PREPARATION OF STEREOCHEMICALLY PURE E- AND Z-ALKENOIC ACIDS
819
Unsaturated acids 3 were synthesized by oxidation
of trimethylsilyl ethers 2b and 2c in acetic acid
according to the procedure described in [13].
Methyl (E)-tetradec-7-enoate (E-4f). Yield 81%,
colorless oily liquid. IR spectrum (CCl4), ν, cm–1: 1741
(C=O), 966 (trans-CH=CH). H NMR spectrum, δ,
1
ppm: 0.87 t (3H, CH3, J = 7.1 Hz), 1.18–1.41 m (12H,
CH2), 1.62 quint (2H, CH2CH2CO, J = 7.4 Hz), 1.90–
2.03 m (4H, CH2CH=), 2.30 t (2H, CH2CO, J =
7.4 Hz), 3.66 s (3H, OCH3), 5.29–5.45 m (2H,
CH=CH). 13C NMR spectrum, δC, ppm: 14.3 (CH3),
22.8 (CH2), 25.0 (CH2), 28.8 (CH2), 29.0 (CH2), 29.4
(CH2), 29.7 (CH2), 31.9 (CH2), 32.5 (CH2), 32.7 (CH2),
34.2 (CH2), 51.6 (OCH3), 130.1 (CH), 130.8 (CH),
174.5 (CO). Found, %: C 74.88; H 11.76. C15H28O2.
Calculated, %: C 74.95; H 11.74.
(E)-Dec-5-enoic acid (E-3b). Yield 69%, colorless
oily liquid. IR spectrum (CCl4), ν, cm–1: 3537 (O–H),
3027 (=C–H), 1711 (C=O), 970 (trans-CH=CH).
1H NMR spectrum, δ, ppm: 0.88 t (3H, CH3, J =
7.0 Hz), 1.20–1.40 m (4H, CH2), 1.69 quint (2H,
CH2CH2CO, J = 7.4 Hz), 1.91–2.00 m (2H, CH2CH=),
2.03 q (2H, CH2CH=, J = 6.9 Hz), 2.34 t (2H, CH2CO,
J = 7.4 Hz), 5.28–5.39 m and 5.39–5.49 m (1H each,
CH=CH), 11.00 br.s (1H, OH). 13C NMR spectrum, δC,
ppm: 14.1 (CH3), 22.3 (CH2), 24.6 (CH2), 31.8 (CH2),
31.9 (CH2), 32.4 (CH2), 33.4 (CH2), 128.8 (CH), 132.0
(CH), 180.2 (C=O). Found, %: C 70.48; H 10.67.
C10H18O2. Calculated, %: C 70.55; H 10.66.
Methyl (Z)-tetradec-7-enoate (Z-4f). Yield 74%,
colorless oily liquid. IR spectrum (CCl4): ν 1741 cm–1
1
(C=O). H NMR spectrum, δ, ppm: 0.88 t (3H, CH3,
(Z)-Dec-5-enoic acid (Z-3b). Yield 70%, colorless
J = 7.0 Hz), 1.19–1.42 m (12H, CH2), 1.62 quint (2H,
CH2CH2CO, J = 7.4 Hz), 1.93–2.07 m (4H, CH2CH=),
2.30 t (2H, CH2CO, J = 7.4 Hz), 3.66 s (3H, OCH3),
5.26–5.42 m (2H, CH=CH). 13C NMR spectrum, δC,
ppm: 14.3 (CH3), 22.8 (CH2), 25.0 (CH2), 27.1 (CH2),
27.4 (CH2), 28.9 (CH2), 29.1 (CH2), 29.5 (CH2), 29.9
(CH2), 31.9 (CH2), 34.2 (CH2), 51.6 (OCH3), 129.6
(CH), 130.3 (CH), 174.4 (C=O). Found, %: C 74.89;
H 11.75. C15H28O2. Calculated, %: C 74.95; H 11.74.
oily liquid. IR spectrum (CCl4), ν, cm–1: 3537 (O–H),
1
3009 (=C–H), 1711 (C=O). H NMR spectrum, δ,
ppm: 0.89 t (3H, CH3, J = 7.0 Hz), 1.20–1.40 m (4H,
CH2), 1.69 quint (2H, CH2CH2CO, J = 7.4 Hz), 1.96–
2.06 m (2H, CH2CH=), 2.09 q (2H, CH2CH=, J =
6.9 Hz), 2.36 t (2H, CH2CO, J = 7.4 Hz), 5.26–5.36 m
and 5.37–5.47 m (1H each, CH=), 11.00 br.s (1H, OH).
