Abstract:
The known data and concepts pertinent to the electrophilic addition of chlorine and of related electrophiles are reviewed.
The racemic chlorohydrins and bromohydrins derived from cinnamic acid, together with their methyl esters, the acetates thereof, and the derived epoxides, have been prepared by routes which, when associated with their physical and chemical properties, establish their structures, including their stereo-chemistry. The results allow correction of some assignment of structure given in the literature.
The kinetics and products of addition of chlorine acetate to some methyl p-substituted cinnamates have been estimated in acetic acid as solvent under a number of conditions. The results show that chlorine acetate in initiating addition behaves in a manner similar to that found when it engages in substitution. However, the product-ratios differ markedly from those of the same products formed by addition initiated by electrophilic chlorine in the same solvent. Different carbonium ionic intermediates must be involved in the reactions initiated by the two reagents. The nature of these species is discussed.
