IB Chemistry Nucleophilic Substitution, SN1, SN2 and protic solvent

1. Class Functionalgp Suffix Example Formula
Alkane C - C - ane ethane CnH2n+2
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H H
H
‫׀‬
H - C – H
‫׀‬
H
H H H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H H H
H H H H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
H H H H
Number
carbon
Word IUPAC
name
Structure formula Molecular
formula
1 Meth Methane CH4 CH4
2 Eth Ethane CH3CH3 C2H6
3 Prop Propane CH3CH2CH3 C3H8
4 But Butane CH3(CH2)2CH3 C4H10
5 Pent Pentane CH3(CH2)3CH3 C5H12
6 Hex Hexane CH3(CH2)4CH3 C6H14
7 Hept Heptane CH3(CH2)5CH3 C7H16
8 Oct Octane CH3(CH2)6CH3 C8H18
9 Non Nonane CH3(CH2)7CH3 C9H20
10 Dec Decane CH3(CH2)8CH3 C10H22
methane ethane propane butane
Saturated hydrocarbon (C – C single bond)
Chemical rxn AlkaneReactivityfor Alkanes
Combustion rxn
Complete combustion – produce CO2 + H2O
• C2H6 + 7/2O2 → 2CO2 + 3H2O
Incomplete combustion – produce C, CO, CO2, H2O
• 2C3H8 + 7O2 → 2C + 2CO + 8H2O + 2CO2
Free Radical Substitution rxn
Free Radical Substitution Mechanism
- Homolytic fission- bond break by radical form.
- Covalent bond split, each atom obtain one electron (unpair e)
- UV needed
- Radical react with molecule
- Radical + radical → molecule
CH4 + CI2 → CH3CI + HCI
• Low reactivity - Strongstable bondbet C - C, C - H
• Low reactivity - Low polarity of C - H bond
• Saturatedhydrocarbon – Non polarbond
Initiation
Propagation
Radical (dot)
Termination
homolytic
fission
Radical recycle again
1
2

2. H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
H H H
‫׀‬ ‫׀‬ ‫׀‬
C = C – C - H
‫׀‬ ‫׀‬
H H
H H H H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
C = C – C – C - H
‫׀‬ ‫׀‬ ‫׀‬
H H H
Unsaturated hydrocarbon (C = C double bond)
H H H H H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
C = C – C – C – C - H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
H H H H
ethene propene butene pentene
Reactivityfor Alkene
- High reactivity - Unstable bondbet C = C
- High reactivity – Weak pi bond overlapbet p orbital
- Unsaturated hydrocarbon – ᴨ bondoverlap
Combustion rxn
Chemicalrxn Alkane
Complete combustion – produce CO2 + H2O
C2H4 + 3O2 → 2CO2 + 2H2O
Incomplete combustion – produce C, CO, CO2, H2O
2C2H4 + 7/2O2 → 2C + CO + 4H2O + CO2
CH2 = CH2 + Br2 → CH2BrCH2Br
CH2 = CH2 + HCI → CH3CH2CI
CH2 = CH2 + H2O → CH3CH2OH
Addition rxn
H H
‫׀‬ ‫׀‬
C = C
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
CI CI
Class Functional Suffix Example Formula
Alkene Alkenyl - ene ethene CnH2n
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
Br Br
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H CI
H H
‫׀‬ ‫׀‬
H - C – C – H
‫׀‬ ‫׀‬
H OH
1
2
Polymerization(Additionrxn)3
Polymers are long chains molecules (plastics)
• Join repeat units call monomers
• Addition and condensation polymerization
• Monomers double bond (unsaturated)
• Repeat units join together by covalent bond without loss of any molecule
ethene polyethene
add monomer
polymer
propene polypropylene
add monomer
H CH3 H CH3
monomer
monomer
chloroethene polychloroethene
(PVC)
tetrafluoroethene polytetrafluoroethene
(PTFE)
H CI H CI
F F
F F
F F
F F
polymerization
polymer
Alkene decolourize
brown liq Br2

