PREPARATIVE SYNTHESIS OF (Z)-5-DECENYL ACETATE
2037
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730 cm ; absence of a band at 980 cm , character-
(Z)-5-Decenyl acetate I. A 0.32-g portion of
Ni(OAc)2 4H2O in 10 ml of absolute ethanol was
bubbled with hydrogen, after which 1.4 ml of a 1 M
alcoholic solution of sodium borohydride was added
in three portions. To the resulting black solution, we
added 0.18 g of anhydrous ethylenediamine and 1.5 g
of decynyl acetate IV; the mixture was stirred at 20 C
in a flow of hydrogen. After the hydrogenation was
complete, the catalyst was filtered off, the filtrate was
evaporated, and the precipitate was diluted with 20 ml
of water and extracted with diethyl ether (3 50 ml).
The extract was washed with 10 ml of water and dried
over magnesium sulfate; the solvent was distilled off.
Yield of I 1.2 g (81%), bp 100 101 C (7 mm Hg),
istic of the E configuration) and by a characteristic
multiplet of the (Z)-CH=CH protons in the H NMR
spectrum at 5.1 5.35 ppm (J = 11.5 Hz).
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EXPERIMENTAL
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The H NMR spectra were recorded on a Varian
Mercury-300 spectrometer (300 MHz) in CDCl3,
internal reference TMS, and the IR spectra, on a
UR-20 spectrometer (thin films). The GLC analysis
was performed on a Chrom-5 chromatograph equipped
with a flame ionization detector and 25000 0.2-mm
glass capillary column coated with SE-30, carrier gas
nitrogen, flow rate 30 ml min .
n2d0 = 1.4400. IR spectrum, , cm : 730 m, 1150 s,
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1245 s, 1370 m, 1390 m, 1465 m, 1658 w, 1745 vs,
3015 m. H NMR spectrum, , ppm: 0.89 t (3H,
CH3CH2, J = 7.1 Hz), 1.3 1.45 m (8H, CH2), 1.95
2.25 m (4H, CH2CH=CHCH2), 1.96 s (3H, COCH3),
4.01 t (2H, OCH2, J = 6.8 Hz), 5.1 5.35 m (2H,
CH=CH, J = 11.5 Hz).
1-Chloro-5-decyne III. Alkyne II (12.8 g) was
added over a period of 15 min at 60 C to sodium
amide prepared from 3.45 g of Na and 0.5 l of liquid
ammonia; the mixture was stirred for 3 h. Then 32.8 g
of 1-iodo-4-chlorobutane was added dropwise over a
period of 2 h. The mixture was stirred for an addition-
al 2 h and allowed to warm up. After evaporation of
ammonia (15 h), 200 ml of anhydrous diethyl ether
was added to the residue, and the mixture was re-
fluxed with stirring for 3 h. After cooling, dilute HCl
(pH 3) was added, and the mixture was extracted with
diethyl ether (3 50 ml). The combined ether extracts
were washed with a Na2S2O3 solution and dried over
magnesium sulfate. Distillation gave 18.1 g (70%) of
III [9], bp 75 76 C (2 mm Hg), n2d0 = 1.4610.
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REFERENCES
1. Franke, W. and Schulz, S., in Comprehensive Natural
Products Chemistry, Amsterdam: Elsevier, 1999,
vol. 8, pp. 197 261.
2. Bestman, H.J., Vostrowsky, K.H., Platz, H., et al.,
Angew. Chem., 1978, vol. 90, no. 10, pp. 815 816.
3. Ohloff, G., Vial, C., Naf, F., and Pawlak, M.,
Helv. Chim. Acta, 1977, vol. 60, no. 112,
pp. 1161 1165.
5-Decynyl acetate IV. Chloroalkyne III (3.45 g)
was added to a mixture of 1.64 g of sodium acetate
and 10 ml of acetic acid in 50 ml of anhydrous DMF.
The mixture was stirred at the boiling point for 10 h,
the solvent was distilled off, 15 ml of water was
added to the residue, and the mixture was extracted
with diethyl ether (3 50 ml). The extract was
washed with water to pH 7 and dried over magnesium
sulfate. The solvent was removed. Vacuum distillation
4. Albores, M., Bestman, H.J., and Dohte, B., Lieb. Ann.,
1994, no. 3, pp. 231 235.
5. Odinokov, V.N., Galeeva, R.I., Sokol’skaya, O.V.,
et al., Dokl. Akad. Nauk SSSR, 1985, vol. 280, no. 3,
pp. 646 649.
6. Romanian Patent 78763.
7. Medarde, M., Gordaliza, M., Castro, M.A., et al.,
Bol. San. Veg. Plagas, 1988, vol. 14, no. 2,
pp. 313 317.
8. Adams, J., Milette, S., Rokach, S., and Zamboni, R.,
Tetrahedron Lett., 1984, vol. 25, pp. 2179 2182.
9. Taylor, W.R. and Strong, F.M., J. Am. Chem. Soc.,
gave 3.2 g (82%) of IV, bp 92 C (2 mm Hg), nd20
=
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1.4460. IR spectrum, , cm : 1745, 2250. H NMR
spectrum, , ppm: 0.9 t (3H, CH3CH2, J = 7 Hz), 1.4
1.7 m (8H, CH2), 1.9 2.15 m (4H, CH2C CCH2),
1.85 s (3H, COCH3), 4.1 t (2H, OCH2, J = 6.8 Hz).
1950, vol. 72, pp. 4263 4265.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 12 2004