Sciencemadness Discussion Board - Hunsdiecker Reaction with Amino Acids Literature/Insight

Hunsdiecker Reaction with Amino Acids Literature/Insight

Mothman - 30-5-2018 at 12:33

The hunsdiecker-borodin-etc. reaction involves a silver salt of a carboxylic acid reacting with bromine in carbon tetrachloride to yield a bromide group in place of the carboxyl group. Personally I want to know if it would work on amino acids.

I've been searching for almost a week now for literature that discusses the Hunsdiecker-borodin reaction when applied to amino acids, of course I'm not the most well versed in organic chemistry so perhaps there's a very simple reason no one has tried such a reaction yet (or they have tried this reaction and I am just a bad researcher, just as likely as I don't know everywhere to look), but in case it hasn't been tried yet and there's no particular reason it has not been explored, I'm already in the process of preparing some silver carbonate from an old dime I found on the ground. It's sad to see something older than I am dissolving in acid but if it means a small amount of knowledge can be gathered it is definitely worth the maybe 15 cents that the dime would be worth had I sold it online.

Anyways, literature and insights are much welcomed, if I'm asking a really stupid question (likely) please educate me, new knowledge is good knowledge unless it's not good knowledge but there's probably a bright side to all knowledge.

-Mothman

Metacelsus - 30-5-2018 at 13:19

I also cannot find any examples (and I searched the entire Reaxys database). Alpha-amino acids are probably unsuitable for this. However, it is compatible with their amides, see: https://doi.org/10.1016/S0040-4020(01)86836-8

Mothman - 30-5-2018 at 15:09

Thank you for your response! I cannot view more than the abstract of the article but the abstract alone is rather interesting assuming I interpreted it correctly. Obviously now I have more questions if you (or others) be willing to entertain them

First of all, why would a Hunsdiecker not likely work on an alpha-amino acid alone? Is it because the amine would react with the halogen on the same carbon if the amine were unprotected? I don't know why this would happen but I know I've never seen a compound with such an arrangement, just compounds with the halogen attached to the nitrogen, does this result because the nitrogen acts as a base to the halogen or is there something different going on? I don't know the terminology for describing such a reaction, if you cannot tell I'm not learning OChem in too systematic of a manner, just looking at compounds and reactions and finding patterns.

Regarding my interpretation of the abstract, I read it as "The procedure removed a carboxyl group adjacent to an acyl amide indicating that protecting groups are necessary on the amine before the carboxyl group can be degraded via the Hunsdiecker reaction without changing the expected location of the halogen on the molecule" Is this correct or am I missing something here? If my interpretation is correct, for amino acids like ornithine, would it be necessary to acylate both amines in the conditions of the hunsdiecker to prevent weirdery (this is as scientific as I can describe it right now) on the non-alpha amine?

Again, thank you for your time
-Mothman

Corrosive Joeseph - 30-5-2018 at 15:27

Quote: Originally posted by Mothman

I cannot view more than the abstract of the article but the abstract alone is rather interesting assuming I interpreted it correctly. Obviously now I have more questions if you (or others) be willing to entertain them

Here is your paper.........

/CJ

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