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- W2094701121 abstract "α-Cyanperoxycarbonsäure-tert-butylester wurden dargestellt, ihre Thermolyse wurde kinetisch und präparativ untersucht. In allen Beispielen wurde Homolyse nachgewiesen, die α-Cyangruppe übt dabei einen zerfallshemmenden Einfluß, im Vergleich mit den unsubstituierten Peroxycarbonsäureestern aus. Dies wird durch einen polaren Substituenteneffekt und eine nur geringe Dehnung der C-α–CO-Bindung im Übergangszustand des Peroxysäureester-Zerfalls gedeutet. Eine allgemeine Beziehung zwischen dem Einfluß von α-Methyl-gruppen auf die Peroxysäureester-Fragmentierung und den Taftschen σI-Konstanten wird aufgezeigt. Organic Peroxides, XVII. Preparation and Thermolysis of tert-Butyl α-Cyanoperoxycarboxylates A series of tert-butyl α-cyanoperoxycarboxylates was prepared. The kinetics and products of their homolysis were investigated. α-Cyano groups exert a rate retarding effect in comparison to the unsubstituted peroxycarboxylates. This is interpretated by only little stretching of the C-α–CO-bond in the transition state and by the influence of a polar substituent effect. A general relationship between the rate enhancing effect of α-methyl groups on peroxyester decompositions and Taft′s σI constants was observed." @default.
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- W2094701121 date "1973-08-01" @default.
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- W2094701121 title "Organische Peroxide, XVII. Darstellung und Thermolyse von α-Cyanperoxycarbonsäure-tert-butylestern" @default.
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- W2094701121 doi "https://doi.org/10.1002/cber.19731060816" @default.
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