Trimethylsilyl chloride

Trimethylsilyl chloride
Ball-and-stick model of the trimethylsilyl chloride molecule	Space-filling model of the trimethylsilyl chloride molecule
Names
	Preferred IUPAC name Chlorotri(methyl)silane
	Other names Trimethylsilyl chloride; Chlorotrimethylsilane; TMSCl; Trimethylchlorosilane; TMCS
Identifiers
CAS Number	75-77-4 ;
3D model (JSmol)	Interactive image;
ChemSpider	6157 ;
ECHA InfoCard	100.000.819
EC Number	200-900-5;
PubChem CID	6397;
RTECS number	VV2710000;
UNII	62UO4690X6 ;
UN number	1298
CompTox Dashboard (EPA)	DTXSID2024822 ;
	InChI InChI=1S/C3H9ClSi/c1-5(2,3)4/h1-3H3 Key: IJOOHPMOJXWVHK-UHFFFAOYSA-N ;
	SMILES C[Si](C)(C)Cl;
Properties
Chemical formula	C3H9SiCl
Molar mass	108.64 g/mol
Appearance	Colorless liquid, fumes in moist air
Density	0.856 g/cm3, liquid
Melting point	−40 °C (−40 °F; 233 K)
Boiling point	57 °C (135 °F; 330 K)
Solubility in water	Reacts
Magnetic susceptibility (χ)	−77.36·10−6 cm3/mol
Structure
Molecular shape	Tetrahedral at Si
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H225, H301, H312, H314, H331, H351
Precautionary statements	P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P280, P281, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P308+P313, P310, P311, P312, P321, P322, P330, P363, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)	3 3 2 W
Flash point	−28 °C (−18 °F; 245 K)
Autoignition; temperature	400 °C (752 °F; 673 K)
Related compounds
Related halosilanes	Trimethylsilyl fluoride; Trimethylsilyl bromide; Trimethylsilyl iodide
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound (silyl halide), with the formula (CH₃)₃SiCl, often abbreviated Me₃SiCl or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry.

Preparation

TMSCl is prepared on a large scale by the direct process, the reaction of methyl chloride with a silicon-copper alloy. The principal target of this process is dimethyldichlorosilane, but substantial amounts of the trimethyl and monomethyl products are also obtained.[1] The relevant reactions are (Me = methyl, CH₃):

x\ {\ce {MeCl + Si}}\longrightarrow {\begin{cases}{\ce {Me3SiCl}},\\[2pt]{\ce {Me2SiCl2}},\\[2pt]{\ce {MeSiCl3}},\\[2pt]{\text{etc.}}\end{cases}}

Typically about 2–4% of the product stream is the monochloride, which forms an azeotrope with MeSiCl₃.

Reactions and uses

TMSCl is reactive toward nucleophiles, resulting in the replacement of the chloride. In a characteristic reaction of TMSCl, the nucleophile is water, resulting in hydrolysis to give the hexamethyldisiloxane:

{\ce {2 Me3SiCl + H2O -> Me3Si-O-SiMe3 + 2 HCl}}

The related reaction of trimethylsilyl chloride with alcohols can be exploited to produce anhydrous solutions of hydrochloric acid in alcohols, which find use in the mild synthesis of esters from carboxylic acids and nitriles as well as, acetals from ketones. Similarly, trimethylsilyl chloride is also used to silanize laboratory glassware, making the surfaces more lipophilic.[2]

Silylation in organic synthesis

By the process of silylation, polar functional groups such as alcohols and amines readily undergo reaction with trimethylsilyl chloride, giving trimethylsilyl ethers and trimethylsilyl amines. These new groups "protect" the original functional group by removing the labile protons and decreasing the basicity of the heteroatom. The lability of the Me₃Si−O and Me₃Si−N groups can later be removed ("deprotected"). Trimethylsilylation can also be used to increase the volatility of a compound, enabling gas chromatography of normally nonvolatile substances such as glucose.

Trimethylsilyl chloride also reacts with carbanions to give trimethylsilyl derivatives.[3] Lithium acetylides react to give trimethylsilylalkynes such as bis(trimethylsilyl)acetylene. Such derivatives are useful protected forms of alkynes.

In the presence of triethylamine and lithium diisopropylamide, enolisable aldehydes, ketones and esters are converted to trimethylsilyl enol ethers.[4] Despite their hydrolytic instability, these compounds have found wide application in organic chemistry; oxidation of the double bond by epoxidation or dihydroxylation can be used to return the original carbonyl group with an alcohol group at the alpha carbon. The trimethylsilyl enol ethers can also be used as masked enolate equivalents in the Mukaiyama aldol addition.