13C NMR spectrum, δC, ppm: 14.1 (CH3), 22.5 (CH2),
24.7 (CH2), 26.5 (CH2), 27.1 (CH2), 32.0 (CH2), 33.5
(CH2), 128.3 (CH), 131.5 (CH), 180.0 (C=O). Found,
%: C 70.47; H 10.68. C10H18O2. Calculated, %:
C 70.55; H 10.66.
Methyl (E)-9-(benzyloxy)non-6-enoate (E-4h).
Yield 63%, colorless oily liquid. IR spectrum (CCl4),
ν, cm–1: 3031 (C–Harom), 1742 (C=O), 970 (trans-
1
CH=CH). H NMR spectrum, δ, ppm: 1.38 q (2H, J =
(E)-Undec-5-enoic acid (E-3c). Yield 76%. The
spectral data were in agreement with those reported
in [32, 33].
7.7 Hz), 1.62 q (2H, J = 7.9 Hz), 2.00 m (2H), 2.24–
2.36 m (4H), 3.48 t (2H, J = 6.9 Hz), 3.66 s (3H,
OCH3), 4.51 s (2H, PhCH2), 5.45 m (2H, CH=CH).
13C NMR spectrum, δC, ppm: 24.4 (CH2), 28.8 (CH2),
32.2 (CH2), 33.0 (CH2), 33.9 (CH2), 51.4 (CH2), 70.1
(CH2), 72.8 (CH2), 126.7 and 127.5 (CH=CH), 127.6
(CHarom), 128.3 (2C, CHarom), 131.8 (2C, CHarom),
138.5 (Carom), 174.2 (C=O). Found, %: C 73.81;
H 8.77. C17H24O3. Calculated, %: C 73.88; H 8.75.
(Z)-Undec-5-enoic acid (Z-3c). Yield 70%. The
spectral data were in agreement with those reported
in [32, 33].
(E)-Oct-5-en-1-ol (E-6). Yield 96%, colorless oily
liquid. IR spectrum (CCl4), ν, cm–1: 3638 (OH), 3020
1
(=C–H), 969 (trans-CH=CH). H NMR spectrum, δ,
ppm: 0.96 t (3H, CH3, J = 7.4 Hz), 1.36 br.s (1H, OH),
1.36–1.47 m (2H, 3-H), 1.52–1.62 m (2H, 2-H), 1.93–
2.06 m (4H, CH2CH=), 3.64 t (2H, CH2OH, J =
6.7 Hz), 5.32–5.51 m (2H, CH=CH). 13C NMR spec-
trum, δC, ppm: 14.1 (CH3), 25.7 (CH2), 25.8 (CH2),
32.4 (2C, CH2), 63.1 (CH2OH), 128.9 (CH), 132.6
(CH). Found, %: C 74.87; H 12.60. C8H16O. Calculat-
ed, %: C 74.94; H 12.58.
Methyl (E)-8-hydroxyoct-5-enoate (E-4i). Yield
85%, colorless oily liquid. IR spectrum (film), ν, cm–1:
3452 (OH), 1738 (C=O), 970 (trans-CH=CH).
1H NMR spectrum, δ, ppm: 1.52 br.s (1H, OH), 1.66–
1.76 quint (2H, 3-H, J = 7.4 Hz), 2.01–2.14 m (2H,
4-H), 2.22–2.35 m (4H, 2-H, 7-H), 3.63 t (2H, 8-H, J =
6.3 Hz), 3.67 s (3H, OCH3), 5.36–5.46 m and 5.46–
5.57 m (1H each, CH=CH). 13C NMR spectrum, δC,
ppm: 24.7 (C3), 32.1 (C4), 33.5 (C2), 36.1 (C7), 51.6
(OCH3), 62.2 (C8), 127.4 (C6), 132.8 (C5), 174.2
(C=O). Found, %: C 62.71; H 9.37. C9H16O3. Calcu-
lated, %: C 62.77; H 9.36.
(Z)-Oct-5-en-1-ol (Z-6). Yield 96%. The spectral
data were consistent with those given in [34].
(E)-8-Iodooct-3-ene (E-7). Triethylamine, 1.0 mL
(7.5 mmol), was added to a solution of 0.64 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017