Dimethyl malonate → HCID 57613442, compound

Participants

Reaction Conditions

Reaction Steps

To a suspension of NaH (1.98 g, 50 mmol, 60% in oil) in DMSO (20 mL) is added dimethyl malonate (5.67 mL, 50 mmol) at 23° C. (cooled by ice-water if necessary). After the evolution of hydrogen has ceased, 4-chloro-6-methylsulfanyl-pyrimidine 2 (3.22 g, 20 mmol) is added. The reaction is further heated at 80° C. for 5 hours. The reaction mixture is then cooled to room temperature, and quenched with saturated NH4Cl solution (50 mL). The organics are extracted with ethyl acetate (3×60 mL). The combined organic layers are washed with brine (2×) and dried over Na2SO4, filtered and concentrated. 50 mL of hexanes are added to the residue and heated at 60° C. for half hour and then cooled to room temperature. The solid is filtered and washed with hexanes to afford 2-(6-methylsulfanyl-pyrimidin-4-yl)-malonic acid dimethyl ester. (If necessary, the hexanes washing can be concentrated and purified by silica gel flash chromatography eluting with ethyl acetate in hexanes from 0% to 40% to afford additional product). 1H NMR 400 MHz (DMSO-d6) Compound A δ 8.92 (s, 1H), 7.53 (s, 1H), 5.20 (s, 1H) 3.70 (s, 6H), 2.56 (s, 3H); Compound B (tautomer of A, the structure is tentatively assigned) 8.37 (s, 1H), 7.34 (s, 1H), 3.66 (s, 6H), 2.48 (s, 3H).

Provenance & Evidence