DIAMMONIUM SALTS DERIVED FROM 1,4-DIAZABICYCLO[2.2.2]OCTANE

The syntheses of a range of quaternary diammonium and some monoammoniu m salts derived from 1,4-diazabicyclo[2.2.2]octane with N-alkyl arms o r N-alkyl arms terminated by a functional group are reported. In aqueo us solution they are susceptible to only very slow Hofmann elimination , and the kinetics were investigated for the onioethyl)4-dodecyl-1,4-d iazoniabicyclo[2.2.2]octa ion, which undergoes a base-induced eliminat ion (k(OH) 6.9X10(-4) dm(3) mol(-1) s(-1) at 55 degrees C) consistent with an E1cB mechanism. In aqueous solution, the diammonium cations ar e not oxidized but undergo irreversible electrochemical reduction belo w -1.2V v. Ag/AgCl, with the reduction potential apparently influenced by the electron-withdrawing or -donating nature of substituent arms.