Methyltrichlorosilane

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Methyltrichlorosilane
Methyltrichlorosilane-2D.png
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Names
Preferred IUPAC name
Trichloro(methyl)silane
Other names
Methyltrichlorosilane
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.000.821 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 200-902-6
PubChem CID
UNII
  • InChI=1S/CH3Cl3Si/c1-5(2,3)4/h1H3 Yes check.svgY
    Key: JLUFWMXJHAVVNN-UHFFFAOYSA-N Yes check.svgY
  • C[Si](Cl)(Cl)Cl
Properties
CH3Cl3Si
Molar mass 149.47 g·mol−1
AppearanceColorless liquid
Density 1.273 g·cm−3
Melting point −77 °C (−107 °F; 196 K)
Boiling point 66 °C (151 °F; 339 K)
Reacts with water
−87.45·10−6 cm3·mol−1
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Highly flammable, reacts with water to release HCl
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-exclam.svg
Danger
H225, H315, H319, H335
P210, P233, P240, P241, P242, P243, P261, P264, P271, P280, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
3
3
2
W
Flash point 8.0 °C (46.4 °F; 281.1 K)
490 °C (914 °F; 763 K)
Safety data sheet (SDS) Fischer Scientific MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methyltrichlorosilane, also known as trichloromethylsilane, is a monomer and organosilicon compound with the formula CH3SiCl3. It is a colorless liquid with a sharp odor similar to that of hydrochloric acid. As methyltrichlorosilane is a reactive compound, it is mainly used a precursor for forming various cross-linked siloxane polymers.

Contents

Preparation

Methyltrichlorosilane results from the direct process of chloromethane with elemental silicon in the presence of a copper catalyst, usually at a temperature of at least 250 °C. [1]

2 CH3Cl + Si → (CH3)4−nSiCln + other products

While this reaction is the standard in industrial silicone production and is nearly identical to the first direct synthesis of methyltrichlorosilane, the overall process is inefficient with respect to methyltrichlorosilane. [2] Even though dimethyldichlorosilane is usually the major product, if methyltrichlorosilane is needed, the amount of metal catalyst is reduced. [1]

Reactions

Hydrolysis and alcoholysis

Methyltrichlorosilane undergoes hydrolysis, shown in idealized form here: [1]

MeSiCl3 + 3 H2O → MeSi(OH)3 + 3 HCl

The silanol is unstable and will eventually condense to give a polymer network:

MeSi(OH)3 → MeSiO1.5 + 1.5 H2O

Methyltrichlorosilane undergoes alcoholysis (reaction with alcohol) to give alkoxysilanes. Methanol converts it to trimethoxymethylsilane:

MeSiCl3 + 3 CH3OH → MeSi(OCH3)3 + 3 HCl

Reduction

Reduction of methyltrichlorosilane with alkali metals forms a highly crosslinked material called poly(methylsilyne):

n MeSiCl3 + 3n Na →[MeSi]n + 3n NaCl

The reaction illustrates the susceptibility of silicon halides to reductive coupling. Poly(methylsilyne) is soluble in organic solvents, and can be applied to surfaces before being pyrolyzed to give the ceramic material, silicon carbide. [3]

Applications

Conversion to polymers and resins

One use for methyltrichlorosilane is in the production of methyl silicone resins (highly crosslinked polymers). Because of the stability of the cross-linked polymers resulting from condensation, the resin is stable to 550 °C in a vacuum, making it an ideal material for electrical insulation at high temperatures. [1] These resins can be used to coat computer chips or other electronic parts since they both repel water and provide thermal isolation.

Surface treatments

Methyltrichlorosilane vapor reacts with water on surfaces to give a thin layer of methylpolysiloxane, which changes the contact angle of the surface to water. This effect arises because of the oriented layer of methyl groups, making a water-repellent film. [4] Filter paper treated with methyltrichlorosilane allows organic solvents to pass through, but not water. Another benefit of such water-repellent films is that the polymers formed are stable: one of the only ways to remove the siloxane film is by acid strong enough to dissolve silicone. [4]

Reagent in organic synthesis

A combination of methyltrichlorosilane and sodium iodide can be used to cleave carbon-oxygen bonds such as methyl ethers.

R'OR + MeSiCl3 + NaI + H2O → R'OH + RI + MeSiCl2(OH) + NaCl

Esters and lactones can also be cleaved with methyltrichlorosilane and sodium iodide to give the corresponding carboxylic acids. Acetals convert to carbonyl compounds. Thus, methyltrichlorosilane can be used to remove acetal protecting groups from carbonyl compounds under mild conditions. [5]

RR'C(OMe)2 + MeSiCl3 + NaI → RR'CO + 2 MeI + MeSiCl2(OMe) + NaCl

Methyltrichlorosilane and sodium iodide can be used as a means of converting alcohols to their corresponding iodides; however, this reaction does not work as well with primary alcohols. [5]

ROH + MeSiCl3 + NaI → RI + MeSiCl2(OH) + NaCl

Silicon carbide epitaxy

Methyltrichlorosilane is used as a reagent in silicon carbide epitaxy to introduce chloride in the gas phase. Chloride is used to reduce the tendency of silicon to react in the gas phase and thus to increase the growth rate of the process. [6] Methyltrichlorosilane is an alternative to HCl gas or to trichlorosilane.

Related Research Articles

<span class="mw-page-title-main">Silicon</span> Chemical element, symbol Si and atomic number 14

Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic table: carbon is above it; and germanium, tin, lead, and flerovium are below it. It is relatively unreactive.

<span class="mw-page-title-main">Silicone</span> Type of polymer

A silicone or polysiloxane is a polymer made up of siloxane (−R2Si−O−SiR2−, where R = organic group). They are typically colorless oils or rubber-like substances. Silicones are used in sealants, adhesives, lubricants, medicine, cooking utensils, thermal insulation, and electrical insulation. Some common forms include silicone oil, silicone grease, silicone rubber, silicone resin, and silicone caulk.

<span class="mw-page-title-main">Trichlorosilane</span> Chemical compound

Trichlorosilane is an inorganic compound with the formula HCl3Si. It is a colourless, volatile liquid. Purified trichlorosilane is the principal precursor to ultrapure silicon in the semiconductor industry. In water, it rapidly decomposes to produce a siloxane polymer while giving off hydrochloric acid. Because of its reactivity and wide availability, it is frequently used in the synthesis of silicon-containing organic compounds.

<span class="mw-page-title-main">Polydimethylsiloxane</span> Chemical compound

Polydimethylsiloxane (PDMS), also known as dimethylpolysiloxane or dimethicone, belongs to a group of polymeric organosilicon compounds that are commonly referred to as silicones. PDMS is the most widely used silicon-based organic polymer, as its versatility and properties lead to many applications.

<span class="mw-page-title-main">Silicone resin</span>

Silicone resins are a type of silicone material which is formed by branched, cage-like oligosiloxanes with the general formula of RnSiXmOy, where R is a non reactive substituent, usually Methyl (Me) or Phenyl (Ph), and X is a functional group Hydrogen (H), Hydroxyl group (OH), Chlorine (Cl) or Alkoxy group (OR). These groups are further condensed in many applications, to give highly crosslinked, insoluble polysiloxane networks.

<span class="mw-page-title-main">Siloxane</span> Si–O–Si chemical bond

A siloxane is a functional group in organosilicon chemistry with the Si−O−Si linkage. The parent siloxanes include the oligomeric and polymeric hydrides with the formulae H(OSiH2)nOH and (OSiH2)n. Siloxanes also include branched compounds, the defining feature of which is that each pair of silicon centres is separated by one oxygen atom. The siloxane functional group forms the backbone of silicones, the premier example of which is polydimethylsiloxane. The functional group R3SiO− (where the three Rs may be different) is called siloxy. Siloxanes are manmade and have many commercial and industrial applications because of the compounds’ hydrophobicity, low thermal conductivity, and high flexibility.

Chlorosilanes are a group of reactive, chlorine-containing chemical compounds, related to silane and used in many chemical processes. Each such chemical has at least one silicon-chlorine bond. Trichlorosilane is produced on the largest scale. The parent chlorosilane is silicon tetrachloride.

<span class="mw-page-title-main">Trimethylsilyl chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Silicone rubber</span> Elastomer

Silicone rubber is an elastomer composed of silicone—itself a polymer—containing silicon together with carbon, hydrogen, and oxygen. Silicone rubbers are widely used in industry, and there are multiple formulations. Silicone rubbers are often one- or two-part polymers, and may contain fillers to improve properties or reduce cost.

<span class="mw-page-title-main">Organosilicon compound</span> Organometallic compound containing carbon–silicon bonds

Organosilicon compounds are organometallic compounds containing carbon–silicon bonds. Organosilicon chemistry is the corresponding science of their preparation and properties. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

Hydrosilanes are tetravalent silicon compounds containing one or more Si-H bond. The parent hydrosilane is silane (SiH4). Commonly, hydrosilane refers to organosilicon derivatives. Examples include phenylsilane (PhSiH3) and triethoxysilane ((C2H5O)3SiH). Polymers and oligomers terminated with hydrosilanes are resins that are used to make useful materials like caulks.

