||This Three definitions of acetylide - which one deals this article with may be confusing or unclear to readers. (March 2015)|
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Acetylide is a carbanion with the chemical formula HC≡C−. This is the ethynyl group with one negative. Substituted acetylides, which have the general structure RC≡C− (where R is an organic substituent) can only normally be isolated in their organometallic forms (HC≡CM) and are useful reagents in organic chemistry. Some acetylides are notoriously explosive.
Acetylide also refers to the anion of the formula C2−
2, which can be viewed as the double deprotonation product of acetylene C2H2. It's closed shell ground state of 1Σg+ is makes it isoelectronic to the neutral molecule N2, this affords it some stability in the gas phase but it reacts rapidly as a strong base in the condensed phase.
Although acetylides are described as anions in salts, they are not. The anion is strongly bonded to a metal cation. Thus, alkalii metal acetylides adopt complex structures exhibiting extended interactions. Nonetheless, the anion names are also used for salt-like materials such as copper acetylide (Cu2C2), lithium hydrogenacetylide (LiC2H), and silver methylacetylide (AgCH3C2). Some metal acetylides are traditionally called carbides. For example, lithium carbide and calcium carbide are really derivatives of C22−.
Acetylide ions are very useful in organic chemistry reactions in combining carbon chains, particularly addition and substitution reactions. One type of reaction displayed by acetylides are addition reactions with ketones to form tertiary alcohols. 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.
Several modifications of the reaction with carbonyls are known:
- In the Arens–van Dorp Synthesis the compound ethoxyacetylene  is converted to a Grignard reagent and reacted with a ketone, the reaction product is a propargyl alcohol.
- In the Isler modification ethoxyacetylene is replaced by beta-chlorovinyl ether and lithium amide.
- In the Favorskii–Babayan synthesis ketones and acetylenic compounds react in presence of alkali.
- Sommerfeld, T.; Riss, U.; Meyer, H.-D.; Cederbaum, L. (August 1997). "Metastable C22- Dianion". Physical Review Letters 79 (7): 1237–1240. doi:10.1103/PhysRevLett.79.1237.
- Midland, M. M.; McLoughlin, J. I.; Werley, Ralph T. (Jr.) (1990). "Preparation and Use of Lithium Acetylide: 1-Methyl-2-ethynyl-endo-3,3-dimethyl-2-norbornanol". Org. Synth. 68: 14.; Coll. Vol. 8, p. 391
- Reich, Melanie (Aug 24, 2001). "Addition of a lithium acetylide to an aldehyde; 1-(2-pentyn-4-ol)-cyclopent-2-en-1-ol". ChemSpider Synthetic Pages. p. 137. Retrieved 5 September 2010.
- Synthesis of alkyl 4-hydroxy-2-alkynoates M. Mark Midland, Alfonso Tramontano, John R. Cable J. Org. Chem.; 1980; 45(1); 28-29. Abstract
- Organic Syntheses, Coll. Vol. 4, p.404 (1963); Vol. 34, p.46 (1954). Link
- van Dorp and Arens, Nature, 160, 189 (1947).
- Favorskii–Babayan synthesis