3. OH
‫׀‬
CH3-C– CH3 + [O] No product
‫׀‬
CH3
OH O
‫׀‬ ‖
CH3- C–CH3 + [O] CH3- C – CH3 + H2O
H
‫׀‬
CH3 – C – OH
‫׀‬
H
Class Functional Suffix Example Formula
Alcohol Hydroxyl - ol methanol CnH2n+1OH
Number
carbon
IUPAC name Structure formula Molecular
formula
1 Methanol CH3OH CH3OH
2 Ethanol CH3CH2OH C2H5OH
3 Propanol CH3CH2CH2OH C3H7OH
4 Butanol CH3(CH2)2CH2OH C4H9OH
methanol ethanol propanol butanol
H
‫׀‬
H - C – OH
‫׀‬
H
H H
‫׀‬ ‫׀‬
H - C – C – OH
‫׀‬ ‫׀‬
H H
H H H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – OH
‫׀‬ ‫׀‬ ‫׀‬
H H H
H H H H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – C – OH
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
H H H H
Hydrocarbon skeleton Functional gp
Chemical rxn AlcoholReactivityfor Alcohol
Primary 1 0
1 alkyl /R gp bond to C attach to OH
CH3 H
‫׀‬ ‫׀‬
CH3 – C – C – OH
‫׀‬ ‫׀‬
CH3 H
Combustionrxn
Complete combustion–produceCO2 + H2O
C2H6OH + 3O2 → 2CO2 + 3H2O
Incomplete combustion-produceC, CO, CO2, + H2O
2C2H5OH + 4O2 → C + 2CO + 6H2O + CO2
Oxidation rxn
Secondary 2 0
2 alkyl/R gp bond to C attach to OH
H
‫׀‬
CH3 – C – OH
‫׀‬
CH3
H H H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H OH H
Tertiary 3 0
3 alkyl/R gp bond to C attach to OH
CH3
‫׀‬
CH3 – C – OH
‫׀‬
CH3
R
‫׀‬
R – C – OH
‫׀‬
R
H
‫׀‬
CH3-CH2-OH + [O] CH3- C = O + H2O
MnO4
-
/H+
K2Cr2O7/H+
Primary 10
– Oxidised to Aldehyde and Carboxylic acid
H OH
‫׀‬ ‫׀‬
CH3- C= O + [O] CH3-C=O
Secondary 20
- Oxidised to Ketone
Tertiary 30
- Cannot be Oxidised
MnO4
-
/H+
K2Cr2O7/H+
MnO4
-
/H+
K2Cr2O7/H+
MnO4
-
/H+
K2Cr2O7/H+
1
1
Esterificationrxn3
O H
‖ ‫׀‬
H - C – O – C – H + H2O
‫׀‬
H
H
‫׀‬
H- O – C – H
‫׀‬
H
O
‖
H - C – O-H +

4. Chemical rxn Alcohol
Oxidation rxn – oxidized carbon attach to OH
Primary 10
– Oxidised to Aldehyde and Carboxylic acid
Secondary 20
- Oxidised to Ketone Tertiary 30
- Cannot be Oxidised
OH
‫׀‬
CH3-C– CH3 + [O] No product
‫׀‬
CH3
MnO4
-
/H+
K2Cr2O7/H+
MnO4
-
/H+
K2Cr2O7/H+
MnO4
-
/H+
K2Cr2O7/H+
Alcohol to Aldehyde (Distillation)
1. Acidified dichromate(VI)/permanganate(VII)
2.Warm it , collect distillate (Distillation)
Aldehyde
Carboxylic acid
-1 + 1
ON carbon increase
Alcohol
H OH
‫׀‬ ‫׀‬
CH3- C= O + [O] CH3- C =O
H H
‫׀‬ ‫׀‬
CH3- C -O-H + [O] CH3- C = O
‫׀‬
H
+ 1 + 3
ON carbon increaseAldehyde
Primary 10
– Oxidised to Aldehyde and Carboxylic acid
Alcohol to Carboxylic acid (Reflux)
1. Acidified dichromate(VI)/permanganate(VII)
2.Warm it , collect distillate (Distillation)
Alcohol oxidize to Aldehyde
• MnO4
-
reduce from purple (Mn7+
) to pink (Mn2+
)
• Cr2O7
2-
reducefrom orange (Cr6+
) to green (Cr3+
)
0 + 2
ON carbon increase
Alcohol Ketone
Alcohol to Ketone (Reflux)
1. Acidified dichromate(VI)/permanganate(VII)
2.Warm it , collect distillate (Distillation)
Click here oxidation alcohol
RCH2OH + [O] → RCHO + H2O
RCH2OH + 2[O] → RCOOH + H2O
RCH(OH)R + [O] → RCOR + H2O
Oxidationeqn(additionof O)
AldehydeAlcohol
Alcohol
Alcohol
Carboxylic acid
Ketone
Alcohol oxidize to Carboxylic acid
• MnO4
-
reduce from purple (Mn7+
) to pink (Mn2+
)
• Cr2O7
2-
reducefrom orange (Cr6+
) to green (Cr3+
)
distillation
reflux
Aldehyde turn to carboxylic acid
Aldehyde
Alcohol
reflux
Alcohol turn to ketone
OH O
‫׀‬ ‖
CH3- C – CH3 + [O] CH3- C – CH3 + H2O

