Preparation of silylalkanethiols

Gornowicz, Gerald A.; Ryan, John W.; Speier, John L.

doi:10.1021/jo01271a067

Cited by 20 publications

(13 citation statements)

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“…reduction (2) or hydrolysis (8) of 2-(trimethylsily1)ethyl thiolacetate (2). Thiolester 2 is prepared by radical addition of thiolacetic acid to vinyltrimethylsilane (8). This yields two regioisomers (2 and 3) in a 90: 10 ratio and distillation on a spinning band column is an excellent method for the removal of 3.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, reactions, and interconversions of some 2-(trimethylsilyl)ethyl substituted sulfur compounds

Schwan¹,

Brillon²,

Dufault³

1994

Can. J. Chem.

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. Can. J. Chem. 72,325 (1994). In an effort to probe the compatibility of the 2-(trimethy 1silyl)ethyl sulfur moiety with standard organosulfur transformations, several 2-(trimethylsily1)ethanethiol derivatives have been prepared in excellent yield. Thus 2-(trimethylsilyl)ethanethiol (l) and 2-(trimethylsily1)ethyl disulfide (4) and its corresponding thiosulfinate 9 and thiosulfonate 10 have been synthesized. One method of formation of 4 involves the breakdown of a 1-(trimethylsily1)ethyl unit while the 2-(trimethylsi1yl)ethyl fragment survives. Oxidation of 4 or 9 to 10 did not proceed efficiently with common reagents, but proceeded well with an iodinetwater system. 2-(Trimethylsily1)ethyl sulfide (11a) and its oxides (13, 14) were also prepared in good yield. Sulfoxide 13 and 2-(trimethylsi1yl)ethyI tert-butyl sulfoxide 15 were shown to be good precursors to 2-(trimethylsi1yl)ethanesulfinyl chloride (16). (Trimethy1silyl)methyl sulfine reacted with 16 in an inefficient manner to give thiosulfonates 10, 19, and 20. 2-(Trimethylsi1yl)ethanesulfenyl chloride could be generated and captured by addition across cyclohexene. The reaction of thiosulfinate 9 with several thiosilanes is an excellent method for the synthesis of 2-(trimethylsily1)ethyl containing mixed disulfides. ADRIAN L. SCHWAN, DENIS BRILLON et ROBERT DUFAULT. Can. J. Chem. 72,325 (1994). Afin de pouvoir Ctudier la compatibilitC de la portion 2-(trimCthylsily1)Cthyle sulfurCe avec les transformations standard des composCs organosulfurCs, on a prepark plusieurs dCrivCs du 2-(trimCthy1silyl)Cthanethiol avec d'excellents rendements. On a ainsi synthCtisC le 2-(trimCthylsilyl)Cthanethiol (I), le disulfure de 2-(trimCthylsi1yl)Cthyle (4) ainsi que les thiosulfinate (9) et thiosulfonate (10) correspondants. Une mCthode de prCparation du composC 4 implique la dCsintCgration d'une unit6 I-(trimCthylsily1)Cthyle alors que le fragment 2-(trimCthylsily1)Cthyle survit. Sous l'influence des rCactifs ordinaires, I'oxydation des composCs 4 ou 9 en 10 ne se produit pas d'une fqon efficace; toutefois, elle se produit bien dans un systtme iodeteau. On a aussi prCparC le sulfure de 2-(trimCthylsily1)Cthyle ( l l a ) et ses oxydes (13 et 14) avec de bons rendements. On a montrC que le sulfoxyde 13 et 2-(trimCthylsily1)Cthyl tert-butyl sulfoxyde sont de bons prCcurseurs du chlorure de 2-(trimCthylsily1)Cthanesulfinyle (16). La (trimCthylsily1)mCthyl sulfine rCagit inefficacement avec le composC 16 pour conduire aux thiosulfonates 10, 19 et 20. Le chlorure de 2-(trimCthylsilyl)CthanesulfCnyle peut &tre gCnCrC et capturC par addition sur du cyclohex~ne. La rkaction du thiosulfinate 9 avec plusieurs thiosilanes est une excellent mCthode de synthtse des disulfures mixtes contenant des unitts 2-(trimCthy1silyl)Cthyles.[Traduit par la rkdaction]

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Section: Resultsmentioning

confidence: 99%

“…Under these hydrolysis conditions the thiol is obtained essentially quantitatively, with 98.5% purity (GC analysis). Distillation affords 1 in 95% yield, which represents an improvement over other methods (2,8).…”

Section: -(Trimethylsily1)ethanethiolmentioning

confidence: 92%

Synthesis, reactions, and interconversions of some 2-(trimethylsilyl)ethyl substituted sulfur compounds

Schwan¹,

Brillon²,

Dufault³

1994

Can. J. Chem.

