First Study of the Thermal and Storage Stability of Arenediazonium Triflates Comparing to 4-Nitrobenzenediazonium Tosylate and Tetrafluoroborate by Calorimetric Methods

Alexander A. Bondarev, Evgeny V. Naumov, Assiya Zh Kassanova, Elena A. Krasnokutskaya, Ksenia S. Stankevich, Victor D. Filimonov

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1 Citation (Scopus)

Abstract

Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography-mass spectrometry (MS) and liquid chromatography-MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.

Original languageEnglish
Pages (from-to)2405-2415
Number of pages11
JournalOrganic Process Research and Development
Volume23
Issue number11
DOIs
Publication statusPublished - 15 Nov 2019

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storage stability
nitrobenzenes
Pyrolysis
thermal stability
heat measurement
Salts
Gravimetric analysis
Calorimetry
isothermal flow
thermal decomposition
Mass spectrometry
Differential scanning calorimetry
salts
Decomposition
Nucleophiles
thermal analysis
Thermolysis
mass spectroscopy
Liquid chromatography
decomposition

Keywords

  • arenediazonium salts
  • isothermal flow calorimetry
  • quantum chemical calculation
  • stability
  • thermolysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

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title = "First Study of the Thermal and Storage Stability of Arenediazonium Triflates Comparing to 4-Nitrobenzenediazonium Tosylate and Tetrafluoroborate by Calorimetric Methods",
abstract = "Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography-mass spectrometry (MS) and liquid chromatography-MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.",
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author = "Bondarev, {Alexander A.} and Naumov, {Evgeny V.} and Kassanova, {Assiya Zh} and Krasnokutskaya, {Elena A.} and Stankevich, {Ksenia S.} and Filimonov, {Victor D.}",
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T1 - First Study of the Thermal and Storage Stability of Arenediazonium Triflates Comparing to 4-Nitrobenzenediazonium Tosylate and Tetrafluoroborate by Calorimetric Methods

AU - Bondarev, Alexander A.

AU - Naumov, Evgeny V.

AU - Kassanova, Assiya Zh

AU - Krasnokutskaya, Elena A.

AU - Stankevich, Ksenia S.

AU - Filimonov, Victor D.

PY - 2019/11/15

Y1 - 2019/11/15

N2 - Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography-mass spectrometry (MS) and liquid chromatography-MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.

AB - Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography-mass spectrometry (MS) and liquid chromatography-MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.

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