5. Class Functional Suffix Formula
Ester Ester - oate R –COO-R
Number
carbon
IUPAC name Structure formula Molecular
formula
1 Methyl methanoate HCOOCH3
R–COO-R
2 Methyl ethanoate CH3COOCH3
R–COO-R
3 Methyl propanoate CH3CH2COOCH3
R–COO-R
4 Methyl butanoate CH3CH2CH2COOCH3 R–COO-R
methyl methanoate methyl ethanoate methyl propanoate
O H
‖ ‫׀‬
H - C – O – C - H
‫׀‬
H
H O H
‫׀‬ ‖ ‫׀‬
H - C - C – O - C - H
‫׀‬ ‫׀‬
H H
H H O H
‫׀‬ ‫׀‬ ‖ ‫׀‬
H - C – C – C – O - C - H
‫׀‬ ‫׀‬ ‫׀‬
H H H
Hydrocarbon skeleton Functional gp
Esterification
O
‖
H - C – O-H
H
‫׀‬
H- O – C – H
‫׀‬
H
O H
‖ ‫׀‬
H - C – O – C – H + H2O
‫׀‬
H
Ester
Condensation rxn
↔+
Methanoic acid Methanol Methyl methanoate
Esterification (reversible rxn)
After reflux – reach equilibrium
Acid and alcohol (reflux)
Conc H2SO4 (catalyst) used
Water produced
condensation
reflux
Ester purified and distill
Click here ester preparation
H O H
‫׀‬ ‖ ‫׀‬
H - C - C – O - C – H + H2O
‫׀‬ ‫׀‬
H H
H
‫׀‬
H- O – C – H
‫׀‬
H
H O
‫׀‬ ‖
H - C - C – OH
‫׀‬
H
CH3COOH + CH3OH → CH3COOCH3 + H2O
H O H H
‫׀‬ ‖ ‫׀‬ ‫׀‬
H – C – C– O - C–C-H
‫׀‬ ‫׀‬ ‫׀‬
H H H
+
Ethanoic acid Methanol Methyl ethanoate
↔
H H
‫׀‬ ‫׀‬
H- O- C– C – H
‫׀‬ ‫׀‬
H H
H O
‫׀‬ ‖
H – C – C - OH
‫׀‬
H
condensation
CH3COOH + CH3CH2OH → CH3COOCH2CH3 + H2O
+
condensation
↔
Ethanoic acid Ethanol Ethyl ethanoate
+ H2O

