Benzenesulfenyl Chloride

Zelčans, Gunars; Hutton, Thomas K.; Rios, Ramón; Shibata, Norio

doi:10.1002/047084289x.rb019.pub3

Cited by 3 publications

(3 citation statements)

References 115 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These entries suggested that a combination of protons and halide anions plays an important role in this reaction. In addition, while camphorsulfonic acid could have been used instead of p-toluenesulfonic acid, other acids tended to decrease the yield according to acidity (entries [10][11][12]. Tetrabutylammonium bromide (TBAB) produced the desired product in the same yield as TBAC, 10 but tetrabutylammonium iodide (TBAI) was not applicable (entries 13 and 14).…”

Section: Scheme 1 Electrophilic Cyclization Of Allylic Amidementioning

confidence: 99%

“…We deduced a plausible mechanism for this reaction from the results of our examination and previous literature (Scheme 4). 11,12 The sulfenylating reagent 2 became A through protonation and generated phenylsulfenyl chloride B from nucleophilic attack of the chloride ion. The olefin of 1 interacted with B to form a thiiranium ion C, and the corresponding oxazoline 3 was obtained by subsequent intramolecular cyclization.…”

Section: Letter Syn Lettmentioning

confidence: 99%

See 1 more Smart Citation

Improved Synthetic Method for 5-[(Phenylthio)methyl]oxazoline Derivatives: Electrophilic Cyclization of Allylic Amide Using a Brønsted Acid and Tetrabutylammonium Chloride under Mild Conditions

Nagao¹,

Hiroya²

2020

Synlett

View full text Add to dashboard Cite

The synthesis of oxazolines using electrophilic cyclization of allylic amide is a simple and powerful method. However, cyclization involving arylsulfenylation requires harsh reaction conditions. We found that the reaction proceeds under mild heating conditions with the combination of a Brønsted acid and tetrabutylammonium chloride. This method enabled the synthesis of 5-[(arylsulfenyl)methyl]oxazoline derivatives under mild conditions and demonstrated high tolerance for various functional groups.

show abstract

Section: Scheme 1 Electrophilic Cyclization Of Allylic Amidementioning

confidence: 99%

Section: Letter Syn Lettmentioning

confidence: 99%

Improved Synthetic Method for 5-[(Phenylthio)methyl]oxazoline Derivatives: Electrophilic Cyclization of Allylic Amide Using a Brønsted Acid and Tetrabutylammonium Chloride under Mild Conditions

Nagao¹,

Hiroya²

2020

Synlett

View full text Add to dashboard Cite

show abstract

“…Discovered by Theodore Zincke in 1911, arenesulfenyl halides are significant if somewhat unusual class of compounds in organic chemistry. [1][2][3] Most notably, they have been employed as reagents for the protection of cysteine side chains 4 and for the difunctionalization of alkenes, [5][6] alkynes, 7 and diazo compounds. 8 Arenesulfenyl halides suffer from limited stability and are prone to decomposition by disproportionation to aryl disulfides and elemental halogens.…”

Section: Introductionmentioning

confidence: 99%

Arenesulfenyl Fluorides: Synthesis, Structure, and Reactivity

Faialaga,

Gephart,

Silva

et al. 2024

Preprint

View full text Add to dashboard Cite

Sulfenyl fluorides are organic compounds of sulfur in formal oxidation state +2 with the formula R–S–F. Although the chloride, bromide, and iodide analogues have been extensively described in the literature, organic sulfenyl fluorides remain essentially unstudied. These structures have been implicated as putative intermediates in established processes to access polyfluorinated sulfur species; however, definitive and direct evidence of their existence has not been achieved, nor has a systematic understanding of their reactivity. Here, we report the synthesis, isolation, and spectroscopic characterization of several arenesulfenyl fluorides, including structural analysis of 2,4-dinitrobenzenesulfenyl fluoride by single-crystal X-ray diffraction. The functional group undergoes direct, efficient, and highly regioselective anti-addition to alkenes and alkynes, as well as insertion by carbenes. The resulting α- or β-fluoro thioether adducts can be readily transformed into useful fluorinated motifs, for example by modification of the sulfur groups (to sulfonamides or sulfonyl fluorides), by sulfur elimination (to generate formal C–H fluorination products), or by Julia–Kocienski olefination (to form vinyl fluorides). Thus, we establish that sulfenyl fluorides are unexpectedly accessible and stable compounds. Further, they serve as versatile reagents for the production of fluorinated organic compounds.

show abstract

Thiol Chlorination with N-Chlorosuccinimide: HCl-Catalyzed Release of Molecular Chlorine and the Dichotomous Effects of Water

et al. 2023

View full text Add to dashboard Cite

The kinetics of the conversion of thiophenols into sulfenyl chlorides using N-chlorosuccinimide (NCS) in dichloromethane have been investigated by in situ 1H NMR and stopped-flow UV–vis spectroscopy. The study reveals that a slow direct chlorination of the thiophenol by NCS initiates a more rapid but indirect process involving in situ generation of a disulfide and then its cleavage by transient Cl2. The latter is released from NCS by HCl and the switch in dominant pathway results in sigmoidal kinetics for the thiophenol consumption. The overall reaction rate can be attenuated by using an alkene to scavenge the sulfenyl chloride before it reacts with the thiophenol. The presence of water in the dichloromethane induces two distinct kinetic regimes, dependent on whether the water is below or above a critical concentration. The value of this critical concentration is dependent on the amount of HCl in the system. As the exogenous water is increased to the critical concentration, there is a proportionate acceleration of the HCl-mediated release of Cl2 from the NCS. At water concentrations above this, there is a progressive reduction in the rate of Cl2 release due to {H2O + nHCl} undergoing a change in speciation or physical phase. Alcohols, e.g., i-PrOH, efficiently catalyze the conversion of thiophenols into sulfenyl chlorides, with further oxidation retarded by trace amounts of disulfide, indicative of analogous HCl-catalyzed slow-release of Cl2. High reactant concentrations can lead to sufficient exothermicity to trigger an abrupt and vigorous release of gaseous HCl. Potential methods to mitigate against developing these hazardous conditions are also discussed.

show abstract

Benzenesulfenyl Chloride

Cited by 3 publications

References 115 publications

Improved Synthetic Method for 5-[(Phenylthio)methyl]oxazoline Derivatives: Electrophilic Cyclization of Allylic Amide Using a Brønsted Acid and Tetrabutylammonium Chloride under Mild Conditions

Improved Synthetic Method for 5-[(Phenylthio)methyl]oxazoline Derivatives: Electrophilic Cyclization of Allylic Amide Using a Brønsted Acid and Tetrabutylammonium Chloride under Mild Conditions

Arenesulfenyl Fluorides: Synthesis, Structure, and Reactivity

Thiol Chlorination with N-Chlorosuccinimide: HCl-Catalyzed Release of Molecular Chlorine and the Dichotomous Effects of Water

Contact Info

Product

Resources

About