Sciencemadness Discussion Board

Synthesis of malonic acid

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Magpie - 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?

experimenter - 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.

Roger86 - 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]

Magpie - 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.


manimal - 21-8-2011 at 17:02

How about the oxidative decarboxylation of aspartic acid with TCCA, followed by hydrolysis of the nitrile?

Synthesis of Malonic acid...

FrankMartin - 21-8-2011 at 21:13

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"

Regards.
Frank

Roger86 - 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 776 times


Ebao-lu - 23-8-2011 at 01:15

[edited]

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

bbartlog - 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.

Roger86 - 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:

Magpie - 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]

Roger86 - 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]

Polverone - 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.

Magpie - 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.

querjek - 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]

Roger86 - 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:)

redox - 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...

querjek - 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?

not_important - 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



querjek - 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!

Roger86 - 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.

Magpie - 27-8-2011 at 11:48

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

Roger86 - 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:(

Magpie - 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.

bbartlog - 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.

Roger86 - 1-9-2011 at 14:33

Quote: Originally posted by Formatik  

By the oxidation of malic acid (Dessaignes, A. 107, 251)


Tried to search for that book on pdf form but couldnt find it, do you have a link?

Not that i have given up on beetroots, but i seriously would like to read that, especially since it's been done on 19th century technology, what should make it simple to do at home

krystaljjang90 - 2-10-2011 at 13:11

hi all..

I'm a chemical engineering student and I need to design malonic acid plant for my plant design subject..
i'll be really grateful if anyone can anyone tell me about the industrial process of malonic acid..

tq...:)

Magpie - 2-10-2011 at 16:14

Quote: Originally posted by krystaljjang90  

i'll be really grateful if anyone can anyone tell me about the industrial process of malonic acid..


Hi krystal,

Have you checked out the Kirk-Othmer Encycopedia of Chemical Technology and Ullman's Encyclopedia of Industrial Chemistry? Most university libraries should have one or both.

[Edited on 3-10-2011 by Magpie]

krystaljjang90 - 2-10-2011 at 22:22

yeah I've checked them n shortlisted 2 processes which are alkaline saponification of cyanoacetic acid and acidic

saponification of chloroacetic acid..i've spent days searching patents and journals but it was not enough..

can you recommend some links or maybe do you know about these processes and the equipments involved??..tq:)





Magpie - 3-10-2011 at 10:26

Quote: Originally posted by krystaljjang90  

can you recommend some links or maybe do you know about these processes and the equipments involved??..tq:)


Sorry, other than the patents I wouldn't know where else to look.

I'm just guessing that malonic acid is being produced today by the usual Indian and Chinese bulk chemical producers. Businesses don't usually publish details on their processes for obvious reasons.

------------------------------------------------------------

Edit: Here's another possibility. Search the archives of these magazines:

Chemical Engineering Progress
Chemical & Engineering News
Chemical Engineering


[Edited on 4-10-2011 by Magpie]

stygian - 28-10-2011 at 20:22

Quote: Originally posted by Sauron  
BTW red P is not mandatory for chlorination of acetic acid, it merely accelerates the rate of the chlorination. Direct chlorination is UV mediated so you need reliable sunlight or preferably a UV reactor. OR chlorinate with CuCl2 (see thread) or N-chlorosuccinimide, both of which monochlorinate the alpha position of carboxylic acids I think. NBS does for sure and bromoacetic acid would work just as well,


May I ask, to which thread do you refer (wrt CuCl2)? I've not been able to find it.

Boffis - 31-10-2012 at 18:50

Once again I find myself reading a long an painful thread with very little useful content. I think we have established there are only really two practical methods to malonic acid for the amateur. The chloroacetic acid + alkali cyanide and the oxidation of malic acid. The first of these suffers from the availability of sodium and potassium cyanide and the second from the fact that the published proceedure are old and often don't appear to work. Other procedures such as the hydrolysis of malononitrile or the oxidation of 1,3 propandiol suffer from the difficult of obtaining the starting material again (if you can get these compounds you can probably buy malonic acid anyway).

I can't add much more to the first technique but the second looks like fertile ground for investigation, malic acid is easily available from home brew suppliers etc and is cheap; there are dozens of easily available oxidizing agents on the high street or the internet.

I am not going to go through my experiments in detail I have attached a copy of my prelimenary experimental findings for anyone who is interested and I have so far only looked at the oxidation and precipitation as calcium malonite. I intend to try the work up of the precipitates in the near future. However, a summary of the work so far is never the less interesting. I tried oxiding dl malic acid with the following reagents:

Sodium dichromate
Sodium hypochlorite
Hydrogen peroxide and tungstate catalyst
sodium chlorate and vanadium pentoxide catalyst

From the attached file you will see that sodium dichromate and hydrogen peroxide did not work for certain as no calcium salt precipitated. The tungstate catalyst was used with hydrogen peroxide because I have somewhere in my documents a reference to Fe salts and H2O2 being used to oxidize malic acid to oxaloacetic acid, though there papers posted on this thread that describe the oxidation of citric acid to malonic acid via several possible intermediates so this route is not closed but clearly requires different conditions.

