Carboxylic Acid Derivatives – Part 2 | Organic Chemistry 3

The Carboxylic Acid Derivatives are studied in this chapter: the Hofmann rearrangement, the naming and properties of alkanenitriles, the hydrolysis of nitriles, their reaction with organometallic reagents, their reduction of nitriles. This chapter is a continuation of chapter 10 – Organic Chemistry 2.

Hofmann Rearrangement



Step 1: Amidate formation


Step 2: Halogenation


Step 3: N-Haloamidate formation


Step 4: Rearrangement with halide elimination


Step 5: Hydration to the carbamic acid and decomposition

Alkanenitriles: Naming and Properties


The ending -ic acid of the carboxylic acid is replaced with -nitrile.
The substituent CN is called cyano.
The cyanocycloalkanes are called cycloalkanecarbonitriles.
Nitrile takes precedence over aldehyde, ketone, amine, alkene, alkyne.




- sp hybridization (linear geometry)
- IR: stretching vibration ~ 2250 cm-1
- NMR: 13C δ ~ 120 ppm

Hydrolysis of Nitriles



Acid-Catalyzed Hydrolysis


Base-Catalyzed Hydrolysis

Nitriles and Organometallic reagents

Reduction of Nitriles