Azidotrimethylsilane
TMSN3 · TRIMETHYLSILYL AZIDE · TMSiA · decomposes · (CH3)3SiN3 · AzidotrimethyL · Trimethylazidosilane · Three methyl azide silane
Identifiers & Physical Properties
| CAS No. | 4648-54-8 |
|---|---|
| Molecular formula | C3H9N3Si |
| Average molar mass | 115.21 g/mol |
| SMILES | C[Si](C)(C)N=[N+]=[N-] |
| InChIKey | SEDZOYHHAIAQIW-UHFFFAOYSA-N |
| PubChem CID | 78378 |
| EC No. | 225-078-5 |
| DTXSID | DTXSID3063542 |
Chemical & Physical Properties
| Topological polar surface area | 14.4 |
|---|---|
| Hydrogen bond donors | 0 |
| Hydrogen bond acceptors | 2 |
| Rotatable bonds | 1 |
| Heavy atoms | 7 |
| Formal charge | 0 |
| Complexity | 97.2 |
| Chemical classes | Metals -> Metalloid Compounds (Silicon) |
| Physical Description | Colorless liquid[Alfa Aesar MSDS] |
| Melting point | -95°C |
| Boiling point | 92-95 °C(lit.) |
| Density | 0.876 g/mL at 20 °C(lit.) |
| Refractive index | n20/D 1.415(lit.) |
| Flash point | 74 °F |
| Storage conditions | 2-8°C |
| Solubility | Miscible with toluene, dichloromethane, diethyl ether and most organic solvents.decomposes |
| Physical state | Liquid |
| Specific gravity | 0.868 |
| Color | Clear colorless to slightly yellow |
| Sensitivity | Moisture Sensitive |
| Hydrolytic Sensitivity | 8: reacts rapidly with moisture, water, protic solvents |
| BRN | 1903730 |
| InChI | 1S/C3H9N3Si/c1-7(2,3)6-5-4/h1-3H3 |
| InChIKey | SEDZOYHHAIAQIW-UHFFFAOYSA-N |
| SMILES | C[Si](C)(C)N=[N+]=[N-] |
| CAS DataBase Reference | 4648-54-8(CAS DataBase Reference) |
| FDA UNII | EM57JSM2Y9 |
| NIST Chemistry Reference | Azidotrimethylsilane(4648-54-8) |
| EPA Substance Registry System | Azidotrimethylsilane (4648-54-8) |
| UNSPSC Code | 12352103 |
| NACRES | NA.23 |
| GHS pictogram | GHS02,GHS06 |
| Signal word | Danger |
| GHS hazard statements | H225-H301+H311+H331 |
| GHS precautionary statements | P210-P280-P301+P310+P330-P302+P352+P312-P304+P340+P311 |
| Personal protective equipment (PPE) | Eyeshields, Faceshields, Gloves, type ABEK (EN14387) respirator filter |
| Hazard symbols | F,T,N |
| Risk statements (R) | 11-23/24/25-50/53-29 |
| Safety statements (S) | 16-36/37/39-45-8-57-36/37-29 |
| UN transport number | UN 1992 3/PG 2 |
| Water hazard class (WGK) | 3 |
| F | 10-33 |
| Autoignition temperature | 300 °C |
| TSCA inventory status | TSCA listed |
| Hazard class | 3Acute Tox. 3 DermalAcute Tox. 3 InhalationAcute Tox. 3 OralFlam. Liq. 2 |
| Packing group | II |
| Customs code | 29310095 |
| Storage class | 3 - Flammable liquids |
| REACH registrations | Active |
| Limited quantities | 1.0 L (0.3 gallon) (liquid) |
| Excepted quantities | Max Inner Pack (30g or 30ml) and Max Outer Pack (500g or 500ml) |
Safety & Regulations
| GHS classification | DangerH225 (100%): Highly Flammable liquid and vapor [Danger Flammable liquids]P210, P233, P240, P241, P242, P243, P261, P262, P264, P270, P271, P273, P280, P301+P316, P302+P352, P303+P361+P353, P304+P340, P316, P321, P330, P361+P364, P370+P378, P391, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)Aggregated GHS information provided per 52 reports by companies from 7 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies. |
|---|---|
| Regulatory information | Chemical: Silane, azidotrimethyl-Status: Active Update: 09-04-2018 https://echa.europa.eu/registration-dossier/-/registered-dossier/23688Trimethylsilyl azide: Does not have an individual approval but may be used under an appropriate group standard |
