{"id":9003,"date":"2015-07-05T05:41:25","date_gmt":"2015-07-05T09:41:25","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=9003"},"modified":"2026-04-18T06:32:31","modified_gmt":"2026-04-18T11:32:31","slug":"thiols-and-thioethers","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2015\/07\/05\/thiols-and-thioethers\/","title":{"rendered":"Thiols And Thioethers"},"content":{"rendered":"<p><strong>Thiols and Thioethers: Properties and Key Reactions<\/strong><\/p>\n<p>If you can get beyond their foul smells, thiols have a lot of similar characteristics to alcohols!<\/p>\n<ul>\n<li>Like alcohols, they can be <strong>deprotonated<\/strong> with base and undergo <strong>S<sub>N<\/sub>2 reactions\u00a0<\/strong>with alkyl halides to give thioethers (sulfides).<\/li>\n<li>Thiols tend to be considerably <strong>more acidic<\/strong> than alcohols since the sulfur atom is more polarizable.<\/li>\n<li>Their conjugate bases, &#8220;thiolates&#8221; are excellent <strong>nucleophiles<\/strong>.<\/li>\n<li>Thiols can undergo oxidation to give <strong>disulfides<\/strong>.<\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-26293\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2022\/08\/0-key-reactions-of-thiols-include-deprotonation-thiols-pka-about-11-also-substitution-with-alkyl-halides-in-sn2-reaction-and-finally-oxidation-of-thiols-to-give-disulfides.gif\" alt=\"key reactions of thiols include deprotonation thiols pka about 11 also substitution with alkyl halides in sn2 reaction and finally oxidation of thiols to give disulfides\" width=\"640\" height=\"448\" \/><\/a><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">Thiols and Thioethers<\/a><\/li>\n<li><a href=\"#two\">First Things First: Thiols Smell Bad<\/a><\/li>\n<li><a href=\"#three\">Thiols Are More Acidic Than Alcohols<\/a><\/li>\n<li><a href=\"#four\">Sulfur: Less Basic, More Nucleophilic Than Oxygen<\/a><\/li>\n<li><a href=\"#five\">Common Reactions of RS(\u2013) : SN2 Reactions With Alkyl Halides<\/a><\/li>\n<li><a href=\"#six\">Key Differences Between Thiols and Alcohols<\/a><\/li>\n<li><a href=\"#seven\">Summary: Thiols and Thioethers<\/a><\/li>\n<li><a href=\"#notes\">Notes<\/a><\/li>\n<li><a href=\"#quiz\">Quiz Yourself!\u00a0<\/a><\/li>\n<li><a href=\"#references\">(Advanced) References and Further Reading<\/a><\/li>\n<\/ol>\n<hr \/>\n<h2><a id=\"one\"><\/a>1. Thiols and Thioethers<\/h2>\n<p>One of the most powerful insights from learning the periodic table\u00a0is the fact elements in the same period (column) have similar chemical properties.<\/p>\n<p>For instance<\/p>\n<ul>\n<li>Alkali metals (Li, Na, K\u2026) all shed an electron relatively easily to form monovalent cations<\/li>\n<li>Halogens (F, Cl, Br) all gain an electron relatively easily to form halide ions.<\/li>\n<li>Noble gases (He, Ne, Ar, Kr\u2026) tend to be chemically inert.<\/li>\n<\/ul>\n<p>So how does what we\u2019ve learned about the reactivity of oxygen (O) based functional groups translate to its heavier cousins sulfur (S) , selenium (Se) and tellurium (Te)?<\/p>\n<p>Specifically, <strong>how does the chemistry of alcohols (ROH) and ethers (ROR)<\/strong> compare with the chemistry of\u00a0<strong>thiols (RSH) and thioethers [aka\u00a0sulfides] (RSR)?<\/strong>.<\/p>\n<p>Great question! That\u2019s the topic of today\u2019s post, specifically <strong>thiols and thioethers<\/strong>. We won\u2019t really talk about selenium chemistry beyond briefly mentioning its acidity, and we definitely won\u2019t go anywhere near tellurium chemistry, following <a href=\"http:\/\/citeseerx.ist.psu.edu\/viewdoc\/download?doi=10.1.1.259.7611&amp;rep=rep1&amp;type=pdf\">W\u00f6hler&#8217;s advice on diethyl tellurium<\/a> that &#8220;<em>its obnoxious and persistent smell is connected to unpleasantness, which one wouldn&#8217;t like to endure a second time<\/em>&#8220;, and that &#8220;<em>the smell is so persistent, that one has to avoid social life for several months in order not to molest other people<\/em>&#8220;.<\/p>\n<p>Let&#8217;s start with what\u2019s similar between alcohols\/thiols, ethers\/thioethers, and then move to what\u2019s vastly different.