Zitieren Sie bitte immer diesen URN: urn:nbn:de:kobv:b43-393232
‘‘Click” analytics for ‘‘click” chemistry – A simple method for calibration–free evaluation of online NMR spectra
- Driven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of 1H spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectralDriven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of 1H spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibrationfree approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h-1 at 25 °C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance.…


| Autor*innen: | Aleksandra Michalik-Onichimowska, Simon KernORCiD, Jens RiedelORCiD, Ulrich PanneORCiD, R. King, Michael MaiwaldORCiD |
|---|---|
| Dokumenttyp: | Zeitschriftenartikel |
| Veröffentlichungsform: | Verlagsliteratur |
| Sprache: | Englisch |
| Titel des übergeordneten Werkes (Englisch): | Journal of Magnetic Resonance |
| Jahr der Erstveröffentlichung: | 2017 |
| Veröffentlichende Institution: | Bundesanstalt für Materialforschung und -prüfung (BAM) |
| Verlag: | Elsevier Inc. |
| Verlagsort: | Oxford |
| Jahrgang/Band: | 277 |
| Erste Seite: | 154 |
| Letzte Seite: | 161 |
| DDC-Klassifikation: | Naturwissenschaften und Mathematik / Chemie / Analytische Chemie |
| Freie Schlagwörter: | Automated Data Evaluation; Click Chemistry; Online NMR Spectroscopy; Process Analytical Technology; Reaction Monitoring; Thiol-ene click chemistry |
| DOI: | 10.1016/j.jmr.2017.02.018 |
| URN: | urn:nbn:de:kobv:b43-393232 |
| URL: | http://www.sciencedirect.com/science/article/pii/S1090780717300575 |
| Verfügbarkeit des Dokuments: | Datei für die Öffentlichkeit verfügbar ("Open Access") |
| Lizenz (Deutsch): | Creative Commons - CC BY-NC-ND - Namensnennung - Nicht kommerziell - Keine Bearbeitungen 4.0 International |
| Datum der Freischaltung: | 13.03.2017 |
| Referierte Publikation: | Ja |
| Datum der Eintragung als referierte Publikation: | 18.05.2017 |
| Schriftenreihen ohne Nummerierung: | Wissenschaftliche Artikel der BAM |


