Chapter 18, Problem 18.70AP

Interpretation Introduction

(a)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

The complete reaction is shown below.

The reaction occurs by the nucleophilic substitution reaction mechanism in which ethanethiolate is substituted and fluoride ion is eliminated.

Explanation of Solution

The reaction to be completed is shown below.

Figure 1

Nucleophilic substitution reaction takes place between $\text{1-fluoro-4-nitobenzene}$ and ethanethiolate to yield $\text{ethyl}\left(\text{4-nitrophenyl}\right)\text{sulfane}$. Fluoride ion is a good leaving group.

The complete reaction is shown below.

Figure 2

Conclusion

The complete reaction is shown in Figure 2.

Interpretation Introduction

(b)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 3

The nucleophilic substitution reaction takes place when $\text{2-chloro-1, 3, 5-trinitrobenzene}$ reacts with a base in acidic medium to yield picric acid.

The complete reaction is shown below.

Figure 4

Conclusion

The complete reaction is shown in Figure 4.

Interpretation Introduction

(c)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

When a base reacts with a compound, it abstracts a proton from the compound.

Catalytic hydrogenation is a reduction process of addition of hydrogen atoms in an alkene or an alkyne by using a metal catalyst. The number of bonds is reduced between carbon atoms.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 5

The hydrogen ion is abstracted from $\text{4-ethylphenol}$ by base $\text{NaOH}$ to produce $\text{4-ethylphenolate}$. The compound formed, $\text{4-ethylphenolate}$ reacts with dimethylsulfate to produce $\text{1-ethyl-4-methoxybenzene}$ which is reduced to $\text{1-ethyl-4-methylcyclohexane}$ on reaction with hydrogen in the presence of a catalyst.

The complete reaction is shown below.

Figure 6

Conclusion

The complete reaction is shown in Figure 6.

Interpretation Introduction

(d)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

No reaction takes place when chlorobenzene reacts with propylamine at $25°\text{C}$.

Explanation of Solution

The reaction to be completed is shown below.

Figure 7

No reaction takes place when chlorobenzene reacts with propylamine at $25°\text{C}$. The nucleophile, ${\text{NH}}_2{}^{-}$, displaces chloride ion only at higher temperatures.

Figure 8

Conclusion

No reaction takes place when chlorobenzene reacts with propylamine at $25°\text{C}$.

Interpretation Introduction

(e)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Suzuki coupling reaction is a cross-coupling reaction in which boronic acid reacts with alkyl, aryl, and vinyl halides in presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ catalyst to yield biphenyls, styrenes, and polyolefins.

Answer to Problem 18.70AP

No reaction takes place when boronic acid reacts with $\text{1-}\left(\text{pyridin-2-yl}\right)\text{ethanone}$.

Explanation of Solution

The reaction to be completed is shown below.

Figure 9

No reaction takes place when boronic acid reacts with $\text{1-}\left(\text{pyridin-2-yl}\right)\text{ethanone}$ as boronic acids reacts only with alkyl, aryl, and vinyl halides in presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ catalyst.

Figure 10

Conclusion

No reaction takes place when boronic acid reacts with $\text{1-}\left(\text{pyridin-2-yl}\right)\text{ethanone}$.

Interpretation Introduction

(f)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Suzuki coupling reaction is a cross-coupling reaction in which boronic acid reacts with alkyl, aryl, and vinyl halides in presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ catalyst to yield biphenyls, styrenes, and polyolefins.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 11

Suzuki coupling reaction occurs when boronic acid reacts with triflate in presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ catalyst to produce $\text{1-cyclohexenyl-3-nitrobenzene}$. The complete reaction is shown below.

Figure 12

Conclusion

The complete reaction is shown in Figure 12.

