Sulfur Dichloride Research Articles

Optimization of Cr/Sc-based multilayer mirrors for water window soft x-rays.

The development of efficient multilayer mirrors for the water window (a spectral region between absorption edges of carbon and oxygen, from 284 to 543 eV) remains a challenge. As the best candidate, the Cr/Sc multilayer provides maximum theoretical reflectivity of about 60% at near-normal incidence around the Sc L2,3 absorption edge (397 eV). However, the maximum measured peak reflectance published so far just slightly exceeds 20%. We report on a new (to the best of our knowledge) approach to design more efficient Cr/Sc-based multilayer coatings using the process of nitridation of chromium during deposition and adding boron carbide as a third material in the multilayer structure. We discuss our strategy of optimization of the CrN/B4C/Sc multilayer system based on experimental studies. The peak reflectance as high as 32% at 396 eV was measured with this type of coating, which is of main interest for various water window applications such as x-ray microscopy.

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

A series of polymers that possessed a backbone solely composed of alternating nitrogen and sulfur single bonds were synthesized for the first time. The structures of these polymers were based on polythiazyl (SN)x, which only possesses nitrogen and sulfur and is electrically conducting at room temperature in the absence of doping and superconducting at low temperatures. The polymers reported in this manuscript were synthesized using the reaction between sulfur dichloride (SCl2) and either anilines or octylamine. The isolated yields ranged from 48% to 74%, and the molecular weights were found using light scattering and refractive index detectors to be 6,200–35,000 g mol–1. The UV–vis spectra of the polymers were obtained, and the polymers possessed peak maxima around 450 nm and appeared red. The poly[(N,N-amino)sulfide] (polyNAS) synthesized from octylamine also was red, which demonstrated that the color was due to conjugation along the NS backbone. These polymers are the first polymers containing a backbone of alternating N and S, and are easily processed due to the groups attached to the nitrogens.

Separation of Rare-Earth Ions from Mine Wastewater Using B12S Nanoflakes as a Capacitive Deionization Electrode Material.

In this study, nanoflakes of B12S were fabricated by plasma-assisted reaction of sulfur dichloride in an ionic liquid at room temperature using europium boride as a hard template. The nanoflakes had an average width and thickness of about 3 1urn and 9.6 nm, respectively, and a large specific surface area of 1197.2 m² g 1. They behaved like typical electric double-layer capacitors with a capacitance of 201.2 F g 1 at 0.2 mA cm ² During capacitive deionization to recover rare-earth ions, the nanoflakes had higher adsorption selectivity for Sm3+ than for other competing ions present in real mine waste water. This is due to the strong interaction of the electron-concentered S-groups (S''') of the nanoflakes with S m3+. This provides an alternative to construct efficient systems to specifically remove Sm3+ from aqueous solution using B12S nanoflakes. This process demonstrates that other boron sulfide compounds can be used to recover valuable ions by capacitive deionization.

A Regioselective Synthesis of Novel Functionalized Organochalcogen Compounds by Chalcogenocyclofunctionalization Reactions Based on Chalcogen Halides and Natural Products.

The regioselective synthesis of novel functionalized condensed organochalcogen compounds by chalcogenocyclofunctionalization reactions based on chalcogen halides and the natural products thymol and carvacrol has been developed. The reactions of selenium dibromide with allyl thymol and allyl carvacrol proceeded in methylene chloride at room temperature in the presence of NaHCO3 affording bis[(7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] and bis[(4-isopropyl-7-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] selenides in 90–92% yield. Similar sulfides were obtained in 70–72% yields by the reaction of sulfur dichloride in chloroform under reflux. Trihalotellanes containing the same organic moieties were synthesized from allyl thymol, allyl carvacrol and tellurium tetrachloride or tetrabromide in quantitative yields. Corresponding functionalized ditellurides were prepared in 91–92% yields by the reduction of the trichlorotellanes with sodium metabisulfite in two-phase solvent system. The comparison of reactivity of sulfur, selenium and tellurium halides in chalcogenocyclofunctionalization and distinguishing features of each reaction were discussed.

Modeling the aluminum-doped and single vacancy blue phosphorene interactions with molecules: a density functional theory study.

