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Synlett 2023; 34(10): 1153-1158
DOI: 10.1055/a-1951-2833
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Dispersion Effects

Investigation of Alkyl–Aryl Interactions Using the Azobenzene Switch – The Influence of the Electronic Nature of Aromatic London Dispersion Donors

Dominic Schatz‡
a   Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
b   Center of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany
,
Anne Kunz‡
a   Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
b   Center of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany
,
Aileen R. Raab
a   Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
b   Center of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany
,
Hermann A. Wegner∗
a   Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
b   Center of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany
› Author AffiliationsThis project was partially funded by the Deutsche Forschungsgemeinschaft (DFG, WE5601/8-1).
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Abstract

Herein we report the synthesis of nonsymmetrically substituted azobenzene derivatives with meta-alkyl substituents on one side and meta-aryl moieties with electron-donating or electron-withdrawing groups on the other side. The half-lives for the thermal (Z)- to (E)-isomerization of these molecules were measured in n-octane, which allows investigation of the strength of the aryl–alkyl interactions between their substituents. It was found that the London dispersion donor strength of the alkyl substrate is the decisive factor in the observed stabilization, whereas the electronic structure of the aryl fragment does not influence the isomerization in a significant way.

Key words

London dispersion - azobenzenes - kinetics - molecular switches - CH–π interactions

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1951-2833.
  • Supporting Information


Publication History

Received: 12 August 2022

Accepted after revision: 27 September 2022

Accepted Manuscript online:
27 September 2022

Article published online:
28 October 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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  • 29 General Procedures Route 1: 1,3-Diphenyl-5-nitrosobenzene (20, 1.0 equiv.) was dissolved in toluene and degassed with a nitrogen stream. The corresponding aniline (14, 15 or 16, 1.0–1.6 equiv.) and acetic acid were added, and the mixture was stirred at 60 °C for the time given in the Supporting Information. The solvent was subsequently removed under reduced pressure, and the residue was purified by column chromatography. Route 2: Under nitrogen atmosphere the corresponding nitrosobenzene (24, 25, or 26, 1.0 equiv.) was dissolved in toluene and was degassed with a nitrogen stream. Acetic acid and a solution of aniline 23 (1.0 equiv.) in toluene were added. The reaction mixture was stirred at 60 °C for the time given in the Supporting Information. The solvent was subsequently removed under reduced pressure, and the residue was purified by column chromatography. Route 3 for 7, 8: Corresponding dibromoazobenzene (29 or 30, 1.0 equiv.) was dissolved in dry THF (transferred under inert conditions), boronic ester 28 (2.1 equiv.), CsF (6.7 equiv.), as well as tris(dibenzylideneacetone)dipalladium(0) (3 mol%) and tri-tert-(butylphosphonium tetrafluoroborate (10–14 mol%) were added and stirred for the time given in the Supporting Information. The solvent was subsequently removed under reduced pressure, and the residue was purified by column chromatography. Route 3 for 9: See the Supporting Information.