DEVELOPMENT OF GENERAL METHODS
955
spectrum, δ, ppm: 1.26 t (3H, CH3, J = 7.6 Hz), 1.76 s
(0.25·3H, CH3C=C), 2.17 s (0.75·3H, CH3C=C), 3.39 s
(0.75·2H, CH2), 3.98 s (0.25·2H, CH2), 4.22 q (2H,
OCH2, J = 7.6 Hz), 5.62 s (0.75H, CH=C), 5.77 s
(0.25H, CH=C), 6.88–7.15 m (4H, Harom). Mass spec-
trum: m/z 223.15 (Irel 100%) [M + H]+. Found, %:
C 70.12; H 6.73. C13H15FO2. Calculated, %: C 70.35;
H 6.82. M 222.26.
Ethyl (E/Z)-4-(2-chlorophenyl)-3-methylbut-2-
enoate (IIc). Yield 66%, colorless oily substance. IR
spectrum, ν, cm–1: 1714 (C=O), 1650 (C=C). 1H NMR
spectrum, δ, ppm: 1.26 t (3H, CH3, J = 7.2 Hz), 1.76 s
(0.21·3H, CH3C=C), 2.20 s (0.79·3H, CH3C=C), 3.08 s
(0.22·2H, CH2), 3.58 s (0.78·2H, CH2), 4.16 q (2H,
OCH2, J = 7.2 Hz), 5.57 s (0.77H, CH=C), 5.82 s
(0.23H, CH=C), 7.18–7.30 m (4H, Harom). Mass spec-
trum: m/z 239.11 (Irel 100%) [M + H]+. Found, %:
C 65.26; H 6.44; Cl 14.81. C13H15ClO2. Calculated, %:
C 65.43; H 6.37; Cl 14.92. M 238.71.
Ethyl (E/Z)-4-(3-chlorophenyl)-3-methylbut-2-
enoate (IId). Yield 97%, colorless oily substance. IR
spectrum, ν, cm–1: 1716 (C=O), 1652 (C=C). 1H NMR
spectrum, δ, ppm: 1.26 t (3H, CH3, J = 6.8 Hz), 1.76 s
(0.28·3H, CH3C=C), 2.16 s (0.72·3H, CH3C=C), 3.11 s
(0.26·2H, CH2), 3.41 s (0.74·2H, CH2), 4.20 q (2H,
OCH2, J = 6.8 Hz), 5.61 s (0.73H, CH=C), 5.79 s
(0.27H, CH=C), 7.06–7.25 m (4H, Harom). Mass spec-
trum: m/z 239.13 (Irel 100%) [M + H]+. Found, %:
C 65.26; H 6.34; Cl 14.68. C13H15ClO2. Calculated, %:
C 65.43; H 6.37; Cl 14.92. M 238.71.
[M + H]+. Found, %: C 61.73; H 5.58. C14H15F3O2.
Calculated, %: C 61.85; H 5.62. M 272.26.
Ethyl (E/Z)-3-benzylpent-2-enoate (IIg). Yield
77%, colorless oily substance. IR spectrum, ν, cm–1:
1
1712 (C=O), 1649 (C=C). H NMR spectrum, δ, ppm:
1.02 t (3H, CH3, J = 6.0 Hz), 1.26 t (3H, CH3, J =
6.5 Hz), 2.41 q (0.65·2H, CH2C=C, J = 6.0 Hz), 2.58 q
(0.35·2H, CH2C=C, J = 6.0 Hz), 3.46 s (0.33·2H,
CH2), 3.69 s (0.67·2H, CH2), 4.13 q (0.61·2H, OCH2,
J = 6.5 Hz), 4.20 q (0.39·2H, OCH2, J = 6.5 Hz), 5.58 s
(0.58H, CH=C), 5.77 s (0.42H, CH=C), 7.20–7.36 m
(5H, Harom). Mass spectrum: m/z 219.16 (Irel 100%)
[M + H]+. Found, %: C 76.83; H 8.21. C14H18O2. Cal-
culated, %: C 77.06; H 8.34. M 218.29.
Ethyl (E/Z)-3-methyl-5-phenylpent-2-enoate
(IIh). Yield 66%, colorless oily substance. IR spec-
1
trum, ν, cm–1: 1715 (C=O), 1648 (C=C). H NMR
spectrum, δ, ppm: 1.26 t (3H, CH3, J = 5.9 Hz), 1.86 s
(0.26·3H, CH3C=C), 2.22 s (0.74·3H, CH3C=C), 2.46 t
(2H, CH2, J = 7.8 Hz), 2.79 t (0.75·2H, CH2, J =
7.6 Hz), 2.92 t (0.25·2H, CH2, J = 7.6 Hz), 4.18 q (2H,
OCH2, J = 5.9 Hz), 5.72 s (1H, CH=C), 7.19–7.28 m
(5H, Harom). Mass spectrum: m/z 219.19 (Irel 100%)
[M + H]+. Found, %: C 77.13; H 8.43. C14H18O2. Cal-
culated, %: C 77.06; H 8.34. M 218.29.
