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Showing papers on "Acetonitrile published in 1974"


Journal ArticleDOI
TL;DR: In this article, the electrochemical and chemical reduction of nitrosobenzene has been studied in acetonitrile and dimethylformamide, and the reduction has been shown to be a kinetically controlled process which initially gives rise to the corresponding radical anion.

36 citations


Patent
18 Oct 1974
TL;DR: The process for the production of malonic acid dinitrile which includes quickly preheating acetonitrile to a temperature between 110° and 700°C is described in this article.
Abstract: The process for the production of malonic acid dinitrile which includes quickly preheating acetonitrile to a temperature between 110° and 700°C. Cyanogen chloride and the preheated acetonitrile, both in the gaseous state, are reacted at a temperature between 700° and 1200°C. Malonic acid dinitrile, in the gaseous state, results. The reaction product mixture of gaseous malonic acid dinitrile, gaseous cyanogen chloride, gaseous acetonitrile and HCl, a reaction byproduct, is chilled with liquid reaction product mixture to a temperature between 40°C. and the boiling point of the reaction product mixture. A liquid reaction product results. Simultaneously with the chilling step, the exhaust gas resulting from the chilling of the reaction product mixture is distilled or refined to separate the cyanogen chloride and acetonitrile from the HCl component in the exhaust gas. The malonic acid dinitrile is isolated from the liquid reaction product mixture and purified.

35 citations


Journal ArticleDOI
TL;DR: In this article, the Stern-Volmer relation was found to be satisfied for β-naphthol-TEA in toluene and in acetonitrile in nonpolar mixed solvents.
Abstract: Proton donor-acceptor interactions in excited states were studied by measuring mainly time-resolved fluorescence spectra for β-naphthol–TEA in toluene and in acetonitrile, and for β-naphthylamine–TEA in nonpolar mixed solvents. The Stern-Volmer relation was found to be satisfied for β-naphthol–TEA in toluene. The rate constant and activation energy of hydrogen bond formation in the excited state of this system were obtained to be 2.2×109 M−1 s−1 at 30 °C and 1.6 kcal/mol, respectively, indicating that the process is diffusion-controlled. The time dependences of the intensities of the fluorescence bands due to the free and complexed β-naphthol were measured with the solutions containing various concentrations of triethylamine in acetonitrile. From the analysis of the result, it is shown that this system is led to the ion-pair formation via the hydrogen-bonded species in the excited state. For β-naphthylamine–TEA in nonpolar mixed solvents, the bands due to hydrogen-bonded species in the ground and excited ...

33 citations


Journal ArticleDOI
TL;DR: The Cr(CO) 3 (CH 3 CN) 3 complex is found to catalyze the 1,4 addition of hydrogen to 1,3-dienes such as 2-methyl-1, 3-butadiene, trans -1,3 pentadiene and trans, trans -2,4-hexadiene at low temperature (40°) and low H 2 pressure (20 psi) as discussed by the authors.

32 citations


Journal ArticleDOI
TL;DR: In this paper, the spin-rotation coupling constants of acetonitrile and acetone were determined, and for the methyl carbon atom the following values were found: c⊥=4.5 kHz, c‖= −39 kHz, and significant contributions of anisotropic chemical shift relaxation to the nitrile carbon relaxation were detected at lower temperatures with a chemical shift anisotropy of Δσ≈450 ppm.
Abstract: Spin‐lattice relaxation times of all carbon atoms in acetonitrile and acetone were measured at various temperatures. Spin‐rotation coupling constants of acetonitrile were determined, and for the methyl carbon atom the following values were found: c⊥=4.5 kHz, c‖= −39 kHz. Considerable contributions of anisotropic‐chemical shift relaxation to the nitrile carbon relaxation was detected at lower temperatures with a chemical shift anisotropy of Δσ≈450 ppm. The relaxation behavior of acetone was also studied in aqueous mixtures. Existence of microheterogeneities in the acetone rich concentration range has been concluded from the carbonyl relaxation in D2O, where a considerable contribution from intermolecular proton‐carbon interaction was found.

30 citations


Journal ArticleDOI
TL;DR: Even in the presence of very small amounts of water hydroxylation is the exclusive reaction of the anthracene cation radical in acetonitrile while in the complete absence of water, high yields of the acetamidation product are obtained as discussed by the authors.
Abstract: Even in the presence of very small amounts of water hydroxylation is the exclusive reaction of the anthracene cation radical in acetonitrile while in the complete absence of water, high yields of the acetamidation product are obtained.

