Acetonitrile → Ethylcoumarin-3-carboxylate

Participants

Reaction Steps

A 1.0 g (1.8 mmol) sample of bis-iodoethoxy-coumarin (from Example 32 or Example 34) and 0.47 g (1.8 mmol) of 1,4,10,13-tetraoxa-7,16-diazacycloctadecane (i.e., 4,13-diaza-18-crown-6) were separately dissolved in 50 ml portions of dry acetonitrile. The combined solutions (100 ml total) were refluxed under nitrogen for six days in the presence of 5 equivalents (0.94 g) anhydrous sodium carbonate. During the reaction, the coarse sodium carbonate was converted to an extremely fine powder. The cooled reaction mixture was filtered and the solution was evaporated to dryness in vacuo. The residue was dissolved in methylene chloride, and the solution was filtered. Evaporation of the methylene chloride using the rotary evaporator at aspirator pressure, followed by oil pump pressure, gave a yellow foam (>100% of the calculated yield). The crude product was purified by chromatography on deactivated neutral alumina first using methylene chloride to elute unreacted starting materials, followed by a 1-5% ethanol/methylene chloride mixture to elute the product. About 50% of calculated amount of the product was recovered, consisting essentially of the desired product (VI). LRMS FAB (triethanolamine) calculated m/e for C28H40N2O10 was 564.27, whereas the observed m/e was 587, [VIII(Na)] +; free [VII]+ was not observed. UV (phosphate buffered saline) Imax =374 nm, 312 nm. Fluorescence (phosphate buffered saline) showed Iex =371 nm and Icm =453 nm.

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