LECTURE NOTES

Session - 2009-10

ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :
1 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 iden-
tification 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.

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 STRUCTURE INDENTIFICATION
Monochlorination:-
Cl / h
(a) (i) CH4 2 CH3Cl + HCl

Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl
Cl

Cl / h
(iii) 2 + HCl
C C
Cl2 / h

(iv) C C C C C C Cl + HCl
C C
Cl
Cl / h
(v) 2 + 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.

Monochlori nation
Ex. (a) C C C 2 Products (structure isomers)
Monochlori nation
(b) C C C C 2 Products (structure isomers)
Monochlori nation
(c) C C C C C 3 Products (structure isomers)
Monochlori nation
(d) C C C C 4 Products (structure isomers)

C
CH3

Monochlori nation
(e) 5 Products (structure isomers)

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

Ans. X = Neopentane

Cl / h
Q. P(C6H14) 2 Two monochloro

How many isomers of P will give two monochloro compounds ?

C C

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 CH2Cl

Cl / h
Ex. 2

64
 Cl / h
Q. X(C8H10) (Aromatic) 2 Two mohochloro
Cl / h
Y(C8H10) (Aromatic) 2 One monochloro

Ans.

(X) (Y)

Catalytic Hydrogenation of C = C; C C
General reaction:-
Ni
(a) R CH = CH R + H2
R CH2 CH2 R
Ni / Pt / Pd
(b) R C C R + 2H2 R CH2 CH2 R
H2

H2
R CH CH R R CH2 CH2 R
(Not isolated)
2H2 / Ni
(c) CH2 = CH CH = CH2 CH3 CH2 CH2 CH3

3H2 / Ni
(d)

CH = CH2 CH CH3
H2 / Ni 2
(e)
room temperature
CH CH3
H 2/Ni 2
(100 150C)

(f) H / Ni, [Reaction cannot be stopped at any intermediate stage]

2

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 hydrogena-

tion.

65
 During catalytic hydrogenation and monochlorination, carbon skeleton remain unchanged.

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

C Cl

2H2 / Ni Cl / h
Ex. (1) 2 Y + Z
(X)

Y = Cl Z =
Cl

CH3 CH3
H / Ni Cl / h
(2) 2 2 5 Monochloro product

CH3 CH3
H / Ni
(3) 2 5 Monochloro product

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

Identify X, Y, Z

Ans. DU = 2
Cl

X , Y , Z

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

C5H12 = 72g

Q. Identify the structure of hexane which gives 3 monochloro products ?

C

Ans. C C C C, CCCCCC
C

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

Ans. DU = 2

2 monochloro product

Q. Find the structural isomers of fully saturated cycloalkane of M.F. C6H12 which gives two monochloro
product?

Ans.

Cl / h
Q. A 2 C 8H17 Cl
(C8H18 ) (Only one type )

Identify A ?

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 C C

Ans. C C CC
C C

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

Ans. (i) C C C C C (ii) C C C C C
C
(b) two monochloro
Ans. Nil

Q. Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogena-
tion 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.

(1) O 3
General Reaction:- R CH = CH R R CH = O + O = CH R + ZnO + H2O
(2) Zn/H2O

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

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

O3 / Zn
(3) CH2 = CH CH2 CH = CH CH3

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

67
 O / Zn
(4) 3 + OHC CH2 CHO (Propandial)

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.

C O3
(1) O = C C C C C = O + O = CH2

Zn
O
C

O ()
(2) 3
Zn

CH = CH CH3 CH = O
low temperatur e
(3)
+ O = CH CH3
O3 / Zn

CH = CH O3
(4) C6H5 CH = O

Zn

H / Ni Cl / h
Q. (P) 2 CnH2n 2 2 CnH2n1Cl
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 H / Ni Cl2
Q. 2 m products
(Unsat. hydrocarbon) h
(m 3 )

O 3 (Zn/H2O)

identify structure of X ?
O

Ans. X =

H / Ni Cl / h
Q. X 2 2 m products
(Unsat. H.C.) (m 7 )

O 3 (Zn/H2O)

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

Identify X ?
C

Ans. X

C=CC

Q.

Identify structure of X ?

Ans. X is

H2
Q. X CCCCCC

O3 (Zn)

CH3CHO + CHO CHO

Identify structure of X ?
Ans. X is C C = C C = C C

69
Q.

CH
3 O3
Sol. 2 +

CH3 Zn, H2O

CH
3 CH3 CH3
O3
C C +2
CH3 Zn, H2O
O O

Q. A 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
Two monochloro products
s
( Saturated
Hydrocarbon)

C C
| |
Sol. A= or B = CCCC C =
| |
C C

Ex.2 Identify -Terpinene and P-Menthane.