Interpretation Introduction

(g)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

The addition of a bromine atom in the given compound is known as bromination. Bromination occurs through an electrophilic substitution reaction. Bromine atom acts as an electrophile which causes the formation of sigma bond in the reaction

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 13

The reaction of Pyrogallol with bromine in the presence of ${\text{CCl}}_{\text{4}}$ undergoes bromination forms $\text{4-bromobenzene-1, 2, 3-triol}$ as the desired product. The substitution of bromine at fifth position on phenyl ring is less reactive due to relatively lower density of electrons at fifth position compared to the fourth position. The complete reaction is shown below.

Figure 14

Conclusion

The complete reaction is shown in Figure 14.

Interpretation Introduction

(h)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Stille coupling reaction is a cross-coupling reaction in which stannanes reacts with alkyl, aryl, and pseudo halides in presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ catalyst to yield biphenyls, styrenes, and polyolefins.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 15

The reaction of $\text{1-Naphthol}$ with triflic anhydride in the presence of pyridine gives triflate ester which undergoes Stille coupling to form $\left(\text{E}\right)\text{-3-}\left(\text{naphthalen-1-yl}\right)\text{-prop-2-en-1-ol}$ as the desired product. The complete reaction is shown below.

Figure 16

Conclusion

The complete reaction is shown in Figure 16.

Interpretation Introduction

(i)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

The treatment of unsaturated halide with an alkene in the presence of a base and a $\text{Pd}$ catalyst forms a substituted alkene. The chemical reacton involved in this process is known as Heck reaction.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 17

The reaction of cyclohexene couples with vinylbromo compound in the presence of $\text{Pd}{\left(\text{OAc}\right)}_{\text{2}}$ gives $\left(\text{E}\right)\text{-methyl}\text{3-}\left(\text{cyclohex-2-enyl}\right)\text{-2-methylacrylate}$ as the desired product. The complete reaction is shown below.

Figure 18

Conclusion

The complete reaction is shown in Figure 18.

Interpretation Introduction

(j)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Oxidation is a process in which an oxygen atom is added, or a hydrogen atom is removed from a compound.

The compounds which oxidise the other compound are known as oxidising agents. Oxidizing agents after oxidise gets reduced.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 19

The reaction of $\text{1-Naphthol}$ with ${\text{K}}_{\text{2}}{\text{Cr}}_{\text{2}}{\text{O}}_{\text{7}}$ in the presence of sulphuric acid which undergoes oxidation of $\text{1-Naphthol}$ to form $\text{naphthalene-1, 4-dione}$ as the desired product. In the given reaction ${\text{K}}_{\text{2}}{\text{Cr}}_{\text{2}}{\text{O}}_{\text{7}}$ acts as a oxidizing agent.

Figure 20

Conclusion

The complete reaction is shown in Figure 20.

Interpretation Introduction

(k)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Oxidation is a process in which an oxygen atom is added, or a hydrogen atom is removed from a compound.

The compounds which oxidize the other compound are known as oxidizing agents. Oxidizing agents after oxidize gets reduced.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 21

The reaction of $\text{m-chlorophenol}$ with ${\text{Na}}_{\text{2}}{\text{Cr}}_{\text{2}}{\text{O}}_{\text{7}}$ in the presence of sulphuric acid to give $\text{2-chlorocyclohexa-2, 5-diene-1, 4-dione}$ as the desired product. In the given reaction ${\text{Na}}_{\text{2}}{\text{Cr}}_{\text{2}}{\text{O}}_{\text{7}}$ acts as an oxidizing agent.

Figure 22

Conclusion

The complete reaction is shown in Figure 22.

Interpretation Introduction

(l)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 23

The reaction of $\text{2, 4-dinitrophenol}$ with mesyl chloride in the presence of pyridine undergoes $\text{O-mesylation}$ to form sulfonate which further reacts with methoxide in the presence of methanol undergoes aromatic nucleophilic substitution to displace ${\text{-OSO}}_{\text{2}}{\text{CH}}_{\text{3}}$ group by ${\text{-OCH}}_{\text{3}}$ group. The complete reaction is shown below.

