Reaction Of Carbon Tetrachloride Research Articles

Kinetics of the oxidation of aromatic C-nitroso compounds by nitrogen dioxide

The oxidation of nitrosobenzene by nitrogen dioxide in carbon tetrachloride has been re-examined, the rate of reaction exhibiting first-order dependence upon the concentrations of both nitrosobenzene and nitrogen dioxide, with a reactant stoichiometry of 1∶1. The rate of reaction is found to be highly sensitive to the presence of trace quantities of water and intensive drying procedures for the solvent have been developed such that the reaction rate could be reduced to a constant level. For nitrosobenzene and a range of substituted nitrosobenzenes the kinetics of the oxidation reaction in carbon tetrachloride have been studied over the temperature range 291–313 K using the stopped flow technique and pseudo-first-order conditions with the nitrogen dioxide in excess. Arrhenius parameters have been obtained for 15 nitrosoarenes and the results obtained are discussed with reference to the Hammett σ constants and the electron population at the nitroso nitrogen as determined by CNDO calculations. It is concluded that the reaction occurs by a radical addition mechanism to the nitroso nitrogen atom giving an unstable aminoxyl intermediate which decomposes rapidly giving the corresponding nitrobenzene and nitric oxide.

An investigation of the Ar+ ion-enhanced reaction of CCl4 on Si(100) by secondary ion mass spectrometry

The Ar+ ion-enhanced reaction of carbon tetrachloride (CCl4) on Si(100) at room temperature is investigated at primary ion energies of 2 and 9 keV using the secondary ion mass spectrometry (SIMS) technique. Static SIMS shows that CCl4 reacts with Si at room temperature. This surface reaction is enhanced by simultaneous sputtering with an Ar+ ion beam, the reaction rate being higher at 9 keV than at 2 keV. Possible products of surface reaction are discussed.

Removal of Oxide Impurities from Alkali Haloaluminate Melts Using Carbon Tetrachloride

Small amounts of oxide impurities in alkali chloroaluminate and fluorochloroaluminate melts can complicate markedly the electrochemical and spectroscopic behavior of other solute species in these melts. A simple method for the removal of oxides from these melts has been developed in our laboratory. This method is based on the reaction of carbon tetrachloride with oxides to convert them to chlorides. Spectroscopic techniques (UV‐visible and IR spectroscopy) have shown that addition of carbon tetrachloride results in the complete conversion of oxides to chlorides.

Stereochemistry of a Chiral Germyl Radical in the Reaction of Carbon Tetrachloride

Abstract A chiral germyl radical produced from an optically active hydrogermane, 1-NpPhMeGe*H, abstracted a chlorine atom from CCl4 to give the corresponding chlorogermane with retention of configuration. Progressive dilution of CCl4 with cyclohexane demonstrated that the chiral germyl radical could also undergo inversion. A mechanism in which inversion of the chiral germyl radical competed with chlorine abstraction was proposed and the relative rate of chlorine abstraction to inversion (kCl⁄kinv) of the chiral germyl radical was found to be (0.52±0.13) mol−1 dm3 at 80 °C. The rate constant for the chlorine abstraction (kCl) by germyl radicals with CCl4 was determined to be (6.6±1.0)×108 s−1 mol−1 dm3 by laser-photolysis experiments. By using this rate constant, the kinv value for the chiral germyl radical was estimated to be ca. 2×109 s−1.

A kinetic and mechanistic study of the oxidative addition of diaryl ditellurides to trans-carbonylchlorobis(triphenylphosphine)iridium(I) in toluene

The oxidative addition of diaryl ditellurides to [IrCl(CO)(PPh3)2] in toluene solution has been followed by visible spectrophotometry. The reaction is first order in the concentration of each reagent. An e.s.r. signal can be detected from the reacting solution. An i.r. spectroscopic study of the reaction in carbon tetrachloride shows the relatively rapid formation of an adduct before the final stages of the process occur. Rate constants and activation parameters for four different ditellurides have been determined. These parameters vary widely with the substituents on the aryl rings of the ditellurides. A mechanism is suggested which involves the initial addition of ditelluride to iridium(II), followed by homolytic cleavage of the Te–Te bond and formation of the final trans product.

