Exchange reactions carbonyls

Zn/EtOAc or THF, reflux, 3-12 h, 40-100% yield. It is more efficient to prepare this ketal by an exchange reaction with the dimethyl or diethyl ketal than directly from the carbonyl compound. Hydrolysis can eilso be effected by acid catalysis. 

The hydration reaction has been extensively studied because it is the mechanistic prototype for many reactions at carbonyl centers that involve more complex molecules. For acetaldehyde, the half-life of the exchange reaction is on the order of one minute under neutral conditions but is considerably faster in acidic or basic media. The second-order rate constant for acid-catalyzed hydration of acetaldehyde is on the order of 500 M s . Acid catalysis involves either protonation or hydrogen bonding at the carbonyl oxygen. 

Trends in reactivity for ligand-exchange reactions of octahedral metal carbonyls. G. R. Dobson, Acc. Chem. Res., 1976, 9, 300-306 (48). 

Pyridones can also be converted to 2-chloropyridines by exchanging the carbonyl functionality using phosphoroxychloride (POCI3) [72]. A combination of N-halosuccinimides and triphenylphosphine has also been applied to introduce halogens in this position [73]. The carbonyl functionality in 2-pyridones makes these systems reactive towards nucleophiles as well, which add in 1,4-reactions with displacement of halides [74]. The use of transition metal mediated couplings like Heck, and Suzuki have also been successfully applied on halogenated 2-pyridones (d. Scheme 10) [36,75]. 

Trinuclear carbonyls have been studied with the anticipation that the retention would prove to be in some way inversely related to the molecular complexity. The values obtained were surprisingly high, despite careful chemical purification, as is shown in Table 10. It was suggested that the reformation mechanism must involve exchange reactions during and after the hot zone, starting with M(CO)4, as building blocks . 

Fraction F3 catalyzes an isotope exchange reaction between CO and the carbonyl group of acetyl-CoA. ... 

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