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 I-2, 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.

Antunes, C., Bietti, M., Lanzalunga, O., & Salamone, M. (2004). 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. JOURNAL OF ORGANIC CHEMISTRY, 69(16), 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

BIETTI, MASSIMO;SALAMONE, MICHELA
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 I-2, 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.
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/06 - Chimica Organica
English
Con Impact Factor ISI
Alcohols; Benzene; Chemical bonds; Hydrogen; Photolysis; Solutions; Substitution reactions; Intramolecular selectivity; Light radiation; Free radicals; (diacetoxyiodo)benzene; argon; cycloalkanol derivative; iodobenzene; radical; unclassified drug; article; chemical bond; cyclization; gas chromatography; mass spectrometry; photolysis; proton nuclear magnetic resonance; ring opening
Antunes, C., Bietti, M., Lanzalunga, O., & Salamone, M. (2004). 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. JOURNAL OF ORGANIC CHEMISTRY, 69(16), 5281-5289 [10.1021/jo049524y].
Antunes, C; Bietti, M; Lanzalunga, O; Salamone, M
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2108/33057
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