Chapter 11, Problem 11.45AP

Interpretation Introduction

(a)

Interpretation:

The product of the reaction of dibutyl sulfide with $1$ equivalent of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ at $\text{25 °C}$ is to be predicated.

Concept introduction:

Hydrogen perioxide $\left({\text{H}}_{\text{2}}{\text{O}}_{\text{2}}\right)$ is an strong oxidizing agent. It is used in many organic synthese to produced oxidized products.

Sulfur containing organic compounds has many similar chemical properties as oxygen contain compound such as ether and aclcohol.

Answer to Problem 11.45AP

The product of the reaction of dibutyl sulfide with $1$ equivalent of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ at $\text{25 °C}$ is shown below.

Explanation of Solution

The dibutyl sulfide undergoes an oxidation reaction with hydrogen peroxide. The dibutyl sulfide reacts with $1$ equivalent of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ at $\text{25 °C}$ to form a oxidation product dibutyl sulfoxide.

The corresponding chemical reaction is shown below.

Figure 1

Conclusion

The product of the reaction of dibutyl sulfide with $1$ equivalent of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ at $\text{25 °C}$ is shown in Figure 1.

Interpretation Introduction

(b)

Interpretation:

The product of the reaction of dibutyl sulfide with $2$ or more equivalents of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ and heat is to be predicated.

Concept introduction:

Hydrogen perioxide $\left({\text{H}}_{\text{2}}{\text{O}}_{\text{2}}\right)$ is an strong oxidizing agent. It is used in many organic synthese to produced oxidized products.

Sulfur containing organic compounds has many similar chemical properties as oxygen contain compound such as ether and aclcohol.

Answer to Problem 11.45AP

The product of the reaction of dibutyl sulfide with $2$ or more equivalents of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ and heat shown below.

Explanation of Solution

The dibutyl sulfide undergoes an oxidation reaction with hydrogen peroxide. The dibutyl sulfide reacts with ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ to form a oxidation product dibutyl sulfoxide. The dibutyl sulfoxide further oxides to form dibutyl sulfone.

The corresponding chemical reaction is shown below.

Figure 2

Conclusion

The product of the reaction of dibutyl sulfide with $2$ or more equivalents of ${\text{H}}_{\text{2}}{\text{O}}_{\text{2}}$ and heat shown in Figure 2.

Interpretation Introduction

(c)

Interpretation:

The product of the reaction of $cis\text{-3-hexene}$ with magnesium monoperoxyphthalate $\left(\text{MMPP}\right)$ is to be predicated.

Concept introduction:

The magnesium monoperoxyphthalate $\left(\text{MMPP}\right)$ is an strong oxidizing agent. It is used in many organic synthese to produced oxidized products. It can oxides alkene to from epoxide. The magnesium monoperoxyphthalate can be used to synthese ester from. Ketone.

Answer to Problem 11.45AP

The product of the reaction of $cis\text{-3-hexene}$ with magnesium monoperoxyphthalate $\left(\text{MMPP}\right)$ is shown below.

Explanation of Solution

The compound $cis\text{-3-hexene}$ undergoes a oxidation reaction with magnesium monoperoxyphthalate $\left(\text{MMPP}\right)$. The magnesium monoperoxyphthalate coverts the alkene into epoxide.

The corresponding chemical reaction is shown below.

Figure 3

Conclusion

The product of the reaction of $cis\text{-3-hexene}$ with magnesium monoperoxyphthalate $\left(\text{MMPP}\right)$ is shown in Figure 3.

Interpretation Introduction

(d)

Interpretation:

The product of the reaction of given compound with ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}{\text{CuCNLi}}_{\text{2}}$ followed by the addition of ${\text{H}}_{\text{3}}{\text{O}}^{+}$ is to be predicated.

Concept introduction:

Epoxides undergo nucleophilic ring-opening reactions which are acid-catalyzed. If the epoxide is unsymmetrical, then the anionic nucleophile will attack the less-hindered carbon atom of the ring. If the reaction conditions are acidic, then the reaction will occur at the more substituted carbon atom.

