Chapter 14 - Aliphatic Monohydroxy-Monocarboxylic Acids and Related Compounds

Abstract

Publisher Summary This chapter discusses the formation, methods of preparation, and reactions of saturated monohydroxy-acids, lactones, unsaturated monohydroxy-monocarboxylic acids, naturally-occurring higher hydroxy-acids and their derivatives, halogen-substituted monohydroxycarboxylic acids and lactones, nitrogen derivatives of monohydroxycarboxylic acids, and sulfur and selenium analogues of monohydroxycarboxylic acids. A direct synthesis of β-hydroxy-acids is based on the reaction of acids with the naphthalene/lithium radical ion system. The unstable 1,2-diethoxyacetylene is hydrolyzed by dilute sulfuric acid to ethyl ethoxyacetate. A facile high-yield photochemical synthesis of α-lactones under conditions that permit spectroscopic observations and investigation of the chemical and photochemical properties are illustrated. A series of δ-lactones is prepared by reaction of δ-oxoacids with Grignard reagents. Ricinoleic acid is oxidized by sodium dichromate in acetic acid in the absence of light to give a mixture of 9,12-dioxo-octadec-10-enoic, 8,12-dioxo-octadec-9-enoic, and 10,12-dioxo-octadec-8-enoic acids. The pheromone isolated from queens of the oriental hornet is identified as the lactone of 5-hydroxyhexadecanoic acid. The Baeyer–Villiger oxidation is applied to a bromo-ketone to give bromo-lactone. Also, γ-Hydroxynitriles are prepared by cathodic crossed hydrocoupling of ketones with acrylonitrile.