ブロモトリメチルシラン

外観

無色～うすい黄色～うすい黄赤色透明液体

溶解性

水に分解する。

使用上の注意

不活性ガス封入

化学的特性

Clear yellow liquid

物理的性質

bp 79°C; d 1.188 g cm?3; n20 D 1.4240; fp 32°C.

使用

Bromotrimethylsilane is a mild and selective reagent for cleavage of lactones, epoxides, acetals, phosphonate esters and certain ethers; effective reagent for formation of silyl enol ethers; can function as brominating agent.
Amines react with TMS-Br to form isolable adducts, which react readily with ketones to form enamines under mild conditions (eq 15).

製造方法

although many methods are reported, only a few are provided here: chlorotrimethylsilane undergoes halogen exchange with either magnesium bromide in Et2O or sodium bromide in MeCN, which allows in situ reagent formation (eq 1); alternatively, hexamethyldisilane reacts with bromine in benzene solution or neat, to afford only TMS-Br with no byproducts (eq 2).4 TMS-Br may also be generated by reaction of hexamethyldisiloxane and aluminum bromide (eq 3).However, it should be noted that the reactivity of in situ generated reagent appears to depend upon the method of preparation.

一般的な説明

Bromotrimethylsilane is used with Cl₃ to catalyze the direct allylation of a variety of alcohols with allyltrimethylsilane.

純化方法

Purify it by repeated fractional distillation and store it in sealed ampoules in the dark. [McCusker & Reilly J Am Chem Soc 75 1583 1953.] Also fractionate it through a 15-plate column (0.8 x 32cm packed with 1/16in single turn helices of Pt-Ir wire). [Gilliam et al. J Am Chem Soc 68 1161 1946, Pray et al. J Am Chem Soc 70 433 1948, Beilstein 4 IV 4008.]