Trimethylsilylacetylene

Trimethylsilylacetylene is the organosilicon compound with the formula (CH3)3SiC2H. A colorless liquid, "tms acetylene", as it is also called, is used as a source of "HC2−" in organic synthesis.

Trimethylsilylacetylene
Names
Preferred IUPAC name
Ethynyltri(methyl)silane
Identifiers
3D model (JSmol)
Abbreviations TMSA
ChemSpider
ECHA InfoCard 100.012.655
EC Number
  • 213-919-9
  • InChI=1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3 checkY
    Key: CWMFRHBXRUITQE-UHFFFAOYSA-N checkY
  • InChI=1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3
  • InChI=1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3
    Key: CWMFRHBXRUITQE-UHFFFAOYSA-N
  • C#C[Si](C)(C)C
Properties
C5H10Si
Molar mass 98.220 g·mol−1
Appearance colorless liquid
Density 0.69 g/mL
Boiling point 53 °C (127 °F; 326 K)
Hazards
GHS labelling:
GHS02: FlammableGHS05: CorrosiveGHS07: Exclamation mark
Danger
H225, H315, H318, H319, H335
P210, P233, P240, P241, P242, P243, P261, P264, P271, P280, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P321, P332+P313, P337+P313, P362, P370+P378, P403+P233, P403+P235, P405, P501
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Use

Trimethylsilylacetylene is used in Sonogashira couplings as the equivalent of acetylene.[1] Using this protected alkyne, as opposed to acetylene itself, prevents further coupling reactions. The trimethylsilyl group can then be cleaved off with TBAF or DBU, either separately or as part of a one-pot Sonogashira reaction to form phenylacetylene derivatives.[2] A less expensive alternative reagent is 2-methylbut-3-yn-2-ol, which after alkynylation is deprotected with base.

Trimethylsilylacetylene is commercially available. It may also be prepared in a manner similar to other silyl compounds: deprotonation of acetylene with a Grignard reagent, followed by reaction with trimethylsilyl chloride.[3]

Trimethylsilylacetylene is a precursor to 1,4-bis(trimethylsilyl)buta-1,3-diyne, a protected form of 1,3-butadiyne.[4]

History

Trimethylsilylacetylene was first synthesized in 1959 by Heinz Günter Viehe. He reduced chloro(trimethylsilyl)acetylene by reaction with phenyllithium in diethyl ether and proceeded with subsequent hydrolysis.[5]

References
  1. Mio, Matthew J.; Kopel, Lucas C.; Braun, Julia B.; Gadzikwa, Tendai L.; Hull, Kami L.; Brisbois, Ronald G.; Markworth, Christopher J.; Grieco, Paul A. (2002). "One-Pot Synthesis of Symmetrical and Unsymmetrical Bisarylethynes by a Modification of the Sonogashira Coupling Reaction". Organic Letters. 4 (19): 3199–3202. doi:10.1021/ol026266n. PMID 12227748.
  2. Godson C. Nwokogu; Saskia Zemolka; Florian Dehme (2007). "Trimethylsilylacetylene". EROS. doi:10.1002/047084289X.rt288.pub2. ISBN 978-0-471-93623-7.
  3. Andrew B. Holmes, Chris N. Sporikou (1987). "Trimethylsilylacetylene". Organic Syntheses: 61. doi:10.15227/orgsyn.065.0061.
  4. Graham E. Jones, David A. Kendrick, and Andrew B. Holmes (1987). "1,4-Bis(trimethylsilyl)buta-1,3-diyne". Organic Syntheses. 65: 52. doi:10.15227/orgsyn.065.0052.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. H. G. Viehe (1959), "Heterosubstituierte Acetylene, III. Nucleophile Substitutionen und Halogen-Metall-Austauschreaktionen an Dreifachbindungen", Chemische Berichte (in German), vol. 92, no. 12, pp. 3064–3075, doi:10.1002/cber.19590921209
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