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

Dominic Schatz; Anne Kunz; Aileen R. Raab; Hermann A. Wegner

doi:10.1055/a-1951-2833

Synlett, Table of Contents

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

cluster

Dispersion Effects

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

Dominic Schatz‡

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

,

Anne Kunz‡

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

,

Aileen R. Raab

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

,

Hermann A. Wegner∗

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

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Abstract

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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

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References

References and Notes
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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.

Supplementary Material

Supporting Information