1 IUPAC Naming

+ - D > lowest locant (branch jis ‘c’ se attached hai uska no.)
NH4CNO NH2–CONH2 > alphabetical order

 Large number of compounds of ‘C' ( m ethyl, e thyl: alphabets priority e > m

.
Tetravalency of carbon P.S.S
 # agar = & ≡ dono aye
Catenation (self linking prop): C–C–C–C– toh = > ≡ agar same no, mile toh
C–C–C

CH4
H sp3–s
 IUPAC Naming of Functional groups
‘H’ 1s1 H—C—H F.G. SUFFIX-2 PREFIX
‘C’ 1s2 2s2 2p2 H
Carboxylic [oic acid] carboxy
acid(–COOH)
Sulphonic [Sulphonic acid] Sulpho
acid(–SO3H)
4sp3 anhydride [oic anhydride] -
O O
C4H10MF
(—C—O—C—)
CH3—CH2—CH2— CH3
Ester [oate] Alkoxycarbonyl
Bond line structure
O
H H H
H
H H (—C—OR)
H acid chloride [oyl chloride] chlorocarbonyl
H H H
 IUPAC Naming Rule O

Prefix + Word root + Suffix–1 + Suffix-2 (—C—Cl )

(functional
acid amide [amide] carbamoyl
Branch No. of ‘C’ C–C ane group)
–R (alkyl) in parent chain C=C ene (–OH) O
–OR (alkoxy) 1 meth C≡C yne (–COOH)
–NO2 (nitro) 2 eth (—C—NH2)
–F (Fluoro) 3 prop
–Cl (Chloro) 4 but cyanide (–CN) [nitrile] cyano
–Br (bromo) 5 pent
–I ( iodo) 6 hex isocyanide [isonitrile] isocyano
–No (nitroso) 7 hept
8 oct (–NC)
–ph (Phenyl) 9 non
10 dec aldehyde [al] aldo and formyl
(–CHO)
ketone [one] keto or oxo
O
 Priority: (—C—)
alcohol (–OH) [ol] hydroxy
PFG (principle funcn group or suffix - 2)
> Multiple bonds (= & ≡) thiol (–SH) [thiol] mercapto
> Number of C atoms
amine (–NH2) [amine] amino
> maximum number of substituents (prefix)
 Aldo or oxo formyl
1
O O O O 1-Butyl cyclopropene
H—C—CH2–CH2–C–OH H—C—CH2–CH2–C–OH 3 2
4 3 2 1 3 2 1 COOH
4-Aldo butane–1– 3-formyl propane–1– 1
oicacid oicacid
Cyclopropane–1–carboxylic acid
3 2
 IUPAC nomenclature of Ester F.G. SPECIAL SUFFIX-2 (Jab ‘c’
O CH3 count na ho raha ho)
2
1 Carboxylic acid Carboxylic acid
3 Super prefix
O Sulphonic acid Sulphonic acid
Methyl prop–2–ene–1–oate Ester Carboxylate
acid chloride Carbonyl chloride
 IUPAC Naming of Cyclo compounds acid amide Carboxamide
cyanide Carbonitrile
Rule: Prefix + Cyclo-Word root + Suffix-1 + Suffix-2
aldehyde Carbaldehyde
Priority: ketone one
PFG > Multiple bonds > Number of C atoms > alcohol ol
Ring thiol thiol
# If carbon containing F.G. is directly attached amine amine
with the ring then they are taken as part of the
 IUPAC Naming Rules of Benzene Derivative
ring. (Ring ki numbering karenge)
1. If organic compound is having one F.G. then
# If no. of carbon atoms are same then priority common name is retained in IUPAC
Ring > Chain COOH COOR OH

 1
1-Propyl cyclopropane Benzene carboxylic acid Alkyl Benzoate phenol
2 3 or Benzoic acid

1 2 SO3H COCl CH3

1-cyclopropyl ethene

Benzene Sulphonic
Benzoyl chloride Toluene
acid

2 1
COOH CONH2 CHO OCH3

2-cyclopropyl ethane–1–oic acid

Benzamide Benzaldehyde Anisole

CN NH2
1 23
4

1-cyclopropyl butane
Benzonitrile Aniline

132
Organic Chemistry
 2. If more than one F.G. are present then 2 1
CH2–COOH
numbering is done according to IUPAC.
1′
OH COOH 6′ 2′ 2–(4′-carboxyphenyl)
1 1
5′ 3′ ethanoic acid
6 2 6 2 4′
5 3 5 3
COOH
4 4
OH COOH
Benzene–1,4–diol Benzene–1,4– IUPAC NAMING OF POLY FUNCTIONAL
 
dicarboxylic acid COMPOUNDS
3. If hydrocarbon is combination of both open If more than two carbon containing
chain and ring part then except Me and Et functional groups are present on adjacent
open chain part is taken as main part. carbons then they are not counted in
1 2 3 1 2
principal chain.
CH2CH3 CH2–CH2–CH3 CH=CH2
1 1 2 3
6 2
5 3 propane–1,2,3–
4
tricarboxylic acid
1–Ethyl benzene 1–phenyl propane 1–phenyl ethene COOH COOH COOH
4. If organic compound is having F.G. then part
having F.G. is taken as main part.
2 1 1 2 3
CH2–COOH CH3
4 propane–1,2,3–
5 3 tricarbonitrile
6 2
1 CN CN CN
2–phenyl ethanoic acid
COOH
4-methyl benzoic acid IUPAC
  Naming of complex branches:
5. If both parts are having F.G. then part having
7 5 3 1
P.F.G. is taken as main part.
4
2 1 8 6 2
CH2–COOH CH2OH 1′
1′ 4
2′ Me2CH–
6′ 2′ 5 3
(CH3)2CH–
5′ 3′ 6 2 4–(1′-methyl ethyl) octane isopropyl
4′ 1
OH COOH
2–(4′-Hydroxy phenyl) 4-Hydroxy methyl
or isopropyl
ethanoic acid benzoic acid
6. If there is choice, priority is given to open
part.

Raaz toh hmara har jagah pr hai

Pasand krne walo ke dil mein, aur
napasand krne walo ke dimag mein.

133
IUPAC Nomenclature
 2 Isomerism

ISOMERS x = no. of ‘c’ in parent

. ck chain
P.S.S o . tri I
Compound having same M.F ic n P. y = no. of branches of ‘c’
Mag r CI &
fo Magic no ⇒ diff ⇒ C.I
but diff physical & chemical prop.
XY same ⇒ P.I

TYPES OF ISOMERISM C.I 1 2 21

2 4 Cl P.I
3 2
1. Structural isomerism Mf = same, structure diff, IUPAC name Cl Cl Cl
1 1 3
diff
2. Stereoisomerism Mf = same, diff orientation of groups 40 31 20 20
in space, IUPAC name same
1
1 CN
TYPES OF STRUCTURAL 3
2
CN C.I
ISOMERISM 4 2
3
40 31
1. Chain Isomerism

Compound having same MF. but different parent 3. Metamerism

chain. MF Same but difference in arrangement of atoms
n
or groups from either side of Bridging func group
(Polyvalent)
2 4
3 2 *
1 C.I O O
1 —O— —NH—
3 —C—O—C—
—S— —N
—C— O
2. Position Isomerism O
O —C—O—
MF = same, different position of branch like R or
—C—NH—
F.G. like OH, NH2, OR, SH —C— O —C—

S —C—N— O
3 1 3 1
2 OH 2 PI
4 4 2 3
1
OH C—C—C—O—C C—C—O—C C—C—O—C—C
—

’ C
3 ‘c al 1‘c’ 1‘c’ 2‘c’ 2‘c’
m
4 4 2 nor Branch

3 PI 1, 2, 3 are metamers
5 2 5 1
3 1 4. Functional isomerism
MF same, different F.G.
O O
2
3 PI keto F.I.
2 1 OH
1
O ene alc.
Some examples of F.I. 2 1O 2 OH
O  1, 5-system sp sp
3 2 3
ail
a. Aldehyde & ketone: H 1,3 f a
Jab hog 4 4
l
O 3 5H Pheno
sp
b. Carboxylic acid & ester: CH3COOH, HCOOCH3
2 1 + –
1,2-system H –C≡N H–N≡C
c. Alcohol & ether: OH
O
d. Cyanide & isocyanide: RCN, RNC

e. 1°, 2°, 3° amines: CALCULATION

 OF NUMBER OF
2° 3° STRUCTURAL ISOMERS
1° NH N
2 NH Degree of unsaturation (D.U)

or, double bond equivalent (D.B.E)
f. 1°, 2°, 3° amides:
H + X- N
NH2 NH N DU=(C + 1) -  
O  2 
 O O
   
g. diene, yne: C = no of 'C' atoms DU = 0 ⇒ all single bond
H = no of 'H' atoms DU = 1
5. Ring Chain Isomerism
X = no of 'X' atoms 1π 1 Ring
MF ⇒ same
N = no of 'N' atoms
1st Ring DU = 2
1π + 1 Ring
2nd Chain 2π
2 Ring
6. Tautomerism
Total structural isomers
Keta-enol system 1 3
O H sp O–H
1, 3-system
CH3–C–CH2 CH3–C=CH2  10 + 0 - 0 
n
Cond for exhibition
α
2 3 α-H 1 C5H10 DU = (5 +1) -  
keto ene+ol  2 
of tauto. +
Intramolecular H enol
1 α–c should be sp
3 transfer = 6 – 5 = 1
1, 3 system
2 Presence of α–H 1π 1 Ring

Examples of Tautomerism:
O Total 10
O

O
O O

O  Alkanes No. of structural isomers

O
O
C4H10 2

Ph–CH=CH–OH C5H12 3

135
Isomerism
 C6H14 5  Ring: -

C7H16 9 a) Two different group at different positions.

b) Hybn sp3
C8H18 18
b
C9H20 35 a a

C10H22 75 Cis-
a sp 3
a
TYPES OF STERO ISOMERISM b
H H
a H
Configurational Isomerism
Trans

H a b
IUPAC name same
    
TYPES OF G.I
TYPES OF CONFIGURATIONAL Case 1: Cis -Trans
ISOMERISM similar groups same side cis
otherwise trans
1. Geometrical Isomerism
Me Me Me H
Arises due to restricted rotation around
C=C, C=N, N=N, Ring C = C C = C
H H H Me
Condn :- Restricted site must have diff groups Cis
Trans
a X a Y
diff. Case 2:
C = C diff. C = C Z/E
b Y b X
zusammen Entgegen
. same side opp. side
 Example of GI P.S.S
Cis/trans fail hoga toh Z/E Sochna hai
No 1
H H3C Br
H I
1) Same C = C 5) C C = C
1
H NH2 Cl NH2
(No) HO
E

Br ××
diff H  C.I.P rules
2) diff C=N 6) C 1. Atomic no , priority
Cl Yes OH Yes Cl
2. Atomic no of 1st atom same

H go for next atom apply rule 1

3) 7) C
×× ××
azo
3. In Isotopes mass no , priority
N=N Yes Cl
R R Comp O C
Always
C = O > C – O'
GI
N C O C
H H C N < C = O
4) C 8) C Same
Cl No H N C
No

136
Organic Chemistry
SPECIAL CASES n +1
P = (n = odd)
Case 1: Odd no. of cumulative double bond 2

Py–Py P –P P –P X
a z z y y CH3–CH=CH–CH=CH–CH=CH–CH3
C C C C
b n = 3
Y
Br Me 3+1 4
P = = = 2
C=C=C=C 2 2
Cl G.I. H Total G.I. = 23–1 + 22–1

Case 2: Odd no. of Rings (spiro) = 22 + 21

X = 4 + 2 = 6
a

b Y PROPERTIES OF
GEOMETRICAL ISOMERISM
Case 3: Cumulative double bond + Ring = odd
a. BP: Cis > Trans (BP ∝ DM)
a X
Me Me H
Me DM
C=C C=C m=0
b Y H
DM ≠ 0 H Me
Case 4: Cycloalkene m≠0
8 memb
b. MP: Cis < Trans

c. Stability: Cis < Trans

d. Solubility: Cis > Trans

2. Optical Isomerism

Chiral carbon

CALCULATION OF G.I. sp3 'c' attached with 4 diff groups

A
Case 1: If molecule is Unsymm OH
*C * H CH3
Total G.I. = 2n,   n = sites where G.I. exhibits X B H *
*
OH H
Y
CH3–CH=CH–CH=CH–CH=CH–CH2Br


n = 3, Total G.I. = 23 = 8. dextrorotatory

If compound CW 'd' or +
Case 2: If molecule is symm. rotates PPL
ACW 'ℓ' or –
Total G.I. = 2n–1 + 2P–1 O.A
laevorotatory
If compound does not
n rotate PPL
P = (n = even) O.I.A
2

137
Isomerism
 condn for exhibition of opti Iso: 1
3CH
3
Br
assymetry(chirality). 4 2 3
H OH HO CH3 Enantiomer
pos cos comp 2
4
Br H
OIA 1
x OIA S
x OIA R
.
x x O.A ← P.S.S
Jab Aankhon se na dikhe

POS (plane of symm) Comp 1 Comp 2
COS (center of symm)
(acyclic & cyclic) cyclic comp R S

A
E
P even membered
ring
Me H Me H
S
R
R
R
pos (x) I
pos ( ) S S
CH3 CH3
* Me Me H Me
H OH H OH
diff cos ( )
Et pos (x) CH3 Case 2 If two chiral carbons are present
cos (x)
pos ( ) CH3 CH3
H OH HO H Enan
H OH HO H
 R/S nomenclature  Br Br

In fischer projection formula CH3 CH3

Case 1 if 4 is on vertical then check direction H OH H OH Diastereo
of movement from 1→2→3 HO H H OH
4H R → Rectus (CW) Br Br
1 3 S S → Sinister (ACW)
 I NH2 Comp 1 Comp 2
Answer
Br D
2 Enan
or R,R R,S
Case 2 if 4 is on horizontal make a switch Iden E
D E D
or
CH3
3
Diastereomer S,R S,S
H
4 1
OH D
2
1) not mirror images
NH2 2) phy & chem prop diff
S
 Relation b/w compounds
Meso Compounds
Case 1 If only 1 chiral carbon is present
Answer : Enantiomer or Identical
atleast 2 chiral carbon c-car( )
Enan: 1) non super imposable mirror images with pos or cos pos( )
c-car(2)
2) phy & chem prop same 2 ) pos( ) meso(X)
a r( ( ) CH3 * meso( )
CH3 CH3 c.cpos H * OH *
H
H OH HO H Enantiomer * OH
meso CH
( ) 3
Br Br

138
Organic Chemistry
RACEMIC MIXTURE EPIMERS
.
equimolar mix of two enantiomers P.S.S
CH3 CH3 Diastereo 1 1
A & B are enantiomers CHO CHO
H * OH HO * H A → OA θ = +30°
but 1 chiral 2 2
H OH HO H
Et carbon
Et B → OA θ = –30° 3 3
par he HO H HO H
A B 4 4
A+B → O.I.A θnet= 0 config H OH H OH
change 5 5
due to external H OH H OH
hoga
compensation 6
CH2OH 6
CH2OH
Glucose C-2 epimer
RESOLUTION
Sep of pure enantiomers from R.M
CALCULATION OF OPTICAL
Rxn
A+B A + B
ISOMERS
RM
Case 1 if molecule is unsym
PSEUDO CHIRAL CENTRES Total O.I = 2n n = chiral carbon
a) 'c' attached with two diff group
O.A = 2n
b) other two groups are same but exhibit G.I or
have chiral carbons meso = 0

*CH(OH)CH OA
CH—
—CH—CH3 3 R.M =
2
— —

**C — OH
— —

**C — OH
H— H—
4
CH3 n = 2 Total OI = 22 = 4 RM = =2
CH(OH)CH3 2
CH—
—CH—CH3 OA = 4
* CH(OH)
meso = 0
* CH(OH)

SPECIAL CASES Et

1 even no. of cumulative 2 even no. of spirane rings

Case 2 If molecule is sym
double bonds A X
n
O.A P=
f — C—
C— —C diff B Y
(a) n = even 2
dif O.A

NH2 n-1 p-1

HO H
HO Total OI = 2 + 2
same
— C—
C— —C O.A H NH2 OA meso
pos ( )
Br Br
OIA OA
R.M =
2
e nyls
3 Biph CH3 n=2 P=1
G G diff NO2 NO2 diff 2-1 1-1
* CH(OH) Total OI = 2 + 2
= 2 + 1
* CH(OH) meso
G G COOH COOH
G → bulky group
POS ( ) O.A
OA CH3
2
G ‡ H,D,T,CN,F,OH RM = = 1
2

139
Isomerism
(b) n = odd 1 2
n-1
Total OI = 2 b) butane CH3—CH2—CH2—CH3
n-1
meso = 2 2
Me
Me Me
OA = OI - meso H 60° Me
θ=60°
OA
R.M = H
2 H H
H H
H H
CH3 n=3
Eclipsed Staggered
* CH(OH) OI = 23-1 = 4
3-1 Fully Eclip Gauche
2
meso = 2 = 2
* CH(OH) Me
O.A = 4-2 = 2 H Me
* CH(OH) H H
2 θ=60°
RM = = 1
CH3 2 θ=60° H H H H
H Me Me
CALCULATION OF STEREO Eclipsed Staggered
ISOMERS Partially Eclip Anti
n = chiral carbon + site of GI exhibition Energy Stability
Total [A < G < PE < FE] [A > G> PE > FE]
n stereogenic area
S.I = 2
* *
GAUCHE EFFECT
CH3—CH——CH—CH—CH3 CH2 CH2 G>A>PE>FE
—

n=2 OH F OH [Stability]
2 CH2 CH2
Total S.I = 2 = 4
G G O H
chelate
Conformational Isomerism G → Hydrogen
H F
bonding Most stable
1) free rotation around σ bonds
conformation
F,O,N H H
2) C—C σ bond H
Gauche ÷ Stablised by
3) Total Conformers = ∞
Hydrogen bonding

CONFORMERS OF ALKANES
CONFORMERS OF CYCLOHEXANE
a) ethane CH3—CH3
dihedral Stability Stability
H angle C > T.B > B > H.C
HH
S > Skew > E

H H θ=60° Energy
chair Energy
S < Skew < E
C< TB < B < HC
H H Twist boat
H H
H H H (Chiral)
max. stable (OA)
Skew min. stable Boat
Staggered Eclipsed
Half chair

Jo kahi geere nahi, unhe kha asmaan ki

uchaiyo ka pata hota hai.

