有机课件-羰基化合物.pptVIP

Chapter 9   carbonyl compounds 一、structure and nomeclature(一) structure Structure: C=O (a) C: SP2 hybridization (four atom lie in one plane)(b)three sp2orbitals lying in one plane(c) л(C-O) perpendicular the plane polarityCH3COH μ=9.0×10-30C.m H3COCH3 μ=9.49×10-30C.m羰基的极性----两个反应中心: 正电中心(C+) 负电中心(O-) 易亲核加成 (二) nomenclature IUPAC  二、physical properties aldehydes and ketones低级醛、酮：水混溶（氢键）eg Formalin 40%甲醛水溶液， 丙酮自身不形成氢键，bp. alcohol IR-C=O 1680~1750cm-1 特征峰O=C-H 2720cm-1 , 2850cm-1 区别醛、酮 1H-NMRO=C-H δ(ppm) 9~10 三、醛、酮的化学性质 （一）nucleophilic addition 脂肪醛、酮活性影响：电性效应和立体效应芳香醛、酮活性影响：芳环取代基电性因素 吸电子?活性增加；给电子? 活性降低 1. 含碳亲核试剂 2．Addition of sodium bisulfite 3．Organic-metal compounds制备醇 4．含氧亲核试剂 5. addition of alcohols 作用:-C=O保护,缩醛、酮-----碱、氧化剂稳定 dehydrant: benzene or toluene 6. addition of ammonia and its derivatives ammonia derivative as nucleophilic reagents （二）reaction of reactive α-hydrgen atom 1. The aldol condensation-----β-hydroxyaldehyde β-hydroxyaldehyde heat α,β-unsaturated ketone small ketones-------β-hydroxy ketones 2. mixed or crossed aldol condensations α-hydrogen and noα-hydrogen (Clainsen, L-Schmidt, J.G) reaction ) 3. 分子内缩合 4．Halogenation and the Haloform reaction(Iodoform Test)halogenation(substitution of α-hydrogens)introduce only one halogen atom 5. Racemizationα-H为受性碳------外消旋（烯醇互变异构） Mannich reaction α-H ketone + formaldehyde + 1o or 2o amine （三）oxidation and reduction 1. oxidation (1)?oxidation of aldehydes → carboxylic acidoxidizing agents: KMnO4, NaCr2O7 etc.?mild oxidizing agent: AgO much milder oxidizing agents: Tollen’s solution, Fehling’s solution Tollen’s solution:an ammoniacal solution of silver nitrate Silver mirror RCHO + 2Ag(NH3)2+OH-→RCOONH4 + 2Ag↓+ 3NH3+H2OFehling’s solution: cupric tartrate complexRCHO +Cu2++NaOH+H2O→RCOONa+Cu2O↓+H+ Clearly differentiate: aldehydes and ketones (2) oxidation of ket