Chapter 6, Problem 59P

(a)

Interpretation Introduction

Interpretation: Effect of change of substrate from ${\text{CH}}_{\text{3}}\text{Cl}$ to ${\text{CH}}_{\text{3}}\text{I}$ for the ${\text{S}}_{\text{N}}2$ reaction of ${\text{CH}}_{\text{3}}\text{Cl}$ should be predicted.

Concept introduction: Bimolecular substitution or ${\text{S}}_{\text{N}}2$ proceeds via single-step mechanism. Thus, it is well known as concerted mechanism. Nucleophile approaches carbon while the leaving group still departs from the rear side (opposite to leaving group). The transition state only illustrates the geometric orientation of the substrates and reagents as they pass through the maxima in the single-step mechanism.

A general ${\text{S}}_{\text{N}}2$ reaction mechanistic pathway is illustrated below:

  

${\text{S}}_{\text{N}}2$ pathway as it is a stereospecific reaction. This essentially means the R stereoisomer can only lead to inverted S stereoisomer and vice versa. Thus, the outcome is the rear side displacement of leaving group.

Polar-aprotic solvents accelerate the rate of ${\text{S}}_{\text{N}}2$ reactions. These solvents possess partial positive and negative charges also. However, they do not liberate any proton to the substrate unlike water, methanol solvents. Acetone, DMSO, THF or DMF are categorized as polar aprotic solvent.

(b)

Interpretation Introduction

Interpretation:Effect of change of nucleophile from ${\text{CH}}_{\text{3}}{\text{O}}^{-}$ to ${\text{CH}}_{\text{3}}{\text{S}}^{-}$ for the ${\text{S}}_{\text{N}}2$ reaction of ${\text{CH}}_{\text{3}}\text{Cl}$ should be predicted.

Concept introduction:Bimolecular substitution or ${\text{S}}_{\text{N}}2$ proceeds via single-step mechanism. Thus, it is well known as concerted mechanism. Nucleophile approaches carbon while the leaving group still departs from the rear side (opposite to leaving group). The transition state only illustrates the geometric orientation of the substrates and reagents as they pass through the maxima in the single-step mechanism.

A general ${\text{S}}_{\text{N}}2$ reaction mechanistic pathway is illustrated below:

  

${\text{S}}_{\text{N}}2$ pathway as it is a stereospecific reaction. This essentially means the R stereoisomer can only lead to inverted S stereoisomer and vice versa. Thus, the outcome is the rear side displacement of leaving group.

Polar-aprotic solvents accelerate the rate of ${\text{S}}_{\text{N}}2$ reactions. These solvents possess partial positive and negative charges also. However, they do not liberate any proton to the substrate unlike water, methanol solvents. Acetone, DMSO, THF or DMF are categorized as polar aprotic solvent.

(c)

Interpretation Introduction

Interpretation:: Effect of change of substrate from ${\text{CH}}_{\text{3}}\text{Cl}$ to ${\left({\text{CH}}_{\text{3}}\right)}_2\text{CHCl}$ for the ${\text{S}}_{\text{N}}2$ reaction of ${\text{CH}}_{\text{3}}\text{Cl}$ should be predicted.

Concept introduction:Bimolecular substitution or ${\text{S}}_{\text{N}}2$ proceeds via single-step mechanism. Thus, it is well known as concerted mechanism. Nucleophile approaches carbon while the leaving group still departs from the rear side (opposite to leaving group). The transition state only illustrates the geometric orientation of the substrates and reagents as they pass through the maxima in the single-step mechanism.

(d)

Interpretation Introduction

Interpretation:Effect of change of solvent from ${\text{CH}}_{\text{3}}\text{OH}$ to ${\left({\text{CH}}_{\text{3}}\right)}_2\text{SO}$ for the ${\text{S}}_{\text{N}}2$ reaction of ${\text{CH}}_{\text{3}}\text{Cl}$ should be predicted.

Concept introduction: Bimolecular substitution or ${\text{S}}_{\text{N}}2$ proceeds via single -step mechanism. Thus, it is well known as concerted mechanism. Nucleophile approaches carbon while the leaving group still departs from the rear side (opposite to leaving group). The transition state only illustrates the geometric orientation of the substrates and reagents as they pass through the maxima in the single-step mechanism.