2-chloroethyl Phenyl Sulfide Research Articles

Preparation and Application of MnO2 Nanoparticles/Zeolite AgY Composite Catalyst by Confined Space Synthesis (CSS) Method for the Desulfurization and Elimination of SP and OPP

In this work, zeolite NaY was prepared by hydrothermal method. Then, silver ions were replaced in the zeolite NaY with silver nitrate (AgNO3) solution via using ion exchange (IE) method. The Manganese dioxide (MnO2) nanoparticles (9.3 and 15.8 wt %) for guest were deposited in the zeolite AgY(host) structure with Mn(NO3)2 aqueous and KMnO4 solutions by confined space synthesis (CSS) method. Synthesized samples were studied and characterized via XRD, SEM/EDAX, FTIR, AAS and N2-BET techniques. The desulfurization and elimination reaction of 2- chloroethyl phenyl sulfide (2-CEPS) and DEPPT (O, S-diethyl phenyl phosphonothioate) have been investigated by 15.8 wt% Nano MnO2/Zeolite AgY composite and MnO2 nanoparticles catalysts and via GC, GC-MS and 31 PNMR.

A Simple and Efficient Chemical Decontamination of Sulfur Mustard (HD) Using 1,8-Diazabicyclo[5,4,0]Undec-7-Ene Hydrobromide-Perbromide

A simple and efficient chemical decontamination method was developed against sulfur mustard (HD), an extremely toxic and persistent chemical warfare agent. The method involves treatment of chemical warfare agent HD and its simulants, i.e., methyl p-tolyl sulfide, 2-chloroethyl phenyl sulfide, and 2-chloroethyl ethyl sulfide, with 1,8-diazabicyclo[5,4,0]undec-7-ene hydrobromide-perbromide at room temperature in 1:3 acetonitrile–water system as well as in aqueous medium. The reagent has efficiency to oxidize sulfur mustard in a controlled manner to form nontoxic sulfoxide avoiding overoxidation to the toxic sulfone. Reaction products of the oxidation were isolated and analyzed by gas chromatography-mass spectrometry and 1H NMR.

L-Gel Formulation and Decontamination Reaction of Its Active Ingredient (Oxone) Against Mustard and VX Nerve Agent Simulants

L-Gel is an effective decontamination reagent against chemical and biological warfare agents. To achieve optimized formulation of L-Gel, several formulations with different proportional amounts of oxone (oxidizer) and Cab-O-Sil (gelling agent) were prepared and their viscosities and densities were measured. Final optimized formulation of gel was obtained as a 0.25 M aqueous solution of oxone gelled with 13%W/W of Cab-O-Sil EH-5. The L-Gel active ingredient (oxone) was tested against O,O,S-triethyl phosphorothioate (TEPT) as VX simulant and methyl phenyl sulfide (MPS) and chloroethyl phenyl sulfide (CEPS) as HD simulants. Decontamination of TEPT by a 10-fold excess amount of oxone was completed within 7.5 min with a kinetic rate constant of 0.097 S−1. In the presence of oxone, MPS was converted to methyl phenyl sulfoxide and methyl phenyl sulfone with a higher reaction rate than CEPS, decontaminated product of which was chloroethyl phenyl sulfone.Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.GRAPHICAL ABSTRACT

Detection of dimethyl methyl phosphonate – a simulant of sarin: The highly toxic chemical warfare – using platinum activated nanocrystalline ZnO thick films

Nanocrystalline ZnO powder was prepared using ultrasonic atomization technique. Thick films of this powder were prepared using simple screen printing technique. Pt-modified-ZnO (platinum activated) films were obtained by dipping pure ZnO films into an aqueous solution of chloroplatnic acid for different intervals of time, followed by firing at 500 °C for 30 min. The sensing performance of the unmodified (pure) and Pt-modified ZnO (Pt–ZnO) films was tested on exposure of CWAs (chemical warfare agents) simulants, such as, dimethyl methyl phosphonate (DMMP), 2-chloroethyl ethyl sulfide (CEES) and 2-chloroethyl phenyl sulfide (CEPS). Both pure ZnO and Pt–ZnO films showed higher response to DMMP than their responses to CEES and CEPS. The simulant response, selectivity, response time and recovery time of the sensors were measured and presented. The role played by surface platinum species in the better simulant sensing performance is discussed.

