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Metal Acetylide




A metal acetylide is an Alkyne that has had a proton (hydrogen) removed from the terminal end by a Metal such as Sodium or an Organolithium . So, for example, the alkyne CH3C≡CH could be Deprotonated to form the acetylide ion CH3C≡C. Once it has been deprotonated it becomes a strong Nucleophile . Some acetylides, eg. Silver Acetylide or Copper Acetylide , are Explosives .

Acetylide ions are very useful in Organic Chemistry reactions in combining carbon chains, particularly Addition and Substitution Reaction s. One type of reaction displayed by acetylides are Addition Reaction s with Ketone s to form Tertiary Alcohol s. In the reaction in ''scheme 1'' the alkyne proton of ''ethyl propiolate'' is deprotonated by N-butyllithium at -78 °C to form lithium ethyl propiolate to which Cyclopentanone is added forming a Lithium Alkoxide . Acetic Acid is added to remove lithium and liberate the free alcohol ''Synthesis of alkyl 4-hydroxy-2-alkynoates'' M. Mark Midland, Alfonso Tramontano, John R. Cable J. Org. Chem. ; 1980; 45(1); 28-29. Abstract .

Coupling reactions of alkynes like the Sonogashira Coupling , the Cadiot-Chodkiewicz Coupling , the Glaser Coupling and the Eglinton Coupling often have metal acetylides as intermediates.

Several modifications of the reaction with carbonyls are known:
  • In the Arens-van Dorp Synthesis the compound ''ethoxyacetylene'' and reacted with a Ketone , the reaction product is a Propargyl Alcohol van Dorp and Arens, Nature, 160, 189 (1947)..

  • In the Isler modification ethoxyacetylene is replaced by beta-chlorovinyl ether and Lithium Amide .

  • In the Favorskii-Babayan synthesis Ketone s and acetylenic compounds react in presence of Alkali http://www.drugfuture.com/organicnamereactions/onr126.htm?.


Formation of acetylides poses a risk in handling of gaseous acetylene in presence of metals like eg. Mercury , Silver or Copper , or alloys with their high content ( Brass , Bronze , silver Solder ).


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