Answer to Problem 11.45AP

The product of the reaction of given compound with ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}{\text{CuCNLi}}_{\text{2}}$ followed by the addition of ${\text{H}}_{\text{3}}{\text{O}}^{+}$ is shown below.

Explanation of Solution

The epoxide undergoes ring-opening reaction in the presence of acid. The dilithium dimethylcyanocuprate molecule generates a nucleophile $\left({}^{-}{\text{CH}}_{\text{3}}\right)$. This nucleophile will attack the more substituted carbon atom of the epoxide ring to from the product. The corresponding chemical reaction is shown below.

Figure 4

Conclusion

The product of the reaction of given compound with ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}{\text{CuCNLi}}_{\text{2}}$ followed by the addition of ${\text{H}}_{\text{3}}{\text{O}}^{+}$ is shown in Figure 4.

Interpretation Introduction

(e)

Interpretation:

The product of the reaction of given compound with solvent ${\text{H}}_{\text{2}}\text{O}$ in acidic solution is to be predicated.

Concept introduction:

Epoxides undergo nucleophilic ring-opening reactions which are acid-catalyzed. If the epoxide is unsymmetrical, then the anionic nucleophile will attack the less-hindered carbon atom of the ring. If the reaction conditions are acidic, then the reaction will occur at the more substituted carbon atom.

Answer to Problem 11.45AP

The product of the reaction of given compound with solvent ${\text{H}}_{\text{2}}\text{O}$ in acidic solution is shown below.

Explanation of Solution

The epoxide undergoes ring opening reaction in the presence of acid. The water molecule acts a nucleophile and attacks on the more substituted carbon atom of the epoxide ring to from diol. The corresponding chemical reaction is shown below.

Figure 5

Conclusion

The product of the reaction of given compound with solvent ${\text{H}}_{\text{2}}\text{O}$ in acidic solution is shown in Figure 5.

Interpretation Introduction

(f)

Interpretation:

The product of the reaction of given compound with periodic acid is to be predicated.

Concept introduction:

The periodic acid acts as a strong oxidizing agent. The periodic acid reacts with a vicinal diol to form two aldehyde after breaking the carbon-carbon bond between the vicinal diol. The gem diol does not react with periodic acid as vicinal diol reacts.

Answer to Problem 11.45AP

The product of the reaction of given compound with periodic acid is shown below.

Explanation of Solution

The given compound is vicinal diol. It reacts with periodic acid to form two aldehydes. The carbon-carbon bond between the carbon atoms attached to two adjacent hydroxyl groups gets breaks. The corresponding chemical reaction is shown below.

Figure 6

Conclusion

The product of the reaction of given compound with periodic acid is shown in Figure 6.

Interpretation Introduction

(g)

Interpretation:

The product of the reaction of given compound with $\text{NaH}$ in $\text{THF}$ followed by ${\text{CH}}_{\text{3}}\text{I}$ is to be predicated.

Concept introduction:

The metal hydride reagents are good reducing agents such as $\text{NaH}$. Sodium hydride is used in many organic syntheses as a reducing agent. Sodium hydride can also be used as a base in the organic syntheses reactions. It abstracts the acidic proton from the organic compounds.

Answer to Problem 11.45AP

The product of the reaction of given compound with $\text{NaH}$ in $\text{THF}$ followed by ${\text{CH}}_{\text{3}}\text{I}$ is shown below.

Explanation of Solution

The base $\text{NaH}$ abstract the proton of the hydroxyl group of alcohol to form an anion. The anion acts as nucleophile and attacks on the carbon atom of ${\text{CH}}_{\text{3}}\text{I}$. The corresponding chemical reaction is shown below.

Figure 7

Conclusion

The product of the reaction of given compound with $\text{NaH}$ in $\text{THF}$ followed by ${\text{CH}}_{\text{3}}\text{I}$ is shown in Figure 7.