| Hazards summary | Reacts with water evolving toxic gasesMay cause irritationToxic by ingestion, inhalation, and skin absorption[Alfa Aesar MSDS] See Hexamethyldisilazane. See Sodium azide. |
| Hazard Classes and Categories | Flam. Liq. 2 (100%) |
| CSL Reaction Information | CSL00010BORON TRIFLUORIDE + AZIDOTRIMETHYLSILANECombinations of TMSN3 and Lewis acids can detonate, presumably due to formation of HN3 from residual water. Avoid Lewis acids.ExplosiveCycloadditionUser-Reported |
| F | 10-33 |
| Personal protective equipment (PPE) | Eyeshields, Faceshields, Gloves, type ABEK (EN14387) respirator filter |
| Water hazard class (WGK) | 3 |
| TSCA inventory status | TSCA listed |
| UN transport number | UN 1992 3/PG 2 |
| Customs code | 29310095 |
| Risk statements (R) | 11-23/24/25-50/53-29 |
| Signal word | Danger |
| GHS pictogram | GHS02,GHS06 |
| Hazard symbols | F,T,N |
| Safety statements (S) | 16-36/37/39-45-8-57-36/37-29 |
| Hazard class | 3Acute Tox. 3 DermalAcute Tox. 3 InhalationAcute Tox. 3 OralFlam. Liq. 2 |
| Storage class | 3 - Flammable liquids |
| Packing group | II |
| GHS hazard statements | H225-H301+H311+H331 |
| Limited quantities | 1.0 L (0.3 gallon) (liquid) |
| Excepted quantities | Max Inner Pack (30g or 30ml) and Max Outer Pack (500g or 500ml) |
| REACH registrations | Active |
| Autoignition temperature | 300 °C |
| GHS precautionary statements | P210-P280-P301+P310+P330-P302+P352+P312-P304+P340+P311 |
Applications & Uses
Uses
Trimethylsilyl azide is used as an azidonation reagent for amines, amides, aldehydes and ketones. It is involved in the preparation of alfa- and beta-siloxy azides from carbonyl compounds and epoxides. It is also used in the preparation of heterocyclic compounds and also acts as an effective substitute for hydrazoic acid. Further, it is used in the Oseltamivir total synthesis.
Uses
Many applications of TMSA in organic synthesis have been reported but only representative examples are described herein.Substitution Reactions. Benzyl,allyl,and substituted alkyl halides are converted to the corresponding azides in 60–100% yields via reactions with TMSA under neutral conditions in a nonaqueous solvent (eq 1).By using tin(IV) chloride as a catalyst, secondary and tertiary cyclic and polycyclic halides are similarly transformed into the corresponding azides in 50–92% yields (eq 1).
Preparation & Synthesis
Preparation
Azidotrimethylsilane may be synthesised by reacting trimethylchlorosilane with sodium azide in hexamethylphosphoramidic triamide. several methods for the synthesis of this azide have been reported.The procedure involving aluminum chloride is not recommended, since an explosive product is formed.Azidotrimethylsilane is now commercially available, and a representative synthetic procedure is as follows. A mixture of sodium azide and chlorotrimethylsilane is refluxed in di-n-butyl ether for 2 days and the azide is safely distilled directly from the reaction vessel. Purer compound (99% content) is obtained by redistillation of the product. Several improved conditions have been reported for the preparation of this azide.In these procedures, trimethylsilyl chloride is reacted with sodium azide either neat or in a high boiling point solvent, such as a mixture of silicone oil and polyethylene glycol. Distillation of the crude product usually provides trimethylsilyl azide (TMSA) in high purity (97.9%) and yield (97%).