Sciencemadness Discussion Board

Easy Route to Acetonedicarboxylic acid?

Sauron - 25-1-2007 at 03:03

The usual method for preparing this interesting compound, employed in a number of fascinating Mannich condensations, is to oxidize anhydrous citric acid in the cold with fuming sulfuric acid, hardly a very convenient process. For one thing the acetonedicarnoxylic acid product has to be scrupulously washed free from all traces of sulfuric acid, or it will soon decompose.

For another, fuming sulfuric acid isn't cheap.

TCCA is cheap, and selectively oxidizes secondary hydroxyls, so maybe it will work with citric acid's hydroxyl group and thus bring about the decarboxylation to acetonedicarboxylic acid, providing a cleaner, stabler product.,

Worth a try, don't you think?

Some of the Mannich reactions employing this b-ketogluaric acid, its esters or anhydride are doubtless familiar to some of the B's from the Hive as they lead to well known and popular derivatives of tropinone.

Maya - 25-1-2007 at 07:13

I'ved used fuming and that worked fine after washing with ether.

Also used chlorosulfonic followed by MeOH then extarction with CHCl3 and distillation to get the Di-ester.

But never heard or tried of using TCCA, why would you think it would work?

Sauron - 25-1-2007 at 07:45

Because the hydroxyl group in citric acid (the alcoholic hydroxyl not the carboxylic ones) is secondary. TCCA is selective for secondary or benzylic hydroxyls, so I see no reason why it should not work on a secondary hydroxyl that is beta to a carboxyl group.

Easy enough to just give it a try. I have plenty citric acid, and will order a few Kg TCCA. I want to try it on glycerine as well. Ought to be a facile way to get 1,3 hydroxyacetone, as the TCCA doesn't oxidize the primary hydroxyls at all (or more precisely the rates are very different, so it's effectively highly selective.)

It's cheap enough from Acros, $50/kg. If I can find a pool supply house it'll be a lot cheaper than that but Bangkok has few swimming pools.

Nicodem - 25-1-2007 at 11:40

Acetone dicarboxylic acid and its esters have two quite acidic methylene groups (pKa of about 10), acidic more than enough to get chlorinated by TCCA extremely easily, even in neutral media, while for sure in acidic reaction media (HCl is a by product of the oxidation step). So there is no way to stop the oxidation of citric acid at the acetone dicarboxylate stage if using trichloroisocyanuric acid. Besides, citric acid is formally a tertiary alcohol and the mechanism of oxidation by fuming H2SO4 is of a particular kind which might not necessarily apply to TCCA as oxidant.

Sauron - 25-1-2007 at 16:45

Oh well, que sera sera. Thanks.

shadow - 15-9-2015 at 19:57

This thread may be very old, but there is a Chinese patent out there using hydrogen peroxide to oxidize the citric acid for 1,3 acetonedicarboxylic acid.

[Edited on 16-9-2015 by shadow]

Boffis - 16-9-2015 at 14:48

@shadow, do you ahve some more details of the patent like a number etc.?

Crowfjord - 16-9-2015 at 17:45

Found it. The patent is CN 103288628. The following is copied from the google translation:

[0021] Example 1

Equipped with a reflux condenser, a stirrer, a thermometer, 500ml round bottom flask was added citric acid monohydrate 210g (lmol), 50ml of water was added, raising the temperature to 55 ° C, then began a 30% solution of hydrogen peroxide an aqueous solution of 136g (1.2mol), was observed to bubble out uniformly, with the addition of an aqueous solution of hydrogen peroxide, the reaction temperature is gradually increased, after the completion of the dropwise addition, at 95 ° C for 3 hours, water was evaporated to dryness under reduced pressure Weighing, the products of 1,3-acetone dicarboxylic acid 141g (0.97mol), yield %% 97% purity, mp I35O (decomposition).


I don't know much about this reaction, does it seem weird that no catalyst (acid, base, metal) is employed?

Waffles SS - 16-9-2015 at 21:56

Interesting If it work !

