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Ammonolysis
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<h2 id="organic-synthesis">Organic synthesis</h2> <h3>Mechanism: Ammonolysis of Esters</h3> <p>This mechanism<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> is similar to the hydrolysis of esters, the ammonia attacks the electrophilic carbonyl carbon forming a <a href="/facts/Tetrahedral_intermediate/YUtR429h">tetrahedral intermediate</a>. The reformation of the C-O double bond ejects the ester. The alkoxide deprotonates the ammonia forming an alcohol and amide as products.<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> </p> <h3>Of haloalkanes</h3> <p>On heating a <a href="/facts/Haloalkane/Enb7LQqt">haloalkane</a> and concentrated ammonia in a sealed tube with ethanol, a series of amines are formed along with their salts.<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a><a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> The tertiary amine is usually the major product.<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> </p> NH 3 → RX RNH 2 → RX R 2 NH → RX R 3 N → RX R 4 N + {\displaystyle {\ce {NH3->[{\ce {RX}}]RNH2->[{\ce {RX}}]R2NH->[{\ce {RX}}]R3N->[{\ce {RX}}]R4N+}}} <p>This is known as Hoffmann's ammonolysis.<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> </p> <h3>Of alcohols</h3> <p><a href="/facts/Alcohol_(chemistry)/Y0SCTDkh">Alcohols</a> can also undergo ammonolysis when in the presence of ammonia. An example is the conversion of <a href="/facts/Phenol/ACJs5NIU">phenol</a> to <a href="/facts/Aniline/eFXck1Rj">aniline</a>, catalyzed by <a href="/facts/Stannic_chloride/MgGG3FJJ">stannic chloride</a>.<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> </p> ROH + NH 3 A → SnCl 4 RNH 2 + H 2 O {\displaystyle {\ce {ROH + NH3 A ->[{\ce {SnCl4}}] RNH2 + H2O}}} <h3>Of carbonyl compounds</h3> <p>The reaction between a <a href="/facts/Ketone/BqQXpLo4">ketone</a> and ammonia results in an <a href="/facts/Imine/yK72z07j">imine</a> and byproduct water. This reaction is water sensitive and thus <a href="/facts/Desiccant/wD2YIcPc">drying agents</a> such as <a href="/facts/Aluminum_chloride/xrhvSxDr">aluminum chloride</a> or a <a href="/facts/Dean%E2%80%93Stark_apparatus/cARLn6f4">Dean–Stark apparatus</a> must be employed to remove water. The resulting imine will react and decompose back into the ketone and the ammonia when in the presence of water. This is due to the fact that this reaction is reversible:<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> </p> R 2 CO + NH 3 ↽ − − ⇀ R 2 CNH + H 2 O {\displaystyle {\ce {R2CO + NH3 <=> R2CNH + H2O}}} . <h2 id="inorganic-synthesis">Inorganic synthesis</h2> <p>Ammonolysis can be used to synthesize <a href="/facts/Nitrides/9vkrCbJ4">nitrides</a> (and <a href="/facts/Oxynitride/MRxCb4xX">oxynitrides</a>) by reacting various metal precursors with ammonia, some options include <a href="/facts/Chemical_vapor_deposition/7khLxeU5">chemical vapor deposition</a>,<a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a> treating metals or metal oxides with ammonia gas,<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a> or liquid <a href="/facts/Supercritical_fluid/rGkUWb7e">supercritical</a> ammonia (also known as "ammonothermal" synthesis, analogous to <a href="/facts/Hydrothermal_synthesis/H1G9vGvD">hydrothermal synthesis</a>).<a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> </p> M + NH 3 ⟶ MN + 3 2 H 2 {\displaystyle {\ce {M + NH3 -> MN + 3/2 H2}}} MO 2 + 4 3 NH 3 ⟶ MN + 2 H 2 O + 1 6 N 2 {\displaystyle {\ce {MO2 + 4/3 NH3 -> MN + 2 H2O + 1/6 N2}}} <p>The products of these reactions may be complex, with mixtures of oxygen, nitrogen, and hydrogen that can be difficult to characterize.<a class="footnote-ref" id="fnref:19" href="#fn:19"><sup>19</sup></a> </p> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Speight, James G. 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