{"id":1186,"date":"2017-10-12T15:47:21","date_gmt":"2017-10-12T15:47:21","guid":{"rendered":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/?post_type=chapter&#038;p=1186"},"modified":"2018-10-05T18:06:42","modified_gmt":"2018-10-05T18:06:42","slug":"hydration-of-alkynes","status":"publish","type":"chapter","link":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/chapter\/hydration-of-alkynes\/","title":{"raw":"Hydration of Alkynes","rendered":"Hydration of Alkynes"},"content":{"raw":"<div class=\"elm-header\">\r\n<div class=\"elm-header-custom\">\r\n<div class=\"textbox learning-objectives\">\r\n<h3>Objectives<\/h3>\r\n<div id=\"elm-main-content\" class=\"elm-content-container\">\r\n<div>\r\n<div id=\"skills\">\r\n\r\nAfter completing this section, you should be able to\r\n<ol>\r\n \t<li>write the equation for the reaction of water with an alkyne in the presence of sulfuric acid and mercury(II) sulfate.<\/li>\r\n \t<li>describe keto-enol tautomerism.<\/li>\r\n \t<li>predict the structure of the ketone formed when a given alkyne reacts with sulfuric acid in the presence of mercury(II) sulfate.<\/li>\r\n \t<li>identify the reagents needed to convert a given alkyne to a given ketone.<\/li>\r\n \t<li>identify the alkyne needed to prepare a given ketone by hydration of the triple bond.<\/li>\r\n \t<li>write an equation for the reaction of an alkyne with borane.<\/li>\r\n \t<li>write the equation for the reaction of a vinylic borane with basic hydrogen peroxide or hot acetic acid.<\/li>\r\n \t<li>identify the reagents, the alkyne, or both, needed to prepare a given ketone or a given cis alkene through a vinylic borane intermediate.<\/li>\r\n \t<li>identify the ketone produced when a given alkyne is reacted with borane followed by basic hydrogen peroxide.<\/li>\r\n \t<li>identify the cis alkene produced when a given alkyne is reacted with borane followed by hot acetic acid.<\/li>\r\n \t<li>explain why it is necessary to use a bulky, sterically hindered borane when preparing vinylic boranes from terminal alkynes.<\/li>\r\n \t<li>predict the product formed when the vinylic borane produced from a terminal alkyne is treated with basic hydrogen peroxide.<\/li>\r\n \t<li>identify the alkyne needed to prepare a given aldehyde by a vinylic borane.<\/li>\r\n<\/ol>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<div class=\"textbox key-takeaways\">\r\n<h3>Key TERmS<\/h3>\r\n<div class=\"elm-header\"><\/div>\r\n<div id=\"elm-main-content\" class=\"elm-content-container\">\r\n<div>\r\n<div>\r\n\r\nMake certain that you can define, and use in context, the key terms below.\r\n<ul>\r\n \t<li>enol<\/li>\r\n \t<li>keto-enol tautomeric equilibrium<\/li>\r\n \t<li>tautomerism<\/li>\r\n \t<li>tautomers<\/li>\r\n<\/ul>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<div id=\"elm-main-content\" class=\"elm-content-container\">\r\n<div id=\"note\">\r\n<div class=\"textbox\">\r\n<div id=\"note\">\r\n<h3 class=\"boxtitle\">Study Notes<\/h3>\r\nRapid interconversion between tautomers is called <em>tautomerism<\/em>; however, as the two tautomers are in equilibrium, the term <em>tautomeric<\/em> <em>equilibrium<\/em> may be used. This section demonstrates the equilibrium between a ketone and an enol; hence, the term <em>keto<\/em>-<em>enol<\/em> <em>tautomeric<\/em> <em>equilibrium<\/em> is appropriate. The term \u201cenol\u201d indicates the presence of a carbon-carbon double bond and a hydroxyl (i.e., alcohol) group. Later in the course, you will see the importance of keto-enol tautomerism in discussions of the reactions of ketones, carbohydrates and nucleic acids.