Sodium chlorate with V2O5 gave only a slight precipitate inspite of the apparently fairly vigorous reaction so once again oxaloacetic acid may be the main product.

It would appear on the basis of the amount of precipitate formed that the sodium hypochlorite method is by far the most successful. However, towards the end of the addition of the hypochlorite the solution became cloudy and heavy mobile droplet formed in the liquid and the whole smelled strongly of chloroform. This suggests that towards the end the conditions become alkaline and the haloform reaction becomes an important side reaction. Experiment with buffering with HCl towards the end were tried to prevent this but there is clearly much scope for improvement. That said the reactants are cheap and easily obtained so modest yields may not be an issue.

Excessive oxidation could theoretically produce oxalic acid which would also precipitate with calcium salts so the formation of a precipitate with calcium chloride does not prove that malonic acid was formed, however, the absence of a precipitate indicates that it was not formed.

One further point is that when using calcium chloride to precipitate free malonic acid hydrochloric acid is liberated potentially dropping the pH to a point where calcium malonate will no longer precipitate. Clearly there is much scope for the optimisation of this method.

The precipitates from the hypochlorite oxidation experiments where subjected to the diphenylamine-sulphuric test for oxalates and gave practically negative results indicating very little calcium oxalate to be present.

Attachment: Malic acid Oxidation Experiments.docx (18kB)
This file has been downloaded 1093 times

[Edited on 1-11-2012 by Boffis]

Boffis - 2-2-2014 at 16:38

I have recently returned to the topic of OTC synthesis of Malonic acid both from the oxidation of malic acid and via cyanoacetic acid. While looking for reasonably recent online papers concerning the former process I came across this one:

Effect of MnII ions on the oxidation of the oxidation of malic and oxaloethanoic acids by aqueous HCrO4-

Zaheer Khan and Kabir-ud-Din, Transition Metal Chemistry, v26, p672-678, 2001

This paper explores the catalytic affect of MnII on this reaction but I could only access the first page, however, on this page there is a claim that following a measurement of the amount of CO2 evolved the reaction must approximate to:

12HCrO4- + 9C4H6O5 + 48H+ ==> 12CrIII + 2C2H4O2(acetic acid) + 7C3H4O4 +11CO2 +39H2O
(14H2O in the paper but this is clearly a typo)

This is a higher ratio of oxidant than I used above but I would still have expected some malonic acid to have been precipitated. I will investigate this further when I get chance.

DoctorZET - 13-4-2014 at 12:43

I know those 2 methods ... and I also tryed the old clasic method (acetic acid --> cyanoacetic acid --> malonic acid) and I observe that it consume a lot of cyanide salts, wich are hard to make (by me), as I'm a home-laboratory-chemist.
But something come into my mind ... there might be a way to obtain malonic acid more easy and in a much more pure form (not using chromates, permanganates, cyanides...)

The process look like this:

CH3-COOH(liquid) + Cl2(gas) --(intense blue light, traces of acetic anhydride and some CCl4, 60-70 *C, probably on an ethanol bath)--> Cl-CH2-COOH + HCl

HCOOH(gas) + Cl-CH2-COOH (gas) --(traces of H2O and AlCl3 cristals deposited in a glass tube at 190-200*C)--> HOOC-CH2-COOH + HCl

It is corect ? ... I hope it is, because I will test this theory :)


[Edited on 13-4-2014 by DoctorZET]

DoctorZET - 13-4-2014 at 13:08

As soon I post that, I can see a big problem : the malonic acid starts to decarboxylate at about 70*C forming acetic acid ... sooo...at about 190*C should be already decomposed into CO2 and acetic acid. :(
So if I want to do the Friedel-Kraft alkylation reaction in the gas phase (because I want to have a fast reaction), I must do it at a lower pressure.
But I also could do it at max.60-70*C for a few hours, with a lot of AlCl3(better use FeCl3) added and excess of formic acid...
Then I can distill the excess of formic acid.
Sounds good...

An easier way to make malonic acid?

