( 774 ) 



mediate products, additive coiMpouuds or dei'ivati\es of (lie oximes, 

 w hieli occasionally have been separated '). These intermediate products 

 then contain a negative gronp (or the group OK) attached to the 

 nitrogen which changes place with the C-combined alkyl- or ai-vl- 

 group. On subsequent treatment with water the amide is generated. 

 AVe tiieii have ; 



RCR' RCR' RCX + H„0 RC = 



I. II ^ TI. II -^ 111. II ^ IV. I 



NOH NX NR' NHR' 



Thai liydroxyl itself <*an assume tiie function of the group \ wliich 



changes place with R' is sh<»\vu by the interesting oliscrvatious of 



Werner and liuss ■), Werner and Skiba '), Posner ") and Auwers 



and CzERNY ^), who have noticed some cases of the BECKM.\NN-reari-an- 



gement in the absence of any reagent. Dibenzhydroxiuiic acid 



Cg Hj CO CO Cg H5 obtained tVoni «'iilorobenzhvdroxiinic acid 



II 

 NOH 



Cg H5 . Cl bv means of silver benzoate, melts at 95° ; according to 



II 

 NOH 



Werner and Buss it changes aftei- some days spontaneonsly into its 



isomer C« H, CO . NHO CO C« H, m.p. 161°; on heating this takes 



place uiore rapidly. Possner observed that (M*yanobenzaldoxime 



changes into its isomer when simply heated above its melting ])oiut ; 



it first melts at 175^, then solidifies and finally melts again at SOS"". 



Here we consequently lia\(' the direct conversion : 



n-^C . C, H, CH NC . C, H, COH / 



II -^ II =.NC.C«H,COxm 



NOH NH V 



Finally, Auwers and Czerny have found that (V-oxy-///-methyl- 



benzopheiioiioxime: HO . H^ C Cg H^ C-C^ H. partly uuderaoes the 



' II " 



NOH 



BECKMANN-rearrangement when submitted to distillation. 



These observations from Werner and his puj»ils, of Posner and 



of Auwers and Czerny are of fuudamental inqtortance for the niidei'- 



1) Reckmann for instance (Ber. 19. OSS) ohtained C^B.^CICI : NCcH- from (CJI-,). CrNOH 

 and PCI-. It is very proliable that ((J,jHt)^ C : NCI is formed first as an inleraiediale 

 prod net. 



2) Ber. 27, 2198 (1894). 

 •') Ber. 32, 1654 (1899). 

 ^) Ber. 30, 1Ü93 (1897). 

 '-) Ber. 31, 2692 (1898). 



