Cited by 97Chemical Reaction MechanismsChemical Synthesis and Reactionsbiodegradable polymer synthesis and properties

Mechanisms of Organocatalytic Amidation and Trans-Esterification of Aromatic Esters As a Model for the Depolymerization of Poly(ethylene) Terephthalate

Horn, Hans W., Jones, Gavin O., Wei, DiDi S., Fukushima, Kazuki, Lecuyer, Julien M., Coady, Daniel J., Hedrick, James L., Rice, Julia E.·2012·The Journal of Physical Chemistry A

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

Crossref · 10.1021/jp304212y

Cites

42 of 42 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

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

Flagged first, then by citations

Cited by

Sorted by citations

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
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