Oxidization of 4-nitrotoluene by nitric acid under excessive pressure and high temperatures

Authors

  • Андрій Сергійович Бушуєв Institute of Chemical Technologies Dal’ East-Ukrainian National University Lenin Street 31, Rubezhnoe, Lugansk oblast, Ukraine 93000, Ukraine

DOI:

https://doi.org/10.15587/1729-4061.2013.14774

Keywords:

oxidation of 4-nitrotoluen, 4-nitrobenzoic acid, nitric acid, pressure, temperature

Abstract

The article studies the kinetics of oxidation of 4-nitrotoluene by nitric acid under excessive pressure and high temperatures. The article investigates the influence of temperature and duration of oxidation on the qualitative and quantitative characteristics of the product - corresponding 4-nitrobenzoic acid.

The determination of content of 4-nitrobenzoic acid was carried out by the titration method and electrometric titration.

It was found that with proper choice of parameters, namely, the pressure in the reactor 60 atm, temperature 180 º C, duration 15 minutes and modules HNO3 = 2, the oxidation by 30%  nitric acid can be carried out with high efficiency with maximum output of 4 -nitrobenzoic acid 95%. Thus obtained desired product is characterized by high quality (98,5-99,0%  of 4-nitrobenzoic acid).

It was found that the increase of the concentration of nitric acid over 45-50% leads to nitration of 4-nitrotoluenu to aromatic ring. Taking into account the use of the regenerated nitric acid it was recommended to limit the upper concentration to 50%.

Thus, the results of these studies can be used to optimize obtaining of 4-nitrobenzoic acid at factories for its synthesis

Author Biography

Андрій Сергійович Бушуєв, Institute of Chemical Technologies Dal’ East-Ukrainian National University Lenin Street 31, Rubezhnoe, Lugansk oblast, Ukraine 93000

