Addition reactions of alkoxygermanes

Addition‐elimination reactions from germanium heterocycles I. Germadioxolanes (XYO) The reactivity of 2‐germa‐1,3‐dioxolanes is studied with unsaturated compounds such as carbonyl compounds (aldehydes and ketones) or heterocumulenes (PhNCO, PhNCS). The formation of mono‐ and di‐insertion derivatives is observed. The structure of these adducts is established and their decomposition process, at atmospheric pressure or at high pressure, is precised. The mechanism of these addition‐elimination reactions is established from 4,5‐disubstitued germadioxolanes. The reaction takes place under steric control. The consecutive elimination reaction proceeds by a mechanism of intramolecular nucleophilic substitution.

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“…La liaison Ge-0 des alcoxygermanes rCagit Cgalement avec divers hCtCrocumulhnes tels que PhNCO [3] ou les carbodiimides [4].…”

Section: Rdactions D'addition-blimination Partir D'hbtbrocyclesunclassified

Réactions d'addition‐élimination à partir d'hétérocycles germaniés du type I. Cas des dioxolannes germaniés

Dousse

Lavayssière

Satgé

1975

Helvetica Chimica Acta

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Réactivité des trialcoylalcoxy‐ et dialcoylalcoxychlorogermanes et de leurs isologues soufrés vis à vis des aldéhydes et des cétones

Dousse¹,

Satgé²

1971

Recl. Trav. Chim. Pays‐Bas

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Aldehydes and ketones add onto the germanium-oxygen bond of triethylmethoxy-and diethylmethoxy-chlorogermanes with formation of the corresponding germanium a etals, the stability, the mode of thermal decompositionThe germanium acetals of hexafluoroacetone are stable. &Elimination reactions are observed from germanium acetals of chloral and hexachloroacetone. The decomposition of the germanium acetals of the aldehydes and ketones takes place, in the presence of HzPtCla, to give the corresponding acetals of the starting carbonyl compounds and trialkylgermanium oxides.Additions and decompositions of the same type are observed in the action of the aliphatic aldehydes on the trialkyl(alky1thio)-and dialkyl(alky1thio)-chlorogermanes. Chloral gives a reversible insertion reaction, however, at 90". besides the ,!?-elimination reaction, a chlorine-methylthio exchange reaction is also observed with formation of tri(methy1thio)acetaldehyde and triethylgermanium chloride.The influence of the inductive effects of the substituents on the germanium or on the carbonyl group in the course of these reactions as well as the catalytic action of the chloroplatinic acid or of zinc chloride seem to confirm the addition mechanism considered. and certain properties o 2 which have been investigated.

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Nouveaux oxamétallocycloalcanes (VII) Synthèse de (germa‐, sila‐, et stanna‐)dioxacycloalcanes et alcènes par insertion de dérivés carbonylés sur la liaison métal‐oxygène d'éthers cycliques organométalliques

Barrau

Massol

Mesnard

et al. 1973

Recl. Trav. Chim. Pays‐Bas

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sila-, et stanna-)dioxacycloalcanes et alches par insertion de dkriviis carbonylb sur la liaison mktal-oxygthe d'kthers cycliques organomktalliquesThe insertion reactions of carbonyl derivatives such as acetaldehyde, chloral, hexachloro-and hexafluoro-acetone on the metal-oxygen bond of alkoxyorganometallic compounds have been studied in the case of numerous cyclic ethers containing silicon, germanium or tin atoms in the ring. These reactions proceed by ring expansion leading to the formation of cyclic acetals : germaoxetanes yield 4-germa-l,3-dioxanes, (sila-, germa-or stanna-) oxacyclopentanes give 1,3-dioxacycloheptanes and (germa-or stanna-) oxacyclopentenes lead to 1,3-dioxacycloheptenes with the group IV element in position 4.The mechanism of these insertion reactions is discussed according to the nature of carbonyl derivatives and metal heteroatom in the starting cyclic compounds, as well as catalytic and solvent effects.

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Addition reactions of alkoxygermanes

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Réactions d'addition‐élimination à partir d'hétérocycles germaniés du type I. Cas des dioxolannes germaniés

Réactions d'addition‐élimination à partir d'hétérocycles germaniés du type I. Cas des dioxolannes germaniés

Réactivité des trialcoylalcoxy‐ et dialcoylalcoxychlorogermanes et de leurs isologues soufrés vis à vis des aldéhydes et des cétones

Nouveaux oxamétallocycloalcanes (VII) Synthèse de (germa‐, sila‐, et stanna‐)dioxacycloalcanes et alcènes par insertion de dérivés carbonylés sur la liaison métal‐oxygène d'éthers cycliques organométalliques

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