Additions and Corrections - Reactions Kinetics of Aliphatic Tertiary Chloroethylamines in Dilute Aqueous Solution. I. The Cyclization Process

CHEMICAL REACTIONS OF THE NITROGEN MUSTARD GASES.1 I. THE TRANSFORMATIONS OF METHYL-BIS(β-CHLOROETHYL)AMINE IN WATER

“…Thus, the picrylsulfonate of the linear compound should consume an amount of bicarbonate equivalent to one-half of the picrylsulfonic acid present in this salt. 5. Finally, the isolated picrylsulfonate agrees in melting point and mixed melting point with the hydrolysis product obtained from the dipicrylsulfonate of the compound IX (c/.…”

“…It should be pointed out, however, that after hydrolysis of MBA, the relative amounts of the various end products given in Figure 1 will vary depending upon the concentration of MBA employed. Cohen (5) has shown that in very dilute solution the predominant reaction is hydrolysis to methyldiethanolamine. As the concentration of MBA is raised, however, the formation of dimers is favored and hydrolysis is reduced.…”

Protonation of phosphoramide mustard and other phosphoramides

“…Early experiments have shown that the rates of aziridinium ion formation for related /3-chloroethylamines paralleled the basicities of the nitrogens. 41 The results of this study indicate that the pKa of the N2 of phosphoramide mustard is much lower than that of mechlorethamine and therefore must reflect the effect the phosphoramide mustard group has on the nitrogen basicity. The electronic charge of the phosphoramide group, as expected, also influences the activity of the mustard.…”