Richard C. Hallcher

Paired Electro‐Organic Syntheses I . Cathodic Adipate with Anodic Bimalonate

A procedure is reported for the co‐electrolysis of ethyl acrylate and diethyl malonate using as solvent/electrolyte system to yield diethyl adipate and tetraethyl ethane‐1,1,2,2‐tetracarboxylate in high (95%) yield and good (60%) current efficiency. A convenient cell which allows experimentation in the 2–5g range was fabricated from a hollowed‐out graphite cylinder (optionally lined with lead) which served as one electrode and a graphite rod machined and held so as to be counterelectrode and mechanical stirrer. General aspects of paired organic syntheses are discussed as well as the specific problems that are involved when the paired reactions are hydrodimerization‐dehydrodimerization.

A practical system for manganese(III)-mediated electrochemical synthesis of sorbic acid precursors

An efficient, practical, electrochemical system was developed for the synthesis of a mixture of 4-acetoxy-5-hexenoic acid and trans-6-acetoxy-4-hexenoic acid via manganese (III)-mediated oxidation of acetic acid-acetic anhydride in the presence of butadiene. Copper (II) co-catalyst enhanced the efficiency of this oxidation and copper (I) was shown to catalyze in situ conversion of the acetoxyhexenoic acids into γ-vinyl-γ- butyrolactone.

Electrogenemtion of Mn(III) in an undivided cell

The electrochemical oxidation of manganous ion to manganic ion in acetic acid may be efficiently carried out in a parallel plate undivided cell. Reduction of manganic ion to manganous ion at the cathode is a relatively inefficient reaction, allowing the formation of solutions of manganic ion as high as 0.05 mol dm−3, at greater than 80% current efficiency. The effects of the major variables have been evaluated.