Figure 24

Conclusion

The complete reaction is shown in Figure 24.

Interpretation Introduction

(m)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 25

The reaction of $\text{1, 2-dibromo-3, 5-dinitrobenzene}$ with $\text{2-methylpropane-1-thiolate}$ to form the desired product which occurs through nucleophilic substitution. The bromine attached to more electron deficient carbon gets displaced by thiolate ion to form the desired product. The complete reaction is shown below.

Figure 26

Conclusion

The complete reaction is shown in Figure 26.

Interpretation Introduction

(n)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

The treatment of ether with substituted halide in the presence of heat to form corresponding alcohol. This process is known as demethylation of the methoxy group.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 27

The reaction of $\text{4},{\text{4}}^{\prime }\text{-Oxybis}\left(\text{methoxybenzene}\right)$ with $\text{HBr}$ forms $\text{4,}{\text{4}}^{\prime }\text{-oxydiphenol}$ which undergoes demethylation of the two methoxy group displaced by a hydroxy group. The complete reaction is shown below.

Figure 28

Conclusion

The complete reaction is shown in Figure 28.

Interpretation Introduction

(o)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Nucleophilic substitution reaction is the reaction in which a nucleophile attacks the electrophilic center and a substituted product is formed. It takes place by the generation of an electrophilic intermediate.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 29

In the first step, the reaction of $\text{3, 3-dimethylbut-1-ene}$ with $\left(\text{Z}\right)\text{-but-2-ene-1, 4-diol}$ in the presence of Grubbs $\text{G2}$ catalyst to give $\left(\text{E}\right)\text{-4, 4-dimethylpent-2-en-1-ol}$ and undergoes sharpless epoxidation using $\left(\text{+}\right)\text{-diethyltartrate}$ forms $\left(2S,3S\right)$ epoxide selectively. In the final step, the basic hydrolysis of the oxirane undergoes ${\text{S}}_{\text{N}}\text{2}$ attack by hydroxide ions to give $\left(\text{2R, 3S}\right)\text{-4, 4-dimethylpentane-1, 2, 3-triol}$ as the desired product. The complete reaction is shown below.

Figure 30

Conclusion

The complete reaction is shown in Figure 30.

Interpretation Introduction

(p)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Grubbs catalyst is used to exchange of substituents between two different alkenes. Catalytic hydrogenation is a reduction process of addition of hydrogen atoms in an alkene or an alkyne by using a metal catalyst like $\text{Pd/C}$, $\text{Sn/HCl}$ and $\text{Fe/HCl}$.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 31

In the first step, the reaction of a diene with Grubbs $\text{G2}$ catalyst undergoes ring-closing metathesis to give a mixture of two optically active compounds with $E$ and $Z$ configuration which further reacts with ${\text{H}}_{\text{2}}$ molecule in the presence of palladium undergoes catalytic hydrogenation to form an optically active compound as the desired product. The complete reaction is shown below.

Figure 32

Conclusion

The complete reaction is shown in Figure 32.

Interpretation Introduction

(q)

Interpretation:

The reaction is to be completed by giving the major product. Also, the explanation for the corresponding reaction is to be stated.

Concept introduction:

Suzuki coupling reaction is a cross-coupling reaction in which boronic acid reacts with alkyl, aryl, and vinyl halides in the presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ a catalyst to yield biphenyls, styrenes, and polyolefins.

Answer to Problem 18.70AP

The complete reaction is shown below.

Explanation of Solution

The reaction to be completed is shown below.

Figure 33

In the first step, the reaction of a given alkene with $\text{9-BBN}$ in which boron group adds to the less hindered terminal carbon from the less crowded side of the alkene to form the hydroboration product which undergoes Suzuki coupling reaction with the vinylic bromide to form the desired product with retention of configuration.

The complete reaction is shown below.

Figure 34

Conclusion

The complete reaction is shown in Figure 34.