Sulfur Monochloride Research Articles

Disulfur Dichloride (S2Cl2)

Disulfur dichloride (S2Cl2), also known as sulfur chloride (SCl), is widely used in organic synthesis as a sulfurizing and chlorinating agent. Sulfide compounds are found in many natural products and may have useful biological properties. [1] This reagent has been explored for the preparation of heteroaryl disulfides, [2] symmetric aryl di-, tri-, and tetrasulfides, [2] [3] episulfides [4] and benzopolysulfides. [5] [6] Moreover, S2Cl2 is a suitable substrate for the synthesis of dialkoxy disulfide, [7] or for the Herz reaction. [8] It decomposes into SO2, HCl, and S8 when exposed to wet air due to reaction with water.

ChemInform Abstract: Transformations of N‐Ethylamines into Amide Derivatives under the Action of Sulfur Monochloride.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Fabrication of Crosslinked Block Copolymer Nanoparticles Using Cold Vulcanization

ABSTRACTThe aim of this study is to understand the crosslinked system of poly(styrene)-bpoly(isoprene) copolymer using cold vulcanization process as a facile method to produce anisometric nanoparticles. The morphologies of block copolymers could be controlled by the type of monomers, block junction, composition, and block size. A systematic methodology, utilizing cylindrical and lamellar morphologies of PS-b-PI copolymer, was used for producing fiber and sheet shaped nanoparticles. The cold vulcanization process was accomplished using sulfur monochloride (S2Cl2) as crosslinking agent. The microstructures and crosslinking density of crosslinked PS-b-PI copolymers were imaged and characterized. This study demonstrated the crosslinking of microphase separated block copolymer as a method to create particles with controlled size, shape, and physical properties.

He I Photoelectron Spectroscopy and Theoretical Investigation on Diaceto Disulfide, CH3C(O)OSSOC(O)CH3

A novel species, diaceto disulfide (CH3C(O)OSSOC(O)CH3), has been generated through the heterogeneous reaction between sulfur monochloride (S2Cl2) and silver acetate (AgOC(O)CH3). Photoelectron spectroscopy (PES) and theoretical calculations are performed to investigate its electronic and geometric structures. This molecule exhibits gauche conformation with both C=O groups syn to the S-O bond. The dihedral angle around the S-S bond is calculated to be -93.1 degrees at the B3LYP/6-311++G(3df,3pd) level. After structural optimizations of the most stable conformer, a theoretical study involving the calculation of the ionization energies using orbital valence Green's functional (OVGF) was performed. The ionization energies of different bands in the photoelectron spectrum are in good agreement with the calculated values from the OVGF method. The first vertical ionization energy of CH3C(O)OSSOC(O)CH3 is determined to be 9.83 eV by photoelectron spectroscopy, which corresponds to the ionization of an electron mainly localized on the sulfur 3p lone pair molecular orbital.

Macroporous Polyisobutylene Gels: A Novel Tough Organogel with Superfast Responsivity

Macroporous gels were prepared by solution crosslinking of butyl rubber (PIB) in frozen benzene solutions using sulfur monochloride (S2Cl2) as a crosslinking agent. The effect of different preparation conditions, including the crosslinker concentration and the gel preparation temperature, on the gel properties was investigated. S2Cl2 was found to be an efficient crosslinking agent even at very low reaction temperatures up to −22 °C and at crosslinker ratios down to about 0.9 mol S2Cl2/mol internal vinyl group on PIB. The gels prepared from frozen solutions of PIB contain about 97% organic liquid, and they are very tough; they can be compressed up to about 100% strain without any crack development, during which the total liquid inside the gel is removed. Further, the compressed gel immediately swells in contact with good solvents to recover its original shape. The low-temperature gels have a porous structure with irregular large pores of 101−102 μm in diameter, separated by pore walls of about 10 μm in wid...

Preparation and properties of nitrogen-substituted thiosulfinyl compounds and related new heterocycles

The reaction of dilithiated N, N′-dimethyl-1,2-diphenylethylenediamine with disulfur dichloride (S 2Cl 2) gave a thiosulfinyl compound (R 2N) 2S S, 2,5-dimethyl-3,4-diphenyl-1,2,5-thiadiazolidine 1-sulfide, whereas the treatment of dilithiated N, N′-bis( p-toluenesulfonyl)-1,2-diphenylethylenediamine with S 2Cl 2 furnished a new heterocycle, 3,6-bis( p-toluenesulfonyl)-4,5-diphenyl-4 H,5 H-1,2,3,6-dithiadiazine.

Transformations of N-ethylamines into amide derivatives under the action of sulfur monochloride

Tertiary N-ethylamines were converted into amide derivatives by reactions with sulfur monochloride and DABCO at 0 °C. Depending on the nature of the substituents in the amine, the reaction can be accompanied by unexpected transformations.