I searched this compound in reaxys for all possible way for synthesis


Attachment: Acetonedicarboxylic acid.pdf (246kB)
This file has been downloaded 1228 times



[Edited on 18-9-2015 by Waffles SS]

shadow - 17-9-2015 at 17:31

Here is the site:
Crow has it right.
Various examples are given

http://www.google.com/patents/CN103288628A?cl=en

shad

nlegaux - 21-9-2015 at 11:16

Would it be possible to create acetonedicarboxylic acid by reacting formaldehyde and a haloacetic acid?

nlegaux

byko3y - 21-9-2015 at 11:21

nlegaux, no.

gdflp - 21-9-2015 at 11:47

Quote: Originally posted by nlegaux  
Would it be possible to create acetonedicarboxylic acid by reacting formaldehyde and a haloacetic acid?

nlegaux

How are you suggesting the two carbon-carbon bonds are formed?

Boffis - 22-9-2015 at 18:01

nlegaux's idea above set me thinking, instead of formaldehyde how about nitromethane?

Treat nitromethane with a base to generate a nitrolic acid salt and then react with sodium chloroacetate to get the Na salt of 3-nitropropanoic acid. Then again base catalysed condensation of this compound with sodium glyoxylate to get either 3-nitro-2-pentenedioic acid or 2-hydroxy-3-nitropentanedioic acid depending on whether or not dehydration occurs. Sound plausible anybody?

If it works this far the next step should be easy, after all the conversion of alpha-hydroxy-nitroalkanes or conjugate nitro alkenes to ketones are probably the two most extensively discussed topics on this forum! :)

Not quite as simple as the hydrogen peroxide route I admit but somewhere on this forum a paper was once posted about the oxidation of citric acid with hydrogen peroxide and I seem to recall that the products were complex so just because its in a patent doesn't necessarily mean its going to work. I think this is the paper as best I recall:

Attachment: Oxidation of quinic acid- to citric acetone dicarboxylic and malonic acids JExBot Hulmes & Arthington 1953.pdf (743kB)
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PHILOU Zrealone - 25-9-2015 at 16:14

Just thinking out loud:
CH3-CO-CH3 + Cl2 --> Cl-CH2-CO-CH2-Cl (lacrymogen and probably carcinogen/ strong alkylating agent)
Cl-CH2-CO-CH2-Cl + 2 Na-C#N --> N#C-CH2-CO-CH2-C#N + 2 NaCl
N#C-CH2-CO-CH2-C#N + 2 H2O -heat/mild acid-> NH4O2C-CH2-CO-CH2-CO2NH4

Waffles SS - 27-9-2015 at 10:13

I tried to make Acetonedicarboxylic acid according to CN103288628 but i got unchanged Citric acid.

After adding H2O2 at 60c to Citric acid solution no bubble released and temp did not increase.

I got clear crystal after refluxing solution for 3-4 Hour at 94c and evaporating the solution at reduced pressure. according to FTIR spectra that is Citric acid.

Someone has tried this method ?



[Edited on 27-9-2015 by Waffles SS]

PHILOU Zrealone - 27-9-2015 at 11:45

Another possible way:

HO2C-CH2-C(-CO2H)(-OH)-CH2-CO2H + halogenating agent --> HO2C-CH2-C(-CO2H)(-X)-CH2-CO2H
HO2C-CH2-C(-CO2H)(-X)-CH2-CO2H + AgNO2 --> HO2C-CH2-C(-CO2H)(-NO2)-CH2-CO2H + AgCl (s)
(part of the nitro enters as nitrite ester!)
HO2C-CH2-C(-CO2H)(-NO2)-CH2-CO2H -spontaneous decarboxylation-> HO2C-CH2-CH(-NO2)-CH2-CO2H + CO2

Then usual conversion of secondary nitrocompound to ketonic group.

[Edited on 27-9-2015 by PHILOU Zrealone]

Waffles SS - 27-9-2015 at 21:55

Thanks PHILOU Zrealone,that is good idea but little expensive

In reaxys search(i put PDF file of it above) there is interesting reaction.


