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NITROGEN COMPOUNDS (Amines)

Physical properties of amines Formation of amines Basicity of amines Reactions of phenylamines

Amines : Physical properties


Amines are derivatives of ammonia ( 1 hydrogen atoms

replaced by carbon chains). Amines are classified as primary, secondary or tertiary.

Quaternary ammonium salt are organic equivalent of

ammonium compounds. E.g: NH4+Clammonium chloride (CH3)4N+Cltetramethylammonium chloride Amines have higher boiling points than hydrocarbon with similar Mr intermolecular hydrogen bonding.

But amines have lower boiling point than alcohol

because intermolecular hydrogen bonding in amines are weaker than alcohols.

Amines are soluble in water

form hydrogen bonds

with water molecules Solubility in water decreases with increasing num. of C atoms.

Naming amines
Use the suffix ylamine after a stem indicating the

number of carbon atoms. E.g : CH3NH2 methylamine (CH3)2NH dimethylamine

Exercise : Name the following compounds. 1. (CH3CH2)2NH 2. (CH3)3N Write the structural formulas of the following compounds: a) Propylamine b) 2-nitrophenylamine

Formation of amines
1)

Nitrile reduction Reagent and condition : LiAlH4 in dry ether or mixture of Na and ethanol or H2, Ni, 140C. Product : alkyl amine

Eg. :

RCN

LiAlH4 Dry ether

RCH2NH2

2) Reduction of nitrobenzene
Reagent & condition : reflux with tin and excess conc.

HCl or Zn or Fe and excess of HCl or H2(g), Ni, 300C. Product : Phenylamine

The metal and acid gives off H2(g) which performs the

reduction. The phenylamine is separated through steam distillation.

Basicity of amines
Amines are weak base. Due to ability of lone pair in the nitrogen atom to accept a

proton (form a dative bond). Are weak alkalis in water.


Reacts with acid, forming a salt. Strength of base depends on: a) Availability of lone pair on N to accept proton. b) Stability of its conjugate acid ion.

Order of base strength : ethylamine > ammonia > phenylamine Base strength pKb : 3.3 4.8 9.4 decrease * The lower the pKb value, the stronger the base.

Ethylamine is stronger base than ammonia.

The EDG ethyl group in ethylamine increases the

electron density on the N atom more available to accept proton than ammonia. The ethyl group pushes electron onto the NH3+ group on the conjugate acid stabilises the ion.

Phenylamine is a much weaker base than

ammonia.

This is due to delocalisation of lone pairs of

electrons on the nitrogen atom over the benzene ring hence less available to accept a proton.

Effect of substituent on basicity of amines.


Electron-donating group (EDG) increases basicity of

amines. E.g : propylamine is more basic than ammonia. The R-group increases electron density on N atom, making it more available to accept a proton.

Electron withdrawing group (EWG) decreases

basicity of amines. E.g 3-chlorophenylamine is weaker then phenylamine. Electron-withdrawing Cl atom makes the lone pair in N atom less available to accept proton.

Reactions of Phenylamine
1.

Reaction with HNO2 Reagent : NaNO2 and conc. HCl Condition : <5C Product : diazonium salt

The aromatic diazonium ion formed is more stable due to delocalisation of electrons to the benzene ring.

The diazonium ion is not stable above 10C

will

decompose to form N2(g) and phenol.

Aliphatic amines (e.g ethylamine) will not give diazonium

salt in this reaction. This is because the diazonium group, -N+ N, is unstable. It decompose quickly to give N2(g), alcohol and alkene.
The benzenediazonium ion reacts with nucleophiles

Coupling of benzenediazonium chloride and phenol formation of dyes.


The N+2 group of the benzenediazonium ion is a strong

electrophile. It can attack the benzene ring, especially those that have EDG such as OH group attached to it. Reagent : diazonium salt and phenol Condition : Cold alkaline solutions Product : bright orange precipitate of (4-hydroxyphenyl) azobenzene. E.g

The compound formed is stable

due to the extensive delocalisation of electrons via the N=N bond. Because it is very stable, the dyes do not fade. This coupling reaction is used in formation of dyestuff. Other aromatic amines and arenes can be used to make dyes.

Reactions of phenylamine.
Reaction with Aqueous Bromine (electrophilic substitution) Aliphatic amines have no reaction with aqueous bromine. Condition : room temperature. Observation : reddish-brown bromine solution decolourised, white ppt of 2,4,6-tribromophenylamine formed and steamy white fumes of HBr liberated.

Phenylamine is more reactive than benzene

due to delocalisation of lone pair electrons from N atom into