LECTURE NOTES

Session - 2009-10

ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :

Structure Identification
* Monochlorination
* Catalytic Hydrogenation
* Ozonolysis
* Elements detection
* Identification of Functional Group by Lab. Test

Refer sheet GOC- I

JEE Syllabus [2009]
Practical organic chemistry: Detection of elements (N, S, halogens); Detection and identification of the following functional groups: hydroxyl (alcoholic and phenolic), carbonyl
(aldehyde and ketone), carboxyl, amino and nitro; Chemical methods of separation of
mono-functional organic compounds from binary mixtures.

63

STRUCTURE INDENTIFICATION
Monochlorination:(a)

Cl / h
CH3Cl + HCl
(i) CH4 2
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl

Cl

Cl / h
2

(iii)

+ HCl

C
C
Cl2 / h
C C C Cl + HCl
(iv) C C C
C
C
Cl

Cl / h
2

(v)

+ HCl

Remarks:- When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction takes
place and a C H bond cleaves and a C Cl bond is formed. If one H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Application:- If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture of
monochloroisomers. All these isomers are position isomers.
Conclusion:- Hence, it can be concluded that the total no. of position isomers (structural) of monochloro compounds
is equal to the number of different types of H-atoms present in the reactant. The different type of H-atoms are
also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.

Ex.

Monochlori nation
2 Products (structure isomers)

(b) C C C C

Monochlori nation
2 Products (structure isomers)

(c) C C C C C

Monochlori nation
3 Products (structure isomers)

(d) C C C C

Monochlori nation
4 Products (structure isomers)

(a) C C C

C
CH3
Monochlori nation
5 Products (structure isomers)

(e)

Q.

Cl / h
only one monochloro isomer..
X(C5H12) 2

Ans.

X = Neopentane

Q.

Cl / h
Two monochloro
P(C6H14) 2

How many isomers of P will give two monochloro compounds ?

Ans.

C C C C only one isomers

Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of Benzene
ring are stable.

CH3
Ex.

CH2Cl
Cl / h
2

64

Q.

Cl / h
Two mohochloro
X(C8H10) (Aromatic) 2
Cl / h
One monochloro
Y(C8H10) (Aromatic) 2

Ans.

(X)

(Y)

Catalytic Hydrogenation of C = C; C C
General reaction:Ni
R CH2 CH2 R
(a) R CH = CH R + H2

Ni / Pt / Pd
R CH2 CH2 R
(b) R C C R + 2H2
H2

H2
R CH CH R R CH2 CH2 R
(Not isolated)
2H2 / Ni

CH3 CH2 CH2 CH3

(c) CH2 = CH CH = CH2

(d)

(e)

3H2 / Ni

CH = CH2

H2 / Ni


room temperature
CH CH3
2

H 2/Ni
(100 150C)

(f)

H / Ni,
2

CH CH3
2

[Reaction cannot be stopped at any intermediate stage]

Remarks:(a) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
(b) All C C bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.

Exceptions:Aromatic bonds which are stable at room temperature but can be hydrogenated at high temperature.

It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated compound is
always a saturated compound.

The no. of moles of H2 consumed by 1 mole of compounds is equal to the no. of bonds presents.

All positional isomers of alkenes or alkynes (due to multiple bond) always give same product on hydrogenation.
65

During catalytic hydrogenation and monochlorination, carbon skeleton remain unchanged.

Ex:- C = C C = C + Cl2 X

Ex.

C CC
C Cl

2H2 / Ni

(1)

Cl

Y =

(X)

Cl / h
2
Y + Z

Z =

Cl
CH3

CH3
H / Ni
2

(2)

CH3

CH3
H / Ni
2

(3)

Q.

Cl / h
2
5 Monochloro product

5 Monochloro product

H / Ni
Cl / h
Z(only one monochloro product)
X(C4H6) 2 Y 2

Identify X, Y, Z
Ans.

DU = 2
X

Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
C C CC

Q.
Ans.

Cl

C5H12

= 72g

Identify the structure of hexane which gives 3 monochloro products ?

Ans.

C
C C C C,
C

Q.

Find the no. of monochloro products of a fully saturated isomer of C4H6.

Ans.

DU = 2

Q.

CCCCCC

2 monochloro product
Find the structural isomers of
product?

fully saturated cycloalkane of M.F. C6H12 which gives two monochloro

Q.

