Author Topic: 3,4-methylenedioxymandelic acid  (Read 2982 times)

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Bwiti

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3,4-methylenedioxymandelic acid
« on: October 18, 2001, 03:43:00 AM »
Anyone know a synthesis for 3,4-methylenedioxymandelic acid? Peace!

  I'm going to help all of you cleanse this diseased planet.

Rhodium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #1 on: October 18, 2001, 07:32:00 AM »
Use piperonal with this procedure to get the mandelonitrile intermediate. Basic hydrolysis should give the substituted mandelic acid.

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.

karel

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #2 on: October 18, 2001, 01:10:00 PM »
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).
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).
I hope it can help you

karel

Rhodium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #3 on: October 18, 2001, 02:34:00 PM »
Karel: That reference would be highly interesting. How did you do the mandelic acid => benzaldehyde conversion?


foxy2

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #5 on: October 18, 2001, 05:00:00 PM »
Check out this thread, I posted lots of good stuff, and it was only about 2 days ago.

Post 225606

(foxy2: "Re: 4-Methylaminorex Synth w/o CNBr", Novel Discourse)




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Aurelius

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Re: 3,4-methylenedioxymandelic acid
« Reply #6 on: October 18, 2001, 05:22:00 PM »
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.

Bwiti

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #7 on: October 18, 2001, 06:54:00 PM »
"hey bwiti, is that what aurelius thinks it is?"

  Only if you've recently changed your username.
  Thanks for the info folks. Check out this patent:

http://l2.espacenet.com/dips/viewer?PN=GB2165536&CY=gb&LG=en&DB=EPD



  I'm going to help all of you cleanse this diseased planet.

Aurelius

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #8 on: October 18, 2001, 10:28:00 PM »
indeed aurelius did.  BTW, how many of your plants are doing well?

Bwiti

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #9 on: October 19, 2001, 10:13:00 AM »
"how many of your plants are doing well?"

  Cool man, I hear you. All of my marigolds and daiseys are doing fine. 8)

  I'm going to help all of you cleanse this diseased planet.

karel

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #10 on: October 19, 2001, 10:19:00 AM »
Hello Rhodium,
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...
Regards

karel

Rhodium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #11 on: October 19, 2001, 12:06:00 PM »
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?

Aurelius

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #12 on: October 19, 2001, 01:40:00 PM »
us patent 5095128

uses nitric acid in HCl solution or somthing along those lines


terbium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #13 on: October 19, 2001, 03:00:00 PM »
Karel: That reference would be highly interesting. How did you do the mandelic acid => benzaldehyde conversion?

High Selectivity in the Oxidation of Mandelic Acid Derivatives and in O-Methylation of Protocatechualdehyde:
New Processes for the Synthesis of Vanillin, iso-Vanillin, and Heliotropin
Org. Proc. Res. Dev. 4(6), 534-543, 2000

http://pubs.acs.org/cgi-bin/jtextd?oprdfk/4/6/html/op0000529.html



3,4-Dioxymethylene Mandelic acid 16.
Benzo[1,3]dioxole (8.20 mmol) was added dropwise over a
period of 30 min to a mixture of 8.41 mmol of glyoxylic
acid, 14.59 mmol of sulphuric acid, and 11.34 mmol of
water at 0-5°C. The reaction was run for 20 hour at 0°C
and then diluted with 20 ml of water.
The 3,4-dioxymethylene mandelic acid precipitated and
was then filtered off. HPLC analysis revealed a yield
of 86% with a selectivity of greater than 95%

Rhodium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #14 on: October 19, 2001, 03:18:00 PM »
Thank you, thank you.

terbium

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #15 on: October 19, 2001, 04:34:00 PM »
I got interrupted, momma called me for lunch. I will
continue on with some of the interesting parts from the
Experimental Section of this article.

Heliotropin 4.
(A) 3,4-Dioxymethylene mandelic acid (5 mmol), Na2S2O8
(6mmol), and AgNO3 (0.05 mmol) in 30 ml of water and 30 ml
of CH2Cl2 were refluxed for 5 h. The CH2Cl2 phase was
removed and analyzed by HPLC; a yield of 96% of
heliotropin was obtained.

(B) 3,4-Dioxymethylene mandelic acid (5 mmol), CuCl2 (0.5 mmol),
and 4.05 g of 37% HCl in 30 ml of toluene was heated at 80°C
and bubbling O2 for 22 h. The organic phase was separated and
analyzed by HPLC; a yield of 98% of heliotropin was
obtained. The aqueous solution is ready to be used for
further oxidation.

(C) Protocatechualdehyde (13.1 g, 0.1 mol), NaOH (12g), and
tetrabutylammonium bromide (3.2g) in 100 ml of water and
100 ml of CH2Cl2 were heated for 4 h at 80°C in an
autoclave. The aqueous phase was then separated and
analysed by HPLC. The aqueous solution was acidified and
extracted with ethyl acetate to recover the unreacted protocatechualdehyde. The conversion was 58.6% and
selectivity in heliotropin 64%.

foxy2

  • Guest
Re: 3,4-methylenedioxymandelic acid
« Reply #16 on: October 19, 2001, 08:48:00 PM »
Jackpot-OTC SYNTHESIS!!!!!!
Al/Hg reduction of Oxylic acid to glyoxylic acid :o)

Glyoxylic acid.    
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.  
Patent No.
HU   15960
HU   173712

Abstract
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. 


This one might bee even better.

Glyoxalic acid.    
(Daicel Chemical Industries, Ltd., Japan).    Jpn. Kokai Tokkyo Koho  (1983),     6 pp.  CODEN: JKXXAF  JP  58198437  A2  19831118  Showa.   Patent  written in Japanese.

Abstract
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.






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PolytheneSam

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Re: 3,4-methylenedioxymandelic acid
« Reply #17 on: October 21, 2001, 08:26:00 AM »
Here's an English abstract of Japanese patent 54-73739



http://www.geocities.com/dritte123/PSPF.html