2-Bromoethanol → 2-Bromoethyl 2-carboxyphenylacetate

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Reaction Steps

2-Bromoethyl 2-carboxyphenylacetate was prepared from heating 10 g of homophthalic acid (56 mmole) and 21 g of 2-bromoethanol (167 mmole) in 175 ml of benzene with a few drops of conc. sulfuric acid at 90°-110° C. for two hours, yield 64%. TLC shows that it is a pure compound. The cyclization of 2-bromoethyl 2-carboxyphenylacetate with PCl5 was performed by a previous method with modification (Tirodkar, and Usgaonkar, Indian. J. Chem. 7, pp 114-1116 (1969)). 1.15 g of 2-bromoethyl 2-carboxyphenylacetate was heated with 2.1 g of PCl5 in 90 ml of benzene at 70° C. for 2 hrs. The benzene was removed and the residue triturated with petroleum ether. The crude product was purified by silica gel column chromatography with methylene chloride as an eluent to give 560 mg of 3-(bromoethyl)-4-chloroisocoumarin (yield, 46%). IR and NMR spectra show it was the desired product. 100 mg of 3-bromoethyl-4-chloroisocoumarin (0.3 mmole) was heated with 60 mg of thiourea (0.8 mmole) in 5 ml of THF at 70° C. for 2 days to give a yellow solid, 50 mg (yield, 40%), m.p. 167°-169° C. (dec); one spot on TLC, RF=0.7 (Butanol:acetic acid:water=6:1:5); NMR spectrum (d6 -DMSO), δ9.1 (2b, 4H), 7.5-8.1 (m, 4H), 4.6 (t, 2H), 3.6 (t, 2H); mass spectrum (FAB+), m/e=299 (M+ -Br). Anal. Calc. for C12H12N2O3Br1Cl1S2 : C, 37.96; H, 3.19; N, 7.38. Found: C, 37.81; H, 3.28; N, 7.71.

Provenance & Evidence