LECTURE NOTES

Session - 2009-10

ORGANIC CHEMISTRY
TOPIC : OXIDATION
Introduction
1. oxidation is defined as the addition of oxygen (electronegative) element to a substance or removal of
hydrogen (electropositive) element from a substance.
or
2. Oxidation of an organic molecule usually corresponds to increasing its oxygen content or decreasing its
hydrogen content.

3. Oxidation of an organic compound may be more broadly defined as a reaction that increases its content of
any element more electronegative than carbon.
eg. replacing hydrogen atoms by chlorine atoms is an oxidation

Ar – CH3 ArCH2 Cl ArCHCl2 ArCCl3

When organic compound is oxidised, something else the oxidising agent is reduced. When an organic
compound is reduced, something else - the reducing agent must be oxidized.

(A) Oxidation of Alkanes : -

Different product are formed by the use of different oxidising agents or different reaction conditions.
(I) Combustion (complete oxidation) : - On complete oxidation product formed are CO2 & H2O.
CH4 + 2O2  CO2 + 2H2O HºC = – 890KJ
7
C2 H6 + O  2CO2 + 3H2O HºC = – 1555 KJ
2 2
CH2 = CH2 + 3O2  2CO2 + 2H2O HºC = – 1400 KJ
2CH  CH + 5O2  4 CO2 + 2H2O HºC = – 1300 KJ
(i) Due to largest amount of heat evolved, alkanes are used in LPG (Liquid petroleum gas). LPG is a mixture of
propane and butane.

Page # 2
 (II) Controlled Combustion : -
2CH4 + 3O2  2CO + 4H2O
(limited)
CH4 + O2  C + 2H2O
(Limited) Carbon Black
(used in blank ink, paints & polishes)

(B) Oxidation of alkenes and alkynes :

(I) Hydroxylation :
(a) Syn Hydroxylation : Reaction with Bayer’s reagent, (cold dilute alkaline KMnO4 solution.
Both OH groups are added from same stereochemical side. This addition is example of syn addition.
| |
General Reaction C=C + KMnO4 + ¯OH, H2O —C—C—
| |
(or OsO4, H2O2) OH OH
(syn addition)

¯ OH
e.g.   
 + MnO2  + H2O
H2O

The same function of syn addition of 2 – OH groups is performed by OsO4 / H2O2

2H O
+  2
  + H2OsO4

eg.

eg.

eg.

(b) ANTI HYDROXYLATION (OXIDATION WITH PEROXIDATION)

An alkene is converted to an epoxide by a peroxyacid.
O O
|| ||
General Reaction C=C +R– C –O– –H + R – C – O – H (acid)

The epoxidation of an alkene is clearly an oxidation, since in oxidation, an oxygen atom is added. Peroxyacids
are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids) and their cor-
responding carboxylic acids are shown below :-

Page # 3
RCO3H = Peroxy acid

HCO3H = PFA (Performic acid)

CH3CO3H = PAA (Peracetic acid)

Ph – CO3H = PBA (Per benzoic acid)

CO H
– 3
= MCPBA (Metachloro perbenzoic acid)
–

Cl
CF3CO3H = TFPAA (Trifluoro peracetic acid)

H , H O
2
General Reaction   

Mech.

 +

e.g.

Page # 4
e.g. +



The more highly substituted olifinic bond is more nucleophilic and therefore reacts faster with the
peroxyacid than the less susbstituted double bond.

HCO3H
  

–HCO2H

eg. RCO3H
  


eg. + Enantiomer

Non Symmetrical alkene Racemic mixture.

eg.-Pent -2-ene, Hex-2-ene
(Cis or trans)

Page # 5
Ex.1 Identify the product in the following reaction:-

KMnO 4
    (x)
Cold

Ans.

Ex.2 Identify the product (X) in the following reaction:-

C H CO H
65 3 (X)
CHCl3 at 298K

Ans. (X) :

Since C = C bond in ring is more substituted than that in open chain.