Assured Fish - 2-10-2016 at 22:16

I read the entire thread and as far as i can tell nobody suggested this but correct me if im wrong.
Simply react allyl alcohol with a hydrogen halide or possibly a halide and aluminium to get allyl halide (1-halo-2-Propene) then after drying it thoroughly react with magnesium in diethyl ether or THF to get the grignard reagent then of coarse either add dry ice or bubble CO2 through the grignard reagent to get 3-buteneoic acid after acidification with H2SO4, then obviously reflux with potassium dichromate or permangenate and neutralize then distil and bobs your uncle your done.

CH2CHCH3-MgBr + CO2 ------> CH2CHCH3COOH

CH2CHCH3COOH + K2Cr2O7 ------> COOHCH2COOH

Allyl alcohol can easily be synthesized OTC from oxalic acid and glycerol, the only annoying part that i can see about this method would be drying the allyl halide but i mean fractional distillation over a dessicant such as calcium chloride or hell even molecular sieves then maybe left to dry over some sodium overnight not really that difficult.
Also given that butanoic acid has a boiling point of 164*C i would speculate that buntenoic acid would have a similar boiling point thus making pretty much all the workups piss easy.
I just dont get why nobody else thought of this.

wg48 - 3-10-2016 at 01:08

Allyl alcohol synthesized from oxalic acid and glycerol ???
How the heck can that happen, you would have to be mad to think that was possible were my first thoughts LOL

Well I checked apparently it is correct but the yield is low. I am still looking for the detailed mechanism.

Ok a little off topic and its probably been posted already:

https://erowid.org/archive/rhodium/chemistry/allylalcohol.ht...

"Experimental

Allyl Alcohol from Glycerol and Oxalic Acid
A mixture of 500g anhydrous oxalic acid and 500g of glycerol was heated in a partial vacuum on a water bath for 4-5h (or longer) until formic acid ceased to distill over. The mixture was then gradually heated to 240°C under ordinary pressure, the flask being fitted with a fractionating column. At 220-225°C, CO2 was given off and a mixture of approximately equal amounts of allyl alcohol and allyl formate distilled over leaving in the distillation flask a residue containing somewhat 50% of the glycerol originally used. Practically no acrolein was produced. The distillate was treated with 50g NaOH in 1000ml water (to hydrolyze the formate), allowed to stand for 12h at room temp, and finally distilled. The first 300 ml of distillate contained all the allyl alcohol, which after fractionation yielded 200-210g of a allyl alcohol/water mixture (bp 87-88°C) which may be dehydrated using anhydrous potassium carbonate yielding approximately 150g of anhydrous allyl alcohol."

[Edited on 3-10-2016 by wg48]

Assured Fish - 4-10-2016 at 12:11

The triethylorthoformate method posted here looks like a better way to go about allyl alcohol preparation, the thread also goes into more detail regarding the oxalic acid glycerol method although the mechanism still seems obscure. I do rest my case however that allyl alcohol should be fairly straightforward and OTC to prepare and then the grignard carbonation and oxidation of the double bond to finish up.

http://www.sciencemadness.org/talk/viewthread.php?tid=6274

wg48 - 4-10-2016 at 13:58

Quote: Originally posted by Assured Fish  
The triethylorthoformate method posted here looks like a better way to go about allyl alcohol preparation, the thread also goes into more detail regarding the oxalic acid glycerol method although the mechanism still seems obscure. I do rest my case however that allyl alcohol should be fairly straightforward and OTC to prepare and then the grignard carbonation and oxidation of the double bond to finish up.

http://www.sciencemadness.org/talk/viewthread.php?tid=6274


Well triethyl orthoformate route to allyl alcohol may be cleaner and more productive but it looks a long way from OTC.

Darkstar - 5-10-2016 at 00:37

Quote: Originally posted by wg48  
I am still looking for the detailed mechanism.

Quote: Originally posted by Assured Fish  
the thread also goes into more detail regarding the oxalic acid glycerol method although the mechanism still seems obscure.


As far as I'm aware, the exact mechanism for the reaction isn't actually known; however, if you're having trouble trying to come up with a way to get from oxalic acid and glycerol to allyl alcohol (it's a little tricky), I've drawn a plausible mechanism that is actually based on some recent literature where deuterium labeling was used:

mechy.png - 255kB

The oxalic acid and glycerol initially react to give a mono-oxalate ester that, upon ring closure, gives 2-hydroxy-4-(hydroxymethyl)-1,3-dioxolan-2-carboxylic acid. This unstable dioxolane ring system then undergoes thermal decarboxylation to the more stable 4-(hydroxymethyl)-1,3-dioxolan-2-ol, which is in equilibrium with both glycerol mono-formate isomers as well as their hydrolysis products, glycerol and formic acid:

equilibrium.png - 77kB

The dioxolane form of glycerol mono-formate then reacts with some of the formic acid produced by the hydrolysis shown above to give a resonance-stabilized carbocation, which gets attacked by the resulting formate ion to give 4-(hydroxymethyl)-1,3-dioxolan-2-formate. The formate ester undergoes a final thermal decarboxylation reaction to give both the desired allyl alcohol as well as give back the formic acid that was consumed.

