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How will you convert: (i) Ethanoic acid into methanamine (ii) Hexanenitrile into 1 -aminopentane (iii) Methanol to ethanoic acid (iv) Ethanamine into methanamine (v) Ethanoic acid into propanoic acid (vi) Methanamine into ethanamine (vii) Nitromethane into dimethylamine (viii) Propanoic acid into ethanoic acid?

Short Answer

Expert verified
Follow each conversion step using specific reactions to transform the starting compound into the desired product.

Step by step solution

01

Ethanoic Acid to Methanamine

Convert ethanoic acid (CH鈧僀OOH) to methanamine (CH鈧僋H鈧) using the Hoffman degradation. First, convert ethanoic acid to acetamide (CH鈧僀ONH鈧) through conversion to an acyl chloride and then treat with ammonia. Then perform Hoffman bromamide degradation by treating acetamide with bromine in an aqueous NaOH solution to form methanamine.
02

Hexanenitrile to 1-Aminopentane

Convert hexanenitrile (C鈧匟鈧佲倎CN) to 1-aminopentane (C鈧匟鈧佲倎NH鈧) via partial hydrolysis of the nitrile using acidic or basic hydrolysis to form pentanoic acid (C鈧匟鈧佲個COOH). Then decarboxylate the acid by converting it into the corresponding amine.
03

Methanol to Ethanoic Acid

Oxidize methanol (CH鈧僌H) to ethanoic acid (CH鈧僀OOH) in two steps. First, oxidize methanol to formaldehyde with a mild oxidizing agent. Then oxidize formaldehyde to ethanoic acid using a stronger oxidizing agent like potassium permanganate (KMnO鈧).
04

Ethanamine to Methanamine

Convert ethanamine (C鈧侶鈧匩H鈧) to methanamine (CH鈧僋H鈧) by first converting ethanamine into ethanamide (C鈧侶鈧匔ONH鈧). Use Hoffman bromamide degradation on ethanamide, which produces methanamine.
05

Ethanoic Acid to Propanoic Acid

To convert ethanoic acid (CH鈧僀OOH) to propanoic acid (C鈧侶鈧匔OOH), perform a two-step process by first converting ethanoic acid to acetyl chloride. Follow this by the Grignard reaction using a methyl magnesium bromide (CH鈧僊gBr), then undergo hydrolysis to form the propanoic acid.
06

Methanamine to Ethanamine

Convert methanamine (CH鈧僋H鈧) to ethanamine (C鈧侶鈧匩H鈧) through indirect means by first preparing cyanomethane from methanamine, followed by the hydrolysis to ethanamine.
07

Nitromethane to Dimethylamine

To convert nitromethane (CH鈧僋O鈧) into dimethylamine (CH鈧)鈧侼H, first reduce nitromethane to methylamine using lithium aluminum hydride (LiAlH鈧). Then, methylate the methylamine with methyl iodide (CH鈧僆) to introduce the second methyl group and form dimethylamine.
08

Propanoic Acid to Ethanoic Acid

Convert propanoic acid (C鈧侶鈧匔OOH) to ethanoic acid (CH鈧僀OOH) using a controlled oxidation and subsequent reduction sequence. First, carry out decarboxylation of propanoic acid to form ethane, followed by oxidation of ethane to form ethanoic acid.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Hoffman Degradation
Hoffman degradation is a fascinating chemical process that allows the transformation of an amide into an amine with one less carbon atom. This can be particularly useful when considering organic chemistry transformations aimed at reducing chain length by a carbon atom. The process starts with the conversion of a carboxylic acid into an amide. For example, ethanoic acid (CH鈧僀OOH) is converted into acetamide (CH鈧僀ONH鈧) by first forming an acyl chloride and adding ammonia to create the amide. Afterward, the actual Hoffman degradation takes place by treating the amide with bromine in an aqueous sodium hydroxide (NaOH) solution. The reaction proceeds by the formylation of the amide to produce an isocyanate intermediate, which then rapidly hydrolyzes to yield the desired primary amine, in this case, methanamine (CH鈧僋H鈧). The key advantage of this transformation is its ability to offer a seemingly straightforward route from a carboxylic acid to an amine while simultaneously eliminating a carbon atom. This makes it extremely valuable for specific synthetic routes in organic chemistry.
Grignard Reaction
The Grignard reaction is a cornerstone of organic synthesis, particularly invaluable for forming carbon-carbon bonds. This reaction involves the use of a Grignard reagent, typically an organomagnesium compound like methyl magnesium bromide (CH鈧僊gBr). The beauty of this reaction lies in its ability to introduce new carbon chains into a molecule. Take the example of converting ethanoic acid (CH鈧僀OOH) to propanoic acid (C鈧侶鈧匔OOH). First, ethanoic acid is transformed into acetyl chloride (CH鈧僀OCl). The addition of the Grignard reagent to acetyl chloride leads to the formation of a tertiary alcohol. This intermediate product then undergoes hydrolysis to yield propanoic acid. What stands out about the Grignard reaction is its versatility: it can be used to extend carbon frameworks, providing synthetic chemists with a host of new compounds. One limitation, however, is its sensitivity to moisture, meaning that the reaction must be carried out in absolutely dry conditions.
Oxidation of Alcohols
The oxidation of alcohols is a crucial transformation in organic chemistry, converting alcohols to either aldehydes, ketones, or acids. It is a two-step process in cases such as the oxidation of methanol (CH鈧僌H) to ethanoic acid (CH鈧僀OOH). Initially, methanol is oxidized to formaldehyde using a mild oxidizing agent. This involves the removal of two hydrogen atoms from methanol. The formaldehyde is then further oxidized to ethanoic acid with the help of a stronger oxidizing agent, often potassium permanganate (KMnO鈧). The overall reaction mechanism relies on the ability of the oxidizing agent to accept electrons from the alcohol, transforming it into a carbonyl compound. The versatility of alcohol oxidation makes it a staple reaction for synthesizing a wide range of organic compounds, although care must be taken to control the reaction conditions to prevent over-oxidation, especially in multi-step syntheses.
Hydrolysis of Nitriles
Hydrolysis of nitriles is an essential technique for converting nitriles into carboxylic acids or amines, depending on the conditions used. For example, turning hexanenitrile (C鈧匟鈧佲倎CN) into 1-aminopentane (C鈧匟鈧佲倎NH鈧) typically starts with the hydrolysis of the nitrile. This can be done with either acidic or basic conditions. In acidic hydrolysis, the nitrile is first converted into the amide form, hexanamide, which can then undergo further hydrolysis to form the corresponding amine. Basic hydrolysis, on the other hand, might progress directly to form the amine. In either case, hexanenitrile ultimately yields pentanoic acid (C鈧匟鈧佲個COOH) before decarboxylating to the amine. The choice between acidic or basic hydrolysis is important, as it influences the reaction speed and product purity. This transformation allows chemists to access a wide range of derivatives from nitriles, highlighting the chemical flexibility and utility of nitrile compounds in synthetic organic chemistry.

