ORGANIC CHEMISTRY I

CHM 213/211 (C) (2 Units)

(Pre-requisite-CHM 102)
(Part)

Dr. A. O. Ogunmoye
[email protected]

Chemical Sciences Department, Olabisi Onabanjo

University Ago-Iwoye.
P.M.B. 2002, Ago-Iwoye, Nigeria.
 COURSE SYNOPSIS (PART)
❖ Functional group chemistry:

• Alcohol and their reactions

• Ether and Epoxides

• Carboxylic acids and their derivatives

❖Methane energy of activation and free radical

substitution reactions in alkanes.

❖Stereochemistry

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Functional group
chemistry

3
Functional group: Is a bond, atom or radicals common to homologous
series which determines their chemical properties. Examples: OH, COOH,
NH2 etc.

Types (2)
Mono-functional group: Single functional group within the system

Bi /Poly functional group: Contain two or more functional group.

Homologous series Functional groups Suffix General formulae

Alkyl ─ -yl CnH2n+1/R
Alkanol -OH -ol ROH
Carboxylic/Alkanoic acid -COOH -oic acid RCOOH
Ester/Alkanoate -COOR -oate RCOOR
Amide -CONH2 -amide RCONH2
Acyl chloride -COCl -chloride RCOCl
Acid anhydride (-CO)2O) -anhydride (RCO)2O)
Ether -O- -alkoxide ROR

4
 Alkanol
• Is an organic compound formed by replacing the H-atom of alkanes
with the hydroxyl (-OH) group.
• It is generally referred to as “alcohols” with the general formula
CnH2n+1OH/ROH or CnH2n+2O and has the functional group –OH. It is
named by replacing the “e” of alkane name with “ol”. Examples are
CH3OH (methanol), C2H5OH (ethanol) etc

N.B: In naming, the C-atoms are numbered in the longest chain with the –
OH group determining the numbering.

Examples are:
i. CH3CH2CH2OH propanol

ii. CH3CH(OH)CH2CH3 propan-2-ol or 2-propanol

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• Some Condensed structural formulas or line-angle structures
for depicting alcohols
IUPAC name

Propanol

1-Butanol/Butanol

2-Propanol/Propan-2-ol

2-Methyl propanol
(Isobutanol)

2-Methyl-2-butanol 2-Methylcyclopentanol
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Tutorial: Name the following alcohols and state the type

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 Classification
Alcohol are classified into three (3) major groups based on the number
of replaceable H attached to the C-atom bearing the hydroxyl group.

i. Primary alcohol (1o): RCH2OH

ii. Secondary alcohol(2o): R2CHOH
iii. Tertiary alcohol (3o): R3COH

Alcohol are also classified into 3 groups based on the number of hydroxyl groups
attached to the compounds

i. Monohydric: CH3OH

ii. Dihydric: CH2(OH)CH2(OH) ethane-1,2-diol

iii. Trihydric: CH2(OH)CH(OH)CH2(OH) propane-1,2,3-triol

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 Preparation

1. Fermentation of starch
The material is crushed and treated with steam to extract the
starch from them. Malt, made from partially germinated
barley, is added and then kept at about 50°C for one hour.
The enzyme diastase, present in the malt, catalyses the
conversion of starch into maltose.

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 Preparation Cont..
Yeast as then added at room temperature. This causes
fermentation, the enzyme maltase in the yeast, converts the
maltose to glucose and another enzyme zymase in yeast, then
decomposes the glucose into ethanoI and carbon (iv) oxide.

10
 Purification of ethanol
The ethanol obtained from the fermentation process can only
give a maximum concentration of 18%, since the yeast cells
die above this concentration. For commercial use, ethanol is
required in various compositions and to achieve further
concentration and purification, fractional distillation is
employed.
Commercial ethanol is sold as pure spirit or rectified spirit or
methylated spirit containing 95% ethanol. When sold to the
public, 5% methanol, which is toxic, is added to prevent it
being consumed as a drink.

2. Hydration of ethene

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 Physical properties
i. Lower members are colourless liquid while those with >C12 are
colourless solid.
ii. Characteristics smell and burning taste.
iii. Solubility decrease as molecular weight increase.
iv. Bpt. increase with molecular weight
v. They are less dense than water.
Chemical properties
1. Combustion: They generally undergo combustion in the presence of
excess air to form Carbon (iv) oxide and water.

C2H5OH + 3O2 → 2CO2 + 3H2O

2. Alkoxide formation: The acidic nature of the -OH group shows up a
their reaction with reactive metals such as sodium, to liberate
hydrogen gas.
2C2H5OH + 2Na → 2C2H5ONa + H2
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 Chemical properties continues
3. Dehydration: Alkanol are readily dehydrated (removal of H2O)
on heating with conc. tetraoxosulphate (VI) to give Alkenes.
RCH2CH2OH → RCH=CH2 (Conc. H2SO4/170oC)
When the alkanol is present in excess, however, the
dehydration occurs between two molecules to form
another class of compounds called alkoxyalkanes (Ether).
2RCH2CH2OH → RCH2CH2OCH2CH2R + H2O (Conc. H2SO4/140oC)

4. Esterification: Alkanol reacts with alkanoic acids in a reversible

reaction to form alkanoate (ester).

