ORGANIC CHEMISTRY REACTION SCHEME

AN OVERVIEW
ALKANES
Preparation of Alkanes
1. Hydrogenation of Alkenes
H2 + Ni, Pd or Pt
CnH2n
CnH2n+2

2. Reduction of Alkyl Halides

a. Hydrolysis of Grignard Reagent
dry ethyl ether
water
RX + Mg
RMgX
RH + Mg(OH)X
*Note: RMgX is the Grignard reagent, alkylmagnesium halide. The alkyl group is covalently bonded to magnesium;
+

and magnesium-halogen bond is ionic ie. [R:Mg] [X] . In the second step of the reaction, it is a displacement
reaction in which water (the stronger acid) displacing the weaker acid (RH) from its salt (RMgX).

b. Reduction by Metal and Acid

+

Zn + H
RX
RH + Zn + X

2+

Reactions of Alkanes
1. Halogenation [Free Radical Substitution]
heat, or UV
CnH2n+1H + X2
CnH2n+1X + HX
2. Combustion
heat
CnH2n+2 + excess O2
nCO2 + (n+1)H2O
3. Pyrolysis Cracking
400-600C
alkane

H2 + smaller alkanes + alkenes

with or w/o catalyst

ALKENES
Preparation of Alkenes
1. Dehydrohalogenation of Alkyl Halides
H
H
H

alcoholic KOH

H OH
reflux

2. Dehydration of Alcohols
H
H
H

excess conc H2 SO4 , 170 C

H
H
or Al2 O3 , 400 C

H+ KX + H2O

H + H2O

or H3PO4 , 200-250 C

OH

3. Dehalogenation of Vicinal Dihalides

H
H
H

Zn
H H

H + ZnX2

Reactions of Alkenes
1. Addition of Hydrogen. Catalytic Hydrogenation
H2 + Ni, Pd or Pt
CnH2n+2
CnH2n
Heat

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2. Addition of Halogens [Electrophilic Addition using bromine/ethene]

H
H
H
H
H

X2 /CCl4
H

dark, room temperature

3. Addition of Aqueous Halogen. Formation of Halohydrin

H
H
H
H

X2 /H2 O
H
H

H
H + HX

OH

Dark, room temp

4. Addition of Hydrogen Halides

H
H

HX
H
H

5. Addition of Water. Hydration

a) Industrial Method
H
H
H

H2 O(g)

conc H3PO4

OH

300C, 60atm

b) Laboratory Method
H
H

conc H2SO4

cold

OSO3H

H2 O, heat

H
(hydrolysis)

6. Oxidation
a) Cold, alkaline KMnO4 Solution
H
H
H

alkaline KMnO4

H
cold

OH

H + H2SO4

OH OH

b) Hot, acidic KMnO4 Solution

H
H

MnO4 /H2 SO4

H

hot

H
O

*Note: Terminal carbons will be oxidized into carbon dioxide.

*Note: Under such oxidizing conditions, the aldehydes will be oxidized to carboxylic acid very quickly. To extract the
aldehyde only, we must use immediate distillation.

7. Combustion

ARENES
Reactions of Benzenes
1. Nitration [Electrophilic Substitution in mononitration of benzene]
NO 2
conc. HNO3

conc. H2 SO4

55oC

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2. Sulphonation

OSO2H
H2 SO4 ( l )

reflux

+ H2O

3. Halogenation
X
+ X2

cold, dark

FeX3 , or AlX3

+ HX

Or Fe
4. Friedel-Crafts Alkylation
R
FeX3 , or AlX3
+ RX

Lewis Acid

+ HX

5. Friedel-Crafts Acylation
COR
Note: acyl group

+ RCOCl / [(RCO) 2O]

FeX3 , or AlX3

+ HX
R

C
H

6. Hydrogenation

+ 3H2

Ni

150C

Preparation of Alkylbenzenes
1. Attachment of Alkyl Group. Friedal-Crafts Alkylation
R
FeX3 , or AlX3
+ RX

