Acetylenic carbonyl compounds Mercury

He showed that sodium salts of aliphatic primary and secondary nitrocompounds react with acids to form carbonyl compounds 2R2CHNO2 = 2R2C0+N2O+ H2O. Nef supported the theory of bivalent carbon. In the preparation of the explosive mercuric salt of nitromethane, he found that mercury fulminate is formed and regarded fulminic acid as C N OH, the reaction being Hg(CH2 N0 0)2==Hg(0-N C)2 + 2H20. He prepared the explosive addition compound of fulminic acid and hydrogen chloride, HON CHCl. In researches on acetylene compounds he prepared explosive di-iodoacetylene, IC-CI (he formulated it IgC.-C). He discovered the reaction between sodium acetylene and a ketone, followed by hydrolysis, to form an acetylenic carbinol ... 

An interesting synthesis of J -butenolides (28) via carbonylation of vinyl-mercurials (27) has been reported. This palladium-catalysed conversion goes in virtually quantitative yield, but its synthetic utility is limited by the availability of the /ra/i5-chlorovinylmercurials (27). These compounds were synthesized from the corresponding acetylenic alcohol by reaction with mercuric chloride-sodium chloride, but yields were generally low (ca. 30%) and the reaction appears to be limited to primary and tertiary acetylenic alcohols. 

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