4,4-Dichloro-1,3-dithietane-2-one

The title compound, 4,4-dichloro-1,3-dithietane-2-one, was encountered when opening a commercial capped amber bottle labeled “thiophosgene” that had been stored in a cold room (4 °C) for decades without any special precautions. Treating it as an unknown, the structure was established by single cryst...

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Main Authors: Tracy R. Thompson, William W. Brennessel, Erik S. Goebel, Matthew J. Turcotte, George Barany
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molbank
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Online Access:https://www.mdpi.com/1422-8599/2025/2/M2021
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author Tracy R. Thompson
William W. Brennessel
Erik S. Goebel
Matthew J. Turcotte
George Barany
author_facet Tracy R. Thompson
William W. Brennessel
Erik S. Goebel
Matthew J. Turcotte
George Barany
author_sort Tracy R. Thompson
collection DOAJ
description The title compound, 4,4-dichloro-1,3-dithietane-2-one, was encountered when opening a commercial capped amber bottle labeled “thiophosgene” that had been stored in a cold room (4 °C) for decades without any special precautions. Treating it as an unknown, the structure was established by single crystal X-ray analysis, and confirmed by <sup>13</sup>C NMR, FTIR, melting behavior, and elemental analysis; its behavior under several mass spectrometric conditions was also examined. The dithietane appears to be a spontaneously formed cyclodimer of thiophosgene in which exactly one (not zero, not both) of the dichloromethylene moieties has been hydrolyzed to a carbonyl function. The relative long-term stability of the hydrolyzed dimer, along with a pathway back to thiophosgene, suggests that it might serve as a storage vehicle for toxic thiophosgene. Furthermore, as noted elsewhere, the title compound reacts with nucleophiles under mild aqueous conditions, suggesting that it may be a useful probe in chemical biology.
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publisher MDPI AG
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spelling doaj-art-40f19d9ecc234eee882b52cbe0f490cb2025-08-20T02:21:08ZengMDPI AGMolbank1422-85992025-06-0120252M202110.3390/M20214,4-Dichloro-1,3-dithietane-2-oneTracy R. Thompson0William W. Brennessel1Erik S. Goebel2Matthew J. Turcotte3George Barany4Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USADepartment of Chemistry, University of Rochester, Rochester, NY 14627, USADepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USADepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USADepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USAThe title compound, 4,4-dichloro-1,3-dithietane-2-one, was encountered when opening a commercial capped amber bottle labeled “thiophosgene” that had been stored in a cold room (4 °C) for decades without any special precautions. Treating it as an unknown, the structure was established by single crystal X-ray analysis, and confirmed by <sup>13</sup>C NMR, FTIR, melting behavior, and elemental analysis; its behavior under several mass spectrometric conditions was also examined. The dithietane appears to be a spontaneously formed cyclodimer of thiophosgene in which exactly one (not zero, not both) of the dichloromethylene moieties has been hydrolyzed to a carbonyl function. The relative long-term stability of the hydrolyzed dimer, along with a pathway back to thiophosgene, suggests that it might serve as a storage vehicle for toxic thiophosgene. Furthermore, as noted elsewhere, the title compound reacts with nucleophiles under mild aqueous conditions, suggesting that it may be a useful probe in chemical biology.https://www.mdpi.com/1422-8599/2025/2/M20214,4-dichloro-1,3-dithietane-2-onethiophosgenelong-term storage of thiophosgenethiophosgene dimerpartially hydrolyzed thiophosgene dimerX-ray structural analysis
spellingShingle Tracy R. Thompson
William W. Brennessel
Erik S. Goebel
Matthew J. Turcotte
George Barany
4,4-Dichloro-1,3-dithietane-2-one
Molbank
4,4-dichloro-1,3-dithietane-2-one
thiophosgene
long-term storage of thiophosgene
thiophosgene dimer
partially hydrolyzed thiophosgene dimer
X-ray structural analysis
title 4,4-Dichloro-1,3-dithietane-2-one
title_full 4,4-Dichloro-1,3-dithietane-2-one
title_fullStr 4,4-Dichloro-1,3-dithietane-2-one
title_full_unstemmed 4,4-Dichloro-1,3-dithietane-2-one
title_short 4,4-Dichloro-1,3-dithietane-2-one
title_sort 4 4 dichloro 1 3 dithietane 2 one
topic 4,4-dichloro-1,3-dithietane-2-one
thiophosgene
long-term storage of thiophosgene
thiophosgene dimer
partially hydrolyzed thiophosgene dimer
X-ray structural analysis
url https://www.mdpi.com/1422-8599/2025/2/M2021
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