The photolysis of bis(acetonitrile)tetrachlorotungsten in acetonitrile

When WCl₆ is dissolved in CH₃CN it is reduced to WCl₄(CH₃CN)₂ in a first-order process with a half-life of 52 s. Irradiation of the WCl₄(CH₃CN)₂ solution at 365 nm yields WO₂Cl₂(CH₃CN)₂. Further irradiation of this solution with access to air yields a blue, partially reduced form of WO₃ · 2H₂O, which eventually precipitates.     

Electrooxidation of low-permittivity solvents in acetonitrile and solubility of trihexylamine in acetonitrile

Journal of the Iranian Chemical Society - In the first part of the work, anodic oxidation of some selected low-permittivity liquids (1,4-dioxane, diethyl ether, diisopropyl ether, dichloromethane,...     

Detection of adulteration in acetonitrile

To address the increasing concern that acetonitrile may be intentionally adulterated to meet the shortfall in global supplies resulting from a downturn in its manufacturing, three analytical techniques were examined in this study. Gas Chromatography with Thermal Conductivity Detection (GC-TCD), Near Infrared (NIR) spectroscopy and Fourier Transform Infrared (FT-IR) spectroscopy were assessed for their ability to detect and quantify potential adulterants including water, alternative organic solvents, and by-products associated with the production of acetonitrile. The results of the assessment of the three techniques for acetonitrile adulteration testing are discussed.     

Deprotonation of calixarenes in acetonitrile

[Structure: see text]. The pKa values for calixarenes in MeCN have been determined by selective titration with bases using a spectroscopic method. These values are as follows: calix[4]arene pKa(1) = 19.06 +/- 0.22, pKa(2) > 33; calix[6]arene pKa(1) = 15.59 +/- 0.06, pKa(2) = 23.85 +/- 0.35, pKa(3) > 33; calix[8]arene pKa(1) = 17.20 +/- 0.20, pKa(2) = 20.32 +/- 0.31, pKa(3) > 33. The trends in acidity are rationalized using structures generated by a DFT model. For mono-deprotonation, the degree and nature of hydrogen bonding in the anion is the dominant factor; for di-deprotonation, spatial separation of the anionic charges becomes important.     

Condensation of perfluoroisobutylene with acetonitrile

Conclusions Perfluoroisobutylene condenses with acetonitrile in the presence of CsF.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 209–210, January, 1982.     

Electropolymerization of phenylacetylene in acetonitrile

The electrooxidation of phenylacetylene (PA) in acetonitrile (0.1 M in LiClO₄) produced poly(phenylacetylene). The product was isolated, purified, and characterized. Spectroscopic data showed the trans structure of the polymer. A radical reaction mechanism was proposed in which the oxidation of PA led to the formation of a PA radical in solution, which initiated a radical polymerization. The theoretical treatment for the radical mechanism yielded a reaction rate equation identical to the experimental one. The average molar mass was determined by gel permeation chromatography to be approximately 3100. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2407–2416, 2005     

Condensation of acylmetallocenes with acetonitrile

Conclusions Ruthenocenyl- and osmocenyl-substituted-hydroxynitriles and,-unsaturated nitriles were synthesized. The NMR spectra of the metallocenyl-substituted,-unsaturated nitriles are discussed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1644–1646, July, 1972.     

Reaction of acetyloxiranes with acetonitrile

2-Acetyloxiranes react with acetonitrile in the presence of equimolar amounts of Lewis acids. It was established that the use of boron trifluoride etherate or sulfuric acid as the catalyst leads to 2,7- and 3,6-diepoxy-1,5-dioxocanes, the use of aluminum trichloride, as well as stannic chloride, leads to the corresponding chlorohydrins, while the use of gaseous boron trifluoride leads to 2-oxazolines in satisfactory yields. It is shown that the reaction is regio- and stereospecific and that the resulting substituted 2-methyl-5-acetyl-2-oxazolines have a cis configuration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 8, pp. 1022–1024, August, 1982.     