29 citations



Patent
18 Oct 1974
TL;DR: Improved yields of 7-[D-α-amino-acetamino]-acetamido]-3-methyl-3-cephem-4-carboxylic acids are obtained by acylating 7-aminodesacetoxycephalosporanic acid with the mixed anhydride (from ethyl chloroformate) of the ring-substituted 2-phenylglycine when the latter's α-aminos group has been blocked by reaction with a β-keto compound such as methyl acetoacetate as mentioned in this paper.
Abstract: Improved yields of 7-[D-α-amino-α-(4-hydroxy- and 3-chloro-4-hydroxy-phenyl)acetamido]-3-methyl-3-cephem-4-carboxylic acids are obtained by acylating 7-aminodesacetoxycephalosporanic acid with the mixed anhydride (from ethyl chloroformate) of the ring-substituted 2-phenylglycine when the latter's α-amino group has been blocked by reaction with a β-keto compound such as methyl acetoacetate. Improved purification processes include the use of dimethylformamide and acetonitrile solvates and solvates and bis-anthraquinone-1,5-disulfonic acid salts.

25 citations


Journal ArticleDOI
TL;DR: In this paper, an ionic concerted intermolecular scheme was proposed as a reaction mechanism for the preparation of I. The data of NMR and IR spectra of I are briefly discussed.
Abstract: Some new alkoxythallium(III) compounds of olefins, C6H5C(R1)(OR3)CH2Tl(OCOR2)2 [I], are prepared from styrene and α-methylstyrene with thallium(III) acetate and isobutyrate in various alcohols. I(R1=H) reacts with copper(I) iodide, bromide, chloride, cyanide and thiocyanate to afford the corresponding alkyl halides and pseudohalides, C6H5CH(OR3)CH2X [II], in various organic solvents, acetonitrile being the solvent of choice for the purpose of preparing II. The addition of potassium salt has a remarkable effect in improving the yield of II. The halo- and pseudohalodethallation occur at the position where thallium is attached previously to alkyl carbon. An ionic concerted intermolecular scheme is proposed as a reaction mechanism for the preparation of II. The data of NMR and IR spectra of I are briefly discussed.

24 citations


Journal ArticleDOI
TL;DR: In this paper, the kinetics of keto-enol tautomerization of acetylacetone were studied in mixed aqueous media by u.v. and NMR spectrometries.

22 citations


Journal ArticleDOI
TL;DR: In this paper, the polarization characteristics of aluminium anodes have been studied in various organic electrolytes containing aluminium chloride, and the small amount of oxide present on the metal was dissolved by an anodic pre-treatment.
Abstract: The polarization characteristics of aluminium anodes have been studied in various organic electrolytes containing aluminium chloride. The small amount of oxide present on the metal was dissolved by an anodic pre-treatment. The charge transfer number of the overall reaction was three. The current density supported by the electrolytes decreased in the order nitromethane>acetonitrile >propylene carbonate, formamide>tetrahydrofuran. The rest potential increased in the order formamide


Journal ArticleDOI
TL;DR: The extent of interaction between methyl radicals and cyanide ions produced in pairs by dissociative electron capture in the two solid phases of acetonitrile has been studied by e.g. as mentioned in this paper.
Abstract: The extent of interaction between methyl radicals and cyanide ions produced in pairs by dissociative electron capture in the two solid phases of acetonitrile has been studied by e.s.r. using CD313C...

Journal ArticleDOI
TL;DR: In this article, a microsecond pulse radiolysis of solutions of a variety of solutes in acetonitrile, absorptions assigned to solute cation radicals, anion radicals, excited states and neutral radicals are observed.
Abstract: Following microsecond pulse radiolysis of solutions of a variety of solutes in acetonitrile, absorptions assigned to solute cation radicals, anion radicals, excited states and neutral radicals are observed. Pulse radiolysis of solutions of tri-p-tolylamine or triphenylamine yields the amine radical cations, whose absorptions are observed to grow-in by a second-order process after the electron pulse. We report rate constants for this process, which is suggested to be electron transfer to acetonitrile radical cation or cation dimer. Yields of G∼0.2 are reported for the oxidizing species. Oxidation via a different route involving hydrogen atom transfer is suggested to occur following pulse radiolysis of solutions of phenol or phenothiazine. Pulse radiolysis of solutions of benzophenone or biphenyl yields the solute radical anions in agreement with previous studies on this system. The mechanism of acetonitrile radiolysis is discussed with a consideration of this and previous studies.


Journal ArticleDOI
TL;DR: In this paper, the electrochemical oxidation of p-phenylenediamine and its derivatives was studied on platinum electrode in acetonitrile, where the oxidation mechanism was composed of two successive one-electron reversible waves.
Abstract: The electrochemical oxidation of p-phenylenediamine and its derivatives was studied on platinum electrode in acetonitrile. The oxidation mechanism was composed of two successive one-electron reversible waves. The hyperfine ESR spectra of the cation radicals were observed by electrolysis on the first wave. The generation of the same cation radicals could be performed by electrolysis on the second wave, indicating the presence of an electron exchange reaction between the dication and the parent molecule in solution.

