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Showing papers on "Nitrobenzene published in 1973"


Journal ArticleDOI
TL;DR: In this paper, the authors made structural proposals for trinuclear compounds based on instrumental analysis and their properties were described and some comments on their reactivity were made, including their properties and properties.

77 citations



Journal ArticleDOI
TL;DR: In this article, the selectivity coefficients of liquid-membrane electrodes for common inorganic anions were measured in electrodes containing tris(l,10-phenanthroline)iron(II), tris (4,7-diphenyl-1,10phenanthyl-iron)iron (II) or tetraheptylammonium ion in nitrobenzene, and tris[n-amyl alcohol as the liquid membrane, suggesting that aqueous phase solvation energies play a predominant role in determining electrode select

46 citations


Journal ArticleDOI
TL;DR: In this article, the pKass values of ion pairs formed by the nitrobenzene radical anion N− and cations M+ have been estimated from polarographic measurements.

44 citations




Journal ArticleDOI
TL;DR: In this paper, the conductances of tris(l,10-phenanthroline)iron(II) and tris2,2'-bipyridine)-iron (II) chlorides, bromides, iodides, and perchlorates were measured in water and nitrobenzene at 25°.

28 citations



Journal ArticleDOI
TL;DR: In this paper, the amount of water transferred to the nitrobenzene phase was determined for the extraction of ion pairs of tris(1,10-phenanthroline)iron(II) and tris (2,2′-bipyridine) iron(II), with halide and pseudohalide anions.
Abstract: The amount of water transferred to the nitrobenzene phase was determined for the extraction of ion pairs of tris(1,10-phenanthroline)iron(II) and tris(2,2′-bipyridine) iron(II) with halide and pseudohalide anions. For both chelate systems the smaller the anion, the greater the amount of water transported, very similar results being obtained for a common anion. The results were discussed in relation to water of crystallization, extractability and temperature effect.

19 citations


Journal ArticleDOI
TL;DR: The percentage of chromium(III) extracted as the complex anion CrY(H2O)- from solutions containing a 10% excess of EDTA (H4Y) by the liquid anion-exchanger Aliquat-336-Cl is shown to increase with change of organic solvent (diluent) in the order amyl alcohol

18 citations


Journal ArticleDOI
01 Apr 1973-Talanta
TL;DR: An indirect atomic-absorption method for boron has been developed and a procedure is described for determination of bor on in steel.


Journal ArticleDOI
TL;DR: In this article, a crystal violet or tetraphenylarsonium cation was used as an ion exchange-site in the liquid nitrobenzene membrane, which exhibits an ideal Nernstian response to the thiocyanate ion down to 10−5 M.
Abstract: Ion-selective electrode membranes responsive to the thiocyanate ion were prepared by using ion-association extraction systems. A crystal violet or tetraphenylarsonium cation was used as an ion exchange-site in the liquid nitrobenzene membrane. The liquid membrane electrode exhibits an ideal Nernstian response to the thiocyanate ion down to 10−5 M. The selectivity of the liquid membrane largely depends on the extractability of the diverse anion into nitrobenzene. The order of the selectivity coefficients, Kj, is as follows:ClO_4^->IO_4^->SCN^->I^->ClO_3^->NO_3^->Br^->BrO_3^->Cl^-High selectivities for thiocyanate over SO42−, H2PO4−, Cl−, BrO3−, and Br were observed. The membrane potential is independent of the pH variation in the region from pH 2 to 12.

Journal ArticleDOI
TL;DR: In this article, the effect of solvents on the hyperfine splittings of anion radical was examined, and a model for the solvent effect considering the hindered rotation of the nitro group in the radical molecule caused by the formation of intermolecular hydrogen bond with solvent was found, taking account of changes in molecular orbital parameters resulting from hydroxylic solvation.
Abstract: In order to examine the effect of solvents on the hyperfine splittings of anion radical the electron spin resonance spectra of substituted nitrobenzene anion radicals were studied. The effect of hydroxylic solvent is enhanced when the nitro group is forced out of the plane of the benzene ring due to the steric influence of the bulky functional group at the ortho position. The effect is reduced when the nitro group forms intramolecular hydrogen bond with the hydroxyl group at the ortho position. A model for the solvent effect considering the hindered rotation of the nitro group in the radical molecule caused by the formation of intermolecular hydrogen bond with solvent is found to be reasonable from a molecular orbital calculation, taking account of changes in molecular orbital parameters resulting from hydroxylic solvation. The shifts in polarographic half wave potentials with the solvent system as well as the dehalogenation reaction in the course of electrochemical reduction of halonitrobenzenes is inter...

Patent
04 Jan 1973
TL;DR: In this article, Nitrobenzene is reduced to aniline with hydrogen under elevated temperatures and pressure in the presence of a catalyst containing 0.1 to 10 percent by weight palladium and vanadium or a compound of vanadium on an aluminum oxide support wherein at least 20 percent thereof has been converted into lithium-aluminum spinel.
Abstract: Nitrobenzene is reduced to aniline with hydrogen under elevated temperatures and pressure in the presence of a catalyst containing 0.1 to 10 percent by weight palladium and 0.1 to 5 percent by weight vanadium or a compound of vanadium on an aluminum oxide support wherein at least 20 percent thereof has been converted into lithium-aluminum spinel.

Journal ArticleDOI
TL;DR: In this article, the electronic spectra of nitrobenzene and benzoic acid were analyzed using the CNDO/2 method (del Bene and Jaffe's version).

Journal ArticleDOI
TL;DR: In this article, the extraction of alkali metal dipicrylaminates into nitrobenzene has been studied at 0-45°C and the values of ΔG ∗, ΔH ∗ and ΔS ∗ for extraction of the dissociated ion pairs are calculated and the influence of temperature changes in the solubility of water in nitrogen in aqueous phase upon the above thermodynamic parameters is discussed.