The Preparation and Characterization of the Cross-Linked Spherical, Cylindrical, and Vesicular Micelles of Poly(styrene-b-isoprene) Diblock Copolymers

PI cores of the micelles of poly(styrene-b-isoprene) (PS-b-PI) diblock copolymers, in PS selective solvents, were cross-linked with sulfur monochloride (S2Cl2). The cross-linked micellar structure was maintained after dialysis in THF (neutral solvent) and did not change during heating. Cross-linking brought about the opportunity for TEM images in a solution state; otherwise, the micellar structure would be destroyed (or changed) during the evaporation of the solvent on a carbon-coated copper grid. The Flory interaction parameter, chi, between the PI block and the solvent was controlled by mixing two selective solvents (DMP/toluene, DMP/DEP and DEP/DBP) which have different degrees of selectivity for the PS block, as well as heating the solutions. Two block copolymers, PS(7.2K)-b-PI(7.8K) and PS(5.5K)-b-PI(18.8K), were studied in order to clarify the effects of the relative chain length of each block on the micelle structure in the selective solvents. PS(7.2K)-b-PI(7.8K), which is nearly symmetric, showed only spherical micelles in the DMP/toluene mixture. The basic spherical micellar shape of PS(7.2K)-b-PI(7.8K) did not change with chi, while the size and aggregation number of the micelles increased as chi increased until 2.05 and then were saturated after that. PS(5.5K)-b-PI(18.8K), which is asymmetric, showed a structural change from spherical to cylindrical to vesicular micelles with an increase in the selectivity of the DMP/DEP and DEP/DBP mixtures (which was also confirmed by TEM and SAXS studies). Giant vesicular micelles with a diameter of approximately 2.5 microm were observed in high-selectivity solvents. The size of the vesicular micelle seemed to decrease as selectivity decreased. The systematic changes of the micellar structures of PS(5.5K)-b-PI(18.8K), via changes in solvent selectivity, could be demonstrated through TEM images, which were prepared by evaporating the solvent of the cross-linked micellar solution onto the carbon-coated grid after dialysis.

Synthesis and Oxidative Ring Contraction of 1,5,3,7-Dichalcogenadiazocanes. Novel Formation of 1,2,4-Diselenazolidines, 1,2,4-Ditellurazolidines, and 1,2,3,4,5,7-Pentathiazocanes

Abstract 1,5,3,7-Dithiadiazocanes, 1,5,3,7-diselenadiazocanes, and 1,5,3,7-ditelluradiazocanes were prepared from a primary amine, formalin, and H2S, NaSeH, or NaTeH, respectively. Oxidation of 1,5,3,7-diselenadiazocanes and 1,5,3,7-ditelluradiazocanes using NBS efficiently afforded 1,2,4-diselenazolidines or 1,2,4-ditellurazolidines, respectively. In contrast, treatment of 1,5,3,7-dithiadiazocanes with bromine-elemental sulfur or disulfur dichloride (S2Cl2) afforded 1,2,3,4,5,7-pentathiazocanes. An unusual oxidative conversion of 1,5,3,7-dichalcogenadiazocanes into these products was assumed to proceed through in situ formation of 1,5,3,7-dichalcogenadiazabicyclo[3.3.0]octane-type dications.

Regioselective synthesis of pentathiepines fused with pyrrole, thiophene, or indole rings

Pentathiepines fused with pyrrole, thiophene, or indole rings were obtained by reactions of the corresponding heterocycles or their tetrahydro derivatives with a prepared mixture of sulfur monochloride and DABCO.

Heterocyclic Chemistry of Sulfur Chlorides — Fast Ways to Complex Heterocycles.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Heterocyclic Chemistry of Sulfur Chlorides – Fast Ways to Complex Heterocycles

AbstractThis microreview highlights the most important advances in the synthetic applications of sulfur dichloride and disulfur dichloride for the preparation of heterocycles. Sulfur chlorides can be considered some of the best sulfur‐transfer reagents for the synthesis of heterocyclic systems. Their high reactivity towards nucleophilic organic compounds such as alkenes, alkynes, amines, nitriles, oximes, and their both chlorinating and sulfurating character explain the extensive use of these reagents. In many cases, the initial reactions give rise to reactive intermediates that can be trapped by nucleophiles in a tandem fashion, expanding the possibilities of the reactions. In this way, several new heterocyclic systems can be obtained by a careful selection of the appropriate combination of reagents. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Abnormally Mild Synthesis of Bis(dithiolo)pyrroles from 2,5-Dimethylpyrroles

[chemical reaction: see text]. Treatment of N-substituted 2,5-dimethylpyrroles 2 with an equilibrated mixture of disulfur dichloride and DABCO in chloroform at 0 degrees C gives pentathiepinopyrroles 3 in moderate yields; further reaction of 3 with the same mixture at room temperature leads, in an extensive reaction cascade, to bis(dithiolo)pyrroles 4 in high yield; 2 can be converted into 4 in a one-pot operation under unusually mild conditions.

