Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors
To circumvent the supervision of law, illicit manufacturers turn to produce drug related precursors. Among them, tert-butoxycarbonyl (t-Boc) substituted drug precursors are the most common type recently. The t-Boc moiety is a common protecting group in organic synthesis. It can prevent a chemical re...
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Editorial Board of Journal of Chinese Mass Spectrometry Society
2025-01-01
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| Series: | Zhipu Xuebao |
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| author | Cui-mei LIU Xue-yan LIU Zhen-dong HUA Hao TANG Yu DU Wei JIA |
| author_facet | Cui-mei LIU Xue-yan LIU Zhen-dong HUA Hao TANG Yu DU Wei JIA |
| author_sort | Cui-mei LIU |
| collection | DOAJ |
| description | To circumvent the supervision of law, illicit manufacturers turn to produce drug related precursors. Among them, tert-butoxycarbonyl (t-Boc) substituted drug precursors are the most common type recently. The t-Boc moiety is a common protecting group in organic synthesis. It can prevent a chemical reaction at one specific group in a molecule, while other functional groups are transformed, and then can be easily chemically removed through a simple carbamate hydrolysis. Due to the lack of control, the readily availability from chemical suppliers, and easy conversion to an immediate, these t-Boc substituted precursors are attractive to illicit manufacturers. The identification of these newly emerging precursors has posed great challenges to forensic science laboratories worldwide. In this study, four types of t-Boc substituted drug precursors, including tert-butyl 4-(phenylamino)piperidine-1-carboxylate (t-Boc-4-AP), tert-butyl 4-((4-fluorophenyl)amino)piperidine-1-carboxylate (t-Boc-4F-AP), tert-butyl 4-((4-bromophenyl)amino)piperidine-1-carboxylate (t-Boc-4Br-AP), and tert-butyl (1-(2-chlorophenyl)-2-oxocyclohexyl)carbamate (t-Boc-norketamine), were analyzed by using gas chromatography-mass spectrometry (GC-MS) and ultra-high performance liquid chromatography-quadrupole time of flight-mass spectrometry (UPLC-QTOF MS). After analyzing the characteristic fragment ions under electron impact (EI) mode and electrospray ionization collision-induced dissociation (ESI-CID) mode, the possible fragmentation pathways of t-Boc substituted drug precursors were deduced. The main product ions of t-Boc substituted drug precursors are tert butyl ion (C4H9+), and product ions of [M−C4H8]+, [M−C4H9O•]+, and [M−C5H8O2]+ under EI mode. Under ESI-CID mode, product ions are mainly formed by the loss of C4H8 and the further loss of CO2. The study of the fragmentation pathways of t-Boc substituted drug precursors in mass spectrometry benefits the structure elucidation of unknown compounds, and provides reference for forensic science laboratories to identify such substances. |
| format | Article |
| id | doaj-art-21aa33f08d58490bb2222a409876254e |
| institution | Kabale University |
| issn | 1004-2997 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Editorial Board of Journal of Chinese Mass Spectrometry Society |
| record_format | Article |
| series | Zhipu Xuebao |
| spelling | doaj-art-21aa33f08d58490bb2222a409876254e2025-01-22T02:33:54ZengEditorial Board of Journal of Chinese Mass Spectrometry SocietyZhipu Xuebao1004-29972025-01-01461404710.7538/zpxb.2024.00282024-028-b31Mass Fragmentation Characteristics of t-Boc Substituted Drug PrecursorsCui-mei LIU0Xue-yan LIU1Zhen-dong HUA2Hao TANG3Yu DU4Wei JIA5Key Laboratory of Drug Monitoring and Control, Drug Intelligence and Forensic Center, Ministry of Public Security, P.R.C., Beijing 100193, ChinaChina Pharmaceutical University, Nanjing 210009, ChinaKey Laboratory of Drug Monitoring and Control, Drug Intelligence and Forensic Center, Ministry of Public Security, P.R.C., Beijing 