Quote:

H2O + Citric acid + Mn2(SO4)3 + K2SO4 = Acetonedicarboxylic acid + Acetone

Reaktion des Trinatriumcitrats beim BelichtenMacMahon; Srivastava; Journal of the Indian Chemical Society; vol. 23; (1946); p. 262; Current Science; vol. 15;(1946); p. 249; ; (1947); p. 1921


it seems reference is not available :(

also another reaction of this reference used FeCl3 instead of K2SO4.

I think oxidation of Citric acid to Acetonedicarboxylic acid is possible even with alone KMnO4 but there is no guarantee that over oxidation do not happen



Sydenhams chorea - 2-10-2015 at 03:01

Quote: Originally posted by Waffles SS  
Quote:

H2O + Citric acid + Mn2(SO4)3 + K2SO4 = Acetonedicarboxylic acid + Acetone

Reaktion des Trinatriumcitrats beim BelichtenMacMahon; Srivastava; Journal of the Indian Chemical Society; vol. 23; (1946); p. 262; Current Science; vol. 15;(1946); p. 249; ; (1947); p. 1921


it seems reference is not available :(


Current Science is available for free online, but that last one (1947) p 1921 is wrong, the volume only +- 300 pages, and nowhere is a Srivastava to be found, neither in other volumes.

I attached volume 15 (1946) p 249. In ithe author says that he examined photochemical reactions of I2 in aq. KI on sodium citrate in light (1000W incandescent) and he added that addition of Mn(II) and Cr(III) salts are most effective. There's not much else he says.

Quote:

also another reaction of this reference used FeCl3 instead of K2SO4.

I think oxidation of Citric acid to Acetonedicarboxylic acid is possible even with alone KMnO4 but there is no guarantee that over oxidation do not happen


KMnO4 oxidation is described in Comptes Rendus 130 (1900) p 32-34. It used to be available to download from the Bibliothèque Nationale de France (Gallica) but they changed their format to tablet style and it seems a lot of functions are not working. So I'll post the link: http://gallica.bnf.fr/ark:/12148/bpt6k3086n/f34.item.r=Denig...

Overoxidation to acetone and CO2 is unavoidable unless the acetonedicarboxylic acid is precipitated immediately as it forms. The author used mercuric sulfate for that, from which acetonedicarboxylic acid can be recovered with a stream of H2S:

(from French) 10g citric acid was dissolved in 20ml hot water and 3g KMnO4 was dissolved in 100ml hot water. Both solutions were brought to 15°C and the permanganate solution was added to the citric acid solution in a water-bath taking care that the temperature didn't rise above 30-35°C. After a couple of hours of standing, the liquid, which had now attained a yellow colour, was added to 100ml of a hot HgSO4 solution previously brought to a boil. A great amount of white precipitate was recovered by filtration, washed with water, and suspended in water where it is decomposed with a stream of H2S. After filtrating the mixture was extracted with ether, from which acetonedicarboxylic acid was recovered.

Attachment: article_id_015_09_0249_0250_0.pdf (148kB)
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EDIT:
I also added "Effect of metal ions on acetone dicarboxylic acid catalyzed peroxomonosulphate reactions", Journal of Molecular Catalysis A Volume 390, August 2014, Pages 22–28., where the oxidation of oxidation of Fe(III), Ni(II) and Co(II) citrates by peroxomonosulphate (PMS, Oxone) in the pH range 3.0–6.0 is examined.

"Conclusion The oxidation of citric acid by peroxomonosulphate in the pH range 3.0–6.0 (citric acid buffer) occurs only in the presence of a metal ion. The Fe(III), Co(II) and Ni(II) citrates follow auto catalyzed mechanism. Acetone dicarboxylic acid is the product which catalyzes the oxidation of metal citrate. In the absence of meta lions, acetone dicarboxylic acid catalyzes the decomposition of PMS at pH 3.0–6.0 as in ketone catalyzed one at neutral or weak alkaline pH. However, the complexation with metal ion changes the mechanism to the acetone dicarboxylic acid catalyzed oxidation of metal–citrate by PMS."

[Edited on 2-10-2015 by Sydenhams chorea]

Attachment: ragukumar2014.pdf (690kB)
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[Edited on 2-10-2015 by Sydenhams chorea]

Waffles SS - 2-10-2015 at 03:26

Thanks @Sydenhams chorea,

That is great.

