Revisiting the mechanism of neutral hydrolysis of esters: Water autoionization mechanisms with acid or base initiation pathways

Journal of Physical Chemistry B

Volumn 117, Issue 21, 2013, Pages 6487-6497

  Da Silva, Poliana Lima ^a   Guimarães, Luciana ^a   Pliego, Josefredo R ^a  

^a FEDERAL UNIVERSITY OF SÃO JOÃO DEL REI   (Brazil)

Author keywords

[No Author keywords available]

Indexed keywords

ESTERIFICATION; HYDROLYSIS; IONS; REACTION KINETICS;

AB INITIO CALCULATIONS; BIFUNCTIONAL CATALYSIS; CONTINUUM SOLVATION MODELS; EXPERIMENTAL KINETICS; INTRINSIC REACTION COORDINATE; MECHANISM AND KINETICS; NEUTRAL HYDROLYSIS; THEORETICAL CALCULATIONS;

ESTERS;

EID: 84878368025     PISSN: 15206106     EISSN: 15205207     Source Type: Journal    
DOI: 10.1021/jp311504d     Document Type: Article

References (63)

1. Suarez, P. A. Z.; Santos, A. L. F.; Rodrigues, J. P.; Alves, M. B. Oils and Fats Based Biofuels: Technological Chalendges Quim. Nova 2009, 32, 768-775
2. Suarez, P. A. Z.; Meneghetti, S. M. P. 70th Anniversary of Biodiesel in 2007: Historical Evolution and Current Situation in Brazil Quim. Nova 2007, 30, 2068-2071
3. Lotero, E.; Liu, Y. J.; Lopez, D. E.; Suwannakarn, K.; Bruce, D. A.; Goodwin, J. G. Synthesis of Biodiesel via Acid Catalysis Ind. Eng. Chem. Res. 2005, 44, 5353-5363
4. Bournay, L.; Casanave, D.; Delfort, B.; Hillion, G.; Chodorge, J. A. New Heterogeneous Process for Biodiesel Production: A Way to Improve the Quality and the Value of the Crude Glycerin Produced by Biodiesel Plants Catal. Today 2005, 106, 190-192
5. Schuchardt, U.; Sercheli, R.; Vargas, R. M. Transesterification of Vegetable Oils: a Review J. Braz. Chem. Soc. 1998, 9, 199-210
6. Pinto, A. C.; Guarieiro, L. L. N.; Rezende, M. J. C.; Ribeiro, N. M.; Torres, E. A.; Lopes, W. A.; Pereira, P. A. d. P.; Andrade, J. B. Biodiesel: An Overview J. Braz. Chem. Soc. 2005, 16, 1313-1330
7. Smith, M. B.; March, J. March's Advanced Organic Chemistry; John Wiley & Sons: New York, 2001.
8. Carey, F.; Sundberg, R. J. Advanced Organic Chemistry. Part A: Structure and Mechanisms; Kluwer Academic/Plenum Publishers: New York, 2000; Vol. 4.
9. Wolfenden, R.; Yuan, Y. The "Neutral" Hydrolysis of Simple Carboxylic Esters in Water and the Rate Enhancements Produced by Acetylcholinesterase and Other Carboxylic Acid Esterases J. Am. Chem. Soc. 2011, 133, 13821-13823
10. Pliego, J. R., Jr.; Riveros, J. M. Free Energy Profile of the Reaction between Hydroxide Ion and Ethyl Acetate in Aqueous and Dimethyl Sulfoxide Solutions: A Theoretical Analysis of the Changes Induced by the Solvent on the Different Reaction Pathways J. Phys. Chem. A 2004, 108, 2520-2526
11. Pliego, J. R., Jr.; Riveros, J. M. A Theoretical Analysis of the Free-Energy Profile of the Different Pathways in the Alkaline Hydrolysis of Methyl Formate in Aqueous Solution Chem.-Eur. J. 2002, 8, 1945-1953
12. Pliego, J. R., Jr.; Riveros, J. M. The Gas Phase Reaction Between Hydroxide Ion and Methyl Formate: a Theoretical Analysis of the Energy Surface and Product Distribution Chem.-Eur. J. 2001, 7, 169-175