Additionally, it's also possible that, instead of attacking the electrophilic carbon, the formate ion instead abstracts the acidic proton to give an unstable carbene that immediately decomposes into carbon dioxide and allyl alcohol:

mechy2.png - 100kB

UC235 - 8-10-2016 at 00:59

http://www.sciencemadness.org/talk/viewthread.php?tid=13122

There are now a few sources of 1,3-propanediol available as a cosmetic ingredient.

Pumukli - 8-10-2016 at 12:03

And also available as antifreeze for solar systems. (At least in the EU.) Not as cheap as ethylene-glycol or 1,2-propane-diol and not so common in every hardware store, but for a 10 or 20 liters can the price is not bad.
(The reason is reportedly 1,3-propane-diol whitstands better the 150+ Celsius range encountered in solar systems than other diols.)

mr.crow - 9-10-2016 at 08:27

Perhaps treating amino acids with TCCA or NaOCl would yield malonic acid.

https://www.sciencemadness.org/whisper/viewthread.php?tid=32...

https://www.sciencemadness.org/whisper/viewthread.php?tid=29...

It looks like the mono-chloroamine of aspartic acid will decompose into an aldehyde and dichloroamine will produce the nitrile.


[Edited on 9-10-2016 by mr.crow]

clearly_not_atara - 13-10-2016 at 13:02

I had a somewhat long synthesis in mind from aspirin, ethyl bromide, sodium ethoxide, and hydrogen peroxide:

acetylsalicylic acid + NaOEt + EtOH + ∆ >> sodium acetylsalicylate + EtOH (g) i.e. just make the sodium salt alkoxide is used here or use something else

sodium acetylsalicylate + EtBr >> NaBr + ethyl acetylsalicylate

ethyl acetylsalicylate + NaOEt (dry) >> 4-hydroxycoumarin (2,4-dioxodihydrobenzopyran) [1]

4-hydroxy-2-chromone + NaOH + H2O + H2O2 >> sodium 2-hydroxyphenyl-1-oxopropanoate (aq)[2] + H2O2 >> catechol + malonic acid [3]

[1] http://www.orgsyn.org/demo.aspx?prep=cv1p0235 (see Discussion; the extension from intermolecular to intramolecular is sort of a leap but usually makes things easier anyway)

[2] http://www.sciencedirect.com/science/article/pii/S1386142506...

[3] http://orgsyn.org/demo.aspx?prep=CV1P0149 (it is an o-hydroxyketone at the end of the day)

-------

Also, the Baeyer-Villiger oxidation of levulinic acid gives 3-acetoxypropanoic acid. Levulinic acid in turn is produced from sucrose and HCl.

-------


EDIT 2:

Maybe you could make 1,3-dinitropropane by the Michael addition of nitromethane to niroethylene? Nitroethylene then is made from nitromethane and formaldehyde!

Reduction with a variety of reagents (CrCl2 reportedly gives oximes IIRC) gives malondialdehyde dioxime, a precursor to malonic acid as well as many other interesting compounds, including malononitrile.

-------

EDIT 3: last one i swear

ethyl chloroacetate + zinc + formaldehyde >> ethyl hydracrylate aka ethyl 3-hydroxypropanoate

(reformatsky reaction)

NB: with acetaldehyde this gives an ethoxide-free preparation of ethyl acetoacetate by oxidation

[Edited on 13-10-2016 by clearly_not_atara]

[Edited on 13-10-2016 by clearly_not_atara]

[Edited on 13-10-2016 by clearly_not_atara]

Boffis - 1-10-2017 at 15:37

I was recently going through a dark corner of my lab when I found 4 samples of calcium salts prepared by the alkaline oxidation of malic acid in the hope of producing malonic acid as described above. I decided to finally complete this work by analysing these precipitates. I decided to proceed by adding just enough sulphuric acid to liberate the organic acid but since I didn't know exactly what compound I had and therefore how much acid it would require I first had to analyse the Ca content. I did this by taking a small sub sample of about 0.2g accurately weighed out and calcining it in a pre-weighed nickel crucible. The calcine was cooled and left in in a plastic box over ammonium carbonate for a few days to ensure conversion of any calcium oxide to carbonate. The calcines were reheated to just 120 degrees in an oven to drive off any water and ammonia and then weighed. The weight of CaCO3 remaining was then used to calculate the amount of sulphuric acid required. The weights seem rather higher than I had been expecting since I had assumed that the precipitate consisted of a mixture of calcium malate, malonate 4 hydrate and oxalate dihydrate. The CaCO3 weights suggested that they were anhydrous and even then there was too much calcium present. For one sample I dissolved to check the calcine by dissolving it in a little dilute HCl, then diluting it to 250ml and titrating it as though it was hard water using a buffer, solochrome black as indicator and standard EDTA solution (bought). This procedure confirmed that the calcine was essentially pure CaCO3.