Journal ArticleDOI
TL;DR: In this paper, the electrochemical synthesis of cis -1,2-diphenyl-1, 2-cyclopentanediol by reduction of 1,3-dibenzoylpropane in acetonitrile is described.

Journal ArticleDOI
TL;DR: In this article, the complexing of the lithium ion with other popular solvents has been studied in acetonitrile (AN) using a monovalent cation-sensitive glass electrode.
Abstract: The complexing of the lithium ion with other popular solvents has been studied in acetonitrile (AN) using a monovalent cation-sensitive glass electrode. A method similar to that developed to study the complexing of the sodium ion was employed. Mono- and di-solvated species were formed for methanol, pyridine, formamide, methylfomamide, and HMPA. Tri-solvated species were also formed for DMF, DMA, and DMSO. In general, the complexing of the lithium ion with these solvents was more pronounced than that of the sodium ion. The formation constants for the mono-solvated lithium ion were 4.5 for methanol, 5.2 for pyridine, 16 for DMF, 20 for formamide, 25 for methylformamide, 49 for DMSO, 62 for DMA, and 2.1×103 for HMPA. When water was the complexing solvent, the equilibrium potential could not be obtained, probably because of the hydrolysis of the hydrated lithium ion. Prior to these experiments, the cation-sensitive glass electrode was confirmed to respond to the lithium-ion activity in different solvents by c...

Journal ArticleDOI
TL;DR: In this paper, the trisacetylacetonato)germanium (IV) was resolved by the crystallization of its hydrogen-R,R-di-benzoyltartrate in a mixture of acetonitrile, ethanol, and water.
Abstract: The tris(acetylacetonato)germanium(IV) has been resolved by the crystallization of its hydrogen-R,R-di-benzoyltartrate in a mixture of acetonitrile, ethanol, and water. The racemization kinetics of perchlorate of the Δ-enantiomer has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane, acetonitrile (AN), and N,N-dimethylformamide, the activation enthalpies (ΔH\eweq/kacl· mol−1) and the activation entropies (ΔS\eweq/cal· K −1 mol−1) being 27.9, 26.6, 24.3, and 23.3, and +3.7, −1.1, −4.4, and −5.0, respectively. The ligand isotopic exchange is much slower than the racemization under similar conditions. Consideration of acid (in TCE) and base (in AN) catalysis, influence of ionic strength and solvent effect suggests an intra-molecular mechanism via an intermediate in which one of the ligands is in unidentate state.

Journal ArticleDOI
TL;DR: In this paper, a mechanism involving a rate-determining attack of protonated dimeric perphosphoric acid 4 on aromatic carbon is presented and discussed, where the rate of anisole and phenol oxidation is expressed as v = k″[ArH][H3PO5]2ho, where ho is the Hammett's acidity function and ArH is phenol or anisoles.

Journal ArticleDOI
TL;DR: In this paper, a disaccharide was synthesized in 55% yield by condensation of 2,3,4,6-tetra-O-benzoyl- α-D-mannopyranosyl bromide with methyl 2.3,O-isopropylidene-α-L-rhamno-pyranoside using mercuric cyanide in acetonitrile.
Abstract: 4-O-α-D-Mannopyranosyl- L-rhamnopyranose has been synthesized in 55% yield by condensation of 2,3,4,6-tetra-O-benzoyl- α-D-mannopyranosyl bromide with methyl 2,3-O-isopropylidene-α-L-rhamno-pyranoside using mercuric cyanide in acetonitrile (Helferich reaction). The disaccharide has m.p. 143–145°, [α]D + 53.0° → 60.3° (c, 1.0 water), and was characterized as the crystalline peracetates of the disaccharide (m.p. 149.5–150.5°, [α]D − 4.4° (c, 4.3 chloroform)) and of the derived alditol (m.p. 84−85°, [α]D −4.4° (c, 1.9 chloroform)).

