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Reactivity and Reaction Pathways of Alkylalkoxybenzene Radical Cations. Part 3. Effects of 2-Alkyl Substituents On the Relative Importance of Ring-Substitution Over Deprotonation of 2-Alkyl-1,4-Dimethoxybenzene Radical Cations

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One-electron oxidation of 2-alkyl-1,4-dimethoxybenzenes 1a-f (2-alkyl = Me, Et, i-Pr,, cy-C3H5CH2, PhCH2 and t-Bu) by 4-nitrobenzoyl peroxide 2 and pentaflurobenzoyl peroxide 3 was proved by the observation of great acceleration of decomposition of the peroxides at room temperature, the detection of the corresponding radical cations 1+. a-f and product analysis. The product studies have disclosed that under the conditions employed (in acetonitrile at 40 °C), the reaction pathways of the radical cations are greatly dependent on the nature of 2-alkyl substituents: Ring- 4-nitrobenzoloxylation product at C5 and C6 were obtained exclusively in the reactions of the donors with aliphatic 2-alkyl substituents bearing at least one α-hydrogen atom, such as 1a, 1b, 1c and 1d; whereas in the case of 1e (with 2-benzyl group), both ring-substitution at C5 (4e) and C6 (5e) and deprotonation/4-nitrobenzoloxylation products 8e were isolated; from the donor without α-hydrogen atom, 1f, de-t-butylation products 12 and t-butyl 4-nitrobenzoate 13 were incorporated with ring-substitution at C5 (4f) and C6 (5f). Furthermore, the product distribution (4 over 5) is also affected by the bulkiness of 2-alkyl group. For all the electron-transfer reactions, large amounts of the benzoic acid (4-NO2-C6H4COOH or C6F5COOH) were generated and trace amounts of de-methylation product (2-alkyl-1,4-benzoqinones 6) were also detected by 1H NMR.

Affiliations: 1: Department of Chemistry, Shanghai Jiaotong University, Shanghai 200240, CHINA; 2: Laboratory of Organo-fluorine Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, CHINA


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