AMINES - RNH2
CLASSIFICATION:
1.
1. SIMPLE AMINES – (CH3)2NH
2. MIXED AMINES – CH3NHC2H5
AMINES
1. PRIMARY AMINES R NH2 (EX )– CH3 NH2
2. SECONDARY AMINES R2NH (EX) - CH3NHCH3
3. TERTIARY AMINES R3N (EX) – CH3 N(CH3)2
1. ALIPHATIC AMINES :CH3NH2
2. AROMATIC AMINES C6H5NH2
3. ARALKYL AMINES C6H5CH2NH2
NOMENCLATURE - RULES
• 1. PRIMARY AMINES are names by replacing the final e of the parent alkane by amine as Alkanamines
[Link] AND TERTIARY AMINES are names as N- substituted derivatives of primary amines.
3. Simplest aromatic amine is called as benzenamine and other amines are derivatives of benzenamine.
Examples:
1.CH3CH2CH2NH2 - Propanamine (10) 1. CH 3NHCH3 N– methylmethanamine (2 0)
2. CH3CH(NH2)CH3 – Propan -2 –amine (10) 2. CH 3CH2CH (CH2CH3)NHCH3 N –methyl pentan -3-amine
(20)
1. (CH3)3N – N, N – dimethyl methanamine (3 0) 2. C 2H5N(CH3)2 – N,N dimethyl ethanamine
1. C6H5NH2 – Aniline / Benzenamine (aryl amine 1 0) 2. C6H5 NH CH3 – N- methyl aniline (20)
3. CH3CH(C6H5)CH2NH2 - 2- phenyl propan1-amine(10) 3. C6H5NHC6H5 – N- phenyl aniline (20)
PREPARATION OF AMINES :
• 1. REDUCTION OF NITRO COMPOUNDS :
• RNO2 + 6[H] + Sn / HCl or ( Fe/HCl) →RNH2 + 2H2O
• 2. REDUCTION OF NITRILES : MENDIUS REACTION
• RC≡N + 4 [H] + H 2/Ni or (Na /Hg – C 2H5OH ) → RCH2NH2
• 3. REDUCTION OF ACID AMIDES :
• RCONH2 + 4 [H] + LiAlH 4 →RCH2NH2
• 4. HOFFMAN’S AMMONOLYSIS :
• NH3 + RX → RNH2 + RX →R2NH + RX →R3N + RX →R4NX
• 5. HOFFMAN BROMAMIDE DEGRADATION REACTION;
• RCONH2 + Br 2 + 4 NaOH → RNH2 + 2NaBr + Na2CO3 + 2 H2O ( step down reaction)
• 6. GABRIEL PTHALIMIDE SYNTHESIS ( ONLY FOR THE PREPARATION OF ALIPHATIC PRIMARY AMINES)
PHYSICAL PROPERTIES
• 1. Methyl amine and ‘ethylamines are gases and higher members are liquids with fishy odour.
• 2. Boiling point : It increases with molecular mass. However amines have lower boiling point than corresponding
alcohols and acids. ( Due to lower electronegativity of Nitrogen when compared to oxygen)
• Alkane < Ethers < amines < aldehydes <alcohol < acid
• 3. Among the isomeric amines Pri > Sec > Tert ( primar undergoes extensive hydrogen bonding )
• 4. Solublity : Aliphatic amines are soluble in water , due to intermolecular hydrogen bonding between amine and
water.
• 5. Basic character of amines ( In GAS PHASE)
• a) amines like ammonia are basic in nature, due to the presence of lone pair of electrons on nitrogen atom, so act as
lewis base.
