KEY CONCEPTS

1. Inductive effect

1.1 Due to electrometric effect :

+ I effect → increase e– density
– I effect → decrease e– density
1.2 Order of +I effect
H3C CH3
– Θ
O > – C – O > H3C – C – > CH3 – CH –
O H 3C > CH3 – CH2 > CH3 > T > D > H

1.3 Order of –I effect

+ ⊕
– NF3> –NR3> –NH3> –NO2> –CN > – C–OH
O > F > Cl > Br > I > –OH > – C ≡ CH > – Ph > – CH = CH2 > H

1.4 +I effect increase → Basicity

Stability of carbocation
stability of free radical
1.5 +I effect decrease → Acidic nature
Stability of carbanian
– I effect show opposite effect to +I effect
2. Resonance

Delocalisation of π e– present in conjugated system examples of conjugated system

(a) Between two D.B. (Double bond)

(b) π e– (D. B) & +ve charge (or vacant orbital)

(c) π e– with –ve charge or lone pair

(d) π e– with free radical

1.7 Resonating structure with more number of covalent bond, non polar with complete octet are more stable.
1.8 Stability order by resonance:
Extended conjugation > cross conjugation > less conjugation

3. Mesomeric effect
Order of +M effect : (Tentative order)
O– > NR2 > NH2 > OH > NH – C – R > O – C – R > Ph > CH ≡ CH > F > Cl > Br > I
O O

Order of –M effect :
 NO2 > CN > C – H > – C – R > – C – OH > – C – OR > –C – NH2
O O O O O

4. Hyper conjugation
Due to presence of α − H in carbocation or π electron system, σ bond delocalisation of C–H bond
+ H effect → alkyl group ∝ no. of αH
– H effect → –CX3 group (decrease e– density)

Stability of intermediate & acidic basic strength Comparision (Generalised concept)

If G group exert ⊕ • Θ O–H NH2
CH2 CH2 CH2

or
G G
G G G Acidic strength Basic strength
Carbonation Free Carboanion (ka) (kb)
stability radical stability

+I Increase Decrease Decrease Increase

–I Decrease Increase Increase Decrease
+M Increase Decrease Decrease Increase
–M Decrease Increase Increase Decrease
+H Increase Decrease Decrease Increase
–H Decrease Increase Increase Decrease
5. SIR effect

Steric inhibition of resonance caused by ortho group affect acidic strength, basic strength, bond length, etc.
properties.
••

COOH COOH NR2 NR2

CH3 a CH3 b
> >

ortho group CH3

steric repulsion
caused-COOH Due to SIR effect
to go out of the Bond length order
plane so acidic a>b
strength increases. Basic strength
a>b

6. Leaving group ability

⇒ L.G.A ∝ stability of –ve charge on leaving group (if present)

⇒ Resonance delocalisation of +ve or –ve or free radical cause stability

7. Aromatic Compound

Essential conditions
→ 4n + 2π electron
→ Cyclic delocalization
→ Planar molecule
Stability order : for similar unsaturated system
Aromatic > Non Aromatic > Anti aromatic
(4nπ electron)
Properties of Intermediate
Carbocation Free radical Carbanion Carbene
⊕

Θ
•

(1) Example R – CH2 R – CH2 R – CH2 R – CH:

(2) Nature Electrophile Electrophile Nucleophile Electrophile

(e– deficient) (e– Rich)

(3) Structure Planar Pyramidal Singlet ↑↓

Planar or
pyramidal Triplet ↑↑

(4) Stability stabilize by e–s

Stabilized by e– attracting group some as carbocation
same as
releasing group
carbocation
8
(5) No. of e– 6 Singlet (diamagnetic)
in outer 7 (Diamagnetic) 6 Triplet (paramagnetic)
(Diamagnetic)
most shell (paramagnetic)

(6) Stability 3° > 2° > 1° 1° > 2° > 3°

order (C6H5)3C⊕>(C6H5)2CH⊕ same as (C6H5)3CΘ>(C6H5)2 C6H5CH: > R CH:
+ > C6H5 CH2⊕ carbocation CHΘ> C6H5CH2Θ

8. Carbocation

Positively charged 'C' atom as reaction intermediate is called carbocation. Generally it contains only six
electrons in three bonds.
8.1 Structure and Hybridisation:
Classical carbocation (carbenium ion) are sp2 hybridised and of planar structure.
Unhybridised vacant 'p' orbital lies below and above the plane.
 + C
120º

sp2

8.2 Stability: Carbocation are stabilised by

(i) + I effect (ii) + M effect
(iii) Hyper-conjugation
For explanation, see in + I, + M and hyper conjugation

8.3 The generation of – C+ (carbocation or carbenium ion):

(a) By the direct ionisation

(b) By the protonation of unsaturated compound
(c) By the protonation of lone pair of electron (in case of carbene)
(d) By electrophilic attack on alkyl halide or acyl halide
(e) By the decomposition of diazonium salt
(f) By attack of super acid on alkane
8.4 Reaction of Carbocation (Carbenium ion):
(a) Proton Loss: To form a multiple bond.
(b) Combination With Nucleophiles
(c) Addition to an alkene
(d) Molecular Rearrangements:
(i) Hydride shift
(ii) Methyl Shift
(iii) Aryl Shift
(iv) Abstraction of hydride ion

9. Carbanion

A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
Ex: ΘCH
3, Methyl carbanion

CH3–CH2Θ Ethyl carbanion

(CH3)2CHΘ Isopropyl carbanion

9.1 Structure and Hybridisation:
On the basis of the structure carbanion are of two types
(a) Tetrahedral carbanion (sp3) hybridized
Tetrahedral with lone pair or pyramidal without lone pair.
 C
120º

sp2

Unhybridised pure ‘p’ orbital

2
(b) Planar carbanion (sp ) hybridized

C
C

9.2 Stability of carbanion:

Carbanions are stabilised by electron withdrawing effects as
(a) – I effect (b) – M effect
(c) Delocalisation of charge.
9.3 Generation of Carbanion:
(a) By action of base on acidic hydrogen of C – H bond
(b) By decarboxylation of carboxylate ion
(c) In the form of organometallic compound
9.4 Reactions of Carbanion:
(a) Attachment of H+:
Ex: –CH3 + H+ → CH4
(b) Loss of Leaving Group:
X

In the system CΘ C , carbanion losses a nucleophile or a base group to form a π bond.

X
–
i.e. –C–CΘ → – C = C – + XΘ

(c) Addition Reaction

10. Carbon Free Radical

Free radical is a species that contain an unpaired electron in valence shell of one of its atom, and if the atom is
carbon atom the free radical is known as CARBON FREE RADICAL. It has three bond pairs and one unpaired
electron i.e.
·
– C – Unpaired electron

10.1 Structure and Hybridisation:

A free radical may be considered as having.
(i) Rapidly interconverting Pyramidal structure, which is sp3 hybridised:
 (ii) Planar structure; sp2 hybridised:

Unhybridised pure
‘p’ orbital
C
120º

C C

(i) Planar sp2 structure.

(ii) Pyramidal sp3 structure which is interconverting.
Note: Although geometry of organic free radical is still controversial but recent studies revealed conclusive
in the favour of planar structure.
10.4 Reaction of Free Radicals
(a) Recombination (Coupling)
(b) Disproportionation
(c) Reaction with hydrogen
(d) Reaction with unsaturated compound
(e) Reaction with metals
(f) Polymerisation

11. Carbene
Carbenes are neutral species containing a carbon atom with two bonds and two non-bonded electrons:
i.e. –C–
(carbene)
11.1 Types of Carbene: Carbenes are classified into two classes.

(i) Singlet Carbene (– C – )

(ii) Triplet Carbene (– C – )

(a) Singlet carbene:

11.2 Generation of carbene:
(i) CH2 = N+ = N¯ →∆
:CH2
Diazomethane
∆
(ii) CH2 = C = O → :CH2
R ∆ R
(iii) C = C = O → C:
R R
(iv) By action of base on chloroform

Cl –
OH Cl
Cl C–H Cl C–
Cl –H2O Cl
 (v) CCl4 + Li-R → R–Cl + Li-CCl3

Li-CCl3 → Cl – C·· – Cl

(vi) CH2Cl2 LiR

→ :CHCl
11.3 Reactions of Carbene:
(i) Attachment with nucleophile:

12. Benzyne
Benzyne may be defined as a neutral highly reactive intermediate in which the aromatic character is not
disturbed.
Benzyne can be represented as

or

12.1 Structure and Hybridisation:

(i) All carbon atoms in benzyne are sp2 hybridised.

(ii) Side way poor overlapping of sp2 orbitals forms π bonds outside the ring and out of the plane of π
system of the ring.
12.2 Generation of Benzyne:
(i) From chlorobenzene
(ii) From chloro bromo benzene
O
C–OΘ
(iii) From:
+
N2
12.3 Reactions of Benzyne :
(i) Benzynes are too unstable to be isolated and react with any nucleophile present in the solution.
NH2 NH2 O–CH3 O–CH3
– –
NH2 NH2
H–NH2
(a) (b) NaNH2
NH3
NH2
CH3 CH3
OH
(c) NaOH
H–OH

13. Nitrene
Nitrene may be defined as the electron deficient species in which nitrogen has a sextet of electrons. Nitrenes
are analogues of carbene also known as unidogen, azene, unene i.e.
 ·· ··
H – N· · or R – N· · are nitrene.
13.1 Generation of Nitrene:
ν
(i) R – N3 h
··
→ N2 + R – N· ·
O O
ν
(ii) R – C – N3 h
··
→ N2 + R – C – N· ·
ν
(iii) H – N = C = O h
··
→ CO + H – N· ·
13.2 Reactions of Nitrene:
(i) Addition to Olefin:
(ii) Rearrangement reaction:
(a) Hofmann rearrangement
(b) Curtius rearrangement
(iii) Insertion Reaction
(iv) Recombination of Two Nitrenes

14. Types of Reaction

In organic chemistry the following types of reactions are more important.
(i) Addition reaction
(ii) Substitution reaction
(iii) Elimination reaction
(iv) Rearrangement reaction
14.1 Addition Reaction
14.1.1 Mechanism of addition reaction
Mechanism of addition reactions can be classified in following ways:
(A) Classification based on the type of attacking reagents.
(B) Classification based on the fashion of addition.
Addition by
Cationic attack

Addition by
Molecular attack

Addition Addition by
Reaction Anionic attack

Addition by
free radical attack

Addition by
Carbene attack
14.1.2 Addition by cationic attack
(Electrophilic addition)
14.1.3 Addition by free radical attack
14.1.4 Addition by anionic attack
(Nucleophilic addition)
14.1.5 Addition by carbene attack
14.1.6 Addition by nitrene attack
14.1.7 Addition by molecular attack
14.1.8 Classification based on fashion of addition
Addition Reaction

Cis addition Trans addition

Addition Addition on
Via cyclic machanism the surface of the
catalyst
Cis Addition: If the group AB adds to – C = C < in such a way that both of A and B attack from same side

the addition is called cis addition.

(a) Addition via cyclic mechanism
Note: For suitable condition
(i) Cis addition on cis form results meso
(ii) Cis addition on trans form results (±)
(iii) Trans addition on cis form results (±)
(iv) Trans addition on trans forms results meso.
(b) Addition on the surface of the catalysts
 Addition to cyclo propane ring
In the case of cyclo propyl ring following type of addition is commonly observed.
Br
+ HBr → CH3 – CH2 – CH2

+ F3CCOOH → CH3 – CH2 – CH – Bu

Bu
O – C – CF3
O
OAc
+ Pb(OAc)Cl →
OAc
 Addition to 1, 3-butadiene :
1,3-butadiene gives two types addition generally if AB or A2 types of reagents are used.
Ex.,
 Br Br Br Br
Br2
CCl4 CH2 – CH–CH=CH2 + CH2–CH=CH–CH2
CH2=CH–CH=CH2

H Cl H Cl
HCl
CH2 – CH–CH=CH2 + CH2–CH=CH–CH2

H H H H
H2
CH2 – CH–CH=CH2 + CH2–CH=CH–CH2
Catalyst
14.2 Substitution reaction

14.2.1Classification of the substitution reaction:

Substitution Reaction

Ionic substitution Free radical

substitution
Nucleophilic Electrophilic
substitution (SN) substitution (SE)

SN1 SN2 SNi SN1' SN2'

Difference between SN1 and SN2

SN2 SN1
1. Second order at lower concentration First order at lower concentration
2. Inversion of configuration always takes place Racemisation takes place but not accurately.
3. No rearrangement is possible. Rearrangement is possible.
4. Rate constant depend upon nature of Nu– Rate constant generally do not depend upon nature of Nu–
5. Greater the stability of possible carbocation poor the Greater the stability of carbocation greater the tendency
tendency of SN2 mechanism. of SN1

Factors that regulate SN1 and SN2 mechanisms:

Any factor that affects the energy of activation of a given type of reaction will affect the rate and/or
mechanism.
These factors may be
1. Polar effect
2. Steric effect
3. The nature of the leaving group
4. The nature of the Nu¯
5. The effect of the solvent
6. Participation of neighbouring group
(II) Electrophilic substitution:
The examples of electrophilic substitution in aliphatic system are very rare.
14.3 Elimination reactions:
 Elimination reaction

1, 2 (β) -Elimination 1, 1 –(α) -Elimination

substitution
E1 mechanism E2 mechanism

One step process Two step process

(via T.S.) (Elc B) (via carbanion)

Via carbocation Via cyclic T.S.

1, 2– (β) Elimination: When two groups or atoms are removed from the two adjacent carbon atoms, the
process is known as β- elimination.
14.3.1 E1 Mechanism:
E1 mechanism may be classified in two classes
(A) Reaction via carbocation
(B) Reaction via cyclic T.S. or cyclic elimination
Factors determining mechanism of elimination:
(i) Greater stability of expected carbocation supports E1 mechanism.
(ii) Greater stability of expected carbanion supports E1 cB.
(iii) Greater strength of the base supports E2.
(iv) Greater concentration of the base supports E2.

15. Rearrangement reaction

It may be defined as the reaction involving reshuffling of the sequence of atom to form a new structure.
Ex.,
(i) Pinacol pinacolone rearrangement
(ii) Wagner meerwein rearrangement
(iii) Beckmann Rearrangement

16. Acidic and basic strength comparision

Compound pKa
+
CH 3 C ≡ N H – 10.1
HI –10
HBr –9
+O H
|| –8
CH3CH
HCl –7
+
CH 3 S H 2 – 6.8
Compound pKa
H2SO4 –5
H
CH 3CH 2 OCH 2 CH 3 – 3.6
+
H
CH 3CH 2 OH –2.4
+
H3O+ –1.7
HNO3 – 1.3
CH3SO3H –1.2
+OH
||
0.0
CH 3 CNH 2
O
||
0.2
F3 CCOH

O 0.64
||
Cl 3 CCOH
+ 0.79
N–OH

+
O2N NH3 1.0

N
1.0
N
+
H
O
||
1.3
Cl 2 CHCOH

HSO −4 2.0
H3PO4 2.1
O
||
2.7
FCH 2 COH
O
||
2.8
ClCH 2 COH
O
||
2.9
BrCH 2 COH
O
||
3.2
ICH 2 COH
Compound pKa
 HF 3.2
HNO2 3.4
O
O2N COH 3.4

O
||
3.8
HCOH
+
Br NH3 3.9

O
Br COH 4.0

O
COH 4.2

O
CH3 COH 4.3

O
CH3O COH 4.5

4.6
+
NH3

O
||
4.8
CH 3 COH

4.9
N+
H
+
CH3 NH3 5.1

N+ 5.2
H
+
CH3O NH3 5.3

+
CH 3 C = N HCH 3
5.5
|
CH 3
O O
|| ||
5.9
CH 3 CCH 2 CH
Compound pKa
H2CO3 6.4
HN
+
NH 6.8

H2S 7.0

O2N OH 7.1

H 2 PO −4 7.2

SH 7.8

N 8.0
+
H H
+
H2 N N H3 8.1
O 8.2
||
CH 3COOH
CH3CH2NO2 8.6
O O
|| || 8.9
CH 3CCH 2 CCH 3
HC ≡ N 9.1
O
9.3
+ N
H H

Cl OH 9.4

+
HOCH 2 CH 2 N H 3 9.5

O
+
|| 9.8
H 3 N CH 2 CO −

OH 10.0

CH3 OH 10.2

HCO 3− 10.2

CH3NO2 10.2

Compound pKa

H2N OH 10.3
CH3CH2SH 10.5
O O
|| ||
10.7
CH 3 CCH 2 COEt

10.7
+
NH3

+
CH 3 CH 2 N H 3 10.7

11.1
+ N
H H

HPO 24− 12.3

CF3CH2OH 12.4

O O
|| || 13.3
EtOCCH 2 COEt

HC ≡ CCH2OH 13.5

O
||
13.7
H 2 NCNH 2

CH 3
+|
CH 3 NCH 2 CH 2 OH 13.9
|
CH 3

N NH 14.4

CH3OH 15.5

H2O 15.7

CH3CH2OH 16.0

O
||
16
CH 3CNH 2

Compound pKa

O
CCH3 16.0
 ~ 17
N
H

O 17
||
CH 3CH

(CH3)3COH 18

O
||
20
CH 3CCH 3

O
||
CH 3COEt 24.5

HC ≡ CH 25

CH3C ≡ N 25

O
||
CH 3CN (CH 3 ) 2 30

ALKANE

1. General Introduction :
• These are the hydrocarbons in which Carbon - Carbon contains single bond (Saturated hydrocarbon).

• These are also called as ‘Paraffin’ (Parum + Affinis i.e. less reactive).

• In alkane if chiral carbon or unsymmetrical carbon is present, then it shows optical isomerism.

• General reagents such as dil. and conc. HCl, dil. and conc. H2SO4, dil. and conc. HNO3, acidic and basic
KMnO4 and K2Cr2O7 usually do not react with alkane.