\r\n\r\nIt is important to note that tautomerism is not restricted to keto-enol systems. Other examples include imine-enamine tautomerism\r\n\r\n<img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86899\/9-4a.png?origin=mt-web\" alt=\"imine-enamine tautomerism\" \/>\r\n\r\nand nitroso-oxime tautomerism\r\n\r\n<img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86900\/9-4b.png?origin=mt-web\" alt=\"nitroso-oxime tautomerism\" \/>\r\n\r\nHowever, at the moment you need only concern yourself with keto-enol tautomerism.\r\n\r\nNotice how hydroboration complements hydration in the chemistry of both alkenes and alkynes.\r\n\r\n<img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86901\/9-4c.png?origin=mt-web\" alt=\"hydroboration and hydration scheme of alkenes and alkynes\" \/>\r\n\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<div id=\"section_1\">\r\n<h3 class=\"editable\"><strong>Reaction: Hydration of Alkynes<\/strong><\/h3>\r\nAs with alkenes,hydration (addition of water) to alkynes requires a strong acid, usually sulfuric acid, and is facilitated by mercuric sulfate. However, unlike the additions to double bonds which give alcohol products, addition of water to alkynes gives ketone products ( except for acetylene which yields acetaldehyde ). The explanation for this deviation lies in <strong>enol-keto tautomerization<\/strong>, illustrated by the following equation. The initial product from the addition of water to an alkyne is an enol (a compound having a hydroxyl substituent attached to a double-bond), and this immediately rearranges to the more stable keto tautomer.\r\n<p style=\"text-align: center\"><img class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143704\/ketentau.gif\" alt=\"image\" \/><\/p>\r\nTautomers are defined as rapidly interconverted constitutional isomers, usually distinguished by a different bonding location for a labile hydrogen atom (colored red here) and a differently located double bond. The equilibrium between tautomers is not only rapid under normal conditions, but it often strongly favors one of the isomers ( acetone, for example, is 99.999% keto tautomer ). Even in such one-sided equilibria, evidence for the presence of the minor tautomer comes from the chemical behavior of the compound. Tautomeric equilibria are catalyzed by traces of acids or bases that are generally present in most chemical samples. The three examples shown below illustrate these reactions for different substitutions of the triple-bond. The tautomerization step is indicated by a red arrow. For terminal alkynes the addition of water follows the Markovnikov rule, as in the second example below, and the final product ia a methyl ketone ( except for acetylene, shown in the first example ). For internal alkynes ( the triple-bond is within a longer chain ) the addition of water is not regioselective. If the triple-bond is not symmetrically located ( i.e. if R &amp; R' in the third equation are not the same ) two isomeric ketones will be formed.\r\n<table cellpadding=\"2\">\r\n<tbody>\r\n<tr>\r\n<td>HC\u2261CH \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ H<sub>2<\/sub>C=CHOH ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 H<sub>3<\/sub>C-CH=O<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>RC\u2261CH \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ RC(OH)=CH<sub>2<\/sub> ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 RC(=O)CH<sub>3<\/sub><\/td>\r\n<\/tr>\r\n<tr>\r\n<td>RC\u2261CR' \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ RHC=C(OH)R' \u00a0 + \u00a0 RC(OH)=CHR' ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 RCH<sub>2<\/sub>-C(=O)R' \u00a0 + \u00a0 RC(=O)-CH<sub>2<\/sub>R'<\/td>\r\n<\/tr>\r\n<\/tbody>\r\n<\/table>\r\n<div class=\"editIcon\"><\/div>\r\nWith the addition of water, alkynes can be hydrated to form enols that spontaneously tautomerize to ketones. Reaction is catalyzed by mercury ions. Follows Markovnikov\u2019s Rule: Terminal alkynes give methyl ketones\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2208\/Figure7.bmp?revision=1&amp;size=bestfit&amp;width=458&amp;height=212#fixme\" alt=\"Figure7.bmp\" width=\"458px\" height=\"212px\" \/>\r\n<ul>\r\n \t<li>The first step is an acid\/base reaction where the \u03c0 electrons of the triple bond acts as a Lewis base and attacks the proton therefore protinating the carbon with the most hydrogen substituents.