Why δ-Valerolactone Polymerizes and γ-Butyrolactone Does Not
Abstract
gamma-Butyrolactone, unlike delta-valerolactone, does not polymerize despite a strain energy of approximately 8 kcal mol-1 which could be relieved by opening the s-cis lactone ester bond to an s-trans ester bond in the polymer. To explain this anomaly, we have applied quantum mechanical methods to study the thermochemistry involved in the ring-opening reactions of gamma-butyrolactone and delta-valerolactone, the conformational preferences of model molecules that mimic their corresponding homopolyesters, and the variation of enthalpy associated to the polymerizability of such two cyclic lactones. The overall results indicate that the lack of polymerizability of gamma-butyrolactone should be attributed to the low strain of the ring, which shows much less geometric distortion in the ester group than delta-valerolactone, and the notable stability of the coiled conformations found in model compounds of poly-4-hydroxybutyrate.
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β-Propiolactone is nearly incapable of polymerization under typical conditions.
“Indeed, the former is nearly incapable of polymerization under typical conditions.”
From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [31]
Four-, six-, and seven-membered rings are favorable for ROP due to their large ring strains, while five-membered lactones such as γ-butyrolactone exhibit a less favorable enthalpy of polymerization and are usually considered nonpolymerizable.
“Four-, six-, and seven-membered rings are favorable for ROP due to their large ring strains while five-membered lactones such as γ-butyrolactone (γ-BL) exhibits a less favorable enthalpy of polymerization and is usually considered as nonpolymerizable.277”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [277]
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
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
Note on an Approximation Treatment for Many-Electron Systems
MØLLER, C. K., & PLESSET, M. S. (1934) · Physical Review · doi:10.1103/physrev.46.618 · Cited by 14,602 · see citing works
Miertuš, S., Scrocco, E., & Tomasi, J. (1981) · Chemical Physics · doi:10.1016/0301-0104(81)85090-2 · Cited by 9,017 · see citing works
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
Frisch, M., Pople, J., & Binkley, J. (1984) · The Journal of Chemical Physics · doi:10.1063/1.447079 · Cited by 7,062 · see citing works
Encyclopedia of polymer science and engineering
Bawn, C. S. H. (1987) · Polymer · doi:10.1016/0032-3861(87)90274-6 · Cited by 4,223 · see citing works
A complete basis set model chemistry. VI. Use of density functional geometries and frequencies
Montgomery, J. A. J., Frisch, M. J., Ochterski, J. W., & Petersson, G. A. (1999) · The Journal of Chemical Physics · doi:10.1063/1.477924 · Cited by 2,731 · see citing works
Miertuš, S., & Tomasi, J. (1982) · Chemical Physics · doi:10.1016/0301-0104(82)85072-6 · Cited by 2,480 · see citing works
Essentials of Computational Chemistry: Theories and Models
Cramer, C. J. (2002) · Cited by 2,435 · see citing works
A complete basis set model chemistry. VII. Use of the minimum population localization method
Montgomery, J. A. J., Frisch, M. J., Ochterski, J. W., & Petersson, G. A. (2000) · The Journal of Chemical Physics · doi:10.1063/1.481224 · Cited by 1,932 · see citing works
Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications
Albertsson, A.-C., & Varma, I. K. (2003) · Biomacromolecules · doi:10.1021/bm034247a · Cited by 1,582 · see citing works
Medical applications of poly-4-hydroxybutyrate: A strong flexible absorbable biomaterial
Martin, D. P., & Williams, S. F. (2003) · Biochemical Engineering Journal · doi:10.1016/s1369-703x(03)00040-8 · Cited by 510 · see citing works
Coulembier, O., Degée, P., Hedrick, J. L., & Dúbois, P. (2006) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2006.08.004 · Cited by 374 · see citing works
Carothers, W. H. (1931) · Chemical Reviews · doi:10.1021/cr60031a001 · Cited by 352 · see citing works
Die konfiguration der carbonestergruppe und die sondereigenschaften der lactone
Huisgen, R., & Ott, H. (1959) · Tetrahedron · doi:10.1016/0040-4020(59)80006-5 · Cited by 174 · see citing works
Conformational Analysis. IX. The Gem-Dimethyl Effect1,2