140
Organic Chemistry
 3 GOC

1. Nucleophilicity O O
–
+
1 1 1 N
Nu− ∝ ∝ ∝
EN Reso Bulkiness.
– Shows –M
O
O
– –  With respect to group already present, it’s
CH3—CH2—O > > CH3—C—O
Meta position is not affected by Meso or
Nu– α LP α –ve charge α size of C– Reso effect.

F– < Cl– < Br– < I– [Polar protic solvent] Only Inductive!
– – – –
Polar Aprotic = F > Cl > Br > I .

2. Priority Order  Cyclic > Linear > Cross conjugation.

A >  M  >  H  >   I.  More equivalent resonating structure of

CB, Acidic Nature
Aromatic mesomeric Hyperconjugation Inductive

3. ORDERS: Rules for Resonating Structure

– – – – Stability:- least stable: (++) or (––) near
Activator s

1. Octet complete.
2. Neutral structure > Charged ones.
+I:– –CH2– > –NH– > –O– > –COO– >
3. Greater No. of p bonds
3°R > – 2°R > – 1°R > – Me – – –
4. More EN = –ve Charge
– – –
Less EN = +ve Charge.
– – –
Deactivators 5. +ve & -ve charge near to each other
–

–SR 2+ > Bredt's Rule

– – – – 1. At bridge head carbon, +ve is not accepted
>–F >–Cl >–Br >–I >–OR >–OH > till total no. of carbon in the ring is 8. After
8-carbon sp2 chalega!
– NH2 – Ph

Cl NR3 NH3 F Effect of Resonance

1. Max e– density.

= to – 1
2. –to = BL ∝
BL ∝ Reso Re so
(No d-orbital )
-I (Not-M) Aromaticity ∝ Reso Energy ∝ Reso
Stability Order:- VIMP TRICK
> >
D  N  P
Conjugated Isolated Cumulated
distance Number Power

HOH Order:- STABILITY ORDERS

y
Onl
e
ctiv
indu+ + +
 CT3 > CD3 > CH3
Hyperconjugation [H > D > T]
n
njug
Hyperco
Alkene:– s – p* overlap
+ + +
 CH3–CH2 > CD3–CH2 > CT3–CH2
Me H CH3 CH3 Me H α-H = 3 3 α-D 3 α-T
C=C C=C C=C +
Me H H H H Me CH2
Geminal Cis trans.

+
Stability: Geminal > Trans > Cis. 9 αH
5 R.S.

+ +
 Heat of hydrogenation is energy released CH2 Ph3C
to convert multiple bond into single bond
in a molecule via addition of H2. Cyclopropyl
1
 Heat of hydrogenation ∝ No of∝ π bond
Very Stable Methyl
Re so +
Dancing
 If No of p bonds are same then C Reso Carbocation.

Stability Stability Order of Carbocation

+ + +
1  C C-H CH2
∝ No. of α–H ∝
HOH.

Reactivity of benzene. Ph3C

+
Ph2CH+

Me Me
α α +
CH2
α CH3 Me–C–H Me–C–Me
α
+
(CH3)3C +

+ + +
[CH3]2CH CH3- CH2 CH3
α–H = 3 α–H = 2 α–H = 1 α–H = 0.
 Reactivity ∝ α–H

142
Organic Chemistry
 CH2 CH2 - - O
OH
 O O
Cross conjugation

-I Max. OH O O O O
n cyclic
+ M dist -I Min
reso >
independent + M. 1>2
CH2 CH2 Bredt rule
Cl
 Ph3C > Ph2CH > PhCH2
Cl Ph3C > Ph2CH > PhCH2
-I Max -I less Ph3C > Ph2CH > PhCH2
–I > +M from m-position
IIT
only inductive !

+ –
 Stability of C and C :-

+ +M, + I
C ∝
-M, - I
-M, - I Ph - CH2
- O
C ∝
+M, + I
One of Most
+
Stable C .
V.imp Examples:-
Equivalent
O
Reso. –
- CH 2 Theory Acid Base
CH3-C-O 1] Arrhenius. +
H (aq) donor –
OH (aq) donor

Proton-donor Proton acceptor

F Cl 2] Bronsted-Lowry
HCl H+ + Cl
–
NH3 + H+ NH4
d orbital
F-C- Cl - C-
3] Lewis L.P. Acceptor. H L.P. Donor
NH3 + H+
Reso. Base Acid
H-N→H
H
F Cl
Acidic nature
CH–2 1 R.S. 1> COOH
Anti H–COOH
5 R.S. 2 R.S. aromatic COOH
(4n ϖe–) 2> HCOOH Ph–COOH CH3–COOH

O 3> COOH H COOH

-M Reso H
CH2- C-H H-bond

O O O H COOH H
-M
-M
— -M — Maleic Acid. COOH
H- C- CH- C-H CH3- CH- C-H
Fumaric Acid.

143
GOC
4> H H 1
H Basicity ∝
CH2= CH Aromaticity.
H–C ≡ C–H
e density
-

sp decreases
Aromatic sp2
zoic acid
Basicity order
only in Ben
Ortho Effect not in P he no l
Guanidine > amidine > aliphatic amine >
Repulsion b/w COOH & ortho group such that aromatic amine > imine > amide > cyanide
COOH goes out of plane & M does not operate. NH2
Acidity ↑ .
Guanidine:- H2N-C = NH

Ortho Substituted Benzoic Acid or 1

Benzoic Acids (m & p-isomer). Basicity ∝
Reso
+ -
(Acidic strength) O
Lp in
SIP effect (for aromatic 1° amine) N N N Reso.
N
Aniline > Ortho substituted aniline sp2 sp2
H H H
 (Basic strength) 1 2 3 4
NH2 NH2 NH2 NH2
Kb :- 1 > 2 > 3 > 4.
Me


CH3
CH3 sp2(p) – sp2(p) overlap

SIR Effect Benzyne

In case of aromatic 3° and 2° amines, due to repulsion C sp3Hyb.

b/w lone pair of N & ortho group such that lone F
F F
pair goes out of plane & M does not operate.
basicity ↑ .
Rearrangement of carbocation
Basic nature of amine
Migratory Aptitude:-
Aliphatic Aromatic

R R H > Ar > R.

NH3 R-NH2 R-N-H R-N-R

1° 2° 3° Reaction
In Gas Phase (or non-polar solvent):-
3° > 2° > 1° > NH3
Substitution Addition
In aq. medium
Rxn Rxn
R = CH3. R = Ethyl.
2 > 1 > 3 > NH3 2 > 3 > 1 > NH3 Single bond or
bond
involved

Lakshya ko pane ki chingari rakho seene mein

Sangarsh se kabi mt daro, tabhi majja hai
jeene mein.
144
Organic Chemistry
 Qualitative, Quantitative
4 Analysis and Purification

QUALITATIVE ANALYSIS OF TEST FOR NITROGEN

ORGANIC COMPOUNDS 1. Sodium fusion extract (NaCN) is boiled
 Carbon and hydrogen are detected by with freshly prepared ferrous sulphate
heating the compound with cupric oxide (FeSO4) solution and then acidified with
(CuO). concentrated sulphuric acid .

2. The formation of Prussian blue colour

 Carbon present in the compound is
confirms the presence of nitrogen.
oxidized to carbon dioxide, which turns
2NaCN + FeSO4 Fe(CN)2 + Na2SO4
lime water milky.
Fe(CN)2 + 4NaCN Na4[Fe(CN)6]
 Hydrogen present in the compound sodium hexacyano ferrate (II)
is converted into water, which turns
On heating with concentrated sulphuric acid
anhydrous copper sulphate into blue. some Iron (II) ions are oxidized to Iron (III) ion,
which reacts with sodium hexacyano ferrate (II)
C + 2CuO D 2Cu+CO2 CO2+Ca(OH)2 CaCO3 to produce iron (III) hexacyanoferrate (II) (ferri
Milky ferrocyanide) which is Prussian blue in colour.
2H +CuO D Cu+H2O H2O+CuSO4 CuSO4⋅5H2O 3Na4[Fe(CN)6] + 2Fe2(SO4)3
Blue +3 +2
Fe4[Fe(CN)6]3 + 6Na2SO4

LASSAIGNE'S EXTRACT Ferriferrocyanide (prussian blue)

 This test fails in case of diazo

 Nitrogen, sulphur, halogens and phosphorus compounds.  –N=N–
present in an organic compound are  If the amount of nitrogen present is less,
detected by Lassaigne's test. then Prussian blue is present in colloidal
form and the solution looks green.
 During preparation of sodium fusion extract,
covalent compound is converted into
TEST FOR SULPHUR
ionic compound.
1. Sodium fusion extract (Na2S ) is acidified
 The following reactions takes place with acetic acid and lead acetate is added
to it, a black precipitate of lead sulphide is
D formed, which indicates presence of sulphur.
Na + C + N NaCN P, S, N, X
Pankaj sir nikle
holiday par
Na2S + (CH3COO)2Pb PbS↓ + 2CH3COONa
2Na + S Na2S Black

2. Sodium fusion extract is treated with freshly

2Na + X 2NaX (X = Cl, Br or I) prepared sodium nitroprusside, appearance
of violet colour (purple) indicates presence
Na + P + O Na3PO4 of sulphur.
 yellow Insoluble in
Na2S+Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS] AgI aqNH3
(violet) Soluble in
(Sodium nitro prusside) AgCl aq NH3
White
 In case both nitrogen and sulphur and
present in an organic compound, sodium NaX + AgNO3 AgX + NaNO3
Partially
thiocyanate is formed, which gives blood AgBr
Soluble in
red colour with neutral solution, FeCl3 Pale yellow
aq NH3
solution
 If Nitrogen and Sulphur are also present in
Na+C+N+S→NaSCN
the compound, the sodium fusion extract
+3
3NaSCN+FeCl3→Fe(SCN)3 + 3NaCl is boiled with concentrated nitric acid to
(blood red) decompose sodium cyanide and sodium
(khooni laal)
2+ +1 sulphide formed during Lassaigne's test,
or[Fe(SCN)]or[Fe(SCN)2] otherwise they interfere with silver nitrate
 If sodium fusion is carried out with excess test for halogens.
of sodium, the thiocyanate decomposes
+ – + –
to yield cyanide and sulphide, these ions
NaCN + HNO3 NaNO3 + HCN
gives their usual tests.
+ 2– + –
Na(Excess)+NaSCN→NaCN+Na2S Na2S + 2HNO3 2NaNO3 + H2S

TEST FOR HALOGENS  If NaCN and Na2S are not decomposed,

Sodium fusion extract (NaX) is acidified then white and black precipitates of AgCN
with nitric acid and then treated with and Ag2S are formed respectively with
silver nitrate solution. silver nitrate solution.
(i) White precipitate, soluble in ammonium + – + –
hydroxide indicates presence of chlorine. NaCN + AgNO3 AgCN + NaNO3
+ – + white ppt
NaC l + A gNO–3 ——→ AgCl↓ + NaNO3
(white ppt)
Na2S + AgNO3
AgCl + 2NH4OH ——→ [Ag(NH3)2]Cl + 2H2O

(soluble complex)
Tollen’s Reagent Ag2S + NaNO3
Pale yellow Partial soluble Black
(ii) Yellowish precipitate, sparingly soluble in
ammonium hydroxide indicates presence of BEILSTEIN'S TEST
bromine.
+ – + 1. A copper wire flattened at one end is heated
NaB r + A gNO–3 ——→ AgBr↓ + NaNO3
in an oxidizing flame of Bunsen burner.
Yellowish ppt

PPt 2. The heating is continued till it does not

Soluble impart blue colur flame.
AgF > AgCl > AgBr > AgI (Solubility)
3. The hot end of copper wire is now touched
(iii) 
Yellow precipitate, insoluble in ammonium
with the organic substance and is once again
hydroxide indicates presence of Iodine.
+– +
kept in flame, the appearance of green of
Na l + A gNO–3 ——→ Agl↓ + NaNO3 blue colour indicates the presence of halogens
Yellow precipitate in the organic compound

146
Organic Chemistry
LIMITATIONS ESTIMATION OF PHOSPHORUS
NH2CONH2 NH2CSNH2
O.C Mg2P2O7 O.C (NH4)3PO4.12MoO3
 Substances such as urea, thio-urea do
(w gm) (w1 gm) (w gm) (w1 gm)
not contain halogen but gives this test.
W
 It does not tell which halogen is present in %P= 62 × 1 ×100 W
%P= 31 × 1 × 100
222 W 1877 W
organic compound.

 Estimation of Nitrogen:
DETECTION OF 'P'
 Nitrogen present in organic compound
Na3PO4+HNO3→H3PO4 (NH4)2MoO4 (NH4)3PO .12MoO3
x 4=
Ammonium
is estimated by
phosphomolybdate
(a) Duma's Method
QUANTITATIVE ANALYSIS (b) Kjeldahl's Method
 Estimation of Carbon and Hydrogen:
 Carbon and hydrogen are estimated by DUMAS METHOD
Liebig's combustion method.
 A weighed amount of organic
C+CuO CO2 44 gm CO2 contains 12 gm ‘C’ compound is heated with cupric oxide
H+CuO H2O 1 gm CO2 contains
12
gm ‘C’ in an atmosphere of carbon dioxide.
44
O.C CO2 12  Carbon and hydrogen present in the
w1 gm contains × w1 gm ‘C’
(w gm) (w1 gm)
44 compound are oxidized to CO2 and
O.C H2O 12 w1
(w gm) (w1 gm) %C = × × 100 H2O, while N2 is set free.
44 w
2 w  The mixture of gases produced is
%H = × 2 × 100
18 w collected over caustic potash solution
(KOH solution) which absorbs CO2
ESTIMATION OF HALOGENS  Nitrogen is collected in the upper part
o.c. AgX of nitrogen meter.
 Carius Method (w gm) w1 gm
2x+y y z 2x+y
Aw X w1 CxHyNz+ CuO xCO2+ H2O+ N 2+ Cu
NaX+AgNO3 → AgX %X
= × × 100 2 2 2 2
MWAgX w
35.5 w ?
%Cl = × 1 × 100 (P – P1)V1 P2V2
143.5 w at any cond n
at STP
=
80 w T1 T2
% Br = × 1 × 100
188 w
127 w1 28 V2(ml)
% I= × × 100 % N = × × 100
235 w 22400 W

ESTIMATION OF SULPHUR 28 V2(ml)

% N = ×
o.c. BaSO4 224 W
32 w
(w gm)    (w1 gm) %S = × 1 × 100
233 w P = Pressure of N2 at T1

147
Qualitative, Quantitative Analysis and Purification
P1 = aq. Tension of H2O PURIFICATION OF ORGANIC
V1 = volume of N2 (ml) at T1 COMPOUNDS
T1 = Temp (K)
Methods of Purification
P2 = 1 atm or 760 mm of Hg
Crystallisation:
T2 = 273K
 It is based on the difference in the solubilities
V2 = volume of N2 gas at STP = ? of the compound & the impurities in a
suitable solvent.

