F. Portela-Cubillo et al. / Tetrahedron 64 (2008) 11908–11916
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4.3.21. 2-(Diphenylmethylleneaminooxy)-2-oxoacetyl chloride
4.3.28. Methyl 3-(2,4-dimethyl-3,4-dihydro-2H-pyrrol-5-
yl)propanoate (25a)
A solution of benzophenone oxime (1 g, 5.0 mmol) in Et2O
(15 mL) was added dropwise to a stirred solution of oxalyl chloride
(0.64 g, 5.0 mmol) in dry Et2O (10 mL) at ꢀ40 ꢃC. After stirring for
1 h at ꢀ20 ꢃC the solvent was evaporated to leave a colorless,
temperature sensitive, powder (96%). 1H NMR (400 MHz, CDCl3), dH
7.23–7.60 (10H, m, CH); 13C NMR, dC 128.8 (CH)ꢁ2, 129.1 (CH)ꢁ2,
129.4 (CH)ꢁ2, 129.8 (CH)ꢁ2, 131.0 (CH), 131.4 (C), 132.3 (CH), 133.8
(C), 155.1 (C), 168.6 (C)ꢁ2; IR, nmax/cmꢀ1 2928, 1766, 1763, 1445.
From benzophenone dioxime oxalate 24c; yellow oil; 61%; 1H
NMR (400 MHz, CDCl3), dH 1.03/1.09 (3H, d, J¼7.2 Hz, CH3), 1.10/1.19
(3H,d,J¼7.2 Hz,CH3),1.61(1H,t, J¼6.7 Hz, CH2), 2.22–2.84(6H,m,CH,
CH2), 3.60 (3H, s, CH3), 3.77/4.01 (1H, m, CH); 13C NMR, dC 16.4/17.1,
20.7/21.9 (CH3), 24.9/25.1, 28.7/29.4, 38.5/39.2 (CH2), 43.4/44.5 (CH),
50.6 (CH3), 64.3/64.7 (CH), 172.8, 177.2 (C); IR, nmax/cmꢀ1 1764, 1646.
4.3.29. Methyl 4-(2,4-dimethyl-3,4-dihydro-2H-pyrrol-5-
yl)butanoate (25d)
4.3.22. 2-(Benzylideneaminooxy)-2-oxoacetyl chloride
White powder; 98%. 1H NMR (400 MHz, CDCl3), dH 777.37–7.51
(3H, m, CH), 7.67 (2H, m, CH), 8.45 (1H, s, CH); 13C NMR, dC 129.4 (C),
129.6 (CH)ꢁ2, 132.6 (CH)ꢁ2, 133.2 (CH), 159.6 (CH), 172.1, 173.0 (C);
IR, nmax/cmꢀ1 2921, 1792, 1767, 1463.
From benzophenone dioxime oxalate 24d; yellow oil; 58%; 1H
NMR (400 MHz, CDCl3), dH 1.01/1.08 (3H, d, J¼7.1 Hz, CH3), 1.11/1.21
(3H, d, J¼7.1 Hz, CH3), 1.59 (1H, m, CH2), 1.86 (2H, m, CH2), 2.18–2.35
(5H, m, CH2), 2.71 (1H, m, CH), 3.60 (3H, s, CH3), 3.75/4.01 (1H, m,
CH); 13C NMR, dC 16.4/17.1 (CH3), 20.48 (CH2), 20.9/21.8 (CH3), 29.3/
29.4, 32.5/32.6, 38.4/39.1 (CH2), 42.9/44.0 (CH), 50.5 (CH3), 64.1/
64.5 (CH), 172.8, 178.2/178.3 (C); IR, nmax/cmꢀ1 1764, 1645.
4.3.23. 2-(2,4-Dimethoxybenzylideneaminooxy)-2-oxoacetyl
chloride
White powder, 93%. 1H NMR (400 MHz, CDCl3), dH 3.86 (6H, s,
CH3), 6.45 (1H, d, J¼2.3 Hz, CH), 6.54 (1H, dd, J¼8.7, 2.3 Hz, CH), 7.86
(1H, d, J¼8.7 Hz, CH), 8.83 (1H, s, CH); 13C NMR, dC 56.0 (CH3)ꢁ2,
98.5 (CH), 106.6 (CH), 109.8 (C), 129.3 (CH), 155.4 (CH), 161.0, 165.4,
172.1, 172.3 (C); IR, nmax/cmꢀ1 2926, 1791, 1760, 1465.
4.3.30. Biphenyl-2-carbaldehyde oxime (29a)
Yellow solid; 74%; 108–110 ꢃC; 1H NMR (400 MHz, CDCl3), dH
7.21–7.42 (8H, m, CH), 7.84 (1H, d, J¼7.6 Hz, CH), 8.04 (1H, s, CH);
13C NMR, dC 126.1, 127.6, 127.7 (CH), 128.4 (CH)ꢁ2, 129.7 (CH)ꢁ2,
129.8, 130.3 (CH), 136.0, 139.5, 145.2 (C), 149.8 (CH); IR, nmax/cmꢀ1
3179, 1631, 1596, 1481.
