Method B. Analogously to that described above 3 (0.201 g, 1 mmol) and 4-nitrobenzaldehyde (0.302 g, 2 mmol)
afforded 11 (0.336 g, 90%).
PMR spectrum (ꢄ, ppm, J/Hz): 8.98 (1H, s, NH), 8.36 (1H, s, H-5), 8.00 (1H, d, J = 8.1, H-3ꢁ,5ꢁ), 7.81 (1H, d, J = 8.9,
H-7), 7.78 (1H, s, H-12), 7.54 (1H, d, J = 8.9, H-8), 7.44 (2H, d, J = 8.1, H-2ꢁ,6ꢁ), 4.26 (2H, t, H-11), 3.21 (2H, t, H-10), 2.02
(3H, s, CH CO).
3
+
+
Mass spectrum (m/z, I , %): 376 (100) [M] , 346 (52.8), 345 (50.7), 333 (50) [M – COCH ] , 303 (52), 318 (4.8)
rel
3
+
[M – NHCOCH ] , 287 (50), 231 (17.4), 198 (18), 184 (3.5), 143 (9.0), 130 (8.3), 101 (6.2).
3
6-Acetylamino-9-(3ꢁ,4ꢁ-dimethoxybenzylidene)deoxyvasicinone (12). Method A. Analogously to that described
above 4 (0.3 g, 1.2 mmol) and 3,4-dimethoxybenzaldehyde (0.216 g, 1.3 mmol) afforded 12 (0.26 g, 54%), C H O N ,
22 21
4 3
mp 314–316°C (aq. DMF), R 0.70 (system B).
f
Method B. Compound 3 (0.1 g, 0.5 mmol) and 3,4-dimethoxybenzaldehyde (0.166 g, 1 mmol) according to the
above method afforded 12 (0.190 g, 88%).
PMR spectrum (ꢄ, ppm, J/Hz): 9.01 (1H, s, NH), 8.31 (1H, s, H-5), 7.75 (1H, d, J = 8.9, H-7), 7.66 (1H, s, H-12), 7.47
(1H, d, J = 7.7, H-6ꢁ), 7.02 (1H, d, J = 8.9, H-8), 6.85 (1H, s, H-2ꢁ), 6.77 (1H, d, J = 7.7, H-5ꢁ), 4.22 (2H, t, H-11), 3.59 [6H,
s, (OCH ) ], 3.17 (2H, t, H-10), 2.02 (3H, s, CH CO).
3 2
3
6-Acetylamino-9-(furfurylidene-2ꢁ)deoxyvasicinone (13). Method A. Analogously to that described above 4
(0.3 g, 1.2 mmol) and furfurol (0.11 mL, 0.127 g, 1.3 mmol, ꢅ = 1.1598 g/cm ) afforded 13 (0.323 g, 81.6%), C H O N ,
3
18 15
3 3
mp 316–318°C (aq. DMF), R 0.77 (system B).
f
3
Method B. Compound 3 (0.1 g, 0.5 mmol) and furfurol (0.082 mL, 0.096 g, 1.0 mmol, ꢅ = 1.1598 g/cm ) afforded
13 (0.14 g, 87%), C H O N , mp 316–318°C (aq. DMF), R 0.77 (system B).
18 15
3
3
f
PMR spectrum (ꢄ, ppm, J/Hz): 8.84 (1H, s, NH), 8.23 (1H, d, J = 2.2, H-5), 7.82 (1H, dd, J = 2.2, 8.7, H-7), 7.42–7.47
(3H, m, H-8,12,5ꢁ), 6.72 (1H, d, J = 3.6, H-3ꢁ), 6.31 (1H, dd, J = 1.8, 3.6, H-4ꢁ), 4.18 (2H, t, J 7.3, H-11), 3.20 (2H, t, J = 7.3,
H-10), 2.01 (3H, s, CH CO).
3
6-Benzoylamino-9-benzylidenedeoxyvasicinone (14). Compound 5 (0.305 g, 1.0 mmol) was dissolved in glacial
3
acetic acid (5 mL), treated with benzaldehyde (0.12 mL, 0.126 g, 1.19 mmol, ꢅ = 1.0498 g/cm ) and refluxed for 3–5 h.
