Chloramine and dimethylchloramine abstract hydrogen from As-H bonds, converting arsine, primary arsines, and secondary arsines to elemental arsenic, diarsines, and tetrasubstituted cyclopolyarsines, respectively. When used in less than stoichiometric quantities and in the presence of an HCl acceptor, free chlorine yields similar products. Secondary arsines react with aminoarsines of the type R2AsNH2 to yield tetrasubstituted diarsines. Several possible mechanisms for the chloramination reactions are discussed. © 1969, American Chemical Society. All rights reserved.