4.3.24. Methyl 4,5-dioxo-8-(pent-4-en-2-yl)-1-phenyl-3,6-dioxa-
2,7-diazaundeca-1,7-dien-11-oate (24a)
Red oil; mixture of isomers; 1H NMR (400 MHz, CDCl3), dH 1.07
(3H, m, CH3), 2.06–2.81 (6H, m, CH2), 3.42 (1H, m, CH), 3.76 (3H, m,
CH3), 5.06 (2H, m, CH2), 5.73 (1H, m, CH), 7.32–7.81 (5H, m, CH),
8.51 (1H, c, CH); 13C NMR, dC 17.0/17.1 (CH3), 24.5/24.4, 29.7/29.8
(CH2), 34.2/39.9 (CH), 38.6/38.7 (CH2), 53.0 (CH3), 110.7 (C), 117.8
(CH2), 129.9 (CH)ꢁ2, 133.6 (CH)ꢁ2, 134.5, 135.4, 159.2 (CH), 164.9,
165.0, 172.7, 173.3 (C); IR, nmax/cmꢀ1 2976, 1779, 1740, 1642.
4.3.31. 1-(Biphenyl-2-yl)ethanone oxime (29b)
66%; yellow solid; mp 35–37 ꢃC. Two isomers 9:1. 1H NMR
(400 MHz, CDCl3), dH 1.58/1.63 (3H, s, CH3), 7.16–7.40 (9H, m, CH);
13C NMR, dC 16.2 (CH3), 127.4, 127.5 (CH), 128.6 (CH)ꢁ2, 129.0
(CH)ꢁ2, 129.1, 129.3, 130.4 (CH), 136.8, 140.7, 141.1, 159.2 (C); IR,
nmax/cmꢀ1 3228, 1595, 1479.
4.3.32. Biphenyl-2-yl(phenyl)methanone oxime (29c)
4.3.25. Methyl 1-(2,4-dimethoxyphenyl)-4,5-dioxo-8-(pent-4-en-
2-yl)-3,6-dioxa-2,7-diazaundeca-1,7-dien-11-oate (24b)
Yellow solid; 56%; 102–104 ꢃC; 1H NMR (400 MHz, CDCl3), dH
6.96–7.50 (14H, m, CH), 9.41 (1H, s, OH); 13C NMR, dC 127.1, 127.2,
127.3, 127.9/128.0 (CH)ꢁ2, 128.2/128.3 (CH)ꢁ2, 128.5 (CH)ꢁ2, 129.2
(CH), 129.4 (CH)ꢁ2, 129.6 (CH), 130.1 (CH), 132.2/132.8, 135.6/136.2,
140.6, 141.3, 158.0/158.8 (C).
Red oil; mixture of isomers; 1H NMR (400 MHz, CDCl3), dH 1.15
(3H, m, CH3), 2.05–2.80 (6H, m, CH2), 3.46 (1H, m, CH), 3.69 (3H, m,
CH3), 3.85 (6H, s, CH3), 5.03 (2H, m, CH2), 5.71 (1H, m, CH), 6.42–6.55
(2H, m, CH), 7.82–7.84 (1H, m, CH), 8.77/8.79 (1H, s, CH); 13C NMR, dC
16.9/17.7 (CH3), 24.2/25.9, 29.3/30.7 (CH2), 34.5/39.9 (CH), 37.9/38.0
(CH2), 52.2/52.4, 55.9, 56.1 (CH3), 98.5, 106.4 (CH), 110.6 (C), 117.9
(CH2), 129.3, 135.2/135.4, 153.8/154.3 (CH), 160.7, 160.8, 164.9, 165.0,
172.7, 173.3 (C); IR, nmax/cmꢀ1 2975, 1788, 1752, 1731, 1601.
4.3.33. 6-Phenylbenzo[d][1,3]dioxole-5-carbaldehyde oxime (29d)
Yellow solid; 68%; 140–142 ꢃC; 1H NMR (400 MHz, CDCl3), dH
6.05 (2H, s, CH2), 6.81 (1H, s, CH), 7.30 (2H, m, CH), 7.43 (3H, m, CH),
7.62 (1H, s, CH), 8.02 (1H, s, CH); 13C NMR, dC 101.9 (CH2), 105.7,
110.4 (CH), 124.0 (C), 128.1 (CH), 128.8 (CH)ꢁ2, 130.2 (CH)ꢁ2, 138.1,
139.7, 147.8, 149.5 (C), 149.9 (CH); IR, nmax/cmꢀ1 3238, 1613, 1480.