Lewis Acid

2. Conversion of side chain

R

+ HX

H
H
C

C
O

Zn(Hg), HCl, heat

or N2H4 , base, heat

+ HX
N2 + H2O

Or H2/Pd,
ethanol
*Note: This is known as the Clemmensen or Wolff-Kishner Reduction

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Reactions of Alkylbenzenes
1. Hydrogenation
R

R
+ 3H 2

Ni, Pt, Pd

150C

2. Oxidation
a. Mild Oxidation
CHO

R
MnO2

oxidation

b. Strong Oxidation
R

COOH

MnO4 /H2 SO4

or acidified K 2Cr2O7

white crystals

3. Free Radical Aliphatic Halogenation

RCH 3

RCH 2X

X2
UV, light or heat

*Note: Reaction above is only a generic reaction. Actual position of the halogen is dependent on the stability of the
carbocation intermediate.

4. Electrophillic Aromatic Halogenation by Electrophillic Addition

R
R

X
X2

FeX3 , FeX5

5. Electrophillic Aromatic Nitration by Electrophillic Addition

R
R

R
NO 2

conc HNO3

conc H2 SO4

30 C

NO 2
6. Electrophillic Aromatic Friedal-Crafts Alkylation by Electrophillic Addition
R
R
R

R1
R1X

AlX3

R1
4

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7. Electrophillic Aromatic Sulphonation by Electrophillic Addition

R
R

OVERVIEW

OSO2H
H2 SO4 ( l )

OSO2H
8. Electrophillic Aromatic Friedal-Crafts Acylation by Electrophillic Addition
R
R

COR1
+ R1COCl / [(R1CO)2O]

FeX3 , or AlX3

COR 1
Alkylbenzenes clearly offers two main areas to attack by halogens: the ring and the side chain. We can
control the position of the attack simply by choosing the proper reaction conditions. Refer to Appendix for
more details.

HALOGEN DERIVATIVES
Preparation of Halogenoalkanes
1. Substitution in Alcohols
a. Using HX (suitable for 3 alcohols)
dry HX, ZnX2 (catalyst)
ROH

RX + H2O
Reflux
b. Using PX3/PX5 (suitable for 1, 2 alcohols)
PX3 /PX 5
ROH
RX + POX3 + HX
Reflux
c. Using SOCl2 (sulphonyl chloride)
SOCl2 , Pyridine(C5H5N)
RCl + SO2 + HCl
ROH
Reflux
*Note: This is the best method because it is very clean. SO 2 can be bubbled off and HCl, being an acid, will react
with pyridine.

2. Electrophillic Addition to Alkenes

a) Addition of Hydrogen Halides
H
H
H

HX
H
H

b) Addition of Halogens
H
H
H

X2 /CCl4
H

dark, room temperature

3. Free Radical Substitution of Alkanes

heat, or UV
CnH2n+1H + X2
CnH2n+1X + HX

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Reactions of Halogenoalkanes
1. Alkaline Hydrolysis of Alcohols [Nucleophilic Substitution]

aqueous KOH
RX + OH
ROH + X
reflux
*Note: Mechanism is S N2 for 1 halogenoalkane and S N1 for 3 halogenoalkane

2. Nitrile Synthesis
aqueous ethanol
RX + NaCN
RCN + NaBr
reflux
o

*Note: Nitriles are useful because they can be used to synthesize 1 amines and carboxylic acids.
Reduction to Amine:
LiAlH4 , dry ether
RCN
RCH2NH2
or 2H , Ni, heat
2

Acidic Hydrolysis:
HCl ( aq )
RCN
RCOOH + NH4
reflux

Basic Hydrolysis:
NaOH ( aq )
RCN
RCOO Na + NH3
reflux

3. Formation of Amines
+

NH3
ethanol, reflux
RX + excess conc NH3
[H3N---R---X]
RNH2 + NH4 X
sealed tube

*Note: NH3 acts as the nucleophile and the base.

