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Configuration and conformation of substituted 1,3,2-dioxaarsenanes
Authors:Yu. Yu. Samitov  N. K. Tazeeva  N. A. Chadaeva  G. Kh. Kamai
Affiliation:(1) A. E. Arbuzov Institute of Organic and Physical Chemistry, Academy of Sciences of the USSR, Kazan
Abstract:The configuration and conformations often 2-, 4-, and 5-substituted 1,3,2-dioxaarsenanes were studied from their PMR spectra. Inversion of the shielding constants of protons in the 4, 6, and 5 positions and of methyl groups in the 5 position was established, and the axial orientation of the As-Cl and As-OR bonds, the equatorial orientation of the 4-CH3 group, and the chair conformation of the six-membered heteroring were proved. The anisotropies of the diamagnetic susceptibility were estimated for the first time: 
$$Delta _{chi _{{text{As - O}}} }  = 4.67  cdot  10^{ - 6}$$
and 
$$Delta _{chi _{{text{As - Cl}}} }  = 5.13  cdot  10^{ - 6}  {text{cm}}^{text{3}}   cdot  {text{mole}}^{{text{ - 1}}}$$
(dipole approximation); 
$$Delta _{chi _{{text{As - O}}} }  = 0.9  cdot  10^{ - 6}$$
and 
$$Delta _{chi _{{text{As - Cl}}} }  = 6.8  cdot  10^{ - 6}  {text{cm}}^{text{3}}   cdot  {text{mole}}^{{text{ - 1}}}$$
(nondipole approximation). The cyclic torsion angle (psgr= 58°) as found for 2-chloro-1,3,2-dioxaarsenane by the ldquoR-factorrdquo method. Conclusions regardiwng the conformation of the ring and substituents were confirmed by a study of the specific effect of an aromatic solvent on the position of the resonance lines.Communication I from the series ldquoInvestigation of the Stereochemistry of Organic Arsenic Compounds by NMR Spectroscopy.rdquoDeceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 457–463, April, 1973.
Keywords:
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