- The Germanium-Carbon Bond Cleavage Reaction of (Germylmethyl)amine Derivatives. Mechanism and Stereochemistry
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A facile cleavage reaction of the germanium-carbon bond of (germylmethyl)amine derivatives to give a germyl anion and an azomethine derivative was developed.The effects of substituents such as phenyl, benzyl, and ethyl groups on the germanium and nitrogen atoms of the (germylmethyl)amine derivatives on the cleavage reaction were investigated.The mechanism was also investigated based on the stereochemistry of the cleavage reaction using an optically active organogermanium compound.
- Terunuma, Daiyo,Masuo, Koujiro,Kizaki, Hiroaki,Nohira, Hiroyuki
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p. 160 - 164
(2007/10/02)
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- Facile Cleavage of Ge-C Bonds of N-(Germylmethyl)benzylamine Derivatives. Generation of Germyl Anions
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The reactions of N-(germylmethyl)benzylamine derivatives with butyllithium were carried out.Facile cleavages of Ge-C bonds of the N-benzylgermylmethylamine derivatives giving the corresponding germyl anions and N-pentylbenzylamine were observed.The reacti
- Terunuma, Daiyo,Kizaki, Hiroaki,Sato, Takashi,Masuo, Koujiro,Nohira, Hiroyuki
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- The effect of substituents on the structure and reactivity of organogermanium anions
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The replacement of the ethyl group in Et3GeH by a phenyl group was shown by equilibrium metallation to halve the pKa value compared with analogous CH acids.NMR showed that the decreased acceptor effect of the phenyl group in the PhEt2Ge- anion is caused by a considerably reduced contribution of the mesomeric effect to anion stabilization compared with what happens in the corresponding carbanions.At the same time, the stabilization of the organogermanium anion increases the role of ?-polarization of the aromatic substituent and this contribution is comparable with the mesomeric effect value.A stabilizing effect of organosilicon and organogermanium substituents due to a high degree of polarizability has been shown by concurrent methanolysis of Et3GeLi and REt2GeLi (R=Me3Si, Et3Si, Me3Ge, Et3Ge, t-Bu, Ph).An unexpected reaction of the trimethylsilyl anion with the Me3SiGeEt2- anion leading to diethylgermane dianion, Et2Ge2- has been revealed.The existence of this process supports the suggested absence of (d-p)? interaction in germanium anions with organo-silicon and -germanium substituents.
- Pigarev, S. D.,Bravo-Zhivotovskii, D. A.,Kalikhman, I. D.,Vyazankin, N. S.,Voronkov, M. G.
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- Photochemical Reactions of Aryltriethylgermanes and Diethyldiphenylgermane
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Aryltriethylgermanes and diethyldiphenylgermane were found to split easily to generate germyl radicals by irradiation with a medium-pressure mercury lamp in hexane or cyclohexane.The germyl free radicals produced reacted with hydrocarbon radicals generated from the solvent by hydrogen abstraction either by recombination or by disproportionation.
- Kobayashi, Michio,Kobayashi, Masanori
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p. 2807 - 2810
(2007/10/02)
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