On Ketone Halogenation
General Reaction Scheme for Ketone Halogenation:
Ketone Halogenation is a process by which the α-carbon (the carbon adjacent to the carbonyl group) is deprotonated under basic conditions. The subsequent carbanion that forms then undergoes a nucleophilic attack on a halogen atom. This reaction is possible due to the lowered pKa (~26) of the hydrogen atoms bonded to the α-carbon. This drastically lowered pKa is the result of the resonance forms possible when the carbanionic species is formed in this reaction. The carbanion can form a highly resonance stabilized enolate form where the oxygen atom carries the negative charge. This resonance stabilized species can then attack a neutral halogen atom, forming a halogenated ketone product. Subsequent halogenation reactions do not normally occur because the halogen atom which bonds to the α-carbon influences the resonance structures of the compound, and greatly decreases the basicity of the hydrogen atoms bonded to the α-carbon atom.
The only man he ever feared...
Luca Brasi, whose packing some serious heat at this very moment, puts a seemingly unsolvable chemistry problem to bed with a single glance.
Fun Fact: In the Godfather, Luca Brasi's death is probably the worst scene in the entire movie. I mean... this is the guy who tied a man down and cut off his arms and legs with an axe. This man threw an infant into a burning furnace. Seriously! Read the book! But he is killed by a knife through the hand and a Garotte wire? I don't buy that for a minute. Poisoned by Don Brian Coppola's chemistry? Now that would be a believable death!
Information for this section derived from:
O’Malley, D.P.; Li, K.; Maue, M.; Zografos, A.L.; Baran, P.S. J. Am. Chem. Soc. 2007, 129, 4762-4775.
Ege, S. Organic Chemistry: Structure and Reactivity, 5th Ed. Boston: Houghton Mifflin, 2004; pp. 693-694.
"AHHHHHHHHHHHH..." (That's a direct quote, by the way.)
Fun Fact: Sonny Corleone, pictured here in the throes of his final seconds, is clearly upset. But, what most people don't know is that he wasn't particularly upset about the hundreds of bullets riddling his body, courtesy of a few dozen Thomson submachine guns. Actually, the expression and gesturing seen above was meant to depict the message: "Oh, shoot! I forgot to tare my flask before doing Rotovap!"
