Reactions of the potassium salt of 1,7,7-trimethyl-N-nitrobicyclo[2.2.1]heptan-2-imine with bromine and nitrous acid: synthesis of 3-exo-bromo-1,7,7-trimethyl-N-nitrobicyclo[2,2,1]heptan-2-imine, 3-endo-bromo-1,7,7-trimethyl-N-nitrobicyclo[2,2,1]heptan-2-imine, 1,7,7-trimethyl-N-nitro-3-nitrosobicyclo[2,2,1]hept-2-en-2-amine and their reactions with nitrogen nucleophiles.

Abstract

The potassium salt (2) of 1,7,7-trimethyl-N-nitrobicyclo[2.2.1]heptan-2-imine (1) reacted with bromine in both acid and alkaline solutions to give, in high yields, 3-exo-bromo-1,7,7-trimethyl-N-nitrobicyclo[2.2.1]heptan-2-imine (3) and 3,3-dibromo-1,7,7-trimethyl-N-nitrobicyclo[2.2.1]heptan-2-imine (8), respectively. On reaction with morpholine, (3) underwent a bromine epimerization to afford, in high yield, 3-endo-bromo-1,7,7-trimethyl-N-nitrobicyclo[2.2.1]heptan-2-imine (5), whereas 3-endo-bromo-1,7,7-trimethylbicyclo[2.2.1] heptan-2-imine (4) was obtained from (3) with ammonia. Nitrimine (5) reacted with aniline to afford 3-endo-bromo-1,7,7-trimethyl-N-phenylbicyclo[2.2.1]-heptan-2-imine (7). Reaction of (2) with nitrous acid gave 1,7,7-trimethyl-N-nitro-3-nitrosobicyclo-[2.2.1]hept-2-en-2-amine (9) in high yield; this behaved in part as the tautomeric 3-hydroxyimino-1,7,7-trimethyl-N-nitrobicyclo[2.2.1] heptan-2-imine to afford with ammonia, hydrazine, and primary amines the corresponding N-substituted 3-hydroxyimino-1,7,7-trimethylbicyclo[2.2.1] heptan-2-imines in high yields.