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Aminolysis of aryl dithio‐2‐thiophenates and dithio‐2‐furoates in acetonitrile
Author(s) -
Oh Hyuck Keun,
Woo So Young,
Shin Chul Ho,
Lee Ikchoon
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:11<849::aid-kin7>3.0.co;2-v
Subject(s) - chemistry , aminolysis , kinetic isotope effect , acetonitrile , deuterium , amine gas treating , aryl , nucleophile , proton , ion , kinetics , medicinal chemistry , photochemistry , organic chemistry , catalysis , physics , alkyl , quantum mechanics
The aminolyses of the title substrates with anilines and benzylamines are investigated in acetonitrile. A clean second‐order kinetics is obtained with a first‐order rate law in the amine concentration, which is uncomplicated by the fast proton transfer step. The large magnitude of ρ Z (ρ 1g ) as well as ρ X (ρ nuc ) together with relatively large positive ρ XZ values is consistent with a stepwise mechanism in which thiophenolate ion expulsion from the intermediate is rate limiting. For the reactions of aryl dithio‐2‐thiophenates with benzylamines the magnitude of ρ X and ρ Z values is relatively smaller suggesting that both the addition and expulsion of thiophenolate are partially rate determining. Relatively large secondary kinetic isotope effects, k H / k D ≥1.7, with deuterated nucleophiles, support involvement a concurrent proton transfer to the departing thiophenolate ion in the transition state. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 849–857, 1998