Allinger, N. L., & Zalkow, V. B. (1960) · The Journal of Organic Chemistry · doi:10.1021/jo01075a006 · Cited by 153 · see citing works
Lipase-Catalyzed Ring-Opening Polymerization of Lactones: A Novel Route to Poly(hydroxyalkanoate)s
Nobes, G. A. R., Kazlauskas, R. J., & MARCHESSAULT, R. H. (1996) · Macromolecules · doi:10.1021/ma951774g · Cited by 152 · see citing works
Polymerization of Cyclic Esters, Urethans, Ureas and Imides
Hall, H. K., & Schneider, A. K. (1958) · Journal of the American Chemical Society · doi:10.1021/ja01556a060 · Cited by 149 · see citing works
Self-citationWiberg, K. B., & Waldron, R. F. (1991) · Journal of the American Chemical Society · doi:10.1021/ja00020a036 · Cited by 144 · see citing works
Blom, C. E., & Günthard, H. H. (1981) · Chemical Physics Letters · doi:10.1016/0009-2614(81)80342-9 · Cited by 130 · see citing works
Chemosynthesis of bioresorbable poly(γ-butyrolactone) by ring-opening polymerisation: a review
Moore, T., Adhikari, R., & Gunatillake, P. A. (2004) · Biomaterials · doi:10.1016/j.biomaterials.2004.10.002 · Cited by 129 · see citing works
Bach, R. D., & Dmitrenko, O. (2006) · Journal of the American Chemical Society · doi:10.1021/ja055086g · Cited by 118 · see citing works
Ring-Opening Polymerization and Copolymerization of Lactones by Samarium(II) Aryloxide Complexes
Nishiura, M., Hou, Z., Koizumi, T., Imamoto, T., & Wakatsuki, Y. (1999) · Macromolecules · doi:10.1021/ma990101l · Cited by 109 · see citing works
Arnett, E. M., & Harrelson, J. A. (1987) · Journal of the American Chemical Society · doi:10.1021/ja00237a028 · Cited by 101 · see citing works
Ring strain and polymerizability of cyclic esters
Saiyasombat, W., Molloy, R., Nicholson, T. M., Johnson, A. F., Ward, I. M., & Poshyachinda, S. (1998) · Polymer · doi:10.1016/s0032-3861(97)10370-6 · Cited by 93 · see citing works
Byun, K., Mo, Y., & Gao, J. (2001) · Journal of the American Chemical Society · doi:10.1021/ja001369r · Cited by 89 · see citing works
Wiberg, K. B., & Wong, M. W. (1993) · Journal of the American Chemical Society · doi:10.1021/ja00056a036 · Cited by 81 · see citing works
Duda, A., Penczek, S., Dúbois, P., Mecerreyes, D., & Jérôme, R. (1996) · Macromolecular Chemistry and Physics · doi:10.1002/macp.1996.021970408 · Cited by 77 · see citing works
Theoretical elucidation of the origin of the anomalously high acidity of Meldrum's acid
Wang, X., & Houk, K. N. (1988) · Journal of the American Chemical Society · doi:10.1021/ja00214a032 · Cited by 71 · see citing works
Self-citationHochdruckreaktionen. II. Die polymerisation von γ‐Butyrolacton und δ‐Valerolactam bei hohen drücken
KORTE, F., & Glet, W. (1966) · Journal of Polymer Science Part B Polymer Letters · doi:10.1002/pol.1966.110041004 · Cited by 69 · see citing works
Mas, C., Ramis, X., Salla, J. M., et al. (2003) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.10826 · Cited by 64 · see citing works
Synthesis and biodegradability of novel copolyesters containg γ-butyrolactone units
Nakayama, A., Kawasaki, N., Aiba, S., Maeda, Y., Arvanitoyannis, I., & Yamamoto, N. (1998) · Polymer · doi:10.1016/s0032-3861(97)00401-1 · Cited by 57 · see citing works
Enthalpies of combustion of γ-butyrolactone, γ-valerolactone, and δ-valerolactone
Leitão, M. L. P., Pilcher, G., Yang, M., Brown, J. M., & Conn, A. D. (1990) · The Journal of Chemical Thermodynamics · doi:10.1016/0021-9614(90)90176-q · Cited by 53 · see citing works
Conformational analysis of succinamide analogs
Alemán, C., Navarro, E., & Puiggalı́, J. (1995) · The Journal of Organic Chemistry · doi:10.1021/jo00124a028 · Cited by 43 · see citing works
Self-citationCrystal Structure and Enzymatic Degradation of Poly(4-hydroxybutyrate)
Su, F., Iwata, T., Tanaka, F., et al. (2003) · Macromolecules · doi:10.1021/ma034546s · Cited by 42 · see citing works
Folding of Methylene Groups in Linear Glutaramide Analogs
Navarro, E., Alemán, C., & Puiggalı́, J. (1995) · Journal of the American Chemical Society · doi:10.1021/ja00133a002 · Cited by 40 · see citing works
Self-citationDirect copolymerization of L ‐lactic acid with γ‐butyrolactone in the absence of catalysts
Fukuzaki, H., Aiba, Y., Yoshida, M., et al. (1989) · Die Makromolekulare Chemie · doi:10.1002/macp.1989.021900707 · Cited by 38 · see citing works
Incorporation of diacids into the polyglycine II structure: Model studies
