CHM 102

Chemistry of Ethers, Amines, Nitriles and Carboxylic

Acid Derivatives

Dr. NELLY A. NDUKWE

Chemistry of Amines
• Amines: are derivatives from ammonia (NH3).
• Aliphatic amines: an amine in which nitrogen is bonded only to alkyl
group or hydrogens.
• Aromatic amines: an amine in which nitrogen is bonded to one or
more aromatic rings.

• Note: amines are classified as primary (°1), secondary (°2) or

tertiary (°3), depending on
• the number of carbon groups bonded to the nitrogen.
•
 Alcohols and Ethers
Alcohols and Ethers can be regarded as derivatives of water
in which one or two of the H atoms has been replaced by an
alkyl group
Methanol, CH3OH
Water, H2O o 0.96 Ao
0.96 A
O
O H C H
H H Saturated molecules
H H 1.43 A o
are sp3 hybridized
104.5o 108.5o
Methoxymethane, CH3OCH3
o - I (net dipole)
1.43 A
O 
H C C H O 
H3C H
H H H H 1.10 Ao
109.5o 111.7o
Electronegativity of oxygen causes an
unsymmetrical distribution of charge
 Alcohols are found to have much higher bpt than those of alkanes or
haloalkanes of comparable size, e.g. Methanol (65 oC),
Chloromethane and Methane are gases ; Ethanol (78.5 oC),
Chloroethane (12 oC) and Ethane is a gas

Methanol and Ethanol are classed as Polar Molecules (Hydrophilic)

– They are Infinitely Soluble in Water

Why? Answer – Hydrogen Bonding

R
R H
O  H
H O O 
 H H  O
H H H
O O
R H
H-bonds weaker than covalent bonds, although these bonds can be
continually broken and reformed – a highly ordered structure
results – H-Bonding to water can also occur
Water (mw = 18) is a liquid, bpt 100oC – otherwise a gas
 Ethanol 1-Pentanol Hydrophilic end
H H H H H H H
As R-group increases in size,
H C C O H C C C C C O
so does the solubility in non-
H H H H H H H H H polar solvents

Hydrophobic end
As the number –OHs increases so does solubility in water
Bpt increase with chain length and number of –OHs

Methanol, CH3OH In the Liver O

[O] O
- Solvent in varnishes, paint H3C OH
H
C
H
C
- Racing Car Fuel (easy to put H OH
Alcohol Dehydrogenase
out flames)
- Highly Toxic – “Blindness” -
Formaldehyde In the Liver O
[O] O
Ethanol, CH3OH CH3CH2OH C C
H3C H H3C OH
-Drinking Alcohol Acetaldehyde
Alcohol Dehydrogenase Acetic Acid
- 50% Ethanol is
flammable Odour on your breath
Symptoms - Hang-over
Ethanol content; Beer, 3-9% ; Wine, 11-13% ; Whisky, 40-45% ; Vanilla Extracts, 35% ;
Night Nurse, 25% ; Listerine, 25%

Preparation of Ethanol
- Fermentation of Sugar – Break down of sugar to CO2
and Ethanol by Yeast Enzymes
- Industrial Process – Hydration of Ethene
H H H2O
CH3CH2OH
H H H3PO4 , 300C
Naming Alcohols hydroxy or alcohol group
CH3 OH CH3 CH2 CH2 OH
CH3 CH2 OH
Methyl alcohol
(methanol) Ethyl alcohol (ethanol) Propyl alcohol (propanol)

CH3 CH OH CH3 CH2 CH CH2 CH3

CH3 CH2 OH
Isopropyl alcohol 2-Ethyl-1-butanol
 Naming Alcohols
Polyhydroxy alcohols are alcohols that possess more than one
hydroxyl group
CH2 CH CH2
CH2 CH2 CH3 CH CH2 HO HO OH
HO OH HO OH 1,2,3-Propanetriol (glycerol)
1,2-Propanediol (propylene glycol)
1,2-Ethanediol (ethylene glycol)

Harmless
Extremely Toxic O O
Calcium Oxalate CH2 CH2 HO C C OH
crystallises in the kidney
HO OH Liver Enzymes Oxalic acid
leading to renal problems
O O
CH3 CH CH2 H3C C C OH
HO OH Liver Enzymes Pyruvic acid
 H CH3 CH3
H3C C OH H3C C OH H3C C OH
H H CH3
o
Secondary (2 ) Alcohol
Primary (1o) Alcohol
Tertiary (3o) Alcohol

Alcohols are very weak Acids

H H
R O H O H R O + H O H
  
Alkoxide
Alcohol

Relative Acidity ; H2O > ROH > R C C H > RH

2 CH3CH2OH + 2 Na 2 CH3CH2 O Na + H2

Vigorous Reaction
STEREOCHEMISTRY

10
Isomers are different compounds that have the same molecular formula
Structural isomers are isomers that differ because their atoms are
connected in a different order

CH3OCH3 ---- dimethyl ether and

CH3CH2OH ---- ethanol

Stereoisomers differ only in the arrangement of

their atoms in space
Geometric Isomers

Cl H Cl H
C2H2Cl2
Cl H H Cl
cis-1,2-Dichloroethene trans-1,2-Dichloroethene
 Enantiomers are stereoisomers whose molecules are
nonsuperimposable mirror images of one another
Objects that are superimposable on their
mirror images are said to be achiral

Involves a tetrahedral sp3 atom

H
CH3 C CH2 CH3
OH
Chiral Centre
2-Butanol
CH3 CH3
HO H H OH Interchanging any two groups at a chiral
C C
centre (stereocentre) that bears four
CH2 CH2 different groups converts one enantiomer
CH3 CH3 into another
 One structure can be superimposed on another

