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Sulfuryl chloride
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<h2 id="synthesis">Synthesis</h2> <p>SO2Cl2 is prepared by the reaction of <a href="/facts/Sulfur_dioxide/jDK1fIDs">sulfur dioxide</a> and <a href="/facts/Chlorine/y27UwYBM">chlorine</a> in the presence of a <a href="/facts/Catalyst/LPBS7TQC">catalyst</a>, such as <a href="/facts/Activated_carbon/YAbaXCcb">activated carbon</a>.<a class="footnote-ref" id="fnref:1" href="#fn:1"><sup>1</sup></a> </p> SO2 + Cl2 → SO2Cl2 <p>The product can be purified by <a href="/facts/Fractional_distillation/DdNf0k8I">fractional distillation</a>. </p> <h3>Legacy routes</h3> <p>Sulfuryl chloride was first prepared in 1838 by the French chemist <a href="/facts/Henri_Victor_Regnault/24Mz0XDX">Henri Victor Regnault</a>.<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p><p>Older routes include oxidation of thionyl chloride: </p> 5 SOCl2 + HgO → ClSSCl + HgCl2 + 3 SO2Cl2 2 SOCl2 + MnO2 → SO2 + MnCl2 + SO2Cl2 <h2 id="reactions">Reactions</h2> <p>Sulfuryl chloride reacts with <a href="/facts/Water_(molecule)/FFsl65l1">water</a>, releasing <a href="/facts/Hydrogen_chloride/7Wzkhomd">hydrogen chloride</a> gas and <a href="/facts/Sulfuric_acid/Wom6fymJ">sulfuric acid</a>: </p> 2 H2O + SO2Cl2 → 2 HCl + H2SO4 <p>For sulfuryl chloride, this happens at room temperature, but the related <a href="/facts/Sulfuryl_fluoride/2BeYmVLJ">sulfuryl fluoride</a> does not hydrolyse at temperatures up to 150 °C. </p><p>SO2Cl2 will also <a href="/facts/Decomposition/6Bve4pgl">decompose</a> when heated to or above 100 °C, about 30 °C above its boiling point. </p><p>Upon standing, SO2Cl2 decomposes to <a href="/facts/Sulfur_dioxide/jDK1fIDs">sulfur dioxide</a> and <a href="/facts/Chlorine/y27UwYBM">chlorine</a>, which gives the older samples a slightly yellowish color.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> </p><p>SO2Cl2 can be used as a source of chlorine in alkane chlorination, initiated by chemicals (usually a peroxide) or light:<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> </p> CH4 + SO2Cl2 → CH3Cl + SO2 + HCl <h2 id="uses">Uses</h2> <p>Sulfuryl chloride is used as a source of Cl2. Because it is a pourable liquid, it is considered more convenient than Cl2 to dispense. </p><p>Sulfuryl chloride is used in the conversion of C−H to C−Cl adjacent to activating substituents such as carbonyls and sulfoxides:<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a><a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> </p> RC(O)CH2R' + SO2Cl2 → RC(O)CHClR' + HCl + SO2 <p>It also chlorinates <a href="/facts/Alkane/Qam7Hvmf">alkanes</a>, <a href="/facts/Alkene/RtYcS6kU">alkenes</a>, <a href="/facts/Alkyne/VHI4N5Wo">alkynes</a>, <a href="/facts/Aromatic_ring/wK0DzRY6">aromatics</a>, ethers (such as <a href="/facts/Tetrahydrofuran/P5t6SkMK">tetrahydrofuran</a>) and <a href="/facts/Epoxide/PLxRI7r1">epoxides</a>. Such reactions occur under <a href="/facts/Free_radical/qFymuVoT">free radical</a> conditions using an initiator such as <a href="/facts/Azobisisobutyronitrile/Q85zrkBs">AIBN</a>. It convert <a href="/facts/Thiol/VemKEDP9">thiols</a> or <a href="/facts/Disulfide/eDx5Xtlg">disulfides</a> into the corresponding <a href="/facts/Sulfenyl_chloride/XLvr27XR">sulfenyl chlorides</a>:<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> RSH + SO2Cl2 → RSCl + HCl + SO2 <p>Occasionally, <a href="/facts/Sulfinyl_chloride/kN3o1LT8">sulfinyl chlorides</a> result from such reactions.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> SO2Cl2 can also convert <a href="/facts/Alcohol_(chemistry)/Y0SCTDkh">alcohols</a> to <a href="/facts/Alkyl_chloride/IbblBkcB">alkyl chlorides</a>. In industry, sulfuryl chloride is most used in producing pesticides. <a href="/facts/Phosphorus_pentachloride/oGLG4kDg">Phosphorus pentachloride</a> is prepared by the reaction of <a href="/facts/White_phosphorus/GarX3byj">white phosphorus</a> with sulfuryl chloride. </p><p>Sulfuryl chloride can also be used to treat wool to prevent shrinking. </p> <h2 id="precautions">Precautions</h2> <p>Sulfuryl chloride is toxic, corrosive, and acts as a <a href="/facts/Lachrymatory_agent/SLJoBYEN">lachrymator</a>. It releases hydrogen chloride upon contact with water, as well as donor solvents such as <a href="/facts/Dimethyl_sulfoxide/T4HSYfuC">dimethyl sulfoxide</a> and <a href="/facts/Dimethylformamide/wjI8UfB4">dimethylformamide</a>. </p> <ul><li><a href="https://web.archive.org/web/20070228150726/http://www.chem.unep.ch/irptc/sids/OECDSIDS/7791255.pdf">"Sulfuryl chloride CAS No.: 7791-25-5"</a> (PDF). <i>OECD SIDS</i>. UNEP Publications. 2004. Archived from <a href="http://www.chem.unep.ch/irptc/sids/OECDSIDS/7791255.pdf">the original</a> (PDF) on 2007-02-28.