836
K. Takami et al.
FEATURE ARTICLE
IR (neat): 3080, 2963, 2936, 2876, 1740, 1732, 1641, 1466, 1418,
1379, 1248, 1171, 1115, 1067, 1026, 999, 966, 916, 843, 789, 743,
700 cm–1.
1H NMR (CDCl3): d = 5.74–5.89 (m, 1 H), 4.95–5.09 (m, 3 H),
2.28–2.51 (m, 6 H), 1.52–1.71 (m, 4 H), 1.30–1.45 (m, 2 H), 0.88 (t,
J = 7.2 Hz, 3 H), 0.91 (t, J = 7.2 Hz, 3 H).
13C NMR (CDCl3): d = 19.59, 25.16, 26.36, 28.39, 32.34, 34.33,
41.25, 44.81, 64.09, 113.33, 142.57, 172.68.
Anal. Calcd for C12H21ClO2: C, 61.93; H, 9.09%. Found: C, 61.92;
H, 9.32%.
Benzyl (2,2-Dimethylcyclopropyl)acetate (4)
Colorless oil.
13C NMR (CDCl3): d = 13.53, 13.54, 16.49, 18.49, 28.63, 32.32,
33.14, 40.42, 78.19, 115.68, 136.56, 172.82, 207.68.
IR (neat): 3065, 3034, 2949, 2870, 2737, 1738, 1647, 1499, 1456,
1418, 1377, 1327, 1250, 1165, 1120, 1094, 1051, 1005, 918, 866,
748, 698 cm–1.
1H NMR (CDCl3): d = 7.26–7.38 (m, 5 H), 5.12 (s, 2 H), 2.35 (d, J =
7.2 Hz, 2 H), 1.03 (s, 3 H), 1.00 (s, 3 H), 0.82–0.90 (m, 1 H), 0.49
(dd, J = 4.8, 7.8 Hz, 1 H), 0.01 (dd, J = 4.8, 4.8 Hz, 1 H).
Anal. Calcd for C13H22O3: C, 68.99; H, 9.80%. Found: C, 69.11; H,
10.08%.
Benzyl 3-Methyl-4-pentenoate (2a¢)
Colorless oil.
IR (neat): 3069, 3034, 2963, 2932, 2874, 1738, 1641, 1499, 1456,
1418, 1379, 1352, 1171, 1103, 997, 916, 739, 698 cm–1.
13C NMR (CDCl3): d = 15.24, 19.36, 19.78, 19.89, 26.88, 34.85,
66.07, 128.18, 128.20, 128.59, 136.26, 173.67.
1H NMR (CDCl3): d = 7.26–7.37 (m, 5 H), 5.75 (ddd, J = 7.2, 10.5,
17.1 Hz, 1 H), 5.10 (s, 2 H), 4.98 (d, J = 17.1 Hz, 1 H), 4.93 (d, J =
10.5 Hz, 1 H), 2.64–2.74 (m, 1 H), 2.26–2.44 (m, 2 H), 1.03 (d, J =
6.9 Hz, 3 H).
HRMS: m/z calcd for C14H18O2: 218.1307; found: 218.1315.
Benzyl 4-Methyl-4-pentenoate (6)
Colorless oil.
13C NMR (CDCl3): d = 19.60, 34.35, 41.20, 66.11, 113.48, 128.27,
IR (neat): 2936, 1738, 1649, 1456, 1153, 891, 737, 698 cm–1.
128.33, 128.60, 136.09, 142.47, 172.49.
1H NMR (CDCl3): d = 1.73 (s, 3 H), 2.35 (t, J = 7.5 Hz, 2 H), 2.52
(t, J = 7.5 Hz, 2 H), 4.68 (s, 1 H), 4.74 (s, 1 H), 5.12 (s, 2 H), 7.31–
7.38 (m, 5 H).
Anal. Calcd for C13H16O2: C, 76.44; H, 7.90%. Found: C, 76.23; H,
8.02%.
13C NMR (CDCl3): d = 22.46, 32.53, 32.61, 60.20, 110.40, 128.17,
2,3,N,N-Tetramethyl-4-pentenamide (2c¢)
128.19, 128.50, 135.96, 143.96, 173.07.
2:1 mixture of diastereomers; colorless oil.
HRMS: m/z calcd for C13H16O2: 204.1150; found: 204.1152.
IR (neat): 3377, 3078, 2970, 2934, 2875, 1628, 1504, 1462, 1421,
1404, 1373, 1259, 1128, 1060, 1001, 968, 916, 827, 781, 750 cm–1.
Anal. Calcd for C13H16O2: C, 76.44; H, 7.90%. Found: C, 76.29; H,
8.07%.
1H NMR (CDCl3): d = 5.55–5.80 (m, 1 H), 4.89–5.07 (m, 2 H), 3.06
(s, 0.67 × 3 H), 3.02 (s, 0.33 × 3 H), 2.97 (s, 0.67 × 3 H), 2.94 (s,
0.33 × 3 H), 2.36–2.66 (m, 2 H), 1.07 (d, J = 6.6 Hz, 0.33 × 3 H),
1.03 (d, J = 6.6 Hz, 0.67 × 3 H), 1.00 (d, J = 6.6 Hz, 0.33 × 3 H),
0.93 (d, J = 6.6 Hz, 0.67 × 3 H).