<\/li>\r\n \t<li>The second step is the attack of the nucleophilic water molecule on the electrophilic carbocation, which creates an oxonium ion.<\/li>\r\n \t<li>Next you deprotonate by a base, generating an alcohol called an enol, which then tautomerizes into a ketone.<\/li>\r\n \t<li>Tautomerism is a simultaneous proton and double bond shift, which goes from the enol form to the keto isomer form as shown above in Figure 7.<\/li>\r\n<\/ul>\r\nNow let's look at some Hydration Reactions.\r\n<div>\r\n<div id=\"section_2\">\r\n<h4 class=\"editable\">Hydration of Terminal Alkyne produces methyl ketones<\/h4>\r\n<strong><img class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2210\/Figure8.bmp?revision=1&amp;size=bestfit&amp;width=462&amp;height=224#fixme\" alt=\"Figure8.bmp\" width=\"462px\" height=\"224px\" \/><\/strong>\r\n\r\nJust as described in Figure 7 the \u03c0 electrons will attack a proton, forming a carbocation, which then gets attacked by the nucleophilic water molecules.\u00a0 After deprotination, we generate an enol, which then tautomerizes into the ketone form shown.\r\n\r\n<\/div>\r\n<\/div>\r\n<div>\r\n<div id=\"section_3\">\r\n<h4 class=\"editable\">Hydration of Alkyne<\/h4>\r\n<div class=\"editIcon\"><\/div>\r\n<strong><img class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2211\/Figure9.bmp?revision=1&amp;size=bestfit&amp;width=518&amp;height=161#fixme\" alt=\"Figure9.bmp\" width=\"518px\" height=\"161px\" \/><\/strong>\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2213\/Figure9mech.bmp?revision=1#fixme\" alt=\"Figure9mech.bmp\" width=\"468\" height=\"332\" \/>\r\n\r\nAs you can see here, the \u03c0 electrons of the triple bond are attacking the proton, which forms a covalent bond on the carbon with the most hydrogen substituents. Once the hydrogen is bound you have a carbocation, which gets attacked by the water molecule. Now you have a positive charge on the oxygen which results in a base coming in and deprotinating the molecule. Once deprotinated, you have an enol, which then gets tautomerized.\r\n\r\n<a title=\"Hydration of Alkynes and Tautomerism\" href=\"\/Organic_Chemistry\/Hydrocarbons\/Alkynes\/Reactions_of_Alkynes\/Hydration_of_Alkynes_and_Tautomerism\" rel=\"internal\">Tautomerism <\/a>is shown here when the proton gets attacked by the double bond \u03c0 electrons forming a covalent bond between the carbon and the hydrogen on the less substituted carbon. Electrons from the Oxygen end up moving to the carbon, forming a double bond with carbon and giving itself a positive charge, which then gets attacked by the base. The base deprotinates the Oxygen resulting in the more stable final product at equilibrium, which is a ketone.\r\n\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<div id=\"section_4\">\r\n<div class=\"textbox exercises\">\r\n<h3 class=\"editable\">Exercises<\/h3>\r\n<ol>\r\n \t<li>Draw the structure of the product formed when each of the substances below is treated with H<sub>2<\/sub>O\/H<sub>2<\/sub>SO<sub>4<\/sub> in the presence of HgSO<sub>4<\/sub>.\r\n<ol>\r\n \t<li>$\\ce{\\sf{CH3-CH2-C#C-H}}$<\/li>\r\n \t<li><img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86911\/9-4-1b-exercise.png?origin=mt-web\" alt=\"3,3-dimethyl-1-alkyne\" \/><\/li>\r\n<\/ol>\r\n<\/li>\r\n \t<li>Draw the structure of the keto form of the compound shown below. Which form would you expect to be the most stable?