Sensing of 2-chloroethyl ethyl sulfide (2-CEES) – a CWA simulant – using pure and platinum doped nanostructured CdSnO 3 thin films prepared from ultrasonic spray pyrolysis technique

Nanostructured perovskite CdSnO 3 and Pt-CdSnO 3 thin films were prepared using ultrasonic spray pyrolysis technique. The nozzle (driven by ultrasonic frequency of 120 kHz) fixed on microprocessor controlled motorized arm could move in X–Y direction and spray onto heated (300 °C) glass substrate to give the films of repeatable thickness and microstructure. Structural and microstructural properties of the films were studied using X-ray diffraction and transmission electron microscopy (TEM), respectively. The sensing performance of the films was tested for CWA simulants, such as, CEES (2-chloroethyl ethyl sulfide C 4H 9ClS), DMMP (dimethyl methyl phosphonate C 3H 9O 3P) and CEPS (2-chloroethyl phenyl sulfide C 8H 9ClS). Both CdSnO 3 and Pt-CdSnO 3 showed higher response, better selectivity and faster speed of response to CEES as compared to their responses of DMMP and CEPS. CEES response of Pt-CdSnO 3 is larger than the response of CdSnO 3. The results are discussed and interpreted.

Conductive electrospun PANi-PEO/TiO2 fibrous membrane for photo catalysis

The integration of electrospinning and electrospraying to prepare the fibrous catalytic filter membrane is demonstrated. The non-conductive polyethylene oxide (PEO) is blended with (±)-camphor-10-sulfonic acid (CSA) doped conductive polyaniline (PANi) for electrospinning. The conductive CSA/PANi-PEO composite fibers are produced upon electrospinning, which are used as the conductive collector for electrospraying process by which titanium dioxide (TiO2) nanoparticles (NPs) are sprayed and allowed to adsorb on the fibers. The degree of adsorption and dispersion of nano TiO2 catalysts on the surface of the CSA/PANi-PEO fibers exhibit a stronger dependence on weight percentage (wt%) of PANi in PEO solution and the strength of electrical conductivity of the fibers used during electrospraying. CSA/PANi-PEO fibers as collector reduce the wastage of TiO2 NPs during electrospraying to lesser than 5%. Among the three different composition of PANi studied, PEO with 12 wt% PANi yields very uniform diameter and beads-free fibrous structure with higher electrical conductivity. 12 wt% CSA/PANi-PEO fibrous membrane is found to support for greater dispersion of TiO2 NPs. The photocatalytic activity of the as-prepared TiO2-PANi-PEO catalytic membrane is tested against the toxicant simulant 2-chloroethyl phenyl sulfide (CEPS) under the ultraviolet light irradiation. It is observed that the TiO2 nanoparticles catalysts embedded PANi-PEO fibrous membrane decontaminated the toxicant CEPS significantly, which is due to uniform dispersion of the catalysts produced by the methodology.

Identification and Quantification of Related Impurities in 2-Chloroethyl Phenyl Sulfide for Industrial Use

A combination of gas chromatography and mass spectrometry (GC-MS) was applied to separate and identify the relative substances in 2-chloroethyl phenyl sulfide (CEPS), an industrial intermediate formed in the synthesis of sulfinpyrazone. Six impurities, including 1,2-dichloroethane, thiophenol, diethylmalonate, tributylamine, diphenyl disulfide, and 1,2-dithiophenylethane, were verified. According to the production technique, the sources of all of these related impurities were analyzed, and some practical suggestions are put forward for their removal from or avoidance in CEPS. Furthermore, a technique involving high-performance liquid chromatography with UV detection (HPLC-UV) was developed to separate and determine thiophenol, the key impurity in CEPS. A linear standard curve was obtained for thiophenol in concentrations between 2.65 × 10−4 and 0.106 mg mL−1, and the detection limit of thiophenol was 1.32 × 10−4 mg mL−1. Excellent precision and accuracy were shown from the method validation, with relative standard deviations (RSDs) of less than 1.5% for both intra- and interday measurements, and recoveries between 95.4% and 97.0%. Based on the above merits, the proposed procedures of GC-MS and HPLC-UV can provide specific information on the impurities in CEPS, and therefore, these methods can be well applied to quality control in the industrial production of CEPS.

Locus-Specific Microemulsion Catalysts for Sulfur Mustard (HD) Chemical Warfare Agent Decontamination

The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.

