Alkenes and Alkynes - Chemistry（烯烃和炔烃u2014u2014化学）.pdfVIP

3 Alkenes and Alkynes Chapter Summary Alkenes have a carbon-carbon double bond and alkynes have a carbon–carbon triple bond. Nomenclature rules are given in Sec. 3.2. Each carbon of a double bond is trigonal, and connected to only three other atoms, all of which lie in a plane with bond angles of o . Ordinarily, rotation around double bonds is restricted. All six atoms of ethylene lie in a 120 single plane. The C=C bond length is 1.34 Å, shorter than a C−C bond (1.54 Å). These facts can be explained by an orbital model with three sp2 hybrid orbitals (one electron in each) and one p orbital perpendicular to these (containing the fourth electron). The double bond is formed by end-on overlap of sp2 orbitals to form a σ bond and lateral overlap of aligned p orbitals to form a π bond (Figures 3.4 and 3.5). Since rotation around the double bond is restricted, cis–trans isomerism is possible if each carbon atom of the double bond has two different groups attached to it. Alkenes react mainly by addition. Typical reagents that add to the double bond are halogens, hydrogen (metal catalyst required), water (acid catalyst required), and various acids. If either the alkene or the reagent is symmetrical (Table 3.2), only one product is possible. If both the alkene and reagent are unsymmetrical, however, two products are possible, in principle. In this case, Markovnikov’s rule (Secs. 3.8–3.10) allows us to predict the product obtained. Electrophilic additions occur by a two-step mechanism. In the first step, the electrophile adds in such a way as to form the most stable carbocation (the stability order is tertiary secondary primary). Then the carbocation combines with a nucleophile to give the