<\/p>\n<h2><a id=\"two\"><\/a>2. First Things First: Thiols Smell Bad<\/h2>\n<p>Open a textbook that discusses thiols and one of the first things they&#8217;ll mention is their vile stench. We wouldn&#8217;t want to break with this honourable tradition here at MOC.<\/p>\n<p>Hydrogen sulfide (H<sub>2<\/sub>S) is responsible for the smell of rotten eggs and bad breath, among other unpleasant things. \u00a0Thiols contribute to the smell of skunks and &#8220;skunky&#8221; beer.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15268\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-thiols-are-associated-with-bad-smells-such-as-rotten-eggs-hydrogen-sulfide-skunk-odor-3-methyl-1butane-thiol-and-skunky-beer.gif\" alt=\"thiols are associated with bad smells such as rotten eggs hydrogen sulfide skunk odor 3 methyl 1butane thiol and skunky beer\" width=\"600\" height=\"148\" \/><\/p>\n<p>During my time in grad school one of the world&#8217;s leading organosulfur chemists had a lab across the hall. These were not people you wanted to be downwind from.\u00a0\u00a0Imagine getting on the city bus and having the people next to you get up from their seats\u00a0and move down to the other end. Those stories were not uncommon from the people in that lab.<\/p>\n<p>BTW: the sulfur chemists&#8217; best friend is bleach (NaOCl), which oxidizes stinky thiols to relatively odourless sulfoxides (see #5, below).<\/p>\n<h2><a id=\"three\"><\/a>3. Thiols Are More Acidic Than Alcohols<\/h2>\n<p>We&#8217;ve seen that alcohols are relatively acidic (pK<sub>a<\/sub>&#8216;s of about 16-17). \u00a0<strong>Thiols are more acidic than alcohols<\/strong> by an average of about 5 pK<sub>a<\/sub> units or so ( pK<sub>a<\/sub> of about 11 for the thiol pictured below). Remember that pK<sub>a<\/sub> is logarithmic, so that means they&#8217;re about 10<sup>5<\/sup> times more acidic.<\/p>\n<p>Why might that be?<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-26333\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2015\/07\/2-acidity-increases-going-down-the-periodic-table-alcohol-pkas-about-16-thiol-pkas-about-10-11-and-selenol-pka-about-6-1.gif\" alt=\"acidity increases going down the periodic table alcohol pkas about 16 thiol pkas about 10-11 and selenol pka about 6\" width=\"630\" height=\"236\" \/><\/a><\/p>\n<p>When understanding acidity trends it greatly helps to think about the stability of the conjugate base<\/p>\n<p>Recall that acidity will be increased by\u00a0<strong>any factor which stabilizes the conjugate base.\u00a0<\/strong>(<em>See post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2010\/09\/22\/five-key-factors-that-influence-acidity\/\">5 Key Factors That Influence Acidity<\/a><\/em>)<\/p>\n<p>[<span style=\"color: #993366;\"><em>Since acid-base reactions are equilibria, if we stabilize the product (conjugate base) we therefore make the equilibrium where the starting material (acid) loses a proton \u00a0more favourable, increasing K<sub>a<\/sub>. In other words, we increase the acidity.<\/em><\/span>]<strong>\u00a0<\/strong><\/p>\n<p>In the case of sulfur, the negative charge will be borne on a larger atom (sulfur &gt; oxygen) and that negative charge dispersed over a greater volume. <strong>Greater volume = more diffuse charge = greater stability.\u00a0<\/strong>(<em>See post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/02\/27\/7-factors-that-stabilize-negative-charge-in-organic-chemistry\/\">7 Factors That Stabilize Negative Charge in Organic Chemistry<\/a><\/em>)<\/p>\n<p>The greater acidity of the thiol is indicated by the lower measured pK<sub>a<\/sub> of the thiol pictured above (about 10-11) relative to alcohols (pK<sub>a<\/sub> 16-18)<\/p>\n<p>The same holds true for selenium, which has an even larger atomic radius. I can&#8217;t find a pK<sub>a<\/sub> value for propaneselenol but would estimate it to be about 7-8. <span style=\"color: #993366;\"><em>[If someone has a better number, please let me know!