Ex.4 Predict the products, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic acid
epoxidations of the following alkenes.

(a) Cis-cyclodecene  (b) Trans-cyclodecene 

(II) Ozonolysis :
(a) Alkene : Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozo-
nolysis is milder, and both Ketones and aldehydes can be recovered without further oxidation.
R R R'
R'
General Reaction C C + (1) O 3
  C O+ O C
R H ( 2 ) ( CH3 )2 S H
R
Ketone
Mech.

O C
C C
O O - O O
O
 C  
O C O+ C O

Molozonide (Primary ozonide) Ozonide

O
R R' R O
C C R'
H
C O+ O C + CH3 S CH3
R
O O R H
Dimethyl sulphoxide
(DMSO)
H H
CH3 CH2 CH  CH2 H O, Zn | |
e.g. O3
1  Butene  2  
  CH3 CH2 C  O  O  CH

e.g. CH3CH2CHO + CH3(CH2)4CHO (65%)

3 - nonene

Page # 6
 CH3 CH3 H
| | |
e.g. O3
CH3  C  CH2  H O, Zn
 2  
 CH3 C  O  O  CH
Isobutylen e

H H
H
C
e. g. O
H C
H O
H

e.g. CHO
CHO
O
(b) Ozonolysis of Alkyne
(i ) O 3
General reaction R – C  C – R (ii  R – COOH + R – COOH
) H2O

(i ) O 3
e.g. CH3 – C  C – CH2CH3 (ii  CH – COOH + CH CH – COOH
) H2O 3 3 2

If an alkyne is treated with aqueous KMnO4 under nearly neutral conditions, an -diketone results.
O O
KMnO 4 || ||
General Reaction R – C  C – R (orO   R  C  C  R
3 & Zn / H2O )

KMnO
4
e.g. CH3  C  C  CH2CH3     CH3–C–C–CH 2–CH3
(or O3 & Zn / H2O )
2  Pentyne OO
Pentane-2,3-dione
Ex.5 Give the product of the following reactions :–
KMnO4
H3 C  H2 C  C  C  CH2CH2 CH3 Neutral
X

H3 C  H2 C  C  C  CH2CH2 CH3 Y

Sol. X = CH3 CH2 C  CCH2 CH2 CH3 Y = CH3CH2COOH + HOOCCH2CH2CH3

|| ||
O O
( diketone)
Ex.11 O 3 , H2 O
C8H10 (A)   Acid (B) Identify (A) and (B) in the above reaction

Sol. (A) C C (B) COOH

Ex.12 A certain hydrocarbon has the formula C16H26. Ozonation followed by hydrolysis gave CH3(CH2)4CO2H and
succinic acid as the only product. What is hydrocarbon
Sol. DU = 4
(III)Oxidation of alkene & alkyne by acidic KMnO4
When alkene & alkyne heated with KMnO4 in acidic or in alkaline medium ; following changes takes place.
RCH= CH2 [
O]
 CO2 + H2O + RCOOH

RC CH [
O]
 CO2 + H2O + RCOOH

R–CH=CH–R [
O]
 2RCOOH

[O]
 2

RC  C – R [
O]
 2RCOOH

Page # 7
 In a KMnO4 hydroxylation, if the solution is warm or acidic or too concentrated, oxidative cleavage of the
glycol may occur. Mixtures of Ketones and carboxylic acids are formed, depending on whether there are any
oxidizable aldehydes in the initial fragments. A terminal = CH2 group is oxidized to CO2 and water.

R R'
General Reaction C O + O C
R OH
Ketone
(Stable)

R R'' R
KMnO / H
C=C   4  C = O + R”COOH
R' H or, K 2 Cr2 O 7 / H

R'

KMnO 4 / H
R – C  C – R’     R – COOH + R’ – COOH
or, K 2 Cr2 O 7 / H

O OH
KMnO4
e.g. + C
Warm O
conc.

