Organic Nitrogen Compounds

11Sc A – BINUS Serpong – 2022-23

 AMINES
CONTENTS
• Prior knowledge
• Structure and classification
• Nomenclature
• Physical properties
• Basic properties
• Nucleophilic properties
• Amino acids
• Peptides and proteins
• Amides
• Check list
 AMINES
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
 STRUCTURE & CLASSIFICATION

Structure Contain the NH2 group

Classification H H

R N: R N:

H R
primary (1°) amines secondary (2°) amines

R R
R N: R N
+ R
R R

tertiary (3°) amines quarternary (4°) ammonium salts

Aliphatic methylamine, ethylamine, dimethylamine

Aromatic NH2 group is attached directly to the benzene ring (phenylamine)
 NOMENCLATURE

Nomenclature Named after the groups surrounding the nitrogen + amine

C2H5NH2 ethylamine

(CH3)2NH dimethylamine

(CH3)3N trimethylamine

C6H5NH2 phenylamine (aniline)

 PREPARATION

Amines can be prepared from halogenoalkanes

Reagent Aqueous, alcoholic ammonia

Conditions Reflux in aqueous, alcoholic solution under pressure

Product Amine (or its salt due to a reaction with the acid produced)

Nucleophile Ammonia (NH3)

Equation C2H5Br + NH3 (aq / alc) ——> C2H5NH2 + HBr ( or C2H5NH3+Br¯ )

 PHYSICAL 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 PROPERTIES

Boiling point Boiling points increase with molecular mass

Amines have higher boiling

points than corresponding
alkanes because of their
intermolecular hydrogen bonding

Quarternary ammonium
salts are ionic and exist as salts

SolubilityLower mass compounds are

soluble in water due to hydrogen
bonding with the solvent.

Solubility decreases as the

molecules get heavier.

Soluble in organic solvents.

 BASIC 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 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

H
electron withdrawing substituents (benzene rings)
decrease basicity as the electron density on N is C 6H 5 N:
lowered and the lone pair is less effective
H
 BASIC 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

H
electron withdrawing substituents (benzene rings)
decrease basicity as the electron density on N is C 6H 5 N:
lowered and the lone pair is less effective
H

H
electron releasing substituents (CH3 groups)
increase basicity as the electron density is CH3 N:
increased and the lone pair is more effective
H
 BASIC PROPERTIES

Measurement the strength of a weak base is depicted by its pK b 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 - WEAK 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 - NUCLEOPHILIC

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 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 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 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 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¯
Making Amines
• Preparing ethylamine
• Preparing phenylamine

Reactions of phenylamine
• Phenylamine with aqueous bromine
• Diazotisation and coupling reactions

Refer to textbook pp. 403-404!

 AMINO ACIDS

Structure Amino acids contain 2 functional groups

R1
amine NH2
H2N C COOH
carboxyl COOH
R2

They all have a similar structure - the identity of R 1 and R2 vary

H H

H2N C COOH H2N C COOH

H CH3
 AMINO ACIDS – OPTICAL ISOMERISM

Amino acids can exist as optical isomers

If they have different R1 and R2 groups
H
Optical isomers exist when a molecule
Contains an asymmetric carbon atom H2N C COOH
Asymmetric carbon atoms have four CH3
different atoms or groups attached

Two isomers are formed - one rotates plane

polarised light to the left, one rotates it to the right

H
Glycine doesn’t exhibit optical isomerism as
there are two H attached to the C atom
H2N C COOH

H
GLYCINE
2-aminopropanoic acid
 AMINO ACIDS - ZWITTERIONS

Zwitterion • a dipolar ion

• has a plus and a minus charge in its structure (see below)
• amino acids exist as zwitterions
• give increased inter-molecular forces
• melting and boiling points are higher

R1

H3N+ C COO¯

R2
 AMINO ACIDS - ACID-BASE PROPERTIES

• amino acids possess acidic and basic properties

• this is due to the two functional groups (see above)
• COOH gives acidic properties
• NH2 gives basic properties
• they form salts when treated with acids or alkalis.

R1

H2N C COOH

R2
 AMINO ACIDS - ACID-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 - FORMATION & 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 - HYDROLYSIS

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 - HYDROLYSIS

Peptides are broken down into their constituent amino acids by hydrolysis

H H CH3

H2N C CO NH C CO NH C COOH
CH3 H CH3

Which amino acids are formed?

 PEPTIDES - HYDROLYSIS

Peptides are broken down into their constituent amino acids by hydrolysis

H H CH3

H2N C CO NH C CO NH C COOH
CH3 H CH3

H H CH3

H2N C COOH + H2N C COOH + H2N C COOH

CH3 H CH3
 PEPTIDES - HYDROLYSIS

Peptides are broken down into their constituent amino acids by hydrolysis

H H H
H2N C CO NH C CO NH C COOH
CH3 H CH3

Which amino acids are formed?

 PEPTIDES - HYDROLYSIS

Peptides are broken down into their constituent amino acids by hydrolysis

H H H
H2N C CO NH C CO NH C COOH
CH3 H CH3

H H

2x H2N C COOH + H2N C COOH

CH3 H
 PROTEINS

• 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

 AMIDES

Structure derivatives of carboxylic acids

amide group is -CONH2

Nomenclature White 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 - CHEMICAL PROPERTIES

Hydrolysis
general 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 and

testing for the evolution of ammonia using moist red litmus paper
is used as a simple test for amides.

Reduction
Reduced to primary amines: CH3CONH2 + 4[H] ——> CH3CH2NH2 + H2O
Thank you….!