( rri ) 



nionf" (Anior. ('hom. .1. 7, 29.40 (1003)). Ho tlioii a,n-i\ os nt tlio fol- 



lowiii*!,' N'ioW'S. 



Tlie analogy of llio IIokm WN-lraiisforDialioii of llio ainidos into 

 amines willi llio UKcKMANN-roanaiiu-omoiil (aii aiialoü;y (irst pointed 

 onl hv Hoo(;kwf,i{|''1' and \ \n Dokt (Koe. e.oT!), 8.J7:> etc.)) and 

 the tact Ihal tho acid a/,i(h's of (Virrns are coin-oi-fcMl with elimina- 

 tion of niti'ogen into I ho same isocyanatos which occur as inter- 

 mediate products in tlie HoFMAN\-ti-ansfonnation, induces Stikglitz 

 to attempt to o\|)hxin tlieso reactions from a same point of view. 

 He believes that in tho thi'oo above transformations there must be 

 formed intermediate molecnle-residnes containing' unixalent nitrogen; 

 with the azides for instance CH^dO.N.N., -^ (ül.CH) . N + N.,; with 

 the bromoamides for instance, CH.CONHBr-^CIl.CO.N -f HBr. These 

 molecnle-residnes are then snp})osod to be converted straight into 

 the isocyanate: (!Il, — (!() . N ^ (!()N(!I[.,. In ordoi' to arrive, in tho 

 transformation of oxinies into amides, at such mok^'ules with univalent 

 N-atoms, StikctUtz assumes that first of all \\V\ is attached to the 

 oxime owing for instance to tlio action of PC!,. il.,C = N()H+HCl 

 -^ RjCCl — NHOIl; this additive comj)ouii(i under the intluence of 

 POlj then loses one mol., of water and gi\es RjCCl — N which 

 molecnle-residne is thou supposed to bo comei'ted into RCXM^NR, 

 which on treatmeul \vilii water yiehls llio amide. 



Now, first of all if is difficult lo soc whoiv tho HCl, which gets 

 attached to tho o.ximo, is lo como from; it is of course known that 

 some oxiinos yield with IH'l. couipouiids such as Iv./ICIN with 

 formation of IKM, bul lliis is uol llie foruialiou which vStikgt.itz had 

 in mind. We also fail lo see how sul[»liuric acid, acling as d(diydra- 

 ting I'oagonl will, iu llio roarraugemeiil, oaiiso a uiol. of waloi' to 

 be first allaclie(l and llioii lo bo again olimiiialed ; neilhor do ^^•o 

 understand ho\v llio Irausformalioii under ili(> iulluenco of, say, r.^(),, 

 or Zn ('b, can be i-eooncilod with llio ideas of STiK(;i,rrz. Kinally, 

 Stikolitz himself admils of his own theory Ihal "it does not agree 

 so well with the more obscure relations of the theory of stereo- 

 isomerism of ketoximes and their influence on the rearrangement 

 of these isomers. It is hoped that future work will remove this 

 difliculty". (x\m. Ch. J. 7, 29, (37). The difficulty is this, that Stikolitz 

 theory utterly ignores a fact of fundamental importance, namely the 

 formation of two different amides from the stereoisomerie ketoximes; 

 these according to Stikcjlitz ought to lead to the same intermediate 

 product from which I he same amide only conld be formetl. And 

 finally the transformalioiis of an oxime into the isomeric amide 

 without any reagent whatever, as observed by Wekeer and his 



