KNOCKHARDY PUBLISHINGKNOCKHARDY PUBLISHING
20152015 SPECIFICATIONSSPECIFICATIONS
AN INTRODUCTION TOAN INTRODUCTION TO
THE CHEMISTRYTHE CHEMISTRYOF AMINESOF AMINES
INTRODUCTION
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AMINESAMINESKNOCKHARDY PUBLISHINGKNOCKHARDY PUBLISHING
CONTENTS
• Prior knowledge
• Structure and classification
• Nomenclature
• Physical properties
• Basic properties
• Nucleophilic properties
• Amino acids
• Peptides and proteins
• Amides
• Check list
AMINESAMINES
Before you start it would be helpful to…
• know the functional groups found in organic chemistry
• know the arrangement of bonds around atoms
• recall and explain nucleophilic substitution reactions
AMINESAMINES
STRUCTURE & CLASSIFICATIONSTRUCTURE & CLASSIFICATION
Structure Contain the NH2 group
Classification
primary (1°) amines secondary (2°) amines
tertiary (3°) amines quarternary (4°) ammonium salts
Aliphatic methylamine, ethylamine, dimethylamine
Aromatic NH2 group is attached directly to the benzene ring (phenylamine)
R N:
H
H
R N:
R
H
R N:
R
R
R
+R N R
R
NOMENCLATURENOMENCLATURE
NomenclatureNamed after the groups surrounding the nitrogen + amine
C2H5NH2 ethylamine
(CH3)2NH dimethylamine
(CH3)3N trimethylamine
C6H5NH2 phenylamine (aniline)
PREPARATIONPREPARATION
Amines can be prepared from halogenoalkanes
Reagent Excess, alcoholic ammonia (WHY USE EXCESS?)
Conditions Reflux in excess, alcoholic solution under pressure
Product Amine (or its salt due to a reaction with the acid produced)
Nucleophile Ammonia (NH3)
Equation C2H5Br + NH3 (alc) ——> C2H5NH2 + HBr ( or C2H5NH3+Br¯ )
PREPARATIONPREPARATION
Amines can be prepared from halogenoalkanes
Reagent Excess, alcoholic ammonia (WHY USE EXCESS?)
Conditions Reflux in excess, alcoholic solution under pressure
Product Amine (or its salt due to a reaction with the acid produced)
Nucleophile Ammonia (NH3)
Equation C2H5Br + NH3 (alc) ——> C2H5NH2 + HBr ( or C2H5NH3+Br¯ )
WHY USE EXCESS AMMONIA?
Ammonia attacks halogenoalkanes because it has a lone pair and is a nucleophile.
The amine produced also has a lone pair C2H5NH2 so can also attack a halogenoalkane;
this leads to the formation of substituted amines. Using excess ammonia ensures that all the halogenoalkane molecules react with theammonia before having the chance to react with any amines produced.
PHYSICAL PROPERTIESPHYSICAL PROPERTIES
The LONE PAIR on the nitrogen atom in 1°, 2° and 3° amines makes them ...
LEWIS BASES - they can be lone pair donors
BRØNSTED-LOWRY BASES - they can be proton acceptors
RNH2 + H+ ——> RNH3+
NUCLEOPHILES - provide a lone pair to attack an electron deficient centre
PHYSICAL PROPERTIESPHYSICAL PROPERTIES
Boiling point Boiling points increase with molecular mass
Amines have higher boilingpoints than correspondingalkanes because of theirintermolecular hydrogen bonding
Quarternary ammonium
salts are ionic and exist as salts
Solubility Lower mass compounds aresoluble in water due to hydrogenbonding with the solvent.
Solubility decreases as themolecules get heavier.
Soluble in organic solvents.
BASIC PROPERTIESBASIC PROPERTIES
Bases The lone pair on the nitrogen atom makes amines basic;
RNH2 + H+ ——> RNH3+ a proton acceptor
Strength depends on the availability of the lone pair and its ability to pick up
protons
• the greater the electron density on the N, the better it can pick up
protons
• this is affected by the groups attached to the nitrogen
BASIC PROPERTIESBASIC PROPERTIES
Bases The lone pair on the nitrogen atom makes amines basic;
RNH2 + H+ ——> RNH3+ a proton acceptor
Strength depends on the availability of the lone pair and its ability to pick up
protons
• the greater the electron density on the N, the better it can pick up
protons
• this is affected by the groups attached to the nitrogen
electron withdrawing substituents (benzene rings)decrease basicity as the electron density on N islowered and the lone pair is less effective
C6H5 N:
H
H
BASIC PROPERTIESBASIC PROPERTIES
Bases The lone pair on the nitrogen atom makes amines basic;
RNH2 + H+ ——> RNH3+ a proton acceptor
Strength depends on the availability of the lone pair and its ability to pick up
protons
• the greater the electron density on the N, the better it can pick up
protons
• this is affected by the groups attached to the nitrogen
electron withdrawing substituents (benzene rings)decrease basicity as the electron density on N islowered and the lone pair is less effective
electron releasing substituents (CH3 groups)increase basicity as the electron density isincreased and the lone pair is more effective
CH3 N:
H
H
C6H5 N:
H
H
BASIC PROPERTIESBASIC PROPERTIES
Measurement the strength of a weak base is depicted by its pKb value
the smaller the pKb the stronger the base
the pKa value can also be used;
it is worked out by applying pKa + pKb = 14
the smaller the pKb, the larger the pKa.
