Incorporation of Molecular Nitrogen into Organic Compounds. Titanium Catalyzed Nitrogenation

Abstract

Incorporation of molecular nitrogen into organic compounds 'was realized using a catalytic amount of Tic14 in the presence of excess TMSCI and Li.Various imides were prepared from the corresponding acid anhydrides by use of this catalytic system.The incorporation of molecular nitrogen into organic compounds is very challenging work.These processes would be realized by use of the transition metals.We have already reported the incorporation of molecular nitrogen into organic compoundsl using the titanium nitrogen complex2 and titanium isocyanate complex3 generated from molecular nitrogen, Mg, and Tic14 or TiC13.By the reaction, many heterocycles such as isoindolinone,lb quinazoline,lb indole,l~ and quinoline derivativeslc were synthesized in good yields.These reactions are very interesting, however, an equimolar amount of the titanium isocyanate complex (2) is required for the preparation of the heterocycle (Schemel).Thus, the next problem is to examine whether the reaction proceeds by a catalytic amount of the titanium nitrogen complex (1) or (2).4In the case of the reaction of the titanium -Dedicated to Dr. Arnold Brossi, Scientist Emeritus NIH, on the occasion of his 70th birthday.2 Me3SiCI 7 .Recently, Prof. Hidai reported the catalytic conversion of molecular nitrogen into silylamines using molybdenum and tungsten dinitrogen complexes in the presence of Na and TMSCI.a) M.