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Q8.14(v):
How will you prepare the following compounds from benzene? You may use any inorganic reagent and any organic reagent having not more than one carbon atom (v) p-Nitrobenzaldehyde.

Solution :

Step 1: Synthesis of Toluene from Benzene

To prepare p-Nitrobenzaldehyde, we must first install an alkyl group on the benzene ring to serve as the precursor for the aldehyde functional group. This is achieved via Friedel-Crafts Alkylation.

Reagents: $CH_3Cl$ (Methyl chloride) and $AlCl_3$ (Anhydrous Lewis acid catalyst).

Reaction: $C_6H_6 + CH_3Cl \xrightarrow{AlCl_3} C_6H_5CH_3 + HCl$ [Per Friedel-Crafts Alkylation mechanism].

Step 2: Nitration of Toluene

The methyl group ($-CH_3$) is an ortho/para-directing activator. Nitration will yield a mixture, but p-nitrotoluene can be separated by fractional crystallization.

Reagents: Conc. $HNO_3$ and Conc. $H_2SO_4$ at $298-303K$.

Reaction: $C_6H_5CH_3 + HNO_3 \xrightarrow{H_2SO_4} p-NO_2-C_6H_4-CH_3 + H_2O$ [Electrophilic Aromatic Substitution].

Step 3: Oxidation of Methyl Group to Aldehyde

Direct oxidation using $KMnO_4$ would oxidize the methyl group to a carboxylic acid. To stop at the aldehyde stage, we use Etard’s reaction or controlled oxidation with Chromyl chloride ($CrO_2Cl_2$).

Reagents: $CrO_2Cl_2$ in $CS_2$ followed by $H_3O^+$.

Reaction: $p-NO_2-C_6H_4-CH_3 \xrightarrow[2. H_3O^+]{1. CrO_2Cl_2, CS_2} p-NO_2-C_6H_4-CHO$ [Etard Reaction Mechanism].

Reaction Scheme Visualization

Benzene Toluene NO₂ p-Nitrotoluene CHO p-Nitrobenzaldehyde

Summary of Transformation Steps

Step Process Reagents Used
1 Friedel-Crafts Alkylation $CH_3Cl, AlCl_3$
2 Electrophilic Nitration Conc. $HNO_3, Conc. H_2SO_4$
3 Etard Reaction $CrO_2Cl_2, CS_2, H_3O^+$

Final Solution: The synthesis of p-Nitrobenzaldehyde from benzene is achieved by first performing a Friedel-Crafts alkylation to obtain toluene, followed by nitration to yield p-nitrotoluene, and finally using the Etard reaction with chromyl chloride to selectively oxidize the methyl group to an aldehyde group.


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