AlkyneAlkadiene1§1 炔烃的结构与命名一、结构C CDissociation Energies of C-C Bonds CH CH ΔHo 229 kcal mol-1 H2C CH2 173 kcal mol-1 H3C CH3 90 kcal mol-12一、命名1、乙炔为母体H2C C C CH H乙烯基乙炔VinylacetyleneCH3 C C CH3 CH3 C C CH(CH3)2二甲基乙炔Dimethylacetylene甲基异丙基乙炔Isopropylmethylacetylene2、IUPAC命名(1) 选主链，定母体；（2）编号；（3)排序H2 H H3C C C C C CH3 H2C CH3eneyne5-甲基-3-庚炔 5-methyl-3-heptyne3烯炔 (enyne)H3 C C C C CH H H使不饱和键的编号尽可能小CH3 C C C CH2 H3-戊烯-1-炔 3-penten-1-yne1-戊烯-3-炔 1-penten-3-yne如两个编号相同，则使双键具有最小的编号H2 CH2 C C C CH H1-戊烯-4-炔1-penten-4-yneH2CCH3 C CH C CH H3-甲基-1-戊烯-4-炔 3-methyl-1-penten-4-yne4§2 炔烃的物理性质Alkynes are relatively nonpolarComparison of the boiling points between alkanes, alkenes and alkynes Ethane -161.7 Ethene -103.7 Ethyne Subl. At -83 under 1 atm Propane -182.5 Propene -47.7 Propyne -84 Butane -138.3 1-Butene -6.5 1-Butyne 8.1 2-Butene Cis 4; Trans 1 2-Butyne 275§3 炔烃的反应一、端炔氢的酸性 RCCH CH + Na 乙炔钠CH CH + 2 Na NaC CNa + H2 乙炔二钠CHCH CNa + H2酸性：H2O RC CH> >CH CNa + H2OCH CH + NaNH2RC CH + NaNH2CH CH + NaOH乙醚乙醚NH3CH CNa + NH3RC CNa + NH36Terminal alkynes are remarkably acidicCH CH pKa 25 H2C CH2 44 CH3CH3 50Hybridizationspsp2sp3CH CHAgNO3/NH3CH CAgHNO 3CH CH + AgNO 3CH3CH2C CHCu(NH3)+CH3CH2C CCuHClCH3 CH2C CH + Cu2Cl27二、还原成烯烃C C H2 Ni H H C CH2 Ni H H C C H HLindlar催化 Pd/CaCO3,Pb or Pd/BaSO4,喹啉 剂： NaBH4 P-2催化 (CH3CO2)2Ni Ni3B 剂：H CH3CH2CH2 C C CH2CH2CH3 Lindlar catalyst Ni3B H2 H C C C2H5 C2H58H C C CH2CH2 CH3CH3CH2CH2HC2H5 C C C2H5R C C RNa/NH3(l)H C C RR H H C C C2H5 C2H5 HC2H5 C C C2H5Na/NH3(l)三、炔烃的亲电加成反应CH2 H2 Br2 (1 mol) C C C CH HCH2 BrH H2 C C C CH BrBr2Br2H2 H H2 CH2 C C C CH CH2 C C C CH H Br Br Stability>9(1) 加卤素H C C H Br2 Br Br H C C HBr2Br Br H C C H Br BrC2H5 BrC2 H5 C C C2H5Br2Br C C C2H5(2) 加卤化氢H C C H HCl H Cl Cl HCl H3C C H H C C H Cl1019212共轭大π键Orbital Hybridization TheoryH动力学控制产物热力学控制产物CH3 H2C CHCN CH3 C CNCH3 H2C CHCN CH3 C CH2CH CN CNH2 H * C C n * CN聚丙烯腈H2C C C CH2 ROOR H H* CH2CH=CHCH2n*聚丁二烯无规聚合，性能较差ROOR 2 RO.H2 RO C C C CH2 H H*H2 H RO. H2C C C CH2 RO C C C CH2 H H HH2C C C CH2 H H* CH2CH=CHCH2n312.配位聚合(Coordination Polymerization)Ziegler-Natta Catalyst (1955)-TiCl4/AlEt3n CH2=CH2 TiCl4/AlEt3 H2 H2 * * C C n 聚乙烯Ti CH2CH3 CH2=CH2Ti CH2CH3 H2C CH2Ti CH2CH3 H2C CH2H2 H2 * C C n * 聚乙烯Ti CH2CH2 CH2CH3Ti CH2CH2CH2CH332n CH2=CH-CH=CH2TiCl4/AlEt3 * CH2 C C H HH2 C*n顺-1,4-聚丁二烯n CH2=C-CH=CH2 CH3TiCl4/AlEt3*CH2 C C H H3CH2 C*n顺-1,4-聚异戊二烯 合成天然橡胶*CH2 H * C C C n H3C H2杜仲胶（天然存在的反-1,4-聚异戊二烯） 用于高尔夫球、冰球等33H3CH C C CH S S CH HH3C C H2H C C CH S SH3C C H2H C C CH S S CH H*CH2 C C H H3C 天然橡胶H2 C*nS8C H2CH2 C C H3CH2 C H3CCH CH2 C C H H3C C C硫化，分子间（烯丙位）交联，改进橡胶的机械强度n PhCH=CH2 + n CH2=CH-CH=CH234Biosynthesis of the two isomers of 3-methylbutenyl pyrophosphateCH3 O OH O OHCH2=CCH2CH2OHHO P OH + HO P OHPhosphoric acid −HOHO HO P O O P OH OH−HOHCH3 O P O OH O P OH OHOHPyrophosphoric acid CH2=CCH2CH2O EnzymeH3C C H3C CHCH2OPPOPPSTEP 1. Ionization to stabilized (allylic) cationOPP−OPP−STEP 2. Electrophilic attack + STEP 3. Proton loss −H+OPP H OPP H OPPOPPGeranyl pyrophosphateSTEP 4. Second oligomerizationOPP OPPGeranyl pyrophosphateGeranyl pyrophosphateOPP HOPPFarnesyl pyrophosphate36四、双烯反应－Diels-Alder ReactionR +R = -X, CN, CHO, CO2R etc.RR特点: (1) 加成产物中仍保持原来双烯和烯烃的构型， 如：CO2CH3 + CO2CH3 CO2CH3 + H3CO2C CO2CH337CO2CH3 CO2CH3 CO2CH338特点: (2) 参与反应的双烯应该为S-顺式；如果双烯的构型 被固定为S-反式，则不能进行双烯反应，如：S-反式－ 不能发生双烯反应O + OO OO O O OO O O O39Application-Synthesis of six-membered cyclic compounds andtheir related compoundsCN + CNCO2H CO2H CO2H CO2HH CO2 H H CO2 HO+O O OO OOO O OO +O O OOO H2/Ni O OOO O O40作业：P103 2 3 4 7 8 9 11 1241。