KJELDAHL'S METHOD  The impure compound is dissolved in a

solvent in which it is sparingly soluble at
H2SO4, Δ
O.C (NH4)2SO4
NaOH
NH4OH (aqNH3) room temperature but appreciably soluble
containing at higher temperature.
basic 'N'
 If the compound is highly soluble in one
1.4 solvent and very little soluble in another
% N = × N × V(ml) (aqNH3)
W solvent, crystallisation can be satisfactorily
carried out in a mixture of these solvents.
W = wt. of organic compound
Distillation
V = vol. of standard acid required for complete
 Principle : Based on difference in b.p. of
titration of evolved ammonia
components of mixture.
N = normal of standard acid solution used
 Also used to separate : Volatile liquids
from nonvolatile impurities
 In this method nitrogen present in the
organic compound is converted into TYPES OF DISTILLATION:
ammonia (NH3)
Simple distillation
 Kjeldahl's method is not applicable To separate liquids which have sufficient difference
to compounds containing nitro in b.p

(–NO2), Nitroso (NO), azo group eg: chloroform (334K) & aniline (457K)
O
Fractional distillation:
(–N = N–), azoxy compound – N = N – To separate liquids which have small difference
in b.p.
and nitrogen present in the ring (pyridine eg: To separate different fractions of crude oil in
petroleum industry.

, quinoline ) because
N N
Vacuum distillation (distillation under
reduced pressure)
nitrogen present in these compound is not
This method is used to purify liquids having very
high boiling points but they decompose at or
quantitatively converted into ammonium
below their boiling points.
sulphate.
eg: Glycerol is separated from spent -lye in soap
industry.

148
Organic Chemistry
Steam Distillation b) Thin layer chromatography (TLC)
To separate substances which are steam volatile  Involves separation of substances of a
and are immiscible with water. mixture over thin layer of an adsorbent
coated on glass plate.
eg: Aniline, Nitrobenzene, o- nitro phenol.
 The components of the mixture move
up along with the eluent to different
CHROMATOGRAPHY
distances depending on their degree of
adsorption and separation takes place.
Types of Chromatography
2) Partition chromatography:
1) Adsorption Chromatography:
 Based on continuous differential
 Based on the fact that different partitioning of components of a mixture
components of a mixture have different between stationary & mobile phase. Also
degrees of adsorption on adsorbent (silica known as liquid paper chromatography
gel or alumina) Stationary phase - liquid
Stationary phase - solid Mobile phase – liquid
Mobile phase - liquid/gas  A special quality paper known as
chromatography paper is used.
a) Column Chromatography
eg: cellulose paper
 Involves separation of a mixture over a
column of adsorbent (stationary phase)  Chromatography paper contains water
packed in a glass tube. trapped in it, which works as Stationary
phase.
 Component of the mixture which is more
soluble in stationary phase is adsorbed  Moving phase is a solvent or a mixture of
solvents in which spotted chromatography
first than the component which is less
paper is suspended.
soluble in stationary phase.
 The solvent rises up the paper by capillary
 The most readily adsorbed substances
action and flows over the spot. The paper
are retained near the top and others selectively retains different components
come down to various distances in the according to their differing partition in the
column two phases. The paper strip so developed
is called Chromatogram

Koshish ke Baawjud ho jati hai kabhi haar,

hoke niraash mat bhaithna mere yaar
Badte rahna aage ho jaisa bhi Mousam,
paa leti hai manjil cheeti bhi gir-gir kr kai
baar.

149
Qualitative, Quantitative Analysis and Purification
 5 Hydrocarbons

ALKANE 2 CH3–CH2–Cl CH3–CH2+CH2–CH3

CH3–CH2–CH2–CH3
M.O.P 1. Hydrogenation
Reagent # H2/Ni or Pt or Pd 2
Br
Case (1) from alkene
H H
H H H2 1 eqv. Na
C == C C – C Cl Br
Ni D.E.

H H H2
CH2 == CH2 CH3 – CH3 3. From carboxylic acid
Ni
Case (1) Soda lime decarboxylation
H H H2
CH3 – CH == CH2 CH3–CH2–CH3 (NaOH+CaO)
Ni
H NaOH+CaO
H H H2
CH = CH2 CH2 – CH3 R – COONa RH + Na2CO3
Ni
R – COONa + NaO  H
Case (2) from alkynes NaOH+CaO
R – COOH R–H
H H
H H 2H2
–C ≡ C– –CH2–CH2– NaOH+CaO
Pt e.g. CH3 – COOH CH4
H H
H H 2H2 H
CH3–CH3 NaOH+CaO
CH ≡ CH COONa
Pt
H H H
H H 2H2
CH3–C ≡ CH CH3–CH2–CH3 Case (2) Kolbe’s electrolysis
Pt
electro
# Alkynes react faster than alkene. 2 R–COONa R + R R – R

# Exothermic rxn 2 CH3–COONa CH3 + CH3 CH3–CH3

2. From alkyl halide 2

Case (1) Redn of R–X COONa
+
with Zn/H
Zn/H+ NaOOC COONa
R–X R–H+HX
H H
Zn/H+ Chemical prop #
CH3–Cl CH4
H H
Zn/H+
CH3–CH2–Br CH3–CH3 1. Halogenation
H H
X2
RH RX + HX
Case (2) Wurtz rxn hv
Na
R–X R–R R – H + X – X
hv
R–X
dry ether

2 R–X R + R R – R
Reactivity: F2 >> Cl2 > Br2 >> I2
2 CH3–Cl CH3 + CH3 CH3–CH3
 How to find total no of products in 4. Controlled oxidation
monohalogenation: CH3 CH3
KMnO4
X2 CH3–C–H [O] CH3–C–OH
CH4 (1)
hv CH3 CH3
X2
CH3–CH3 (1) 5. Combustion Rxn
hv
CxHy + x + y O2 → x CO2 + y H2O
X2
(2) Excluding stereo 4 2
hv
X2 (2) PHYSICAL PROP
X + *
hv Boiling Point:
X
1 + 2 = 3 Including stereo
4 X2 (1) B.P α no. of C atoms
1 4 Excluding stereo
3 hv
2 6 Including stereo
(2) If no. of C atoms are same
How to find major product in 1
BP α
monohalogenation no. of branches

(a)
Chlorination Bromination
More reactive, less More selective, (b)
selective less reactive ce
ti
rp : rs : rt = 1 : 3.8 : 5 rp : rs : rt Prac
Cl2 Br2
= 1 : 82 : 1600 Q. CH4 A Na/ether B
hv hv
np r p 3° > 2° > 1° CH3–Cl CH3–CH3
% 1° = × 100
nprp + nsrs + ntrt
2 CH3–Cl
CH3+CH3
np = no of 1°H
CH3–CH3
ns = no of 2°H d
/P E Alkyne
Zn/H+
2H
2
nt = no of 3°H D
C B CH≡CH
 H H
Cl CH3–CH2–Br CH3–CH3
Cl2 Br2 Br
, Zn/H+
hv (major) hv (major) CH3–CH3
np = 9 np r p = 9 × 1
ns = 0, nt = 1 nsrs = 0 × 3.8 = 0 Q. R – COONa
H
COONa
ntrt = 1 × 5 H2+Pt Electro NaOH
H A B C
H
2. Aromatisation CaO

Cr2O3 or V2O5 Monohalo, Sodium salt of

carboxylic acid
or MO2O3
Total no. of products COONa
500°C
Cl Cl
10–20atm
* +
2 1 CH3–Cl CH3–CH2–Cl
=3 Na/ether
C D + E
3. Isomerisation Rxn Alkyl

AlCl3/HCl chloride
E is higher
+ homologue
of D

151
Hydrocarbons
ALKENE 2 
More stable alkene product is the major
product
M.O.P 1. Partial Hydrogenation
CH3 CH3
R β α β Alc. KOH Saytzeff
–C≡C– –CH=CH– CH3–C–CH–CH2–Ph CH3–C=CH–CH2–Ph
R 1 H2 + Pd/C H Cl Minor

2 H2 + Pd/BaSO4 CH3
CH3–C–CH=CH–Ph
Lindlar’s catalyst
Hoffman H Major
H H H2+Pd/C
CH≡CH CH2=CH2
H H H2+Pd/C 3 
Also known as β-elimination or α,
CH3–C≡CH CH3–CH=CH2
β-elimination or E2 elimination
# syn addition
3. Dehalogenation
CH3 CH3
H H H2+Pd
CH3–C≡C–CH3 C=C Vicinal dihalide Zn Alkene
BaSO4 or NaI/acetone
H H
Zn
D D –C–C– or NaI/acetone –C=C–
D D D2+Pd/C
C≡C–CH3 C=C
xZnx
Cis CH3 Zn
CH3–CH–CH2 or NaI/acetone CH3–CH=CH2

# Birch Reduction BrznBr

R Cl
Zn
–C≡C– –CH=CH– Zn or NaI/acetone
R Li or Na liq NH3 Cl

H Na+liq NH3 H CH3

CH3–C≡C–CH3 Zn
C=C Geminal dihalide or Alkene
H Na/ether
CH3
Trans H
X X
2. Dehydrohalogenation C 2Zn C C=C
X X
R
Alkyl halide Alkene 4Na

R Alc. KOH, RO– Na+/ROH CH3 Cl 2 Zn CH3 CH3

2 C C=C
RO– K+/ROH Cl
H H H
CH3O– Na+/CH3OH
H
Alc. KOH CH3 Cl Cl CH3
–C–C– –C=C–
β α C 2Zn C
H X H Cl Cl H
Alc. KOH
CH2–CH2–Cl CH2=CH2
β α 4. Dehydration of Alcohol E1 mech
R
R–OH Alkene
Point
Imp.
R → H+/Δ, conc H2SO4
1 Anti elimination conc H3PO4
H+ +
Et H Et R–OH R–O–H
β Cl Alc. KOH H
α
β H H
Alkene Δ R+ Rearrange if possible
CH3 CH3

152
Organic Chemistry
Q. +
CH3–CH2–OH2
+ H+/Δ
CHEMICAL PROPERTIES
1. Hydrogenation of alkene
H+
+ Δ 2. Addition of halogen
CH2–CH2 CH2=CH2
(a) In CCl4
α
X
Rearrangement × X2
C=C C–C
× CCl4
a) H Shift
X
# Anti addition
+ + H+/Δ x
CH3–CH2–CH2–OH2 CH3–CH=CH2 x X2
CH3–CH=CH–CH3 CH3–CH–CH–CH3
x CCl4
Δ
(b) In H2O x
2 1+ +
CH3–CH–CH2 CH3–CH–CH3 X2 + H2O → HO X
– +
α α
H 6αH
X
+ – HO–X+
CH3–CH=CH2 CH3–CH–CH2
2αH
+I OH Cl
+ – Cl +H O
b) Me Shift CH=CH2
2 2
CH–CH2
CH3 HO–Cl+
+ + H+/Δ OH
CH3–C–CH2–OH2 +I
3. Addition of HX
CH3
Alkene HX Alkyl halide
CH3 + – H+ +
CH3–CH=CH2 CH3–CH–CH3
CH3–C–CH2–CH3 X–
α + α
CH3 CH3 CH3–CH–CH3

CH2=C–CH2–CH3+CH3–C=CH–CH3 X
H H
Minor 5αH Major qαH + – HBr +
CH3–C–CH=CH2 + CH3–C–CH–CH3
H
Ring Expansion CH3 CH3
+ Br +
+ + CH3–C–CH2–CH3
CH2 CH2 CH3–C–CH2–CH3 Br–
CH2 CH3
+ H CH3
CH2 ×
+ +
H – +
HCl
+ + +
(a) CH2–OH2 1 CH2 + CH2 H+

H /Δ+ α
Cl H
2 III Cl
– +
+ +
Δα α
# In presence of peroxide
+ + + HBr Peroxide Anti-markownikoff’s
(b) CH2–OH2 CH2
+
H+/Δ + α α HBr/peroxide
≡ CH3–CH=CH2 + – CH3–CH2–CH2–Br
H Br
Major
+
+ + + HCl HBr/peroxide
(c) CH2–OH2 CH2 CH3
+ Peroxide Anti mark
+ H – Br
H /Δ
+
Cl
7αH 4αH
major minor Cl

153
Hydrocarbons
4. Addition of H2O/H+ 5. Addition of OH group (Hydroxylation)

H2SO4

H H+ –OSO3H ’s Syn addition Anti addition

+ – H2O/H
+
y er t
e n
CH3–C–CH=CH2 dil H SO Ba age (a) dil AlK. KMnO4 (a) RCO3H/H2O
2 4
r e
CH3 H + (b) OSO 4 (b) HCO3H
H B.R
+ CH3–CH–CH–CH3
CH3–C–CH–CH3
OH OH
CH3 CH3–CH=CH–CH3
OH
OH HCO3H
H2O + CH3–CH–CH–CH3
CH3–C–Et CH3–C–CH2–CH3
OH
CH3 CH3

6. Ozonolysis

Reductive Oxidative
R O3 + CCl4/Zn R O3 + CCl4/H2O
or or
O3 + CCl4/Zn+H2O O3 + CCl4/H2O2
or or
+
O3 + CCl4/Me2S KMnO4/H or KMnO4/Δ
CH3 o o H O3+CCl4 CH3 CH3 o oo H O3+CCl4 CH3
C=C C=O oC=Co C=O
Zn H2O +
H H H H H HO
H OH
O=C
CO2+H2O←H2CO3← O=C
H OH

PSS (CO2 + H2O)

OH
O=C
OH

O H
O + O=C D
H H OH D
OH SO 4 AlK
KMnO4/H+
dilH 2 i O OH
/N dil KMn 4
O Bae er’s
y OH
D2
O O3+CCl4 – reagent Cl
CCl4
O Zn + Cl 2/
+
+ O=CH2 + Br NO Cl– Cl NO
–

H e Tilde
xid
+
H n re
ro HCl Br agen
P e 2 +H t
2O
Anti-mar. HO –
Br + Br Cl
Br
H +
OH
Cl

154
Organic Chemistry
ALKYNES 2. Addition Rxn
(a) Hydrogenation
M.O.P 1. From carbides (b) Addition of HX
Mg2C3 + X
CaC2 + – 2HX–
H2O H2O R–C≡CH R–C–CH3
X
CH≡CH CH3–C≡CH Geminal dihalide
2+ – – 2+ 3– – Br
CaC2→Ca+C≡C Mg2C3→2Mg+C–C≡C + – HBr
– + – + C≡CH 2 mol –C–CH3
2OH 2H 4OH 4H
Br
Ca(OH)2 CH≡CH 2Mg(OH)2 CH3–C≡CH
(c) Addition of X2/CCl4
Δ x x
CaCO3 CaO + CO2 x x 2 X2
C (–CO) R–C≡C H R–C–CH
x x CCl4
x x
CaC2 Tetrahalide
3+ 4– Cl Cl
Cl Cl
H2O Al4C3→4Al + 3C C≡C–CH3 C–C–CH3
Al4C3 CH4 – + Cl Cl
2 Cl2
12OH 12H
CCl4 Cl Cl
H2O
Be2C CH4 4Al(OH)3 3CH4 2+
2+ 4–
(d) Addition of H2O/Hg or HgSO4/dil.H2SO4
H2O Be2C→2Be + C Kucherov rxn
B4C X – + OH
4OH 4H 2+
H2O + – Hg /H2O
SiC X 2Be(OH)2 CH4 R→C≡CH +–
2H OH
R–C–CH3