Maybe we can use Barium or Calcium salts instead of Mercury sulfate for precipitating Acetonedicarboxylic salt.This need to know which salt of Acetonedicarboxylic is insoluble in water.



[Edited on 2-10-2015 by Waffles SS]

Sydenhams chorea - 2-10-2015 at 17:55

Quote: Originally posted by Waffles SS  
Thanks @Sydenhams chorea,

That is great.

Maybe we can use Barium or Calcium salts instead of Mercury sulfate for precipitating Acetonedicarboxylic salt.This need to know which salt of Acetonedicarboxylic is insoluble in water.

[Edited on 2-10-2015 by Waffles SS]


I am more concerned about generating H2S. Although soluble mercury salts have to be handled with care, I feel more comfortable carefully handling solid then setting up a H2S-generator. For 10g of citric acid the equimolar amount of acetonedicarboxylic acid is 7.61g (assuming full conversion) so that would require about 16g of HgSO4, which is not such a great amount. Besides, after precipitating with H2S, all mercury is recovered as the sulfide (cinnaber).

HgSO4 decomposes in water into HgSO4.2HgO (mercuric subsulfate) and H2SO4. The subsulfate is a yellow insoluble compound, but does dissolve in a hot diluted sulfuric acid.After isolating and washing the Hg(II) complex I would suggest to suspend it in dilute HCl and carefully add the equivalent amount of ammonium sulfide required to generate the necessary amount of H2S in situ.

As for trying other metals, better to chose those with a high atomic mass who also can be recovered as insoluble sulfides such as lead, bismuth, tin, zinc, antimony.

Attached is another method of oxidation of citric acid with Mn(III), an aqueous suspenion of freshly precipitated Mn2O3, which they prepared by mixing warm aqueous solutions of 50g MnSO4 and 20g KMnO4, filtering the precipitate and washing with water. It is probably the gamma-polymorph analoguous to the gamma-polymorph of MnO2 prepared in this manner with twice the amount of permanganate, and known as the most active, desired form for use in organic synthesis. Two polymorphs of Mn2O3 are known, alpha- and gamma-. The paper doesn't specify any mount, they just state that citric acid is added to the stirring suspension of oxidant.

Attachment: Mn2O3_Chem.Zentr.1917.pdf (568kB)
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shadow - 8-10-2015 at 19:24

@Waffles
I tried CN103288628 last year, my first sample melted at 139, and I got excited, but subsequent samples were higher around the mp of citric acid. I set the product aside, but I'm looking for something that one or the other, but not both is soluble in.

Waffles SS - 8-10-2015 at 23:02

I had no success by this method too.

No bubble and no heat after adding H2O2.

It seems registration of bullshit patent is not difficult in china!

Boffis - 9-10-2015 at 07:15

@shadow and Waffles; I know it is not mentioned in the chinese patent but in every case that I have used H2O2 as an oxidising agent in organic systems there is always a catalyst such a tungstate (amino to nitro groups), ferric nitrate (substituted N-heterocylics to heterocyclic carboxylic acids), ferrous acetate (carbohydrates to sacchric acid or similar) etc.

With citric acid forming remarkably stable stable complexes with ferric iron I think that iron based catalyst probably will not work but tungstate or heteropoly tungstophorphoric acid and similar derivatives may be better. Also give the reference to the use of hydrated Mn3+/Mn4+ oxide a manganese compound may also work.

I am not at home at present but when I am I may look into these possibilities.

ronstark - 5-6-2017 at 11:39

10g Citric Acid was dissolved in 20mL boiling dH2O.
Solution #1 was cooled to 15°C.

3g KMnO4 was dissolved in 100mL boiling dH2O.
Solution #2 was cooled to 15°C.

Solution #1 was added dropwise over solution #2.
The temperature was kept between 30°C - 35°C upon addition (10 minutes).

Fizzing and bubbling indicating the evolution of CO2.

The smell is reminiscent of Coca-Cola.

After 2h on standing, the liquid, which had now attained a yellow colour, was esterified with NaOH and EtOH.
Let's see in the morning if something precipitates out.

