Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines

Yoshimi Sueishi, Takanori Fujimoto, Tohru Yoshida, Takeharu Kurita, Shunzo Yamamoto, Norio Nishimura

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)387-394
Number of pages8
JournalJournal of Physical Organic Chemistry
Volume8
Issue number6
DOIs
Publication statusPublished - 1995

Fingerprint

Trinitrotoluene
Proton transfer
Deuterium
Amines
deuterons
Rate constants
amines
Derivatives
Arrhenius plots
trinitrotoluene
Kinetics
protons
kinetics
Isotopes
Chlorides
Temperature
bells
isotope effect
plots
chlorides

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines. / Sueishi, Yoshimi; Fujimoto, Takanori; Yoshida, Tohru; Kurita, Takeharu; Yamamoto, Shunzo; Nishimura, Norio.

In: Journal of Physical Organic Chemistry, Vol. 8, No. 6, 1995, p. 387-394.

Research output: Contribution to journalArticle

Sueishi, Yoshimi ; Fujimoto, Takanori ; Yoshida, Tohru ; Kurita, Takeharu ; Yamamoto, Shunzo ; Nishimura, Norio. / Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines. In: Journal of Physical Organic Chemistry. 1995 ; Vol. 8, No. 6. pp. 387-394.
@article{98e64c7470f3491694b85cac7a4310a4,
title = "Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines",
abstract = "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.",
author = "Yoshimi Sueishi and Takanori Fujimoto and Tohru Yoshida and Takeharu Kurita and Shunzo Yamamoto and Norio Nishimura",
year = "1995",
doi = "10.1002/poc.610080602",
language = "English",
volume = "8",
pages = "387--394",
journal = "Journal of Physical Organic Chemistry",
issn = "0894-3230",
publisher = "John Wiley and Sons Ltd",
number = "6",

}

TY - JOUR

T1 - Kinetic study of proton/deuteron transfer reactions of 2,4,6‐trinitrotoluene and its derivatives with tertiary amines

AU - Sueishi, Yoshimi

AU - Fujimoto, Takanori

AU - Yoshida, Tohru

AU - Kurita, Takeharu

AU - Yamamoto, Shunzo

AU - Nishimura, Norio

PY - 1995

Y1 - 1995

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84985450400&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84985450400&partnerID=8YFLogxK

U2 - 10.1002/poc.610080602

DO - 10.1002/poc.610080602

M3 - Article

VL - 8

SP - 387

EP - 394

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

SN - 0894-3230

IS - 6

ER -