Phosphanalkylene, 55 Reaktionen von Alkylidentriphenylphosphoranen mit nitrierenden Reagentien

Phosphane Alkylenes, 55.— Reactions of Alkylidenetriphenylphosphoranes with Nitrating Reagents The reaction of phosphonium ylides 1 with N2O4 (2) is strongly influenced by the natur of the substituents of the starting ylide. Formation of α-nitro-α-nitrosoalkanoates 8, nitrolic acid 11, and nitriles 13 was realized. Nitration at the phenyl group of benzylidenephosphoranes 24 or at the γ-position of allylidenephosphoranes 30 accompanied by transylidation and oxidation processes leads to the formation of nitro-substituted ylides 26 and 32, respectively. Strongly basic ylides and ethyl nitrate (34) undergo complex reactions as is shown in the formation of the aziridinyl-substituted ylide 40 from ethylidenetriphenylphosphorane (9) and 34. Allylidenetriphenylphosphoranes 41 are nitrated by ethyl nitrate (34) at the γ-position affording (γ-nitroallylidene)triphenylphosphoranes 43, from which nitro dienes 45 are available. In the reaction of 1-(dimethylamino)-2-nitroethylene (46) with phosphonium ylides nitro-vinylation of the starting ylide takes place.