OH
2. From Vicinal Dihalide –H2O
R–C–CH3
Dehydrohalogenation O
H H
Alc.KOH
3. Polymerisation Rxn
–βC –βC – NaNH2
–C≡C– (a) Coupling Rxn of CH≡CH
α α
X X 3CH≡CH R.H.T
H H –
CH CH
+

Alc.KOH +
CH3–C–C–H CH3–C≡CH CH
CH–
NaNH2
+
–CH≡CH
Cl Cl
3CH3–C≡CH R.H.T
Acidic character:
Chemical Prop # (Alkyne > Alkene > Alkane) 3CH3–C≡C–CH3 R.H.T

1. Alkynes are acidic in nature Ni(CN)2

(b) 4CH≡CH
DMF
+
R–C≡CH→R–C≡C+H ↓
Stable Non aromatic
H–C–NMe2
SP
O
(a) Rxn with Na/Δ Tub-like struc
(c) Linear coupling
– 1
R–C≡C–H Na/Δ R–C≡CNa +
+
H ↑ Cu2Cl2
2 2 2CH≡CH CH2=CH–C≡CH
NH4Cl
H–C≡C–H Na/Δ
+ – – +
Na C≡CNa + H2↑ Vinyl acetylene
(Excess) + + –
–
CH≡CH H–C≡CH
(b) Rxn with NaNH2 (d) Oxidative coupling
– + NaNH2 – O
R–C≡C–H R–C≡CNa++NH3↑
2R–C≡C–Cu R–C≡C–C≡C–R
2
+
– + NaNH – –
H–C≡C–H 2
Na+C≡CNa++2NH3↑ R–C≡C–Cu+O2+Cu–C≡C–R
(Excess)

155
Hydrocarbons
TEST OF TERMINAL ALKYNE Q. Convert acetic acid → Benzene

Tollen’s test CH3–COOH Benzene

AgNO3
R–C≡C–H R–C≡C– Ag Na/Δ R.H.T
NH4OH
White ppt CH≡CH Alc.KOH/NaNH2
CH3COONa
Cuprous chloride test Br2
Cu2Cl2 NaOH+CaO CH2=CH2 CCl CH2–CH2
R–C≡C–H R–C≡C–Cu 4
NH4OH Br Br
Red ppt CH4 AlCKOH
nal CH3–CH2–Br
e r mi Br2/hv
T H–C≡C–H   R–C≡C–H Cl2/hv
Na/ether
non-terminal R–C≡C–R' CH3–Br CH3–CH3

PSS ne – +1
ityle CH3–C≡CNa+ H
Mes CH3–C≡C–Cu
a/Δ 2 2
RH Cl 2 N
T Cu 2 H
O + –
NH 4 NaNH2 – +
AgNO3 CH3–C≡CNa+NH3
+ –
CH3–C≡CAg CH3→C≡CH +–
NH4OH HBr Br
D2/Pd 2m
CH3 H ol CH3–C–CH3
C=C BaSO4 2Cl2
dil Br
D D HgSO4/H2SO4 Cl C
CCl4 CH l
2 3 –C–
CH3–C–CH3 Taut H C–H
o 2 +N
O i Cl C
CH3–C=CH2 l
OH

BENZENE Types of E.A.S

1 Nitration +
M.O.P 1. Sodalime decarboxylation NO2
1 Conc. HNO3 + Conc. H2SO4
Ph COONa NaOH Ph–H 2 NO+2 BF–4
CaO
3 Solid N2O5 (NO2+NO3–)
Ph COONa + NaOH 4 NO2ClO4
5 HNO2/HNO3
Ph–H + Na2CO3
NO2
2. Rxn of phenol with Zn +
NO2
Zn
Ph–OH Ph H + Zno
Ph–O–H Ph–H + Zno 2 Halogenation Rxn
Zn Reagent (1) X2 + Anhy AlCl3

CHEMICAL PROPERTIES      (2) X2 + Anhy FeCl3

X
1. E.A.S (Electrophilic Aromatic) substitution
X
or
E.S.R or Ar SE or SEAr
3 Sulphonation
(Electrophilic substitution Rxn)
Reagent 1) Fuming H2SO4
H E SO3H 2)
      H2S2O7
E SO3
+ H+       3) SO3/H2SO4

156
Organic Chemistry
 4 Friedel craft's Rxn b) Acylation O
a) Alkylation Reagent 1) R–C–Cl + Anhy AlCl3
Reagent 1) R–X + Anhy AlX3 O O
2) ROH + H+ 2) R–C–O–C–R + Anhy AlCl3
3) Alkene + H+ +
O
R+ R R–C=O C–R

Rearrange if No rearrangement
possible

PSS CH3
CH≡CH anhy
H2O RHT CH3–Cl/AlCl3 OH
CaC2 A B xx
+ C
CH3 H+
OH/H+
SO3 m +
eu
Ol Conc. HNO3 + OH2
Conc. H2SO4 NO2 D
–

SO3H
Al l
O

H
C

3
Cl

E
+ C–

H
–

Cl2/Anhy FeCl3
Ph

hy

+ 2αH
An

G xx +
HO–NO2 H +
CO Ph F H2O–NO2
+ – +
Cl Cl–Cl+FeCl3 6αH
+
+
– NO2
Cl + FeCl4

Mechanism of E.A.S # xx
E E –OH (+ M) –C–NH2(–M)
+
H O
E xx xx
E
–OCH3 (+ M) –O–C–CH3(+M)
1. Generation of E
2. Attack of E O
ϖ complex +
3. Removal of H+ –N = O (–M) –C–O–CH3(–M)
Sp3 O
–
O
E E E
E H H H –C–OH(–M)
+ + O xx (+M&–M)
–CH2–CH2–CH3(+M) –N=O
E Wheeland xx
σ complex H Intermediate –NH–C–CH3(+M)
xx (+M&–M)
–S–CH3
Resonance Hybrid O O
+M (O, P directing)
Directive influence of a F.G in mono substituted
benzene OH +OH OH

+M –M

+
+M group # G OH OH
st
1 atom Lp
G –CH3
–CH2CH3 +M +M +M
G 1st atom ϖ e E
–M group # E
+
+
G –NH3, –CX3
E

157
Hydrocarbons
–M (Meta directing) B.H.C (Benzene hexa chloride) C6H6Cl6

O O O O O O Lindane or Gammaxene
N N N

Q. Compare reactivity in E.A.S

a)
Cl(+M<–I) Cl Cl
NO2
O O O O
N N , ,
1 2 3 NO2 NO2
1 2 3
–M –M
E
b)
E CH3 CH3 NO2

, ,
Q. CH3 + M CH3 CH3
NO2 1 2 3 NO2 NO2
Conc. HNO3
+
Conc. H2SO4 1 2 3
+
NO2
NO2

c)
–M CH3 NO2
T = 60°C NO2 NO2
Conc. HNO3 +
NO2 , ,
Q. NO2
Conc. H2SO4 T > 60°C 1 3 2
NO2 1 2 3
(2 mol)
+
NO2
d)
Cl
Q. CHO – M CHO
>
Br2
anhy FeBr3
+ Br
Br
Q. Total type of products Ans.3

Q. Cl
Cl2(excess)
Cl Cl CH3
anhy FeCl3 CH3 CHO CH3–CO CHO CH3COCOCH3
Cl Cl O3+CCl4 + +
(H.C.B) (C
Cl 6Cl6) Zn
CHO
Hexachloro benzene
CH3 CH3 O
o CH3
2. Addition Rxn o o H C C O
o 2 C O + H C
o H
3 H2/Ni o O methyl glyoxal
(a) glyoxal
H.T & HP
CH3
o CH3
Cl
o CH3 CH3 + H O
— o C 2
Cl2(excess) Cl Cl C
O C
(b) o o C
—

— O
hv O
o H
Cl Cl Dimethyl
Cl glyoxal glyoxal

158
Organic Chemistry
 +
PSS +M
Br –
COONa NaOH + +
Br H
Soda Br2 H+ 1 +
H
A B C +
lime Anhy FeBr3 2 +
Br
+M Cl
– Cl 3
+
CH3 l
CH3 CH y A
3
Zn Cl +
h
An D K/Δ
E β α H2/Ni
J Conc. F G
PhoH
(Excess) HNO3 PhO K – +
E
2 H
CH3 H
O2N NO2 +
Conc H2SO4 HCl/anhy AlCl3
K Electrolysis
Explosive I H
NO2
Sodium salt
T.N.T CH3–CH2–COONa
2R–COONa
R+R
R–R

Na thake abi aur na abi himmat hari hai,

Hoshla hai zindgi mai kuch kar dikhane ka
isiliye safar abi zaari hai.

159
Hydrocarbons
 6 Haloalkanes & Haloarenes

HALOALKANES c) Rxn with PCl5

PCl5
R–O–H R–Cl+POCl3+HCl
M.O.P 1. From Alcohols SN2
R – O      – H
a) Rxn with HX/ZnX2 # No rearrangement
Cl – PCl3– Cl
x x H+ +
R–OH R–OH2
Q.
OH PCl5 Cl
X–
R–X R Rearrange if
possible d) Darzen’s reaction
Reactivity 3° > 2° > 1°
SOCl2
# NaBr/H2SO4 → HBr R–O–H RCl+SO2↑+HCl↑
R – O    – H
# No rearrangement
HCl 4αH Cl – SO – Cl
Q. H
ZnCl2
+ OH2
SOCl2
Cl– 8αH
Q.
Cl OH Cl

Q. SOCl2
Q. + OH Cl
+
OH2
Br
NaBr # If SOCl2/Pyridine is present then inversion
H2SO4 occurs
H+ CH3 CH3
+ + Br
- SOCl2
1 +
H OH H Cl
SNi
2 C2H5 C2H5
SN2 SOCl2/Pyridine
b) Rxn with PX3 and Red P/X2 (X = Br, I)
CH3
PX3
R–O–H SN2
R–X + H3PO3 Cl H

R – O – H X C2H5

R – O – H + P X 2. From alkanes and alkenes
R – O – H X
a) From alkane
# No rearrangement
X2
R–H R–X
Q. PCl3
hν

Cl
b) From alkenes
OH
i) R–CH=CH2 HX Alkyl Halide
OH Br X2
Q. RedP/Br2 ii) R–CH=CH2 Vicinal dihalide
PBr3 CCl4
Q. + – xx +
CH2–CH=CH2 CH2 OH CH2 CH2 Cl
+ – + –
HBr/Peroxide Q. HCl– Cl
HCl CH2–CH2–CH2–Br
+ OH HO OH
CH2–CH–CH3
Br
Br2
+ Cl Q.
CH–CH2–CH3 CCl4
– CH–CH2–CH3 Br
Cl
4. Allylic & Benzylic substitution

Br2 CH3–CH=CH2
Q. Br +
hν
3°>2°>1° (ease of Minor Br CH3
Major
abstraction of H)
a) Bromination b) Chlorination
Br2/hν Cl2/500°
3. Halogen exchange Br
NBS
N-bromosuccinimide Cl2/hν
a) Finkelstein Rxn
O t-buOCl
NaI
R–X R–I
acetone N-Br SO2Cl2/hν
(X=Cl, Br) Cl
O
# No rearrangement (SN2)
NBS
b) Swart's rxn R- X + AgF Q. CH3–CH=CH2 CH2–CH=CH2
Br
Heavy metal Br
Inorganic
R- X R - F + AgX
Fluorides Q. CH3 CH2–Cl

AgF, Hg2F2, CoF2, SbF3 # No rearrangement Cl2/500°C

Cl
SbF3
Q.
Cl F CHEMICAL PROPERTIES
NaI
I
1. Nucleophilic substitution Rxn
Q. Br
acetone
Nu
R–X R–Nu + X
CH2–Cl CH2 F
(1) SN Rxn PPS→Polar protic solvent
1

AgF Nu
Q. R–X R++X– R–Nu
б+
Br Br H б– б+ б– б+ б–
O.............R–X.............H–O
Practice H H
+ – HBr # Two step Rxn
Q. Ph – CH = CH2 Ph – CH – CH3
+ (2) SN2 Rxn Polar aprotic solvent
–

H Br x
+ – xx Nu
Ph – CH – CH3 Br Nu R–Xxx Nu ..........R..........X
xx bf bb
Br Transition state
CH2–CH3
Br2
Q.
O2N hν O2N # one step Rxn Nu–R+X

161
Haloalkanes & Haloarenes
SN1 :

SN2 :

ts SN1 SN2
OP Poin + – Nu Nu
R–X R +X R–Nu R–X Nu .....R.....X→Nu–R+X–
# 2 step rxn R2
+C # one step rxn
R1
# r = K[Rx] R3 # r = K[Rx][Nu]
# Reactivity (Rx) 3°>2°>1° # Reactivity (Rx) :1°>2°>3°
ity ity
R e activ activ
# R–I>R–Br>R–Cl>R–F # Re R–I>R–Br>R–Cl>R–F
# Racemisation occurs # Inversion occurs
# PPS:H2O, ROH, RCOOH etc # PAS O O O
, H–C–NMe2 S
Acetone DMF DMSO

Reagent Nu Substitution product Class of main product

1. NaOH/KOH OH R OH Alcohol
2. H2O H2O ROH Alcohol
3. R'ONa R'O R–OR' Ether
4. NaI I R–I Alkyl iodide
5. NH3 NH3 R–NH2 1° amine
6. R'NH2 R'NH2 R–NHR' 2° amine
7. KCN CN R–CN Cyanide
8. AgCN AgC≡Nxx R–NC Isocyanide
–
9. KNO2 O–N=O R–O–N=O nitrite
10. AgNO2 AgNO2 R–NO2 nitro alkane
–
11. R'COOAg R'COO R–OCOR' Ester
12. LiAlH4 H R–H Alkane
13. R' M R' R–R' Alkane

162
Organic Chemistry
PSS
xx
K+xxO – N = O
K+CN xx)C≡Nxx )
=O
O –NK
– NO N CH3–CH2–C≡N
– CH 2 2 KC
CH 3
xx CH3–CH2–Cl
–N =O AgCN
A g–O O2 Ag
–C
A gN –
CH3–CH2–NO2 N CH3–CH2–NC

xx
Q. Compare reactivity of Rx in SN1 & SN2

1
Br 2 1 in SN
Br
2
1 2 1 2 in SN

Q. More stable Less stable

OH
a b +
CH3 CH3 CH3 β β
α
H2O a & b are F F
H Cl H OH + HO H F
1 enantiomers
SN # E 2a
C2H5 C2H5 C2H5
# No rearrangement +
Racemisation
# More stable Major Minor
D D carbanion will decide
aq KOH the major product
Q. H Br HO H
OH
T SN
2
T 3. Rxn with metals
Walden Inversion t
d en
a) G.R formation n ar eag
ig r
2. Elimination Rxn Gr G.R)
Alc.KOH Mg 2+ ( –
R–X Alkene R–X R Mg X
dry ether
H H –
Alc.KOH R б R
+
R Mg x O
β β
α H+ –OH
Cl 6αH (Trans- 2αH 2+
isomer is Minor R Mg X–
2
# E mechanism major product) Hoffman R–H б–
O
# No rearrangement Saytzeff R R
# Anti elimination b) Wurtz Rxn
Na/dry
Alc. KOH 2R–X R–R
+ ether

R–X+2Na+X–R
X Major Minor
X = Cl, Br, I

163
Haloalkanes & Haloarenes
Q. Mg/dry 2+ Q.
CH3–CH2–Cl A CH3CH2MgCl I
ether – +
CH3–OH HBr/peroxide
C Na/dry ether
NaI/acetone
CH3–CH2–CH2–CH3 B Br
CH3–CH3 Cl
Q.
OH
Practice
Alc. KOH aq KOH
HBr Br
Q. OH CH3–CH2–C≡CH peroxide
SOCl2
CH≡C Na
+ Q. Alc. KOH
Cl CH3–CH2–Br A C4H9Br B Alkene
AlC.KOH NaNH βα
2 Br (1° halide)
1 equ CH≡CH HBr
AlC. KO H
Br2 H/NaN Na/D.E.
CH2=CH2 CH2–CH2 H2
CCl4 C isomer of A
Br Br D

