THE BEHAVIOUR OF PHENANTHRENEQUINONE DERIVATIVES TOWARDS ACYCLIC AMINOPHOSPHINES

Abstract

Tris(dimethylamino)phosphine (IIIa) and/or Bis-dimethylaminophenyl-phosphine (IIIb) react with 9,10-dihydro(9-dicyanomethylene)phenanthrene-10-one (Ib) to produce 1:1 adducts which have the aminophosphonium dipolar ion structure (V) in the crystalline state and in solutions. The 1:1 adduct isolated from the reaction of IIIb with 9,10-phenanthrenequinonemonoimine (Ic) has a similar dipolar structure (XII) in the crystalline state. Solutions of the latter contained the same molecular species (XII) in equilibrium with a cyclic aminophospholene species (XIII). Only decomposition products could be observed from the reaction of IIIa with Ic. The products in this case were the phosphoroamidate (X), 9,10-phenanthrenequinone (Ia) and phenanthroxazine XI. A mechanism is proposed to explain the formation of these compounds.

Key Words:

• Tris(dimethylamino)phosphine (IIIa)
• bis-(dimethylamino)-phenyl-phosphine (IIIb)
• 9,10-dihydro(9-dicyanomethylene)phenanthrene-10-one (Ib)
• 9,10-phenanthrenequinonemonoimine (Ic)
• phosphonium dipolar ions (V,XII)
• cyclic aminophospholene ring system (XIII)
• phenanthroxazine (XI)
• hexamethylphosphoroamidate (X)