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C. Danieli et al. / Tetrahedron 60 (2004) 11493–11501
5.3.5. Preparation of (E)-N-propyl-3,4-dimethyl-5-
propylimino-pyrrolidin-2-one (10). According to the
general procedure, the rearrangement of 5 (0.22 g,
1 mmol) with n-propylamine (2 mL) at 100 8C for 16 h
gave 10 (61 mg, 29%) as an unseparable mixture of cis/trans
diastereoisomers (23/77); yellow oil; [found: C, 68.64; H,
10.59; N, 13.33. C12H22N2O requires C, 68.53; H, 10.54; N,
13.32]; IR (liquid film) 1671 cmK1 (C]N), 1736 cmK1
(C]O); 1H NMR (400 MHz, CDCl3): trans diastereo-
isomer (77%) d 0.84 (3H, t, JZ7.5 Hz, N(1)CH2CH2CH3),
0.90 (3H, t, JZ7.4 Hz, C]NCH2CH2CH3), 1.18 (3H, d,
JZ7.2 Hz, C(4)CH3), 1.19 (3H, d, JZ7.4 Hz, C(3)CH3),
1.56 (2H, m, N(1)CH2CH2), 1.58 (2H, m, C]NCH2CH2),
2.22 (1H, m, JZ1.9, 7.4 Hz, C(3)H), 2.61 (1H, m, JZ1.9,
7.2 Hz, C(4)H), 3.20–3.53 (4H, m, CH2NC]NCH2); cis
diastereoisomer (23%) d 0.83 (3H, t, JZ7.4 Hz, N(1)CH2-
CH2CH3), 0.91 (3H, t, JZ7.4 Hz, C]NCH2CH2CH3), 1.02
(3H, d, JZ7.3 Hz, C(4)CH3), 1.15 (3H, d, JZ7.4 Hz,
C(3)CH3), 1.55 (2H, m, N(1)CH2CH2), 1.57 (2H, m,
C]NCH2CH2), 2.71 (1H, m, JZ7.8 Hz, C(3)H), 3.12
(1H, m, JZ7.7 Hz, C(4)H), 3.20–3.53 (4H, m, CH2-
NC]NCH2); 13C NMR (100 MHz, CDCl3): trans dia-
stereoisomer (77%) d 11.18 (N(1)CH2CH2CH3), 11.77
(C]NCH2CH2CH3), 17.57 (C(3)CH3), 18.57 (C(4)CH3),
20.43 (N(1)CH2CH2), 24.85 (C]NCH2CH2), 37.67 (C(4)),
40.32 (N(1)CH2), 44.50 (C(3)), 50.96 (C]NCH2), 161.03
(C(5)), 179.06 (C(2)); cis diastereoisomer (23%) d 9.44
(C(3)CH3), 11.23 (N(1)CH2CH2CH3), 11.82 (C]NCH2-
CH2CH3), 13.27 (C(4)CH3), 20.47 (N(1)CH2CH2), 24.83
(C]NCH2CH2), 33.11 (C(4)), 38.89 (C(3)), 40.36
(N(1)CH2), 51.05 (C]NCH2), 161.63 (C(5)), 178.35
(C(2)); MS (EI, 70 eV) m/z: 210 (65, MC), 195 (43), 181
(45), 167 (35), 153 (100), 140 (52), 111 (32), 55 (20), 41
(18).
