Nitration of Toluene and Chlorobenzene with HNO3/Ac2O Catalyzed by Caprolactam-based Bronsted Acidic Ionic Liquids

• Autorzy: Ql X. , Cheng G. , Lu Ch. , Qian D.
• Języki publikacji: EN

Abstrakty

EN

Several new caprolactam-based Bronsted acidic ionic liquids [Caprolactam]X (X- = pTSO-, BSO-, BF4-, NO3-) with relatively lower cost and lower toxicity were synthesized and for the first time used in catalyzing organic reaction. They showed good catalytic activity in the nitration of toluene and chlorobenzene with HNO3/Ac2O under mild conditions. Among them, [Caprolactam]pTSO was the best one probably because of its better affinity to aromatics than the others. [Caprolactam]pTSO catalyzed the nitration of toluene with achieving a high yield (99.7%, calculated by quantitative GC) and better para-selectivity (ortho/para=1.03) than the traditional mixed acid methodology. And the catalyst can be recycled for four times.

Słowa kluczowe

EN

nitration; caprolactam-based Bronsted acidic ionic liquids; HNO3/Ac2O; aromatics; catalyze

• Wydawca: Sieć Badawcza Łukasiewicz - Instytut Przemysłu Organicznego
• Czasopismo: Central European Journal of Energetic Materials
• Rocznik: 2007
• Tom: Vol. 4, nr 3
• Strony: 105--113
• Opis fizyczny: Bibliogr. 10 poz.

Twórcy

autor

Ql X.

autor

Cheng G.

autor

Lu Ch.

autor

Qian D.

• School of Chemical Engeering, Nanjing University of Science & Technology, Nanjing, 210094, China,

Bibliografia

• [1] see for example: (a) Suzuki H.,.Tatsumi A, Suzuki H.M., MaedaK., A novel non-acidic method for the preparation of 2,2,2-trifluoro-1 -(3-nitropheny1)ethanone and 1 -nitro-3- trifluoromethylbenzene, versatile starting materials for trifluoromethyl-containing aromatic compounds, Synthesis, 1995, 1353; Suzuki H,, Mori T., Ozone-mediated nitration of chloro- and bromo-benzenes and some methyl derivatives with nitrogen dioxide. High or//zo-directing trends of the chlorine and bromine substituents, J. Chem. Soc. Perkin Trans. 2,1994,479; Suzuki H., Mori T, Maeda K., Ozone-mediated reaction of polychlorobenzenes and some related halogeno compounds with nitrogen dioxides: A novel non-acid methodology for the selective mononitration of moderately deactivated aromatic systems, Synthesis, 1994, 841; Suzuki H., Tomaru J., Murashima T., Iron (Ill)-catalysed nitration of non-activated and moderately activated arenas with nitrogen dioxide-molecular oxygen under neutral conditions, /. Chem. Soc., Perkin Trans. 1, 1996, 23 5; (b) Barrett A.G.M., Braddock D.C., Ducray R., Mckinnell R.M., Waller F.J., Lanthanide triffate and triflide catalyzed atom economic nitration of fluoro arenes, Synlett., 2000, 57; Waller F.J., Barrett A.G.M., Braddock D.C., Ramprasad D., Lanthanide(III) triflates as recyclable catalysts for atom economic aromatic nitration, Chem. Commun., 1997, 613; (c) Delaude L., Laszlo P., Smith K., Heightened selectivity in aromatic nitrations and chlorinations by the use of sokid supports and catalysts, Ace. Chem. Res., 1993, 26, 607; GiganteB., PrazeresA.O., Marcelo-CurtoM.J., Mild and selective nitration by claycop, J. Org. Chem., 1995, 60,3445; Kwok T.J., Jayasuriya K., Damavarapu R., Brodman B. W, Applicat ion of H-ZSM-5 zeolite for regioselective mononitration of toluene, J. Org. Chem., 1994, 59, 4939; Vessena D., Kogelbauer A., Prins R., Potential routes for the nitration of toluene and nitrotoluene with solid acids, Catal. Today, 2000, 60,275; Dagade S.P., Waghmode S.B., Kadam VS., Dongare M.K., Vapor phase nitration of toluene using dilute nitric acid and molecular modeling studies over beta zeolite, Appl Catal, A, 2002,226,49; Peng X., Suzuki H., Lu C., Zeolite-assisted nitration of neat toluene and chlorobenzene with a nitrogen dioxide/molecular oxygen system, Remarkableenhancement of para-selectivity, Tetrahedron Letters, 2001, 42, 4357.
• [2] see for example: (a) Sheldon R., Catalytic reactions in ionic liquids, Chem. Commun., 2001, 2399; (b) Dupont J., Souza R.F., Suarez P.A.Z., Ionic liquid (Molten salt) phase organometallic catalysis, Chem. Rev., 2002, 102, 3667; (c) Cole A.C., Jensen J.L., Ntai I., Tran K.L.T., Weaver K. J., Novel Bransted acidic ionic liquids and their use as dual solvent-catalysts, J. Am. Chem. Soc., 2002,124, 5962; (d) Gui J.Z., Ban J.Y., Cong X.H., Zhang XT., Sun Z.L., Selective alkylation of phenol with tert-butyl alcohol catalyzed by Bransted acidic imidazolium salts, J. Mol. Catal A, 2005, 225, 27; (e) Joseph T., Sahoo S., Halligudi S.B., Bransted acidic ionic liquids, A green, efficient and reusable catalyst system and reaction medium for Fischer esterification, ibid. A, 2005, 234, 107; (f) Angueira E.J., White M.G., Arene carbonylation in acidic, chloro aluminate ionic liquids, ibid, 2005, 227, 51; (g) Li D. M., Shi F., Peng J.J, Guo S., Deng Y.Q., Application of functional ionic liquids possessing two adjacent acid sites for acetalization of aldehydes, J. Org. Chem., 2004, 69, 3582.
• [3] Laali K. K., Gettwert V. J., Electrophilic nitration of aromatics in ionic liquid solvents, J. Org. Chem., 2001, 66, 35.
• [4] Smith K., Liu S.F., El-Hiti G.A., Regioselective mononitration of simple aromatic compounds under mild conditions in ionic liquids, Ind. Eng. Chem. Res., 2005, 44, 8611.
• [5] Qiao K., Yokoyama C., Nitration of aromatic compounds with nitric acid catalyzed by ionic liquids, Chem. Lett., 2004, 33, 808.
• [6] (a) Dal E., Lancaster N.L., Acetyl nitrate nitrations in [bmpy][N{Tf)2] and [bmpy][OTf] and the recycling of ionic liquids, Org. Biomol. Chem., 2005, 3, 682, (b) Lancaster N.L., Llopis-Mestre V., Aromatic nitrations in ionic liquids: the importance of cation choice, Chem. Commun., 2003, 2812.
• [7] Swatloski R., Holbrey J., Memon S., Caldwell G., Caldwell K., Rogers R., Using Caenorhabditis elegans to probe toxicity of l-alkyl-3-methylimidazolium chloride based ionic liquids, Chem. Commun., 2004, 668.
• [8] Du Z.Y., Li Z.P., Guo S., Zhong J., Zhu L.Y., Deng Y.Q., Investigation of physicochemical properties of lactam-based Bransted acidic ionic liquids, J. Phys. Chem., B, 2005,109, 19542.
• [9] Yang Y.L., Kou Y, Determination of the Lewis acidity of ionic liquids by means of an IR spectroscopic probe, Chem. Commun., 2004, 226.
• [10] Parry E.P., An infrared of pyridine adsorbed on acidic solids, characterization of surface acidity, J. Catal., 1963,2, 371.