Carboxylic Acid Derivatives – Part 2 | Organic Chemistry 3
Additional reactions of carboxylic acid derivatives are studied in this chapter: Hofmann rearrangement, name and properties of alkanenitriles, hydrolysis of nitriles, reactions between nitriles and organometallic reagents, reduction of nitriles
Hofmann Rearrangement
Mechanism:
- Amidate formation:
- Halogenation:
- N-haloamidate formation:
- Rearrangement with halide elimination:
- Carbamic acid hydration and decomposition:
Alkanenitriles: Nomenclature and Properties
Nomenclature:
The -ic acid ending of the corresponding carboxylic acid is replaced with -nitrile. The substituent -CN is called cyano. A cycloalkane with a cyano group attached to the ring is called cycloalkanecarbonitriles
Nitrile takes precedence over aldehyde, ketone, amine, alkene, alkyne
Properties:
- sp hybridization ⇒ linear geometry
- IR: stretching vibration ~ 2250 cm-1
- NMR: 13C δ ~ 120 ppm
Hydrolysis of Nitriles
Mechanisms:
Acid-catalyzed hydrolysis:
Base-catalyzed hydrolysis: