Trimethylsilyl cyanide
TMSCN · TRIMETHYLSILANECARBONITRILE · trimethylsilylformonitrile · CYANOTRIMETHYLSILANE · TRIMETHYLCYANOSILANE · TRIMETHYLSILYLNITRILE · trimethylsilylmethanenitrile · DK897
Identifiers & Physical Properties
| CAS No. | 7677-24-9 |
|---|---|
| Molecular formula | C4H9NSi |
| Average molar mass | 99.21 g/mol |
| Monoisotopic mass | 99.05042582 g/mol |
| SMILES | C[Si](C)(C)C#N |
| InChIKey | LEIMLDGFXIOXMT-UHFFFAOYSA-N |
| PubChem CID | 82115 |
| EC No. | 231-657-3 |
| DTXSID | DTXSID9064766 |
Chemical & Physical Properties
| Topological polar surface area | 23.8 |
|---|---|
| Hydrogen bond donors | 0 |
| Hydrogen bond acceptors | 1 |
| Rotatable bonds | 0 |
| Heavy atoms | 6 |
| Formal charge | 0 |
| Complexity | 81.5 |
| Chemical classes | Nitrogen Compounds -> Nitriles |
| SpringerMaterials Properties | 29Si nuclear magnetic resonance spectrum |
| Physical Description | Colorless liquidmp = 11-12 deg C[MSDSonline] |
| Melting point | 8-11 °C(lit.) |
| Boiling point | 114-117 °C(lit.) |
| Density | 0.793 g/mL at 20 °C(lit.) |
| Refractive index | n20/D 1.392(lit.) |
| Flash point | 34 °F |
| Storage conditions | Inert atmosphere,2-8°C |
| Solubility | Miscible with organic solvents.reacts |
| Physical state | liquid |
| Specific gravity | 0.744 |
| Color | Yellow |
| Sensitivity | Moisture Sensitive |
| Hydrolytic Sensitivity | 8: reacts rapidly with moisture, water, protic solvents |
| BRN | 1737612 |
| Exposure limits | NIOSH: IDLH 25 mg/m3 |
| Stability | Moisture Sensitive |
| InChIKey | LEIMLDGFXIOXMT-UHFFFAOYSA-N |
| CAS DataBase Reference | 7677-24-9(CAS DataBase Reference) |
| EPA Substance Registry System | Silanecarbonitrile, trimethyl- (7677-24-9) |
| GHS pictogram | GHS02,GHS06,GHS09 |
| Signal word | Danger |
| GHS hazard statements | H225-H300+H310+H330-H410 |
| GHS precautionary statements | P210-P233-P273-P280-P303+P361+P353-P304+P340+P310 |
| Hazard symbols | F,T+,T,N |
| Risk statements (R) | 11-26/27/28-29-50/53 |
| Safety statements (S) | 16-36/37/39-45-61-28A-26 |
| UN transport number | UN 3384 6.1/PG 1 |
| Water hazard class (WGK) | 3 |
| F | 10-21 |
| Hazard Note | Highly Flammable/Toxic |
| TSCA inventory status | TSCA listed |
| Hazard class | 6.1 |
| Packing group | II |
| Customs code | 29310095 |
| REACH registrations | Active |
Safety & Regulations
| GHS classification | DangerH225 (100%): Highly Flammable liquid and vapor [Danger Flammable liquids]P210, P233, P240, P241, P242, P243, P260, P262, P264, P270, P271, P273, P280, P284, P301+P316, P302+P352, P303+P361+P353, P304+P340, P316, P320, 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 82 reports by companies from 8 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies. |
|---|---|
| Regulatory information | Chemical: Silanecarbonitrile, trimethyl-Status: Active Update: 25-10-2022 https://echa.europa.eu/registration-dossier/-/registered-dossier/34122Trimethylsilyl cyanide: HSNO Approval: HSR004750 Approved with controls |
| Hazards summary | Reacts violently with waterHighly toxic by inhalation, skin absorption, and ingestionAn irritant[MSDSonline] See NITRILES. |
| Hazard Classes and Categories | Flam. Liq. 2 (100%) |
| Treatment | Antidotes to cyanide poisoning include hydroxocobalamin and sodium nitrite, which release the cyanide from the cytochrome system, and rhodanase, which is an enzyme occurring naturally in mammals that combines serum cyanide with thiosulfate, producing comparatively harmless thiocyanate. Oxygen therapy can also be administered. (L97) |
| Health effects | Exposure to high levels of cyanide for a short time harms the brain and heart and can even cause coma, seizures, apnea, cardiac arrest and death. Chronic inhalation of cyanide causes breathing difficulties, chest pain, vomiting, blood changes, headaches, and enlargement of the thyroid gland. Skin contact with cyanide salts can irritate and produce sores. (L96, L97) |
| Adverse effects | Other Poison - Chemical Asphyxiant |
| Exposure routes | Inhalation (L96)oral (L96)dermal (L96) |