• b) RNH2 + H2O ↔RNH3+ + OH_
• Kb = [RNH3+ ][OH-] / [RNH2]
• PKb = - log Kb
• Smaller the Pkb , larger the Kb , stronger is the base
• C) +I group ( electron donating group) increases basic character, whereas - I group ( electron
withdrawing group) decreases basic character
• Therefore 30 > 20 > 10
BASIC CHARACTER OF AMINES – Aqueous phase
• In aqueous phase, the basic character depends upon:
• 1. H- bonding : 1>2>3
• 2. +I effect : 3>2>1
• 3. steric factor ( smaller group like methyl) 1>2>3
• ( Bulky group ) does not favour H bonding
• Based on this in aqueous phase : ( CH 3) 2NH > (CH3NH2) > (CH3)3N ( 20 > 10 > 30)
• (CH3CH2)2NH > (CH3CH2)3N > CH3CH2NH2 ( 20 > 30 > 10)
Comparative strength of basic character of amines
• Aromatic amines < Ammonia< aralkylamine < primary < secondary < tertiary amines
Aniline < N- methyl aniline < N, N dimethyl aniline < Ammonia < Benzylamine <
Ethylamine<triethylamine < diethylamine
Effects of substituents on the basicity of aromatic amines:
1) –I group ( NO2, CN, SO3H, COOH , Cl, C6H5 decreases basic character.
2) +I group ( NH2 , OR, R etc increases the basic character.
Basic character of aromatic amines
Effects of substituents on the basicity of aromatic amines:
1) –I group ( NO2, CN, SO3H, COOH , Cl, C6H5 decreases basic character.
2) +I group ( NH2 , OR, R etc increases the basic character.
3) p > m > o
Effect of substituents on N atom
2) N,N dimethyl aniline > N- methylaniline > aniline
2) Ethyl group being bigger than methyl , has more basic character than N- methyl aniline
• C6H5N (C2H5)2 > C6H5NH C2H5 > C6H5N(CH3)2 > C6H5NHCH3 > C6H5NH2 > C6H5NHC6H5S
CHEMICAL PROPERTIES OF AMINES
• 1. REACTION WITH ACIDS:
• All three types of amines have lone pair of electrons on N atom which make them react as base / Nucleophile
• RNH2 + HCl →RNH3Cl( alkyl ammonium chloride
• 2. REACTION WITH WATER:
• Amines dissolve in water to funish OH - ions in solution
• RNH2 + HOH →RNH3OH
• 3. REACTION WITH ALKYL HALIDES : ( HOFFMAN’S AMMONOLYSIS)
• RNH2 + RX →RNHR(20) + RX →RNR2 (30) + RX →R4NX( quarternary ammonium salt)
• Aromatic amines also undergo similar reaction.
• [Link] WITH ACID CHLORIDES / ACYLATION:
• RNH2 + RCOCl →RNHCOR (N- substituted amide) + HCl
• B) reaction with aromatic amines : ACETANILIDE PREPARATION
CHEMCIAL TEST TO DISTINGUISH BETWEEN AMINES
• 4. CARBYLAMINE REACTION: ( only for primary amines)
• RNH2 + CHCl3 + 3 KOH →RNC + 3 KCl + 3 H2O.
• Carbylamines/ isocyanides possess very bad smell. Used to distinguish between primary amines from sec, ter amines
• [Link] WITH NITROUS ACID: ( ALIPHATIC VS AROMATIC)
Aliphatic amines on diazotisation gives nitrogen gas, whereas aromatic amines give white ppt of benzene
diazonium chloride.
[Link] WITH HINSBERG REAGENT:
Primary amines reacts with Hinsberg reagent (C 6H5SO2Cl ) and the resultant mixture dissolves in NaOH.
C6H5SO2Cl + CH3NH2 → C6H5SO 2NHCH 3 + KOH→ C6 H 5 SO2NKCH3(watersoluble)
With secondary amines , it reacts , but insoluble in KOH
• C6H5SO 2Cl + R2NH →water insoluble, ether solubleC 6H5SO2NR2 + KOH→No action
Tertiary amine do not react with Hinsberg reagent.
• C6H 5SO 2Cl+R3N→ No reaction.
ELECTROPHILIC SUBSTITUTION REACTION OF AMINES
• BROMINATION
Bromination
• FRIDEL CRAFTS ALKYLATION:
• Aniline does not undergo fridel- crafts alkylation because, aniline is a weak base which reacts with
• lewis acid catalyst anhydrous AlCl 3 to produce salt. Due to salt formation it, deactivates the ring for
• Electrophilic substitution.
TEXT BOOK EXERCISE:
DIAZONIUM SALTS
ARRANGE THE FOLLOWING:
CONVERSIONS: