Hydroxylamines sulfonic acid amides

Other Applications. Hydroxylamine-O-sulfonic acid [2950-43-8] h.2is many applications in the area of organic synthesis. The use of this material for organic transformations has been thoroughly reviewed (125,126). The preparation of the acid involves the reaction of hydroxjlamine [5470-11-1] with oleum in the presence of ammonium sulfate [7783-20-2] (127). The acid has found appHcation in the preparation of hydra2ines from amines, aUphatic amines from activated methylene compounds, aromatic amines from activated aromatic compounds, amides from esters, and oximes. It is also an important reagent in reductive deamination and specialty nitrile production. 

NITRILES Chlorosulfonylisocyanate. Dimethylaluminum amide. Hydroxyl-amine. Hydroxylamine-O-sulfonic acid. Selenium dioxide. Triethoxydiiodophos-phorane. Trifluoroacetic anhydride-Pyridine. Trimethylamine-Sulfur dioxide. 

Citterio, A., Gentile, A., Minisci, F., Serravalle, M., Ventura, S. Polar effects in free-radical reactions. Carbamoylation and a-N-amidoalkylation of heteroaromatic bases by amides and hydroxylamine-O-sulfonic acid. J. Org. Chem. 1984,49, 3364-3367. 

Amines can be obtained under mild conditions from amides by reduction with borane and also from ethylene derivatives with borane and hydroxylamine-O-sulfonic acid or chloramine A modified Schmidt reaction gives good yields of N-subst. trifluoro-acetamides... 

Amide of 2, 5 -tetramethyl-3-imidazoline-l-oxyl-4-carboxylic acid (31). To a suspension of 4-rcrt-butyliminomethyl-2,2,5,5-tetramethyl-3-imidazoline-l-oxyl (68a) (1.12 g, 5 mmoles) in water (10 ml), hydroxylamine-0-sulfonic acid (0.68 g, 6 mmoles) is added with stirring. The solution is washed with ether, then 6 % aqueous H2O2 (10 ml) is added to the aqueous solution and 2n NaOH solution (5 ml) is added dropwise with stirring. The reaction mixture is stirred for 1 h. Amide 31 is extracted with chloroform, rhe extract is dried with MgS04, filtered, and evaporated. The yield is 0.64 g (70 %), m.p. 204-205°C (from ethanol). UV (ethanol), Inm (Ig e) 230 (3.65), 338 (2.58). IR (in KBr), vcm-% 3350 and 3230 (NH2), 1710,1670 and 1620 (C=N). 

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