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[Edited on 5-6-2017 by ronstark]

Waffles SS - 5-6-2017 at 19:14

Oxidation of Citric acid by KMNO4/H2SO4 result different route.are you sure you got Acetonedicarboxylic acid?

Attachment: kuyper1933.pdf (397kB)
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ronstark - 6-6-2017 at 00:33

No, I don't have Acetonedicarboxylic Acid. But I am pretty sure that I got Acetonedicarboxylic Acid monoethyl ester monosodium salt.

http://www.orgsyn.org/demo.aspx?prep=CV1P0237

Quote:
The solution is allowed to cool down to room temperature in the bath and finally to stand about twelve hours.


After the decarboxylation, I continued with the equimolar amount of NaOH and EtOH.

Looks like something precipitates after all.

0.430g

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[Edited on 6-6-2017 by ronstark]

Waffles SS - 6-6-2017 at 05:56

According to reference that i provide in my last post this reaction can proceed by some route.You should ensure about your product.can you check it melting point?can you check it solubility in different solvent?

ronstark - 6-6-2017 at 07:09

The Citric Acid was oxidized by KMnO4 without H2SO4. Next time, will try to precipitate it with HgSO4 prepared in situ from Hg added in H2SO4 (from the same method).

mp for that small amount was 150°C.

Any viable method instead of this one or H2SO4 / SO3? It must have an O2 source. NaIO4?

[Edited on 6-6-2017 by ronstark]

Waffles SS - 6-6-2017 at 07:31

I dont think NaIO4 can do it.you can try oxidation by peroxomonosulphate.This method mentioned by @Sydenhams chorea at page 1.


[Edited on 6-6-2017 by Waffles SS]

clearly_not_atara - 6-6-2017 at 16:09

I've heard of Fe2(SO4)3 being used for reactions like this one in the presence of a radical initiator IIRC... here's a version that uses cobalt salts with caroate (HSO5-):

http://nopr.niscair.res.in/bitstream/123456789/30959/1/IJCA%2054A(3)%20333-344.pdf

Chemi Pharma - 7-6-2017 at 05:39

Acetone dicarboxilic acid esters may be produced from the oxidation of citric acid esters with cromic acid (potassium dichromate) and sulfuric acid at room temperature, producing only CO2, and not CO like the oxidation of citric acid with oleum.

I think acetone dicarboxilic acid may be produced the same way as it's esters, cause the conditions are the same.

Permanganate (with sulfuric acid) oxidations seems to produce only low yield of acetone dicarboxilic acid esters and major quantities of formaldehyde, carbon dioxide and formic acid, as said in the patent i'm bringing to the comunity as an attachment.

If you intend to produce 2-carbomethoxytropinone, this may be a bether way to produce the methyl monoester of acetonedicarboxilic acid, to employ as a reagent at the manich condensation.

Also, the precursor mono-methyl-ester of citric acid can be achieved by the esterification of citric acid with methyl alcohol with pyridine and sulfuric acid as a catalyst, like said at the another patent i bring too:

See the patents below:



Attachment: Acetonedicarboxylic acid esthers synthesis.pdf (3.5MB)
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Attachment: Citric Acid Esters.pdf (486kB)
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Boffis - 7-6-2017 at 10:02

Quote: Originally posted by PHILOU Zrealone  
Just thinking out loud:
CH3-CO-CH3 + Cl2 --> Cl-CH2-CO-CH2-Cl (lacrymogen and probably carcinogen/ strong alkylating agent)
Cl-CH2-CO-CH2-Cl + 2 Na-C#N --> N#C-CH2-CO-CH2-C#N + 2 NaCl
N#C-CH2-CO-CH2-C#N + 2 H2O -heat/mild acid-> NH4O2C-CH2-CO-CH2-CO2NH4


Quite coincidently I have just spotted a old synthesis of citric acid that would seem to vindicate PZ's suggested method from acetone. In Richter's Organic Chemistry 3rd edition 1944 p664-665 under citric acid there is described the synthesis of citric acid from 1,3-dichloroacetone via the conversion the the cyanohydrin then reacting the two chloro groups with sodium cyanide to give the hydroxytricyano derivative which on hydrolysis gives citric acid. The cyanohydrin formation requires free hydrogen cyanide so the natural alkalinity of sodium cyanide may prevent the formation of a cyanohydrin and simply replace the chloro groups. Maybe cuprous cyanide would work too.