*Note: In the presence of excess RX, there will be polyalkylation of the halogenoalkane and 1, 2, 3 and even 4 ammonium
salt will be formed.
+

RX
RX
RX
RX
NH3

RNH2

R2NH

R3N

R4 N X

4. Williamson Synthesis (Formation of Ether) Conc H2SO4, 140oC

RX + R'ONa+
ROR' + NaX
*Note: The sodium or potassium alkoxide (anion of alcohol) is prepared by dissolving sodium and potassium in appropriate

+
alcohol. ROH + Na
RO Na + H2

5. Dehydrohalogenation (Elimination)
H
H
H

alcoholic KOH
H
H OH (aq )
reflux

H + KX + H2O

Preparation of Halogenoarenes (Aryl Halides)

1. Electrophilic Aromatic Halogenation by Substitution
X
+ X2

cold, dark

FeX3 , or AlX3

+ HX

Reactions of Halogenoarenes
1. Industrial Hydrolysis (Replacement of Halogen Atom, difficult due to strong CX bond)
+
X
O Na
2NaOH

350C, 150atm

+ NaX + H2O

+
O Na

OH

+ Na+

H ( aq )

2. Williamson Synthesis (Formation of Ether)

+
ROAr + NaX
RX + ArO Na
o

Conc H2SO4, 140 C

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HYDROXY COMPOUNDS
Preparation of Alcohols
1. Alkene Hydration. Addition of Water.
H
H

conc H2SO4

cold

OSO3H

H2 O, heat

H
(hydrolysis)

OH

H + H2SO4

2. Alkaline Hydrolysis of Halogenoalkanes

aqueous KOH
RX + OH
ROH + X
reflux
3. Reduction of Carboxylic Acids, Aldehydes and Ketones
a. Carboxylic Acids and Aldehydes are reduced to their primary alcohols.
H
R
+

4[H]

1. LiAlH4 (ethoxyethane), reflux 2.H /H2 0

or H2 , Ni

HO

OH

+ H2O

H
H

R
+

4[H]

1. LiAlH4 (ethoxyethane), reflux 2.H /H2 0

or H2 , Ni

OH

b. Ketones are reduced to their secondary alcohols.

R

R
+

4[H]

1. LiAlH4 (ethoxyethane), reflux 2.H /H2 0

or H2 , Ni

R1

R1

OH

*Note: Lithium aluminium hydride (or Lithium tetrahydridoaluminate(III)), LiAlH4, is one of the few reagents that can
reduce an acid to an alcohol; the initial product is an alkoxide which the alcohol is liberated by hydrolysis.

The H ion acts as a nucleophile, and can attack the carbon atom of the carbonyl group. The intermediate then
reacts with water to give the alcohol.
OH
R
O
H3C
H3C
H2O
C
C
O
C
H
H

H
H
H
H
H2O
Carboxylic Acid: 4RCOOH + 3LiAlH 4
4H2 + 2LiAlO2 + (RCH2O)4AlLi
4RCH2OH
H2O
Ketones: 4R2C=O + LiAlH4
(R2CHO)4AlLi
4R2CHOH + LiOH + Al(OH)3

Reactions of Alcohols
1. Substitution in Alcohols
a. Using HX (suitable for 3 alcohols)
dry HX, ZnX2 (catalyst)

RX + H2O
ROH
Reflux
b. Using PX3/PX5 (suitable for 1, 2 alcohols)
PX3 /PX 5
RX + POX3 + HX
ROH
Reflux
c. Using SOCl2 (sulphonyl chloride)
SOCl2 , Pyridine(C5H5N)
RCl + SO2 + HCl
ROH
Reflux
*Note: This is the best method because it is very clean. SO 2 can be bubbled off and HCl, being an acid, will react
with pyridine.

2. Reaction with Sodium/Potassium

H
H

H
Sodium/Potassium

O Na

1
H2
2

*Note: Alcohols are too weak to react with hydroxides and carbonates.

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3. Oxidation to Carbonyl Compounds and Carboxylic Acids

a. Primary Alcohols are oxidized to aldehydes first, then carboxylic acids.
R
R
R
OH
K 2 Cr2 O7 /H2 SO4
K 2 Cr2 O7 /H2 SO4
C
O
C

immediate
or KMnO4 /H2 SO4
distillation
H
H
HO
H

*Note: MnO2 is also a milder oxidizing agent.

b. Secondary Alcohols are oxidized to ketones.

R
R
OH
K 2 Cr2 O7 /H2SO4
C
C

or KMnO4 /H2SO4
R1
R1
H
c.

Tertiary alcohols are not readily oxidized.

4. Dehydration to Alkenes
a. Excess conc H2SO4
H
H
H

excess conc H2 SO4 , 170 C

H
H
or Al2 O3 , 400 C

H + H2O

or H3PO4 , 200-250 C

OH

b. Excess alcohol
140C
RCH2OH + conc H2SO4
RCH2O CH2R
excess alcohol
5. Esterification

O
R

R1

heat
(can use acid or
alkaline as catalyst)

OH

conc H2SO4

R1

H2 O

6. Acylation
a. Acid Chloride

Cl

Note: acyl group

R1

OH

room temperature

R1

+ HCl
R

b. Acid Anhydride

room temperature

+ R1 OH

R1

OH

O
H

7. Tri-Iodomethane (Iodoform) Formation

*Note: Reaction is only positive for alcohol containing a methyl group and a hydrogen atom attached to the carbon at
which the hydroxyl group is also attached.

CH3

H
R

OH

I2 , NaOH ( aq )

warm

CHI 3

CH3

a. Step 1: Oxidation of Alcohol to the corresponding carbonyl compound by iodine.

R

CH

OH

I2 + 2 HO

CH3

+ 2 H2 O

+ 2I

CH3

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b. Step 2: Further oxidation to carboxylate salt and formation of iodoform

+ 3 I2 + 4HO

+ CHI 3 + 3 I + 3 H2O

+ CHI 3 + 5 I

CH3
c.

Overall Equation:
H

OH + 4 I 2 + 6HO

C
O

CH3

Preparations of Phenols

1. Replacement of OH group in diazonium salts

N

+ 5 H2O

O
-

+
N O

NH2

OH

OH

water, H , heat

NaNO2 , H2 SO4

Reactions of Phenols
1. Reaction with Reactive Metals (e.g. Na or Mg)
+

O Na

OH

Na

1
H
2 2

2. Reaction with NaOH

-

OH

O Na

+ NaOH

1
H O
2 2

*Note: Phenols have no reactions with carbonates

3. Esterifications
-

OH

O Na
NaOH

RCOCl

O
C
R

*Note: Phenols do not react with carboxylic acids but their acid chlorides to form phenyl esters.
*Note: Esterification is particularly effective in NaOH(aq) as the alkali first reacts with phenol to form phenoxide ion which is a
stronger nucleophile than phenol.

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4. Halogenation
a. With bromine(aq)
OH
OH

Br

Br

+ 3HBr

3Br2 ( aq )

Br
*Note: 2,4,6-tribromophenol is a white ppt.

b. With bromine(CCl4)
OH

OH

Br2 (CCl4 )

OH

+
Br

Br

5. Nitration
a. With conc nitric acid

OH

OH
O 2N

NO 2

conc HNO3

NO 2
b. With dilute nitric acid
OH

OH

dil HNO3

OH

+
NO 2

O 2N

6. Reaction with FeCl3(aq)

*Note: This is a test for phenol. Violet complex upon adding iron(III) chloride will confirm presence of phenol. Colour may vary
depending on the substitution on the ring.
3--

OH
3+

Fe

Fe
6

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CARBONYL COMPOUNDS
Preparation of Aldehydes
1. Oxidation of Primary Alcohols
R
OH
K 2 Cr2 O7 /H2 SO4

C
immediate
distillation
H
H

R
C
H

Preparations of Ketones
1. Oxidation of Secondary Alcohols
R
R
OH
K 2 Cr2 O7 /H2SO4
C
C

or KMnO4 /H2SO4
R1
R1
H
2. Oxidative Cleavage of Alkenes
R2
R3

C
R1

+ H2O

R2

R3

MnO4 /H2SO4

hot

H2 O

R1

R4

R4

Reactions of Carbonyl Compounds

1. Addition of Cyanide. Cyanohydrin formation.
[Nucleophilic Addition of Hydrogen Cyanide to Aldehyde and Ketone]
H
H
H
C
HCN, small amount of base
+ CN
C
CN
H
O

OH

*Note: Cyanohydrins can be hydrolysed to form 2-hydroxy acids.