• General formula is CnH2n+2. (n = 1, 2, 3, 4..............)

• Hybridisation state of carbon is sp3.

• Geometry of carbon is tetrahedral.

• Bond angle is 109º28’.

• Number of bond angle in methane are six, while in ethane are twelve.
 H H H
H 4

3 1 2
1 6 5
2 5
3 6
2
H 1 3
4 5 4
H 6 H H H H
Methane Ethane

• C–C bond length is 1.54 Å while C–H bond length is 1.12 Å.

• C–C bond energy is 84 kcal/ mole while C–H bond energy is 98 kcal /mole.

• Alkane shows only chain, position isomerism.

• First three member methane, ethane and propane do not exhibit any isomerism, while butane and
pentane shows only chain isomerism.

H
|
H– C –H CH3–CH3 CH3–CH2–CH3
|
H

Methane Ethane Propane

CH3–CH2–CH2–CH3 CH3–CH –CH3

|
CH3

n-Butane Iso-butane

CH3
|
CH3–CH2–CH2–CH2–CH3 CH3–CH –CH2–CH3 CH3–C–CH3
| |
CH3 CH3

n-Pentane Iso-Pentane Neo-Pentane

CH3
CH3–CH2–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH2–CH3 CH3–CH–CH2–CH3
CH3 CH3

n-Hexane 3-Methyl pentane Neohexane

CH3–CH–CH2–CH2–CH3 CH3–CH–CH–CH3
CH3 CH3 CH3

Isohexane 2, 3-Dimethyl butane

• The molecules of alkanes are angular, so carbon chains in these molecules are zig- zag type (not
straight) which may be branched or unbranched as shown below.
 (Unbranched) (Branched) (Branched)

2. Physical Properties
• Alkanes are colourless, odourless and tasteless.
• Physical state:
C1–→ C4 Gaseous state

C5 –→ C17 Liquid state (except neo pentane)

C18 & above –→ Solid like wax

• Alkanes are lighter than water, so it floats over water.

• Solubility: [Like dissolves like]
Alkanes are non-polar or weakly polar compounds so these are soluble in non-polar solvents (benzene,
ether, chloroform, carbon tetrachloride etc.) and are insoluble in polar solvents (water etc.).
• Boiling point:
For homologues B.P. ∝ Molecular weight
Because Mol. wt. ↑ = Surface area ↑ = Intermolecular Vander wall's interaction ↑ = B.P. ↑
1
For isomers B.P. ∝
No. of branches

Because Branches ↑ = Spherical shape ↑ = Surface area ↓ = B.P. ↓

• Melting point:
The melting point of alkanes depends upon molecular weight as well as packing in crystal lattice
Variation of boiling point and melting point in alkanes
Name Formula Molecular mass B.P. (ºC) M.P. (ºC)
Methane CH4 16 –162 –183
Ethane CH3 CH3 30 –88.5 –172
Propane CH3 CH2 CH3 44 –42 –187
n-Butane CH3 (CH2 )2 CH3 58 0 –138
Isobutane (CH3 )2 CHCH3 58 –12 –159
n-Pentane CH3 (CH2 )3 CH3 72 36 –130
Isopentane (CH3 )2 CHCH2 CH3 72 28 –160
Neopentane (CH3 )4 C 72 9.5 –17
n-Hexane CH3 (CH2 )4 CH3 86 69 –95
n-Heptane CH3 (CH2 )5 CH3 100 98 –90.5
n-Octane CH3 (CH2 )6 CH3 114 126 –57

• Graphical representation:
 [Irregular or zig-zag graph]
B.P. [regular graph] M.P.

No. of carbon atoms No. of carbon atoms

↑ M.P. (even to odd) > ↑ M.P. (odd to even)

3. Chemical properties of alkane

Halogenation
R–X
X2/hν or UV light
(F2 > Cl2> Br2 > I2)
O
Nitration
R–N
HNO3/400ºC
O
Sulphonation
R–SO3H
H2S2O7

Reed reaction
R–SO2Cl
SO2 + Cl2/hν

R–H
Isomerisation
or Branched alkane
R–R AlCl3/HCl

Pyrolysis
Alkenes + CH4 or C2H6
500–700ºC

Cr or Mo or V oxide
Aromatic compound
+Al2O3/500ºC

CH2N2/∆
Higher alkane
step up reaction

O2
CO2 + H2O
combustion

O2 / Cu R–CH2OH
Catalytic MoO
R–CHO
Oxidation (AcO)2 Mn
R–COOH
4. Preparation methods of Alkane
NaOH + CaO/∆
RCOOH
Soda lime

Kolbe's electrolysis
RCOONa

Na / ether
R–X
Wurtz reaction

Zn / Ether
R–X
Frankland's reaction

(i) Li (ii) CuX (iii) R–X

R–X
Corey-House synthesis

R–H
Zn/HCl or LiAlH4 or Red P/HI
R–X or
Reduction
R–R

HOH or ROH
R–Mg–X
or NH3 or RNH 2

HI / red P / 140ºC
RCOOH or ROH or R–C–R or RCHO
Reduction
O

Zn–Hg/HCl
R–C–R or R–C–H
Clemmenson's reduction
O O

H2N–NH2 / KOH
R–C=O or R–C=O
Wolff Kishner reduction
R H

200–300ºC, H2/Ni
R–C≡CH or R–CH=CH2
Sabatier Senderen's reaction

5. Special Points

• LPG is called as liquefied petroleum gas or kitchen gas which is a mixture of propane and butane.
 • A mixture of n-butane and isobutane is called as Calore gas.
• Methane reacts with ozone to make formaldehyde.
• When methane is heated (at about 1500º C) in presence of nickel it makes acetylene.
• Sabatier Senderen's reaction:
Ni/200ºC
CO + 3H2 CH4 + H2O

Ni/200ºC
CO2 + 3H2 CH4 + 2H2O

• Preparation of synthesis gas:

CH4 + H2O Ni
/1000
 ºC
→ CO + 3H2

ALKENE

1. General Introduction :
• These are the acyclic hydrocarbons in which unsaturation (C=C) is present.
• These are also known as olefins (i.e. oleum, oil + fines, forming) because lower alkene react with
halogens to form oily substances.
• General formula is CnH2n (n = 2, 3, 4, 5..........).

• Hybridisation of unsaturated ‘C’ atoms are sp2

• Geometry of unsaturated ‘C’ carbon is trigonal planar.
• Bond angle on sp2 carbon is 120º.
• C=C bond length is 1.34 Å.
• C–H bond length is 1.10 Å.
• C=C bond energy is 142 kcal/mole
• C–H bond energy is 106 kcal/mole
• Alkene shows chain, position, functional (ring chain), optical & geometrical isomerism.
(i) Chain isomers → CH3–CH2–CH=CH2 and CH3–C=CH2
|
CH3

(ii) Position isomers → CH2=CH–CH2–CH3 and CH3 – CH = CH – CH3

(iii) Functional isomers (ring chain isomerism) → CH3–CH2–CH=CH2 and CH2– CH2
| |
CH2– CH2
(iv) Geometrical isomers → CH3–C–H and CH3–C–H
|| ||
CH3–C–H H–C–CH3
 (cis -2-butene) (trans-2-butene)
*
(v) Optical isomerism → CH3CH2–CH–CH=CH2
CH3
NOTE: Cumulated polyene can exhibit geometrical as well as optical isomerism.
CH3 H
C=C=C
H CH3
This molecule is simplest example of cumulated polyene which can exhibit optical isomerism because
this is a chiral molecule. Similarly suitably substituted polyene containing odd no. of double bond can
exhibit geometrical isomerism as this is a planar molecule.
CH3 CH3
C=C=C=C
H H

a
• Cumulated polyene having even no. of double bonds which has = C system at the both end can
b
exhibit optical isomerism but cannot exhibit geometrical isomerism.

a
• Cumulated polyene having odd no. double bonds which have = C system at both end can exhibit
b
geometrical isomerism but cannot exhibit optical isomerism.

2. Physical Properties

• Alkenes are colourless and odourless.

• These are insoluble in water and soluble in organic solvents.

• Physical state:

C2—C4 ––→ gaseous

C5—C15 ––→ liquid

C16 and above ––→ solid like wax

Molecular weight
Boiling and Melting point ∝
No. of branches
 Name Formula B.P.(ºC) M.P.(ºC)
Ethylene CH2 =CH2 –102 –169
Propylene CH3 –CH=CH2 –48 –185
1-Butene CH3 CH2 –CH=CH2 –6.5 –171
cis-2-Butene cis–CH3 –CH=CH–CH3 4 –139
trans-2-Butene trans–CH3 –CH=CH–CH3 1 –106
Isobutylene (CH3 )2 C=CH2 –7 –141

• B.P and M.P. decreases with increase in branches in alkene.

• The melting points of cis isomers are lower than trans isomers because isomer is less symmetrical than
trans. Thus trans packs more tightly in the crystal lattice and hence has a higher melting point.

• The boiling points of cis isomers are higher than trans isomers because cis–alkenes has greater polarity
(Dipole moment) than trans one.

• These are lighter than water.

 Chemical properties of alkenes

 HX
R–CH–CH3

HBr/Peroxide X
R–CH2–CH2Br
X2
R–CH–CH2X

HOCl X
R–CH–CH2Cl
OH
dil. H2SO4
R–CH–CH3
OH
(i) (AcO)2Hg (ii) H2O
R–CH2–CH2–OH
(iii) NaBH4 H2O/H⊕
R–CH2CH3
Hydrolysis
BH3
(RCH2CH2)3B
Hydroboration
H2O2/OH
H2/Ni R–CH2CH2–OH
R–CH2–CH3 Oxidation
200–300ºC
OsO4/H3O⊕
R–CH–––CH2

OH OH
OH
Baeyer reagent
R–CH=CH2 R–CH–––CH2
1% alkaline KMnO4
OH OH
OH
per acid H3O⊕
R–CH–––CH2 R–CH–––CH2
Prelischave's reaction
O OH OH
OH
O3 + H2O + Zn
R–CHO + HCHO
ozonolysis
O3 + H2O
RCOOH + HCOOH
ozonolysis
Strong oxidant
RCOOH + CO2 + H2O
KMnO4/H⊕
O2
CO2 + H2O
combustion
Cl2
Allylic substitution product (Cl–H2C–CH=CH2)
500ºC

NBS/∆
Allylic substitution product (Br–H2C–CH=CH2)
Al2(SO4)3
Isomerisation
200–300ºC

3. Preparation methods of Alkene

 conc. H2SO4/170ºC
R–CH2–CH2–OH
–H2O

alc. KOH
R–CH2–CH2–X
–HX

NaNH2
R–CH2–CH2–X
–HX

Zn dust
R–CH–CH2
–X2 R–CH=CH2
X X or CnH2n
H2
R–C≡CH
Pd + BaSO4/CaCO3

Kolbe's electrolysis
R–CH–COOK
R–CH–COOK

R R
⊕ ∆
N OH
R CH2–CH2–R Pyrolysis

∆
R–C–O–CH2–CH2–R
Pyrolysis
O

R
R–N O ∆
Pyrolysis
CH2–CH2–R

4. Special Points
• Ethene is used in the artificial ripening of fruits.
• Water solution of sodium or potassium salt of succinic acid on electrolysis gives ethene at anode.
• Ethene react with sulphur monochloride (S2Cl2) to form poisonous mustard gas (β, β-dichloro diethyl
sulphide). Gas is used as a war gas. (Used in 1st world war)

CH2 Cl Cl CH2 ClCH2 CH2Cl

|| + | | + || → | | +S
CH2 S–S CH2 H2C––S––CH2

Mustard gas (β, β’-dichloro diethyl sulphide)

• Some other reactions of ethene are:

 NOCl
Cl–CH2–CH2–N=O
Tilden's reagent

CH2N2/∆ (Cyclopropane)

N2O3
O2N–CH2–CH2–N=O (Ethylene nitrosite)

N2O4
CH2=CH2 O2N–CH2–CH2–NO2 (Ethylene nitrosate)

CH3COCl/AlCl3
CH3–C–CH2–CH2–Cl
CH3 O
CH3–C–Cl/AlCl3
CH3
CH3
CH3–C–CH2–CH2–Cl

CH3

CH3–O–CH2–Cl/AlCl3
CH3–O–CH2–CH2–CH2–Cl

CO + H2
CH3–CH2–CHO

CO + H2O
CH3–CH2–COOH
 ALKYNE

1. General Introduction :
• These are the acyclic hydrocarbons in which unsaturation (C≡C) is present.
• Hybridisation state of triple bonded carbon in alkyne is sp.
• Geometry of unsaturated carbon is linear in alkynes.
• Bond angle in alkyne on sp carbon atom is 180º.
• Their general formula is CnH2n–2 (n = 2, 3, 4, 5 ..........................)
• C–C triple bond length is 1.20 Å.
• C–H bond length is 1.08 Å.
• C–C triple bond energy is 200 kcal/mol.
• C–H bond energy is 121 kcal/mol.
• Alkyne shows chain, position and functional isomerism. They are functional isomer with cycloalkene
and alkadiene.
ex.: Isomers of C4H6 are:
CH3–C≡C–CH3 CH3–CH2–C≡CH CH3–CH=C=CH2 CH2=CH–CH=CH2

2-Butyne 1-Butyne 1,2 –Butadiene 1,3-Butadiene

Cyclobutene

CH3 CH2

CH3
1-Methyl cyclopropene 3-Methyl cyclopropene Methylidene cyclopropane Bicyclobutane

2. Physical Properties
• Alkynes are colourless, odourless and tasteless.
• Lower alkynes are partially soluble in H2O. (It is due to its polarizability).
• Higher alkynes are insoluble in water due to more % of covalent character.
• Completely soluble in organic solvents.
• Melting point and boiling point increases with molecular mass and decreases with number of
branches.
• Physical state:
C2–C4 → Gaseous C5–C11 → Liquids C12 & above → Solids
Molecular weight
Boiling point and Melting point ∝
No. of branches
 Name Formula B.P. (ºC) M.P. (ºC)
Acetylene HC ≡ CH –75 –82
Propyne CH3 –C≡CH –23 –101.5
1-Butyne CH3 CH2 –C≡CH 9 –122
2-Butyne CH3 –C≡C–CH2 27 –24
3. Chemical properties of alkyne
Br
HBr
R–C–CH3
Br
HBr/Peroxide
R–CH–CH2–Br
Br

Cl Cl
Cl2
R–C––CH
Cl Cl

HOCl Cl
R–C–CH
Cl
O

BH3/H2O2/OH
R–CH2–CHO
H2/Ni
R–CH2–CH3
H2/Pd–BaSO4
R–CH=CH2

CH3OH OCH3
R–CH (Methylal)
(BF3–HgO) OCH3

HCN/Ba(CN)2 CN
R–C≡CH R–CH2–CH
CN

CH3COOH/Hg+2 OCOCH3
R–CH2–CH
OCOCH3
NaNH2
R–C≡C–Na
AgNO3 + NH4OH
R–C≡C–Ag
(Tollen's Reagent)
Cu2Cl2+ NH4OH
R–C≡C–Cu

Baeyer Reagent
R–C–CHO
O
+2
H2O/Hg
R–C–CH3
O
O3/H2O/Zn
R–C–C–H
ozonolysis
O O

KMnO4/H⊕
R–COOH + CO2 + H2O
Strong oxidant

Combustion
CO2 + H2O
4. Preparation methods of Alkyne
alc KOH or NaNH2
CH2–CH2
Br Br

Br alc KOH or NaNH2

CH3–CH
Br
Cl
Ag powder
HC Cl
∆
Cl

Br Br Zn dust HC≡CH
CH–CH or
Br Br CH3–C≡C–R

Zn dust
Br–CH=CH–Br

alc. KOH or NaNH2

CH2=CH–Cl
∆

HC–COONa Kolbe's electrolysis

HC–COONa

(i) Na
CH3–C≡CH
(ii) R–X

(i) CH3MgI
CH3–C≡CH
(ii) R–X

5. Special Points

• Ethyne is used in oxy-acetylene flame (2800-3200ºC) which is used for cutting and welding of metal.
• Ethyne is used in carbide lamps for lightning (is an illuminating agent in hawker's lamp)
• When electric arc is passed in atmosphere of hydrogen between carbon electrode, ethyne is formed
(Berthelot Method).
• Mixture of ethyne and nitrogen in electric spark converted into HCN.
• Ethyne burns with sooty flame due to presence of high % of carbon.
• Acetylene is used in artificial ripening of fruits.
• Pure acetylene (NARCYLENE) is odourless and impure acetylene has odour like garlic. It is due to
impurities of Arsine (AsH3) & Phosphine (PH3).
• Acetylene & 1- alkyne are acidic in nature. It is due to greater electronegativity of sp hybridised
carbon.
• Acetylene has two acidic hydrogen atoms. It can neutralise two equivalents of base at the same time.
So it is also called as dibasic acid. But the base should be very stronger as NH2 or CH3etc.
• Some other reactions of acetylene are.
Cl AsCl2
AsCl3
HC=CH (Lewisite)

CO + H2
CH2=CH–CHO
Hydroformylation

CO + ROH
CH2=CH–COOR

CO + H2O
CH2=CH–COOH
(Hydrocarboxylation)

H2O/Hg+2
HC≡CH CH3–CHO
Kuchrov's reaction

Dimerisation
CH2=CH–C≡CH
Cu2Cl2 + NH4Cl/∆

Trimerisation
Red hot Fe tube

Tetramerisation
Ni(CN)2

(conc.) H2SO4 HSO4

CH3–CH
HSO4
nd
• Lewisite is highly explosive gas which was used in II world war. British anti-lewisite (B.A.L.) is an
organic compound whose structure is CH2–CH–CH2

OH SH SH
1. Preparation methods of benzene :

NaOH + CaO / ∆
COOH Sodalime

H2O / ∆
SO3H

H 2O
Mg – Br

Zn Benzene
OH
reduction

Cr2O3 + Al2O3
500ºC

red hot Fe tube

HC ≡ CH
Polymerisation

CH2
(i) CH2 = CH2
HC
(ii) Platforming
HC
CH2
2. Chemical properties of benzene

Cl2/AlCl3
Cl
Halogenation

HNO3+ H2SO4
NO2
Nitration
H2SO4
SO3H
Sulphonation

CH3CH2–Cl/AlCl3
CH2CH3
Friedal-Craft alkylation
O
O
CH3–C–Cl/AlCl3
C–CH3
Friedal-Craft acetylation
(CO + HCl)/AlCl3
CHO
Gattermann-Koch reaction

(HCN +HCl)/AlCl3 H3O⊕

CH=N CHO
Gattermann reaction
(HCHO + HCl)/ZnCl2 HCl
CH2OH CH2Cl
Blace reaction ZnCl2

O3/H2O/Zn CHO
Ozonolysis (Glyoxal)
CHO
Cl Cl
Cl2/sunlight
Cl Cl (BHC or 666)

Benzene Cl Cl
H2/Pd or Pt or Ni
H.T.P.

