Silanes trimethylsilane/trimethylsilyl

Trichloromethyl trimethylsilane (trimethylsilyl trichloromethane) ]5936-98-l] M 191.6, m 130-132 , b 146-156 /749mm. This silane distils at atmospheric pressure without decomposition and readily sublimes at 70°/10mm. It has one peak in the H NMR spectrum (CD2CI2) with 5 at 0.38. [Speier JA/w Chem Soc 73 824 1951, Hergott Simchen Synthesis 626 1980, Beilstein 4IV 3892.]... 

The second route involves the palladium catalyzed coupling of iodoaniline 51 with the acyl silane 54 in the presence of DABCO to give the 2-trimethylsilyl indole 55. The acyl silane 54 was prepared by alkylation of 1,3-dithianyl-trimethylsilane with (3-bromopropyl)-dimethylamine to give 56, followed by removal of the dithioacetal with mercuric oxide and mercuric chloride. Finally, desilylation of 55 in aqueous HCl and methanol afforded rizatriptan (4). 

V,7V-Diethylcarbamoyl trimethylsilane has been prepared by the reaction of bis(trimethylsilyl) sulphide with bis(A,A-diethylcarbamoyl) mercury (Scheme 30)16. Silylation of the carbamoyl cuprate reagent derived from a lithium amide, by addition of copper(I) cyanide and subsequent exposure to carbon monoxide (1 atm), is also effective75,110. Poor to moderate yields of carbamoyl silanes may be isolated by treatment of lithium silylamides with carbon monoxide and methyl iodide, in a reaction sequence involving a nitrogen to carbon silyl shift in an intramolecular silylation (Scheme 31)111. 

Several different methods have been employed for the preparation of diazo(trimethylsilyl)meth-ane (1). At present, the best synthetic method seems to be the diazo transfer reaction between diphenylphosphoryl azide and (trimethylsilyl)methylmagnesium chloride.However, the product often contains (chloromethyl)trimethylsilane and hexamethyldisiloxane as impurities. This method can also be employed for the synthesis of diazo(triethylsilyl)methane and diazo(di-ethylmethylsilyl)methane. The diazo transfer reaction can also be carried out with (trimethyl-silyl)methyllithium and tosyl azide. Other methods are the silylation of diazomethane with (trimethylsilyl)trifluoromethanesulfonate or chloro(trimethyl)silane and the base-induced cleavage of A-nitroso-A-[(trimethylsilyl)methyl]urea or the related carbamate or acet-amide.2° =... 

Trimethylsilyl acetamide CAS 13435-12-6 EINECS/ELINCS 236-565-7 Synonyms Acetamide, N-(trimethylsilyl)- (Acetylamino) trimethylsilane N-(Trimethylsilyl) acetamide Classification Silane Empirical CsHisNOSi Formula CH3CONHSi(CH3)3 Properties Wh. moist crystals m.w. 131.25 m.p. 52-54 C b.p. 103-105 C (35 mm) flash pt. 57 C Toxicology LDLo (IP, mouse) 350 mg/kg poison by IP route may be harmful by inh., ing., skin absorp. may cause eye/skin irritation may cause decreased immune response TSCA listed... 

Lithium-Halogen Exchange. Reaction of (dibromomethyl)-trimethylsilane with n-butyllithium at — 110°C results in the formation of trimethylsilylbromomethyllithium. The silane and the -BuLi are added simultaneously in order to suppress side reactions. Treatment of the intermediate lithium reagent with chlorotrimethylsilane (eq 1) or mercury(II) bromide (eq 2) affords bis(trimethylsilyl)bromomethane or bis(trimethylsilyl-bromDmethyl)mercury, respectively. If the lithium reagent is... 

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