<\/em><\/span>]<\/p>\n<p>A corollary of the fact that the conjugate base is more stable is that thiolates [the conjugate bases of thiols] are weaker bases than alkoxides. [&#8220;The stronger the acid, the weaker the conjugate base&#8221;]. (<em>See post:<\/em> <a href=\"https:\/\/www.masterorganicchemistry.com\/2010\/09\/29\/how-to-use-a-pka-table\/\"><em>How to Use a pKa Table<\/em><\/a>)<\/p>\n<h2><a id=\"four\"><\/a>4. Sulfur: Less Basic, More Nucleophilic<\/h2>\n<p>Remember how alkoxides [RO<sup>\u2013<\/sup>] can act as nucleophiles\u00a0in\u00a0S<sub>N<\/sub>2 reactions as well as the base in elimination (E2) reactions? (<em>See post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2014\/10\/30\/williamson-ether-synthesis-planning\/\">Williamson Ether Synthesis &#8211; Planning<\/a><\/em>)<\/p>\n<p>With thiolates [RS<sup>\u2013<\/sup>],\u00a0<strong>E2 reactions aren&#8217;t\u00a0an issue<\/strong>.\u00a0\u00a0The weaker basicity of thiolates means that only S<sub>N<\/sub>2 reactions occur with alkyl halides.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26334\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2015\/07\/3-thiols-versus-alkoxides-thiols-are-less-basic-but-more-nucleophilic-they-react-more-rapidly-with-electrophiles-nucleophilicity-increases-going-down-the-periodic-table-1.gif\" alt=\"-thiols versus alkoxides thiols are less basic but more nucleophilic they react more rapidly with electrophiles nucleophilicity increases going down the periodic table\" width=\"630\" height=\"251\" \/><\/a><\/p>\n<p>Thi<span style=\"text-decoration: underline;\">ols<\/span> are more nucleophilic than alcohols, and thiol<span style=\"text-decoration: underline;\">ates<\/span> are more nucleophilic than alkoxides. <a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/06\/06\/nucleophilicity-vs-basicity\/\">Since nucleophilicity is measured by reaction rate<\/a>, \u00a0that means that these sulfur nucleophiles tend to react faster with typical electrophiles (like alkyl halides) than their oxygen-based cousins.<\/p>\n<p>Why? As we&#8217;ve discussed before, the lower electronegativity of sulfur (relative to oxygen) means that its pairs of electrons are held onto less tightly than oxygen, <strong>making them more readily available for donation to electrophiles<\/strong> (like alkyl halides).<\/p>\n<p>This trend continues as we <strong>descend<\/strong> a column of the periodic table, so in general, nucleophilicity increases\u00a0in this direction as well (i.e. RSe<sup>\u2013<\/sup> is even more nucleophilic than RS<sup>\u2013<\/sup> ).<\/p>\n<h2><a id=\"five\"><\/a>5. Common Reactions of Thiolates: S<sub>N<\/sub>2 Reactions<\/h2>\n<p>We&#8217;ve seen that one of the most important reactions to form ethers is the Williamson ether synthesis. (<em>See post: <a href=\"https:\/\/www.masterorganicchemistry.com\/wp_quiz\/williamson-ether-synthesis\/\">The Williamson Ether Synthesis<\/a><\/em>)<\/p>\n<p>Here&#8217;s a textbook example of the sulfur analogue of this reaction: substitution of alkyl halides with thiolates to form thioethers (also known as sulfides).<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15271\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-thiol-version-of-williamson-ether-synthesis-thioether-synthesis-deprotonate-thiuol-and-treat-with-alkyl-bromide-sn2-reaction.gif\" alt=\"thiol version of williamson ether synthesis thioether synthesis deprotonate thiuol and treat with alkyl bromide sn2 reaction\" width=\"600\" height=\"209\" \/><\/p>\n<p>This process resembles the Williamson to a tee.<\/p>\n<ul>\n<li>First, a strong base deprotonates the thiol (we use NaH here, but many other bases could also be used).<\/li>\n<li>Secondly, we add an alkyl halide, and an S<sub>N<\/sub>2 reaction results in formation of S-C and breakage of C-Br with inversion of stereochemistry.<\/li>\n<\/ul>\n<p>As mentioned above, note that if we were using an alkoxide, we&#8217;d have to worry about the E2 reaction competing with the S<sub>N<\/sub>2. With thiolates, it&#8217;s not an issue due to their decreased basicity.