Acidic Hydrolysis
R
H

R
CN

water, HCl (aq)

heat

OH

+ NH4Cl

COOH

OH

Basic Hydrolysis
R
H

R
water, NaOH ( aq )

H
heat

CN

OH

COO Na

NH3

OH

*Note: Cyanohydrins can undergo reduction.

R
H

R
CN

LiAlH4 in dry ether

or H2 , Ni, heat

OH

R2

CH 2NH 2

OH

2. Reaction with 2,4-Dinitrophenylhydrazine (Bradys Reagent). Condensation Reaction.

R2
C

O + H2N

NH

NO 2

NH

NO 2 +

H2O

R1

R1
O 2N

O 2N

*Note: 2,4-dinitrophenylhydrazones formed are orange or yellow crystalline solids with characteristic melting points. They are
useful for identifying individual aldehydes and ketones.

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3. Oxidation Reactions
*Note: Aldehydes are easily oxidized to carboxylic acids. Ketone are not.

a. Oxidation of Aldehydes using hot, acidified potassium dichromate(VI)

*Note: K2Cr2O7 turned from orange to green if test is positive.

OH
C

K 2 Cr2 O7 /H2SO4

heat

O
O

O
K 2 Cr2 O7 /H2 SO4

heat

H
R1

OH

K 2 Cr2 O7 /H2 SO4

No Reaction
heat

b. Oxidation of Aldehydes using hot, acidified potassium manganate(VII)

*Note: KMnO4 turned from purple to colourless if test is positive.

OH
C

K 2MnO4 /H2 SO4

heat

O
O

O
C

K 2MnO4 /H2 SO4

heat

c.

OH

Oxidation of Aliphatic Aldehydes using Fehlings Solution (Fehlings Test)

R

H
C

Fehling's Solution

warm

Cu 2O (s)

O
O
C

Fehling's Solution

No Reaction
warm

R1
C

Fehling's Solution

No Reaction
warm

O
*Note: Aliphatic aldehydes reduce the copper(II) in Fehlings solution to the reddish-brown copper(I) oxide.
2+

RCHO + 2Cu + 5OH

RCOO + Cu2O (s) + 3H2O
*Note: Methanal (strongest aldehyde reducing agent) produces metallic copper as well as copper( I) oxide.

HCHO + Cu2O + OH
HCOO + 2Cu (s) + H2O

d. Oxidation of Aldehydes using Tollens Reagent (Silver Mirror Test)

R

H
C

R
Tollen's Reagent

warm

O
C

Ag (s)

O
O

O
Tollen's Reagent

warm

C
H

+ Ag (s)
O

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d. Oxidation of Aldehydes using Tollens Reagent (Silver Mirror Test) (Contd)

R
R1
Tollen's Reagent
C

No Reaction
warm

O
*Note: Aldehydes redyce the Ag(I) in Tollens reagent to Ag, forming a silver mirror.
+

heat
RCHO + 2[NH3AgNH3] + 3OH
RCOO + 2Ag (s) + 4NH3 + 2H2 O

4. Reduction Reactions
a. Reduction of Aldehydes to Primary Alcohols
LiAlH4 in dry ether
RCHO + 2[H]
RCH2OH
or NaBH4 ( aq )
Ni catalyst
RCHO + H2
RCH2OH
heat
b. Reduction of Ketones to Secondary Alcohols

R1
C

H2

LiAlH4 in dry ether

or NaBH4 ( aq )

O
R

OH
H

R1
C

R1

H2

Ni catalyst

heat

R1

OH

5. Reaction with Alkaline Aqueous Iodine (Tri-Iodomethane (Iodoform) Formation)

*Note: Reaction is only positive for alcohol containing a methyl group attached to the carbon at which the carbonyl group
is also attached i.e. methyl carbonyl compounds. For aldehydes, only ethanal will form iodoform. All methyl ketones will
form iodoform.
NaOH, warm
R
C
O + CHI 3 + 3I
+ 3H2O
R
C
O + 3 I 2 + 4HO

CH3

6. Chlorination using Phosphorus Pentachloride (PCl 5)

*Note: Aldehydes and ketones react with phosphorus pentachloride to give geminal-dichloro (cf. vicinal) compounds. The
oxygen atom in the carbonyl group is replaced by two chlorine atoms.

