Sodium-Chloro trimethylsilane

Butyroin has been prepared by reductive condensation of ethyl butyrate with sodium in xylene, or with sodium in the presence of chloro-trimethylsilane. and by reduction of 4,5-octanedlone with sodium l-benzyl-3-carbamoyl-l,4-dihydropyridine-4-sulfinate in the presence of magnesium chloride or with thiophenol in the presence of iron polyphthalocyanine as electron transfer agent.This acyloin has also been obtained by oxidation of (E)-4-octene with potassium permanganate and by reaction of... 

Phenyl trimethylsilyi selenide benzeneselenol. The reaction of this anion, generated in. situ from diphenyl diselenide and sodium in THF, with chloro-trimethylsilane gives phenyl trimethylsilyi selenide in 72% yield..The product is sensitive to oxygen, but is stable under N2 indefinitely. It reacts rapidly with an alcohol to form benzeneselenol in high yield. 

Acyloin condensation of 2,2-dimethylmalonate with sodium in liquid ammonia using chloro-trimethylsilane gave the c 5-l,2-bis(trimethylsilyl) ether 5. ... 

Cyclization of dimethyl (.R)-2-methylbutanedioate by sodium in the presence of chloro-trimethylsilane gave the (/ )-3-methyl-l,2-bis(trimethylsiloxy)cyclobutene [(7 )-14] in 78% yield. Then, successive addition of one equivalent of bromine in pentane at — 50 "C and of 2 M sodium hydroxide solution at 0 yielded, after acidification with 2 M hydrochloric acid, directly the (1 5,27 )-1 -hydroxy-2-methylcyclopropanecarboxylic acid (95%). Esterification with methanol (acidified by thionyl chloride) at reflux for 18 hours gave methyl (1 S,2R )-l -hydroxy-2-methylcyclopropanecarboxylate [(15,2i )-15] containing 5% of the (l/ ,2/ )-diastereomer. By heating (15, 2/ )-15 in methanol (acidified by thionyl chloride) at reflux for five days it was shown that the hydroxy ester (IR,2R) was not a product of isomerization of the major stereoisomer (15,27 ). 

The synthesis of hexamethyldisilathiane from sodium sulfide and chloro-trimethylsilane is described here. The present method is based on the convenient in situ syntheses of alkali metal selenides and diselenides. Commercial sodium sulfide or lithium sulfide are reported to be poor substitutes for in situ generated sulfides in this reaction. For example, in 1961 Abel reported that disodium sulfide reacts with chlorotrimethylsilane in pressure vessels at 250°C for 20 h to produce I. Our procedure is very convenient, utilizing readily available starting materials and apparatus under mild conditions. The yields are t3q)ically 80-88% at 0.3-mol scale. However, it can be improved to 90-95% on small scale ( 50-mmol) reactions. This procedure can be applied to the synthesis of various disilathianes. 

The synthesis of nucleosides using iodotrimethylsilane has been modified to a one-pot procedure with a mixture of chloro-trimethylsilane and sodium iodide uracil derivatives of D-ribose and D-xylose were conveniently prepared. 

Finally,. an alternative approach to alkoxyorganylsilanes is the treatment of chloro-organylsilane with carboxylic acids or their esters and sodium in HMPA/THF. Thus, from acetic acid, Me3SiCl and sodium l,l-bis(TMS)-l-(TMS-oxy-)ethane (582) is obtained, whereas Me3SiCl and /Mialogenoesters (583) yield (1-alkoxycyclopropan-l-yloxy)trimethylsilanes (584) (equations 294 and 295)313. 

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