トリメチルシリルシアニド
トリメチルシリルシアニド · トリメチル(シアノ)シラン · (トリメチルシラン)カルボニトリル · トリメチルシアノシラン · トリメチルシランカルボニトリル · トリメチルシリルカルボニトリル · (トリメチルシリル)シアニド · シアノトリメチルシラン
識別子と物理属性
| CAS No. | 7677-24-9 |
|---|---|
| 分子式 | C4H9NSi |
| 平均分子量 | 99.21 g/mol |
| 単同位体質量 | 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 |
| 現地名 | トリメチルシリルシアニド |
化学・物理的性質
| 極性表面積 | 23.8 |
|---|---|
| 水素結合供与体数 | 0 |
| 水素結合受容体数 | 1 |
| 回転可能結合数 | 0 |
| 重原子数 | 6 |
| 形式電荷 | 0 |
| 複雑度 | 81.5 |
| 物質分類 | Nitrogen Compounds -> Nitriles |
| SpringerMaterials Properties | 29Si nuclear magnetic resonance spectrum |
| Physical Description | Colorless liquidmp = 11-12 deg C[MSDSonline] |
| 融点 | 8-11 °C(lit.) |
| 沸点 | 114-117 °C(lit.) |
| 密度 | 0.793 g/mL at 20 °C(lit.) |
| 屈折率 | n20/D 1.392(lit.) |
| 引火点 | 34 °F |
| 貯蔵条件 | Inert atmosphere,2-8°C |
| 溶解度 | 有機溶剤と混和します。反応する |
| 外観・状態 | 液体 |
| 比重 | 0.744 |
| 色 | 黄色 |
| BRN | 1737612 |
| 安定性 | 湿気に敏感 |
| InChIKey | LEIMLDGFXIOXMT-UHFFFAOYSA-N |
| CAS データベース | 7677-24-9(CAS DataBase Reference) |
| EPAの化学物質情報 | Silanecarbonitrile, trimethyl- (7677-24-9) |
化学的特性
Trimethylsilyl cyanide (TMSCN) is a commercial reagent used as cyanide source for nucleophilic reactions. It is a clear colorless to yellow liquid, moisture sensitive, with a boiling point of 114–117 °C, which was first synthetized by the reaction of trimethylsilicon halides TMSX and AgCN in 1952.TMSCN is a versatile reagent that can be used in several different reactions, but it is generally used in nucleophilic additions to aldehydes, ketones and imines to form cyanohydrin silyl ethers (Scheme 1a) and α-aminonitriles in Strecker-type reactions (Scheme 1b).Reactions of Trimethylsilyl Cyanide
安全性と法規制
| GHS 分類 | 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. |
|---|---|
| 規制情報 | 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 |
| 有害性の概要 | 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) |
| 健康影響 | 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) |
| 有害作用 | Other Poison - Chemical Asphyxiant |
| 暴露経路 | Inhalation (L96)oral (L96)dermal (L96) |
| 毒性の概要 | 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) |
用途
解説
シアノトリメチルシラン，trimethylsilyl cyanide．C4H9NSi(99.21)．(CH3)3SiCN．クロロトリメチルシランとシアン化カリウム，あるいはシアン化銀との反応により得られる．無色の液体．沸点117 ℃．d20D0.7834．n26D1.389．引火性がある．有毒．カルボニル化合物に付加し，シアノヒドリンのシリルエーテルを与える．そのほか，アルケンのシアノシリル化，キノンの保護，ニトリル合成など，合成試薬として用いられる．
用途
医薬、電子材料。
使用
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.
製法・合成法
製造方法
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
純化方法
The material should have only one sharp signal in the 1H NMR (in CCl4 with CHCl3 as internal standard) : 0.4ppm and IR with max at 2210cm1 [McBride & Beachall J Am Chem Soc 74 5247 1952, Prober J Am Chem Soc 77 3224 1955]; otherwise purify it by fractionating through an 18 x 1/4inch column. [Evers et al. J Am Chem Soc 81 4493 1959.] It has also been carefully distilled using a 60cm vacuum jacketed column. If the volume of sample is small, the cyanide can be chased (in the distillation) with xylene that had been previously distilled over P2O5. It is HIGHLY TOXIC and FLAMMABLE. [Evans et al. J Org Chem 39 914 1974, Beilstein 4 IV 3893.]