One of the samples was too small to be worth treating but the other three were then reacted with the appropriate amount of 1M sulphuric acid which resulted in copious evolution of a colourless odorless gas, certainly CO2. The slurry was warmed a little to ensure complete reaction and then chilled overnight to allow the calcium sulphate to cystallise then evaporate down on a water bath in a shallow ceramic bowl to a thick solution and left to crystallise. Only further calcium sulphate was recovered. No evidence of organic acids could be found in the residues, not even acetic acid from the breakdown of malonic acid.

From this I conclude that the alkaline oxidation of Malic acid (more correctly malate salts) results not in malonic or even oxalic acid but instead carbonate ions, chloroform and only organic acids that form soluble calcium salts such as formate or acetate. The method therefore is a complete failure.

Just thought you ought to know! Back to the drawing board.

clearly_not_atara - 3-10-2017 at 09:29

There's a prep of 2-methylmalonic acid on Orgsyn which proceeds via 3-methyl-2-oxosuccinic acid. Apparently the ester of this is pyrolysed and undergoes some kind of carbonyl-elimination rearrangement.

Starting from diethyl malate, oxidation with an anhydrous CrO3 synthon (such as PCC or something) should give oxaloacetic acid -- be aware that alpha-ketoesters hydrolyse easily. Pyrolysis of this ester may, if the analogy holds, generate diethyl malonate.

I think it's worth a try, at least. There's also the possibility of somehow reducing alloxan to barbituric acid.

Claisen condensation

Niter of Potash - 15-10-2017 at 02:30

My idea is to make malonic acid by mixed claisen condensation between ethyl formate and ethyl acetate.

That /product/ (i'm not good at naming compounds) would be ester on one side, and aldehyde on another. Oxidizing that aldehyde with HNO3, KMnO4 or something silimar, sould yield monoester of malonic acid, or pure acid, if ester gets hydrolised.

Since I can't really get or make pure Na metal (I tried NurdRage's dioxane method, but since my stirrer is broken, I couldnt extract decent quantaty of Na metal), I would probbaly use Na/MgO aggregate, mix that with dry EtOH, and filter, to get sodium ethoxide solution, and use that in reaction.

Sadly, I'm pretty buisy so I can't try this out, but can anyone confirm that it would work at all, or why not?

EDIT:

As soon as I posted reply, I relalised what could go wrong.

http://www.prepchem.com/synthesis-of-benzyl-benzoate/

Reactions similar to this could accure, and that would yield malonic acid - 3-hydroxypropionic acid ester.

That,however, is not a huge issue, as 3-hydroxypropionic acid could be further oxidised to form malonic acid.

Not a big deal, I guess, and this would only make extraction and purification steps a bit more complex

[Edited on 15-10-2017 by Niter of Potash]

Boffis - 18-10-2017 at 10:52

Will diethyl carbonate undergo a cross claisen condenstion with ethyl acetate to give diethyl malonate directly? Or is this just wishful thinking?

:)

clearly_not_atara - 18-10-2017 at 10:59

In order to achieve the desired selectivity I would think you want to use diMethyl carbonate and tert-butyl acetate, although isopropyl acetate is similar and much more OTC.

I think it's possible... yields may be complicated by the formation of acetoacetate.

AvBaeyer - 18-10-2017 at 12:51

Most of what is being proposed here is too far fetched for the typical hobby or home lab. Why not just buy diethyl malonate which is cheaply available from perfume chemical suppliers. It is essentially OTC. The diester can serve as the basis for lots of chemistry including the preparation of the the half-ester and malonic acid itself.

I realize folks like to speculate on all sorts of possible chemical reactions, but most of the time it's just easier to buy what you need. Do not mean to offend, just my thoughts.

AvB

Boffis - 18-10-2017 at 23:34

Quote: Originally posted by AvBaeyer  
Most of what is being proposed here is too far fetched for the typical hobby or home lab. Why not just buy diethyl malonate which is cheaply available from perfume chemical suppliers. It is essentially OTC. The diester can serve as the basis for lots of chemistry including the preparation of the the half-ester and malonic acid itself.

I realize folks like to speculate on all sorts of possible chemical reactions, but most of the time it's just easier to buy what you need. Do not mean to offend, just my thoughts.

