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Author: Subject: Synthesis of malonic acid
Boffis
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[*] posted on 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.. :)
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[*] posted on 19-10-2017 at 10:25


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



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[*] posted on 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]
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[*] posted on 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]




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 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?




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[*] posted on 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?


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[*] posted on 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.
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[*] posted on 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]




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[*] posted on 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.
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[*] posted on 27-12-2017 at 20:13


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



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[*] posted on 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.
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[*] posted on 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
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[*] posted on 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.




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 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]
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[*] posted on 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]




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 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

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[*] posted on 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.
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[*] posted on 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.




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[*] posted on 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%.




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 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]




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[*] posted on 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]
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[*] posted on 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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