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

Hydrogenation of Alkynes Hydrogenation of Alkynes alkene is an intermediate Heats of Hydrogenation Partial Hydrogenation 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. 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 Metal-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 1 Suggest efficient syntheses of (E)- and (Z)-2-heptene from propyne and any necessary organic or inorganic reagents. Problem 1 Strategy Problem 1 Synthesis RCH2CH2R cat catalyst = Pt, Pd, Ni, or Rh RC CR + 2H2 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 cat H2 RC CR cat H2 RCH CHR RCH2CH2R cat H2 RC CR cat H2 RCH CHR + H2 Lindlar Pd CH3(CH2)3 (CH2)3CH3 H H (87%) CH3(CH2)3C C(CH2)3CH3 C C RCH2CH2R RC CR RCH CHR CH3CH2 CH2CH3 H H (82%) CH3CH2C CCH2CH3 C C Na,