(a)
Interpretation:
The synthesis of the given product from pyridine is to be predicted.
Concept introduction:
The replacement or substitution of one
Answer to Problem 26.39AP
The synthesis for the given product from pyridine is shown below.
Explanation of Solution
In the first step, pyridine undergoes oxidation on nitrogen atom to form pyridine-N-oxide on reaction with 30 % H2O2 solution.
In the second step, the treatment of pyridine-N-oxide with Me3SiCN, Et3N, MeCN followed by Me3SiOH occurs and it undergoes a nucleophilic
In the final step, the reduction of 2-cyanopyridine with the help of lithium aluminum hydride takes place to form the given product. The steps of conversion are shown below.
Figure 1
The synthesis for the given product from pyridine is shown in Figure 1.
(b)
Interpretation:
The synthesis of the given product from pyridine is to be predicted.
Concept introduction:
The formation of diazonium salt from aromatic
The addition of the nitro group is known as nitration.
Answer to Problem 26.39AP
The synthesis for the given product from pyridine is shown below.
Explanation of Solution
In the first step, pyridine undergoes oxidation on nitrogen atom to form pyridine-N-oxide on reaction with 30 % H2O2 solution. In the second step, pyridine-N-oxide with the nitric acid undergoes nitration reaction at the fourth position to form 4-nitropyridine-N-oxide.
In the third step, the reduction of 4-nitropyridine-N-oxide takes place with the help of H2, Pd/C in which nitro group and N-oxide group gets reduced.
In the fourth step, 4-aminopyridine reacts with NaNO2, HCl followed by reaction with CuBr and gives 4-bromopyridine.
In the fifth step, 4-bromopyridine with sodium ethylthiolate in presence of methanol undergoes nucleophilic substitution to form the desired product.
The overall reaction is shown below.
Figure 2
The synthesis for the given product from pyridine is shown in Figure 2.
(c)
Interpretation:
The synthesis of the given product from furfural is to be predicted.
Concept introduction:
Grignard reagents are
Answer to Problem 26.39AP
The synthesis of the given product from furfural is shown below.
Explanation of Solution
In the first step, the treatment of fufural with CH3MgBr followed by acid hydrolysis takes place.
In the second step, the product obtained with the help of pyridinium chlorochromate undergoes oxidation to form the corresponding
In the final step, methyl ketone reacts with the furfural in the presence of NaOH solution to form α,β-unsaturated carbonyl compound. This reaction is known as aldol condensation.
The overall reaction is shown below.
Figure 3
The synthesis of the given product from furfural is shown in Figure 3.
(d)
Interpretation:
The synthesis of the given product from furfural is to be predicted.
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 26.39AP
The synthesis of the given product from furfural is shown below.
Explanation of Solution
In the first step, the reaction of furfural with KMnO4 solution undergoes oxidation reaction to form furoic acid.
In the second step, furoic reacts acid with thionyl chloride to form furoyl chloride. The type of reaction is nucleophilic acyl substitution reaction.
In the third step, furoyl chloride with 1-propanol in the presence of trimethylamine undergoes esterification to form the desired product.
The overall reaction is shown below.
Figure 4
The synthesis of the given product from furfural is shown in Figure 4.
(e)
Interpretation:
The synthesis of the given product from 3-methylpyridine is to be predicted
Concept introduction:
Oxidation is the process of addition of oxygen. Oxidation is also defined as loss of electrons. In the oxidation process, there is increasing in the oxidation state. The acid is added in the reaction for protonation.
The oxidizing agent is defined as the species which oxidizes others and itself gets reduced.
Answer to Problem 26.39AP
The synthesis of the given product from 3-methylpyridine is shown below.
Explanation of Solution
In the first step, 3-methylpyridine with KMnO4 forms nicotine as product.
In the second step, the reaction between nicotinic acid and thionyl chloride takes place in the presence of ethanol and gives the corresponding methyl ester as product.
In the third step, the reaction between methyl ester with hydrazine in the presence of NaNO2, HCl takes place and forms the corresponding acyl azide.
In the fourth step, the acyl azide on heating with benzene gives isocyanate as the product.
In the fifth step, the isocyanate is treated with pyridin-3-amine to give the desired product.
Figure 5
The synthesis of the given product from 3-methylpyridine is shown in Figure 5.
(f)
Interpretation:
The synthesis of the given product from 4-ethylpyridine is to be predicted.
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 26.39AP
The synthesis of the given product from 4-ethylpyridine is shown below.
Explanation of Solution
In the first step, the reaction of 4-ethylpyridine with methyl iodide undergoes methylation at nitrogen atom to form N-methyl-4-ethyl pyridinium iodide as product.
In the second step, N-methyl-4-ethyl pyridinium iodide with triethylamine undergoes abstraction of a proton from ethyl carbon of pyridine. The resulting anion is stabilized by resonance with the help of electronegative nitrogen atom, followed by the nucleophilic substitution reaction with the vinyl nitrile to form the desired product.
The overall reaction is shown below.
Figure 6
The synthesis of the given product from 4-ethylpyridine is shown in Figure 6.
(g)
Interpretation:
The synthesis of the given product from 2-methylpyridine is to be predicted.
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 26.39AP
The synthesis of the given product from 2-methylpyridine is shown below.
Explanation of Solution
In the first step, 2-methylpyridine with 1 equivalent of butyl lithium undergoes abstraction of proton from methyl group to form resonanace stabilized anion.
In the second step, the treatment of resonance stabilized anion with sodium cyanide followed by hydrolysis gives a
In the third step, the treatment of 2-(pyridin-2-yl)acetic acid with 2 equivalents of butyl lithium undergoes proton abstraction at the methylene carbon to form resonance stabilized anion.
In the final step, the resonance stabilized anion undergoes a nucleophilic substitution reaction with propyl bromide to form the desired product.
The overall reaction is shown below.
Figure 7
The synthesis of the given product from 2-methylpyridine is shown in Figure 7.
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Chapter 26 Solutions
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