1) Halogenoalkanes undergo nucleophilic substitution reactions where the halogen is replaced. Alkenes undergo electrophilic addition reactions where atoms or groups are added across the carbon-carbon double bond. 2) Electrophiles are electron deficient species that accept electron pairs from nucleophiles. Common electrophiles include halogen atoms, protons, and carbocations. 3) The reactivity of alkenes is due to the weak pi bond and presence of electron-rich pi electrons on the carbon atoms of the double bond, which attract electrophiles for addition reactions.

1. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
C - Br
Reactivityfor halogenoalkane
• Carbon bondto halogen – F, CI, Br, I
• High electronegativityon halogen gp
• High reactivity – due to polarity of C+
- CI -
C - Br
ᵟ+ ᵟ-
electron
Electron deficient carbon
OH
..ᵟ-ᵟ+
Nucleophilic Substitutionrxn
CH3CH2CI + OH-
→ CH3CH2OH + CI-
H H
‫׀‬ ‫׀‬
H - C – C – CI
‫׀‬ ‫׀‬
H H
+ OH-
ᵟ+ ᵟ-
H H
‫׀‬ ‫׀‬
H - C – C – OH + CI-
‫׀‬ ‫׀‬
H H
H Br H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H H H
CH3CHBrCH3 + OH-
→ CH3CHOHCH3 + Br-
+ OH-
H OH H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H + Br-
‫׀‬ ‫׀‬ ‫׀‬
H H H
ᵟ+ ᵟ-
Nucleophilic SubstitutionElectrophilicAddition
vs
Reactivityof Alkene
- High reactivity - Unstable bondbet C = C
- High reactivity – Weak pi bond overlapbet p orbital
- Unsaturated hydrocarbon – ᴨ bondoverlap
C = C
Electron rich π electron
ᵟ- ᵟ-
H
ᵟ+
C = C
ᵟ-ᵟ-
E
ᵟ+
E+ Electron deficient
Nu
ᵟ-
ᵟ-
Nucleophile
– Lone pair electron
– Donate electron pair
- Lewis Base
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br
ᵟ- ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
ᵟ-
+ H – CIᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
ElectrophilicAddition rxn

2. ᵟ-
Electron rich region
ElectrophilicSubstitutionrxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br
ᵟ+
+ NO2
+
ᵟ+
ElectrophilicSubstitution
vs
C = C
Electron rich π electron
ᵟ- ᵟ-
ᵟ+
C = C
ᵟ-ᵟ-
E
ᵟ+
E+ Electron deficient
E
ᵟ+
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br
ᵟ- ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
ᵟ- + H – CIᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
ElectrophilicAddition rxn
E
Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
ᵟ++
H E
+ H
Electron rich region
H
Br
+ HBr
C6H6 + HNO3 C6H5NO2 + HCI
AICI3 dry ether
warm/conc H2SO4
H NO2
Reactivityof Alkene
- High reactivity - Unstable bondbet C = C
- High reactivity – Weak pi bond overlapbet p orbital
- Unsaturated hydrocarbon – ᴨ bondoverlap
Reactivityof Benzene (Unreactive)
- Delocalization ofelectron in ring
- Stabilitydue to delocalized π electron
- Substitution instead of Addition
C6H6 – no reaction
with brown Br2(I)
ethene decolourize
brown Br2(I)
Benzene –stable (unreactive) toward addition rxn
Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
H
ElectrophilicAddition

3. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
C - Br OH
..ᵟ-ᵟ+
NucleophileElectrophile
ᵟ+
C = C
ᵟ-
Nucleophile
– Lone pair electron
– Donate electron pair
- Lewis Base
Organic Rxn
Addition rxn
Substitution rxn
Nucleophilic Substitution
Free RadicalSubstitution
ElectrophilicSubstitutionElectrophilicAddition rxn
Free radicle
CI CI
CI CI. .
:
Radical (unpair electron)
uv radiation
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ Br – Br
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
ᵟ+
ᵟ-
H H
‫׀‬ ‫׀‬
H - C – C – CI
‫׀‬ ‫׀‬
H H
+ OH-
H H
‫׀‬ ‫׀‬
H - C – C – OH + CI-
‫׀‬ ‫׀‬
H H
ᵟ-ᵟ+
H
E+ + H
Eᵟ+
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
CI CI
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H OH
Add HCI
CI2 / UV
H H
‫׀‬ ‫׀‬
H - C – C – CI
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – OH + CI-
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – NH2 + CI-
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – CN + CI-
‫׀‬ ‫׀‬
H H
NH3
OH-
CN-
H
‫׀‬
H - C – H
‫׀‬
H
H
‫׀‬
H - C – CI + H
‫׀‬
H
CI2 → 2 CI•
CH3• + CI2 → CH3CI + CI•
CI• + CH4 → HCI + CH3•
H

4. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
C - Br OH
..ᵟ-ᵟ+
NucleophileElectrophile
H
ᵟ+
C = C
ᵟ-
Nucleophile
– Lone pair electron
– Donate electron pair
- Lewis Base
Free radicle
CI CI
CI CI. .
:
Radical (unpair electron)
uv radiation
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
CI CI
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H OH
Add HCI
CI2 / UV
H H
‫׀‬ ‫׀‬
H - C – C – CI
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – OH + CI-
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – NH2 + CI-
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – CN + CI-
‫׀‬ ‫׀‬
H H
NH3
OH-
CN-
H
‫׀‬
H - C – H
‫׀‬
H
H
‫׀‬
H - C – CI + H
‫׀‬
H
CI2 → 2 CI•
CH3• + CI2 → CH3CI + CI•
CI• + CH4 → HCI + CH3•
Alkene – Addition rxn Halogenoalkane – Substitution rxn Alkane - Radical substitution
H OH
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H H
H O
‫׀‬ ‖
H - C – C – H
‫׀‬
H
H O
‫׀‬ ‖
H - C – C – OH
‫׀‬
H
H O H
‫׀‬ ‖ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬
H H
H OH H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H H H
H OH H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H CH3 H
Alcohol – Oxidation rxn
10 alcohol 20 alcohol 30 alcohol
carboxylic acid aldehyde ketone
no reaction

5. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
Reactivityof Alkene
- High reactivity - Unstable bondbet C = C
- High reactivity – Weak pi bond overlapbet p orbital
- Unsaturated hydrocarbon – ᴨ bondoverlap
C = C
Electron rich π electron
ᵟ- ᵟ-
Br
ᵟ+
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ H – Br
ᵟ-ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
H
ElectrophilicAddition
SymmetricalAlkene
HBr polar
CH2=CH2 + HBr → CH3CH2Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H Br
CH2=CH2 + Br2 → CH2BrCH2Br
Electrophilicaddition to symmetricalalkene
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ Br – Br
ᵟ+ ᵟ-
Br2 non polar :
induced dipole due to C=C
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
carbocation
carbocation
Heterolytic fission
Heterolytic fission
CH2=CH2 + Br2/H2O → CH2BrCH2Br
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ Br – Br
Heterolytic fission
ᵟ+ ᵟ-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: OH- from
H2O
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br OH
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
CH3 – C = C – CH3
+ H – Br
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H Br
+ H – Br
H H
‫׀‬ ‫׀‬
CH3 – C – C – CH3
‫׀‬ ‫׀‬
H Br
only 1 product
H CH3
‫׀‬ ‫׀‬
H – C = C – H
AsymmetricalAlkene
+ H – Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
H Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
Br H
carbocation
2 product

