Understanding Reactivity Patterns of the Dialkylaniline Radical Cation

Abstract

N,N-Dimethylaniline and N,N-diethylaniline react with Cu2+ to form the corresponding amine radical cations. The radical cations were characterized by their absorption spectra. In the absence of any nucleophiles, the radical cations dimerize to give tetraalkylbenzidines, and this reaction can be monitored by absorption spectroscopy. In the presence of nucleophiles such as Cl[negative in circle], Br[negative in circle], or SCN[negative in circle], the radical cations undergo nucleophilic substitution to give para-substituted dialkylanilines in good yields.

Cooperative Recognition of a Copper Cation and Anion by a Calix[4]arene Substituted at the Lower Rim by a β‐Amino‐α,β‐Unsaturated Ketone

“…Note that in addition to the phenolic OH, [14] the amino groups of b-amino-a,b-unsaturated ketones of calix[4]arene 2 might also be involved in the autoreduction of Cu II . [24] The binding of Cu I with 4 was supported by 1 H NMR titration experiments ( Figure S20 in the Supporting Information). Furthermore, the formation of 4·Cu I was confirmed by analysis of the ESI + mass spectrum, which showed a peak at m/z 393.9 for C 22 H 21 CuNO 2 (4·Cu I ).…”

Iron(III)‐Catalyzed C–H Functionalization: ortho‐Benzoyloxylation of N,N‐Dialkylanilines and Its Application to 1,4‐Benzoxazepines

“…However, in case of para-unsubstituted N,N-dialkylanilines, the expected products para-benzoyloxylation and benzidine were not observed in accordance to SET mechanism, [13] and also the absence of other possible products in similar kind of reactions [14] led us to discard the radical cation mechanism and support the polar Friedel-Craftstype mechanism (Scheme 6).…”

“…Thin-layer chromatography plates were visualized by exposure to UV or Iodine, and/or by immersion in an acidic staining solution of phosphomolybdic acid followed by heating on a hot plate. 1 H NMR spectra were obtained with 300 or 500 MHz spectrometers, 13 C NMR spectra were obtained with 75 or 100 MHz spectrometers, and 2D (gDQCOSY, TOCSY, and NOESY) NMR spectra of compounds were recorded with a Bruker Avance 600 MHz ( 13 C at 125 MHz) spectrometer in CDCl 3 at 298 K with tetramethylsilane and CDCl 3 as the internal standard. Chemical shifts (δ) are reported in ppm relative to the residual solvent signal (δ = 7.26 ppm for 1 H NMR and δ = 77.0 ppm for 13 C 6 NMR).…”

“…FTIR: ν = 2927, 2834, 2783, 1743, 1505, 1453, 1262, 1236, 1141, 1096, 1056, 1024 8.22-8.20 (m, 2 H), 7.67-7.64 (m, 1 H), 7.54-7.51 (m, 2 H), 7.32-7.26 (m, 2 H), 6.91-6.89 (m, 1 H), 2.75 (s, 6 H) ppm. 13 C NMR (100 MHz, CDCl 3 ): δ = 164. 4, 144.8, 143.5, 133.6, 130.1, 129.4, 129.2, 128.6, 126.6, 120.0, 113.8, 112.8, 43.0 ppm.…”

“…FTIR: ν = , 1022 2 H),1 H),2 H),7.50 (dd,J = 2.14,8.54 Hz,1 H),7.41 (d,J = 1.98 Hz,1 H),6.78 (d,J = 8.54 Hz, 1 H), 2.77 (s, 6 H) ppm. 13 C NMR (100 MHz, CDCl 3 ): δ = 164. 4, 145.4, 143.5, 135.5, 133.7, 132.2, 130.2, 130.1, 129.2, 128.6, 128.4, 120.5, 82.3, 42.9 ppm.…”