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The Journal of Organic Chemistry
Dimethyl 2-(pent-4-enoyl)succinate (3d). Colorless oil (76.5 mg, 67%); 1H NMR (400 MHz, CDCl3) δ 2.31-2.36 (m, 2H), 2.67-2.75 (m, 1H),
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2.78-2.86 (m, 2H), 2.95-3.01 (m, 1H), 3.66 (s, 3H), 3.73 (s, 3H), 3.98 (dd, J = 6.0, 8.0 Hz, 1H), 4.96-5.05 (m, 2H), 5.73-5.81 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 27.4, 32.2, 42.0, 52.2, 52.9, 53.8, 115.5, 136.8, 168.9, 171.9, 203.2; IR (neat) 1642, 1736 cm-1; MS m/z (relative intensity) 197 ([M-
OMe]+, 17), 196 (42), 169 (13), 168 (13), 164 (14), 145 (15), 137 (17), 136 (11), 114 (33), 113 (35), 83 (100), 55 (86); HRMS (EI) m/z calcd for C10H13O4
([M-OMe]+) 197.0814, found: 197.0804.
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Dibutyl 2-(pent-4-enoyl)succinate (3e). Colorless oil (76.7 mg, 49%); H NMR (400 MHz, CDCl3) δ 0.90 (dt, J = 1.6, 7.2 Hz, 6H), 1.35 (sext, J =
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8.0 Hz, 4H), 1.54-1.61 (m, 4H), 2.28-2.36 (m, 2H), 2.65-2.75 (m, 1H), 2.78-2.87 (m, 2H), 2.93-3.00 (m, 1H), 3.95-3.98 (m, 1H), 4.04 (t, J = 6.4 Hz,
2H), 4.11 (dt, J = 0.8, 6.8 Hz, 2H), 4.94-5.06 (m, 2H), 5.73-5.84 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 13.7, 13.8, 19.2, 19.2, 27.5, 30.5, 30.6, 32.5,
42.1, 54.0, 65.0, 65.7, 115.5, 136.8, 168.5, 171.6, 203.4; IR (neat) 1642, 1715 cm-1; MS m/z (relative intensity) 239 ([M-OBu]+, 28), 238 (45), 211 (11),
182 (27), 156 (23), 137 (19), 136 (23), 101 (15), 100 (50), 83 (100), 81 (22), 69 (33), 57 (35), 55 (77); HRMS (EI) m/z calcd for C13H19O4 ([M-OBu]+)
239.1283, found: 239.1291.
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3-(Pent-4-enoyl)cyclopentanone (3f). Colorless oil (42.4 mg, 51%); H NMR (400 MHz, CDCl3) δ 1.93-2.03 (m, 1H), 2.16-2.39 (m, 6H), 2.45-
2.71 (m, 3H), 3.20-3.28 (m, 1H), 4.96-5.06 (m, 2H), 5.74-5.84 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 26.1, 27.6, 37.6, 40.2, 40.8, 47.9, 115.7, 136.9,
209.9, 216.8; IR (neat) 1641, 1711, 1744 cm-1; MS m/z (relative intensity) 167 ([M-H+]+, 20), 149 (43), 111 (13), 95 (29), 83 (49), 81 (61), 69 (100), 57
(38), 55 (55); HRMS (EI) m/z calcd for C10H14O2 ([M-H+]+) 166.0994, found: 166.0992.
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3-(Pent-4-enoyl)cyclohexanone (3g). Colorless oil (52.3 mg, 58%); H NMR (400 MHz, CDCl3) δ 1.62-1.77 (m, 2H), 2.01-2.09 (m, 2H), 2.27-
2.41 (m, 5H), 2.49-2.67 (m, 3H), 2.83-2.88 (m, 1H), 4.97-5.06 (m, 2H), 5.74-5.84 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 25.0, 27.4, 27.6, 40.2, 41.0,
42.5, 50.3, 115.6, 136.9, 210.0, 210.1; IR (neat) 1641, 1713 cm-1; MS m/z (relative intensity) 180 ([M]+, 19), 126 (12), 125 (35), 120 (12), 98 (18), 97
(92), 85 (10), 83 (77), 69 (32), 55 (100); HRMS (EI) m/z calcd for C11H16O2 ([M]+) 180.1150, found: 180.1147.
