In Class-2 Exam-Revision-Dr. Sherif Fahmy2

Advanced Chemistry
Help Session-Revision
Prepared and Presented by Dr. Sherif Ashraf Fahmy
Assistant Professor of Chemistry
s.fahmy@gaf.edu.eg
s.fahmy@herts.ac.uk
Definitions & Important Notes
Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

1- Electrophilic Reaction: A reaction which involves electrophile attack on a negatively charged centre in a molecule
2- Nucleophilic Reaction: One involving attack on a positively charged center in a molecule.
3- Nucleophile: A species which attacks a positively charged center in a molecule; An electron pair donor.
4- Esterification (condensation reaction): Two molecules link together with the removal
of a molecule of water (or another small molecule such as HCl or NH3).
5- Fats: Are esters of the trihydric alcohol, glycerol, and long-chain fatty acids. They are known as triglycerides
6- When fats or oils are boiled with sodium hydroxide solution they are hydrolysed to glycerol and the sodium
salts of the fatty acids (soap).
7- Biodiesel: Is a mixture of methyl ester of long-chain carboxylic acids and is produced by reacting vegetable
oils with methanol in the presence of a catalyst.
One catalyst which can be used is a combination of aluminium oxide and potassium iodide

8- Basicity of amines
A base is a proton acceptor
The nitrogen atom in ammonia and the amines has a lone-pair of electrons. This allows them to accept a
proton (H+ ion) and act as a base.
R R
+
R N: + H R N H
R R

Basicity of amines
The strength of the amines as bases depends on the nature of the R- groups attached to the nitrogen atom
Alkyl is electron donating Aryl is electron withdrawing

Increases the electron density on the nitrogen atom Decreases the electron density on the nitrogen atom
thus it increases the availability of the lone pair thus it decreases the availability of lone pair,
therefore, it will attract protons more strongly. therefore it will attract protons less strongly.
This increases the base strength. This decreases the base strength.
Alkyl groups are electron donating Aryl groups are electron withdrawing
The order of base strength is: The order of base strength is:
CH3-NH-CH3 Dimethylamine CH3-NH2 Methylamine

CH3-NH2 Methylamine NH3 Ammonia
NH2
NH3 Ammonia Phenylamine
Decreasing base strength Decreasing base strength

9- Zwitterion: Amino acids contain both a basic group (-NH2) H
and an acidic group (-COOH). In solution the carboxyl group

H3N
+
C
-
COO
can lose a proton and the amino group can gain one the give
R
an ions with a positive and negative charge.
10- Isomers are different chemical compounds which have the same molecular formula
11- Structural Isomerism: The isomers have different structural formulae.
12- Stereoisomerism: The isomers have the same structural formula but the atoms are
arranged differently in three-dimensional space.

13- Optical isomers are a pair of non-identical mirror image forms of a molecule.
This occurs when a molecules contains a chiral centre. i.e. a carbon atom attached to 4 different atoms or
groups. A molecule can also exist as optical isomers if it contains no plane of symmetry.
Enantiomers of lactic
acid
14- Enantiomers: Non-identical mirror image forms.
15- When a compound is synthesised using a chemical method a mixture of equal amounts
of both enantiomers is formed.
This is called a Racemate or Racemic Mixture
A racemate shows no optical activity.

Isomerism Practice
CH3 H
C C NO
CH3 H
methylpropene
H H
H Cl
C C YES
C C
Z E
CH3 Cl
CH3 H
1-chloropropene

Isomerism Practice
CH3 CH2 CH3
C C NO
CH3 H
2-methylpent-2-ene
H CH2 CH2 CH3
C C
NO
H CH2 CH3
2-ethylpent-1-ene

Isomerism Practice
CH3 CH3 H CH3
C C C C YES
E Z
H CH2 CH3 CH3 CH2 CH3
3-methylpent-2-ene
H H
C C
NO
H CH2 CH3
but-1-ene

16- Why primary, secondary and tertiary halides undergo different substitution
mmechanisms?
because of the stability of the carbocation (carbonium ion) involved.
Because of the slight electron donating effect of alkyl groups, the tertiary carbocation is the
most stable, followed by the secondary, with the primary carbocation being the least stable.
CH3 H H
+ + +
H3C C H3C C H3C C
CH3 CH3 H
Most Stable Least Stable
17- Condensation Polymers

Condensation Reaction: Two molecules combine with the removal of a small molecule, e.g.
water, ammonia or HCl

18- Polymerisation is a reaction in which a large number of small molecules (monomers)
react to form long-chain molecules (polymers).
19- Condensation Polymers
Condensation Reaction: Two molecules combine with the removal of a small molecule, e.g.
water, ammonia or HCl

