Synthesis and characterization of 3- and 4-phenylgermatranes: X-ray crystal structures of N(CH 2CH 2O) 2(CH 2CHPhO)GeZ (Z=F, OSiMe 3, CCPh) and N(CH 2CH 2O) 2(CHPhCH 2O)GeOH

Abstract

Reaction of excess of product A [(HOCH 2CH 2) 2NCH 2CH(Ph)OH ( 1):(HOCH 2CH 2) 2NCH(Ph)CH 2OH ( 2)=9:1] with GeCl 4 led to a mixture of 1-chloro-3-phenylgermatrane ( 3) and 1-chloro-4-phenylgermatrane ( 4). Compound 4 was isolated in yield 9% from this mixture. Reaction of (EtO) 3GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane ( 5) was prepared in yield 31% by treatment of (EtO) 3GeCCPh with product A. Reaction of product A with mixture of GeO 2 and H 2O produced N(CH 2CH 2O) 2(CH 2CHPhO)GeOH ( 6) in yield 73%. The presence of N(CH 2CH 2O) 2(CHPhCH 2O)GeOH ( 7) among the products of this reaction was confirmed by 1H-, 13C-NMR spectroscopy and X-ray analysis. N(CH 2CH 2O) 2(CH 2CHPhO)GeF ( 8) is formed by the treatment of 6 with BF 3·Et 2O. N(CH 2CH 2O) 2(CH 2CHPhO)GeOSiMe 3 ( 9) was obtained by silylation of 6 with (Me 3Si) 2NH or Me 3SiCl–Et 3N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded [N(CH 2CH 2O) 2(CH 2CHPhO)Ge] 2O ( 10). 9 reacted with SOCl 2, Me 3SiBr and Me 3SiOTf to give N(CH 2CH 2O) 2(CH 2CHPhO)GeX ( 3, X=Cl; 11, X=Br; 12, X=OTf), respectively. Reaction of 11 with Et 3SnOMe led to the formation of N(CH 2CH 2O) 2(CH 2CHPhO)GeOMe ( 13). Germatranes N(CH 2CH 2O) 2(CH 2CHPhO)GeY [ 14, Y=Flu (fluorenyl); 15, Y=N(SiMe 3) 2] were obtained from the nucleophilic substitution of the substituent X in N(CH 2CH 2O) 2(CH 2CHPhO)GeX (X=OSiMe 3, Br) with the corresponding LiY. All compounds were characterized by 1H- and 13C-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5 and 7– 9 were determined by X-ray diffraction studies.