en
Scientific article
German

Effect of Substituents, Solvent, and Temperature on the Reactivity of the Zwitterionic Peroxides Arising from the Photo-Oxygenation of 2-(Methoxymethylidene)- and 2-(Phenoxymethylidene)adamantane

Published inHelvetica chimica acta, vol. 67, no. 8, p. 2210-2217
Publication date1984-12-19
Abstract

The photo-oxygenation of 2-(methoxymethylidene)adamantane (3) creates a zwitterionic peroxide which may be captured by acetaldehyde to give the corresponding pair of diastereoisomeric tricyclo[3.3.1.13,7]decane-2-spiro-6′ -(3′ -methyl-5′ -methoxyl′, 2′, 4′ -trioxanes) (4). Ease of capture depends strongly on solvent polarity and temperature. When these are low, yields of trioxine are high (∼ 80%). Conversely, 1,2-dioxetane formation is favoured at high temperature and solvent polarity. 2-(Phenoxymethylidene)adamantane (5), on photo-oxygenation, only gives the corresponding 1,2-dioxetene, even in the presence of acetaldehyde. From a Hammett, study of the-oxygenation of the enol ether 5 and p-methoxy, p-methyl, p-chloro and m-chloro derivatives, 9, 11, 13, and (15), a good linear relation was found between substituent constants and oxygenation rates which yielded reaction constants (ρ) of 2.59, −2.40, −1.09, and −0.90 in benzene, AcOET, CH2Cl2, and MeOH respectively. This data to the formation of a zwitterionic peroxide which enjoys stabilization from its won substituents and by competing solvation and further explains the predominance of dioxetane to the detriment of trioxane formation.

eng
Citation (ISO format)
JEFFORD, Charles et al. Effect of Substituents, Solvent, and Temperature on the Reactivity of the Zwitterionic Peroxides Arising from the Photo-Oxygenation of 2-(Methoxymethylidene)- and 2-(Phenoxymethylidene)adamantane. In: Helvetica chimica acta, 1984, vol. 67, n° 8, p. 2210–2217. doi: 10.1002/hlca.19840670824
Main files (1)
Article (Published version)
accessLevelRestricted
Identifiers
ISSN of the journal0018-019X
12views
0downloads

Technical informations

Creation03/31/2023 9:59:10 AM
First validation03/31/2023 10:48:11 AM
Update time03/31/2023 10:48:11 AM
Status update03/31/2023 10:48:11 AM
Last indexation01/17/2024 11:29:12 PM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack