Trimethylsilyl azide

Last updated
Trimethylsilyl azide
Trimethylsilyl azide.png
Trimethylsilyl-azide-3D-spacefill.png
Names
Preferred IUPAC name
Azidotri(methyl)silane
Identifiers
3D model (JSmol)
1903730
ChemSpider
ECHA InfoCard 100.022.798 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 225-078-5
PubChem CID
  • InChI=1S/C3H9N3Si/c1-7(2,3)6-5-4/h1-3H3 Yes check.svgY
    Key: SEDZOYHHAIAQIW-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3H9N3Si/c1-7(2,3)6-5-4/h1-3H3
    Key: SEDZOYHHAIAQIW-UHFFFAOYAJ
  • [N-]=[N+]=N[Si](C)(C)C
Properties
C3H9N3Si
Molar mass 115.211 g·mol−1
Appearancecolorless liquid
Density 0.8763 g/cm3 (20 °C)
Melting point −95 °C (−139 °F; 178 K)
Boiling point 52 to 53 °C (126 to 127 °F; 325 to 326 K) at 175 mmHg (92 to 95 °C at 760 mmHg)
reacts to form dangerous hydrazoic acid
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H225, H301, H311, H331, H410
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P273, P280, P301+P310, P302+P352, P303+P361+P353, P304+P340, P311, P312, P321, P322, P330, P361, P363, P370+P378, P391, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
4
3
0
Flash point 6 °C (43 °F; 279 K)
>300 °C (572 °F; 573 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Trimethylsilyl azide is the organosilicon compound with the formula (CH3)3SiN3. A colorless liquid, it is a reagent in organic chemistry, serving as the equivalent of hydrazoic acid. [1]

Contents

Preparation

Trimethylsilyl azide is commercially available. It may be prepared by the reaction of trimethylsilyl chloride and sodium azide: [2]

(CH3)3Si−Cl + NaN3 → (CH3)3Si−N3 + NaCl

Reactions

The compound hydrolyzes to hydrazoic acid: [3]

(CH3)3SiN3 + H2O → (CH3)3SiOH + HN3

The compound adds to ketones and aldehydes to give the siloxy azides and subsequently tetrazoles: [1]

(CH3)3SiN3 + R2CO → R2C(N3)OSi(CH3)3

It ring-opens epoxides to give azido alcohols.

It has been used in the Oseltamivir total synthesis.

Safety

Trimethylsilyl azide is incompatible with moisture, strong oxidizing agents, and strong acids. Azides are often explosive, as illustrated by their use in air bags.

Related Research Articles

In chemistry, azide is a linear, polyatomic anion with the formula N−3 and structure N=N+=N. It is the conjugate base of hydrazoic acid HN3. Organic azides are organic compounds with the formula RN3, containing the azide functional group. The dominant application of azides is as a propellant in air bags.

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

Sodium azide is an inorganic compound with the formula NaN3. This colorless salt is the gas-forming component in some car airbag systems. It is used for the preparation of other azide compounds. It is an ionic substance, is highly soluble in water, and is very acutely poisonous.

<span class="mw-page-title-main">Hydrazoic acid</span> Unstable and toxic chemical compound

Hydrazoic acid, also known as hydrogen azide or azoimide, is a compound with the chemical formula HN3. It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

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

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Sodium bis(trimethylsilyl)amide</span> Chemical compound

Sodium bis(trimethylsilyl)amide is the organosilicon compound with the formula NaN(Si 3)2. This species, usually called NaHMDS, is a strong base used for deprotonation reactions or base-catalyzed reactions. Its advantages are that it is commercially available as a solid and it is soluble not only in ethers, such as THF or diethyl ether, but also in aromatic solvents, like benzene and toluene by virtue of the lipophilic TMS groups.

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

Trimethylsilyldiazomethane is the organosilicon compound with the formula (CH3)3SiCHN2. It is classified as a diazo compound. Trimethylsilyldiazomethane is a commercially available reagent used in organic chemistry as a methylating agent and as a source of CH2 group. Its behavior is akin to the less convenient reagent diazomethane.

<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">Organosilicon chemistry</span> Organometallic compound containing carbon–silicon bonds

Organosilicon chemistry is the study of organometallic compounds containing carbon–silicon bonds, to which they are called organosilicon compounds. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

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

Trimethylsilyl cyanide is the chemical compound with the formula (CH3)3SiCN. This volatile liquid consists of a cyanide group, that is CN, attached to a trimethylsilyl group. The molecule is used in organic synthesis as the equivalent of hydrogen cyanide. It is prepared by the reaction of lithium cyanide and trimethylsilyl chloride:

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

Iodine monochloride is an interhalogen compound with the formula ICl. It is a red-brown chemical compound that melts near room temperature. Because of the difference in the electronegativity of iodine and chlorine, this molecule is highly polar and behaves as a source of I+.

Bis(trimethylsilyl)amine (also known as hexamethyldisilazane and HMDS) is an organosilicon compound with the molecular formula [(CH3)3Si]2NH. The molecule is a derivative of ammonia with trimethylsilyl groups in place of two hydrogen atoms. An electron diffraction study shows that silicon-nitrogen bond length (173.5 pm) and Si-N-Si bond angle (125.5°) to be similar to disilazane (in which methyl groups are replaced by hydrogen atoms) suggesting that steric factors are not a factor in regulating angles in this case. This colorless liquid is a reagent and a precursor to bases that are popular in organic synthesis and organometallic chemistry. Additionally, HMDS is also increasingly used as molecular precursor in chemical vapor deposition techniques to deposit silicon carbonitride thin films or coatings.

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

Hexamethyldisiloxane (HMDSO) is an organosilicon compound with the formula O[Si(CH3)3]2. This volatile colourless liquid is used as a solvent and as a reagent in organic synthesis. It is prepared by the hydrolysis of trimethylsilyl chloride. The molecule is the protypical disiloxane and resembles a subunit of polydimethylsiloxane.

<span class="mw-page-title-main">Lithium bis(trimethylsilyl)amide</span> Chemical compound

Lithium bis(trimethylsilyl)amide is a lithiated organosilicon compound with the formula LiN(Si(CH3)3)2. It is commonly abbreviated as LiHMDS or Li(HMDS) (lithium hexamethyldisilazide - a reference to its conjugate acid HMDS) and is primarily used as a strong non-nucleophilic base and as a ligand. Like many lithium reagents, it has a tendency to aggregate and will form a cyclic trimer in the absence of coordinating species.

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

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.

Silylation is the introduction of one or more (usually) substituted silyl groups (R3Si) to a molecule. Silylations is are core methods for production of organosilicon chemistry. Silanization involves similar methods but usually refers to attachment of silyl groups to solids.

Organosodium chemistry is the chemistry of organometallic compounds containing a carbon to sodium chemical bond. The application of organosodium compounds in chemistry is limited in part due to competition from organolithium compounds, which are commercially available and exhibit more convenient reactivity.

Beryllium azide, Be(N3)2, is an inorganic compound. It is a beryllium salt of hydrazoic acid HN3.

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

Silicon tetraazide is a thermally unstable binary compound of silicon and nitrogen with a nitrogen content of 85.7%. This high-energy compound combusts spontaneously and can only be studied in a solution. A further coordination to a six-fold coordinated structure such as a hexaazidosilicate ion [Si(N3)6]2− or as an adduct with bicationic ligands Si(N3)4·L2 will result in relatively stable, crystalline solids that can be handled at room temperature.

In organic chemistry, thiocarboxylic acids or carbothioic acids are organosulfur compounds related to carboxylic acids by replacement of one of the oxygen atoms with a sulfur atom. Two tautomers are possible: a thione form and a thiol form. These are sometimes also referred to as "carbothioic O-acid" and "carbothioic S-acid" respectively. Of these the thiol form is most common.

An organic azide is an organic compound that contains an azide functional group. Because of the hazards associated with their use, few azides are used commercially although they exhibit interesting reactivity for researchers. Low molecular weight azides are considered especially hazardous and are avoided. In the research laboratory, azides are precursors to amines. They are also popular for their participation in the "click reaction" between an azide and an alkyne and in Staudinger ligation. These two reactions are generally quite reliable, lending themselves to combinatorial chemistry.

References

  1. 1 2 Nishiyama, Kozaburo; Wang, Cheng; Lebel, Hélène (2016). "Azidotrimethylsilane". Encyclopedia of Reagents for Organic Synthesis. pp. 1–16. doi:10.1002/047084289X.ra117.pub3. ISBN   9780470842898.
  2. L. Birkofer and P. Wegner (1970). "Trimethylsilyl azide". Organic Syntheses . 50: 107. doi:10.15227/orgsyn.050.0107.
  3. Jafarzadeh, Mohammad (2007). "Trimethylsilyl Azide (TMSN3): A Versatile Reagent in Organic Synthesis". Synlett. 2007 (13): 2144–2145. doi: 10.1055/s-2007-984895 .