6. H
‫׀‬
CH3 – C – CI
‫׀‬
H
H
‫׀‬
H - C – CI
‫׀‬
H
H H
‫׀‬ ‫׀‬
H - C – C – CI
‫׀‬ ‫׀‬
H H
H H H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – CI
‫׀‬ ‫׀‬ ‫׀‬
H H H
Hydrocarbon skeleton Functional gp
Primary 1 0
1 alkyl /R gp bond to C attach to CI
Secondary 2 0
2 alkyl/R gp bond to C attach to CI
H
‫׀‬
CH3 – C – CI
‫׀‬
CH3
H H H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬
H CI H
Tertiary 3 0
3 alkyl/R gp bond to C attach to CI
CH3
‫׀‬
CH3 – C – CI
‫׀‬
CH3
R
‫׀‬
R – C – CI
‫׀‬
R
Reactivityfor Halogenoalkane
Class Functional Prefix Example
Halogenoalkane F, CI, Br, I - chloro chloroethane
Number
carbon
IUPAC name Structure formula Molecular
formula
1 chloromethane CH3CI CH3CI
2 chloroethane CH3CH2CI C2H5CI
3 chloropropane CH3CH2CH2CI C3H7CI
4 chlorobutane CH3(CH2)2CH2CI C4H9CI
chloromethane chloroethane chloropropane
Reactivityfor halogenoalkane
• Carbon bondto halogen – F, CI, Br, I
• High electronegativityon halogen gp
• High reactivity– due to polarity of C+
- Br -
Nucleophile
– Lone pair electron
– Donate electron pair (Lewis base)
Chemical rxn Halogenoalkane
C - Br
ᵟ+ ᵟ-
electron
Electron deficient
carbon
O–H
..
..
ᵟ- ᵟ+
C
ᵟ+
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-
CH3 H
‫׀‬ ‫׀‬
CH3 – C – C – CI
‫׀‬ ‫׀‬
CH3 H

7. 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-
Nucleophile and SubstitutionElectrophileandAddition
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

8. Electrophile
- Electron deficient
- Accept lone pair
- Positive charge
- Lewis Acid
ᵟ-
Electron rich region
ElectrophilicSubstitutionrxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br
ᵟ+
+ NO2
+
ᵟ+
Electrophileand SubstitutionElectrophileandAddition
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 bond bet C = C
- High reactivity – Weak pi bond overlap bet p orbital
- Unsaturated hydrocarbon– ᴨ bond overlap
Reactivityof Benzene (Unreactive)
- Delocalization ofelectron in ring
- Stabilitydue to delocalized π electron
- Substitution instead of Addition
ethene decolourize
brown Br2(I)
benzene –stable (unreactive) toward addition rxn
H
C6H6 – no rxn
with brown Br2(I)

9. 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

10. 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

11. ‫׀‬ ‫׀‬
C- C –OH
‫׀‬ ‫׀‬
O
‖
C – C – C
O
‖
C – C – H
O
‖
C – C – OH
O
‖
C –C – C– O – C – C
O H
‖ ‫׀‬
C – C – N – C – C
No
reaction
1o
alcohol
[O]/Cr2O7/H+
Aldehyde
Ketone Carboxylic Acid
Free radical substitution
CI2/ UV
Halogenoalkane
Alkane
3o
alcohol
[O]/ Cr2O7/H+
Substitution
warm / OH-
Alcohol
Substitution / CN-
Amine
Nitrile
Alcohol
Condensation
Amide
Amine
Carboxylic Acid
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
‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C – C – CN
‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C – C – NH2
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬
C – C – C –NH2
‫׀‬ ‫׀‬ ‫׀‬
‫׀‬ ‫׀‬
C – C – COOH
‫׀‬ ‫׀‬
Start here
PolyAlkene
‫׀‬ ‫׀‬
C – C
‫׀‬ ‫׀‬
H H