Ethyl (E/Z)-3,6-dimethylhept-2-enoate (IIi).
Yield 64%, colorless liquid. IR spectrum, ν, cm–1: 1718
(C=O), 1651 (C=C). 1H NMR spectrum, δ, ppm: 0.88–
0.94 m (6H, CH3), 1.26 t (3H, CH3, J = 8.2 Hz), 1.33–
1.39 m (2H, CH2), 1.47–1.60 m (1H, CH), 2.12–
2.16 m (3H, CH3C=C), 2.42 t and 2.64 t (1H each,
CH2C=C, J = 8.9 Hz), 4.15 q (2H, OCH2, J = 8.2 Hz),
5.62 s (0.3H, CH=C), 5.70 s (0.7H, CH=C). Mass
spectrum: m/z 185.22 (Irel 100%) [M + H]+. Found, %:
C 71.56; H 10.83. C11H20O2. Calculated, %: C 71.74;
H 10.96. M 184.28.
Ethyl (E/Z)-3,5-dimethylhexa-2,4-dienoate (IIj).
Yield 46%, colorless liquid. IR spectrum, ν, cm–1: 1709
(C=O); 1656, 1645 (C=C). 1H NMR spectrum, δ, ppm:
1.26 t (3H, CH3, J = 6.1 Hz), 1.71 s (0.45·3H, CH3),
1.80 s (0.55·3H, CH3), 2.09 s (0.41·3H, CH3), 2.22 s
(0.59·3H, CH3), 2.77 s (0.72·3H, CH3C=C), 3.80 s
(0.28·3H, CH3C=C), 4.14 q (2H, OCH2, J = 6.1 Hz),
4.75 s (0.65H, CH=C), 4.82 s (0.35H, CH=C), 5.64 s
(0.35H, C=CH–C=O), 5.74 s (0.65H, C=CH–C=O).
Mass spectrum: m/z 169.25 (Irel 100%) [M + H]+.
Found, %: C 71.34; H 9.48. C10H16O2. Calculated, %:
C 71.45; H 9.67. M 168.23.
Ethyl (E/Z)-4-(4-chlorophenyl)-3-methylbut-2-
enoate (IIe). Yield 75%, colorless oily substance. IR
spectrum, ν, cm–1: 1715 (C=O), 1648 (C=C). 1H NMR
spectrum, δ, ppm: 1.26 t (3H, CH3, J = 7.1 Hz), 1.76 s
(0.24·3H, CH3C=C), 2.11 s (0.76·3H, CH3C=C), 3.40 s
(0.77·2H, CH2), 3.94 s (0.23·2H, CH2), 4.19 q (2H,
OCH2, J = 7.1 Hz), 5.68 s (0.78H, CH=C), 5.79 s
(0.22H, CH=C), 7.10 d and 7.28 d (2H each, Harom
,
J = 8.6 Hz). Mass spectrum: m/z 239.09 (Irel 100%)
[M + H]+. Found, %: C 65.36; H 6.28; Cl 15.07.
C13H15ClO2. Calculated, %: C 65.43; H 6.37; Cl 14.92.
M 238.71.
Ethyl (E/Z)-3-methyl-4-[3-(trifluoromethyl)-
phenyl]but-2-enoate (IIf). Yield 68%, colorless oily
substance. IR spectrum, ν, cm–1: 1718 (C=O), 1653
1
(C=C). H NMR spectrum, δ, ppm: 1.26 t (3H, CH3,
J = 6.4 Hz), 1.76 s (0.31·3H, CH3C=C), 2.07 s
(0.69·3H, CH3C=C), 3.18 s (0.3·2H, CH2), 3.49 s
(0.7·2H, CH2), 4.15 q (2H, OCH2, J = 6.4 Hz), 5.70 s
(0.71H, CH=C), 5.81 s (0.29H, CH=S), 7.30–7.53 m
(4H, Harom). Mass spectrum: m/z 273.10 (Irel 100%)
tert-Butyl 2-[(E/Z)-3-ethoxy-1-methyl-3-oxoprop-
1-en-1-yl]morpholine-4-carboxylate (IIk). Yield
74%, colorless oily substance. IR spectrum, ν, cm–1:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014