Reaction of Disulfide and Trisulfide with N-Chlorocarboxamide

Furukawa, Mitsuru; Fujino, Yoko; Kojima, Y.; Ono, M.; Hayashi, Seigoro

doi:10.1248/cpb.20.2024

Cited by 11 publications

(3 citation statements)

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“…The impact of HCl was further manifested in the second stage of the overall reaction, i.e., the chlorination of the disulfide to generate the sulfenyl chloride ( 2 → 3 ). There was no reaction between NCS and independently synthesized disulfide 2 until addition of HCl, upon which sulfenyl chloride 3 and NHS were cleanly generated, see the Supporting Information Section S3.1.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2023

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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.

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Section: Resultsmentioning

confidence: 99%

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

et al. 2023

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“…(3) 223±225 C [lit. (Furukawa et al, 1972) 210 C]. For each compound, crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in EtOH.…”

Section: Synthesismentioning

confidence: 99%

Conformational preferences in 2-nitrophenylthiolates: interplay between intra- and intermolecular forces; structures of (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, S-(2-nitrophenyl)benzenecarbothiolate and 1-(2-nitrophenylthio)-2,5-pyrrolidinedione

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McCarron

et al. 2000

Acta Crystallogr Sect B

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In (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, C15H13NO2S (1) (orthorhombic Pbca), the nitro group is almost coplanar with the adjacent aryl ring, but the dihedral angles between the nitro-aryl and styryl fragments is approximately 121 degrees. The molecules are linked by paired C-H...O hydrogen bonds in a chain of rings. In S-(2-nitrophenyl)benzenecarbothiolate, C13H9NO3S (2) (monoclinic P2(1)/a), the nitro group is rotated by 33.0 (2) degrees out of the plane of the adjacent aryl ring and the thiobenzoate group is strongly twisted away from the plane of the disubstituted aryl ring. The molecules of (2) are linked into chains by C--H...O hydrogen bonds, and each chain is linked to two neighbouring chains by means of aromatic pi... pi stacking interactions. In 1-(2-nitrophenylthio)-2,5-pyrrolidinedione, C10H8N2O4S (3) (monoclinic P2(1)/a), the nitro group is again almost coplanar with the adjacent aryl ring, but the pyrrolidinedione unit is almost orthogonal to the O2NC6H4SN plane. There are three types of C-H...O hydrogen bond in the structure, and these link the molecules into a two-dimensional net. The conformations of these molecules have been investigated by SCF calculations and two energy minima have been identified for each: the molecules of (1) and (3) adopt conformations in their crystals which are close to those at the overall energy minima calculated for isolated molecules, while molecules of (2) adopt a conformation in the crystal close to that calculated for the local energy minimum. Comparisons are made with the structures of some related compounds and it is concluded that, while the nature of the two conformational minima is determined by intramolecular forces, the choice between them is determined primarily by intermolecular forces.

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“…The latter were prepared by heating a disulfide with N-bromosuccinimide according to a standard procedure (7). An exception wasp-tosyloxyphenylsulfensuccinimide which could not be prepared in this manner nor by an alternative procedure whereby the corresponding sulfenyl chloride was added to succinimide in the presence of a tert-amine (8).…”

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confidence: 99%