反应详情

Compound 4 (0.1 g, 0.0302 mmol) was dissolved in DCM (15 mL) and freshly activated 4° A M.S (0.15 g) was added and reaction mixture stirred for 10 minutes. DIPEA (0.215 mL, 1.2 mmol) and DMAP (0.05 g) were added and reaction mixture cooled to 0° C. p-Nitrophenyl chloroformate (0.15 g, 0.0757 mmol) in DCM was added slowly and reaction mixture stirred at 0° C. for 1 hour, followed by an additional 4 hours at room temperature. The remaining procedure was followed as described for compound 5 to obtain compound 6 (E:Z isomers). Yield: 0.11 g (76%). 1H NMR (500 MHz, CDCl3) δ 3.79 (s, 3H, Hn (OMe), for Z), 3.82 (s, 3H, Hn (OMe), for E), 3.99 (s, 3H, aromatic-OMe for Z), 4.00 (s, 3H, aromatic-OMe for E), 4.58 (s, 2H, Hf for Z), 4.71 (s, 2H, Hf for E), 5.21 (s, 2H, Hl for Z), 5.34 (s, 2H, Hi for E), 6.22-6.28 (m, 1H, Hb for Z), 6.44-6.50 (m, 2H, Hb for E), 6.52-6.60 (m, 1H, He for Z), 6.64-6.70 (m, 1H, He for E), 6.84-6.95 (m, 2H, He for Z), 7.30-7.40 (m, 2H, He for E), 7.42-7.50 (m, 1H, Ha for Z), 7.50-7.54 (m, 1H, Ha for E), 7.54-7.58 (m, 2H, Hn for Z), 7.68-7.75 (m, 2H, Hn for E), 7.80-7.90 (m, 4H, Hd for Z and E), 8.08-8.14 (m, 2H, Ho for Z), 8.22-8.30 (m, 2H, Ho for E). 13C NMR (125 MHz, CD3SOCD3) δ 52.3, 52.44 (Cn), 55.4, 56.34 (aromatic-OMe), 65.2, 65.2 (Cf), 67.3, 67.4 (Cl), 70.1, 70.4, 100.2 (Cc), 104.2, 105.3 (Cb), 115.62, 116.9 (Ci), 118.0, 120.04, 121.5, 121.7, 121.75, 122.8, 122.9, 125.3, 126.0, 128.7, 128.9, 129.2, 135.9, 137.3, 145.3, 152.3, 154.4, 155.4, 158.7, 161.7, 168.7 (CO). ESI-MS: [M+H]+ C24H22N3O9 calcd 496.1356, obsd 496.12.

1. additionwas added
2. customreaction mixture
3. customreaction mixture
4. additionwas added slowly
5. customreaction mixture
6. stirringstirred at 0° C. for 1 hour
7. waitfollowed by an additional 4 hours at room temperature