Bromo-acetamide

The partial synthesis from solasodine of nitrogen-containing analogues of ecdysone has been explored.22 In the successful route, 7V,0-diacetylsolasodine (16b) was treated with TV-bromo acetamide and HCI04. The bromohydrin (26a) that was formed was reductively debrominated with chromous acetate and butanethiol to... 

Ladenheim, H., and H. Moeawetz Reaction of polymers vdth reagents carrying two interacting groups II. Bromine displacement from ot-bromo-acetamide and the bromoacetate ion by poly(methacryIic acid) and poly-(vinylpyridine betaine). J. Am. Chem. Soc. 81, 4860 (1959). 

The key steps in the first total synthesis of (+)-momilactone A by P. Deslongchamps et al. were a highly diastereoselective transannular DIels-Alder cycloadditlon and the Prdvost reaction The 3-ketolactone moiety was installed by first treating the tricyclic alkene with A/-bromo acetamide and silver acetate to obtain the trans bromoacetate with excellent diastereoselectivlty. The cIs stereochemistry of the lactone was achieved a few steps later by the intramolecular nucleophilic displacement of the bromide with the carboxylate ion on the adjacent six-membered ring. 

Oxidation, reagents Barium permanganate. Bismuth trIoxide. Blue tetrazolium. N-Bromo-acetamide. Bromocarbamide. N-Bromoiucclnlmldc. l-Butyl chromate. r-Butyl hypochlorite. r-Butylhydroperoxide. Caro i. acid. Ceric ammonium nitrate. o-Chloranll. m-Chloropei benzoic acid. NChloroauccinlmlde. Chromic Mid In dll. HiSOi, in acetone (Jonee reagent)i... 

Strong KIE (4 to 9) are measured in the presence of chromic or ferric acids but small values (1 to 2) are observed with NaOCl, N-bromo acetamide or vanadium V. 

Br14CH2-14CH2OH is obtained in 90% yield from [14C]ethylene by use of A-bromo-acetamide.294... 

It should be noted that A-bromo compounds can act as oxidizing agents e.g., A-bromo-acetamide and NBS oxidize secondary alcohols to ketones, and use of this has been made in steroid syntheses.355 Aldehydes, semiacetals, and finally esters are formed from primary alcohols by NBS, and disulfides from thiols (for references see Homer and Winkelmann354). Iodine is liberated from acidified KI solution, a reaction that can be utilized for quantitative determination of NBS and for detection of unchanged NBS in a reaction. 

Recommended reagents for mild dehydrogenation of primary and secondary alcohols are A-bromoacetamide45 5 and A-bromosuccinimide,456 also the A-halo imides A-bromophthalimide, A-chlorosuccinimide, isocyanuric bromide and chloride, and A-bromohexanolactam. These differ in oxidizing activity under comparable conditions A-chlorosuccinimide and isocyanuric chloride have greater efficiency than isocyanuric bromide but less than A-bromo-acetamide. Because of the mildness of the conditions required they find particular use in stereoselective oxidation of steroid alcohols.455... 

The chemical basis of the inactivation of j8-galactosidase by iV-bromo-acetylgalactosylamine is the alkylation of one of the 21 methionyl residues of the enzyme, also accomplished, though less efficiently, by bromo-acetamide. The identity of this residue, in the polypeptide chain, has not been established, nor is the mechanism of inactivation understood. There is reason to believe that the site-directed reagent binds to a site other than the substrate-binding site since A -bromoacetylglucosylamine also shows a much enhanced activity in alkylation of this same methionyl residue."... 

Early investigations with poly(methacrylic acid) showed that this polymer can catalyze the nucleophilic displacement of bromine ion from a-bromo-acetamide. 

---