<\/p>\n<p>Since it comes up so much in exams, the <strong>intramolecular<\/strong> version is important to note. You&#8217;ll see that we&#8217;re still forming C\u2013S here and breaking a carbon-halide bond. Don&#8217;t forget that inversion occurs on the stereocenter on the secondary carbon!<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15272\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-intramolecular-sn2-of-thiols-deprotonation-with-nah-formation-of-thiolate-then-sn2-reaction-with-alkyl-halide-giving-new-3-membered-ring.gif\" alt=\"intramolecular sn2 of thiols deprotonation with nah formation of thiolate then sn2 reaction with alkyl halide giving new 3 membered ring\" width=\"600\" height=\"127\" \/><\/p>\n<h2><a id=\"six\"><\/a>6. Key Differences Between Alcohols And Thiols<\/h2>\n<p><b>A. Oxidation<\/b><\/p>\n<p>In previous posts we saw that primary alcohols are oxidized to aldehydes and secondary alcohols are oxidized to ketones (<em>See post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/05\/06\/alcohol-oxidation-strong-and-weak-oxidants\/\">Oxidation of Alcohols<\/a><\/em>)<\/p>\n<p>This doesn&#8217;t work with thiols! Thiols aren\u2019t oxidized to \u03c0 bonds in the same way. The C\u2013S \u03c0 bond is actually quite weak due to poor orbital overlap. [<a href=\"#noteone\"><strong>Note 1<\/strong><\/a>]<\/p>\n<p>Instead, two different types of oxidation reactions occur with thiols.<\/p>\n<ul>\n<li>\u00a0Thiols can be oxidized to\u00a0<b>disulfides<\/b> through treatment with a mild oxidant like iodine (I<sub>2<\/sub>).<\/li>\n<li>A second oxidation pathway involves oxidation of sulfides to sulfoxides and sulfones through treatment with oxidants such as O<sub>3<\/sub> (ozone) and peroxyacids such as m-chloroperoxybenzoic acid (m-CPBA). Note that sulfur can exceed an octet of electrons whereas oxygen cannot.<\/li>\n<\/ul>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15273\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-oxidation-of-thiols-with-iodine-or-molecular-oxygen-gives-disulfides-also-sulfides-can-be-oxidized-to-sulfoxides-or-sulfones.gif\" alt=\"oxidation of thiols with iodine or molecular oxygen gives disulfides also sulfides can be oxidized to sulfoxides or sulfones\" width=\"600\" height=\"453\" \/><\/p>\n<p>The oxidation of thiols to disulfides has important biological implications. The important amino acid <a href=\"https:\/\/en.wikipedia.org\/wiki\/Cysteine\">cysteine<\/a> contains a thiol group and disulfide bonds are responsible for the tertiary structures of proteins. They act like &#8220;hooks&#8221; that help to hold disparate parts of the peptide chain together.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15274\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/7-oxidation-of-thiol-cysteine-to-disulfide-linkage-found-in-proteins.gif\" alt=\"oxidation of thiol cysteine to disulfide linkage found in proteins\" width=\"600\" height=\"268\" \/><\/p>\n<p>&nbsp;<\/p>\n<p><strong>B. Hydrogen Bonding Isn&#8217;t As Significant With Thiols<\/strong><\/p>\n<p>The electronegativity of sulfur is only 2.6 \u00a0whereas hydrogen is 2.2. That means there isn&#8217;t much of a dipole in the S-H bond, and <strong>hydrogen bonding is not significant<\/strong>. Contrast H<sub>2<\/sub>O, with a boiling point of 100\u00b0C, with H<sub>2<\/sub>S and its boiling point of \u201360\u00b0C. Intermolecular forces are not very strong!<\/p>\n<p><strong>C. Reactions With Acids Are Slightly Different<\/strong><\/p>\n<p>In this series on alcohols and ethers we have seen countless examples of treating an alcohol or ether with H+ and <a href=\"https:\/\/www.masterorganicchemistry.com\/2014\/10\/06\/how-to-make-alcohols-more-reactive\/\">converting it to its conjugate acid<\/a>, making a better leaving group in the process.<\/p>\n<p><strong>This isn&#8217;t as significant for thiols<\/strong>. The S-H bond is significantly weaker than the O-H bond [81 kcal\/mol vs. 109 kcal\/mol].<\/p>\n<p>Secondly, due to the smaller dipole (electronegativity difference) of the S-H as opposed to O-H, there is less partial negative charge on sulfur and therefore less electrostatic attraction between S and the H of various acids.