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Author: Subject: Preparation of Succinic Acid
LearnedAmateur
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[*] posted on 3-2-2018 at 08:48


Since alternate syntheses are popping up and that butanediol (I was a bit wary for obvious reasons) has been mentioned, I’ll insert mine which I’m planning to try. I’ve been exploring the Sandmeyer reaction recently, and it is entirely possible to get to succinic acid from GABA, which is easy to procure and still OTC in the States as far as I’m aware.

GABA is reacted with in situ, dilute nitrous acid to form the alkyldiazonium intermediate. Allowing the temperature to rise, it subsequently reacts with water to form GBL-GHB equilibrium with evolution of nitrogen. When this is complete, the aqueous layer is extracted using DCM or similar solvent which is distilled and recovered to leave GBL. After determining yield, a solution of KMnO4 is prepared, into which the GBL is added. GBL will undergo ring opening wherein the exposed hydroxyl group will be oxidised (under gentle heating or reflux, that’s up for determination) forming the monopotassium salt of succinic acid, which can then be acidified to give succinic acid. Ether can be used to extract this if necessary, possibly DCM but I’m not sure considering that it is barely soluble in chloroform and I can’t find much more information regarding the solubility in immiscible polar solvents.

By playing with more gentle oxidising agents, which is where I’m not entirely sure about, succinic semialdehyde may be synthesised instead if anyone needs to procure any.

Edit: decided to remove the ‘censors’ since the first part of the procedure is easy to find around anyway.

[Edited on 3-2-2018 by LearnedAmateur]




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Boffis
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[*] posted on 3-2-2018 at 14:32


@Magpie; some years ago now I bought a job lot of old chemicals from a guy on ebay, when I went to pick them up he asked me if I was interested in any of his other chemicals; he had quite a collection. I took the butanediol because it was in a 2.5L winchester with the acid resistant GL45 caps which are really expensive, the bottle was about a third full so I transferred it to a smaller bottle. There was about 800ml but at the time I had no particular use for it.

My succinic acid preparation is going fairly well, chilled to 6-7 C over night, stirred up to disperse the crystals formed and then filtered using a glass frit funnel. I rinsed it with a little water to give a moderate amount of pale blue crystal. If you use enough water they become white but I was worried about loosing too much to the wash water so I used a little water and I will recrystallise them. The yield of crude succinic acid was 12.274g, which is less than 50% yield but with 300ml of chromic sulphate solution there may be significant material left in solution.

A question. What to do with the 300ml of chromic sulphate solution. It is completely reduced to Cr3+ and is a lovely deep greenish blue colour but how to recover something useful from it? I could add ammonium or potassium sulphates to precipitate much of the chromium as an alum then concentrate the liquor, the chromium tends to form a sulphato complex on boil which is slow to crystallised giving the succinic acid a chance to crystallise before the remainder of the alum?

Is say ether extraction of the liquor possible to recover more succinic acid possible?

Nitric acid looks like a cleaner route but as I said above that depends on the local availability of nitric acid.

@ learned amateur; I was writing this post while yours appeared so I'll edit to incorporate a response to your post too. I was looking for a use for my diol rather than the best method to succinic acid but your post made me think.

There are several routes to nitriles from amines etc so maybe it would be simpler to try oxidizing GABA directly with say TCCA and NaOH to see if you can get 4-nitrilobutyric acid, filter off the insoluble isocyanuric acid and the extract the nitrile with a weakly polar immiscible solvent. The nitrile can then be hydrolysis to succinic acid. Other oxidizing agents may work (N-chlorosuccinimide etc) and there are several threads on SM covering versions of this idea.

[Edited on 3-2-2018 by Boffis]
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[*] posted on 3-2-2018 at 19:31


Boffis,

Oxidation of GABA with TCCA to give 3-cyanopropionic acid should work as you proposed - good thought. Oxidation of readily available aspartic acid will also work and is documented. See attached.

The hydrolysis of the nitrile should be facilitated by the nearby carboxylic acid function.

AvB

Attachment: An Insight of the Reactions of Amines with Trichloroisocyanuric Acid[1].pdf (160kB)
This file has been downloaded 67 times

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[*] posted on 4-2-2018 at 02:45


Oh yeah, whatever is easiest and most readily available would ideally be the best route so focusing on 1,4-BD oxidation would be most appropriate in your case, I just wanted to propose an alternate idea since I have all of the reagents lying around whereas TCCA isn’t something I need or am willing to spend out on right now. If I do happen to procure any then I’ll be happy to explore that route; for the sake of science it may be a good idea for us to all explore their respective syntheses and compare yields and other observations.



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[*] posted on 9-2-2018 at 15:12


Chromic oxidation of butanediol continued

I tried an ether extraction of the chromic sulphate solution with about 40ml of ether, removal of the ether left 0.450g of colourless moist crystals that smelled slightly of sweaty feet. I added these to original crystals and recrystallised them from water. About 25ml was the minimum workable amount, it gave me a clear deep greenish blue solution that crystallised nicely on cooling. The crystals were filtered off, washed with a little cold water and dried. The very pale blue/ white crystals of succinic acid weighed 8.193g (from 12.72g). I tried cleaning up the residue by turning it into the sodium salt with excess alkali hoping that this would precipitate the the remaining chromium as hydroxide but no precipitate formed. I may try evaporating the solution down until it crystallises and see what I get.