C2H5OH + CH3COOH ↔ CH3COOC2H5 + H2O

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5. Oxidation: Primary and secondary alkanols are oxidised, by
dehydrogenation, to form alkanals and alkanones respectively. In
primary alkanols, the initial alkanal product may be oxidised further
to an alkanoic acid, if excess oxidising agent is used, but alkanones
cannot be readily oxidised. 3O Alkanols have no H atom on the alkyl
group adjacent to the -OH group and they are, therefore, not
readily oxidised .
• N.B: The oxidation can be achieved using oxidising agents such as
KMnO4 or K2Cr2O7.
• 1O RCH2OH → RCHO → RCOOH
2O R2CHOH → RCOR
3O R3COH → No reaction
6. Iodoform reactions
Ethanol and methanol react with a mixture of iodine and NaOH to
form a yellow precipitate of triodomethane CHl3(iodoform).
CH3CH2OH + 4l2 + 6NaOH → CHl3 + HCOONa + 5NaI + 5H2O

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 Tests
1. Lucas test: The presence of alkanol is confirmed based on the
differences in the rate of reaction of primary, secondary and
tertiary alkanol with Lucas reagent (mixture of conc. HCI and
ZnCl2).
• ROH → RCl (conc. HCl/ZnCl2 as cat.)

• N.B: At room temperature, a tertiary alkanol reacts with Lucas reagent to give
immediately turbidity (cloudy) of the chloride. Secondary alkanols also react at
room temperature, however, the reaction is a lot slower and the turbidity only
appears after about 5 minutes. Primary alkanols does not react with Lucas
reagent at room temperature at all. However, the turbidity can be observed
when the reaction mixture is heated.
2. Oxidation test
• 1o, forms aldehyde/carboxylic acid, 2o forms ketone and 3o alcohol is
resistance to oxidation.

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 Applications
i. As industrial solvent for soap, perfumes etc
ii. As raw materials in production of chemicals like ethanal, ester etc.
iii. As sterilization and preservation for biological specimen and food.
iv. As antiseptic in hospitals and laboratory.
v. As anti-freeze in automobile radiator.
vi. As fuel in racing cars and rockets

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 Ether and Epoxide/Cyclic ether (ROR)
Ether
• Ether are compounds with general formula R-O-R, Ar-O-R or Ar-O-Ar and
functional group –O-.
• It could either be an alkyl derivatives of alkanol (R-OH → R-O-R ) or dialkyl
derivatives of water (H-O-H → R-O-R).
• It could either be simple/symmetrical ether e.g. CH3OCH3, C2H5OC2H5
or Mixed/unsymmetrical ether e.g. CH3OC2H5 PhOCH3 etc.
Rules for common names of Ether
1. Name each –R group.
2. Arrange them alphabetically.
3. End with the word “ether.”
• The IUPAC system for naming ethers:
1. Longest continuous carbon chain is used as parent name (might
have substituents)
2. Other chain is named as an alkoxy-substituent: change the “yl” part
of the other alkyl chain to “oxy” (e.g. methyl to methoxy)
3. Name as alkoxy name then the parent chain. Number the alkoxy
substituent to indicate where it attaches to the parent alkane.

1-Ethoxybutane 1-Methoxy-2-methylpropane 2-methoxypentane

Alcohol group has higher priority

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4-Methoxy-2-butanol
Other examples are:
CH3OCH3 (methoxy methane/dimethyl ether),
C2H5OC2H5 (ethoxy ethane/diethyl ether),
CH3OC2H5 (methoxy ethane/methyl ethyl ether),
PhOCH3 (methoxy benzene/methyl phenyl ether/anisole),
(CH3CH2)(CH3)CHOCH3 (2-methoxy butane)
CH3CH2OCH2CH(CH3)CH3 (ethoxy-2-methylpropane) and
(CH3)2CHOCH3 (2-methoxy propane).
ISOMERISM IN ETHER
• Because ethers contain C, H, and O atoms, the possibilities for
isomers is greater than for hydrocarbons.
• For example, an ether having two to three carbon chains will have
the following constitutional isomers:

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 Preparation
1.Dehydration of excess 1O alcohol with conc. H2SO4 at 140oC
2C2H5OH → C2H5OC2H5

2. Passing vapour of alcohol over heated alumina (Al2O3) at 250oC

2C2H5OH → C2H5OC2H5

3. Treatment of 1o alcohol with diazomethane in the presence of BF3

as catalyst.

4. Heating alkyl halides with Na/K alkoxide (Willamson’s synthesis)

C2H5OH + C2H5Cl → C2H5OC2H5 + NaCl

N.B: Ether may come in contact with air to form peroxide which is highly explosive.
Purification/removal of this peroxide can be done by washing ether with a solution
of ferrous salt which reduces peroxide to alcohol or by distillation with conc. H2SO4
which oxidizes peroxides

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 Chemical reactions
1. Combustion
C2H5OC2H5 + 4O2 → 4CO2 + 5H2O
2. Oxidation
C2H5OC2H5 → 3CH3CHO ((Acidified KMnO4/K2Cr2O7)
3. Dehydration
C2H5OC2H5 → 2CH2=CH2 + H2O ( Al2O3/238oC)
4. Halogenation
In the absence of sunlight, halogen substituted derivatives are formed
C2H5OC2H5 → CH3CH(Cl)OC2H5 → CH3CH(Cl)OCH(Cl)CH3 (Cl2/HCl in dark)
α-chloroether α-αI -chloroether
In the presence of sunlight, all the H-atom of ether is substituted by halogens
C2H5OC2H5 → C2Cl5OC2Cl5 + 10HCl (Cl2/sunlight)

5. Formation of peroxide
C2H5OC2H5 + [o] → C2H5OC2H5 → O
This reaction is highly explosive and the unstable peroxides decomposes
violently on heating, but it can be avoided by storing ether in the dark and
wrapped with black paper.
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 Chemical reactions contd….
6. Formation of phenol
PhOC2H5 + H2O → PhOH + C2H5Br ( HBr/H2O, reflux)

Basic Nature of ether

They are basic due to unshared pairs of electrons on oxygen, thus react
with conc. HCl/H2SO4 in cold condition to give oxonium salts.
C2H5OC2H5 + HCl → [ C2H5-OH-C2H5]+Cl-