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Most popular questions from this chapter

Give plausible explanation for each of the following: (i) Why are amines less acidic than alcohols of comparable molecular masses? (ii) Why do primary amines have higher boiling point than tertiary amines? (iii) Why are aliphatic amines stronger bases than aromatic amines?

Give one chemical test to distinguish between the following pairs of compounds. (i) Methylamine and dimethylamine (ii) Secondary and tertiary amines (iii) Ethylamine and aniline (iv) Aniline and benzylamine (v) Aniline and N-methylaniline.

Give the structures of \(A, B\) and \(C\) in the following reactions: (i) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{I} \stackrel{\mathrm{NaCN}}{\longrightarrow} \mathrm{A} \frac{\mathrm{OH}^{-}}{\text {Partial hydrolys } \mathrm{s}}{\longrightarrow} \mathrm{B} \stackrel{\mathrm{NaOH}+\mathrm{Br}_{2}}{\longrightarrow} \mathrm{C}\) (ii) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{~N}_{2} \mathrm{Cl} \stackrel{\mathrm{OuCN}}{\longrightarrow} \mathrm{A} \stackrel{\mathrm{H}_{2} \mathrm{O} / \mathrm{H}^{+}}{\longrightarrow} \mathrm{B} \frac{\mathrm{NH}_{3}}{\Delta} \longrightarrow \mathrm{C}\) (iii) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{Br} \stackrel{\mathrm{KCN}}{\longrightarrow} \mathrm{A} \stackrel{\mathrm{LiAlH}_{4}}{\longrightarrow} \mathrm{B} \frac{\mathrm{HNO}_{2}}{0^{\circ} \mathrm{C}} \longrightarrow \mathrm{C}\) (iv) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NO}_{2} \stackrel{\mathrm{Fe} / \mathrm{HCl}}{\longrightarrow} \mathrm{A} \frac{\mathrm{NaNO}_{2}+\mathrm{HCl}}{273 \mathrm{~K}} \longrightarrow \mathrm{B} \frac{\mathrm{H}_{2} \mathrm{O} / \mathrm{H}^{+}}{\Delta} \longrightarrow \mathrm{C}\) (v) \(\mathrm{CH}_{3} \mathrm{COOH} \underset{\Delta}{\stackrel{\mathrm{NH}_{3}}{\longrightarrow}}{\longrightarrow} \mathrm{A} \stackrel{\mathrm{NaOBr}}{\longrightarrow} \mathrm{B} \stackrel{\mathrm{NaNO}_{2} / \mathrm{HCl}}{\longrightarrow} \mathrm{C}\) (vi) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NO}_{2} \stackrel{\mathrm{Fe} / \mathrm{HCl}}{\longrightarrow} \mathrm{A} \frac{\mathrm{HNO}_{2}}{273 \mathrm{~K}} \longrightarrow \mathrm{B} \stackrel{\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH}}{\longrightarrow} \mathrm{C}\)

Describe a method for the identification of primary, secondary and tertiary amines. Also write chemical equations of the reactions involved.

Write short notes on the following: (i) Carbylamine reaction (ii) Diazotisation (iii) Hofmann's bromamide reaction (iv) Coupling reaction (v) Ammonolysis (vi) Acetylation (vii) Gabriel phthalimide synthesis.

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