One-Pot Synthesis of N-Substituted Alkylaminocyclohexanols by the Addition of Electrophiles Formed in situ in the System Н2О2 + HBr (HCl)

Conformational Aspects of the Reaction Products of Oxidative Hydroxyhalogenation of Alkyl Cyclohexenes

“…This is due to the fact that in the initial period, oxidatively generated HlgOH f orm a π -c om pl ex ( 3 ) w i th a d ou b l e b on d , alkylcyclohexenes, which then turns into an activated transition state (4) with an internal ion pair. Then this complex regroups into reaction products (5).…”

“…Based on the spectral data of table 2, it was found that the products The conformational equilibrium of the obtained conformers was carried out according to the width (W 1/2 ) of the signal of the H + proton located at position 2 observed and calculated according to the spin-spin coupling constants with a chemical shift of 4.46 ppm. As a result of the spin-spin interaction of H + with axial and equatorial vicinal protons at the C 3 atom (CSSC) J aa -11.8 Hz, J ae -3.6 and J ee -2.8 Hz for conformers 4-methyl and J aa -12.2 Hz, J ee -4.2 and J ee -3.3 Hz for conformers of 1acetyl derivatives [8] for conformers (5) are respectively ≈ 7 and 16 Hz. The position of conformational equilibrium, the difference in conformational energies, the conformational equilibrium constant (K), and the diaxial and diequatorial contents of the halogen atom (Cl, Br) and the hydroxyl group of the C aa and C ee conformers in equilibrium with 2-chloro(bromo)-4methylcyclohexanes were determined and 1-[1-chloro(bromo)-2-hydroxycyclohexyl]ethan-1-ones and established the spatial position of the methyl and acetyl groups relative to the C-Hlg and C-OH bond cycle.…”

“…It was revealed that conformers with a diaxial spatial position of halogen atoms and a hydroxyl group (85-93%) (5) and an equatorial position of the methyl-ethenyl and acyl groups, where the carbonyl bond penetrates the transoidal configuration relative to C-Hlg in the ring are predominant in the equilibrium mixture [6].…”

“…Hydroxychloro(bromo)ide acid of these cyclo-olefins are obtained by the previously developed method [4,5]. In this case, the synthesis process is carried out sequentially in several stages, with the formation of hydroxychloro-2 (a-d) and hydroxybromide-3 (a-d) according to the scheme:…”