Reaction of Alkane 1 Iodoform Test 24

Mechanism of Free Radical Substitution of Alkane 2 Preparation of Carboxylic Acid 25

Reactions of Alkene 3-4 Reactions of Carboxylic Acid 26
Mechanism of Dehydration of Alcohol to form Alkene 5 Methanoic Acid as a Reducing Agent 27
Mechanism of Hydration of Alkene 6 Preparation of Amine 28
Mechanism of Hydrohalogenation of Alkene 7 Reactions of Amine 29
Reactions of Benzene 8 Hinsberg Test 30
Mechanism of Electrophilic Aromatic Substitution 9 - 11 Nitrous Acid Test 31
Reactions of Haloalkane 12 Formation of Azo Compounds via Coupling Reaction 32
SN1 and SN2 13 Reactions of Amino Acid 33
Reactions of Alcohol 14 Addition Polymerisation 34
Oxidation of Alcohol 15 Condensation Polymerisation 35
Preparation of Alcohol using Grignard Reagent 16
Identification Test for 1o, 2o and 3o Alcohol
(Lucas Test and Oxidation)
17
Reaction of Phenol 18
Preparation of Aldehyde and Ketone 19
Reaction of Aldehyde 20
Reaction of Ketone 21
Identification Test for Carbonyl Compounds
(Brady’s Test and Fehling’s Test)
22
Identification Test for Carbonyl Compounds
(Tollen’s Test and Schiff’s Test)
23
 REACTIONS OF ALKANE

COMBUSTION HALOGENATION
Type of Reaction: Free Radical Substitution

NOTE: Needs the presence

Excess oxygen Extreme lack of oxygen of UV light or high
temperature and an inert
CH4 + 2O2 → CO2 + 2H2O organic solvent (e.g. CH2Cl2)
CH4 + O2 → C + 2H2O

PRODUCTS: Haloalkanes
Limited oxygen with a side product of acid
(the acid formed depends on
UV
3 CH4 + Cl2 CH2Cl2 CH3Cl + HCl the halogen used)
CH4 + 2 O2 → CO + 2H2O

REACTION
MECHANISM: Chain
initiation, chain propagation,
NOTE: For alkanes with more than chain termination
2 C atoms (n>2), more than one
haloalkane will be formed
(major product and minor products)

Page 1 of 35
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 MECHANISM OF FREE RADICAL SUBSTITUTION OF ALKANE

INITIATION
(CHAIN
STEP 1

STEP) Br Br
UV
CH2Cl2 +

H H H H
PROPAGATION
STEP 2 (CHAIN

H C C H + H C C H + H Br
STEP)

H H H H
H H
+
Br Br H C C H +
H Br
TERMINATION STEP)

Br Br
STEP 3 (CHAIN

H H

+ H C C H

H
H
H C C H
+

H H

Page 2 of 35
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 Halogenation in water
(+X2 in H2O)
Product(s): Halohydrin
Halogenation in inert solvent
(+X2 in CH2Cl2)
Product(s): Vicinal dihalide
Hydrohalogenation (+HX) Hydrohalogenation in the
presence of peroxides (+HBr
Product(s): Haloalkane
in ROOR)
RCHCH2
Product(s): Haloalkane

_
_
RCHCH2 RCHCH2 X H
_
_

_
_
HO X X X RCHCH2

_
_
H Br

Oxidation - Baeyer’s Test

(+dilute cold alkaline KMnO4)
Oxidation (+conc. hot Catalyst: Platinum, Pt, Nickel,
acidified KMnO4) Ni or Palladium, Pd
Product(s): Carboxylic acid,
REACTIONS OF ALKENE
Product(s): Diols
CO2 and H2O (RCH=CH2) RCHCH2
RCOOH + CO2 + H2O

_
_
HO OH

Markovnikov
Hydration, halogenation,
Hydration (+ acidified H2O) Ozonolysis (+ O3 followed by Hydrogenation (+H2) hydrohalogenation,
Zn or H2O) hydrohalogenation (HCl) in
Catalyst: Dilute H2SO4 or H3PO4 Catalyst: Platinum, Pt, peroxide
Product(s): Aldehyde/ketone Nickel, Ni or Palladium, Pd
Product(s): Alcohol
R H Anti-Markovnikov
RCHCH2 Product(s): Alkane
C= O + C= O Hydrohalogenation (HBr) in
_
_

