N-bromobutanimide → 5'-Amino-5-bromo-2',5'-dideoxyuridine

HRID 1974223Notes

Reaction equation

[NH2:1][CH2:2][C@H:3]1[O:7][C@@H:6]([N:8]2[CH:15]=[CH:14][C:12](=[O:13])[NH:11][C:9]2=[O:10])[CH2:5][C@@H:4]1[OH:16].[Br:17]N1C(=O)CCC1=O>C([O-])(=O)C.[Na+]>[NH2:1][CH2:2][C@H:3]1[O:7][C@@H:6]([N:8]2[CH:15]=[C:14]([Br:17])[C:12](=[O:13])[NH:11][C:9]2=[O:10])[CH2:5][C@@H:4]1[OH:16]

Participants

Conditions

Temperature: 60 °C

Procedure

To a solution of 5'-amino-2',5'-dideoxyuridine (0.113 g 0.5 mmole) in 100 ml of 0.05 M sodium acetate buffer, pH 6.0, is added 0.8 g (2.5 mmole) mercuric acetate. The solution is heated at 60° C for 5 hours and cooled on ice. Chelex 100 resin, 20 g, is added and the slurry stirred for 15 minutes at 0° C. The resin is removed by filtration and 0.177 g (1.0 mmole) of N-bromosuccinimide is added. The solution is stirred at room temperature for 30 minutes. The extent of bromination is followed spectrophotometrically at 300 nm, and the reaction terminated by the addition of aniline-ethanol when the absorbance increase plateaus. The reaction mixture is applied directly to a 2 × 15 cm column of Dowex 50 (H+) resin, the column washed with 200 ml of water, and eluted with 1 molar ammonium hydroxide. The solvent is removed at 40° C under reduced pressure, and the residue crystallized from ethanol-ether to provide 100 mg (69%) of the desired product.

Workup

temperaturecooled on ice
additionis added
stirringThe solution is stirred at room temperature for 30 minutes
customthe reaction terminated by the addition of aniline-ethanol when the absorbance
temperatureincrease plateaus
washthe column washed with 200 ml of water
washeluted with 1 molar ammonium hydroxide
customThe solvent is removed at 40° C under reduced pressure
customthe residue crystallized from ethanol-ether

Sources & evidence

ORD record: ord-778c5af0425c40838192184d0ca09fc6
Source dataset: uspto-grants-1976_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04000260

Reaction notes

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