Syntheses and Structural Characterizations of a Novel Bowl-Type Germanol and Its Derivatives
作者:Kei Goto、Isao Shimo、Takayuki Kawashima
DOI:10.1246/bcsj.76.2389
日期:2003.12
A novel bowl-type triarylgermyl group, tris(2,2″,6,6″-tetramethyl[1,1′:3′,1″-terphenyl]-5′-yl)germyl (denoted as TRMG), was designed, and a germanol and its derivatives bearing this framework were synthesized. X-ray crystallographic analysis of TRMG–OH (5) revealed that there is no OH···O hydrogen bonding between adjacent molecules, although the possible presence of a weak intermolecular OH···π interaction was suggested. In sharp contrast to organogermanols known so far, 5 is extremely resistant to self-condensation; no digermoxane was obtained when 5 was subjected to the conditions under which Ph3GeOH (8) affords the corresponding digermoxane. On the other hand, germanol 5 was readily converted to various derivatives. The crystal structure of TRMG–SH (12) was also determined.
一种新颖的碗型三芳基锗基团,三(2,2″,6,6″-四甲基[1,1′:3′,1″-联苯]-5′-基)锗(简称为TRMG),被设计出来,并合成了带有该框架的锗醇及其衍生物。对TRMG–OH (5) 的X射线晶体学分析显示,尽管可能存在微弱的分子间OH···π相互作用,但相邻分子之间并没有OH···O氢键。与迄今已知的有机锗醇形成鲜明对比,5对自缩合具有极强的抵抗力;在将5置于Ph3GeOH (8) 生成相应的双锗氧烷的条件下,未得到双锗氧烷。另一方面,锗醇5可以很容易地转化为各种衍生物。TRMG–SH (12) 的晶体结构也得到了确定。