HO H H RCHCH2

_
_
H peroxide
H H

Page 3 of 35
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 H H Br Br

_
_

_
_
H RCHCH2 RCHCH2

HO Br

Hydrogenation
H2, Pt/Ni/Pd

_
_
RCHCH2
Markovnikov
Hydration
Halogenation H OH Br H Anti-Markovnikov
_
_

_
_
RCHCH2 RCHCH2
Hydrohalogenation Hydrohalogenation (HBr) in
peroxide
Hydrohalogenation (HCl) in
peroxide

H2O, dilute H2SO4

Hydration
Anti-Markovnikov
R Cl H
RCH=CHR´ C=CHR´´
Hydrohalogenation (HBr) in
peroxide
R´
R O
O H
_

C O _ RC OH
_

_ HO H
RC OH R´
_
_
_ + R+ H
C O
+ + CO RCHCH2 __

_
2
O O HO OH
_ _ + H
_

_
_

R´C OH R´´C OH H2 O RCHCH2

Page 4 of 35
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 MECHANISM OF DEHYDRATION OF ALCOHOL TO FORM ALKENE

(PROTONATION
OF ALCOHOL)
CH3 H
CH3 CH3 H
CH3
H
STEP 1

H3C C C C2 H 5 + H H
+ O H H3C C C C2 H 5 + O
CH3 OH H +
CH3 O H
H

H H
(FORMATION OF
CARBOCATION)

+
+
STEP 2

CH3 H
H 1,2-methyl shift If necessary and when
H3C C C C2H 5 possible, a more stable
+ carbocation will be formed
H CH3

CH3 H CH3
(FORMATION
OF ALKENE)

H3C C C C2H 5 +
H
STEP 3

+ H3C C C C2 H 5 +
+ O H
H CH3
CH3 H

Page 5 of 35
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 MECHANISM OF HYDRATION OF ALKENE

STEP 1
CH3 H H CH3 H
+ H H
H3C C C CH3
+ O H H3C C C CH3 + O
+
H H H

CH3 H CH3 H

H3C C C CH3 + H3C C C CH3

STEP 2

+ +
H H O H
H
H

CH3 H H
+ H3C C C CH3 +
+ O H
STEP 3

OH H H

Page 6 of 35
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 MECHANISM OF HYDROHALOGENATION OF ALKENE

STEP 1
CH3 H CH3 H
slow -
+ H Br H3C C C CH3 + Br
H3C C C CH3 +
H H

CH3 H CH3 H
STEP 2

- fast
H3C C C CH3 + Br H3C C C CH3
+
H Br H
H

Page 7 of 35
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 O
_
R
_C
R

R → alkyl group
X → halogen

Halogenation
X2, UV
NO2
COOH

X RX

Page 8 of 35
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 MECHANISM OF ELECTROPHILIC AROMATIC SUBSTITUTION

Nitration Halogenation Friedel-Crafts Friedel-Crafts

Alkylation Acylation
STEP 1 – Formation of electrophile

R Cl AlCl3
HSO4-

δ+ δ_
+
+

FeX4-

AlCl4-
+
+

X+
OSO3H

R+
O
H H
_

FeX3

AlCl3

resonance structure
+

Acylium ion
+ +
O NO2

+
_ _

NO2+

Cl
_

_
H

X → halogen R

Electrophile
R → alkyl group

Page 9 of 35
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 H
H H
+
+
+ E E
STEP 2 – Formation of arenium ion

H H
H

H H H
H H H H H H
+
E E E
+ +
H H H H H H
H H H

Arenium ion resonance structure

E+ Electrophile

Page 10 of 35
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 STEP 3 – Loss of proton (regeneration of catalyst)
H

Page 11 of 35
H H

+
NO
E 2 NO2
-

+
HSO4
H H
H
Nitration

H2SO4

X
+

HX
X
FeX4-
+
Halogenation

FeX3

R
+

HX
R
AlX4-
Alkylation

+
Friedel-Crafts

AlX3

AlX4-
Acylation
Friedel-Crafts

AlX3
- Rimau -
 H H H H
H H
H C C OH C C
H2O, H+
H C C H
H H H H
H H
H H O

KOH, EtOH
H H
(i) CO2
H C C C
(ii) H2O, H+

Δ
H C C CN
H H OH H
H H
REACTIONS OF O H H OH
H H HALOALKANE H C H
excess NH3 H C C C H
(i) dry ether
H C C NH2 Δ H H
(ii) H2O, H+
H H H H
H C C Cl
H H O
H H H H OH
H C R
H H H C C C R
g+

dry ether
(i) dry ether
OA
-

Mg
(ii) H2O, H+
H C C O R H H H H
O

O
H H H H OH
R

R' C R
O H H H H H C C C R
(i) dry ether
(ii) H2O, H+ H H R'
R C O C C H H C C Mg Cl

