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

 


Mechanism:

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

Naming:

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.

 

 

Properties:

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

Hydrolysis of Nitriles

 


Mechanism:

Acid-Catalyzed Hydrolysis
 

 

Base-Catalyzed Hydrolysis
 

Nitriles and Organometallic reagents

Reduction of Nitriles