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Author: Subject: Synthesis of malonic acid
Magpie
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[*] posted on 17-9-2010 at 10:39


I have recently tried a preparation of calcium malonate using an older procedure by Subramaniam et al, as offered by DJF90. This procedure, as excerpted, is shown below:

"Oxidation of Malic Acid by Hydrogen Peroxide in the Presence of Ammonia.

dl-Malic acid (5 g.) was dissolved in a 20-volume (6%) solution of hydrogen peroxide (100 c.c.), and the liquid was made just alkaline with concentrated aqueous ammonia and diluted to 150 C.C. with water. After 30 hours the reaction mixture was shaken with animal charcoal (5 g.) to remove the undecomposed hydrogen peroxide still present. The solution was filtered, boiled, and treated with an excess of calcium chloride solution. After concentration to 100 C.C. and subsequent standing for 3 days, the white crystalline precipitate (5.25 g.) was collected, washed with water, and dried in a vacuum [Found : Ca, 21.7. Calc. for CH2(CO*O),Ca,2H20: Ca, 22.3%].

A quantity of this calcium salt (1-5 g.) was heated in a sealed tube with glacial acetic acid (5 c.c.) and freshly distilled cinnamaldehyde (30 drops) at 100" for 10 hours. The product was purified as detailed in a previous case and yielded 0.32 g., which melted at 208" (decomp.), alone or mixed with authentic cinnamylidenemalonic acid of m. p. 208" (decomp.) (0.1510 g. required 274 C.C. of NI20-NaOH. Calc., 27.7 c.c.)."

A white precipitate of the stated weight was indeed obtained. However, extraction of the acidified salt with ether did not yield the desired malonic acid.

Although a method for identifying the salt as a malonate is presented in the article, it appears cumbersome. Does anyone have any other suggestions as to how putative Ca malonate can be identified?




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[*] posted on 25-7-2011 at 09:44


By reacting glycerol with HCl/ZnCl2 (Lucas test) the middle hydroxyl group (OH) could be substituted by Cl. So you get CH2(OH)-CHCl-CH2(OH). From this, substitute the chloride ion with hydrogen (using Zn) in order to obtain 1,3 propanediol. Oxidize this to the malonic acid.

I don't know if this could work. Probably you will see no turbidity in the first reaction because the chlorinated product is water-soluble (because of two hydroxyl groups). Isolation of this product from the unreacted glycerol could be another problem.
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[*] posted on 17-8-2011 at 12:59


Quote: Originally posted by Magpie  
Malonate salts are indeed present in the juice of beets. Precipitation of Ca malonate is a problem for industrial refiners of sugar beets. It is present at something around 2% in sugar beets IIRC. It would be an interesting challenge to extract malonate from beets IMO.


If its intresting, then i hope you dont mind in helping me,i decided to do just that

I think that getting calcium malonate from beetroot is an achivement id like to have, has anyone written extraction guide yet, because id like to try, im not expert at chemistry but i have degree as a lab worker and i dont mind trying many times

what i believe i should do first is to make some calculations on economics

in my country beetroot costs 0,9€ per kilogram and if there is 2 % calcium malonate the price of extracted malonate at 0% loss would be 45€ per kilogram witch would be a good price, and i also like doing some cooking:)

Since its economicaly a sound plan im going to start my experiments next monday when i get some money for chemicals

and of course the game plan, witch i hope i can get some feedback on

1.Im going to cut the beetroot to slices and boil them in water for some amount of time, since i have no experience in cooking beetroot i have no idea for how long, but i will do so for as long as it takes to soften them up.Then im going to use blender to break the stuff in to a paste,to help the color dissolve in water.I know from a reliable source that calcium malonate will not dissolve in water.There is no source as to how low the solubility is but what iv read, calcium malonate is 'cheese like precapitate'.im going to save the water and drink it for its vitamins and antioxidants.

2.im going to put fresh water in and put the beetroots from steel cooking pot to plastic bucket and add some acid, i plan to use sulfuric from battery acid.Battery acid should be pretty pure ~30%.Calcium sulfate is going to precapitate at this point.Maybe, i might not see anything because calcium malonate is already insoluble, it might just get replaced by the sulfate.