6. H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ H – Br
ᵟ-ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
H
HBr polar
CH2=CH2 + HBr → CH3CH2Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H Br
CH2=CH2 + Br2 → CH2BrCH2Br
Addition to symmetricalalkene
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ Br – Br
ᵟ+ ᵟ-
Br2 non polar :
induced dipole due to C=C
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
carbocation
Heterolytic fission
Heterolytic fission
CH2=CH2 + Br2/H2O → CH2BrCH2Br
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
+ Br – Br
Heterolytic fission
ᵟ+ ᵟ-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ +
Br
: OH- from
H2O
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br OH
H CH3
‫׀‬ ‫׀‬
H – C = C – H + H – Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
H Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
Br H
Addition to asymmetricalalkene
CH2=CHCH3 + HBr → CH3CHBrCH3 or CH2BrCH2CH3
major
minor
CH3 CH3
‫׀‬ ‫׀‬
H – C = C – CH3 + H – Br
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
H Br
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
Br H
major
minor
✓
✓
Markovnokov rule
- Hydrogen/electrophileadd to carbonwith most H2 bonded
- Due to stable carbocationintermediateformed
R
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
H
30 carbocation
> > >
20 carbocation 10 carbocation

7. H CH3
‫׀‬ ‫׀‬
H – C ← C – H
+ ‫׀‬
H
H CH3
‫׀‬ ↓
H – C → C – H
‫׀‬ +
H
+ H – Br
ᵟ-ᵟ+
: Br-
: Br-
2 alkyl gp – positive inductive effect
– push electron to carbocation (more stable)
Heterolytic
fissionH CH3
‫׀‬ ‫׀‬
H – C = C – H
Addition to asymmetricalalkene
CH2=CHCH3 + HBr → CH3CHBrCH3
major
minor
CH3 CH3
‫׀‬ ‫׀‬
H – C = C–CH3 + H – Br
CH3 CH3
‫׀‬ ↓
H – C → C ← CH3
‫׀‬ +
H
CH3 CH3
↓ ‫׀‬
H – C ← C – CH3
+ ‫׀‬
H
major
minor
✓
✓
Markovnokov rule
- H add to carbon with most H2 bonded
- Due to stable carbocationformed
R
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
R
> >
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬‫׀‬
H Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬‫׀‬
Br H
1 alkyl gp – positive inductive effect
– push electron to carbocation (less stable)
ᵟ+ ᵟ -
: Br-
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – CH3
‫׀‬ ‫׀‬
H Br
3 alkyl gp – positive inductive effect
– push electron to carbocation (more stable)
: Br-
2 alkyl gp – positive inductive effect
– push electron to carbocation (less stable)
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – CH3
‫׀‬ ‫׀‬
Br H
30 carbocation
most stable
10 carbocation
least stable
H CH3
‫׀‬ ↓
H – C → C – H
‫׀‬ +
H
H CH3
‫׀‬ ‫׀‬
H – C ← C – H
+ ‫׀‬
H
>
20 carbocation
– greater positive inductive effect
- more stable/lower charge density carbocation
CH3 CH3
‫׀‬ ↓
H – C → C ← CH3
‫׀‬ +
H
>
CH3 CH3
↓ ‫׀‬
H – C ← C – CH3
+ ‫׀‬
H
30 carbocation
– greater positive inductive effect
- more stable/lower charge density carbocation

