Chapter 11, Problem 11.60AP

Interpretation Introduction

(a)

Interpretation:

The given reaction is to be completed with principal organic products.

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 group by attacking the electron-deficient carbon atom.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

${\text{CH}}_{\text{3}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}-\text{Br}+{\text{Na}}^{+}{\text{EtO}}^{-}\underset{\text{EtOH}}{\to }$

The oxygen atom of sodium ethoxide can act as a nucleophile and attack the carbon atom of ${\text{CH}}_{\text{3}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}-\text{Br}$ which is attached to electronegative bromine atom to form an ether. The corresponding chemical reaction is shown below.

Figure 1

Conclusion

The completed given reaction is shown in Figure 1.

Interpretation Introduction

(b)

Interpretation:

The given reaction is to be completed with principal organic products.

Concept introduction:

Substitution reaction is a type of reaction in which an atom or group of atoms is replaced or substituted by another atom or group of atoms. An elimination reaction is a type of reaction in which two atoms are eliminated in the presence of solvent. Elimination reactions are usually favored in the alcoholic conditions.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 2

The given alkyl halide is a tertiary alkyl halide and the base involved in the reaction also have tertiary alkyl group in it. Therefore, a $\beta \text{-}$ elimination reaction is favored over substitution reaction. The alkyl halide has two different $\beta$ carbon atoms in it. Therefore, two different alkenes will be formed in the reaction. The corresponding chemical reaction is shown below.

Figure 3

Conclusion

The completed given reaction is shown in Figure 3.

Interpretation Introduction

(c)

Interpretation:

The given reaction is to be completed with principal organic products.

Concept introduction:

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

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 4

The mercuric acetate $\text{Hg}{\left(\text{OAc}\right)}_{\text{2}}$ in ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CH}-\text{OH}$ solvent reacts with the alkene to form an 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 ether due to the use of ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CH}-\text{OH}$ as solvent.

The corresponding chemical reaction is shown below.

Figure 5

Conclusion

The completed given reaction is shown in Figure 5.

Interpretation Introduction

(d)

Interpretation:

The given reaction is to be completed with principal organic products. The stereochemistry of the product is to be predicted.

Concept introduction:

An epoxide is cyclic ether. It can be prepared by the reaction of alkene with percarboxylic acid with removal of carboxylic acid. An epoxide undergoes ring opening reactions with an acid to give a product with inversion of configuration.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 6

The alkene attacks on the peroxide linkage of the given percarboxylic acid to form an epoixde ring with elimination of carboxylic acid. The oxygen atom of the epoxide will be pointed inwards that is into the plane of the molecule. The corresponding chemical reaction is shown below.

Figure 7

Conclusion

The completed given reaction is shown in Figure 7.

Interpretation Introduction

(e)

Interpretation:

The given reaction is to be completed with principal organic products.

Concept introduction:

The addition of one or more than one halogen atom in an alkene is known as halogenation reaction. The pathway of the halogenation reaction depends on the structure of the substrate. In this, the halogen is added to $\text{C}=\text{C}$ bond of the alkene to form haloalkane.

The compound chromium $\left(\text{III}\right)$ oxide ${\text{CrO}}_{\text{3}}$ is good oxidizing agent. It can convert alcohol into aldehyde or ketone.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

${\text{H}}_{\text{3}}\text{C}-\text{CH}={\text{CH}}_{\text{2}}+{\text{H}}_{\text{2}}\text{O}+{\text{Br}}_{\text{2}}\to \underset{\text{pyridine}}{\overset{{\text{CrO}}_{\text{3}}}{\to }}$

The propene molecule undergoes halohydrin reaction with bromine gas in the presence of water molecule to form bromine substituted alcohol. The alcohol gets oxidized by ${\text{CrO}}_{\text{3}}$ into a ketone. The corresponding chemical reaction is shown below.

Figure 8

Conclusion

The completed given reaction is shown in Figure 8.

Interpretation Introduction

(f)

Interpretation:

The given reaction is to be completed with principal organic products.

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.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 9

The epoxide is converted into gem diol after the addition of water in it. The gem diol gets converted into two different aldehydes after breaking the bond between carbon atoms attached to the hydroxyl group. The corresponding chemical reaction is shown below.

Figure 10

Conclusion

The completed given reaction is shown in Figure 10.

Interpretation Introduction

(g)

Interpretation:

The given reaction is to be completed with principal organic products. The stereochemistry of the product is to be predicted.

Concept introduction:

Potassium permanganate is a strong oxidizing agent. Potassium permanganate can oxidize an alkene into alcohol. It can also oxidize an alcohol into carbonyl compound and the carbonyl compound can be further oxidized to form a carboxylic acid.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 11

The oleic acid reacts with alkaline ${\text{KMnO}}_{\text{4}}$ in the presence of base to form gem diol. The potassium permangent is a good oxidizing agent. It can convert an alkene part into diol. The corresponding chemical reaction is shown below.

Figure 12

Conclusion

The completed given reaction is shown in Figure 12.

Interpretation Introduction

(h)

Interpretation:

The given reaction is to be completed with principal organic products. The stereochemistry of the product is to be predicted.

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 basic or neutral, then the reaction will occur at the less substituted carbon atom.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 13

The compound epoxide undergoes ring-opening reaction in the presence of sodium azide. The azide ion acts a nucleophile and attacks on the carbon atom of the epoxide ring to from final compound. The corresponding chemical reaction is shown below.

Figure 14

Conclusion

The completed given reaction is shown in Figure 14.

Interpretation Introduction

(i)

Interpretation:

The given reaction is to be completed with principal organic products.

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 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 15

The ether 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 form final product. The corresponding chemical reaction is shown below.

Figure 16

Conclusion

The completed given reaction is shown in Figure 16.

Interpretation Introduction

(j)

Interpretation:

The given reaction is to be completed with principal organic products.

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 group by attacking the electron-deficient carbon atom.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

${\text{ClCH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}\text{Cl}+{\text{Na}}_{\text{2}}\text{S}\underset{\begin{array}{l}\text{DMF}\\ \left(\begin{array}{l}\text{a polar aprotic}\\ \text{ solvent}\end{array}\right)\end{array}}{\to }{\text{a compound with the formula C}}_4{\text{H}}_8\text{S}$

The compound ${\text{ClCH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}\text{Cl}$ undergoes nucleophilic substitution reaction to replace one chloro group with nucleophile ${\text{S}}^{2-}$. Another chloro group is removed to form a cyclic compound with formula ${\text{C}}_4{\text{H}}_8\text{S}$. The corresponding chemical reaction is shown below.

Figure 17

Conclusion

The completed given reaction is shown in Figure 17.

Interpretation Introduction

(k)

Interpretation:

The given reaction is to be completed with principal organic products.

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 group by attacking on the electron-deficient carbon atom.

Answer to Problem 11.60AP

The completed given reaction is shown below.

Explanation of Solution

The incomplete given reaction is shown below.

Figure 18

The replacement of the hydroxyl group is not easy. Therefore, alcohol is first converted into tosylate ester with the help of tosyl chloride. The tosylate ester group is then substituted with ${}^{-}\text{OH}$ group. The corresponding chemical reaction is shown below.

Figure 19

Conclusion

The completed given reaction is shown in Figure 19.