<\/p>\n<p>A better way of converting sulfur to a good leaving group is by treating it with Lewis acids such as Hg(OAc)<sub>2 <\/sub>. We haven&#8217;t really covered\u00a0\u00a0<a href=\"https:\/\/en.wikipedia.org\/wiki\/HSAB_theory\">Hard-Soft Acid Base (HSAB) theory<\/a> here on MOC (which is an advanced topic) \u00a0but in order to further understand the differences in reactivity of O and S with various acids, the linked Wikipedia article is a useful primer.<\/p>\n<p><strong>D. There are no &#8220;thio&#8221; versions of many reactions of alcohols<\/strong><\/p>\n<p>We&#8217;ve seen many interesting reactions that have led to alcohols and epoxides. For example, <a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/07\/01\/reagent-friday-oso4-osmium-tetroxide\/\">treatment of alkenes with OsO<sub>4<\/sub> results in vicinal diols<\/a>. It&#8217;s tempting to think that there might be an analogous reaction between alkenes and OsS<sub>4<\/sub> to give vicinal dithiols. There isn&#8217;t (and it&#8217;s not for lack of trying). Nor is there a sulfur equivalent to the formation of epoxides from alkenes with, say, the sulfur equivalent of <a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/06\/17\/reagent-friday-m-cpba-meta-chloroperoxybenzoic-acid\/\">mCPBA<\/a>. So while moving down a column of the periodic table can sometimes provide useful inspiration for new reactions, often &#8211; for unclear reasons &#8211; it does not.<\/p>\n<h2><a id=\"seven\"><\/a>7. Summary: Thiols and Thioethers<\/h2>\n<p>In the next post (our last on alcohols) we&#8217;ll tie all the reactions we&#8217;ve learned together into a &#8220;reaction map&#8221;.<\/p>\n<p><strong>Next Post: \u00a0<a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/07\/27\/synthesis-6-reactions-of-alcohols\/\">Synthesis (6) Reactions of Alcohols<\/a><\/strong><\/p>\n<hr \/>\n<h2><a id=\"notes\"><\/a>Notes<\/h2>\n<div class=\"related-articles\"><p><strong>Related Articles<\/strong><\/p><ul><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/07\/25\/calculating-the-oxidation-state-of-a-carbon\/\" class=\"\"><span>Calculating the oxidation state of a carbon<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/05\/06\/alcohol-oxidation-strong-and-weak-oxidants\/\" class=\"\"><span>Alcohol Oxidation: \u201cStrong\u201d and \u201cWeak\u201d Oxidants<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2010\/09\/29\/how-to-use-a-pka-table\/\" class=\"\"><span>How to Use a pKa Table<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2010\/09\/22\/five-key-factors-that-influence-acidity\/\" class=\"\"><span>Five Key Factors That Influence Acidity<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/02\/27\/7-factors-that-stabilize-negative-charge-in-organic-chemistry\/\" class=\"\"><span>7 Factors that stabilize negative charge in organic chemistry<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2014\/10\/24\/the-williamson-ether-synthesis\/\" class=\"\"><span>The Williamson Ether Synthesis<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/06\/06\/nucleophilicity-vs-basicity\/\" class=\"\"><span>Nucleophilicity vs. Basicity<\/span><\/a><\/li><\/ul><\/div>\n<p><strong><a id=\"noteone\"><\/a>Note 1. <\/strong>In grad school a visiting speaker gave a talk on making thioaldehydes and thioketones. I missed it, but an emeritus professor who had a hood in our lab was able to attend. He reported back: &#8220;What I learned from today&#8217;s seminar about the C=S bond&#8230;. is that you don&#8217;t want to make compounds with C=S bonds&#8221;, he said with a laugh. [They&#8217;re quite unstable]<\/p>\n<p>[Caveat: This applies to thioaldehydes\/thioketones. Molecules like thioamides or thioureas \u00a0where an atom like N or O are adjacent to the carbon bearing C=S are generally reasonably stable]<\/p>\n<p><strong><a id=\"notetwo\"><\/a>Note 2<\/strong>: Relevant video for this post.