Substituent and Solvent Effects on the Electrochemical Oxidation of para- and meta-Substituted Anilines

Bhuvaneshwari, D. S.; Elango, Kuppanagounder P.

doi:10.1515/znb-2006-1012

Cited by 12 publications

(5 citation statements)

References 24 publications

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“…First at all, standard potentials (E 0 ) are substituent dependent to reach a range of ~600 mV between BoX-CHO and BoX-OMe. As expected [18][19][20][21][22], a linear dependence between the electrophilic substituent constants (Brown-Okamoto constant σ p + for radical cations [23,24]) and the redox potentials is observed (Figure 3 as described by Raymo and al. [25]).…”

Section: Preliminary Resultssupporting

confidence: 76%

The stepwise oxidation of indolino[2,1-b]oxazolidine derivatives

Hadji

Szalóki

Alévêque

et al. 2015

Journal of Electroanalytical Chemistry

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International audience

This work presents an original strategy to modulate the electrochemical properties of the indolino[2,1-b]oxazolidine core appropriately substituted in position 5 (para-substitution of the phenyl ring) by acceptor or donor groups (CHO, OMe, Me, F, H, Cl, Br). Supported by spectroelectrochemical experiments and confronted to electrochemical simulations, the stepwise oxidation of indolino[2,1-b]oxazolidine derivatives involves an electrochemical mechanism which depends on the para-substitution of the phenyl ring and leads to either the formation of a stable radical cation, the opening of the oxazolidine ring or an
irreversible aryl C-C coupling.

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Section: Preliminary Resultssupporting

confidence: 76%

The stepwise oxidation of indolino[2,1-b]oxazolidine derivatives

Hadji

Szalóki

Alévêque

et al. 2015

Journal of Electroanalytical Chemistry

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International audience

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“…It appears that the relatively polar acetonitrile solvent is exerting some stabilizing effect on indoles with stronger ground-state dipole moments. 43 …”

Section: Resultsmentioning

confidence: 99%

“…It is also worth noting that the anodic peak potential trend correlates with calculated dipole moment of the indoles. It appears that the relatively polar acetonitrile solvent is exerting some stabilizing effect on indoles with stronger ground-state dipole moments …”

Section: Resultsmentioning

confidence: 99%

UV-Photoelectron Spectroscopy of BN Indoles: Experimental and Computational Electronic Structure Analysis

Chrostowska

Mazière

et al. 2014

J. Am. Chem. Soc.

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We present a comprehensive electronic structure analysis of two BN isosteres of indole using a combined UV-photoelectron spectroscopy (UV-PES)/computational chemistry approach. Gas-phase He I photoelectron spectra of external BN indole I and fused BN indole II have been recorded, assessed by density functional theory calculations, and compared with natural indole. The first ionization energies of these indoles are natural indole (7.9 eV), external BN indole I (7.9 eV), and fused BN indole II (8.05 eV). The computationally determined molecular dipole moments are in the order: natural indole (2.177 D) > fused BN indole II (1.512 D) > external BN indole I (0.543 D). The λmax in the UV–vis absorption spectra are in the order: fused BN indole II (292 nm) > external BN indole I (282 nm) > natural indole (270 nm). The observed relative electrophilic aromatic substitution reactivity of the investigated indoles with dimethyliminium chloride as the electrophile is as follows: fused BN indole II > natural indole > external BN indole I, and this trend correlates with the π-orbital coefficient at the 3-position. Nucleus-independent chemical shifts calculations show that the introduction of boron into an aromatic 6π-electron system leads to a reduction in aromaticity, presumably due to a stronger bond localization. Trends and conclusions from BN isosteres of simple monocyclic aromatic systems such as benzene and toluene are not necessarily translated to the bicyclic indole core. Thus, electronic structure consequences resulting from BN/CC isosterism will need to be evaluated individually from system to system.

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“…Aniline and its derivatives are used as intermediates for the manufacturing of various organic compounds such as colorants, agrochemicals and pharmaceutical agents. Therefore, a serious effect on human health over a long period of time is possible, even if aniline is in low concentrations 1 .…”

Section: Introductionmentioning

confidence: 99%