12. H
‫׀‬
CH3 – C – Br
‫׀‬
H
CH3 H
‫׀‬ ‫׀‬
CH3 – C – C – Br
‫׀‬ ‫׀‬
CH3 H
Reactivityfor halogenoalkane
• Carbon bondto halogen – F, CI, Br, I
• High electronegativityon halogen
• High reactivity – polarityof C+
- Br -
Nucleophile
– Lone pair electron
– Donate electron pair
- (Lewis base)
Chemical rxn Halogenoalkane
C - Br
ᵟ+ ᵟ-
electron
Electron deficient
carbon
O–H
..
..
ᵟ-
C
ᵟ+
H H
‫׀‬ ‫׀‬
H - C – C – Br
‫׀‬ ‫׀‬
H H
+ OH-ᵟ+ ᵟ-
H H
‫׀‬ ‫׀‬
H - C – C – OH + Br-
‫׀‬ ‫׀‬
H H
Nucleophilic Substitution
Primary 10
- SN2
Primary 10
- SN2
- Experimentallyrate expression= k [CH3CH2Br][OH-]
- Rate dependent on conc- CH3CH2Brand OH-
- Molecularity= 2
- No bulky alkyl gp, less steric effect
- Allow nucleophileto attackelectron deficient carbon
from opposite site (Inversion of configuration)
CH3CH2Br + OH-
→ CH3CH2OH + Br-
SN2
Substitution
Bimolecular collision
bet 2 molecule
Nucleophilic
Bimolecular Nucleophilic Substitution
OH-
+ CH3CH2Br [ HO---CH2(CH3)---Br]- CH3CH2OH + Br-
HO-
Bond breaking and making
in transition state
+ Br-
One step mechanism – Bond break and making in transitionstate
nucleophile
attack
leaving gp
Click here to view SN2
slow step
(RDS)
fast step
slow step (RDS) fast step
✓1ₒ SN2

13. Hydrolysis bromoethane (1o
)
H
‫׀‬
OH-
+ CH3 – C – Br
‫׀‬
H
Bond Breaking and Making at transition state Br leaving gp substituted with OH-
H H
‫׀‬ ‫׀‬
CH3 - C – Br + OH-
CH3 – C – OH + Br -
‫׀‬ ‫׀‬
H H
Nucleophile collide with bromoethane
CH3CH2Br + OH-
→ CH3CH2OH + Br-
Single step
Nucleophilic Substitution
Click here view SN2
SN2
Substitution
Nucleophilic
Bimolecular Nucleophilic Substitution
Bimolecular collision
bet 2 molecule
- Experimentallyrate expression= k [CH3CH2Br][OH-]
- Rate dependent on conc = CH3CH2Brand OH-
- Molecularity= 2
- No bulky alkyl gp, less steric effect
- Allow nucleophileto attackelectron deficient carbon
from the opposite site (Inversion of configuration)
Formation of ethanol
1 step mechanism
(concerted)
SN21ₒ

14. Nucleophile
– Lone pair electron
– Donate electron pair
- (Lewis base)
CH3
‫׀‬
CH3 – C – Br
‫׀‬
CH3
CH3
‫׀‬
CH3 – C – Br
‫׀‬
CH3
R
‫׀‬
R – C – Br
‫׀‬
R
Reactivityfor halogenoalkane
• Carbon bondto halogen gp – F, CI, Br, I
• High electronegativityon halogen gp
• High reactivity – polarityof C+
- Br -
Chemical rxn Halogenoalkane
C - Br
ᵟ+ ᵟ-
electron
Electron deficient
carbon
O–H
..
..
ᵟ-
C
ᵟ+
+ OH-ᵟ+ ᵟ-
Nucleophilic Substitution
Tertiary 30
– SN1
Tertiary 30
– SN1
- Experimentallyrate expression= k [(CH3)3CBr]
- Rate dependent on conc - (CH3)3CBr
- Molecularity= 1
- 3 Bulky alkyl gp, Steric hindrance effect
- 30 carbocationmore stable due to inductive effect
• 3 alkyl gp stabilize carbocation by inductive effect
push electron to carbocation
(reducingpositive charge) makingit more stable
SN1
Substitution
Unimolecular (1 molecule)
Nucleophilic
UnimolecularNucleophilic Substitution
+ :OH-
carbocation
(Intermediate)
+ Br-
1st step mechanism – carbocationformation
nucleophile
attack
Click here to view SN1
(CH3)3CBr + OH-
→ (CH3)3COH + Br-
CH3
‫׀‬
CH3 – C – OH + Br -
‫׀‬
CH3
slow step
(RDS)
heterolytic fission
Br leaving gp
fast step
2nd step mechanism – OH attackcarbocation
(CH3)3CBr → (CH3)3C+
+ Br-
1st step (slow)
(CH3)3C+
+ OH-
→ (CH3)3COH 2nd step (fast)
✓3ₒ SN1