Though stable at low temperature and high conc. of acid, but are
decomposed back to ether and acid when diluted with water since it is a
stronger base than ether.
Formation of Coordination complexes with lewis acid (Bf3, AlCl3, RMgX
etc)

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 Diethyl ether/ether (C2H5)2O
The above is formed when excess of ethyl alcohol is heated with conc.
H2SO4 at 140oC
Step 1 C2H5OH → C2H5HSO4 + H2O
Step 2 C2H5HSO4 + C2H5OH → C2H5OC2H5 + H2SO4

Physical properties
1. Colourless, highly volatile liquid with pleasant odour and sweetish
burning taste.
2. Boiling point is 34.6oC, slightly soluble in water and inert due to
absence of active group unsaturated bond.
3. Reagents like alkalis, dil. Acid, ammonium and metallic Na has no
action on it.
Chemical reactions
1. Reaction with PCl5 to form ethyl chloride on heating
(C2H5)2O + PCl5 → 2C2H5Cl + POCl3
2. Halogenation with Br2/Cl2 in dark
(C2H5)2O + Cl2 → CH3CHClOC2H5 + HCl

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 Chemical reactions contd….
3. Peroxide formation
(C2H5)2O + [O] → (C2H5)2O → O
4. Hydrolysis
(C2H5)2O → 2C2H5OH (H2O/boil)
5. Reduction
(C2H5)2O + PCl5 → 2C2H6 + H2O (P + HI/4H)
6. Combustion
(C2H5)2O + 6O2 → 4CO2 + 5H2O

Applications

i. As a refrigerant.
ii. As local anesthetic agents.
iii. As solvent, reagents and fuel when mixed with ethyl alcohol.

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Cyclic ether/Epoxide
Epoxide/Oxide of alkenes are cyclic ether formed between O-atom and 2-
adjacent C-atom.
Nomenclature
Although cyclic ethers have IUPAC names, their common names are more widely
used
-IUPAC: prefix ox- shows oxygen in the ring
-the suffixes -irane, -etane, -olane, and -ane show three, four, five, and six
atoms in a saturated ring
2 3 O

1O O O O O
Oxirane Oxetan e Oxolane Oxan e 1,4-D ioxane
(Ethylene oxid e) (Tetrahydrofuran) (Tetrahydropyran)

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 Preparations
The chemistry of the ether functional group is the same, whether open or
ring. The simplest epoxide is ethylene oxide and is produced as shown
below;

In the laboratory, it is prepared by treatment of alkenes with peroxy acid

(RCO3H)

N.B: The only group of cyclic ether that behaves differently from open
chain ether is the 3 membered ring compounds due to their strain, which
makes them highly reactive and gives them unique chemical reactivity.
RCONH2 + H2O ↔ RCOOH + NH4+ ( in acidic medium)
RCONH2 + NaOH → RCOO-Na+ NH3 ( in alkaline medium)
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Epoxidation/Ring formation
It is accomplished using different peroxy acids e.g. Magnesium
monoperoxyphthalate (MMPP).
O
Peroxy Acid

Cl OH
O
(MCPBA)

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 Some Peroxyacids
O
O

Cl OH OOH
O Mg2+

CO2
2
(MCPBA) (MMPP)
O

O O
OOH

H3C OOH H OOH

Peroxyacetic acid Peroxyformic acid Peroxybenzoic acid
(paracetic acid) (performic acid) (perbenzoic acid)

• Reactive, Often Unstable Species: Chemists use More Stable

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 Ring opening reaction of epoxide continues…..
Treatment of an epoxide with LiAlH4, H3O+ reduces the epoxide to an
alcohol.

i.

ii

iii

N.B: Most ethylene glycol used for automobile antifreeze are produced from acid
catalyzed hydration of ethylene oxide in USA.
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 Reactions of Epoxides
– the value of epoxides is the variety of nucleophiles that will open the
ring and the combinations of functional groups that can be prepared
from them
CH3
CH3 HOCH2 CHOH CH3
HSCH2 CHOH A glycol HC CCH2 CHOH
A -mercaptoalcohol A -alk yn ylalcoh ol
H2 O/ H3 O+
- +
+ -
Na SH / H2 O CH3 1 . HC C Na
H2 C CH 2 . H2 O

+ - O NH3
Na C N / H2 O Methyloxiran e
CH3 CH3
N CCH2 CHOH H2 NCH2 CHOH
A -hydroxynitrile A -aminoalcohol

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 Crown Ethers
Structure
cyclic polyethers derived from repeating —OCH2CH2— units

Properties
form stable complexes with metal ions

Applications
synthetic reactions involving anions

Naming
• Named as x-crown-y
– x is the total number of atoms in the ring
– y is the number of oxygen atoms
– 18-crown-6 ether: 18-membered ring containing 6 oxygen atoms
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 Examples
O
O O

O O
O
15-crown-5 18-crown-6

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 Ion-Complexing and Solubility

O O

O O F– O O

K+
toluene
O O O O

O O

18-crown-6 complex of K+ dissolves

in benzene

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 Ion-Complexing and Solubility

O O

O O O O

K+
toluene
O O O O

O O

F– carried into toluene + F–

to preserve electroneutrality

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 Application of crown ether to organic synthesis

Complexation of K+ by 18-crown-6 "solubilizes"

potassium salts in toluene
Anion of salt is in a relatively unsolvated state in
toluene (sometimes referred to as a "naked
anion")
Unsolvated anions are very reactive
Only catalytic quantities of 18-crown-6 are needed

