columbia大学有机化学课件 （三十七）.pptVIP

9.8Reactions of Alkynes Reactions of Alkynes Acidity (Section 9.5) Hydrogenation (Section 9.9) Metal-Ammonia Reduction (Section 9.10) Addition of Hydrogen Halides (Section 9.11) Hydration (Section 9.12) Addition of Halogens (Section 9.13) Ozonolysis (Section 9.14) 9.9Hydrogenation of Alkynes Hydrogenation of Alkynes alkene is an intermediate Heats of Hydrogenation Partial Hydrogenation Alkenes could be used to prepare alkenes if acatalyst were available that is active enough to catalyze the hydrogenation of alkynes, but notactive enough for the hydrogenation of alkenes. Lindlar Palladium There is a catalyst that will catalyze the hydrogenationof alkynes to alkenes, but not that of alkenes to alkanes. It is called the Lindlar catalyst and consists ofpalladium supported on CaCO3, which has been poisoned with lead acetate and quinoline. syn-Hydrogenation occurs; cis alkenes are formed. Example 9.10Metal-Ammonia Reductionof Alkynes Alkynes ? trans-Alkenes Partial Reduction Another way to convert alkynes to alkenes isby reduction with sodium (or lithium or potassium)in ammonia. trans-Alkenes are formed. Example Mechanism four steps (1) electron transfer (2) proton transfer (3) electron transfer (4) proton transfer Mechanism Step (1): Transfer of an electron from the metalto the alkyne to give an anion radical. Mechanism Step (2) Transfer of a proton from the solvent (liquid ammonia) to the anion radical. Mechanism Step (3): Transfer of an electron from the metalto the alkenyl radical to give a carbanion. Mechanism Step (4) Transfer of a proton from the solvent(liquid ammonia) to the carbanion . Problem 9.12 Suggest efficient syntheses of (E)- and (Z)-2-heptene from propyne and any necessary organic or inorganic reagents. Problem 9.12 Strategy Problem 9.12Synthesis 9.11Addition of Hydrogen Halidesto Alkynes Follows Markovnikovs Rule Alkynes are slightly less reactive than alkenes Termolecular Rate-Determining Step Two Molar Equivalents of Hyd