<img src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86913\/9-4-2-exercise.png?origin=mt-web\" alt=\"1-hydroxycyclohexene\" \/>&nbsp;<\/li>\r\n<\/ol>\r\n<h3>Solutions<\/h3>\r\n[reveal-answer q=\"847797\"]Show Answer[\/reveal-answer]\r\n[hidden-answer a=\"847797\"]\r\n\r\n1.\r\n<ol>\r\n \t<li style=\"list-style-type: none\">\r\n<ol>\r\n \t<li><img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86909\/9-4-1a-answer.png?origin=mt-web\" alt=\"2-butanone\" \/><\/li>\r\n \t<li><img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86910\/9-4-1b-answer.png?origin=mt-web\" alt=\"3,3-dimethyl-2-butanone\" \/><\/li>\r\n<\/ol>\r\n<\/li>\r\n \t<li><img class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86912\/9-4-2-answer.png?origin=mt-web\" alt=\"cyclohexanone\" \/>\r\n\r\nThe keto form should be the most stable.[\/hidden-answer]<\/li>\r\n<\/ol>\r\n<div id=\"s61714\">\r\n<div id=\"section_11\">\r\n<h3 id=\"Questions-61714\">Questions<\/h3>\r\n<strong>1.<\/strong>\r\n\r\nWhat alkyne would you start with to gain the following products, in an oxidation reaction? Keep in mind resonance.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143706\/9-4qu.png\" alt=\"\" width=\"363\" height=\"158\" \/>\r\n\r\n<strong>2.<\/strong>\r\n\r\nPropose a reaction scheme for the following compound starting from the alkyne and showing required reagents and intermediates.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143708\/9-4-2qu.png\" alt=\"\" width=\"80\" height=\"148\" \/>\r\n\r\n<\/div>\r\n<div id=\"section_12\">\r\n<h3 id=\"Solutions-61714\">Solutions<\/h3>\r\n[reveal-answer q=\"317128\"]Show Answer[\/reveal-answer]\r\n[hidden-answer a=\"317128\"]\r\n\r\n<b>1.<\/b>\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143709\/9-4sol.png\" alt=\"\" width=\"380\" height=\"457\" \/>\r\n\r\n<strong>2.<\/strong>\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143711\/9-4-2sol.png\" alt=\"\" width=\"605\" height=\"175\" \/>[\/hidden-answer]\r\n\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<div id=\"section_5\">\r\n<h3 class=\"editable\">Contributors<\/h3>\r\n<ul>\r\n \t<li><a class=\"external\" title=\"http:\/\/science.athabascau.ca\/staff-pages\/dietmark\" href=\"http:\/\/science.athabascau.ca\/staff-pages\/dietmark\" target=\"_blank\" rel=\"external nofollow noopener\">Dr. Dietmar Kennepohl<\/a> FCIC (Professor of Chemistry, <a class=\"external\" title=\"http:\/\/www.athabascau.ca\/\" href=\"http:\/\/www.athabascau.ca\/\" target=\"_blank\" rel=\"external nofollow noopener\">Athabasca University<\/a>)<\/li>\r\n \t<li>Prof. Steven Farmer (<a class=\"external\" title=\"http:\/\/www.sonoma.edu\" href=\"http:\/\/www.sonoma.edu\" target=\"_blank\" rel=\"external nofollow noopener\">Sonoma State University<\/a>)<\/li>\r\n \t<li>William Reusch, Professor Emeritus (<a class=\"external\" title=\"http:\/\/www.msu.edu\/\" href=\"http:\/\/www.msu.edu\/\" target=\"_blank\" rel=\"external nofollow noopener\">Michigan State U.<\/a>), <a class=\"external\" title=\"http:\/\/www.cem.msu.edu\/~reusch\/VirtualText\/intro1.htm\" href=\"http:\/\/www.cem.msu.edu\/%7Ereusch\/VirtualText\/intro1.htm\" target=\"_blank\" rel=\"external nofollow noopener\">Virtual Textbook of\u00a0Organic\u00a0Chemistry<\/a><\/li>\r\n<\/ul>\r\n<\/div>\r\n<\/div>","rendered":"<div class=\"elm-header\">\n<div class=\"elm-header-custom\">\n<div class=\"textbox learning-objectives\">\n<h3>Objectives<\/h3>\n<div id=\"elm-main-content\" class=\"elm-content-container\">\n<div>\n<div id=\"skills\">\n<p>After completing this section, you should be able to<\/p>\n<ol>\n<li>write the equation for the reaction of water with an alkyne in the presence of sulfuric acid and mercury(II) sulfate.<\/li>\n<li>describe keto-enol tautomerism.<\/li>\n<li>predict the structure of the ketone formed when a given alkyne reacts with sulfuric acid in the presence of mercury(II) sulfate.<\/li>\n<li>identify the reagents needed to convert a given alkyne to a given ketone.