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Benzene Diazonium Chloride | chemca

Benzene Diazonium Chloride | chemca
Organic Chemistry

Benzene Diazonium Chloride

Preparation (Diazotization) and Synthetic Applications.

By chemca Team • Updated Jan 2026

Benzene Diazonium Chloride ($C_6H_5N_2^+Cl^-$) is a highly versatile intermediate in organic synthesis. The diazonium group ($N_2^+$) is an excellent leaving group, allowing the introduction of various functional groups onto the benzene ring.

1. Preparation (Diazotization)

From Aniline

It is prepared by treating ice-cold solution of Aniline in excess mineral acid ($HCl$) with cold aqueous Sodium Nitrite ($NaNO_2$) at low temperature (273-278 K).

$$ \underset{\text{Aniline}}{C_6H_5NH_2} + NaNO_2 + 2HCl \xrightarrow{273-278 K} \underset{\text{Benzene Diazonium Chloride}}{C_6H_5N_2^+Cl^-} + NaCl + 2H_2O $$
Critical Condition: The temperature must be maintained between 0-5°C. Above this temperature, the diazonium salt hydrolyzes to form Phenol and nitrogen gas escapes.

2. Physical Properties

  • State: Colorless crystalline solid.
  • Solubility: Highly soluble in water due to ionic nature.
  • Stability: Stable in cold aqueous solution but decomposes when warmed. Unstable in dry state.
  • Reactivity: Never stored; prepared in situ and used immediately.

3. Reactions involving Displacement of Nitrogen

The $N_2$ group is replaced by other groups like $Cl, Br, I, CN, OH, H, NO_2, F$.

A. Sandmeyer Reaction

Treatment with Cuprous salts ($Cu_2X_2$) yields aryl halides or cyanides.

$$ C_6H_5N_2^+Cl^- \xrightarrow{Cu_2Cl_2/HCl} C_6H_5Cl + N_2 $$ $$ C_6H_5N_2^+Cl^- \xrightarrow{Cu_2Br_2/HBr} C_6H_5Br + N_2 $$ $$ C_6H_5N_2^+Cl^- \xrightarrow{CuCN/KCN} C_6H_5CN + N_2 $$

B. Gattermann Reaction

Uses Copper powder ($Cu$) and halo-acid instead of cuprous salt.

$$ C_6H_5N_2^+Cl^- \xrightarrow{Cu/HCl} C_6H_5Cl + N_2 + CuCl $$

C. Other Replacements

1. Replacement by Iodine (Reaction with KI):

$$ C_6H_5N_2^+Cl^- + KI \xrightarrow{\text{Warm}} \underset{\text{Iodobenzene}}{C_6H_5I} + KCl + N_2 $$

2. Replacement by Fluorine (Balz-Schiemann Reaction):

$$ C_6H_5N_2^+Cl^- + HBF_4 \rightarrow C_6H_5N_2^+BF_4^- \xrightarrow{\Delta} \underset{\text{Fluorobenzene}}{C_6H_5F} + BF_3 + N_2 $$

3. Replacement by Hydrogen (Reduction to Benzene):

Uses mild reducing agents like Hypophosphorous acid ($H_3PO_2$) or Ethanol.

$$ C_6H_5N_2^+Cl^- + H_3PO_2 + H_2O \rightarrow C_6H_6 + N_2 + H_3PO_3 + HCl $$ $$ C_6H_5N_2^+Cl^- + CH_3CH_2OH \rightarrow C_6H_6 + N_2 + CH_3CHO + HCl $$

4. Replacement by Hydroxyl (Hydrolysis to Phenol):

$$ C_6H_5N_2^+Cl^- + H_2O \xrightarrow{\text{Warm, } 283K} C_6H_5OH + N_2 + HCl $$

4. Reactions involving Retention of Nitrogen (Coupling)

Azo Dye Formation

Diazonium salts act as weak electrophiles and react with electron-rich aromatic rings (Phenols, Amines) to form colored Azo compounds ($-N=N-$). This is called Azo Coupling.

A. Coupling with Phenol (in basic medium, pH 9-10):
$$ Ph-N_2^+Cl^- + Ph-OH \xrightarrow{OH^-} \underset{\text{p-Hydroxyazobenzene (Orange Dye)}}{p\text{-}N=N-C_6H_4-OH} + Cl^- $$
B. Coupling with Aniline (in acidic medium, pH 4-5):
$$ Ph-N_2^+Cl^- + Ph-NH_2 \xrightarrow{H^+} \underset{\text{p-Aminoazobenzene (Yellow Dye)}}{p\text{-}N=N-C_6H_4-NH_2} + Cl^- $$
Position: Coupling invariably takes place at the Para position to the activating group (-OH or -NH2). If para is blocked, it occurs at ortho.

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