C8H18 which is different from Br

H Br
the comp formed when n-butyl
Q. Br
β bromide is treated with Na
α
AlC.KOH Na
HBr Br

Br
Q. OH CH3–CH2–C≡N

SOCl2
D
Cl KCN

Br
PSS
Br

Na/dry ether
Cl
A
Alc. KOH E Cl2/500°C
F
Br2 hv Alkene
Br D+
D
B Mg/ether D 2O
C D
Mg Br
PBr3
AgNO2
OH G H
NO2
Alcohol

164
Organic Chemistry
HALOARENES CHEMICAL PROPERTIES
1. Nucleophilic substitution
M.O.P 1. From Benzene
Rxn (NAS)
E.A.S X X
X
X
X2 Nu
FeX3 XXX

[X = Br, Cl] 1 Partial double bond character
I2+NO2+H2O b/w C & X
I +
+
I2 HNO3 2 Instability of C
+ HI
HIO3 Dow’s process

I2+H2O
Cl OH
2. Sandmeyer's Rxn i) NaOH
+
ii) H
NH2 N2+Cl–
NaNO2+HCl 623K, 300 atm

0-5°C
Diazotization Cu2Cl2 Cl OH
Cu2Br2 i) NaOH
Br Cl
ii) H+
NO2 r1 NO2 Cl OH
NO2 NO2
for iodination (Sizzi's Rxn) i) NaOH
+
N2+Cl– I ii) H
NO2 r2 NO2
KI
Cl NO OH
O2N O2N NO2
for fluorination +
N2 Cl –
F
2
i) NaOH
Balz schieman Rxn HBF4 ii) H
+

HF+BF3 NO2 r3 NO2

r3>r2>r1
CH3 (+M) CH3 CH3 Reactivity in NAS
Cl2 Cl
Q.
FeCl3
+
Minor
MECH OF NAS
(Cl ) Cl
Major
Cl Cl OH
OH
OH
+
MgBr Slow Fast
R.H.
Br2 Mg NO2 NO2 NO2
Q. A B
FeBr3 ether Cl Cl Cl OH Cl
OH OH OH OH
(Br+) Br +
H2O / H Meisenheimer
complex
NO2 NO2 NO2 NO2 NO2
C

165
Haloalkanes & Haloarenes
2. EAS (4) F.C Alkylation

Cl Cl Cl
Cl (+M) Cl Cl CH3
E CH3Cl
E⊕ +
+ Anhy AlCl3

Minor CH3
E
Major (5) F.C Acylation

Cl Cl Cl
(1) Chlorination CH3COCl
COCH3
+
Anhy AlCl3
Cl Cl Cl
Cl2 Cl COCH3
+ 3. Rxn with metals
FeCl3
+ a) Fittig Rxn
(Cl) Cl
Na
2Ph–X Ph–Ph
(2) Nitration X+2Na+X

Cl Cl b) Ullman Rxn
Cl
NO2 Cu
Conc HNO3 2 I
+
Conc H2SO4 I+2Cu+I
+
(NO2) NO2
c) Wurtz-fittig Rxn
(3) Sulphonation Na
Ph–X+R–X Ph–R
Cl Cl Cl
SO3H Ph X+2Na+X R
Conc H2SO4
+
Δ Na
Q. Ph–Cl+CH3–CH2–Cl Ph–CH2–CH3
SO3H
Ph–Cl+2Na+Cl–CH2–CH3

PSS –
Br
+ Cl )
N2 300 atm Zn
(623K, I
i) NaOH J
NH2 Br 2 B + OH
Cu 2 ii) H
Cl
NaNO2+HCl
CH
3
A CH3
0–5°C H
Cu2Cl2
CH3–Cl Br2 /Fe
C +
Major )
I
Na G (Br
HBF4
KI Br
D Conc HNO3
E + Br CH2–Br
F 2 /hv
D Conc (Br •
Cu K ) M
Mg/ether H2SO4 Major i)
F NaO
Cl H
L N OH
Ph–Ph ii) H +
PhΘMg2+I–

NO2 NO2

Hazaro uljhane hai Rahoon mai aur kosise behisaab

Ise ki naam zindgi hai, chalte rahiye janaab.

166
Organic Chemistry
 Alcohols, Phenols and Ethers
7
ALCOHOLS c) OMDM (oxymercuration demercuration)
(i) Hg(OAC)2/H2O
M.O.P 1. From Alkenes R–CH=CH2 R–CH–CH3
(ii) NaBH4
H+–OH MAR OH
a) Catalytic hydration OH
Mech R–CH–CH3
+
dil H2SO4/H (H2O)≡H3O + R–CH=CH2

+ – H+ + Hg–OAC
R–CH=CH2 R–CH–CH3
xx OAC H
e H2O
a ng OH
r
ar S б+ H2O
Re PO R–CH–CH3 Cyclic R–CH–CH R–CH–CH2
i f 2
OH mercurinium Hg +
Hg
ion
b) HBO (Hydroboration oxidation) OAC
OAC
(i) B2H6/THF
R–CH=CH2
(ii) H2O2/–OH
R–CH2–CH2–OH H3O+ HBO OMDM
#Carbocation # 4MCTS # cyclic
H+–OH Anti MAR mercurinium ion
THF→Tetrahydro furan #syn addition #anti addition
O +– +–
Role is to break dimer of B2H6 #H OH Anti #H OH MAR
B2H6 mar
BH3+ +
Q
O Electrophile O H
BH3 + +
б– б+ H3O
A
+ – H–BH2 +
R–CH=CH2 R–CH–CH2
OMDM HBO
–
H+BH2 H – –
BH2 H+OH H+OH
(major)
4 MCTS Syn addition MAR Anti. mar
OH
+ B C
–
б+ б– R–CH=CH2
R–CH2–CH2–BH–H
+– OH
R–CH2–CH2–BH–CH2–CH2–R
OH
+
б б–
R—CH=CH2 2. Reduction Rxn
A. Redn of carbonyl comp
HO OH
HO OH H H R
R–CH2–CH2–B–CH2–CH2–R C=O C–OH
OH
H
HO
CH2–CH2–R
R a) H2 + Pd/Pt/Ni
H2O2 (–H3BO3)
b) LiAlH4
3 R–CH2–CH2–OH c) NaBH4
 B. From acid Q.
H – 2+
O R OMgBr
R–C–OH R–CH2–OH CH3–C–H
HH H H+–OH
O– +
R 1) H2 + Pd/Pt/Ni
2+
(i) PhMgBr Ph OH2
CH3–C–H A
2) LiAlH4 + (ii)H2O Ph–CH–CH3
+
HCl/ZnCl2
C. From ester
H Alc.KOH
O R C B
α
Ph–CH–CH3
R–C–OR' R–CH2OH+R'OH Ph–CH=CH2 β
HH H Cl
Styrene
R 1) H2 + Pt/Pd/Ni
2) LiAlH4 CHEMICAL PROPERTIES
OH O 1. Acidic Nature
Q. OH H OH
H
CH2–C–OCH3 CH2–C–OCH3 –
ROH→RO +H
+
HH
Na
SBH a) ROH RO–Na+ + H2
LAH SA WA
NaOH
b) ROH RO–Na+ + H2O
OH Acidic strength CH3OH>H2O>ROH
CH2–CH2OH + CH3OH
AI
d) ROH –H2↑
(RO)3Al

Q.
H 1
O # Acidic strength α – I α
H OHH +I
H H
H
HO Q. OH OH
SBH (–I) F
H2+Pd 1 2 I
O A.S. 1 2
OH
HO HO OH

3. From G.R. Q. OH OH OH
– 2+
+ – RMgx – 2+
C=O C–O Mg X Cl NO2 CH3
1 (–I) 2 3 (+I)
R (–I)
+ –
H OH A.S
r1>r2>r3 2 1 3
C–OH
R
r1 2. Esterification #
H (i) RMgx
C=O R–CH2–OH
H (ii) H2O 1° Alcohol
– +
R'O H
RCOOH
RCOOR'
r2 R– O
R' (i) RMgx O C–+
C=O R'–CH–OH – O O
H (ii) H2O R–C–Cl –
–

R 2° Alcohol + C–
r3 O R
R' (i) RMgx O
C=O R'–C–OH 3° Alcohol R–C–OR'+HCl
R'' (ii) H2O R–C–OR'
R'' R + RCOOH

168
Organic Chemistry
3. Lucas Test R
Conc. HCl 1° Alcohol Aldehyde
R–OH anhy ZnCl R–Cl
2
R
ClCrO3–
H+ 2° Alcohol Ketone
Cl – N+
+
R–OH2→R+ R Mild Oxidising agent H

1° ROH, 2°ROH, 3°ROH R → 1 PCC (Pyridinium chlorochromate)

No turbidity turbidity in turbidity in 2 PDC (Pyridinium dichromate)
min sec 3 Collin’s reagent
CrO3.2Py
Q. Compare time for turbidity 4 CrO3+ acetone 2–
+N Cr2O7
OH 5 Cu/300°C
H 2
OH
βCH CH2
OH 3
α Cu/300°C
1 2 3 CH3–C–OH CH3–C
time CH3 CH3
1 2 3 (reactivity 1°<2°<3°)

**3° ROH and Resonance stabilised R

 1° ROH & 2° ROH 1° Alcohol Acid
give Immediate turbidity H OH
[O]
OH R–C–OH R–C–OH
+ H H
turbidity in sec Reso
R → Strong O.A O
+
CH–CH3 CH–CH3 a) KMnO4/H +
R–C–H
Reso
OH turbidity in sec or
KMnO4/Δ [O]
4. Rxn with PX3, PX5, SOX2, Red P/X2 (X = Br, I) O
b) K2Cr2O7/H+
R R–C–OH
R–OH R–X
5. Dehydration of Alcohol Allylic & Benzylic
Alcohol
H+ + Conc H2SO4 MnO2
R–OH R–OH2 alkene CH2=CH–CH2–OH CH2=CH–CHO
443K mild O.A.
or +
H /Δ
Q.
Δ
R+ Alkene OH
6. Oxidation of Alcohols
H OH O OH
[O]
R–C–OH R–C–OH R–C–H MnO2

H H PCC
O OH
H OH
[O] O O
R–C–OH R–C–OH
H H
R' R'
R' O
[O] R–C–R'
R–C–OH X
R''

169
Alcohols, Phenols and Ethers
 PSS CH 2 CH 2
+ +
Δ OH
+ + OH OH
+ OH2 2 1
H
H+/Δ NBS Aq. KOH
A B MnO2 LAH
Br C D K
OMDM Br
H+–OH Na/Δ
CrO3 J
OH

E 1 CH3MgBr OH H + x L gas H2 at STP

O Na+ 1
–
CHO 2 H O F PDC
2 HC–C G mol H2
H 2
3
PCl5 O C–CH i.e. 11.2 L
3
Cl
I
H C–CH3

PHENOLS CHEMICAL PROPERTIES

M.O.P 1. Acidic Nature
– +
1. from chloro benzene PhOH PhO + H
Carbolic
Dow's process acid
– +
Cl O Na OH
(a) Rxn with metal
NaOH HCl – +
623 K PhOH + Na PhO Na + 1 H2
300 atm 2
(b) Rxn with NaOH
2. from Benzene – +
PhOH + NaOH PhONa + H2O
SO3H OH
SA WA
oleum 1) NaOH (fuse)
+ (c) Rxn with NaNH2
2) H
– +
PhOH + NaNH2 PhO Na + NH3
3. from aniline SA WA
+ – (d) Rxn with NaHCO3
NH2 N2Cl OH
NaNO2/HCl H2O – +
OH ONa
0–5°C warm + –
+ NaHCO3 + H2CO3
4. from cumene
(mostly SA
WA
CH3
Me backwards)
C–H CH3–C–O–O–H
Me # Nitrophenol + NaHCO3 salt + H2O + CO2
O2
SA WA
O=O – +
OH ONa
H+
OH + NaHCO3 + H2O + CO2
O
SA WA
+ CH3–C–CH3 NO2 NO2

170
Organic Chemistry
Acidic strength 3. E.A.S
Nitration:
1
A.S α –I & –M α (a) In dil HNO3
+I & + M
OH OH OH
+
Q. 1 2 3 NO2 NO2
+
OH OH OH
NO2 A NO2
, ,
NO2 Intra B
–M & –I molecular Inter
–I NO2
H-Bonding molecular
P O M
–M & –I H-Bonding
3>1> 2
B.P B > A
volatility B < A
Q. OH
O2N NO2 OH (b) In conc HNO3
OH OH OH
NO2
1 , , conc HNO3 NO2
NO2 NO2
2 +
2 > 3 > 1 3 NO2
–M&–I –I NO2
2,4,6-trinitro phenol
or
Q. 1 OH 2 OH 3 OH Picric acid
(poor yield)

O2N NO2 , , Bromination:

–I CH3 (+ M& +I)
(a) In Br2/CS2
1 > 2 > 3
OH OH OH
Phenol > ROH
Br2/CS2 Br
+
2. Esterification
+
Br
minor Br
+ – O major
– + RCOOH (b) In Br2/H2O
=

PhOH R–C–OPh
H+ OH OH
O O
– Br2/H2O Br Br
=

=
+

+ – R–C–O–C–R +
RCOCl O Br
Br
O
=

R–C–OPh 2,4,6-tribromo phenol

=

R–C–OPh
4. Kolbe's Rxn #
– +
Aspirin formation OH ONa
NaOH
COOH
– + O O
OH + – H+ i) CO2(ii) H+
=

+ CH3–C–O–C–CH3
Salicylic COOH O OH
acid
=

O–C–CH3 COOH
O-acetyl salicylic acid
(Aspirin) salicylic acid

171
Alcohols, Phenols and Ethers
Mech O– O– OH
OH +
CH CHO H CHO
– +
OH +
O Na OH
+ –
NaOH 6. Rxn with Zn

Zn
Ph–O–H Ph–H
O=C=O zn
1
O O–
2 H 7. Oxidation
3
C O

OH O
OH OH Na2Cr2O7
COO –
H2SO4
H+ COOH
O
P-Benzoquinone
5. Reimer-Tiemann Rxn
Practice
OH OH OH Q.
CHCl3 CHO
+
KOH OH +M OH OH
salicylaldehyde
(major) CHO dil HNO3 O2N
+

Cl Cl +H
– NO2
OH –
Cl C H Cl C xx α-elimination
Cl Cl Q.