Q.

Ans.

Cl / h
2

A
C 8H17 Cl
(C8H18 )
(Only one type )

Identify A ?
66

Q.

Ans.

C C
C C CC
C C

Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
CC

C
(ii) C C C C C
C

Ans.

(i) C C C C C

(b)
Ans.

two monochloro
Nil

Q.

Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogenation produce such an alkane which gives two monochloro products ?

Ans.

C = C = C or C C C

Q.

Determine the M.W. of maximum unsaturated hydrocarbon which on hydrogenation gives C6H12 which on
further chlorination gives two monochloro.
CH2

Ans.
CH2

CH2

C6H6 = 78g

Ozonolysis:
It tells about position of unsaturation.
Remarks:(1)

Alkene and polyalkene on ozonolysis undergo oxidative cleavage.

(2)

(a) The reagent of reductive ozonolysis is

(i) O3 (ozone)
(ii) Zn and H2O or Zn and CH3COOH or (CH3)2 S
(b) The reagent of oxidative ozonolysis is O3 and H2O2.

(3)

The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.

(4)

Ozonolysis does not interfere with other F.G.s.

General Reaction:- R CH = CH R

Ex:-

(1) CH2 = CH2

(1) O 3
R CH = O + O = CH R + ZnO + H2O
(2) Zn/H2O

(1) O 3
CH2 = O + CH2 = O
(2) Zn/H2O

(2) CH3 CH2 CH = CH2

(1) O 3
CH3 CH2 CH = O + O = CH2
(2) Zn/H2O

(3) CH2 = CH CH2 CH = CH CH3

O3 / Zn

CH2 = O + O = CH CH2 CH = O + O = CH CH3

67

O / Zn
3 + OHC CH2 CHO (Propandial)

(4)

Applications:
The process is used to determine the position of C = C in a molecule.
If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except
aromatic ones) undergo oxidative cleavage under normal conditions.
At higher temperature, the aromatic double bonds can also undergo ozonolysis.

O3

O = C C C C C = O + O = CH2

(1)

Zn

O ()
3

(2)

(4)

Q.

CH = CH CH3

low temperatur e

CH = O

(3)

Zn

O3 / Zn

+ O = CH CH3

O3

C6H5 CH = O

CH = CH

Zn

H / Ni
Cl / h
2 CnH2n 2 2
CnH2n1Cl
(P)
CnH2n 2
(Q )
(m products)
Single Compound
m3
(no isomer )

CH3
HCOOH + CH3 C COOH
CH3

Identify P ?

Ans.

P=

Q.

An unsaturated hydrocarbon on ozonolysis produces 1 mole of

, 1 mol CO2, 1 mol

Find the structure of the hydrocarbon and the no. of monochloro products formed followed by hydrogenation.
Ans.

5 monochloro product

68


X
(Unsat. hydrocarbon)

H / Ni
2

Q.

Cl2

m products
h
(m 3 )

O 3 (Zn/H2O)

O
identify structure of X ?

Ans.

Q.

X =

H / Ni
2
X
(Unsat. H.C.)

Cl / h
2
m products
(m 7 )

O 3 (Zn/H2O)

HCHO + 4(1-oxoethyl) Cyclohexan-1-one.

Identify X ?

C
X

Ans.

C=CC

Q.

Identify structure of X ?

Ans.

X is

Q.

H2
CCCCCC
X

O3 (Zn)

CH3CHO + CHO CHO

Identify structure of X ?
Ans.

X is C C = C C = C C

69

Q.

O3

Zn, H2O

CH3

CH
3

O3

Zn, H2O

CH3

CH3

CH3
C C
+2

CH
3

Sol.

O O

Q.

Methyl glyoxal + Formaldehyde

Ex.1

Identify A,B & C with the help of following reactions.

Cl2 / h

(A) (C 9H18 )

Single monochloro produc

( Saturated
Hydrocarbon )

t
Cl2 / h
(B) (C8H18)

Single monochloro product

Cl / h

(C) (C 7H14 ) 2
s
Two monochloro products
( Saturated
Hydrocarbon)

Sol.

A=

or

Ex.2

C C
| |
B = CCCC
| |
C C

C =

Identify -Terpinene and P-Menthane.

Sol.

-Terpinene

Ex.3

Identify A & B

Sol.

