( 681 ) 



So when I obtained 5-chloro-4-6-dibromo-2-amido-m-xylene as b}-- 

 product in the reduction of 4-6-dibromo-2-nitro-Hi-xylene, I tried to 



CII3 CHs 



Br ,/ \ XO; Bi- ./ \ XHj 



'x J CHj ~* CI I J CHs 



Br Br 



introduce halogen atoms into the core, taking the simplest case, 

 namely, the reduction of nitrobenzene with tin and hjdrochlorid acid. 

 As is well-known, \arious intermediate products ai"e formed in 

 the reduction of nitrobenzene to auiline. The formation of chloro- 

 aniline from nitrobenzene may be explained in the following manner: ') 



C,H,XO, + 4 H = C,H,NHOH + H,0 

 C.H^XHOH + HCl = C,H,NHC1 + H,0 

 C,H,XHC1 -^ C1C,H,NH, {0. + ^j.)- 

 The fact that, in the reduction of niti'obenzene, phenylhydroxylamine 

 occurs as an intermediate compound, has been demonstrated by 

 Bamberger, who has also proved that, on boiling phenylhydroxylamine 

 with hydrochloric acid, 0- and ^^-chloroaniline are formed '). It has 

 also been proved by Lob that 0- and ^j-chloroanilines are formed in 

 the electrolytic reduction of nitrobenzene in alcoholic hydrochloric 

 acid solution '). The object of the experiments to be described was 

 to try and conduct the reduction of nitrobenzene with tin and hydro- 

 chloric acid in such a manner that instetid of aniline, as much as 

 possible chloroaniline was formed. 



The experiment had, therefore, to be carried out in sucli a way, 

 that the phenylhydroxylamine formed was not at once further reduced 

 to aniline, but to give this substance an opportunity to be converted 

 into chloroaniline, under the influence of hydrochloric acid. The 

 conditions were also to be such that the phenylchloroamine CsH^NHCl, 

 which is formed intermediary, could be readily converted into chloro- 

 aniline. 



The intramolecular conversion of phenylchloroamine into 0- and 

 ^-chloroaniline is, however, but little known, as the first substance 

 is very unstable but the conditions under which acetylchloroanilide 

 is converted into />chloroacetanilide have been closeh' investigated. 

 It has been shown that this reaction is very much accelerated by 

 increase of the temperature and also by addition of iiydrochlorid acid*). 



1) LÖB, Die Electrochemie der OrganischenVerbindungenp. ](56, oeAuflage(1905). 



-) Ber. 28, 451. B.^mberger and Lagutt, Rer. 31, 1503. 



s) Ber. 29, 1S96. 



*) BE.NDER, Bar. 19, 2273. Bl.\nksma, RecueU 21, 3ÜG, 22, 290. 