Incidently Richter also states that acetonedicarboxylic acid can be prepared from ethyl cyanoacetoacetate ester which I presume is available via a mixed Claissen condensation between ethyl cyanoacetate and ethyl acetate.

I like the suggested route with oxidation of the di-ester of citric acid but the posted patent above only concerns the long chain di-alkyl citrates what about the methyl and ethyl derivatives? Could the diethyl ester be prepared by the partial hydrolysis of the tri-ethyl ester which is fairly easily available as a food additive?

Waffles SS - 7-6-2017 at 10:37

Chemi Pharma provide interesting patent and i think making diester of citric acid is only possible by separation of esterified citric acid.In this case separation of diethylester from mono and triester.

[Edited on 7-6-2017 by Waffles SS]

ronstark - 7-6-2017 at 10:57

Quote:
Citric acid is both an alpha and beta-hydroxy acid, and exhibits the characteristic reactions of each. When heated to 175°C, it is partially converted to aconitic acid by elimination of water, and to acetonedicarboxylic acid by the loss of carbon dioxide and water. At temperature above 175°C, citric acid yields an oily distillate, which crystallizes as itaconic acid. Further heating yields a non-crystallizable oil which is citraconic anhydride. The hydrogenation of citric acid yields tricarballylic acid.


Maybe a simple distillation or a dry one @ 175°C should do the trick? Funny that further heating yields citraconic anhydride, just like further heating of tartaric acid yields succinic anhydride. Thanks for the info Chemi Pharma!

[Edited on 7-6-2017 by ronstark]

Attachment: Citric Acid.pdf (2.8MB)
This file has been downloaded 1204 times


Sigmatropic - 7-6-2017 at 10:59

It is possible to separate the esters of citric acid by using their calcium salts. The calcium salt of citric acid, the monoester and the unsymmetrical diester are insoluble in acetone and methanol. The calcium salt of the diester is insoluble in acetone. The triester does not form salts.

According to this article (1), the mixture resulting from fischer esterferication is neutralized with Ca(OH)2, solids removed (citric acid and its mono, and unsym. diester are removed here) and the filtrate evaporated to dryness. The residual solids are then washed with acetone to remove the triester. The symmetric diester can be liberated from the solids with hydrochloric acid. They report a yield of 25%.

I suppose one can use any calcium salt and a base to do the neutralization. I also suppose one can remove the triester with most other apolar solvents
.
(1) CHEMISTRY LETTERS, pp. 191-194, 1980. (C The Chemical Society of Japan 1980)
"A FACILE PREPARATION OF ASYM-MONOMETHYL, SYM-MONOMETHYL AND
ASYM-DIMETHYL CITRATE"



Attachment: Dimethylcitrate.pdf (5.7MB)
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[Edited on 7-6-2017 by Sigmatropic]

Boffis - 7-6-2017 at 10:59

Quote: Originally posted by Waffles SS  
Chemi Pharma provide interesting patent and i think making diester of citric acid is only possible by separation of esterified citric acid.In this case separation of diethylester from mono and triester.

[Edited on 7-6-2017 by Waffles SS]


And how do you do that? It may be possible to remove the mono and diesters with, say, sodium bicarbonate which may be basic enough to dissolve the ester with free acid groups and remove the triester as an immiscible oil. The mono and diesters can then be liberated with acid but how then do you separate these two?

Waffles SS - 7-6-2017 at 12:07


Quote:

ethyl cyanoacetoacetate ester which I presume is available via a mixed Claissen condensation between ethyl cyanoacetate and ethyl acetate.


Acetocyanoacetate are not stable in Claissen condensation and you can not synthesis it by this way.
Ethylacetocyanoacetate synthesis by reaction of Bromoethyl acetoacetate with sodium Cyanide.

Troostwijk,C.B.; Kellogg,R.M.Journal of the Chemical Society, Chemical Communications, 1977 , p. 932 -933


Quote:

The mono and diesters can then be liberated with acid but how then do you separate these two?