A = CH3 C CH CH CH2
|
CH3

B = CH3 CH CH2 CH2 CH3

|
CH3
70

Ex.4

Identify A & m

A = Ph C C Ph
|
|
CH3 CH3

Sol.

m=3

Ex.5

H 2 / Ni
A

Cl / h n-products
2

O3
Zn/H 2O

H C H +

H C C CH2 CH2 C C H

Sol.

A=

n=7

71

1.1

Identification of Elements in Organic Compounds

Element

1. Nitrogen

Test / Reaction

Remark

Lassaignes test

The appearance of green or

Na + C + N NaCN

prussian blue colour confirms

FeSO4 + 6NaCN Na4 [Fe(CN)6] + Na2SO4

the persence of nitrogen.

3Na4[Fe(CN)6] + 4FeCl3 Fe4[Fe(CN)6]3 + 12NaCl

2. Sulphur

Formation of a white ppt.

(a) Oxidation test

indicates presence of sulphur

3KNO3 3KNO2 + 3[O]

Na2CO3 + S + 3[O] Na2SO4 + CO2
BaCl2(aq) + Na2SO4(aq) BaSO4 + 2NaCl(aq)

Appearance

(b) Lassaignes test

purple

colouration confirms the

2Na + S Na2S
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NO.S]

3. Halogens

of

presence of sulphur

Lassaignes test

A white ppt. soluble in NH4OH

X + Na NaX

solution indicates chlorine.

NaX + AgNO3 NaNO3 + Ag X

A dull yellow ppt. partly soluble

in NH4OH solution indicates
bromine.
A yellow ppt. completely in-

soluble in NH4OH solution indicates iodine

A white ppt. of magnesium

4. Phosphorus

pyrophosphate indicates
phosphorus
H3PO4 + Magnesia mixture MgP2O7 + H2O
2MgNH4PO4 Mg2P2O7 + 2NH3 + H2O

5. Nitrogen
and
Sulphur

Blood red colouration confirms

Lassaignes test
FeCl

Na + C + N + S NaSCN
3 Fe(SCN)3

presence of both nitrogen &

sulphur

72

73

Bubbles of H2 come out

(3) Cloudiness appears
immidiately
(2) Cloudiness appears within
5 min.
(1) Cloudiness appear after
30 min.

Lucas Reagent
[Conc. HCl + anhyd. ZnCl2]

ROH
3
2
1

White ppt.

R OH + HCl

white ppt

+ H2 O
cloudiness

R C C Ag (white)

R C C Cu (red)

RCOOH + RCOOH

2HCHO

2ROH + Na 2RONa + H2

R C CH + Ag+

R C CH + CuCl

Red ppt.

Na

(b) AgNO3 + NH4OH

(a) Cuprous chloride + NH4OH

R C C R

Acid formed.

= O Compounds

O3(ozone)

O3

Red colour decolourises

H2C = CH2 + O3

--------------

NR
NR
NR
NR
Pink colour
Disappears

Reaction

Observation

Br2 / H2O

[Bayers reagent]
alk. dil. cold KMNO4

conc. H2SO4
conc. NaOH
KMnO4
LiAlH4

Reagent

(R OH)

R C CH

CC

CC

C=C/
CC

CC

Functional
Groups

1.2 Identification of Functional Groups by Laboratory Tests

Lucas Test
I. ter.alcohol
II. sec. alcohol
III. pri.alcohol

Presence of active H

Ozonolysis

Ozonolysis

Bromination

Hydroxylation

Inert paraffins

Remarks

74

Amides

Ester

CH3CHO

or ArCOCH3
or

R COCH3

R CHO

Ar OH
Enols

Functional
Groups

(yellow orange ppt.)

Sodium bicarbonate
test

Effervescence evolve.

Pink colour

disappear on heating.

Smell of NH3

Conc. NaHCO3 solution

NaOH, phenophthalein.

Conc. NaOH,

RCOONa + NH3

Schiffs reagent : p-Rosiniline hydrochloride saturated with SO2 so it is colourless. The pink colour is resumed by RCHO.

RCONH2 + NaOH

R COOH + R OH (Colourless solution)

(pink)

R COOR + NaOH + Phenophthalein

Litmus test.

Iodoform reaction

Tollens test

Fehlings test

DNP-test

Test of
enols / phenols

Remarks

Litmus change to red.

