The extensive application of the halogen-metal interconversion reaction to aryl halides and the two-stage metalation of a number of halogenated aryl ethers [reactions (I) and (II)] have suggested a study of the effect of orientation, the kind of halogen and the nature of the RLi compound on the reactions of some halogenated phenyl ethers.Orientation.-The first illustrations of the halogen-metal interconversion reaction with bromoaryl ethersla,b,c involved bromine ortho to the ether linkage [reaction (IV)]. In subsequent studies,ld,e however, it was found that it is not necessary to have bromine in the ortho posi-
Iodo Derivatives of Diphenyl Ether ous solution was acidified with hydrochloric acid and the o-nitrobenzene sulfone anilide precipitate was recrystallized twice from alcohol. The yield was 64 g. (85%). The dimethylauiline was removed from the ether layer by washing it three times with dilute hydrochloric acid, neutralizing this solution with sodium hydroxide, and extracting the free amine with ether. The ether solution was dried and distilled. The yield of dimethylaniline was 21.4 g. (85%). The ether solution containing the o-nitrobenzene sulfone methyl anilide was concentrated and a dark, dirty red-brown product was obtained which was then treated with alcoholic sodium hydroxide to hydrolyze any disulfone derivative that might have been formed from the aniline. This solution was then diluted with water and extracted three times with ether, the ether evaporated and the resuiting red-brown solid was recrystallized three times from alcohol. The yield of the pure o-nitrobenzene sulfone methyl anilide was 52 g. (74%).The two purified yields of the above o-nitrobenzene sulfonanilide and methyl anilide were then subjected to the concentrated alkali hydrolysis procedure as described previously (80 g. of sodium hydroxide and 20 cc. of water). The distillates of aniline and methylaniline were extracted with ether, dried and distilled. The yield of aniline was 15.3 g. and of methylaniline 13.1 g. The percentage yield of aniline for this reaction was 71% and for methylaniline, 70%. The over-all yield of aniline was 61.2% while that of methylaniline was 52.4%.
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