3.Im going to filter the liquid that i get from that. I should now have pink malonic acid solution.Now this is the part id need theoretical help.Should i now proceed with options;

a)dry this off (pain in the ass) and esterify and distill.

b) use calcium compound to precapitate it and then wash with water

c)put non water miscible solvent like ether and extract with that


As a conclusion,i know that im not going to get pure stuff, its going to be contaminated with the red color and some organics from the vegetable, but i dont really need it to be analytically pure.I dont even have a use for malonic acid yet but i wanted to do some kitchen friendly chemistry for a while.

Has someone already done this, and if can i get link to the quide?if not i'd like to make experiments and reading and write the guide.

Ps.should i use beetroot or sugar beet?

[Edited on 17-8-2011 by Roger86]
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Magpie
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[*] posted on 17-8-2011 at 14:51


Here's a reference you might want to read:

http://pubs.acs.org/doi/pdf/10.1021/ie50495a018

I have never tried this. I do have in my notes that the industrial juice extraction was done at 70-74C for 100 minutes.

Ether extraction may be the best way to separate the malonic acid from the other water solubles such as amino acids. Other acids may tag along with the malonic acid.





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[*] posted on 21-8-2011 at 17:02


How about the oxidative decarboxylation of aspartic acid with TCCA, followed by hydrolysis of the nitrile?
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[*] posted on 21-8-2011 at 21:13
Synthesis of Malonic acid...


This may be done via enolate (crossed claisen) chemistry, vis:

Etn-Butyrate + DiEthylCarbonate = diethyl ethylmalonate + EtOH

Using NaEthoxide as a reagent.

The "diethyl ethylmalonate" is also known as "Ethyl Malonic Ester"
Presumably simple DiEthylMalonicAcid needs EtAcetate instead of Etn-Butyrate.

This patent gives this and similar examples:
US2367632 And the process is/was called "Carbalkoxylation"

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[*] posted on 22-8-2011 at 09:19


As i sayed i started today working towards OTC source of malonates.With attachement is a quide i wrote for myself, please help me to improve it.I got to step 7 today.Tomorrow im going out to the hardware store to buy some impure NaOH and some CaCl2.

But, i cooked the vegetable for 60 minutes, untill it got soft, i didnt have blender so i just let the H2SO4 work for 15 minutes with mixing.

I did some reading and it seems that the colour of the beetroot is dependent on PH.I washed most of the colour from the plant away, but when sulfuric acid was added, the colour became more violet than red.Now i have 1,5dl of beetroot juice with sulfuric acid in it(actually, from this point it smelled like blackcurrants. I plan to make it basic with lye and put CaCl2 to make it precapitate.I read that the violet color turns to yellow at caustic PH.

When i'm done with this quide, is it ok to have link to my guide, or do i just post it here as document? problem is that upload limit is 2MB witch doesnt leave much to get creative with...

And i read Magpie's link, would it be possible to get glutamic acid from it too? because i would love to have some GABA:D

Attachment: Calcium Malonate.rtf (1kB)
This file has been downloaded 730 times

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[*] posted on 23-8-2011 at 01:15


[edited]

[Edited on 23-8-2011 by Ebao-lu]




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[*] posted on 23-8-2011 at 07:31


Quote: Originally posted by Roger86  
I plan to make it basic with lye and put CaCl2 to make it precapitate


Not sure where you got your procedure, but I believe you will precipitate CaSO4 along with your calcium malonate. 2NaOH + H2SO4 -> Na2SO4 + 2H2O, then CaCl2 + Na2SO4 -> 2NaCl + CaSO4 (driven by solubility as the CaSO4 is relatively insoluble). This may not be an insuperable objection if you have some way in mind to separate calcium malonate from calcium sulfate, but in any case don't assume that all that white precipitate is malonate.
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[*] posted on 23-8-2011 at 07:40


I dont expect the precapitate to be pure malonate, the process is so that i dont have to evaporate tons of water.I now have a plan to esterify the malonic acid to make diethylmalonate and then distill.

