トリメチルシリルシアニド

危険有害性情報のコード(GHS)

• 絵表示(GHS)

  

• 注意喚起語

  Danger

• 危険有害性情報

  H225：引火性の高い液体および蒸気

  H410：長期的影響により水生生物に非常に強い毒性

• 注意書き

  P210：熱/火花/裸火/高温のもののような着火源から遠ざ けること。－禁煙。

  P233：容器を密閉しておくこと。

  P273：環境への放出を避けること。

  P280：保護手袋/保護衣/保護眼鏡/保護面を着用するこ と。

  P303+P361+P353：皮膚（または髪）に付着した場合：直ちに汚染された衣 類をすべて脱ぐこと/取り除くこと。皮膚を流水/シャワー で洗うこと。

トリメチルシリルシアニド 価格

MSDS Information

• Cyanotrimethylsilane

トリメチルシリルシアニド 化学特性,用途語,生産方法

• 外観

  無色～うすい黄赤色～黄色透明液体

• 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 ℃．d²⁰_D0.7834．n²⁶_D1.389．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。

• 特徴

  結晶学的分子対称Cs，Si－C(Me) 180～181 pm，Si－C(CN) 182 pm

  

• 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

• 物理的性質

  Trimethylsilane cyanide is a colorless volatile liquid with almond odor, soluble in most organic solvents, such as dichloromethane, chloroform, etc.; it reacts violently with protic solvents such as water. This compound is used in organic synthesis as a replacement reagent for highly toxic HCN to introduce cyano groups into molecules.

• 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

• 反応性

  Trimethylsilyl cyanide is a useful silicon reagent which reacts readily with aldehydes and ketones in the presence of catalytic amounts of Lewis acids or of cyanide ion, to give the trimethylsilyl ethers of the corresponding cyanohydrins (Evans,Carroll and Truesdale,1974).Even normally unreactive ketones react readily with trimethylsilyl cyanide due to the formation of the strong Si-O bond which displaces the equilibrium in favour of the derivative.The reaction provides a valuable alternative to the base-catalysed addition of hydrogen cyanide to carbonyl compounds which often gives only poor yields.Tetralone，for example,is reported not to form a cyanohydrin, but it gives a trimethylsilyl derivative in excellent yield.The silylated cyanohydrins can be hydrolysed to a-hydroxy acids(Corey, Crouse and Anderson,1975) and on reduction with lithium aluminium hydride they afford the corresponding 3-amino alcohols in excellent yield.This sequence provides a better route to these valuable intermediates (they are used in the ring expansion of cyclo- alkanones)than the classical methods through reaction of hydrogen cyanide or nitromethane with the carbonyl compound.The derivatives from aromatic aldehydes are excellent acyl anion equivalents and have been used in 'umpolung' conversion of aldehydes into ketones and acyloins by reaction of the derived anions with alkyl halides and aldehydes or ketones (Deuchert et al，1979;Hnig and Wehner,1979).

• 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 2210cm
  1 [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.]

• 参考文献

  M.J. Barrow, Acta Crystallogr., Sect. B, 38, 150 (1982), DOI: 10.1107/S0567740882002258.

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