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Carboxylation of toluene by CO2 generating p - toluic acid / Antaram N. Sarve in Industrial & engineering chemistry research, Vol. 51 N° 14 (Avril 2012) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 51 N° 14 (Avril 2012) . - pp. 5174-518 Titre : Carboxylation of toluene by CO2 generating p - toluic acid : A kinetic look Type de document : texte imprimé Auteurs : Antaram N. Sarve, Auteur ; Pralhad A. Ganeshpure, Auteur ; Pradip Munshi, Auteur Année de publication : 2012 Article en page(s) : pp. 5174-518 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Kinetics  Carbon  dioxide  Carboxylation Résumé : A kinetic study involving stoichiometry, order of reaction, rate constants (k), and rate laws has been performed on carboxylation of toluene by CO2 generating p-toluic acid by two routes: (a) Friedel—Crafts reaction, C6H5―CH3 + CO2 + Al2Cl6 → CH3―C6H4―COOAl2Cl5 + HCl and (b) Friedel―Crafts reaction with incubation method involving two steps, CO2+ + Al2Cl6 → CO2:Al2Cl6 and CO2:Al2Cl6 + C6H5―CH3→ CH3―C6H4―COOAl2Cl5 + HCl. The adduct OCO:Al2Cl6 was estimated by monitoring the peak at 1662 cm―1 in the FT1R spectra. The k values for the Friedel-Crafts reaction was found to be 2.28 × 10―9 mol―2 h―1, which is much lower than that for the reactions involved in the incubation method, viz, 5.4 × 10―5 and 1.9 X 10―3 mol―1 h―1, respectively. ΔE, ΔG, ΔS, ΔH, and the Arrhenius constant (A) have been calculated for the above reactions. Comparison shows that the incubation method is faster than the Friedel-Crafts reaction. However, both the reactions follow first order kinetics with respect to each of the reactants. ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=25783425 [article] Carboxylation of toluene by CO2 generating p - toluic acid : A kinetic look [texte imprimé] / Antaram N. Sarve, Auteur ; Pralhad A. Ganeshpure, Auteur ; Pradip Munshi, Auteur . - 2012 . - pp. 5174-518. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 14 (Avril 2012) . - pp. 5174-518 Mots-clés : Kinetics  Carbon  dioxide  Carboxylation Résumé : A kinetic study involving stoichiometry, order of reaction, rate constants (k), and rate laws has been performed on carboxylation of toluene by CO2 generating p-toluic acid by two routes: (a) Friedel—Crafts reaction, C6H5―CH3 + CO2 + Al2Cl6 → CH3―C6H4―COOAl2Cl5 + HCl and (b) Friedel―Crafts reaction with incubation method involving two steps, CO2+ + Al2Cl6 → CO2:Al2Cl6 and CO2:Al2Cl6 + C6H5―CH3→ CH3―C6H4―COOAl2Cl5 + HCl. The adduct OCO:Al2Cl6 was estimated by monitoring the peak at 1662 cm―1 in the FT1R spectra. The k values for the Friedel-Crafts reaction was found to be 2.28 × 10―9 mol―2 h―1, which is much lower than that for the reactions involved in the incubation method, viz, 5.4 × 10―5 and 1.9 X 10―3 mol―1 h―1, respectively. ΔE, ΔG, ΔS, ΔH, and the Arrhenius constant (A) have been calculated for the above reactions. Comparison shows that the incubation method is faster than the Friedel-Crafts reaction. However, both the reactions follow first order kinetics with respect to each of the reactants. ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=25783425

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]  in Industrial & 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