加州大学伯克利分校有机化学课件19.pptVIP

? University of California ? Univesity of California Chapter 19: Carboxylic Acids Naming: Alkanoic Acids Physical Properties 1H NMR Chemical Shifts 13C NMR Chemical Shifts IR Spectroscopy Resonance Acidity Basicity Reactions Nucleophilic Substitution by Addition- Elimination Base Catalyzed Mechanism Acid Catalyzed Mechanism B. Anhydrides C. Esters: D. Amides Mechanism: H+ mineral acid, e.g., H2SO4, HCl, proceeds initially like acetalization of aldehydes and ketones Note: Carbonyl oxygen is always more basic than hydroxy oxygen, because of resonance in the protonated product. * Carboxy group: -COOH, -CO2H, IUPAC: Replace –e of alkane name with –oic acid 4-Methylhexanoic acid C1 Cyclic: Cycloalkanecarboxylic acids Cyclohexanecarboxylic acid 1-Naphthalenecarboxylic acid C1, as in cyclic aldehydes Common Names Carboxylic acids take precedence over other groups: Include as many functions as possible in stem (Better than 4-acetylheptanoic acid) Planar structure, trigonal carbonyl carbon The carboxy group is polar, undergoes hydrogen bonding, and forms dimers: Dimerization causes relatively high melting and boiling points 10-13 ppm 2-2.5 ppm cf. aldehydes and ketones Aldehyde like H C O O H Not quite as low field as aldehyde or ketone Two important bands: νO-H = 2500-3300 cm-1, νC=O = 1710 cm-1 ~200 ppm ~180 ppm The carboxy group is relatively acidic: Acetate Reasons: 1. Carbonyl carbon is inductively strongly electron withdrawing, 2. Carboxylate ion is stabilized by resonance Compare … 2-Propenyl (allyl) BH + pKa ~ 40 + Electron withdrawing groups increase the acidity (decrease pKa): CF3COOH pKa ~ 0.23 Distance affects acidity: pKa 4.19 pKa 3.98 Protonated on the carbonyl oxygen: Allows for allylic resonance 1. Oxidation of primary alcohols and aldehydes With KMnO4; or CrO3, H2O; or HNO3; or H2O2; or Cu2+, or Ag+. Recall Cr(VI) oxidation: Preparation In H2O: Hydrate, which oxidizes to acid 2. Carbonation: Organometa