20- Biodegradability
There is concern about the environmental dangers of waste plastics.
Some plastics persist in the environment for a considerable time as they do not degrade.
Other plastics can degrade under the influence of bacteria or sunlight.
Condensation polymers
Addition polymers such as contain either ester groups
polyethene or polypropylene (-CO-O-) or amide groups (-
contain stable C-C bonds and are CO-NH-) and are more
not biodegradable. likely to be biodegradable.
However some polyester
Solution: Recycling fibres and nylon are very
stable and biodegrade very
slowly.
21- WHY PET is better for environment?
Biodegradability
Addition polymers such as Condensation polymers

polyethene or polypropylene contain either ester groups
contain stable C-C bonds and are (-CO-O-) or amide groups (-
not biodegradable. CO-NH-) and are more
likely to be biodegradable.
Solution: Recycling However some polyester
fibres and nylon are very
stable and biodegrade very
slowly.

Naming

1- Aromatic Compounds
NO2 Cl Cl
Cl
Benzene Nitrobenzene Chlorobenzene 1,2-dichlorobenzene

CH3 COOH CHO
Cl
Methylbenzene Benzenecarboxylic acid Benzenecarbaldehyde

Cl
Toluene Benzoic acid Benzaldehyde 1,4-dichlorobenzene

2. Alkyl halides
Br
I Cl
Cl
2-Iodo-2-methylbutane 3-Choro-2-methylpentane 1-bromo-3-chloro-4-methylpentane

( tert. pentyl iodide)
Br
2-bromo-5-methylhexane

3. Alcohols
CH3-OH Methanol
CH3-CH2-OH Ethanol
CH3-CH2-CH2-OH Propan-1-ol
CH3-CH(OH)-CH3 Propan-2-ol
CH3-CH2-CH2-CH2-OH Butan-1-ol
CH3-CH2-CH(OH)-CH3 Butan-2-ol
(CH3)3C-OH Methylpropan-2-ol
4. Carbonyl compounds
Structure Name
Pentanal
2-methybutanal
2, 2-dimethypropanal
Pentan-3-one
? Pentan-2-one
5. Carboxylic acids
Ethanoic acid (Acetic Acid)
Propanoic acid
Benzene carboxylic acid (Benzoic acid)

Classifications

1- Classification of alkyl halides:
Primary Secondary Tertiary
H3C CH2 Cl CH3 CH3
H3C CH Cl H3C C Cl
CH3

2- Classification of Alcohols
H H CH3
H3C C CH3 H3C C CH3

H3C C OH
OH OH
H
Primary (1o) Alcohol o

Secondary (2 ) Alcohol Tertiary (3o) Alcohol

3- Classification of Amines
N N N
R1 H R1 H R1 R3
H R2 R2
Primary Secondary Tertiary
1° 2° 3°

Preparations

1- Preparation of alkyl halides:-
a) Free radical halogenation of alkanes:-
H H
H C H + Cl2 light + HCl
H C Cl
H H
b) Hydrohalogenation of alkenes:
CH3 CH3
HX (X = Cl, Br)
C CH2 C CH2
H H
X H
C) Halogenation of alkenes:
Br Br
H2C CH2 + Br2 H2C CH2
ethene 1,2-dibromoethane
2- Preparation of Alcohols -Getting a higher alcohol content by Distillation
A. Fermentation of Glucose -Fermented liquid is boiled in a closed container .
YEAST
C6H12O6 2 CO2 (g) + C2H5OH -Ethanol has a lower boiling point than water
(78Oand 100O), so boils off first.
B- Hydration of Ethene
Reaction between Ethene and Steam over a phosphoric acid catalyst;
H2C=CH2 (g) + H2O (g) → C2H5OH (g)
C- Hydrolysis of a Halogenoalkane (Substitution Reaction)

CH3-CH2-Br + NaOH CH3-CH2-OH + NaBr
If a Halogenoalkane is boiled with an aqueous Sodium Hydroxide solution, the Halogen atom
gets Substituted by a hydroxyl-group Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021
3- Preparation of aldehydes and ketones
[O]
Primary Alcohols ALDEHYDES
CH3-CH2-OH + [O] → CH3-CHO + H2O
[O]
Secondary Alcohols KETONES
CH3-CH(OH)-CH3 + [O] → CH3-CO-CH3 + H2O
H3C CH CH3 + [O] → H3C C CH3 + H2O

OH O
4- Preparation of Carboxylic acids
a) Strong oxidation with a mixture of sodium dichromate and sulphuric acid, of
Primary alcohols;
CH3-CH2-OH + 2 [O] → CH3-COOH + H2O
Or
Aldehydes;
CH3CHO + [O] → CH3COOH
b) The hydrolysis of a nitrile by boiling with dilute hydrochloric acid.
CH3-CH2-CN + 2 H2O → CH3-CH2-COOH + NH3

