Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy
A large variety of 1,2,3-thiadiazoles and 1,2,3-triazoles are used extensively in modern pure and applied organic chemistry as important structural blocks of numerous valuable products. Creation of new methods of synthesis of these isomeric compounds requires the development of reliable analytical t...
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MDPI AG
2023-01-01
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| Online Access: | https://www.mdpi.com/1420-3049/28/3/977 |
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| author | Dmitrii M. Mazur Elettra L. Piacentino Giel Berden Jos. Oomens Victor Ryzhov Vasiliy A. Bakulev Albert T. Lebedev |
| author_facet | Dmitrii M. Mazur Elettra L. Piacentino Giel Berden Jos. Oomens Victor Ryzhov Vasiliy A. Bakulev Albert T. Lebedev |
| author_sort | Dmitrii M. Mazur |
| collection | DOAJ |
| description | A large variety of 1,2,3-thiadiazoles and 1,2,3-triazoles are used extensively in modern pure and applied organic chemistry as important structural blocks of numerous valuable products. Creation of new methods of synthesis of these isomeric compounds requires the development of reliable analytical tools to reveal the structural characteristics of these novel compounds, which are able to distinguish between isomers. Mass spectrometry (MS) is a clear choice for this task due to its selectivity, sensitivity, informational capacity, and reliability. Here, the application of electrospray ionization (ESI) with ion detection in positive and negative modes was demonstrated to be useful in structural studies. Additionally, interconversion of isomeric 4,5-functionalized 1,2,3-triazoles and 1,2,3-thiadiazoles was demonstrated. Application of accurate mass measurements and tandem mass spectrometry in MS2 and MS3 modes indicated the occurrence of gas-phase rearrangement of 1,2,3-triazoles into 1,2,3-thiadiazoles under (+)ESI-MS/MS conditions, independent of the nature of substituents, in line with the reaction in the condensed phase. Infrared multiple photon dissociation (IRMPD) spectroscopy enabled the establishment of structures of some of the most crucial common fragment ions, including [M+H-N<sub>2</sub>]<sup>+</sup> and [M+H-N<sub>2</sub>-RSO<sub>2</sub>]<sup>+</sup> species. The (−)ESI-MS/MS experiments were significantly more informative for the sulfonyl alkyl derivatives compared to the sulfonyl aryl ones. However, there was insufficient evidence to confirm the solution-phase transformation of 1,2,3-thiadiazoles into the corresponding 1,2,3-triazoles. |
| first_indexed | 2024-03-11T09:34:09Z |
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| language | English |
| last_indexed | 2024-03-11T09:34:09Z |
| publishDate | 2023-01-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-33b6206345f8451087b907ebbe2705f42023-11-16T17:25:49ZengMDPI AGMolecules1420-30492023-01-0128397710.3390/molecules28030977Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion SpectroscopyDmitrii M. Mazur0Elettra L. Piacentino1Giel Berden2Jos. Oomens3Victor Ryzhov4Vasiliy A. Bakulev5Albert T. Lebedev6Organic Chemistry Department, Lomonosov Moscow State University, 119992 Moscow, RussiaDepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USAFELIX Laboratory, Institute for Molecules and Materials, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The NetherlandsFELIX Laboratory, Institute for Molecules and Materials, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The NetherlandsDepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USATechnology of Organic Synthesis Department, Ural Federal University, 620002 Yekaterinburg, RussiaOrganic Chemistry Department, Lomonosov Moscow State University, 119992 Moscow, RussiaA large variety of 1,2,3-thiadiazoles and 1,2,3-triazoles are used extensively in modern pure and applied organic chemistry as important structural blocks of numerous valuable products. Creation of new methods of synthesis of these isomeric compounds requires the development of reliable analytical tools to reveal the structural characteristics of these novel compounds, which are able to distinguish between isomers. Mass spectrometry (MS) is a clear choice for this task due to its selectivity, sensitivity, informational capacity, and reliability. Here, the application of electrospray ionization (ESI) with ion detection in positive and negative modes was demonstrated to be useful in structural studies. Additionally, interconversion of isomeric 4,5-functionalized 1,2,3-triazoles and 1,2,3-thiadiazoles was demonstrated. Application of accurate mass measurements and tandem mass spectrometry in MS2 and MS3 modes indicated the occurrence of gas-phase rearrangement of 1,2,3-triazoles into 1,2,3-thiadiazoles under (+)ESI-MS/MS conditions, independent of the nature of substituents, in line with the reaction in the condensed phase. Infrared multiple photon dissociation (IRMPD) spectroscopy enabled the establishment of structures of some of the most crucial common fragment ions, including [M+H-N<sub>2</sub>]<sup>+</sup> and [M+H-N<sub>2</sub>-RSO<sub>2</sub>]<sup>+</sup> species. The (−)ESI-MS/MS experiments were significantly more informative for the sulfonyl alkyl derivatives compared to the sulfonyl aryl ones. However, there was insufficient evidence to confirm the solution-phase transformation of 1,2,3-thiadiazoles into the corresponding 1,2,3-triazoles.https://www.mdpi.com/1420-3049/28/3/977mass spectrometryelectrospray ionization1,2,3-thiadiazoles1,2,3-triazolesisomer identification |
| spellingShingle | Dmitrii M. Mazur Elettra L. Piacentino Giel Berden Jos. Oomens Victor Ryzhov Vasiliy A. Bakulev Albert T. Lebedev Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy Molecules mass spectrometry electrospray ionization 1,2,3-thiadiazoles 1,2,3-triazoles isomer identification |
| title | Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy |
| title_full | Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy |
| title_fullStr | Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy |
| title_full_unstemmed | Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy |
| title_short | Differentiation between Isomeric 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles by ESI-HRMS and IR Ion Spectroscopy |
| title_sort | differentiation between isomeric 4 5 functionalized 1 2 3 thiadiazoles and 1 2 3 triazoles by esi hrms and ir ion spectroscopy |
| topic | mass spectrometry electrospray ionization 1,2,3-thiadiazoles 1,2,3-triazoles isomer identification |
| url | https://www.mdpi.com/1420-3049/28/3/977 |
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