Na/liq. NH3
Birch reduction

(i) CrCl3 + AlCl3

Cr Sandwitch compound
(ii) Na2S2O4

V2O5/300ºC
OH (Phenol)
Oxidation
O O
V2O5/400º-500ºC OH – H2O
O (maleic anhydride)
Oxidation OH
O O
Combustion
6CO2 + 3H2O
 3. Aromaticity
Benzene and other organic compounds which resemble benzene in certain characteristics properties are called
aromatic compounds. These characteristic properties constitute what is commonly known as aromatic
character or Aromaticity.
Such Important properties are summarised below.
(i) Unusual stability
(ii) Substitution rather than addition reaction.
(iii) Resistant to oxidation
(iv) C=C bond length value
(v) Ring current.
Note: According to modern concepts aromaticity can now be defined as the ability to sustain an induced
current.
In general aromatic compounds are those which are
(i) Cyclic (ii) Planar
(iii) Containing a total of (4n + 2) π electrons where n may be 0, 1, 2, 3, ...........
Third condition is well known as Huckel rule.
ex. :

(i) (ii)

4n + 2 = 6 4n + 2 = 10
n=1 n=2
∴ Aromatic ∴ Aromatic

(iii) (iv)

4n + 2 = 10 4n + 2 = 10
n=3 n = 3/2
∴ aromatic ∴ Not aromatic

H H sp3
sp2
⊕
(v) (vi)
(vii) (viii)
4n + 2 = 0 4n + 2 = 2
n = 1/2 n=0 4n + 2 = 2 4n + 2 = 4
∴ Anti aromatic It is not aromatic because it n=0 n = 1/2
is not planar and does not
∴ Aromatic ∴ Anti aromatic
have cyclic resonance
(Because it is planar)
 H H sp3

(v) (vi)

4n + 2 = 0 4n + 2 = 2 O
n = 1/2 n=0
⊕
∴ Anti aromatic It should be aromatic but is (ix) (x)
not, because it is not planar ⊕
and does not have cyclic 4n + 2 = 2 4n + 2 = 2
resonance n=0 n=0
sp2
⊕
∴ Aromatic ∴ Aromatic
⊕
(vii) (viii)
(xi) (xii)
4n + 2 = 2 4n + 2 = 4
n=0 n = 1/2 4n + 2 = 4 4n + 2 = 6
∴ Aromatic ∴ Anti aromatic n = 1/2 n=1
(Because it is planar) ∴ Aromatic
∴ Anti aromatic

sp2 sp2 (xv) (xvi)

(xiii) O (xiv) N–H sp2 N
N N

4n + 2 = 6 4n + 2 = 6 4n + 2 = 6 4n + 2 = 6
n=1 n=1 n=1 n=1
∴ Aromatic ∴ Aromatic ∴ Aromatic ∴ Aromatic
sp3
(xvii) (xx)
(xviii)
4n + 2 = 6 4n + 2 = 8 Aromatic
n=1 n = 3/2
∴ not ∴ but anti
i aromatic (xxi)
sp2
⊕
(xix)
4n + 2 = 6 It is Aromatic because
n=1 only peripheral p electrons
∴ Aromatic should be considered
 (xxiv)

4n + 2 = 10
n=2
But not aromatic because
not planar

(xxv)

O O 4n + 2 = 10
⊕ n=2
(xxii)
∴ Aromatic
(Tropone)
(because it is planar also)
This compound is aromatic
This compound is partly
aromatic and partly non
aromatic which can be explained
on the basis of resonance (xxvi)

(xxiii)

(Azulene) 4n + 2 = 18
4n + 2 = 10 n=4
n=2 [18] Anulene
∴ Aromatic It is an
Note : Despite the wide utility of the Huckel's rule a number of systems are known which do not contain (4n + 2) p
electrons but are still aromatic. Well-known examples of these anomalous cases are heptalene,
acenaphthene, etc., and they posses considerable delocalization energies.

heptalene acenaphthen

4. Do yourself
Suggest the product (On the concept of aromaticity)
O

(i) + HBr → ?

H5C6 O – C4H9

(ii) HCl
→

H 5C 6 C 6H 5
 Cl

(iii) + SbCl5 → ?

Ph C−Cl
(iv) 3 → ?

5. Miscellaneous examples
CH3 CH3 O=C–CH3
OH NH2

o-Cresol o-Toluidine Acetophenone

(A) Sulphonation – Benzene forms benzene sulphonic acid with hot concentrated sulphuric acid while with fuming
sulphuric acid or oleum (conc. H2SO4 + SO3) at high temperature, m-benzene disulphonic acid is formed.

SO3H SO3H

H 2SO Oleum
←4   →
80 C H 2S2O7 SO3H
Benzenesulphonic acid Benzene m-Benzenedisulphonic acid
So for sulphonation, it must be hot and conc. H2SO4 and the attacking species is SO3.
(B) Acylation (Reaction with acid chloride or acid anhydride)
Aromatic ketones are formed.
R–C=O

C6H6 + RCOCl    →

anhydrous AlCl3

(C) Sub situation in monosubstituted benzene derivatives

A substituent already present on the benzene ring exercises two types of influence on further substitution.

(a) Directive effect

The substituent already present on the benzene ring directs the incoming substituent to occupy ortho,
meta or para position. This direction depends on the nature of the first substituent and is called directive
effect.
(b) Activity effects
The substituent already present can increase or decrease the rate of further substitution.
Directive effects of sustituents
There are two types of substituents –
(i) Those which direct the incoming group to ortho- and para- positions simultaneously (neglecting meta
all together).
 (ii) Those which direct incoming group to meta-position only (neglecting ortho and para- positions all
together.)
Class- I (o-, p- directing groups)
– R (alkyl), – OH, –NH2, – OR, – Cl, – Br, – I,
Class- II (m-directing groups)
– SO3H, – NO2, – CHO, – COOH, – CN, – COCl, – COR,

6. Theory of ortho-para directing

S
+S +S δ+ S
+S
– δ−
– δ−
≡
– δ−

S S
δ+ S E
δ− δ− Orthoattack
+
Para
 → E →
attack

δ− E
ortho product para product
The above mechanism is followed when S is
– OH, – NH2, – Cl2, – Br, – I, – OR etc.
Ιn methyl or alkyl group, the +I effect of the methyl group or alkyl group initiates the resonance effect.
Thus methyl or alkyl group directs all electrophiles to ortho and para positions.

7. Meta directing
The substituent ‘S’ withdraws electrons from ortho and para positions. Thus m– position becomes a point of
relatively high electron density and further substitution by electrophile occurs at meta position.For example,
–NO2 group is a meta directing (electron withdrawing). Its mechanism can be explained as:

Θ Θ Θ Θ
Θ Θ
O ⊕ O O ⊕ O– O ⊕ OΘ O ⊕
N
O O ⊕
N
O
N N N
⊕
⊕

All meta-directing groups have either a partial positive charge or a full positive charge on the atom directly
attached to the ring.
1. Chemical Properties of Halo-alkane
(Wurtz reaction) Na/dry ether
R–R
(Frankland reaction) Zn/dry ether
R–R
Corey-House reaction
R–R′
(i) Li (ii) CuX (iii) R′–X
Reduction
R–H
LiAlH4 or NaBH4 or Ph3SnH

R–MgX or RLi or RNa or R2Zn

R–R
or R2CuLi (Organo metallic reagents)
R–CH=CH–MgX
R–CH=CH–R
R–C≡C–Na or R–C≡C–MgX
R–C≡C–R
(Finkelstein reaction) NaI/acetone
R–I

(Swart reaction) AgF/DMSO

R–F
(Williamson reaction) RONa
R–O–R
(Streker reaction) Na2SO3
R–X R–SO3Na
ROH or dry Ag2O
R–O–R
H2O or aq. NaOH or moist Ag2O
R–OH

RCOONa or RCOOAg
R–COOR
••
N H3 ••
R– N H 2
••
R– N H 2 ••
R– N H –R
••
R– N H –R ••
R3 N
••
R3 N ⊕
R4 N X
KCN/(Ionic)
R–C≡N
AgCN (covalent) 
R–N = C
KO–N=O (Ionic)
R–O–N=O

Ag–O–N=O (covalent) O
R–N
O
2. Preparation Methods of Halo-alkane

X2/hν
R–H

HX
Alkene

HBr/Peroxide
Alkene

Cl–N=O
R–NH2
(Tilden reagent)

Darzen reaction
R–OH
SOCl2/Pyridine

R–X

PCl3 or PCl5
R–OH

HI or HBr or
R–OH
NaBr + H2SO4

HCl + ZnCl2
R–OH
(Lucas reagent)

Br2/CCl4
R–C–OAg
Hunsdiecker reaction
O
3. Chemical properties & preparation methods of dihalides

aq. NaOH CH 2 − OH
|
CH 2 − OH

Cl2 alc. KOH/∆

H2C=CH2 HC≡CH
CH 2 − Cl or NaNH2
|
CH 2 − Cl

CH 2 − OH PCl5 Vicinal dihalide Zn

| H2C=CH2
CH 2 − OH
O
||
(i) alc. KCN CH2– C
(ii) H3O⊕ | O
CH2– C
(iii) ∆ ||
O

OH
aq. NaOH –H2O
2HCl CH3–CH CH3–CHO
HC≡CH
(Unstable) OH

alc. KOH/∆
HC≡CH
or NaNH2
Cl
PCl5
CH3–CH=O CH3–CH
Cl
Zn
CH3–CH=CH–CH3
Gem dihalide

PCl5 (i) alc. KCN

CH2–CH2
CH3–CH2–COOH
(ii) H3O⊕ (iii) ∆
O
 aq. NaOH
CH2CH2CH2CH2
OH OH

PCl5
CH2CH2CH2CH2 alc. KOH or
CH2=CH–CH=CH2
OH OH NaNH2
CH2CH2CH2CH2
Cl Cl
α,ω−dihalide Zn
Cl2/hν

(i) alc. KCN O

(ii) H3O⊕ (iii) ∆

4. Chemical Properties & preparation methods of chloroform

O
Lab. Method aq. NaOH
CH3– CH − CH3 H–C–ONa (salt)
| (CaOCl 2 + H2O)/∆ (excess)
OH
O
OH
CH3–C–CH3
Ind. Method CH3–C–CH3 Chloretone
CH 3 − CH − H (Hyprotic)
| aq. NaCl/electrolysis Cl CCl3
OH H–C Cl
Cl Cl
NaOH HO–NO2/∆
O2N–C Cl +H2O Chloropicrin or
H – C – CCl 3 Chloroform (–H2O)
|| Cl Nitro chloroform
O (Tear Gas)
(Chloral)
(i) alc. KOH 
R–N = C
3Cl2/hν ••
CH4 (ii) R–NH2
air & light
COCl2 + HCl
(Oxidation) Phosgene (Poisonous)

Zn+HCl
CH2Cl2
Reduction (–HCl)

Zn+H2O
CH4
(–3HCl)
Ag/∆
HC≡CH
5. Chemical Properties & preparation methods of carbon tetra chloride

aq. NaOH
Na2CO3
Cl2/hν (excess)
CHCl3 (salt)
(–HCl)

3Cl2/AlCl3 2HF/SbCl5
CS2 Cl Cl CF2Cl2+ 2HCl
(–S2Cl2)
C (Freon-012)
Cl Cl

4Cl2/hν Carbon tetra Oxidation

CH4 COCl2+2HCl
(–4HCl) chloride H2O[Steam] Phosgene (Poisonous)

9Cl2/500ºC
CH3–CH2–CH3 Reduction
(–C2Cl6) CHCl3
Fe/H2O
(–8HCl)
 ALCOHOL

1. General methods of preparation

H2O/H⊕
CH2 = CH2
Θ
BH3/H2O2/OH
CH2 = CH2

(AcO)2 Hg/H2O/NaBH4
CH2 = CH2

aq. NaOH
CH3CH2–Cl

CH3MgBr/H3O⊕
H–C–H
||
O
H2/Pd or LiAlH4/H⊕
CH3–CH=O
reduction

LiAlH4/H⊕
CH3–C–Cl CH3CH2OH
|| reduction
O Ethyl alcohol
LiAlH4/H⊕
CH3–C–OCH2CH3
|| reduction
O
NaOH
CH3–C–OCH2CH3
||
O
H 3O ⊕
CH3–C–OCH2CH3
|| reversible reaction
O
NaNO2 + HCl
CH3CH2–NH2
or HNO2

dil. H2SO4
CH3CH2–O–CH2CH3
∆
2. Chemical reactions of alcohol
PCl3 or PCl5 or SOCl2
R–Cl

Lucas reagent
R–Cl
(H–Cl + ZnCl2)

H–NH2/Al2O3/∆
R–NH2
(–H2O)

H–O–NO2/100ºC
R–O–NO2 (Alkyl nitrate)
(–H2O)

H2SO4/100ºC
R–HSO4 (Alkyl hydrogen sulphate)
(–H2O)

O
O
R'–C–OH/H⊕
R'–C–OR
(–H2O)

O
O
CH3–C–Cl
CH3–C–OR'
(–HCl)

R–O–H (i) Na (ii) R'–X

R–O–R'
Alcohol Williamson synthesis

CH2=C=O
CH3–C–OR
Ketene
O
HN=C=O
H2N–C–OR
Isocyanic acid
O

R'MgX
R'–H
Grignard reagent

O
O
Ph–C–Cl
Ph–C–OR
Schotten-Baumann reaction

HI + red P
R–H
reduction

CH2N2/∆
R–O–CH3

H2SO4/170ºC
Alkene

H2SO4/140ºC
R–O–R
Oxidation [O]
aldehyde/ketone Carboxylic acid
 3. Formation of ethanol by fermentation

(1) Cane sugar Crystalisa

  tion → molasses Invertase
 →
Sucrose hydrolysis

Invert sugar  → EtOH


Zymase

30% Surcose (30-32% Invert sugar)

(2) grain 
→ Starch   → maltose 
Diastase
→ glucose 
Maltase
→ EtOH

Zymase
HOH hydrolysis

ETHER

1. General methods of preparation

dry Ag2O
(1) C2H5I

C2H5ONa
(2) C2H5I
Williamson ether synthesis

Conc. H2SO4, 140ºC

(3) C2H5OH C2H5–O–C2H5
Williamson continuous ether process

Cl2–CH2–O–CH2–CH3
(4) C2H5–Mg–Br
Lower ether

Al2O3
(5) C2H5OH
180-200ºC
2. Chemical reactions

H2SO4 ⊕
[CH3CH2–OH–CH
•• 2CH3] HSO4

BF3 CH3CH2 O
••
BF3
CH3CH2
••
CH3CH2 – O –CH2CH3
RMgX
R–Mg–X
Grignard reagent
CH3CH2–O–CH
•• 2CH3

HF ⊕
[CH3CH2–OH–CH
•• 2CH3] F

HCl ⊕
[CH3CH2–OH–CH
•• 2CH3] Cl

HI or HBr
CH3CH2I + CH3CH2OH (Ziesel reaction)
(Cold and conc.)