<\/li>\n<li>identify the alkyne needed to prepare a given ketone by hydration of the triple bond.<\/li>\n<li>write an equation for the reaction of an alkyne with borane.<\/li>\n<li>write the equation for the reaction of a vinylic borane with basic hydrogen peroxide or hot acetic acid.<\/li>\n<li>identify the reagents, the alkyne, or both, needed to prepare a given ketone or a given cis alkene through a vinylic borane intermediate.<\/li>\n<li>identify the ketone produced when a given alkyne is reacted with borane followed by basic hydrogen peroxide.<\/li>\n<li>identify the cis alkene produced when a given alkyne is reacted with borane followed by hot acetic acid.<\/li>\n<li>explain why it is necessary to use a bulky, sterically hindered borane when preparing vinylic boranes from terminal alkynes.<\/li>\n<li>predict the product formed when the vinylic borane produced from a terminal alkyne is treated with basic hydrogen peroxide.<\/li>\n<li>identify the alkyne needed to prepare a given aldehyde by a vinylic borane.<\/li>\n<\/ol>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<div class=\"textbox key-takeaways\">\n<h3>Key TERmS<\/h3>\n<div class=\"elm-header\"><\/div>\n<div id=\"elm-main-content\" class=\"elm-content-container\">\n<div>\n<div>\n<p>Make certain that you can define, and use in context, the key terms below.<\/p>\n<ul>\n<li>enol<\/li>\n<li>keto-enol tautomeric equilibrium<\/li>\n<li>tautomerism<\/li>\n<li>tautomers<\/li>\n<\/ul>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<div id=\"elm-main-content\" class=\"elm-content-container\">\n<div id=\"note\">\n<div class=\"textbox\">\n<div id=\"note\">\n<h3 class=\"boxtitle\">Study Notes<\/h3>\n<p>Rapid interconversion between tautomers is called <em>tautomerism<\/em>; however, as the two tautomers are in equilibrium, the term <em>tautomeric<\/em> <em>equilibrium<\/em> may be used. This section demonstrates the equilibrium between a ketone and an enol; hence, the term <em>keto<\/em>&#8211;<em>enol<\/em> <em>tautomeric<\/em> <em>equilibrium<\/em> is appropriate. The term \u201cenol\u201d indicates the presence of a carbon-carbon double bond and a hydroxyl (i.e., alcohol) group. Later in the course, you will see the importance of keto-enol tautomerism in discussions of the reactions of ketones, carbohydrates and nucleic acids.<\/p>\n<p>It is important to note that tautomerism is not restricted to keto-enol systems. Other examples include imine-enamine tautomerism<\/p>\n<p><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86899\/9-4a.png?origin=mt-web\" alt=\"imine-enamine tautomerism\" \/><\/p>\n<p>and nitroso-oxime tautomerism<\/p>\n<p><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86900\/9-4b.png?origin=mt-web\" alt=\"nitroso-oxime tautomerism\" \/><\/p>\n<p>However, at the moment you need only concern yourself with keto-enol tautomerism.<\/p>\n<p>Notice how hydroboration complements hydration in the chemistry of both alkenes and alkynes.<\/p>\n<p><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86901\/9-4c.png?origin=mt-web\" alt=\"hydroboration and hydration scheme of alkenes and alkynes\" \/><\/p>\n<\/div>\n<\/div>\n<\/div>\n<div id=\"section_1\">\n<h3 class=\"editable\"><strong>Reaction: Hydration of Alkynes<\/strong><\/h3>\n<p>As with alkenes,hydration (addition of water) to alkynes requires a strong acid, usually sulfuric acid, and is facilitated by mercuric sulfate. However, unlike the additions to double bonds which give alcohol products, addition of water to alkynes gives ketone products ( except for acetylene which yields acetaldehyde ). The explanation for this deviation lies in <strong>enol-keto tautomerization<\/strong>, illustrated by the following equation. The initial product from the addition of water to an alkyne is an enol (a compound having a hydroxyl substituent attached to a double-bond), and this immediately rearranges to the more stable keto tautomer.