The Effect of Electrolytically Released Halogens on an Absolute Methyl Alcohol Solution of Cinnamic Acid

Electrochemical Bifunctionalization of Olefins in the Presence of Halide Ions

“…Indeed epoxidation of lower alkenes with electrochemically generated HOCl has become a commercially viable route to olefin oxides (1). Other examples in the literature describe the formation of the halohydrin ethers of cinnamic acid (2) and trans-stilbene (3) on electrolysis of these olefins in methanol containing chloride or bromide electrolytes. We were interested in extending the scope of electrochemical halofunctionalization to include introduction of other nucleophiles especially those containing nitrogen.…”

“…In general the method involves the reaction of a cyclic halonium ion intermediate (1) with a suitable nucleophile to give a halofunctionalized (2) or bifunctionalized derivative (3) (eqs. 1 and 2) of the olefin.…”

“…Hassner and co-workers (6-9) are largely responsible for developing the corresponding reactions allowing introduction of nitrogen substituents to give synthetically useful haloadducts (2; X = I, C1, or Br, and R = NO,, N,, NCO, and Halonium ion 1 can be partitioned between starting material and 2. Since 1 may be regarded as an ion pair, electrochemical oxidative removal of halide ion from 1 suggested itself as a means of driving [ l ] and [2] to the right.…”