Reactions & Mechanisms

I. Electrophilic Aromatic Substitution Reaction
/H NO2
HNO3 2SO4 + H 2O
(Nitration)
Nitrobenzene
/ AlX X
X2 3 + HCl (Halogenation)
X=Cl..Chlorobenzene
X=Br..Bromobenzene
R
RBr / AlCl3 (Friedel - Crafts
+ HBr
Alkylation )
Alkylbenzene
O
RCOCl / AlCl3 R + (Friedel - Crafts

HCl
Acylation )
Acyl benzene
1) Nitration of benzene
 Reagent of nitration: mixture of Conc HNO3/ H2SO4
 The electrophile : nitronium ion NO2+
 The product of reaction: nitrobenzene
NO2
H2SO4
+ HNO3 + H 2O (Nitration)
Nitrobenzene
Reduction of Nitrobenzene
Nitrobenzene is a useful intermediate in synthesis as it can be easily reduced to phenylamine (aniline)
The reduction is carried out using tin metal and concentrated hydrochloric acid as the reducing agent.
O
+
N Sn(s) + HCl NH2
-
O
+ 6H+ + 2H2O

Mechanism of Nitration
Step 1: Generation of electrophile (NITRONIUM ION)
+ H + -
HNO3 2SO4
H2NO3 + HSO4
H2NO3+ NO2+ + H 2O
Step 2: Addition of nitronium to benzene

H H
H H H
H
+ NO + NO2
2
H H H H
H H
Step 3: Deprotonation to regenerate aromaticity & give nitrobenzene
H
H H
H H NO2
NO2 + H
+
H H H H
H H
2) Halogenation of benzene:
 Reagent of halogenation: Cl2 in presence of lewis acid( AlCl3)
 The electrophile : Cl+
 The product of reaction: chlorobenzene
AlCl3 Cl
+ Cl2 + HCl

Mechanism of Halogenation
Step 1: Generation of electrophile (CHLORONIUM ION)
Cl Cl
Cl Al + Cl Cl
Cl Al
–
Cl + Cl+
Cl
Cl
Step 2: Addition of Cl+ to benzene

H H
H H H
H
+ Cl+ Cl
H H H H
H H
Step 3: Deprotonation to regenerate aromaticity & give chlorobenzene
H
H H
H H Cl
Cl + H
+
H H H Dr. Sherif Ashraf Fahmy

H Revision In-class 2 Exam
H H
Spring 2021
3) Friedel Craft alkylation:
It is the reaction of benzene with alkyl halide in presence of AlCl3 to give alkylbenzene
 Reagent of alkylation: alkyl halide / AlCl3
 The electrophile : R+
 The product of reaction: alkylbenzene
R
+ RCl AlCl3
+ HCl

Mechanism of Alkylation
Step 1: Generation of electrophile (For example Methyl cation)

Cl Cl
+
– +
Cl Al Cl CH3
Cl Al + H3C Cl
Cl
Cl
Step 2: Addition of CH3+ to benzene
H H
H H H
H
+ CH + CH3
3
H H H H
H H
Step 3: Deprotonation to regenerate aromaticity & give methylbenzene
H
H H
H H CH3
CH3 + H
+
H H H H Dr. Sherif Ashraf Fahmy

H Revision In-class 2 Exam
H Spring 2021
II-Reactions of Alkyl halides
Substitution Reactions Elimination Reactions

The halogen atom is replaced by a Hydrogen halide is removed from the
different atom or group. halogenoalkane to form an alkene.
Replacement of the halogen by Nucleophiles
HO- NH3 or RNH2 CN-

a hydroxy group to an amino group Cyanide
form an alcohol to form an amine to form a nitrile
Dr. Sherif Ashraf Fahmy

Revision In-class 2 Exam
Spring 2021
Mechanism of Substitution Reactions
H3C CH2 Cl
A- Primary Halogenoalkanes
Experiment shows that:
Rate = k[Halogenoalkane][OH-]
The reaction is second order overall and the rate determining step must involve a reaction
between one molecule of the halogenoalkane and one OH- ion.
This is the SN2 Mechanism
H H
H3C C Cl + :OH - H3C C OH + Cl-
H H
Mechanism of Substitution Reactions
CH3
B- Tertiary Halogenoalkanes H3C C Cl
CH3
Here the rate equation is:
Rate = k[Halogenoalkane]
The reaction is first order and implies that the rate determining step involves only one molecule
of the halogenoalkane.
This is the SN1 Mechanism
CH3 H3C
+
+
H3C C Cl H3C C Cl-
CH3 CH3
H3C CH3
H3C C
+
+ :OH- H3C C OH
CH3 CH3 Revision In-class 2 Exam
Spring 2021
2. Elimination Reactions
Elimination of hydrogen halide from a halogenoalkane is carried out by warming it with a
solution of sodium hydroxide in ethanol (not water(aqueous)!)
H3C CH2 Br + NaOH H2C CH2 + NaBr + H2O
HALOGENOALKANE ALKENE
Mechanism of Elimination