Reactions of Chemical Warfare Agent Simulants in the Common Ion Binary Ionic Liquid 1,2-Dimethyl-3-propylimidazolium/Copper(II) Bis(trifluoromethylsulfonyl)amide

Ionic liquids have the potential for being ideal alternatives for organic solvents in chemical warfare agent reactions and demilitarization processes. They are considered to be an excellent substitute, because of their extraordinarily wide liquid range, low melting points, chemical and thermal stability, high conductivity, and nonvolatility. In addition, many have excellent hydrophobic properties and immiscibility with water and offer the opportunity to isolate the chemical agents and reaction products from the environment. In this report, we describe a two-step process in which chemical warfare simulants are reacted with hydrogen peroxide (H2O2) followed by basic methanol in a common ion binary ionic liquid that consists of 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)amide and copper(II) bis(trifluoromethylsulfonyl)amide. The chemical agent simulants used in this study are diisopropylfluorophosphate, bis(2-ethylhexyl) phosphite, and 2-chloroethylphenyl sulfide, which simulate agents GB, ...

Decontamination Reactions of Chemical Warfare Agent Simulants with Alcohols in the Basic Ionic Liquid Tetramethylammonium Hydroxide/1,2-Dimethyl-3-propylimidazolium Bis(trifluoromethylsulfonyl)amide

Increased acts of international terrorism called for the development of rapid and reliable chemical agent decontamination reactions to minimize human exposure and material loss. Even though many chemical reaction processes have been reported, most remain unattractive for various reasons. In order to eliminate many of the adversities, these processes were studied in an ionic liquid solvent. In this report, we describe the reaction between chemical warfare simulants with alcohols in the ionic liquid 1,2-dimethyl-3-propylimmidazolium bis(trifluoromethylsulfonyl)amide made basic with tetramethylammonium hydroxide pentahydrate. The chemical agent simulants used in this study were diisopropylfluorophosphate, bis(2-ethylhexyl) phosphite, and chloroethylphenyl sulfide, which simulate agents GD, VX, and HD, respectively. The reactions were rapid, and products were identified by LC/MS-TOF and GC/MS. All of the reaction products of the VX and HD simulants remained in the ionic liquid, whereas the products from GD si...

Thiocompounds as simulants of sulphur mustard for testing of protective barriers

The protective potential of protective devices such as respirators, suits, gloves, and overboots is widely evaluated using the standard colorimetric test (spot disc breakthrough time test, also called SD BTT) involving sulfur mustard (SM) as the challenge chemical. The vesicant nature of SM makes the test inconvenient and poses stringent safety demands. Moreover, such tests are allowed only at a limited number of facilities, causing delay in product development and supply. This prompted the present study on the search for suitable SM simulant responsive to SD BTT test. The diffusivities at BTT (DBTT) of 10 commercially available thiocompounds through butyl rubber (IIR) were compared vis-a-vis DBTT of SM. For three representative thiocompounds, namely methyl (phenyl thio)acetate, 2-chloroethyl phenyl sulfide (2-CEPS) and phenyl-n-propyl sulfide (PNPS), the transport parameters through IIR were obtained. PNPS and 2-CEPS were further compared with respect to DBTT in elastomers such as IIR, ethylene–propylene–diene methylene rubber, polydimethylsiloxane, nitrile rubber, polybutadiene, and natural rubber. 2-CEPS showed generally same order of DBTT as SM implying its potential use as a simulant. The transport parameters for various 2-CEPS/elastomer systems were also determined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Sulfide oxidation with H 2O 2 catalyzed by manganese complex of N, N′, N″-tris(2-hydroxypropyl)-1,4,7-triazacyclononane

[MnL](ClO 4) 2 (L = N, N′, N″-tris(2-hydroxypropyl)-1,4,7-triazacyclononane) has been tested for catalyzing sulfide oxidation. In the presence of this complex, ethyl phenyl sulfide, butyl sulfide and phenyl sulfide are completely oxidized to the corresponding sulfoxides and sulfones with H 2O 2 as the oxidant. 2-Chloroethyl phenyl sulfide oxidation yield 2-chloroethyl phenyl sulfone and phenyl vinyl sulfone. In ethyl phenyl sulfide oxidation, effects of complex and H 2O 2 concentration and temperature on the reaction rate have been discussed. Through controlling reaction conditions, ethyl phenyl sulfoxide and ethyl phenyl sulfone may be produced selectively. The UV–Vis and electron paramagnetic resonance (EPR) studies on catalyst solution indicate that metal centre of the complex is transformed from Mn(II) to Mn(IV) after the addition of H 2O 2. At 25 °C, rate constant for ethyl phenyl sulfide oxidation is 4.38 × 10 −3 min −1.

