Restricted rotation in hindered aryl methyl sulfoxides as detected by low-temperature proton magnetic resonance

Abstract

other ROX type intermediates with ethyl iodide could give ether. To shed light on the mechanism of ether formation, reactions of alkyl iodides with hypochlorites were studied. X RI + ROX -RI^-* ROR + IX OR Chlorine oxide, CI2O, and I2O5 could be formed from ICIO3 by a self-oxidation reaction, with transfer of oxygens from chlorine to iodine. The reaction of chlorine oxide with 2 mol of ethyl iodide in carbon tetrachloride at 0°was found to give ethyl chloride (40% yield), diethyl ether (20%), and ethyl acetate (8%). Since chloride was not detected in the dichlorine heptoxide reaction, chlorine oxide cannot be the reactive intermediate.

Conformational Studies by Dynamic NMR. 80.1 Cog-Wheel Effect in the Stereolabile Helical Enantiomers of Dimesityl Sulfoxide and Sulfone

“…In addition to this theoretical indication, an experimental support for the existence of a correlated motion in 1 can be found in the very low barrier measured for the rotation process of 1 compared with those of other aryl sulfoxides: − a correlated motion renders in fact more facile the interconversion processes. 5b, To further strengthen this interpretation, we investigated the NMR spectrum of mesitylphenyl sulfoxide, 3 which is the less hindered analogue of 1 .…”

An ab initio Quantum-Chemical Study of C6H5S(O)CH3 and C6H5S(O)CF3

“…As shown in [28333], the S=O groups are approximately coplanar to the phenyl rings to which they are bonded. For aryl methyl sulfoxides substituted in the ring, the same conclusion follows from the effects of shift reagents on the 13 C and 17 O NMR spectra [19], from the n J(HF) and n J(CF) coupling constants [20], from the low-temperature 1 H NMR spectra [34], and from the photoelectron spectra considered in combination with the 13 C NMR spectra [17]. Wehry [35] showed that the steric interactions (introduction of o-CH 3 groups) only weakly affect the s constants of the S(O)CH 3 group, suggesting stable conformation of methyl aryl sulfoxides.…”

Chemo- and Product-selective Electrooxidation of 3-(Arylthiomethyl)-Δ³-cephems

“…Hz, 1 H), 6.51 (d, J = 9 Hz, 1 H), 6.83 (d, J = 9 Hz, 2 H), 7.22-7.35 (m, 9 H) 13. C NMR (75 MHz, CDCl 3 ): d = 28.27, 31.95, 35.81, 38.40, 43.31, 55.12, 57.83, 58.95, 64.33, 67.55, 113.86, 123.94, 126.81, 127.07, 127.67, 128.31, 129.12, 129.42, 130.43, 130.71, 131.76, 133.71, 144.56, 159.83, 161.11, 164.41, 171.16.…”