Date of Award
N-Cyclohexyl -2-methylbenzylamine was metalated with two equivalents of n-butyllithium activated with one equivalent of tetramethylethylenediamine (T.M.E.D.A.) , and the solvent system, time, and temperature were varied to establish a maximum yield . It was experimentally found that a thirty minute ice-water bath metalation in diethyl ether, followed by a fifteen minute condensation with benzophenone in refluxing diethyl ether gave the best yield with the benzophenone electrophile. The product was characterized by N.M.R. and found · to be 2- ( cyclohexylamino)-2-(2-toluyl ) -1 ,1-diphenylethanol (the benzylic adduct) in a 29% yield.
When N-cyclohexyl -2-methylbenzylamine was metalated for three hours in an ice-water bath using diethyl ether as the solvent, then condensed wi th excess dry ice, two products were isolated with near quantitative total yield. While the products were not amiable to characterizati on by melt point or N.M.R. it was assumed that they are amino acids. It is also possible that the two products are different salts of the same amino acid.
N- (2-toluyl) -benzylamine was metalated with two equivalents of n-butyllithium activated with one equivalent of T.M.E.D.A . and the solvent system, temperature, and time were varied to give the maximum yield of the benzophenone adduct . It was experimentally found that maximum yield occurred in diethyl ether with a thirty minute metalation in an ice-water bath, and fifteen minute condensation with benzophenone in refluxing diethyl ether. A maximum yield of 69.2% of ether N-(2-toluyl -6-diphenyl-hydroxymethyl )-benzylamine, or N-(2-toluyl)-2-diphenyl-hydroxymethylbenzylamine, the (orth-adducts) were obtained.
N-(2-toluyl)-benzylamine was metalated in hexane wi th two equivalents of n-butyllithium activated with one equivalent of T.M.E.D.A. for thirty minutes in an ice-water bath , then condensed with benzophenone at reflux for fifteen minutes. Two products were obtained that were not fully characterized , but 33% of the product appeared to be the ortho-adduct(s) and 67% of the product appeared to be 2- (2-amino-N-benzylphenyl)-1 , 1-diphenylethanol ,the (side-chain adduct) . With a combined overall yield of 32.8% of theoretical .
Franks, Richard Patrick, "DILITHIATION REACTIONS OF N-SUBSTITUTED BENZYLAMINES" (1985). Theses, Dissertations & Honors Papers. 322.