15. Formation of 2 methylpropan-2-ol
Hydrolysis 2-bromo- 2- methylpropane (3o
)
CH3
│
CH3 - C – Br
│
CH3
Carbocation formation (Intermediate) Nucleophile OH-
attack carbocation
Heterolytic fission - Carbocation and Br-
form
(CH3)3CBr → (CH3)3C+
+ Br-
1st step (slow)
(CH3)3C+
+ OH-
→ (CH3)3COH 2nd step (fast)
CH3 CH3
‫׀‬ ‫׀‬
CH3 - C – Br + OH-
CH3 –C – OH + Br -
‫׀‬ ‫׀‬
CH3 CH3
Nucleophilic Substitution
Click here to view
- 3 Bulky alkyl gp - Steric hindrance effect
- 30 carbocation more stable due to inductive effect
• 3 alkyl gp stabilize carbocation by inductive effect
push electron to carbocation (reducing positive charge)
making it more stable
SN1 Unimolecular (1 molecule)
Substitution
Nucleophilic
UnimolecularNucleophilic Substitution
2 step mechanism
3ₒ SN1

16. H Br H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H
‫׀‬ ‫׀‬ ‫׀‬ ‫׀‬‫׀‬
H H H
+ :OH-
ᵟ+
Nucleophilic Substitution
Secondary20
- SN1 and SN2
- Experimentallyrate expression= k [CH3CHBrCH3][OH-]
- Rate dependent conc = CH3CHBrCH3 and OH-
- Molecularity= 2
- No bulky alkyl gp, less steric effect
- Allow nucleophileto attackelectron deficient carbon
from opposite site (Inversion of configuration)
SN2
Substitution
Bimolecular collision
bet 2 molecule
Nucleophilic
Bimolecular Nucleophilic Substitution
HO-
Bond breaking and making
in transition state
+ Br-
One step mechanism – Bond break and making in transitionstate
nucleophile
attack
leaving gp
slow step
(RDS)
fast step
CH3CHBrCH3 + OH-
→ CH3CH(OH)CH3 + Br-
H OH H
‫׀‬ ‫׀‬ ‫׀‬
H - C – C – C – H + Br -
‫׀‬ ‫׀‬ ‫׀‬
H H H
CH3 CH3
CH3
SN1
Substitution
Nucleophilic
Unimolecular (1 molecule)
Unimolecular Nucleophilic Substitution
heterolytic fission
Br leaving gp
slow step
(RDS)
carbocation
(Intermediate)
+ Br-
nucleophile
attack
+ :OH-
CH3
1st step mechanism – carbocationformation
fast step
+
+
2nd step mechanism – OH attackcarbocation
CH3
Click here SN1 vs SN2
1 step mechanism
(concerted)
CH3CHBrCH3 → CH3CH+
CH3 + Br-
1st step (slow)
CH3CH+
CH3 + OH-
→ CH3CHOHCH3 2nd step (fast)
2 step mechanism CH3CHBrCH3 + OH-
→ CH3CH(OH)CH3 + Br-
Click here SN1 vs SN2 Khan academy
✓
2ₒ SN1SN2

17. 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+ Br+ NO2
+ :OH- :CN- H2O: :NH3
Homolytic fission Heterolytic fission
CI CI:
uv radiation
CI CI..
fish hook arrow
Single electron movement
A B:
A B:
A – B A + :B
Double headed arrow
pair electron movement
Control by electronic
factor (charges)
vs vs
vs
Nucleophilic Substitution
Primary 10
- SN2 Secondary20
-SN1 and SN2 Tertiary 30
– SN1
SN1
SN2
Control by
steric factor (alkyl gp)
SN2 SN1
Favour 10 30
Nature
mechanism
1 step
(transition state)
2 step
(carbocation)
Rate lower higher
Solvent Polar aprotic Polar protic
Reaction
profile
Click here SN1 vs SN2

