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Author: Subject: 1,3 Acetonedicarboxylic Acid
Aikimike
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[*] posted on 16-8-2008 at 05:53
1,3 Acetonedicarboxylic Acid


Hello all,

I have some Glutamic Acid and find myself in need of 1,3 Acetonedicarboxylic Acid. All I need to do is to remove the amino group, add a Hydroxy group and then oxidise the Hydroxy to a Carbonyl.

Sounds easy but as Im just starting advanced chem, I really am not too sure as to how I can go about doing this. If anyone can offer any advice as to how this may be acomplished it would be very much appreciated.
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[*] posted on 16-8-2008 at 06:14


You are going the wrong way round the block and probably, will get lost.

Rather than trying to find a bew way to make acetonedicarboxylic acid, why not take the path of least resistance?

Buy ANHYDROUS citric acid. OUTSIDE or in a good fume hood, treat this with 20% oleum (fuming sulfuric acid.) All the details are available online in Org.Syn.

This reaction gives off lots of carbon monoxide, which is why you should only do it outside or in a good hood. Otherwise = death.

You work up the acetonedicarboxylic acid as its diethyl ester and recrystallize that from ethyl acetate to purify. The free acid is not very stable. Better to store it as the diester unless you want to use it right away.




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Aikimike
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[*] posted on 16-8-2008 at 06:20


As much as the Oleum route is a much easier way to go, I had a distinct desire to avoid using Oleum (horribly toxic, fumes SO3 etc. etc.) So was wondering whether this method would be feasible.

Also I believe that there was a refernce posted on here about the use of Hot Sulphuric Acid (not fuming) which I tried- this however proved less than fruitful because there was no easy way in which to filter the product from the Sulphuric Acid as H2SO4+ filter paper= no more filter paper.

If there is any way in which the previously stated synthesis could work, advice would be much appreciated.

Thank you very much Sauron for your swift response!
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[*] posted on 16-8-2008 at 06:32


Try using a fritted glass filter funnel or buying glass microfiber filters instead of using cellulose paper.
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[*] posted on 16-8-2008 at 07:16


I thought something wasn't right:
Check glutamic acid:


Now check acetonedicarboxylic acid:



The NH2 is not in the correct position, you'd be making alpha ketoglutaric acid, a well-known biochemical metabolic product in the citric acid cycle:





[Edited on 16-8-2008 by chemoleo]




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[*] posted on 16-8-2008 at 07:26


It is possible to get acetonedicarboxylic acid from anhydrous citric acid and conc H2SO4 rather than oleum, but the yields are poor and you still have all that CO to deal with. It is the CO effluent and not the SO3 (which is only within the reaction flask) that you have to worry about.



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Aikimike
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[*] posted on 16-8-2008 at 07:48


Hmm, I see:

If I were to conduct a mild oxidation of glycerol with Hydrogen Peroxide and A ferrous salt as catalyst (Idea from Wiki: http://en.wikipedia.org/wiki/Dihydroxyacetone) to make Dihydroxyacetone and glyceraldehyde firstly how could I separate the products and secondly, would it be reasonable to assume that carboxylation would take place with formic acid? Or perhaps chlorination with Thionyl chloride and then treatment with formic acid to yield the desired product?

Thanks for your time.
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[*] posted on 16-8-2008 at 09:42


Procedures with DHA and glyceraldehyde look fine on paper but are usually a nightmare in reality.

Citric acid is cheap. So is conc H2SO4. So, to hell with the low yield, go this route and accumulate as much ADCA as you need. Remember, it won't keep except as the diester, or the anhydride (if you have acetic anhydride around.)

Otherwise acetonedicarboxylic acid just turns into acetone and CO2.




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[*] posted on 18-8-2008 at 01:30


Quote:
Originally posted by Aikimike
Hmm, I see:

If I were to conduct a mild oxidation of glycerol with Hydrogen Peroxide and A ferrous salt as catalyst (Idea from Wiki: http://en.wikipedia.org/wiki/Dihydroxyacetone) to make Dihydroxyacetone and glyceraldehyde firstly how could I separate the products and secondly, would it be reasonable to assume that carboxylation would take place with formic acid? Or perhaps chlorination with Thionyl chloride and then treatment with formic acid to yield the desired product?

Thanks for your time.

It appears to me you lack some basic knowledge of organic chemistry. Try reading some books on basic organic chemistry and then some describing the reaction mechanisms. I know this can take years, but trust me, it will help you a lot to know the theory when doing experiments. The worst thing when working in the lab is not so much the poor practical skills, but not knowing what is going on in the reaction flask. This lack of knowledge can kill when doing experiments on larger scale. Once you have the basic knowledge you can start with experiments on a 10 mmol scale and if everything goes well increase the reaction scale.

Poor man's oleum can be made by mixing sodium pyrosulfate with conc. sulfuric acid and decanting from the resulting Na2SO4. There is at least one patent describing the process (and probably something on this forum as well).

Sodium pyrosulfate (Na2S2O7) can be prepared by heating the NaHSO4 monohydrate melt (can be bought in just about any larger supermarket) till correct weight drop (-1.5 H2O). You can do this on a hot plate in a stainless steel vessel (which will corrode a bit tainting the product green, but not much). Alternatively, you can thermolyse sodium persulfate like Garage_chemist did: http://www.sciencemadness.org/member_publications/SO3_and_ol...

Citric acid monohydrate can be bought in the supermarkets or pharmacies. The process for its dehydration is relatively easy and is quite probably also described somewhere on this forum.