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 Carboxylic acid and their Derivatives
• Carboxylic acid is an organic compound with the general formula RCOOH
and functional group –COOH. Examples are HCOOH, CH3COOH,
CH3(CH2)16COOH, CH2ClCOOH etc.
• Natural Sources: HCOOH (ants), CH3COOH (Vinegar) etc.
Preparation
1. Oxidation of primary alcohol and alkanal.
RCH2OH → RCOOH (Acidified KMnO4)
RCHO → RCOOH (Acidified KMnO4)
2. Hydrolysis of ester
• RCOOR’ + H2O ↔ RCOOH + R’OH
Physical properties
i. They are colourless liquid with pungent smell and sour taste.
ii. Extreme high Mpt. and Bpt. due to dimer formation.
iii. Density decreases with increasing Molar mass.
iv. They are soluble in water. 36
 Chemical properties of carboxylic acids
1. Reaction with active metal
2CH3COOH + 2Na → 2CH3COONa + H2
2. Neutralization
CH3COOH + NaOH → CH3COONa + H2O
3. Formation of acyl chlorides
CH3COOH + PCl3 → CH3COCl
4. Formation of acid anhydride
2CH3COOH → (CH3CO)2O + H2O (P2O5)
5. Formation of amide
RCOOH + SOCl2 → RCOCl
RCOCl + 2NH3 → RCONH2 + NH4Cl
6. Ester formation
RCOOH + R’OH ↔ RCOOR’ + H2O
7. Reduction
RCOOH → RCH2OH ( LiAlH4/dry ether) 37
 Laboratory test
Reaction of alkanoic acid with NaCO3/NaHCO3 to liberate carbon (iv)
oxide. The evolution of CO2 is used as evidence.
CH3COOH + NaHCO3 → CH3COONa + H2O + CO2

Applications
i. HCOOH is used an dyeing, electroplating, tanning and rubber
coagulation
ii. Higher alkanoic acid are used for making soaps and detergents
iii. As solvents for adhesives, thinner etc
iv. As flavour enhancers
v. As Polymers e.g Nylon 6.6, Terylene
vi. As preservatives for food like salad, juices, jams etc.

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 Derivatives of carboxylic acid
There are four (4) major derivatives of carboxylic acid namely:
1. Acyl chloride (RCOCl)

2. Acid anhydride (RCO)2O)

3. Amide (RCONH2)

4. Ester (RCOOR)
Applications
i. As preservatives for foods
ii. As polymers i.e. Nylon 6.6
iii. As solvents for adhesives
iv. As flavour enhancers

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1. Ester (RCOOR)
The name consist of two words in the form “alkyl alkanoate”, the alkyl is
from the original alkanol while the alkanoate is from the initial carboxylic
acid. RCOOH + R’OH ↔ RCOOR’ + H2O
Examples: CH3COOCH3, HCOOC2H5, CH3COOCH(CH3)2, (CH3)2CHCOOC2H5

Preparation
2RCOOH + R’OH ↔ RCOOR’ + H2O

Chemical reactions
i. Hydrolysis
RCOOR’ + H2O ↔ RCOOH + R’OH ( Acid catalyzed H+)
RCOOR’ + NaOH → RCOO-Na+ C2H5OH ( Base catalyzed OH-)
N.B: The above reaction is used in soap making.

ii. Reduction
RCOOR’ 4[H] → RCH2OH + R’OH ( LiAlH4/dry ether, H2O)
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2. Amide (RCONH2)
They are the least reactive of the derivatives with respect to nucleophilic
substitution because –NH2 is an electron donating group which is difficult
to displace
Examples: CH3CONH2, C2H5CONH2, CH3CON(CH3)2, CH3CH2CONHC2H5

Preparation
RCOOH + SOCl2 → RCOCl
RCOCl + 2NH3 → RCONH2 + NH4Cl
Chemical reactions
i. Hydrolysis
RCONH2 + H2O ↔ RCOOH + NH4+ ( in acidic medium)
RCONH2 + NaOH → RCOO-Na+ NH3 ( in alkaline medium)
ii. Reduction
RCONH2 + 4[H] → RCH2NH2 (LiAlH4/dry ether)
iii. Dehydration
RCONH2 → RC≡N + H2O ( P2O5/heat)
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3. Acyl chloride (RCOCl)
It has the general formula RCOCl and named with an IUPAC suffix –oyl chloride.
Examples: CH3COCl (ethanoyl chloride), C3H7COCl (butanoyl chloride)
CH2ClCOCl( 2-chloro ethanoyl chloride), PhCOCl (benzoyl chloride) etc.
Preparation
RCOOH + SOCl2 → RCOCl
N.B: The RCOCl formed must be stored in anhydrous condition because it can
easily hydrolised to acid. (PCl3, PCl5 can also be used)
RCOCl + H2O → RCOOH + H2O

Chemical reactions
i. Hydrolysis
CH3COCl + H2O ↔ CH3COOH + HCl
ii. Alcoholysis
CH3COCl + CH3OH → CH3COOCH3 + HCl
iii. Ammonolysis
CH3COCl + 2NH3 → CH3CONH2 + NH4Cl
iv. Reaction with primary ammine
RCOCl + 2R’NH2 → RCONHR’ + R+NH3C-l
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4. Acid anhydride (RCO)2O
It has the general formula (RCO)2O and named as carboxylic anhydride with the
IUPAC suffix –oic anhydride.
Examples are given below:

Preparation
P2O5 produces acid anhydride through the elimination of water molecule from
carboxylic acid.

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 Chemical reactions
i. Hydrolysis
(CH3CO)2O + H2O ↔ 2CH3COOH

ii. Alcoholysis
(CH3CO)2O + CH3OH → CH3COOCH3 + CH3COOH

iii. Ammonolysis
(CH3CO)2O + NH3 → CH3CONH2 + CH3COOH

iv. Reaction with primary ammine

(CH3CO)2O + CH3NH2 → CH3CONHCH3 + CH3COOH

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Methane energy of activation and free radical
substitution reactions in alkanes.

