No abstract

No abstract

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%.

Reactions of 1-Chloro-3-buten-2-ol 2955 enins), XI, and in a total synthesis of the sex hormone equilenin, XII. In the latter case the procedures have been refined so that the racemic form of the hormone can be prepared in about 28% over-all yield in eight steps from l-keto-7-methoxy-1,2,3,4-tetrahydrophenanthrene, Ilia. The steps involve formylatioti (step 1) followed by treatment with hydroxylamine (step 2) to produce an isoxazole Va, which is isomerized with alkoxide and methylated (step 3) to give the cyano ketone Vila. Condensation of Vila with dimethyl suc-cinate in the presence of potassium i-butoxide (step 4) affords, in one operation, 15-carbomethoxy-14,15-dehydroequilenin methyl ether, Villa (R' = CHg), which is hydrolyzed (step 5) to the free acid IXa, and decarboxylated (step 6) to give 14,15-dehydroequilenin methyl ether, Xa. Hydrogenation of Xa (step 7) followed by demethylation (step 8) gives df-equilenin XII, which on resolution affords d-equilenin, identical with the natural product.