13. Blumberger, J.; Klein, M. L. Revisiting the Free Energy Profile for the Nucleophilic Attack of Hydroxide on Formamide in Aqueous Solution Chem. Phys. Lett. 2006, 422, 210-217
14. Blumberger, J.; Ensing, B.; Klein, M. L. Formamide Hydrolysis in Alkaline Aqueous Solution: Insight from Ab Initio Metadynamics Calculations Angew. Chem., Int. Ed. 2006, 45, 2893-2897
15. Pliego, J. R., Jr. Basic Hydrolysis of Formamide in Aqueous Solution: A Reliable Theoretical Calculation of the Activation Free Energy Using the Cluster-Continuum Model Chem. Phys. 2004, 306, 273-280
16. Zahn, D. Theoretical Study of the Mechanisms of Acid-Catalyzed Amide Hydrolysis in Aqueous Solution J. Phys. Chem. A 2003, 107, 12303-12306
17. Stirling, A. HCO3- Formation from CO2 at High pH: Ab Initio Molecular Dynamics Study J. Phys. Chem. B 2011, 115, 14683-14687
18. Galib, M.; Hanna, G. Mechanistic Insights into the Dissociation and Decomposition of Carbonic Acid in Water via the Hydroxide Route: An Ab Initio Metadynamics Study J. Phys. Chem. B 2011, 115, 15024-15035
19. Wang, B.; Cao, Z. Hydration of Carbonyl Groups: The Labile H3O+ Ion as an Intermediate Modulated by the Surrounding Water Molecules Angew. Chem., Int. Ed. 2011, 50, 3266-3270
20. Yamabe, S.; Tsuchida, N.; Hayashida, Y. Reaction Paths of the Water-Assisted Neutral Hydrolysis of Ethyl Acetate J. Phys. Chem. A 2005, 109, 7216-7224
21. Gorb, L.; Asensio, A.; Tuñón, I.; Ruiz-López, M. F. The Mechanism of Formamide Hydrolysis in Water from Ab Initio Calculations and Simulations Chem.-Eur. J. 2005, 11, 6743-6753
22. Schmeer, G.; Sturm, P. A Quantum Chemical Approach to the Water Assisted Neutral Hydrolysis of Ethyl Acetate and its Derivatives Phys. Chem. Chem. Phys. 1999, 1, 1025-1030
23. Kallies, B.; Mitzner, R. Models of Water-Assisted Hydrolysis of Methyl Formate, Formamide, and Urea from Combined DFT-SCRF Calculations J. Mol. Model. 1998, 4, 183-196
24. Wolfe, S.; Kim, C.-K.; Yang, K.; Weinberg, N.; Shi, Z. Hydration of the Carbonyl Group. A Theoretical Study of the Cooperative Mechanism J. Am. Chem. Soc. 1995, 117, 4240-4260
25. Antonczak, S.; Ruiz-Lopez, M. F.; Rivail, J. L. Ab Initio Analysis of Water-Assisted Reaction Mechanism in Amide Hydrolysis J. Am. Chem. Soc. 1994, 116, 3912-3921
26. Merz, K. M. Gas-Phase and Solution-Phase Potential Energy Surfaces for Carbon Dioxide + n-Water (n = 1,2) J. Am. Chem. Soc. 1990, 112, 7973-7980
27. Almerindo, G. I.; Pliego, J. R., Jr. Ab Initio Investigation of the Kinetics and Mechanism of the Neutral Hydrolysis of Formamide in Aqueous Solution J. Braz. Chem. Soc. 2007, 18, 696-702
28. Slebocka-Tilk, H.; Sauriol, F.; Monette, M.; Brown, R. S. Aspects of the Hydrolysis of Formamide: Revisitation of the Water Reaction and Determination of the Solvent Deuterium Kinetic Isotope Effect in Base Can. J. Chem. 2002, 80, 1343-1350
29. Estiu, G.; Merz, K. M. The Hydrolysis of Amides and the Proficiency of Amidohydrolases. The Burden Borne by kw J. Phys. Chem. B 2007, 111, 6507-6519
