反应详情

Saturated aqueous NaHCO3 (70 mL) was added to a solution of 5-chloro-2-methoxynenzensulfonyl chloride (3.83 g, (15.9 mmol and orcinol monohydrate (3.39 g, 23.9 mmol) in di-n-butyl ether (53 mL) and tetrahydrofuran (17 mL). The biphasic solution was mixed vigorously at 50° C. for 7 h then at ambient temperature overnight. The reaction mixture was combined with that from a previous reaction (which used 4.53 g 18.8 mmol of 5-chloro-2-methoxybenzenesulfonyl chloride), the layers were separated, and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic extracts were washed with brine (250 mL), dried over Na2SO4, filtered, and evaporated to give 18.25 g of a clear brown oil. The product was purified by flash column chromatography (1% to 4% ethyl acetate in dichloromethane) to give the title compound (9.86 g, 86%) as a pale yellow oil which crystallized upon standing. 1H-NMR (300 MHz, CDCl3) (7.81 (d, 1H, J=2.6 Hz), 7.55 (dd, 1H, J=8.9, 2.6 Hz), 7.02 (d, 1H, J=8.9 Hz), 6.53 (m, 2H), 6.41 (t, 1H, J=2.2 Hz), 3.99 (s, 3H), 2.24 (s, 3H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C14H13ClO5S: 351.0 (M+Na). Found: 351.1.

1. additionThe biphasic solution was mixed vigorously at 50° C. for 7 h
2. customat ambient temperature
3. customovernight
4. customthe layers were separated
5. extractionthe aqueous layer was extracted with ethyl acetate (2×100 mL)
6. washThe combined organic extracts were washed with brine (250 mL)
7. dry with materialdried over Na2SO4
8. filtrationfiltered
9. customevaporated