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“…15 For unsaturated silanes, it has been demonstrated that silicon stabilises the free radical. 16,17 Addition of thiols to vinyltrimethylsilane seems a unique example of free radical addition to vinyl derivatives leading also to a secondary free radical intermediate (Scheme 1). 17 To synthesise more efficiently 2-(trimethylsilyl)ethyl sulfides, 2-(trimethylsilyl)ethanethiol (4) (BEST: b-ethylsilyl thiol) has been prepared by free radical addition of thiolacetic acid followed by methanolysis, ammonolysis or hydrolysis of the resulting thioacetate 3 (Scheme 2).…”

Section: Synthesis Of 2-(trimethylsilyl)ethanethiol and Derivativesmentioning

confidence: 99%

“…16,17 Addition of thiols to vinyltrimethylsilane seems a unique example of free radical addition to vinyl derivatives leading also to a secondary free radical intermediate (Scheme 1). 17 To synthesise more efficiently 2-(trimethylsilyl)ethyl sulfides, 2-(trimethylsilyl)ethanethiol (4) (BEST: b-ethylsilyl thiol) has been prepared by free radical addition of thiolacetic acid followed by methanolysis, ammonolysis or hydrolysis of the resulting thioacetate 3 (Scheme 2). [17][18][19] Fuchs et al have improved the yield of 2-(trimethylsilyl)ethanethiol (4) by reduction of the thioacetate intermediate 3 with LiAlH 4 19 and more recently, Schwan et al reported a 95% yield for this step using potassium carbonate as a base in a methanol-water solution.…”

Section: Synthesis Of 2-(trimethylsilyl)ethanethiol and Derivativesmentioning

confidence: 99%

“…17 To synthesise more efficiently 2-(trimethylsilyl)ethyl sulfides, 2-(trimethylsilyl)ethanethiol (4) (BEST: b-ethylsilyl thiol) has been prepared by free radical addition of thiolacetic acid followed by methanolysis, ammonolysis or hydrolysis of the resulting thioacetate 3 (Scheme 2). [17][18][19] Fuchs et al have improved the yield of 2-(trimethylsilyl)ethanethiol (4) by reduction of the thioacetate intermediate 3 with LiAlH 4 19 and more recently, Schwan et al reported a 95% yield for this step using potassium carbonate as a base in a methanol-water solution. 13 2-(Trimethylsilyl)ethanethiol and 2-(trimethylsilyl)ethyl sulfides can be also prepared by photochemical addition of hydrogen sulfide to vinyltrimethylsilane (Scheme 2).…”

Section: Synthesis Of 2-(trimethylsilyl)ethanethiol and Derivativesmentioning

confidence: 99%

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The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

Chambert¹,

Désiré²,

Décout³

2002

Synthesis

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The trimethylsilylethyl sulfur group present in 2-(trimethylsilyl)ethyl sulfides, sulfones, sulfoxides and in 2-(trimethylsilyl)ethylsulfonamido derivatives has proved its potential in synthesis. Presence of sulfur and silicon on adjacent carbon atoms provides routes for preparing interesting sulfur or non-sulfur, silicon or non-silicon derivatives like thiols, methyl disulfides, thioesters, thiocyanates, unsaturated derivatives and amines through the selective removal of the trimethylsilylethyl or the trimethylsilyl group. 5 Conclusion

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2-(Trimethylsilyl)ethanethiol

Schwan

2004

Encyclopedia of Reagents for Organic Synthesis

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Preparation of silylalkanethiols

Cited by 20 publications

References 3 publications

Synthesis, reactions, and interconversions of some 2-(trimethylsilyl)ethyl substituted sulfur compounds

Synthesis, reactions, and interconversions of some 2-(trimethylsilyl)ethyl substituted sulfur compounds

The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

2-(Trimethylsilyl)ethanethiol

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