ORGANIC CHEMISTRY EC025

ALKANES

H3C CH2 CH3

Combustion Free radical substitution

limited O 2 Br2 , CH2Cl2 uv

7/2O 2 3CO + 4H 2O Br Br
3CO2 + 4H2O
Excess O 2 +H3C CH CH3 H3C CH2 CH2
5O2
(minor)
(major)

ALKENES

ELIMINATION

OH OH XX
H2C CH2 CH3 or H3C C CH3 H2C CH2 CH3 or H3C C CH3

H H

conc. H 2SO4 ,  KOH, ethanol reflux (X = Cl or Br)

H2C C CH3
H

ELECTROPHILIC ADDITION

H3C CH2 CH3 H2 HBr Br
Pt or Pd or Ni H2O2 H2C CH2 CH3 (anti Markovnikov)
Cl Cl CH3
H2C CH Cl2 or Br2 + OH
CH2Cl2 H3C C CH3
@ H2O/H
H
Br Br
H2C CH CH3

Cl CH3 Cl OH
H3C CH H2C HC CH3
HCl or HBr Cl2 or Br2
@ H2O @

Br CH3 Br OH
H3C CH H2C HC CH3

OXIDATION

OH OH - i. O 3 O O
H2C HC CH3 ii. Zn / H 2O HC H
KMnO4 , OH + H3C C H
cold

(depends on the types of alkenes)

KMnO4 , H+, 

O

+ +H3C C OH H2O
CO2

(depends on the types of alkenes)

BENZENE AND ITS DERIVATIVES

OR

NH2 O AlCl 3 X
R C Cl
X2
HNO3 , conc. H 2SO4 FeX3
(X may be Cl or Br)
o

50 - 55 C

COOH CH3 CH2Cl

KMnO4 , H+ Cl2
 uv

(for alkylbenzene with benzylic hydrogen only)

HALOALKANES (Alkyl Halides)

R OR' R CN
KCN
R OR'

R' OH R'ONa

R NH2 excess NH3 RX NaOH (aq) R OH
 (X is a halogen atom)
KOH , ethanol
R' COONa Mg dry ether reflux
R' COOR
R MgX alkenes
(Grignard reagent)

H3C CH3 + i. CO 2 R COOH

H2O/H +

ii. H 3O

O O + O
i. H C H ii. H 3O+ i. R' C H i. R' C R'' ii. H 3O+
ii. H 3O
OH OH
HCH OH R' C R''
R' C H
R R
1o alcohol R 3o alcohol
2o alcohol

HYDROXY COMPOUNDS (Aliphatic alcohols)

Grignard reagent

+

aldehyde or ketone

Alkenes H3O+ RX
R OH NaOH(aq)
H2O
H+

+R X H2O HX PX3 +R X

H3PO3

+ +R X PCl5 SOCl2
POCl3 HCl pyridne +R X H3PO3

ZnCl2 /HCl +Na
+(Lucas Test) R Cl H2O R O-Na+ H2

O , H+ O
R1 C OH
Alkenes conc.H2SO4 +R1 C O R H2O
 

H3C OH [SO] CO2 + H2O
(methanol)

[SO] O
R C OH (carboxylic acid)

oxidation H PCC O
CH2Cl2 R C H (aldehyde)
R C OH

H
(1o alcohol)

OH [SO] O
R C R1 R C R1 (ketone)

H [SO] No reaction Note
(2o alcohol) - [SO] is strong oxidising agents

OH (such as KMnO4, H+ or
R C R1 K2Cr2O7, H+ or CrO3, H+)
- X may be Cl or Br in HX and PX3
R2
(3o alcohol)

HYDROXY COMPOUNDS (Aromatic alcohols)

-+ Na Identification Test of Phenol
OH
O Na
FeCl3 (aq)
+H2 FeCl 3

OH Observation : purple complex

O-Na+ Br OH
Br
+H2O
NaOH Br2 , H2O

Br
Observation : white precipitate formed

CARBONYL COMPOUNDS (Aldehyde)

o PCC i. O 3 Alkenes
CH2Cl2
1 alcohol O
RC H
OH
R CH

H

Nucleophilic Addition NaHSO 3 [O] ii. Zn/H 2O

OH Oxidation
O
R CH R C OH
SO 3-Na +

OH OH O
R CH H3O+ R C H
KCN Cu2+ complex , OH - +– Cu2O
COOH CN
+ R CO

H (for aliphatic aldehyde only)

OH [Ag(NHJ 3)2]+ , OH - O
R CH
H2O +– Ag
OH
R CO

OR'' OH R'-OH i. R'MgX / dry ether OH
R CH R''-OH ii. H3O+ R CH

OR' R CH R'

OR'

