378
T. Yamashita et al. / Tetrahedron 63 (2007) 374–380
135.49, 154.86, 169.13; IR (CHCl3, cmꢁ1): 3442, 2972,
2229, 1675, 1505. HRMS calcd for C17H22N2O: 270.1732;
found: 270.1680. Calcd for C17H22N2O: C, 75.52; H, 8.20;
N, 10.36%. Found C, 75.43; H, 8.08; N, 10.29%.
118.94, 123.69, 126.96, 131.99, 140.98, 153.99, 169.80.
HRMS calcd for C15H18N2O: 242.1419; found: 242.1373.
4.2.7. 4-(4-Amino-4-methyl-2-pentenyl)benzonitrile
1
(2d0). The acetamide; a yellow oil; H NMR d 1.42 (s,
4.2.2. (E)-4-(4-Amino-1-methyl-2-pentenyl)benzonitrile
(2b). A yellow oil; IR (neat, cmꢁ1): 3287, 2972, 2228. The
acetamide; a yellow oil; 1H NMR d 1.22 (t, J¼6.8 Hz,
3H), 1.35 (d, J¼7.0 Hz, 3H), 1.96 (s, 3H), 3.45–3.55 (m,
1H), 4.50–4.60 (m, 1H), 5.47 (ddd, J¼15.5, 5.4, 1.2 Hz,
1H), 5.63 (br s, 1H), 5.71 (ddd, J¼15.5, 6.5, 1.3 Hz, 1H),
7.30 (d, J¼8.4 Hz, 2H), 7.58 (d, J¼8.3 Hz, 2H); 13C NMR
d 20.65, 20.70, 20.92, 23.24, 41.69, 46.18, 109.76, 119.00,
128.13, 131.73, 132.24, 133.16, 151.37, 169.41. HRMS
calcd for C15H18N2O: 242.1417; found: 242.1408.
6H), 1.93 (s, 3H), 3.42 (d, J¼6.6 Hz, 2H), 5.46 (br s, 1H),
5.60 (dt, J¼15.6, 6.7 Hz, 1H), 5.81 (dt, J¼15.6, 1.3 Hz,
1H), 7.30 (d, J¼8.3 Hz, 2H), 7.57 (d, J¼8.3 Hz, 2H); 13C
NMR d 27.55, 38.54, 53.77, 109.90, 119.00, 124.46,
129.29, 132.18, 138.67, 146.17, 169.15. HRMS calcd for
C15H18N2O: 242.1419; found: 242.1468.
4.2.8. 4-(1-Aminomethyl-3-methyl-2-butenyl)benzo-
nitrile (2d00). The acetamide; a yellow oil; 1H NMR d 1.66
(d, J¼1.1 Hz, 3H), 1.75 (d, J¼1.0 Hz, 3H), 1.93 (s, 3H),
3.30–3.42 (m, 1H), 3.49–3.60 (m, 1H), 3.77–3.87 (m, 1H),
5.20–5.27 (m, 1H), 5.58 (br s, 1H), 7.34 (d, J¼8.2 Hz,
2H), 7.60 (d, J¼8.4 Hz, 2H); 13C NMR d 18.24,
23.14, 25.82, 44.18, 44.65, 110.23, 118.78, 123.69,
128.35, 132.34, 136.15, 148.43, 170.07. HRMS calcd for
C15H18N2O: 242.1419; found: 242.1376.