•• HI or HBr
CH3CH2 –O– 2 CH3CH2I + H2O
•• CH2CH3 (Hot and cond.)
Diethyl ether
BCl3
3 CH3CH2–Cl + (CH3CH2)3BO3

PCl5 / ∆
2 CH3CH2–Cl + POCl3

CH3COCl /AlCl3
CH3CH2–Cl + CH3–C–OCH2CH3
O
CO / BF3 / HgO / ∆ CH3CH2–C–O–CH2CH3
O
dil.H2SO4 / ∆
2 CH3CH2–OH
Cl2 / dark
CH3–CH–O–CH–CH3 (α,α'-dichloro ether)
Cl Cl
Cl2 / sunlight
CCl3–CCl2–O–CCl2–CCl3 (Per chloro ether)
3. General reactions

air
(1) Et-O-CH(CH3)-O-O-H

(2) PC C2H5Cl + POCl3

(Hot & Conc.) 2HI

(3) 2C2H5I + H2O
Determination of alkoxy
groups by Ziesel's method

(Cold & Dil) HI

(4) C2H5I + C2H5OH

Cl2, 20ºC
(5) α, α'- Dichloro ether
dark, ∆

Cl2
(6) (C2Cl5)2O penta chloro eth
hν, sunlight
••
CH3CH2 –O–
••
CH2CH3
Diethyl ether
Conc. H2SO4
(7) Oxonium salt

BF3
(8) (Et)2O→BF3

CO, 150ºC
(9) Et–COOEt
H2O & BF3, 500 atm

CH3COCl
(10) CH3COOC2H5
anhy ZnCl2

Al2O3
(11) CH2=CH2
380ºC

dil. H2SO4
(12) EtOH
 PHENOL

 Synthesis of phenol & chemical reactions

OH
H2O
Br Br
ONa
Br2 Br
Na or OH OH
NaOH Halogenation CCl4 or Br
+
CS2
NaHCO3
Br
NH2 OH OH
dil. HNO3
NH3/Al2O3/∆ NO2
+
(–H2O) Nitration NO2

OH
Zn HNO3
O2N NO2
H2SO4
Reduction
Cl NO2

PCl5 OH
+ Ph3PO4 25ºC SO3H
(Major) Sulphonation
O H2SO4 OH
HO OH CH3–C–CH3 / H2SO4 100ºC

CH3–C–CH3 (–H2O) SO3H

(Bis-Phenol- A)
OH OH
O CH3Cl / AlCl3
OH CH3
O O C C O
+
O C C Friedel – Craft
H2SO4
OH reaction
–H2O CH3
(Phenolphthalein)
O OH OH
O
O COCH3
C–Cl CH3–C–Cl / AlCl3
C–O +
Schotten Baumann Friedel – Craft
OH reaction OH reaction
COCH3
60º / AlCl3 O OH
OH
O–C–CH3
O
Phenol CH3Cl / KOH (alc.) CHO
COCH3 Fries CH3–C–Cl +
Rearrangement
Reimer-Tiemann
(–HCl)
reaction
CHO
OH 100ºC/AlCl3 OH
OH
COCH3 OH
CCl4 / KOH COOH
H2 / Pd +
Reimer-Tiemann
reaction
(Cyclohexanol) COOH

OH OH

FeCl3
Voilet colour (i) HCN + HCl / AlCl3 CHO
Neutral +
(ii) H3O⊕
OH Gattermann Reaction CHO

K2S2O8 / KOH OCOONa OH

(Quinol) (i) NaOH
Elb's pursulphate (ii) CO2 / 140ºC H rearranged COONa
oxidation
OH Kolbe-schmidt
reaction
OH
COOH
H OH KMnO4 / H⊕ Liebermann nitroso test H2SO4 H2O
oxidation NaNO2 + H2SO4 Green Red
H OH
NaOH
COOH
N=O Blue
(mesotartaric acid)
O OH OH
Lederer Mannase
NaOH
air & light Reaction CH2OH Bakelite
CH2=O/H⊕ + ∆
Polymer

O CH2OH
 ALDEHYDES AND KETONES

1. Preparation methods of carbonyl compounds

O3/ H2O / Zn
C=C
H2O / HgSO4
—C≡C—
Θ
BH3 / H2O2 / OH
—C≡C—

Cl ar. NaOH
(Gemdihalide) C=C
Cl
C=O
oxidation
(1º/2º-alcohol) CH–OH Aldehyde
PCC or collin's
reagent or
Ketone
H 3O ⊕
Oxime C=N–OH

OR H3O⊕
acetal / Ketal C
OR
(i) RMgX
R–C≡N (ii) H3O⊕

(i) SnCl2 / HCl

R–C≡N (ii) H3O⊕

O
H2 /Pd + BaSO4
R–C–Cl
Rosenmund
reduction
2. Chemical properties of carbonyl compounds

Θ
H–CN / OH cat. OH
C (Cyanohydrin)
CN

(i) R–MgX OH
C
(ii) H3O ⊕
(alcohols)
R

(i) Br Zn CH2 COOR OH

(Reformatsky reaction)
C
(ii) H2O CH2–COOR

Θ⊕
OH
(i) R–C≡C Na (Acetylinic alcohol)
C
(ii) H⊕ C ≡ C–R

OH
NaHSO3 (White Crystal)
C
SO3Na

H2O / H⊕ OH
C (Unstable)
OH

2 RO–H / H⊕ OR
(Acetal or Ketal)
C
(–H2O) OR
C=O
Aldehyde 2 RS–H / H⊕ SR
Thioacetal or Thioketal
C
or (–H2O) SR
Ketone
H–O–CH2
⊕ O–CH2
H–O–CH2 H
C (Cyclic acetal or ketal)
(–H2O) O–CH2

aldol reaction
β–Hydroxy aldehyde / Ketone
dil. NaOH

COOR
(i) H2C Pyridine
COOR
C = CH–COOH (Knoevenagel reaction)
(ii) H3O⊕ / ∆

H2N–Z / H⊕ C = N–Z
(–H2O )
Witting reaction
C = CH2 + Ph3P=O
Ph3P= CH2

H2 / Pd or LiAlH4 / H⊕ CH–OH

Zn – Hg / HCl Reduction
CH2

NH2–NH2 / KOH
CH2
∆
3. Special points

1 Distinction between formaldehyde, acetaldehyde and acetone :

S.No. Reagent / Test HCHO CH3CHO CH3COCH3

Coloured Coloured
1 Brady reagent / DNP Coloured Crystal
crystal crystal

2 Tollen's reagent Silver mirror Silver mirror ×

3 Fehling's solution Red Red ×

4 Benedict's solution Red Red ×

Corrosive sublimate
5 Black Black ×
(HgCl2)

6 Schiff's reagent Pink Pink ×

7 Iodoform test × Yellow Yellow

8 Pyrogallol test White × ×

Legal test
9 (Sod. nitropruside / × Red Red
NaOH)

m-dinitrobenzaldehyde
10 × × Blue
test
 Preparation methods of carboxylic acid

Cl
aq. NaOH
R–C Cl
Cl

R–MgCl (i) CO2

(ii) H3O⊕

H2O/H⊕
R–C–Cl
O

H2O/H⊕
R–C–OR′
O

R–C–OH
COOH
H 2C ∆ O
(–CO2)
COOH Carboxylic acid
or CnH2nO2
H2O/H⊕
R–C≡N

⊕
R–C–H KMnO4/H /∆
oxidation
O
KMnO4/H⊕/∆
R–CH2OH oxidation

(AcO)2Mn
CH3–CH3 oxidation

O3/H2O
R–CH=CH2

O3/H2O
R–C≡CH

CO H2O
RONa RCOONa
High temp.

H3PO4
R–CH=CH2 CO + H2O
High temp. & Pres.
 Chemical properties of carboxylic acid

Sodalime Na 1
R–H ∆ R–C–ONa + H2 ↑
|| 2
O
(i) NaOH NaOH
R–R R–C–ONa + H2O
(ii) electrolysis ||
O
NaHCO3
R–C–ONa + H2O + CO2 ↑
||
(i) AgOH O

H
R–Br

OO
(ii) Br2/CCl4 Na2CO3
R–C–ONa + H2O + CO2 ↑

C
of
||

-H
O

e to
Ca(OH)2 CH2N2

Du
R–C–R ∆ R–C–OCH3 + N2 ↑
||
O O O
||
R′–C–Cl
R–C–OH R–C–O–C–R′ + HCl
MnO || || ||
R–C–R O
300°C O O
O
Carboxylic acid CH2=C=O
R–C–O–C–CH3
|| ||
O O
GR
Alkane
p
l grou

R′OH/H⊕
R–C–OR′
f Alky

(–H2O) ||
H
Due to -O

O
α-H o
Due to

PCl3/PCl5/SOCl2
R–C–Cl
||
O
P2O5/∆
(–H2O)
R–C–O– C–R
H.V.Z Reaction || ||
R–CH–COOH Br2/red P/∆ O O
|
Br ●●
NH3 ⊕ ∆
R–C–ONH4 R–C–NH2
(–H2O) ||
||
α-Halogenation product O
O
is obtained by Hell-Volhard-
Zelinsky reaction HI/red P/∆
reduction
R–CH3

LiAlH4/H⊕
reduction
R–CH2OH
 1. Preparation methods of acid chloride

HCl
CH2=C=O

PCl5/PCl3/SOCl2
CH3–C–OH CH3–C–Cl
∆
O O
or Acetyl
Chloride
(CH3CO)2O

PCl5/PCl3/SOCl2
CH3–C–ONa ∆
O

2. Chemical properties of acid chloride

O
/AlCl3
CH3–C– + HCl
Friedal craft acylation
Acetophenone
H2O
CH3–COOH + HCl O
Acetic acid Hydrolysis H2/Pd/BaSO4
C2H5ONa Rosenmund reaction CH3–C–H + HCl
CH3–COOC2H5 + NaCl Ethanol
Sod. ethoxide
Ethyl ethanoate
LiAlH4/H2O
CH3–CH2–OH + HCl
CH3–COOC2H5 + HCl C2H5OH Complete reduction
Ethanol
Ethyl ethanoate Alcoholysis or
(Esterification)
O
NH3 CH3–C–Cl (CH3)2 Cd
CH3–CONH2 + HCl CH3–C–CH3 + CdCl2
Ammonolysis Dimethyl cadmium
Ethylamide O Propanone
Acetyl chloride
O
ZnCl2
(i) CH2N2
CH3COOC2H5 + CH3COCl C2H5OC2H5 CH3–CH2–C–OH [ARNDT-EIENSTERT]
Ethyl ethanoate (ii) Ag2O (iii) H2O
Propanoic acid reaction
CH3–NH2 KCN
CH3–CONHCH3 + HCl CH3COCN +KCl
N-methylethanamide Methyl amine Ethanoyl chloirde
Ο
⊕
CH3–C–ONa
CH3–CO–O–COCH3 + NaCl
Sod. Acetate
Acetic anhydride

CH3–CO–O–COCH3 + HCl CH3COOH

Acetic anhydride Pyridine
3. Preparation methods of ester
H–OCH2CH3/H2SO4
CH3–C–OH
|| (–H2O)
O

O
||
CH3–C–O
H–OCH2CH3
O
(–CH3COOH)
CH3–C–O
||
O

H–OCH2CH3
CH3–C–OCH2CH3
CH3–C–Cl ||
(–HCl) O
||
O Ethyl acetate

CH3CHO
CH3–C–OAg
|| (–AgBr)
O
Tischenko reaction
2CH3–CH=O
(Al(OEt)3

Baeyer villiger oxid.

CH3–C–CH2CH3
|| (CF3CO3H
O
CH2=CH2
CH3–COOH
CH3COOH, BF3
CH2=CH2

4. Chemical properties of ester

O O
500ºC H2O/H⊕
CH3– C –OH + CH2=CH2 Pyrolysis CH3– C –OH + C2H5OH
Ethanoic acid Ethene Acid hyrolysis
Ethanoic acid
O O
NaOH
CH3– C –OH
–C2H5I Alkaline hydrolysis CH3– C –ONa + C2H5OH
Ethanoic acid Sod. ethanoate

O NaBH4/H2O
No reaction
NH3 Reduction
CH3– C –NH2
–C2H5OH
Ethanamide
O O
CH3–NH2 LiAlH4/H2O
CH3– C –NHCH3 + C2H5OH CH3– C –OC2H5 2C2H5OH
Reduction
N-Methyl Ethanamide Ethyl ethanoate Ethanol

O ⊕ Na/C2H5OH
C2H5ONa
CH3– C –CH2COOC2H5 + C2H5OH Bouveault 2C2H5OH
Ethyl aceto acetate (β-ketoester)
Claisen Blanc reduction Ethanol
condensation
O PCl5/∆
C3H7–O–H/Alkoxide CH3COCl + C2H5Cl
CH3– C –O–C3H7 –POCl3
Trans esterification Ethanoyl chloride
Propyl ethanoate

H2N – OH
CH3– C –NH–OH
OH Hydroxyl amine
CH3MgBr/H3O⊕ O
CH3–C–CH3 N-Hydroxy ethanamide
Grignard reagent
CH3 NH2–NH2
Tert. Butyl alcohol CH3– C –NH–NH2
Hydrazine
O
5. Preparation methods of acid anhydride

CH3COOH
CH2=C=O

O O
|| ||
CH3–C–ONa
CH3–C–OH
(–NaCl)

O
||
O O CH3–C
|| || O
CH3–C–OH/Pyridine CH3–C
CH3–C–Cl (–HCl) ||
O O
|| P2O5/∆
2CH3–C–OH Acetic
(–H2O)
anhydride
O
||
O–C–CH3 Distillation/∆
CH3–CH (–CH3CHO)
O–C–CH3
||
O

6. Chemical properties of acid anhydride

H2O (i) LiAlH4 (ii) H3O⊕
2CH3COOH Hydrolysis 2CH3CH2OH
Reduction Ethanol
Acetic acid
O O O
C2H5OH H2N–
CH3– C –OC2H5 –NH–C–CH3 + CH3–C–OH
–CH3COOH Aniline Acetanilide
Ethyl acetate (Acetic acid)

O O O O O
2NH3 PCl5
CH3–C–NH2 + CH3–C–ONH4 CH3 – C –O– C –CH3 2CH3–C–Cl + POCl3
Ammonolysis Acetyl chloride
Ethanamide Amm.acetate Acetic O O
O O anhydride N–O–N O
Cl2/hν O O O
CH3–C–Cl + ClCH2–C–OH 2CH3–C–O–N
Nitrogen pentaoxide
Acetylchloride Monochloro acetic acid Acetyl nitrate O
O O
O
Dry HCl
C2H5NH2 CH3C–Cl + CH3–C–OH
CH3–C–Cl–NHC2H5 + CH3COOH Acetyl chloride Acetic acid
N-Ethyl ethanamide Acetic acid
O
O CH3CHO/AlCl3
CH3 C–OCH3
Acetaldeyde C
C–CH3 + CH3COOH H C–OCH3
/AlCl3
Anhy. AlCl3 O
Acetophenone (Friedal Craft Acylation) Ethylidene acetate
Perkin reaction
–CH=CH–COOH
–CHO/CH3COONa Cinnamic acid
7. Preparation methods of acid amide

••
NH3
CH3–C–Cl
|| (–HCl)
O

••
NH3
CH3–C–OCH3
|| (–CH3OH)
O

H2O/OH CH3–C–NH2
CH3–C≡N ||
Partial hydrolysis
O
Acetamide

⊕ ∆
CH3–C–ONH4 (–H2O)
||
O

8. Chemical properties of acid amide

P2O5/∆ H2O/H⊕
CH3–C≡N CH3–C–OH + NH3↑
(–H2O)
O
CH3–C–NH2
Reduction NaOH
CH3–CH2–CH2 O CH3–C–ONa + NH3↑
Na/EtOH
or LiAlH4/H⊕ Acetamide O

Br2 + KOH NaNO2 + HCl

CH3–NH2 CH3–C–OH
Hoffmann or HNO2
bromamide O
reaction
 9. Method of preparation & Chemical properties of formic acid

(1) CO2+H2O+2Ag+Ag2O
Tollen's Reagent

(2) +2 HgCl2 Hg2Cl2 + CO2 + 2HCl

White ppt

+Hg2Cl2
(a) 2HCl + CO2 + 2Hg
black ppt.

Fehling Solution
(3) Cu2O + H2O + CO2
+2CuO (red ppt.)
acidic. dichromate
(4)
2 KHSO4 + Cr2(SO4)3 + 2H2O + 3CO2
200ºC H2SO4 green + K2Cr2O7+ 5H2SO4 (Orange)
CO + NaOH
6-10 atm.HCOONa –Na2SO4 Acidic permangnate
(5)
+2MnSO4 + 2KHSO4 + 5CO2 + 8H2O
BF3 200-300ºC HCOOH
CO + H2O +2KMnO4 + 3H2SO4 (Colour less)
20-25 atm. Formic acid
alkaline permaganate
(6)
Oxid. 2MnO2 + 3K2CO3 + 5H2O + 2KMnO4+
CH3OH Oxid. HCHO 4KOH (brown ppt.) pink

160º, ∆ H2O + CO
(7)

conc. H2SO4
(8)
H2O + CO

Oxid.
(9)
CO2 + H2O

Na-Salt
(10)
COONa
360º C
+ H2
COONa
 10. Method of preparation & Chemical properties of benzoic acid

(1) due to COOH

HOH NaOH or NaHCO3

(1) C6H5COCl or C6H5CONH2 C6H5COONa
(1)
or C6H5COOR

NO2 (2) Ca(OH)2

(C6H5COO)2 Ca
CO COOH
(2) HOH ∆
O
COOH Ammomium Salt
CO (200-300ºC) PO
(3) C6H5CONH2 2 5 C6H5CN
∆, –H2O
(Zn, Cr, Ni)

Distillation of
(4) (C6H5)2C = O
CO2, H2O Ca salt
(3) C6H5MgBr Benzophenone
C6H5COOH
(m-directing)
CaCl2/AlCl3 PCl3,PCl5, SOCl2
(4) C6H6 (5) C6H5COCl
H 2O

(5) HO–C6H4–COOH
Zn/∆ (6) Hunsdiecker reac. C6H5Br
(o, m, p) Ag-salt+Br2

P 2O 5
(6) C6H5–CH3 Side-chain Oxidation (7) (C6H5CO)2O
MnO −4 /OH –H2O

KOH, Fe C2H5OH
(7) C6H5 CCl3 (8) C6H5COOC2H5

HOH LiAlH4
(8) C6H5–CN (9) C6H5CH2OH

oxid. oxid.
(9) C6H5–CH2OH C6H5CHO Cl2/FeCl3
(10)
m-chloro benzoic acid

Conc. H2SO4
(11)
m-sulphobenzoic acid

COOH COOH

nitration 140ºC
(12)
30ºC
NO2 NO2 NO2

Note : Test of benzoic acid

C6H5COOH + FeCl3(Neutral) → Acid complex (Red Brown ppt.)