H2O + CO2

RCHO + Ag+ RCOOH + 2Ag (Silver mirror)

RCHO + Cu+2 RCOOH + Cu2O + 2H2O

Fehling soln.
Red

+ H2

Reaction

Blue litmus

Yellow ppt of CHI3 (iodoform)

Pink colour resume

Schifts Reagent *

I2 / NaOH

Black ppt. or silver mirror

Tollens reagent

Red ppt.

Yellow orange ppt.

2, 4-Dinitrophenyl hydrazine
(2, 4-DNP) solution

Fehling solution
A&B

Coloured ppt.
(violet, blue, green buff)

Observation

FeCl3 (Neutral)

Reagent

75

Violet colour
Blue colour

Ninhydrin reagent (0.2 % sol.n)

Amino acids

Reddish violet colour.

Molischs reagent
(10% -naphthol in alcohol).

(i) NaNO2 + H2SO4

(ii) Phenol

R2NH
Sec. Amines

red colouration
Liebermann test

Orange red dye is formed

Effervescence of N2

Nauseating odour
(Carbylamine)

black ppt

Observation

Carbohydrate

HNO2 (NaNO2 + HCl)

+ -Naphthol

HNO2 (NaNO2 + HCl)

CHCl3, KOH

Mullikens test

Reagent

Ar. amines.
ArNH2

Amines (pri.)
RNH2

Nitro
Compounds
(RCH2NO2) or
ArNO2

Functional
Groups

ArNHOH

C=N C
(Blue colour)

CO

CO

C
OH

CO

+ H2N.CHR.COOH
(Amino acid)
OH

OH

(Ninhydrin)

CO

CO

Benzenediazonium
chloride
Naphthol

N=N-Cl +

OH
N=N

OH

+ CO2+ RCHO + H2O

orange-red dye

+ 2H2O

N2Cl

NH2.HCl

ROH + N2 + H2O
NaCl + HNO2

+ HNO2

Ag
Ag

RNC + 3KCl + 3H2O

NaNO2 + HCl

R NH2 + HONO

R NH2 + CHCl3 + 3KOH

Reaction

Ninhydrin test

Dye test

Carbylamine
Reaction

Remarks

Examples
1.

: Structure Determination

Identification of Organic Compounds on the bacis of Physical Properties

(a) Physical state
(b) Odour
(c) Water solubility
(d) m.p. / b.p.
(e) relative

Ex. 1

Ex. 2

Ex. 3

Ex. 4.

2.

Identification of Organic Compounds on the bacis of Chemical Properties

Ex.5

Which of the following will not give (+ve) L.S. test for Nitrogen.
(A) CH3CH2NH2
(B)
(C)

(D) NH4NO3 ( Here is no carbon for the formation of CN)

76

Instant turbidity with Lucas reagent

H2C = CH CH2 OH

CH2 = CH CH+ CH2+ CH = CH2

Allyl C+ , 1

Benzyl C+ , 1

Angle strain / less stable / unstable C+

Although 3 , but has angle strain , slow rn with HCl/ZnCl2

Other Examples

Ex.1

Ans.

Ex.2

Ans.

Ex.3

Ans.

Ex.4

CH3 CH2 C C CH2 CH3

Ans.

77

Ex.5

Ans.

CH3 CH2 CHO

Ex.6

C4H8

Ans.

CH3 CH = CH CH3

Ex.7

(A)

Ans.

A=

Ans.

CH3 CH2 COOH

Ans.

O
||
CH3 C O CH3

Ans.

A=

Ex.8

Ex.9

Na metal ve
Ex.10

A (C7H8O)

FeCl3 (neutral)

ve

Lucas
ve
Reagent
Ex.11

R gives following tests.

Ans.

78

1.

How will you distinguish the following pair of compounds.

Compounds Isomers

Reagents

(I)
(a) CH3 CH2 COOH
(b) CH3 C O CH3

NaHCO3 (+)
NaHCO3 ()

Acidic odour
Fruity/Sweet
odour

Na metal (+)
Na metal ()

O
(II)
(a) Ph CH2 C OH
Same

O
(b) Ph C O CH3

Same

Same

O
(III)
(a) Ph CH2 CH = CH2

Br2/H2 O (+)

Dil KMnO4 (+)

(b) Ph

Br2/H2O ()

Dil KMnO4 ()

(IV)
(a) CH3 CH2 CH2 OH

Na metal (+)

(b) CH3 CH2 O CH3

Na metal ()

Ceric Ammonium
Nitrate (+)
,, ()

(V)

CH3
(a) CH3 C OH
CH3

Lucas Reagent
instant turbidity

Na metal (+)

Ceric Ammonium (+)

In 5 min.

