Chemical behavior of charge-transfer complexes. VII. Solvolysis of alkyl arenesulfonate donors in the presence of aromatic acceptors

Autor:	Allan K. Colter, Robert E. C. Turkos
Rok vydání:	1978
Předmět:	chemistry.chemical_classification Acetic acid chemistry.chemical_compound chemistry Organic Chemistry Reactivity (chemistry) General Chemistry Solvolysis Photochemistry Medicinal chemistry Catalysis Alkyl
Zdroj:	Canadian Journal of Chemistry. 56:585-590
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v78-095
Popis:	Rates of solvolysis of several ethyl and 2-propyl arenesulfonates having π donor leaving groups were measured in the absence of accepter and in the presence of the π acceptors 1,3,5-trinitrobenzene (TNB) and 2,4,7-trinitrofluorenone (TNF). With four of the nine combinations investigated, added accepter produced small but measurable rate enhancements. Ester–TNF 1:1 association constants were measured spectrophotometrically at 20, 30, and 40 °C in acetic acid for 2-propyl 4-methoxy-1-naphthalenesulfonate (3b), 4,8-dimethoxy-1-naphthalenesulfonate (4), 3,7-dimethyl-1-naphthalenesulfonate (5), and 1-pyrenesulfonate (6). From the equilibrium and kinetic data, the reactivity of the 1:1 ester–TNF complex relative to that of the uncomplexed ester (kc/ku) in acetolysis at 85.73 °C was estimated to be lessthan 4.2 and 1.4 for 3b and 4, respectively, 4.4 ± 2.0 for 5, and 2.8 ± 0.4 for 6. The value of kc/ku for 6 determined from analysis of the kinetic data alone is 2.7 ± 0.8.
Databáze:	OpenAIRE
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