Sol. -Terpinene

Ex.3 Identify A & B

Sol. A = CH3 C CH CH CH2 B = CH3 CH CH2 CH2 CH3

| |
CH3 CH3

70
Ex.4 Identify A & m

Sol. m=3 A = Ph C C Ph
| |
CH3 CH3

Ex.5 H 2 / Ni
A Cl / h n-products
2

O3
+ H C H +
Zn/H 2O

H C C CH2 CH2 C C H

Sol. A= n=7

71
1.1 Identification of Elements in Organic Compounds
Element Test / Reaction Remark
1. Nitrogen 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 (a) Oxidation test Formation of a white ppt.

3KNO3 3KNO2 + 3[O] indicates presence of sulphur

Na2CO3 + S + 3[O] Na2SO4 + CO2

BaCl2(aq) + Na2SO4(aq) BaSO4 + 2NaCl(aq)

Appearance of purple
(b) Lassaignes test
colouration confirms the
2Na + S Na2S
presence of sulphur
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NO.S]

Lassaignes test A white ppt. soluble in NH4OH

3. Halogens
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 indi-

cates iodine

A white ppt. of magnesium

4. Phosphorus
pyrophosphate indicates
phosphorus

H3PO4 + Magnesia mixture MgP2O7 + H2O

2MgNH4PO4 Mg2P2O7 + 2NH3 + H2O

5. Nitrogen Lassaignes test Blood red colouration confirms

and presence of both nitrogen &
FeCl
3 Fe(SCN)3
Na + C + N + S NaSCN sulphur
Sulphur

72
 1.2 Identification of Functional Groups by Laboratory Tests

Functional Reagent Observation Reaction Remarks

Groups

CC conc. H2SO4 NR
NR Inert paraffins
conc. NaOH --------------
KMnO4 NR
LiAlH4 NR

[Bayers reagent] Pink colour Hydroxylation

alk. dil. cold KMNO4 Disappears
C=C/
CC
Br2 / H2O Red colour decolourises white ppt Bromination

O3(ozone) = O Compounds Ozonolysis

CC H2C = CH2 + O3 2HCHO

CC O3 Acid formed. R C C R RCOOH + RCOOH Ozonolysis

(a) Cuprous chloride + NH4OH Red ppt. R C CH + CuCl R C C Cu (red)

R C CH
(b) AgNO3 + NH4OH White ppt. R C CH + Ag+ R C C Ag (white)

(R OH) Na Bubbles of H2 come out 2ROH + Na 2RONa + H2 Presence of active H

ROH Lucas Reagent (3) Cloudiness appears Lucas Test

3 [Conc. HCl + anhyd. ZnCl2] immidiately R OH + HCl + H2 O I. ter.alcohol
2 (2) Cloudiness appears within cloudiness II. sec. alcohol
1 5 min. III. pri.alcohol
(1) Cloudiness appear after
30 min.

73
 Functional Reagent Observation Reaction Remarks
Groups
Coloured ppt. Test of
Ar OH FeCl3 (Neutral)
(violet, blue, green buff) enols / phenols
Enols

+ H2
2, 4-Dinitrophenyl hydrazine
Yellow orange ppt. DNP-test
(2, 4-DNP) solution
H (yellow orange ppt.)

Fehling solution Red ppt. RCHO + Cu+2 RCOOH + Cu2O + 2H2O Fehlings test
A&B Fehling soln. Red
R CHO Tollens reagent Black ppt. or silver mirror Tollens test
RCHO + Ag+ RCOOH + 2Ag (Silver mirror)

Schifts Reagent * Pink colour resume

R COCH3
or ArCOCH3
or I2 / NaOH Yellow ppt of CHI3 (iodoform) Iodoform reaction
CH3CHO

Blue litmus Litmus change to red. Litmus test.