It seems Sigmatropic method is effective for this.





[Edited on 7-6-2017 by Waffles SS]

Boffis - 8-6-2017 at 01:26

@ Sigmatropic, that was effecient! You answered my question before I asked it. This procedure looks very workable though. I wonder if the oxidation of dimethyl citrate to dimethyl acetonedicarboxylate works better with the sym-diester which looks likely or whether it works with either?

Waffles SS - 8-6-2017 at 08:02

Quote: Originally posted by ronstark  

Maybe a simple distillation or a dry one @ 175°C should do the trick? Funny that further heating yields citraconic anhydride, just like further heating of tartaric acid yields succinic anhydride. Thanks for the info Chemi Pharma!


Interesting.I read your reference and also there is good procedure for making Citraconic anhydride, Itacnic anhydride and Aconitic acid from Citric acid by dry distillation but nothing for making Acetonedicarboxylic acid by this method.I think there is no possible way for synthesis it by this method.
According to Merck index it decompose at 138C(melting point) and sure it should be very unstable at 175C
http://orgsyn.org/demo.aspx?prep=CV2P0140
http://orgsyn.org/demo.aspx?prep=CV2P0368
http://orgsyn.org/demo.aspx?prep=CV2P0012


[Edited on 8-6-2017 by Waffles SS]

ronstark - 18-6-2017 at 22:15

Seems like it can be oxidized by MnO2 to Acetonedicarboxylic Acid or Pentabromoacetone. Could the second be used in a Mannich type reaction? With other starting products of course...

Attachment: J. Biol. Chem.-1944-Goldberg-33-46.pdf (883kB)
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[Edited on 19-6-2017 by ronstark]

ronstark - 19-6-2017 at 03:19

Quote:
The initial oxidation product is acetonedicarboxylic acid (Wang and Stone, 2006a; Meichtry et al., 2011).


Maybe that Cu complex can be stripped off.

Attachment: jefferson2015.pdf (1.2MB)
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[Edited on 19-6-2017 by ronstark]

ronstark - 19-6-2017 at 03:44

Quote: Originally posted by Waffles SS  
I dont think NaIO4 can do it.


Quote:
Huebner et al. [266] and Courtois [267] observed a slow oxidation of citric acid by sodium metaperiodate NaIO4 and by periodic acid HIO4, with the formation of an intermediate acetone dicarboxylic acid and finally formic acid and carbon dioxide.


[266] - Huebner CF, Ames SR, Bubl E (1946) Periodate oxidation of certain methylene groups. J Am Chem Soc 68:1621–1628
[267] - Courtois J (1949) Oxidation of citric acid with periodic acid. Ann Pharm Francaises 7:77–89

[Edited on 19-6-2017 by ronstark]

Waffles SS - 19-6-2017 at 07:01

Thanks ronstark.
I read first reference and it seems second reference is not available online.


Quote:

Citric acid is slowly oxidized by periodate, probably with acetone dicarboxylic acid as an intermediate as proposed by Smith and Duke for perchlorato-ceric acid.


I said "I dont think periodate can oxidise citric acid to acetone dicarboxylic acid " this mean we cant get acetone dicarboxylic acid by this method.Reference mentioned probably acetone dicarboxylic acid is intermediate and formic acid + CO2 is final product.You can get Acetonedicarboxylic acid by permmanganate or chromic oxidation but i dont think you can do it by periodate.



[Edited on 19-6-2017 by Waffles SS]

ronstark - 19-6-2017 at 08:09

2 C6H8O7 + MnO2 > 2 C5H6O5 + 2 H2O + 2 CO2 + Mn

10 g Citric Acid (anh.) dissolved in 10 mL dH2O. When MnO2 was added bubbling started without being exothermic. Only CO2 evolved. The temperature staid the same the whole time (1h). Filtered. Mn staid on the filter. The yellow solution was put in the freezer overnight, already water separates out leaving behind a yellow solid. I'm positive about this one.