AvB


Agreed but we can dream.. :)

DraconicAcid - 19-10-2017 at 10:25

And here I was wondering if it was possible to easily make esters out of malonic acid....

Niter of Potash - 29-10-2017 at 06:04

What about allyl alcohol/acrylic acid route?
Allyl alcohol is not hard to make, just pretty nasty :(

In theory, you could do anti-markovnikov addition of HBr to acrylic acid, hydrolise 3-bromopropionic acid, and then oxidise 3-hydroxypriopinic acid to form malonic acid.

Also, what would happen if you try to oxidise that double bond with KMnO4 or nitric acid, for example?

Would you end up with malonic acid, epoxide, or that double bound gets cleaved with final products being oxalic and formic acid?

[Edited on 29-10-2017 by Niter of Potash]

clearly_not_atara - 29-10-2017 at 19:20

AvBaeyer: if everyone could buy diethyl malonate this thread might not be here.


However I believe I have a route using only sulfuric acid, malic acid, copper sulfate, and magnesium acetate. I have noticed that magnesium malonate appears to be significantly less soluble than the sulfate:
Quote:
A. Magnesium Malonate: 180.6 g of magnesium acetate tetrahydrate (Mg(OAc)2.4H2O) was dissolved in 500 ml deionized water. Separately, 89.4 g malonic acid (C3O4H4) was dissolved in 60 ml deionized water. The solutions were mixed, bringing about immediate precipitation of Mg(C3O4H2)3.nH2O. After filtering and washing, the yield was 136 g.
https://www.google.com/patents/US6193904

This allows malonic acid to be separated from solutions containing sulfuric acid by the action of magnesium acetate.
In particular, some references indicate that malic acid is converted to formylacetic acid by the action of concentrated sulfuric acid.
https://books.google.com/books?id=mnsKyupepQEC&pg=PA125&...
It's possible that the oxidation with nitric acid depends on formylacetic acid as an intermediate. Nitric acid is known to oxidize aldehydes.
This suggests that malic acid oxidation could also occur in concentrated sulfuric acid containing anhydrous copper (II) sulfate, since Cu2+ oxidizes aldehydes as well. The reaction can then be quenched with magnesium acetate. Copper sulfate has the advantage of producing no gaseous byproducts; copper is filtered from the rxn mixture or reoxidized by dioxygen. Malonic acid can probably be recovered from the magnesium salt by the action of oxalic acid, since magnesium oxalate is highly insoluble and oxalic acid is much stronger than malonic acid. If oxalic acid is unavailable, phosphoric acid might work.
The instability of malonic acid is annoying however so it might be more reasonable to perform a double displacement on magnesium malonate by treating it with hot sodium carbonate solution; IIRC the malonate ion has a much longer lifetime in solution than the free acid (I know this is true of acetoacetic acid). Malonic diesters can then be prepared directly from sodium malonate by alkylation with alkyl halides.

[Edited on 30-10-2017 by clearly_not_atara]

Magpie - 29-10-2017 at 20:07

In the US diethyl malonate is easily purchased from perfume suppliers as stated by UC235.

In Prepublication I have posted a synthesis using 1,3 propandiol. A few years ago this was more difficult to get. Now it is readily available from cosmetic suppliers and Amazon, as previously mentioned. Are these sources not available to you?

Niter of Potash - 30-10-2017 at 12:05

I just found this document online.

Seems like that malonic acid can me made by oxidation of malic acid by sodium hypochloride, in somewhat acceptable yield.

Sadly, HNO3 was not tested in this article as oxidising agent, and NaClO used was industrial strenght (I can only get 5% hypochlorite :( )

I guess I will just have to buy malic acid and try HNO3 oxidation myself.

Any ideas why dichromate and H2O2 methods don't work?


Attachment: Malic acid Oxidation Experiments.docx (18kB)
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Niter of Potash - 30-10-2017 at 12:40

Quote: Originally posted by Magpie  
In the US diethyl malonate is easily purchased from perfume suppliers as stated by UC235.

In Prepublication I have posted a synthesis using 1,3 propandiol. A few years ago this was more difficult to get. Now it is readily available from cosmetic suppliers and Amazon, as previously mentioned. Are these sources not available to you?


So far, I wasn't able to find 1,3PD locally, and i'm a bit too paranoid to order it online, outside my country.

Oh well, I spent months trying to distill toluene from various nitro thinners, and pretty much failed every time(I couldn't purify it to desired purity), just to find out that all this time, one specific, very cheap paint thinner was 100% toluene...so yeah, maybe 1,3PD is just in front of my nose all this time as well.

Magpie - 30-10-2017 at 14:10

1, 3 propanediol is an ingredient for making cosmetics at home and is available at
Somerset Cosmetics. I think your paranoia meter is unnecessarily pegged.