13C NMR (CDCl3): For major isomer: d = 15.78, 18.84, 35.68,
37.49, 40.66, 41.68, 115.05, 141.72, 176.58; for minor isomer, d =
14.29, 15.98, 35.67, 37.47, 40.11, 40.67, 113.88, 142.18, 176.61.
Benzyl 2-Methyl-4-phenyl-3-butenoate (10c)
E/Z = 90:10; colorless oil.
IR (neat): 3030, 2934, 1732, 1600, 1497, 1165, 964, 746, 694 cm–1.
1H NMR (CDCl3): d = 1.31 (d, J = 7.2 Hz, 0.10 × 3 H), 1.38 (d, J =
7.2 Hz, 0.90 × 3 H), 3.37 (dq, J = 7.8, 7.8 Hz, 1 H), 5.15 (s, 2 H),
5.71 (dd, J = 7.8, 11.7 Hz, 0.10 H), 6.29 (dd, J = 7.8, 15.9 Hz, 0.90
H), 6.48 (d, J = 15.9 Hz, 0.90 H), 6.56 (d, J = 11.7 Hz, 0.10 H),
7.19–7.39 (m, 10 H).
HRMS: m/z calcd for C9H17NO: 155.1310; found: 155.1308.
13C NMR (CDCl3): For major isomer: d = 17.37, 43.10, 66.26,
126.08, 127.29, 127.79, 127.92, 128.29 (2C), 128.33, 131.04,
135.77, 136.57, 173.87.
N-[(E)-2-Tridecenyl]-3-methyl-4-pentenamide (2f¢)
White solid.
IR (nujol): 3285, 3080, 2681, 1643, 1551, 1310, 1250, 1207, 993,
966, 912 cm–1.
HRMS: m/z calcd for C18H18O2: 266.1307; found: 266.1320.
1H NMR (CDCl3): d = 5.75 (ddd, J = 17.1, 10.2, 6.9 Hz, 1 H), 5.58
(dt, J = 15.3, 6.6 Hz, 1 H), 5.34–5.50 (m, 2 H), 5.01 (d, J = 17.1 Hz,
1 H), 4.94 (d, J = 10.2 Hz, 1 H), 3.78 (t, J = 6.0 Hz, 2 H), 2.62–2.72
(m, 1 H), 2.04–2.23 (m, 2 H), 1.97 (dt, J = 6.6, 6.6 Hz, 2 H), 1.20–
1.38 (m, 16 H), 1.02 (d, J = 6.9 Hz, 3 H), 0.85 (t, J = 6.9 Hz, 3 H).
13C NMR (CDCl3): d = 13.98, 19.53, 22.56, 29.02, 29.05, 29.23,
29.37, 29.50, 29.51, 31.80, 32.11, 34.67, 41.34, 43.80, 113.50,
125.63, 134.04, 142.95, 171.53.
Anal. Calcd for C18H18O2: C, 81.17; H, 6.81%. Found: C, 80.95; H,
7.00%.
2-[(E)-2-Phenylethenyl]-4-butanolide [(E)-10d]
Pale-yellow powder.
IR (nujol): 2932, 2858, 1747, 1261, 1180, 1032 cm–1.
1H NMR (CDCl3): d = 2.23–2.37 (m, 1 H), 2.51 (m, 1 H), 3.38–3.48
(m, 1 H), 4.30 (ddd, J = 6.6, 9.0, 9.0 Hz, 1 H), 4.44 (ddd, J = 3.3,
9.0, 9.0 Hz, 1 H), 6.26 (dd, J = 6.3, 15.9 Hz, 1 H), 6.58 (d, J = 15.9
Hz, 1 H), 7.20–7.40 (m, 5 H).
HRMS: m/z calcd for C19H35NO: 293.2719; found: 293.2718.
13C NMR (CDCl3): d = 29.23, 42.45, 66.67, 123.80, 126.30, 127.82,
128.49, 133.30, 136.13, 176.99.
6-Chlorohexyl 3-Methyl-4-pentenoate (2h¢)
Colorless oil.
IR (neat): 3080, 2935, 2862, 1737, 1641, 1456, 1417, 1354, 1252,
1177, 1090, 1049, 995, 916, 880, 731 cm–1.
Anal. Calcd for C12H12O2: C, 76.57; H, 6.43%. Found: C, 76.27; H,
6.47%.
1H NMR (CDCl3): d = 5.74 (ddd, J = 17.1, 10.2, 6.9 Hz, 1 H), 4.99
(d, J = 17.1 Hz, 1 H), 4.92 (d, J = 10.2 Hz, 1 H), 4.04 (t, J = 6.6 Hz,
2 H), 3.50 (t, J = 6.6 Hz, 2 H), 2.58–2.74 (m, 1 H), 2.18–2.36 (m, 2
H), 1.70–1.80 (m, 2 H), 1.55–1.66 (m, 2 H), 1.28–1.49 (m, 4 H),
1.02 (d, J = 6.9 Hz, 3 H).
2-[(Z)-2-Phenylethenyl]-4-butanolide [(Z)-10d]
Pale-yellow powder.
IR (nujol): 2926, 1755, 1600, 1448, 1377, 1159, 1020, 970, 952,
750, 694 cm–1.
Synthesis 2005, No. 5, 824–839 © Thieme Stuttgart · New York