Reaction Of Carbon Tetrachloride Research Articles

Fluorodinitroethyl Ortho-carbonate and -formate as Potential High Energy Dense Oxidizers

Tetrakis(2-fluoro-2,2-dinitroethyl) ortho-carbonate (1) and tris(2-fluoro-2,2-dinitroethyl) orthoformate (2) were synthesized by the reaction of carbon tetrachloride, respectively chloroform, with 2-fluoro-2,2-dinitroethanol and catalytic amounts of anhydrous iron(III) chloride. The compounds were characterized by single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and multi-temperature DSC measurements. The suitability of the compounds as potential oxidizers in energetic formulations has been investigated and discussed. The heats of formation of the products were determined experimentally using bomb calorimetric methods. With this value and the experimental (X-ray) density, several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code. The sensitivity towards impact, friction and electrostatic discharge was tested using the BAM drop hammer, a friction tester and a small-scale electrostatic discharge device.

The complexes of copper with grafted ionic liquids in the environmentally important processes

The complexes of copper (II) chloride with quaternary ammonium salts grafted on various mineral supports (the modifications of SiO2 – KSK, silochrome, Perlkat) are highly active in two environmentally important processes: the reaction of carbon tetrachloride with alkanes and the oxidative coupling of thiols. The effectiveness of the catalysts depends on the transition metal, the ionic liquid, and the support nature. In CCl4 transformations, the highest activity is shown by the complexes with alkylamines derivatives grafted on silica with wide pores. In case of thiol oxidation, complexes with heterocycles derivatives grafted on Perlkat with narrow pores are most active. The effectiveness of the CCl4 transformations catalysts increases upon the addition of alcohol to the reaction mixture.

Catalysts based on the immobilized complexes of copper with quaternary ammonium bases for chlorination of alkanes with carbon tetrachloride

The complexes of copper chloride with quaternary ammonium bases supported on silica are highly active in the reaction of carbon tetrachloride with decane was found in the presence of an electron donor (ethanol). The effectiveness of the catalysts depends on the method of their deposition onto the support. The catalysts obtained as a result of covalent binding with the surface through the formation of siloxane bonds (immobilization) exhibit high stability and higher activity than the analogues prepared by the impregnation of the support with the catalytic complex. The introduction of ethanol into the reaction system substantially increases the activity and stability of all of the catalysts.

CHNO Based Molecules Containing 2,2,2‐Trinitroethoxy Moieties as Possible High Energy Dense Oxidizers

AbstractTetrakis(2,2,2‐trinitroethyl) orthocarbonate (1) and 2,2,2‐trinitroethyl formate (2) were synthesized by the reaction of carbon tetrachloride, respectively chloroform, with the corresponding equivalents of 2,2,2‐trinitroethanol and catalytic amounts of anhydrous iron(III)chloride. 2,2,2‐Trinitroethyl formal (3) was prepared by the condensation of paraformaldehyde with 2,2,2‐trinitroethanol. The compounds were fully characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and multi‐temperature DSC measurements. Due to the positive oxygen balance, the suitability of all three compounds mentioned as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were determined experimentally using bomb calorimetric methods. With this value and the experimental (X‐ray) density, several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code. Furthermore, the sensitivity towards impact, friction and electrical discharge was tested using the BAM drop hammer, a friction tester as well as a small‐scale electrical discharge device.

ChemInform Abstract: Reactions of Carbon Tetrachloride and Carbon Tetrabromide with Anions and Carbanions

ChemInform Abstract: Reactions of Carbon Tetrachloride and Carbon Tetrabromide with Anions and Carbanions

Ordered Mesoporous Carbons Enriched with Nitrogen: Application to Hydrogen Storage

Nitrogen functional groups were incorporated in ordered mesoporous carbons, and their influence on hydrogen storage was investigated. Two experimental methods were used to dope nitrogen atoms onto and/or into the organic adsorbent. First, a surface treatment using ammonia enabled doping up to 3.9 mass % of nitrogen while preserving a high surface area above 1300 m(2).g(-1). Second, carbon nitrides were synthesized using the hard template method and the reaction of carbon tetrachloride and ethylenediamine. In the latter instance, high contents, around 20 mass %, of nitrogen were obtained whereas the specific surface areas reached 630 m(2).g(-1). These materials were fully characterized by nitrogen and carbon dioxide adsorption, X-ray diffraction, X- ray photoelectron spectroscopy, and temperature-programmed desorption. Hydrogen storage in nitrogen-enriched mesoporous carbons was then studied. On one hand, physical adsorption under a wide panel of conditions (temperature, from 77 to 373 K, and pressure) shows that the texture of the adsorbent dominates the storage capability. On the other hand, electrochemical hydrogen storage enables one to store more than 0.5 wt % of hydrogen at ambient pressure and temperature. The nitrogen surface groups are involved in the electrochemical adsorption process, and an irreversible oxidation of these groups may prevent further hydrogen storage.

Reaction of carbon tetrachloride with the nanoscale particles of silver and copper in a liquid phase

The nanoscale particles of silver and copper coated with amorphous carbon (Ag/C and Cu/C) react with liquid carbon tetrachloride at 25–30°C to selectively form hexachloroethane in 60% yield.

