Q.(a) Arrange the following compounds in decreasing order of their boiling point values: Ethanol, Propan-1-ol, Pentan-1-ol, Butan-1-ol and Butan-2-ol.

In Williamson ether synthesis, an alkyl halide is treated with a sodium alkoxide (or sodium phenoxide). The alkoxide ion acts as a nucleophile and displaces the halide by an $S_N2$ reaction, forming the ether: …

Williamson synthesis is one of the most reliable methods for making ethers, especially unsymmetrical ones. The key insight is that you need to control which carbon gets the oxygen — and that control comes from the reaction mechanism itself.

The reaction works by treating an alcohol with a strong base (like NaH or Na metal) to generate an alkoxide ion. This alkoxide is a strong nucleophile. You then add an alkyl halide (or tosylate), and the alkoxide attacks the electrophilic carbon of the alkyl halide, displacing the halide ion.

Why does this have to be $S_N2$? Because the alkoxide is a strong base and a good nucleophile, and the alkyl halide is typically primary (to avoid elimination side reactions). The reaction proceeds through a single step — backside attack with inversion of configuration — which is the hallmark of $S_N2$.

Let's walk through the reasoning step by step.

1. Identify the reactants and products. In Williamson synthesis, you have:

The oxygen from the alkoxide ends up bonded to the carbon that originally held the halogen. This is a substitution — the halide is replaced by the alkoxide.

2. Consider the mechanism.

   The alkoxide ion is negatively charged and electron-rich. It attacks the carbon bearing the halogen, which is partially positive due to the electronegativity of the halogen. This attack happens from the opposite side of the leaving group, in a single concerted step. There is no carbocation intermediate.

3. Rule out $S_N1$.

   $S_N1$ reactions proceed through a carbocation intermediate. In Williamson synthesis, if you use a secondary or tertiary alkyl halide, elimination (forming an alkene) becomes a major side reaction. The method works best with primary alkyl halides, where $S_N2$ is favoured and $S_N1$ is essentially impossible (primary carbocations are too unstable).

4. Rule out electrophilic addition.

   Electrophilic addition involves adding something across a double bond. There is no double bond in the reactants here — just an alkoxide and an alkyl halide. This mechanism is irrelevant.

5. Rule out elimination. …

The question describes a fundamental reaction in organic chemistry for synthesizing ethers. To understand why a specific name is associated with it, we need to break down the roles of the reactants and the type of transformation occurring.

Concept and Intuition: Nucleophilic Substitution for Ether Formation

Ethers have the general structure $R-O-R'$, where $R$ and $R'$ are alkyl or aryl groups. To form an ether, we need to create a new carbon-oxygen bond. One very effective way to do this is through a nucleophilic substitution reaction.

Imagine an alkyl halide, $R-X$, where $X$ is a good leaving group (like $\text{Cl}$, $\text{Br}$, $\text{I}$). The carbon atom bonded to the halogen is partially positive ($\delta^+$) because the halogen is electronegative. This makes the carbon an electrophilic center, meaning it's susceptible to attack by electron-rich species.

Now consider a sodium alkoxide, $R'-O^- Na^+$. The alkoxide ion ($R'-O^-$) is a strong nucleophile because the oxygen atom carries a full negative charge and has lone pairs of electrons available to donate. It's also a strong base.

When these two species meet, the nucleophilic alkoxide oxygen attacks the electrophilic carbon of the alkyl halide, displacing the halide ion. This is a classic $S_N2$ (bimolecular nucleophilic substitution) pathway, leading directly to the formation of an ether.

Step-by-Step Explanation

1. Identify the Reactants and Product:

   • Alkyl halide: An organic compound with a halogen atom ($X$) bonded to an alkyl group ($R$). General formula: $R-X$.
   • Sodium alkoxide: A salt formed from an alcohol and sodium, containing an alkoxide ion ($R'-O^-$) and a sodium cation ($Na^+$). General formula: $R'-O^- Na^+$.
   • Ether: An organic compound with an oxygen atom bonded to two alkyl or aryl groups. General formula: $R-O-R'$.

2. Role of Reactants:

   • The alkoxide ion ($R'-O^-$) acts as a strong nucleophile, seeking an electron-deficient center.
   • The alkyl halide ($R-X$) acts as an electrophile, with the carbon atom bonded to the halogen being the site of nucleophilic attack. The halogen ($X$) serves as a good leaving group.

3. Mechanism of Reaction:

   The reaction proceeds via an $S_N2$ mechanism. The alkoxide nucleophile attacks the carbon atom bearing the halogen from the backside, simultaneously displacing the halide ion. This is a concerted, one-step process.

For example, if we react bromoethane with sodium methoxide:

(Bromoethane) + (Sodium methoxide) $\longrightarrow$ (Ethyl methyl ether) + (Sodium bromide) …