[Edited on 30-10-2017 by Magpie]

[Edited on 31-10-2017 by Magpie]

Niter of Potash - 27-12-2017 at 17:20

So I took a look at Magpie's malonic acid synthesis (this one:)

http://www.sciencemadness.org/talk/viewthread.php?tid=13122

Is there any reason why 6M nitric acid was used?
What would happen if you used something like 30%,40%, or even higher percentage nitric acid?
Are there any drawback (malonic acid decomposing,for example), except maybe having harder time controlling reaction?

Benefits would be less water to evaporate after synthesis.

Magpie - 27-12-2017 at 20:13

You can easily get a dangerous runaway reaction if the nitric is too strong or added too fast.

Jackson - 22-2-2019 at 08:44

I know this thread is kinda old, but I think its going to be better to ask a question on an existing thread, rather than start a new thread. I know that tartaric acid can be oxidized by nitric acid to tartronic acid, which is also known as 2-Hydroxymalonic acid. My question is, can this be dehydrated to Malonic acid? I don’t think it would, but seeing as tartaric acid, or at least Pottasium hydrogen tartrate is readily available, it would be very accessible to most people.

Tsjerk - 22-2-2019 at 08:59

Of course synthesizing is fun, but this might be easier (I never worked with them, but it came up on the first page of Google).

http://www.thegoodscentscompany.com/data/rw1004331.html

clearly_not_atara - 22-2-2019 at 11:31

Jackson: no, I don't think that's a realistic possibility. Maybe it could be reduced by Pd/H2 in acid conditions, but that is literally a wild guess and not worth wasting palladium on. Plus the very similar oxidation of malic acid with nitric acid turns out to be touchy.

Perhaps some other oxidation of malic acid could work. For example, bromine water is known to convert hydroxyacids to carbonyls and H2O2 oxidizes aldehydes to acids, so maybe NaBr/H2O2 would work. However, overoxidation of malonic acid is possible.

Mush - 7-5-2020 at 16:06

potassium dichromate, water
Dessaignes; Justus Liebigs Annalen der Chemie; vol. 107; (1858); p. 251

ammonium hydroxide, dihydrogen peroxide, T= 20 °C
Subramaniam; Stent; Walker; Journal of the Chemical Society; (1929); p. 2490

silver(l) oxide
Behrend; Dreyer; Justus Liebigs Annalen der Chemie; vol. 416; (1918); p. 219

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beebeautiful.org.uk used to have Cherry Fragrance Oil containing 25-50 diethyl malonate

https://beebeautiful.org.uk/shop/wp-content/uploads/2014/06/...

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[Edited on 8-5-2020 by Mush]

clearly_not_atara - 8-5-2020 at 09:56

Oxidative degradation of linoleic acid with KMnO4 or H2O2/WO3 ought to generate malonic acid actually. This is extremely OTC and easy although the atom efficiency is dismal.

Extracting malonic acid from the other products -- hexanoic acid and azelaic acid -- you can probably take advantage of different solubilities in neutral water: hexanoic 1% w/w, azelaic 0.2% w/w, malonic 76% w/w.

[Edited on 8-5-2020 by clearly_not_atara]

kmno4 - 9-2-2021 at 04:23

During searching something via Google, I came across an article:
The Abiotic Oxidation of Organic Acids to Malonate
It is rather fresh (end of 2016) and seems not to be posted on the board.
It is about Fenton-like oxidation of several organic acids, including malic and citric ones. The article is, however, too optimistic.
There are many acid by-produscts of the reactions and it may be difficult to extract malonic acid directly form these post-reaction mixtures.
Possibly, converting all acids into its methyl esters, would give better way of separation.
Anyway, the article is short and the oxidations are very cheap, at least in theory :P

Attachment: malo.pdf (985kB)
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Boffis - 9-2-2021 at 06:37

Interesting. Many years ago I did a lot of similar work oxidizing particularly malic acid with H2O2 and various catalysts and then precipitating the malonic acid as its Ca salt I reported th work on SM. The Ca salt was isolated and the free acid liberated with a calculated quantity of sulphuric acid. Under mildly acid conditions only oxalic acid should interfere. In the end oxalic acid was all I got!! Malonic acid and oxalic acid are easily separated by fractional crystallisation, oxalic acid crystallises first. My conclusion was that under neutral or mildly acid conditions (free malic acid) it was hard to stop the oxidation at malonic acid and oxalate and unreacted malic acid result. Under alkaline conditions carbonate is the main product.

I look at this paper again but it appears to be a bit light on actual experimental detail but it may be worth another bash.