CH3CHO + PCl5
CH3CHCl2 + POCl3
CH3COCH3 + PCl5
CH3CCl2CH3 + POCl3

CARBOXYLIC ACIDS & DERIVATIVES

Preparation of Carboxylic Acids
1. Oxidation
a. Oxidation of Primary Alcohols and Aldehydes
R
R
R
OH
K 2 Cr2 O7 /H2 SO4
K 2 Cr2 O7 /H2 SO4
C
O
C

immediate
or KMnO4 /H2 SO4
distillation
H
H
HO
H
b. Oxidative Cleavage of Alkenes
H
H
C
H

KMnO4 /H2 SO4 , heat

O
C
OH

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C
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Oxidation of an Alkylbenzene (Formation of Benzoic Acid)

O
CH3

C
+ 3[O]

OH

KMnO4/H2 SO4 , heat

+ H2 O

2. Hydrolysis
a. Hydrolysis of Nitriles (RCN)
Acidic Hydrolysis
+
HCl ( aq )
RCN
RCOOH + NH4
reflux

Basic Hydrolysis

+
NaOH ( aq )
RCN
RCOO Na + NH3
reflux

b. Hydrolysis of Esters (RCOOR)

Acidic Hydrolysis

RCOOR + H2O

HCl ( aq ), reflux

RCOOH + ROH

conc H2 SO4

Basic Hydrolysis

NaOH (aq )
RCOOR + H2O
RCOO Na + ROH
reflux

H
RCOONa+
RCOOH
reflux
+

Reactions of Carboxylic Acids

1. Salt Formation
a. Reaction with Metal

+
RCOOH + Na
RCOO Na + H2
b. Reaction with Bases

+
RCOOH + NaOH
RCOO Na + H2O
c. Reaction with Carbonates

+
2RCOOH + Na2CO3
2RCOO Na + H2O + CO2
2. Esterification

O
R

O
C

R1

OH

conc H2SO4

O
H

heat
(can use acid or
alkaline as catalyst)

R1

H2 O

3. Conversion into Acyl Chlorides (RCOCl)

RCOOH + PCl5
RCOCl + POCl3 + HCl
3RCOOH + PCl3
3RCOCl + H3PO3
RCOOH + SOCl2
RCOCl + HCl + SO2
4. Reduction to Alcohols
1. LiAlH4 in dry ether
RCH2OH + H2O
RCOOH + 4[H]
2. H2SO4 ( aq )
Preparation of Acyl Chlorides
1. From Carboxylic Acid
RCOOH + PCl5
RCOCl + POCl3 + HCl
3RCOOH + PCl3
3RCOCl + H3PO3
RCOOH + SOCl2
RCOCl + HCl + SO2

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Reactions of Acyl Chlorides

1. Conversion into Acid. Hydrolysis
RCOCl + H2O
RCOOH + HCl
ArCOCl + H2O
ArCOOH + HCl
*Note: Benzoyl chloride reacts much slower than acyl chlorides because of the reduce in the positive nature of the carbonyl
carbon caused by resonance.

2. Ester Formation. Alcoholysis.

room temperature
RCOCl + ROH
RCOOR + HCl
*Note: Reaction is slow when phenol is directly reacted with acyl chloride.
slow
RCOCl + ArOH
RCOOAr + HCl
*Note: Because phenol is a weaker nucleophile (lone pair of electron delocalizes into the ring), it is converted to phenoxide to
increase nucleophilic strength.

