Phenylacetyl chloride → [1-Bromo-6-(3-phenylacetyl-benzo[b]thiophen-2-yl)-naphthalen-2-yloxy]-acetic acid ethyl ester

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Reaction Steps

A mixture of (6-benzo[b]thiophen-2-yl-1-bromo-naphthalen-2-yloxy)-acetic acid ethyl ester (4.35g, 9.86 mmol), phenylacetyl chloride (4.0 mL, 30 mmol) in two portions and tin (IV) chloride (4.3 mL, 37 mmol) in chloroform (220 mL) was refluxed for five hours. It was then allowed to cool to ambient temperature and poured into ice water. It was diluted with additional chloroform and washed with water and brine. It was then dried with anhydrous magnesium sulfate, filtered and solvent evaporated. After stirring the residue in ether and filtering, the filtrate was concentrated and purified by flash chromatography using (1) 25–35% methylene chloride in hexane and 100% methylene chloride and (2) 1–8% ethyl acetate in hexane. It was then purified by HPLC using 85% acetonitrile (0.1% trifluoroacetic acid) in water as the mobile phase. Evaporating the solvent and extracting with ethyl acetate, washing with water and brine, drying with anhydrous magnesium sulfate, filtering, concentrating and drying in vacuo at 60° C. for one hour yielded [1-bromo-6-(3-phenylacetyl-benzo[b]thiophen-2-yl)-naphthalen-2-yloxy]-acetic acid ethyl ester as a yellow semi-solid (0.491 g, 8.89%); mass spectrum (+EI, [M+H]+) m/z 559/561. 1H NMR (500 MHz, DMSO-d6): δ8.28 (d, 1H, J=7.19 Hz), 8.17 (d, 1H, J=1.98 Hz), 8.12 (d, 1H, J=9.01 Hz), 8.06–8.10 (m, 1H), 7.90–7.93 (m, 1H), 7.81 (dd, 1H, J=8.78 Hz and 1.91 Hz), 7.54 (d, 1H, J=9.16 Hz), 7.45–7.50 (m, 2H), 7.13–7.19 (m, 3H), 6.91–6.94 (m, 2H), 5.13 (s, 2H), 4.19 (q, 2H, J=7.13 Hz), 3.81 (s, 2H), 1.22 ppm (t, 3H, J=7.10 Hz). Elemental Analysis for C30H23BrO4S+0.10 mol H2O: Calcd: C, 64.19; H, 4.17; N, 0.00; Found: C, 63.85; H, 4.03; N, 0.00.

Provenance & Evidence