Compound Formula pKb Comments
ammonia NH3 4.76
methylamine CH3NH2 3.36 methyl group is electron releasing
phenylamine C6H5NH2 9.38 electrons delocalised into the ring
strongest base methylamine > ammonia > phenylamine weakest base smallest pKb largest pKb
CHEMICAL REACTIONS - CHEMICAL REACTIONS - WEAK BASESWEAK BASES
Water Amines which dissolve in water produce weak alkaline solutions
CH3NH2(g) + H2O(l) CH3NH3+(aq) + OH¯(aq)
Acids Amines react with acids to produce salts.
C6H5NH2(l) + HCl(aq) ——> C6H5NH3+Cl¯(aq) phenylammonium
chloride
This reaction allows one to dissolve an amine in water as its salt.
Addition of aqueous sodium hydroxide liberates the free base from its salt
C6H5NH3+Cl¯(aq) + NaOH(aq) ——> C6H5NH2(l) + NaCl(aq) +
H2O(l)
CHEMICAL REACTIONS - CHEMICAL REACTIONS - NUCLEOPHILICNUCLEOPHILIC
Due to their lone pair, amines react as nucleophiles
Reagent Product Mechanism
haloalkanes substituted amines nucleophilic substitution
acyl chlorides N-substituted amides addition-elimination
NUCLEOPHILIC SUBSTITUTIONNUCLEOPHILIC SUBSTITUTION
HALOALKANES
Amines are also nucleophiles (lone pair on N) and can attack halogenoalkanes to produce a 2° amine. This too is a nucleophile and can react further producing a 3° amine and, eventually an ionic quarternary ammonium salt.
C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, 2° amine
NUCLEOPHILIC SUBSTITUTIONNUCLEOPHILIC SUBSTITUTION
HALOALKANES
Amines are also nucleophiles (lone pair on N) and can attack halogenoalkanes to produce a 2° amine. This too is a nucleophile and can react further producing a 3° amine and, eventually an ionic quarternary ammonium salt.
C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, 2° amine
(C2H5)2NH + C2H5Br ——> HBr + (C2H5)3N triethylamine, 3° amine
NUCLEOPHILIC SUBSTITUTIONNUCLEOPHILIC SUBSTITUTION
HALOALKANES
Amines are also nucleophiles (lone pair on N) and can attack halogenoalkanes to produce a 2° amine. This too is a nucleophile and can react further producing a 3° amine and, eventually an ionic quarternary ammonium salt.
C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, 2° amine
(C2H5)2NH + C2H5Br ——> HBr + (C2H5)3N triethylamine, 3° amine
(C2H5)3N + C2H5Br ——> (C2H5)4N+ Br¯ tetraethylammonium bromide
a quaternary (4°) salt
NUCLEOPHILIC SUBSTITUTIONNUCLEOPHILIC SUBSTITUTION
HALOALKANES
Amines are also nucleophiles (lone pair on N) and can attack halogenoalkanes to produce a 2° amine. This too is a nucleophile and can react further producing a 3° amine and, eventually an ionic quarternary ammonium salt.
C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, 2° amine
(C2H5)2NH + C2H5Br ——> HBr + (C2H5)3N triethylamine, 3° amine
(C2H5)3N + C2H5Br ——> (C2H5)4N+ Br¯ tetraethylammonium bromide
a quaternary (4°) salt
Uses Quarternary ammonium salts with long chain alkyl groups are used as cationic surfactants in fabric softening e.g. [CH3(CH2)17]2N+(CH3)2 Cl¯
AMINO ACIDSAMINO ACIDS
Structure Amino acids contain 2 functional groups
amine NH2
carboxyl COOH
They all have a similar structure - the identity of R1 and R2 vary
H2N C COOH
H
H
H2N C COOH
CH3
H
H2N C COOH
R2
R1
AMINO ACIDS – AMINO ACIDS – OPTICAL ISOMERISMOPTICAL ISOMERISM
Amino acids can exist as optical isomersIf they have different R1 and R2 groups
Optical isomers exist when a moleculeContains an asymmetric carbon atom
Asymmetric carbon atoms have fourdifferent atoms or groups attached
Two isomers are formed - one rotates planepolarised light to the left, one rotates it to the right
Glycine doesn’t exhibit optical isomerism asthere are two H attached to the C atom
H2N C COOH
CH3
H
H2N C COOH
H
H
GLYCINE2-aminoethanoic acid
AMINO ACIDS - AMINO ACIDS - ZWITTERIONSZWITTERIONS
Zwitterion • a dipolar ion
• has a plus and a minus charge in its structure
• amino acids exist as zwitterions
• give increased inter-molecular forces
• melting and boiling points are higher
H3N+ C COO¯
R2
R1
• amino acids possess acidic and basic properties
• this is due to the two functional groups
• COOH gives acidic properties
• NH2 gives basic properties
• they form salts when treated with acids or alkalis.
