郑州大学 有机化学8卤代烃 金属有机化合物PPT.ppt

Chapter 8 Halohydrocarbons (卤代烃)Organometallic Compounds (有机金属化合物);8.1 Classification (分类), Nomenclature (命名), Structure (结构) and Physical Properties (物理性质);按与卤素相连的碳原子的级数分类;8.2 Reactions;8.2.1 Nucleophilic Substitution (亲核取代);Inversion of configuration(构型翻转): Walden inversion ;Energy Diagram;Side Reaction;SN1;Racemization;Energy Diagram;Side Reaction;8.2.1.2 Factors affecting SN1 and SN2;8.2.1.2.1 The structures of alkyl groups;SN1反应速度: PhCH2X , CH2=CHCH2X 3oRX 2oRX 1oRX CH3X CH2=CHX, PhX;8.2.1.2.2 Leaving groups;~0;SN1;8.2.1.2.3 The nucleophile;质子溶剂中亲核性 I-F-：1)可极化度; 2)溶剂化效应 ;a. In a group of nucleophiles in which the nucleophilic atom is the same, nucleophilicities parallel basicities (试剂中亲核原子相同时，亲核性与碱性一致). RO- HO- ArO- RCOO- ROH H2O b. Nucleophilicity decrease to the right in an row of the peridoic table (同一周期中亲核性自左向右逐渐降低，与碱性一致). NH2- OH- F- R3C- R2N- RO- F- c. Nucleophilicity usually increases in going down a column of the periodic table (同一主族自上而下亲核性增强，与碱性相反)(在质子溶剂中). F- Cl- Br- I- HO- HS- RO- RS-;2)Nucleophilicity affected by solvents (亲核性受溶剂影响);;3) Sterically hindered nucleophiles are poor ones (位阻大的试剂亲核性差);8.2.1.2.4 The solvent effects(溶剂效应);对于带正电的底物，溶剂极性增强，将使SN1速率有所降低 ;SN2;亲核性强 ;4）I-既是一个好的离去基团又是一个好的亲核试剂;8.2.2 Elimination (消除反应)——E1 and E2;SN versus E;60% 40%;× ;8.2.3 Neighboring-group Participation (邻基参与);The reaction is 3200 times faster!;苏式;赤式;8.2.4 Reduction (还原);4) HI ;8.3 Preparation;8.3.3 Preparation from alcohols(由醇制备);8.3.6 Preparation via haloform reaction(由卤仿反应制备);Iodoform reaction:;They invented a tool to make carbon-carbon bonds in organic chemistry The tool is called palladium-catalyzed cross-coupling It has applications in a range of fields from medicine to electronics;Organometallic Compounds (有机金属化合物);8.4 Organicmetallic Nomenclature;8.5 Preparation;8.5.2 Via reaction of organometallics with salts (通过有机金属与无机盐反应) ;8.5.3 Via reaction of organometallics with hydrocarbons (通过有机金属与烃反应) ;8