45
Introduction

Hydrocarbons are organic compounds that contains mainly H and C.

Alkanes are hydrocarbons with the general formula, CnH2n+2 (four bonds
to each carbon and only single bonds) e.g. CH4 methane, C2H6 ethane,
C3H8 propane Etc.

Methane is the first member of the alkanes homologous series with the
formula CH4 and the structural formula is as written below;

46
 Physical Properties of Methane

•It has Sp3 tetrahedral with 109.5o bond angles.

•It is Non-polar – van der Waals (London forces)
•Gas at room temperature, mp = -183oC bp = -161.5oC
•Water insoluble
•Colorless and odorless gas
•“swamp gas” ; fossil fuel found with petroleum & coal
•Important fuel/organic raw material

47
 Chemical Properties of Methane
Methane is typically unreactive. It does not react with
water, acids, bases, active metals, oxidizing agents, reducing
agents, or halogens.

• CH4 + H2O → NR (no reaction)

• CH4 + conc. H2SO4 → NR
• CH4 + conc. NaOH → NR
• CH4 + sodium metal → NR
• CH4 + KMnO4 → NR
• CH4 + H2/Ni → NR
• CH4 + Cl2 → NR

N.B: Methane however undergo combustion halogenation

and substitution reaction.
48
 Reactions of methane
•Combustion (oxidation)
a) Complete oxidation
CH4 + 2 O2 , flame or spark → CO2 + H2O + energy

b) Partial oxidation
6 CH4 + O2 , 1500o → CO + H2 + H2C2
(acetylene)

CH4 + H2O , Ni, 850o → CO + H2

•Halogenation

CH4 + X2 , Δ or hυ → CH3X + HX

Where X2 = Cl2 or Br2

a) Requires heat (Δ) or UV light (hυ)
b) May proceed further
c) Cl2 reacts faster than Br2
d) No reaction with I2
49
 Reactions of methane continues
•Substitution reaction

• CH4 + Cl2 → NR (requires heat or uv light)

• CH4 + I2, heat → NR (does not react with I2)

• CH4 + Br2, hv → CH3Br + HBr

• CH4 + Cl2, hv → CH3Cl + HCl

• CH3Cl + Cl2, hv → CH2Cl2 + HCl

• CH2Cl2 + Cl2, hv → CCl3H + HCl

• CCl3H + Cl2, hv → CCl4 + HCl

50
• The Reactions of methane with Halogens
• Methane undergo substitution reactions with halogens such as
fluorine, bromine and chlorine in the presence of heat or light

– Multiple Substitution Reactions versus Selectivity

• Radical halogenation can yield a mixture of halogenated compounds
because all hydrogen atoms in an alkane are capable of substitution

– In the reaction above all degrees of methane halogenation will be

seen
• Monosubstitution can be achieved by using a large excess of the alkane

– A large excess of methane will lead to predominantly

monohalogenated product and excess unreacted methane
 Mechanism for chlorination of methane
Three distinct steps are involved namely;

• Initiation (homolytic covalent bonds cleavage)

• Propagation (chain propagation)

• Termination

N.B: The above steps requires a Chain reactions which is a stepwise

mechanism in which each step generates the reactive intermediate that
causes the next cycle of the reaction to occur
1. Chain initiation: It involves one step reaction
– Chlorine radicals is formed by dissociation when the chlorine molecule is
subjected to heat or light
– Chlorine radicals formed is then used in the chain propagation steps below

2. Chain propagation: It involves two steps reactions

– A chlorine radical reacts with a molecule of methane by abstracting a proton
to generate a methyl radical
– A methyl radical also reacts with a molecule of chlorine by abstracting a
chlorine atom to yield chloromethane and regenerate chlorine radical

N.B: A chlorine radical reacts with another methane molecule, continuing the
chain reaction while a single chlorine radical can lead to thousands of chain
propagation cycles
3. Chain termination: It involves two/three
steps reactions
– Occasionally the reactive radical intermediates are
quenched by reaction pathways that do not generate new
radicals e.g

Step 1

Step 2

Step 3
 Rates of chemical reactions

The rate of a chemical reactions depends on

three factors namely:
• Collision frequency (collision per unit time)
• Probability factor (fraction of collisions with
correct geometry)
• Energy factor (fraction of collisions with
sufficient energy)

55
 Energy of activation
• Activation energy is a term introduced in 1889 by the Swedish scientist
Svante Arrhenius.
• It is defined as the energy that must be overcome in order for a chemical
reaction to occur.
• Activation energy may also be defined as the minimum energy required to
start a chemical reaction or minimum energy required for a collision to go
to the product.
• The activation energy of a reaction is usually denoted by Ea, and given in
units of kilojoules per mole. E.g

CO(g) + NO2(g) ----> CO2(g) + NO(g)

• The CO + NO2 mixture from above has an Ea = 134 kJ. This means that the
colliding molecules must have a total KE of 134 kJ/mol if they are to react.

56
 Properties of the Activation energy, Ea
• It is a positive quantity, Ea>0
• It depends upon the nature of the reaction. "Fast" reactions usually
have a small Ea; those with a large Ea usually proceed slowly.
• It is independent of temperature and concentrations.

The relationship between activation energy (Ea) and enthalpy of formation (ΔH)
with and without a catalyst, plotted against the reaction coordinate.
57
 Energy of activation continues
• A substance that modifies the transition state to lower the
activation energy is termed a catalyst; a biological catalyst is
termed an enzyme.

