Combined influence of fluorinated solvent and base in friedel − crafts reaction of toluene and CO2 / Pradip Munshi in Industrial & engineering chemistry research, Vol. 49 N° 14 (Juillet 2010)  

Public ISBD [article]  inIndustrial & engineering chemistry research > Vol. 49 N° 14 (Juillet 2010) . - pp 6678–6682 Titre : Combined influence of fluorinated solvent and base in friedel − crafts reaction of toluene and CO2 Type de document : texte imprimé Auteurs : Pradip Munshi, Auteur ; Eric J. Beckman, Auteur ; Sudhakar Padmanabhan, Auteur Année de publication : 2010 Article en page(s) : pp 6678–6682 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Reaction Toluene Résumé : As disclosed in preceding studies [Munshi and Beckman Ind. Eng. Chem. Res. 2009, 48, 1059−1062 and Beckman and Munshi US Patent 7,271,286, 2007], aluminum chloride is superior among Lewis acids in making p-toluic acid from toluene and 6.9 MPa CO2 offering 80% stoichiometric yield, with respect to Al2Cl6, and 98% selectivity at 80 °C in 18 h. Attempts to improve the efficiency resulted in the finding that H+ exchange between HCl and Tol-COOAl2Cl5 is the key step in making the reaction catalytic. Introduction of a base complemented by a fluorinated solvent can only bring Al2Cl6 into catalytic cycle, provided pKa[Tol-COOH] > pKa[BH+] > pKa[HCl]. Efficiency of the reaction depends upon the nature of the fluorinated solvents and reaction parameters employed. Turnover number of 7.87 for p-toluic acid in 6 h is obtained employing 2.68 mmol quinoxaline, 15 mL 1,3,5-tris(trifluoromethyl)benzene, and 2.68 mmol of Al2Cl6 and CO2 at a pressure of 6.9 MPa CO2 and 100 °C. The base and fluorinated solvent could be recyclable and reused. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie100533c [article] Combined influence of fluorinated solvent and base in friedel − crafts reaction of toluene and CO2 [texte imprimé] / Pradip Munshi, Auteur ; Eric J. Beckman, Auteur ; Sudhakar Padmanabhan, Auteur . - 2010 . - pp 6678–6682. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 14 (Juillet 2010) . - pp 6678–6682 Mots-clés : Reaction Toluene Résumé : As disclosed in preceding studies [Munshi and Beckman Ind. Eng. Chem. Res. 2009, 48, 1059−1062 and Beckman and Munshi US Patent 7,271,286, 2007], aluminum chloride is superior among Lewis acids in making p-toluic acid from toluene and 6.9 MPa CO2 offering 80% stoichiometric yield, with respect to Al2Cl6, and 98% selectivity at 80 °C in 18 h. Attempts to improve the efficiency resulted in the finding that H+ exchange between HCl and Tol-COOAl2Cl5 is the key step in making the reaction catalytic. Introduction of a base complemented by a fluorinated solvent can only bring Al2Cl6 into catalytic cycle, provided pKa[Tol-COOH] > pKa[BH+] > pKa[HCl]. Efficiency of the reaction depends upon the nature of the fluorinated solvents and reaction parameters employed. Turnover number of 7.87 for p-toluic acid in 6 h is obtained employing 2.68 mmol quinoxaline, 15 mL 1,3,5-tris(trifluoromethyl)benzene, and 2.68 mmol of Al2Cl6 and CO2 at a pressure of 6.9 MPa CO2 and 100 °C. The base and fluorinated solvent could be recyclable and reused. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie100533c

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