Anodic oxidation. Part III. The electrolysis of methyl hydrogen cis-cyclopropane-1,2-dicarboxylate

Abstract

The electrolysis of methyl hydrogen cis-cyclop:opane-l,2-dicarboxylate has been reinvestigated. The products include dimethyl bicyclopropyl-2,2'-dicarboxylates, which arise by radical coupling, and methyl 2-methoxybut-3-enoate, which is formed through a carbonium ion intermediate. Cyclopropanecarboxylic acid has been electrolysed in sulpholan.FICHTER AND SPIEGELBERG reported 2 in 1929 that the Kolbe-coupled product. Saponification of the ester electrolysis of sodium methyl cis-cyclopropane-1,2-di-gave the di-acid, C,HloO,, which on the basis of its carboxylate in methanol and in water in each case gave rapid reaction with alkaline permanganate and the coa low yield of an ester, C10H1404, corresponding to the incidence of its melting point with that of a compound

Synthesis and Properties of Oligocyclopropyl-Containing Natural Products and Model Compounds

“…While spontaneous oligomerization of cyclopropenes did not lead to defined, homogeneous products, , “dimerizations” of suitable precursors were successfully applied (Scheme ): The parent bicyclopropane ( 3 ) was first synthesized in 1952 from cyclopropyl chloride ( 4 ) and lithium by a Wurtz coupling in low yield . Slightly better yields were observed for the electrolysis of carboxylate 5 leading to 2,2‘-dicarboxylic esters 6 ; however, only a complex mixture containing five diastereoisomers was obtained . It is interesting to note that 1-nitrocyclopropyl anions 13 generated from compound 7 led to, depending on the order of reagent addition, either nitroaldol adducts or the dimers 8 .…”

“…11 Slightly better yields were observed for the electrolysis of carboxylate 5 leading to 2,2′-dicarboxylic esters 6; however, only a complex mixture containing five diastereoisomers was obtained. 12 It is interesting to note that 1-nitrocyclopropyl anions 13 generated from compound 7 led to, depending on the order of reagent addition, either nitroaldol adducts or the dimers 8. 14 A general method to bicyclopropanes was not based on the finding.…”

1,2-Disubstituted cyclopropane and cyclobutane derivatives related to acetylcholine

“…(±)-frans-l-Dimethylaminomethyl-2-hydroxymethylcydopropane (20). To 12.5 g (0.33 mole) of LAH in 250 ml of dry Et2Q was added 13.7 g (0.08 mole) of 19 in 50 ml of dry Et20 over 2 hr, then the mixt was refluxed with stirring for 2 hr.…”