1. Preparation methods of amine
Br2 + KOH (excess)
R–C–NH2
|| Hoffmann bromamide reaction
O
N3H/H⊕
R–C–OH
|| Schmidt reaction
O

(i) NaN3 (ii) H3O⊕

R–C–Cl
|| Curtius reaction
O

H (i) dry HCl (ii) H3O⊕

R–C–N
|| OH Lossen reaction
O

O
|| (i) KOH (ii) R–X (iii) H3O⊕
C N–H
C Gabriel phthalimide reaction
||
O

(i) NH3/H⊕ (ii) H2/Pd

C=O Reductive amination
(ald./ketone)

Cl–NH2 R–NH2
R–MgCl (–MgCl2) Alkyl amine

NH3/∆
R–X or R–OH

H3O⊕
R–N C
Complete hydrolysis

2KOH
R–N=C=O
Wurtz reaction
O
|| LiAlH4/H2O
R–C–NH2 Reduction

LiAlH4/H2O
R–C≡N
Reduction

O LiAlH4/H2O
R–N O
Reduction

(Baryta water) Ba(OH)2

R–CH–NH2
| –BaCO3 , –H2O
COOH
2. Chemical properties of amine

O
||
⊕ H 2O Cl–C–Cl R–N=C=O
R–NH3 OH (–2 HCl) (Alkyl isocyanate)
O
O ||
⊕ || CH3–C–OH CHCl3+alc.KOH
RNH3 O–C–CH3 R–N C
Hoffmann
n (Pungent smell)
Carbyl amine rx

⊕
HCl CH3–CH=O/H⊕ CH –CH=N–R
R–NH3 Cl 3
(Schiff's Base)

⊕
R–NH3 HAuCl4 HAuCl4 Cl–N=O
R–NH2 R–Cl
Tilden reagent
NO2
⊕
Na(Metal) 1
NO2 HO NO2 R–NHNa + H 2↑
⊕ 2
NO2
R–NH3 O NO2
Picric acid R–X
NO2 R–NH–R → R3N
(–HX)
2° amine 3° amine
O
⊕ –2 || O
H2SO4 CH3–C–Cl ||
R–NH3 2 SO 4 R–NH–C–CH3
(–HCl)
O O
|| ||
⊕ –2 Ph–C–Cl
∆ H2PtCl6 R–NH–C–Ph
Pt metal RNH3 PtCl6 (–HCl)
Schotten Bauman reaction

CH3MgCl Cl
CH4 + Mg
NHR

Br2 + KOH
Halogenation R–NH–Br

CS2 , HgCl2
RNCS
Hoffmann's
mustard oil reac.
C6H5 – SO2Cl
R–NH–SO2–C6H5
Hinsberg reagent

HNO2
R–OH
3. Preparation methods of aniline

Br2+KOH
C–NH2 (excess)
O

N3H/H⊕
C–OH

(i) NaN3 (ii) H3O⊕

C–Cl

(i) dry HCl (ii) H3O⊕

C–NH–OH
••
NH2
O

(i) NaNH2
Cl Aniline
(ii) NH3(liq.)

H 3O ⊕
N C

2 KOH
N=C=O

O Sn/HCl
N Reduction
O

Cl – NH2
C6H5MgBr

NH3
OH
ZnCl2, 300°C
[B] Reactions due to NH2 group :
⊕
NH3Cl

HCl

••
NH–R

R–X
–HX

O O
C –Cl ••
NH–C
•• –HCl
NH2

⊕
O=CH /H ••
Aniline N=CH
(–H2O)

Cl ••
C=O N=C=O
Cl
(–2HCl)

N C
CHCl3/alc. KOH

RMgX
C6H6

Hofmann
Mustard oil reaction
C6H5NCS

Hinsberg reagent
C6H5 – NH – SO2C6H5
C6H5SO2Cl2

Na
C6H5NH–Na+ + H2

NOCl
NO reaction
[C] Reactions due to ring :

CH3COCl
o- & p- Nitro aniline + H2O
then nitration mix

Direct nitration
o- & p- Nitro aniline
Exception

CH3COCl
o- & p- Bromo aniline
then Br2/CCl4 + H2O

Br2/H2O
2,4,6-Tribromo aniline (white ppt)
Test

NH2 NH2
Fuming-H2SO4
180º C Rearrangement
Aniline
SO2OH
Sulphanilic Acid

C6H5N2Cl
p- amino azo benzene
Ni/H2

Ni/H2 C6H11NH2
Cyclohexylamine test

NH2

NaOCl Light
Voilet colour

Na2Cr2O7
Aniline black
Conc. H2SO4

Na2Cr2O7
O= =O
dil. H2SO4
p-benzo quinone
* BENZENE DIAZONIUM CHLORIDE IS USED IN SYNTHESIS OF FOLLOWING AROMATIC COMPOUNDS :
H3PO2 or C2H5OH
reduction

CuCl Cl

CuBr Sandmeyer reaction

Br

CuCN/∆
CN

KI
I

NaBF4
∆
F (Beltz-Schiemann reaction)

Cu/HCl
Cl

Cu/HBr
Br Gattermann reaction

⊕ Cu/HNO2
N2Cl NO2

H2O
OH
Benzene
diazonium
chloride R–OH
O–R

N=N
OH

N=N OH

NH2
(Orange dye)

N=N NH2
Coupling reaction (ESR)
Me (yellow dye)
N
Me
Me
N=N N
Me
(yellow dye)

OH N=N
OH
(Red dye)
β-Naphthol
4. Preparation Methods and chemical properties of nitro benzene

NO2 NO2
Conc. HNO3 HNO3
∆
NO2 NO2 NO2
E.S.R NO2
Fuming H2SO4

SO3H
NO2
Cl2/AlCl3

Cl NO2 NO2
HNO3 NaNH2 NH2 +
H2SO4
O
NH2
CH3–C–O–NO2/∆ NO2 NO2
NO2
(–CH3COOH) N.S.R OH
NaOH +
NH2
Nitro Benzene OH
CF3CO3H
Oxidation NO2 NO2
⊕ CH3ONa OCH3 +
Reduction

N2Cl
Sn/HCl
HNO2/Cu NH2
or LiAlH4/H2O OCH3
Gattermann reaction or H2/Pd
Fe/H2O
N= O

dil.H2SO4
NH2
Electrolysis
rearranged
Conc.H2SO4 NH–OH HO NH2

O
Na3AsO3 or
N=N (Azoxy benzene)
CH3OH/NaOH
or glucose/NaOH
Na2SnO3 or
N=N (Azobenzene)
CH3OH/NaOH/Zn

H2O/NaOH/Zn
NH–NH (Hydrazobenzene)
 5. Preparation methods and chemical properties of nitroalkane

Sn/HCl
CH3CH2–NH2
H2/Pd
CH3CH2–NH2
Na/EtOH
CH3CH2–NH2
⊕
LiAlH4/H
CH3CH2–NH2
Zn/NH4Cl
CH3CH2–NH–OH
AgNO2 H2O/H⊕
CH3CH2–Cl CH3–CHO
O Nef reaction
CH3CH2–N
O NO2
Fuming HNO3 O==N–OH
CH3–CH3 colourless CH3–C N–OH (Nitrolic acid)
600°C
sweet
smelling
∆ liquid Tautomerism O
(aci-nitro form)
CH3–CH–COOH CH3–CH=N
| (–CO2) OH
NO2 CH3MgBr
CH4
(α-Nitro acid)
CH3
CH3CHO |
CH3–CH–CH–NO2 (Nitro-alcohol)
|
OH
Cl2/NaOH
CH3–CH–NO2
(–HCl)
Cl

∆
CO2↑ + N2↑ + H2O
Pyrolysis
 6. Preparation methods and chemical properties of Alkyl cyanide

KCN H2/Pd
CH3–Cl reduction CH3CH2–NH2

Na/EtOH
CH3CH2–NH2
reduction
LiAlH4/H⊕
P2O5/∆ CH3CH2–NH2
CH3–C–NH2 reduction
|| (–H2O)
O SnCl2/HCl H3O⊕
CH3–C ≡ N Stephen reduction
CH3–CH=NH CH3–CHO
Methyl cyanide
(i) CH3MgBr CH3–C–CH3
P2O5/∆ (ii) H3O⊕ ||
CH3–CH==N–OH O
(–H2O) (i) ROH
CH3–C–OR
(ii) H3O⊕ ||
O
H2O/OH
CH3–C–NH2
||
O
Cl–CN H2O/H⊕
CH3MgBr CH3–C–OH
||
O

7. Preparation methods and chemical properties of Alkyl isocyanide

AgCN H3O⊕
CH3–Cl CH3NH2 + HCOOH

H2/Pd
CH3–NH–CH3
reduction
CH3–N C
P2O5 Na/EtOH
CH3–NH–C–H Methyl CH3–NH–CH3
|| ∆ reduction
isocyanide
O
O3/∆
CH3–N=C=O + O2↑

CHCl3 2HgO
CH3–NH2 CH3–N=C=O + Hg2O
alc. KOH
(MIC)
  Carbohydrate
Nut shell classification of Carbohydrates

Sugars Non - Sugars

Polysaccharides
Monosaccharides Oligosaccharides
Triose Disaccharide
(Glyceraldehyde (sucrose, Maltose, Homopolysaccharide Hetropolysaccharide
Dihydroxyacetone) Lactose) (Starch, cellulose, glycogen (Hygluronic acid, chondritin sulphate,
Trisaccharide chitin, dextrin, insulin) heparin, pectine, hemicellulose)
Tetrose
(raffnose)
D-Erythrose
Pentose Tetrasaccharide etc.
(D-Ribose)
Hexose

Aldohexose Ketohexose
(Glucose) (Fructose)

 Glucose

Preparation of glucose

(1) From sucrose

+
C12H22O11 + H2O H→ C6H12O6 + C6H12O6

sucrose glucose fructose

(2) From starch

+
(C6H10O5)n + nH2O H 
→ nC6H12O6
393K, 2 – 3 atm
 HI, ∆
n-hexane

CHO CH = N – OH
NH2OH
(CHOH)4 (CHOH)4

CH2OH CH2OH
OH
CH
HCN CN
(CHOH)4
CH2OH

COOH
Br2/H2O
(CHOH)4
CH2OH
Gluconic acid
Ac2O
Penta Acetate
COOH
HNO3
Saccharic acid (CHOH)4

Chemical reaction COOH

Cyclic structure of glucose

O
H – C – OH H –C 1 HO – C – H

H OH H 2
OH H OH
O O
HO H HO 3 H HO H

H OH H 4
OH H OH

H H 5
OH H

CH2OH 6 CH2OH
CH2OH
α - D - (+) Glucose β - D - (+) - Glucose

m.p. = 419 K m.p. = 423 K

≈ 36%
≈ 64%
θ = + 112° Final θ = + 52.7
θ = + 19.2
 6
CH2OH CH2OH
O 5 O O
H H H H H OH
4 1
HO OH H OH HO OH H H
3 2

Pyran H OH H OH

α - D - (+) - Glucopyranose β - D - (+) - Glucopyranose

Disaccharide
(1) Sucrose →
C12 H22 O11 + H2O → C6 H12 O6 + C6 H12 O6
Dextrorotatory D (+) glucose D(–) fructose
θ = + 52.5 θ = – 92.4°
→ C1 – (α - glucose) & C2 (β - fructose) Glucosidic linkage
→ Inversion take place
(2) Maltose →
C1 (α - D-Glucose) & C4 (α - D-glucose) Glucosidic linkage
(3) Maltose → (Milk Sugar)
Glycosidic linkage between C1 of galactose and C4 of glucose
Reducing Sugar → All monosaccharide, Lactose, maltose
Non Reducing Sugar → Polysaccharide, Sucrose

Structure of fructose

CH2OH
HOCH2 – C – OH C=O HO – C – CH2OH

HO H HO H HO H
O
O
H OH H OH H OH

H H OH H

CH2OH CH2OH CH2OH

α - D (–) fructo furanose D (–) - fructose β - D - (–) - fructo furanose
6
O O
HOH2C CH2OH HOH2C OH
5 2
H OH H CH2OH
HO H HO 1
H 4 3
OH H OH H
α - D - (–) - fructofuranose
 Polysaccharide

Starch Cellulose Glycogen

Amylose → α-D (+) glucose C1 – C4 Glucosidic linkage
by C1 – C4 glucosidic linkage in β - D-glucose unit Similar to amylopectin
Unbranched linkage

Amylopectin →
α - D - glucose (C1 – C4)
glucosidic linkage→ Branched

 Protein
Proteins are the most abundant biomolecules of the living system. Chief sources of proteins are milk, cheese,
pulses, peanuts, fish, meat, etc. They occur in every part of the body and form the fundamental basis of
structure and functions of life. They are also required for growth and maintenance of body. The word protein is
derived from Greek word, ‘‘Proteios’’ which means primary or of prime importance. All proteins are polymers
of α-amino acids.
Amino Acids :-
Amino acids contains amino (–NH2) and carboxyl (–COOH) functional groups. Depending upon the relative
position of amino group with respect to carboxyl group, the amino acids can be classified as α, β, γ, δ and so on.
Only α-amino acids are obtained on hydrolysis of proteins. They may contain other functional groups also.
R – CH – COOH
NH2
α-amino acid (R = side chain)
All α-amino acids have trivial names, which usually reflect the property of that compound or its source. Glycine
is so named since it has sweet taste (in Greek glykos means sweet) and tyrosine was first obtained from cheese
(In Greek, tyros means cheese). Amino acids are generally represented by a three letter symbol, sometimes one
letter symbol is also used. Structures of some commonly occurring amino acids along with their 3-letter and 1-
letter symbols are given in Table

COOH
Natural Amino Acids H2N H
R

Name of the Characteristic feature Three letter One letter

amino acids of side chain, R symbol code
1. Glycine H Gly G

2. Alanine – CH3 Ala A

3. valine* (H3C)2CH– Val V

4. Leucine* (H3C)2CH-CH2– Leu L

 5. Isoleucine* H3C–CH2–CH– Ile I
CH3
6. Arginine* HN=C–NH–(CH2)3– Arg R
NH2

7. Lysine* H2N–(CH2)4– Lys K

8. Glutamic acid HOOC–CH2–CH2– Glu E

9. Aspartic acid HOOC–CH2– Asp D

10. Glutamine H2N–C–CH2–CH2– Gln Q

11. Asparagine H2N–C–CH2– Asn N

12. Threonine* H3C–CHOH– Thr T

13. Serine HO–CH2– Ser S

14. Cysteine HS–CH2– Cys C

15. Methionine* H3C–S–CH2–CH2– Met M

16. Phenylalanine* C6H5–CH2– Phe F

17. Tyrosine (p)HO–C6H4–CH2– Tyr Y

–CH2
18. Tryptophan* Trp W

N
H
H 2C
19. Histidine* NH His H

N
COOHa
20. Proline HN H Pro P

CH2

* essential amino acid, a = entire structure

Classification of Amino Acids

 Amino acids are classified as acidic, basic or neutral depending upon the relative number of amino and carboxyl
groups in their molecule. Equal number of amino and carboxyl groups makes it neutral; more number of amino
than carboxyl groups makes it basic and more carboxyl groups as compared to amino groups makes it acidic.
The amino acids, which can be synthesized in the body, are known as non-essential amino acids. On the other
hand, those which cannot be synthesized in the body and must be obtained through diet, are known as
essential amino acids (marked with asterisk in Table).
Amino acids are usually colourless, crystalline solids. These are water-soluble, high melting solids and behave
like salts rather than simple amines or carboxylic acids. This behaviour is due to the presence of both acidic
(carboxyl group) and basic (amino group) groups in the same molecule. In aqueous solution, the carboxyl group
can lose a proton and amino group can accept a proton, giving rise to a dipolar ion known as zwitter ion. This is
neutral but contains both positive and negative charges.
O O

R – CH – C – O – H R – CH – C – O–
+
:NH2 NH3
(Zwitter ion)

In zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids and bases.
Except glycine, all other naturally occurring α-amino acids are optically active, since the α-carbon atom is
asymmetric. These exist both in ‘D’ and ‘L’ forms. Most naturally occurring amino acids have L-configuration. L-
Aminoacids are represented by writing the –NH2 group on left hand side.

Structure of Proteins :-
You have already read that proteins are the polymers of α-amino acids and they are connected to each other by
Peptide bond or peptide linkage. Chemically, peptide linkage is an amide formed between –COOH group and –
NH2 group. The reaction between two molecules of similar or different amino acids, proceeds through the
combination of the amino group of one molecule with the carboxyl group of the other. This results in the
elimination of a water molecule and formation of peptide bond –CO–NH–. The product of the reaction is called
a dipeptide because it is made up of two amino acids. For example, when carboxyl group of glycine combines
with the amino group of alanine we get a dipeptide, glycylalanine.

H2N–CH2–COOH + H2N – CH – COOH

–H2O CH3

H2N – CH2 – CO – NH – CH – COOH

CH3
Peptide linkage

Glycylalanine (Gly-Ala)
If a third amino acid combines to a dipeptide, the product is called a tripeptide. A tripeptide contains three
amino acids linked by two peptide linkages. Similarly when four, five or six amino acids are linked, the
respective products are known as tetrapeptide, pentapeptide or hexapeptide, respectively. When the number
of such amino acids is more than ten, then the products are called polypeptides. A polypeptide with more than
hundred amino acid residues, having molecular mass higher than 10,000 u is called a protein. However, the
distinction between a polypeptide and a protein is not very sharp. Polypeptides with fewer amino acids are
likely to be called proteins if they ordinarily have a well defined conformation of a protein such as insulin which
contains 51 amino acids.
Proteins can be classified into two types on the basis of their molecular shape.
(a) Fibrous proteins
When the polypeptide chains run parallel and are held together by hydrogen and disulphide bonds, then
fibre-like structure is formed. Such proteins are generally insoluble in water. Some common examples are
keratin (present in hair, wool, silk) and myosin (present in muscles), etc.
(b) Globular proteins
This structure results when the chains of polypeptides coil around to give a spherical shape. These are
usually soluble in water. Insulin and albumins are the common examples of globular proteins.
Structure and shape of proteins can be studied at four different levels, i.e., primary, secondary, tertiary
and quaternary, each level being more complex than the previous one.
(i) Primary structure of proteins : Proteins may have one or more polypeptide chains. Each polypeptide in
a protein has amino acids linked with each other in a specific sequence and it is this sequence of amino
acids that is said to be the primary structure of that protein. Any change in this primary structure i.e.,
the sequence of amino acids creates a different protein.
(ii) Secondary structure of proteins: The secondary structure of protein refers to the shape in which a long
polypeptide chain can exist. They are found to exist in two different types of structures viz. α-helix and
β-pleated sheet structure. These structures arise due to the regular folding of the backbone of the
O
polypeptide chain due to hydrogen bonding between –C– and –NH– groups of the peptide bond.
α-Helix is one of the most common ways in which a polypeptide chain forms all possible hydrogen
bonds by twisting into a right handed screw (helix) with the –NH group of each amino acid residue
hydrogen bonded to the C= O of an adjacent turn of the helix as shown in figure.
 α-Helix structure of proteins

In β-structure all peptide chains are stretched out to nearly maximum extension and then laid side by
side which are held together by intermolecular hydrogen bonds. The structure resembles the pleated
folds of drapery and therefore is known as β-pleated sheet.