18. FactoraffectingRate of Nucleophilic Substitution
• Bond polaritydecrease ↓
• Bond strength decrease ↓
• Rate fastest (Halogen leave easily)
Iodo > Bromo > Chloro > Fluoro
Nucleophilic Substitution
• SN 1 > SN 2 mechanism
• 3o > 2o
> 1o
• 3o
– SN 1 - Carbocation - faster
• 1o
- SN 2 – Transitionstate - slower
Nature of solvent
Nature of Halogen
CH3
‫׀‬
CH3 – C – Br
‫׀‬
CH3
H
‫׀‬
CH3 – C – Br
‫׀‬
CH3
H
‫׀‬
CH3 – C – Br
‫׀‬
H
> >
CH3CH2 – I > CH3CH2 – CI > CH3CH2 – F
fastest slowest
weak bond strong bond
C - Br OH
Nucleophile
ᵟ-
H bond to O or N
H2 bonding/donateH+
H2O, NH3 CH3OH, CH3CH2OH
Able to solvate cation and anion
Polar protic Polar aprotic
Lack acidic H, no H2 Bonding
Acetone/CH3COCH3,DMSO, CH3CN
Solvate cation–nucleophilefree for SN2
H H
‫׀‬ ‫׀‬
H - C – C – OH
‫׀‬ ‫׀‬
H H
H
‫׀‬
H -– C – OH
‫׀‬
H
ᵟ+
Nature of Halogenoalkane
SN1
polar + H2 bonding
:O:
‖
CH3 – C – CH3
:O:
‖
CH3 – S – CH3
polar only
SN2
Rate of hydrolysis of halogenoalkane
C4H9CI + H2O → C4H9OH + H+ + CI-
C4H9Br + H2O → C4H9OH + H+ + Br-
C4H9I + H2O → C4H9OH + H+ + I-
Reaction Time ppt to appear Observation
1-chlorobutane slowest white ppt
1-bromobutane cream ppt
1-iodobutane fastest yellow ppt
Method:
- Prepare 3 test tube contain 2 ml of ethanol each
- Pipette 0.1ml of chloro, bromo and iodobutane to each test tube
- Leave 3 test tube in 60C bath.
- Add 1ml AgNO3, mix and record time ppt to form
Ag+ react CI- → AgCI (white ppt)
Ag+ react Br- → AgBr (cream ppt)
Ag+ react I- → AgI (yellow ppt)
fastest slowest
1-iodobutane 1-chlorobutane ✓
+ Ag+

19. FactoraffectingRate of Nucleophilic Substitution
Click here protic/aprotic solvent
Nucleophilic Substitution
Nature of solvent
H bond to O or N
H2 bonding/donateH+
H2O, NH3 CH3OH, CH3CH2OH
Able to solvate cation and anion
+ Br-
Polar protic Polar aprotic
Lack acidic H, no H2 Bonding
Acetone/CH3COCH3,DMSO
Solvate cation–nucleophilefree for SN2
NaOH → Na+ + OH-
SN1 SN2
H2O solvate carbocationandBr- form
Stabilizeit – exist in intermediate state
H H
‫׀‬ ‫׀‬
H - C – C – Br
‫׀‬ ‫׀‬
H H
+ OH-
H H
‫׀‬ ‫׀‬
H - C – C – OH + Br-
‫׀‬ ‫׀‬
H H
H H
‫׀‬ ‫׀‬
H - C – C – OH
‫׀‬ ‫׀‬
H H
CH3
│
CH3 - C – Br
│
CH3
carbocation solvated
by H2O
anion solvated
by H2O
H
‫׀‬
H -– C – OH
‫׀‬
H
Acetone solvate cation – nucleophile free for SN2
No H2 bond- unable to solvate anion/nucleophile
:O:
‖
CH3 – C – CH3
:O:
‖
CH3–C–CH3
Na+ solvated by
CH3COCH3
nucleophile free
to attack
C - Br OH
Nucleophile
ᵟ+ ᵟ-
Click here protic/aprotic solvent
:O:
‖
CH3 – C – CH3
:O:
‖
CH3 – S – CH3
Click here expt
protic/aprotic solvent