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NCERT Exemplar · Q3

Q.Identify the compound Y in the following reaction.

Aniline reacting via NaNO2/HCl (273-278 K) to benzenediazonium chloride, then Cu2Cl2 to give Y + N2, drawn as real benzene rings matching the NCERT Exemplar page
Figure
Options (i)-(iv): chlorobenzene, benzene, 1,3-dichlorobenzene, and 1,4-dichlorobenzene, drawn as real benzene rings matching the NCERT Exemplar page
Figure
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✓ Free question

The reaction is the Sandmeyer reaction: the diazonium group is replaced by chlorine using Cu2Cl2\mathrm{Cu_2Cl_2}, giving chlorobenzene (C6H5Cl\mathrm{C_6H_5Cl}) as product Y.

Diazotization and Sandmeyer route
Diazotization and Sandmeyer route

The key to this question is recognising the Sandmeyer reaction — a classic method for replacing the diazonium group (−N2+-\mathrm{N_2^+}) with a halogen using a copper(I) halide. Let’s walk through the chemistry step by step.

  1. First step: Diazotisation Aniline (C6H5NH2\mathrm{C_6H_5NH_2}) reacts with NaNO2\mathrm{NaNO_2} and HCl\mathrm{HCl} at low temperature (273–278 K). This converts the amino group into a diazonium group:

C6H5NH2+NaNO2+2HCl→273−278 KC6H5N2+Cl−+NaCl+2H2O\mathrm{C_6H_5NH_2 + NaNO_2 + 2HCl \xrightarrow{273-278\,K} C_6H_5N_2^+Cl^- + NaCl + 2H_2O}

The product is benzenediazonium chloride, a key intermediate in aromatic substitution. The low temperature is critical — diazonium salts decompose above about 5°C.

  1. Second step: The Sandmeyer reaction The diazonium salt is then treated with Cu2Cl2\mathrm{Cu_2Cl_2} (copper(I) chloride). This is the classic Sandmeyer reaction, where the diazonium group is replaced by a chlorine atom. The mechanism involves a single-electron transfer from Cu(I) to the diazonium ion, generating an aryl radical, which then abstracts chlorine from Cu(II) to form the aryl chloride.

C6H5N2+Cl−→Cu2Cl2C6H5Cl+N2\mathrm{C_6H_5N_2^+Cl^- \xrightarrow{Cu_2Cl_2} C_6H_5Cl + N_2}

The nitrogen gas (N2\mathrm{N_2}) bubbles off, driving the reaction forward.

  1. What about the options?
    • (i) Chlorobenzene — This is the direct product of the Sandmeyer reaction with Cu2Cl2\mathrm{Cu_2Cl_2}.
    • (ii) Benzene — This would require reduction of the diazonium group (e.g., with H3PO2\mathrm{H_3PO_2}), not with Cu2Cl2\mathrm{Cu_2Cl_2}.
    • (iii) 1,3-Dichlorobenzene and (iv) 1,4-Dichlorobenzene — These would require two chlorine substitutions, but the reaction conditions only introduce one chlorine. No further chlorination occurs here.
Watch out

A common mistake is to think that Cu2Cl2\mathrm{Cu_2Cl_2} causes a second substitution or that the reaction is a simple displacement. It is not — it’s a radical mechanism specific to the Sandmeyer reaction, and only one chlorine is introduced.

Tip

Remember the mnemonic: Sandmeyer for Cl, Br, CN using CuX\mathrm{CuX} or CuCN\mathrm{CuCN}; Schiemann for F using HBF4\mathrm{HBF_4}; and Gattermann for Cl, Br using Cu\mathrm{Cu} + HX\mathrm{HX}.

  1. Confirming the product The reaction is clean: one diazonium group, one chlorine atom replaces it, and nitrogen is lost. The product is chlorobenzene, C6H5Cl\mathrm{C_6H_5Cl}.
✓Final answer

The compound Y is chlorobenzene, option (i).

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