<\/p>\n<p><iframe src=\"https:\/\/www.youtube.com\/embed\/ACo7mgawxZs\" width=\"560\" height=\"315\" frameborder=\"0\" allowfullscreen=\"allowfullscreen\"><\/iframe><\/p>\n<hr \/>\n<h2><a id=\"quiz\"><\/a>Quiz Yourself!<\/h2>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1679-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0576-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0577-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0578-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0579-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/2136-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1680-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n<hr \/>\n<h2><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/h2>\n<ol>\n<li><strong>Acidic dissociation constants of thiols<br \/>\n<\/strong>James P. Danehy and K. N. Parameswaran<strong><br \/>\n<\/strong><em>Journal of Chemical &amp; Engineering Data<\/em><strong> 1968, <\/strong><em>13<\/em> (3), 386-389<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/je60038a025\">1021\/je60038a025<\/a><br \/>\nThis contains a list of pK<sub>a<\/sub>\u2019s for over 100 thiols. Very useful reference.<\/li>\n<li><strong>Synthesis of thiols, sulfides, sulfoxides and sulfones<br \/>\n<\/strong>Christopher M. Rayner<strong><br \/>\n<\/strong><em>Synth.<\/em><strong> 1995<\/strong>, <em>2<\/em>, 409-440<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.rsc.org\/en\/content\/articlelanding\/1995\/co\/co9950200409#!divAbstract\">10.1039\/CO9950200409<\/a><br \/>\nNice review on sulfur chemistry in organic synthesis.Notable medicinal chemist Derek Lowe has a series of posts titled \u201cThings I won\u2019t work with\u201d on his (excellent) blog. Two of the compounds below make the list because of their vile smells \u2013 thioacetone (CH<sub>3<\/sub>CSCH<sub>3<\/sub>) and selenophenol (PhSeH).<\/li>\n<li><strong>&#8220;Things I Won&#8217;t Work With: Thioacetone&#8221;. [<a href=\"https:\/\/blogs.sciencemag.org\/pipeline\/archives\/2009\/06\/11\/things_i_wont_work_with_thioacetone\">Link<\/a>]<\/strong><\/li>\n<li>&#8220;<strong>Things I Won&#8217;t Work With: Selenophenol&#8221;<\/strong>. [<a href=\"https:\/\/blogs.sciencemag.org\/pipeline\/archives\/2012\/05\/15\/things_i_wont_work_with_selenophenol\"><strong>Link<\/strong><\/a>]<br \/>\nAmusing articles on the astonishingly powerful odor of thioacetone and (to a lesser extent) selenophenol, from Derek Lowe&#8217;s &#8220;In The Pipeline&#8221; blog.Sulfur atoms on an adjacent carbon can \u2018assist\u2019 with reactivity. This is known as \u2018Neighboring Group Participation\u2019 or \u2018Anchimeric Assistance\u2019. This was first observed by the famed chemist Prof. Saul Winstein (UCLA), who made fundamental contributions to Physical Organic Chemistry.<\/li>\n<li><strong>Kinetics of Hydrolysis and Displacement Reactions of \u03b2,\u03b2\u2032-Dichlorodiethyl Sulfide (Mustard Gas) and of \u03b2-Chloro-\u03b2\u2033-hydroxydiethyl Sulfide (Mustard Chlorohydrin)<\/strong><br \/>\nPaul D. Bartlett and C. Gardner. Swain<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1949,<\/strong> <em>71<\/em> (4), 1406-1415<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja01172a076\">10.1021\/ja01172a076<\/a><\/li>\n<li><strong>The Hydrolysis of Bis(2-chloroethyl) Sulfide (Sulfur Mustard) in Aqueous Mixtures of Ethanol, Acetone and Dimethyl Sulfoxide<\/strong><br \/>\nIan Tilley<br \/>\n<em>Aust. J. Chem.<\/em> <strong>1993<\/strong>, <em>46<\/em>, 293-300<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/www.publish.csiro.au\/CH\/ExportCitation\/CH9930293\">10.1071\/CH9930293<\/a><br \/>\nOne of the prime examples of neighboring group participation is the hydrolysis of \u2018sulfur mustard\u2019. The sulfur atom allows this molecule to hydrolyze extremely easily (yielding HCl), since it can form a 3-membered episulfonium intermediate.