反应详情

To a pale pink solution of methyl 4-(4′-formyl-2′-methoxyphenoxy)butanoate (4) (3 g, 12.3 mmol) in DCM (20 cm3) was added dropwise, at 0° C. fuming nitric acid (1.5 cm3, 37.0 mmol). The resulting green solution was stirred at 00° C. for a further 30 mins before being allowed to spontaneously warm to r.t., where it remained for 3 hours. The subsequent bright yellow suspension was poured onto iced water (50 cm3) and extracted with DCM (3×30 cm3). The combined organic phase was washed with sat. NaHCO3 solution (2×50 cm3), followed by water (2×50 cm3) before being dried and concentrated in vacuo providing a bright yellow solid. The desired compound 5 was used without further purification (2.48 g, 68%). A small amount of material (250 mg, 0.84 mmol) was purified via column chromatography (SiO2, CH2Cl2) so that complete characterisation data could be obtained, m.p. 75° C. [lit. (D. L. McMinn and M. M. Greenberg, Tetrahedron, 1996, 52, 3827.) m.p. 76-78° C.]. Found C, 52.7; H, 5.2; N, 4.8; C13H15NO7 requires C, 52.5; H, 5.1; N, 4.7%; Rf 0.44 (SiO2, CH2Cl2); νmax (KBr disc)/cm−1 3100-2700 (m), 1735 (s), 1690 (s), 1290, 1220; 6, (200 MHz, CDCl3) 2.23 (2H, q, J=7.1 Hz, CH2), 2.57 (2H, t, J=7.1 Hz, CH2), 3.71 (3H, s, OCH3), 3.99 (3H, s, OCH3), 4.21 (2H, t, J=7.1 Hz, CH2), 7.40 (1H, s, H-3′), 7.61 (1H, s, H-6′), 10.44 (1H, s, CHO) ppm; δC (100 MHz, CDCl3) 24.1 (CH2), 30.2 (CH2), 51.8 (OCH3), 56.6 (OCH3), 59.6 (CH2), 108.1 (CH), 109.9 (CH), 125.5, 143.8, 151.7, 153.4, 173.2 (COOCH3), 187.8 (CHO) ppm; m/z (FAB) 298 [(MH+), 40%].

1. waitwhere it remained for 3 hours
2. extractionextracted with DCM (3×30 cm3)
3. washThe combined organic phase was washed with sat. NaHCO3 solution (2×50 cm3)
4. custombefore being dried
5. concentrationconcentrated in vacuo
6. customproviding a bright yellow solid
7. customThe desired compound 5 was used without further purification (2.48 g, 68%)
8. customcould be obtained