Selective Nitration of Toluene using Nitrogen(V) Oxide in Dichloromethane and Catalysts

• Autorzy: Maksimowski Paweł , Nastała Andrzej , Tomaszewski Waldemar

Identyfikatory

DOI

10.22211/cejem/158420

• Języki publikacji: EN

Abstrakty

EN

A series of toluene nitration reactions was carried out using a nitrogen(V) oxide (N₂O₅)solution in dichloromethane (CH₂Cl₂), with and without the addition of solid catalysts. N₂O₅ in CH₂Cl₂ was found to be a more active and selective mixture compared to 100% nitric acid and a mixture of nitric acid(V) in CH₂Cl₂. Temperature has a significant effect on the composition of the products of nitration of toluene with N₂O₅ in CH₂Cl₂; as the reaction temperature was decreased, the amount of meta-nitrotoluene decreased to approx. 1-1.2%, at a nitration temperature below -40 °C. The use of molecular sieves with toluene adsorption resulted in a quite powerful para effect, demonstrated by a significant increase in the amount of the para isomer, while reducing the ortho- and meta-isomers. The most pertinent effect was obtained when using 13X molecular sieves. In addition to improving the selectivity, the use of molecular sieves also leads to a higher degree of nitration of toluene (toluene/N₂O₅ = 1:1) due to the resulting nitric acid being absorbed by the pores of the molecular sieve.

Słowa kluczowe

EN

nitration; nitrogen(V) oxide; toluene; nitrotoluenes

• Wydawca: Sieć Badawcza Łukasiewicz - Instytut Przemysłu Organicznego
• Czasopismo: Central European Journal of Energetic Materials
• Rocznik: 2022
• Tom: Vol. 19, no. 4
• Strony: 424--437
• Opis fizyczny: Bibliogr. 22 poz., tab., wykr.

Twórcy

autor

Maksimowski Paweł

• Warsaw University of Technology, Warsaw, Poland

• https://orcid.org/0000-0003-0945-7149

autor

Nastała Andrzej

• Warsaw University of Technology, Warsaw, Poland

• https://orcid.org/0000-0002-9457-2557

autor

Tomaszewski Waldemar

• Warsaw University of Technology, Warsaw, Poland

Bibliografia

• [1] Ribeiro, E.N.; Silva, F.T.; Paiva, T.C.B. Ecotoxicological Evaluation of Wastewater from 2,4,6-TNT Production. J. Environ. Sci. Health Part A 2012, 47: 184-191.
• [2] Rodrigues, M.B.; Silva, F.T.; Paiva, T.C.B. Characterization of Wastewater from the Brazilian TNT Industry. J. Hazard. Mater. 2009, 385-388.
• [3] Technology Evaluation for Treatment/Disposal of TNT Red Water. USATHAMA Report, 1990.
• [4] Millar, R.W.; Arber, A.W.; Endsor, R.M.; Hamid, J.; Colclough, M.E. Clean Manufacture of 2,4,6 Trinitrotoluene (TNT) via Improved Regioselectivity in the Nitration of Toluene. J. Hazard. Mater. 2011, 29: 88-114.
• [5] Urbański, T.; Hackel, J.; Mortka, S.; Szyc-Lewińska, K.; Ślebodziński, T.; Witek, W. About the Possibility of Improving the Production of TNT. (in Polish) Biull. WAT 1959, 84(1): 71-79.
• [6] Sreedhar, I.; Suresh Kumar Reddy, K.; Ramakrishna, M.; Kulkarni, S.J.; Raghavan, K.V. Studies on para-Selectivity and Yield Enhancement in Zeolite Catalyzed Toluene Nitration. Can. J. Chem. Eng. 2008, 86: 219-227.
• [7] Millar, R.W.; Arber, A.W.; Hamid, J.; Endsor, R.M. Elimination of Redwater Formation from TNT Manufacture. QinetiQ Report, UK, 2007.
• [8] Hogget, J.G.; Moodie, R.B.; Penton, J.R.; Schofield, K. Nitration and Aromatic Reactivity. Cambridge University Press, Cambridge, 1971.
• [9] Dagade, S.P. Nitration of Aromatic Compounds Over Solid Acid Catalysts. University of Pune, Pune, 2002.
• [10] Hagen, J. Industrial Catalysis. A Practical Approach. Wiley VCH, Weinheim, 2006.
• [11] Butters, M. Zeolite-assisted Organic Synthesis – a Survey. In: Solid Supports and Catalysts in Organic Synthesis. (Smith, K., Ed.), Ellis Horwood Ltd., Chichester, W. Sussex UK, 1992, Ch. 5.
• [12] van der Waal, J.C.; Van Bekkum, H. Zeolite Beta and Its Uses in Organic Reactions. In: Supported Catalysts and Their Applications. (Sherrington, D.C.; Kybett, A.P., Eds.) Royal Society of Chemistry, Cambridge, UK, 2001.
• [13] Smith, K. Selectivity Through the Use of Heterogeneous Catalysis. In: Supported Catalysts and Their Applications. (Sherrington, D.C.; Kybett, A.P., Eds.) Royal Society of Chemistry, Cambridge, UK, 2001; and references contained therein.
• [14] Vassena, D.; Kogelbauer, A.; Prins, R. Potential Routes for the Nitration of Toluene and Nitrotoluene with Solid Acids. Catal. Today 2000, 60: 275-287.
• [15] Bernasconi, S.; Pirngruber, G. D.; Kogelbauer, A.; Prins, R. Factors Determining the Suitability of Zeolite BEA as para-Selective Nitration Catalyst. J. Catal. 2003, 219: 231-241.
• [16] Sheemol, V.N.; Tyagi, B.; Jasra, R.V. Nitration of o-Xylene Over Rare Earth Cations Exchanged Zeolite-β with Nitric Acid and Acetic Anhydride. J. Mol. Catal. A: Chem. 2006, 252: 194-201.
• [17] Catalytic Nitration of Toluene (Elimination of Red Water). ARDEC Report, 2009.
• [18] Damavarapu, R.; Jayasuriya, K.; Thomas, J. Regioselective Nitration of Aromatic Compounds by Dinitrogen Pentoxide and the Reaction Products Thereof. Patent US 5977418, 1999.
• [19] Claridge, R.P.; Lancaster, N.L.; Millar, R.W.; Moodie, R.B.; Sandall, J.P.B. Zeolite Catalysis of Aromatic Nitrations with Dinitrogen Pentoxide. J. Chem. Soc. Perkin Trans. 1999, 2: 1815-1818.
• [20] Millar, R.W.; Colclough, M.E.; Arber, A.W.; Claridge, R.P.; Endsor, R.M.; Hamid, J. Clean Nitration Using Dinitrogen Pentoxide (N₂O₅) ‒ a UK Perspective. In: Energetic Materials Chemistry, Hazards and Environmental Aspects. (Howell, J.R.; Fletcher, T.E., Eds.) Nova Science Publishers, Hauppauge, 2011; ISBN 978-1-60876-267-5.
• [21] Ma, X.; Li, B.; Lu, C.; Lu, M.; Wu, J.; Liang, L. An Efficient and Eco-friendly MoO₃-SiO₂ Solid Acid Catalyst for Electrophilic Aromatic Nitration with N₂O₅. Catal. Lett. 2011, 141: 1814-1820.
• [22] Yilmaz, M.S.; Özdemir, Ö.D.; Pişkin, S. Synthesis and Characterization of MCM-41 with Different Methods and Adsorption of Sr²⁺ on MCM-41. Res. Chem. Intermed. 2015, 41: 199-211.