| Toxicity summary | Organic nitriles decompose into cyanide ions both in vivo and in vitro. Consequently the primary mechanism of toxicity for organic nitriles is their production of toxic cyanide ions or hydrogen cyanide. Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L97) |
| Signs and Symptoms | Cyanide poisoning is identified by rapid, deep breathing and shortness of breath, general weakness, giddiness, headaches, vertigo, confusion, convulsions/seizures and eventually loss of consciousness. (L96, L97) |
| Carcinogen Classification | No indication of carcinogenicity to humans (not listed by IARC). |
| F | 10-21 |
| Water hazard class (WGK) | 3 |
| TSCA inventory status | TSCA listed |
| UN transport number | UN 3384 6.1/PG 1 |
| Customs code | 29310095 |
| Risk statements (R) | 11-26/27/28-29-50/53 |
| Signal word | Danger |
| GHS pictogram | GHS02,GHS06,GHS09 |
| Hazard symbols | F,T+,T,N |
| hazard_note | Highly Flammable/Toxic |
| Safety statements (S) | 16-36/37/39-45-61-28A-26 |
| Hazard class | 6.1 |
| Packing group | II |
| GHS hazard statements | H225-H300+H310+H330-H410 |
| REACH registrations | Active |
| GHS precautionary statements | P210-P233-P273-P280-P303+P361+P353-P304+P340+P310 |
Applications & Uses
Uses
Reacts with aldehydes and ketones to give cyanohydrin-TMS ethers which can be reduced to β-aminoethyl alcohols.Trimethylsilyl cyanide (TMSCN) participates in carbonyl aminomethylation via α-silyloxy nitriles.TMSCN can be used as a reagent in the:Trimethylsilyl cyanide was used in the second step of an oxidative Michael addition of cyanide anion to Baylis–Hillman adducts. The importance of the addition of cyanide to α,β-unsaturated carbonyl derivatives is that the products can be converted into a variety of compounds including γ-aminobutyric acids. The reaction took place in a liquid ionic medium ([bmim]Br), which was reused several times without losing its activity. The β-cyano carbonyl compounds were obtained with high regioselectivity and yields (>79%).Cyanosilylation of carbonyl compounds using various catalysts.Synthesis of α-aminonitriles by one-pot, three-component Strecker reaction of ketones with various amines using Brønsted acid catalyst.Cyanation of aryl halides using palladium-complex as a catalyst.
Uses
Cyanotrimethylsilane is a highly versatile reagent that reacts with a multitude of functional groups to yield an array of products and/or highly valuable synthetic intermediates. Aldehydes and ketones are readily transformed into the corresponding cyanohydrin trimethylsilyl ethers when treated with cyanotrimethylsilane in the presence of Lewis acids (eq 1), triethylamine,or solid bases such as CaF2 or hydroxyapatite. The products can be readily hydrolyzed to the corresponding cyanohydrins. The cyanosilylation of aromatic aldehydes can be achieved with high enantioselectivity in the presence of catalytic amounts of a modified Sharpless catalyst consisting of titanium tetraisopropoxide and L-(+)-diisopropyl tartrate (eq 2).Catalysis with chiral titanium reagents yields aliphatic and aromatic cyanohydrins in high chemical and optical yields (eq 3). Cyanohydrins can be subsequently transformed into a variety of useful synthetic intermediates (eq 4).
Uses
Trimethylsilyl Cyanide is used as a reagent in the synthesis of optically active cyanohydrins. Used in the preparation of Reissert compounds, which represent reactive polyamides. Toxic to humans.
Preparation & Synthesis
Preparation
Trimethylsilyl cyanide, (CH3)3 Si-CN, is obtained by reacting trimethylsilyl chloride with an approximately equimolar amount of an alkali metal cyanide in the absence of water and in the presence of catalytic, sub-stoichiometric amounts of both an alkali metal iodide and N-methylpyrrolidone, at a temperature of from 15°-25° C. Trimethylsilyl cyanide is very toxic. All reactions in this sequence should be carried out in a hood. Preparation of trimethylsilyl cyanide TRIMETHYLSILYL CYANIDE: CYANOSILATION OF p-BENZOQUINONE