PAPER
Acidic Alumina Catalyzed Reactions of b-Dicarbonyls with Conjugated Nitroalkenes
3019
Table 3 Spectroscopic Data of Michael Adducts 3 (continued)
Compd
IR
(nujol, cm–1) (400 MHz, CDCl3)
1H NMR
13C NMR
(100 MHz, CDCl3)
Elemental analysis
3ac
solid
1561, 1726 1.05 (t, J = 7.3 Hz, 1.8 H), 1.28 (t, J = 7.3 Hz,
14.0, 14.2, 30.3, 30.5, 42.0,
42.1, 61.5, 61.6, 62.6, 62.9,
Anal. Calcd for
C14H16N2O7: C, 51.85;
1.2 H), 2.14 (s, 1.2 H), 2.33 (s, 1.8 H), 3.99 (dq,
diastereomeric
mixture
J = 1.3, 7.3 Hz, 1.2 H), 4.04 (d, J = 9.4 Hz, 0.4 H), 77.1, 77.4, 124.3, 124.5, 129.3, H, 4.97; N, 8.64
4.13 (d, J = 9.8 Hz, 0.6 H), 4.24 (dq, J = 1.3, 7.3
129.4, 144.2, 144.4, 147.9,
Found: C, 54.38;
H, 5.30; N, 8.21
Hz, 0.8 H), 4.28–4.41 (m, 1 H), 4.77 (d, J = 6.5 Hz, 149.7, 166.5, 167.2, 199.6,
1.2 H), 4.84–4.90 (m, 0.8 H), 7.39–7.45 (m, 2 H), 200.5
8.14–8.20 (m, 2 H)
3ad
1559, 1741a 1.17 (t, J = 7.3 Hz, 1.5 H), 1.27 (t, J = 7.3 Hz,
14.1, 14.2, 30.1, 30.6, 36.5,
36.6, 59.6, 59.9, 62.4, 62.5,
Anal. Calcd for
C12H15NO6: C, 53.53;
viscous oil
diastereomeric
mixture
1.5 H), 2.16 (s, 1.5 H), 2.29 (s, 1.5 H), 4.04–4.27
(m, 3 H), 4.28–4.39 (m, 1 H), 4.77–4.83 (m, 2 H), 75.8, 75.9, 108.5, 108.8, 110.8, H, 5.62; N, 5.20
6.16–6.19 (m, 1 H), 6.26–6.30 (m, 1 H), 7.31–7.34 110.9, 142.8, 142.9, 149.9,
(m, 1 H)
Found: C, 53.31;
H, 5.32; N, 5.51
150.1, 167.1, 167.5, 200.5,
201.1
3ae
oil
1563, 1737a 0.81–0.90 (m, 3 H), 1.18–1.47 (m, 11 H), 2.28 (s, 14.1, 14.2, 22.5, 22.6, 26.5,
1.5 H), 2.29 (s, 1.5 H), 2.76–2.92 (m, 1 H), 3.72 (d, 26.6, 29.6, 30.2, 31.6, 31.7,
Anal. Calcd for
C13H23NO5: C, 57.13;
H, 8.48; N, 5.12
diastereomeric
mixture
J = 6.4 Hz, 0.5 H), 3.76 (d, J = 7.7 Hz, 0.5 H),
36.6, 36.7, 60.2, 60.6, 62.1,
4.17–4.25 (m, 2 H), 4.41–4.71 (m, 2 H)
62.2, 76.1, 76.7, 168.2, 168.3, Found: C, 57.41;
202.0, 202.2
H, 8.80; N, 4.88
3bd
1563, 1722a 1.03–1.09 (m, 1.5 H), 1.14–1.20 (m, 1.5 H), 3.97– 14.0, 14.1, 37.2, 37.3, 54.2,
Anal. Calcd for
viscous oil
diastereomeric
mixture
4.07 (m, 1 H), 4.13–4.20 (m, 1 H), 4.48–4.65 (m,
1 H), 4.79–4.84 (m, 1 H), 4.92–5.03 (m, 2 H),
55.1, 62.3, 62.4, 75.9, 76.0,
108.8, 108.9, 110.7, 128.8,
C17H17NO6: C, 61.63;
H, 5.17; N, 4.23
Found: C, 61.88;
