Preparation of 3,4,5-trimethoxybenzaldehyde , Hive Chemistry Discourse
 
    Rhodium (Chief Bee) 12-10-01 07:44
No 246115
      Preparation of 3,4,5-trimethoxybenzaldehyde<br> <i title="This post has been up-rated by the moderators">(Rated as: excellent)</i> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246115&Number=246115&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> To 300g gallic acid in 300ml H2O was added 900ml warm 50% NaOH while bubbling alkaline pyrogallol-washed nitrogen through the solution and then 900g Me2SO4 within 1h at 40-50C. The mixt. cooled and 75 g. NaOH added, the mixt. refluxed for 3 hrs. and cooled again, 900ml conc HCl with 1 kg crushed ice added, the ppt. sepd., washed with H2O, dissolved in 2000ml 40% EtOH, and kept 12 hrs. at 0C pptg. 3,4,5-trimethoxybenzoic acid. <br><br>200 g 3,4,5-trimethoxybenzoic acid was refluxed with 114g SOCl2 for 2 h, excess SOCl2 distd. off at reduced pressure, the mixt. cooled, and the solidified product suspended in petroleum ether, refluxed 10 min. with 1% activated carbon, filtered, and cooled to 0C yielding 3,4,5-trimethoxybenzoyl chloride. <br><br>To 150g 3,4,5-trimethoxybenzoyl chloride in 2100ml Et2O was added slowly with stirring 120g aniline in 510ml Et2O and the mixt. allowed to stand 1h, filtered, stirred with 2% NaCl, filtered, and washed with NaCl soln. yielding the anilide, of which (100 g) with 75 g PCl5, warmed to 70C to evolve HCl and heated further to dist. off excess PCl5 yielded the imidochloride. To 90 g if the imidochloride in 2000ml Et2O was added an ethereal SnCl2 soln., the mixt. held at 0 for 12 hrs., the pptd. Sn salt sepd., washed with Et2O, and refluxed with AcOH-HCl-H2O (200:175:325 ml) for 1h, cooled, diluted with H2O and extd. 3 times with Et2O, dried. and crystd. to yield 3,4,5-trimethoxybenzaldehyde. <br><br>Reference: Arch. ital. sci. farmacol. [3] 2, 376-83 (1952); Chem Abs 3314h (1956) </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post246175"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> demorol<br> <i>(<span title="The user's title at the time of posting">Hive Bee</span>)</i><br> <span title="Posting date">12-10-01 12:23</span><br> <span title="Link to this post by using the markup [246175]">No 246175</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <title>Re: Preparation of 3,4,5-trimethoxybenzaldehyde </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246175&Number=246175&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> Thanks Rhodium! I have some gallic acid and I just wanted to post a question what to do with it. Now, I just have one question. Since in most drug syntheses is used non-iodized NaCl, can I use regular NaCl in this one, or is iodine a problem again.<hr>Give me some chemicals and I'll give you pleasure. </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post246179"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> <font color="#FF0033">Rhodium</font><br> <i>(<span title="The user's title at the time of posting">Chief Bee</span>)</i><br> <span title="Posting date">12-10-01 12:36</span><br> <span title="Link to this post by using the markup [246179]">No 246179</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <b title="The subject of this post">Re: Preparation of 3,4,5-trimethoxybenzaldehyde</b> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246179&Number=246179&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> Iodized salt is okay to use here. Another variation of the procedure can be found here: <a href="http://chemistry.mdma.ch/hiveboard/rhodium/chemistry /mescaline.txt" target="_blank" title="Jump to this external site">../rhodium/chemistry /mescali<wbr>ne.txt</a> </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post246208"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> PrimoPyro<br> <i>(<span title="The user's title at the time of posting">Hive Addict</span>)</i><br> <span title="Posting date">12-10-01 14:03</span><br> <span title="Link to this post by using the markup [246208]">No 246208</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <b title="The subject of this post">Re: Preparation of 3,4,5-trimethoxybenzaldehyde</b> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246208&Number=246208&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> Would the alkoxys interfere with reducing the carboxyl to an aldehyde with calcium formate described awhile ago for benzoic acid? (whew, long sentence <img src="../forum/images/icons_lightgrey/wink.gif" alt="wink" title="Wink" heigth="15" width="15">)<br><br>If the trimethoxy-benzoic acid is basified with calcium carbonate to the salt, then reacted with calcium formate, it should reduce to the aldehyde, the same way for benzoic acid, correct?<br><br>Me hopes so.<br><br>SOCl2 = yucky.<br>Ca(OOCH)2 = <img src="../forum/images/icons_lightgrey/smile.gif" alt="smile" title="Smile" heigth="15" width="15"> + OTC via some 'tone an' shock <img src="../forum/images/icons_lightgrey/wink.gif" alt="wink" title="Wink" heigth="15" width="15"><br><br>                                                  PrimoPyro<br><hr><font color="blue"><i>Vivent Longtemps la Ruche!