H H H H

Page 12 of 35
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 SN1 Mechanism SN2 Mechanism
Unimolecular Nucleophilic Substitution Bimolecular Nucleophilic Substitution
Carbocation as the intermediate Has transition stage
𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋] 𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋][𝑁𝑢− ]
- First order reaction - Second order reaction
Two-step mechanism One-step mechanism
Brˉ
+

-
Nu
fast
ˉ fast
+ Nu H3C CH2 C CH3
H
CH3
Brˉ + Nu C
H
H

Order of reactivity Order of reactivity

Methyl halide < 1o < 2o < 3o 3 < 2o < 1o < Methyl halide
o

Nuˉ is nucleophile

Page 13 of 35
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 CH3 H
-
O Na H
+ H O H H

C O H C C C H H C C C H H C C C H

H O H H H H H H H H H

H C C C H O
H3 C
H H H C
OH

H Cl H REACTIONS OF H
+
NaOH ALCOHOL H2O, H
H C C C H Δ H C C C H
H OH H
H H H H H H
H C C C H

H H H

H Cl H H Br H

H C C C H H C C C H

H H H H H H

Page 14 of 35
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 OXIDATION OF ALCOHOL

H O
KMnO4, H+
H OH H C C OH
Δ
H
1o alcohol H C C H H O
PCC
H H CH2Cl2 H C C H
H

H OH H H O H
KMnO4, H+
2o alcohol H C C C H
Δ
H C C C H
H H H H H

3o alcohol No reaction

* Oxidation of primary alcohols using strong oxidising agents (e.g. KMnO4) first produces aldehydes. The aldehyde is then further oxidised into
carboxylic acid.

Page 15 of 35
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 PREPARATION OF ALCOHOL USING GRIGNARD REAGENT

H
(i) H C MgBr H OH
O
1o alcohol H
H C C H
H C H (ii) H3O+
H H

H
H OH H
O (i) H C MgBr

2o alcohol H H C C C H
H C CH3
(ii) H3O+ H H H

O (i) H C MgBr H OH H

3o alcohol H3C C CH3

H H C C C H
(ii) H3O+
H CH3 H

Page 16 of 35
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 IDENTIFICATION TESTS FOR ALCOHOL

LUCAS TEST OXIDATION

OH
HCl
R C H No observable changes
o ZnCl2 * refer pg. 15
1 alcohol H

Obs: No cloudy solution formed after 15 minutes

For 1o an 2o alcohols;
Observation using KMnO4: Purple colour of solution
decolourises
OH Cl
HCl
R C R' R C R' Observation using K2Cr2O7: Orange colour of
2o alcohol H
ZnCl2
H
solution turns green

Obs: Cloudy solution forms within 15 minutes

For 3o alcohols;
Observation: No observable changes
OH Cl
HCl
R C R' R C R'
o ZnCl2
3 alcohol R'' R''
Obs: Cloudy solution forms immediately

Page 17 of 35
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 CHEMICAL REACTIONS IDENTIFICATION TESTS

- +
O Na OH
1
H2 +
2

FeCl3
Purple complex
REACTIONS OF
- +
O Na PHENOL
NaOH
H2O + OH

Br

OH
Phenol can undergo reactions of benzene as
well
Example: Br Br
OH OH
Br2, FeBr3 White precipitate
Br

Page 18 of 35
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 PREPARATION OF
H OH ALDEHYDE H H
(i) O3
PCC H C C C C H
H C C H CH2Cl2 O (ii) Zn, H2O
H H H H
H H
Oxidation of 1o alcohol H3C C H Ozonolysis of alkene

Friedel-Craft Acylation can be used to

prepare aromatic ketones

O There are other

H3C C CH2
alkenes that can also
C CH3 CH3 be used

Oxidation of alkene
AlCl3
+

KMnO4, H+
O

Δ
Cl C CH3

PREPARATION OF
H OH H KETONE H H
KMnO4, H+ (i) O3
H C C C H O H C C C C H
Δ
(ii) Zn, H2O
H H H H CH3 CH3 H
Oxidation of 2o alcohol H3C C CH3 Ozonolysis of alkene

Page 19 of 35
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 N R' OH

R C H R C H
OR'

H2N
OH
NaBH4
CH3OH R C H

R'
SO3-Na+

REACTIONS OF
OH OH
ALDEHYDE +
H2 HCN @ KCN, H
R C H O R C H
Pt @ Pd @ Ni
CN
H
R C H
OH

KMnO4, H+
LiAlH4
R C H
H3O+
Δ OH

Reaction of carbonyl compounds (aldehyde/ketone) with OR'

Grignard reagent is to prepare alcohol O R C H
*refer preparation of alcohol using Grignard reagent (pg. 16)
R C OH OR'

Page 20 of 35
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 N R'' OH

R C R' R C R'
OR''

H2N
OH
NaBH4
CH3OH R C R'

R''
- +
SO3 Na

REACTIONS OF
OH OH
KETONE +
H2 HCN @ KCN, H
R C R' Pt O R C R'

H CN
R C R'

OH

KMnO4, H+
LiAlH4
R C R'
H3O+
Δ OH

Reaction of carbonyl compounds (aldehyde/ketone) with OR''

Grignard reagent is to prepare alcohol No reaction
R C R'
*refer preparation of alcohol using Grignard reagent (pg. 16)
OR''
Page 21 of 35
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 IDENTIFICATION TESTS FOR CARBONYL COMPOUNDS

Brady’s Test FUNCTION: To test for carbonyl compounds

O 2N
(2,4-dinitrophenylhydrazine) Example: CH3
O O 2N H3C C N NH NO 2
O 2N +
H3C C CH3 H2N NH NO 2
H2N NH NO 2 +

H2O

Obs: Orange/yellow precipitate forms

FUNCTION: To test for aliphatic aldehydes

Example:
O O
Cu2+ complex, OHˉ
+ Cu2O ↓
Fehling’s Test H3C C H H3C C O
-

Obs: Brick-red precipitate forms

Page 22 of 35
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 FUNCTION: To test for aldehydes

Example:
O O
[Ag(NH3)2]+, OHˉ
+ Ag ↓
Tollen’s Test H3C C H H3C C O
-

Obs: Silver mirror forms

FUNCTION: To test for aldehydes and propanone

Schiff’s Test REAGENT: Schiff’s reagent (Fuchsin, NaHSO3, HCl)

OBSERVATION: Magenta-pink colour solution forms

Page 23 of 35
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 IODOFORM TEST

To test for methyl carbinol and methyl carbonyl

OH
O
H3C C R
H3C C R
H
methyl carbinol methyl carbonyl

Example: Example:

OH O O
O ˉ
I2, OHˉ - I2, OH -
H 3C C H H C O + CHI3 ↓ H C O + CHI3 ↓
H3C C H
H H H

Obs: Yellow precipitate forms Obs: Yellow precipitate forms

Page 24 of 35
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 Oxidation of 1o alcohol Oxidation of aldehyde

OH O O
O KMnO4, H+
KMnO4, H+
R C H R C H Δ R C OH
Δ R C OH
H

Oxidation of alkyl benzene

KMnO4, H+
Hydrolysis of acyl chloride R HOOC
Δ
O O
PREPARATION OF
+
H2O, H CARBOXYLIC ACID *R group must contain benzylic
R C Cl R C OH
hydrogen

Hydrolysis of nitriles Carboxylation of Grignard reagents

O O
+ (i) CO2
H2O, H R MgX
R CN R C OH (ii) H2O, H+ R C OH

Page 25 of 35
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 O O
O O
R' C OH
R C O C R' R C Cl
O
R'
C
OH

NaOH

REACTIONS OF

R'
O
CARBOXYLIC ACID
Na

N
Δ

R''
O-Na+
O
R C

H
R C OH
Na2CO3

R'
R ''
R'
N
OH, conc. H2SO4
H
Δ

O R''
H R'
R C N
R C OH O

H R C O R' R' OH

Page 26 of 35
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 METHANOIC ACID AS
A REDUCING AGENT
O

H C OH

Using KMnO4 Using Tollen’s Test

O KMnO4, H+ O [Ag(NH3)2]+, OHˉ

CO2 ↑ + H2O Ag ↓ + CO2 ↑ + H2O
Δ
H C OH H C OH

Page 27 of 35
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 Reduction of Nitro Compounds Reduction of Amides
Example: Example:
(1o amide → 1o amine)
Zn @ Fe @ SnCl2
NO2 NH2 H
HCl O
LiAlH4
R C NH2
R C NH2 H2O, H+
H

(2o amide → 2o amine)

Reduction of Nitrile Compounds
O R' H R'
Example: LiAlH4
H H R C NH
LiAlH4 PREPARATION OF R C NH H2O, H+
R CN R C N H
H2O, H+ AMINE
H H
* NaBH4 in CH3OH @ H2 with Pt (3o amide → 3o amine)
catalyst can also be used
O R' H R'
LiAlH4
R C N R C N
H2O, H+
H R''
Hofmann Degradation of Amides R''

Example:
* NaBH4 in CH3OH can also be used
O X2
R NH2 + 2NaX + Na2CO3 + 2H2O
R C NH2 4NaOH

Page 28 of 35
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 REACTIONS OF
AMINE

Reaction with Acid Chloride Reaction with Carboxylic Acid

O O O O H

R NH2 + R'R C Cl NH3 + R C OH Δ R C N H

R' C NH R

O
R' O O R' Δ
R' C OH
+
R NH R'' C Cl R'' C N R
O

R'' C OH Δ

Bromine Water Test (to identify aniline)

Br
Obs: 1) Brown colour of solution decolourises
Br2 (aq) @ Br2, H2O
NH2 Br NH2 2) White precipitate forms

Br

Page 29 of 35
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 HINSBERG TEST

O + O O
K H
excess KOH HCl
1O amine

-
R NH2 + Cl S R N S R N S

R, R’ and R’’ can either be alkyl group or aryl group

O O O
Obs: Clear solution is Obs: White precipitate
formed is formed

R' O R' O
2O amine

excess KOH HCl

R NH + Cl S R N S No observable changes

O O
Obs: White precipitate
is formed

R' O R'
3O amine

excess KOH HCl + -

R N R'' + Cl S No observable changes R N R'' Cl

O H
Obs: Clear solution is
formed

Page 30 of 35
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 NITROUS ACID TEST Nitrous acid, HNO2 is prepared in-situ
using NaNO2 and HCl

ALIPHATIC AMINES AROMATIC AMINES

H2C CH2
1O amine

+
NaNO2, HCl NaNO2, HCl + -
H3C CH2 NH2 H3C CH2 OH + N2 ↑ NH2 N N Cl
0 – 5 oC 0 – 5 oC
+
H3C CH2 Cl
Obs: Colourless gas bubbles are released Obs: No release of colourless gas bubbles

CH3 CH3 CH3 CH3

2O amine

NaNO2, HCl
0 – 5 oC NaNO2, HCl
H3C NH H3C N N O NH N N O
0 – 5 oC
Obs: Yellow oil is formed Obs: Yellow oil is formed

CH3 CH3 CH3 CH3

NaNO2, HCl +
H3C N CH3 NaNO2, HCl
H3C N CH3 0 – 5 oC N CH3 O N N CH3
3O amine

HCl
- 0 – 5 oC
+
Obs: Colourless solution CH3 Nitroso (-N=O) will be substituted at
remains the para position of the benzene ring
+
H3C N CH3
- Obs: Yellow precipitate is formed
NOCl

Page 31 of 35
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 FORMATION OF AZO COMPOUNDS
(COUPLING REACTION)

+ - NaOH
N NCl + OH N N OH

Obs: Yellow/orange precipitate (dye) is formed

Azo group (-N=N-) will bond at the para

position of phenol

Page 32 of 35
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 H H
- + - +
Cl H3N C COOH H2N C COO Na

R R

HO C COOH
REACTIONS OF
R
H AMINO ACIDS +
R' OH, conc. H2SO4 NaNO2, HCl H
H2N C COOR' H
Δ 0 – 5 oC
Cl C COOH
R H2 N C COOH
R
R
+
H

C COOH

H R
+
H2 N C COOH H O H
N2 ↑
O
R' H2N C C HN C COOH +
H H
R R'

Page 33 of 35
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 ADDITION POLYMERISATION

R R' R R'

n C C H C C H

R'' R''' R'' R'''

n

Requires organic peroxides

(e.g. benzoyl peroxide) as
initiator

H Cl H Cl H H
n C HC C C nHH2C C C CH2 H CH2 C C CH2 H
H H H H CH3 CH3
n n

Page 34 of 35
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 CONDENSATION POLYMERISATION

Monomers must each have

at least two functional
groups

Example:
O O O O

H2N NH2 + H NH NH C C O H
HO C C OH
n
+
O
H H

Example:
O O O O

HO CH2 CH2 OH + CH3O C C CH3O H O CH2 CH2 O C C O

n
+
CH3OH

Page 35 of 35
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