columbia大学有机化学课件 （三十一）.pptVIP

Chapter 8Nucleophilic Substitution 8.1Functional Group Transformation By Nucleophilic Substitution Nucleophilic Substitution nucleophile is a Lewis base (electron-pair donor) often negatively charged and used as Na+ or K+ salt substrate is usually an alkyl halide Nucleophilic Substitution Table 8.1 Examples of Nucleophilic Substitution Example Table 8.1 Examples of Nucleophilic Substitution Example Table 8.1 Examples of Nucleophilic Substitution Example Table 8.1 Examples of Nucleophilic Substitution Example Table 8.1 Examples of Nucleophilic Substitution Example Table 8.1 Examples of Nucleophilic Substitution Example 8.2Relative Reactivity of Halide Leaving Groups Generalization Reactivity of halide leaving groups in nucleophilic substitution is the same as for elimination. Problem 8.2 Br is a better leaving group than Cl Problem 8.2 11 4 13 Y : – R X Y R + + : X – Substrate cannot be an a vinylic halide or an aryl halide, except under certain conditions to be discussed in Chapter 23. X C C X + R X gives an ether Alkoxide ion as the nucleophile .. O: .. R – + : X R .. O .. R – (CH3)2CHCH2ONa + CH3CH2Br Isobutyl alcohol (CH3)2CHCH2OCH2CH3 + NaBr Ethyl isobutyl ether (66%) + R X gives an ester Carboxylate ion as the nucleophile .. O: .. RC – + : X R .. O .. RC – O O OK + CH3(CH2)16C CH3CH2I acetone, water + KI O CH2CH3 CH3(CH2)16C Ethyl octadecanoate (95%) O O + R X gives a thiol Hydrogen sulfide ion as the nucleophile .. S: .. H – + : X R .. S .. H – KSH + CH3CH(CH2)6CH3 Br ethanol, water + KBr 2-Nonanethiol (74%) CH3CH(CH2)6CH3 SH + R X gives a nitrile Cyanide ion as the nucleophile – + : X R – C N : : C N : DMSO Cyclopentyl cyanide (70%) Br NaCN + CN + NaCN + R X gives an alkyl azide Azide ion as the nucleophile + : X R – .. – N N N .. : : – + .. N N N .. : – + NaN3 + CH3CH2CH2CH2CH2I 2-Propanol-water CH3CH2CH2CH2CH2N3 + NaI Pentyl azide (52%) + R X gives an alkyl iodide Iodide ion as the nucleophile + : X R – – .. : I .. .. : I ..