IB Chemistry on Electrophilic Addition and Synthetic routes

1. http://lawrencekok.blogspot.com
Prepared by
Lawrence Kok
Tutorial on Electrophilic Addition and Synthetic Routes

2. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
C - Br
Reactivity for halogenoalkane
• Carbon bond to halogen – F, CI, Br, I
• High electronegativity on halogen gp
• High reactivity – due to polarity of C+
- CI -
C - Brᵟ+ ᵟ-
electron
Electron deficient carbon
OH
..ᵟ-ᵟ+
Nucleophilic Substitution rxn
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 SubstitutionElectrophilic Addition
vs
Reactivity of Alkene
- High reactivity - Unstable bond bet C = C
- High reactivity – Weak pi bond overlap bet p orbital
- Unsaturated hydrocarbon – ᴨ bond overlap
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
Electrophilic Addition rxn

3. ᵟ-
Electron rich region
Electrophilic Substitution rxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br
ᵟ+
+ NO2
+
ᵟ+
Electrophilic Substitution
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
Electrophilic Addition 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
Reactivity of Alkene
- High reactivity - Unstable bond bet C = C
- High reactivity – Weak pi bond overlap bet p orbital
- Unsaturated hydrocarbon – ᴨ bond overlap
Reactivity of Benzene (Unreactive)
- Delocalization of electron in ring
- Stability due 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
Electrophilic Addition

4. 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 Radical Substitution
Electrophilic SubstitutionElectrophilic Addition 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

5. 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

6. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
Reactivity of Alkene
- High reactivity - Unstable bond bet C = C
- High reactivity – Weak pi bond overlap bet p orbital
- Unsaturated hydrocarbon – ᴨ bond overlap
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
Electrophilic Addition
Symmetrical Alkene
HBr polar
CH2=CH2 + HBr → CH3CH2Br
: Br-
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H Br
CH2=CH2 + Br2 → CH2BrCH2Br
Electrophilic addition to symmetrical alkene
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
Asymmetrical Alkene
+ H – Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
H Br
H CH3
‫׀‬ ‫׀‬
H – C – C – H
‫׀‬ ‫׀‬
Br H
carbocation
2 product

7. 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 symmetrical alkene
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 asymmetrical alkene
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/electrophile add to carbon with most H2 bonded
- Due to stable carbocation intermediate formed
R
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
R – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
R
H
‫׀‬
H – C +
‫׀‬
H
30 carbocation
> > >
20 carbocation 10 carbocation

8. 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 asymmetrical alkene
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 carbocation formed
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

9. 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 asymmetrical alkene
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 carbocation formed
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

10. ᵟ-
Electron rich region
Electrophilic Substitution rxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br
ᵟ+
+ NO2
+
ᵟ+
Electrophilic SubstitutionElectrophilic Addition
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
Electrophilic Addition 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
Reactivity of Alkene
- High reactivity - Unstable bond bet C = C
- High reactivity – Weak pi bond overlap bet p orbital
- Unsaturated hydrocarbon – ᴨ bond overlap
Reactivity of Benzene (Unreactive)
- Delocalization of electron in ring
- Stability due 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

11. + 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
Reactivity of Benzene (Unreactive)
- Delocalization of electron in ring
- Stability due to delocalized π electron
- Substitution instead of Addition
Electrophilic Substitution
H
E
ᵟ+
+
+ H
E
Electron rich region
C6H6 + Br2 C6H5Br + HBr
AICI3 dry ether
H
+ Br-Br
ᵟ+
+ HBr
Br
✓

12. 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

13. ‫׀‬ ‫׀‬
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
AlcoholAlkene
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

14. 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

15. 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 – C OOH
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

16. 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

17. Acknowledgements
Thanks to source of pictures and video used in this presentation
Thanks to Creative Commons for excellent contribution on licenses
http://creativecommons.org/licenses/
Prepared by Lawrence Kok
Check out more video tutorials from my site and hope you enjoy this tutorial
http://lawrencekok.blogspot.com