– +
Electrophile OH
CCl2 + – O
A.R CH3COCl HNO3
A B O C CH3
O H2SO4
xx major
– + (+M) O C CH3 (NO2)
1
OH OK O
2 H NO2
CCl2 –
+ KOH 3 CCl2

O–
OH
CHCl2 –
CCl2
–
2OH(SN2)

172
Organic Chemistry
 OH
OH OH
PSS Zn Br
G Br
1) NaOH Br2/CS2
oleum B C + D
A
2) H+ major minor
SO3H NaO +
NO3 PhONa
–
H
n cH E + H2O
co
i) NaOH salt
CO 3 F
NaH ii) CO2
H2O + CO2 + I OH

H
iii) H+

KO
O2N NO2 O

3/
O–Na+ H (CH3CO)2O
Cl O–C–CH3
CH
O2N – + Aspirin
NO2 OH OH+ H
NO2 COOH
CHO COOH
NO2 J + K O
+ –
OH Intra- CH3–C–O–COCH3
H Bonding

CHO

ETHERS 2. Williamson-ether synthesis

M.O.P (WES)
1. Dehydration of Alcohols R'O Na+
R–X
Conc. H2SO4
R–OH Alkene R'O /SN2 R–X
443 K 1°>2°
Conc H2SO4 R–O–R'
R–OH ROR
CH3
413 K
+
–

xx H+ R–O–H CH3–Cl + CH3–C–O Na

CH3
+

R–O–H
–

CH3 –
CH3–C–O–CH3
–

H
–

xx
SN2 ROH CH3
Q. β CH2– H
R–O–R ← R–O–R
+

–
–

H CH3–C–Cl + CH3–O Na+

α
–

conc H2SO4 CH3

C2H5OH CH3–CH2–O–CH2–CH3
E2
+
H CH2
+

CH3–CH2–OH2 CH3–C isobutene

–

xx
CH3
CH3–CH2OH
Q. A + B Ph–O–CH3
Salt R–X
– +

CH3–CH2–O–CH2–CH3 –
– a+ CH3–X Ph O CH3–X
H
conc H2SO4 PhON –
R–O–H+H–O–R R–O–R CH3 O Ph–X
413K x

173
Alcohols, Phenols and Ethers
Q. O–CH3 CH3
HX

–
A + B Q. CH –O–C–CH
3 3
XX
Salt R–X

–
– + CH3
O Na –
O H+
+ CH3–X CH3
CH3–X +

–
CH3–O–C–CH3
X

–
–
– H CH3
CH3O
CH3

–
Q. ? Ph–O–CH=CH2 CH3OH + +C–CH3
– CH3

–
No Rxn – X CH3 X
Ph O

–
X –CH=CH2 X–C–CH3
xx
–

–
CH2=CH–O X Ph–X CH3
xx

HX
O Q. Ph–CH2–O–CH3
A + B
+
Q. Salt R–X H
– + – +
ONa X O Ph–CH2–O–CH3
X
X

–
H 2 – H
PhC X
+
CHEMICAL PROPERTIES Ph–CH2+CH3OH

1. Rxn with HX HX
Q. Ph–O–CH
3
HX H
+
R–O–R' Reactivity
XX + –
+ of HX Ph–O— CH3 X PhOH+CH3–X
H
HI > HBr > HCl
–

H
+ X
–
R–O–R' # Rxn with Excess HX
–

H
δ+ δ– δ+ Excess
*∞ R–O–R' R–X
# if R or R' 3°, 1° & 2° Resonance stabilised H+X–
X HH X +
e.g., benzyl allyl SN1 R'–X
∞ CH3
#* if R or R' 1° & 2° SN2 Excess
–

CH3 — O — C —CH3
HX
X HH X
–

HX CH3
Q. CH3–O–CH2–CH3 CH3
XX
+
– –

H CH3–X + X–C–CH3
+
CH3–O–CH2–CH3 CH3
–

H
– xx Excess
X SN2 Q. Ph–O–CH3 PhOH + CH3X
H X HX
CH3–X + CH3–CH2–OH

174
Organic Chemistry
2. EAS Na/Δ –
Q. PhOH A PhONa+
CH3Cl
x
x OR +M (O,P directing) – Br PhOH CH3–Br
OR OR Excess
Ph O — CH3 B D + E
E+ E H HBr
+ Alkyl
+
Br2/CH3COOH Halide
Br
Minor E
OCH3 C major
Major

A. Bromination
Br
OCH3 OCH3 OCH3
Br3 Br Practice
+
CH3COOH
+ Minor OCH3
Br
(Br)
Major Q. A + B
Salt RX
B. Friedel crafts Rxn
NO2
– +
(a) Alkylation O Na

+ CH3–X
OCH3 OCH3 OCH3 NO2 x
CH3Cl CH3 x
X
+ X
Anhy AlCl3 – +
+ Minor + CH3O Na
CH3
CH3
Major NO2

(b) Acylation

O O–C2H5
OCH3 OCH3 O OCH3 HBr
–
–

CH3–C–Cl C CH3 Q. 2 PhOH + C2H5Br

Anhy AlCl3 + SN
Br
+ Minor
x
x

CH3–C=O O=C–CH3 Ph–O–C2H5

Major H

C. Nitration

Q. OC2H5 OC2H5 OC2H5

OCH3 OCH3 conc HNO3 NO2
OCH3
conc HNO3 NO2 +
conc H2SO4
conc H2SO4 + + minor
NO2 NO2
+ Minor major
NO2 NO2
Major

175
Alcohols, Phenols and Ethers
 I I
PSS O
conc H2SO4 Excess
OH 413K A B
HI
2CH3–CH2–I
conc H2SO4 Na/Δ – +
443 K C2H5ONa

F C + 1
H
+ 2 2
CH3–CH2–OH2
PhCH2Cl CH2OC2H5
+ + Cl
CH3–CH2
Anhy AlCl3 E
HSO4– major
D
CH2=CH2 Ph–CH2–O–C2H5 H +
(+M) +

Apni kisi bhi mehnat ko bekar mat maan

Manjil tumhe jaror milegi bs haar
mt maan.

176
Organic Chemistry
 Med Easy
Carbonyl Compounds and Carboxylic Acid
8
M.O.P. of carbonyl Compounds OH H
o
1. From oxidation of alcohols α Cu/300 C
Q. Ph C CH2 Ph C CH2
β
R CH3 CH3
1oROH Aldehyde
R
2oROH Ketone Q. A O +CCl
o CH CH3 3 4
O + CH3 CHO
3 ROH No oxidation Zn
R Reagents O+O CH CH3

a. PCC
b. PDC M.O.P. of Aldehyde
c. Collin's reagent (CrO3 + 2Py)
1. Rosenmund reduction
d. (CrO3 + acetone)
e. Cu/300oC (dehydration) (with 3° ROH E2) O O
2. Ozonolysis H2 + Pd
R C Cl R C H
R H H BaSO4
Alkene Carbonyl compound

R 1. O + CCl /Zn 2. Stephen's reduction

3 4

2. O3 + CCl4 /Zn + H2O SnCl2 + 2HCl SnCl4 + 2[H]

3. O3 + CCl4 /Me2S H H SnCl2 + HCl
R C N R CHO
3. Kucherov Reaction H2O
dil H2SO4 + dil HgSO4 OH +
Alkyne Carbonyl compound H H2O
or R CH NH R CHO
Hg2+ / H2O HO– H+

3. Reduction by DiBAL-H
Q. H
A
CrO3

OH
acetone
AlH R CN R CHO
O 2
[O] OH
–H2O
H H 1) DIBAL– H
OH R C N
2) H2O
OH
Hg2+ 2[H]
Q. CH3 C CH CH3 C CH2
+I + –
H2O
Tauto
OH
CH3 C CH3 H H2O
R CH NH R CHO
HO H
O
OH
O O
MnO2
Q. Ph
H
Ph C CH2 CH3 1) DiBAL– H
R C OR' R CHO + R'OH
[o]
–H 2
O
H H 2) H2O
4) Etard Reaction etc 2) From nitriles

– 2+ R'
Chromium complex R'Mg X +
CH3 CH(OCrOHCl2)2 CHO R C N R C N–Mg X
H2O
CrO2Cl2 H3O+
R'

CH(OCOCH3)2 R C NH
OH H
(CH CrO OH H

3 CO
3
H 3O
+ H2O
)2 O
R C R'
Benzaldehyde diacetate
O
3) F. C acylation
5) Side Chain Oxidation
O
CH3 CHCl2
C R
2Cl2/hv
RCOCl
Anhy AlCl3
aq KOH
O
CHO +
R C

Practice
O
Q. CrO3
OH H
6) Gattermann Koch Reaction

CHO Q. CH3 CHO

1) CrO2Cl2
CO + HCl
2) H2O
Anhy AlCl3
F F
O
– MnO2
H C Cl Q. CH2 CH CH2 OH CH2 CH CHO
+
O O O3 + CCl4
Q. CH3 CH CH CH3 CH3CHO
Zn
M.O.P. of Ketones
DiBAL–H
Q. CH3 C N CH3 CHO
1) From acid chloride H2O

O
2RMgCl + CdCl2 → R2Cd + 2MgCl2
C CH3
O O + – Anhy
R2Cd Q. + CH3COCl
AlCl3
R' C Cl R' C R
O O
Q. (PhCH2)2Cd + 2CH3COCl

R' C Cl + Cd + Cl C R' O

CH3 C CH2 Ph
R R

178
Organic Chemistry
 O Mechanism:
+ – Hg /H2O2+
Q. CH3 C CH CH3 C CH3
+I * *– SO3H SO3Na
+
NaHSO3 – +
C O C O Na C OH

Properties:
C. Reaction with alcohols
1) Nucleophilic addition Reaction

A. Reaction with HCN Mechanism:

+ – H R
+ – HCN +
O OR
C O C OH
or * *
ROH
KCN/NaCN CN C O C OH C OH
H2O Cyanohydrin
xx dry HCl
+
H

Mechanism: –+
+ – ROH
C O C OH
+ –
– NaCN – OR
C O C O

CN OR
H
+ 2ROH
C O C
OR
C OH HOR acetal or ketal
C O
CN HOR

O
B. Reaction with NaHSO3 HO
C O C
HO O
Aldehyde & methyl ketones
cyclic acetal or ketal

+ – NaHSO3
C O C OH
+– D. Reaction with NH2–Z
HSO3Na
SO3Na

C O + H2N Z C N Z
Aldehyde & aliphatic methyl ketone give this Rxn

Z Reagent name Product Product name

H ammonia >C=NH imine

R 1o amine >C=NR Schiff's base

NH2 Hydrazine >C=N–NH2 hydrazone

NHpH Phenyl hydrazine >C=N–NHph phenyl hydrazone

OH hydroxylamine >C=N–OH Oxime

179
Aldehyde, Ketones & Carboxylic Acids
 O
NHCONH2 Semicarbazide semicarbazone
C N NH C NH2

NO2 2, 4-dinitrophenyl NO2 2, 4-dinitrophenyl hydrazine

NO2
hydrazine (2, 4 DNP R = Orange/ Yellow ppt.
–NH
reagent) (Brady's C N NH NO2
reagent) R

Mechanism: Q.
–
H O
+ NaHSO3
H N Z CH3 C CH2 CH3
H2N Z + + –
C OH HSO3Na
C O
H+ OH
Semicarbazide NH Z
O C CH3 C CH2 CH3
* OH
H2N NH C NH2 SO3Na
More
Nu C N Z

Q.
E. Reaction with G. R CH3OH CH3 OH
o
CH3 CHO + C
Ald → 1 AlCO H
H OCH3
HCHO
CH3 – +
Ald → 2o AlCO + – CH3OH
C O Hemi acetal
RCHO
H
Ket → 3o AlCO
RCOR Q.
Practice O CH3 OCH3
Q. NH2OH 2CH3OH
O + N OH CH3 C CH3 C
H H+ CH3 OCH3
H2NOH
Ketal
Q. CH3 HOCH3
O
C O
R CH CH CHO + NH2 C NH NH2 CH3 HOCH3
+
H O

R CH CH CH N NH C NH2 Q.

–
Q. O OH
– Mozingo Reaction HS H
CH3MgBr CH3 S
HS H
H2O CH3 CHO C
H+ H S
Q CN H H
+ –
HCN
Ph C OH CH3 Thioketal
PhCHO HS
C O +
H H2/Ni
+ – H
Ph C O HS
CH3–CH3
H

180
Organic Chemistry
 b) Oxidation of Ketones :- Popoff's rule: It states
2) Reduction Reaction that the C=O of unsymmetrical ketone always
a) Carbonyl → Alcohol stays at the side where smaller alkyl group is
present.
H H [H]
C O C OH O
R OOH
R
H OH 2CH3 C OH
1 2
R 1
OH OH
i. LiAlH4 (LAH) ii. NaBH4 (SBH) 1) Conc HNO3 H H
2
iii. H2/Ni, pt, pd 2) KMnO4 3 3
Stable enol
b) Carbonyl → Alkane 3) K2Cr2O7 [O]
H H [H] 2CH3COOH
C O CH2

H H R O

R Test for carbonyl compound:

i. Zn(Hg)/ conc HCl 1) Tollen's Test
Clemmensen reduction Alipha. aldehyde Ketone
ii. N2H4/ethylene glycol, KOH Aromatic Aldehyde Hemi acetal
wolff kishner reduction α-hydroxy ketone HCOOH
Q.
H OH OH Tollen's reagent:
N2H4/ , KOH i. AgNO3 + NH4OH
Ph C H OH B
H H ii. [Ag(NH3)2]+
LAH Ph CH3 –
R–CHO + 2[Ag(NH3)2]+ + 3OH → RCOO–+
Ag ↓ + 2H2O + 4NH3
A
Ph CH2 OH 2) Fehling's Test

Q. Alipha. aldehyde Ketone

HO H Aromatic Aldehyde
Zn(Hg) Fehling's A
HH
Conc. HCl aq. CuSO4
+ + Cl RCHO +2Cu
2+ – –
+ 5OH → RCOO + Cu2O ↓ + 3H2O
H2O
red brown
Q. O OH
Fehling's B
H SBH Rochelle's salt: sodium potassium tartarate

O O O O COONa

3) Oxidation of Carbonyl compound: CHOH

a) Oxidation of aldehyde CHOH

O O
[O] COOK
R C H R C OH
R Name Rxns
R 1. Aldol condensation#
1) Conc HNO3 2) KMnO4 a) α–H
3) K2Cr2O7
b) Reagent # dil KOH, NaOH, Na2CO3 etc

181
Aldehyde, Ketones & Carboxylic Acids
 O O O
α O O
CH3–C–H H–C–H CH3–C–H
CH2–C–H CH3–C–CH2–CHO
α–H H
O H
α α α OH H O HO
CH3–C–CH3 –C–H
A CH3–C–CH–C–H
α H O
α–H H
le α–H
Ru
+ – + – E1cb
C=O + H–Z OH OH
OH
CH3–CH–CH–CHO CH3–CH–CH–CHO
C–O–H
H
Z B CH3–CH=CH–CHO
dil NaOH Δ dil.NaOH/Δ ≡H+
Q 2 CH3CHO A B

CH3 + + –
– Q.
C=O + H–CH2CHO
H
dil NaOH Δ
OH β α crotonaldehyde 2 CH3COCH3 A B
β-hydroxy CH3 Δ
CH3–CH=CH–CHO
C β H
Aldol
H CH–CHO α, β-unsaturated CH3 + O
α – + –
aldehyde C=O + H–CH2–C–CH3
A
B CH3
Mech#
OH Mesityl oxide
– β-hydroxy CH3 C Δ
CH
dil OH Δ H 3–C=CH–COCH
A B βα
3
CH3CHO Ketol CH3 β CH–C–CH3 CH3
O α
OH A O α, β-unsaturated
H–CH2–CHO CH2–C–H Carbonyl comp
Note: H+ (ketone)
CH3CHO B
O–
CH2=C–H
enolate ion

O
dil NaOH
Q. CH3–CHO+CH3–C–CH3
Δ
CH3 + + –
–
CH3 + OH C=O + H–CH2COCH3
– + – CH3
C=O + H–CH2–CHO C H H
H H CH–CHO
Δ CH3 OH
Self Aldol C H CH3–CH=CHCOCH3
CH3–CH=CH–CHO H CH–COCH3
Cross product
CH3 + + – CH3 OH
– Δ CH3 +
C=O + H–CH2COCH3 C H – + –
CH3 CH3 CH–COCH3 C=O + H–CH2CHO
CH3

CH3–C=CH–COCH3
CH3 OH
CH3 C H CH3–C=CH–CHO
CH3 CH CHO CH3
Cross product

182
Organic Chemistry
Q. R
–
dil.OH 2 HCHO HCOONa + CH3OH
PhCHO+CH3CHO Total Product
Δ
CH3 + R 1 conc NaOH or KOH
– + –
C=O + H–CH2CHO 2 50% NaOH or KOH
H
O O O
Ph + + – [O] KOH
–
CH3 + OH
C=O H–CH2CHO a) H–C–H H–C–OH H–C–OK
H C H CH3–CH=CH–CHO
H CH–CHO Self HO
2[H]
Ph OH b) H–C–H CH3–OH
C H Ph CH=CH–CHO H
H CH–CHO Mech
Cross product O O
H–C–H OH H–C–H
Q. dil/NaOH OH H
O
Δ shift
H–C–H
+ –
+ O– + H O O
–+
O H–C–OH + CH3–O
O
OH Δ –
H H–C–O
+
O O CH3OH
# R.D.S → H Shift
–
Q. Ph–CHO+PhCOCH dil OH # Disproportionation Rxn
3 Δ
Major
α H α H H–CHO H–COOK + H– CH2OH
X
50%KOH
Cross product Ph–CHO Ph–COOK + Ph–CH2OH