30. Cascella, M.; Raugei, S.; Carloni, P. Formamide Hydrolysis Investigated by Multiple-Steering ab Initio Molecular Dynamics J. Phys. Chem. B 2004, 108, 369-375
31. Gunaydin, H.; Houk, K. N. Molecular Dynamics Prediction of the Mechanism of Ester Hydrolysis in Water J. Am. Chem. Soc. 2008, 130, 15232
32. Zhang, X.; Houk, K. N. Acid/Base Catalysis by Pure Water: The Aldol Reaction J. Org. Chem. 2005, 70, 9712-9716
33. Guthrie, J. P.; Cullimore, P. A. Effect of the Acyl Substituent on the Equilibrium Constant for Hydration of Esters Can. J. Chem. 1980, 58, 1281-1294
34. Jencks, W. P.; Carriuolo, J. General Base Catalysis of Ester Hydrolysis 1 J. Am. Chem. Soc. 1961, 83, 1743-1750
35. Fedor, L. R.; Bruice, T. C. Nucleophilic Displacement Reactions at the Thiol Ester Bond. IV. General Base Catalyzed Hydrolysis of Ethyl Trifluorothiolacetate. Kinetic Evidence for the Formation of a Tetrahedral Intermediate1 J. Am. Chem. Soc. 1965, 87, 4138-4147
36. Venkatasubban, K. S.; Davis, K. R.; Hogg, J. L. Transition-state Structure for the Neutral Water-Catalyzed Hydrolysis of Ethyl Trifluorothiolacetate J. Am. Chem. Soc. 1978, 100, 6125-6128
37. Venkatasubban, K. S.; Bush, M.; Ross, E.; Schultz, M.; Garza, O. Transition State Structure for the Water-Catalyzed Hydrolysis of p-Nitrophenyl Trifluoroacetate in Acetonitrile J. Org. Chem. 1998, 63, 6115-6118
38. Frasson, C. M. L.; Brandao, T. A. S.; Zucco, C.; Nome, F. Solvent Effect and Proton Inventory in the Hydrolysis of p-Methylphenyl Trichloroacetate J. Phys. Org. Chem. 2006, 19, 143-147
39. Kutt, A.; Leito, I.; Kaljurand, I.; Soovali, L.; Vlasov, V. M.; Yagupolskii, L. M.; Koppel, I. A. A Comprehensive Self-Consistent Spectrophotometric Acidity Scale of Neutral Bronsted Acids in Acetonitrile J. Org. Chem. 2006, 71, 2829-38
40. Xu, X.; Zhang, Q.; Muller, R. P.; Goddard, W. A., III An Extended Hybrid Density Functional (X3LYP) with Improved Descriptions of Nonbond Interactions and Thermodynamic Properties of Molecular Systems J. Chem. Phys. 2005, 122, 014105-14
41. Xu, X.; Goddard, W. A., III. The X3LYP Extended Density Functional for Accurate Descriptions of Nonbond Interactions, Spin States, and Thermochemical Properties Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 2673-2677
42. Su, J. T.; Xu, X.; Goddard, W. A., III. Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional J. Phys. Chem. A 2004, 108, 10518-10526
43. Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. Energies, Structures, and Electronic Properties of Molecules in Solution with the C-PCM Solvation Model J. Comput. Chem. 2003, 24, 669-681
44. Cossi, M.; Barone, V. Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model J. Phys. Chem. A 1998, 102, 1995-2001
45. Mennucci, B.; Tomasi, J. Continuum Solvation Models: a New Approach to the Problem of Solute's Charge Distribution and Cavity Boundaries J. Chem. Phys. 1997, 106, 5151-5158
