columbia大学有机化学课件 （二十四）.pptVIP

Chapter 6Reactions of Alkenes:Addition Reactions Reactions of Alkenes The characteristic reaction of alkenes is addition to the double bond. 6.1Hydrogenation of Alkenes Hydrogenation of Ethylene exothermic DH° = –136 kJ/mol catalyzed by finely divided Pt, Pd, Rh, Ni Example Problem 6.1 What three alkenes yield 2-methylbutane on catalytic hydrogenation? Problem 6.1 What three alkenes yield 2-methylbutane on catalytic hydrogenation? Mechanism of Catalytic Hydrogenation: Figure 6.1 Mechanism of Catalytic Hydrogenation: Figure 6.1 Mechanism of Catalytic Hydrogenation: Figure 6.1 Mechanism of Catalytic Hydrogenation: Figure 6.1 Mechanism of Catalytic Hydrogenation: Figure 6.1 Mechanism of Catalytic Hydrogenation: Figure 6.1 6.2Heats of Hydrogenation can be used to measure relative stability of isomeric alkenes correlation with structure is same as when heats of combustion are measured Heats of Hydrogenation of Isomers Heats of Hydrogenation (kJ/mol) Ethylene 136 Monosubstituted 125-126 cis-Disubstituted 117-119 trans-Disubstituted 114-115 Terminally disubstituted 116-117 Trisubstituted 112 Tetrasubstituted 110 Problem 6.2 Problem 6.2 6.3Stereochemistry of Alkene Hydrogenation Two spatial (stereochemical) aspects ofalkene hydrogenation: syn addition of both H atoms to double bond hydrogenation is stereoselective, corresponding to addition to less crowded face of double bond syn-Additon versus anti-Addition Example of Syn Addition Stereoselectivity A reaction in which a single starting materialcan give two or more stereoisomeric productsbut yields one of them in greater amounts thanthe other (or even to the exclusion of the other)is said to be stereoselective. Example of Stereoselective Reaction Example of Stereoselective Reaction Example of Stereoselective Reaction Example of Stereoselective Reaction 5 6 6 8 9 9 9 9 9 13 14 15 16 16 17 + A—B C C A C C B + H—H s p s s C C H C C H H H H H H H H H H2, Pt (73%) CH2 H3C H3C CH3 H H3C H3C H