Structural, electronic, binding energies and magnetic properties of aluminum-doped and single vacancy blue phosphorene interacting with pollutant molecules are investigated using the density functional theory (DFT) with periodic boundary conditions. Acetylene, ozone, sulfur trioxide, hydrogen selenide, and sulfur dichloride molecules are considered to show the efficiency and enhancement of the sensing properties in comparison with the pristine blue phosphorene. Acetylene, sulfur trioxide, hydrogen selenide, and sulfur dichloride show chemisorption (> 0.5eV/molecule) when interacting with the aluminum-doped system, but the ozone molecule dissociates in all configurations and symmetry sites. On the other hand, the acetylene, ozone, and sulfur trioxide with the single vacancy blue phosphorene exhibit chemisorption, the hydrogen selenide molecule exhibit a weak interaction energy, and the sulfur dichloride dissociates in all configurations and symmetry sites. In all the cases, the enhancement in the interaction energy was achieved when compared to other results for the same molecules. Finally, the single vacancy blue phosphorene shows a magnetic moment of ~1 μB/supercell, as induced by the vacancy.

Adsorption of small pollutant molecules on monolayer blue phosphorus

Binding, electronic and optical properties of small pollutant molecules adsorbed on pristine monolayer blue phosphorus (BlueP) are investigated using the density functional theory (DFT). Ozone (O3), sulfur trioxide (SO3), hydrogen selenide (H2Se), sulfur dichloride (SCl2) and acetylene (C2H2) molecules are considered to explore the efficiency and versatility of the BlueP as a gas sensor in comparison with other materials. Results show while O3, SO3 have high binding energy (>0.5 eV/molecule), H2Se, SCl2 and C2H2 exhibit small binding energies (<0.5 eV/molecule) on BlueP. However, even when SCl2 and C2H2 interact weakly with BlueP, a strong modification is observed in the density of states, electronic band structure and the optical absorption of BlueP by the reduction of electronic and optical gaps from ∼2.1 eV to ∼1.5 eV. These changes in electronic and optical properties are some mandatory pre-requisites for any sensing material. Thus, our results suggest that BlueP can be considered as a promising candidate to solve different current problems of environmental pollution.

Synthesis of (1,3-oxathiolan-2-ylmethyl) sulfide and disulfide by cyclofunctionalization of 2-(vinylsulfanyl)ethanol with sulfur dichloride and monochloride

Synthesis of (1,3-oxathiolan-2-ylmethyl) sulfide and disulfide by cyclofunctionalization of 2-(vinylsulfanyl)ethanol with sulfur dichloride and monochloride

Bis(tetrahydro-2H-pyran-2-ylmethyl)sulfide and -Sulfoxide from Sulfur Dichloride and 5-Hexen-1-ol

The reaction of sulfur dichloride with 5-hexen-1-ol has given bis(tetrahydro-2H-pyran-2-ylmethyl)-sulfide in 87% yield. Oxidation of the latter with NaIO4 has afforded bis(tetrahydro-2H-pyran-2-ylmethyl)-sulfoxide in 96% yield.

Synthesis of Fused Compounds on the Basis of Chalcogen Chlorides and 2-Allylphenols

Efficient methods have been developed for regioselective synthesis of new organochalcogen compounds containing 2,3-dihydro-1-benzofuran-2-ylmethyl and 7-methyl-2,3-dihydro-1-benzofuran-2-ylmethyl substituents by reactions of selenium and sulfur dichlorides and tellurium tetrachloride with 2-allylphenol and 2-allyl-6-methylphenol.

Method for Derivatization and Detection of Chemical Weapons Convention Related Sulfur Chlorides via Electrophilic Addition with 3-Hexyne.

Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) are important precursors of the extremely toxic chemical warfare agent sulfur mustard and classified, respectively, into schedule 3.B.12 and 3.B.13 of the Chemical Weapons Convention (CWC). Hence, their detection and identification is of vital importance for verification of CWC. These chemicals are difficult to detect directly using chromatographic techniques as they decompose and do not elute. Until now, the use of gas chromatographic approaches to follow the derivatized sulfur chlorides is not reported in the literature. The electrophilic addition reaction of sulfur monochloride and sulfur dichloride toward 3-hexyne was explored for the development of a novel derivatization protocol, and the products were subjected to gas chromatography-mass spectrometric (GC-MS) analysis. Among various unsaturated reagents like alkenes and alkynes, symmetrical alkyne 3-hexyne was optimized to be the suitable derivatizing agent for these analytes. Acetonitrile was found to be the suitable solvent for the derivatization reaction. The sample preparation protocol for the identification of these analytes from hexane spiked with petrol matrix was also optimized. Liquid-liquid extraction followed by derivatization was employed for the identification of these analytes from petrol matrix. Under the established conditions, the detection and quantification limits are 2.6 μg/mL, 8.6 μg/mL for S2Cl2 and 2.3 μg/mL, 7.7 μg/mL for SCl2, respectively, in selected ion monitoring (SIM) mode. The calibration curve had a linear relationship with y = 0.022x - 0.331 and r(2) = 0.992 for the working range of 10 to 500 μg/mL for S2Cl2 and y = 0.007x - 0.064 and r(2) = 0.991 for the working range of 10 to 100 μg/mL for SCl2, respectively. The intraday RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and interday RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S2Cl2 and SCl2, respectively.

Novel and Simple Synthesis of Brominated 1,10-Phenanthrolines

A novel, simple, and reasonably efficient synthesis of 3,8-dibromo-1,10-phenanthroline, 3,6-dibromo-1,10-phenanthroline, 3,5,8-tribromo-1,10-phenanthroline, and 3,5,6,8-tetrabromo-1,10-phenanthroline is presented herein. The crucial role of a new catalyst (sulfur dichloride – SCl2) for the bromination of 1,10-phenanthroline is reported. The bromination of 1,10-phenanthroline monohydrate in the presence of SCl2 and pyridine yielded the brominated compounds, previously only possible through the complicated multi-step and tedious Skraup synthesis method. The application of the bromination catalyst SCl2 as a medium-strength Lewis acid is demonstrated for the first time, and the results are compared with the behaviours of known weak (sulfur chloride – S2Cl2) and strong (thionyl chloride – SOCl2) bromination catalysts. A reaction mechanism was proposed.

ChemInform Abstract: Synthesis of Bis(1,2,2‐trichloroethyl) and Bis(dichlorovinyl) Selenides by Electrophilic Reaction of Selenium Dichloride with 1,2‐Dichloroethylene.

AbstractThe reaction of 1,2‐dichloroethylene (I) with selenium dichloride is studied.

Atomic scale investigation of a PbTiO3/SrRuO3/DyScO3 heterostructure

An epitaxial PbTiO3 thin film grown on self-organized crystalline SrRuO3 nanowires deposited on a DyScO3 substrate with ordered DyO and ScO2 chemical terminations is investigated by transmission electron microscopy. In this PbTiO3/SrRuO3/DyScO3 heterostructure, the SrRuO3 nanowires are assumed to grow on only one type of substrate termination. Here, we report on the structure, morphology, and chemical composition analysis of this heterostructure. Electron energy loss spectroscopy reveals the exact termination sequence in this complex structure. The energy loss near-edge structure of the Ti–L2,3, Sc–L2,3, and O K edges shows intrinsic interfacial electronic reconstruction. Furthermore, PbTiO3 domain walls are observed to start at the end of the nanowires resulting in atomic steps on the film surface.

Synthesis of bis(1,2,2-trichloroethyl) and bis(dichlorovinyl) selenides by electrophilic reaction of selenium dichloride with 1,2-dichloroethylene

Electrophilic reactions of sulfur dichloride with unsaturated systems underlie one of the most general methods for the synthesis of bis(2-chloroalkyl) sulfides [1]. Reactions of analogous unsaturated compounds with selenium tetrachloride yield the corresponding bis-adducts containing a four-coordinate selenium atom (>SeCl2) [2]. In recent years we performed systematic studies on reactions of SeCl2 with alkenes and their oxygenand sulfur-containing derivatives [3, 4]. Reactions with chlorinated ethylenes, such as chloroethene, 1,1and 1,2-dichloroethenes, and trichloroethene were reported only for SCl2, and they required the presence of Lewis acids as catalyst [5]. Garratt et al. [6] showed that SeCl4 failed to react with 1,2-dichloroethene in the presence of AlCl3 as catalyst. Nevertheless, we succeeded in adding SeCl2 to bis(2-chlorovinyl) selenide (a selenium-containing derivative of 1,2-dichloroethene) in the absence of a catalyst [7]. Sulfur and selenium dichlorides are known to act as chlorinating agents toward alkylsulfanyl derivatives of polychloroethenes, e.g., alkyl 2,2-dichlorovinyl sulfides [8].