<span class="mw-page-title-main">Tetraethyl orthosilicate</span> Chemical compound

Tetraethyl orthosilicate, formally named tetraethoxysilane (TEOS), ethyl silicate is the organic chemical compound with the formula Si(OC2H5)4. TEOS is a colorless liquid. It degrades in water. TEOS is the ethyl ester of orthosilicic acid, Si(OH)4. It is the most prevalent alkoxide of silicon.

Dimethyldichlorosilane is a tetrahedral, organosilicon compound with the formula Si(CH3)2Cl2. At room temperature it is a colorless liquid that readily reacts with water to form both linear and cyclic Si-O chains. Dimethyldichlorosilane is made on an industrial scale as the principal precursor to dimethylsilicone and polysilane compounds.

The direct process, also called the direct synthesis, Rochow process, and Müller-Rochow process is the most common technology for preparing organosilicon compounds on an industrial scale. It was first reported independently by Eugene G. Rochow and Richard Müller in the 1940s.

<span class="mw-page-title-main">Silsesquioxane</span> Molecular compound with applications in ceramics

A silsesquioxane is an organosilicon compound with the chemical formula [RSiO3/2]n. Silsesquioxanes are colorless solids that adopt cage-like or polymeric structures with Si-O-Si linkages and tetrahedral Si vertices. Silsesquioxanes are members of polyoctahedral silsesquioxanes ("POSS"), which have attracted attention as preceramic polymer precursors to ceramic materials and nanocomposites. Diverse substituents (R) can be attached to the Si centers. The molecules are unusual because they feature an inorganic silicate core and an organic exterior. The silica core confers rigidity and thermal stability.

Polysilazanes are polymers in which silicon and nitrogen atoms alternate to form the basic backbone. Since each silicon atom is bound to two separate nitrogen atoms and each nitrogen atom to two silicon atoms, both chains and rings of the formula occur. can be hydrogen atoms or organic substituents. If all substituents R are H atoms, the polymer is designated as Perhydropolysilazane, Polyperhydridosilazane, or Inorganic Polysilazane ([H2Si–NH]n). If hydrocarbon substituents are bound to the silicon atoms, the polymers are designated as Organopolysilazanes. Molecularly, polysilazanes are isoelectronic with and close relatives to Polysiloxanes (silicones).

<span class="mw-page-title-main">Polysilane</span>

Polysilanes are organosilicon compounds with the formula (R2Si)n. They are relatives of traditional organic polymers but their backbones are composed of silicon atoms. They exhibit distinctive optical and electrical properties. They are mainly used industrially as precursors to silicon carbide. The simplest polysilane would be (SiH2)n, which is mainly of theoretical, not practical interest.

Polysilynes are organosilicon compounds with the formula [RSi]n. Although their name suggests a relationship to alkynes, polysilynes are a class of silicon-based random network polymers primarily composed of tetrahedral silicon centers, each connected to one carbon and three Si centers. These compounds are prepared by Wurtz coupling of alkyltrichlorosilanes (RSiCl3):

<span class="mw-page-title-main">Methyltrimethoxysilane</span> Chemical compound

Methyltrimethoxysilane is an organosilicon compound with the formula CH3Si(OCH3)3. It is a colorless, free-flowing liquid. It is a crosslinker in the preparation of polysiloxane polymers.

Silanes refers to diverse kinds of charge-neutral silicon compounds with the formula SiR
4
. The R substituents can any combination of organic or inorganic groups. Most silanes contain Si-C bonds, and are discussed under organosilicon compounds.

References

  1. 1 2 3 4 Rösch, L; et al. "Silicon Compounds, Organic." Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH, Weinheim, 2005. doi : 10.1002/14356007.a24_021
  2. Rochow, E. The Direct Synthesis of Organosilicon Compounds. J. Am. Chem. Soc.1945, 67, 963. doi : 10.1021/ja01222a026
  3. Bianconi, Patricia A.; Pitcher, Michael W.; Joray, Scott. "A method of preparing poly(methyl- or ethyl-silyne) and silicon carbide ceramics therefrom." U.S. (2006), 15 pp. CODEN: USXXAM US 6989428 B1 20060124 CAN 144:129423 AN 2006:65860.
  4. 1 2 Rochow, E. "An Introduction to the Chemistry of the Silicones." New York: John Wiley & Sons, Inc., 1946. ISBN   1-4437-2286-3
  5. 1 2 Olah, G; et al. "Methyltrichlorosilane." Encyclopedia of Reagents for Organic Synthesis. New York: John Wiley & Sons, Inc., 2001. doi : 10.1002/047084289X.rm265
  6. Bosi, M; et al. "Defect structure and strain reduction of 3C-SiC/Si layers obtained with the use of a buffer layer and methyltrichlorosilane addition" CrystEngComm 2016, 18, 2770-2779 doi : 10.1039/C6CE00280C