STEREOSELECTIVE SYNTHESIS OF 11(E)-TETRADECEN-1-YL ACETATE
1173
–
1
ν, cm : 3342 (OH), 2893, 2872, 2848, 1717, 1589,
1
0.05 g of TsOH. This mixture was stirred at room
temperature for 24 h and concentrated. To the residue
was added 50 ml of diethyl ether followed by washing
1
440, 1375, 1215, 1059, 966 (trans-HC=). H NMR
spectrum, δ, ppm: 0.92 t (3H, CH , J 7.4 Hz), 1.53–
3
1
2
5
1
.62 m (2H, CH CH O), 1.91–2.05 m (4H, CH CH=),
with NaHCO and NaCl saturated solutions, drying
2
2
2
3
.74 s (1H, OH), 3.57 t (2H, CH OH, J 6.6 Hz), 5.31–
over Mg SO and concentrating. The residue obtained
2
2
4
1
3
.50 m (2H, CH=CH). С NMR spectrum, δ, ppm:
was chromatographically purified (SiO , hexane–ether,
2
7
6
3
2
20
D
3.80 (С ), 25.42 (С ), 28.71 (С ), 32.35 (C ), 62.11
1:1). Yield 0.602 g (67%), n 1.4562. IR spectrum, ν,
cm : 3335 (OH), 2961, 2926, 2853, 1458, 1057, 964
(trans-HC=). H NMR spectrum, δ, ppm: 0.97 t (3H,
1
4
5
–1
(
(
C ), 128.35 (C ), 132.49 (C ). Mass-spectrum, m/z
Irel, %): 114 (3.15), 96 (19.44), 81 (100), 79 (15.79),
1
6
8 (23.72), 67 (32.08), 57 (10.79), 55 (35.81), 54
CH , J 7.3 Hz), 1.21–1.41 m (14H, CH ), 1.50-1.61 m
3
2
(
21.29), 53 (12.91).
(2H, CH
2
CH
2
OH), 1.91–2.06 m (4H, CH CH=), 3.39 s
2
(
(
(
(
(
(
(
1H, OH), 3.64 t (2H, CH OH, J 6.6 Hz), 5.34–5.48 m
2
1
-Bromo-4(Е)-heptene (VII). To a solution of
1
3
2H, CH=CH). С NMR spectrum, δ, ppm: 13.91
2
.211 g (8.43 mmol) of triphenylphosphine in 40 ml of
1
4
13
3
С ), 25.52 (C ), 25.70 (C ), 29.11 (CH ), 29.39
2
chloroform was added solution of 1.347 g (8.43 mmol)
of bromine in 10 ml of chloroform under stirring and
cooling (Ar, 10°С). To the formed suspension of
PPh ·Br was added 0.936 g (8.2 mmol) of alcohol VI
CH ), 29.45 (CH ), 29.50 (CH ), 29.55 (CH ), 29.59
2
2
2
2
1
0
2
1
CH ), 32.50 (С ), 32.71 (C ), 62.83 (C ), 129.31
2
1
1
12
C ), 131.80 (C ). Mass-spectrum, m/z (I , %): 96
rel
3
2
25.74), 95 (26.66), 82 (48.17), 81 (35.47), 69 (31.24),
8 (44.86), 67 (54.38), 55 (100), 54 (31.60), 43
33.06), 41 (96.59).
