On the Oxidation of Amino-acids and of related substances with chloramine-T

Abstract

Reference has already been made [1916, 1, 2] to the oxidation of certain amino-acids with hypochlorite and with chloramine-T. The latter term is the abbreviated name for sodio-p-toluenesulphochloroamine, a substance which appears to constitute a useful addition to the small-class of neutral oxidising agents. These experiments seemed worth extending, partly because interesting products of oxidation were likely to be met with and also as preliminary to a study of the mode of antiseptic action of substances of the chloroamine group. In the case of glycine, alanine, leucine, and a-aminophenylacetic acid it was found that the first product of oxidation, using one molecule of oxidising agent, was an aldehyde, as is usually the case with hypochlorite oxidation, as shown by Langheld. On using two molecules of chloramine-T for the oxidations, nitriles were formed, sometimes in good yield. With histidine, no aldehyde1 could be isolated, but an excellent yield of cyanomethylglyoxaline was obtained.The present communication deals especially with the oxidation of the neutral salts of glutamic, aspartic, and methylaspartic acids and asparagine, valine and isoleucine. Glutamic actd may be considered first since the reaction is less complex than with the other substances.On acting on a dilute aqueous solution of the mono-sodium salt of glutamic acid (1 mol.) with chloramine-T (1 mol.) an excellent yield of the semi-aldehyde of succinic acid (,-aldehydopropionic acid) is obtained. It is most readily separated and identified by means of its nitrophenylhydrazone, but the substance itself may be isolated and distilled although with considerable 1 It would appear that Langheld's observations on the formation of iminazoleacetaldehyde by the action of hypochlorite on histidine require confirmation.Bioch. xi 6

Reactions of Hypochlorous Acid with Tyrosine and Peptidyl-tyrosyl Residues Give Dichlorinated and Aldehydic Products in Addition to 3-Chlorotyrosine

“…Formation of an aldehyde from an ␣-amino acid by HOCl was first reported at the beginning of the last century (60,61). Recent reinvestigation of the issue showed that formation of a chloramine at the ␣-amino group is the first reaction step (24).…”

Analytical Applications of Chloramine-T

“…If a stoichiometric reaction is to take place between chloramine-r and the substance titrated, no further reaction is allowable. It is surprising that there are no reports of any recent investigation to determine whether there is any further reaction between these two cornpounds, for H. D. Dakin reported, 51 in 1917, that benzaldehyde p-sulfonamide is formed when they are heated together in aqueous solution.…”

Identification of the Eight‐Membered Heterocycles Hicksoanes A–C from the Gorgonian Subergorgia hicksoni

“…Gas chromatography analysis was performed with a Hewlett-Packard HP 5980 gas chromatograph Compound 1 (14.5 mg, 0.03 mmol) was dissolved by sonication in neutral 1 % aqueous solution of chloramine-T (N-chloro-p-toluenesulfonamide sodium salt; 10.26 mg, 0.045 mmol), and the reaction was allowed to run for 10 min. [47] Excess alkali was neutralized with acetic acid. The reaction products were oxidized by Jones reagent under synchronous stirring for 10 min at 50°C.…”