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Bwiti
(Hive Addict)
10-18-01 03:43
No 226201
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3,4-methylenedioxymandelic acid
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Anyone know a synthesis for 3,4-methylenedioxymandelic acid? Peace!<br><hr> I'm going to help all of you cleanse this diseased planet.
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<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">10-18-01 07:32</span><br>
<span title="Link to this post by using the markup [226259]">No 226259</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Use piperonal with this procedure to get the mandelonitrile intermediate. Basic hydrolysis should give the substituted mandelic acid.<br><br>To a solution of 40g NaHSO3 (sodium bisulfite) in 360ml water heated to 40°C, 44 g 4-Methoxybenzaldehyde (0.324 mol) is added with vigorous stirring. After 20 min, cool the reaction mixture down to 0°C, add 200 mL diethyl ether and add a solution of 17 g NaCN in 70 mL water dropwise. Let stir for 30 min at 0°C, separate the organic phase and extract the aqueous phase twice with 50 mL portions of ether. The combined ether extracts are then dried over anhydrous calcium chloride. After the evaporation of the solvent under a vacuum at 35-40°C, the remaining oil is cooled and allowed to solidify.
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karel<br>
<i>(<span title="The user's title at the time of posting">Stranger / Eraser</span>)</i><br>
<span title="Posting date">10-18-01 13:10</span><br>
<span title="Link to this post by using the markup [226365]">No 226365</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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I used this acid as intermediate for preparation of piperonal. It can be synthesized from 1,3-benzodioxole (1,2-methylenedioxybenzene) and 50% glyoxylic acid in sulfuric acid. See article from Cerveny, Kozel, Marhoul in Perfumer and Flavorist, year 1989 (I don't remember the page, but i can find it in about two weeks).<br>I didn't have an access to glyoxylic acid that time, so I made it by electrolysis of oxalic acid in dilute sulfuric acid (lead electrodes) and evaporated (<40 deg C, glyoxylic acid is unstable at elevated temperature) catholyte used directly for synthesis. Yields of piperonal were about 50% from benzodioxole (Cerveny states 80% with pure 50%glyoxylic acid).<br>I hope it can help you<br><br>karel
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<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">10-18-01 14:34</span><br>
<span title="Link to this post by using the markup [226403]">No 226403</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Karel: That reference would be highly interesting. How did you do the mandelic acid => benzaldehyde conversion?
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PolytheneSam<br>
<i>(<span title="The user's title at the time of posting">Master Searcher</span>)</i><br>
<span title="Posting date">10-18-01 15:38</span><br>
<span title="Link to this post by using the markup [226417]">No 226417</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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See this patent<br><a href="http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=/netahtml/srchnum.htm&r=1&f=G&l=50&s1=%274190583%27.WKU.&OS=PN/4190583&RS=PN/4190583" target="_blank" title="Jump to this external site">http://patft.uspto.gov/netacgi/nph-Parse<wbr>r?Sect1=<wbr>PTO1&Sec<wbr>t2=HITOF<wbr>F&d=PALL<wbr>&p=1&u=/<wbr>netahtml<wbr>/srchnum<wbr>.htm&r=1<wbr>&f=G&l=5<wbr>0&s1=%27<wbr>4190583%<wbr>27.WKU.&<wbr>OS=PN/41<wbr>90583&RS<wbr>=PN/4190<wbr>583</a><br><hr>http://www.geocities.com/dritte123/PSPF.<wbr>html
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foxy2<br>
<i>(<span title="The user's title at the time of posting">Distinctive Doe</span>)</i><br>
<span title="Posting date">10-18-01 17:00</span><br>
<span title="Link to this post by using the markup [226483]">No 226483</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Check out this thread, I posted lots of good stuff, and it was only about 2 days ago. <br><span title="Jump to this post"><a href="../novel/000212038.html#Post225606">Post 225606</a> <i>(foxy2: "Re: 4-Methylaminorex Synth w/o CNBr", Novel Discourse)</i></span><br><br><br><hr>Do Your Part To Win The War
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Aurelius<br>
<i>(<span title="The user's title at the time of posting">Stranger</span>)</i><br>
<span title="Posting date">10-18-01 17:22</span><br>
<span title="Link to this post by using the markup [226505]">No 226505</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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hey bwiti, is that what aurelius thinks it is? from that patent aurelius sent you? if so, it's about damn time somebody looked at it seriously.