Electrochemistry of copper in aqueous acetonitrile

The electrochemical characteristics of the Cu (II)/Cu (I) and the Cu (I)/Cu (0) couples at platinum, carbon, mercury and copper have been studied in acetonitrile-water (AN-H₂O) mixtures. All the electrode processes are moderately fast with mercury the fastest but slower on platinum and carbon paste in that order. A slow chemical step precedes oxidation of Cu (I) to Cu (II) on allectrodes in solutions of high AN content. The slow step may be partial removal of AN from the solvated Cu (I) ion prior to electron transfer. Electrode processes are faster in chloride ions than in sulfate ion solutions. Reduction of Cu (I) in AN–H₂O is quite slow on glassy carbon. Adsorption of AN on platinum and carbon influences the processes. Diffusion coefficients in sulfate solutions are in the order, Cu (I) (AN–H₂O)>Cu (II)(AN–H₂O)>Fe (III)(H₂O) and 2-hydroxy-cyanoethane (2-HCE) strongly decreases the mobility of Cu (I) when added to H₂O. The relevance of the measurements to hydrometallurgical processes is considered. CuSO₄ in 30% v/v AN–H₂O is a faster oxidant than the common oxidant Fe₂(SO₄)₃ in H₂O because of the greater mobility and faster electron acceptance from a corroding surface of Cu (II). Only in solutions of very high nitrile content is the reduction potential of CuSO₄ as high as that of Fe₂(SO₄)₃ in H₂O.     

Mechanism of TBD-catalyzed hydrolysis of acetonitrile

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) has recently been shown to be an effective organocatalyst for the hydrolysis reaction of acetonitrile. This reaction involves the acetamide-forming reaction of acetonitrile hydrolysis and the further hydrolysis of acetamide to form acetic acid and NH₃. Density functional theory (DFT) and Hartree–Fock (HF) methods were employed to comprehensively investigate these two hydrolysis steps to elucidate the TBD-catalyzation mechanism. Structures and energies of the reactants, intermediates, transition states and products along the reaction path were presented. Charge population and bond orders were given by natural bond orbital (NBO) analysis to clarify the computed atomic and molecular behaviors. The results showed that compared with the noncatalyzed reaction, the TBD-catalyzed process had significantly lower energy barriers in both the hydration steps and the isomerization steps. As a result, the whole reaction process could be accelerated and the TBD-catalyzation mechanism was clarified.     

NH-acid properties of porphyrins in acetonitrile

The thermodynamics of acid dissociation of synthetic porphyrins (H₂P) in alkaline acetonitrile solution is studied. The low stability of the anionic species is attributed to the previously formulated electronic, steric, and solvation factors. The solvent plays an important role in the stabilization of anionic porphyrin species in acetonitrile. The electronic absorption spectra of anionic species of H₂P are analyzed.     

Reaction of cyclic sulfites with acetonitrile

A. V. Bogatskii Physicochemical Institute, Ukraine National Academy of Science, Odessa 270080. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, p. 25. February, 1995. Original article submitted January 15, 1995.     

The dimer radical anion of acetonitrile

The dimer radical anion of acetonitrile has been identified in the upper crystalline phase of acetonitrile after γ irradiation at 77°K, whereas the monomer radical anion is produced in the lower crystalline phase under the same irradiation conditions. ESR studies on these species in aligned and polycrystalline samples are summarized and possible structures for the dimer radical anion are discussed. Dimer radical anions of other organic cyanides have also been observed in γ-irradiated crystals.     

Anodic bromination of aromatic compounds in acetonitrile

The electrochemical bromination of benzene, toluene and p-xylene has been investigated in acetonitrile; even if the mechanism was found to be somewhat similar to that postulated in a previous paper for acetic acid as the solvent, the yields of the brominated products in this case are near to 100% because the solvent is not brominated in these conditions.