Alcohol Phenol And Ethers

11.43

The driving force of all the reactions given to the question is that the alkoxy group is an ortho and para directing group because it exerts its +R effect in the benzene ring. Para position being comparatively more stable than the ortho position is usually preferred because ortho position leads to stearic hindrance, hence the major product is mostly the para- substituted compound.

As seen from the resonating structures above the structure in which the negative charge is in the para position will form a more stable product when attacked by an electrophile. Hence in the following reactions, we will be considering that resonating structure as the starting material.

The mechanism is given below:

2- The driving force of all the reactions given to the question is that the alkoxy group is an ortho and para directing group because it exerts its +R effect in the benzene ring. Para position being comparatively more stable than the ortho position is usually preferred because ortho position leads to stearic hindrance, hence the major product is mostly the para-substituted

As seen from the resonating structures above the structure in which the negative charge is in the para position will form a more stable product when attacked by an electrophile. Hence in the following reactions, we will be considering that resonating structure as the starting material.

Nitration of anisole gives p-nitroanisole as the major product.

The mechanism is given below:

3- The driving force of all the reactions given to the question is that the alkoxy group is an ortho and para directing group because it exerts its +R effect in the benzene ring. Para position being comparatively more stable than the ortho position is usually preferred because ortho position leads to stearic hindrance, hence the major product is mostly the para-substituted

As seen from the resonating structures above the structure in which the negative charge is in the para position will form a more stable product when attacked by an electrophile. Hence in the following reactions, we will be considering that resonating structure as the starting material.

Bromination of anisole in ethanoic acid medium gives p-bromoanisole as the major product.

4-The driving force of all the reactions given to the question is that the alkoxy group is an ortho and para directing group because it exerts its +R effect in the benzene ring. Para position being
comparatively more stable than the ortho position is usually preferred because ortho position leads to stearic hindrance, hence the major product is mostly the para-substituted compound.

As seen from the resonating structures above the structure in which the negative charge is in the para position will form a more stable product when attacked by an electrophile. Hence in the following reactions, we will be considering that resonating structure as the starting material.

The Friedel-Craft's acetylation of anisole gives 4- methoxyacetophenone as the major product

The mechanism is given below:

11.42 

The reaction of HI with methoxymethane yields two different sets of products depending upon the initial amount of HI taken.

(i) When equal moles of HI and methoxymethane are taken, a mixture of methyl alcohol and methyl iodide is

The mechanism is given below:

In the first step, methoxymethane reacts with hydrogen iodide to extract a proton to give the dimethyloxonium ion.

In the second step of the reaction, the Dimethyloxonium ion reacts with the iodide ion present to yield methyl iodide and methyl alcohol as the product via SN² pathway.

(ii) If an excess of HI is used the methyl alcohol formed in Step II is also converted into methyl iodide by the following mechanism : -

In the first step, methoxymethane reacts with hydrogen iodide to extract a proton to give the dimethyloxonium ion.

In the second step of the reaction the Dimethyloxonium ion reacts with the iodide ion present to yield methyl iodide and methyl alcohol as the product via SN2 pathway.

In the third step of the reaction Methyl alcohol formed above reacts with hydrogen iodide to extract a proton to give the protonated methyl alcohol which finally reacts in the fourth step with the iodide ion via SN² pathway to give methyl iodide and water as the product.

11.41

(i) In aryl alkyl ethers the +R effect of the alkoxy group leads to an increase in the electron density of the benzene ring as they push electrons into the ring making the benzene ring activated towards electrophilic substitution reactions. This could be understood more clearly from the following resonating structures : -

(ii) It could be clearly seen from the above resonating structures that the electron density increases more at the ortho and para positions as compared to the meta positions. Hence, we can conclude that the alkoxy group directs the incoming substituents to ortho and para positions in the benzene ring.

For example –

11.39 

The preparation of ether by acid dehydration of primary alcohol involves the nucleophilic addition of alcohol molecule to the protonated alcohol molecule as shown below: -

However, under these conditions secondary and tertiary alcohols forms alkenes rather than ethers. The reason for this being that due to stearic hindrance, nucleophilic attack by the alcohol molecule on the protonated alcohol molecule does not take place. Instead protonated 2⁰ and 3⁰ alcohols lose a molecule of water to form stable carbocations. The stable carbocations so formed prefers to lose a proton to form alkenes instead of forming ethers by undergoing nucleophilic attack by another alcohol molecule. This could be seen clearly from the following reactions : -

11.36 

During the reaction, an alkoxide ion is formed which is then added to an alkyl halide to form the ether via S_N2 mechanism.

In the primary step, the nucleophile is formed (O^- ) which will the approach to the alkyl halide and after the transition stage, the substitution takes place.

During the reaction, an alkoxide ion is formed which is then added to an alkyl halide to form the ether via S_N2 mechanism.

During the reaction, an alkoxide ion is formed which is then added to an alkyl halide to form the ether via S_N2 mechanism.

During the reaction, an alkoxide ion is formed which is then added to an alkyl halide to form the ether via S_N2 mechanism.