The resistance of chromium sulphate solution to hydrolysis even by alkalis once they have been boiled is well known so no surprises there. In the cold the sulphochromate complexes slowly revert to chromium sulphate hydrates so I may just let the mixture stand for a few week and see what happens.

The chromium sulphate solution was evaporated down to about 150ml and now resembles black strap molasses. After 24 hours the original viscous liquid has become a viscous slurry so it looks like crystals have formed in it but it's going to be a right b**** to filter:). The liquid is immiscible even with ethanol, only water seems to dissolve it (rapidly) so not much use for washing the crystals.
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[*] posted on 12-2-2018 at 12:58


Interesting observation; the blue residue from recrystallising the first crop of succinic acid was made alkaline with sodium carbonate solution and as mentioned above no precipitate formed. However, after a couple of days a precipitate is forming and the solution becoming paler so hopefully the residual chromium can be precipitated. The Original chromium III sulphate liquor has become an almost porridge like consistency.
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[*] posted on 15-5-2018 at 13:22


I have made some further experiements into the oxidation of butanediol to succinic acid.

Firstly I tried using sodium chlorite and hydrochloric acid. A strong solution of sodium chlorite was added dropwise to butanediol diluted with about 4 times its volume of water and to which a small amount of conc 36% HCl was added. The solution turned yellow immediately and developed the characterisitc pungent smell of chlorine dioxide but to my surprise no other reaction took place even on heating. It appears that chlorine and chlorine dioxide do not oxidize 1,4-butanediol at all. Heating simply expels and decomposes the gas.

Next I tried TCCA as per De Luca et al J.Org.Chem. 2003 pp4999-5001. This reaction uses a vast excess of TCCA in the presence of a bromide salt and catalystic amounts of TEMPO to oxidize aliphatic alcohols to acids. Unfortunately when I tried to carry out this reaction following the published procedure I ran into problems that serious question the authenticity of the origin preparation. For a start the procedure calls for 15ml of 15% sodium bicarbonate solution mixed with the substrate (5 mmol) in 50ml of acetone cooled to 0 C. The problem is that at 0 C a saturated solution of NaHCO3 is about 7% and a saturated solution of 60 C is about 15% but stars to loose CO2. Never mind I though, given that my substrate is water soluble and being a diol I only need 2.5mmol I replaced the bulk of the acetone with water. I added a little acetone about, 4-5ml, with the TEMPO and potassium bromide really to help dissolve the former. during the addition of the first 2/5 of the TCCA powder a copious precipitate of isocyanuric acid formed. This made the slurry difficult to stir so at this point I filtered the solution and continued the addition of the TCCA to the filtrate. Strangely no further precipitate formed so the reaction mixture is being left stirring over night. The reaction is not particularly exothermic and it is easy to manage the rise in temperature, foaming in the early stages is a bigger problems.

I'll let you know how I get on with the work up tomorrow.
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[*] posted on 15-5-2018 at 19:12


Butanediol should be convertible to succinic acid with nitric acid. Please see my conversion of propanediol to malonic acid in Prepublication.



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[*] posted on 16-5-2018 at 05:03


@Magpie, yes I have seen your malonic acid post and good work it is too. But if you read the thread above you will seen that I am trying to find a route that avoids the now difficult to obtain nitric acid. In the US you can probably still by conc nitric acid but in the UK the nanny state has decided that we are not to be trusted with it, after all we might hurt ourselves and that would never do!

There are many other methods of oxidizing alcohols to acids, some are very substrate specific but many are claimed to be general. As I am finding out many of the leave much to be desired or need much substrate specific customisation.

According to the Luca paper when the reaction is over the excess TCCA is "simply" neutralised with solid sodium metabisulphite. Mmmmm this is proving to be messy with clouds of chlorine evolved for some mysterious reason. I can only assume that the bisulphite is oxidised to bisulphate and that this is acidic enough to cause the TCCA to react with chloride ions to generate chlorine before the excess bisulphite can reduce it. If I try to add the bisulphite faster the mixture foams badly.

By the way, if I want succinic acid I can buy it on-line as permitted food additive and it is cheap c £40/kg including tax and delivery
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[*] posted on 21-5-2018 at 14:08


Well, I worked up the reaction product; lots of cyanuric acid filtered off. Then I evaporated the filtrate slowly to dryness with stirring, dried the granular mass of salt and then extracted it with hot isopropanol. Most of the isopropanol was distilled off and the remainder allowed to evaporate in a small bowl. The very small amount of residue contained little organic material and was mostly inorganic salts (as determined by heating on a spatula).

So butanediol + TCCA = failure.

Looks like I am going to have to buy my succinic acid

During the evaporation of the water from the salt rich residue there was a strong pungent cheesy small remeniscient of butyric acid. Could this be 4-hydroxybutyric acid? What does butyrolactone smell like?
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