Abstract
<jats:title>Abstract</jats:title> <jats:p> <jats:chem-struct-wrap> <jats:chem-struct> <jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" position="anchor" xlink:href="urn:x-wiley:9780470842898:media:ra057:nra057sf.001"> <jats:alt-text>image</jats:alt-text> </jats:graphic> </jats:chem-struct> </jats:chem-struct-wrap> <jats:table-wrap position="anchor"> <jats:table frame="void"> <jats:col/> <jats:col/> <jats:col/> <jats:tbody> <jats:tr> <jats:td>(X = Br)</jats:td> <jats:td/> <jats:td/> </jats:tr> <jats:tr> <jats:td> <jats:italic>[</jats:italic> <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="cas-registration-number" xlink:href="1730-25-2"> <jats:italic>1730‐25‐2</jats:italic> </jats:ext-link> <jats:italic>]</jats:italic> </jats:td> <jats:td> C <jats:sub>3</jats:sub> H <jats:sub>5</jats:sub> BrMg </jats:td> <jats:td>(MW 145.29)</jats:td> </jats:tr> </jats:tbody> </jats:table> </jats:table-wrap> </jats:p> <jats:p> InChI = <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="inchi" xlink:href="InChI=1S/C3H5.BrH.Mg/c1-3-2;;/h3H,1-2H2;1H;/q;;+1/p-1">1S/C3H5.BrH.Mg/c1‐3‐2;;/h3H,1‐2H2;1H;/q;;+1/p‐1</jats:ext-link> </jats:p> <jats:p> InChIKey = <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="inchi" xlink:href="InChIKey=FEMBXICCJNZMMC-UHFFFAOYSA-M">FEMBXICCJNZMMC‐UHFFFAOYSA‐M</jats:ext-link> </jats:p> <jats:p> <jats:table-wrap position="anchor"> <jats:table frame="void"> <jats:col/> <jats:col/> <jats:col/> <jats:tbody> <jats:tr> <jats:td>(X = Cl)</jats:td> <jats:td/> <jats:td/> </jats:tr> <jats:tr> <jats:td> <jats:italic>[</jats:italic> <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="cas-registration-number" xlink:href="2622-05-1"> <jats:italic>2622‐05‐1</jats:italic> </jats:ext-link> <jats:italic>]</jats:italic> </jats:td> <jats:td> C <jats:sub>3</jats:sub> H <jats:sub>5</jats:sub> ClMg </jats:td> <jats:td>(MW 100.84)</jats:td> </jats:tr> </jats:tbody> </jats:table> </jats:table-wrap> </jats:p> <jats:p> InChI = <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="inchi" xlink:href="InChI=1S/C3H5.ClH.Mg/c1-3-2;;/h3H,1-2H2;1H;/q;;+1/p-1">1S/C3H5.ClH.Mg/c1‐3‐2;;/h3H,1‐2H2;1H;/q;;+1/p‐1</jats:ext-link> </jats:p> <jats:p> InChIKey = <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" ext-link-type="inchi" xlink:href="InChIKey=PLYLAFITHJUEGX-UHFFFAOYSA-M">PLYLAFITHJUEGX‐UHFFFAOYSA‐M</jats:ext-link> </jats:p> <jats:p> (allylating agents capable of easy addition to carbonyl compounds, <jats:sup> <jats:bold>15–23</jats:bold> </jats:sup> nitro compounds <jats:sup> <jats:bold>57</jats:bold> </jats:sup> and nitriles, <jats:sup> <jats:bold>58–61</jats:bold> </jats:sup> imines <jats:sup> <jats:bold>43–50</jats:bold> </jats:sup> and aza aromatics, <jats:sup> <jats:bold>51–56</jats:bold> </jats:sup> unactivated alkenes, <jats:sup> <jats:bold>30–42</jats:bold> </jats:sup> and of displacement reactions on halo compounds <jats:sup> <jats:bold>6,24–28,53,54</jats:bold> </jats:sup> ) </jats:p> <jats:p> <jats:list list-type="simple"> <jats:list-item> <jats:p> <jats:italic>Physical Data:</jats:italic> Br: fp −40 °C; <jats:italic>d</jats:italic> 0.851 g cm <jats:sup>−3</jats:sup> (commercial reagent). Cl: fp −17 °C; <jats:italic>d</jats:italic> 0.995 g cm <jats:sup>−3</jats:sup> (commercial reagent). </jats:p> </jats:list-item> <jats:list-item> <jats:p> <jats:italic>Solubility:</jats:italic> Br: very sol ether. Cl: slightly sol ether; sol THF. </jats:p> </jats:list-item> <jats:list-item> <jats:p> <jats:italic>Form Supplied in:</jats:italic> Br: 1.0 M solution in Et <jats:sub>2</jats:sub> O packaged under N <jats:sub>2</jats:sub> . Cl: 2.0 M solution in THF packaged under N <jats:sub>2</jats:sub> . </jats:p> </jats:list-item> <jats:list-item> <jats:p> <jats:italic>Preparative Methods:</jats:italic> allylmagnesium bromide and chloride can be easily prepared by direct reaction of <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="urn:x-wiley:9780470842898:xml-component:rm001">Magnesium</jats:ext-link> with <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="urn:x-wiley:9780470842898:xml-component:ra045">Allyl Bromide</jats:ext-link> and <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="urn:x-wiley:9780470842898:xml-component:ra046">Allyl Chloride</jats:ext-link> , respectively <jats:sup> <jats:bold>2–5</jats:bold> </jats:sup> in diethyl ether and/or tetrahydrofuran. An excess of Mg (preferably 10%) is recommended. <jats:sup> <jats:bold>6,7</jats:bold> </jats:sup> Prior amalgamation of <jats:italic>very pure</jats:italic> Mg <jats:sup> <jats:bold>3,4</jats:bold> </jats:sup> suppresses the formation of 1,5‐hexadiene. An improved preparation <jats:sup> <jats:bold>8</jats:bold> </jats:sup> uses a THF slurry of Mg, obtained by co‐condensation in a rotating solution reactor. <jats:sup> <jats:bold>9</jats:bold> </jats:sup> Preactivation of Mg by dry stirring in an inert atmosphere is also highly beneficial. <jats:sup> <jats:bold>10</jats:bold> </jats:sup> Allylpotassium can be readily converted into the magnesium analogs by simply adding a solution of <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="urn:x-wiley:9780470842898:xml-component:rm003">Magnesium Bromide</jats:ext-link> in THF. <jats:sup> <jats:bold>11,12</jats:bold> </jats:sup> Most of the work on allylic Grignards has been carried out with the bromide. Indeed, the bromide can be prepared in slightly higher yield than the chloride and shows a greater solubility in ether. <jats:sup> <jats:bold>1</jats:bold> </jats:sup> </jats:p> </jats:list-item> <jats:list-item> <jats:p> <jats:italic>Handling, Storage, and Precautions:</jats:italic> both moisture‐sensitive; highly inflammable; react violently with water; induce burns. Bottles of these reagents should be flushed with N <jats:sub>2</jats:sub> , kept tightly sealed to preclude contact with oxygen, and stored far from sparks. In case of contact with eyes and skin, wash immediately with abundant water. </jats:p> </jats:list-item> </jats:list> </jats:p>