml of
5% aqueous HCl and 10 ml of hexane, the organic layer
was separated, the water layer was extracted with hexane
(2 × 10 ml). The combined organic solutions were washed
with saturated solution of NaHCO3, dried with Na2SO4,
and concentrated. The reaction product was isolated
by column chromatography. Yield 0.385 g (88%), oily
substance. IR spectrum, cm–1: 3339 br (OH), 2955, 2926,
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(4Е)-Tridec-4-en-1-yl acetate (I). To a solution of
0.24 g (1.21 mmol) of compound VII in 3 ml of anhydrous
diethyl ether was added 0.115 g (1.45 mmol) of pyridine
and 0.114 g (1.45 mmol) of acetyl chloride at 0°С. The
mixture was stirred at room temperature for 1 h. Then
the mixture was diluted with 5 ml of water and 10 ml of
hexane, the organic layer was separated, the water layer
was extracted with hexane (2 × 10 ml). The combined
organic solutions were washed with saturated solution
of NaHCO3, dried with Na2SO4. The solvent was dis-
tilled off, the reaction product was isolated by column
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013