I havent added the calcium chloride yet, so i havent really made the mistake yet:)

But, i could always separate malonic acid from the sulfuric acid by just letting it dry, couldnt i? i suspect its going to be a very long process, but as i stated earlier, im not afraid to do some hard work:cool:
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[*] posted on 23-8-2011 at 08:38


I went to the library and looked up the article in the scientific journal I cited above. Did you? There is absolutely no mention of malonic acid or malonates in this article. This articles covers the analysis of the contents of juice extract of sugar beets from at least 3 different regions of the US.

I have done a little researching and can find no reference to malonates in beets in scientific journals. Several, however, make reference to malic acid or malates. So, I don't know why Wiki and its clones keep mentioning malonic acid as a constituent of beets.

I think that the separation of a particular organic acid or its salt from beet juice would be difficult. The scientists resorted to several different ion exchange resins to get these acid anion separations.

[Edited on 23-8-2011 by Magpie]




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[*] posted on 23-8-2011 at 10:42


I advanced in my work, i got to step 8 :)

Turns out that you get precapitate even without CaCl2, not much but the precapitate would indicate that i have saturated solution of sodium malonate, and i used very dilute acid and base, so i have a lot of the solution.I never learned to make in small amounts.Would i be optimistic to assume that the precapitate is sodium malonate?

I checked that Encylopedia Britannica also states that there is calcium malonate in beetroot

http://www.britannica.com/EBchecked/topic/360443/malonic-aci...

And if both Wikipedia and Encylopedia Britannica say there's some in it, it's worth trying out.

BTW, where did you get the 2% number? If there was 2% it would be in correlation with what i got as what i think is sodium malonate

Also, i read about the acid being unstable, any info on how long i can store it?


Edit. didnt notice you sayed scientific journals, but i trust wiki and Britannica:D

[Edited on 23-8-2011 by Roger86]
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[*] posted on 23-8-2011 at 11:39


Quote: Originally posted by Magpie  
I went to the library and looked up the article in the scientific journal I cited above. Did you? There is absolutely no mention of malonic acid or malonates in this article. This articles covers the analysis of the contents of juice extract of sugar beets from at least 3 different regions of the US.

I have done a little researching and can find no reference to malonates in beets in scientific journals. Several, however, make reference to malic acid or malates. So, I don't know why Wiki and its clones keep mentioning malonic acid as a constituent of beets.

I think that the separation of a particular organic acid or its salt from beet juice would be difficult. The scientists resorted to several different ion exchange resins to get these acid anion separations.


According to several older references, malonic acid is present in sugar beets. No quantitative information was found in these pre-war publications. Ullmann's says "Malonic acid is found in small amounts in sugar beet and green wheat, being formed by oxidative degradation of malic acid." Malic acid is not that abundant in beets to begin with. I would guess that while malonic acid is technically present in beets, it's futile to attempt preparative extraction.




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Magpie
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[*] posted on 23-8-2011 at 11:50


Quote: Originally posted by Roger86  

Turns out that you get precapitate even without CaCl2, not much but the precapitate would indicate that i have saturated solution of sodium malonate, and i used very dilute acid and base, so i have a lot of the solution.I never learned to make in small amounts.Would i be optimistic to assume that the precapitate is sodium malonate?


Yes, sodium malonate is soluble to 148g/L according to:

http://www.chemicalbook.com/ChemicalProductProperty_EN_CB870...


Quote: Originally posted by Roger86  

BTW, where did you get the 2% number? If there was 2% it would be in correlation with what i got as what i think is sodium malonate


I can't remember where I got that 2%. It is not in my notes.




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[*] posted on 24-8-2011 at 13:27


I'm not too sure if this pathway would work--what about :
Serine + oxidant -> 1,3-propanedioic acid 2-amine (sorry if the name is off--I'm out of practice!)
1,3-propanedioic acid 2-amine + HNO2 -> the diazo form of the previous product
diazo compound + reductant -> malonate

What I'm mostly unsure about is the diazotization reaction--I know HNO2 can be kinda finicky depending on the constituents of the compounds involved.