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Bwiti<br>
<i>(<span title="The user's title at the time of posting">Hive Addict</span>)</i><br>
<span title="Posting date">10-18-01 18:54</span><br>
<span title="Link to this post by using the markup [226571]">No 226571</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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"hey bwiti, is that what aurelius thinks it is?"<br><br> Only if you've recently changed your username.<br> Thanks for the info folks. Check out this patent: <a href="http://l2.espacenet.com/dips/viewer?PN=GB2165536&CY=gb&LG=en&DB=EPD" target="_blank" title="Jump to this external site">http://l2.espacenet.com/dips/viewer?PN=G<wbr>B2165536<wbr>&CY=gb&L<wbr>G=en&DB=<wbr>EPD</a><br><hr> I'm going to help all of you cleanse this diseased planet.
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Aurelius<br>
<i>(<span title="The user's title at the time of posting">Stranger</span>)</i><br>
<span title="Posting date">10-18-01 22:28</span><br>
<span title="Link to this post by using the markup [226653]">No 226653</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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<br>
indeed aurelius did. BTW, how many of your plants are doing well?
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Bwiti<br>
<i>(<span title="The user's title at the time of posting">Hive Addict</span>)</i><br>
<span title="Posting date">10-19-01 10:13</span><br>
<span title="Link to this post by using the markup [226813]">No 226813</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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<br>
"how many of your plants are doing well?"<br><br> Cool man, I hear you. All of my marigolds and daiseys are doing fine.<img src="../forum/images/icons_lightgrey/cool.gif" alt="cool" title="Cool" heigth="15" width="15"><br><hr> I'm going to help all of you cleanse this diseased planet.
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karel<br>
<i>(<span title="The user's title at the time of posting">Stranger / Eraser</span>)</i><br>
<span title="Posting date">10-19-01 10:19</span><br>
<span title="Link to this post by using the markup [226815]">No 226815</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Hello Rhodium,<br>conversion of methylenedioxymandelic acid to piperonal is very simple - just adding equivalent amount of 0.5M nitric acid and gentle boiling, theoretical amount of carbon dioxide is evolved in 0.5 h. Then extract or steam distill...<br>Regards<br><br>karel
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<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">10-19-01 12:06</span><br>
<span title="Link to this post by using the markup [226841]">No 226841</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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An equimolar amount of 0.5M HNO3, is that what you say? Do you have any references for this, or is it just practical experience? Yields?
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Aurelius<br>
<i>(<span title="The user's title at the time of posting">Stranger</span>)</i><br>
<span title="Posting date">10-19-01 13:40</span><br>
<span title="Link to this post by using the markup [226871]">No 226871</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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<br>
us patent 5095128<br><br>uses nitric acid in HCl solution or somthing along those lines<br><br>
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terbium<br>
<i>(<span title="The user's title at the time of posting">Old P2P Cook</span>)</i><br>
<span title="Posting date">10-19-01 15:00</span><br>
<span title="Link to this post by using the markup [226907]">No 226907</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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<font color="blue">Karel: That reference would be highly interesting. How did you do the mandelic acid => benzaldehyde conversion? </font color="blue"><br><br><b>High Selectivity in the Oxidation of Mandelic Acid Derivatives and in O-Methylation of Protocatechualdehyde:<br>New Processes for the Synthesis of Vanillin, iso-Vanillin, and Heliotropin</b> Org. Proc. Res. Dev. 4(6), 534-543, 2000<br><br><a href="http://pubs.acs.org/cgi-bin/jtextd?oprdfk/4/6/html/op0000529.html" target="_blank" title="Jump to this external site">http://pubs.acs.org/cgi-bin/jtextd?oprdf<wbr>k/4/6/ht<wbr>ml/op000<wbr>0529.htm<wbr>l</a><br><br><i><b>3,4-Dioxymethylene Mandelic acid 16.</b> <br>Benzo[1,3]dioxole (8.20 mmol) was added dropwise over a<br>period of 30 min to a mixture of 8.41 mmol of glyoxylic<br>acid, 14.59 mmol of sulphuric acid, and 11.34 mmol of <br>water at 0-5°C. The reaction was run for 20 hour at 0°C <br>and then diluted with 20 ml of water. <br>The 3,4-dioxymethylene mandelic acid precipitated and <br>was then filtered off. HPLC analysis revealed a yield <br>of 86% with a selectivity of greater than 95%</i>
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<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">10-19-01 15:18</span><br>
<span title="Link to this post by using the markup [226913]">No 226913</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Thank you, thank you.