in 10 ml of chloroform and this mixture was stirred for
h at room temperature under argon. Then mixture
was diluted with 150 ml of hexane, filtered and filtrate
was concentrated. The residue was purified by column
6
(
3
11(E)-Tetradecen-1-yl acetate (I). A mixture of
chromatography (SiO , pentane). Yield 1.338 g (92%),
0.367 g (1.73 mmol) of alcohol II, 1.23 g of absolute
pyridine and 0.88 g of acetic anhydride was stirred at
room temperature for 24 h. Then 20 ml of diethyl ether
was added and mixture was sequentially washed with
2
20
–1
n
D
1.4733. IR spectrum, ν, cm : 2963, 2932, 2872,
2
847, 1437, 1238, 1055, 968 (trans-HC=), 648, 565
1
(
CBr). H NMR spectrum, δ, ppm: 0.97 t (3H, CH ,
3
J 7.4 Hz), 1.87–2.06 m (4H, CH CH=), 2.11–2.19 m
NaHCO and NaCl saturated solutions, dried over
2
3
(
(
(
1
1
2H, CH CH Br), 3.41 t (2H, CH Br), 5.30-5.58 m
Mg SO and concentrated. The residue was chromato-
2
2
2
2
4
1
3
2H, CH=CH). С NMR spectrum, δ, ppm: 13.80
graphically purified (SiO , hexane–ether, 9:1). Yield
2
7
6
3
2
1
20
D
–1
С ), 25.53 (С ), 30.79 (С ), 32.46 (C ), 33.19 (C ),
0.414 g (94%), n 1.4481. IR spectrum, ν, cm : 2957,
4
5
26.85 (C ), 133.67 (C ). Mass-spectrum, m/z (I , %):
2926, 2853, 1744 (C=O), 1366, 1238, 1040, 966
rel
1
78 (12.17), 176 (12.86), 97 (45.03), 81 (33.76), 69
(trans-HC=). H NMR spectrum, δ, ppm: 0.97 t (3H,
(
45.37), 67 (22.55), 55 (100), 54 (16.63), 53 (13.93).
1(E)-Tetradecen-1-ol (II). To a suspension of
.160 g (0.84 mmol) of CuI in 6 ml of absolute THF
CH
3
, J 7.4 Hz), 1.22–1.43 m (14H, CH ), 1.58–1.71 m
2
(
2H, CH СH O), 1.94–2.18 m (7H, CH C=O,
2
2
3
1
CH CH=), 4.06 t (2H, CH O, J 6.6 Hz), 5.34–5.50 m
2
2
0
1
3
(
(
(
(
(
(
2H, CH=CH). С NMR spectrum, δ, ppm: 13.91
was added 0.131 g (0.84 mmol) of 2,2'-bipyridyl. The
mixture was stirred for 0.5 h under argon atmosphere
at 20°С, cooled to 2°С and a solution of 0.745 g
1
4
13
3
С ), 20.86 (CH С=О), 25.52 (C ), 25.85 (C ), 28.57
3
2
C ), 29.09 (CH ), 29.18 (CH ), 29.43 (3CH ), 29.59
2
2
2
1
0
1
11
CH ), 32.49 (С ), 64.55 (C ), 129.28 (C ), 131.82
2
(
4.21 mmol) of bromide VII in 3 ml of absolute THF
1
2
C ), 171.04 (C=O). Mass-spectrum, m/z (I , %): 96
rel
was added. The reaction mixture was stirred for 15 min
followed by dropwise addition for 1 h of Grignard
reagent prepared from 1.527 g (5.47 mmol) of 1-bromo-
34.41), 82 (72.55), 81 (37.93), 69 (29.43), 68 (77.45),
6
7 (52.06), 55 (62.13), 43 (100), 41 (58.77).
7
-[(tetrahydro-2H-pyran-2-yl)oxy]heptane (prepared
11(Z)-Tetradecen-1-yl acetate was prepared by
1
3
14
accordingly to [17]) and 0.146 g (6 mmol) of magne-
sium raspings in 5 ml of absolute THF. The reaction
mixture was stirred for 2 h at 2°С and 6 h at room
[18]. С NMR spectrum, δ, ppm: 14.35 (С ), 20.48
1
3
3
10
(C ), 20.97 (CH
С=О), 25.88 (C ), 27.06 (C ), 28.59
), 29.48 (3CH ), 29.74 (CH ), 64.63
3
2
(C ), 29.22 (2CH
2
2
2
1
11
12
temperature. Then 10 ml of NH Cl saturated solution
(C ), 129.28 (C ), 131.50 (C ), 171.19 (C=O).
4
was added and mixture was stirred for 1 h. Organic
layer was separated and water layer was extracted with
ether (3×10 ml). Organic solution was concentrated;
residue was dissolved in 20 ml of methanol containing
REFERENCES
1. Struble, D.L. and Lilly, C.E., Can. Entomol., 1977,
vol. 109, no. 2, p. 261.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009