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Kinetics and mechanism of aminolysis of propargyl and 1‐methyl‐propargyl arenesulphonates
Author(s) -
Oh Hyuck Keun,
Cho In Ho,
Jin Min Jeong,
Lee Ikchoon
Publication year - 1994
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610071107
Subject(s) - aminolysis , chemistry , propargyl , kinetics , acetonitrile , reaction rate constant , mechanism (biology) , medicinal chemistry , photochemistry , organic chemistry , catalysis , philosophy , physics , epistemology , quantum mechanics
Kinetic studies were carried out on the aminolysis of propargly and 1‐methylpropargyl arenesulphonates in acetonitrile at 45·0°C. The cross‐interaction constants, ρ xz and β xz , are similar to, but smaller than, those for the S N 2 processes at other primary and secondary carbon centers. Compared with the allyl series, the smaller magnitude of ρ xz and β xz reflects a looser transition state, which in turn leads to a lower rate despite the greater Taft's σ* value and the lower intrinsic (Δ E 0 ≠ ) and thermodynamic barriers (Δ E 0 ).