</i></font color="blue"> <font color="red"><b>STRIKE</b></font color="red"> For President! </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post246211"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> <font color="#FF0033">Rhodium</font><br> <i>(<span title="The user's title at the time of posting">Chief Bee</span>)</i><br> <span title="Posting date">12-10-01 14:12</span><br> <span title="Link to this post by using the markup [246211]">No 246211</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <b title="The subject of this post">Re: Preparation of 3,4,5-trimethoxybenzaldehyde</b> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246211&Number=246211&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> No, I don't believe the alkoxys will stand in your way. Where is that procedure posted? It seems like a twisted canizzaro rxn... </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post246213"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> PrimoPyro<br> <i>(<span title="The user's title at the time of posting">Hive Addict</span>)</i><br> <span title="Posting date">12-10-01 14:15</span><br> <span title="Link to this post by using the markup [246213]">No 246213</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <b title="The subject of this post">Re: Preparation of 3,4,5-trimethoxybenzaldehyde</b> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=246213&Number=246213&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> <span title="Jump to this post"><a href="http://chemistry.mdma.ch/hiveboard/chemistrydiscourse/000227286.html#Post227441">Post 227441</a> <i>(halfapint: "Re: Alternative Way To Make Benzaldehyde", Chemistry Discourse)</i></span><br><hr><font color="blue"><i>Vivent Longtemps la Ruche!</i></font color="blue"> <font color="red"><b>STRIKE</b></font color="red"> For President! </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> <td align="left" valign="top" class="text_bg"> <img src="../forum/images/left_top.gif" border="0" height="12" width="9"></td> <td colspan="7"><a name="Post250434"></a><a name="last"></a></a> </td> <td align="right" valign="top"><img src="../forum/images/right_top.gif" border="0" height="12" width="9"></td> </tr> <tr class="text_bg"> <td rowspan="2"> </td> <td rowspan="2"> </td> <td valign="top" align="center" rowspan="2"> halfapint<br> <i>(<span title="The user's title at the time of posting">Ubiquitous Precursor Medal Winner</span>)</i><br> <span title="Posting date">12-25-01 14:00</span><br> <span title="Link to this post by using the markup [250434]">No 250434</span><br> </td> <td rowspan="2">  </td> <td rowspan="2" width="1" class="vert_ruler"> <img src="../forum/images/hr.gif" border="0" width="1" height="1"> </td> <td rowspan="2">  </td> <td class="text_bg" align="left" valign="top"> <b title="The subject of this post">Re: Preparation of 3,4,5-trimethoxybenzaldehyde</b> </td> <td class="text_bg" align="right" valign="top">  <a href="https://www.the-hive.ws/forum/favorites.pl?Cat=&option=add&number=250434&Number=250434&page=82&view=&sort=5&part=&vc=&new=&backto=showflat" title="Add this post to your bookmark list in your Private Area">Bookmark</a>  </td> <td> </td> </tr> <tr class="text_bg"> <td colspan="2" valign="top" align="left"> <br> Re: <span title="Jump to this post"><a href="http://chemistry.mdma.ch/hiveboard/chemistrydiscourse/000227286.html#Post227441">Post 227441</a> <i>(halfapint: "Re: Alternative Way To Make Benzaldehyde", Chemistry Discourse)</i></span><br>This rxn is real enough, but I've become more gloomy about its prospects. It's a dry decomposition reaction, read that as sorta high temperature. My attempt to get an aldehyde from the calcium salt of asarylic acid, mixed with an equivalent of calcium formate, ended with just a few beads of liquid in the condenser. Evidently my hotplate just wasn't getting hot enough. Heating mantle has a short, and not much open flame work happens around here.<br><br>Have found yet another old text reference: Textbook of Organic Chemistry, E. Wertheim, 1939, p.523.<blockquote title="Quoted text"><hr><p>The following methods are available for the preparation of the aromatic aldehydes...<br>(4) Aromatic aldehydes are formed <i><b>(usually in very low yield)</b></i> by heating the calcium salts of aromatic acids with calcium formate:<br>(C<sub>6</sub>H<sub>5</sub>COO)<sub>2</sub>Ca + (HCOO)<sub>2</sub>Ca --> 2(CaCO<sub>3</sub>) + 2(C<sub>6</sub>H<sub>5</sub>CHO) Benzaldehyde<br>This reaction has its identical counterpart in the aliphatic series.<p><hr></blockquote><p>The part I emphasized is what makes me glum. I get happier when a ref states "usually in very high yield."<br><hr>turning <b>science fact</b> into <b><i><font color="red"><<science fiction>></font color="red"></i></b> </td> <td> </td> </tr> <tr class="text_bg"> <td align="left" valign="bottom"><img src="../forum/images/left_bottom.gif" border="0" height="12" width="9"></td> <td valign="middle" align="center" colspan="7"> </td> <td align="right" valign="bottom"><img src="../forum/images/right_bottom.gif" border="0" height="12" width="9"></td> </tr> <tr class="page_bg"> <td colspan="9"> </td> </tr> </body> </html>