Using nitrogen isotope fractionation to assess the oxidation of substituted anilines by manganese oxide.

We explored the N isotope fractionation associated with the oxidation of substituted primary aromatic amines, which are often the position of initial attack in transformation processes of environmental contaminants. Apparent (15)N-kinetic isotope effects, AKIE(N), were determined for the oxidation of various substituted anilines in suspensions of manganese oxide (MnO(2)) and compared to reference experiments in homogeneous solutions and at electrode surfaces, as well as to density functional theory calculations of intrinsic KIE(N)for electron and hydrogen atom transfer reactions. Owing to the partial aromatic imine formation after one-electron oxidation and corresponding increase in C-N bond strength, AKIE(N)-values were inverse, substituent-dependent, and confined to the range between 0.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.

Experimental and theoretical investigations into the unusual regioselectivity of 4,5-, 5,6-, and 6,7-indole aryne cycloadditions.

The 6,7-indolyne shows remarkable regioselectivity in its cycloaddition with 2-substituted furans. Electron-donating groups give predominantly the more sterically crowded product, while electron-withdrawing groups display the opposite regioselectivity. By contrast, 4,5- and 5,6-indolynes show no regioselectivity.