<\/p>\n<p style=\"text-align: center\"><img decoding=\"async\" class=\"aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143704\/ketentau.gif\" alt=\"image\" \/><\/p>\n<p>Tautomers are defined as rapidly interconverted constitutional isomers, usually distinguished by a different bonding location for a labile hydrogen atom (colored red here) and a differently located double bond. The equilibrium between tautomers is not only rapid under normal conditions, but it often strongly favors one of the isomers ( acetone, for example, is 99.999% keto tautomer ). Even in such one-sided equilibria, evidence for the presence of the minor tautomer comes from the chemical behavior of the compound. Tautomeric equilibria are catalyzed by traces of acids or bases that are generally present in most chemical samples. The three examples shown below illustrate these reactions for different substitutions of the triple-bond. The tautomerization step is indicated by a red arrow. For terminal alkynes the addition of water follows the Markovnikov rule, as in the second example below, and the final product ia a methyl ketone ( except for acetylene, shown in the first example ). For internal alkynes ( the triple-bond is within a longer chain ) the addition of water is not regioselective. If the triple-bond is not symmetrically located ( i.e. if R &amp; R&#8217; in the third equation are not the same ) two isomeric ketones will be formed.<\/p>\n<table cellpadding=\"2\">\n<tbody>\n<tr>\n<td>HC\u2261CH \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ H<sub>2<\/sub>C=CHOH ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 H<sub>3<\/sub>C-CH=O<\/td>\n<\/tr>\n<tr>\n<td>RC\u2261CH \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ RC(OH)=CH<sub>2<\/sub> ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 RC(=O)CH<sub>3<\/sub><\/td>\n<\/tr>\n<tr>\n<td>RC\u2261CR&#8217; \u00a0 + \u00a0 H<sub>2<\/sub>O \u00a0 + \u00a0 HgSO<sub>4<\/sub> &amp; H<sub>2<\/sub>SO<sub>4<\/sub> \u00a0 \u2014\u2014<strong>&gt;<\/strong>\u00a0 [ RHC=C(OH)R&#8217; \u00a0 + \u00a0 RC(OH)=CHR&#8217; ] \u00a0 \u2014\u2014<strong>&gt;<\/strong> \u00a0 RCH<sub>2<\/sub>-C(=O)R&#8217; \u00a0 + \u00a0 RC(=O)-CH<sub>2<\/sub>R&#8217;<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<div class=\"editIcon\"><\/div>\n<p>With the addition of water, alkynes can be hydrated to form enols that spontaneously tautomerize to ketones. Reaction is catalyzed by mercury ions. Follows Markovnikov\u2019s Rule: Terminal alkynes give methyl ketones<\/p>\n<p><img decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2208\/Figure7.bmp?revision=1&amp;size=bestfit&amp;width=458&amp;height=212#fixme\" alt=\"Figure7.bmp\" width=\"458px\" height=\"212px\" \/><\/p>\n<ul>\n<li>The first step is an acid\/base reaction where the \u03c0 electrons of the triple bond acts as a Lewis base and attacks the proton therefore protinating the carbon with the most hydrogen substituents.<\/li>\n<li>The second step is the attack of the nucleophilic water molecule on the electrophilic carbocation, which creates an oxonium ion.<\/li>\n<li>Next you deprotonate by a base, generating an alcohol called an enol, which then tautomerizes into a ketone.<\/li>\n<li>Tautomerism is a simultaneous proton and double bond shift, which goes from the enol form to the keto isomer form as shown above in Figure 7.<\/li>\n<\/ul>\n<p>Now let&#8217;s look at some Hydration Reactions.<\/p>\n<div>\n<div id=\"section_2\">\n<h4 class=\"editable\">Hydration of Terminal Alkyne produces methyl ketones<\/h4>\n<p><strong><img decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2210\/Figure8.bmp?revision=1&amp;size=bestfit&amp;width=462&amp;height=224#fixme\" alt=\"Figure8.bmp\" width=\"462px\" height=\"224px\" \/><\/strong><\/p>\n<p>Just as described in Figure 7 the \u03c0 electrons will attack a proton, forming a carbocation, which then gets attacked by the nucleophilic water molecules.