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LearnedAmateur
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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]
In chemistry, sometimes the solution is the problem.
It’s been a while, but I’m not dead! Updated 7/1/2020. Shout out to Aga, we got along well.
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Boffis
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@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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AvBaeyer
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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 540 times
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LearnedAmateur
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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.
In chemistry, sometimes the solution is the problem.
It’s been a while, but I’m not dead! Updated 7/1/2020. Shout out to Aga, we got along well.
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Boffis
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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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Boffis
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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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Boffis
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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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Magpie
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Butanediol should be convertible to succinic acid with nitric acid. Please see my conversion of propanediol to malonic acid in Prepublication.
The single most important condition for a successful synthesis is good mixing - Nicodem
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Boffis
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@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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Boffis
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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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steadyhand
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I believe all the consternation regarding MSG+HCl->glutamic acid is due to the high concentrations.
My first run was done using similar proportions as chemplayer and Magpie. Mud, crud, and generally a big mess. This was done at about 3.75M. I
reasoned that the problem was due to the rapid crash upon adding HCL, probably precipitating both glutamic acid and its HCL salt leaving a bunch of
MSG in solution.
I tried again closer to 0.9M, and this is a totally different experience! 150g MSG in 800mL boiling water (0.889 moles). 0.893 moles HCl in 200mL H20
(85mL 10.5M HCL diluted to 200mL). I let it cool very slowly, eventually into the fridge and was afforded very nice xtals. Yields on 6 runs:
68,70,71,71,73,76%. Total 538g Glutamic acid from 1.128kg MSG (includes crappy mud yield run) I didn't bother to purify any further.
From solubility of Glutamic acid: 140g/L (100C) down to 3.4g/L (0C), I expected 96% max, leaving some behind. But I don't trust solubility numbers for
pure substances anyway. Probably could have boiled it down for more crops. Perhaps making sure the pH is correct for Glutamic acid, with Na-Cl
equimolar. But given that MSG is $3.50/kg from the local Asian market and only $1 worth of HCl is needed, I'd say this is a fine yield.
Also, I used 10% Ammonium hydroxide to make Ammonium glutamate and later on Ammonium succinate. Why all the trouble to use Ammonium carbonate? I used
Kleanstrip denatured alcohol (60:40 EtOH:MeOH) to recrystallize the Succinimide just fine. Total yield of Succinimide was 300g from 1.125kg MSG,
about 50%. Total cost was <$10. The experience, priceless.
Bromination to NBS wasn't pretty. I have ideas though for the second batch.
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TinyPlanets
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I had success preparing succinic acid and succinic anhydride in the past from MSG.
The MSG reacts with an equimolar amount of hypochlorite to form the monochloroglutamate which then decomposes spontaneously to succinic semialdehyde
(if I recall correctly)
The aldehyde can then be oxidised to succinic acid. This preparation was a pain because the chloro amino acid is very unstable and you can quickly
end up with a soup of side products if you're not careful to keep things freezing cold when forming the monochloro product. It needs to be decomposed
and processed very fast with rapid heating after that.
Sorry I don't have my lab notes.
I think the yeild was pretty bad but I did get some of my desired product which I purified by dehydration and sublimation.
[Edited on 31-5-2022 by TinyPlanets]
[Edited on 31-5-2022 by TinyPlanets]
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Triflic Acid
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Just read over this, and would like to issue a warning to all SM members. DO NOT BUY Pd/C FROM CHEMCENTER. I noticed I'm not the only one to notice
this. I paid $56 for a 10g bottle and got a bunch of powdered charcoal. If you need Pd/C, buy palladium bullion and make it yourself. You'll get a lot
more Pd/C for the same cost of raw palladium, and bullion is both guaranteed pure and easily buyable.
There wasn't a fire, we just had an uncontrolled rapid oxidation event at the power plant.
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Mateo_swe
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I have also bought some dirt cheap Pd/C from China some time ago, i havent even opened the jar yet but i suspect its all bad.
I will try test it, but im not expecting it to be good.
If one want Pd/C, buying some Pd metal is the way to go and preferably a bullion as these usually are the real deal if buying from a known company
trading in such metals.
Making the Pd/C i hear is not especially hard to do.
I also bought a supposedly platinum coated anode from a chinese seller on ebay and its not platinum coated even it says so.
I tried put some H2O2 on it and it doesnt form any bubbles, a test one can make to verify that its precious metals.
Same thing with this one, if it sounds to good to be true, it is not true.
So buy the platinum bullion and make it yourself and you are sure to get what you want.
Or maybe, if the seller is very known to sell the real deal and have a long record of happy customers one can risk a purchase.
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