4.2.3. 4-(4-Amino-1,1,3-trimethyl-2-butenyl)benzonitrile
(2c). The acetamide of E-isomer; a colorless oil; H NMR
1
d 1.13 (d, J¼1.1 Hz, 3H), 1.42 (s, 6H), 2.02 (s, 3H), 3.57
(d, J¼5.9 Hz, 2H), 5.61 (d, J¼1.3 Hz, 1H), 6.11 (br s, 1H),
7.46 (d, J¼8.6 Hz, 2H), 7.57 (d, J¼8.6 Hz, 2H); 13C NMR
d 15.80, 23.22, 31.00, 39.87, 47.53, 109.13, 119.13,
127.04, 132.04, 133.83, 135.35, 156.18, 170.17; IR (neat,
cmꢁ1): 3448, 3019, 2229, 1667. HRMS calcd for
C16H20N2O: 256.1575; found: 256.1566. The acetamide of
4.2.9. (E)-4-(4-Amino-2,3-dimethyl-2-butenyl)benzo-
nitrile (2e). The acetamide; a yellow oil; H NMR d 1.61
1
(d, J¼0.8 Hz, 3H), 1.77 (d, J¼0.8 Hz, 3H), 1.98 (s, 3H),
3.55 (s, 2H), 3.95 (d, J¼5.5 Hz, 2H), 5.56 (br s, 1H), 7.25
(d, J¼8.3 Hz, 2H), 7.58 (d, J¼8.3 Hz, 2H); 13C NMR
d 17.37, 19.00, 23.30, 40.00, 48.33, 110.62, 119.11,
128.02, 129.27, 130.38, 132.32, 146.12, 170.12. HRMS
calcd for C15H18N2O: 242.1419; found: 242.1376.
1
Z-isomer; a colorless oil; H NMR d 1.14 (d, J¼1.2 Hz,
3H), 1.44 (s, 3H), 1.45 (s, 3H), 1.93 (s, 3H), 3.40–3.57 (m,
2H), 5.47 (d, J¼1.2 Hz, 1H), 5.55 (br t, 1H), 7.48 (d,
J¼8.3 Hz, 2H), 7.61 (d, J¼8.3 Hz, 2H); 13C NMR d 19.86,
23.31, 24.97, 26.70, 44.43, 50.61, 109.85, 118.90, 127.78,
129.44, 132.15, 136.25, 152.68, 170.24. HRMS calcd for
C16H20N2O: 256.1575; found: 256.1564.
4.2.10. 4-(1-Aminomethyl-1,2-dimethylallyl)benzonitrile
1
(2e0). The acetamide; a yellow oil; H NMR d 1.40 (s,
4.2.4. 4-(4-Amino-2,4-dimethyl-2-pentenyl)benzonitrile
(2c0). The product was obtained as a mixture of E and Z iso-
mers. The acetamide of E-isomer; a colorless oil; 1H NMR
d 1.50 (s, 6H), 1.57 (d, J¼1.2 Hz, 3H), 1.80 (s, 3H), 3.65
(s, 2H), 5.65 (br s, 1H), 5.86 (br s, 1H), 7.30 (d, J¼8.1 Hz,
2H), 7.57 (d, J¼8.1 Hz, 2H); 13C NMR d 23.96, 24.16,
28.69, 38.04, 52.89, 109.83, 119.02, 129.42, 132.13,
132.23, 134.76, 145.35, 168.92; the acetamide of Z-isomer;
1H NMR d 1.48 (s, 6H), 1.61 (d, J¼1.2 Hz, 3H), 1.93 (s, 3H),
3.32 (s, 2H), 5.54 (br s, 1H), 5.79 (br s, 1H), 7.30 (d,
J¼8.1 Hz, 2H), 7.57 (d, J¼8.1 Hz, 2H); 13C NMR d 16.54,
23.86, 28.53, 47.35, 52.89, 109.83, 119.20, 129.63,
132.13, 132.99, 134.57, 145.97, 168.70. HRMS calcd for
C16H20N2O: 256.1575; found: 256.1575.
3H), 1.52 (d, J¼0.9 Hz, 3H), 1.97 (s, 3H), 3.64 (dd,
J¼13.2, 5.0 Hz, 1H), 3.78 (dd, J¼13.2, 6.5 Hz, 1H), 5.06
(s, 1H), 5.16–5.17 (m, 1H), 5.33 (br s, 1H), 7.40 (d,
J¼8.4 Hz, 2H), 7.64 (d, J¼8.4 Hz, 2H); 13C NMR d 20.19,
23.46, 23.90, 42.52, 45.78, 110.62, 113.82, 118.80,
127.45, 132.42, 147.68, 150.47, 170.33. HRMS calcd for
C15H18N2O: 242.1419; found: 242.1376.
