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Chapter 19

Amines

Amines: Introduction
Amines: Introduction
Amines are organic derivatives of ammonia. They are formed by replacing one or more ammonia protons with alkyl or aryl groups. Depending upon the number ...
Nomenclature of Primary Amines
Nomenclature of Primary Amines
Primary, secondary, and tertiary amines are compounds consisting of one, two, and three alkyl groups connected to the amino group (–NH2), ...
Nomenclature of Secondary and Tertiary Amines
Nomenclature of Secondary and Tertiary Amines
The secondary and tertiary amines are derivatives of ammonia, where two and three of its hydrogens are replaced by alkyl groups, respectively. Secondary ...
Nomenclature of Aryl and Heterocyclic Amines
Nomenclature of Aryl and Heterocyclic Amines
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is ...
Structure of Amines
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which ...
Physical Properties of Amines
Physical Properties of Amines
Amines with low molecular weight are usually gaseous at room temperature, while those with high molecular weight are liquid or solids in nature. Usually, ...
Basicity of Aliphatic Amines
Basicity of Aliphatic Amines
Amines can behave as Brønsted–Lowry bases by accepting a proton from the acid to form corresponding conjugate acids. Due to a lone pair of ...
Basicity of Aromatic Amines
Basicity of Aromatic Amines
The basicity of aromatic amines is much weaker than that of aliphatic amines due to the involvement of the lone pair of electrons over the N atom in ...
Basicity of Heterocyclic Aromatic Amines
Basicity of Heterocyclic Aromatic Amines
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine ...
NMR Spectroscopy Of Amines
NMR Spectroscopy Of Amines
In proton NMR spectroscopy, primary amines and secondary amines showcase their N–H protons as a broad signal in the chemical shift range between ...
Mass Spectrometry of Amines
Mass Spectrometry of Amines
In mass spectroscopy, amines undergo fragmentation to give parent ions with odd molecule weights. This observed mass spectrum follows the nitrogen rule: a ...
Preparation of Amines: Alkylation of Ammonia and Amines
Preparation of Amines: Alkylation of Ammonia and Amines
Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines ...
Preparation of 1° Amines: Azide Synthesis
Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide ...
Preparation of 1° Amines: Gabriel Synthesis
Preparation of 1° Amines: Gabriel Synthesis
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred ...
Preparation of Amines: Reduction of Oximes and Nitro Compounds
Preparation of Amines: Reduction of Oximes and Nitro Compounds
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and ...
Preparation of Amines: Reduction of Amides and Nitriles
Preparation of Amines: Reduction of Amides and Nitriles
Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an ...
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, ...
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary ...
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl ...
Amines to Amides: Acylation of Amines
Amines to Amides: Acylation of Amines
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction ...
Amines to Alkenes: Hofmann Elimination
Amines to Alkenes: Hofmann Elimination
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. ...
Amines to Alkenes: Cope Elimination
Amines to Alkenes: Cope Elimination
Cope elimination reaction involves the conversion of tertiary amines to alkene using hydrogen peroxide under thermal conditions, as depicted in figure 1. ...
1&deg; Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO<sub>2</sub> Overview
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa ...
1&deg; Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO<sub>2</sub> Mechanism
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic ...
2&deg; Amines to <em>N</em>-Nitrosamines: Reaction with NaNO<sub>2</sub>
2° Amines to N-Nitrosamines: Reaction with NaNO2
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from ...
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. ...
Diazonium Group Substitution: &ndash;OH and &ndash;H
Diazonium Group Substitution: –OH and –H
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in ...
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of ...
Amines to Sulfonamides: The Hinsberg Test
Amines to Sulfonamides: The Hinsberg Test
The Hinsberg test is a method to identify primary, secondary and tertiary amines, named after its pioneer, Oscar Hinsberg. Here, amines are treated with ...
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