Organic Chemistry Fourth Edition：有机化学第四版精选.pptVIP

18 19 19 Hydrogenation of Alkynes RCH2CH2R cat catalyst = Pt, Pd, Ni, or Rh alkene is an intermediate RC CR + 2H2 Hydrogenation of Alkynes Heats of Hydrogenation 292 kJ/mol 275 kJ/mol Alkyl groups stabilize triple bonds in the same way that they stabilize doublebonds. Internal triple bonds are more stable than terminal ones. CH3CH2C CH CH3C CCH3 RCH2CH2R Alkynes 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. cat H2 RC CR cat H2 RCH CHR Partial Hydrogenation 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. RCH2CH2R cat H2 RC CR cat H2 RCH CHR Lindlar Palladium + H2 Lindlar Pd CH3(CH2)3 (CH2)3CH3 H H (87%) CH3(CH2)3C C(CH2)3CH3 C C Example Alkynes ? trans-Alkenes Metal-Ammonia Reductionof Alkynes RCH2CH2R Another way to convert alkynes to alkenes isby reduction with sodium (or lithium or potassium)in ammonia. trans-Alkenes are formed. RC CR RCH CHR Partial Reduction CH3CH2 CH2CH3 H H (82%) CH3CH2C CCH2CH3 C C Na, NH3 Example four steps (1) electron transfer (2) proton transfer (3) electron transfer (4) proton transfer Metal (Li, Na, K) is reducing agent; H2 is not involved Mechanism Step (1): Transfer of an electron from the metalto the alkyne to give an anion radical. M . + R R C C R R C .. . – C M+ Mechanism Step (2) Transfer of a proton from the solvent (liquid ammonia) to the anion radical. H NH2 .. R R C .. . – C . R R C C H NH2 .. – : Mechanism Step (3): Transfer of an electron from the metalto the alkenyl radical to give a carbanion. M . + . R R C C H M+ R R C C H .. – Mechanism Step (4) Transfer of a proton from the solvent(liquid ammonia) to the carba