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Organic Compounds Containing Nitrogen - Cyanides and Isocyanides

Grade 12ICSEChemistry

Review the key concepts, formulae, and examples before starting your quiz.

πŸ”‘Concepts

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Alkyl Cyanides (Alkanenitriles) are organic compounds with the general formula Rβˆ’C≑NR-C \equiv N. They are functional isomers of Alkyl Isocyanides (Rβˆ’N≑CR-N \equiv C).

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Cyanide ion (CNβˆ’CN^-) is an ambident nucleophile. Reaction of alkyl halides with alcoholic KCNKCN yields alkyl cyanides because of the ionic nature of KCNKCN, while reaction with AgCNAgCN yields alkyl isocyanides due to the covalent nature of Agβˆ’CAg-C bond.

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The Mendius Reaction involves the reduction of alkyl cyanides with sodium and ethanol to produce primary amines: Rβˆ’CN+4[H]β†’Na/C2H5OHRβˆ’CH2NH2R-CN + 4[H] \xrightarrow{Na/C_2H_5OH} R-CH_2NH_2.

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Partial hydrolysis of cyanides with cold conc. HClHCl or alkaline H2O2H_2O_2 yields amides (RCONH2RCONH_2), while complete hydrolysis with boiling dilute acids or alkalies yields carboxylic acids (RCOOHRCOOH).

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Alkyl isocyanides, upon reduction with LiAlH4LiAlH_4 or H2/NiH_2/Ni, produce secondary amines containing a methyl group (Rβˆ’NHβˆ’CH3R-NH-CH_3).

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The Carbylamine Reaction is a test for primary amines where they react with chloroform (CHCl3CHCl_3) and alcoholic KOHKOH to form foul-smelling alkyl isocyanides (Rβˆ’NCR-NC).

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Hydrolysis of isocyanides with dilute acids yields primary amines and formic acid (HCOOHHCOOH); notably, isocyanides are not hydrolyzed by alkalies.

πŸ“Formulae

Rβˆ’X+KCNβ†’EtOHRβˆ’C≑N+KXR-X + KCN \xrightarrow{EtOH} R-C \equiv N + KX

Rβˆ’X+AgCNβ†’EtOHRβˆ’N≑C+AgXR-X + AgCN \xrightarrow{EtOH} R-N \equiv C + AgX

Rβˆ’C≑N+2H2Oβ†’H+Rβˆ’COOH+NH4+R-C \equiv N + 2H_2O \xrightarrow{H^+} R-COOH + NH_4^+

Rβˆ’N≑C+2H2Oβ†’H+Rβˆ’NH2+HCOOHR-N \equiv C + 2H_2O \xrightarrow{H^+} R-NH_2 + HCOOH

Rβˆ’CONH2β†’P2O5,Ξ”Rβˆ’CN+H2OR-CONH_2 \xrightarrow{P_2O_5, \Delta} R-CN + H_2O

Rβˆ’NH2+CHCl3+3KOH(alc.)β†’Ξ”Rβˆ’NC+3KCl+3H2OR-NH_2 + CHCl_3 + 3KOH (alc.) \xrightarrow{\Delta} R-NC + 3KCl + 3H_2O

πŸ’‘Examples

Problem 1:

How will you convert Methyl chloride (CH3ClCH_3Cl) to Ethanoic acid (CH3COOHCH_3COOH)?

Solution:

CH3Cl→KCN(alc.)CH3CN→H3O+/ΔCH3COOHCH_3Cl \xrightarrow{KCN(alc.)} CH_3CN \xrightarrow{H_3O^+ / \Delta} CH_3COOH

Explanation:

Methyl chloride reacts with alcoholic KCNKCN via nucleophilic substitution to form Methyl cyanide (CH3CNCH_3CN). Complete acid hydrolysis of the cyanide group converts it into a carboxylic acid group, increasing the chain length by one carbon.

Problem 2:

Identify the products AA and BB: C2H5NC→H2/PtAC_2H_5NC \xrightarrow{H_2/Pt} A and C2H5NC→H3O+BC_2H_5NC \xrightarrow{H_3O^+} B.

Solution:

A=C2H5NHCH3A = C_2H_5NHCH_3 (Ethyl methyl amine), B=C2H5NH2B = C_2H_5NH_2 (Ethylamine) + HCOOHHCOOH (Formic acid).

Explanation:

Reduction of an isocyanide (C2H5NCC_2H_5NC) adds hydrogen across the functional group to form a 2∘2^\circ amine. Acid hydrolysis of an isocyanide breaks the Nβˆ’CN-C bond to yield a 1∘1^\circ amine and formic acid.

Problem 3:

Why do alkyl cyanides have higher boiling points than the corresponding alkyl halides?

Solution:

Due to the presence of the polar βˆ’C≑N-C \equiv N group, cyanides possess strong intermolecular dipole-dipole interactions.

Explanation:

The large dipole moment of the cyanide group (>3.9D> 3.9 D) leads to stronger associations between molecules compared to the weaker dipole-dipole forces in alkyl halides (Rβˆ’XR-X).

Cyanides and Isocyanides - Revision Notes & Key Formulas | ICSE Class 12 Chemistry