KMnO4
e.g. + CO2
Warm COOH
COOH
conc.
O

O
(1) KMnO 4 , NaOH O
( 2) H
|| ||
e.g. CH3 – C  C – CH2CH3        CH3  C  OH + HO  C  CH2CH3

O
(1) KMnO 4 , NaOH
( 2) H ||
e.g. CH3CH2CH2 – C  CH        CH3 CH2CH2  C  OH + CO2

O / Zn
3. 3 +

KMnO4/OH - + R'COOH

KMnO / H + R'COOH
  4 


K Cr2O 7 / H / 
2      + R'COOH
or, CrO3 / H / 

dil.KMnO 4
     HIO 4 +
cold   

alk . KMnO ( cold dil.)

    4   
 + MnO2  (actually black)
Baeyer ' s reagent

1, 2-diol syn-add. (Brown ppt)

( i ) OsO
4
    
( ii ) 2H 2 O ( Na 2 SO 3 )

1, 2-diol syn-add.

Page # 8
 R " COOOH ( peroxy acid ) H O
       + R"COOH 2

SN1 type (anti-addition)

( i) O
(II) R—CC—R'   3 
 R—COOH + R'—COOH .......... most common
( ii) H2O

(1) KMnO / H / OH

 4 
 R—COOH + R'—COOH
K 2CH2O7 / H

( i) O
  3   R— C — C —R' .......... -diketone
(ii) Zn / H2O || ||
O O
( i) O
  3   R— CH — CH —R
(ii) LAH or NBH | |
OH OH
Baeyer ' s
   R— C — C –R (Pink colour decolourized)
reagent || ||
O O
OsO4
  Not reported.
PCC
 no reaction
 

CrO / H
 3 cleavag.
(D) Oxidation Reaction of Alcohols

(I) Oxidation of primary alcohols

Oxidation of a primary alcohol initially forms an aldehyde. Obtaining the aldehyde is often difficult, since
most oxidizing agents strong enough to oxidize agents strong enough to oxidize primary alcohols also
oxidize aldehydes. CrO3 acid generally oxidizes a primary alcohol of all the way to the carboxylic acid

PCC = Pyridinium chlorochromate

+ CrO3 + HCl CrO3Cl -

.N. N+
–

(II) Oxidation of secondary alcohols

Sec. alcohols are easily oxidized to give excellent yields of ketones. The chromic acid reagent is often best
for laboratory oxidations of secondary alcohols. The active species in the mixture is probably chromic acid,

H2CrO4, or the acid chromate ion, .

Page # 9
 R R
| |
K 2Cr2O7 or CrO3 / H


R  CHOH         R  C O
A ketone

(III)Resistance of tertiary alcohols to oxidation

Oxidation of ter-alcohol is not an important reaction in organic chemistry. Ter-alcohols have hydrogen atoms
on the carbinol carbon atom, so oxidation must take place by breaking C – C bonds. These oxidations
require severe conditions and result in mixtures of products.

R
| KMnO 4
 no reaction
R  C  OH   
|
R

(A) Primary Alcohols:-

Page # 10
 (B) Secondary Alcohols:-
H

– –
1– 8
R – C – R'   R – C – R’
OH O
(C) Tertiary Alcohols:
R'

– –
1– 8
 no reaction (inert) (Note : Gives dehydration product)
R – C – R''  
OH
3. Cu/300ºC (Dehydrogenation) (–2H)
(i) Cu / 300ºC
R—CH2OH    R—CH = O

(ii) Cu / 300ºC



(iii)

