Studies in the Chemistry of Carbazole Derivatives. Use of Acid Ionization of 3-Nitrocarbazole for Its Quantitative Determination

The combination of equations (1–2) makes it possible to describe the anodic current as a function of the mole fractions of the elements at the electrode and of the interaction parameters \(B_{ij}\) in boundary systems. A similar thermodynamic approach is applicable to the derivation of equations describing the electrochemical dissolution of oxides, including nonstoichiometric ones. The parameters \(B_{ij}\) are determined experimentally; another possible method for their determination is comparison, with the aid of an electronic computer, of experimental curves or individual peaks with a mathematical model of the process implemented on the computer [5].

References

1. A. A. Kashlin. In: “Advances in Polarography with Accumulation.” Publishing House of TPU, Tomsk, 1973, pp. 133–136.
2. A. A. Kashlin, T. F. Ryashentseva, ibid., pp. 137–139.
3. A. I. Men’, Yu. P. Vorob’ev, G. I. Chufarov. Physicochemical Properties of Nonstoichiometric Oxides, Moscow, Khimiya, 1973.
4. G. I. Chufarov et al. In: Physical Chemistry of Oxide Systems, Nauka Publishing House, 1971, pp. 95–106.
5. A. A. Kashlin et al. In: “Advances in Polarography with Accumulation,” Publishing House of TPU, Tomsk, 1973, pp. 65–66.

STUDIES IN THE CHEMISTRY OF CARBAZOLE DERIVATIVES. USE OF ACID IONIZATION OF 3-NITROCARBAZOLE FOR ITS QUANTITATIVE DETERMINATION.

V. P. Lopatinskii, I. P. Zherebtsov, S. P. Yudina, L. P. Belyanina

Ionization of 3-nitrocarbazole according to the acid type proceeds in sufficiently basic media with formation of an anion, whose light-absorption maximum is located rather far from the absorption maximum of the neutral molecule and lies in the visible region of the spectrum /1/. On the other hand, 9-alkyl derivatives of 3-nitrocarbazole have insignificant absorption in the region of the anion, which makes it possible to use a photometric method for the determination of 3-nitrocarbazole in its mixture with 9-substituted compounds.

Experimental Part

3-Nitrocarbazole was obtained according to /2/, m.p. \(216^\circ\). 3-Nitro-9-ethylcarbazole was obtained according to /3/, m.p. \(130^\circ\). 3-Nitro-9-(2-hydroxy)-ethylcarbazole was obtained according to /4/, m.p. \(183–184^\circ\). 3-Nitro-9-(2-hydroxy)propylcarbazole was obtained by reaction of 3-nitrocarbazole with propylene oxide in acetone in the presence of caustic potash, by analogy with /4/, m.p. \(144.5^\circ\). For photometric measurements, solutions were used—

agents: acetone, “chemically pure,” rectified ethyl alcohol.

Construction of the Calibration Graph

To construct the calibration graph, a series of standard solutions is prepared, the concentrations of which cover the range from 0 to \(7.44 \cdot 10^{-5}\) M 3-nitrocarbazole. Into a 25-ml volumetric flask are added the required amount of a solution of 3-nitrocarbazole in acetone with an initial concentration of \(3.72 \cdot 10^{-4}\) M, acetone in such an amount that its total content is 10 ml, 2.0 ml of 0.5 N potassium hydroxide solution, and ethyl alcohol to the mark.

The resulting mixture is thoroughly mixed and allowed to stand for 10 minutes at room temperature. The optical densities of the solutions are measured on an electrophotocolorimeter with a light filter whose transmission maximum is 460 nm, in cuvettes 1 cm thick. A mixture not containing 3-nitrocarbazole is placed in the reference cuvette.

The calibration graph in the form of the straight line \(D = f(c)\) is constructed from eight points, treating the results by the least-squares method /5/ on the “Promin-M” computer using a standard program.

Procedure for the Determination

A solution of the analyzed mixture of 3-nitrocarbazole with its 9-alkyl-substituted derivatives is prepared in acetone or ethyl alcohol. Into a 25-ml volumetric flask are placed from 1 to 10 ml of the prepared solution so that the measured optical density corresponds approximately to the middle of the calibration graph. Acetone is added to the same flask in such an amount that its total content is 10 ml, 2.0 ml of 0.5 N potassium hydroxide solution in water, and ethyl alcohol to the mark, after which the optical density is measured by the method described above. From the graph, the amount of 3-nitrocarbazole corresponding to the optical density found for the solution is determined.

To study the influence of the presence of 9-substituted 3-nitrocarbazole derivatives on the result of the analysis and to assess the accuracy and relative error of the method, a series of arti-

solutions with the same content of 3-nitrocarbazole in them, in admixture with different amounts of 3-nitro-9-(2-hydroxy)propylcarbazole (from 0 to \(7.44 \cdot 10^{-5}\) M).

Statistical processing of the results was carried out according to / 6 /.

The relative error from eight determinations, with a confidence probability of 95%, is 4.05%.

It was found that similar results are also obtained for mixtures containing, in addition to 3-nitrocarbazole, its 9-(2-hydroxy)ethyl or 9-ethyl derivatives.

References

1. R. Stewart, J. P. O’Donnel, Canad. J. Chem. Soc., 42, 1681, 1964.
2. R. Eikman, B. Dukalevich, E. Silaeva. POKh, 6, No. 2, 93, 1959.
3. E. E. Sirotkina. Dissertation. Tomsk, 1964.
4. V. P. Lopatinskii, I. P. Zherebtsov. Author’s certificate 183209, BI, 13, 1966.
5. K. Laidler. Kinetics of Organic Reactions. “Mir,” Moscow, 1969.
6. L. P. Adamovich. Rational Methods for Compiling Analytical Procedures. Publishing House of Kharkov University, 1966.

SYNTHESIS AND PROPERTIES OF PHENYLIODOSO-N-ACETYLAMINOBUTYRATE

S. S. Makarchenko, N. I. Izotova, A. N. Novikov

A representative of the group of phenyliodosocarboxylates, hitherto undescribed in the literature, has been obtained—phenyliodoso-N-acetylaminobutyrate. Among the products of thermal decomposition of the latter, iodobenzene, N-acetylaminobutyric acid, phenyl-N-acetylaminobutyrate, and acetylamine iodide were found. Upon decomposition of one mole of phenyliodosoacetylaminobutyrate, 0.4 mole of carbon dioxide is evolved. A scheme is proposed for the thermal decomposition reaction.

The first representatives of phenyliodosocarboxylates of the formula \(C_6H_5I(OCOR)_2\) were obtained at the end of the last century. Until the 1950s, phenyliodosocarboxylates were regarded as exotic substances. Their systematic investigation began after the discovery of interesting properties—the ability...