32740-24-2Relevant academic research and scientific papers
The Synthesis of Specifically and Selectively Deuteriated 4,4'-Bisalkoxyazoxybenzene Derivatives
Boden, Neville,Bushby, Richard J.,Clark, Leslie D.
, p. 543 - 551 (2007/10/02)
In connection with deuterium n.m.r. studies of molecular motion in liquid crystals we have developed a number of methods for the synthesis of selectively deuteriated 4,4'-bisalkoxyazoxybenzenes.This paper is concerned with (i) the labelling of specific methylene segments of the alkoxy-chains, (ii) the labelling of the aromatic nucleus, and (iii) the selective enrichment of the deuterium content of one alkoxy-chain relative to the other.Our studies of the n.m.r. spectra of these liquid crystals have shown that there is not (as has sometimes been supposed) a monotonic decrease in C-D quadrupole splitting in passing from the oxygen to the CD3 end of the alkoxy-chain.In -PAA (p-azoxyanisole) we have also shown that the smaller splitting is associated with the CD3O group nearest to the NO end of azoxy-group.Whereas the photorearrangement of azoxy-compounds is normally regiospecific, the photorearrangement of PAA selectively deuteriated in one methoxy-group is unusual in that it leads to isotopically scrambled products.
Electrolysis of Potassium Butyrate in Acetonitrile. A Deuterium NMR Study
Laurent, Eliane,Thomalla, Marc,Marquet, Bernard,Burger, Ulrich
, p. 4193 - 4198 (2007/10/02)
The anodic oxidation of 2,2-dideuteriobutyrate ion in acetonitrile gives rise to radical-derived and cation-derived C3 products.By 2H FT NMR spectroscopy, the radical-derived propane and propene are found to be formed without scrambling of the label.Similarly, the products derived from the intermediate isopropyl cation, i.e., the remainder of the propene and N-isopropylamides, bear deuterium only at the terminal C-1 and C-3 positions of the C3 fragment.However, the 1:1:1 label distribution found in the N-n-propylamides and the formation of cyclopropane strongly suggest that ring closure of the n-propyl cation to rapidly scrambling pr otonated cyclopropane is an important reaction pathway.Atom scrambling at the level of protonated cyclopropane shows a large H/D isotope effect.