8. H CH3
‫׀‬ ‫׀‬
H – C ← C – H
+ ‫׀‬
Br
H CH3
‫׀‬ ↓
H – C → C – H
‫׀‬ +
Br
+ Br – CI
ᵟ-ᵟ+
: CI-
: CI-
2 alkyl gp – positive inductive effect
– push electron to carbocation (more stable)
Heterolytic
fissionH CH3
‫׀‬ ‫׀‬
H – C = C – H
Addition to asymmetricalalkene
CH2=CHCH3 + BrCI → CH2BrCHCICH3
major
minor
CH3 CH3
‫׀‬ ‫׀‬
H – C = C–CH3 + I – CI
CH3 CH3
‫׀‬ ↓
H – C → C ← CH3
‫׀‬ +
I
CH3 CH3
↓ ‫׀‬
H – C ← C – CH3
+ ‫׀‬
I
major
minor
✓
✓
Markovnokov rule
- H add to carbon with most H2 bonded
- Due to stable carbocationformed
R
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
R
> >
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬‫׀‬
Br CI
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬‫׀‬
CI Br
1 alkyl gp – less positive inductive effect
– (less stable)
ᵟ+ ᵟ -
: CI-
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – CH3
‫׀‬ ‫׀‬
I CI
3 alkyl gp – positive inductive effect
– push electron to carbocation (more stable)
: CI-
2 alkyl gp – less positive inductive effect
– (less stable)
CH3 CH3
‫׀‬ ‫׀‬
H – C – C – CH3
‫׀‬ ‫׀‬
CI I
30 carbocation
most stable
10 carbocation
least stable
H CH3
‫׀‬ ↓
H – C → C – H
‫׀‬ +
Br
H CH3
‫׀‬ ‫׀‬
H – C ← C – H
+ ‫׀‬
Br
>
20 carbocation
– greater positive inductive effect
- more stable/lower charge density carbocation
CH3 CH3
‫׀‬ ↓
H – C → C ← CH3
‫׀‬ +
I
>
CH3 CH3
↓ ‫׀‬
H – C ← C – CH3
+ ‫׀‬
I
30 carbocation
– greater positive inductive effect
- more stable/lower charge density carbocation
EN CI higher
EN CI higher

9. ᵟ-
Electron rich region
ElectrophilicSubstitutionrxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br
ᵟ+
+ NO2
+
ᵟ+
ElectrophilicSubstitutionElectrophilicAddition
vs
C = C
Electron rich π electron
ᵟ- ᵟ-
ᵟ+
C = C
ᵟ-ᵟ-
E
ᵟ+
E+ Electron deficient
E
ᵟ+
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br
ᵟ- ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
ᵟ- + H – CIᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
ElectrophilicAddition rxn
E
Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
ᵟ++
H E
+ H
Electron rich region
H
Br
+ HBr
C6H6 + HNO3 C6H5NO2 + HCI
AICI3 dry ether
warm/Conc H2SO4
H NO2
Reactivityof Alkene
- High reactivity - Unstable bondbet C = C
- High reactivity – Weak pi bond overlapbet p orbital
- Unsaturated hydrocarbon – ᴨ bondoverlap
Reactivityof Benzene (Unreactive)
- Delocalization ofelectron in ring
- Stabilitydue to delocalized π electron
- Substitution instead of Addition
C6H6 – no reaction
with brown Br2(I)
ethene decolourize
brown Br2(I)
Benzene –stable (unreactive) toward addition rxn
Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
H

10. + Br – Br
ᵟ-ᵟ+
Cyclohexene(Addition) vs Benzene (Substitution)
✓
Positive charge distributed
in benzene ring
(carbocation intermediate)
Benzene highly unreactive
to addition rxn
: Br-
+
+ Br – Br
+ Br – Br
AICI3 dry ether
Benzene undergo substitution rxn
Cyclohexene undergo addition rxn
Benzene undergo electrophilic substitution (Bromination)
Loss H+ enable
aromatic ring to reform
Br - Br
Br Br
Benzene undergo electrophilic substitution (Nitration)
+NO2
NO2 NO2
Positive charge distributed
in benzene ring
(carbocation intermediate)
Loss H+ enable
aromatic ring to reform C6H6 + HNO3 C6H5NO2
Conc H2SO4
50C
Conc HNO3 + H2SO4 produce NO2
+ electrophile
+
H
Reactivityof Benzene (Unreactive)
- Delocalization ofelectron in ring
- Stabilitydue to delocalized π electron
- Substitution instead of Addition
ElectrophilicSubstitution
H
E
ᵟ+
+
+ H
E
Electron rich region
C6H6 + Br2 C6H5Br + HBr
AICI3 dry ether
H
+ Br-Br
ᵟ+
+ HBr
Br
✓

