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Q8.17(v):

Complete each synthesis by giving missing starting material, reagent or products.

 

Solution :

Given Reaction Analysis

The transformation involves the conversion of a disubstituted benzene derivative, specifically 3-nitrobenzaldehyde, into 3-nitrobenzoic acid.

Chemical Equation: $C_6H_4(NO_2)CHO \xrightarrow{[O]} C_6H_4(NO_2)COOH$

Step 1: Identification of Functional Group Transformation

The starting material is an aromatic aldehyde (3-nitrobenzaldehyde). The product is an aromatic carboxylic acid (3-nitrobenzoic acid). This transformation requires the oxidation of the formyl group ($-CHO$) to a carboxyl group ($-COOH$). [Per the principles of organic oxidation, aldehydes are readily oxidized to carboxylic acids under mild to strong oxidative conditions.]

Step 2: Selection of Reagents

To achieve this oxidation, several common laboratory reagents can be employed. The selection depends on the sensitivity of other functional groups present. In this case, the nitro group ($-NO_2$) is inert to most standard oxidants.

  • Reagent A: Potassium permanganate ($KMnO_4$) in an alkaline or acidic medium, followed by acidic workup ($H_3O^+$).
  • Reagent B: Jones Reagent (Chromic acid, $CrO_3/H_2SO_4$).
  • Reagent C: Tollens' reagent ($[Ag(NH_3)_2]^+$), which oxidizes aldehydes to carboxylate ions, followed by acidification.

The most standard academic reagent for this conversion is alkaline $KMnO_4$ followed by acidification.

Step 3: Reaction Mechanism

The reaction proceeds via the formation of a gem-diol intermediate or a transient radical species.
1. $R-CHO + [O] \rightarrow R-COOH$
2. In the presence of $KMnO_4/OH^-$, the intermediate is a salt ($R-COO^-K^+$).
3. Addition of $H^+$ (acidification) yields the final carboxylic acid product. [Per Bronsted-Lowry acid-base theory].

3-Nitrobenzaldehyde KMnO4 / H3O+ 3-Nitrobenzoic acid

Step 4: Summary of Chemical Synthesis

Reactant Reagent Product
3-Nitrobenzaldehyde $KMnO_4$ / $H^+$ 3-Nitrobenzoic acid

Final Solution: The missing reagent required to complete the synthesis of 3-nitrobenzoic acid from 3-nitrobenzaldehyde is Potassium permanganate ($KMnO_4$) in an acidic or basic medium, followed by acidification.


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