N N N

RCH RCH RCH

C O C O
H C O H HN
N N
HCR HCR HCR
C C
C O O H
O H H N
N
N
RCH RCH RCH
C C C
H O O
N H O
HCR N H
N
HCR
C HCR
C C
Figure : β-Pleated sheet structure of proteins

(iii) Tertiary structure of proteins: The tertiary structure of proteins represents overall folding of the
polypeptide chains i.e., further folding of the secondary structure. It gives rise to two major molecular
shapes viz. fibrous and globular. The main forces which stabilize the 2° and 3° structures of proteins are
hydrogen bonds, disulphide linkages, van der Waals and electrostatic forces of attraction.
 (iv) Quaternary structure of proteins: Some of the proteins are composed of two or more polypeptide
chains referred to as sub-units. The spatial arrangement of these subunits with respect to each other is
known as quaternary structure.
A diagrammatic representation of all these four structures is given in figure where each coloured ball
represents an amino acid.

Primary Secondary Tertiary Quaternary

structure structure structure structrue

Figure : Diagrammatic representation of protein structure (two sub-

units of two types in quaternary structure)

Figure : Primary, (a) Primary (b) Secondary (c) Tertiary (d) Quaternary
secondary, tertiary structure structure structure structure
and quaternary
structures of C N R groups
haemoglobin H O Haeme group
Denaturation of Proteins :-
Protein found in a biological system with a unique three-dimensional structure and biological activity is called a
native protein. When a protein in its native form, is subjected to physical change like change in temperature or
chemical change like change in pH, the hydrogen bonds are disturbed. Due to this, globules unfold and helix get
uncoiled and protein loses its biological activity. This is called denaturation of protein. During denaturation
2° and 3° structures are destroyed but 1° structure remains intact. The coagulation of egg white on boiling is a
common example of denaturation. Another example is curdling of milk which is caused due to the formation of
lactic acid by the bacteria present in milk.
 POLYMERS

COMMON ADDITION POLYMERS

Monomer Name Polymer Uses

H2C = CH2 Ethylene Polyethylene Bags, coatings, toys

H2C = CH–CH3 Propylene Polypropylene Beakers, milk cartons

H2C = CHCl Vinyl chloride Polyvinyl Chloride(PVC) Raincoats, pipes, floor tiles etc.

H2C = CHCN Acrylonitrile Polyacrylonitrile (PAN) Rugs

H2C = CH–C6H5 Styrene Polystyrene Cast articles

H2C=CHCH2.CO-O-CH3 Methyl Methacrylate Polymethyl High quality transparent cast

methacrylate object

F2C = CF2 Tetrafluroethylene Teflon Gaskets, insulation, bearings,

pan coatings etc.

CHF = CH2 Vinyl fluoride Tedlar Coating

CH3 – CCH3 = CH2 Isobutylene Vistanex Pressure sensitive adhesives

IMPORTANT PLASTICS & POLYMERS

NAME MADE FROM USES

Acrylic Derivatives of acrylic acid Synthetic fibres, paints

Bakelite Phenol + Formaldehyde Pens, combs, switches, electri-

cal fittings etc.

Buna- S Styrene and 1,3- butadiene Synthetic rubber

Butyl rubber Methylpropene, methyl butadiene Inner tubes

Celluloid Cellulose nitrate, camphor` Photographic films

Neoprene Chloroprene, CH2 = CCl – CH = CH2 Synthetic rubber

Nylon 66 ( Polyamide) Hexamethylene diamine + adipic acid Synthetic rubber

Orion Acrylonitrile, CH2 = CHCN Synthetic fibres

Terylene or Polyester or Dacron Ethylene glycol + Dimethyl terphthalate Synthetic fibres

Teflon CF2 = CF2 (Tetrafluroethylene) Anticorrosive, non- sticking

utensils

Polythene Ethene, CH2 = CH2 Films, bags, pipes, containers

Polyvinyl chloride (PVC) CH2 = CHCl ( Vinyl Chloride) Electrical insulation, water

proof clothing

Polyvinyl acetate (PVA) Vinyl acetate, CH2 = CHOCOCH3 Adhesive

Polyurethane Isocyanates, organic alcohols Plastic foams, adhesives

Polystyrene Styrene, CH2 = CHC6H5 Plastic foam

Polymethyl methacrylate Methyl methacrylate Substitute for glass

(Perspex)

Rayon Cellulose Synthetic fibres

Isoprene (Rubber) CH2 = CCH3 – CH = CH2 Insulators, tyres

Nylon-6 6- aminohexanoic acid Moulded articles

Lexan Bisphenol-A + Diphenylcarbonate Resins

List of Monomers & Polymers

Structure of Polymer/
Monomer(s) Common uses
Name of Polymer
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
1 G
G Branched chain
polymer
 G = –CH3
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
2 CH3 Natural rubber
CH3 Polyisoprene
(Isoprene)
G = Cl
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
3 Cl Synthetic rubber
Cl
Polychloroprene or Neoprene
(Chloroprene)
House ware, containers, bottles,
[ CH–CH2 ]n
4 CH2=CH2 (ethylene) toys, polyethylene sheets, and
Polyethene
films for packaging

[ CH–CH2 ]n House ware, toys, disposable, food

containers, packaging (Styrofoam),
5 CH=CH–Ph (styrene) Ph
cabinets for electrical and
Polystyrene
electronic gadgets
Tubes and pipes for electrical
[ CH–CH ]n
fitting, sanitary pipes, floor tiles,
6 CH2=CH–Cl (vinyl chloride) Cl
insulation for cables, as a
Polyvinyl Chloride (PVC)
substitute for leather.
[ CH2–CH ]n
CH2 = CH – C ≡ N In sweaters, blankets, and clothing
7 CN
(acrylonitrile) as a substitute for wool
Poly acrylonitrile (PAN) or Orlon

[ CF2–CF2 ]n Non-stick cooking utensils,

8 CF2 = CF2 gaskets, bearings, and insulating
Polytetrafluoro ethylene or Teflon fittings.
[ CH2–CH=CH2–(CH2)2–CH ]n
CH2=CH–CH=CH2 +
9 Ph Synthetic rubber
Ph–CH=CH2
Styrene-Butadiene Rubber (BuNA-S)
CH2=CH–CH=CH2 + [ CH2–CH=CH–CH2–CH–CH ]n
10 CH=CH2 CN Synthetic rubber
CN (BuNA-N)
COOH
O O
+
CH2–OH
11 C C–O–C–C–O Fiber, Tyre, Belts
CH2–OH
Terylene or Dacron n
COOH
COOH
COOH as a binding material for mixed
12 CH2–OH
+ plastic
CH2–OH
 O O
C C–O–C–C–O

n
Glyptal
O O
13 N–H [ NH–(CH2)5–C ]n Fiber, rope, plastic
Caprolactum Nylon-6
NH2–(CH2)6–NH2
O O
Hexamethyl diamine + Adipic
14 [NH–(CH2)6–NH–C–(CH2)4–C]n Fiber, parachutes
acid
Nylon–66
COOH–(CH2)4–COOH
O
15 Urea + HCHO [NH–C–NH–(CH2]n Fiber, unbreakable cups & plates
Urea formaldehyde resin
NH2 N NH2–CH2
H2N N NH2
N N
N N + H–C–H NH
16 Plastic sheets
NH2 O
Melamine Melamine
formaldehyde resin

OH OH
OH
Insulating material for electrical
17
+ HCHO n goods thermosetting plastic

Bakellite
[ CH2–CH ]n Synthetic carpets, automobile
CH2 =CH–CH3
18 CH3 parts, packaging, toys, and house
(Propylene)
Polypropylene ware
[ CH2–CH ]n
CH2=CH–OCOCH3
19 OCOCH3 Adhesives, as binder for paints
(Vinyl acetate)
Polyvinyl acetate

[ CH2–CH ]n
CH2=CH–CO2CH3
20 COOCH3 As a substitute of glass
(methyl methacrylate)
Polymethyl methacrylate
(Plexiglass, Lucite)
 Cl Air and water proof packaging
CH2=CCl2 [ CH2–C ]n films. Its copolymer with vinyl
21 [Vinylidine chloride] Cl chloride is used for making
(1, 1-dichloroethene) Polyvinylidine conveyer belts and acid proof
chloride
(Saran) ropes.

CH3
As lining and insulators for cables
CH2=C(CH3)2 [ CH2–C ]n
22 Its copolymer with isoprene is
(Isobutene) CH3
used for manufacturing tyres.
Polyisobutene
Electrical switches, lamination,
23 Phenol and formaldehyde Bakelite
etc.
Ion-exchange resin, adhesives,
24 Urea and formaldehyde Urea-formaldehyde resin electrical fittings grease resisting
textile, foams, lamination,
Kitchen ware (melamine
crockery), furniture, laminates,
25 Melamine and formaldehyde Melamine-formaldehyde resin
electrical insulators, adhesives,
fabric and paper treatment.
Adipic acid and Hexa-
26 Nylon 6, 6 Synthetic fiber
methylenediamine
27 Caprolactam Nylon 6 Synthetic fiber
Synthetic fiber of high tensile
Terphthalic acid and Ethylene
28 Polyester (Terylene, Dacron) strength with anti-wrinkle
glycol (or its ester)
properties
Used extensively in automobile
industry, table cutlery, as
Bis-phenol A and Carbonic acid
29 Polycarbonate protective covering, compact disc
derivative
(CD), as bullet proof sheets, safety
glasses, etc.
As adhesive in shoe soles, tyres,
30 Diisocyanates Diols Polyurethanes and foam surface coating in paints
and varnishes.
 1. Qualitative analysis

The qualitative analysis of an organic compound involves the detection of all the elements present in
it.
2.1 Detection of Carbon and Hydrogen : A small amount of the dry and powdered substance is mixed
with about double the amount of pure and dry copper oxide. The mixture is heated in a well dried
hard glass tube (fig) delivery tube is packed with glass wool containing anhydrous copper sulphate
(white) . When the mixture is heated , the carbon present in the compound is oxidised to carbon
dioxide which turns lime water milky. The hydrogen present in the organic compound is oxidised to
water which turns anhydrous copper sulphate in the bulb to blue.
Anhydrous copper sulphate
Organic compounds
+
Copper oxide Lime water

Fig. Detection of carbon and hydrogen in an

organic compound.

C + 2CuO Heat
→ CO2 + 2Cu
from organic compound
CO2 + Ca(OH)2 → CaCO3 + H2O
lime water milky
2H + CuO Heat
→ H2O + Cu
from organic compound
CuSO4 + 5H2O → CuSO4 . 5H2O
anhydrous hydrated copper sulphate
copper sulphate (blue)
(white)
This method is known as copper oxide test.
2.2 Detection of Nitrogen : Nitrogen in an organic compound is detected by the following tests :
(a) Soda lime test. A pinch of an organic compound is heated strongly with soda lime (NaOH + CaO)
in a test tube. If ammonia gas evolves, it indicates nitrogen.
CH3CONH2 + NaOH CaO
→ CH3COONa + NH3
acetamide
Limitation : This method has a limitation. A large number of organic compounds such as nitro and
diazo compounds do not liberated ammonia on heating with sodalime.
(b) Lassaigne’s method : A small piece of a dry sodium metal is heated gently in a fusion tube till it
melts to a shining globule. Then , a small amount of organic substance is added and the tube is
heated strongly till it becomes red hot. The red hot tube is then cooled and filtered. The filtered
liquid is known as sodium extract or Lassaigne’s extract.
 The Lassaigne’s extract is usually alkaline. If not, it may be made alkaline by adding a few drops of a
dilute solution of sodium hydroxide added to a part of sodium extract a small amount of a freshly
prepared ferrous sulphate solution is and the contents are warmed. A few drops of ferric chloride
solution are then added to the contents and the resulting solution is acidified with dilute hydrochloric
acid. The appearance of a bluish green or a blue colouration confirms the presence of nitrogen in the
organic compound.
The following chemical reactions occur during the test :
Na + C + N –––––→ NaCN
from organic compound
FeSO4 + 2NaCN –––––→ Fe(CN)2 + Na2SO4
Fe(CN)2 + 4NaCN –––––→ Na4[Fe(CN)6]
sodium ferrocyanide
3Na4[Fe(CN)6] + 4FeCl3 ––→ Fe4[Fe(CN)6]3 + 12NaCl
ferric ferrocyanide
(blue colour)
2.3 Detection of Sulphur : The sulphur in the compound reacts with sodium metal to form sodium
sulphide.
2Na + S –––––→ Na2S
from organic compound
The Lassaigne’s extract is divided into two parts and following tests are performed.
(i) Sodium nitroprusside test. The one portion of the extract, a few drops of sodium nitroprusside
are added. The appearance of violet colouration indicates sulphur.
Na2S + Na2 [Fe(CN)5NO] –––––→ Na4[Fe(CN)5NO.S]
sod.nitroprusside violet colouration
(ii) Lead acetate test : The other part of the Lassaigne’s extract is acidified with acetic acid and then
lead acetate solution is added. Formation of black precipitate confirms the presence of sulphur.
Na2S + Pb(CH3COO)2 –––––→ PbS + 2CH3COONa
lead acetate black
2.4 Detection of Halogens : Lassaigne’s test. Sodium extract is prepared as already. During fusion,
sodium will combine with the halogen (from the organic compound) to form sodium halide
→ NaX (X = Cl , Br, I)
Na + X Fusion
(i) A white precipitate soluble in ammonium hydroxide solution indicates the presence of chlorine
in the organic compound
NaCl + AgNO3 –––––→ AgCl + NaNO3
white ppt.
(ii) A dull yellow precipitate partially soluble in ammonium hydroxide solution indicates the presence
of bromine in the organic compound.
NaBr + AgNO3 –––––→ AgBr + NaNO3
dull yellow ppt.
 (iii) A bright yellow precipitate, completely insoluble in ammonium hydroxide solution, indicates the
presence of iodine in the organic compound.
NaI + AgNO3 –––––→ AgI + NaNO3
bright yellow ppt
Special test for bromine and iodine.
2NaBr + Cl2 –––––→ 2NaCl + Br2
(turns CS2 layer orange)
2NaI + Cl2 ––––––→ 2NaCl + I2
(turns CS2 layer violet)

Example
based on Qualitative Analysis
Ex.1 In Lassaigne’s test when both N and S are present, blood red colour obtained is due to the
formation of –
(A) Ferric ferrocyanide
(B) Ferric sulphocyanide
(C) Ferric cyanide
(D) None Ans.(B)
Sol. 3 NaCNS + FeCl3 ––––→ Fe(CNS)3 + 3NaCI
(Red)

Ex.2 Lassaigne’s test for the detection of nitrogen will fail in case of –
(A) NH2CONH2
(B) H2NCONHNH2 . HCI
(C) H2N . NH2 . 2HCl
(D) C6 H5NHNH2 . 2HCl Ans.(C)
Sol. For Lassaigne’s test of N, compound must contain N in addition to carbon, so that NaCN can be
formed in sodium extract.