t, JZ7.4 Hz, N(1)CH2CH2CH3), 0.97 (3H, t, JZ7.4 Hz,
C]NCH2CH2CH3), 1.55 (2H, m, N(1)CH2CH2), 1.68 (2H,
m, C]NCH2CH2), 1.89 (3H, q, JZ1.1 Hz, C(3)CH3), 2.16
(3H, q, JZ1.1 Hz, C(4)CH3), 3.52 (2H, t, JZ7.2 Hz,
N(1)CH2), 3.72 (2H, t, JZ6.8 Hz, C]NCH2); (Z)-dia-
stereoisomer (15%) d 0.88 (3H, t, JZ7.4 Hz, N(1)CH2CH2-
CH3), 0.98 (3H, t, JZ7.3 Hz, C]NCH2CH2CH3), 1.57
(2H, m, N(1)CH2CH2), 1.70 (2H, m, C]NCH2CH2), 1.87
(3H, m, C(3)CH3), 1.93 (3H, q, JZ1.1 Hz, C(4)CH3), 3.66
(2H, m, C]NCH2), 3.67 (2H, m, N(1)CH2); 13C NMR
(100 MHz, CDCl3): (E)-diastereoisomer (85%) d 8.18
(C(3)CH3), 11.33 (N(1)CH2CH2CH3), 11.76 (C]NCH2-
CH2CH3), 14.40 (C(4)CH3), 21.87 (N(1)CH2CH2), 25.45
(C]NCH2CH2), 39.70 (N(1)CH2), 51.05 (C]NCH2),
132.53 (C(3)), 136.65 (C(4)), 152.93 (C(5)), 171.01
(C(2)); (Z)-diastereoisomer (15%) d 8.70 (C(3)CH3), 9.51
(C(4)CH3), 11.33 (N(1)CH2CH2CH3), 11.76 (C]NCH2-
CH2CH3), 22.66 (N(1)CH2CH2), 25.35 (C]NCH2CH2),
43.11 (N(1)CH2), 50.25 (C]NCH2), 130.55 (C(3)), 139.42
(C(4)), 151.02 (C(5)), 170.81 (C(2)); MS (EI, 70 eV) m/z:
208 (100, MC), 193 (43), 179 (73), 165 (53), 151 (83), 138
(48), 123 (22), 108 (48).
5.3.8. Preparation of N-propyl-3-chloro-4-methyl-5-pro-
pylimino-3-pyrrolin-2-one (13). According to the general
procedure, the rearrangement of 7 (0.28 g, 1 mmol) with
n-propylamine (2 mL) at K13 8C for 0.5 h gave 13 (0.15 g,
68%) as an unseparable mixture of E/Z diastereoisomers
(89/11); orange oil; [found: C, 57.64; H, 7.56; N, 12.17.
C11H17ClN2O requires C, 57.77; H, 7.49; N, 12.25]; IR
1
(liquid film) 1657 cmK1 (C]N), 1734 cmK1 (C]O); H
NMR (400 MHz, CDCl3): (E)-diastereoisomer (89%) d 0.84
(3H, t, JZ7.4 Hz, N(1)CH2CH2CH3), 0.96 (3H, t, JZ
7.4 Hz, C]NCH2CH2CH3), 1.56 (2H, m, N(1)CH2CH2),
1.68 (2H, m, C]NCH2CH2), 2.27 (3H, s, C(4)CH3), 3.56
(2H, t, JZ7.2 Hz, N(1)CH2), 3.72 (2H, t, JZ6.8 Hz,
C]NCH2); (Z)-diastereoisomer (11%) d 0.88 (3H, t, JZ
7.4 Hz, N(1)CH2CH2CH3), 0.97 (3H, t, JZ7.3 Hz,
C]NCH2CH2CH3), 1.56 (2H, m, N(1)CH2CH2), 1.68
(2H, m, C]NCH2CH2), 2.01 (3H, s, C(4)CH3), 3.67 (2H,
t, JZ6.8 Hz, C]NCH2), 3.70 (2H, t, JZ7.7 Hz, N(1)CH2);
13C NMR (100 MHz, CDCl3): (E)-diastereoisomer (89%) d
11.18 (N(1)CH2CH2CH3), 11.66 (C]NCH2CH2CH3),
14.40 (C(4)CH3), 21.72 (N(1)CH2CH2), 25.15
(C]NCH2CH2), 40.22 (N(1)CH2), 51.31 (C]NCH2),
132.55 (C(3)), 134.22 (C(4)), 149.71 (C(5)), 164.20
(C(2)); (Z)-diastereoisomer (11%) d 9.89 (C(4)CH3),
10.89 (N(1)CH2CH2CH3), 11.66 (C]NCH2CH2CH3),
23.56 (N(1)CH2CH2), 25.09 (C]NCH2CH2), 43.81
(N(1)CH2), 50.58 (C]NCH2), 127.0 (C(3)), 143.5 (C(4)),
147.5 (C(5)), 164.20 (C(2)); MS (EI, 70 eV) m/z: 228 (100,
MC), 213 (20), 199 (77), 185 (47), 171 (35), 158 (42), 151
(72), 145 (27), 128 (53).
