Mechanisms of Organocatalytic Amidation and Trans-Esterification of Aromatic Esters As a Model for the Depolymerization of Poly(ethylene) Terephthalate
Abstract
We describe investigations with B3LYP density functional theory to probe mechanisms for the organocatalyzed depolymerization of poly(ethylene) terephthalate (PET) into ester and amide products. These investigations utilize model systems involving the trans-esterification and amidation of methylbenzoate (MB) with ethylene glycol (EG), ethylenediamine (EDA), and ethanolamine (EA) organocatalyzed by 1,5,7-triazabicyclododecene (TBD) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Mechanisms for reactions in which TBD acts as the lone catalyst have been compared with pathways in which TBD and DBU catalyze these processes with an additional molecule of the amine or alcohol acting as a cocatalyst. Calculations suggest that the combination of an organocatalyst with a molecule of an alcohol or amine cocatalyst is slightly more activating than a lone catalyst. Our results predict that nucleophilic attack is the rate-determining step in reactions involving EDA and EG and that TBD is a better catalyst than DBU in the amidation of MB with EDA; in addition, both organocatalysts activate alcohols more than amines during nucleophilic attack. Amidation and trans-esterification possess similar barriers for reactions involving EA; but the amide, which is the thermodynamic product, is preferentially formed instead of the ester.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Calculations suggest that these reactions likely involve a bifunctional mechanism in which the alcohol reactant activates the carbonyl group of these polyesters while the organocatalyst activates the reacting alcohol.
“The calculations suggest that these reactions likely involve a bifunctional mechanism in which the alcohol reactant activates the carbonyl group of these polyesters while the organocatalyst activates the reacting alcohol.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [408]
In one example of glycolytic depolymerization of PET by TBD or DBU, Horn et al showed that the rate-determining step for the depolymerization is the ethylene glycol involved nucleophilic attack.
“In one example of glycolytic depolymerization of PET by TBD or DBU, Horn et al 408 showed that the rate-determining step for the depolymerization is the ethylene glycol involved nucleophilic attack.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [408]
Cites
Density-functional thermochemistry. III. The role of exact exchange
Becke, A. D. (1993) · The Journal of Chemical Physics · doi:10.1063/1.464913 · Cited by 103,767 · see citing works
Lee, C., Yang, W., & Parr, R. G. (1988) · Physical Review B · doi:10.1103/physrevb.37.785 · Cited by 100,874 · see citing works
Grimme, S., Antony, J., Ehrlich, S., & Krieg, H. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3382344 · Cited by 59,686 · see citing works
Stephens, P. J., Devlin, F. J., Chabalowski, C. F., & Frisch, M. J. (1994) · The Journal of Physical Chemistry · doi:10.1021/j100096a001 · Cited by 23,329 · see citing works
Vosko, S. H., Wilk, L., & Nusair, M. (1980) · Canadian Journal of Physics · doi:10.1139/p80-159 · Cited by 20,807 · see citing works
General atomic and molecular electronic structure system
Schmidt, M., Baldridge, K., Boatz, J., Elbert, S., Gordon, M., Jensen, J., Koseki, S., Matsunaga, N., Nguyen, K., Su, S.-J., et al. (1993) · Journal of Computational Chemistry · doi:10.1002/jcc.540141112 · Cited by 17,380 · see citing works
Hehre, W. J., DITCHFIELD, R., & Pople, J. A. (1972) · The Journal of Chemical Physics · doi:10.1063/1.1677527 · Cited by 15,901 · see citing works
The influence of polarization functions on molecular orbital hydrogenation energies
Hariharan, P. C., & Pople, J. A. (1973) · Theoretical Chemistry Accounts · doi:10.1007/bf00533485 · Cited by 15,848 · see citing works
Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions
Kendall, R. A., Dunning, T. H., & Harrison, R. J. (1992) · The Journal of Chemical Physics · doi:10.1063/1.462569 · Cited by 15,736 · see citing works
Unified Approach for Molecular Dynamics and Density-Functional Theory
Car, R., & Parrinello, M. (1985) · Physical Review Letters · doi:10.1103/physrevlett.55.2471 · Cited by 10,737 · see citing works