Pulse radiolysis of porphyrin and ferriporphyrin solutions in 2-propanol-carbon tetrachloride systems. Protonation and ligand exchange kinetics

Pulse radiolysis of aqueous and nonaqueous 2-propanol-acetone-carbon tetrachloride mixtures has been investigated by means of conductivity measurements and spectrophotometry. In these solvent mixtures, a pulse of hydrochloric acid originating from either primary events of solvent radiolysis or from further reactions of carbon tetrachloride with radicals derived from 2-propanol and acetone, is produced within ca 100 nanoseconds. Further production of hydrochloric acid occurs as a result of chain reactions involving hydrogen abstraction by CCl/sub 3/ or CCl/sub 3/O/sub 2/ radicals. These latter radicals appear to be much more reactive and are likely to be involved in the reaction unless the solutions have been thoroughly deoxygenated. Protonation Reactions of porphyrins and ferriporphyrins, which do not react rapidly with the above radicals, were followed by means of spectrophotometric measurements. In turn, these reactions may be used to monitor hydrochloric acid formation. Spectrophotometric measurements on porphyrins corroborate conductivity results, although a quantitative comparison is not feasible because of differences in solvent properties. 6 figures.

Corrosion of metals in carbon tetrachloride-containing solvents

Mixtures of carbon tetrachloride with ethers and alcohols attack stainless steels appreciably. This corrosive reaction is especially severe in dry solvents and in the presence of light. Reaction of carbon tetrachloride with ether and alcohol groups, with liberation of hydrogen chloride, also takes place in the absence of metals and should be kept in mind whenever using carbon tetrachloride. The attack by these solvents on stainless-steel high-performance liquid chromatography equipment is considered.

Addition of carbon tetrachloride and methyl trichloroacetate to silicon-functional vinylsilanes

Compounds of type XCCl 2CH 2CHClSiY 3 (X = Cl, COOMe; Y = Me, Cl, OEt) were obtained in good yields by the reactions of carbon tetrachloride and methyl trichloroacetate with vinylchlorosilanes or with vinylethoxysilanes in the presence of dichlorotris(triphenylphosphine)ruthenium(II).

Reactions of organic anions. 89. Reactions of carbon tetrachloride with carbon acids in catalytic two-phase system

Reactions of organic anions. 89. Reactions of carbon tetrachloride with carbon acids in catalytic two-phase system

Über Derivate des Hydrazins, VII Darstellung und Charakterisierung von Bis(trimethylsilyl)aminoisocyanid.

By reaction of carbon tetrachloride with lithium tris(trimethylsilyl)hydrazide and then with lithium butyl a compound with formula (Me3Si)2N2C is formed. From the way of preparation, spectroscopic investigations, and chemical reactions the substance is characterized as bis(trimethylsilyl)aminoisocyanide (3). 3 hydrolyzes, and does not react with oxygen. The compound combines with chlorine and bromine forming aminoisocyanide dihalides, and with carbon disulfide forming an adduct. At higher temperatures 3 isomerizes to bis(trimethylsilyl)carbodiimide (1).

Organic syntheses by means of metal complexes—XI : Copper complex catalyzed addition reactions of organic polyhalides to acrylic monomers

Telomerization, especially 1:2 adduct formation from organic polyhalides and acrylic monomers catalyzed by a copper complex has been studied. Reaction of carbon tetrachloride with acrylic monomers catalyzed by a copper salt gave a 1:2 adduct. Methyl trichloroacetate afforded a 1:2 adduct with acrylic monomers, addition of LiCl increased the yield. No 1:2 adduct was obtained from CHCl 3 even in the presence of LiCl. The 1:2 adduct formation mechanism is discussed.