Condensation

H NH2OH H2NNH2 H
R C N OH R C N NH2
H
HH H H2N N NO 2
R CNN H2N N
O2N HH
R CNN NO2

Reduction O2N

[H] Note
- [O] is oxidising agents (such as
OH
R CH KMnO4, H+ or K2Cr2O7, H+)
- [H] is reducing agents (such as
H
LiAlH4/H3O+ or NaBH4 in
methanol or H2/Pt)

CARBONYL COMPOUNDS (Ketone)

o (to produce aromatic ketone)

1 alcohol O

OH R C Cl AlCl 3
R C R1
[O] i. O 3 Alkenes
H
O

RC 1 ii. Zn/H 2O

R

Nucleophilic Addition Oxidation

OH NaHSO 3 [O]

1

R CR

-+

SO3 Na

OH + OH
R C R1
H3O R C 1 KCN Cu2+ complex , OH - No reaction
COOH H+
R

CN

OH H2O -

1 [Ag(NHJ 3)2]+ , OH

R CR

OH

OR'' R''-OH OH R'-OH i. R'MgX / dry ether OH
R C R1 R C R1 ii. H3O+ R C R1

OR' OR' R'

Condensation

R1 NH2OH H2NNH2 R1
R C N OH R C N NH2

1 H H NO 2 1
H2N N H2N N
RH RH
R CNN O2N
R CNN NO2

Reduction O2N

[H] Note
- [O] is oxidising agents (such as
OH
KMnO4, H+ or K2Cr2O7, H+)
1 - [H] is reducing agents (such as

R CR LiAlH4/H3O+ or NaBH4 in
H methanol or H2/Pt)

CARBOXYLIC ACIDS AND ITS DERIVATIVES

Hydrolysis of nitrile Carbanation of Oxidation
compound Grignard reagent
R CN
R Mg X Alkylbenzene (with benzylic hydrogen)
+ 1o alcohol

H3O i. CO 2 aldehyde
ii. H 3O+

[O]

O

R C OH

O O

+- + H2 Na NaOH +R C O-Na+ H2O
Na2CO3 @ NaHCO 3
R C O Na

Formation of acyl chloride

O O

+ +- + PCl 3 +R C Cl H 3PO 3

R C O Na
CO2 H2O

O

R CH2 OH i. LiAlH 4 PCl 5 + +R C Cl
POCl 3 HCl
+ SOCl 2
pyridine
ii. H 3O

O Formation of amide O
C NH2
+H2O R NH3 + +R C Cl
 SO 2 HCl

Formation of acid anhydride

O R1 N H O O O
H R1 C OH R CO
+H2O R C NH  +C R1 H2O
P2O5 , 
1 1

R R NH
R2
O  O OO
R1 C Cl
+H2O R 2 +R C O C R1 HCl
P2O5 , 
C NR

1

R

Formation of ester R'OH , conc. H 2SO4 , 

O Note

+R C O R' H2O [O] is oxidising agents
(such as KMnO4, H+ or
K2Cr2O7, H+ or
CrO3, H+)

AMINES

Reduction Hoffmann's degradation of primary amides
( X = Cl or Br )

i. LiAlH4 R CH2 NH2 X , OH- O
ii. H3O+ Aliphatic 2 R CH2 C NH2

R CN

Nitrile compound

NH2 NO 2

Zn @ Fe @ Sn /H+ @ SnCl2 / H+

Aniline i. LiAlH4 nitrobenzene
ii. H3O+
Reduction R CH2 NH2
O H

R C NH2 R CH2 N R1
R2
OH
R C N R1 R CH2 N R1

O R2
R C N R1

AMINO ACIDS

HO
H2N C C OH

R

HN HO NaOH HCl H HO
H C C O-Na + H N+ C C OH

R HR

HO R'-OH , conc H 2SO4 NaNO 3, HCl HO
H N C C OR'  0-5oC Cl -N2+ C C OH

HR R

H2O -H+ X-

HO O HO
HO C C OH H2C C C OH X C C OH

R R R

PREPARATION NAME POLYMER POLYMER

polyethene MONOMER HH
HH CC
polystyrene CC HH
HH
ADDITION n
HH
CC HH
CC
H
H

polyvinyl HH n
chloride CC
H Cl HH
CC
Polyester Dacron O O H Cl
HO C C OH
n
+
OO
HO CH2 CH2 OH C C O CH2CH2 O
O
n
H2N (CH2)5 C OH
Polyamide Nylon 6 O

CONDENSATION Nylon 6,6 H2N (CH 2)6 NH 2 N (CH2)5 C O
Kevlar n
+
H
OO O

N (CH2)6 NH C (CH2)4 C
Hn

HO C (CH2)4 C OH
OO

HO C C OH

+ OO

N NH C C
Hn

H2N NH2

CHEMICAL TEST