Mechanism (with Cr+6 oxidising agents):-

(i) CrO3 + H2O H2CrO4 =

H O
–H2 O rds
(ii) R – C – OH + H – O – Cr – OH     R – C = O + H2CrO3
H O H

.. OH OH O
H2O H2 CrO 4 rds
– –

(iii) R – C = O R – C – OH    R – C – O – Cr – OH  R – C = O + H2CrO3

–

H H H O OH
Gemdiol Acid
unstable

Remarks:-
(1) Primary alcohol forms a chromate ester with chromic acid.
(2) The chromate ester decomposes in 2nd slow step with the elimination of -hydrogen. So the first
oxidation product, an aldehyde is obtained.
(3) In aqueous medium, aldehyde forms a gemdiol (hydrated aldehyde). It is further oxidised to an
acid by similar mechanism.
(4) The following reactivity orders can be explained by this mechanism:-
Rate of Oxidation
(a) RCH2OH > R2CHOH > R3C – OH (inert)

(b) CH3OH > CH3 – CH2 – OH >

Page # 11
 (c) R – CH2OH > R – CD2OH (B. E. = C – H < C – D )
(d) RCHO > RCH2OH
(e) RCHO > RCDO

Examples
1. CH3 – CH = CH – CH – CH2 – CH2 – OH

–
OH
(X)
O
K 2 Cr2 O 7
X     CH3 – C – OH + HOOC – C – CH2 – C – OH
(1) H 2SO 4
O O

PCC
X  
 CH – CH = CH – C – CH – CHO
( 2) 3 2

Oppenau er oxidation
X        
 CH3 – CH = CH – C – CH2 – CHO
(3)
O

CrO3 / aq.
X (    CH – CH = CH – C – CH – COOH
4) acetone 3 2

MnO2
X (   CH3  CH  CH  C  CH2  CH2  OH
5)
||
O
2. X = (C7H16O), optically active alcohol, give no response with CrO3 / H+. Find X.

May be isopropyl or n-propyl or

3. C8H10O, chiral, decolorises alkaline KMnO4 solution & with hot alkaline KMnO4 it forms benzoic
acid. D.U. = 4

KMnO 4
4.  
–

OH / 

HIO4 oxidation (vicinal diols)

General reaction
(a) HIO4
 R  CH + CH  R
 
|| ||
O O
HIO4
(b)  R  C  OH + OH  C  R
 
|| ||
O O

Page # 12
 R
HIO4 |
(c)  R  C + HO  C  R
 
|| ||
O O

HIO
4 HIO
4
(d)  
   
  R – CHO + HCOOH + R – CHO

e.g. 2CH2O + 3HCOOH + CO2 (5 moles of HIO4 is needed)

Mechanism

R R
| |
RC + CR
|| ||
O18 18 O

HIO4  H5IO6

 2H O
 2

Remarks
(1) HIO4 (periodic acid) oxidises vicinal diols (1, 2-diols).
(2) It brings about oxidative cleavage of vicinal diol.
(3) It can also oxidise -hydroxy carbonyl compound, -dicarbonyl compound and -hydroxy acid.
(4) HIO4 forms a cyclic periodate ester as an intermediate. So the two – OH groups should have syn-
conformation.
(5) In cyclic diols only cis-vicinal diols are oxidised. Trans isomers are not oxidised.

Example

(1) HIO
4
 
 

(2) HIO 4
 no reaction
 

Page # 13
(E) Oxidation Reactions of Aldehydes & Ketones :

RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO that can be oxidised to CO2) by weak
oxidising agents like ammonical AgNO3 (Tollen’s reagent) hence they are better reducing agents.

 Aldehydes reduce Tollen’s reagent to Ag and appears in the form of silver mirror is called silver-mirror test.
It is given by all aldehydes and reducing sugars.

RCHO + 2[Ag(NH3)2+ ] + 3OH–  RCOO– + 2Ag + 4NH3 + 2H2O

 Aldehydes (except benzaldehyde) reduce Fehling’s solution (Cu2+ reduced to Cu+) which is an alkaline
solution of cupric (Cu2+) ion complexed with tartrate ion.

