The C-C beta-scission reactions of 1-alkylcycloalkoxyl radicals, generated photochemically by visible light irradiation of CH2Cl2 solutions containing the parent 1-alkylcycloalkanols, (diacetoxy)-iodobenzene (DIB), and I2, have been investigated through the analysis of the reaction products. The 1-alkylcycloalkoxyl radicals undergo competition between ring opening and C-alkyl bond cleavage as a function of ring size and of the nature of the alkyl substituent. With the 1-propylcycloheptoxyl, 1-propylcyclooctoxyl and 1-phenylcyclooctoxyl radicals, formation of products deriving from an intramolecular 1,5-hydrogen atom abstraction reaction from the cycloalkane ring has also been observed. The results are discussed in terms of release of ring strain associated to ring opening, stability of the alkyl radical formed by C-alkyl cleavage, and with cycloheptoxyl and cyclooctoxyl radicals, also in terms of the possibility of achieving a favorable geometry for intramolecular hydrogen atom abstraction.

Photolysis of 1-alkylcycloalkanols in the presence of (diacetoxyiodo)benzene and I-2. Intramolecular selectivity in the beta-scission reactions of the intermediate 1-alkylcycloalkoxyl radicals / Antunes, Csa; Bietti, M; Lanzalunga, Osvaldo; Salamone, M.. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 69:(2004), pp. 5281-5289. [10.1021/jo049524y]

Photolysis of 1-alkylcycloalkanols in the presence of (diacetoxyiodo)benzene and I-2. Intramolecular selectivity in the beta-scission reactions of the intermediate 1-alkylcycloalkoxyl radicals

LANZALUNGA, Osvaldo;
2004

Abstract

The C-C beta-scission reactions of 1-alkylcycloalkoxyl radicals, generated photochemically by visible light irradiation of CH2Cl2 solutions containing the parent 1-alkylcycloalkanols, (diacetoxy)-iodobenzene (DIB), and I2, have been investigated through the analysis of the reaction products. The 1-alkylcycloalkoxyl radicals undergo competition between ring opening and C-alkyl bond cleavage as a function of ring size and of the nature of the alkyl substituent. With the 1-propylcycloheptoxyl, 1-propylcyclooctoxyl and 1-phenylcyclooctoxyl radicals, formation of products deriving from an intramolecular 1,5-hydrogen atom abstraction reaction from the cycloalkane ring has also been observed. The results are discussed in terms of release of ring strain associated to ring opening, stability of the alkyl radical formed by C-alkyl cleavage, and with cycloheptoxyl and cyclooctoxyl radicals, also in terms of the possibility of achieving a favorable geometry for intramolecular hydrogen atom abstraction.
2004
ALKOXYL RADICALS; PHOTOLYSIS; FRAGMENTATION
01 Pubblicazione su rivista::01a Articolo in rivista
Photolysis of 1-alkylcycloalkanols in the presence of (diacetoxyiodo)benzene and I-2. Intramolecular selectivity in the beta-scission reactions of the intermediate 1-alkylcycloalkoxyl radicals / Antunes, Csa; Bietti, M; Lanzalunga, Osvaldo; Salamone, M.. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 69:(2004), pp. 5281-5289. [10.1021/jo049524y]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/46361
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