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

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

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
lipophilic.^[2]

Silylation in organic synthesis

By the process of
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.
alkynes such as bis(trimethylsilyl)acetylene
. Such derivatives are useful protected forms of alkynes.
In the presence of
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
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-tri ketones to give tricyclic pyrroles.^[7]
Reduction of trimethylsilyl chloride give hexamethyldisilane:
${\ce {2 Me3SiCl + 2 Na -> 2 NaCl + Me3Si-SiMe3}}$

References

ISBN 978-3527306732.{{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.

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); Collected Volumes, vol. 1, p. 327.

ISBN 978-0-470-13260-9. {{cite book}}: |journal= ignored (help
)

^ L. Birkofer and P. Wegner (1970). "Trimethylsilyl azide". Organic Syntheses. 50: 107; Collected Volumes, vol. 6, p. 1030.

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

Retrieved from "https://en.wikipedia.org/w/index.php?title=Trimethylsilyl_chloride&oldid=1184479451"

[Roeshe-1] ISBN 978-3527306732.{{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] 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); Collected Volumes, vol. 1, p. 327.

[5] ISBN 978-0-470-13260-9. {{cite book}}: |journal= ignored (help
)

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

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

[2]

[5]

[6]

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