RCHO + 2Cu2+ + 3OH– 

RCOO– + 2Cu  + 2H2O
red ppt.
 Aldehydes also reduce Benedict’s solution (Cu2+ complexed with citrate ion) to Cu+
Oxidation of > C = O group by acidic KMnO4 & acidic K2Cr2O7 : -
Aldehydes are oxidised to carboxylic acid having same number of C atoms as aldehyde.
HCHO + [O]  HCOOH
RCHO + [O]  RCOOH
Ketones are oxidised with difficulty. They are oxidised only on heating with a strong oxidising agent.

2–
Cr2 O 7  H
+ [O]      CH3COOH + CO2 + H2O
or KMnO4 H
In case of mixed ketones the >C = O group remains with the smaller alkyl group. (Pop off’s rule)
[O]
CH3COCH2CH3  2 CH3COOH

CH3COCH2CH2CH3  [O] CH COOH + CH CH COOH

 3 3 2
chromium compounds also bring out the cleavage of cyclic ketones

CrO 3
 
H

(Cyclohexanone)
Oxidative Cleavage of ketones:

+ CH3–COOH

Ketones on heating with KMnO4 (acidic or alkaline) undergo oxidative cleavage and a mix of two acids
or a mix of acid + ketone (smaller) is formed. In the major set of products the C– of lies with
smaller alkyl group in the product acids. The cleavage takes place through enolization.

Mechanism:

Page # 14
Oxidation of > C = O compound by SeO2 :

When heated with SeO2 the – CH2 – group – to the carbonyl group gets oxidised into carbonyl group.

CH3CHO + SeO2  OHC – CHO + Se + H2O
(Glyoxal)


CH3CH2 CH = O + SeO2  + Se + H2O


+ SeO2  CH3COCHO + Se + H2O


CH3 + SeO2  CH3COCOCH3 + Se + H2O
(Dimethylglyoxal)

C6H5COCH2CH3 + SeO2  C6H5–CO–COCH3


+ SeO2 

SeO 2
  

The Baeyer – Villiger Oxidation of Aldehydes and ketones

The Baeyer – Villiger oxidation is a useful method for conversion of aldehydes and ketones to esters by the
insertion of an oxygen atom from a peroxycarboxylic acid (RCO3H). For example, treating acetophenone
with a peroxycarboxylic acid converts into phenyl acetate:

The Baeyer – Villiger oxidation is also widely used for synthesizing lactones (cyclic esters) from cyclic
ketones. A common reagent used to carry out the Baeyer–Villiger oxidation is m-chloroperoxybenzoic acid
(MCPBA). The following is a mechanism proposed for Baeyer–Villiger oxidation by a peroxycarboxylic acid.
Mechanism :

Page # 15
 The products of this reaction show that a phenyl group has a greater tendency to migrate than a methyl
group. Had this not been the case, the product would have been C6H5COOCH3 and not CH3COOC6H5. This
tendency of a group to migrate is called its migratory aptitude. Studies of the Baeyer – Villiger oxidation
and other reactions have shown that the migratory aptitude of groups is H > phenyl > 3o alkyl > 2o alkyl >
1o alkyl > methyl. In all cases, this order is for groups migrating with their electron pairs, that is, as anions.

Ex. (3º alcohols or ketones not oxidized)

Oxidation of side chain or groups in Aromatic compounds :-

(i) KMnO / OH , 

4  
(I)    
(ii) H

Remarks : At least one benzylic – H must be present

Page # 16
Ex. 







X (C12H18) 


KMnO / OH
 No reaction.
  4  

(II) Polycyclic :

KMnO / OH 
  4  


KMnO / OH 
Ex.   4  



more readily oxidized

KMnO / OH 
  4  


KMnO / OH 
(III)   4  


KMnO / OH 
  4  


Page # 17
 KMnO / OH 
(IV)   4  


KMnO / OH 
  4  


KMnO / OH 
  4  


KMnO / OH 
(V)   4  


KMnO / OH 
(VI)   4  


Page # 18