Copper‐Catalyzed Synthesis of 1,2‐Disubstituted Cyclopentanes from 1,6‐Dienes by Ring‐Closing Kharasch Addition of Carbon Tetrachloride

AbstractThe reaction of carbon tetrachloride (CCl4) with various 1,6‐heptadienes catalyzed by copper homoscorpionate complexes affords cyclization products in moderate to high yields. The process involves the addition of the trichloromethyl radical to the diene followed by a 5‐exo‐trig cyclization reaction, resulting in the formation of the cis‐3‐chloromethyl‐4‐(2,2,2‐trichloroethyl)cyclopentane isomers in a highly regiospecific and stereospecific manner. We have studied the use of magnesium (Mg) as reducing agent for the regeneration of copper(I) catalysts. This method has afforded heterocycles in high yields even in the cases of diallyl ether (DAE) and tert‐butyl N,N‐diallylcarbamate (TBDAC).

New size effect in the catalysis by interacting copper nanoparticles

Highly active catalysts consisting of copper nanoparticles deposited on surface-oxidized silicon were prepared by a new method of laser electrodispersion. This method allows fabricating the stable monodispersive nanoparticles comprised of amorphous copper core (the size is ≈3.5 nm) covered by the thin (<1 nm) Cu 2O oxide shell. Taking chlorohydrocarbon conversions (dichlorobutene isomerization, carbon tetrachloride addition to 1-octene and carbon tetrachloride reaction with decane) as examples the unusually high activity (10 4–10 5 product mol/(metal mol h)) of closely packed ensembles of nanoparticles was observed. These catalysts are several orders of magnitude superior in activity than usual supported metal catalysts. In all the reactions studied, strong dependence of the catalytic activity on the particle surface density and on the polarity of the reactant solution was found. These results are in a good agreement with theoretical estimations indicating that nanoparticle charging, which occurs due to thermally activated electron tunneling between closely located particles is responsible for the formation of highly active catalytic system.

Tribological Properties of Films Formed by the Reaction of Carbon Tetrachloride with Iron

The tribological properties of halide films grown on iron by reaction with carbon tetrachloride vapor at a temperature of 617 K and a pressure of 1.7 Torr are compared, in ultrahigh vacuum, with FeCl2 films evaporated onto the surface. It is found that the reactively formed film has a slightly lower limiting friction coefficient than the evaporated layer (~0.06 compared to ~0.08), which may be due either to the diffusion of some carbon into the substrate or the formation of a more oriented layer when this is formed reactively. The major difference between the reactively grown and evaporated film is that the evaporated layer attains the minimum friction when ~40 A of FeCl2 has been evaporated, while the reactively formed layer has a minimum friction coefficient when a film of 6±2 A has been deposited. In the case of the evaporated FeCl2 film, the growth of second and subsequent layers proceeds before the first layer is complete. It has been shown that the friction coefficient reaches its minimum value after completion of the first monolayer, a process that is complete after the evaporation of ~40 A of FeCl2. In the case of the film formed by reaction with CCl4, the halide film grows directly on the surface implying that the FeCl2 monolayer thickness is ~6 A. This value is in good agreement with the layer thickness in bulk ferrous chloride.

Reaction of Carbon Tetrachloride with Hydrogen Peroxide

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reaction of carbon tetrachloride with hydrogen peroxide

Reaction of carbon tetrachloride with aqueous hydrogen peroxide in the presence of anhydrous iron(III) chloride was studied. Optimal conditions for the preparation of phosgene were found on the basis of analysis of the kinetic data and mechanism of the process. The reaction rate and yield (the latter reaching 95% in the stationary mode) are determined mainly by the amount of the heterogeneous catalyst. According to the experimental data, the reaction follows a radical mechanism.

A Facile Procedure for the Generation of Dichlorocarbene from the Reaction of Carbon Tetrachloride and Magnesium using Ultrasonic Irradiation

An improved method for the generation of dichlorocarbene was developed that utilizes ultrasound in the reaction of carbon tetrachloride with magnesium. High yields of gem-dichlorocyclopropane derivatives can be obtained in the presence of olefins by this method.

Kinetics and Mechanism of the Reaction of Carbon Tetrachloride with Copper in Dimethylacetamide

The reaction of copper with carbon tetrachloride in dimethylacetamide was studied. In the absence of atmospheric oxygen, the oxidative dissolution of copper occurred by the mechanism of single-electron transfer with the formation of C2Cl6 and copper(I) complexes. The kinetic and thermodynamic parameters of the reaction were found. The reaction mechanism is discussed.

