111944-29-7

Upstream product

• 79-37-8 oxalyl dichloride 
• 3597-91-9 biphenyl-4-yl methanol 
• 644-08-6 4-Methylbiphenyl 
• 111944-28-6 4-phenylbenzyl ethyl oxalate 

Downstream Products

• 644-08-6 4-Methylbiphenyl 
• 3597-91-9 biphenyl-4-yl methanol 

Relevant academic research and scientific papers

Electro-organic reactions. Part 27. The mechanism of cathodic cleavage of activated esters; oxalates, squarates and oxamates

Esters of oxalic acid, 3,4-dihydroxy-3-cyclobutene-1,2-dione (squaric acid), and oxamic acid, are reduced cathodically at modest potentials. In aprotic solvent, and on the cyclic voltammetric time scale, the esters are cleaved to the corresponding alkane. For oxalates, the mechanism of cathodic cleavage was investigated thoroughly by voltammetry, coulometry, and detailed product analysis. On the time scale of controlled potential electrolysis the rapid electrogenerated base-catalysed hydrolysis of the esters by adventitious water competes with cathodic cleavage. Similarly, rapid base-catalysed transesterification involving oxalates and added alcohols is observed which provides a practical method of reductively cleaving alcohols to alkanes by co-electrolysis of a mixture of alcohol and readily available oxalate (e.g. diethyloxalate). The leaving group in such cathodic fragmentation is the half-ester anion and the efficiency of reaction depends on the stability of the other, radical, fragment.

ELECTRO-ORGANIC REACTION: PART 28. PREPARATIVE APPLICATIONS OF THE OXALATE CATHODIC CLEAVAGE REACTION INCLUDING ONE-POT CONVERSIONS OF ALDEHYDES AND KETONES

Alcohols and vicinal diols, when co-electrolysed with oxalate esters, undergo transesterification catalysed by cathodically generated base.Under mild conditions at modest cathodic potentials the esters formed in situ give good yields of the corresponding alkanes and alkenes.Furthermore, because diols (pinacols) and alcohols may be efficiently prepared electrochemically from aldehydes and ketones, a one-pot conversion of the carbonyl compounds into alkanes and alkenes has been devised.The method involves prior electrolysis to alcohol or pinacol, addition of an oxalate ester, and further electrolysis for reductive de-oxygenation.Good results are obtained for aromatic ketones and aldehydes.Several oxalate esters have been used in such reactions; diethyloxalate is the most convenient.Esters of squaric acid and of oxamic acid undergo cathodic de-oxygenation but are not convenient in preparative use.