Studies of tertiary amine oxides. 4. Thermal rearrangement of N-aryl amine oxides to O-arylhydroxylamines

Abstract

varing the positions and isotropic vibrational amplitudes of the C, 0, and Fe atoms led to R = 0.089. Six further cycles of least-squares refinement of the atomic parameters with anisotropic vibrational amplitudes for the C, O, and Fe atoms converged to R = 0.068. A difference Fourier map calculated at this stage revealed peaks of density appropriate to all hydrogen atoms. Keeping the vibrational amplitudes for the hydrogens fixed (B(H) = B(C) + 1.0 A)1 2 and refining with anisotropic IPs for all the C, O, and Fe atoms, we obtained a final R of 0.033. The atomic scattering factors were taken from the literature.12 All the calculations were performed on the FACOM M-200 computer in the computer center of Kyushu University with the (12) "International Tables for X-ray Crystallography"; Kynoch Press:

Pd‐Catalyzed Aryl Amination Mediated by Well Defined, N‐Heterocyclic Carbene (NHC)–Pd Precatalysts, PEPPSI

“…[45] 4-(4-Nitrophenyl)morpholine (Figure 3 158-159 8C). [46] The spectral data were in accordance with those reported in the literature. [47] 4-(4-Fluorophenyl)morpholine (Figure 3): Following general procedure B, 116 mg (64 % yield, X = Cl) and 121 mg (67 % yield, X = Br) of the title compound were isolated (R f = 0.30, 20 % Et 2 O in pentane) as a light yellow oil.…”

Rhodium-Catalyzed Annulation of Tertiary Aniline N-Oxides to N-Alkylindoles: Regioselective C–H Activation, Oxygen-Atom Transfer, and N-Dealkylative Cyclization

“…These results were in contrast to previous report that the C–N cleavage commonly occurred at the less sterically hindered alkyl group, which provides a mechanistic implication of a different C–N bond activation process (vide infra). In addition, N -oxides derived from N , N -dimethyl 4-nitroaniline, 4-cyanoaniline, 1-naphthylamine, 2-naphthylamine, N -methyldiphenylamine, and 1-ethyl-1,2,3,4-tetrahydroquinoline failed to work under the current reaction conditions. − …”

Regioselective synthesis of cyclopentenones from 4-thianone

“…1,1985, 893. (10) CtiH6CH2CH2Br B 15f 80 0 Method A: sulfone 14 (2 mmol), alkyl halide (4 mmol), K2C03 (6 mmol), dry acetone (40 mL), reflux 6-10 h. Method B: sulfone 14 (2 mmol), alkyl halide (4 mmol), NaH (2.5 mmol), dry DMP (20 mL), 70 °C, 20-24 h. by Claisen rearrangement of allyl vinyl ether11 (Scheme III).…”