Chapter 8, Problem 8.47SP

(a)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The conversion of an alkene into an alkyl borane is done by ${\text{BH}}_{\text{3}}/\text{THF}$. Oxidation of alkyl borane in the presence of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}/{\text{OH}}^{-}$ leads to the formation of an alcohol through syn addition (anti-Markonikov’s rule).

(b)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The $\text{MCPBA}$ reagent is an important oxidising agent, used for the synthesis of epoxide. The synthesis of an epoxide is done by the reaction of an alkene with $\text{MCPBA}$ reagent.

(c)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The reaction of an alkene with ozone leads to the formation of a cyclic compound called molozonide or primary ozonide. The molozonide consist of two peroxy linkage which is quite unstable. It rearranges rapidly, at low temperature and forms an ozonide. These ozonides are often unstable. They react with reducing agent like zinc or dimethyl sulphide and forms aldehydes/ketones as oxidative cleavage product.

(d)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: Osmium tetraoxide or osmic acid with ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ is preferably used for syn dihydroxylation of alkenes. The mechanism proceeds through formation of osmate ester followed by hydrolysis of osmate ester by ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$. Hydrogen peroxide also re-oxidizes osmium to osmium tetra oxide to continue the dihydroxylation process.

(e)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The oxidative cleavage of an alkene by hot concentrated ${\text{KMnO}}_{\text{4}}$, produces ketones and carboxylic acid.

(f)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: A solution of peroxyacetic acid in water is preferably used for anti dihydroxylation of alkenes. The mechanism proceeds through formation of epoxide followed by of anti addition of diol through hydrolysis. The further sulphuric acid catalyzed reaction converts these alcohols into respective alkenes.

(g)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The hydrogenation of an alkene is done by ${\text{H}}_{\text{2}}$ in the presence of metal catalyst like nickel, palladium or platinum.

(h)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The reaction of an alkene with $\text{HBr}$ is an example of electrophilic addition reaction which results addition of bromine and hydrogen through Markonikov orientation.

(i)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The reaction of an alkene with $\text{HBr}$ is an example of electrophilic addition reaction which results addition of bromine and hydrogen through Markonikov orientation.

(j)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The reaction of bromine in the presence of water with an alkene results Markonikov orientation, anti-stereochemistry and no rearrangement.

(k)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The halogenation reaction of an alkene with chlorine results anti-stereochemistry addition of chlorine.

(l)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The reaction of an alkene with $\text{Hg}{\left(\text{OAc}\right)}_2,\text{MeOH}$ and ${\text{NaBH}}_{\text{4}}$ is an example of oxymercuration-demercuration reaction. This reaction works through Markonikov orientation.

(m)

Interpretation Introduction

To determine: The structure of the expected product when limonene reacts with the given reagent in excess amount.

Interpretation: The structure of the expected product when limonene reacts with the given reagent in excess amount is to be stated.

Concept introduction: The mixture of ${\text{CHBr}}_{\text{3}}$ and and $50\%\text{aq}\text{NaOH}$ results dibromo carbine with removal of sodium bromide and water. The dibromo carbene reacts with alkene and forms cyclopropane ring through alpha elimination.