Interpretation Introduction

(h)

Interpretation:

The product of the reaction of $\left(E\right)\text{-3-methyl-3-hexene}$ with $\text{Hg}{\left(\text{OAc}\right)}_{\text{2}}$ in ethanol solvent followed by ${\text{NaBH}}_{\text{4}}$ is to be predicated.

Concept introduction:

Oxymercuration reaction is a type of reaction in which an alkene get converted into an alcohol. The mercuric acetate is used in the reaction as reagent. This reagent attacks the alkene to form a cyclic intermediate compound which further undergoes reduction to form alcohol.

Answer to Problem 11.45AP

The product of the reaction of $\left(E\right)\text{-3-methyl-3-hexene}$ with $\text{Hg}{\left(\text{OAc}\right)}_{\text{2}}$ in ethanol solvent followed by ${\text{NaBH}}_{\text{4}}$ is shown below.

Explanation of Solution

The mercuric acetate $\text{Hg}{\left(\text{OAc}\right)}_{\text{2}}$ in ethanol solvent reacts with $\left(E\right)\text{-3-methyl-3-hexene}$ to from a intermediate product which is reduced by the addition of ${\text{NaBH}}_{\text{4}}$ in the reaction mixture. The end product formed in the reaction is an ether due to the use of ethanol as solvent.

The corresponding chemical reaction is shown below.

Figure 8

Conclusion

The product of the reaction of $\left(E\right)\text{-3-methyl-3-hexene}$ with $\text{Hg}{\left(\text{OAc}\right)}_{\text{2}}$ in ethanol solvent followed by ${\text{NaBH}}_{\text{4}}$ is shown in Figure 8.

Interpretation Introduction

(i)

Interpretation:

The product of the reaction of the given compound with acidic methanol is to be predicated.

Concept introduction:

The replacement or substitution of one functional group with another different functional group in any chemical reaction is termed as a substitution reaction. In a nucleophilic substitution reaction, nucleophile takes the position of leaving the group by attacking the electron-deficient carbon atom.

Answer to Problem 11.45AP

The product of the reaction of the given compound with acidic methanol is shown below.

Explanation of Solution

The proton of the acid will protionate the ether. The protonated ether will increase the electrophilic characters of carbon atom attached to the oxygen atom. The methonal can acts as nuclephile, however the nucleophilic charater of methoxy-group and ethoxy group is similar. Therefore, no further reaction will take place.

The corresponding chemical reaction is shown below.

Figure 9

Conclusion

The product of the reaction of the given compound with acidic methanol is shown in Figure 9.

Interpretation Introduction

(j)

Interpretation:

The product of the reaction of $\left(R\right)\text{-3-Methyl-1-bromopentane}$ with $\text{Mg}$ in ether followed by addition of ethylene oxide, then with ${\text{CH}}_{\text{3}}\text{I}$ is to be predicated.

Concept introduction:

Grignard reagents are organometallic compounds which are prepared using alkyl halides in the presence of magnesium metal in dry ether. These reagents act as strong nucleophiles and bases. Grignard reagents react with carbonyl compounds to form alcohol.

Answer to Problem 11.45AP

The product of the reaction of $\left(R\right)\text{-3-Methyl-1-bromopentane}$ with $\text{Mg}$ in ether followed by addition of ethylene oxide, then with ${\text{CH}}_{\text{3}}\text{I}$ is shown below.

Explanation of Solution

The alkyl halide will react with magnisum metal to from gridnard reagent. These Grignard reagent reacts with epoixde to form alcohol. The alcohol reacts with ${\text{CH}}_{\text{3}}\text{I}$ to form ether.

The corresponding chemical reaction is shown below.

Figure 10

Conclusion

The product of the reaction of $\left(R\right)\text{-3-Methyl-1-bromopentane}$ with $\text{Mg}$ in ether followed by addition of ethylene oxide, then with ${\text{CH}}_{\text{3}}\text{I}$ is shown in Figure 10.