14276-98-3Relevant academic research and scientific papers
Kinetics of elimination reactions of cumyl chloride and its substituted derivatives in acetonitrile
Balachandran,Santhosh Kumar
, p. 1731 - 1734 (2007/10/03)
A cent per cent unimolecular elimination reaction of tertiary aralkyl halides in acetonitrile is being reported for the first time. The reversibility in the rate determining step can be prevented by the addition of a weak base like pyridine in cumyl chloride and its α- and p-substituted derivatives. A plot of logarithmic rate constants of α-substituted cumyl chloride against Charton's steric parameter 'v' gives a linear relationship.
Variable Electronic Properties of the CSNMe2 Group
Creary, Xavier,Aldridge, Timothy
, p. 4280 - 4285 (2007/10/02)
The ?I value for the CSNMe2 group has been determined and the value of 0.23 indicates that this group is inductively electron withdrawing.The effect of the p-CSNMe2 group on the solvolysis rate of cumyl chloride has also been determined and, relative to the p-H analogue, this group has a negligible effect on rate. p-CSNMe2 substitution slows the hydrolysis rate of substituted benzaldehyde dimethyl acetals. p-CSNMe2 substitution enhances the solvolysis rate of ArCH(OMs)PO(OEt)2.These variable rate effects on reactions involving cationic intermediates have been interpreted in terms of variable electronic properties of the CSNMe2 group.This group can be cation stabilizing, electroneutral, or cation destabilizing, depending on the charge demands of specific cations.This is a result of a conjugative interaction of CSNMe2 with a cationic center and resultant delocalization of positive charge onto sulfur.The importance of such conjugation is a function of the amount of transition-state charge developed on the carbon bearing the CSNMe2 group.The electronic effects of the amphielectronic p-CSNMe2 group are compared to the more conventional effects of CONMe2 and the m-CSNMe2 analogues.
The Electronic Effect of the Phenylazo and t-Butylazo Groups
Byrne, Christopher J.,Happer, Duncan A. R.,Hartshorn, Michael P.,Powell, H. Kipton J.
, p. 1649 - 1654 (2007/10/02)
Hammett ?p+-values for arylazo and t-butylazo groups have been determined by measurements of the kinetics of solvolysis of the appropriately substituted arylpropan-2-yl chlorides.They have been found to be considerably more positive than expected and differ significantly from earlier estimates based on the rates of electrophilic attack on azobenzene.An interpretation of the discrepancy has been advanced based on the differing orientations of the azo linkage with respect to the aromatic ring in the transition state.The introduction of methyl groups into positions ortho to the phenylazo and t-butylazo substituents causes a change in character from -I, -R to -I, +R.This is true not only for the solvolysis reaction but also for benzoic acid ionisation.
