Menu
Home
People
Places
Arts
History
Plants & Animals
Science
Life & Culture
Technology
Reference.org
Thiophosphoryl chloride
open-in-new
<h2 id="synthesis">Synthesis</h2> <p>Thiophosphoryl chloride can be generated by several reactions starting from <a href="/facts/Phosphorus_trichloride/PsQ1HXcl">phosphorus trichloride</a>. The most common and practical synthesis, hence used in industrial manufacturing, is directly reacting <a href="/facts/Phosphorus_trichloride/PsQ1HXcl">phosphorus trichloride</a> with excess <a href="/facts/Sulfur/IK0amTfM">sulfur</a> at 180 °C.<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p> PCl3 + S → PSCl3 <p>Using this method, yields can be very high after purification by distillation. Catalysts facilitate the reaction at lower temperatures, but are not usually necessary. Alternatively, it is obtained by combining phosphorus pentasulfide and phosphorus pentachloride.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> </p> 3 PCl5 + P2S5 → 5 PSCl3 <h2 id="structure">Structure</h2> <p>Thiophosphoryl chloride has <a href="/facts/Tetrahedral_molecular_geometry/583AL1sP">tetrahedral molecular geometry</a> and C3v <a href="/facts/Molecular_symmetry/BrDxAkTK">molecular symmetry</a>, with the structure S=PCl3. According to <a href="/facts/Gas_electron_diffraction/W9DGcMct">gas electron diffraction</a>, the phosphorus–sulfur bond length is 189 <a href="/facts/Picometre/Cb54mVBX">pm</a> and the phosphorus–chlorine bond length is 201 pm, while the Cl−P−Cl <a href="/facts/Bond_angle/7USG5zDn">bond angle</a> is 102°.<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> </p> <h2 id="reactions">Reactions</h2> <p>PSCl3 is soluble in <a href="/facts/Benzene/Fguue7nr">benzene</a>, <a href="/facts/Carbon_tetrachloride/S2ekjT0E">carbon tetrachloride</a>, <a href="/facts/Chloroform/gvzuJMXa">chloroform</a>, and <a href="/facts/Carbon_disulfide/b04Tadmy">carbon disulfide</a>.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> However, it <a href="/facts/Hydrolyzes/JTvwIHPs">hydrolyzes</a> rapidly in <a href="/facts/Base_(chemistry)/M9wA7qeM">basic</a> or <a href="/facts/Hydroxylic/1Hs2QAEv">hydroxylic</a> solutions, such as <a href="/facts/Alcohols/Y0SCTDkh">alcohols</a> and <a href="/facts/Amines/SN7W44fv">amines</a>, to produce <a href="/facts/Thiophosphate/djY5nEmv">thiophosphates</a>.<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> In water PSCl3 reacts, and contingent on the reaction conditions, produces either <a href="/facts/Phosphoric_acid/l6NbwyCv">phosphoric acid</a>, <a href="/facts/Hydrogen_sulfide/UbCqjMMk">hydrogen sulfide</a>, and <a href="/facts/Hydrochloric_acid/HqItJlUT">hydrochloric acid</a> or dichlorothiophosphoric acid and hydrochloric acid.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> PSCl3 + 4 H2O → H3PO4 + H2S + 3 <a href="/facts/Hydrogen_chloride/7Wzkhomd">HCl</a> PSCl3 + H2O → HO−P(=S)Cl2 + HCl <p>An intermediate in this process appears to be <a href="/facts/Tetraphosphorus_nonasulfide/W7bEcQpx">tetraphosphorus nonasulfide</a>.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> </p><p>PSCl3 is used to thiophosphorylate organic compounds (to add thiophosphoryl group, P=S, with three free <a href="/facts/Valence_(chemistry)/ck7cHByj">valences</a> at the <a href="/facts/Phosphorus/27xCeIqs">P</a> atom, to <a href="/facts/Organic_compounds/gqCNaN45">organic compounds</a>).<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> This conversion is widely applicable for amines and alcohols, as well as <a href="/facts/Aminoalcohol/UV48HH61">aminoalcohols</a>, <a href="/facts/Diols/pmaVtfKx">diols</a>, and <a href="/facts/Diamine/y12h63fj">diamines</a>.<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> Industrially, PSCl3 is used to produce <a href="/facts/Insecticides/1xYL3MSD">insecticides</a>, like <a href="/facts/Parathion/YPC72KuT">parathion</a>.