Extensive ab initio study of the electronic states of SCl including spin-orbit coupling

The effect of different basis sets for calculation of the spectroscopic constants of the ground state of sulfur monochloride (SCl) was analyzed using scalar relativistic multireference configuration interaction with single and double excitations plus Davidson correction. Then the generally contracted all-electronic correlation-consistent polarized valence quintuple zeta basis sets were selected to compute the electronic states of SCl including 12 valence and 9 Rydberg lambda-S states. The spin-orbit coupling effect was calculated via the state interaction approach with the full Breit-Pauli Hamiltonian. This effect splits these lambda-S states into 42 omega states. Potential-energy curves of all these states are plotted with the help of the avoided crossing rule between the electronic states of the same symmetry. The structural properties of these states are analyzed. Spectroscopic constants of bound excited states that have never been observed in experiment are obtained. The transition dipole moments and the Franck-Condon factors of several transitions from low-lying bound excited states to the ground state were also calculated.

A Direct Preparation of Functionalized Aryl and Heteroaryl Disulfides from Functionalized Zinc Organometallics by Using Sulfur Monochloride (S2Cl2).

A range of functionalized aryl and heteroaryl disulfides has been prepared from zinc organometallics by using sulfur monochloride (S 2 Cl 2 ). The zinc reagents were obtained by transmetalation from magnesium or lithium reagents with ZnBr 2 .

Preparation of poly( N-methylpyrrole) modified with pentathiepin rings and its application to positive active material for lithium secondary

Lithium secondary batteries with high energy density are key devices for portable electrical equipments. The specific capacity of metal oxide-based positive active materials is considerably lower than that of lithium metal. Organosulfur compounds, such as disulfide compounds are useful as a positive active material for lithium secondary cells. We prepared modified poly( N-methylpyrrole) (PMPy) with pentathiepin rings (S-PMPy) from PMPy and disulfur dichloride at room temperature. The S-PMPy electrode showed electrochemical responses in the organic electrolyte solution (mixture of propylene carbonate (PC) and 1,2-dimethoxyethane (DME) (1:1, v/v) containing 1 mol dm −3 LiClO 4). The maximum capacity of the test lithium secondary cell with the S-PMPy electrode was 14.8 A h kg −1 (per kilogram of S-PMPy) and the average capacity was 11.5 A h kg −1 (10 cycles) under the constant charge–discharge current condition at room temperature.

Reaction of Sulfur Chlorides with Metal β-Diketonates

Metal β-diketonates react with sulfur dichloride to form sulfenyl chlorides irrespective of β-substituent. Bulky phenyl and tert-butyl groups do not prevent formation of fully substituted complexes. The possibility of preparing sulfenyl chloride derivatives of rhodium, ruthenium, and vanadium β-diketonates was demonstrated. A new procedure was suggested for preparing chlorosulfenyl-substituted β-diketonates. Disulfur dichloride reacts with metal chelates with the substitution of both chlorine atoms and formation of polynuclear complexes in which the diketonate groups are linked by disulfide bridges.

The preparation and characterization of 5-substituted-4-chloro-1,2,3-dithiazolium salts and their conversion into 4-substituted-3-chloro-1,2,5-thiadiazoles.

A series of monosubstituted acetonitriles were treated with disulfur dichloride at room temperature in CH2Cl2 to afford 5-substituted-4-chloro-1,2,3-dithiazolium chlorides 1. Where the 5-substituent was not a good leaving group the chloride salts were converted into the corresponding perchlorate salts 2 which were sufficiently stable and soluble to provide both 1H- and 13C-NMR and cyclic voltammetry data. Several of the dithiazolium chlorides were converted into their corresponding 4-substituted-3-chloro-1,2,5-thiadiazoles 13 on treatment with aqueous ammonia. Mechanisms for all reactions are proposed.

A Direct Preparation of Functionalized Aryl and Heteroaryl Disulfides from Functionalized Zinc Organometallics by Using Sulfur Monochloride (S2Cl2)

A range of functionalized aryl and heteroaryl disulfides has been prepared from zinc organometallics by using sulfur monochloride (S 2 Cl 2 ). The zinc reagents were obtained by transmetalation from magnesium or lithium reagents with ZnBr 2 .

Synthesis of 1,3,4‐Thiadiazoles from Aldehyde Hydrazones.

AbstractFor Abstract see ChemInform Abstract in Full Text.