+
ArOH + NaOH
ArO Na + H2O

RCOCl + ArO
RCOOAr + Cl

3. Amide Formation. Ammonolysis.

RCOCl + NH3
RCONH2 + HCl
RCOCl + RNH2
RCONHR + HCl
RCOCl + RRNH
RCONRR + HCl
4. Reduction to Aldehyde, then Alcohol
LiAlH4 in dry ether
LiAlH4 in dry ether
RCOCl
RCHO
RCH2OH
H2SO4 ( aq )
Preparations of Esters
1. Condensation Reaction of Acid and Alcohol
a. Ethyl Ethanoate

O
R

O
C

R1

OH

conc H2SO4

O
H

heat
(can use acid or
alkaline as catalyst)

R1

H2 O

b. Phenyl Benzoate

+
ArOH + NaOH
ArO Na + H2O
ArCOCl + ArONa+
ArCOOAr + NaCl

Reaction of Esters
1. Hydrolysis
a. Acidic Hydrolysis
RCOOR + H2O

HCl ( aq ), reflux
conc H2 SO4

RCOOH + ROH

b. Basic Hydrolysis
NaOH (aq )
RCOONa+ + ROH
RCOOR + H2O
reflux

2. Reduction to Primary Alcohols

LiAlH4 in dry ether
RCOOR
RCH2OH
H2SO4 ( aq )
Preparation of Polyesters
1. Condensation Reaction
acid
( OCRCOORO )
nHOOCRCOOH + nHOROH
reflux

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NITROGEN COMPOUNDS
Preparation of Amines
1. Reaction of Halides with Ammonia or Amines. Ammonolysis
+

+
NH3
ethanol, reflux
RX + excess conc NH3
[H3N---R---X]
RNH2 + NH4 X
sealed tube

RX
RX
RX
RX
NH3

RNH2

R2NH

R3N

R4N X

2. Reduction
a. Reduction of Amide
LiAlH4 in dry ether
RCONH2
RNH
RCH22NH2
H2 / Ni or Pt

b. Reduction of Nitrile
LiAlH , dry ether
RCN
RCH2NH2
or 2H , Ni, heat
4

c.

Reductive Amination
H

H
C

+ NH3

NH

H2 , Ni

H
or NaBH3 CN

NH2

imine

Reactions of Amines
1. Salt Formation
+

RNH2 + HCl
RNH3 Cl
+
RNH2 + RCOOH
RNH3 OOCR

NH2

NH3 Cl

HCl

*Note: Phenylamine is not soluble in water but dissolves in acid.

2. Formation of Amides. Acylation.

R'COCl

R'CONHR + HCl

RNH2

ArSO2 Cl

ArSO2NHR + HCl

RR'NH

R''COCl

R''CONRR' HCl
ArSO2 Cl

ArSO2NRR' HCl

RR'R''N

R'''COCl

no reaction
ArSO2 Cl

no reaction

*Note: Since HCl is formed, some of the ammonia/amine will be protonated and cannot act as a nucleophile. Hence, at least
double the amount of ammonia / amine must be used.
*Note: Acylation of 1 and 2 amines leads to the formation of substituted amides. 3 do not undergo acylation because they
do not have any replaceable H atoms.
CH3CH2NH2 + CH2COCl
CH3CH2NHCOCH3 + HCl
ArNH2 + ArCOCl
ArNHCOAr + HCl
ArNH2 +RCOCl
ArNHCOR + HCl

3. Ring Substitution Reactions of Aromatic Amines

a. Halogenation
NH2

NH2
Br

3Br2 (aq)

Br

(s)

+ 3HBr

White ppt

Br

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*Note: To get monosubstituted compounds, react phenylamine with ethanoyl chloride to reduce the strongly
activating nature of the amino group to form phenylacetamide.
NH2

NHCOCH 3

CH 3COCl

*Note: NHCOCH3 is also 2,4-directing but moderately activating. Halogenation of ArNHCOCH 3 will give N-(2bromophenyl)acetamide or N-(4-bromophenyl)acetamide. Reacting this with aqueous NaOH and heating will give
2-bromophenylamine or 4-bromophenylamine.

