17873-08-4

Usage

Uses

Used in Organic Synthesis:
(PHENYLTHIOMETHYL)TRIMETHYLSILANE is used as a one-carbon homologating agent for the synthesis of aldehydes via sila-Pummerer rearrangement. This reaction provides a convenient method for the preparation of aldehydes, which are important intermediates in the synthesis of various organic compounds.
(PHENYLTHIOMETHYL)TRIMETHYLSILANE is also used as a reagent in the Peterson alkenation, which is a widely used method for the synthesis of vinyl sulfides. This reaction allows for the formation of vinyl sulfides from the corresponding carbonyl compounds, offering a valuable synthetic route to these important functional groups.
Furthermore, (PHENYLTHIOMETHYL)TRIMETHYLSILANE is used in the preparation of vinylsilanes from silyl epoxides. This reaction provides a direct and efficient method for the synthesis of vinylsilanes, which are valuable building blocks in organic chemistry.
Physical properties of (PHENYLTHIOMETHYL)TRIMETHYLSILANE include a boiling point of 158-159 °C at 52 mmHg, a density of 0.967 g/cm3 at 20°C, and a refractive index of 1.5390 at 20°C. These properties make it suitable for use in various chemical reactions and processes.

Purification Methods

If the sample is suspect, then add H2O, wash it with 10% aqueous NaOH, H2O again, dry (anhydrous CaCl2) and fractionally distil it through a 2ft column packed with glass helices. [Cooper J Am Chem Soc 76 3713 1954.]

InChI:InChI=1/C10H16SSi/c1-12(2,3)9-11-10-7-5-4-6-8-10/h4-8H,9H2,1-3H3

Upstream product

• 18243-41-9 (bromomethyl)trimethylsilane 
• 930-69-8 sodium thiophenolate 
• 2344-80-1 Chloromethyltrimethylsilane 
• 75-77-4 chloro-trimethyl-silane 
• 100-68-5 methyl-phenyl-thioether 
• 108-98-5 thiophenol 
• 3561-67-9 bis(phenylthio)methane 
• 13307-75-0 (phenylthio)methyllithium 
• 5219-61-4 (phenylthio)acetonitrile 
• 100-42-5 styrene 
• 79239-13-7 trimethylsilane 
• 110-83-8 cyclohexene 
• 141-05-9 Diethyl maleate 
• 1257879-99-4 CpCr[(2,6-Me₂C₆H₃NCMe)2CH](CH₂SiMe₃) 

Downstream Products

• 17872-92-3 (phenylsulfonylmethyl)trimethylsilane 
• 33521-89-0 <(Phenylthio)methylene>adamantane 
• 13112-46-4 2,2-diphenyl-1-phenylthioethene 
• 71341-87-2 3-<(phenylthio)methylene>-1-cyclohexene 
• 13640-71-6 2-methyl-1-(phenylthio)-1-propene 
• 78375-76-5 3-phenylthio-3-trimethylsilylpropane-1-ol 
• 13865-50-4 methoxymethyl phenyl sulfide 
• 74032-25-0 1-((Z)-1-Phenyl-2-phenylsulfanyl-vinyl)-aziridine 
• 74032-24-9 1-((E)-1-Phenyl-2-phenylsulfanyl-vinyl)-aziridine 
• 87729-80-4 Tris(trimethylsilyl)(phenylthio)methane 
• 530-48-3 1,1-Diphenylethylene 
• 13307-77-2 1,1-diphenyl-2-(phenylthio)ethan-1-ol 
• 121086-92-8 (1,1-Diphenyl-2-phenylsulfanyl-ethoxy)-trimethyl-silane 
• 79409-24-8 3-<(phenylthio)(trimethylsilyl)methyl>cyclohexanone 

Relevant academic research and scientific papers

Preparation of Thioanisole Biscarbanion and C-H Lithiation/Annulation Reactions for the Access of Five-Membered Heterocycles

The synthesis, isolation, and X-ray structure of a thioanisole-based trilithium complex are reported. On the basis of the double-lithiation strategy, two novel synthetic methodologies have been developed under mild reaction conditions (room temperature): (1) reactions of lithiated thioanisoles with nitriles give benzoisothiazoles via a [3 + 2]-type of approach with two new bond formations and (2) formation of benzothiophenes from thioanisoles and amides through a [4 + 1] pattern forming 4 new chemical bonds.

Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (?)-Cyclosmenospongine

We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (?)-cyclosmenospongine. A highly convergent three-component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans-decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.

