生物化学 Chapter6 Reactions Of Alkenes Addition Reactions.ppt

Chapter 6 Reactions Of Alkenes: Addition Reactions Exercises: 5.1-----5.14 5.19---5.24 5.15------5.18 5.25 5.28 5.29 5.32 5.35 Exercises 6.1------6.5 6.7-----6.10 6.22----6.28 6.11-----6.21 6.29-----6.37 Addition Reaction 两个或两个以上分子彼此结合生成单一分子的反应，称为加成反应。 能发生加成反应的底物最常见的是具有重键（双键和叁键）或含有小环的化合物 §6.1 Hydrogenation of Alkenes Hydrogenation is the addition of H2 to a multiple bond. The mechanistic representation of heterogeneous catalysis in the hydrogenation of alkenes: 氢化反应特点∶ Syn addition: 顺式加成产物为主 定量反应: 反应可逆: 加氢/脱氢 Examples: Alkenes can be reduced to alkanes with H2 in the presence of metal catalysts such as Pt, Pd, Ni or Rh. The two new C-H s bonds are formed simultaneously from H atoms absorbed into the metal surface. The reaction is stereospecific giving only the syn addition product. The overall reactions is exothermic. This reaction forms the basis of experimental heats of hydrogenation which can be used to establish the stability of isomeric alkenes. Heat of hydrogenation is positive quantity equal to - ?H°for the reaction. §6.2 Heats of Hydrogenation can be used to measure relative stability of isomeric alkenes correlation with structure is same as when heats of combustion are measured Ethylene 136 Monosubstituted 125-126 cis-Disubstituted 117-119 trans-Disubstituted 114-115 Terminally disubstituted 116-117 Trisubstituted 112 Tetrasubstituted 110 §6.3 Stereochemistry 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 §6.4 Electrophilic Addition of  Hydrogen Halides to Alkenes Electrophilic Addition 亲电加成 含有重健的化合物进行加成时，反应速率的控制步骤（即慢的一步）是亲电试剂首先进攻重键原子生成正离子中间体，然后正离子中间体再与亲核试剂反应生成产物，这种加成称为亲电加成 Mechanism of Addition of  Hydrogen Halides to alkenes §6.5 Regioselectivity of hydrogen Halide Addition : Markovnikov’s Rule Markovnikov’