Barone, V., & Cossi, M. (1998) · The Journal of Physical Chemistry A · doi:10.1021/jp9716997 · Cited by 10,264 · see citing works
Fully optimized contracted Gaussian basis sets for atoms Li to Kr
Schäfer, A., Horn, H. W., & Ahlrichs, R. (1992) · The Journal of Chemical Physics · doi:10.1063/1.463096 · Cited by 9,633 · see citing works
Self-citationCossi, M., Rega, N., Scalmani, G., & Barone, V. (2003) · Journal of Computational Chemistry · doi:10.1002/jcc.10189 · Cited by 8,056 · see citing works
Clark, T., Chandrasekhar, J., Spitznagel, G. W., & Schleyer, P. V. R. (1983) · Journal of Computational Chemistry · doi:10.1002/jcc.540040303 · Cited by 7,242 · see citing works
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Service, I., & Shirazi, M. A. (2005) · Proceedings of the Water Environment Federation · doi:10.2175/193864705783867675 · Cited by 6,674 · see citing works
Woon, D. E., & Dunning, T. H. (1995) · The Journal of Chemical Physics · doi:10.1063/1.470645 · Cited by 2,950 · see citing works
Organocatalytic Ring-Opening Polymerization
Kamber, N. E., Jeong, W., Waymouth, R. M., Pratt, R. C., Lohmeijer, B. G. G., & Hedrick, J. L. (2007) · Chemical Reviews · doi:10.1021/cr068415b · Cited by 1,489 · see citing works
Self-citationUse of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation
Ribeiro, R. F., Marenich, A. V., Cramer, C. J., & Truhlar, D. G. (2011) · The Journal of Physical Chemistry B · doi:10.1021/jp205508z · Cited by 1,091 · see citing works
Organocatalysis: Opportunities and Challenges for Polymer Synthesis
Kiesewetter, M. K., Shin, E. J., Hedrick, J. L., & Waymouth, R. M. (2010) · Macromolecules · doi:10.1021/ma9025948 · Cited by 907 · see citing works
Self-citationGuanidine and Amidine Organocatalysts for Ring-Opening Polymerization of Cyclic Esters
Lohmeijer, B. G. G., Pratt, R. C., Leibfarth, F. A., Logan, J. W., Long, D. A., Dove, A. P., Nederberg, F., Choi, J., Wade, C. G., Waymouth, R. M., et al. (2006) · Macromolecules · doi:10.1021/ma0619381 · Cited by 815 · see citing works
Self-citationChemical Recycling of Poly(ethylene terephthalate)
Paszun, D., & Spychaj, T. (1997) · Industrial & Engineering Chemistry Research · doi:10.1021/ie960563c · Cited by 661 · see citing works
Pratt, R. C., Lohmeijer, B. G. G., Long, D. A., Waymouth, R. M., & Hedrick, J. L. (2006) · Journal of the American Chemical Society · doi:10.1021/ja060662+ · Cited by 543 · see citing works
Self-citationThiourea-Based Bifunctional Organocatalysis: Supramolecular Recognition for Living Polymerization
Dove, A. P., Pratt, R. C., Lohmeijer, B. G. G., Waymouth, R. M., & Hedrick, J. L. (2005) · Journal of the American Chemical Society · doi:10.1021/ja0543346 · Cited by 439 · see citing works
Self-citationOrganocatalytic Ring Opening Polymerization of Trimethylene Carbonate
Nederberg, F., Lohmeijer, B. G. G., Leibfarth, F. A., Pratt, R. C., Choi, J., Dove, A. P., Waymouth, R. M., & Hedrick, J. L. (2006) · Biomacromolecules · doi:10.1021/bm060795n · Cited by 346 · see citing works
Self-citationDepolymerization of poly(ethylene terephthalate) recycled from post‐consumer soft‐drink bottles
Baliga, S., & Wong, W. (1989) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1989.080270625 · Cited by 288 · see citing works
Chuma, A., Horn, H. W., Swope, W. C., Pratt, R. C., Zhang, L., Lohmeijer, B. G. G., Wade, C. G., Waymouth, R. M., Hedrick, J. L., & Rice, J. E. (2008) · Journal of the American Chemical Society · doi:10.1021/ja0764411 · Cited by 282 · see citing works
Self-citationOrganocatalytic depolymerization of poly(ethylene terephthalate)
Fukushima, K., Coulembier, O., Lecuyer, J. M., Al‐Megren, H. A., Alabdulrahman, A. M., Alsewailem, F. D., McNeil, M., Dúbois, P., Waymouth, R. M., Horn, H. W., et al. (2011) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24551 · Cited by 250 · see citing works
Self-citationPratt, R. C., Nederberg, F., Waymouth, R. M., & Hedrick, J. L. (2007) · Chemical Communications · doi:10.1039/b713925j · Cited by 243 · see citing works
Self-citationThe Mechanism of TBD-Catalyzed Ring-Opening Polymerization of Cyclic Esters
Simón, L., & Goodman, J. M. (2007) · The Journal of Organic Chemistry · doi:10.1021/jo702088c · Cited by 230 · see citing works
Cyclic Guanidine Organic Catalysts: What Is Magic About Triazabicyclodecene?
