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Boffis
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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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DraconicAcid
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And here I was wondering if it was possible to easily make esters out of malonic acid....
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Niter of Potash
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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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clearly_not_atara
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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]
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Magpie
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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?
The single most important condition for a successful synthesis is good mixing - Nicodem
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Niter of Potash
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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)
This file has been downloaded 671 times
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Niter of Potash
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| 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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Magpie
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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]
The single most important condition for a successful synthesis is good mixing - Nicodem
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Niter of Potash
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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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Magpie
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You can easily get a dangerous runaway reaction if the nitric is too strong or added too fast.
The single most important condition for a successful synthesis is good mixing - Nicodem
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Jackson
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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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Tsjerk
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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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clearly_not_atara
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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.
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Mush
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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
Attachment: behrend1918.pdf (1MB)
This file has been downloaded 545 times
Attachment: subramaniam1929.pdf (614kB)
This file has been downloaded 501 times
beebeautiful.org.uk used to have Cherry Fragrance Oil containing 25-50 diethyl malonate
https://beebeautiful.org.uk/shop/wp-content/uploads/2014/06/...
Attachment: Cherry-Fragrance-Oil.pdf (73kB)
This file has been downloaded 540 times
[Edited on 8-5-2020 by Mush]
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clearly_not_atara
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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]
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kmno4
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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 
Attachment: malo.pdf (985kB)
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Boffis
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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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Fery
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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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clearly_not_atara
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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%.
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kmno4
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| 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  . 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.
Attachment: phosp.pdf (723kB)
This file has been downloaded 415 times
[Edited on 10-2-2021 by kmno4]
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student
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| 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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Fery
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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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SplendidAcylation
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Malonic acid from acrolein via hydracrolein?
Like many, I have been interested in the synthesis of malonic acid for some time, but I have been foiled by the apparent necessity of cyanides.
I have tried my best to UTFSE and I've read the threads about malonic acid on here, specifically this one, and while there were a lot of very interesting ideas, none of them seemed very likely to be practical or to work.
On page 7 of the above thread, it was suggested "Another possible approach would be elimination of the secondary alcohol group of glycerine to give
3-hydroxypropanal, followed by oxidation."...
Anyway, I was looking at the Wiki page for 1,3-propanediol, and I was surprised to read "1,3-Propanediol is mainly produced by the hydration of
acrolein."
I wouldn't have considered this in the first place, based on the assumption that hydration of the above unsaturated aldehyde would follow
Markovnikov's rule and end up with the hydroxy in the alpha position, on the 2 carbon, but no! It ends up in the beta position, on the 3 carbon.
I don't know exactly why this is, but I'm guessing that, if the mechanism involves a carbocation intermediate, then it is obvious why this would
happen, because the formyl (aldehyde) group is electron-withdrawing, so this would have the secondary carbocation less stable and the primary one more
stable, the opposite to addition to an alkene where the secondary carbocation is more stable due to the alkyl electron-donating group.
So, having discovered that hydration of acrolein (and, of course, reduction!) can possibly yield 1,3-propanediol, which could of course be readily
oxidised to malonic acid, I did a bit more searching, and came to a few conclusions:
There wouldn't be much point in turning acrolein into 1,3-propanediol, which involves reduction of the aldehyde group, just to
oxidise it again
It would perhaps be possible to simply hydrate the acrolein, forming 3-hydroxypropanal (also known as hydracrolein) and then oxidise this to the
acid
Another possible approach would be to oxidise acrolein to acrylic acid, followed by hydration thereof
The latter would also work, as Wiki says "3-Hydroxypropionic acid can be obtained by base-induced hydration of acrylic acid", so again, another way to
add the hydroxy to the beta position!
Anyway, oxidation of acrolein to acrylic acid doesn't seem to be too straightforward, so the hydracrolein approach seems more interesting.
I found this paper: Hydration of Unsaturated Compounds. XI. Acrolein and Acrylic Acid
I have attached it as a PDF.
Within this paper, there is a reference to an earlier paper, this one:
Dissociationsvorgänge in der Glycol-Glycerinreihe
Also attached as PDF.
It is in German, which I cannot read, but I can infer, thanks to Google Translate, that it says that a solution of acrolein should be heated in a
sealed tube for a number of hours, whereupon the water and unreacted acrolein are distilled off, and the hydracrolein is vacuum-distilled, whereupon
it solidifies upon cooling.
Seems easy, but it doesn't mention yield, and of course, acrolein is pure evil.
If it were successful to make hydracrolein this way, it would presumably (but not necessarily) be easy to oxidise it to malonic acid, perhaps sodium
hypochlorite could be used as the oxidiser, whereupon the solution could be acidified to remove any carbonate and hydroxide ions, and a soluble
calcium or magnesium salt added to precipitate the malonic acid as an insoluble malonate salt.
[Edited on 25-10-2022 by SplendidAcylation]
Attachment: ja01260a057.pdf (527kB)
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Attachment: hydracrolein nef1904.pdf (2.2MB)
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andyloris
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Just got a random idea while looking at the strecker degradation wikipedia page:
Could serine undergo strecker degradation to form 3-hydroxypropanal and then be oxidised to malonic acid ?
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Texium
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Nope. Not enough carbons. You’d end up with glycolaldehyde.
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