Conc. NaHCO3 solution Effervescence evolve. Sodium bicarbonate

H2O + CO2 test

Ester NaOH, phenophthalein. Pink colour R COOR + NaOH + Phenophthalein

(pink)
disappear on heating.
R COOH + R OH (Colourless solution)

Amides Conc. NaOH, Smell of NH3

RCONH2 + NaOH RCOONa + NH3

74
Schiffs reagent : p-Rosiniline hydrochloride saturated with SO2 so it is colourless. The pink colour is resumed by RCHO.
 Functional Reagent Observation Reaction Remarks
Groups
Nitro
Compounds black ppt
Mullikens test ArNHOH Ag
Ag
(RCH2NO2) or
ArNO2
Nauseating odour R NH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O Carbylamine
CHCl3, KOH (Carbylamine) Reaction
Amines (pri.)
RNH2
Effervescence of N2 R NH2 + HONO ROH + N2 + H2O
HNO2 (NaNO2 + HCl)
NaNO2 + HCl NaCl + HNO2
NH2.HCl N2Cl
Orange red dye is formed
Ar. amines. HNO2 (NaNO2 + HCl)
+ HNO2 + 2H2O
ArNH2 + -Naphthol
OH Dye test
OH
N=N-Cl +
N=N
Benzenediazonium
chloride
Naphthol
orange-red dye
red colouration
R2NH (i) NaNO2 + H2SO4
Liebermann test
Sec. Amines (ii) Phenol
Reddish violet colour.

Carbohydrate Molischs reagent Violet colour

(10% -naphthol in alcohol).

Amino acids Ninhydrin reagent (0.2 % sol.n) Blue colour CO OH

C + H2N.CHR.COOH
CO OH (Amino acid)
(Ninhydrin)
Ninhydrin test

CO CO
C=N C + CO2+ RCHO + H2O
CO C
(Blue colour) OH

75
 Examples : Structure Determination
1. 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. CH3 CH2 C C CH2 CH3

Ex.2 Ans.

Ex.3 Ans.

Ex.4 - Ans.

77
Ex.5 Ans. CH3 CH2 CHO

Ex.6 C4H8 Ans. CH3 CH = CH CH3

Ex.7 (A) Ans. A=

Ex.8 Ans. CH3 CH2 COOH

O
||
Ex.9 Ans. CH3 C O CH3

Na metal ve
Ex.10 A (C7H8O) Ans. A=
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
1 2 3
(I)
(a) CH3 CH2 COOH NaHCO3 (+) Acidic odour Na metal (+)
(b) CH3 C O CH3 NaHCO3 () Fruity/Sweet Na metal ()
O odour
(II)
(a) Ph CH2 C OH
O Same Same Same
(b) Ph C O CH3
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 (+) Ceric Ammonium
Nitrate (+)
(b) CH3 CH2 O CH3 Na metal () ,, ()

(V)
CH3

(a) CH3 C OH Lucas Reagent Na metal (+) Ceric Ammonium (+)

CH3 instant turbidity

(b) CH3 CH CH2 CH3 In 5 min. Na metal (+) (+)

OH
In 30 min. Na metal (+) (+)
(c) CH3 CH2 CH2 CH2 OH

(VI) NaNO2/HCl Na metal (+)

(a) CH3 CH2 CH2 CH2 NH2
(N2 gas )

(b) CH3 CH2 CH2 NH CH3 N2 gas not Na metal (+)

liberated

2. Tick mark the reagents which will give positive response Ans.
with the following compound. A
O (A) Na metal C
D
O (B) NaHCO3
O F
H2N (C) 2, 4-DNP G
(D) AgNO3 + NH4OH H
OH I
(E) Fehling solution
J
(F) NaNO2/HCl (cold)
(G) ZnCl2 (Anhyahous)/HCl
(H) Cu2Cl2 + NH4OH
(I) Br2/H2O
(J) Dil KMnO4 (cold)
3. T (C7H6O2) is an aromatic white solid which liberates a Sol.
colourless odourless gas on heating with NaHCO3.
Write S.F. of X and its all possible functional isomers
(all aromatic)
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.
Separation of Binary mixtures of organic compounds.
The usual systematic scheme for separating a solid binary mixture is discussed below.
(i) Separation with water
(ii) Separation with sodium bicarbonate
(iii) Separation with sodium hydroxide
(iv) Separation with hydrochloric acid
Solubility of two components.
Separation Scheme

Solvent H O
2

(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 +

Identify I & II.

Sol. I A, II B

Ex.3 +

Identify I & II
Sol. Q, P

Ex.4 + +

P+Q+R

Identify P, Q, R
Sol. PI Q II R III

82
Ex. 5. Mixture separation

(1)

(2) Succinic Acid + Phthalic Acid + orthoCresol

(3) + + III

83