Trimethylsilylacetylene#History
{{Chembox
| Watchedfields = changed
| verifiedrevid = 470615876
| ImageFile = Trimethylsilylacetylene.svg
| ImageSize =
| PIN = Ethynyltri(methyl)silane
| OtherNames =
|Section1={{Chembox Identifiers
| InChI = 1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3
| InChIKey1 = CWMFRHBXRUITQE-UHFFFAOYSA-N
| InChI1 = 1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 1066-54-2
| Abbreviations = TMSA
| PubChem = 66111
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 59499
| EC_number = 213-919-9
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = CWMFRHBXRUITQE-UHFFFAOYSA-N
| SMILES = C#C[Si](C)(C)C
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C5H10Si/c1-5-6(2,3)4/h1H,2-4H3
}}
|Section2={{Chembox Properties
| Formula = {{chem2|(CH3)3Si\sC\tCH}}
| C=5 | H=10 | Si=1
| Appearance = colorless liquid
| Density = 0.709 g/mL https://www.sigmaaldrich.com/US/en/product/mm/814226
| MeltingPt =
| BoilingPtC = 53
| Solubility =
}}
|Section3={{Chembox Hazards
| ExternalSDS = [http://fscimage.fishersci.com/msds/20433.htm External MSDS]
| GHSPictograms = {{GHS02}}{{GHS05}}{{GHS07}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|225|315|318|319|335}}
| PPhrases = {{P-phrases|210|233|240|241|242|243|261|264|271|280|302+352|303+361+353|304+340|305+351+338|310|312|321|332+313|337+313|362|370+378|403+233|403+235|405|501}}
| FlashPt =
| AutoignitionPt =
}}
}}
Trimethylsilylacetylene is the organosilicon compound with the formula {{chem2|(CH3)3Si\sC\tCH}}. A colorless liquid, "tms acetylene", as it is also called, is used as a source of Acetylide anion in organic synthesis.
Use
Trimethylsilylacetylene is used in Sonogashira couplings as the equivalent of acetylene. 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 to form phenylacetylene derivatives.{{cite encyclopedia|title=Trimethylsilylacetylene| encyclopedia=EROS|author=Godson C. Nwokogu |author2=Saskia Zemolka |author3=Florian Dehme |year=2007|doi=10.1002/047084289X.rt288.pub2| isbn=978-0-471-93623-7}} Trimethylsilylacetylene is also used to synthesize diphenylacetylene derivatives in a one-pot Sonogashira coupling, in which the phenylacetylene derivative reacts with a second aryl halide after in-situ deprotection.{{cite journal |last1=Mio |first1=Matthew J. |last2=Kopel |first2=Lucas C. |last3=Braun |first3=Julia B. |last4=Gadzikwa |first4=Tendai L. |last5=Hull |first5=Kami L. |last6=Brisbois |first6=Ronald G. |last7=Markworth |first7=Christopher J. |last8=Grieco |first8=Paul A. |date=2002 |title=One-Pot Synthesis of Symmetrical and Unsymmetrical Bisarylethynes by a Modification of the Sonogashira Coupling Reaction |journal=Organic Letters |volume=4 |issue=19 |pages=3199–3202 |doi=10.1021/ol026266n|pmid=12227748}} 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.{{OrgSynth | title = Trimethylsilylacetylene | author = Andrew B. Holmes, Chris N. Sporikou | volume65 | page = 61 | year = 1987|doi=10.15227/orgsyn.065.0061}}
Trimethylsilylacetylene is a precursor to 1,4-bis(trimethylsilyl)buta-1,3-diyne, a protected form of 1,3-butadiyne.{{cite journal |doi=10.15227/orgsyn.065.0052|title=1,4-Bis(trimethylsilyl)buta-1,3-diyne|journal=Organic Syntheses|year=1987|volume=65|page=52|author=Graham E. Jones, David A. Kendrick, and Andrew B. Holmes}}
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.{{citation|surname1=H. G. Viehe|periodical=Chemische Berichte|title=Heterosubstituierte Acetylene, III. Nucleophile Substitutionen und Halogen-Metall-Austauschreaktionen an Dreifachbindungen|volume=92|issue=12|at=pp. 3064–3075|date=1959|language=German|doi=10.1002/cber.19590921209
}}