[Edited on 24-8-2011 by querjek]

[Edited on 24-8-2011 by querjek]




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[*] posted on 26-8-2011 at 05:15


I't doesnt matter if this isnt full succes, i know i probably have a mix of inorganics and some malates in the precapitate, but i like trying things.So if it doesnt succeed, at least i had fun:)
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[*] posted on 26-8-2011 at 07:06


Quote: Originally posted by querjek  
I'm not too sure if this pathway would work--what about :
Serine + oxidant -> 1,3-propanedioic acid 2-amine (sorry if the name is off--I'm out of practice!)
1,3-propanedioic acid 2-amine + HNO2 -> the diazo form of the previous product
diazo compound + reductant -> malonate

What I'm mostly unsure about is the diazotization reaction--I know HNO2 can be kinda finicky depending on the constituents of the compounds involved.

[Edited on 24-8-2011 by querjek]

[Edited on 24-8-2011 by querjek]


Maybe I remember wrong, but I thought diazotisation wasn't possible on aliphatic compounds. The resonance in aromatics stabilizes the diazo compound, but aliphatic compounds don't have these stabilizing effects. I think when you diazotise your acid it will release nitrogen immediately and form 2-hydroxymalonic acid.

Here's a ref: http://in.answers.yahoo.com/question/index?qid=2011051821215...




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[*] posted on 26-8-2011 at 13:23


Quote: Originally posted by redox  
Quote: Originally posted by querjek  
I'm not too sure if this pathway would work--what about :
Serine + oxidant -> 1,3-propanedioic acid 2-amine (sorry if the name is off--I'm out of practice!)
1,3-propanedioic acid 2-amine + HNO2 -> the diazo form of the previous product
diazo compound + reductant -> malonate

What I'm mostly unsure about is the diazotization reaction--I know HNO2 can be kinda finicky depending on the constituents of the compounds involved.

[Edited on 24-8-2011 by querjek]

[Edited on 24-8-2011 by querjek]


Maybe I remember wrong, but I thought diazotisation wasn't possible on aliphatic compounds. The resonance in aromatics stabilizes the diazo compound, but aliphatic compounds don't have these stabilizing effects. I think when you diazotise your acid it will release nitrogen immediately and form 2-hydroxymalonic acid.

Here's a ref: http://in.answers.yahoo.com/question/index?qid=2011051821215...

I've heard that before too about aliphatic compounds. However, could the pH of solution be played with in order to provide resonance stability via the two carboxylates?




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[*] posted on 27-8-2011 at 05:47


Alpha-amino acids can be successfully diazotised. See the following discussion from obscure site http://www.sciencemadness.org/talk/viewthread.php?tid=11148


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[*] posted on 27-8-2011 at 10:41


Quote: Originally posted by not_important  
Alpha-amino acids can be successfully diazotised. See the following discussion from obscure site http://www.sciencemadness.org/talk/viewthread.php?tid=11148



Haha. Sorry for not using the search here more effectively and thanks for the link!




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[*] posted on 27-8-2011 at 11:16


I really could use data on what malonic acid, sodium malonate and calcium malonate are soluble in, especially if the solvent is non water miscible.I used google and it didnt provide much help.
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[*] posted on 27-8-2011 at 11:48


http://www.sciencemadness.org/talk/viewthread.php?tid=11698&...



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[*] posted on 28-8-2011 at 00:38


Quote: Originally posted by Magpie  
http://www.sciencemadness.org/talk/viewthread.php?tid=11698&...


I cant open the page, it says im not permitted:(
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[*] posted on 28-8-2011 at 06:29


Quote: Originally posted by Roger86  

I cant open the page, it says im not permitted:(


You will have to request permission from an administrator via U2U.




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[*] posted on 29-8-2011 at 12:27


In this case, though, the reference that is provided in the linked-to post is just a page or two from Atherton Seidell's 1919 book on solubilities. You can find it in Google Books even if you don't get access to the Reference forum. You may be disappointed, though, as it only gives data for malonic acid proper and not for the salts; not only that, but it looks like malonic acid is more or less soluble in all of the listed solvents and so there is no real prospect for crashing it out of solution by addition of some other compound.
My CRC handbook suggests that calcium malonate is rather insoluble, though.
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