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terbium<br>
<i>(<span title="The user's title at the time of posting">Old P2P Cook</span>)</i><br>
<span title="Posting date">10-19-01 16:34</span><br>
<span title="Link to this post by using the markup [226948]">No 226948</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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I got interrupted, momma called me for lunch. I will <br>continue on with some of the interesting parts from the<br>Experimental Section of this article.<br><br><b>Heliotropin 4.</b><br>(A) 3,4-Dioxymethylene mandelic acid (5 mmol), Na2S2O8 <br>(6mmol), and AgNO3 (0.05 mmol) in 30 ml of water and 30 ml<br>of CH2Cl2 were refluxed for 5 h. The CH2Cl2 phase was<br>removed and analyzed by HPLC; a yield of 96% of <br>heliotropin was obtained.<br><br>(B) 3,4-Dioxymethylene mandelic acid (5 mmol), CuCl2 (0.5 mmol), <br>and 4.05 g of 37% HCl in 30 ml of toluene was heated at 80°C<br>and bubbling O2 for 22 h. The organic phase was separated and<br>analyzed by HPLC; a yield of 98% of heliotropin was<br>obtained. The aqueous solution is ready to be used for<br>further oxidation.<br><br>(C) Protocatechualdehyde (13.1 g, 0.1 mol), NaOH (12g), and<br>tetrabutylammonium bromide (3.2g) in 100 ml of water and<br>100 ml of CH2Cl2 were heated for 4 h at 80°C in an <br>autoclave. The aqueous phase was then separated and<br>analysed by HPLC. The aqueous solution was acidified and<br>extracted with ethyl acetate to recover the unreacted protocatechualdehyde. The conversion was 58.6% and<br>selectivity in heliotropin 64%.
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foxy2<br>
<i>(<span title="The user's title at the time of posting">Distinctive Doe</span>)</i><br>
<span title="Posting date">10-19-01 20:48</span><br>
<span title="Link to this post by using the markup [227024]">No 227024</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Jackpot-OTC SYNTHESIS!!!!!!<br>Al/Hg reduction of Oxylic acid to glyoxylic acid :o)<br><br>Glyoxylic acid. <br>Dukai, Jozsef; Varkonyi-Rozsa, Agnes; Barath, Mrs. Miklos. (Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Rt., Hung.). Hung. Teljes (1979), 20 pp. CODEN: HUXXBU HU 15960 19790127 Patent written in Hungarian. <br>Patent No.<br>HU 15960<br>HU 173712<br> <br>Abstract<br>X:CHCO2H (X = O, H2NCONHN, and H2NCSNHN) and 2-hydroxyquinoxaline were prepd. by Hg or Hg2+ activated Al redn. of oxalic acid (I). Thus, a mixt. of 2.5 L MeOH, 35 g 99.5% Al turnings, and 10 mL 1% HgCl2 in MeOH was stirred 10-15 min, stirred 6 h at 20-30° with 296 g I, kept overnight, filtered, and the MeOH replaced by H2O. The soln. was passed through Varion KS (H+) cation-exchange resin, concd. at 40-50° to deposit unreacted I, and filtered to give a soln. contg. 75-80 g glyoxylic acid. <br><br><br>This one might bee even better.<br><br>Glyoxalic acid. <br>(Daicel Chemical Industries, Ltd., Japan). Jpn. Kokai Tokkyo Koho (1983), 6 pp. CODEN: JKXXAF JP 58198437 A2 19831118 Showa. Patent written in Japanese.<br><br>Abstract<br>OHCCO2H (I) was prepd. by reaction of aq. oxalic acid (II) with Cl. Thus, Cl was introduced to 1850.2 g aq. soln. contg. 5.03% II and 0.48% I over 19 h at 15-18° to give 1984.3 g aq. soln. contg. 5.08% I. Conversion of II and selectivity for I were 92.8% and 83.4%, resp. <br><br><br><br><br><br><hr>Do Your Part To Win The War
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PolytheneSam<br>
<i>(<span title="The user's title at the time of posting">Master Searcher</span>)</i><br>
<span title="Posting date">10-21-01 08:26</span><br>
<span title="Link to this post by using the markup [227485]">No 227485</span><br>
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<b title="The subject of this post">Re: 3,4-methylenedioxymandelic acid</b>
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Here's an English abstract of Japanese patent 54-73739<br><br><img src="../picproxie_docs/000226201-file_8noo.jpg"><br><hr>http://www.geocities.com/dritte123/PSPF.<wbr>html
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