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Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines
Author(s) -
Sueishi Yoshimi,
Fujimoto Takanori,
Yoshida Tohru,
Kurita Takeharu,
Yamamoto Shunzo,
Nishimura Norio
Publication year - 1995
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.610080602
Subject(s) - chemistry , trinitrotoluene , kinetic isotope effect , deuterium , proton , reaction rate constant , arrhenius equation , steric effects , solvent , photochemistry , computational chemistry , kinetics , organic chemistry , atomic physics , nuclear physics , activation energy , explosive material , physics , quantum mechanics
The rate of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene (TNT), 2,2′4,4′6,6′‐hexanitrobibenzyl (HNBB) and 2,4,6‐trinitrobenzyl chlorides (TNB) with tertiary amines was followed spectrophotometrically. The rate constants obtained under various conditions were interpreted in terms of isotope, solvent and steric effects. The Arrhenius plots curved upward at low temperatures for TNT and TNB, indicating clearly the intervention of tunnelling. The tunnelling parameteres were calculated semi‐empirically on the basis of Bell's theory. The observed rate constants at low temperatures agreed well with the predicted values. In the present systems, some side and consecutive reactions involving the formation of 2,2′,4,4′6,6′‐hexanitrostilbene took place, and in some cases interrupted the rate measurements in the proton/deuteron transfer steps.