Dehydrations

Dehydration of metal chlorides with trimethylsilyl chloride in THF gives the solvate as illustrated by the case of chromium trichloride:[5]

{\ce {CrCl3 * 6 H2O + 12 Me3SiCl -> CrCl3(THF)3 + 6 (Me3Si)2O + 12 HCl}}

Other reactions

Trimethylsilyl chloride is used to prepare other trimethylsilyl halides and pseudohalides, including trimethylsilyl fluoride, trimethylsilyl bromide, trimethylsilyl iodide, trimethylsilyl cyanide, trimethylsilyl azide,[6] and trimethylsilyl trifluoromethanesulfonate (TMSOTf). These compounds are produced by a salt metathesis reaction between trimethylsilyl chloride and a salt of the (pseudo)halide (MX):

{\ce {MX + Me3Si-Cl -> MCl + Me3Si-X}}

TMSCl, lithium, and nitrogen molecule react to give tris(trimethylsilyl)amine, under catalysis by nichrome wire or chromium trichloride:

{\ce {3 Me3SiCl + 3 Li}}+{\tfrac {1}{2}}\,{\ce {N2 -> (Me3Si)3N + 3 LiCl}}

Using this approach, atmospheric nitrogen can be introduced into organic substrate. For example, tris(trimethylsilyl)amine reacts with α,δ,ω-triketones to give tricyclic pyrroles.[7]

Reduction of trimethylsilyl chloride give hexamethyldisilane:

{\ce {2 Me3SiCl + 2 Na -> 2 NaCl + Me3Si-SiMe3}}

References

Röshe, L.; John, P.; Reitmeier, R. "Organic Silicon Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a24_021.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
Such as in Norbert Zander and Ronald Frank (2005). "The use of polystyrylsulfonyl chloride resin as a solid supported condensation reagent for the formation of esters: Synthesis of N-[(9-fluorenylmethoxy)carbonyl]-L-aspartic acid; α tert-butyl ester, β-(2-ethyl[(1E)-(4-nitrophenyl)azo]phenyl]amino]ethyl ester". Organic Syntheses. 81: 235.
Stephanie Ganss; Julia Pedronl; Alexandre Lumbroso; Günther Leonhardt-Lutterbeck; Antje Meißner; Siping Wei; Hans-Joachim Drexler; Detlef Heller; Bernhard Breit (2016). "Rhodium-Catalyzed Addition of Carboxylic Acids to Terminal Alkynes towards Z-Enol Esters". Org. Synth. 93: 367–384. doi:10.15227/orgsyn.093.0367.
Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa (1979). "One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenone: 2-Cyclohepten-1-one". Organic Syntheses. 59: 113.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 1, p. 327
Philip Boudjouk; Jeung-Ho So (1992). "Solvated and Unsolvated Anhydrous Metal Chlorides from Metal Chloride Hydrates". Inorganic Syntheses. pp. 108–111. doi:10.1002/9780470132609.ch26. ISBN 978-0-470-13260-9. {{cite book}}: |journal= ignored (help)
L. Birkofer and P. Wegner (1970). "Trimethylsilyl azide". Organic Syntheses. 50: 107.; Collective Volume, vol. 6, p. 1030
Brook, Michael A. (2000). Silicon in Organic, Organometallic, and Polymer Chemistry. New York: John Wiley & Sons. pp. 193–194.

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[Roeshe-1] Röshe, L.; John, P.; Reitmeier, R. "Organic Silicon Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a24_021.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)

[2] Such as in Norbert Zander and Ronald Frank (2005). "The use of polystyrylsulfonyl chloride resin as a solid supported condensation reagent for the formation of esters: Synthesis of N-[(9-fluorenylmethoxy)carbonyl]-L-aspartic acid; α tert-butyl ester, β-(2-ethyl[(1E)-(4-nitrophenyl)azo]phenyl]amino]ethyl ester". Organic Syntheses. 81: 235.

[3] Stephanie Ganss; Julia Pedronl; Alexandre Lumbroso; Günther Leonhardt-Lutterbeck; Antje Meißner; Siping Wei; Hans-Joachim Drexler; Detlef Heller; Bernhard Breit (2016). "Rhodium-Catalyzed Addition of Carboxylic Acids to Terminal Alkynes towards Z-Enol Esters". Org. Synth. 93: 367–384. doi:10.15227/orgsyn.093.0367.

[4] Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa (1979). "One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenone: 2-Cyclohepten-1-one". Organic Syntheses. 59: 113.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 1, p. 327

[5] Philip Boudjouk; Jeung-Ho So (1992). "Solvated and Unsolvated Anhydrous Metal Chlorides from Metal Chloride Hydrates". Inorganic Syntheses. pp. 108–111. doi:10.1002/9780470132609.ch26. ISBN 978-0-470-13260-9. {{cite book}}: |journal= ignored (help)

[6] L. Birkofer and P. Wegner (1970). "Trimethylsilyl azide". Organic Syntheses. 50: 107.; Collective Volume, vol. 6, p. 1030

[7] Brook, Michael A. (2000). Silicon in Organic, Organometallic, and Polymer Chemistry. New York: John Wiley & Sons. pp. 193–194.