R. L.SHRINER, G. F. GRILLOT AND W. 0. TEETERS
946
Vol. 68
[CONTRIBUTION FROM THE NOYESLABORATORY OF CHEMISTRY OF THE UNIVERSITY OF ILLINOIS]
p-Aminobenzoates of Piperidino- and Morpholinomethylnaphthols BY R. L. SHRINER, G. F. GRILLOTAND W. 0. TEETERS' washed with a small amount of alcohol. Crystallization from 95% alcohol gave colorless crystals which melted at 94.5-95.5'. The yield amounted t o 198 g. (82a/o). ~ ~ &led. l for . c~~H~~O N,N 5.81. : Found: N, 5.69. 1-Piperidinomethyl-2-naphthyl +Nitrobenzoate O C G __ - ~ N H , Hydrochloride.-Fifteen grams of the above naphtho1 base was dissolved in 100 ml. of warm dry toluene and was added to 11.5 g. of p-nitrobenzoyl ~JJ-cH.RI. chloride which had Dreviouslv been dissolved in 100 ml. of dry toluene. The mixture was warmed on a steam cone for five hours. It was then cooled I 11 and filtered. The solid was reyystallized from 95% alcohol and melted a t 184-191 . A yield of 21 g. or (where -NRz are piperidino and morpholino groups) %%of the theoretical was obtained. Upon recrysformulas I and 11. These compounds were de- tallization from 95% alcohol, the compound melted a t sired in order to explore the pharmacological be- 190-191 '. I t formed beautiful light yellow needles. Anal. Calcd. for GsHzrO4NtCl: N, 6.56; C1, 8.32. havior of these isomers. The first step in their Found: N, 6.25, 6.22; C1, 8.21, 8.29. preparation involved carrying out the Mannich2 1-Piperidinomethyl-2-naphthyl pAminobenzoate Hyreaction on a- and &naphthols using formalde- drmhloride.-Ten grams of the purified l-piperidinohyde and piperidine and morpholine, respectively. methyl-2-naphthyl p-nitrobenzoate hydrochloride was The substituted aminomethylnaghthols (111) were suspended in 250 ml. of 95% alcohol and 0.2 g. of platitreated with p-nitrobenzoyl chloride to produce num oxide catalyst was added. Reduction was completed fifteen minutes a t 25' and 40 lb. per sq. in. pressure of the monohydrochlorides of the p-nitrobenzoic in hydrogen. The platinum was removed by filtration and most of the alcohol was evaporated. The amine salt RnNH separated as buff-colored crystals. A yield of 7.3-7.8 g. (aand p) CIOH~OH CloH