ChemInform Abstract: Selenium and Sulfur Dichlorides as Chlorinating Agents in the Reaction with Alkyl 2,2‐Dichlorovinyl Sulfides.

AbstractThe chlorination of dichlorovinyl sulfides (I) is performed by using selenium or sulfur dichloride in the presence of FeCl3 or AlCl3 as catalyst.

Selenium and sulfur dichlorides as chlorinating agents in the reaction with alkyl 2,2-dichlorovinyl sulfides

The chlorination of dichlorovinyl sulfides (I) is performed by using selenium or sulfur dichloride in the presence of FeCl3 or AlCl3 as catalyst.

ChemInform Abstract: Reaction of Bis(prop‐2‐yn‐1‐yl) Sulfide with Sulfur Dichloride. First Example of Cyclization of Bis(prop‐2‐yn‐1‐yl) Chalcogenides by the Action of Chalcogen Halides.

Abstract(E,E)‐2,6‐Bis(chloromethylidene)‐1,4‐dithiane (II) is regio‐ and stereoselectively obtained in an anti‐Markovnikov addition at both triple bonds of compound (I).

Synthesis and characterization of novel thermally stable poly(ether-amide)s containing dinaphthosulfone units in the main chain

Abstract A New type of sulfone (4) containing 1,1´-thiobis(2- hydroxynaphthalene) diacid as a monomer was synthesized from the reaction of 2-hydroxynaphthalene (1) and sulfur dichloride, followed by reaction with methylchloroactate to obtain diester (2). Oxidation of this product in the presence of hydrogen peroxide followed by basic hydrolysis led to corresponding sulfone diacid (4) in good yield. Six organic-soluble poly(ether-amide)s bearing sulfone groups were synthesized via direct polycondensation of diacid (4) with commercially available aromatic diamines in the presence of calcium chloride as dehydrating agent. The resulting polyamides had inherent viscosity ranging from 0.38 to 0.46 dLg-1 at concentration of 0.5 gdL-1 in N,N-dimethylacetamide at 30 °C. The glass transition temperatures of these polyamides were recorded between 276-327 °C in air atmosphere. These polymers were also characterized by IR, 1H NMR and elemental analysis and their physical properties including viscosity, solubility properties, thermal stability and thermal behaviour were studied. These polyamides showed very good thermal stability and solubility in polar aprotic solvents.

Reaction of bis(prop-2-yn-1-yl) sulfide with sulfur dichloride. First example of cyclization of bis(prop-2-yn-1-yl) chalcogenides by the action of chalcogen halides

(E,E)-2,6-Bis(chloromethylidene)-1,4-dithiane (II) is regio- and stereoselectively obtained in an anti-Markovnikov addition at both triple bonds of compound (I).

Detection of Multivalency Charge States in Complex and Elemental Transition Metal Oxides by X-ray Absorption Spectroscopy: Controlled Multivalency as a Pathway to Device Functionality

Multivalent charge states, or simply multivalency, introduced in transition metal elemental and complex oxides by substitutional alloy formation, provide a pathway for introducing new device functionalities. This article discusses alloy induced multivalency in three transition metal oxides resulting in different functionalities. These are: (i) an insulator to metal transition in GdScO3 by substitution of tetravalent Ti for trivalent Sc in the ScO2 planes of cubic perovskite structured GdSc1-xTixO3 alloys, above a percolation threshold of x = 0.165: (ii) double exchange magnetism in LaMnO3 by substitution of divalent Sr for trivalent La for the alloy composition La0.80Sr0.20MnO3; and (iii) controlled introduction of O-vacancy negative ion states as a pathway to current-controlled memory devices in tetravalent TiO2–trivalent Ti2O3 Magnéli phase alloys with a general formula TinO2n-1. In two of these alloys, the GdSc1-xTxO3 and TinO2n-1 alloys, additional valence states, as Ti2+ and Sc2+ in the Gd scandates, and Ti2+ in the Magnéli phases, are introduced by strain-reduction compensation associated with the ∼9% difference between the ionic radii Ti4+ and Ti3+. Spectroscopic detection is based on charge transfer multiplet theory as applied to Ti, Sc, and Mn L2,3 X-ray absorption spectra., in which the number of features in the L2 and L3 spectral regimes is significantly increased when either Ti or Mn is present in more than one valence state.