III. Reactions of alcohols
i- Dehydration
An Elimination Reaction
The Removal of a water molecule from an Alcohol molecule to form an Alkene, either by:
1- Heating the alcohol with excess concentrated H2SO4 (A powerful dehydrating agent) at
180O.
Or,
2- Passing the alcohol vapour over heated Aluminium Oxide (acts as a catalyst for the
Dehydration).
C2H5OH (l) → CH2=CH2 (g) + H2O (l)

Ethene

ii- Esterification
A condensation Reaction
Reaction conditions:
- Warming
- Concentrated H2SO4: Catalyst
Alcohol + Carboxylic acid → Ester + Water
R-COOH (l) + R’-OH (l) → R-CO-O-R’ (l) + H2O (l)
CH3COOH + C2H5OH → CH3COOC2H5 + H2O

Ethyl Ethanoate
H3C C OH + HO CH2 CH3 H3C C O CH2 CH3 + H2O
O O
iii- Oxidation (K2Cr2O7/ H2SO4)
Mild oxidation
C2H5OH + [O] → CH3CHO + H2O
Ethanal
Strong oxidation
C2H5OH + 2 [O] → CH3COOH + H2O
Ethanoic acid
Secondary alcohols form ketones on being oxidised.

H3C CH CH3 + [O] H3C C CH3 + H2O
OH O
CH3
Tertiary Alcohols do not
H3C C CH3
OH
Tertiary (3o) Alcohol

IV. Reactions of Carbonyl compounds
1- OXIDATION
Distinguishing ALDEHYDES and KETONES
ALDEHYDES CARBOXYLIC ACIDS
E.g.: Acidified sodium dichromate solution (Na2Cr2O7 in H2SO4 )

CH3CHO + [O] → CH3COOH
2- Distinguishing ALDEHYDES and KETONES via Oxidation
Oxidation of Carbonyl Compounds
ALDEHYDES are easily oxidised.

KETONES are not easily Dr. Sherif Ashraf Fahmy
So can act as reducing agents. oxidised Revision In-class 2 Exam
Spring 2021
2- Nucleophilic Addition of Hydrogen Cyanide (HCN)
(A method of adding an extra carbon atom into a carbon chain)
When a carbonyl compound is warmed with a slightly alkaline solution of KCN, the product
contains a –CN (nitrile) group and an –OH (hydroxyl) group, And so is a Hydroxyl Nitrile.
Mechanism

Spring 2021
3- Reduction
Sodium tetrahydridoborate (NaBH4) can reduce Carbonyl compounds to Alcohols, in solution in water.
A- Aldehydes reduced to primary alcohols.
CH3CHO + [H-] + H+ → CH3-CH2-OH
B- Ketones reduced to secondary alcohols.
CH3-CO-CH3 + [H-] + H+ → CH3-CH(OH)-CH3

V. Reactions of Carboxylic acids/acyl chlorides/acid anhydride
1- Esterification (also in alcohols)
E.g. The reaction between propanoic acid and methanol is:
CH3-CH2-COOH + CH3-OH → CH3-CH2-CO-O-CH3 + H2O
Also, acyl chloride and acid anhydride;

Acyl chloride + Alcohol → Ester + HCl
CH3COCl + CH3-CH2-OH → CH3-CO-O-CH2-CH3 + HCl
Acid anhydride + Alcohol → Ester + Carboxylic acid
CH3-CO-O-CO-CH3 + CH3-CH2-OH → CH3-CO-O-CH2-CH3 + CH3-COOH

4- Reactions with ammonia and primary amines to form amides (acyl chlorides/acid
anhydride) :
CH3COCl + NH3 → CH3-CO-NH2 + HCl
CH3-CO-O-CO-CH3 + NH3 → CH3-CO-NH2 + CH3-COOH
CH3COCl + CH3-NH2 → CH3-CO-NH-CH3 + HCl
CH3-CO-O-CO-CH3 + CH3-NH2 → CH3-CO-NH-CH3 + CH3-COOH

Preparation of Aspirin
Ethanoic anhydride is used to acetylate 2-hydroxybenzoic acid in the manufacture of
aspirin.
O O
OH H3C C O C CH3
+ O + H3C COOH
H3C C COOH
COOH
O

