Chapter 10, Problem 10.31P

(a)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidation of primary alcohol to carboxylic acid: A primary alcohol is oxidized to a carboxylic acid by chromic acid. The mechanism involves initial formation of an alkyl chromate intermediate, followed by reaction with base to remove a proton, generating the carbonyl group of an aldehyde and simultaneously reducing the chromium (VI) to chromium (IV). An initially formed aldehyde adds water, generating an aldehyde hydrate, which is oxidized according to the same mechanism to give the carboxylic acid.

(b)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Reaction with$SOC{l}_2$: Alcohols react with $SOC{l}_2$ it initially give an alkyl chlorosulfite intermediate, which is displaced from the backside by chloride ion to give the chloroalkane.

(c)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Reaction with$HBr,HI,andHCl$: Alcohols react with $\text{HBr,}\text{HI,}\text{and}\text{HCl}$ by ${\text{S}}_{\text{N}}\text{2}$ mechanism. The strong acid protonate $\text{-OH}$ alcohol group, converting to good leaving group, setting up either ${\text{S}}_{\text{N}}\text{2}$ or ${\text{S}}_{\text{N}}1$ reactions; tertiary alcohols react by ${\text{S}}_{\text{N}}1$ mechanism with formation of carbocation intermediate.

Secondary alcohols may react by ${\text{S}}_{\text{N}}\text{2}$ or ${\text{S}}_{\text{N}}1$, depending on experimental conditions and the alcohol. Primary beta-branching react by ${\text{S}}_{\text{N}}1$ involving formation of a rearrangement carbocation.

(d)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Reaction with$HBr,HI,andHCl$: Alcohols react with $\text{HBr,}\text{HI,}\text{and}\text{HCl}$ by ${\text{S}}_{\text{N}}\text{2}$ mechanism. The strong acid protonate $\text{-OH}$ alcohol group, converting to good leaving group, setting up either ${\text{S}}_{\text{N}}\text{2}$ or ${\text{S}}_{\text{N}}1$ reactions; tertiary alcohols react by ${\text{S}}_{\text{N}}1$ mechanism with formation of carbocation intermediate.

Secondary alcohols may react by ${\text{S}}_{\text{N}}\text{2}$ or ${\text{S}}_{\text{N}}1$, depending on experimental conditions and the alcohol. Primary beta-branching react by ${\text{S}}_{\text{N}}1$ involving formation of a rearrangement carbocation.

(e)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidation of primary alcohol to carboxylic acid: A primary alcohol is oxidized to a carboxylic acid by chromic acid. The mechanism involves initial formation of an alkyl chromate intermediate, followed by reaction with base to remove a proton, generating the carbonyl group of an aldehyde and simultaneously reducing the chromium (VI) to chromium (IV). An initially formed aldehyde adds water, generating an aldehyde hydrate, which is oxidized according to the same mechanism to give the carboxylic acid.

(f)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidative cleavage of a glycol: ${\text{HIO}}_4$ react with glycol to form a five-membered cyclic periodate intermediate that undergoes carbon-carbon bond cleavage to form two carbonyl groups.

(g)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidative cleavage of a glycol: ${\text{HIO}}_4$ react with glycol to form a five-membered cyclic periodate intermediate that undergoes carbon-carbon bond cleavage to form two carbonyl groups.

(h)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Reaction with$SOC{l}_2$: Alcohols react with $SOC{l}_2$ it initially give an alkyl chlorosulfite intermediate, which is displaced from the backside by chloride ion to give the chloroalkane.

(i)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidation of primary alcohol to an aldehyde: The oxidation of a primary alcohol to an aldehyde can be carried out using pyridinium chlorochromate (PCC). Because there is no water, the aldehyde does not form the hydrate, and the oxidation reaction stops at the aldehyde stage. Alternatively, Swern or Dess-martin oxidation can be used.

(j)

Interpretation Introduction

Interpretation:

The major product of each of the given reaction has to be drawn.

Concept Introduction:

Oxidation of primary alcohol to an aldehyde: The oxidation of a primary alcohol to an aldehyde can be carried out using pyridinium chlorochromate (PCC). Because there is no water, the aldehyde does not form the hydrate, and the oxidation reaction stops at the aldehyde stage. Alternatively, Swern or Dess-martin oxidation can be used.