DECOMPOSITION OF A PHOSPHORYLATED TRIAZOLINE - EVIDENCE FOR ABSENCE OF REARRANGEMENT OF NORBORNYL SKELETON

Diethyl phosphorazidate (II) and norbomene (II) condense in benzene to give a phosphorylated amidate VI as major product and two minor products, one tentatively identified as an N-phosphorylated eneamine. 5,6-Dideuteronorbornene undergoes the same reaction to give the analogous deuterated products. Hydrolysis of the 5,6-dideuterated phosphorylated amidate XII gave 5,6-dideuteronoreamphor XIV in high yield; XIV was synthesized by deuteration of dehydronorcamphor XVI, On the basis of this evidence and previously obtained kinetic data, the phosphorylated triazoline intermediate formed initially from I and II is postulated to decompose by a highly concerted process in which hydrogen is transferred from C-2 to C-3 in conversion to VI without any major skeletal rearrangement of the norbornyl system. © 1969.