Sciencemadness Discussion Board

Hunsdieker reaction for the amateur chemist

Assured Fish - 25-6-2016 at 20:18

I know there are already a couple threads that partly talk about the hunsdieker reaction on the forum already but non of them really yeilded much behond the hunsdieker reaction being water sensitive and potentially using other salts such as lithium or acetate. But this reaction is still not easily attempt able by the amateur chemist due to the use of carbon tetrachloride or bromide which along with it being toxic to the cetral nervious system it also has potential to cause some rather unwanted long term health effect to do with the liver, carbon tetrachloride is also rather difficult to buy or get your hands on unless someone knows of a good way to synthesize it.

Ideally I would like to find a way to carry out this reaction on aromatic carboxylic acids suck as benzoic acid or salicylic acid or other substituted aromatics without the need to use potentially hazardous solvents. I have found a paper recently, however i don't think i have access to it in full but it describes using several different catalysts namely lithium acetate, triethylamine and tetrabutyl ammonium trifluoroacetate and a halogenating agent N-halosuccinimide in various solvents such as dichloromethane and acetonitrile to successfully decarboxylate alpha and beta unsaturated carboxylic acids. I was wondering if this could alternatively be used to do the same with aromatics such as salicylic acid and benzoic acid and if so identify specifically what role the catalyst plays in the mechanism of this reaction?

https://www.thevespiary.org/rhodium/Rhodium/Vespiary/talk/fi...

http://www.sciencedirect.com/science/article/pii/S0040402099...

careysub - 25-6-2016 at 20:38

Quote: Originally posted by Assured Fish  
... carbon tetrachloride is also rather difficult to buy or get your hands on unless someone knows of a good way to synthesize it....


http://www.sciencemadness.org/talk/viewthread.php?tid=14927

Assured Fish - 26-6-2016 at 00:01

Well shit :mad: why did i not try searching for that in the first place. Well at least i suppose people can still use this thread to discuss the hunsdieker reaction in detail or whatever, but just for the sake of curiosity i still wonder if the catalytic hunsdieker would still work on aromatics for people who do not either have a good set up for dealing with CCl4 or dont want to take the risk.