Fluorophobic enhanced decontamination of a mustard simulant by porous monolithic flow-through columns

Monolithic polymer columns have been prepared by the in situ copolymerization of divinylbenzene and chloromethylstyrene in stainless steel tubes followed by a derivatization treatment with ethylenediamine or diethylenetriamine. These columns function for the flow-through non-destructive removal of a “mustard gas” simulant – 2-chloroethyl phenyl sulfide (CEPS), from the fluorinated solvent HFE-7100 (a mixture of methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether). More polar solvents such as THF efficiently flush the adsorbed CEPS from the column. Two parameters, half-life time of decontamination and total percentage of removed CEPS, were used to characterize column activity, which depended on monomer composition, polymer functionalization, and temperature. Polyamine-modified columns had a high affinity for CEPS, with removal efficiencies of up to 97% from contaminated HFE-7100 (4 h) being observed. The effect of “poisoning” amino containing columns by purportedly inert HFE-7100 at high temperature was established.

Performance of an emerging all-weather decontamination solution against nerve and mustard agent simulants at subfreezing temperatures

Solutions for decontaminating chemical and biological agents should be able to perform in all climatic conditions, including subfreezing temperatures. Below 0 °C, aqueous-based decontamination solutions or their components can freeze, rendering them inactive and difficult to handle. Moreover, rates of neutralization will be dramatically slower than at normal room temperature. In a series of replicated laboratory studies, we quantified the efficacy of an emerging decontamination solution, DECON Green, against the VX nerve-agent simulant bis-(2-ethyl hexyl) phosphite and the HD mustard agent simulant 2-chloroethyl phenyl sulfide. The efficacy of the DECON Green formulations was tested at 4, − 5 and − 15 °C using both contact-hazard assessments and mass balance approaches. Contact-hazard assessments simulated the transfer of simulant to skin. The mass balance approach addressed the fate of simulant by quantifying recovery following each step of the decontamination process. Two formulations of DECON Green were investigated: the “standard” formulation, New DECON Green, and the “cold weather” formulation, CA 2 WT. Simulants were spread on chemical-agent-resistant-coating-treated aluminum disks (CARC coupons). The CARC coupons were subsequently decontaminated using standard U.S. Army operating procedures. At all temperatures investigated, sequential contact hazards of the simulant were three to four times lower in concentration for the mustard simulant and nerve-agent simulant, respectively, following the application of DECON Green and washing than without DECON Green or without washing. The mass balance data showed that washing with a propylene glycol:H 2 O solution was an important part of the decontamination process. DECON Green both degraded the simulants and increased the simulants removed during washing. These findings indicate that at both − 5 and − 15 °C, temperatures at which water-based procedures would be problematic, the cold-formula DECON Green plus washing with propylene glycol:H 2 O was effective at reducing surface contact hazards from the two chemical agent simulants.

Polymeric decontaminant 2 (N,N-dichloropolystyrene sulfonamide): Synthesis, characterization, and efficacy against simulant of sulfur mustard

A polymeric decontaminant N,N-dichloropolystyrene sulfonamide was synthesized by different steps from starting material polystyrene and followed by sulfonation, chlorosulfonation, and amidification. Halogeno-sulfonamide was obtained by treatment of sodium hypochlorite with sulfonamide resin. It was characterized by FTIR, solubility, viscosity, DSC, and TGA techniques. Efficiency of this polymer as decontaminant was evaluated by reaction with 2-chloro ethyl phenyl sulfide, a simulant of sulfur mustard (SM) at room temperature. This decontamination reaction was monitored by gas chromatography (GC) and products were identified by gas chromatography-mass spectrometry (GC-MS). The positive chlorine content of this polymer was checked by standard iodometry titration. The synthesized positive chlorine compound is observed to be a promising decontaminant against simulant of sulfur mustard, chiefly in the situation where use of aqueous medium such as acetonitrile : water (2 : 1) is precluded. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Sulfide oxygenation by tert-butyl hydroperoxide with mononuclear (Me 3TACN)Mn catalysts

