Description

• Title:
  3‑Substituted Benzo[e][1,2,4]triazines: Synthesis and Electronic Effects of the C(3) Substituent
• Creator:
  Bodzioch, Agnieszka;
  Pomikło, Dominika;
  Celeda, Małgorzata;
  Pietrzak, Anna;
  Kaszynski, Piotr
• Contributor:
  Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Łodź , Poland;
  Faculty of Chemistry, University of Łodź , 91-403 ́ Łodź , Poland;
  Department of Chemistry, Middle Tennessee State University, Murfreesboro, Tennessee 37132, United States;
  Faculty of Chemistry, Łodź University of Technology, 90-924 Łodź , Poland
• Description:
  A series of 19 structurally diverse C(3)-substituted derivatives of benzo[e][1,2,4]triazine were synthesized from 3-chloro- (1c) and 3-iodobenzo[e][1,2,4]triazine (1d) obtained in three steps from 2-nitroaniline in 37–55% yields. Nucleophilic aromatic substitution and metal-catalyzed (Pd, Cu) reactions led to functional derivatives that include alkyl (C5H11), (het)aryl (Ph, 2-thienyl, ferrocenyl), ArC≡C, amine (NHPh and morpholine), PO(OEt)2, sulfanyl (SBu-t), alkoxide (OEt, OMe), and CN. The synthesis of C(3)–CF3 derivative 1g via the Ruppert reaction with 1d and its 1-oxide analogue 2d led to the substitution followed by formal addition of HCF3 to the C═N bond. Pd-catalyzed carbonylation reactions of 1d and 2d did not give the corresponding C(3)-carboxylic acids. Therefore, acid 1f was obtained through hydrolysis of the CN. The substituent effect on the electronic structure of the benzo[e][1,2,4]triazine ring was investigated by spectroscopic methods (UV–vis and NMR) augmented with density functional theory calculations. Results show significant effect of the C(3) substituent on the π–π*(1) transition energy and good correlation of the 1H NMR chemical shift with the substituent constant σp. Molecular and crystal structures of six derivatives were established with the single-crystal X-ray diffraction method, and the substituent impact on the molecular geometry was investigated.;
  This work was supported by the Foundation for Polish Science Grant (TEAM/2016-3/24) and National Science Foundation (XRD facility MRI-1626549).
• Object availability:
  free access
• Rights:
  Uznanie autorstwa 4.0 Międzynarodowe;
  http://creativecommons.org/licenses/by/4.0
• Date:
  2023.07.31;
  2019
• Type:
  Article
• Language:
  English
• Format:
  application/pdf
• Publisher:
  American Chemical Society
• Relation:
  The Journal of Organic Chemistry;10;
  84
• Subject:
  Anions;
  Aromatic compounds;
  Reaction products;
  Reagents;
  Substituents
• Identifier:
  J. Org. Chem. 2019, 84, 6377−6394;
  0022-3263;
  http://hdl.handle.net/11089/47735 ;
  1520-6904;
  10.1021/acs.joc.9b00716
• Data provider:
  Repozytorium Uniwersytetu Łódzkiego
• Can I use it?:
  check license
• Type:
  image