• It is important to note that a catalyst increases the rate of

reaction without being consumed by it. In addition, while the
catalyst lowers the activation energy, it does not change the
energies of the original reactants or products. Rather, the
reactant energy and the product energy remain the same and
only the activation energy is altered (lowered).

• Rate determining step (RDS) = the step in the mechanism that

determines the overall rate of a reaction. In a “chain
reaction” this will be the slowest propagating step.
58
Activated Complex- an intermediate species that is an unstable,
high energy species that must be formed before the reaction can
occur.
• forward reaction exothermic (∆H<0), Ea is smaller than Ea1
• forward reaction endothermic (∆H>0), Ea is larger than Ea1
• if ∆H = +200 kJ, then Ea = Ea1 + ∆ H = Ea1 + 200 kJ

59
 Free radical substitution mechanism
Radicals are highly reactive species

• X 2 → 2 X•

• X • + CH4 → HX + CH3•

• CH3• + X2 → CH3X + X•

• 2 X• → X2

• X• + CH3• → CH3X

• 2 CH3• → CH3CH3
60
Stereochemistry
chemistry in three
dimensions

61
 Isomerism
Isomerism: This is the phenomenon by which a compound exist with the
same molecular formula but has different structural formula
(Connectivity).
The are two major types, namely:

i. Constitutional isomerism

ii. Stereoisomerism: geometrical isomerism

optical isomerism

62
 Constitutional isomers
i. Constitutional isomers (also known as structural isomers): These are
isomers that have the same molecular formula but different structural
formula (connectivity).
Examples are: Skeletal, Positional and Functional isomers.

a. Skeletal isomers: - same molecular formula but different structural

formula. They are typical constitutional or structural isomers.

63
 Constitutional isomers continues…..
b. Positional isomers: - Compounds with same molecular formula, same functional groups
but variation in their position.

OH OH
NO2
and

NO2

c. Functional isomers: - Compounds of identical molecular formula but which have different
functional groups.

C2H6O: C2H5OH and CH3OCH3

64
ii. Stereoisomerism – These is the phenomenon where isomers have
the same molecular and structural formula but differ in the way the
atoms are arranged in space (configuration) within the molecules.
There are two types namely: Geometric and Optical isomerism
a. Geometrical isomerism is the phenomenon by which a molecule
have the same structural formula but differs in the atoms
arrangement along the doubly bonded carbon atom .

b. Optical isomers This are isomers which arises from different

arrangements of atoms or groups in three dimensional space
resulting in them having a mirror image of each other.

65
 Terms related to stereochemistry
Some Stereochemistry terms that are needed to be learned in order to
fully communicate and understand the concepts.
1. Stereoisomers – Compounds with the same connectivity (structural
formula), but different arrangement in space.

2. Enantiomers – Stereoisomers that are non-superimposible mirror

images; only properties that differ are direction (+ or -) of optical
rotation.

3. Diastereomers – Stereoisomers that are not mirror images; different

compounds with different physical properties.

4. Chiral compound – A compound that is optically active (will rotate light)

5. Asymmetric center – Sp3 carbon with 4 different groups attached.

6. Stereocenter (or stereogenic atom) - Is any atom at which the

interchange of two groups gives a stereoisomer.
66
Terms related to stereochemistry continues
7. Achiral compound - Molecule that has a plane of symmetry or optically
inactive molecule or molecule whose mirror image can superimoposed.

8. Optical activity – The ability of a compound to rotate the plane of

plane –polarized light.

9. plane polarized light – light that has been passed through a nicol prism
or other polarizing medium so that all of the vibrations are in the same
plane.

10. Polarimeter – device that measures the optical rotation of the chiral
compound.

11. dextrorotatory – Clockwise rotation of the plane of polarized light

when viewed through a polarimeter.

12. levorotatory – when the plane of polarized light is rotated in a anti-

clockwise direction when viewed through a polarimeter.
67
Terms related to stereochemistry continues
13. Specific rotation – the angle of rotation of plane polarized light by a
1.00 gram per cm-3 sample in a 1 dm tube.
14. Racemate/Racemic mixture: of Enantiomers -
is an equimolar proportion ( 50:50) mixture of the two enantiomers of a
chiral compound.

15. Resolution of Enantiomers - a process of separating a racemate into

pure enantiomers.

16. Meso-Compounds: These are molecule that are superimposable on

their mirror image despite containing a chiral centre. And they are
optically inactive due to internal compensation

17. Configurations - possible spatial arrangements of atoms within a

molecule.

68
1. Stereoisomers – These are isomers have the same molecular and
structural formula (connectivity) but differ in the way the atoms are
arranged in space (configuration) within the molecules. These
phenomenon is known as stereoisomerism.

Configuration – Is the spatial arrangement of atoms within a molecule.

Therefore stereoisomers have similar structural formula but different
configuration.

cis-2-butene trans-2-butene

69
 Types of stereoisomers
There are two types namely:
i. Geometrical isomers
ii. Optical isomers
i. Geometrical isomers: These are isomers which possess the same
structural formula but differ in the spatial arrangement of the atoms around
the double bond. The phenomenon is called geometrical isomerism.
This isomerism is shown by alkenes or their derivatives. When similar
groups lie on the same side, it is the cis-isomer; while when the similar
groups lie on opposite (adjacent) sides, it is a trans- isomer.

70
 Examples of geometric isomers

Tutorial: Draw the structures of the Cis and trans form of

2-butene-1,4-dioc acid

2,3-dichloro-but-2-ene
N.B: geometrical isomerism is possible only when each of the doubly bonded carbon atom
has two different groups. Below compounds will not show geometrical isomerism

71
 Distinction between cis -and trans- isomers.
(a) Generally, the cis-isomer cyclises on heating to form the corresponding
anhydride while the trans-isomer does not form its anhydride at all.