H2N C COOH
R2
R1
AMINO ACIDS - AMINO ACIDS - ACID-BASE PROPERTIESACID-BASE PROPERTIES
AMINO ACIDS - AMINO ACIDS - ACID-BASE PROPERTIESACID-BASE PROPERTIES
Basic properties:
with H+ HOOCCH2NH2 + H+ ——> HOOCCH2NH3+
with HCl HOOCCH2NH2 + HCl ——> HOOCCH2NH3+ Cl¯
Acidic properties:
with OH¯ HOOCCH2NH2 + OH¯ ——> ¯OOCCH2NH2 + H2O
with NaOH HOOCCH2NH2 + NaOH ——> Na+ ¯OOCCH2NH2 + H2O
PEPTIDES - PEPTIDES - FORMATION & STRUCTUREFORMATION & STRUCTURE
Amino acids can join together to form peptides via an amide or peptide link
2 amino acids joined dipeptide
3 amino acids joined tripeptide
many amino acids joined polypeptide
a dipeptide
PEPTIDES - PEPTIDES - HYDROLYSISHYDROLYSIS
Peptides are broken down into their constituent amino acids by hydrolysis
• attack takes place at the slightly positive C of the C=O
• the C-N bond is broken
• hydrolysis with water is very slow
• hydrolysis in alkaline/acid conditions is quicker
• hydrolysis in acid/alkaline conditions (e.g. NaOH) will produce salts
with HCl NH2 becomes NH3+Cl¯
H+ NH2 becomes NH3+
NaOH COOH becomes COO¯ Na+
OH¯ COOH becomes COO¯
PEPTIDES - PEPTIDES - HYDROLYSISHYDROLYSIS
Peptides are broken down into their constituent amino acids by hydrolysis
H2N C CO
CH3
H
NH C CO
H
H
NH C COOH
CH3
CH3
Which amino acids are formed?
PEPTIDES - PEPTIDES - HYDROLYSISHYDROLYSIS
Peptides are broken down into their constituent amino acids by hydrolysis
H2N C CO
CH3
H
NH C CO
H
H
NH C COOH
CH3
CH3
CH3
H
H2N C COOH
H
H
H2N C COOH
CH3
CH3
H2N C COOH++
H2N C CO
CH3
H
NH C CO
H
H
NH C COOH
H
CH3
PEPTIDES - PEPTIDES - HYDROLYSISHYDROLYSIS
Peptides are broken down into their constituent amino acids by hydrolysis
Which amino acids are formed?
H2N C CO
CH3
H
NH C CO
H
H
NH C COOH
H
CH3
PEPTIDES - PEPTIDES - HYDROLYSISHYDROLYSIS
Peptides are broken down into their constituent amino acids by hydrolysis
CH3
H
H2N C COOH
H
H
H2N C COOH2 x +
PROTEINSPROTEINS
• are polypeptides with high molecular masses • chains can be lined up with each other • the C=O and N-H bonds are polar due to a difference in electronegativity • hydrogen bonding exists between chains
dotted lines ---------- represent hydrogen bonding
AMIDESAMIDES
Structure derivatives of carboxylic acids
amide group is -CONH2
NomenclatureWhite crystalline solids named from the corresponding acid(remove oic acid, add amide)
CH3CONH2 ethanamide (acetamide)
C2H5CONHC6H5 N - phenyl propanamide - the N tells you the
substituent is on
the nitrogen
Nylons are examples of polyamides
Preparation Acyl chloride + ammonia
CH3COCl + NH3 ——> CH3CONH2 + HCl ethanoyl chloride ethanamide
AMIDES - AMIDES - CHEMICAL PROPERTIESCHEMICAL PROPERTIES
Hydrolysisgeneral reaction CH3CONH2 + H2O ——> CH3COOH + NH3
acidic soln. CH3CONH2 + H2O + HCl ——> CH3COOH + NH4Cl
alkaline soln. CH3CONH2 + NaOH ——> CH3COONa + NH3
Identification Warming an amide with dilute sodium hydroxide solution andtesting for the evolution of ammonia using moist red litmus
paperis used as a simple test for amides.
ReductionReduced to primary amines: CH3CONH2 + 4[H] ——> CH3CH2NH2 + H2O