V77P0141(DessMartin氧化剂的制备).pdfVIP

Organic Syntheses, Coll. Vol. 10, p.696 (2004); Vol. 77, p.141 (2000). THE DESS-MARTIN PERIODINANE: 1,1,1-TRIACETOXY-1,1- DIHYDRO-1,2-BENZIODOXOL-3(1H)-ONE [ 1,2-Benziodoxol-3(1H)-one, 1,1,1-tris(acetyloxy)-1,1-dihydro- ] Submitted by Robert K. Boeckman, Jr., Pengcheng Shao, and Joseph J. Mullins1 . Checked by Kevin P. Minbiole and Amos B. Smith, III. 1. Procedure Caution: Compounds 1 and 2 are heat- and shock-sensitive compounds, showing exotherms when heated (130°C). All operations should be conducted behind an explosion shield. A. 1-Hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide (1) . A 2-L, three-necked, round-bottomed flask, fitted with a mechanical stirrer, condenser, and an immersion thermometer is charged with 80.0 g (0.48 mol) of potassium bromate (KBrO3) and 750 mL of 2.0 M sulfuric acid (Note 1),(Note 2),(Note 3). The resulting clear solution is heated to 60°C in an oil bath and 80.0 g of finely powdered 2-iodobenzoic acid (0.323 mol) is added in 10-g portions over 40 min (Note 4), (Note 5). The solution becomes red- orange, bromine vapor is evolved, and a white solid begins to separate (Note 6). After the addition is complete, the temperature is maintained at an internal temperature of 65°C for 2.5 hr (Note 3). The reaction mixture is cooled to 2-3°C in an ice-water bath, and the resulting solids are collected by vacuum filtration (Note 7), (Note 8). The filter cake is thoroughly washed successively with 500 mL of cold deionized water, 2 × 80 mL of absolute ethanol , and 500 mL of cold deionized water affording 88.2 g (98% of theoretical) of moist solid iodinane oxide 1 (Note 9), (Note 10). B. 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (2) . A 1-L, three-necked, round- bottomed flask, equipped for magnetic stirring and fitted with an immersion thermometer, is charge