</li> <li>Maynard, G. D. (2001). <a href="http://onlinelibrary.wiley.com/o/eros/articles/rs140/frame.html">"Sulfuryl Chloride"</a>. <i>Encyclopedia of Reagents for Organic Synthesis</i>. John Wiley & Sons. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1002%2F047084289X.rs140">10.1002/047084289X.rs140</a>. <a href="/facts/ISBN_(identifier)/15AdSPa9">ISBN</a> 978-0471936237.</li></ul> <h2 id="further-reading">Further reading</h2> <ul><li>Lautens, M.; Bouchain, G. (2002). "[4+3] Cycloaddition in Water. Synthesis of 2,4-<i>endo</i>,<i>endo</i>-Dimethyl-8-Oxabicyclo[3.2.1]oct-6-en-3-one". <i><a href="/facts/Organic_Syntheses/WLFePEzH">Organic Syntheses</a></i>. 79: 251. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.15227%2Forgsyn.079.0251">10.15227/orgsyn.079.0251</a>.</li> <li>McKee, R. H.; Salls, C. M. (1924). "Sulfuryl Chloride". <i><a href="/facts/Industrial_and_Engineering_Chemistry/aU7YQaSD">Industrial and Engineering Chemistry</a></i>. 16 (4): 351–353. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1021%2Fie50172a008">10.1021/ie50172a008</a>.</li> <li>Moussa, V. N. (2012). "Sulfuryl Chloride: A Versatile Alternative to Chlorine". <i><a href="/facts/Australian_Journal_of_Chemistry/1ePspFqb">Australian Journal of Chemistry</a></i>. 65 (1): 95–96. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1071%2FCH11367">10.1071/CH11367</a>.</li> <li>North, H. B. (1910). <a href="https://zenodo.org/record/2166706">"The Action of Thionyl and Sulphuryl Chlorides on Mercury and Mercury Oxide"</a>. <i><a href="/facts/Journal_of_the_American_Chemical_Society/MbBz2Jo5">Journal of the American Chemical Society</a></i>. 32 (2): 184–187. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1021%2Fja01920a004">10.1021/ja01920a004</a>.</li> <li>North, H. B.; Hageman, A. G. (1913). "Some New Reactions with Thionyl Chloride". <i><a href="/facts/Journal_of_the_American_Chemical_Society/MbBz2Jo5">Journal of the American Chemical Society</a></i>. 35 (5): 543–546. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1021%2Fja02194a004">10.1021/ja02194a004</a>.</li></ul> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>F. Fehér (1963). "Sulfuryl Chloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY, NY: Academic Press. pp. 382–384. <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Regnault, Victor (1838). "Sur l'acide chlorosulfurique et la sulfamide" [On sulfuryl chloride and sulfamide]. Annales de Chimie et de Physique. Série 2 (in French). 69: 170–184. Reprinted as: Regnault, Victor (1839). "Ueber die Chlorschwefelsäure und das Sulfamid" [On sulfuryl chloride and sulfamide]. Journal für Praktische Chemie (in German). 18: 93–104. doi:10.1002/prac.18390180104. <a href="/wiki/Henri_Victor_Regnault" target="_blank">/wiki/Henri_Victor_Regnault</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>F. Fehér (1963). "Sulfuryl Chloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY, NY: Academic Press. pp. 382–384. <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Roberts JD, Caserio MC. "Practical Halogenations and Problems of Selectivity". Basic Principles of Organic Chemistry. <a href="https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_Basic_Principles_of_Organic_Chemistry_(Roberts_and_Caserio)/04%3A_Alkanes/4.06%3A_Practical_Halogenations_and_Problems_of_Selectivity" target="_blank">https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_Basic_Principles_of_Organic_Chemistry_(Roberts_and_Caserio)/04%3A_Alkanes/4.06%3A_Practical_Halogenations_and_Problems_of_Selectivity</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Mark Lautens, Giliane Bouchain (2002). "[4+3] Cycloaddition in Water. Synthesis of 2,4-endo,endo-Dimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one". Organic Syntheses. 79: 251. doi:10.15227/orgsyn.079.0251. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Cragoe, Jr, Edward J.; Robb, Charles M. (1960). "3-Hydroxyquinoline". Organic Syntheses. 40: 54. doi:10.15227/orgsyn.040.0054. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Barrett, Anthony G. M.; Dhanak, Dashyant; Graboski, Gregory G.; Taylor, Sven J. (1990). "(Phenylthio)Nitromethane". Organic Syntheses. 68: 8. doi:10.15227/orgsyn.068.0008. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Page, P. C. B.; Wilkes, R. D.; Reynolds, D. (1995). "Alkyl Chalcogenides: Sulfur-based Functional Groups". In Ley, Steven V. (ed.). Synthesis: Carbon with One Heteroatom Attached by a Single Bond. Comprehensive Organic Functional Group Transformations. Elsevier. pp. 113–276. ISBN 9780080423234. <a href="9780080423234" target="_blank">9780080423234</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> </ol>