トリエチルシラン

解説トリエチルシランとは、化学式(C2H5)3SiHであらわされる有機ケイ素化合物です。 外観は無色透明の液体であり、室温で液体のもっとも単純なトリアルキルシランの1つとして、有機合成用途に頻繁に用いられます。トリエチルシランの合成方法としては、Rochow法として知られる金属ケイ素と銅触媒を用いる反応によって、得られたクロロシランを原料とする方法が一般的です。 トリエチルシランは、消防法において第4類第一石非水に、安衛法において引火性の物に指定されています。

用途有機薬品。

説明Triethylsilane is a useful versatile reductant since it has a active hydride. It can be used for mediated the palladium-catalyzed dehalogenation reaction of alkyl or aryl halides, the reduction of primary, secondary, and tertiary chlorides, bromides, and iodides catalyzed by iridium, as well as efficient reduction of multiple bonds, azides, imines, and nitro groups, as well as benzyl group and allyl group deprotection. It is also specifically for the hydrosilation of olefins to give alkyl silanes. It is also the catalyst for synthesis of a spiro-oxindole blocker of Nav1.7 for the treatment of pain, redox initiated cationic polymerization and Beckmann rearrangement of cyclododecanone oxime as well as regioselective reductive coupling of enones and allenes.

使用Triethylsilane is a trialkylsilicon hydride used in the synthesis of alkylsilanes via hydrosilation of olefins. It acts as a reducing agent in the reduction of 2-chromanols, since it has an active hydride. It acts as a catalyst for redox initiated cationic polymerization, regioselective reductive coupling of enones and allenes, and Beckmann rearrangement of cyclododecanone oxime. It is associated with trifluoroacetic acid and involved in the selective reduction of alkenes.

使用用途トリエチルシランは、ヒドロシリル化やシリルエーテルの出発物質としての用途が挙げられますが、還元剤としての用途が最も知られています。トリエチルシランは他の還元剤と比較して安定性が高く安全であり、さまざまな官能基に対して用いることが可能です。 また、重金属を含まないため環境負荷が小さいという点も利点として挙げられます。トリエチルシランを用いた還元反応は、イオン機構、ラジカル機構のいずれの機構でも進行することが知られています。 さらに、酸性条件下でも安定なことから、、アルケン、アルデヒドやケトンなど、さまざまな化合物の還元剤として使用可能です。

A synthetic method of triethylsilane comprises the following steps: reacting sodium hydride with trimethyl borate to prepare trimethoxy sodium borohydride; adding triethylchlorosilane to trimethoxy sodium monohydroborate to react to obtain triethylsilane.To a 500ml reaction flask, 20g (0.5mol) of 60% sodium hydride and 80g of anhydrous tetrahydrofuran were added. Stirring and cooling to 0-10 ℃ under the protection of nitrogen, the mixture was then maintained under nitrogen protection, stirred, and the liquid temperature at 0-10 ℃, and dropwise added 57.2g (0.55mol) of trimethyl borate. After the dropwise addition, the temperature was kept at 0-10 ℃ and stirred for 1 hour.Maintaining the nitrogen protection, stirring and liquid temperature of the reaction liquid at 0-10 ℃, and then dropwise adding 67.7g (0.45mol) of triethylchlorosilane. After the dropwise addition, continuously keep the temperature at 0-10 ℃ and stir for 1 hour. The reaction solution was then filtered at room temperature. Rectifying the filtrate at normal pressure and collecting fractions with the boiling range of 109-110 ℃ as triethylsilane to obtain 46.1g of triethylsilane, which yields 88.2%. 45-64 ℃: a mixed solution of trimethyl borate and tetrahydrofuran; 64-109 ℃:a mixture of tetrahydrofuran and a small triethylsilane.

純化方法Reflux triethylsilane over molecular sieves, then distil it. It is passed through neutral alumina before use [Randolph & Wrighton J Am Chem Soc 108 3366 1986]. [Beilstein 4 IV 3895.]