were used for determination of infrared spectra which were obtained with a Perkin-Elmer infrared spectrometer, Model 12-c. 3a-Hydroxy-11,20-diketo- Alb-pregnene (II).--111 a solution of 30 ml. of acetic acid and 10 ml. of water, 3.065 g. of 3a-hydroxy-21-acetoxy -11,aO-diketo-12a -bromo -AI6-pregnene (I) was stirred for ten minutes a t 15" with 6 g. of zinc dust. The suspended material was removed by filtration, washed \+ith methanol and the combined filtrates were evaporated under reduced pressure nearly to dryness. Addition of water precipitated material which weighed 1.9 g. Crystallization four times fr?m methanol-water gave material which melted a t 220-222 , [cY]'~"D S91' (CHCla), Xms, 235 mp, e 7,400. Sinety-eight per cent. of the theoretical amount of hromide ion was present in the aciii~ous ph:tse.ilnal. Calcd. for CLiH1~O1: C, 76.34; 13, 9.15. Fomtl: C' , 76.10; €1, 9.07. LYhen treatment with zinc was carried out a t 15" for three minutes a 71% yield of I1 was obtained, n1.p. 208-3~~,2Oa-Dihydroxy-ll-keto-Al@-pregnene (III).-The combined mother liquors from the preceding experiment (I1 from 3.065 g. of I ) were concentrated under reduced pressure and yielded 800 mg. of crystalline solid. Recrystallization from ethyl acetate gave a product m-hich melted at 1&3-185", [ ( Y ]~~" D +61' (CHC13). When treatment with zinc was extended to 130 minutes at 30-38", the yield of crude material, m.p. 178-1XOo, [ a ] 2 4~ +60° (CHCld), was 43%. Recrystallization several times from ethyl acetate raised the melting point to 189-190°, [ a ] z 4~ +57" (CEfC13j. This compound did not have an absorption maximum between 225 and 250 m p and did not show an acetate band in the infrared spectrum. It gave a negative a-keto1 test with alkaline 2,3,5-triphenyltetrazolium chloride reagent and a positive test for unsaturation with tetranitromethane. a solution of 990 mg. of 3a-hydroxy-l1,20diketo-~~~-pregnene in 4 ml. of chloroform and 1 rnl. of acetic acid was added 0.33 ml. (130%) of 28.7 N aqueous chromic acid. After vigorous stirring for 15 minutes a t O", 0.33 ml. of 18 N sulfuric acid was added and the mixture was stirred for one hour a t 0". Water and chloroform were added and the organic phase was washed with dilute hydrochloric acid, a 5% solution of sodium carbonate, and with water, dried and evaporated under reduced pressure. Crystallization from mrthanol afforded 446 mg. of product which melted at 196-). 198". Addition of water to the methanol gave 306 mg. as a second crop, m.p. 180-185°. Recrystallization of the firzt crop from methanol raised the melting point to 20*5-210 , Anal. Calcd. for CaH&: C, 76.80; H, 8.39. liound: C, 76.97; H, 8.57.da-Hydroxy-l1,2O-diketopregnane (V) .-Hydrogenation of 500 mg. of 3~~-hydroxy-ll,20-diketo-A~~-pregnene was carried out in 10 ml. of methanol with 1.5 g. of 2% palladium hydroxide on calcium carbonate at room temperature and atmospheric pressure. After 11 minutes the catalyst mas filtered out, the solution was concentrated under reduced pressure, the product was precipitated wit...

March, 1949 0-, m-AND P-t-BUTYLTOLUENES 873

No abstract

386which was induced to crystallize by trituration with 10 ml. of water containing six drops of 6 N hydrochloric acid.Recrystallization of the solid (0.50 9.) from carbon tetrachloride provided 0.380 g. (68%) of XVII, In a similar experiment the oxazolidinedione IV was recovered unchanged after treatment with an equimolar amount of sodium hydride in dry dioxane. Reaction of XX with Aqueous SodiumHydroxide.-To a solution of 0.100 g. (0.261 millimole) of the diamide XX in 5 ml. of 95% ethanol and 1.5 ml. of dioxane at 0" was added 0.261 ml. of 1.00 N sodium hydroxide. After standing a t 0" for five minutes, the solution was diluted with water and extracted with chloroform. The chloroform extract was filtered and evaporated under reduced pressure to a yellow oil which solidified upon trituration with petroleum ether. Further trituration of the solid with water-methanol yielded almost colorless benzyl phenaceturate (0.020 g., 27.1%), m.p. 94-95'.Aminolysis of 1V.-To a suspension of 0.350 g. (0.00104 mole) of the heterocycle in 10 ml. of dry benzene was added 0.242 g. (0.00208 mole) of benzylamine. Reaction took place immediately and after ten minutes the colorless solid which had precipitated was collected by filtration. The yield of N,N'-dibenzyloxamide, m.p. 220.5-222.0", was 0.275 g. (98.5%). Evaporation of the filtrate and tritura-

We wish to report a convenient method for the preparation of relatively large quantities of ¿-butylamine by catalytic hydrogenation of 2,2dimethylethyleneimine. The imine was prepared according to the method of Cairns,1 i. e., by the sulfation of 2-amino-2-methyl-1-propanol followed by alkali treatment of the 2-amino-2-methyl-lpropanolsulfuric acid. It is interesting to note that no isobutylamine was detected from the hydrogenation of 2,2-dimethylethyleneimine, a product expected by cleavage of the nitrogen at the tertiary carbon.Both 2,2-dimethylethyleneimine and ¿-butylamine were obtained in a state of purity and their constants determined and recorded below.