A study into the stability of 3,6-dihydro-2H-thiopyran rings: Key linkages in the RAFT hetero-diels-alder click concept

Sinnwell, S., Synatschke, C. V., Junkers, T., Stenzel, M. H., & Barner-Kowollik, C. (2008) A study into the stability of 3,6-dihydro-2H-thiopyran rings: Key linkages in the RAFT hetero-diels-alder click concept. Macromolecules, 41(21).

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Abstract

The combination of RAFT chemistry and hetero-Diels-Alder (HDA) cycloaddition provides a convenient conjugation tool for the construction of macromolecular architectures. The actual conjugation linkage, which is formed in the RAFT HDA approach, consists of a 3,6-dihydro-2H-thiopyran ring. Herein, a careful study into the stability of polymer linked by 3,6-dihydro-2H-thiopyran rings under different thermal and pH conditions is performed. As polymeric model system, a 3,6-dihydro-2H-thiopyran functionalized poly(ethylene glycol) (PEG) obtained after a HDA cycloaddition between a diene functionalized PEG and 1-phenylethyl (diethoxyphosphoryl)dithioformate or 1-phenylethyl pyridin-2-yldithioformate is used. Electrospray ionization mass spectrometry (ESI-MS) is employed to map the generated products. The stability tests under thermal conditions showed for the diethoxyphosphoryl derivative the preservation of the polymer end-groups after 24 h at temperatures up to 80°C. At higher temperatures degradation reactions of the 3,6-dihydro-2H-thiopyran ring including the retro HDA reaction occurred. A complete fragmentation was observed after 24 h at 160°C. The pyridinyl derivative was found to be slightly more temperature stable since its structure was unaffected at conditions up to 24 h at 120°C and full cleavage was only observed after 24 h at 180°C. In this case the fragmentation mechanism occurred exclusively via the retro HDA reaction and the resulting diene functionalized polymer was the only detected product species. Both conjugates showed an excellent stability toward hydrolysis in aqueous media under strong acidic (0.1 and 1 M HCL) and strong basic (0.1 and 1 M NaOH) conditions. © 2008 American Chemical Society.

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ID Code: 99196
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :41
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Stenzel, M. H.; Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email: m.stenzel@unsw.edu.au
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Keywords: ABS resins, Acids, Cycloaddition, Directive antennas, Electrospray ionization, Ethylene, Ethylene glycol, Glycols, High performance liquid chromatography, Macromolecules, Mass spectrometry, Polyethylene glycols, Polyethylene oxides, Polymers, System stability, Aqueous medias, Degradation reactions, Electrospray ionization mass spectrometries, Fragmentation mechanisms, Functionalized, Functionalized polymers, Higher temperatures, Macromolecular architectures, Model systems, PH conditions, Poly(ethylene glycol), Stability tests, Temperature stables, Functional polymers
DOI: 10.1021/ma8013959
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 10 Oct 2016 05:02

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