PhD

References

  1. Чекалин, М. А. Технология органических красителей и промежуточных продуктов / М.А. Чекалин, Б.В. Пассет, Б.А. Иоффе – 2-е изд., перераб. - Л. : Химия, 1980. – 472 с.
  2. Получение п-нитробензойной кислоты окислением п-нитротолуола разбавленной азотной кислотой под давлением / В.Г. Сущеев, Е. Н. Вишневский, Ю. В. Долматов, В. Ф. Селиванов, М. М. Александров // Журнал прикладной химии . –1982. –Т 55. №8. – с. 1904–1907.
  3. Russell, G. A. Oxidation of carbanions. Oxidation of p-nitrotoluene and derivatives in basic solution / G.A. Russell, A.J. Moye, E. Janzen // J. Organ. Chem. – 1967, 32, №1, 137–146.
  4. Radhakrishnamurti P.S. Kinetic evidence for radical-anions in the oxidation of p-nitrotoluene by alkaline hexacyanoferrant (III) in aqueous dimethyl sulphoxide / P.S. Radhakrishnamurti, S.N. Mahapotro // Indian J. Chem. – 1976. –Т 14. №8. – с. 613–614.
  5. А.с. 1148848 СССР, кл. С 07 С 79/46. Непрерывный способ получения п-нитробензойной кислоты. Вишневский Е. Н., Игнатьева О. Д., Ласкин В. М., Лекомцев А. И., Наградский М. И., Сущеев В. Г., Удамова Н. П. (СССР).– № 4124968/23-04; Заявл. 25.09.86; опубл. 07.09.1988 – Бюл.№33.
  6. Радхакришнамурти, П. С. Кинетика окисления орто- и пара-нитротолуолов гексацианоферратом (3+); необычная реакционная способность некоторых устойчивых субстратов / П.С. Радхакришнамурти // Indian J. Chem. –1975. – Т 13.- №10. – с. 1029 – 1031.
  7. Эфрос, Л. С. Химия и технология промежуточных продуктов / Л.С. Эфрос, М.В. Горелик. – Л. : Химия, 1980. – 544 с.
  8. Пат. SE 202125 Швеция, С 07 с / 12 о : 14. Förfarande för seliktiv ftallning av p-nitrobensoeszra gemon oxidation av en isomerblandning av o-, м-, och p-nitrotoluener / Mayurnik G.; заявл. 8.04.57. опубл. 22.02.66.
  9. Атрощенко, В. И. Технология азотной кислоты / В.И. Атрощенко, С.И. Каргин. – М.: Химия, 1970. 496 с.
  10. Titov, A. I. The free radical mechanism of nitration / A. I. Titov // Tetrahedron. – 1963. Vol. 19, № 4. – Р. 557-580.
  11. Tchekalin M.A., Passet B.V., Ioffe B. A. (1980). Technology of organic dyes and intermediate Products, (2) Leningrad, USSR: Chemistry Publishing.
  12. V.G. Suscheev, E. N. Vishnevskiy, Y.V. Dolmatov, V.F. Selivanov, M. M. Aleksandrov. The receiption of p-nitrobenzoic acid by the oxidization of p-nitrotoluene by nitric acid under pressure. (1982). Russian Journal of Applied Chemistry, 55 (8), 1904-1907.
  13. Russell G.A., Moye A.J., Janzen E. (1967). Oxidation of carbanions. Oxidation of p-nitrotoluene and derivatives in basic solution. J. Organ. Chem., 32 (1), 137-146.
  14. Radhakrishnamurti P.S., Mahapotro S.N. (1976). Kinetic evidence for radical-anions in the oxidation of p-nitrotoluene by alkaline hexacyanoferrate (III) in aqueous dimethyl sulphoxide. Indian J. Chem., 14. (8), 613-614.
  15. Author's certificates of the USSR С 07 С 79/46. The continuous way of receiving of the p-nitrobenzoic acid / Vishnevsky E. N, Ignatyev O. D., Laskin V. M., Lekomtsev A. I. Nagradsky M.I., Sushcheev V. G., Udamova N. P.; declared 25.09.86. published . 07.09.88
  16. P.S. Radhakrishnamurti and S.N. Mahapatro, "Kinetic Evidence for Radical Anions in the Oxidation of 4-Nitro and 2,4-Dinitrotoluenes by Alkaline Hexacyanoferrate (III) in Dimethyl Sulphoxide," Indian J. Chem., 1976, 14A, 613.
  17. Efros L.S., Gorelik M.V. (1980). Chemistry and technology of intermediate products, Leningrad, USSR: Chemistry Publishing.
  18. Pat. SE 202125, С 07 с / 12 о : 14. Förfarande för seliktiv ftallning av
  19. p-nitrobensoeszra gemon oxidation av en isomerblandning av o-, м-, och p-nitrotoluener / Mayurnik G.; declared 8.04.57. published 22.02.66.
  20. Atroshchenko V. I., Kargin S.I. (1970). Technology nitric acid. Moscow, USSR: Chemistry Publishing.
  21. Titov A. I. (1963). The free radical mechanism of nitration. Tetrahedron, 19 (4), 557-580.

Downloads

Published

2013-06-19

How to Cite

Бушуєв, А. С. (2013). Oxidization of 4-nitrotoluene by nitric acid under excessive pressure and high temperatures. Eastern-European Journal of Enterprise Technologies, 3(6(63), 4–8. https://doi.org/10.15587/1729-4061.2013.14774

Issue

Vol. 3 No. 6(63) (2013): Technologies of organic and inorganic substances

Section

Technology organic and inorganic substances

License

Copyright (c) 2014 Андрій Сергійович Бушуєв

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

The consolidation and conditions for the transfer of copyright (identification of authorship) is carried out in the License Agreement. In particular, the authors reserve the right to the authorship of their manuscript and transfer the first publication of this work to the journal under the terms of the Creative Commons CC BY license. At the same time, they have the right to conclude on their own additional agreements concerning the non-exclusive distribution of the work in the form in which it was published by this journal, but provided that the link to the first publication of the article in this journal is preserved.

A license agreement is a document in which the author warrants that he/she owns all copyright for the work (manuscript, article, etc.).
The authors, signing the License Agreement with TECHNOLOGY CENTER PC, have all rights to the further use of their work, provided that they link to our edition in which the work was published.
According to the terms of the License Agreement, the Publisher TECHNOLOGY CENTER PC does not take away your copyrights and receives permission from the authors to use and dissemination of the publication through the world's scientific resources (own electronic resources, scientometric databases, repositories, libraries, etc.).
In the absence of a signed License Agreement or in the absence of this agreement of identifiers allowing to identify the identity of the author, the editors have no right to work with the manuscript.
It is important to remember that there is another type of agreement between authors and publishers – when copyright is transferred from the authors to the publisher. In this case, the authors lose ownership of their work and may not use it in any way.