\u00a0 After deprotination, we generate an enol, which then tautomerizes into the ketone form shown.<\/p>\n<\/div>\n<\/div>\n<div>\n<div id=\"section_3\">\n<h4 class=\"editable\">Hydration of Alkyne<\/h4>\n<div class=\"editIcon\"><\/div>\n<p><strong><img decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2211\/Figure9.bmp?revision=1&amp;size=bestfit&amp;width=518&amp;height=161#fixme\" alt=\"Figure9.bmp\" width=\"518px\" height=\"161px\" \/><\/strong><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/chem.libretexts.org\/@api\/deki\/files\/2213\/Figure9mech.bmp?revision=1#fixme\" alt=\"Figure9mech.bmp\" width=\"468\" height=\"332\" \/><\/p>\n<p>As you can see here, the \u03c0 electrons of the triple bond are attacking the proton, which forms a covalent bond on the carbon with the most hydrogen substituents. Once the hydrogen is bound you have a carbocation, which gets attacked by the water molecule. Now you have a positive charge on the oxygen which results in a base coming in and deprotinating the molecule. Once deprotinated, you have an enol, which then gets tautomerized.<\/p>\n<p><a title=\"Hydration of Alkynes and Tautomerism\" href=\"\/Organic_Chemistry\/Hydrocarbons\/Alkynes\/Reactions_of_Alkynes\/Hydration_of_Alkynes_and_Tautomerism\" rel=\"internal\">Tautomerism <\/a>is shown here when the proton gets attacked by the double bond \u03c0 electrons forming a covalent bond between the carbon and the hydrogen on the less substituted carbon. Electrons from the Oxygen end up moving to the carbon, forming a double bond with carbon and giving itself a positive charge, which then gets attacked by the base. The base deprotinates the Oxygen resulting in the more stable final product at equilibrium, which is a ketone.<\/p>\n<\/div>\n<\/div>\n<\/div>\n<div id=\"section_4\">\n<div class=\"textbox exercises\">\n<h3 class=\"editable\">Exercises<\/h3>\n<ol>\n<li>Draw the structure of the product formed when each of the substances below is treated with H<sub>2<\/sub>O\/H<sub>2<\/sub>SO<sub>4<\/sub> in the presence of HgSO<sub>4<\/sub>.\n<ol>\n<li>$\\ce{\\sf{CH3-CH2-C#C-H}}$<\/li>\n<li><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86911\/9-4-1b-exercise.png?origin=mt-web\" alt=\"3,3-dimethyl-1-alkyne\" \/><\/li>\n<\/ol>\n<\/li>\n<li>Draw the structure of the keto form of the compound shown below. Which form would you expect to be the most stable?<img decoding=\"async\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86913\/9-4-2-exercise.png?origin=mt-web\" alt=\"1-hydroxycyclohexene\" \/>&nbsp;<\/li>\n<\/ol>\n<h3>Solutions<\/h3>\n<div class=\"qa-wrapper\" style=\"display: block\"><span class=\"show-answer collapsed\" style=\"cursor: pointer\" data-target=\"q847797\">Show Answer<\/span><\/p>\n<div id=\"q847797\" class=\"hidden-answer\" style=\"display: none\">\n<p>1.<\/p>\n<ol>\n<li style=\"list-style-type: none\">\n<ol>\n<li><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86909\/9-4-1a-answer.png?origin=mt-web\" alt=\"2-butanone\" \/><\/li>\n<li><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86910\/9-4-1b-answer.png?origin=mt-web\" alt=\"3,3-dimethyl-2-butanone\" \/><\/li>\n<\/ol>\n<\/li>\n<li><img decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/chem.libretexts.org\/@api\/deki\/files\/86912\/9-4-2-answer.png?origin=mt-web\" alt=\"cyclohexanone\" \/>\n<p>The keto form should be the most stable.<\/p><\/div>\n<\/div>\n<\/li>\n<\/ol>\n<div id=\"s61714\">\n<div id=\"section_11\">\n<h3 id=\"Questions-61714\">Questions<\/h3>\n<p><strong>1.<\/strong><\/p>\n<p>What alkyne would you start with to gain the following products, in an oxidation reaction? Keep in mind resonance.