| Revision as of 14:15, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 424029543 of page Trimethylsilyl_chloride for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 22:03, 28 December 2024 edit JWBE (talk | contribs)Extended confirmed users10,126 edits removed Category:Chlorosilanes; added Category:Organochlorosilanes using HotCat |
| Line 1: |
Line 1: |
|
|
{{short description|Organosilicon compound with the formula (CH3)3SiCl}} |
|
{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
|
|
|
{{Redirect|TMCS|the history of Ticketmaster Online–CitySearch (TMCS)|IAC (company)#1980s and 1990s|the Turtle Mountain Community School in North Dakota|Belcourt School District}} |
|
{{chembox |
|
{{chembox |
|
|
| Watchedfields = changed |
|
| verifiedrevid = 412832233 |
|
|
|
| verifiedrevid = 470615723 |
|
| Name = Trimethylsilyl chloride |
|
|
|
| Name = Trimethylsilyl chloride |
|
| ImageFile = tmscl_stick2.png |
|
|
|
| ImageFile = tmscl_stick2.png |
|
| ImageSize = 150px |
|
|
| ImageName = TMSCl |
|
| ImageName = TMSCl |
|
|
| ImageSize = 150px |
|
| ImageFileL1 = Trimethylsilyl-chloride-from-xtal-2006-3D-balls.png |
|
|
|
| ImageFileL1 = Trimethylsilyl-chloride-from-xtal-2006-3D-balls.png |
|
| ImageSizeL1 = 150px |
|
|
| ImageNameL1 = Ball-and-stick model of the trimethylsilyl chloride molecule |
|
| ImageNameL1 = Ball-and-stick model of the trimethylsilyl chloride molecule |
|
| ImageFileR1 = Trimethylsilyl-chloride-from-xtal-2006-3D-vdW.png |
|
| ImageFileR1 = Trimethylsilyl-chloride-from-xtal-2006-3D-vdW.png |
|
|
| ImageNameR1 = Space-filling model of the trimethylsilyl chloride molecule |
|
| ImageSizeR1 = 150px |
|
|
|
| PIN = Chlorotri(methyl)silane |
|
| ImageNameR1 = Space-filling model of the trimethylsilyl chloride molecule |
|
|
| IUPACName = Trimethylsilyl chloride |
|
| OtherNames = Trimethylsilyl chloride<br />Chlorotrimethylsilane<br />TMSCl<br />Trimethylchlorosilane<br />TMCS |
|
|
|Section1={{Chembox Identifiers |
|
| OtherNames = Chlorotrimethylsilane<br />TMSCl<br/>Trimethylchlorosilane<br>TMCS |
|
|
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| Section1 = {{Chembox Identifiers |
|
|
| SMILES = C(C)(C)Cl |
|
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
|
| ChemSpiderID = 6157 |
|
| ChemSpiderID = 6157 |
|
|
| EC_number = 200-900-5 |
|
| PubChem = 6397 |
|
| PubChem = 6397 |
|
|
| CASNo = 75-77-4 |
|
| InChI = 1/C3H9ClSi/c1-5(2,3)4/h1-3H3 |
|
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
| InChIKey = IJOOHPMOJXWVHK-UHFFFAOYAM |
|
|
|
| UNII_Ref = {{fdacite|correct|FDA}} |
|
|
| UNII = 62UO4690X6 |
|
|
| UNNumber = 1298 |
|
|
| RTECS = VV2710000 |
|
|
| SMILES = C(C)(C)Cl |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChI = 1S/C3H9ClSi/c1-5(2,3)4/h1-3H3 |
|
| StdInChI = 1S/C3H9ClSi/c1-5(2,3)4/h1-3H3 |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey = IJOOHPMOJXWVHK-UHFFFAOYSA-N |
|
| StdInChIKey = IJOOHPMOJXWVHK-UHFFFAOYSA-N |
|
| CASNo = 75-77-4 |
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|
| RTECS = VV2710000 |
|
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|Section2={{Chembox Properties |
|
| Formula = C<sub>3</sub>H<sub>9</sub>SiCl |
|
| Formula = C<sub>3</sub>H<sub>9</sub>SiCl |
|
| MolarMass = 108.64 g/mol |
|
| MolarMass = 108.64{{nbsp}}g/mol |
|
| Appearance = Colorless liquid, fumes in moist air |
|
| Appearance = Colorless liquid, fumes in moist air |
|
| Density = 0.856 g/cm<sup>3</sup>, liquid |
|
| Density = 0.856{{nbsp}}g/cm<sup>3</sup>, liquid |
|
| Solubility = reacts |
|
| Solubility = Reacts |
|
| MeltingPt = −40 °C (233.2 K) |
|
| MeltingPtC = −40 |
