ORGANIC SYNTHESES BY MEANS OF NOBLE METAL COMPOUNDS .39. PALLADIUM-CATALYSED CARBONYLATION OF PROPARGYL COMPOUNDS

Pd catalyzed carbonylations of propargyl chloride and acetylenic alcohols have been carried out. Propargyl chloride gave 3-chloro-3-butenoate and itaconate in alcohol. Propargyl alcohol yielded in methanol methyl 2-methoxymethylacrylate, itaconate and aconitate. Carbonylation of 2-methyl-3-butyn- 2-ol in alcohol, produced teraconate and other products, but in benzene teraconic anhydride was obtained selectively. Similarly carbonylation of 2,5-dimethyl-3-hexyn-2,5-diol gave diisopropylidenesuccinic anhydride as a main product in benzene, and diisopropylidenesuccinate in alcohol. The mechanism of these carbonylation reactions is discussed. The reactions described in this paper afford very useful synthetic methods for itaconic acid and their derivatives. © 1969.