Na metal (+)

(+)

In 30 min.

Na metal (+)

(+)

(VI)
(a) CH3 CH2 CH2 CH2 NH2

NaNO2/HCl
(N2 gas )

Na metal (+)

(b) CH3 CH2 CH2 NH CH3

N2 gas not
liberated

Na metal (+)

(b) CH3 CH CH2 CH3

OH
(c) CH3 CH2 CH2 CH2 OH

2.

Tick mark the reagents which will give positive response

with the following compound.
(A) Na metal
O
O
H2N

Ans.
A
C
D
F
G
H
I
J

(B) NaHCO3
(C) 2, 4-DNP
(D) AgNO3 + NH4OH

OH

(E) Fehling solution

(F) NaNO2/HCl (cold)
(G) ZnCl2 (Anhyahous)/HCl
(H) Cu2Cl2 + NH4OH
(I) Br2/H2O

3.

(J) Dil KMnO4 (cold)

T (C7H6O2) is an aromatic white solid which liberates a
colourless odourless gas on heating with NaHCO3.
Write S.F. of X and its all possible functional isomers
(all aromatic)

Sol.

T =

79

POC - II
Separation of binary mixture of organic compounds
Theory of separation : Organic compounds have different solubilities in different solvents. So they can be
separated by use of appropriate solvents.

Purification of organic compounds :

The organic compounds derived from natural sources or prepared in the laboratory are seldom pure. They are
usually contaminated with other substances.

Purification means the removal of undesirable impurities associated with a particular organic compound, i.e
to obtain the organic compound in pure state.

Various methods have been developed to purify organic compounds

1.

Physical methods : (i) Crystallisation

(ii) Sublimation
(iii) Distillation
(iv) Solvent extraction
(v) Chromatography

2.

Chemical methods:Chemical methods of separation depend upon the nature of the functional group present in the component.
Hence these can be applied to solid as well as liquid compounds.

A chemical method can be applied only when one of the components of the mixture is soluble in a particular
solvent while the other is insoluble in the same solvent .

Separation is the first step during the actual analysis of organic mixture. It is the most important step in the
sense that if separation is incomplete the result will not be correct because the impure compound will give
tests of different functional group and its melting point will also be very much different from that of the pure
compound obtained from complete separation.

(i)
(ii)
(iii)
(iv)

Separation of Binary mixtures of organic compounds.

The usual systematic scheme for separating a solid binary mixture is discussed below.
Separation with water
Separation with sodium bicarbonate
Separation with sodium hydroxide
Separation with hydrochloric acid
Solubility of two components.
Separation Scheme
Solvent H O

(1)

Some important point :

The mixture of organic compounds can be separated by using appropriate solvent.

Most of the aromatic compounds are water insoluble due to large hydrophobic group of six carbon atom

Aromatic acids are insoluble in water but soluble in aqueous NaHCO3 solution or NaOH solution, due to salt
formation.

Aromatic hydroxy compounds are water insoluble but are soluble in aqueous NaOH solution due to salt
formation.

Aromatic amine (Aniline 1, 2, 3) are organic base and water insoluble but are soluble in aqueous HCl
solution due to salt formation.

Aliphatic compoud with atleast two functional group ( which can form H-bonding) are water soluble.
Ex. Diacids, diols. diamines, hydroxy acids ( OH, COOH), Amino acids ( NH2 , COOH) .
oxalic acid , malonic acid, maleic acid, fumaric acid, glycol, glycerol, sucrose, glucose.
80

Ex.1

Binary mixtures - (Two components)

Compound A

Compound B

Appropriate Solvent

(1)

H2O

(2)

H2O

81

(3)

Fructose

H2O

(4)

aq. NaHCO3

(5)

aq. NaOH

(6)

aq. HCl

Ex.2

Sol.

Identify I & II.

I A, II B

Ex.3

Identify I & II
Sol.

Q,

Ex.4

P+Q+R

Identify P, Q, R
Sol.

PI

Q II

R III

82

Ex. 5. Mixture separation

(1)

(2)

(3)

Succinic Acid + Phthalic Acid + orthoCresol

III

83