|
|
| MeltingPt_notes = |
|
| BoilingPt = 57 °C (330.2 K) |
|
|
|
| BoilingPtC = 57 |
|
| Viscosity = |
|
|
|
| BoilingPt_notes = |
|
|
| Viscosity = |
|
|
| MagSus = −77.36·10<sup>−6</sup>{{nbsp}}cm<sup>3</sup>/mol |
|
}} |
|
}} |
|
| Section3 = {{Chembox Structure |
|
|Section3={{Chembox Structure |
|
| MolShape = tetrahedral at Si |
|
| MolShape = Tetrahedral at Si |
|
| Dipole = |
|
| Dipole = |
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
|Section7={{Chembox Hazards |
|
| ExternalMSDS = |
|
| ExternalSDS = |
|
|
| NFPA-H = 3 |
|
| EUClass = Flammable ('''F''')<br />Corrosive ('''C''') |
|
|
| NFPA-H = 3 |
|
| NFPA-F = 3 |
|
| NFPA-F = 3 | Reactivity=2 | Other=<s>W</s> |
|
| NFPA-R = 2 |
|
| NFPA-R = |
|
| NFPA-S = W |
|
| RPhrases = {{R11}}, {{R14}}, {{R20}}, {{R21}}, {{R35}}, {{R37}} |
|
| GHSPictograms = {{GHS02}}{{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}} |
|
|
| GHSSignalWord = Danger |
|
| SPhrases = {{S16}}, {{S26}}, {{S36}}, {{S37}}, {{S39}}, {{S45}} |
|
|
|
| HPhrases = {{H-phrases|225|301|312|314|331|351}} |
|
| FlashPt = −28 °C |
|
|
|
| PPhrases = {{P-phrases|201|202|210|233|240|241|242|243|260|261|264|270|271|280|281|301+310|301+330+331|302+352|303+361+353|304+340|305+351+338|308+313|310|311|312|321|322|330|363|370+378|403+233|403+235|405|501}} |
|
| Autoignition = 400 °C |
|
|
|
| FlashPtC = −28 |
|
|
| AutoignitionPtC = 400 |
|
}} |
|
}} |
|
| Section8 = {{Chembox Related |
|
|Section8={{Chembox Related |
|
| Function = ]s |
|
| OtherFunction_label = ]s |
|
| OtherFunctn = ]<br />]<br />]<br /> |
|
| OtherFunction = ]<br />]<br />] |
|
}} |
|
}} |
|
}} |
|
}} |
|
|
'''Trimethylsilyl chloride''', also known as '''chlorotrimethylsilane''' is an ] (]), with the formula {{chem2|(CH3)3SiCl}}, often abbreviated '''{{chem2|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 '']'', the reaction of ] with a silicon-copper alloy. The principal target of this process is ], but substantial amounts of the trimethyl and monomethyl products are also obtained.<ref name=Roeshe>{{Ullmann | author = Röshe, L.; John, P.; Reitmeier, R. | title = Organic Silicon Compounds | doi = 10.1002/14356007.a24_021}}</ref> The relevant reactions are (Me = ], {{chem2|CH3}}): |
|
|
<math chem display=block>x\ \ce{MeCl + Si} \longrightarrow \begin{cases} |
|
|
\ce{Me3SiCl}, \\ |
|
|
\ce{Me2SiCl2}, \\ |
|
|
\ce{MeSiCl3},\\ |
|
|
\text{etc.} |
|
|
\end{cases}</math> |
|
|
|
|
|
Typically about 2–4% of the product stream is the monochloride, which forms an ] with {{chem2|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 ] to give the ]: |
|
|
<math chem display=block>\ce{2 Me3SiCl + H2O -> Me3Si-O-SiMe3 + 2 HCl}</math> |
|
|
The related reaction of trimethylsilyl chloride with alcohols can be exploited to produce ] solutions of ] in alcohols, which find use in the mild synthesis of ]s from ]s and ]s as well as, ]s from ]s. Similarly, trimethylsilyl chloride is also used to silanize ], making the surfaces more ].<ref>Such as in {{OrgSynth | title =<nowiki>The use of polystyrylsulfonyl chloride resin as a solid supported condensation reagent for the formation of esters: Synthesis of N--L-aspartic acid; α tert-butyl ester, β-(2-ethylphenyl]amino]ethyl ester</nowiki> | volume = 81 | pages = 235 | year = 2005 | prep = v81p0235 | author = Norbert Zander and Ronald Frank}}</ref> |
|
|
|
|
|
===Silylation in organic synthesis=== |
|
|
