Phenylthiomethyl trimethylsilane

Analysis of Reagent Purity by GC or NMR analysis. Preparative Methods by reaction of phenylthiomethyllithium with chlorotrimethylsilane.  

Handling, Storage, and Precautions irritant foul smelling use in a fume hood. 

Akira Hosomi Makoto Hojo University ofTsukuba, UK 

Georges Hareau Philip Kocienski Southampton University 

Synthesis of Vinyl Sulfides. Anion (2) adds to aldehydes, ketones, and enones, in the last-named case in either 1,2- or 1,4-manner depending on the reaction conditions.In the case of 1,2-addition the -hydroxysilane adduct usually cannot be isolated owing to rapid elimination (Peterson alkenation) to vinyl sulfides (eq 5), which can be hydrolyzed to the corresponding aldehydes. The vinyl sulfides are not formed stereoselectively unless there are proximate bulky substituents. Peterson alkenation products have also been observed in the reaction of (2) with amides, ureas, and carbonates.  

---

Phenyl trimethylsilylmethyl sulphide [(phenylthiomethyl)trimethylsilane] [17873-08-4] M 196.4, b 48°/0.04mm, 113-115°/12mm, 158.5°/52mm, d4° 0.9671, n3D° 1.5380. If the sample is suspect then add H2O, wash with 10% aqueous NaOH, H2O again, dry (anhydrous CaCl2) and fractionally distil through a 2ft column packed with glass helices. [JACS 76 3713 7954]. 

Recently, (phenylthiomethyl)trimethylsilane (1), or the anion (2) thereof, has been used to synthesize vinylsilanes from a-trimethylsUyloxiranes, in Peterson-type olefination reactions to generate vinyl sulfides, and also as a radical precursor under electrochemical conditions. Addition reactions of (phenylth-iomethyl)trimethylsilyl carbene (10), prepared via two independent methods, to olefins have also heen disclosed. ... 

Related Reagents. (4a/ )-(4aa,7a,8a/3)-Hexahydro-4,4,7-trimethyl-4//-l,3-benzoxathiin 2-Lithio-l,3-dithiane 1,1,3,3-Tetramethylbutyl Isocyanide Benzothiazole Bis(phenylthio)-methane Af,Af-Diethylaminoacetonitrile Diethyl Morpholino-methylphosphonate 1,3-Dithiane 2-(2,6-Dimethylpiperidino) acetonitrile Cyanotrimethylsilane Samarium(II)iodide-l,3-dioxolane (Phenylthiomethyl)trimethylsilane. 

The reductive cleavage of just one C-S bond yields the mono(lithiomethyl)silanes. This transformation is well known and used in the Peterson olefmation for the preparation of (lithiomethyl)trimethylsilane (15) [5], We employed it as a method to exchange the thiophenyl-group in the (phenylthiomethyl)silanes 5-14 with lithium, thus creating the corresponding poly(lithiomethyl)silanes (see, e.g.. Scheme 3 for methylsilanes) [4]. 

---