中国农业大学：《有机化学》课程教学课件（PPT讲稿）第九章 卤代烃 Alkyl Halides

Chapter 9.Alkyl Halides

Chapter 9. Alkyl Halides

9.1 Classification , nomenclature andstructural isomers of alkyl and arylhalides9.1.1 Classification9.1.2 NomenclatureCH3CHCH,CHCHCH3CH2CHCH2Br

9.1 Classification , nomenclature and structural isomers of alkyl and aryl halides 9.1.1 Classification 9.1.2 Nomenclature CH3 CH2 CHCHCH3 CH3 Cl CH2 CHCH2 Br

CH2Br9.1.3Isomerism碳干异构、卤原子位置异构

9.1.3 Isomerism 碳干异构、卤原子位置异构 Cl Cl CH2 Br

练习：命名下列化合物BICH3CHBrBr

Cl CH3 Cl Br F Cl Br Br CH3 Cl 练习：命名下列化合物

9.2 Alkyl monohalides9.2.1Physical properties9.2.2 Chemical propertieso+C-X

9.2 Alkyl monohalides 9.2.1 Physical properties 9.2.2 Chemical properties C X  +  -

卤代烃CH,CH,CICH,CH,BrCH,CH,I偶极矩2.05D2.03D1.91D极化度（极化率）：共价键对外界电场的感受能力不同卤代烃的静态极性次序(CH3)3C-X > (CH3)2CH-X > CH3CH2-X > CH3-X

卤代烃 CH3CH2Cl CH3CH2Br CH3CH2 I 偶极矩 2.05D 2.03D 1.91D 极化度（极化率）：共价键对外界电场的感 受能力 不同卤代烃的静态极性次序 (CH3) 3 C-X > (CH3) 2 CH-X > CH3 CH2-X > CH3-X

9.2.3.1 Nucleophilic SubstitutionCCX + Nu:NuR-R-C+产物底物亲核试剂离去基团亲核取代反应：由富电子试剂进攻缺电子中心而进行的取代反应

9.2.3.1 Nucleophilic Substitution 亲核取代反应：由富电子试剂进攻缺电子中心而进行的 取代反应 底物 亲核试剂 产物 离去基团  +  - R C X + Nu: - R C Nu + X -

(1) HydrolysisRX +OH> R-OH +(2)Alcoholysisor phenolysisRONa → ROR+ NaXRX +ArONa → ArOR + NaX

(1) Hydrolysis (2) Alcoholysis or phenolysis ▽ R X + OH R OH + X RX + RONa 1 R1 OR + NaX ArONa ArOR + NaX

(3)AmmonolysisNH3RNH2 + HXRX +H2NR1 —RNHR1 + HXCH3CH3CH3CH3CH30CH2C0CINH2 + Br-CHCO0CH3NHCHCOOCH3CH3CH3CH3CH3CHCOOCH3甲霜灵（杀菌剂）COCH,OCH3CH3

(3) Ammonolysis NH3 RNH2 + HX H2 NR1 RNHR1 + HX RX + CH3 CH3 NH2 + Br CHCOOCH3 CH3 CH3 CH3 NHCHCOOCH3 CH3 CH3OCH2COCl CH3 CH3 N CHCOOCH3 CH3 COCH2OCH3 甲霜灵(杀菌剂)

(4)Reactionwithmetal cyanide乙醇R-X + NaCNR-CN+ NaX腈H20RCOOHH orOH

(4) Reaction with metal cyanide 乙醇 R X + NaCN ▽ R CN+ NaX RCOOH 腈 H2 O H orOH