The chemistry of polycyclic arene imines. V. Reactions of phenanthrene 9,10‐imine with nucleophiles under phase transfer conditions

Reactions of phenanthrene 9,10‐imine (1) with alkyl halides, sodium azide and ammonium thiocyanate in two liquid phase systems were investigated. In the presence of aqueous sodium hydroxide and alkyl halides triethylbenzylammonium (TEBA) salts promote N ‐alkylation of 1 with preservation of the aziridine ring. Tetrabutylammonium (TBA) salts catalyze nucleophilic substitutions in which the three membered ring is cleaved. Aqueous sodium azide reacts with 1 to give trans ‐10‐azido‐9,10‐dihydro‐9‐phenanthrenamine (2) . Ammonium and potassium thiocyanate cause expansion of the aziridine ring; while the unsubstituted imine 1 yields the 2‐thiazolamine derivative 4 , N ‐butylphenanthrene 9,10‐imine (8) froms trans ‐3a,11b‐dihydro‐3‐butylphenanthro[9,10‐ d ]thiazol‐2‐imine (9) with an exocyclic CN bond. The structure of 9 was established by X‐ray crystal analysis.