Journal ArticleDOI
TL;DR: In this article, the second-order dependence of the rate on Na+TCNQ\ewdot was investigated in methanol and acetonitrile with a stopped-flow apparatus, and the results were interpreted in terms of rapid formation of a protonated intermediate in the initial stage of the reaction.
Abstract: The kinetics of the protonation of sodium salt of 7,7,8,8-tetracyanoquinodimethane (Na+TCNQ\ewdot) by hydrogen chloride in alcohols and acetonitrile was investigated, using a stopped-flow apparatus. In methanol, the protonation rate is first-order in HCl and second-order in Na+TCNQ\ewdot, while in ethanol, the rate is one-half-order in HGl and second-order in Na+TCNQ\ewdot. The protonation rate in acetonitrile is first-order in HCl, but it deviates from second-order in Na+TCNQ\ewdot. These results are interpreted in terms of the rapid formation of a protonated intermediate in the initial stage of the reaction, according to TCNQ\ewdot+H+\ightleftharpoonsHTCNQ\ewdot The reversibility of this reaction is well demonstrated by the second-order dependence of the rate on Na+TCNQ\ewdot. The rate is also compared with the protonation rate of semiquinones, such as sodium salts of p-chloranil and 2,3-dicyano-l,4-benzoquinone, from the view point of the difference in reactivity between carbon and oxygen acids.


Journal ArticleDOI
TL;DR: In this article, the anodic oxidation of NO − 2 ion dissolved as AgNO 2 in ACN, in the range − 12° to 68°C, was investigated using platinum electrodes.


Journal ArticleDOI
TL;DR: Me3N,BH2X (X = Cl, Br, F, CN, NCS, NCO, or BH3CN) gave high yields in tetrahydrofuran as mentioned in this paper.
Abstract: Exchange reactions (i)(X = Cl, Br, F, CN, NCS, NCO, or BH3CN) of Me3N,BH2I give high yields in tetrahydrofuran. Monoglyme and acetonitrile are less suitable solvents. The new compounds Me3N,BH2(NCS) and Me3N,BH2I + MX → Me3N,BH2X + MI (i) Me3N,BH2(NCO) have been isolated and characterised. A convenient two-stage preparation of Me3N,BH2(CN)(78% yield) from Me3N,BH3via in situ formation of Me3N,BH2I is described. The compounds Me3N,BH2X (X = Cl or Br) and Me3N,BHX2(X = Br or I) do not appear to undergo similar exchange reactions.

Journal ArticleDOI
TL;DR: In this article, a trialkylchlorosilanes can be synthesized in high yield and excellent purity using cupric chloride in acetonitrile by the use of cupric acid.
Abstract: Trialkylchlorosilanes can be synthesized in high yield and excellent purity from corresponding trialkylsilanes by the use of cupric chloride in acetonitrile.

Journal ArticleDOI
TL;DR: In this paper, the conductance of potassium perchlorate in mixtures of ethylene carbonate and acetonitrile covering the range 82.6 ≥ D ≥ 36.0 in dielectric constant has been measured.
Abstract: The conductance of potassium perchlorate in mixtures of ethylene carbonate and acetonitrile covering the range 82.6 ≥ D ≥ 36.0 in dielectric constant has been measured. The Walden products in these aprotic solvents are approximately one-half as large as the products for the same salt in isodielectric mixtures of water and tetramethylene sulfone. This alters the distribution between electrostatic and hydrodynamic terms in the theoretical conductance function in such a way that the calculated association constants for potassium perchlorate are much smaller in the aprotic mixtures.

Patent
Balwant Singh1
01 Aug 1974
TL;DR: In this paper, the synthesis of ethambutol hydrochloride, d,d'-2,2'-(ethylenediimino)di-1-butanol dihydrochloride is described.
Abstract: D-2-Amino-1-butanol, for the synthesis of ethambutol hydrochloride, d,d'-2,2'-(ethylenediimino)di-1-butanol dihydrochloride, is produced in high purity and good yields by the reaction of butene-1, a nitrile, preferably an excess of acetonitrile, and chlorine to form N-[1-(chloromethyl)propyl]acetimidoyl chloride which is hydrolyzed to dl-2-amino-1-butanol, which can be isolated as the hydrochloride, or free base, or a mixture, resolved with L(+)- tartaric acid and the d-2-amino-1-butanol reacted with ethylene dichloride and then hydrochloric acid to form ethambutol hydrochloride. A minimum of by-products which are conveniently split out permits the economical synthesis of a pharmaceutical grade product.

Patent
17 Dec 1974
TL;DR: In this article, the methods of reducing aqueous solutions of cupric sulfate to cuprous solutions by using organic nitrile compositions are disclosed, using acetonitrile and sulphur dioxide.
Abstract: Methods of reducing aqueous solutions of cupric sulfate to cuprous solutions by using organic nitrile compositions are disclosed. The particular nitrile used is acetonitrile and the reductant is sulphur dioxide. The method has application commercially to leaching ores containing oxidised copper to obtain cuprous ion solutions. Such solutions can be treated by electrochemical or thermal disproportionation methods to obtain very pure copper.