4.3.26. Methyl 4,5-dioxo-8-(pent-4-en-2-yl)-1,1-diphenyl-3,6-
dioxa-2,7-diazaundeca-1,7-dien-11-oate (24c)
Red oil; mixture of isomers; 1H NMR (400 MHz, CDCl3), dH 1.03
(3H, m, CH3), 1.93–2.71 (6H, m, CH2), 3.28–3.31 (1H, m, CH), 3.50–
3.64 (3H, m, CH3), 4.94 (2H, m, CH2), 5.60 (1H, m, CH), 7.06–7.64
(10H, m, CH); 13C NMR, dC 17.0/17.7 (CH3), 24.2/25.7, 29.3/30.5
(CH2), 34.3/39.8 (CH), 37.9/38.1 (CH2), 52.2/52.5 (CH3), 118.0 (CH2),
128.7 (CH)ꢁ2, 128.9 (CH)ꢁ2, 129.4 (CH), 129.5 (CH)ꢁ2, 130.7 (CH),
131.6 (C), 131.9 (CH)ꢁ2, 134.2 (C), 135.1 (CH), 158.5, 160.2, 166.4,
172.6, 173.2 (C); IR, nmax/cmꢀ1 2977, 1756, 1743, 1641.
4.3.34. Biphenyl-2-carbaldehyde dioxime oxalate (30a)
White solid; 97%; 1H NMR (400 MHz, CDCl3), dH 7.17/7.24 (4H, m,
CH), 7.31–7.41 (10H, m, CH), 7.49 (2H, td, J¼7.5,1.5 Hz, CH), 8.02 (2H,
d, J¼7.8 Hz, CH), 8.40 (2H, s, CH); 13C NMR, dC 126.8 (C)ꢁ2, 127.5
(CH)ꢁ2, 127.9 (CH)ꢁ2, 128.2 (CH)ꢁ2, 128.7 (CH)ꢁ4, 129.7 (CH)ꢁ4,
130.5 (CH)ꢁ2, 132.0 (CH)ꢁ2, 138.6 (C)ꢁ2, 144.0 (C)ꢁ2, 157.5
(CH)ꢁ2, 163.7 (C)ꢁ2; IR, nmax/cmꢀ1 1768, 1734, 1610, 1591, 1451.
4.3.35. 1-(Biphenyl-2-yl)ethanone dioxime oxalate (30b)
White solid; 95%; 1H NMR (400 MHz, CDCl3), dH 1.74 (6H, s, CH3),
7.12–7.53 (18H, m, CH); 13C NMR, dC 17.4 (CH3)ꢁ2, 126.5 (CH)ꢁ2,
126.8 (CH)ꢁ2, 127.7 (CH)ꢁ4, 127.8 (CH)ꢁ4, 128.5 (CH)ꢁ2, 129.3
(CH)ꢁ2, 129.4 (CH)ꢁ2, 133.0 (C)ꢁ2, 139.0 (C)ꢁ2, 139.8 (C)ꢁ2, 168.3
(C)ꢁ2; IR, nmax/cmꢀ1 1787, 1764, 1684.
4.3.27. Methyl 4,5-dioxo-8-(pent-4-en-2-yl)-1,1-diphenyl-3,6-
dioxa-2,7-diazadodeca-1,7-dien-12-oate (24d)
Red oil; mixture of isomers; 1H NMR (400 MHz, CDCl3), dH 1.04/
1.13 (3H, d, J¼6.9 Hz, CH3), 2.05–3.26 (9H, m, CH, CH2), 3.61/3.68
(3H, s, CH3), 4.98 (2H, m, CH2), 5.63 (1H, m, CH), 7.33–7.61 (10H, m,
CH); 13C NMR, dC 16.9/17.7 (CH3), 20.7/21.2, 24.3/25.7, 29.3/30.4,
31.3/33.3 (CH2), 34.2/39.8 (CH), 52.2/52.3 (CH3), 117.7/117.8 (CH2),
128.8 (CH)ꢁ2, 128.9 (CH)ꢁ2, 129.4 (CH)ꢁ2, 129.5 (CH)ꢁ2, 130.6/
130.7, 131.9, 135.1/135.4 (CH), 131.7, 134.2, 135.0, 158.5, 160.1, 166.4,
173.2 (C); IR, nmax/cmꢀ1 2977, 1755, 1743, 1641.
4.3.36. Biphenyl-2-yl(phenyl)methanone dioxime oxalate (30c)
White solid; 97%; 1H NMR (400 MHz, CDCl3), dH 6.81–7.58 (28,
m, CH); 13C NMR, dC 126.1 (CH)ꢁ2, 126.6 (CH)ꢁ2, 127.2 (CH)ꢁ4,
127.3 (CH)ꢁ4, 127.5 (CH)ꢁ2, 127.6 (CH)ꢁ2, 128.1 (CH)ꢁ4, 128.2