Триметилсилилацетилен

Химические свойства

CLEAR COLORLESS LIQUID

Физические свойства

bp 53 °C; d 0.695 g cm?3.

Использование

Trimethylsilylacetylene is a valuable reagent used in ethynylation by palladium(0)-catalyzed coupling/condensation with aryl and vinyl halides and triflates, or by nucleophilic attack of the corresponding acetylide on electrophilic centers; reacts with alkyl iodides, tin hydrides,6 and dichloroketene in a regioselective and stereoselective manner, participating in the following synthesis reactions: Ethynylations, Palladium(0)-Catalyzed Coupling Reactions,Reaction of Trimethylsilylacetylides with Electrophiles, Radical-Initiated and Transition Metal-Catalyzed Additions, Cycloaddition Reactions, Ethynylations, Cycloaddition Reactions, Further Transformations etc.

Общее описание

Laser-induced polymerization of gaseous ethynyltrimethylsilane was used for efficient chemical vapour deposition of polycarbosilane films. Ethynyltrimethylsilane acts as substrate for nickel-catalyzed cross-coupling with benzonitriles.

Синтез

A solution of chlorotrimethylsilane (152 mL, 130 g, 1.197 mol) in dry THF (100 mL) is placed in the 1-L dropping funnel. It is added (20 min) to the cooled and stirred solution of ethynylmagnesium chloride at a rate sufficient to maintain a reaction temperature of about 15–20°C. Finally, the dropping funnel is replaced by an efficient double-surface condenser and calcium chloride drying tube, and the reaction mixture is heated under reflux for 1 hr. The reflux condenser is replaced by a distillation head, and a double-surface condenser is connected to a receiver flask, which is cooled in an ice bath. The reaction mixture is distilled under nitrogen with stirring until all the azeotrope of trimethylsilylacetylene and THF (700–800 mL, bp ca. 66°C) has been distilled. The distillate is washed with ice–water portions (10 × 500 mL) to remove the THF. Washing is continued until the organic layer stays constant in volume. Distillation of the organic layer under an atmosphere of nitrogen through a short Vigreux column gives trimethylsilylacetylene, bp 50–52°C/760mm, nD20 1.391.

Методы очистки

Distil it through an efficient column. The IR has bands at max 2041 (CC) and 3289 (C-H) cm-1. [Kr.hnke & Goss Chem Ber 92 30 1959, Beilstein 4 IV 3937.]