4.2.11. 4-(4-Amino-1,2,3,4-tetramethyl-2-cyclopentenyl)-
benzonitrile (2f). The acetamide of cis-isomer; a white
1
solid; mp 141.5–142.0 ꢂC (from benzene); H NMR d 1.35
(s, 3H), 1.42 (s, 3H), 1.47 (s, 3H), 1.63 (s, 3H), 1.90 (s,
3H), 2.02 (d, J¼13.5 Hz, 1H), 2.67 (d, J¼13.5 Hz, 1H),
6.03 (s, 1H), 7.57 (d, J¼8.5 Hz, 2H), 7.63 (d, J¼8.5 Hz,
2H); 13C NMR d 9.79, 10.86, 23.79, 24.29, 26.86, 52.76,
54.32, 65.90, 108.99, 119.36, 127.93, 131.79, 135.84,
138.29, 155.22, 169.63; IR (CHCl3, cmꢁ1): 3442, 2973,
2227, 1673, 1506. HRMS calcd for C18H22N2O: 282.1731;
found: 282.1765. The acetamide of trans-isomer; a yellow
4.2.5. 4-(1-Aminomethyl-1,3-dimethyl-2-butenyl)benzo-
nitrile (2c00). The acetamide; a colorless oil; 1H NMR
d 1.70 (s, 3H), 1.75 (s, 6H), 1.85 (s, 3H), 3.33 (d, J¼
5.3 Hz, 2H), 5.20 (br s, 1H), 5.72 (br s, 1H), 7.48 (d,
J¼8.4 Hz, 2H), 7.59 (d, J¼8.4 Hz, 2H); 13C NMR d 22.11,
23.02, 28.69, 31.62, 40.04, 40.37, 109.47, 118.90, 127.03,
129.63, 133.52, 138.14, 156.66, 169.86. HRMS calcd for
C16H20N2O: 256.1575; found: 256.1525.
1
oil; H NMR d 1.30 (s, 3H), 1.47 (s, 3H), 1.52 (s, 3H),
1.69 (s, 3H), 1.95 (s, 3H), 2.01 (d, J¼13.8 Hz, 1H), 2.69
(d, J¼13.7 Hz, 1H), 6.07 (s, 1H), 7.31 (d, J¼8.4 Hz, 2H),
7.59 (d, J¼8.4 Hz, 2H); 13C NMR d 9.79, 11.13, 23.99,
25.16, 25.53, 53.32, 54.04, 65.84, 109.22, 119.10, 127.26,
132.04, 136.39, 138.41, 155.22, 169.75; IR (CHCl3,
cmꢁ1): 3449, 3019, 2229, 1667, 1517. HRMS calcd for
C18H22N2O: 282.1731; found: 282.1740.
4.2.6. 4-(4-Amino-1,1-dimethyl-2-butenyl)benzonitrile
(2d). The acetamide; a yellow oil; 1H NMR d 1.40 (s, 6H),
2.00 (s, 3H), 3.89 (dt, J¼5.9, 1.2 Hz, 2H), 5.49 (dt,
J¼15.6, 5.6 Hz, 1H), 5.70 (br s, 1H), 5.75 (dt, J¼15.6,
1.2 Hz, 1H), 7.42 (d, J¼8.4 Hz, 2H), 7.58 (d, J¼8.6 Hz,
2H); 13C NMR d 23.24, 28.33, 40.76, 41.36, 109.73,
4.2.12. 4-(2-Amino-1,1,2-trimethylpropyl)benzonitrile
(2g). The acetamide; a white solid; mp 133.0–133.5 ꢂC