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[*] posted on 18-8-2008 at 03:41


I have had a look at some of your previous posts and I would ask how many previous organic chemistry experiments have you performed on your own?
While I would not wish to discourage you in any way, I would question if an experiment that involves oleum and produces carbon monoxide as a byproduct is one to include in your first 50 or even 100 experiments if you are doing them on your own without a more experienced 'mentor' to keep an eye on things.
Experimental chemistry is as much an art as a science and even very experienced chemists have 'leg it' moments :(
If you have not already made some benzamide, iodoform, methyl salicylate etc may I suggest you try those first.
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[*] posted on 18-8-2008 at 09:44


I don't think the synthesis of acetonedicarboxylic acid is impossible for beginners. I think he should try it out, but with all due precautions and on a small scale (doing a 10mmol reaction outside represents no danger from CO poisoning). Even though it is quite likely he would fail without having some experience with simpler preparations, I think one can learn just as much from failures as from successes.

Yet Aikimike, I would rather encourage you into understanding theory where you are weakest before even venturing into such involved experiments. Meanwhile you can do some simpler organic preparations to get some practical skills.

Edit: Thread moved to Organic chemistry section.

[Edited on 18/8/2008 by Nicodem]




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[*] posted on 18-8-2008 at 12:06


Have a look at the OrgSyn procedure. For an idea on low yields with just conc. H2SO4, see this thread by Axt. Some physical and reaction data from Beilstein I 763: easily soluble in water, alcohol, more difficultly soluble in acetic ether, even more difficultly soluble in ether, insoluble in CHCl3, ligroin, and benzene. Melts at 135 deg., forming CO2 and acetone; these two also result by boiling with water, or warming with acids or alkalis. Its salts even decompose in the cold to eventually form acetone and carbonates. Gives violet color with iron chloride, conc. KOH solution splits it into acetic and malonic acids. Letting it stand with H2SO4 forms citracumalic acid C10H8O8.
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[*] posted on 18-8-2008 at 12:42


Trading off the hazard and expense of oleum for low yield is a good idea for a novice. There remains the CO hazard, best dealt with IMO by doing this outdoors.

Once acid is obtained it has to be thoroughly freed from H2SO4 and preferably esterified for storage. The free acid will not keep unless rigorously, scrupulously acid free by repeated recrystallizations from if I recall, EtOAc.

Also, go to the trouble of obtaining as many of the old preps referenced from Org.Syn. as possible. In several cases, the procedures were simpler than in Org Syn and better yield. A careful comparison of about half a dozen procedures will arm you with the tools you need to get this right first time.

Also do yourself a BIG favor and buy anhydrous citric acid rather than the hydrated USP or BP acid.

[Edited on 19-8-2008 by Sauron]




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[*] posted on 18-8-2008 at 15:04


I would point out that Aikimike is quite young so encouraging him to make his own oleum and recrystallise from flammable solvents may not be the best idea.
By my reckoning he will have taken his GCSE science exams this summer.
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[*] posted on 19-8-2008 at 00:24


Science Squirrel- My age really should not be a factor here. yes I have just taken my GCSE exams- but what relevance is that? I have a real passion for chemistry, all I want to do is learn. I have a safe well equipped lab in which I practice Organic Chemistry in preperation for A level and beyond.

I do have Oleum, a litre of it in fact. Its not dangerous unless it is mis-used. The same is true for solvents.
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[*] posted on 19-8-2008 at 02:49


Like it or lump it society feels that as people get older they gain more responsibility for their actions.
Some people will not agree with me but I think that there is a difference between encouraging an eighteen year old to do an experiment and encouraging a sixteen year old to do an experiment.
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[*] posted on 19-8-2008 at 03:09


I do hear where you are coming from, but surely it should depend upon the actions and the intent of person, as well as there relative maturity. I know of many 16 year olds who are markedly more intelligent than 18 year olds, as well as being more responsible and frankly more competent in a lab.

I disagree however that that belief is prominent throughout all of society, many of my teachers for example recognise my passion and treat me as an equal, something which I do respect. In much the same was as I respect Sauron for his chemical experience, I respect him for his non-bias against me because of my age.

Apologies for the OT- I shall try again with hot, conc H2SO4 and Anhydrous Citric Acid and report back.
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[*] posted on 19-8-2008 at 04:11


I don't really want to disgress more than already done, but I hardly think Oleum is the kind of product that is only dangerous when misued. Not at all like solvents.

Most solvents can be used without excessive safety precautions, basic common sense and there isn't much to be afraid off.

Oleum is another kind of beast. A single drop will eat through alot, even your skin. Not really the kind of liquid you transfer from flask to flask on a bench. Even chemist with over 10-15 yeasr training take alot of precautions when handling such corrosive, they are dangerous even when correctly used.
There is much to be planned before, and only lengthy experience can help you be prepared to what will happen when you handle such a reagent.

I mean, the bottle surely weighs over 2kg, how do you plan on transfering a small amount? Can you imagine what would happen if at that precise moment you get a cramp? How are you going to take care of that little drop slwoly running down the beaker/flask while you have on hand full of heavy, fuming liquid you shouldn't take your eyes off? Etc etc

I'm not implying your are not capable off facing such manipualtions strickly becasue of your age, but because for such reagents to be handled safely, one needs in-depth training and especially experience, that I doubt you could have after passing a GCSE. Relative maturity is certainly not the sole requirement for handling dangerous reagents.

There are much, much things to do with safer reagents, that can be very interesting and challenging. If you like chemistry as much, which is a very good thing, think of your futur, and act safely. You would loose all of it if you burn your hand off, or turn blind.

This is just an advice. I remember how I was at your age, and in retroscpetive, I'm glad I couldn't acces Oleum and such, as I would surely have felt confident enough to use it, and not humble enough to let it sit for a few years before even thinking of using it.

I know this is disgressing from the origianal topic, but I strongly feel that we can't just let it a 16 year old say he will use some oleum at home without warning him of the consequences and disencouraging him to do it, for his own sake. You might thank us some day.




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