<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> </p> PSCl3 + 2 CH3CH2OH → (CH3CH2−O−)2P(=S)−Cl + 2 HCl (CH3CH2−O−)2P(=S)−Cl + Na+[−O−C6H4−NO2] → (CH3CH2−O−)2P(=S)−O−C6H4−NO2 + <a href="/facts/Sodium_chloride/MWcXl3Mb">NaCl</a> <p>PSCl3 reacts with <a href="/facts/Tertiary_(chemistry)/2tdmz8wG">tertiary</a> <a href="/facts/Amide/C6kCzYEA">amides</a> to generate <a href="/facts/Thioamides/x807Hnby">thioamides</a>.<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> For example: </p> C6H5−C(=O)−N(−CH3)2 + PSCl3 → C6H5−C(=S)−N(−CH3)2 + <a href="/facts/Phosphoryl_chloride/fwbrqPWI">POCl3</a> <p>When treated with <a href="/facts/Methylmagnesium_iodide/fpqQ5eBV">methylmagnesium iodide</a>, it give tetramethyldiphosphine disulfide (H3C−)2P(=S)−P(=S)(−CH3)2.<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> </p> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 doi:10.1002/047084289X.rt104. Article Online Posting Date: April 15, 2001 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Betterman G, Krause W, Riess G, Hofmann T (2005). "Phosphorus Compounds, Inorganic". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730. <a href="3527306730" target="_blank">3527306730</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Martin, D. R.; Duvall, W. M. “Phosphorus(V) Sulfochloride” Inorganic Syntheses, 1953, Volume IV, p73. doi:10.1002/9780470132357.ch24. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Kuchitsu, Kozo; Moritani, Tohei; Morino, Yonezo (1971). "Molecular structures of phosphoryl fluoride, phosphoryl chloride, and thiophosphoryl chloride studied by gas electron diffraction". Inorganic Chemistry. 10 (2): 344–350. doi:10.1021/ic50096a025. <a href="/wiki/Inorganic_Chemistry_(journal)" target="_blank">/wiki/Inorganic_Chemistry_(journal)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 doi:10.1002/047084289X.rt104. Article Online Posting Date: April 15, 2001 <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>Betterman G, Krause W, Riess G, Hofmann T (2005). "Phosphorus Compounds, Inorganic". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730. <a href="3527306730" target="_blank">3527306730</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Fee, D. C.; Gard, D. R.; Yang, C. “Phosphorus Compounds” Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons: New York, 2005 doi:10.1002/0471238961.16081519060505.a01.pub2 <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>Almasi, Lucreţia (1971). "The Sulfur–Phosphorus Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. p. 69. ISBN 0-8247-1615-9. LCCN 70-154612. <a href="0-8247-1615-9" target="_blank">0-8247-1615-9</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Betterman G, Krause W, Riess G, Hofmann T (2005). "Phosphorus Compounds, Inorganic". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730. <a href="3527306730" target="_blank">3527306730</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 doi:10.1002/047084289X.rt104. Article Online Posting Date: April 15, 2001 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>Fee, D. C.; Gard, D. R.; Yang, C. “Phosphorus Compounds” Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons: New York, 2005 doi:10.1002/0471238961.16081519060505.a01.pub2 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> <li id="fn:12"><p>Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 doi:10.1002/047084289X.rt104. Article Online Posting Date: April 15, 2001 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li> <li id="fn:13"><p>G. W. Parshall "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. doi:10.15227/orgsyn.045.0102 <a href="/wiki/G._W._Parshall" target="_blank">/wiki/G._W._Parshall</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li> </ol>