Synthesis of aromatic tetracyclic tin compounds by template and transmetallation reactions: Alkyl vs aryl migration from tin to nitrogen

The syntheses of [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]diphenyltin (1) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]dichloro-phenyl-stannate (2) by template reactions using 3,5-di-tert-butylcatechol, aqueous ammonia and SnPh2Cl2 are reported. We also report the syntheses of compounds 2, [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]trichloro-stannate (4), [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)methylamine]chloro-methyltin (5), and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)-n-butylamine]n-butyl-chlorotin (6) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]n-butyl-dichloro-stannate (7), performed by transmetallation reactions of the octahedral zinc coordination compound Zn[3,5-di-tert-butyl-1,2-quinone-(3,5-di-tert-butyl-2-hydroxy-1-phenyl)imine]2 (3) with SnPhCl3 or SnPh2Cl2, SnCl4, SnMe2Cl2, Sn(nBu)2Cl2 and Sn(nBu)Cl3, respectively. The X-ray diffraction structures of compounds 1, 2, 4 and 6 are reported. The transmetallation reactions with Sn(alkyl)2Cl2 afforded pentacoordinated tin compounds, where an alkyl group migrated from tin to nitrogen, while similar reactions with Sn–Ph compounds did not present any phenyl group migration.

SnPh2 (1) and SnCl2Ph stannate (2) derived from tetraalkyl diphenolamine were prepared by template reactions using 3,5-di-tert-butylcatechol, NH4OH and SnPh2Cl2. Compounds 2 and SnCl3 stannate (4), SnClMe (5), SnCl(nBu) (6) and SnCl2(nBu) stannate (7), were prepared by transmetallation of a Zn complex with PhSnCl3, Ph2SnCl2, SnCl4, SnMe2Cl2, Sn(nBu)2Cl2 and Sn(nBu)Cl3. X-ray diffraction analyses of 1, 2, 4 and 6 are reported. Transmetallation reactions from Sn to N occurs only for alkyl and not for phenyl groups.Figure optionsDownload as PowerPoint slide