11. OH O
‫׀‬ ‖
CH3-C–CH3 + [O] CH3- C– CH3
H
‫׀‬
CH3-CH2-OH + [O] CH3- C = O
Reduction rxnOxidation rxn
MnO4
-
/H+
K2Cr2O7/H+
10
Alcohol – Oxidised to Aldehyde and Carboxylic acid
20
Alcohol - Oxidised to Ketone
MnO4
-
/H+
K2Cr2O7/H+
MnO4
-
/H+
K2Cr2O7/H+
Oxidation vs Reduction rxn
O
‖
CH3-COH
Oxidation of Alcohol
Acidified dichromate(VI)/permanganate(VII)
Reduction carbonyl (C = O)
Sodium borohydride (NaBH4)
Lithium aluminium hydride (LiAIH4) / dry ether
O
‖
CH3-COH CH3CHO CH3CH2OH
O OH
‖ ‫׀‬
CH3-C–CH3 CH3- C– CH3
[H-] [H-]
NaBH4 NaBH4
Carboxylic acid reduced to aldehyde / alcohol
NaBH4
[H-]
Ketone reduced to alcohol
Hydride ion (nucleophile) :H-
produce
hydride ion / :H-
O
‖
CH3-COH CH3CH2OH
Carboxylic acid reduced alcohol
[H-]
LiAIH4 dry ether with acid
stronger reducing agent
Sn / conc HCI / reflux
Nitrobenzene reduced to phenylamine
NH3
+NO2 NH2
NaOH
phenylammonium
ion
reducing agent
Convert benzene to phenylamine
Convert propanoic acid to propanol
Convert ethanal to ethanol
O
‖
CH3CH2 COH CH3CH2CH2OH
[H-]
stronger reducing agent
LiAIH4 dry ether / acid
CH3CHO CH3CH2OH
[H-]
NaBH4
50C
NO2
conc HNO3 + H2SO4
Sn / conc HCI / reflux
NH3
+
NaOH
NH2

12. ‫׀‬ ‫׀‬
C - C –OH
‫׀‬ ‫׀‬
O
‖
C – C – C
O
‖
C – C – H
O
‖
C – C – OH
O
‖
C –C – C– O – C – C
No
reaction
1o
alcohol
[O]/Cr2O7/H+
Aldehyde
Ketone
Carboxylic Acid
Free radical substitution
CI2/ UV
Halogenoalkane
Alkane
2o
alcohol
[O]/ Cr2O7/H+
[O]/ Cr2O7/H+
3o
alcohol
[O]/ Cr2O7/H+
Substitution
warm / OH-
Alcohol
Alcohol
Alkene
Elimination
100C /Conc alcoholic OH-
Alkane Halogenoalkane Dihalogenoalkane
Condensation
Ester
Addition
Polymerisation
X
‫׀‬ ‫׀‬
C – C – CI
‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
C – C – C – C
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
H CI
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
CI CI
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
Br Br
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C – C – OH
‫׀‬ ‫׀‬
Start here
PolyAlkene
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
H H
[H]/ NaBH4[H]/ NaBH4
[H]/ NaBH4
oxidation
reduction
oxidation
oxidation
reduction
reduction
conc HNO3 / H2SO4
50C
NO2
Sn / conc HCI / reflux
NH3
+
NaOH
NH2

13. C – C = C – C → C – C – C – C
‖
O
Synthetic routes
C –C –C – I → C – C – C-H
‖
O
Two steps
1 - Addition of H2O
2 - Oxidation alcohol to ketone
Two steps
1– Substitution with OH- to alcohol
2- Oxidation alcohol to aldehyde
But-2-ene to Butanone 1-iodopropane to propanal
1-chloropropane to propanoic acid
C –C –C –CI → C – C–COOH
Three steps
1 – Substitution with OH- to alcohol
2- Oxidation alcohol to aldehyde
3 - Oxidation aldehyde to carboxylic acid
C – C = C – C
C – C – C – C
‫׀‬ ‫׀‬
H OH
C – C – C – C
‖
O
H2O /300C
H2SO4 catalyst
[O] oxidation
K2Cr2O7/H+
C – C – C – I C – C – C – H
‖
O
C – C – C–OH
warm NaOH
SN2
[O] oxidation
K2Cr2O7/H+
C – C – C – CI C – C – COOH
C – C – C–OH C – C – C – H
‖
O
warm NaOH
SN2
[O] oxidation
K2Cr2O7/H+
Propane to propanoic acid
C –C –C → C –C –COOH
C – C – C C – C – COOH
C – C – C–CI C – C – C–OH
[O] oxidation
K2Cr2O7/H+
reflux
Warm NaOH
SN2
Free radical
substitution
UV / CI2
Three steps
1 – Free radical substitution to halogenoalkane
2– Substitution with OH- to alcohol
3 – Oxidation alcohol to carboxylic acid
[O] oxidation
K2Cr2O7/H+
reflux