Ph + 50%KOH
– + – (CH3)3C–CHO Me3C–COOK+Me3C–CH2OH
C=O + H–CH2COPh
H Cross cannizaro
50%KoH
Ph OH HCHO + PhCHO H COOK + PhCH2OH
Δ
C H Ph CH=CHCOPh # W
 hen one of the reactant is formaldehyde then
H CH–COPh it will be oxidised always
# Redox reaction:
2. Cannizaro Rxn# HCHO + Me3CCHO
50%NaOH
H COONa +
Me3C — CH2OH
O H O
H α–
No α-H–C–H CH3–C–H
Intramolecular cannizaro
CHO COOK
50%KOH
O CHO CH2OH
–C–H *
CHO COOK
H 50%KOH
No α-
CHO CH2OH

183
Aldehyde, Ketones & Carboxylic Acids
Q. COOH COOK COOK O O
50%KOH + OH
CHO COOK CH2OH R–C–CX3 R–C–CX3
OH
Q.
CHO COOK CH2OH
O
50%KOH R–C–OH + CX3

CH2–Cl CH2 CH2 O

OH OH R–C–O–+CHX3

OH
X2+KOH
3. Haloform Rxn Q. R–C–CH3 RCOOK+CHX3
OH H
Methyl ketones , R–CH–CH3 [O]
O
O
R–C–CH3 , CH3–CH2–OH
R–C–CH3
O
X2+KOH O
R–C–CH3 Br2+KOH
Q. Ph–C–CH Ph COOK + CHBr3
3
a) Halogenation
O O O
H X–X
R–C–C H X–X R–C–CX3 Ph–C–C Br3
H X–X Ok H

b) Hydrolysis Q.
O
KOH X2+KOH
R–C–CX3 R COOK + CHX3 CH3–CH–OH HCOOK+CHX3
Ok H Haloform H KOH
O
[O]
Mech# O H–C–CX3
3X 2 Ok H
H–C–CH3
O
Q. OH
R–C CH2 CH3–CHO + HCHO
(Excess)
H + – + –
O O C=O + H–CH2CHO
OH H
R–C–CH2–H R.D.S R–C–CH2
H OH
X–X C
H CH2–CHO
–
i) OH OH
–
H2C=O CH2OH
R–C–CHX2 R–C–CH2–X
ii) X2 HOCH2–CH–CHO
H2C=O
HOCH2–C–CHO
O – O OH–
i) OH CH2OH CH2OH
ii) X2 CH2OH HO
–
OH –
OH
HCHO+CH2–C–CHO HCOO +
R–C–CX3
OH CH2OH HO
O OH

184
Organic Chemistry
CARBOXYLIC ACIDS B. From acid derivative

O Z = Cl acid chloride
M.O.P 1. From 1° Alcohols and Aldehyde –
R–C–Z
H Z = NH2 acid amide
+
OH
R Z = OR ester
R–CH2–OH R–COOH
Z = OCOR anhydride
+ O
R → 1 KMnO4/H or Hot KMnO4
R–C–OH+Z–H
2 K2Cr2O7/H+
O
3 Conc HNO3 R–C–Cl R COOH + HCl
OH H
4 CrO3 + H2SO4 Jone’s reagent

O O O
R
R–C–NH2 R COOH + NH3
R–C–H R–C–OH OH H

O
CrO3 COOH
Q. R–C–OR R COOH + ROH
OH H2SO4 OH H

O O O
2. From alkyl benzene
R–C–O–C–R R–C–OH+ R COOH
OH H
R COOH

KMnO4/KOH Q. O
H H3O+
+
H Ph–C–Cl A Ph COOH
OH
H2+Pd
CH3 COOH BaSO4
+
A K2Cr2O7/H
KMnO4/KOH B
+ Ph–CHO
H

Cl2/hν
COOH Q. CH A CH3–Cl
4
2
KCN/SN
KMnO4/KOH
D B CH3–C≡N
H+ Soda lime H3O+
C CH –COOH
3
COOH
KMnO4/KOH 4. From G.R
+
H 1 CO2
RMgX RCOOH
COOH 2 H2O+

O
3. Hydrolysis O=C=O
R R–C–O
+
H
A. From cyanide
R COOH
OH H +
O
OH H H3 O
R–C≡N R–C–OH i) CO2
OH H CH3MgBr CH3–COOH
ii) H2O

185
Aldehyde, Ketones & Carboxylic Acids
 i) CO2 Ans. 3
PhMgBr Ph–COOH
ii) H2O
Q. Compare A.S.

+ i) CO2 COOH COOH COOH

MgBr COOH
ii) H2O CH3
+I
CH3
CHEMICAL PROPERTIES +I
a) b) c) CH3 +M
1. Acidic strength
(a) a > b > c
O O
+ COOH COOH COOH
R–C–OH R–C–O + H
Stable NO2
–I
NO2
Acidic strength α –I & –M –I
a) b) c) NO2 –M
1
Ka ↑, pka↓ α (b) a > c > b
+I&+M
[H+] ↑, pH↓
Q. Compare PKa values

SA Na 1 CH3SO3H COOH
RCOO–H+ RCOONa+ H2↑ (a)
Na + 2 a) Br
OH –
Na + Ka: a > b
NH RCOONa+H2O pKa: a < b b)
–
2 WA
+ –
Na HCO3
RCOONa+NH3
WA (b) F OH
CO2+H2O COOH COOH
RCOONa+H2CO3
a) b)
WA
CH3 NO2
Order of acidic strength COOH COOH
c) d)
H3O+ > R–SO3H > HCOOH > PhCOOH > RCOOH>
Ka : d > a > b > c
nitro phenols > H2CO3 > PhOH > RNH+3 > CH3OH
> H2O > ROH > CH≡CH > CH2=CH2 > CH3–CH3 pKa : d < a < b < c

Q. How many of the following will give 2. Rxn with PCl3, PCl5, SOCl2
Na+HCO–3 test?
OH O O
R
R–C–OH R–C–Cl
CH3 SO3H , , CH3 COOH
# SOCl2 is the best method for preparation
OH of acid halide
O O
SOCl2
CH3CH2OH , , CH3OH R–C–OH R–C–Cl+SO2↑
Cl–SO–Cl +HCl↑
NO2

186
Organic Chemistry
3. Anhydride formation 7. Decarboxylation

O O O
H+/Δ NaOH + CaO
R–C–OH R–C–O–C–R R-COOH R-H
or
R-COONa + NaOH R-H
P2O5
O O
8. E.A.S
R–C–OH+HO–C–R
+
NO2
4. Esterification COOH COOH
conc HNO3
R–COOH+R'OH H+ RCOOR' conc H2SO4
O NO2

R–C–OH+HOR' +
Br
COOH COOH
Br2
5. Rxn with NH3/Δ
FeBr3
O O Br
NH3 – +
R–C–OH R–CO NH4
# Benzoic acid does not give F.C.R
O
Δ
C–OH H 9. H.V.Z Rxn (Hell volhard zelinskey rxn)
H–N
H
C–OH O X=Br, I
H α i) Red P/X2
O α–
R–C–NH2 R–CH2–COOH R–CH–COOH
ii) H2O

–
X
COOH COONH4
NH3
COOH COONH4 Q.

Δ β α
CH3–CH–COOH
O

–
CONH2 i) Red P/Br2 Br
C Strong
NH CH3–CH2–COOH A
ii) H2O
C Heating H
CONH2
c KO
CH2=CH–CH2OH
O Al
LAH
C B
6. Reduction CH2=CH–COOH
PCC
LAH
R–COOH R–CH2OH
or
B2H6 D
CH2=CH–CHO
LAH
CH3–COOH CH3–CH2–OH

COOH CH2OH

B2H6

NO2 NO2

187
Aldehyde, Ketones & Carboxylic Acids
 O PhCH=NOH
PSS NH3/Δ M K + E

–
–
PhCOOH A Ph–C–NH2 H PhCH2OH
KO Salt
PhCOOK
0%

NH 2
SO O 5 –
Cl + O
l

OH
–
–
NaOH/CaO 2 C–C C H
Ph– H2+Pd Ph SBH CH3COOH
C D E H O
BaSO4 H+
B PhCH2OH

–
–
CH3–C–O–CH2Ph
+–
H HCN

g)
PhCOO H3O+

Cl
(H
COOH

.H
Zn
Br2 OH

nc
L I PhCH 3 N H3O+

co
FeBr3

–
F G Ph–CH–COOH
Br + P2O5 OH
Br PhCH
NB CN
J O O +–
S
KCN
–
–

–
–

Ph–C–O–C–Ph O P Ph–CH2–CN
SN2
PhCH2Br

Shakshiyat damdar hoti hai tabi dushman

bante hai...
varna kamjoro se to log sahanubhooti
rakhte hai.

188
Organic Chemistry
 MED Easy
9 Amines and Diazonium Salts

AMINES Hoffmann Elimination

α
CH3
M.O.P α β –
+ α
OH/∆
CH3 N CH2 CH3
1. Reduction of nitro compound E2a
α CH3 –
R OH
R NO2 R NH2 CH3
a. H2 + Pd / C2H5OH For Aliphatic nitro + –
CH3 N CH2 CH2 CH2 CH2 + Me3N
we can use LAH also
b. Sn / HCl
CH3
c. Fe / HCl (Best MOP)
5. Gabriel phthalimide Synthesis
NO2 NH2
O O
R
C – C
OH – R X
N H N
2. Reduction of nitriles SN2
C C
H H LiAlH4
H H or O O
H2 + Ni O
R C N R CH2 NH2
or +–
NaOOC NaO C
Na(Hg) + C2H5OH NaOH
H
N
NH2 R+ R
3. Reduction of amides
H
+–
NaOOC NaO C
H O H R
X
R NH2 O
LiAlH4 1o 1o
R C NH2 R CH2 NH2
H H H2O 6. Hoffmann bromamide degradation
4. Ammonolysis O
+ Br2
NH3 – H+ R C NH2 R NH2
R X R NH3 R NH2 KOH
1o Mech
R X
R NH2 R NH R O O O
2o OH Br Br
R NH H+X R
R C NH H R C NH R C N Br

H
R X –
OH
R NH R R N R
O

R N R R NH2 + K2CO3 KOH R

H
N
OK
C O R C N Br
R H OK

3o Purely intra retention

H + X R Practice
** R X + Q.
R N R R4 NX– CH3 CH2 Cl CH3 CH2 CH2 NH2
4o ammonium salt KCN / SNH
2
H
R H H
Reactivity R I >R Br > R Cl > R F CH3 CH2 C N H2+ Ni
 NH3/∆ Br2/KOH NaNO2 + HCl
Q. CH3COOH A B Ph NH2 PhN2+Cl–
o
O CH3 HONO 0–5 C
NH2
Diazonium chloride
CH3 C NH2 4. Reaction with aryl sulphonyl chloride
Hinsberg's Test
Q. COCH3 COOK
Br2/KOH O O
+ CHBr3
Ph S Cl + H NHR Ph S NH R
CONH2 NH2
O O
CHEMICAL PROPERTIES Soluble in alkali
1. Acylation O O
O
Ph S Cl + H NR2 Ph S N R
CH3COCl
R NH2 R NH C CH3
O O O R
O Insoluble in alkali
R NH – H + Cl C CH3
O
Ph S Cl + R3N X
(CH3CO)2O
R NH2 R NH C CH3
O
O O
5. Basic strength in amines
R NH H + CH3 C O C CH3 ** ** **
R N R> R N R>R NH2
2. Carbyl amine Reaction (Test of 1o amine)
R H
CHCl3
R NH2 R NC Basicity 3 > 2 > 1o o o gas phase
KOH
Isocyanide Test 1
Basicity ∝ + I & + M ∝
mech – I & – M
H CCl2 (D. C. C) H
In aq Medium
R * + –
H OH2
N CCl2 R N C Cl
*
aq. +
RNH2 R N H OH2
H H Cl
–
2OH H OH2
R
+ –
R N C aq. +
R2NH R N H OH2
3. Reaction with nitrous acid
HNO2 or NaNO2 + HCl H OH2
R
–
HNO2 OH aq.
R NH2 R+ ROH +
R3N R N H OH2
HONO Rearrange if pos
H H
NH2 HNO
HONO
2
+ In aq Medium

OH if R = CH3
– + Basicity 2o > 1o > 3o > NH3
OH
if R = C2H5

190
Organic Chemistry
Basicity 2o > 3o > 1o > NH3 for mono nitration
6. E. A. S
O
A. Bromination
NH H NH C CH3
NH2 NH2 + –
Br CH3COCl
Br
Br2 +
NO2
H2O
Br Conc HNO3
Tribromination
Conc H2SO4
for mono bromination NH2 O
O + – – +
H OH NH C CH3
– C CH3
NH H+ O NH

CH3 + – NO2
C Cl
+
CH3COOH NO2
Br2 + CH3COOH
O C. sulphonation
– +
NH2 NH C CH3 +
– NH2 NH3HSO4–
H+ OH
H2SO4

Br Br
+ 453 –473K
CH3COOH
+
NH3 NH2
B. Nitration
O
Zwitter ion
– C CH3
NH H + O NH
+ – SO3– SO3H
CH3 C Cl
D. Aniline does not give F.C.R
H
Br2 + CH3COOH
xx AlCl3 + –
R NH2 R N AlCl3
O
– + H
NH2 NH C CH3
Practice
–
+
H OH
+ Na(Hg)
NaCN
CH3 CH2 I A B
Br Br SN2 C2H5OH
+
CH3COOH H H CH3–CH2–CH2–NH2
CH3–CH2–C–
– N
H H

191
Amines and Diazonium Salts
Q. 2. Gattermann Reaction
Fe/HCl NaNO2 + HCl +
Ph NO2 A B N 2 Cl– Cl
0–5°C
Ph-NH2 + –
Ph-N2Cl Cu/HCl
CHCl3
Q. Ph NH2 A
KOH
Ph NC Cu/HBr

Cl + Cl
NO2
Br
ConcHNO3
Q. A
ConcH2SO4
NO2
–
Fe + HCl 3. Replacement of I ion (Sizzi's Reaction)
+
N Cl– I
B 2

Cl KI

4. Balz-Schiemann Reaction

NH2 N+2 Cl– N+2 BF–4 F

+
DIAZONIUM SALTS HBF4– ∆ + N2
R–N2+X– Ph– N2+X–  + BF3
R = Alkyl 5. Replacement by H
– – – – +
X = Cl , Br , HSO4 , BF4 N 2 Cl– H
M.O.P H3PO2
NH2 N+2 Cl H2O
NaNO2/HCl
o
0–5 C CH3CH2OH
Benzene diazonium
Chloride H

CHEMICAL PROPERTIES
1. Sandmeyer's Reaction
Cl 6. Replacement by OH
N+2 Cl– OH
N+2 Cl– CuCl/HCl
Warm
Br H2O
CuBr/HBr
7. Replacement by NO2

N+2 Cl– N+2 BF4– NO2

CN
CuCN/HCN
HBF4 NaNO2
Cu / ∆

192
Organic Chemistry
8. Coupling Reaction Practice
a) With phenol Q. Convert P-nitro toluene to O-bromo benzoic acid
– COOH
+ – OH CH3
N 2 Cl + OH Br

(i) KMnO4/KOH
(ii) H+ CH
N N OH CH3 3
NO2
Br
Br H3PO2
Orange dye Br2 / Fe

P-hydroxy azobenzene N2+Cl

–
CH3 CH3
a) With amine (aniline) Br Br
Sn/HCl
+ NaNO2 + HCl
N+2 Cl– + H
NH2 NO2 NH2 0–5oC

Q. Convert m-methyl aniline to m-nitro toluene

N N NH2 NO2
NH2

yellow dye
P-amino azobenzene CH3
CH3
NaNO2 + HCl
0–5oC NaNO2/Cu/∆

N2+Cl– N2+Bf4–
HBF4

CH3 CH3

NO2

S NH2
PS O
CH CH RHT A Conc HNO3 Fe + HCl
B C xx
Conc H2SO4 Ph C O Ph
NaNO2 / HCl
0 –5oC Ester J
+
a N2Cl–
ky
to
, PhO H G
e ef ein ai…
kl m eh Cl
a
i t ene jat ai
. CuCl / HCl COOH
o D CuCN
k e m E
i ij m e KCN H H3O
+
na ha tha een r I
sh jja n s HB warm H2O CN
g ar a ffa ho /
i Br Cu
m u
an k t ag
l L NaOH + CaO
o i s haa ade g
k k b aa F
a e b K
N ad Ja G OH A
B
H3PO2
A

193
Amines and Diazonium Salts
 MED Easy

10 Biomolecules

CARBOHYDRATES
Hydrates of carbon are called carbohydrate
General formula # Cx (H2O)y
Exp ÷ C6(H2O)6 C6H12O6
Exception ÷ C2(H2O)2 = C2H4O2 CH3COOH (acetic acid)
Not a carbohydrate

Classification
(a) Monosaccharides (b) Oligosaccharides (c) Polysaccharides
   
Does not hydrolyse further.    
Produces 2 to 10 monosca units on    
P
 roduces large no. of monosac
Exp ÷ Glucose hydrolysis units on hydrolysis

     Fructose Disac → 2 unit Exp ÷ Starch, cellulose etc.