(b) The cis-isomer of a symmetrical alkene (alkenes in which both the

carbon atoms have similar groups) has a definite dipole moment, while
the trans-isomer has zero dipole moment. For example, 1, 2-
dichloroethylene and butene-2

N.B: In trans-isomer of the symmetrical alkenes, the effect produced in one half of the
molecule is cancelled by that in the other half of the molecule

In case of unsymmetrical alkenes, the cis-isomer has higher dipole

moment than the corresponding trans-isomer. For example

72
ii. Optical isomers This are isomers which arises from different
arrangements of atoms or groups in three dimensional space resulting in
them having a mirror image of each other.

Optical isomers contain an asymmetric (chiral) carbon atom (a carbon atom

attached to four different atoms or groups) in their molecules. For example,
lactic acid, mandelic acid, alanine, malic acid etc.

N.B: Optical isomers have similar chemical and physical properties and differ
only in their behaviour towards plane polarised light .

73
 2. Enantiomers: Compounds that are non superimposable mirror images
or mirror-image stereoisomers. Any molecule that has a chiral center are
typical examples of an enantiomer.

Enantiomers are related to each other much like a right hand is related to a
left hand

74
 Properties of enantiomers
a) Physical: Enantiomers have identical physical properties with the
exception that they rotate the plane of polarized light in opposite
directions although is identical.

b) Chemical: They have identical chemical properties except for their

reaction with reagents which are, themselves, optically active. In this
case, reaction rates differ and depend on which enantiomer of the
reagent is used.

(+)-Glucose is central to the fermentation process whereas (-)-glucose

doesn’t react!

75
Properties of Enantiomers……….
In general, enantiomers have the same physical properties
(bp, mp, density, etc). Enantiomers will rotate plane polarized
light the same magnitude () but in opposite directions (+ or -).
O O R CO H
HO 2 HO2C S OH
H3C CH3
H NH2 H2N H
CH3 H3C HO OH
D-DOPA L-DOPA
(R)-(-)-carvone no biological effect used for the treatment of
(S)-(+)-carvone
spearmint oil ParkinsonDisease
caraway seeds (rye)
O O O O
NH HN
S CH3 H3C R
N S O O R N H N CH3 H3C N H
H H H H
O O
(S)-Thalidomide (S)-methampetamine (R)-methamphetamine
(R)-Thalidomide
teratogen no biological effect
sedative

Enantiomers can have significantly different biological properties

76
3. Diastereomers are stereoisomers that are non superimposable non
mirror images of each other or non mirror image stereoisomers.

They are stereoisomers that are not enantiomers. They are non-
superimposable, non-mirror image isomer (more than one chiral center).
Examples are; geometric isomers (diastereomers): E / Z alkene isomers (cis,
trans and configurational isomers)

77
• Cis-trans isomers are not mirror images, so these are
diastereomers.

78
 CH3 CH3 CH3 CH3
H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl
CH2 CH2 CH2 CH2
CH3 CH3 CH3 CH3
I II III IV

I & II are enantiomers; III & IV are enantiomers; I & III are
diastereomers; I & IV are diastereomers…

79
4. Chirality is the ability of Molecules to rotate a plane polarised light
(optically active) due to the present of a chiral carbon.
A point in a molecule where four different groups (or atoms) are attached
to carbon is called the chiral carbon.
Chirality is a necessary and sufficient condition for the existence of
enantiomers.
Therefore a chiral molecule is that which are nonsuperimposable on their
mirror images. They are optically active. E.g. enantiomers
N.B: Compounds with one chiral center will show optical activity while
compounds with more than one chiral center may or may not show optical
activity depending on whether or not they are non-superimposable on
their mirror image (chiral) or superimposable (achiral).

80
5. Asymmetric center – Is the carbon with four different groups which results
in a chiral molecule. It is also referred to as a chiral, or chirality, or stereogenic
center.
O
CH3CH2CHBrCH3
*
H
*
(+)-carvone

6. Stereogenic center is a carbon bonded to four different atoms or group.

It is also called stereocenter. A swapping of groups at the center leads to a
stereoisomer:
CO2H CO2H
H3C H H CH3
NH2 H2N

alanine

81
 * * * *
aldohexose CH2-CH-CH-CH-CH-CH=O
OH OH OH OH OH

n chiral centers → 2n maximum stereoisomers

n = 4 → 24 = 16 stereoisomers

* *
2,3-dichloropentane CH3CHCHCH2CH3
Cl Cl

n = 2 → 22 = 4 stereoisomers

*
CH3
H
CH H * *
3
* * Cholesterol: eight chiral centers
* * H *H
28 = 256 possible stereoisomers
HO
H (only one of which is naturally occurring)
82
7. Achiral Molecules these are molecules that are super imposable on their
mirror images.
Molecules are not chiral if they contain a plane of symmetry: a plane that cuts
a molecule in half so that one half is the mirror image of the other half.
Symmetry in Achiral Structures - Any molecule with a plane of symmetry or
a center of symmetry must be achiral.
achiral chiral

symmetry
plane
O
H H Not a
symmetry
H C O
C C H plane
H H O H OH O
H
H C O CH3
C C H
H H O

Chiral center
(stereogenic, asymmetric) 83
 Achiral
• Mirror images that can be superposed are achiral (not chiral).

Achiral Molecules with Two Chirality Centers

Br H H Br
Br Br Br Br

H Br Br H
H H H H

meso (achiral) chiral

Meso: molecules that contain chiral atoms but are achiral because they also
possess a plane of symmetry.
84
8. Optical activity – when a substance rotates the plane of plane polarized
light. (1815 by Biot)
9. Plane polarized light – light that has been passed through a nicol prism or
other polarizing medium so that all of the vibrations are in the same plane.

non-polarized polarized

10. polarimeter – an instrument used to measure optical activity.