VI. Ester hydrolysis
Esters can be hydrolysed in two ways
Acid Hydrolysis Alkaline Hydrolysis
Ester is boiled with a dilute acid. Ester is boiled in a Sodium hydroxide solution
O O
H2O NaOH
H3C C O CH2CH3 H3C C O CH2CH3
O O
H3C C OH + HO CH2CH3 H3C C O Na + HO CH2CH3

Acid Alcohol Sodium salt of the Carboxylic acid Alcohol
Alkaline Hydrolysis is faster than acid

hydrolysis and goes to completion
VII. Formation of a dipeptide (condensation reaction)

VIII. Polymers
Polymers can be of two types depending on the type

of reaction by which they are formed:
1- Addition reactions 2- Condensation reactions

form addition polymers form condensation
polymers that contain
either:
Ester group: -CO-O-
Amide group: -CO-NH-

Polyesters
These are formed from a dicarboxylic acid (acid) and a diol (alcohol).
This is also known as terylene or poly(ethylene terephthalate)

PET
O O
O H 2C H 2C O C C
Repeat unit Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021
Polyesters
It is also possible to produce a polymer form a monomer which has two functional groups
which react together.
E.g. HO-CH2-CH2-COOH
Draw a section of the polymer chain formed from this monomer containing three repeating
units.
O O O
O H2C CH2 C O CH2 CH2 C O CH2 CH2 C
Draw the repeat unit of the polymer
O
O H2C CH2 C
n
Tests

1-To differentiate between primary, secondary and tertiary alcohols:
Use A mixture of Sodium Dichromate (Na2Cr2O7) and H2SO4 acid.
Primary and Secondary alcohols
The Orange dichromate ion gets reduced to Green Chromium (III)
Tertiary Alcohols are resistant to OXIDATION.

2- Distinguishing ALDEHYDES and KETONES via Reduction
i- Fehling’s Reagent
Copper (II) ions as a Tartrate complex.

When warmed with an ALDEHYDE, Copper (II) is reduced to a red/orange precipitate of
Copper (I) oxide.
Cu2+ → Cu2O
Oxidized Species: ALDEHYDE

Reducing Agent: ALDEHYDE
Reduced Species: Cu2+ in Fehling’s Reagent

Oxidizing Agent: Cu2+ in Fehling’s Reagent

Ii- Tollens Reagent (Silver mirror test)
When warmed with an ALDEHYDE,

Silver (I) (Ag+) is reduced to a coating of SILVER (Ag)
on the tube walls.
Ag+ → Ag
Oxidized Species: ALDEHYDE
Reducing Agent: ALDEHYDE
Reduced Species: Ag+ in Tollens Reagent
Oxidizing Agent: Ag+ in Tollens Reagent

3-To test carboxylic acids:
Carboxylic acids can be identified by their reaction with carbonates:

Effervescence:
Although they are weak acids, they will release carbon dioxide from
carbonates;
CH3-COOH + Na2CO3 → 2 CH3-COONa + H2O + CO2

Uses

1- Uses of Alcohols
In Lamps In Alcoholic drinks As Fuels As Antiseptics
2- Uses of Esters
Esters are liquids with pleasant fruity smells.
Used as fragrances and flavouring agents in perfumes and soaps.
2- Uses of Acyl chlorides and acid anhydrides : are acylating agents.

Ethanoic anhydride is used to acetylate 2-hydroxybenzoic acid in the manufacture of
aspirin. O
O
OH H3C C O C CH3
+ O + H3C COOH
H3C C COOH
COOH
O
Mass SPECTROSCOPY IR SPECTROSCOPY
SPECTROSCOPY
NMR SPECTROSCOPY
1H-NMR 13C-NMR

Mass Spectrometry

Spring 2021
Mass Spectrometry
 When an organic compound is analysed using Mass Spectrometry:
it undergoes Fragmentation.
 Consequently, a number of PEAKS are recorded on the Spectrum.
These PEAKS correspond to the:
1. Complete Molecular Ion (has not been fragmented)
2. Fragments of lower molecular mass.
The most important PEAK on a Mass Spectrum is that of highest mass.
This corresponds to the complete molecule and is called the Molecular Ion PEAK.
The mass of this PEAK is the molecular mass of the compound.

Mass Spectrometry
Focus on the Ethanol spectrum, and try to observe and deduce the following;
 The PEAK of maximum mass is at 46.
 This corresponds to the C2H5OH+ ion.
 This tells us that the molecular mass
of Ethanol is 46.
Mass spectrum of Ethanol

Mass Spectrometry
 Identifies the Molecular Ion (M+), which corresponds to the peak with the greatest
M/Z value.
 This determines the molecular mass of the molecule
 Excess energy from the ionisation process causes the Molecular Ion to vibrate, its bonds get
weakened, and it breaks into Fragments.
 We can then use fragment ions to help identify the molecule.
 The mass spectrum acts as a fingerprint that can be identified from a spectral data base

Problem
Employing Spectroscopic Information to arrive at the IDENTITY of an
unknown Compound
Compound R contains 61.0% carbon and 11.9% Hydrogen by mass.

