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NEET CHEMISTRYMedium

In SN2S_N2 substitution reaction of the type R-Br+ClDMFR-Cl+Br\text{R-Br} + \text{Cl}^- \xrightarrow{\text{DMF}} \text{R-Cl} + \text{Br}^-, which one of the following has the highest relative rate?

A

CH3-CH2-CH2Br\text{CH}_3\text{-CH}_2\text{-CH}_2\text{Br}

B

CH3-CH(CH3)-CH2Br\text{CH}_3\text{-CH(CH}_3\text{)-CH}_2\text{Br}

C

CH3-C(CH3)2-CH2Br\text{CH}_3\text{-C(CH}_3)_2\text{-CH}_2\text{Br}

D

CH3CH2Br\text{CH}_3\text{CH}_2\text{Br}

Step-by-Step Solution

The given reaction proceeds via an SN2S_N2 mechanism. The rate of an SN2S_N2 reaction is highly dependent on the steric hindrance (spatial arrangement) around the electrophilic carbon atom. As the steric bulk around the α\alpha-carbon increases, the approach of the incoming nucleophile (Cl\text{Cl}^-) is hindered, leading to a lower reaction rate. Among the given primary alkyl bromides, bromoethane (CH3CH2Br\text{CH}_3\text{CH}_2\text{Br}) has the least steric hindrance. Branching at the β\beta-carbon (as seen in the other options: propyl, isobutyl, and neopentyl bromides) increases steric resistance, making the approach of the nucleophile difficult. Thus, CH3CH2Br\text{CH}_3\text{CH}_2\text{Br} has the highest relative rate.

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