117 



lost liydrobromic acid, leaving monovalent nitrogen, which, by its reac- 

 tivity, drew to itself the radical originally attached to carbon. As Stieg- 

 litz has pointed out, this explanation would account for the Beclimanu 

 rearrangement, and for that of the acid azides. 



It seemed not without interest, therefore, to dcteraiiue experimentally 

 the position of the amide hydrogen in the halogen amide molecule. The 

 two possible positions of this atom. K CO— N H/Cl and EC— (OH)=N CI, 

 correspond to the two classes of alkyl derivatives, chlor alliyl acid amides. 

 R CO N R/Cl, and chlorimido acid esters, whose properties are now 

 known. But the fact that the salts of such a molecule may have a differ- 

 ent constitution from that of the free acid would make quite uncertain any 

 conclusions drawn from the results obtained from the usual methods of 

 introducing an alkyl X'adical. 



Von Peckmann has shown tliat substances of an acid character react 

 readily with diazomethane. forming a methyl der;-. :itive of the substance, 

 the methyl entering where the hydrogen was attached. As the reaction 

 is carried out with the free acid in absolute ethereal solution tlie proba- 

 bility of a rearrangement of the molecule dui-ing the process of methyla- 

 tiou is reduced to a minimum. Ransom has shown, also, in two cases, 

 that this method of methylation can be used to advantage in deciding 

 delicate questions of constitution. 



With these ideas in view, the following work was undertaken: Benz- 

 chloramide is best made by adding a solution of chloride of lime to a cold 

 saturated solution of benzamide, which had previously been acidified 

 with acetic acid, and extracting the oil which is formed with ether. 

 On drying the ethereal solution with calcium chloride and evaporating 

 the ether in vacuo without heating, a crystalline residue results which 

 after recrystallizing from benzol was found to be 98.1 per cent. pure. 

 The purity was determined by finding the percentage of active chlorine 

 in the substance, by adding potassium iodide to a dilute alcoholic solution 

 and titrating the free iodine with sodium thiosulphate. An ethereal 

 solution of diazomethane was then prepared and some of the benzchlora- 

 mide. suspended in a little ether, added to it until the yellow color of 

 the diazomethane had nearly disappeared. Nitrogen was evolved in large 

 quantities. When the action had ceased the ether was evaporated and 

 there was left an oil with a peculiar but not unpleasant ethereal odor. 

 The oil did not solidify even in a freezing mixture. Some of it was dis- 

 solved in ligroin and dry hydrogen chloride passed into the solution. 