2. Quantitative analysis

3.1 Estimation of Carbon and Hydrogen :

Principle. A known weight of the given dry organic compound is heated strongly with dry cupric oxide
in an atmosphere of air or oxygen free from CO2. The carbon and hydrogen of the organic compound
are oxidised to CO2 and water vapour as :
C + 2CuO –––––→ CO2 + 2Cu
(from compound)
2H + CuO –––––→ H2O + Cu
(from compound)
Procedure :
Let the mass of organic compound taken = w g
 Mass of water formed = x g
(increase in CaCl2 U-tube)
Mass of carbon dioxide formed = y g
increase in potash tubes)
(a) Percentage of Carbon
We know that 1 mole of carbondioxide (44 g) contains 1 gram atom of carbon (12g)
CO2 ≡ C
44 g of CO2 contain C = 12 g
12
Y g of CO2 contains C = ×yg
44
Hence
12 y
Percentage of carbon = × 100
44 × w
(b) Percentage of Hydrogen
We know that one mole of water (18g) contains 2 gram atom of hydrogen (2g)
H2O = 2H
18g of H2O contain H = 2g
2
∴ x g of H2O contains H = ×xg
18
2x
Percentage of hydrogen = x 100
18x w
Percentage of C
12 Mass of CO 2 formed
= × × 100
44 Mass of compound taken
Percentage of H
2 Massof H 2 Oformed
= × × 100
18 Massof compound taken
3.2 Estimation of Nitrogen :
There are two methods for the estimation of nitrogen
(i) Duma’s method (ii) Kjeldahl’s method
(i) Duma’s method :
Principle of the method. A known mass of an organic compound is heated with dry cupric oxide in an
atmosphere of carbon dioxide. The carbon and hydrogen are oxidised to carbon dioxide and water
respectively while nitrogen is set free. If any oxide of nitrogen is produced during this process, it is
reduced to nitrogen by passing over a heated copper gauze. The gaseous mixture is collected over an
aqueous solution of KOH when all the gases except nitrogen are absorbed. The volume of nitrogen
produced is measured at room temperature and atmospheric pressure. From the volume of N2
produced, percentage of nitrogen in the sample can be calculated.
C + 2CuO –––––→ CO2 + 2Cu
 2H + CuO –––––→ H2O + Cu
2N + CuO –––––→ N2 + oxides of nitrogen
Oxides of nitrogen + Cu → CuO + N2
Let the mass of organic compound = w g
The volume of nitrogen collected = Vcm3
Atmospheric pressure (from barometer)
= P mm of Hg
Room temperature = t C 0

Aqueous tension at t0C = a mm of Hg

Pressure of dry nitrogen = (P - a) mm of Hg
Let us first convert the volume of nitrogen to volume at S.T.P.
Experimental conditions S.T.P. conditions
P1 = (P - a) mm Hg P2 = 760 mm
T1 = (273 + t) K T2 = 273
V1 = V cm3 V2 = ?
P1V1 PV
Applying gas equation = 2 2
T1 T2
P1V1T2 (P − a ) x V x 273
∴ V2 = = = x cm3 (say)
P2 T1 760 (273 + t )
Now 22400 cm3 of N2 at S.T.P. weight = 28 g
x cm3 of N2 at S.T.P. will weigh
28
= ×xg
22400
∴ Percentage of nitrogen
Mass of nitrogen
= × 100
Mass of organic compound
28x × 100
=
22400 × w

(ii) Kjeldahl’s method : This method cannot be used for

(i) Organic compounds containing nitrogen in the ring such as pyridine, quinoline, etc.
(ii) Organic compounds containing nitrogen (-NO2) and diazo (-N = N-) groups.
Principle : A known weight of the organic compound is heated with conc. H2SO4 so that nitrogen is
quantitatively converted into ammonium sulphate. The solution is then heated with excess of sodium
hydroxide. The ammonia gas evolved is passed into a known but excess volume of standard acid (HCl
or H2SO4). The acid left unused is estimated by titrating the solution with standard alkali. From the
amount of acid left unused the amount of acid used for neutralisation of ammonia can be calculated.
From this percentage of nitrogen can be calculated.
C, H, S Conc
 → CO2 + H2O + SO2
.H 2SO 4

(from organic compound)

N Conc
 →
.H 2SO 4
(NH4)2SO4
(from organic ammonium sulphate
compound)
 (NH4)2SO4 + 2NaOH Heat
→ Na2SO4 + 2NH3 + 2H2O
2NH3 + H2SO4 → (NH4)2SO4
NH3 + HCl → NH4Cl
Calculations
Let the mass of organic compound = w g
Volume of standard acid taken = V cm3
Normality of acid = N1
Let vol. of standard alkali used for neutralisation of unused acid = V2 cm3
Normality of standard alkali = N2
N1V1 N 2 V2
  = 
alkali acid

Let this volume of v cm3

∴ Vol. of acid used for neutralisation of ammonia = (V - v) cm3 of N1 normality
∴ Ammonia liberated = (V - v) cm3 of N1 solution
Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
14(V − v) × N 1
(V - v) cm3 of N1 NH3 solution contains nitrogen = g
1000
Percentage of nitrogen
Mass of nitrogen
= × 100
Mass of organic compound
1.4(V − v) × N 1 100 1.4(V − v) × N1
N%= × =
1000 w w

3.3 Estimation of Halogens :

Principle : A known mass of the organic substance is heated with fuming HNO3 in a Carius tube. The
silver halide so obtained is separated, washed, dried and weighed. From the weight of silver halide
formed, the percentage of halogen can be calculated.
X + AgNO3 –––––→ AgX
Halogen
Carbon, hydrogen or sulphur present in the compound will be oxidised to CO2, H2O and H2SO4
respectively.
3 → CO2
C + 2O HNO

2H + O HNO
3 → H2O

S + H2O + 3O HNO
3 → H2SO4
Calculations :
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now , AgX = X
 108 + X parts by weight of silver halide contains X parts by weight of halogen
(X is its atomic mass)
(108 + X) g of silver halide give halogen = X
a g of silver halide will give halogen
X
= ×ag
(108+ X)
∴ Percentage of halogen
Mass of ha logen
= × 100
Mass of organic compound
X×a 100
= ×
(108 + X) w
Here X is the atomic mass of halogen, ex.
Cl = 35.5, Br = 80 (79.9 exact), I = 127
(126.9 exact)
Percentage of halogen =
Atomic mass of halogen × Mass of silver halide
× 100
(108 + At. mass of halogen ) × Mass of org. subs tan ce

3.4 Estimation of Sulphur

Sulphur is estimated by Carius method.
Principle : A known mass of the organic compound is heated with fuming HNO3 in a sealed tube
when sulphur is quantitatively converted into sulphuric acid. It is then precipitated with barium
chloride as barium sulphate. The precipitate is filtered, washed, dried and weighed. From the weight
of BaSO4 formed, the percentage of sulphur can be calculated. The main reactions are :

S + H2O + 3O HNO
3 → H2SO4
H2SO4 + BaCl2 → BaSO4
ppt.
Calculations :
Let the mass of organic compound = w g
Mass of BaSO4 formed = a g
BaSO4 ≡ S
137 + 32 + 64 = 32
= 233
233 g of BaSO4 contain sulphur = 32 g
32 × a
a g of BaSO4 will contain sulphur = g
233
Percentage of sulphur
Mass of sulphur
= × 100
Mass of organic compound
32a 100
= ×
233 w

Example
based on Quantitative Analysis
Ex.3 0.2475g of an organic compound gave on combustion 0.4950g of carbon dioxide and 0.2025 g of
water. The percentage of carbon and hydrogen are–
(A) 54.54, 9.09 (B) 52.54, 8.09
(C) 120 , 5.8 (D) None Ans. (A)
Sol. Wt. of organic compound = 0.2475 g
Wt. of CO2 produced = 0.4950 g
Wt. of H2O produced = 0.2025 g
Percentage of carbon
12 Wt. of CO 2
= × × 100
44 Wt. of compound
12 0.4950
= × × 100 = 54.54
44 0.2475
Percentage of hydrogen
2 Wt. of H 2 O
= × × 100
18 Wt. of compound
2 0.2025
= × × 100 = 9.09
18 0.2475

Ex.4 In a Dumas nitrogen estimation 0.3 g of an organic compound gave 50 cm3 of nitrogen collected at
300 K and 715 mm pressure. The percentage of nitrogen in the compound (vapour pressure of
water at 300K is 15 mm) is
(A) 15.46 (B) 17.46
(C) 50 (D) 70 Ans. (B)
Sol. Vapour pressure of gas = 715 - 15 = 700 mm
To calculate the volume of N2 at S.T.P.
V1 = 50 cm3 V2 = ?
P1 = 700 mm P2 = 760 mm
T1 = 300 K T2 = 273 K
P1V1 PV
Applying = 2 2 or
T1 T2
P1V1T2
V2 =
P2 T1
700 × 50 × 273
∴ V2 = = 41.9 cm3
760 × 300
22400 cm3 of nitrogen at S.T.P. weigh= 28 g
41.9 cm3 of nitrogen at S.T.P weight
28 × 41.9
= = 0.0524g
22400
0.0524
Percentage of nitrogen = × 100
0.3
= 17.46%

Ex.5 0.257 g of an organic substance was heated with conc H2SO4 and then distilled with excess of
strong alkali. The ammonia gas evolved was absorbed in 50 ml of N/10 HCl which required 23.2
ml of N/10 NaOH for neutralisation at the end of the process. The percentage of nitrogen in the
compound is–
 (A) 14.6 (B) 18.0
(C) 17.0 (D) 15.5 Ans.(A)
N
Sol. Volume of HCl taken = 50ml
10
N
Volume of NaOH used for neutralisation of unused acid = 23.2 ml
10
Now N1 V1(NaOH) = N2V2(HCl)
N N
23.2 ml of NaOH ≡ 23.2 ml of HCl
10 10
N
∴ Volume of HCl unused = 23.2 ml
10
∴ Volume of N/10 HCl required for neutralization of NH3 = 50 - 23.2 = 26.8 ml
N
26.8 ml of HCl = 26.8 ml of N/10 NH3
10
1000 ml of 1N NH3 solution contains nitrogen = 14 g
26.8 ml of NH3 solution contains nitrogen
14 × 26.8
=
10 × 1000
14 × 26.8 × 100
Percentage of nitrogen =
10 × 1000 × 0.257
= 14.6%
Ex.6 0.15 g of an organic compound gave 0.12 g of AgBr by Carius method. The percentage of
bromine in the compound is
(A) 43 (B) 54
(C) 34 (D) 66 Ans. (C)
Sol. Mass of AgBr formed = 0.12 g
AgBr ≡ Br
188 g of AgBr contain bromine = 80 g
0.12 g of AgBr will contain bromine
80 × 0.12
= = 0.051 g
188
0.051
Percentage of bromine = × 100 = 34%
0.15
Ex.7 0.395 g of an organic compound by Carius method for the estimiation of sulphur gave 0.582 g of
BaSO4. The percentage of sulphur in the compound is–
(A) 20.24 (B) 35
(C) 40 (D) 45 Ans. (A)
Sol. Mass BaSO4 = 0.582 g
We know BaSO4 ≡S
233 32
233 g of BaSO4 contain sulphur = 32 g
 0.582 g of BaSO4 contains sulphur
32
= × 0.582
233
Percentage of sulphur
Wt. of sulphur
= × 100
Wt. of compound
32 × 0.582
= × 100 = 20.24 %
233 × 0.395

3. Identification of Functional groups

(i) All organic compound are grouped into smaller number, each group exhibits similar chemical
properties.
(ii) This means that all the compounds of the group must have something common, this common
feature is known as functional group or reactive functional group.
(iii) It is defined as the group which largely determine the properties of a compound ex., CH3OH
C2H5OH, C3H7OH are all collectively called alcohol as the common reactive group in all is – OH.
(iv) Some common and important functional group usually encountered in organic compounds are
given in following table.
Some common Functional groups
Name of Functional group Example
the family
or group
Alkene C=C CH2 = CH2

Alkyne –C≡C– HC ≡ CH

Alcohol –OH, (Alcoholic) CH3OH

Phenol Ar–OH (Phenolic) C6H5OH
(–OH group attached
to aromatic ring)
Aldehyde –CHO, Aldehydic CH3CHO
Ketone C = O, ketonic CH3COCH3

Carboxylic –COOH, Carboxylic CH3COOH

acid
Amine – NH2, amino CH3NH2
Nitro alkane – NO2 – Nitro CH3 – NO2
Cyanide – CN – Cyano CH3 – CN

4.1 Characteristic of functional group

(i) The physical and chemical properties of compound containing different functional groups are
different.
(ii) There exists a homologous series of compound containing each type of functional group.For
example, homologous series of alcohol like CH3OH, CH3CH2OH, CH3CH2OH etc.
 (iii) The chemical properties of compound containing same functional group are similar. For example
methyl alcohol [CH3OH] & ethyl alcohol (C2H5OH) have similar chemical properties. Therefore,
(iv) Chemical identification of a class of compounds involues the same type of tests.
(A) Significance of functional groups
(i) The study of so large number of known organic compounds becomes systematic.
(ii) Identification of organic compound has become easy on the basis of functional groups.
(iii) The properties and nature of a newly synthesised compound can be established if the presence
of the functional group in it is identified.
4.1.1 Test for unsaturation
(i) Unsaturation in an organic is indicated by
C = C or – C ≡ C – bonds in its structure.
(ii) Because of the presence of this π bonds these compounds are bound to undergo addition
reaction & therefore, unsaturation in the organic compound (aliphatic) can be detect by
exporting their this addition reaction.
(iii) Two methods used for detecting unsaturation in organic compounds are -
(A) Bromine test :
(i) Discharge bromine solution to colourless without evolving HBr.
Br Br
C=C + Br2 → C–C
Alkene Orange Dibromo alkane
(Colourless)
(B) Baeyer’s test or Permanganate test :
(i) When alkaline solution of potassium permanganate (2%) is added, decolourization of pink colour
of kMnO4 indicates unsaturation. A brown ppt. of MnO2 is also observed.
3 CH2 = CH2 + 2KMnO4 + 4H2O →
2KOH + MnO2 + 3CH2OHCH2OH Brown Glycol
(Colourless)
CH ≡ CH + KMnO4 + H2O → (COOH)2 + MnO2 + KOH
Oxalicacid Brown
chemical identification of a class number of compounds involves the same type of tests.

Note :-
(1) Apply both tests, since some compounds react slowly with bromine.
(2) Enols (–OH group containing compounds) are also found to decolourise bromine as well as
permanganate solution. but the type of reaction which takes place with bromine is somewhat
different in this case than with unsaturated compounds. Enols are substituted by bromine and an
equivalent of HBr is evolved. So during the reaction white fumes will come, when a glass rod
moistened with concentrated ammonia solution is held near the mouth of the test tube.
HBr + NH3 → NH4Br
4.1.2 Test for Terminal Alkyne
 Acetylene and other terminal alkyne (1 – alkyne) are weakly acidic in character. They react with
ammonical solution of cuprous chloride and silver nitrate to form the corresponding copper and
silver alkynide.
R – C ≡ C – H + 2 [CuCNH3)2] Cl → Cu C ≡ C Cu + 2NH4Cl + 2NH3
Diammine copper (Ι) chloride Dicopper acetylide (red ppt)
R – C ≡ C – H + 2 [Ag (NH3)2] → AgC ≡ C Ag + 2 NH4NO3 + 2NH3
Diamine silver (Ι) nitrate Disilver acetylide (white ppt)
Note :- Non terminal Alkynes will not give this test
CH3C ≡ CCH3 + 2 [Ag(NH3)2] NO2 → No reaction
4.1.3 Tests for Alcoholic (–OH) group
(i) – OH group is called alcoholic or hydroxy group, but it is different from the hydroxy group of
inorganic compounds.
(ii) For example, – OH group of sodium hydroxyide and methanol have entirely different properties.
Sodium hydroxide is a base and turns red litmus blue but methanol does not give this test.
(A) Sodium metal test or Xanthate test :-
(i) Take compound in an absolutely, dry test tube. Acid a small quantity of anhydrans calcium
chloride to absorb moisture, decant it into another test tube.
(ii) Add a small piece of dry sodium metal to it (sodium should be handled with (are) . Efferuescence
with the evolution of hydrogen gas indicate the presence of alcoholic group in the
compounds.
1
C2H5OH() + Na(s) → C2H5ONa + H2 (g)
2
Ethanol Sodium Sodium Ethoxide Hydrogen
Note : -
(i) Test tube & alcohol should not contain even trace of moisture as water also reacts with sodium
metal to evolve hydrogen gas.
(ii) Cerric ammonium nitrate test :- To about 1 ml. of the substance in test tube add a few drops a
cerric ammonium nitrate solution. Appearance of red colour indicate the presence of
alcohols.
CH3OH + (NH4)2 Ce(NO3)6 →(CH3OH)2 Ce (NO3)4 + 2NH4NO3
(colourless) Cerric ammonium nitrate (Red) (colourless)
(Yellow)
(iii) Ester test :-
When alcohol is treated with acetic acid in the presence of conc. H2SO4, a characteristic fruity
smell due to the formation of ester indicates the presence of alcohol.

CH3COOH   → CH3COOC2H5 + H2O

Conc. H 2SO 4
C2H5OH +
(iv) When a compound is treated with acetyl chloride and a rod dipped in NH4OH is brought in
contact with gas. If the white fume are produced, indicate the presence of alcohol.
ROH + CH3COCl → CH3 – COOR + HCl
Alcohol Acetylchloride Ester
HCl + NH4OH → NH4Cl + H2O
(white fumes)
4.1.4 Test for Phenolic ( ≥ OH) group : -
(i) Compound containing one or more hydroxyl group attached to a aromatic ring are called phenols
ex., C6H5OH, Cresol (CH3C6H4OH) catechol (C6H4 (OH)4) etc. Phenolic group in organic
compound can be detected by following test :-
(a) Ferric chloride test :-
(i) Take about 5 ml of ferric chloride solution (neutral) in test tube.
(ii) Add into it 2-3 drops or pitch of compound.
(iii) Appearance of dark green, red or violet colour indicate the presence of phenolic group in the
compound.
OH O–

6 + FeCl3 → [( )6 Fe]3– + 3HCl

Phenol Violet complex

(b) Litmus test
(i) Take about are 1 ml of blue litmus solution in test tube. Add into it small amount of the
compound.
(ii) If the litmus turn red, then Phenolic group may be present in compound. Phenol behave like
weak acid.
Note :-
(i) Carboxylic acid also turn blue litmus red but phenol being very weak acid do not give
effervescence with sodium-bicarbonate.
(c) With Phthalic anhydride- Many Phenols udergo condensation with Phthalic anhydride to give
useful product.
(iii) Phenol when heated with phthalic anhydride in the presence of concentrated H2SO4 given
phenolphthalein, a colourless compound which produce beautiful pink colour with alkali solution
due to the formation of coloured sodium salt.
HO OH
HO OH
H H
O Conc
 →
. H 2SO 4

C
C
O O NaOH
→
C C
O O
Phenolphthalein(colourless)
O –
O Na +

COO–Na+
Sodium salt of Phenophlhatein (Pink)
(d) Liebermann’s reaction :-
To a small amount of substance in as test tube add few crystals of solid sodium nitrite and then
few drops of conc. H2SO4.
 A green or blue colour is obtained which change to red on dilution and again turn blue or green
an making the solution alkaline with NaOH.
Note : -
(i) Nitrophenols and p-substituted phenol do not give this test.
(ii) This test is also shown by o-cresol.
(e) Cerric Ammonium nitrate test :-
To Cerric Ammonium nitrate add a pinch of given compound.Appearance of green or brown
precipitates indicate the presence of phenolic group in the given compound.
4.1.5 Test for Carboxylic (– COOH ) group
Compound containing this group behave like acid and almost all the tests meant for acids can be
applied for testing this group.
(i) Litmus test :-
Place a small quantity of the organic substance an a piece of moist blue litmus paper, or in a blue
litmus solution. If the colour change to red, carboxylic group may be present.
(ii) Sodium bicarbonate test : -
Take 5 ml of dilute solution of sodium bicarbonate in a test tube and add a small quantity of
substance to it strong effervescence with the evolution of carbon dioxide gas indicate the
presence of carboxylic acid.
CH3COOH + NaHCO3 → CH3COOHNa + CO2↑ + H2O
(iii) Ester test :-
To a small quantity of substance add 5 drops of ethyl alcohol and two drops of conc. H2SO4.
warm the tube an water both. A fruity small of ester indicate the presence of
– COOH group.
CH3COOH + C2H5OH Conc
 →
. H 2SO 4
CH3COOC2H5 + H2O
Ethyl acetate
(iv) To a mixture of about 3 ml 0.1% acriflavine solution and 3 ml 1% potassium chromate solution
add a few drops of aqueous solution of substance (if it is liquid then it may be added as such).
Appearance of a yellow or brown-yellow precipitate confirms the presence of carboxylic acid.
4.1.6 Test for Aldehydes :-
To 2 ml of substance, if it is liquid or to its 2 mole cold aqueous solution add 2ml Schiff’s reagent*
(Rosaniline decolourised with SO2) and shake for 2 minutes. Do not heat or warm. A deep
violet-red or red colour indicates the presence of aldehydic group.

