Which of the following reagents is used in the preparation of nitroalkane from haloalkane?

Which of the following reagents is used in the preparation of nitroalkane from haloalkane?
  1. Potassium cyanide
  2. Sodium nitrite
  3. Potassium nitrite
  4. Silver nitrite

Solution

Haloalkanes undergo nucleophilic substitution with nitrite ions ($\text{NO}_2^-$), which are ambident nucleophiles capable of attacking through either oxygen or nitrogen atoms.

Alkali metal nitrites like KNO$_2$ and NaNO$_2$ are predominantly ionic, with oxygen's higher electronegativity making it the preferred nucleophilic site, yielding alkyl nitrites: R–X + KNO$_2$ $\rightarrow$ R–O–N=O + KX.

Silver nitrite (AgNO$_2$) is covalent, with the Ag–O bond reducing oxygen's nucleophilicity and favoring nitrogen attack, producing nitroalkanes: R–X + AgNO$_2$ $\rightarrow$ R–NO$_2$ + AgX.

To prepare nitroalkanes from haloalkanes, silver nitrite is the preferred reagent.

Asked in: MHT CET 2025 (05 May Shift 2)

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