Preparaton of the Dess-Martin Periodinane; 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-oneSyntheticPage 51 (2001)
Submitted 15th Aug 2001, published 15th Aug 2001
A contribution from the Caddick Group, Sussex
Potassium bromate (15.2 g, 91 mmol, 1 equiv) was added over a 30 minute period to a vigorously stirred solution of 2-iodobenzoic acid (17.2 g, 69 mmol, 0.75 equiv) and 14.6 mL of 0.73 M H2SO4. The temperature of the reaction was maintained below 55 oC by the aid of an ice bath. The resulting mixture was warmed to 65 oC and stirred for 4 h. The slurry was cooled to 0oC, filtered and washed with water (200 mL), ethanol (2x20 mL) and dry ether (3x20 mL) leaving a slightly pink solid.
To a stirring solution of the pink solid [1-hydroxy-1,2-benziodoxol-3(1H)-one] (20g, 71 mmol, 1 equiv) in acetic anhydride (80 mL, 286 mmol, 4 equiv) was added TsOH.H2O (100 mg). The flask was equipped with a drying tube and was heated in an oil bath at 80 oC for 2 h. The resulting brown slurry was cooled to 0 oC in ice-water and filtered thruogh a fritted glass funnel. The resulting white solid was washed with anhydrous ether (5x50 mL) resulting in a white crystalline solid (15.2 g, 40 %)
This procedure has been succesfully carried out numerous times within the group on scales ranging from 5 g to 30 g of the produced D-M reagent. The literature claims that the first formed product is explosive but we have had no problems thus far. However, the preparation should only be carried out behind a blast shield. One problem with the first part of this procedure is that stirring becomes very difficult when addition of the potassium bromate is almost complete and hot pockets are produced in the mixture. This is prevented by the use of an overhead stirrer. The D-M reagent should be stored in a freezer in an amber bottle.
1H nmr (300 MHz, CdCl3) 2.26 (3H, s), 7.71 (1H, dt, J=0.9, 7.8 Hz), 7.92 (1H, dt, J=1.5, 7.4 Hz), 8.00 (1H, d, J=8.1 Hz), 8.25 (1H, dd, J=1.2, 7.5 Hz)
Dess, D.B.; Martin, J.C.; J. Org. Chem., 1983, 48, 4156; Ireland, R.E.; Liu, L.; J. Org. Chem., 1993, 58, 2899.
Greenbaum, F.R.; Am. J. Pharm, 1936, 17.
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User comments on this page
Thu, 23rd Aug 2001 13:59:40
|For a good example of a dess-martin oxidation, see SP 126.
Thu, 23rd Aug 2001 15:05:31
|See [SyntheticPage 126] for the oxidation of allylic alcohols to enones using the DMP reagent
Wed, 13th Mar 2002 17:30:38
|An nice alternative to the use of KBrO3/H2SO4 in the first step is oxone, see Frigerio, Marco; Santagostino, Marco; Sputore, Simona. A user-friendly entry to 2-iodoxybenzoic acid (IBX). J. Org. Chem. (1999), 64(12), 4537-4538.
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