Mononuclear (Me 3TACN)MnX 3 compounds, where X is Cl −, Br −, or N 3 −, and Me 3TACN is 1,4,7- N, N′, N″-trimethyl-1,4,7-triazacyclononane, have been tested for catalyzing both sulfide oxygenation and styrene epoxidation by tert-butyl hydroperoxide (TBHP) and display turnover frequencies (TOF) up to 200 h −1 at room temperature. Sulfoxides or sulfones may be produced selectively by varying reaction conditions. Product distribution from the oxygenation reactions of ethyl phenyl sulfide, 2-chloroethyl phenyl sulfide, and styrene is consistent with a mechanism involving an early single-electron transfer (SET) step.

Liquid permeation through nonporous barrier materials

Permeation of chemical warfare agents (CWAs) and relatively nontoxic simulants in several elastomer compounds is examined using a new design flooded surface, liquid permeation cell. Diffusivity ( D) and permeability are determined for sulfur mustard and sarin CWA, and for the simulants: dichlorohexane, chloroethyl phenyl sulfide, diethyl methylphosphonate and diisopropyl methylphosphonate. Values of D calculated by several kinetic methods at different stages of the permeation process and from steady-state permeability are generally in agreement but lower than those obtained from immersion kinetics. Barrier effectiveness of the elastomer compounds towards the CWA and simulant liquids decreases in the order: butyl > EPDM > nitrile ≫ silicone. Simulant and CWA permeation are correlated in terms of relative permeability and reduced breakthrough time.

Facile oxygenation of organic sulfides with H2O2 catalyzed by Mn–Me3TACN compounds

Two binuclear Mn–Me3TACN (Me3TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane) compounds catalyze the oxygenation of organic sulfides utilizing H2O2 under ambient conditions. Both phenyl sulfide and ethyl phenyl sulfide were converted to the corresponding sulfones and chloroethyl phenyl sulfide proceeds to its elimination product of phenyl vinyl sulfone.

Quaternary ammonium O,O′-dialkylphosphorodithioate surfactants and their reactions with 2-chloroethyl phenyl sulfide, a mustard simulant

Single- and double-chain quaternary ammonium O,O′-dialkylphosphorodithioate surfactants 1– 3 were synthesized: 1, hexadecyltrimethylammonium O,O′-diethylphosphorodithioate; 2a, didodecyldimethylammonium O,O′-dimethylphosphorodithioate; 2b, didodecyldimethylammonium O,O′-diethylphosphorodithioate; 3, didodecyldimethylammonium O,O′-didodecylphosphorodithioate. Surfactant 1 was characterized by Krafft temperature and critical micelle concentration measurements, and its aqueous aggregates were characterized by dynamic laser light scattering and 1H NMR spectroscopy. Compounds 2 and 3 are largely insoluble in H 2O, even at temperatures >23 °C. The reaction of micellar 1 with 4 (2-chloroethyl phenyl sulfide), a simulant for the chemical warfare agent mustard [bis(2-chloroethyl) sulfide], gave 10 [ S-[2-(phenylthio)ethyl] O,O′-diethylphosphorodithioate] in a pH 9.0 borate buffer at 23 °C. The conversion of 4 into 10 corresponds to the decontamination of 4.

Renewables in the land of the midnight sun

Nanocrystalline ZnO powder was prepared using ultrasonic atomization technique. Thick films of this powder were prepared using simple screen printing technique. Pt-modified-ZnO (platinum activated) films were obtained by dipping pure ZnO films into an aqueous solution of chloroplatnic acid for different intervals of time, followed by firing at 500 °C for 30 min. The sensing performance of the unmodified (pure) and Pt-modified ZnO (Pt–ZnO) films was tested on exposure of CWAs (chemical warfare agents) simulants, such as, dimethyl methyl phosphonate (DMMP), 2-chloroethyl ethyl sulfide (CEES) and 2-chloroethyl phenyl sulfide (CEPS). Both pure ZnO and Pt–ZnO films showed higher response to DMMP than their responses to CEES and CEPS. The simulant response, selectivity, response time and recovery time of the sensors were measured and presented. The role played by surface platinum species in the better simulant sensing performance is discussed.