Easily acquired synth for malonic acid

[jimmyboy]

My post stems from the fact that chloroacetic acid and sodium cyanide are not particularly easy to make or
friendly - i would like to find another way to synth that would use precursors that are easier to acquire even if the yields arent particularly great.

If anyone could help i would appreciate it - ive been poring over organic chemisty books for a good while now - the only detailed reference I've found is from vogel and i dont relish the thought of toying with sodium cyanide and chloroacetic acid - i found some more useful hints here -

http://4.1911encyclopedia.org/M/MA/MALONIC_ACID.htm

and here

http://77.1911encyclopedia.org/M/MA/MALIC_ACID.htm

It still doesnt give enough details -- i have some permanganate and sulfuric around -- i wonder if they could perform the same oxidation or if they would spoil malic acid(easy to acquire) - or maybe i could oxidize with a copper catalyst - would love any ideas/leads - thanks

[jimmyboy]

found an interesting patent here -- might try it out

http://l2.espacenet.com/espacenet/viewer?PN=CN1410409&CY=gb&LG=en&DB=EPD

anyone have a good test for determination of malonic acid?

[stratosphere]

what about sodium succinate with strong base (eg. sodium tert-butoxide, or calcium carbide) for alpha dehydrogenation?

if that wouldn't work a synth for an alpha-halo succinic acid or ester followed by a treatment with strongbase probobly would.

[jimmyboy]

hmm would that work? i looked again at my patent and found that calcium cyanoacetate is pretty hard to get hold of as well (i couldnt even find a MSDS for it) - so no go there - will keep searching

[stratosphere]

wait, i was getting confused with malic acid.

you might find this link helpful

http://4.1911encyclopedia.org/M/MA/MALONIC_ACID.htm

it mentiones it can be extracted from the sugar beat, id also do some research into some other bio-sources and bio-synthesis, as it seems to be present in alot of plants.

also malic acid can be purchased otc as a vitamin, the link above mentions that it can oxidized to malonic acid, im not sure if it is best done chemically or biologically (for instance with yeast or something)

[Rhodium]

if there is a way to make 2-halo-succinic acid

Yup, it's called the

Hell-Volhard-Zelinsky reaction

(http://themerckindex.cambridgesoft.com/TheMerckIndex/NameReactions/ONR180.htm)

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000477537-file_3j5o.gif" title="View this image">

[jimmyboy]

Yes -- oxidation of malic acid was my first idea -- the page

http://77.1911encyclopedia.org/M/MA/MALIC_ACID.htm

says that potassium bichromate can be used but i cant find a reference for this reaction anywhere - temperatures/amounts - I have even found some books saying contrary things about oxidation of malic acid -- was wondering if permanganate/sulfuric could be used instead of the chromate ion -- anyone know how determine an organic acid besides spectro or mass calc? I'm pretty sure malonic is much more acidic than malic.

How does a halogenation reaction fit into this Rhodium? please explain.

[Rhodium]

I just answered the question in

Post 478005

(stratosphere: "what about sodium succinate with strong base...", Chemistry Discourse)

[stratosphere]

my thought on 2-halo-succinic was in regards to malic so isn't entirly relevant here.
but for the case of 2-halo-succinic acid is the Hell-Volhard-Zelinsky going to give you any 2,3-dihalo-succinic, or is the 2-halo suffeciently deactivating to keep the 3 halogenation from occuring?