14. Synthetic routes
Propane to propyl propanoate
Butene to butanone
Three steps
1 – Addition HBr
2– Substitution with OH –
3 – Oxidation of alcohol to ketone
Four steps
1 – Free radical substitution/UV
2– Substitution with OH-
3 – Oxidation alcohol to carboxylic acid
4 – Esterification with conc acid
Ethene to ethanoic acid
C – C
‫׀‬ ‫׀‬
H OH
C – C – H
‖
O
C – COOH
Three steps
1 – Addition using H2O
2- Oxidation alcohol to aldehyde
3 – Oxidation aldehyde to carboxylic acid
Ethanol to ethyl ethanoate
C – C-OH → C–COO–C–C
C – C – O – C – C
‖
O
C–C–OH
C – COOH
Esterification
Ethanol + ethanoic acid
Conc H2SO4
Two steps
1 – Oxidation alcohol to carboxylic acid
2– Esterification with ethanol/conc acid
C = C → C – COOH
Free radical
substitution
UV / CI2
C–C–C–CI
C – C – C
C–C–C–OH
Warm NaOH
SN2
C–C–COOH
[O] oxidation/reflux
K2Cr2O7/H+
C – C – C – O – C – C – C
‖
O
Esterification
Propanol + propanoic acid
Conc H2SO4
C – C = C – C C – C – C – C
‖
OAddition HBr
C – C – C – C
‫׀‬ ‫׀‬
Br H
Warm NaOH
SN2
C – C – C – C
‫׀‬ ‫׀‬
OH H
[O] oxidation
K2Cr2O7/H+ [O] oxidation
K2Cr2O7/H+
reflux
C – C = C – C → C – C – C – C
‖
O
C = C
H2O /300C
H2SO4 catalyst
[O] oxidation
K2Cr2O7/H+
[O] oxidation
K2Cr2O7/H+
reflux
C – C – C → C – C – C –O–C–C–C
‖
O

15. Synthetic routes
Benzene to phenylamine
Ethanoic acid to ethyl ethanoate
Two steps
1 – Reduction to alcohol
2– Esterification with ethanoic acid/conc acid
C – COOH
C–C–OH
Three steps
1 – Nitration substitution of benzene
2– Reduction of nitrobenzene
3 – Addition NaOH
Ethanoic acid to ethanol
C – C
‫׀‬ ‫׀‬
H OH
C – C – H
‖
O
C – COOH
Two steps
1 – Reduction acid to aldehyde
2- Reduction aldehyde to alcohol
C – COOH → C –COO–C–C
C – C – O – C – C
‖
O
Reduction [H-]
LiAIH4 dry ether
acid
Esterification
Ethanol + ethanoic acid
Conc H2SO4
Ethane to Ethanol
C – C → C–C-OH
C – C
C – C – CI
Two steps
1 – Free radical substitution/UV
2– Substitution with OH-
NO2
NH2
NH2
NH3
+
conc HNO3
conc H2SO4
50C
Sn / conc HCI / reflux
NaOH
C – COOH → C – C-OH
Reduction [H-]
NaBH4
Reduction [H-]
NaBH4
Free radical
substitution
UV / CI2
C – C
‫׀‬ ‫׀‬
H OH
warm NaOH
SN2