A methanol solution of commercially available p-nitrobenzyl chloride is 

 refluxed yjxth an excess of norpholine to yield N-p-nitrobenzyl morpholine, 

 Leffler and Volv^iler produced this compound from the same tvj-o reactants 

 in benzene solution (7). The nitrocompound is reduced vrith hydrogen in 

 the presence of Adams' catalyst at tliree atmospheres yielding N-p-anino- 

 benzyl morpholine. This method vfas found to be better than the iron- 

 alcohol reduction en ployed by Leffler and Volvdler (7)» Our yields were 

 9Q% as opposed to a 76/0 yield obtained by the chemical method of the 

 former vforkers. The amino compound is converted to the intermediate 

 diazonium salt by reaction Td.th sodium nitrite and sulfuric acid. Decom- 

 position of this salt with a boiling 70;J sulfui'ic acid solution gives a 

 3^% yield of N~p-hydroxybenzyl morpholine. 



The preparation of N-p-hydroxybenzylaminoethanol is illustrated in Fig, 

 Jl, p-Hydroxybenz aldehyde is added to an ethanol solution of ethanolamine. 

 The Schiff base, II, separates out almost immediately in 77/^ yield. The 

 latter is readily reduced virith hydrogen in the presence of Adams' catalyst 

 at three atmospheres to give a 9$% yield of N-p-hydroxybenzylaminoethanol, 

 isolated as an oil. For aialysis, the compound is converted to the 

 5~nitrobarbituric acid derivative salt. 



For comparison purposes v/ith the benzyl morpholine compounds previously 

 described, the nitro and amino analogues of N^p-hydroxs'^benzylaninoethanol 

 were prepared a? shovm in Fir-;. VII. A methanol solution of p-nitrobenzyl 

 chloride is refltixed with excess ethanolamine to give N-p-nitrobenzyl- 

 aminoethanol in $8% yield. Barbiere reported the synthesis of this com- 

 pound by mixing the t'.ro reactants directly, but the reaction is very 

 exothermic and considerable decomposition may occur (8), Reduction 

 of the nitro compovxnd with hydrogen in tlie presence of Adams' catalyst at 

 three atmospheres yields N-p-aminobenzylaminoethanol in 83/^ of the theo- 

 retical amount. 



The preparation of the diethanol compounds is shovm in Fig, VIII. Barbiere 

 synthesized 2, 2 '-(p-nitrobenzylmino) diethanol by mixing p-nitrobenzyl 

 chloride and diethanolamine (8). However, the reaction, like that for the 

 making of the monoethanol compound by this method, is very exothermic and 

 considerable decomposition may occur. Again, our method consists of re- 

 fluxing a methanol solution of p-nitrobenzyl chloride with an excess of 

 diethanolamine to give 2,2 '-(p-nitrobenzylimino) diethanol in 62;^ yield. 

 Reduction of the nitro compound with hydrogen in the presence of Adams' 

 catalyst at three atmospheres gives a quantitative yield of 2,2 '-(p-amino- 

 benzylimino) diethanol, isolated as an oil. For analysis, the compound is 

 converted to the 5-nitrobarbituric acid salt derivative. Conversion of 

 the amino compound to the corresponding phenol has not yet been accomplished, 

 in view of the knoijvn susceptibility of tertiary amines to nitrous acid under 

 some conditions, the method used in going from 2,2 '-(p-aminobenzylimino) 

 diethanol to the phenol may have to be modified. 



0.3 



