Nitrogen-centered free radicals. VI. Electron spin resonance studies of N-alkoxy-N-alkylamino, N-alkoxy-N-arylamino, and N-alkoxy-N-carboethoxyamino radicals in solution

Reactions of t-Butyl Peresters, XVIII Peroxyester Reaction of t-Butyl N,N-Dimethylperoxyamidate

“…The ether was removed on a rotating evaporator at 20-23 °C/10-15 torr to yield a liquid (148 g, n?ß 1.4285) still containing £-butyl hydroperoxide detectable by NMR. This residue could not be distilled [4,16], even in small quantities at reduced pressure (0.1 torr), without a slight decomposition. Purification was achieved by pumping the stirred material for 24 h at 0.1 torr.…”

Electrochemical study of stable N-alkoxyarylaminyl radicals

“…High resolution FAB mass spectra (HRFABMS) were recorded with a JEOL JMS-7000T mass spectrometer. (2) and N-tert-butoxy-2,4,6-tris(4-chlorophenyl)phenylaminyl (3) were prepared by our previously reported methods [12,16,17]. N-[(4-Nitrophenyl)thio]-2,4-bis(4-chlorophenyl)-6-tert-butylphenylaminyl (9) was prepared according to our previously reported method [21].…”

“…The E red 1/2 s for 1b and 2 are 95-123 mV less negative than that of 1a, and the E ox 1/2 s are 60-98 mV more positive. The less negative E red 1/2 s and more positive E ox 1/2 s of 1b and 2 can be ascribed to the presence of the electron-withdrawing Cl atoms on the 2-and 4-phenyl groups (1b) and can be ascribed to the presence of an electron-withdrawing ester group (2).…”

“…Although N-alkoxyaminyl radicals were extensively studied by ESR spectroscopy over a long time [1][2][3][4][5][6][7][8][9][10], the first isolation of N-alkoxyaminyls by our group was quite recent [11][12][13][14][15][16][17]. We obtained isolable N-alkoxyarylaminyls by two methods.…”

Use of two‐parameter correlations for studying the radical reactivity of aromatic compounds

“…We found that eq. (1) correlates parameters of the spectra for class S radicals, namely, the frequencies of long-wave maxima of absorption spectra for (p-XC6H4)3N-+ [48] (p* = 0.078 f 0.011, r* = 0.083 f 0.006,s = 0.028, r = 0.990); the coupling constants AN of electron spin resonance spectra for p-XC6H4T(JOBut [51] and p-XC6H&But [52]; and the coupling con- As one can expect, substituted benzyl radicals belong to class S. Therefore all substituents reduce the spin density of the CH2 group (owing to the delocalization of unpaired electrons to substituents) and correspondingly decrease the BDE of XC6H4CH2-H. The delocalization of unpaired electrons to substituents is confirmed by a molecular orbital study of the spin density for substituted benzyl radicals [58].…”