Kiesewetter, M. K., Scholten, M. D., Kirn, N., Weber, R. L., Hedrick, J. L., & Waymouth, R. M. (2009) · The Journal of Organic Chemistry · doi:10.1021/jo902369g · Cited by 213 · see citing works
Self-citationRecycling of waste PET into useful textile auxiliaries
Shukla, S. R., Harad, A. M., & Jawale, L. S. (2008) · Waste Management · doi:10.1016/j.wasman.2006.11.002 · Cited by 141 · see citing works
Vaidya, U. R., & Nadkarni, V. M. (1987) · Industrial & Engineering Chemistry Research · doi:10.1021/ie00062a003 · Cited by 133 · see citing works
Chen, C., Chen, C., Lo, Y., Mao, C.-F., & Liao, W.-T. (2001) · Journal of Applied Polymer Science · doi:10.1002/app.1174 · Cited by 128 · see citing works
Coady, D. J., Fukushima, K., Horn, H. W., Rice, J. E., & Hedrick, J. L. (2011) · Chemical Communications · doi:10.1039/c0cc03987j · Cited by 127 · see citing works
Self-citationComparative reactivity of glycols in PET glycolysis
Pardal, F., & Tersac, G. (2006) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2006.05.016 · Cited by 105 · see citing works
Recyclability of PET from virgin resin
Mancini, S. D., & Zanín, M. (1999) · Materials Research · doi:10.1590/s1516-14391999000100006 · Cited by 57 · see citing works
Kamber, N. E., Tsujii, Y., Keets, K., Waymouth, R. M., Pratt, R. C., Nyce, G. W., & Hedrick, J. L. (2010) · Journal of Chemical Education · doi:10.1021/ed800152c · Cited by 54 · see citing works
Self-citationPreparation of oligoester diols by alcoholytic destruction of poly(ethylene terephthalate)
Halacheva, N., & Novakov, P. (1995) · Polymer · doi:10.1016/0032-3861(95)93119-7 · Cited by 54 · see citing works
Farahat, M. S., & Nikles, D. E. (2001) · Macromolecular Materials and Engineering · doi:10.1002/1439-2054(20011101)286:11 · Cited by 37 · see citing works
Buis, N., French, S., Ruggiero, G. D., Stengel, B. F., Tulloch, A. A. D., & Williams, I. H. (2006) · Journal of Chemical Theory and Computation · doi:10.1021/ct600265c · Cited by 23 · see citing works
Jin, L., Wu, Y., Kim, C. K., et al. (2009) · Journal of Molecular Structure THEOCHEM · doi:10.1016/j.theochem.2009.12.012 · Cited by 15 · see citing works
Anderson, C. C. (1968) · Industrial & Engineering Chemistry · doi:10.1021/ie50704a013 · Cited by 6 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Catalysis as an Enabling Science for Sustainable Polymers
Zhang, X., Fevre, M., Jones, G. O., & Waymouth, R. M. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00329 · Cited by 936 · see citing works
Self-citationKrall, E. M., Klein, T. W., Andersen, R. J., Nett, A. J., Glasgow, R. W., Reader, D. S., Dauphinais, B. C., Mc Ilrath, S. P., Fischer, A. A., Carney, M. J., et al. (2014) · Chemical Communications · doi:10.1039/c4cc00541d · Cited by 224 · see citing works
Venkataraman, S., Ng, V. W. L., Coady, D. J., Horn, H. W., Jones, G. O., Fung, T. S., Sardon, H., Waymouth, R. M., Hedrick, J. L., & Yang, Y. Y. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b06355 · Cited by 97 · see citing works
Self-citationSanchez-Sanchez, A., Rivilla, I., Agirre, M., Basterretxea, A., Etxeberria, A., Veloso, A., Sardon, H., Mecerreyes, D., & Cossío, F. P. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b13080 · Cited by 93 · see citing works
- Authors
- Horn, H. W., Jones, G. O., Wei, D. S., Fukushima, K., Lecuyer, J. M., Coady, D. J., Hedrick, J. L., & Rice, J. E.
- Affiliations
- IBM Research - Almaden (US)
- University of Denver (US)
- Yamagata University (JP)
- Corresponding author
- Horn, Hans W.
- Venue
- The Journal of Physical Chemistry A
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-12-14
- Volume
- 116
- Issue
- 51
- Pages
- 12389-12398
- ISSN
- 1089-5639 (ISSN-L)
- 1520-5215
- OpenAlex
- W2017346643
- Cited by
- 97
- References
- 42
- Citations by year
- 2026: 9 · 2025: 6 · 2024: 8 · 2023: 9 · 2022: 6 · 2021: 9 · 2020: 12 · 2019: 8 · 2018: 8 · 2017: 4 · 2016: 3 · 2015: 4 · 2014: 7 · 2013: 2 · 2012: 1
- FWCI
- 2.06
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry A (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Synthesis and Reactions
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- organocatalysis, amidation, transesterification, aromatic esters, ethylene glycol, ethylenediamine, monoethanolamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, reaction mechanism, nucleophilic attack, cocatalyst effect, catalyst activation
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review