46. Cances, E.; Mennucci, B.; Tomasi, J. A New Integral Equation Formalism for the Polarizable Continuum Model: Theoretical Background and Applications to Isotropic and Anisotropic Dielectrics J. Chem. Phys. 1997, 107, 3032-3041
47. Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Ab Initio Study of Solvated Molecules: A New Implementation of the Polarizable Continuum Model Chem. Phys. Lett. 1996, 255, 327-335
48. Su, P.; Li, H. Continuous and Smooth Potential Energy Surface for Conductorlike Screening Solvation Model Using Fixed Points with Variable Areas J. Chem. Phys. 2009, 130, 074109-13
49. Granovsky, A. A. Firefly, version 7.1.F; Moscow State University, 2009, http://classic.chem.msu.su/gran/firefly/index.html.
50. Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions J. Phys. Chem. B 2009, 113, 6378-6396
51. Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. General Atomic and Molecular Electronic Structure System J. Comput. Chem. 1993, 14, 1347-1363
52. Truhlar, D. G.; Pliego, Jr., J. R., Transition State Theory and Chemical Reaction Dynamics in Solution. In Continuum Solvation Models in Chemical Physics: From Theory to Applications; Mennucci, B.; Cammi, R., Eds.; Wiley-VCH: Chippenham, Wiltshire, Great Britain, 2007; pp 338-365.
53. Soteras, I.; Blanco, D.; Huertas, O.; Bidon-Chanal, A.; Luque, F. J., Solvent Effects in Chemical Equilibria. In Continuum Solvation Models in Chemical Physics: From Theory to Applications; Mennucci, B.; Cammi, R., Eds.; Wiley-VCH: Chippenham, Wiltshire, Great Britain, 2007; pp 323-337.
54. Levine, I. N. Physical Chemistry; McGraw Hill: Singapore, 2009; Vol. 6.
55. Chipot, C.; Pohorille, A. Calculating Free Energy Differences Using Perturbation Theory. In Free Energy Calculations; Chipot, C.; Pohorille, A., Eds.; Springer-Verlag: Berlin, 2007; pp 33-75.
56. Westphal, E.; Pliego, J. R., Jr. Absolute Solvation Free Energy of Li+ and Na+ Ions in Dimethyl Sulfoxide Solution: A Theoretical Ab Initio and Cluster-Continuum Model Study J. Chem. Phys. 2005, 123, 074508
57. Pliego, J. R., Jr.; Riveros, J. M. The Cluster-Continuum Model for the Calculation of the Solvation Free Energy of Ionic Species J. Phys. Chem. A 2001, 105, 7241-7247
58. Asthagiri, D.; Pratt, L. R.; Kress, J. D.; Gomez, M. A. The Hydration State of HO-(aq) Chem. Phys. Lett. 2003, 380, 530-535
59. Grabowski, P.; Riccardi, D.; Gomez, M. A.; Asthagiri, D.; Pratt, L. R. Quasi-Chemical Theory and the Standard Free Energy of H+(aq) J. Phys. Chem. A 2002, 106, 9145-9148
60. Asthagiri, D.; Pratt, L. R.; Ashbaugh, H. S. Absolute Hydration Free Energies of Ions, Ion-Water Clusters, and Quasichemical Theory J. Chem. Phys. 2003, 119, 2702-2708
61. Riveros, J. M.; Jose, S. M.; Takashima, K. Gas-Phase Nucleophilic Displacement Reactions Adv. Phys. Org. Chem. 1985, 21, 197
62. Chandrasekhar, J.; Smith, S. F.; Jorgensen, W. L. Theoretical-Examination of the Sn2 Reaction Involving Chloride-Ion and Methyl-Chloride in the Gas-Phase and Aqueous-Solution J. Am. Chem. Soc. 1985, 107, 154-163
63. Takashima, K.; Riveros, J. M. Gas-Phase Pathways for Ester Hydrolysis J. Am. Chem. Soc. 1978, 100, 6128-6132