Catalyst- and solvent-free synthesis of 2-fluoro-N- (3-methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide through a microwave-assisted Fries rearrangement: X-ray structural and theoretical studies

R. Moreno-Fuquen, K. Arango-Daraviña, D. Becerra, J.-C. Castillo, A. R. Kennedy, M. A. Macías

Research output: Contribution to journalArticle

Abstract

An efficient approach for the regioselective synthesis of (5-amino-3-methylsulfanyl- 1H-1,2,4-triazol-1-yl)(2-fluorophenyl)methanone, C10H9FN4OS, (3), from the N-acylation of 3-amino-5-methylsulfanyl-1H-1,2,4-triazole, (1), with 2-fluorobenzoyl chloride has been developed. Heterocyclic amide (3) was used successfully as a strategic intermediate for the preparation of 2-fluoro-N-(3- methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide, C10H9FN4OS, (4), through a microwave-assisted Fries rearrangement under catalyst- and solvent-free conditions. Theoretical studies of the prototropy process of (1) and the Fries rearrangement of (3) to provide (4), involving the formation of an intimate ion pair as the key step, were carried out by density functional theory (DFT) calculations. The crystallographic analysis of the intermolecular interactions and the energy frameworks based on the effects of the different molecular conformations of (3) and (4) are described.
LanguageEnglish
Pages359-371
Number of pages13
JournalActa Crystallographica Section C: Structural Chemistry
VolumeC75
Issue numberPart 3
Early online date20 Feb 2019
DOIs
Publication statusPublished - 1 Mar 2019

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acylation
Acylation
Amides
amides
Density functional theory
Conformations
Chlorides
chlorides
Microwaves
Ions
density functional theory
microwaves
catalysts
X rays
preparation
Catalysts
synthesis
ions
x rays
interactions

Keywords

  • Fries rearrangement
  • heterocyclic amides
  • crystal structure
  • amino-1,2,4-triazole
  • prototropy process
  • microwave-assisted reaction
  • DFT
  • computational chemistry
  • Hirshfeld surface maps

Cite this

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title = "Catalyst- and solvent-free synthesis of 2-fluoro-N- (3-methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide through a microwave-assisted Fries rearrangement: X-ray structural and theoretical studies",
abstract = "An efficient approach for the regioselective synthesis of (5-amino-3-methylsulfanyl- 1H-1,2,4-triazol-1-yl)(2-fluorophenyl)methanone, C10H9FN4OS, (3), from the N-acylation of 3-amino-5-methylsulfanyl-1H-1,2,4-triazole, (1), with 2-fluorobenzoyl chloride has been developed. Heterocyclic amide (3) was used successfully as a strategic intermediate for the preparation of 2-fluoro-N-(3- methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide, C10H9FN4OS, (4), through a microwave-assisted Fries rearrangement under catalyst- and solvent-free conditions. Theoretical studies of the prototropy process of (1) and the Fries rearrangement of (3) to provide (4), involving the formation of an intimate ion pair as the key step, were carried out by density functional theory (DFT) calculations. The crystallographic analysis of the intermolecular interactions and the energy frameworks based on the effects of the different molecular conformations of (3) and (4) are described.",
keywords = "Fries rearrangement, heterocyclic amides, crystal structure, amino-1,2,4-triazole, prototropy process, microwave-assisted reaction, DFT, computational chemistry, Hirshfeld surface maps",
author = "R. Moreno-Fuquen and K. Arango-Daravi{\~n}a and D. Becerra and J.-C. Castillo and Kennedy, {A. R.} and Mac{\'i}as, {M. A.}",
year = "2019",
month = "3",
day = "1",
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language = "English",
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journal = "Acta Crystallographica Section C: Structural Chemistry",
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Catalyst- and solvent-free synthesis of 2-fluoro-N- (3-methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide through a microwave-assisted Fries rearrangement : X-ray structural and theoretical studies. / Moreno-Fuquen, R.; Arango-Daraviña, K.; Becerra, D.; Castillo, J.-C.; Kennedy, A. R.; Macías, M. A.

In: Acta Crystallographica Section C: Structural Chemistry, Vol. C75, No. Part 3, 01.03.2019, p. 359-371.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Catalyst- and solvent-free synthesis of 2-fluoro-N- (3-methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide through a microwave-assisted Fries rearrangement

T2 - Acta Crystallographica Section C: Structural Chemistry

AU - Moreno-Fuquen, R.

AU - Arango-Daraviña, K.

AU - Becerra, D.

AU - Castillo, J.-C.

AU - Kennedy, A. R.

AU - Macías, M. A.

PY - 2019/3/1

Y1 - 2019/3/1

N2 - An efficient approach for the regioselective synthesis of (5-amino-3-methylsulfanyl- 1H-1,2,4-triazol-1-yl)(2-fluorophenyl)methanone, C10H9FN4OS, (3), from the N-acylation of 3-amino-5-methylsulfanyl-1H-1,2,4-triazole, (1), with 2-fluorobenzoyl chloride has been developed. Heterocyclic amide (3) was used successfully as a strategic intermediate for the preparation of 2-fluoro-N-(3- methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide, C10H9FN4OS, (4), through a microwave-assisted Fries rearrangement under catalyst- and solvent-free conditions. Theoretical studies of the prototropy process of (1) and the Fries rearrangement of (3) to provide (4), involving the formation of an intimate ion pair as the key step, were carried out by density functional theory (DFT) calculations. The crystallographic analysis of the intermolecular interactions and the energy frameworks based on the effects of the different molecular conformations of (3) and (4) are described.

AB - An efficient approach for the regioselective synthesis of (5-amino-3-methylsulfanyl- 1H-1,2,4-triazol-1-yl)(2-fluorophenyl)methanone, C10H9FN4OS, (3), from the N-acylation of 3-amino-5-methylsulfanyl-1H-1,2,4-triazole, (1), with 2-fluorobenzoyl chloride has been developed. Heterocyclic amide (3) was used successfully as a strategic intermediate for the preparation of 2-fluoro-N-(3- methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide, C10H9FN4OS, (4), through a microwave-assisted Fries rearrangement under catalyst- and solvent-free conditions. Theoretical studies of the prototropy process of (1) and the Fries rearrangement of (3) to provide (4), involving the formation of an intimate ion pair as the key step, were carried out by density functional theory (DFT) calculations. The crystallographic analysis of the intermolecular interactions and the energy frameworks based on the effects of the different molecular conformations of (3) and (4) are described.

KW - Fries rearrangement

KW - heterocyclic amides

KW - crystal structure

KW - amino-1,2,4-triazole

KW - prototropy process

KW - microwave-assisted reaction

KW - DFT

KW - computational chemistry

KW - Hirshfeld surface maps

UR - http://journals.iucr.org/c/

U2 - 10.1107/S2053229619002572

DO - 10.1107/S2053229619002572

M3 - Article

VL - C75

SP - 359

EP - 371

JO - Acta Crystallographica Section C: Structural Chemistry

JF - Acta Crystallographica Section C: Structural Chemistry

SN - 2053-2296

IS - Part 3

ER -