Methyl chloroacetate → HCID 73035684, compound

Participants

Reaction Steps

NaN3 (22.2 g, 341 mmol) was added slowly to a solution of methyl chloroacetate (20.0 mL, 227 mmol) in DMSO (100 mL). After stirring at room temperature for 24 h, water (150 mL) was added and the mixture was extracted with Et2O (3×100 mL). The combined organic fractions were dried (MgSO4) and concentrated in vacuo to 50 mL. Then, a solution of aldehyde 15 (5.37 g, 25.0 mmol) in MeOH (50 mL) was added and the mixture was cooled to −30° C. After that, the reaction mixture was treated with 5.4 M NaOMe/MeOH (35.0 mL, 189 mmol) within 30 min at −30° C., warmed to 0° C. and diluted with MeOH (50 mL). After stirring for 16 h at 0° C., water (200 mL) was added and the mixture was extracted with CH2Cl2 (3×200 mL). The combined organic fractions were washed with brine (200 mL), dried (MgSO4), and the solvent was removed in vacuo to give 16 (6.84 g, 88% from 15) as a pale yellow solid that was used for the next step without further purification. 1H NMR (300 MHz, CDCl3): δ=3.84 (t, J=6.1 Hz, 2 H, 2″-H2), 3.87, 3.88 (2×s, 6 H, OMe, CO2Me), 4.29 (t, J=6.1 Hz, 2 H, 1″-H2), 6.83 (s, 1 H, 1′-H), 6.87 (d, J=8.5 Hz, 1 H, 5-H), 7.36 (dd, J=8.5, 2.1 Hz, 1 H, 6-H), 7.53 (d, J=2.1 Hz, 1 H, 2-H) ppm; 13C NMR (50.3 MHz, CDCl3): δ=41.6 (C-2″), 52.8 (CO2Me, 56.0 (OMe), 69.3 (C-1″), 111.5 (C-2), 116.2 (C-5), 123.4 (C-2′), 125.4, 126.0, 126.2 (C-1, C-1′, C-6), 147.1, 150.9 (C-3, C-4), 164.1 (C═O) ppm.

Provenance & Evidence