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Kinetics and Mechanism of the Reactions of o- and p-Nitrohalobenzenes With the Sodium Salt of Ethyl Cyanoacetate Carbanion: a Non-Chain Radical Nucleophilic Substitution Mechanism

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The nucleophilic substitution reactions of o-nitrochlorobenzene (1a), o -nitrobromobenzene (1b, p-nitrofluorobenzene (1c), p-nitrochlorobenzene (1d), p-nitrobromobenzene (le), and p-nitroiodobenzene (If) with the sodium salt of ethyl cyanoacetate carbanion (2) in DMSO all gave the corresponding substitution products in almost quantitative yields. With the exception of the reaction of 1c with 2, the ESR spectra for the corresponding reactive intermediates, the radical anions of nitrophenyl halides were recorded. The relative intensity of ESR absorption versus time curves at various temperatures for the o-nitrochlorobenzene radical anion (3a), p-nitrochlorobenzene radical anion(3d), and p-nitrobromobenzene radical anion (3e) formed in the reactions of la, 1d, and le with 2 respectively in DMSO were measured by means of an ESR F/F lock technique. The kinetic curves obtained are consistent with the successive pseudo first-order reaction, and the rate constants for the single electron transfer reactions of 1a, 1d, and 1e with 2 respectively and for the dissociation reactions of 3a, 3d, and 3e and the corresponding activation parameters were calculated. The results provide conclusive evidence that the thermal reactions of o- and p-nitrohalobenzenes (with the possible exception of 1c) with 2 proceed via a non-chain radical nucleophilic substitution mechanism.

Affiliations: 1: National Laboratory of Applied Organic Chemistry Lanzhou University Lanzhou, Gansu 730000, People's Republic of China


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