Navarro, E., Tereshko, V., Subirana, J. A., et al. (1995) · Biopolymers · doi:10.1002/bip.360360605 · Cited by 38 · see citing works
Alemán, C. (1994) · Biopolymers · doi:10.1002/bip.360340704 · Cited by 35 · see citing works
Self-citationThe Mechanism of the Thermal Decomposition Reaction of Azines
Zimmerman, H. E., & SOMASEKHARA, S. (1960) · Journal of the American Chemical Society · doi:10.1021/ja01507a024 · Cited by 35 · see citing works
Conformational Analysis of N,N,N‘,N‘-Tetramethylsuccinamide: The Role of C−H···O Hydrogen Bonds
Vargas, R., Garza, J., Dixon, D. A., et al. (2000) · The Journal of Physical Chemistry A · doi:10.1021/jp000030o · Cited by 31 · see citing works
Quantification of Solvent Effects on the Acidities of Z and E Esters from Fluid Simulations
Evanseck, J. D., Houk, K. N., Briggs, J. M., et al. (1994) · Journal of the American Chemical Society · doi:10.1021/ja00102a032 · Cited by 29 · see citing works
Self-citationThermal degradation behavior of poly(4-hydroxybutyric acid)
Kim, K. J., Doi, Y., Abe, H., & Martin, D. P. (2006) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2006.04.011 · Cited by 22 · see citing works
Ito, K., Inoue, T., & Yamashita, Y. (1970) · Die Makromolekulare Chemie · doi:10.1002/macp.1970.021390111 · Cited by 21 · see citing works
Alemán, C., Navarro, E., & Puiggalı́, J. (1996) · The Journal of Physical Chemistry · doi:10.1021/jp961245u · Cited by 21 · see citing works
Self-citationCasanovas, J., & Alemán, C. (1994) · Journal of Computer-Aided Molecular Design · doi:10.1007/bf00125378 · Cited by 19 · see citing works
Self-citationCopolymerization of γ‐butyrolactone and β‐butyrolactone
Lee, C. W., Urakawa, R., & Kimura, Y. (1997) · Macromolecular Chemistry and Physics · doi:10.1002/macp.1997.021980414 · Cited by 17 · see citing works
Systematic Evaluation of the Conformational Properties of Aliphatic ω-Hydroxy Acids
Alemán, C., Casanovas, J., Zanuy, D., et al. (2005) · The Journal of Organic Chemistry · doi:10.1021/jo0478407 · Cited by 15 · see citing works
Self-citationTowards the Understanding of the Folding of Methylene Units in the Glutamine Residue
Alemán, C., Vega, M. C., Navarro, E., & Puiggalı́, J. (1996) · Journal of Peptide Science · doi:10.1002/psc.75 · Cited by 7 · see citing works
Self-citationSystematic Evaluation of the Conformational Properties of Aliphatic ω-Methoxy Methyl Esters
Alemán, C., Casanovas, J., & Hall, H. K. (2005) · The Journal of Organic Chemistry · doi:10.1021/jo051167j · Cited by 7 · see citing works
Self-citationNotes - The Dimethylamine-1,3,5-Tritrobenzene Complex in Dioxane
Labes, M. M., & Ross, S. D. (1956) · The Journal of Organic Chemistry · doi:10.1021/jo01115a617 · Cited by 6 · see citing works
Rajendran, G. P., Mahadevan, V., & Srinivasan, M. (1982) · European Polymer Journal · doi:10.1016/0014-3057(82)90150-1 · Cited by 4 · see citing works
Zezin, A. B., & Osada, Y. (1999) · Macromolecules · Cited by 1 · see citing works
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Hong, M., & Chen, E. Y.-X. (2017) · Green Chemistry · doi:10.1039/c7gc01496a · Cited by 876 · see citing works
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Zhu, J.-B., Watson, E. M., Tang, J., & Chen, E. Y.-X. (2018) · Science · doi:10.1126/science.aar5498 · Cited by 709 · see citing works
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- Authors
- Houk, K. N., Jabbari, A., Hall, H. K., & Alemán, C.
- Affiliations
- University of Arizona (US)
- Venue
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2008-03-07
- Volume
- 73
- Issue
- 7
- Pages
- 2674-2678
- ISSN
- 0022-3263 (ISSN-L)
- 1520-6904
- OpenAlex
- W2333397163
- Cited by
- 176
- References
- 55
- Citations by year
- 2026: 3 · 2025: 6 · 2024: 14 · 2023: 12 · 2022: 15 · 2021: 15 · 2020: 12 · 2019: 13 · 2018: 17 · 2017: 12 · 2016: 12 · 2015: 7 · 2014: 12 · 2013: 6 · 2012: 6
- FWCI
- 2.01
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Organic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Keywords
- δ-valerolactone, gamma-butyrolactone, ring-opening polymerization, cyclic lactones, strain energy, conformational analysis, poly-4-hydroxybutyrate, polymerizability
- MeSH terms
- Esters, Models, Chemical, Pyrones, Quantum Theory, Thermodynamics, 4-Butyrolactone, Molecular Structure
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