By the process of ], polar functional groups such as ] and ]s readily undergo reaction with trimethylsilyl chloride, giving ]s and ] ]s. These new groups ] the original functional group by removing the labile protons and decreasing the basicity of the heteroatom. The ] of the {{chem2|Me3Si\sO}} and {{chem2|Me3Si\sN}} groups allow them to be easily removed afterwards ("deprotected"). ]ation can also be used to increase the volatility of a compound, enabling ] of normally nonvolatile substances such as ]. |
|
|
|
|
|
Trimethylsilyl chloride also reacts with carbanions to give trimethylsilyl derivatives.<ref>{{cite journal|author1=Stephanie Ganss|author2 =Julia Pedronl|author3 =Alexandre Lumbroso|author4= Günther Leonhardt-Lutterbeck|author5 =Antje Meißner|author6 =Siping Wei|author7 =Hans-Joachim Drexler|author8= Detlef Heller|author9 = Bernhard Breit|title=Rhodium-Catalyzed Addition of Carboxylic Acids to Terminal Alkynes towards Z-Enol Esters|journal=Org. Synth.|year=2016|volume= 93|pages= 367–384|doi=10.15227/orgsyn.093.0367|doi-access=free}}</ref> Lithium acetylides react to give trimethylsilyl] such as ]. Such derivatives are useful protected forms of alkynes. |
|
|
|
|
|
In the presence of ] and ], ]isable ]s, ]s and ]s are converted to ] ]s.<ref>{{OrgSynth|author=Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa | year = 1979 | title = One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenone: 2-Cyclohepten-1-one | volume = 59 | pages = 113 | collvol = 1 | collvolpages = 327 | prep = CV6P0327 }}</ref> Despite their hydrolytic instability, these compounds have found wide application in organic chemistry; ] of the ] by ] or ] can be used to return the original ] group with an ] group at the alpha carbon. The ] ]s can also be used as masked ] equivalents in the ]. |
|
|
|
|
|
===Dehydrations=== |
|
|
Dehydration of metal chlorides with trimethylsilyl chloride in THF gives the solvate as illustrated by the case of ]:<ref>{{cite book|chapter=Solvated and Unsolvated Anhydrous Metal Chlorides from Metal Chloride Hydrates|journal=Inorg. Synth.|volume=29|author=Philip Boudjouk |author2=Jeung-Ho So |title=Inorganic Syntheses |year=1992|pages=108–111|doi=10.1002/9780470132609.ch26|isbn=978-0-470-13260-9}}</ref> |
|
|
<math chem display=block>\ce{CrCl3 * 6 H2O + 12 Me3SiCl -> CrCl3(THF)3 + 6 (Me3Si)2O + 12 HCl}</math> |
|
|
|
|
|
===Other reactions=== |
|
|
Trimethylsilyl chloride is used to prepare other trimethylsilyl halides and ]s, including trimethylsilyl fluoride, trimethylsilyl bromide, ], ], ],<ref>{{OrgSynth | volume = 50 | pages = 107 | collvol = 6 | collvolpages = 1030 | year = 1970 | prep = cv6p1030 | author = L. Birkofer and P. Wegner | title = Trimethylsilyl azide}}</ref> and trimethylsilyl trifluoromethanesulfonate (TMSOTf). These compounds are produced by a ] between trimethylsilyl chloride and a salt of the (pseudo)halide (MX): |
|
|
<math chem display=block>\ce{MX + Me3Si-Cl -> MCl + Me3Si-X}</math> |
|
|
TMSCl, lithium, and nitrogen molecule react to give ], under catalysis by ] wire or ]: |
|
|
<math chem display=block>\ce{3 Me3SiCl + 3 Li} + \tfrac{1}{2} \, \ce{N2 -> (Me3Si)3N + 3 LiCl}</math> |
|
|
Using this approach, atmospheric nitrogen can be introduced into organic substrate. For example, tris(trimethylsilyl)amine reacts with α,δ,ω-tri]s to give tricyclic ]s.<ref>{{ cite book | last = Brook | first = Michael A. | title = Silicon in Organic, Organometallic, and Polymer Chemistry | year = 2000 | publisher = John Wiley & Sons | location = New York | pages = 193–194 }}</ref> |
|
|
|
|
|
Reduction of trimethylsilyl chloride give ]: |
|
|
<math chem display=block>\ce{2 Me3SiCl + 2 Na -> 2 NaCl + Me3Si-SiMe3}</math> |
|
|
|
|
|
==References== |
|
|
{{reflist}} |
|
|
|
|
|
{{DEFAULTSORT:Trimethylsilyl Chloride}} |
|
|
] |
|
|
] |
|
|
] |