100193, ChinaKey Laboratory of Drug Monitoring and Control, Drug Intelligence and Forensic Center, Ministry of Public Security, P.R.C., Beijing 100193, ChinaChina Pharmaceutical University, Nanjing 210009, ChinaKey Laboratory of Drug Monitoring and Control, Drug Intelligence and Forensic Center, Ministry of Public Security, P.R.C., Beijing 100193, ChinaTo circumvent the supervision of law, illicit manufacturers turn to produce drug related precursors. Among them, tert-butoxycarbonyl (t-Boc) substituted drug precursors are the most common type recently. The t-Boc moiety is a common protecting group in organic synthesis. It can prevent a chemical reaction at one specific group in a molecule, while other functional groups are transformed, and then can be easily chemically removed through a simple carbamate hydrolysis. Due to the lack of control, the readily availability from chemical suppliers, and easy conversion to an immediate, these t-Boc substituted precursors are attractive to illicit manufacturers. The identification of these newly emerging precursors has posed great challenges to forensic science laboratories worldwide. In this study, four types of t-Boc substituted drug precursors, including tert-butyl 4-(phenylamino)piperidine-1-carboxylate (t-Boc-4-AP), tert-butyl 4-((4-fluorophenyl)amino)piperidine-1-carboxylate (t-Boc-4F-AP), tert-butyl 4-((4-bromophenyl)amino)piperidine-1-carboxylate (t-Boc-4Br-AP), and tert-butyl (1-(2-chlorophenyl)-2-oxocyclohexyl)carbamate (t-Boc-norketamine), were analyzed by using gas chromatography-mass spectrometry (GC-MS) and ultra-high performance liquid chromatography-quadrupole time of flight-mass spectrometry (UPLC-QTOF MS). After analyzing the characteristic fragment ions under electron impact (EI) mode and electrospray ionization collision-induced dissociation (ESI-CID) mode, the possible fragmentation pathways of t-Boc substituted drug precursors were deduced. The main product ions of t-Boc substituted drug precursors are tert butyl ion (C4H9+), and product ions of [M−C4H8]+, [M−C4H9O•]+, and [M−C5H8O2]+ under EI mode. Under ESI-CID mode, product ions are mainly formed by the loss of C4H8 and the further loss of CO2. The study of the fragmentation pathways of t-Boc substituted drug precursors in mass spectrometry benefits the structure elucidation of unknown compounds, and provides reference for forensic science laboratories to identify such substances.https://zpxb.xml-journal.net/article/doi/10.7538/zpxb.2024.0028gas chromatography-mass spectrometry (gc-ms)ultra-high performance liquid chromatography-quadrupole time of flight-mass spectrometry (uplc-qtof ms)drug precursortert-butoxycarbonyl (t-boc)fragmentation pathway |
| spellingShingle | Cui-mei LIU Xue-yan LIU Zhen-dong HUA Hao TANG Yu DU Wei JIA Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors Zhipu Xuebao gas chromatography-mass spectrometry (gc-ms) ultra-high performance liquid chromatography-quadrupole time of flight-mass spectrometry (uplc-qtof ms) drug precursor tert-butoxycarbonyl (t-boc) fragmentation pathway |
| title | Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors |
| title_full | Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors |
| title_fullStr | Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors |
| title_full_unstemmed | Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors |
| title_short | Mass Fragmentation Characteristics of t-Boc Substituted Drug Precursors |
| title_sort | mass fragmentation characteristics of t boc substituted drug precursors |
| topic | gas chromatography-mass spectrometry (gc-ms) ultra-high performance liquid chromatography-quadrupole time of flight-mass spectrometry (uplc-qtof ms) drug precursor tert-butoxycarbonyl (t-boc) fragmentation pathway |
| url | https://zpxb.xml-journal.net/article/doi/10.7538/zpxb.2024.0028 |
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