The remainder is Oxygen.
The MASS spectrum of R contains a molecular ion peak at m/z = 118.
(a) Use these data to show that the molecular formula of R is C6H14O2.

% O = 100 % - [61.0 % + 11.9 %] = 27.1 %
3 : 7 : 1
C3H7O = 59 which is half of Mr (118)

so MF = 2 X EF

Infra-Red Spectroscopy

Stretching vibrations
Single Bonds and

Triple Double bending vibrations
Bonds to H bonds bonds
Fingerprint
Region
O-H C≡C C=O C-C

N-H C≡N C=C C-N
C-H C-O
4000 cm-1 2700 cm-1 2000 cm-1 1500 cm-1 600 cm-1
Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam

Spring 2021
Infrared Spectroscopy
Octane
Alkanes – combination of C-C and C- H
H C
H bonds H
• C-C stretches and bends in the

fingerprint region
• sp3 C-H between 2850-2950
cm-1 below 3000
(w – s)

Spring 2021
1-Octene
H
Alkenes – addition of the C=C and vinyl C
H C
C-H bonds H
• sp2 C-H stretch occurs at 3000-
3100 cm-1 above 3000
• C=C stretch at 1600-1650 cm-1
(w – m)
(w – m)

Spring 2021
propionitrile
Nitriles (the cyano- or –C≡N group) N
C
• Principle group is the carbon nitrogen
triple bond at 2100-2280 cm-1
• more intense than that of the alkyne
due to the electronegativity difference
between carbon and nitrogen
(s)

Spring 2021
1-butanol
Alcohols
H
• Strong, broad O-H stretch from O
3200-3400 cm-1
• The shape is due to the presence
of hydrogen bonding
(m– s)
br
(s)

Spring 2021
3-methyl-2-pentanone
O
Carbonyl compounds
• C=O stretch occurs at 1650-1800
cm-1
(s)

Spring 2021
4-phenylbutyric acid
Carboxylic Acids: O
• C=O band occurs between 1705- C
O
H
1725 cm-1
• The highly dissociated O-H bond
has a broad band from 2400-3500
cm-1 covering up to half the IR
spectrum in some cases
(w – m) (s)
br
Spring 2021
Pause and Review
• Inspect the bonds to H region (2700 – 4000 cm-1)
• Above 3000 cm-1 Learn shapes, not wavenumbers!:
3000 cm-1
Very Broad peak
-O—H bond of
carboxylic acid
Broad U-shape
peak -O—H bond
just above below
3000 cm-1 3000 cm-1
C=C—H or C-C—H
Ph—H sp2 sp3
3300 2850-3200
Spring 2021
Pause and Review
• Inspect the bonds to H region (2700 – 1500 cm-1)
• Learn shapes, not wavenumbers!:
1650-1800 1600-1650
–C≡N or –C≡C- cm-1 C=O cm-1 C=C
2200 1650
Spring 2021
IR spectrum
C—H
1650-1800 1600-1650
cm-1 C=O cm-1 C=C
3000 cm-1
Very Broad peak Ignore the fingerprint

-O—H bond of region
carboxylic acid
–C≡N
or
Broad U-shape C≡C-
peak -O—H bond
1500
3300 3000 2200 1650
Spring 2021
(b) The infrared spectrum of R (C6H14O2) is shown below.

Spring 2021
1- Infrared peak/absorbance at 3400 (cm-1) = Alcoholic O-H
2- No peak between 1680-1750 cm-1,
therefore: NO C=O,
therefore: Not an aldehyde/ Not acid
3- Peak at 1000-1300 cm-1
therefore: C–O present

Spring 2021
NMR

How the samples are prepared
NMR spectra are usually run in solution
Samples are dissolved in inert solvents with no 1H atoms, So a solvent containing
Deuterium rather than hydrogen is used; CDCl3
A small amount of TMS (tetramethylsilane) is added as a reference standard (to tell
the instrument where is the “zero” and to measure how far the frequency of the
signals of the compound has shifted away from that of the TMS.
TMS is used because:

1. It only gives one signal
2. It is non-toxic and inert
3. It has a low boiling point and so can be removed
from sample easily

13C NMR Spectroscopy
All organic compounds contain a very small amount of the isotope
13C
1- How many 2- Chemical Shifts

different Chemical
Environments
Where are the peaks in
the spectrum
How many peaks in the Indication of the functional
spectrum group present
Indication of the number of C
Spring 2021
1-Chemical Environments
In a C13 NMR spectrum, there is one signal (peak) for each chemical environment
Each carbon atoms are in different chemical environment except
1-Same groups are attached to a common atom
2-There is a plane of symmetry (a line that split the molecule in to 2 equal
halves).
How many different chemical environments are there for the Carbon atoms
in this molecule?
Cl 6 carbons …6 chemical environments….6 peaks
2 carbons …2 chemical environments….2 peaks
3 carbons …3 chemical environments….3 peaks