5.3.6. Preparation of N-propyl-3-methyl-4-(propyl-
amino)methyl-3-pyrrolin-2-one (11). According to the
general procedure, the rearrangement of 5 (0.22 g, 1 mmol)
with n-propylamine (2 mL) at 80 8C for 16 h gave 11
(0.14 g, 68%) as a pale yellow oil; [found: C, 68.51; H,
10.58; N, 13.40. C12H22N2O requires C, 68.53; H, 10.54; N,
1
13.32]; IR (liquid film) 1681 cmK1; H NMR (400 MHz,
CDCl3): d 0.80 (3H, t, JZ7.5 Hz, N(1)CH2CH2CH3), 0.81
(3H, t, JZ7.5 Hz, NHCH2CH2CH3), 1.40 (2H, m, NHCH2-
CH2), 1.48 (2H, m, N(1)CH2CH2), 1.73 (3H, s, C(3)CH3),
2.45 (2H, m, NHCH2), 3.29 (2H, t, JZ7.3 Hz, N(1)CH2),
3.47 (2H, s, C(4)CH2), 3.77 (2H, d, JZ1.4 Hz, C(5)H2); 13
C
NMR (100 MHz, CDCl3): d 8.79 (C(3)CH3), 11.18
(N(1)CH2CH2CH3), 11.58 (NHCH2CH2CH3), 21.78
(N(1)CH2CH2), 22.96 (NHCH2CH2), 43.72 (N(1)CH2),
46.08 (C(3)CH2), 51.58 (NHCH2), 52.01 (C(5)), 130.08
(C(3)), 147.63 (C(4)), 172.18 (C(2)); MS (EI, 70 eV) m/z:
210 (1, MC), 181 (4), 151 (100).
5.3.7. Preparation of N-propyl-3,4-dimethyl-5-propyl-
imino-3-pyrrolin-2-one (12). According to the general
procedure, the rearrangement of 6 (0.26 g, 1 mmol) with
n-propylamine (2 mL) at 100 8C for 16 h gave 12 (52 mg,
25%) as an unseparable mixture of E/Z diastereoisomers
(85/15); yellow oil; [found: C, 69.08; H, 9.71; N, 13.40.
C12H20N2O requires C, 69.19; H, 9.68; N, 13.45]; IR (liquid
5.3.9. Preparation of (E)-N-propyl-5-propylimino-
pyrrolidin-2-one (14). According to the general procedure,
the rearrangement of 7 (0.28 g, 1 mmol) with n-propyl-
amine (2 mL) at 80 8C for 16 h gave 14 (80 mg, 44%) as an
orange-yellow oil; [found: C, 65.78; H, 9.88; N, 15.41.
C10H18N2O requires C, 65.90; H, 9.95; N, 15.37]; IR (liquid
1
film) 1671 cmK1 (C]N), 1739 cmK1 (C]O); H NMR
1
film) 1656 cmK1 (C]N), 1718 cmK1 (C]O); H NMR
(400 MHz, CDCl3): d 0.88 (3H, t, JZ7.4 Hz, N(1)CH2-
CH2CH3), 0.92 (3H, t, JZ7.4 Hz, C]NCH2CH2CH3), 1.59
(400 MHz, CDCl3): (E)-diastereoisomer (85%) d 0.85 (3H,