New Alpha and Beta Chloroalkyl Silanes. Further Studies on the Alpha Silicon Effect¹

Abstract

1. Triethylsilane reacts with alkyl and aryllithium compounds in diethyl ether to give tetrasubstituted silanes.2. No reaction occurs between triethylsilane and propyllithium or butylsodium in low-boiling petroleum ether.3. Triethylsilane and ethanol in the presence of lithium ethoxide give ethoxytriethylsilane.4. Ethyldichlorosilane has been prepared by direct action of ethyl chloride on copper silicon.

Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

“…What is more intriguing and unexpected is that the D atoms primarily appeared at the carbon of the α-position of silicon in the corresponding product, likely due to the αsilicon effect. 20 Additionally, the high H/D ratio on the desired silanol product suggests that a single molecule of H 2 O existing in a dry solvent may be more reactive than bulkier water/D 2 O, possibly due to hydrogen-bonding interactions. 21 This information implies that the reaction mechanism is not as straightforward as described in Figure 2 (path A) for classic Rh-catalyzed Si−C bond cleavage 18,22 and its transformation with the capture of H 2 O.…”

Organosilicon Derivatives of Sulfur

“…Triorganosilyl hydrosulfates or triorganosilyl sulfates are evidently intermediates in syntheses of triorganohalosilanes from hexaorganodisiloxanes, sulfuric acid, and ammonium halides [315,363,436,448,565,657,662,666,667].…”

“…This reaction is carried out in the presence of ammonium sulfate, which prevents the reverse reaction of the organochlorosilane with sulfuric acid: (2.186) Reaction (2.186) is used to prepare trialkylhalosilanes, when the bis(triorganosilyl) sulfate is treated with an ammonium halide instead of a hydrogen halide [9,315,363,436,448,565,657,662,666,667,679]. This eliminates the need to prepare the dry hydrogen halide beforehand, and the need to add ammonium sulfate, since the latter is formed directly in the reaction mixture during the process itself.…”

Über Silanolester anorganischer Säuren, II. Reaktionen von Phosphorsäurechloriden mit Alkylsiloxanen und Alkylalkoxysilanen

“…(CH3)3SiOCH(c,jH& + Poc13 -(C&)2CHCI + (CH3)3SiOPOC12 (10) Jahrg. 93 unter Bildung von substituiertem Alkylchlorid und Dichlorophosphorsau-silylester 10).…”