1 2 3
Spring 2021
a
OH
3 chemical environments….3 peaks
b
c
a
Both methyls are attached to the same C… so both methyls will have the
same environment
a
CH3
3 methyls are attached to the same C… so the
H 3C c 3 methyls will have the same environment
b Br
CH3 d 4 chemical environments….4 peaks

Spring 2021
H H H
a a
H C C C H
b
a a H O H
H
1 chemical environment….1 peak 2 chemical environments….2 peaks
b
c a OH
a a
c a OH b
b
3 chemical environments….3 peaks 2 chemical environments….2 peaks

Spring 2021
O
O
Isopropyl Propanoate
Each PEAK corresponds to
an atom in one particular
Chemical Environment.
C13 NMR Spectrum

Spring 2021
2-The Chemical Shift δ
Where are the peaks in the spectrum
 Not all the C13 atoms in a molecule resonate at exactly the same radio frequency.
 Carbon atoms in different functional groups feel the magnetic field differently. This
is because all nuclei are shielded from the external magnetic field by the electrons
that surround them.
 Nuclei with more electrons around them are better shielded. The greater the
electron density around a carbon-13 atom, the smaller the magnetic field felt by the
nucleus and the lower the frequency at which it resonates.

Spring 2021
The Chemical Shift δ
Where are the peaks in the spectrum
 How much a Resonance frequency of a certain nucleus

shifts away from a set Standard Frequency (TMS) is known
as its Chemical Shift.
 Chemical Shift of a particular nucleus is measured in parts

per million, ppm.
 An NMR spectrum plots absorbance against δ/ppm as

shown for ethanol.

Spring 2021
13C Chemical Shift Values

Spring 2021
13C NMR
For the spectra on the next 2 slides:
1 Draw the structural formula of the compound.
2 State the number of chemical environments of the carbon

atoms in the molecule.
3 Identify the carbon atom(s) in each chemical environment
4 Using the table of chemical shifts identify which peak

corresponds to each chemical environment.

Spring 2021
H H
H
H 4 C 2 C
C 3 C 1 H
H O
But-3-en-2-one
Spring 2021
13C NMR of Ethanol
Spring 2021
There are 4 isomers of the alcohol C4H10O.
Draw their structural formulae and deduce which gives the spectrum
below?

Spring 2021
C4H10O
CH3 CH3
H2 H2
H3C C OH C CH3
H H2C HC
C C H3C C H3C C CH3
H2 H2
HO CH3
OH OH
A
B C D
Spring 2021
The compound below also has the formula C4H10O but is not an alcohol.
State the number of chemical environments of the carbon atoms and suggest a
structure for it.

Spring 2021
Proton NMR Spectroscopy
Dr. Sherif Ashraf Fahmy Revision In-class 2

Exam Spring 2021
1H (Proton) NMR
Like 13C, protons also have an odd number of nucleons

and so undergo nuclear magnetic resonance.
1- How many 2- Chemical 3- Integration 4- splitting

different Shifts
Chemical
Environments
How many Where are the the peak size Number of

peaks in the peaks in the Hydrogen
Proportion to
spectrum spectrum atoms on
number of H
Indication of the Adjacent
atoms in the peak
functional group
Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Atoms
present Spring 2021
1-Chemical Environments
In a H1 NMR spectrum, there is one signal (peak) for each chemical environment
H will have the same chemical environment when:
1-Hydrogens that are attached to the same carbon atom
2-Same groups are attached to a common atom
3-There is a plane of symmetry (a line that split the molecule in to 2 equal halves).
How many different chemical environments are there for the Hydrogen in
this molecule?
Cl 6 chemical environments….6 peaks

Spring 2021
a
d
OH
b
c
a
Both methyls are attached to the same C… so both methyls will have the
same environment
a
CH3
3 methyls are attached to the same C… so the
H 3C 3 methyls will have the same environment
b Br
CH3 c 3 chemical environments….3 peaks

Spring 2021
a b a
a a H H H
a
H C C C Ha
H O H
a
a a
a
c H
1 chemical environment….1 peak 3 chemical environments….3 peaks
b b
c a
b OH c
d
a a
d b OH
c a b b
c
4 chemical environments….4 peaks 3 chemical environments….3 peaks
Spring 2021
2- Chemical Shifts

Spring 2021
Low Resolution 1H (Proton) NMR
Which of the above compounds gives the

NMR spectrum shown?
Spring 2021
3- Integration
The integration or the size of the peak is proportional to number of
hydrogen atoms in each chemical environment
Spectrum shows peaks

due to the hydrogen atoms
in the molecule.
The numbers next to

the peaks give the relative
numbers of hydrogen
atoms.

