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Author: Subject: Easy Route to Acetonedicarboxylic acid?
Waffles SS
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[*] posted on 5-6-2017 at 19:14


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

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ronstark
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[*] posted on 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]
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Waffles SS
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[*] posted on 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?
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ronstark
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[*] posted on 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]
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Waffles SS
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[*] posted on 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]
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clearly_not_atara
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[*] posted on 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
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Chemi Pharma
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[*] posted on 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:



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Boffis
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[*] posted on 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?
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Waffles SS
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[*] posted on 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]
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[*] posted on 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]

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[*] posted on 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"



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[Edited on 7-6-2017 by Sigmatropic]
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Boffis
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[*] posted on 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?
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Waffles SS
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[*] posted on 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]
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[*] posted on 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?
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Waffles SS
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[*] posted on 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]
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ronstark
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[*] posted on 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...

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[Edited on 19-6-2017 by ronstark]
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[*] posted on 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.

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[Edited on 19-6-2017 by ronstark]
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[*] posted on 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]
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Waffles SS
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[*] posted on 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]
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[*] posted on 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]
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[*] posted on 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]
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[*] posted on 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]
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[*] posted on 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.

IMG_9006.PNG - 873kB IMG_9007.PNG - 863kB

[Edited on 25-6-2017 by ronstark]
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[*] posted on 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.
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[*] posted on 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]
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