8-Purinyl versus 2-Benzimidazolyl Carbanions: Charge Demands of the Heterocycles and Ligand Properties of the Bis(heteroaryl)methanes(1).
Two new purinyl derivatives, 8-benzyl-7-methylpurine (8) and bis(7-methylpurin-8-yl)methane (9), have been synthesized and their corresponding carbanions investigated in DMSO. The application of our previously proposed pi-charge/shift relationships to the (13)C and (15)N shifts of the carbanions has made it possible to map pi-charges and obtain the values of the charge demand of the heterocyclic rings, a resonance index of the pi-electron-withdrawing power of the substituent. The charge demand of the 7-methylpurin-8-yl substituent is found to be the highest among the previously investigated azinyl and azolyl substituents and is comparable with that of the strongest classical electron-withdrawing functions. The replacement of the fused benzene ring in the benzimidazolyl substituent by a pyrimidine ring containing the nitrogen atoms in appropriate positions causes a considerable increase in the electron-withdrawing capacity of the heterocycle. Spectroscopic and reactivity data confirm the strong electron-withdrawing nature of the purinyl ring. The (13)C NMR spectrum shows the existence of the carbanions of both purinyl derivatives as a mixture of geometric isomers, a consequence of the high double-bond character along the bond linking the carbanionic carbon to C(8) of the purinyl ring. Bis(7-methylpurin-8-yl)methane can be easily converted to its stable NH tautomer by means of basic catalysis. It behaves as an "active methylene" compound giving high-yield condensations with electrophiles. Finally, unlike the corresponding benzimidazol-2-yl derivative, bis(7-methylpurin-8-yl)methane reacts with metal acetates to give neutral methanates [ML(2)] (M = Zn, Cu, Co; LH = bis(7-methylpurin-8-yl)methane), where the ligand is present as an anionic system. On the basis of this and previous data, it is concluded that charge demand plays a strategic role in obtaining stable chelates of this sort.
Abbotto
Alessandro
A
Dipartimento di Scienza dei Materiali, Università di Milano, via Emanueli 15, I-20126 Milano, Italy, and Centro CNR Speciali Sistemi Organici, via Golgi 19, I-20133 Milano, Italy.
Facchetti
Antonio
A
Bradamante
Silvia
S
Pagani
Giorgio A.
GA