2-(1-(Pent-4-enoyl)cyclohexyl)malononitrile (3h). Colorless oil (63.4 mg, 55%); 1H NMR (300 MHz, CDCl3) δ 1.40-2.00 (m, 8H), 2.00-2.15 (m,
2H), 2.40 (q, J = 7.0 Hz, 2H), 2.70 (t, J = 7.0 Hz, 2H), 4.05 (s, 1H), 4.95-5.15 (m, 2H), 6.75-6.90 (m, 1H); 13C NMR (75 MHz, CDCl3) δ 21.4, 24.5, 27.5,
27.9, 29.8, 36.8, 54.8, 111.3, 116.0, 136.2, 207.9; IR (neat) 3080, 2935, 2255, 1706, 1641, 1458 cm-1; Anal. Calcd. for C14H18N2O: C, 73.01; H, 7.88; N,
12.16. Found: C, 73.0; H, 7.8; N, 12.2.
4-Oxonon-7-enenitrile (3i). Colorless oil (51.6 mg, 66%), mixture of E/Z = 71/29; E isomer: 1H NMR (500 MHz, CDCl3) δ 1.62-1.65 (m, 3H),
2.27-2.31 (m, 2H), 2.49-2.52 (m, 2H), 2.57-2.60 (m, 2H), 2.78-2.80 (m, 2H), 5.38 (dt, J = 15.5, 6.0 Hz, 1H) 5.44-5.53 (m, 1H); 13C NMR (100 MHz,
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CDCl3) δ 11.4, 18.0, 26.7, 37.9, 42.3, 119.2, 126.6, 128.9, 205.9; Z isomer: H NMR (500 MHz, CDCl3) δ 1.62-1.65 (m, 3H), 2.33-2.38 (m, 2H), 2.49-
2.52 (m, 2H), 2.57-2.60 (m, 2H), 2.78-2.80 (m, 2H), 5.31 (dt, J = 10.5, 7.5 Hz, 1H), 5.47-5.53 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 12.8, 21.3, 26.7,
37.9, 42.2, 119.2, 125.7, 128.1, 205.9; IR (neat) 1719, 2249 cm-1; MS m/z (relative intensity) 151 ([M]+, 20), 36 (29), 123 (12), 108 (23), 97 (59), 94
(46), 82 (85), 69 (100), 55 (45); HRMS (ESI) m/z calcd for C9H13ONNa ([M+Na]+) 174.0889, found: 174.0859.
4-Oxotetradec-7-enenitrile (3j). Colorless oil (64.0 mg, 59%), mixture of E/Z = 74/26; E isomer: 1H NMR (500 MHz, CDCl3) δ 0.88 (t, 3H, J = 7.0
Hz), 0.24-0.33 (m, 8H), 1.94-1.98 (m, 2H), 2.27-2.31 (m, 2H), 2.51 (t, 2H, J = 7.0 Hz), 2.58 (t, 2H, J = 6.5 Hz), 2.79 (t, 2H, J = 7.0 Hz), 5.35 (dtt, 1H, J =
15.5, 6.5, 1.0 Hz), 5.45 (dtt, 1H, J = 15.0, 7.0, 1.0 Hz); 13C NMR (100 MHz, CDCl3) δ 11.3, 14.1, 22.6, 26.7, 28.8, 29.4, 31.7, 32.5, 37.8, 42.4, 119.1,
127.6, 132.2, 205.8; Z isomer: 1H NMR (500 MHz, CDCl3) δ 0.88 (t, 3H, J = 7.5 Hz), 0.24-0.33 (m, 8H), 2.00-2.04 (m, 2H), 2.31-2.36 (m, 2H), 2.50 (t,
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