Fery - 9-2-2021 at 09:50

I love these beautiful ideas you have guys and pioneering experiments you did / are doing / will be doing to bring this interesting acid to hobbyists. Who does not want to see Belousov - Zhabotinsky reaction with one's own eyes?
Due to my laziness I've bought this acid very cheaply from https://chemcraft.su/product/24482 and diethylmalonate (beautiful apple scent) from an ebay seller from USA. I saw malonic acid also at s3 chemicals https://shop.es-drei.de/komplexchemie/8766/malonsaeure-min.-... just somewhat more expensive, but they sell to individuals too.

clearly_not_atara - 9-2-2021 at 09:54

I wonder if you could remove most of the oxalic acid from the solution by precipitating potassium tetraoxalate? As far as I know, there are no insoluble salts of potassium and malonate at any stage of protonation, but the solubility of KH3(C2O4)2 is very low, about 2.5% w/w in distilled water and probably lower at its equilibrium pH ~1.5.

Probably no good if there's no actual malonate produced, but if you're getting mostly oxalate and a little malonate, being able to isolate the yield would be something. The ammonia/H2O2 method linked by Mush yields around 20%.

kmno4 - 9-2-2021 at 22:55

Quote: Originally posted by Fery  
Who does not want to see Belousov - Zhabotinsky reaction with one's own eyes?
Due to my laziness I've bought this acid very cheaply from ....

As it is known, the Belousov - Zhabotinsky reaction works with many other reductors, for example citric acid, only (any soluble) bromate is important component.
Alibaba offers malonic acid in prices around several $'s / 1 kg if you order amount > 10 kg.
Unfortunately, shippment from China is very expensive (at least to central Europe). But I am going to order it anyway, I am lazy too :D. This acid and its esters are EXTREMELY useful in OS.
I also like the smell of the esters.

Boffis, I have read about your experiments. In general, oxalic acid is end product of oxidation of many, many organic compounds. That is why I prepared my malonic acid by standard procedure (chloroacetic + cyanide). But without continuous extraction with ether, its separation it is real pain in the ass. Also same malonic acid and its solutions decompose above ~90 C or so. This is not good compound for preparation :(

One more important thing about the article I posted.
It still looks too good for me, but it may work because of not so obvious reasons.
See this article:
DISODIUM PHOSPHATE AS A CATALYST FOR THE QUANTITATIVE OXIDATION OF GLUCOSE TO CARBON DIOXIDE WITH HYDROGEN PEROXIDE.
(in attachment)

So, their "phosphate buffer" may act not only as a buffer, but also as true catalyst.


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[Edited on 10-2-2021 by kmno4]

student - 17-5-2021 at 09:08

Quote: Originally posted by clearly_not_atara  
Oxidative degradation of linoleic acid with KMnO4 or H2O2/WO3 ought to generate malonic acid actually. This is extremely OTC and easy although the atom efficiency is dismal.

I came up with this idea independently, and you mostly stole my thunder. Having recently thought about what could be made using ozonolysis, I realized that acids like linoleic acid have double bonds separated by a methylene group, so that ozonolysis, with an oxidative work-up, would yield one mole of malonic acid per methylene group.

Linoleic acid isn't the best precursor for this because it has only one isolated methylene per molecule. But checking a list of omega 3 fatty acids, there can be up to six isolated methylenes in natural fatty acids. I couldn't find a good source of a fatty acid with six methylenes - DHA is a major constituent of fish oil, but it isn't a majority of the oil and pure DHA isn't economical.

However, a-linolenic acid has three isolated methylenes, and that fatty acid is 55% of the content of flax oil (which also contains 15% linoleic acid), available by the liter. While looking into this I learned that, although flax oil is also called linseed oil, and linseed oil is available at hardware stores, the hardware store stuff, typically called "boiled" linseed oil, has been processed to conjugate the double bonds, rendering it useless for our purpose. The flax oil needed is the food grade oil kept in the refrigerated section of health food stores.

If this approach works, it could allow an inexpensive (once set up), accessible and cost-effective approach to producing malonic acid. Another possible approach would be elimination of the secondary alcohol group of glycerine to give 3-hydroxypropanal, followed by oxidation.

However, while the opportunity lasts, I would prefer to buy malonic acid from a vendor like chemcraft, or even the diester off ebay.

[Edited on 17-5-2021 by student]

Fery - 17-5-2021 at 11:59

Hi student and welcome here. It is nice to obtain the desired product by own synthesis for the beauty of the chemistry.
Recently I've bought 1 L of diethylmalonate for 46 EUR from s3 chemicals (Germany).
https://shop.es-drei.de/ester/695/malonsaeurediethylester-mi...
More time ago I've bought 2 x 500 ml bottles from the ebay seller you linked. I'm very satisfied with both sellers.

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