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Type: Artigo de periódico
Title: The Use Of Radioisotopes In Studies Of Reaction Mechanism. Part Iii. Thiocyano-exchange And Azido-dethiocyanation Of 2,4-dinitro-1-thiocyanobenzene
Author: Miller J.
Kendall F.H.
Abstract: The reactions of 2,4-dinitro-1-thiocyanobenzene with azide and thiocyanate ions in methanol and with thiocyanate ions in NN-dimethylformamide (DMF) have been studied using radioactive tracer techniques. The results are compared with those obtained previously for reactions of 2,4-dinitro-1-thiocyanobenzane with methoxide ion and for 1-iodo-2,4-dinitrobenzene with all three nucleophiles. The results show that thiocyano-exchange in methanol is a true SNAr reaction in which the mobility of the thiocyano-group is similar to that of iodine. Both reactions exhibit a characteristic heavy nucleophile interaction in methanol but not in DMF. A significant increase in ease of displacement of the thiocyano-group in azido-dethiocyanation is speculatively ascribed to a favourable interaction between thiocyano- and azido-groups in the rate-limiting transition state. The much larger increase with methoxide ion in methanol, demonstrated in earlier studies, is linked with alternative attack at the cyano carbon atom. Thiocyano-exchange in DMF is very similar to thiocyano-deiodination in DMF. In both, the faster reaction in DMF than in methanol (solvent rate ratio <100) is a result of less negative ΔS‡ values, with ΔH‡ essentially unchanged.
Rights: aberto
Identifier DOI: 
Date Issue: 1974
Appears in Collections:Unicamp - Artigos e Outros Documentos

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