Boron Carbide Deposition on Urania and Urania-Gadolinia Fuels

Pure uranium dioxide and uranium dioxide-gadolinium oxide (5 and 10%) fuels used in this study were prepared by the solution-gelation (sol-gel) technique. The fuels were then coated with boron carbide by chemical vapor deposition. Boron carbide was produced from the reaction of carbon tetrachloride and boron trichloride with excess hydrogen, in a tube furnace at 1000, 1100, and 1175°C. The Fourier transform infrared data of boron carbide deposited on a silica glass were in agreement with the ones in the literature. The experiments showed that the composition of the coating changed with deposition temperature. There was boron-rich coating at low-temperature deposition, and carbon-rich coating at high-temperature deposition. The morphology and the thickness of the coating have been investigated by using scanning electron microscopy and X-ray diffraction spectroscopy.

A reduction-pyrolysis-catalysis synthesis of diamond

Diamond powder was synthesized through a metallic reduction-pyrolysis-catalysis route with the reaction of carbon tetrachloride and sodium at 700 degreesC, in which the sodium was used as reductant and flux. This temperature is much lower than that of traditional methods. The x-ray powder diffraction patterns showed three strong peaks of diamond. The Raman spectrum showed a sharp peak at 1332 inverse centimeters, which is characteristic of diamond. Although the yield was only 2 percent, this method is a simple means of forming diamond.

The reaction of carbon tetrachloride with gallium arsenide (001)

Carbon tetrachloride dissociatively adsorbs on the Ga-rich (4×2) reconstruction of GaAs (001) at 200 °C. Upon heating to 440 °C, the chlorine desorbs as GaCl, which etches the surface. Scanning tunneling micrographs reveal that this reaction transforms the (4×2) into a Ga-rich (3×2) structure that is interlaced with As-rich (2×4) phases. The (3×2) is well ordered, while the (2×4) phases exhibit a high degree of disorder. This work establishes the surface reaction pathway for carbon doping of GaAs with CCl4.

Reactions of trichloromethanesulfonyl chloride and carbon tetrachloride with silyl enol ethers catalyzed by a ruthenium(II) phosphine complex

The reactions of trichloromethanesulfonyl chloride with trimethylsilyl enol ethers of acetophenones in the presence of a ruthenium(II) phosphine complex gave 1-aryl-3,3-dichloropropen-1-one together with α-chloroacetophenones. The product ratio depended on the substituent on the aromatic ring of the silyl enol ether. The reactions of carbon tetrachloride with the silyl enol ethers under similar conditions afforded 1-aryl-3,3-dichloropropen-1-one in good yield.

A study of the non-aqueous dealumination and gallium impregnation of H-mordenite by chlorinated reagents

The in vacuo dealumination of H-mordenite by carbon tetrachloride followed by gallium impregnation using gallium(III) chloride has been studied by diffuse reflectance IR spectroscopy (DRIFTS), 71Ga, 29Si, and 27Al solid-state magic-angle spinning (MAS) NMR. Comparative studies of the interaction of carbon tetrachloride with silica and γ-alumina were also performed. IR and DRIFTS analyses of silica and γ-alumina samples show that the reaction of carbon tetrachloride at elevated temperatures can completely remove silanol and aluminol moieties at the surface of the respective oxides. The removal of intra-lattice aluminium ions is consistent with abstraction by Al3+ ion pairs. Solid state 1H NMR data, in conjunction with IR and DRIFTS analysis of the dealuminated and gallium-impregnated H-mordenite samples confirms the formation of strong Brønsted acid protons by the reaction of carbon tetrachloride. The in vacuo probe reactions of H-mordenite, dealuminated H-mordenite and gallium impregnated H-mordenite, with methanol vapour, were studied as a function of temperature. The probe reactions show that the conversion of methanol vapour with the treated H-mordenite material is a function of the reaction temperature and the chemical modification to the H-mordenite. The activity of the treated H-mordenite to produce hydrocarbons from methanol follows the series gallium impregnated H-mordenite > dealuminated H-mordenite > H-mordenite. The product distribution supports the observation that the surface adsorbed mechanisms are consistent with a series of ionogenic intermolecular reactions occurring at dual Brønsted acid–base environments within the zeolite channels. These mechanisms account for the formation of higher alcohols from methanol by the combination of carbo-ionogenic moieties and hydrocarbons produced from the dehydration of alcohols.

Destructive Adsorption of Chlorinated Hydrocarbons on Ultrafine (Nanoscale) Particles of Calcium Oxide. 2

As a one-step approach to the safe destruction of chlorocarbons, the reaction of carbon tetrachloride with ultrafine particles of calcium oxide to give calcium chloride and carbon dioxide (CCl4(g) + 2CaO(s) → CO2(g) + 2CaCl2(s)) has been studied in detail. Calcium oxide prepared by an aerogel/hypercrytical drying method (AP−CaO) is superior to a conventionally prepared (CP−CaO) sample, and both are vastly superior to commercial CaO (CM−CaO). Optimum temperature for this gas−solid reaction is 450 °C, although AP−CaO reacted with reasonably high capacity as low as 300 °C. The effects of surface −OH, added water, CCl4 pressure, and a wide range of temperatures are discussed. Conditions for the suppression of byproducts C2Cl4 and Cl2CO are presented. Morphological changes in the particles after CCl4 reaction were studied by atomic force microscopy. A wide range of other techniques have been applied toward complete characterization of the process and products, including FT-IR, pulsed U-tube reaction studies, g...