Exploring chromium(III)-alkyl bond homolysis with CpCr[(ArNCMe) 2CH](R) complexes

A range of paramagnetic Cr(III) monohydrocarbyl complexes CpCr[(ArNCMe)2CH](R) (Ar = ortho-disubstituted aryl; R = primary alkyl, trimethylsilylmethyl, benzyl, phenyl, alkenyl, or alkynyl) were synthesized to investigate how varying the steric and electronic properties of the R group affected their propensity for Cr-R bond homolysis. Most complexes were prepared by salt metathesis of known CpCr[(ArNCMe)2CH](Cl) compounds in Et2O with commercial RMgCl solutions, although more sterically demanding combinations of Ar and R groups necessitated the use of halide-free MgR2 reagents and the Cr(III) tosylate or triflate derivatives. Alternative synthetic routes to Cr(III)-R species using the previously reported Cr(II) compounds CpCr[(ArNCMe)2CH] and sources of R? radicals (e.g., BEt3 and air) were also explored. The UV-vis spectra of the CpCr[(ArNCMe)2CH](R) complexes possessed two strong bands with maximum absorbances in the ranges 395-436 nm and 535-582 nm, with the band in the latter range being particularly characteristic of the Cr(III)-R compounds. The Cr-CH2R bond lengths as determined by single-crystal X-ray diffraction were longer than those in the corresponding Cr-CH3 complexes, typically falling in the range 2.10 to 2.13 A. The Cr(III) benzyl compounds displayed longer Cr-CH2Ph distances, while the bond lengths for the alkenyl and alkynyl species were substantially shorter. The rate of Cr-R bond homolysis at room temperature was determined by monitoring the reaction of Cr(III) neopentyl, benzyl, and isobutyl complexes with excess PhSSPh using UV-vis spectroscopy. Although the other primary alkyl, phenyl, and alkenyl compounds did not undergo appreciable homolysis under these conditions, they were cleanly converted to CpCr[(ArNCMe)2CH](SPh) by photolysis.

Organylthio(silyl)carbenes

The title carbenes 5 can be generated either from diazo compounds 9 by copper-catalyze d catalysis or from chloro(organylthio)methylsilanes 12 by base-induced α-elimination, This is confirmed, by [2+1] cycloadditions with alkenes to give the cyclopropanes

Reaction of trimethylsilanes with Arenes and Alk-1-enes in the Presence of Lewis Acid: Syntheses of - and (1-Arylthioalk-3-enyl)-trimethylsilanes

Treatment of equimolar amounts of the trimethylsilanes (2) or (3) and electron-rich arenes with an equimolar amount of Lewis acid (SnCl4 or TiCl4) gave the Friedel-Crafts reaction products, trimethylsilanes (4) or (5), in high yields.Similar treatment of the chlorides (2) or (3) with alk-1-enes gave ene type products, trimethylsilanes (12) or (13), in moderate yields.Some chemical transformations of these products are also described.

EFFICIENT SYNTHETIC METHODOLOGY FOR 1-(PHENYLTHIO)CYCLOPROPYLSILANES, PRECURSORS OF 1-(LITHIO)CYCLOPROPYLSILANES

Two one flask connective methods for preparing 1-(phenylthio)-cyclopropylsilanes, precursors of 1-(lithio)cyclopropylsilanes, are described.

Preparation of Vinylic Sulphones by Peterson Olefination using Phenyl Trimethylsilylmethyl Sulphone

The anion generated from phenyl trimethylsilylmethyl sulphone using butyl-lithium in dimethoxyethane, readily reacts at -78 deg C with various carbonyl compounds to afford vinylic sulphones on work-up at room temperature.The reaction conditions are tolera

Synthesis of Aldehydes from Phenylthiotrimethylsilylmethane

Phenylthiotrimethylsilylmethyl-lithium (4) reacts with alkyl halides to give 1-phenylthio-1-trimethylsilylalkanes (5), which can also be prepared by the addition of alkyl-lithium to 1-phenylthio-1-trimethylsilylethene (8), or from bis(phenylthio)acetals (11).The 1-phenylthio-1-trimethylsilylalkanes (5) can be converted into the corresponding aldehyde (15) by oxidation to the sulphoxide (13), thermal rearrangement, and hydrolysis of the resultant O-silyl thioacetal (14).

The Formation of Allyl Sulphides by Phenylthio-migration: Control by Silicon

When γ-silyl-β-phenylthio-alcohols are treated with acid, the strategically placed silyl group encourages the rearrangement of the phenylthio-group, both from a secondary migration origin to a secondary migration terminus, and from a secondary migration origin to a tertiary migration terminus (4)->(6).Geraniol/nerol (12) and linalool (14) have been synthesised from a common intermediate (11) using this type of reaction.Phenylthio-migration from a tertiary migration origin (17)->(3) can be controlled to a limited extent by a suitably placed silyl group, but it is easier to achieve direct β-elimination of the silyl and phenylthio-groups (17)->(18).

A NEW METHOD FOR PREPARING 1-PHENYLTHIO-1-TRIMETHYLSILYLALKANES: THE PREPARATION OF α-SILYLCARBANIONS AND OLEFINS.

1-Phenylthio-1-trimethylsilylalkanes(1) are prepared in high yield from 1,1-bis(phenylthio)acetals(2) by reaction with lithium naphthalenide(3) followed by chlorotrimethylsilane. α-Silylcarbanions are formed from the alkanes(1) and lithium naphthalenide(3).Subsequent reaction with carbonyl compounds gave the olefins(4) via the Peterson reaction.