     Galactose etc. Exp ÷ Sucrose, Maltose, Lactose etc.

Trisac → 3 unit
Exp ÷ Raffinose

Classification
Reducing Nonreducing
Reduces  Tollen’s reagent Do not reduce   T.R
F.R
Fehling’s reagent
B.R
Benedict’s reagent Exp ÷ Sucrose
Exp ÷ (i) Monosac like Glucose, Fructose, Galactose
(ii) Disac like maltose, lactose etc.

Classification of Monosaccharides
No. of ‘C’ atoms Ald Ket

3 Aldotriose Ketotriose

4 Aldotetrose Ketotetrose

5 Aldopentose Ketopentose

6 Aldohexose Ketohexose
MOP of Glucose
(1) From sucrose (2) From starch
Sucrose Glucose Fructose (C6H10O5)n
H3O+
nC6H12O6
H3O+
C12H22O11 C6H12O6 + C6H12O6
Glucose
Cane sugar (+) (–)
(+) (d) dextro (l) laevo
(d) dextro

d l

Inversion of cane sugar

Chemical R×n
+ –
R×n with H C N n
(1) (2) R× with HI/Red P
OH H H
+ H CH == O
H C = O– C – CN
* H H
H OH H OH
H OH
H H
HO H HO H
+ – HO H H
HC N
H
H OH H OH n-hexane
H H OH
H
H OH H OH H H OH
CH2OH CH2OH H
CH2 – OH
H H

(3) R×n with NH2OH (4) R×n with acetic anhydride

H C = O H2 NOH CH = NOH O O
–
H OH H OH CHO CH3–C–O–C–CH3
+
– +
H OH
HO H HO H
+ –
+ –
AC – O – AC CHO
HO H    
H OH H OH Excess
– + (CHOAc)4
H OH
H OH H OH
– +
CH2OAc
CH2OH CH2OH H OH
– + Glucose
Glucose oxime CH2OH
penta acetate

(5) R×n with Br2 + H2O (6) R×n with Conc � HNO3

CHO COOH CHO COOH

H OH H OH H OH H OH

HO H HO H HO H HO H
Conc.

H OH H OH H OH HNO3 H OH

H OH H OH H OH H OH
CH2OH CH2OH CH2OH COOH
Gluconic acid Glucharic acid
Conc � HNO3
or
Saccharic acid

195
Biomolecules
(7) Osazone formation
Reagent→Phenyl hydrazine Ph–NH–NH2

CH=O H2 N–NHPh CH=N–NHPh CH=N–NHPh CH=N–NHPh

H OH HO OH O H2 NNHPh N–NHPh
HO H HO H HO H HO H
1 mol 1 mol 1 mol
H OH PhNHNH2 H OH PhNH–NH2 H OH PhNHNH2 H OH
H H

H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

+ Osazone
.
P.S.S   Total no. of moles of PhNH2 (Glucosazone)
PhNHNH2 used = 3 +
NH3

Important points in the fav. of cyclic structure

1. Glucose does not give NaHSO3 test
2. Glucose does not give Schiff’s test
3. Glucose penta acetate does not react with NH2OH

Cyclic Structure of Glucose

6
CH2OH
1 5
H–C–OH O
H H
2 H
H OH
3 4 1
+ *CH–OH HO H OH H
CH=O – 4
H OH HO OH
3 2
H OH H OH H 5 O
HO H HO H 6 H OH
H OH H OH CH2OH
– + α-D-(+)-Glucopyranose
H OH H O 1
OH–C– H 6
CH2OH CH2OH 2 CH2OH
H OH
5
HO 3 H O
4 H OH
H OH H
Pyran 5
H O 4 1
O OH H
6 HO
CH2OH 3 2 H

H OH
β-D-(+)-Glucopyranose
Important Points
1. Muta rotation
α β
Equi of α & β-isomer

196
Organic Chemistry
 2. α and β isomers are C1 anomers (anomers are diastereomers)
3. Total no. of chiral carbons in cyclic structure of glucose = 5

Cyclic Structure of Fructose

1
6 CH2OH
1
CH2OH O
2
HOCH2–C–OH
5 2
HO 3 H
CH2OH CH2OH H H OH OH
H 4 OH
– 4
+ O * OH H 5 O (α–) 3
HO H HO H 6CH OH
2 OH H
H OH H OH
– + α-D-(-)- fructofuranose
H OH H O 2 1
6 OH
CH2OH
HO–C–CH2OH CH2OH O
CH2OH
HO 3 H 5 2
H 4 OH
H H HO CH2OH
H 5 O (β–)
1
furan 4
6CH OH 3
2
O OH H
β-D-(-)-fructofuranose
Important points
1. Muta rotation
α β
Equi of α & β-isomer
2. α and β isomers are C1 anomers (anomers are diastereomers)
3. Total no of chiral carbons in cyclic structure of fructose = 4

Cyclic Structure of Sucrose:

–H2O
α-D-Glucose & β–D-fructose sucrose

OH OH mono –O– mono

sac sac
OH
O Glycosidic
O OH O
linkage at
C1 and C2
CH2OH CH2OH

Cyclic Structure of Maltose

a-D-glucose + a–D–glucose
H H H H
O O O O
1 4
OH HO O
Glycosidic linkage at C1 and C4

197
Biomolecules
Cyclic Structure of Lactose
β-D-galactose + β–D–glucose
HO O OH H O OH HO O H O OH
O
H H HO H H H H
Glycosidic linkage at
C1 and C4
Cyclic Structure of Starch
1. Amylose
Linear polymer of a-D–glucose
All glycosidic linkages are present at C1 and C4
H O H H O H H O H

HO OH OH OH HO OH

H O H H O H H O H

O O O O

2. Amylopectin
Branched polymer
Glycosidic linkages are present at C1 and C4 and Branching at C6
O H

OH
CH2–OH CH2OH CH2OH
H O H H O H H O H
H H H
HO OH OH OH HO OH

CH2O– CH2O– CH2O–

H O H H O H H O H
H H H
O O O O

Difference Between Amylose and Amylopectin

Amylose Amylopectin
1. Linear polymer 1. Branched polymer

2. 15–20% starch 2. 80-85% starch

3. Water soluble 3. Water insoluble

4. Glycosidic linkage at C1 and C4 4. Glycosidic linkage at C1 and C4 and branch at C6

198
Organic Chemistry
Cyclic Structure of Cellulose
Linear polymer of β-D-Glucose All glycosidic linkages are present at C1 and C4

H O OH OH
H O OH H O

HO H HO H HO
H

O H
O H
O O
O
O O
H

Super Trick to Remember All Monosaccharides

CHO
D-Glyceraldehyde
ALDOTRIOSE OH

CH2OH
ALDOTETROSE
CHO H OH CHO
H OH HO H HO H
Erythro
H OH Threo H OH

CH2OH CH2OH
Erythro Threo
ALDOPENTOSE

H OH HO H H OH HO H
Ribose Arabinose Xylose Lyxose

CHO CHO
CHO CHO
H OH HO H H OH
H OH HO H
H OH HO H
H OH HO H
H OH
H OH
CH 2 OH H OH
CH 2 OH
CH 2 OH
CH 2 OH
ALDOHEXOSE

H OH HO H H OH HO H H OH HO H H OH HO H
CHO CHO CHO CHO CHO CHO CHO CHO
OH HO H H OH HO H H OH H H OH HO H
H HO
OH H OH HO H HO H H OH H OH HO H HO H
H
OH H OH H OH HO H HO HO H HO H
H OH H H
OH H OH H OH H OH H OH H OH H OH H OH
H
CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH
Allose Altrose Glucose Mannose Gulose Iodose Galactose Talose

199
Biomolecules
 G 4. Benedict’s Test (for reducing sugar)
GET
E T aq CuSO4 + Sodium citrate
COONa
R A X L
Rekha Amitabh Ka Lafda HO C CH2COONa

A A G m G I G T CH2COONa

aag main Bill Gates and O Bama

Girgit
Blue Green Orange Brick
Red
TEST
No sugar Small Moderate Large
1. Molisch Test (For carbohydrates) sugar sugar sugar
5. Tollen’s Test (for reducing sugar)
a–naphthol + EtOH
T�R AgNO3 + NH4OH
OH
Carbohydrates –CHO –COO–
    
Ag+ Ag
H2SO4  ppt
6. Fehling’s Test (for reducing sugar)
Purple ring at the junction of two liq


aq CuSO4 + NaKT
COONa
Monosacch fast purple
di & polysac slow CHOH

2. Seliwanoff's Test (for ketose) CHOH

Resorcinol + HCl COOK

OH Sodium potassium
tartarate
Ketose like fructose
OH –CHO COO–
Cu2+ Cu2O
Cherry Red ppt
Red ppt
for difference of Aldose and ketose
7. Iodine Test (for starch)
3. Barfoed Test (for monosaccharides) I2
Starch Blue-Black colouration
CuSO4 + CH3COOH due to adsorption of iodine

monosac PROTEINS
Red/Brown ppt
α-amino acids
+1
— COOH
2+
Cu Cu2O Based on R R—CH—
Red Brown NH2
1. if R contains COOH Acidic amino acid

200
Organic Chemistry
2. If R contains NH2 basic amino acids
3. If R neither contain COOH nor NH2 Neutral amino acids

Importance of α-amino acids

Three letter symbol Name Structure
NH
Tyr Tyrosine – 2
HO CH2–CH
COOH
NH
Ser Serine – 2
HO–CH2–CH
COOH
NH
Gly Glycine – 2
H–CH
COOH
NH
Ala Alanine – 2
Me–CH
COOH
NH
Phe Phenyl alanine – 2
Ph–CH2–CH
COOH
NH
Val Valine – 2
Me2CH–CH
COOH
NH
Leu Leucine – 2
Me2CH–CH2–CH
COOH
NH2
–
Ile Isoleucine Et–CH–CH
COOH
–

Me
NH2
Lys Lysine H2N–(CH2)4–CH –
COOH
NH
Asp Aspartic acid – 2
HOOC–CH2–CH
COOH
NH
Glu Glutamic acid – 2
HOOC–CH2–CH2–CH
COOH
NH
NH2
–
–

Arg Arginine H2N–C–NH–(CH2)3–CH –

COOH
Guanidine

Zwitter ion +
NH2 (Basic)
NH3
— —
(Dipolar ion)
R–CH— R–CH—
NH2 NH2 (Basic) COOH+(Acidic) COO–
Sulphonation (Zwitter ion)

Depending upon the pH of solution zwitter ion

SO3H +
(Acidic) exist in 3 different forms
+
NH3 NH2 NH3
+
NH3
+

R–CH – –
R–CH – –
R–CH –
COO COO COOH
(Zwitter ion)
SO–
3

201
Biomolecules
 Prop
+ +
H H
Anionic form Zwitter Cationic
OH ionic form OH form
COOH
pH ↓ es
High pH Intermediate pH Low pH 1. Belongs to L family H2N H

. r Aaj katreena R
P.S.S
pe
Su ick
tr
Anionic Zwitter Cation 2. Glycine is only optically inactive α-amino acids.

High Inter Low pH

* # α -amino acid is
Hill station par hai α-amino acid R—CH—COOH
the monomer of

—
NH2 protein
Calculation of pH of Zwitter ion
# There are
Case I: Neutral amino acid 23-natural
NH
+
pKa1
occuring
– 3 given α-amino acids
R–CH –
COO pKa2

pKa1 + pKa2 3. High M.P. and B.P.

pH =
2

+ Ala–Gly
NH pKa1 = 4.8
– 3
Q. R–CH
COO– pKa2 = 1.2 OH H

pH =
4.8 + 1.2
=
6
= 3 H2N–CH–COOH–HNH–CH2–COOH
2 2
Me
Case II: For acidic amino acid
+ H2N–CH–C–NH–CH2–COOH
NH3 pKa1
R–CH – – Me O Peptide
– COO pKa2
COO linkage
pKa3

pKa2 + pKa3 Ala–Gly–Val

pH =
2
OH H OH H
Case III: For basic amino acid
+
NH pKa1 O
– 3
R–CH CHMe2
+
–
COO pKa2 H2N–CH–C–OH+HNH–CH2–C–OH
NH3
pKa3 + HNH–CH
Me O
pKa1 + pKa2 COOH
pH = –2H2O
2
O O
M.O.P H2N–CH–C–NH–CH2–C–NH–CH–CHMe2
Strecker's synthesis
Me COOH
+ –
+ NH4CN – +
PROTEINS
–
C=O C–O NH4
CN –H2O Globular and Fibrous are 2 main types of proteins
+
α H3O with a 3D structure
C–NH2 C–NH2
COOH CN

202
Organic Chemistry
 Fibrous Globular
Molecules Long, thin Lies side by side to form fibres Fold into spherical 3-D shape
Examples  Keratin (in hair)  Haemoglobin
 Collagen (in skin and bone)  Insulin
 Enzymes
Solubility in Insoluble Soluble
water
Roles Structual Metabolic
 Collagen in bone and cartilage  Enzymes in all organisms
 Keratin in fingernails and hair  Plasma proteins, antibodies in
mammals

STRUCTURE OF PROTEINS
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11

(a) Primary structure Chain of amino acids

Hydrogen A1 A2 A3 A4
Bonds
A2 A6 A10 A7 A6 A5
=O–HN–
A1 A5 A9
A3 A7 A11 A8 A9 A10 A11
Alpha helix
A4 A8
β-pleated sheet
α-helix (b) Secondary structure (pleated sheet)

4 Heme

Heme units

Heme

Denaturation of Proteins

heat

203
Biomolecules
NUCLEIC ACID
DNA
cell Nucleus chromosome

Ribose
Pentose Deoxyribose
sugar HOCH2 O OH HOCH2 O OH
Nucleic
H H 1′ H H 1′
acid 2′ H H 2′ H
nitrogenous H OH H
OH OH
base b-D-Ribose
Derivative of Derivative
purine pyrimidine
phosphate
N
ester N N
Tri
mono N NH N
O
O
di
RO—P—OR O HO—P—OR

OR HO—P—OR OH

OR

NUCLEIC ACID d)
i c aci
ic c l e
ni ne n ucle ) bo nu Uracil
Ade ribo acid (Ri
D e oxy
(
DNA RNA
Cytosine
Thymine Adenine
Guanine
Cytosine Guanine
AGC T DNA
U RNA
Nucleotides join together through 3′ and 5′ phosphate linkage to give polynucleotides, which further
forms nucleic acid.
Purine Pyrimidine

A G C T U
NH2 NH2 O
O O
Me
N
N N NH
N NH NH

O N O N
NH N NH O N
N NH2
H H
H

204
Organic Chemistry
 5'
Base
Phosphate CH2 O
1'
4'
Nucleotide
H
H 3' 2'

OH OH

Sugar

VITAMINS Enzymes
Fat soluble vitamins KEDA Catalyst
Fat
Vitamin A (Retinol)
1. Catalyse the R×n in body.
Vitamin K
2. Small quantity can do millions of the R×n.
Vitamin E
3. Also known as biochemical catalyst
Vitamin D
4.
B key
Water Water Soluble Vitamins
soluble Vitamin: Name: R+E E
C product + E
B1 Thiamine lock R
B2 Riboflaviin Complex
B3 Niacin Exp maltase
Maltose Glucose
B5 Pantothenic Acid
B6 Pyridoxine
B7 Biotin
B9 Folate
B12 Cobalamin
C Ascorbic Acid

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hai...
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hai .

205
Biomolecules