Journal ArticleDOI
TL;DR: In this paper, the emission spectra of benzonitrile, aniline, N, N-dimethylaniline and nitrobenzene under controlled electron-impact excitation (60-300 eV) were investigated at a very low pressure.
Abstract: The emission spectra of benzonitrile, aniline, N,N-dimethylaniline, and nitrobenzene under controlled electron-impact excitation (60–300 eV) were investigated at a very low pressure. Bands of the parent molecules were observed in the 260–410 nm region on benzonitrile and anilines, and were assigned to the S1–S0 transitions. However, no emission of the parent molecule was observed on nitrobenzene and this was attributed to the spinorbit coupling effect of the nitro group and the predissociation of the excited parent molecule. Bands of the following fragment species were observed for all four compounds: H(Balmer series, CH(A2Δ2–X2II), and CN(B2Σ–X2Σ). In addition, NH(A3II–X3II) band on aniline and NO(A2Σ–X2II, B2II–X2II), CO(b3Σ–a3II), and CO+ (A2II–X2Σ, B2Σ–X2Σ) bands on nitrobenzene were observed. The linear relationships between the electron beam current and the emission intensities of the parent molecules and the fragment species indicated that most of the excited species were produced by primary electr...

Journal ArticleDOI
TL;DR: In this paper, three methods for hromination of pyrimidine were investigated: (a) bromination in aromatic solvents, (b) vapor phase bromification, and (c) pyrolysis of pyridine hydrochloride perbromide.

Journal ArticleDOI
TL;DR: In this article, the effect of HCl on the rate of thermal decomposition of polyvinylidene chloride (PVDC) in nitrobenzene solution was measured with the object of determining the catalytic activity of HCL.
Abstract: The effect of HCl on the rate of thermal decomposition of poly(vinylidene chloride) (PVDC) in nitrobenzene solution was measured with the object of determining the catalytic activity of HCl. Unlike those reports dealing with PVC decompositions, this study shows that in the absence of a cocatalyst, molecular HCl does not catalyze the decomposition of PVDC. In the presence of metals which can react with HCl to form Lewis acids (e.g., Fe0), a strong accelerating effect was observed. The uncatalyzed reaction shows a large rate increase with increasing polarity of the solvent, suggesting that in nitrobenzene the decomposition is mainly heterolytic in nature.




Patent
05 Jun 1973
TL;DR: Henke et al. as discussed by the authors used zinc dust and ammonium chloride to accomplish this type of reduction and showed that high pressures are preferred for the formation of aniline rather than p-aminophenol.
Abstract: A method for the purification of p-aminophenol. The impure paminophenol is dissolved in an aqueous acid solution and extracted with nitrobenzene. SPECIFICATION BACKGROUND OF THE INVENTION The phenylhydroxylamine is not isolated and its conversion to the desired p-aminophenol is accomplished by means of strong acid, usually sulfuric acid. The use of zinc dust and ammonium chloride to accomplish this type of reduction is shown in U.S. Pat. No. 2,132,454 (Bassford). The catalytic hydrogenation of nitrobenzene in the presence of a strong acid such as sulphur acid, to prepare p-aminophenol, is shown in U.S. Pat. No. 2,198,249 (Henke et al). Hydrogen pressures of from about 400 to about 500 lbs. per sq. inch gauge are preferred, as are temperatures within the range of 135.degree.C and 155.degree.C. High pressures are stated to favor the formation of aniline rather than p-aminophenol. SUMMARY OF THE INVENTION

Journal ArticleDOI
TL;DR: In this paper, the synthesis of 3,4-dinitrobenzoic acid from pentafluorophenylhydrazine in nitrobenzene is described.
Abstract: 2,3,4,5,6-Pentafluorobiphenyl reacts with boiling fuming nitric acid to give 2,4-dinitrobenzoic acid, but under mild conditions the 2′-, 3′-, and 4′-nitro-derivatives are formed in the ratio 3·4 : 1·0 : 8·7. All three nitro-compounds may be synthesised unambiguously by mixed Ullmann reactions. 2,3,4,5,6-Pentafluoro-3′-nitrobiphenyl is also isolated following the oxidation of pentafluorophenylhydrazine in nitrobenzene, and reacts with hot fuming nitric acid to give 3,4-dinitrobenzoic acid. Syntheses of 2,3,5,6-tetrafluoro-4-hydroxy-, -4-methoxy-, and -4-iodo-biphenyl are also described; irradiation of the iodo-compound in benzene gives 2′,3′,5′,6′-tetrafluoro-p-terphenyl, and its Ullmann condensation provides a good route to 2′,2″,3′,3″,5′,5″,6′,6″-octafluoro-p-quaterphenyl.

Journal ArticleDOI
TL;DR: The metabolism of [ 14C]-nitrobenzene and [14C]-4-dimethyl-aminoazobenzene was examined in a tick and a spider and the reduction of both compounds to aniline is reported in both species.

Journal ArticleDOI
TL;DR: In this article, the reaction of o-dinitrobenzene with sodium borohydride in aqueous dimethyl sulphoxide at room temperature gives n- and p-nitrotoluenes in low yields.
Abstract: The reaction of o-dinitrobenzene with sodium borohydride in aqueous dimethyl sulphoxide at room temperature gives nitrobenzene and benzofurazan in low yields. Deuterium is incorporated specifically into the ortho position of nitrobenzene when the reaction is performed with sodium borodeuteride. 2,3-Dinitrotoluene gives mainly m-nitrotoluene, but 3,4-dinitrotoluene gives both m- and p-nitrotoluenes.