Spring 2021
4- splitting
When an NMR spectrum is obtained under high resolution some of the
peaks can be split into a number of smaller peaks.

Spring 2021
High Resolution 1H (Proton) NMR
• This splitting is called spin-spin coupling and is caused by interactions with the
protons on adjacent carbon atoms.
– 1 Peak Singlet
– 2 Peaks in a cluster Doublet
– 3 Peaks in a cluster Triplet
– 4 Peaks in a cluster Quartet
• The magnetic field experienced by a proton can be influenced by the combination of

spins of the protons on an adjacent atom.

Spring 2021
High Resolution 1H (Proton) NMR
The effect of adjacent hydrogen atoms in a spectrum is:
0 Adjacent hydrogens Singlet
1 Adjacent hydrogen Doublet 1:1
2 Adjacent hydrogens Triplet 1:2:1
3 Adjacent hydrogens Quartet 1:3:3:1
This is called the N+1 rule
Splitting = adjacent Hs + 1
Spring 2021
H H O H
H C C C O C H
H H H
Quartet
(Yielded by the 2 BLUE hydrogens)
Singlet
(Yielded by the 3 GREEN hydrogens)
Triplet
(Yielded by the 3 PINK hydrogens)

Spring 2021
NMR Spectrum for C4H8O2
What information can you get from
this spectrum?

Spring 2021
Spring 2021
NMR Spectrum for Ethanol
Explain the splitting pattern below

Spring 2021
The proton N.M.R. spectrum of R contains FIVE peaks.
The chemical shift values, integration ratios and splitting patterns of these peaks
are given in the table below;

Spring 2021
6 Hydrogens
NEIGHBOURED
by 0 Hydrogens
are responsible
for this peak
2 Hydrogens NEIGHBOURED by 2 Hydrogens

1 Hydrogen NEIGHBOURED by 0 Hydrogens
are responsible for this peak
is responsible for this peak
3 Hydrogens NEIGHBOURED by 0 Hydrogens 2 Hydrogens NEIGHBOURED

are responsible for this peak by 2 Hydrogens
Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam are responsible for this peak
Spring 2021

In Class-2 Exam-Revision-Dr. Sherif Fahmy2

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Advanced Chemistry

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

2- Nucleophilic Reaction: One involving attack on a positively charged center in a molecule.

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Alkyl is electron donating Aryl is electron withdrawing

CH3-NH-CH3 Dimethylamine CH3-NH2 Methylamine

Decreasing base strength Decreasing base strength

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

and an acidic group (-COOH). In solution the carboxyl group

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

14- Enantiomers: Non-identical mirror image forms.

A racemate shows no optical activity.

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

H CH2 CH2 CH3

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Most Stable Least Stable

17- Condensation Polymers

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

19- Condensation Polymers

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Other plastics can degrade under the influence of bacteria or sunlight.

Addition polymers such as Condensation polymers

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Benzene Nitrobenzene Chlorobenzene 1,2-dichlorobenzene

Methylbenzene Benzenecarboxylic acid Benzenecarbaldehyde

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

2-Iodo-2-methylbutane 3-Choro-2-methylpentane 1-bromo-3-chloro-4-methylpentane

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Ethanoic acid (Acetic Acid)

Benzene carboxylic acid (Benzoic acid)

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Primary Secondary Tertiary

H3C CH2 Cl CH3 CH3

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

H3C C CH3 H3C C CH3

Primary (1o) Alcohol o

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

C- Hydrolysis of a Halogenoalkane (Substitution Reaction)

CH3-CH2-OH + [O] → CH3-CHO + H2O

CH3-CH(OH)-CH3 + [O] → CH3-CO-CH3 + H2O

H3C CH CH3 + [O] → H3C C CH3 + H2O

b) The hydrolysis of a nitrile by boiling with dilute hydrochloric acid.

CH3-CH2-CN + 2 H2O → CH3-CH2-COOH + NH3

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

RCOCl / AlCl3 R + (Friedel - Crafts

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Step 2: Addition of nitronium to benzene

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Step 2: Addition of Cl+ to benzene

H H H Dr. Sherif Ashraf Fahmy

Dr. Sherif Ashraf Fahmy Revision In-class 2 Exam Spring 2021

Step 1: Generation of electrophile (For example Methyl cation)

H H H H Dr. Sherif Ashraf Fahmy

Substitution Reactions Elimination Reactions

HO- NH3 or RNH2 CN-

Dr. Sherif Ashraf Fahmy