生物化学 Chapter20+Carboxylic+Acids.ppt

Chapter 20  Carboxylic Acids §20.1 Carboxylic Acid Nomenclature Functional group suffix = -oic acid (review) If the acid is substituted onto a ring the suffix -carboxylic acid is used. The anion derived by deprotonation of a carboxylic acids is the carboxylate Dicarboxylic Acids Aliphatic diacids are usually called by their common names (to be memorized). For IUPAC name, number the chain from the end closest to a substituent. Two carboxyl groups on a benzene ring indicate a phthalic acid. The principal group is assigned according to the following priorities: §20.2 Physical Properties The polar nature of both the O-H and C=O bonds (due to the electronegativity difference of? the atoms) results in the formation of strong hydrogen bonds with other carboxylic acid molecules or other H-bonding systems (e.g. water). The implications are: higher melting and boiling points compared to analogous alcohols high solubility in aqueous media hydrogen bonded dimers in gas phase and dimers or aggregates in pure liquid Intermolecular hydrogen bonding between two carboxylic acid molecules. Acetic acid, b.p. 118?C §20.3 Spectroscopic Analysis IR Spectroscopy NMR Spectroscopy Mass Spectrometry Peak for the molecular ion, M+, is usually prominent. Fragments due to loss of OH (M - 17)+ and then loss of CO (M - 45)+ Mass Spectrometry §20.4 Structure and Bonding Carbon is sp2 hybridized. Bond angles are close to 120?. O-H eclipsed with C=O, to get overlap of ? orbital with orbital of lone pair on oxygen. §20.5 Acidity of Carboxylic Acids Acidity: Carboxylic acids are the most acidic simple organic compounds (pKa ~ 5). Resonance stabilization of the carboxylate ion allows the negative charge to be delocalised between the two electronegative oxygen atoms (compare with alcohols, pKa ~ 16). Adjacent electron withdrawing substituents increase the acidity by further stabilizing the carboxylate. The inductive effect of the carbonyl group The resonance ef