March 20. 1959
COR.IZfUNICATIONS TO THE
EDITOR
1519
flux to give 2-(T\j-methylphenethylamino)-propionanilide (111), m.p. 65-67', in Sly0 yield. The CH3 A I , k o reduction of I11 with lithium aluminum hydride in tetrahydrofuran afforded 5070 of N2-methyl-N2phenethyl-N1-phenyl-1,2-propanediamine (IV), b.p. ~ When IV was 138-144' (0.2 mm.), n z 7 1.584. OPKBz 'HO acylated with propionic anhydride N- [2-(methylI I1 phenethy1amino)-propyl]-propionanilide (Ib), b.p. 174-175" (0.5 mm.), n * 6 ~1.548, was obtained in S3YO yield. The sulfate, m.p. 110-111", crystallized from ethanol-ether in 85% yield. Anal. Calcd. for CZ1HjON2O6S: C, 59.7; H , 7 . 2 ; X j 6.6; S, i . 6 . Found: C , 59.4; H, 7.4; N , 6.G; s, 7.4. A benzene solution of aniline and 1-(2-bromopropionyl) -piperidine7 was heated under reflux to give 1-(2-anilinopropiony1)-piperidine(V), m:p. 90-91' in S170 yield. The reduction of V wlth a striking similarity. Paper chromatography in lithium aluminum hydride in tetrahydrofuran a system designed to separate closely related cardenyielded 8670 of 1-(2-anilinopropyl)-piperidine (VI), olides3 proved I11 to be homogeneous. It has an b.p. 108-112' (0.4 mm.), nZ9D1.537. Acylation of Rfvalue midway between digitoxigenin (11) and VI with propionic anhydride gave I%-( l-methyl-2- Kaiser's monodigitoxoside.4 Splitting of 0.5 mg. piperidinoethy1)-propionanilide (IC),b.p. 124-128' of I11 in methanol under conditions of transglyco(0.2 mm.), f i z *1.518, ~ in S8y0 yield. The hydro- sidation and paper chromatography of the resulting chloride, m.p. 201-202', was obtained in 887, material in the same system gave a single spot, yield by treating IC with ethanolic hydrogen chlo- coincident in position with digitoxigenin (11). ride and ether. Anal. Calcd. for C17H2iC1N20: X similar quantity of I11 (0.4 mg.) was hydrolyzed C, G5.S; H, 5.8; C1, 11.4; N, 9.0. Found: in a manner to yield the free sugar rather than its C , (35.7; H , 8.7; C1, 11.4; N , 9.3. methyl glycoside. This was likewise chromatographed, but in a system suitable for sugars only. (7) C A Bischoff, Bev 31, 2839 (1898) The result again was a single spot (detected by a ORGANIC CHEMICAL RESEARCH SECTION reagent employed for deoxy sugars5) coinciding LEDERLE LABORATORIES DIVISION AMERICAYCYAVAMID COMPAXY~ ~ I L L I A B M \$'RIGHT, JR exactly with digitoxose (2,G-dideoxy-D-rabo-hexoPEARL RIVER,SEX TORK HERBERT J BRABAYDER pyranose). ROBFRT -1.H A R D \J ,R . The securing of a monodigitoxoside of digitoxiI