85
11. Dextrorotatory – when the plane of polarized light is rotated in a
clockwise direction when viewed through a polarimeter.
(+) or (d) do not confuse with D
12. Levorotatory – when the plane of polarized light is rotated in a
counter-clockwise direction when viewed through a polarimeter.
(-) or (l) do not confuse with L
The angle of rotation of plane polarized light by an optically active
substance is proportional to the number of atoms in the path of the
light.

The isomer which rotates the plane polarised light to left is known as
laevo (l) while that which rotates the plane polarised light to the right is
known as dextro (d)

86
13. Specific rotation – the angle of rotation of plane polarized light by a
1.00 gram per cm-3 sample in a 1 dm tube. [α ]D (D = sodium lamp, λ =
589 mμ).

α
[ α ]D = where α = observed rotation
l * dl
l = length (dm)
d = concentration (g/cc)
(+)-alanine [ α ]D = +8.5
(-)-lactic acid [α ]D = -3.8

87
 Example
When one of the enantiomers of 2-butanol is placed in a polarimeter, the
observed rotation is 4.05° counterclockwise. The solution was made by
diluting 6 g of 2-butanol to a total of 40 mL, and the solution was placed
into a 200-mm polarimeter tube for the measurement. Determine the
specific rotation for this enantiomer of 2-butanol.

Solution

Since it is levorotatory, this must be (–)-2-butanol The concentration is 6 g

per 40 mL = 0.15 g/mL, and the path length is 200 mm = 2 dm. The
specific rotation is
– 4.05°
25
[ ] = = –13.5°
D
(0.15)(2)

88
14. Racemic mixture (Racemate) is an equimolar proportion ( 50:50) mixture
of the two enantiomers of a chiral compound.

Because the two enantiomers have equal and opposite specific rotations, a
racemic mixture has a specific rotation of zero, i.e., it is optically inactive due
to external compensation.
H H
H
HBr H3C
H3C
CH3 CH3 But do we get (R) or (S)?
addition reaction Br
H H

(E)-2-butene 2-bromobutane
achiral chiral

We get both!

CH3 CH3
H3C H3C
H Br Br H

50% (S)-2-bromobutane 50% (R)-2-bromobutane

89
15. Resolution of Enantiomers - A process of separating a racemate into pure
enantiomers. The enantiomers of the racemate must be temporarily
converted into diastereomers.

N.B: 50:50 mixture of enantiomers is a racemic mixture or racemate,

denoted by (±) or (d,l)

16. Meso-Compound – A compound that has chiral centers but is

optically inactive du e to internal plane of symmetry

90
Features of meso-compound
• Meso compounds have a plane of symmetry.
• If one image was rotated 180°, then it could be superimposed
on the other image.
• Meso compounds are achiral even though they have chiral
centers.
• They are achiral compound with chiral carbons
Stereoisomers of 2,3-Dichlorobutane

CH3CHCHCH3
Cl Cl

CH3 CH3 CH3 CH3

H C Cl
_________ Cl C H
_________ Cl C H H C Cl
H C Cl Cl C H H C Cl Cl C H
CH3 CH3 CH3 CH3

Meso Compound Enantiomers

91
17. Configuration – the arrangement in space of the four different
groups about a chiral center.

How do we show configurations?

“wedge” formulas Fischer projections

“cross structures”
use only for chiral centers!

Br Br
H Cl H
F Cl F

92
specification of configuration: The R/S system.
Cahn, Ingold, Prelog sequence rules:
sequence rule 1: the atom attached to the chiral center with the highest
atomic number = 1, next = 2, etc.
sequence rule 2: if the four atoms attached to the chiral center are not all
different, the sequence is determined at the first point of difference.
sequence rule 3: =X is equal to two –X, etc.
R/S:
1. Using the Cahn, Ingold, Prelog sequence rules, assign numbers to each of
the four groups attached to the chiral center.
2. Rotate the number 4 group away from you and observe the sequence 1 →
2 → 3 for the remaining groups.
3. If going from 1 → 2 → 3 is clockwise, then the configuration is R (rectus).
If the sequence 1 → 2 → 3 is counter-clockwise, then the configuration is S
(sinister).
93
 1 1

Br OH
2 Cl H 4 4 H CH3 3
F CH2Br
3 2
3
CH2CH3
1 Br CH=CH2 2
H
4

94
With group #4 rotated away:

1 2 2 1

3 3

R S

95
 2
2
rotate #4 away
Cl Cl
4 H F 3 3 F
Br Br
1
1

(S)-configuration

96
 References
• Brown, G. I. (1978). An Introduction to Organic Chemistry. Lagos:
Longman Publishers.
• Bajah, S. T., Teibo, B. 0., Onwu G and Obikwere, A. (2002). Senior
Secondary Chemistry - Textbook 2.Lagos. Longman Publishers.
• Tewari, K.S., Mehrotra V. and Vishnoi, N.K. 'Textbook of Organic
Chemistry'.
• Osei Yaw Ababio (2002). New School Chemistry. Onitsha: Africana-Fep
Publishers.
• R.T. Morrison and R.N. Boyd, Organic Chemistry, (6th Ed.), India:
Prentice-Hall Pvt. Ltd.
• Lloyd N. Ferguson, Textbook of Organic Chemistry, (2nd Ed.), Affiliated
East-West Press Pvt. Ltd.
• S.M. Mukherji, S.P. Singh and R.P Kapoor, Organic Chemistry, Vol. I
and II Wiley Eastern Ltd.
• P.L. Soni and H.M. Chawla, Textbook of Organic Chemistry, (24th Ed.),
Sultan Chand and Sons. 97