Solvent was distilled off. The solid was recrystallized from aqueous DMF to afford 14 (2.55 g, 64.8%), mp 288–290°C,
R 0.58 (system B).
f
PMR spectrum (ꢄ, ppm, J/Hz): 9.03 (1H, s, NH), 8.42 (1H, d, J = 2.5, H-5), 7.99 (1H, dd, J = 2.5, 9.1, H-7), 7.71 (1H,
t, J = 2.8, H-12), 7.53 (1H, d, J = 9.1, H-8), 7.48 (2H, t, J = 7.4, 8.8, H-3ꢁ,5ꢁ), 7.24–7.26 (3H, m, H-3ꢁ,4ꢁ,5ꢁ), 7.14–7.17 (5H, m,
H-2ꢁ,6ꢁ,2ꢁꢁ,4ꢁꢁ,6ꢁꢁ), 4.22 (2H, t, J = 7.0, H-11), 3.19 (2H, t, J = 7.0, 2.8, H-10).
6-Benzoylamino-9-(4ꢁꢁ-hydroxybenzylidene)deoxyvasicinone (15). Analogously to that described above 5
(0.15 g, 0.5 mmol) and 4-hydroxybenzaldehyde (0.073 g, 0.6 mmol) afforded 15 (0.124 g, 62%), mp 339–341°C (aq. DMF),
R 0.64 (system B).
f
PMR spectrum (ꢄ, ppm, J/Hz): 9.01 (1H, s, NH), 8.39 (1H, d, J = 2.1, H-5), 7.98 (1H, d, J = 8.8, H-7), 7.64 (1H, s,
H-12), 7.49 (3H, d, J = 8.8, H-8, 2ꢁꢁ,6ꢁꢁ), 7.22–7.25 (3H, m, H-2ꢁ,4ꢁ,6ꢁ), 7.14 (2H, t, J = 7.7, H-3ꢁ,5ꢁ), 6.71 (2H, d, J = 8.8,
H-3ꢁꢁ,5ꢁꢁ), 4.23 (2H, t, J = 7.0, H-11), 3.13 (2H, t, J = 7.0, H-10).
6-Benzoylamino-9-(4ꢁꢁ-dimethylaminobenzylidene)deoxyvasicinone (16). Compound 5 (0.305 g, 1.0 mmol) and
4-dimethylaminobanzaldehyde (0.164 g, 1.61 mmol) analogously to that described above afforded 16 (0.337 g, 86.5%),
mp 320–322°C (aq. DMF), R 0.68 (system B).
f
PMR spectrum (ꢄ, ppm, J/Hz): 9.03 (1H, s, NH), 8.48 (1H, d, J = 2.3, H-5), 8.00 (1H, dd, J = 2.3, 8.9, H-7), 7.76 (1H,
t, J = 5.5, H-12), 7.58 (1H, d, J = 8.9, H-8), 7.49 (4H, dd, J = 8.2, H-2ꢁꢁ,3ꢁꢁ,5ꢁꢁ,6ꢁꢁ), 7.41 (2H, dd, J = 8.9, H-2ꢁ,6ꢁ), 7.27 (1H, tt,
J = 8.8, H-4ꢁ), 7.14 (1H, t, J = 8.8, H-3ꢁ,5ꢁ), 4.27 (2H, t, J = 6.8, H-11), 3.18 (2H, t, J = 6.8, 5.5, H-10), 3.07 [6H, s, N(CH ) ].
3 2
6-Benzoylamino-9-(4ꢁꢁ-nitrobenzylidene)deoxyvasicinone (17). The reaction was carried out analogously to that
described above. Compound 5 (0.305 g, 1.0 mmol) and 4-nitrobenzaldehyde (0.166 g, 1.1 mmol) afforded 17 (0.27 g, 61.6%),
mp 326–327°C (aq. DMF), R 0.74 (system B).
f
PMR spectrum (ꢄ, ppm, J/Hz): 9.07 (1H, s, NH), 8.48 (1H, d, J = 2.5, H-5), 8.02 (3H, d, J = 8.8, H-7, 3ꢁꢁ,5ꢁꢁ), 7.81 (1H,
d, J = 2.8, H-12), 7.60 (1H, d, J = 8.8, H-8), 7.50 (2H, d, J = 7.4, H-2ꢁ,6ꢁ), 7.45 (2H, d, J = 8.8, H-2ꢁꢁ,6ꢁꢁ), 7.27 (1H, t, J = 7.4,
H-4ꢁ), 7.14 (2H, t, J = 7.4, H-3ꢁ,5ꢁ), 4.28 (2H, t, J = 7.0, H-11), 3.22 (2H, t, J = 7.0, 2.8, H-10).
6-Benzoylamino-9-(3ꢁꢁ,4ꢁꢁ-dimethoxybenzylidene)deoxyvasicinone (18). Analogously to that described above 5
(0.305 g, 1.0 mmol) and 3,4-dimethoxybenzaldehyde (0.18 g, 1.1 mmol) afforded 18 (0.384 g, 84.7%), mp 314–316°C (aq.
DMF), R 0.57 (system B).
f
266