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NotesVol. 70 enediamine |di hydrochloride was found to be 0.86 c./m./ mg. This indicates that 2.6% of the succinic acid radioactivity was in the methylene carbon atoms.Oxidation of Malic Acid.-To a solution of 109.7 mg. of C14-labeled malic acid (275 c./m./mg. or 30,100 c./m. total.) in 10 ml. of 1.0 N sulfuric acid in a 100-ml. flask equipped with nitrogen inlet bubbler, reflux condenser and dropping funnel was added 20 ml. of 0.15 M chromic acid solution during two hours on the steam-bath.The carbon dioxide evolved was collected in carbonatefree sodium hydroxide solution and precipitated with barium chloride to give 326 mg. (101%) of barium carbonate.The specific activity was found to be 81.5 c./m./mg. or 26,600 c./m. total. Acetic acid was obtained from the residual solution upon steam distillation. It was converted to barium acetate (80% yield based on titer of steam distillate) which was recrystallized from water. From the specific activity (2.0 c./m./mg.) and the theoretical yield (112 mg.), the activity in the a and /3 carbon atoms of the malic acid, 224 c./m., can be determined accurately without interference from carboxyl activity. Incomplete recovery of the carbon dioxide and overoxidation of the malic acid is assumed to have caused the loss of carboxyl activity.

of carbon monoxide to increase from 0.26 at 15°t o 0.37 at 100°in the vapor phase vyhereas the yield in paraffin solution increased from 0.01 to 0.30 in the same temperature interval. The difference between the two cases may be due to the Franck-Rabinowitch effect. The yield of ethylene decreased in both cases with increase in temperature, but the change was not very pronounced. Thus the general phenomena in di-«-propyl ketone and in methyl «-butyl ketone are similar.The formation of acetone and propylene in what appears to be a single step with yield independent of temperature is an interesting phenom-

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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.