有机化学课件10Carboxylic Acids and Derivatives.ppt

* CHAPTER 10 Carboxylic Acids and Derivatives Carboxylic acid RCN Acid halide Acid anhydride Ester Amide Nitrile 10.1 Spectroscopy of Carboxyl Acids and Derivatives 10.1.1 1H-NMR Table 10.1 Characteristic Infrared Absorptions of Carboxylic Acids and Derivatives(cm-1) Dissociated: 3520, 3400 Associated: 3780, 3350 1640, 1600 Dissociated: ~3550 Associated: 3000 ~2500 1250 O-H, N-H 1400 1300 ~ 1050 1310 ~ 1045 1250 C-O, C-N 1785 ~ 1765, 1750 ~ 1735 1700 ~ 1680 -Ar- 1800 ~ 1750 Dissociated: 1720 Associated: 1690 C=C-C=O Dissociated: 1690 Associated: 1650 1735 1860 ~ 1800 1800 ~ 1700 1800 Dissociated: 1750 ~ 1720 Associated: 1710 C=O Amides Esters Acid anhydrides Acid halides Carboxyl acids 10.1.2 IR 10.2 Synthesis of Carboxylic Acids and Derivatives 10.2.1 Synthesis of Carboxylic Acids 10.2.2 Synthesis of Acid Halides, Acid anhydride, Esters and Amides Less reactive More reactive 10.3 Acidity of Carboxylic Acids 16 10 – 16 C2H5OH 4.75 1.76x10 – 5 CH3COOH 4.25 5.6x10 – 5 H2C=CHCOOH 4.19 6.46x10 – 5 PhCOOH 3.75 1.77x10 – 4 HCOOH 2.85 1.4x10 – 3 CH2ClCOOH 1.48 3.3x10 – 2 CHCl2COOH 0.64 0.23 CCl3COOH Stronger acid –7 107 HCl pKa Ka Name Weaker acid Table 10.2 Acid Strengths of Some Carboxylic Acids From Fundamentals of Organic Chemistry, John McMurry,2002 pKa1 pKa2 2.0 3.0 6.5 4.5 10.4 The Important Reactions of Carboxylic Acids and Derivatives 10.4.1 Claisen Condensation Reaction Dieckmann Condensation 10.4.2 Reformatsky Reaction 10.4.3 Darzens Reaction 10.4.4 酯的双分子还原 Na Inert solvent (Benzene) 10.4.5 Reaction of Esters with Grignard Reagents 10.4.6 Michael Reaction 亲核的碳原子对?，?不饱和体系的共轭加成，称为Michael Reaction。 *