R CH.SO2NH
H.SO2NH OH C NH
C NH2  
→ R CH.SO2NH
2 R .CHO
− H 2SO 3
H.SO2NH
SO2 OH
Schiff’s reagent (colourless) Violet-red
(ii) Fehling’s test - In a test tube mix 1 ml each of Fehling A (CuSO4 in water with few drops of acetic
acid) and Fehling B (Rochelle salt and NaOH solution) solutions when a deep blue colour appears.
To this add 0.1gm or 2-3 drops of substance and boil for 5 minutes. The blue colour of Fehling’s
solution slowly fades away and a reddish-brown precipitate of Cu2O is obtained indicating the
presence of aldehydic group.
 CH C  O–
O O CHOH.COO–
∆
2 Cu + R.CHO + 2H2O 
→ 2 + R.COOH + Cu2O ↓
O O CHOH.COO–
CH C  O–
Tartrato-cuprate anion (blue) cuprous oxide (Red)
(Fehling’s solution)

(iii) Tollen’s test -To 2 ml Tollen’s reagent in a test tube (To 1 ml ANO3 solution add few drops of
NaOH solution add few drops of NaOH solution and dissolve the precipitate of silver oxide by
adding excess NH4OH) add 2-3 drops or 0.1 gm of substance. Keep the test tube in boiling water
without disturbing for 5 minutes when a shining silver mirror deposits on the walls of test tube
indicating the presence of aldehydic group.
2Ag (NH3)2OH + R.CHO + H2O → R.COONH4 + NH3 + 2NH4OH + 2Ag ↓
Tollen’s reagent
4.1.7 Test for Ketones :-
If the tests for aldehydes are negative perform following tests for ketones.
(a) To a solution of 0.5 gm or 0.5 ml substance in 5 ml dilute HCl add 2 ml of solution of
2, 4-dinitrophenylhydrazine in dilute HCl. Cool and allow to stand for 2 minutes when a yellow,
orange or red coloured crystalline precipitate (in case Schiff’s test is negative) indicates the
presence of kentonic group.
(b) To 2-3 drops of substances add 1 ml freshly prepared sodium nitroprusside solution and then
NaOH solution drop by drop. A wine red or orange red colour confirms the presence of ketonic
group.
4.1.8 Test for Esters and Lactones :-
(a) Dissolve about 0.5 gm or 0.5 ml substance in 10 ml alcohol, add a drop of phenolphthalein and
few drops of NaOH solution. A pink colour is produced by phenolphthalein in alkaline medium
Heat the reaction mixture for 5 minutes when NaOH solution is used up in the hydrolysis of ester
or lactone and the pink colour of phenolphthalein disappears.
R.COOR’ + NaOH → R.COONa + R’OH
(b) To 3-4 drops or 0.2 gm of substance add 0.2 gm solid hydroxylamine hydrochloride and 5m 10%
NaOH solution. Boil the solution gently for 2 minutes, cool and acidify the solution with dilute
HCl. Then add 2-3 drops of FeCl3 solution when a violet or deep red brown colour due to
formation of ferric complex of hydroxamic acid, indicates the presence of ester group.
∆
R.CO.OR’ + NH2OH 
→ R.CO.NHR’OH + R’OH

Ester Hydroxylamine Hydroxamine acid

O
3R. CO. NHOH + FeCl3 → R–C Fe + 3HCl
NH–O

Coloured Complex
4.1.9 Test for Ethers :-
If the compound responds to none of the above tests then the presence of ether group may be
confirmed by following tests.
 (a) Feigl’s test - Take 2 ml of substance in a boiling tube and cover the mouth of the tube with a
filter paper moistened with a mixture of cupric acetate and benzidine hydrochloride. Heat the
tube or 3-5 minutes when a deep blue colour appears on filter paper due to formation of
benzidine blue, confirming the presence of ether group.
R
R.O.R’ + O (from air) → O→O
R'
Ether Ether peroxide
R
O→O + Cu++ → R.OR + CuO2
R'
Cupric peroxide

H2N NH2.NH HCl + CuO2 →

Benzidine hydrochloride

H 2N NH2.NH =

Benzidine blue

NH . HCl

(i) Ethers may be distinguished from hydrocarbons by iodine test.

Dissolve 2-3 drops of substance in 5ml benzene and to this add 5 ml of very dilute solution of
iodine in benzene and shake when the solution acquires a brown tint.
Note: -
Before proceeding with the identification of compound with the help of specific tests it is advisible to
find out if the compound is saturated or unsaturated and whether it is aliphatic or aromatic.
4.1.10 Test for primary amines :-
Whether aliphatic or aromatic, all primary amines respond to carbylamine test.
(a) Carbylamine test - To a small amount of substance add 2ml alcoholic KOH solution, 3-4 drops of
chloroform and heat the mixture. Highly offensive odour of carbylamine or isocyanide is
produced.
R.NH2 + CHCl3 + 3KOH → R.N C + 3KCl + 3H2O
Some derivatives of amines such as acetyl derivatives which get hydrolysed under the conditions
of the reaction, may also respond to this test. In addition, aromatic primary amines respond to
dye test.]
(b) Dye test - Dissolve a small amount of substance in 2 ml dil. HCl. If the substance is insoluble add
3-4 ml water and cool the mixture to 0°. To this then add precooled 2 ml 2% NaNO2 solution in
such small amounts that no brown fumes escape from the solution. If light turbidity is obtained,
ignore it.
Add 1 ml of this solution to a solution of β-naphthol in alkali when an orange-red coloured dye is
obtained.
Ar. NH2 + NaNO2 + 2HCl → Ar.N2Cl + 2H2O + NaCl
 Ar. N2Cl → N=N OH

Diazonium salt
4.1.11 Test for secondary amines :-
Dissolve a small amount of substance in 2 ml HCl, dilute it with 3-4 ml water and add 2 ml of 2%
NaNO2 solution. If white or yellow oily emulsion is obtained or a low melting solid separates the
compound is a secondary amine.
Ar. NH.R + HNO2 → Ar. N(NO). CH3 + H2O
Nitrosamine
4.1.12 Test for tertiary amines :-
Most of the aromatic tertiary amines respond to following test :
On adding 2 ml of 2% NaNO2 solution to a solution of substance in dilute HCI, if a yellow or yellow-
green colour is produced which turns dark greenish on making the solution alkaline then the
compound may be an aromatic tertiary amine. Refer to Section G.

NR2 + HNO2 → ON NR2 + H2O

Tertiary amine p-Nitroso derivative

4.1.13 Test for nitro compound :-
(a) Mulliken’s test. To a small amount of substance add 2 ml alcohol, 1 ml CaCl2 solution and a pinch
of zinc dust or 1-2 small tin pieces. Boil the mixture for 5 minutes, cool and filter. To the filtrate
add Tollen’s reagent (ammoniacal AgNO3) when a white precipitate, turning grey and finally
black, is produced
R.NO2 + 4[H] → R.NHOH + H2O
Hydroxylamine derivative

On reduction of nitro compound a hydroxylamine derivative is formed which reduces Tollen’s

reagent.
Note :- If the amino group is absent then these nitro compounds may be reduced to amino
compounds which can be tested either by carbylamine test or dye test.
4. Distinction between pairs of organic
compounds
(i) The compounds belonging to a group have similar chemical properties. In some cases the
properties of the two compounds are so similar that sometimes these created great confusion.
(ii) Therefore, a knowledge of the tests to distinguish between such pairs of organic compounds is of
vital significance. Here below, some such pairs have been dealt.
5.1 Distinction between methanol and ethanol
Methanol, CH3OH, and ethanol, C2H5OH, both contain the same functional group – OH. Therefore
most of their chemical properties are similar. However, the alkyl group in the two are different.
In methanol, alkyl group is CH3 whereas in ethanol it is C2H5. This difference in alkyl group makes
some of the properties of the two different.
 (i) Boiling point of ethanol is 78°C whereas that of methanol is 60°C. This is because of the high
molecular weight of ethanol as compared to methanol.
(ii) Both get oxidised by mild oxidising agent, but the products formed in the two are different
CH3OH Oxidation
 → HCHO

Methanol Formaldehyde
CH3CH2OH Oxidation
 → CH3CHO

Ethanol Acetaldehyde
As acetaldehyde forms iodoform with Ι1 and alkali, therefore, iodoform test can be employed to
distinguish ethanol from methanol.
CH3CH2OH Ι → CHI3
2 / NaOH

Iodoform
CH3OH Ι →
2 / NaOH
No iodoform

5.2 Distinction between benzaldehyde and acetone

Benzaldehyde, C6H5CHO, both contain carbonyl group, > C = O. Both are liquids and colourless.
The two can be distinguished by exploting the reducing nature of aldehyde. That is, aldehydes are
reducing in nature, whereas ketones are not. So aldehydes respond to Schiff’s reagent, Fehling’s
solution and Tollen’s reagent, whereas ketones do not.
–
C6H5CHO + [Ag(NH3)2]+ + 3 O H → C6H5COO¯ + 2Ag
Benzaldehyde Tollen’s reagent Benzoate ion Metallic silver
CH3COCH3 +Tollen’s reagent → No silver mirror
–
C6H5CHO + 2Cu2+ + 5 O H → Cu2O + C6H5COO¯ + 3H2O
Fehling’s solution Cuprous oxide(red)
CH3CO.CH3 + Fehling’s solution → No red precipitates
On the other hand, acetone undergoes iodoform test whereas benzaldehyde does not.
CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI + 3H2O
Acetone Iodoform
C6H5CHO + I2 + NaOH → No reaction.
Some physical properties, like odour and boiling point, of the two are also different. Benzaldehyde
possesses smell of bitter almonds whereas acetone has a pleasant smell.
5.3 Distinction between ethanol and phenol
Ethanol, C2H5OH and phenol, C6H5OH, both contain – OH group. But in ethanol this – OH group is
attached an alkyl group whereas in phenol, it is attached to a aromatic benzene ring. This different in
the two makes the following properties different.
(i) Phenol is acidic in nature while ethanol is not.
(ii) Phenol gives characteristic colour with ferric chloride solution while ethanol does not give any.
(iii) Ethanol undergoes iodoform reaction i.e. it gives yellow precipitates with I2/NaOH. Phenol does
not exhibit this reaction.
 (iv) Being aromatic, Phenol burns with a sooty flame. Ethanol burns with a blue flame.
(v) Viscosity and boiling points of the two are also different. Phenol is more viscous and has high
boiling point as compared to ethanol.
5.4 Distinction between phenol and benzoic acid
Phenol, C6H5OH and benzoic acid, C6H5COOH, both are aromatic in nature and turn blue litmus red.
Thus, both exhibit acidic character also. But with sodium bicarbonate only benzoic acid gives
effervescence. Phenol, being a very weak acid, does not evolve carbon dioxide with sodium
bicarbonate.
C6H5COOH + NaHCO3 → C6H5COONa + H2O + CO2
Benzoic acid Sod bicarbonate Carbon dioxide
C6H5OH + NaHCO3 → No reaction
Phenol gives violet colour with neutral ferric chloride solution whereas benzoic acid does not give
any.
5.5 Distinction between aniline and phenol
Aniline C6H5NH2 and phenol, C6H5OH, both are aromatic. Both have almost same boiling point. Except
these two similarities, the two compounds differ widely.
(i) Aniline is basic in nature whereas phenol is acidic.
(ii) Aniline contains nitrogen as extra element, phenol does not contain any extra element.
(iii) Aniline contains amino, -NH2, group whereas phenol contains – OH group. Therefore, aniline
respond to carbylamine test whereas phenol does not.
(iv) Phenol gives violet colour with ferric chloride solution whereas aniline does not.
(v) Aniline also gives dye test whereas phenol does not.
Note : -
Do not inhale the vapours of isocyanides. These are very poisonous. Destroy the isocyanide after the
test by cooling and adding excess of conc. HCl in the tube.
Example
based on Identification of Functional Groups
Ex.8 You are provided with four jar containing hydrogen, methane, ethylene and acetylene
separately. How would you identify which jar contains which gas ?
Sol. (i) Acetylene can be detected by bringing a filter paper moisten with ammonical cuprous
chloride solution near the mouth of gas jars, the jar that turns this paper red contains
acetylene.
HC ≡ CH + Cu2Cl2 + 2NH4OH → Cu.C ≡ C.Cu ↓ + 2NH4Cl + 2H2O
Cuprous acetylide (red)
(ii) Among the remaining three gases (C2H4, CH4 and H2), ethylene can be detected by its reaction
with bromine water. The jar that discharge bromine water colour must contain ethylene.
CH2 = CH2 + Br2 → CH2Br.CH2Br
(iii)Of the remaining two gases (CH4 and H2), methane can be detected by the fact that one
burning in air it gives CO2 which in turn changes lime water milky. So a burning splinter is
introduced in
each of the remaining gas jar, when whole of the gas is burnt away, lime water is added - the
jar in which lime water turns must contain carbon dioxide, i.e. methane; and thus the other
must contain hydrogen.
(a) CH4 + 2O2 → CO2 + 2H2O
 Ca(OH)2 + CO2 → CaCO3 ↓ + H2O
(milky)
(b) 2H2 + O2 → 2H2O
(No CO2 is produced)
Ex.9 One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo compound
C5H10O2. Substance (A) on treatment with cold, dilute alkaline KMnO4 solution forms a
compound C5H12O2. On ozonolysis (A) gives equimolar quantities of propanone and ethanol
Deduce the structural formula of (A).
Sol. Since the hydrocarbon (A) adds one molecule of bromine to form C5H10Br2, compound (A) must
have a double bond. The position of the double bond is clearly indicated by its ozonolysis to
propanone CH3.COCH3 and ethanol, CH3CHO. To obtain the structure of the parent olefin,
remove the oxygen atoms of the carbonyl groups and join their two carbon atoms by a double
bond. Hence compound (A) must be having following structure.
(i ) O3
(CH3)2 C = O + OHC.CH3 (  →
ii ) H 2 O / Zn
(CH3)2C = CHCH3
Propanone Ethanol 2-Methyl-2-butene (A)

Ex.10 The aqueous solution of a nitrogen and chlorine containing organic compound (A) is acidic to
litmus. (A) on treatment with aqueous NaOH gives a compound (B) containing nitrogen, but not
chlorine. Compound (B) on treatment with C6H5SO2Cl in the presence of NaOH gives an insoluble
product(C), C13H13NO2S. Give structures of (A) and (B)
Sol. Since the compound B reacts with C6H5SO2Cl in presence of NaOH to give insoluble product C, B
must be secondary amine.

NH + CIO2SC6H5 → NSO2C6H5

[B] [C] C13H13NO2S
Thus the alkyl (or aryl) groups of the secondary amine B is C7H9 or C6H5 – and CH3–. Thus B and A
are
C 6H 5 C6H5 +
NH NH2Cl¯
CH3 CH3
[B] [A]

Ex.11 An organic compound (A) reacts with ethanol to give (B) and (C). On acid hydrolysis, (C) yields (B)
and (D). Oxidation of (D) gives (B). (B) is an acid and forms a salt with Ca (OH)2 which on dry
distillation gives (E), C3H6O. Give structures of (A) to (E) with proper reasoning.
Sol. Summary of the given reactions.
(i) A + C2H5OH → B + C
+
(ii) C H→ B + D
.→ B
(iii) D oxi
B
(iv) (  → E
i ) Ca ( OH ) 2
(Acid) ( ii ) dry distil

Reaction (iv) indicates that the acid B is acetic acid. Further formation of B by acidic hydrolysis of
C indicates that C should be an ester of acetic acid. Oxidation of D
(an alcohol) to give B (CH3COOH) indicates that D is C2H5OH. hence C must be ethyl acetate, and
 thus finally A must be acetic anhydride (anhydrides on treatment with alcohol give acids and
ester).
CH3CO
O + C2H5OH →
CH3CO
[A] CH3COOH + CH3COOC2H5
[B] [C]
+
CH3COOC2H5 H→ CH3CH3COOH +C2H5OH
[C] [B] [D]
2CH3COOH Ca
( OH
 )2
→ (CH3COO)2Ca dry → CH3COCH3
distil

[B] [E]