b. Nitration

NH2

NH2
O 2N

NO 2

conc HNO3
+ conc H SO
2
4

NO 2
*Note: The same steps as above can be taken if we want monosubstituted nitrophenylamine.
Preparations of Amides
1. Ammonolysis of Acid Derivatives
RCOCl + NH3
RCONH2 + HCl
RCOCl + RNH2
RCONHR + HCl
RCOCl + RRNH
RCONRR + HCl
2. Reaction between Amine and Acid Chloride
R'COCl

R'CONHR + HCl
RNH2
ArSO2 Cl

ArSO2NHR + HCl
RR'NH

R''COCl

R''CONRR' HCl
ArSO2 Cl

ArSO2NRR' HCl

Reactions of Amides
1. Acidic Hydrolysis
+
HCl, H2O
RCOOH + NH4
RCONH2
heat

2. Basic Hydrolysis

NaOH, H2O
RCOO + NH3
RCONH2
heat

Preparations of Amino Acids

1. Hell-Volhard-Zelinsky Reaction
H
Br2 , PBr3

heat

C
H

COOH

C
Br

H
excess conc NH3

COOH
H2N
R

C
R

COOH

Reactions of Amino Acids

1. Salt Formation
+
a. Reaction with H . Cationic
+

+
+
H3NCH2COO (aq) + H (aq)
H3NCH2COOH (aq)

b. Reaction with OH . Anionic

+

H3NCH2COO(aq) + OH (aq)
H2NCH2COO (aq) + H2O(l)
*Note: The above two equations explains the buffering capability of amino acids.

2. Acylation (Formation of Amides)

CH3COCl + H2NCH2COOH
CH3CONHCH2COOH + HCl

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3. Esterification
H2NCH2COOH + ROH

HCl

H3NCH2COOR + H2O

4. Peptide Formation
*Note: A peptide is any polymer of amino acids linked by amide bonds between the amino grup of each amino acid and the
carboxyl group of the neighbouring amino acid. The CONH (amide) linkage between the amino acids is known as a
peptide bond.

H2N

CH

OH

+ H2N

CH

R1

OH

H2N

5. Hydrolysis of Peptides
a. Acidic Hydrolysis
H
O
H

------

H
------

C
R

R1

------

H2 SO4 ( aq )

-----heat

R1

CH

R1

OH

------

NaOH ( aq )

-----heat

OH

H3N

------

R1

+ H2O

b. Basic Hydrolysis
O
H

CH

H
-

H2N

------

R1

*Note: A peptide bond can be cleaved by hydrolysis in the presence of a suitable enzyme (trypsin, pepsin etc) or by
heating in acidic or alkaline medium.

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APPENDIX
Halogenation of Alkylbenzenes: Ring vs Side chain
Alkylbenzenes clearly offer two main areas to attack by halogens: the ring and the side chain. We can
control the position of attack simply by choosing the proper reaction conditions.
Halogenation of alkanes requires conditions under which halogen atoms are formed, that is, high
temperature or light. Halogenation of benzene, on the other hand, involves transfer of positive halogen,
which is promoted by acid catalysts like ferric chloride (FeCl3).
heat or light
CH4 + Cl2
CH3Cl + HCl
Cl

FeCl3 , cold
+ Cl2

+ HCl

We might expect, then, that the position of attack in, for example, methylbenzene would be governed by
which the attack particle is involved, and therefore by the conditions employed. This is so: if chlorine is
bubbled into boiling methylbenzene that is exposed to ultraviolet light, substitution occurs almost exclusively
in the side chain; in the absence of light and in the presence of ferric chloride, substitution occurs mostly in
the ring.

CH3

Cl

Atom: Attacks side chain

Cl+

Ion: Attacks ring

Markovnikovs Rule
In the ionic addition of an acid to the carbon-carbon double bond of an alkene, the hydrogen of the acid
attaches itself to the carbon atom that already holds the greater number of hydrogens.
Saytzeffs Rule
For elimination reactions, the preferred product is the alkene with the most alkyl groups attached to the
doubly bonded carbon atoms i.e. the most substituted product.

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