<\/li>\n<li><strong>Hydrolysis of mustard derivatives in aqueous acetone-water and ethanol-water mixtures<\/strong><br \/>\nYu Chu Yang, J. Richard Ward, and Thomas Luteran<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1986,<\/strong> <em>51<\/em> (14), 2756-2759<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo00364a025\">10.1021\/jo00364a025<\/a><\/li>\n<li><strong>Neighboring group participation by sulfur involving four-membered-ring intermediates (RS-4)<\/strong><br \/>\nErnest L. Eliel and David E. Knox<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1985,<\/strong> <em>107<\/em> (10), 2946-2952<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/ja00296a019\">10.1021\/ja00296a019<\/a><br \/>\nSulfur atoms further out can also act as neighboring groups, geometry permitting.Disulfide bond formation:<\/li>\n<li><strong>Kinetics and mechanism of the oxidation of n-dodecanethiol and pyridine-substituted ethanethiols by iodine molecule in acetonitrile<br \/>\n<\/strong>David L. De Leeuw, W. Kenneth Musker, and Joyce Takahashi Doi<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1982,<\/strong> <em>47<\/em> (25), 4860-4864<br \/>\n<strong>DOI:<\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00146a008\">1021\/jo00146a008<\/a><br \/>\nThis goes over the mechanism of the oxidation of thiols with I<sub>2<\/sub>, and includes a mechanism and kinetic rate equation.<\/li>\n<li><strong>Oxidation of cysteine to disulfides.\u00a0<\/strong><br \/>\n<a href=\"https:\/\/www.sigmaaldrich.com\/technical-documents\/protocols\/chemistry\/fmoc-spps-cysteine-peptides.html#disulfide\">Sigma-Aldrich Technical Bulletin.<\/a><br \/>\nThe oxidation of thiols to disulfides is <em>hugely <\/em>important in biology, due to the naturally occurring amino acid Cysteine. The importance of Cysteine in biochemistry is due to the fact that the -SH group can form disulfide bonds, which is one of the forces leading to the tertiary structure of peptides and proteins. Synthetic peptides with 2 or more Cys residues can be oxidized to give a disulfide bond, and when 3 or more are present, this is something that needs to be done selectively, as the link explains.Due to their even <em>worse<\/em> smells, organoselenium and -tellurium chemistry has progressed much slower than related thiol chemistry.<\/li>\n<li><strong>Theoretical Calculation of pK<sub>a<\/sub>s of Selenols in Aqueous Solution Using an Implicit Solvation Model and Explicit Water Molecules<\/strong><br \/>\nBishnu Thapa and H. Bernhard Schlegel<br \/>\n<em>The Journal of Physical Chemistry A<\/em> <strong>2016,<\/strong> <em>120<\/em> (44), 8916-8922<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/acs.jpca.6b09520\">10.1021\/acs.jpca.6b09520<\/a><br \/>\nTheoretical calculations are not the same as experimental determination, but this gives a place to start.<\/li>\n<li><strong>Phenylseleno neighboring group. Solvolysis of 2-phenylselenoethyl chloride<\/strong><br \/>\nSamuel P. McManus and David Hinkle Lam<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1978,<\/strong> <em>43<\/em> (4), 650-651<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00398a028\">10.1021\/jo00398a028<\/a><br \/>\nSelenium can also engage in neighboring group participation.<\/li>\n<li><strong>Organotellurium Compounds.\u00a0<\/strong><br \/>\n<a href=\"http:\/\/citeseerx.ist.psu.edu\/viewdoc\/download?doi=10.1.1.259.7611&amp;rep=rep1&amp;type=pdf\">Sigma-Aldrich Technical Bulletin.\u00a0<\/a><br \/>\nThis publication by Sigma-Aldrich contains a review on organotellurium chemistry.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>Thiols and Thioethers: Properties and Key Reactions If you can get beyond their foul smells, thiols have a lot of similar characteristics to alcohols! Like <\/p>\n","protected":false},"author":1,"featured_media":15267,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1420],"tags":[],"post_folder":[],"class_list":["post-9003","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-alcohols-epoxides-ethers"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Thiols And Thioethers &#8211; Master Organic Chemistry<\/title>\n<meta name=\"description\" content=\"Thiols: Properties, reactions, and a contrast of the properties of thiols with those of alcohols. 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