H, 5.41; N, 4.01
6.10–6.19 (m, 1 H), 6.21–6.30 (m, 1 H), 7.20–7.23 128.9, 129.0, 129.1, 134.1,
(m, 0.5 H), 7.31–7.35 (m, 0.5 H), 7.42–7.52 (m,
2 H), 7.55–7.65 (m, 1 H), 7.91–7.96 (m, 1 H),
7.98–8.04 (m, 1 H)
134.4, 135.8, 135.9, 142.7,
142.9, 149.9, 150.0, 167.2,
167.5, 192.8, 193.0
3be
oil
diastereomeric
mixture
1554, 1718a 0.81–0.91 (m, 3 H), 1.12–1.52 (m, 11 H), 2.96–
3.09 (m, 1 H), 4.11–4.24 (m, 2 H), 4.56–4.68 (m,
2 H), 4.70–4.80 (m, 1 H), 7.47–7.53 (m, 2 H),
7.56–7.65 (m, 1 H), 7.92–8.02 (m, 2 H)
14.2, 22.6, 26.6, 26.7, 29.5,
30.3, 31.6, 31.7, 37.3, 37.4,
54.6, 55.3, 61.7, 62.2, 76.5,
76.7, 128.9, 129.0, 129.1,
129.2, 134.2, 134.3, 136.2,
136.3, 168.4, 168.5, 194.1,
194.5
Anal. Calcd for
C18H25NO5: C, 64.46;
H, 7.51; N, 4.18
Found: C, 64.01;
H, 7.19; N, 4.42
3ca
solid
mp 110–112 °C
1560, 1738
1567, 1733
1566, 1727
1570, 1732
1.92 (s, 3 H), 2.27 (s, 3 H), 4.18–4.27 (m, 1 H),
4.36 (d, J = 10.7 Hz, 1 H), 4.60–4.64 (m, 2 H),
7.15–7.20 (m, 2 H), 7.24–7.35 (m, 3 H)
29.8, 30.7, 43.0, 70.9, 78.4,
128.1, 128.8, 129.5, 136.2,
201.3, 202.0
Anal. Calcd for
C13H15NO4: C, 62.64;
H, 6.07; N, 5.62
Found: C, 62.90;
H, 6.29; N, 5.29
3cb
solid
mp 125–127 °C
1.96 (s, 3 H), 2.28 (s, 3 H), 4.18–4.26 (m, 1 H),
4.32 (d, J = 11.1 Hz, 1 H), 4.58–4.61 (m, 2 H), 7.12 129.5, 129.7, 134.6, 134.7,
(d, J = 8.5 Hz, 2 H), 7.30 (d, J = 8.5 Hz, 2 H)
29.9, 30.6, 42.3, 70.6, 78.1,
Anal. Calcd for
C13H14ClNO4: C, 55.04;
H, 4.97; N, 4.94
Found: C, 55.47;
H, 5.19; N, 4.77
200.8, 201.6
3cc
solid
mp 128–130 °C
1.98 (s, 3 H), 2.29 (s, 3 H), 4.17–4.28 (m, 1 H),
4.33 (d, J = 10.9 Hz, 1 H), 4.56–4.62 (m, 2 H),
7.38–7.44 (m, 2 H), 8.13–8.22 (m, 2 H)
30.0, 30.5, 42.4, 70.7, 78.0,
124.4, 129.4, 144.5, 148.1,
200.8, 201.6
Anal. Calcd for
C13H14N2O6: C, 53.06;
H, 4.80; N, 9.52
Found: C, 52.78;
H, 4.51; N, 9.81
3cd
2.06 (s, 3 H), 2.25 (s, 3 H), 4.28–4.40 (m, 2 H),
30.1, 31.4, 37.4, 68.6, 76.6,
Anal. Calcd for
waxy solid
4.64 (d, J = 5.6 Hz, 2 H), 6.13–6.16 (m, 1 H), 6.26– 109.6, 111.6, 143.6, 150.3,
6.29 (m, 1 H), 7.32–7.34 (m, 1 H) 201.6, 202.2
C11H13NO5: C, 55.23;
H, 5.48; N, 5.86
Found: C, 55.49;
H, 5.77; N, 5.59
Synthesis 2007, No. 19, 3017–3020 © Thieme Stuttgart · New York