CH3 CH3 If any of the groups

H C OH HO C H attached to the
tetrahedral atom are
CH3 CH3 the same, the centre
is achiral.
2-Propanol

The ultimate way to test for Screwdriver is achiral

molecular chirality is to construct Socks are achiral
models of the molecule and its
Golf club is chiral
mirror image and then determine
Gloves are chiral
whether they are superimposable

A molecule will not be chiral if it possess a

centre or plane of Symmetry
 Properties of Enantiomers
Enantiomers have identical melting points and boiling points
Enantiomers have identical solubilities in solvents
Enantiomers have identical spectra and refractive index
Enantiomers interact, and react with achiral molecules in the
same manner
Enantiomers interact and react with other
chiral molecules at different rates
Enantiomers rotate plane-polarised light by
equal amounts but in opposite directions
Chiral molecules are
optically active Plane-polarised light

Oscillation of electrical field of ordinary light

occurs in all possible directions
Polarimeter is a devise used to measure the effect of plane-
polarised light on an optically active compound
 No Correlation between the direction of rotation of plane
polarised light and the absolute configuration of a molecule
Clockwise Rotation (+) – dextrorotatory
Anti-Clockwise Rotation (-) – levorotatory

Same Configuration

CH3 CH3
H2C H2C
C H C H
HO Cl
CH2CH3 CH2CH3

(R)-(+)-2-Methyl-1-butanol (R)-(-)-1-Chloro-2-methylbutanol

An equimolar mixture of two enantiomers is called a Racemic Mixture

It is Optically Inactive
15
O O

H
H

S-(+)-Carvone R-(-)-Carvone

Principle component of Principle component

Caraway seed oil and of Spearmint oil and
responsible for the responsible for the
characteristic odour characteristic odour

Receptor Sites in the Nose are Chiral

16
Acidic H2O and Nitriles
 The cyano group is hydrolyzed in aqueous acid to a
carboxyl group and ammonium ion.
O
H2 O + -
Ph CH2 C N + 2 H2 O + H2 SO4 Ph CH2 COH + NH4 HS O4
he at
Phenylacetonitrile Phenylacetic Ammonium
acid hydrogen sulfate

• Protonation of the cyano nitrogen gives a cation that reacts with

water to give an imidic acid.
• Keto-enol tautomerism gives the amide.
OH Acid
+ O
+
R-C N + H2 O H R-C NH R-C-NH2
Ammoniu
An imidic acid An amide
(enol of an amide) m
ion
18-17
Basic H2O and Nitriles
• Hydrolysis of a cyano group in aqueous base gives a carboxylic
anion and ammonia; acidification converts the carboxylic anion
to the carboxylic acid.
O
NaOH, H2 O - +
CH3 ( CH2 ) 9 C N CH3 ( CH2 ) 9 CO Na + NH3
heat
Undecanenitrile Sodium undecanoate

HCl H2 O

O
CH3 ( CH2 ) 9 COH + NaCl + NH4 Cl
Undecanoic acid

18-18
Synthesis: Reaction with H2O - Nitriles
• Hydrolysis of nitriles is a valuable route to
carboxylic acids.
O
KCN H2 S O 4 , H2 O
CH 3 ( CH2 ) 8 CH2 Cl CH3 ( CH2 ) 9 C N CH3 ( CH2 ) 9 COH
ethanol, heat
1-Chlorodecane water Undecanenitrile Undecanoic acid

OH OH
CHO HCN , KCN H2 S O 4 , H2 O
CN COOH
ethanol, heat
water
Benzaldehyde Benzaldehyde cyanohydrin 2-Hydroxyphenylacetic acid
(Mandelonitrile) (Mandelic acid)
(racemic) (racemic)

18-19
Synthesis: Grignards + Nitriles ->ketone 1

NMgX NH
R'MgX H2O
RC N RCR' RCR'
diethyl
ether
 Grignard reagents add to carbon-nitrogen triple
bonds in the same way that they add to carbon-
oxygen double bonds.
 The product of the reaction is an imine.

18-20
Synthesis: Grignards + Nitriles ->ketone 2

NMgX NH
R'MgX H2O
RC N RCR' RCR'
diethyl
ether H3O+

Imines hydrolyzed to ketones.

O

RCR'

18-21
Carboxyl Derivatives
Classes shown, formally, via dehydration.

O O O O O
RCCl RCOCR' RCOR' RCNH2 RC N
An acid An acid An ester An amide A nitrile
chloride anhydride

-H2 O
-H2 O -H2 O -H2 O -H2 O
O O O O O HO H
RC-OH H-Cl RC-OH H-OCR' RC-OH H-OR' RC-OH H-NH2 RC= N
The enol of
an amide

18-22
Structure: Acid Chlorides
 The functional group of an acid halide is an acyl group
bonded to a halogen.
• The most common are the acid chlorides.
• To name, change the suffix -oic acid to -oyl halide.
O O
O O Cl Cl
Cl
RC- CH3 CCl
O
An acyl Ethanoyl chloride Benzoyl chloride Hexanedioyl chloride
group (Acetyl chloride) (Adipoyl chloride)

18-23
18-24
Autoxidation of Ethers
 Autoxidation is the spontaneous oxidation of a compound in air. In the
presence of oxygen, ethers slowly autoxidize to form hydroperoxides
and dialkyl peroxides. If concentrated or heated, these peroxides may
explode. To prevent such explosions, ethers should be obtained in small
quantities, kept in tightly sealed containers, and used promptly.

18-25
18-26