Addition of carbon tetrachloride to 3,3,4,4-tetrafluorohexa-1,5-diene

The free-radical reaction of carbon tetrachloride with 3,3,4,4-tetrafluoro-1,5-hexadiene is described. Initiation of the chain process by a variety of redox-transfer systems has been studied. The cyclic isomeric monoadducts have been shown to possess four-, five-, six-, and seven-membered ring structures. The extent of rearrangement observed in the products is greatly influenced by metallic salt additives and by the solvent. However, the solvent effect is not observed in the presence of some copper(II) species.

A novel reaction of carbon tetrachloride with [(diphenylphosphino)methyl]trimethylsilane

[(Diphenylphosphino)methyl]trimethylsilane reacts with carbon tetrachloride, in an ionic reaction, to yield chloroform, trimethylchlorosilane, and a polymer which does not contain silicon.

The Structures of the Adducts from the Reaction of Carbon Tetrachloride and Isoprene

The Structures of the Adducts from the Reaction of Carbon Tetrachloride and Isoprene

Fluorenylidene and 2,7-Dibromofluorenylidene

Abstract Photolysis of 9-diazofluorene or 2,7-dibromo-9-diazofluorene in diethyl maleate or diethyl fumarate was found to give cyclopropane derivatives nonstereospecifically. Irradiation of 9-diazofluorene in 1,2-dichloroethylene gave no addition product, but did 9-chlorofluorene in 85–89% yield. The same reaction in carbon tetrachloride gave 9,9′-dichloro-9,9′-bifluorenyl in 48% yield. Thus fluorenylidene has strong abstraction character. These chemical results suggest that fluorenylidene and 2,7-dibromofluorenylidene react in triplet state. Furthermore the ground states of these carbenes were confirmed to be triplet by ESR spectra. Concerning to zero-field parameter little effect of bromine substituent was observed in 2,7-dibromofluorenylidene.

Charge-transfer complexes. Part II. Complex formation between halogenomethanes and aromatic amines

The spectra of n-hexane solutions of NN-dimethylaniline and NNN′N′-tetramethyl-p-phenylenediamine with added carbon tetrachloride, chloroform, and dichloromethane have been studied. The results have been interpreted in terms of weak donor–acceptor complex formation between the amine and the halogenomethane. Values for the association constants of the complexes, derived from the Benesi–Hildebrand equation, are discussed in terms of current theories on the role of solvent in the evaluation of association constants for weak complexes. Inaccuracies in the evaluation of association constants when a halogenomethane is used as solvent are discussed in terms of a competition between the solvent and the acceptor for the available donor. Some reactions of carbon tetrachloride are interpreted in terms of an intermediate donor–carbon tetrachloride complex.

Carbonium-ion rearrangements in the addition of bromine to some olefins

The olefins Ph2ArC·CRCH2(R = H, Me; Ar = Ph, p-C6H4·OMe) have been treated with bromine in various solvents and their rates of reaction in carbon tetrachloride at 25° have been measured. The extent of rearrangement of the group Ar depends on the nature of this group and of R, and on the solvent. The mechanisms of the reactions are discussed.

Diimide. An Intermediate in the Reaction of Carbon Tetrachloride and Hydrazine

Diimide. An Intermediate in the Reaction of Carbon Tetrachloride and Hydrazine

Reactions of carbon tetrachloride with unsaturated compounds in presence of dicyclohexyl peroxydicarbonate or oxidation-reduction systems

1. The oxidation-reduction system benzoyl peroxide-dimethylaniline initiates the addition of carbon tetrachloride to alkyl vinyl ethers and the telomerization of allyl acetate with carbon tetrachloride at 25–30dg. 2. The oxidation-reduction system benzoyl peroxide-(p-tolylsulfonyl)methanol-iron triacetylacetonate initiates the telomerization of allyl acetate with carbon tetrachloride at 30–32dg. 3. Dicyclohexyl peroxydicarbonate initiates the addition of carbon tetrachloride to butyl vinyl ether at 30° and the telomerization of allyl acetate, allyl chloride, and 1-octene with carbon tetrachloride at 55–60dg.

391. The reaction of carbon tetrachloride with sulphide ions

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