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143706\/9-4qu.png\" alt=\"\" width=\"363\" height=\"158\" \/><\/p>\n<p><strong>2.<\/strong><\/p>\n<p>Propose a reaction scheme for the following compound starting from the alkyne and showing required reagents and intermediates.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143708\/9-4-2qu.png\" alt=\"\" width=\"80\" height=\"148\" \/><\/p>\n<\/div>\n<div id=\"section_12\">\n<h3 id=\"Solutions-61714\">Solutions<\/h3>\n<div class=\"qa-wrapper\" style=\"display: block\"><span class=\"show-answer collapsed\" style=\"cursor: pointer\" data-target=\"q317128\">Show Answer<\/span><\/p>\n<div id=\"q317128\" class=\"hidden-answer\" style=\"display: none\">\n<p><b>1.<\/b><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143709\/9-4sol.png\" alt=\"\" width=\"380\" height=\"457\" \/><\/p>\n<p><strong>2.<\/strong><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/1518\/2017\/10\/05143711\/9-4-2sol.png\" alt=\"\" width=\"605\" height=\"175\" \/><\/div>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n<div id=\"section_5\">\n<h3 class=\"editable\">Contributors<\/h3>\n<ul>\n<li><a class=\"external\" title=\"http:\/\/science.athabascau.ca\/staff-pages\/dietmark\" href=\"http:\/\/science.athabascau.ca\/staff-pages\/dietmark\" target=\"_blank\" rel=\"external nofollow noopener\">Dr. Dietmar Kennepohl<\/a> FCIC (Professor of Chemistry, <a class=\"external\" title=\"http:\/\/www.athabascau.ca\/\" href=\"http:\/\/www.athabascau.ca\/\" target=\"_blank\" rel=\"external nofollow noopener\">Athabasca University<\/a>)<\/li>\n<li>Prof. Steven Farmer (<a class=\"external\" title=\"http:\/\/www.sonoma.edu\" href=\"http:\/\/www.sonoma.edu\" target=\"_blank\" rel=\"external nofollow noopener\">Sonoma State University<\/a>)<\/li>\n<li>William Reusch, Professor Emeritus (<a class=\"external\" title=\"http:\/\/www.msu.edu\/\" href=\"http:\/\/www.msu.edu\/\" target=\"_blank\" rel=\"external nofollow noopener\">Michigan State U.<\/a>), <a class=\"external\" title=\"http:\/\/www.cem.msu.edu\/~reusch\/VirtualText\/intro1.htm\" href=\"http:\/\/www.cem.msu.edu\/%7Ereusch\/VirtualText\/intro1.htm\" target=\"_blank\" rel=\"external nofollow noopener\">Virtual Textbook of\u00a0Organic\u00a0Chemistry<\/a><\/li>\n<\/ul>\n<\/div>\n<\/div>\n","protected":false},"author":44985,"menu_order":3,"template":"","meta":{"_candela_citation":"[]","CANDELA_OUTCOMES_GUID":"","pb_show_title":"on","pb_short_title":"","pb_subtitle":"","pb_authors":[],"pb_section_license":""},"chapter-type":[],"contributor":[],"license":[],"class_list":["post-1186","chapter","type-chapter","status-publish","hentry"],"part":25,"_links":{"self":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapters\/1186","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapters"}],"about":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/wp\/v2\/types\/chapter"}],"author":[{"embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/wp\/v2\/users\/44985"}],"version-history":[{"count":5,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapters\/1186\/revisions"}],"predecessor-version":[{"id":2318,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapters\/1186\/revisions\/2318"}],"part":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/parts\/25"}],"metadata":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapters\/1186\/metadata\/"}],"wp:attachment":[{"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/wp\/v2\/media?parent=1186"}],"wp:term":[{"taxonomy":"chapter-type","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/pressbooks\/v2\/chapter-type?post=1186"},{"taxonomy":"contributor","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/wp\/v2\/contributor?post=1186"},{"taxonomy":"license","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-mcc-organicchemistry\/wp-json\/wp\/v2\/license?post=1186"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}