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[Edited on 19-6-2017 by ronstark]

BlackDragon2712 - 21-6-2017 at 20:36

Quote: Originally posted by ronstark  
2 C6H8O7 + MnO2 > 2 C5H6O5 + 2 H2O + 2 CO2 + Mn

10 g Citric Acid (anh.) dissolved in 10 mL dH2O. When MnO2 was added bubbling started without being exothermic. Only CO2 evolved. The temperature staid the same the whole time (1h). Filtered. Mn staid on the filter. The yellow solution was put in the freezer overnight, already water separates out leaving behind a yellow solid. I'm positive about this one.



[Edited on 19-6-2017 by ronstark]


Soo... how did this go? any yields of some kind or identification of the product?
Also, how unstable acetonedicarboxylic acid actually is? would I be able to store it solid for a week or so?

[Edit]

has anyone tried with sodium percarbonate?

[Edited on 05/12/2013 by BlackDragon2712]

ronstark - 22-6-2017 at 06:10

Based on this drying agent chart chart:

https://drugs-forum.com/chemistry/chemistry/equipment/drying...

(MgSO4 can dry carboxylic acids)

... ~50g MgSO4 (anh.) was added to the yellow solution and let in the freezer for over two days. The MgSO4 absorbed the water and the solution separated out and decanted based on the density. Some pics will be uploaded tomorrow.

Don't think if Acetonedicarboxylic Acid will interact with MgSO4 and even if so, it's much easier to continue as it is. Will see.

[Edited on 22-6-2017 by ronstark]

ronstark - 24-6-2017 at 23:57

On the left: 6.204g of a substance that @ 25°C starts to transform into a gelatinlike liquid. Small crystalline structure still visible. Acetone / Formic Acid smell above 30°C.

On the right: Water trapped by MgSO4 (anh.).

Did anyone know some tests for Acetonedicarboxylic Acid presence?

Based on the density > 1mL of this substance = 1.459g. Close, but need more validation.

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[Edited on 25-6-2017 by ronstark]

Tsjerk - 25-6-2017 at 11:12

Wash with a solvent you know your product does not dissolve in and determine the melting T. Its not perfect but for an amateur quite doable.

ronstark - 26-6-2017 at 11:00

The only known insoluble solvent is Chloroform, but still water remains trapped. It was extracted in Ethyl Acetate to remove the trapped water (below). Will see after distillation its melting point.

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[Edited on 26-6-2017 by ronstark]

Boffis - 9-7-2017 at 13:46

Does anyone know anything about the salts of acetone dicarboxylic acid such as the alkali or alkaline earth salts or have any references to such salts? What I am thinking about is the relative stability and solubility of such salts with a view to understanding how these salts behave. The free acid is very unstable, the pure esters are much more stable but what about the salts. There is a fair amount of published information about the esters but very little about the inorganic salts.

Tellurium - 21-7-2017 at 01:17

Quote: Originally posted by Boffis  
Does anyone know anything about the salts of acetone dicarboxylic acid such as the alkali or alkaline earth salts or have any references to such salts?about the inorganic salts.

Quote: Originally posted by ronstark  

Did anyone know some tests for Acetonedicarboxylic Acid presence?
[Edited on 25-6-2017 by ronstark]

On lambdasyn it says, that in ethanolic solution it turns wine red with addition of some iron(III)chloride solution, so this could maybe help you ronstark:)

On the same page it says, that acetonedicarboxylic acid is decomposed to acetone and CO2 by hot water, acids and bases. So i think it wouldn't be the greatest idea to add some NaOH to get the sodium salt.

So maybe using a citrate salt instead of citric acid could do the trick? But than no acid should be used or it will displace the citric acid out of the salt:(

[Edited on 21-7-2017 by Tellurium]

ronstark - 24-7-2017 at 00:26

For now is still in Ethyl Acetate. It was too hot outside these weeks to work on synth's. Will try both after distillation and yield calculation. Thanks!

[Edited on 24-7-2017 by ronstark]

ronstark - 6-10-2017 at 02:41

2.834g after removal of Ethyl Acetate. The solid started to decompose @ RT with a very powerful smell of formic acid. Maybe this works after all.

[Edited on 6-10-2017 by ronstark]