MADHAPUR

Oxidation reactions
I)
a) KMnO4

Alkaline KMnO4

i) 1% cold, dilute, alkaline KMnO4 is known as Bayer’s reagent Bayer’s test is a

preliminary test to distinguish between unsaturated and saturated
hydrocarbons. The purple colour of Bayer’s reagent is lost (gets decolourised)
when passed through unsaturated hydrocarbons due to formation of vicinal
diols.
ii) Cis-hydroxylation or per hydroxylation takes place (syn-1,2 diols)
OH OH
MnO4−
C=C ⎯⎯⎯
OH
→ C=C
−

1
Mechanism:

R O O R O O− R O OH −
OH −
+ Mn Mn ⎯⎯⎯ → Mn
O O O O O−
R R R O− O

R OH
MnO 2  MnO3− +
R OH
HIO 4
RCHO + R CHO
Examples

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 1
1)
Me
−
⎯⎯⎯
MnO4
OH
→ A ⎯⎯⎯
HIO4
→B
Me
Me OH
A→ B → CH3CHO + CH3CHO
2) Me OH

−
⎯⎯⎯
MnO4
→
OH OH
3) OH

4)

5)

Alkynes in presence of alkaline KMnO4 gives carboxylic acid or a di ketone

In case of terminal alkynes, carboxylic acids containing one carbon less
are obtained
In case of non- terminal alkynes di ketones are obtained
OH OH
−2H 2 O
R − C  C − R ⎯⎯⎯→
Bayer 's
reagent
R − C − C − R ⎯⎯⎯→ R −C−C−R
OH OH O O
dione (or diketone)

OH OH
−2H 2O
H − C  C − H ⎯⎯⎯→
Bayer 's
reagent
H − C − C − H ⎯⎯⎯ →H − C− C− H
OH OH O O
ethanedial (CN:glyxal

2)

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 2
 OH OH
−2H 2O
CH3 − C  C − H ⎯⎯⎯→
Bayer 's
reagent
H 3C − C − C − H ⎯⎯⎯ → H3C − C − CH
OH OH O O
Benzene with a side chain (alkyl substituted) will undergo oxidation in
presence of alkaline KMnO4 irrespective of the length of the chain to give
benzoic acid if it has benzylic hydrogen!

COOH

alk KMnO4
[O ]

COOH
alk KMnO4
[O]
COOH

alk KMnO4
[O]
No Reaction ( Absence of Benzylic hydrogen)

NOTE :1) Hydroxylation preferentially occurs at sterically less hindered carbon

2) Alkanes are highly stable. However, if 30 hydrogens are present then in

presence of alkaline KMnO4 it is oxidized to OH gp. [Relative. rates of oxidation
of 10 ,20 & 30 − H → 1:110 : 7000

(CH3 ) − C − H − ⎯⎯⎯⎯
KMnO4
−
→ ( CH3 )3 C − OH
OH
Alkenes Types of Addition nature of product
1) Cis Anti Racemic
2) Trans Anti Meso
3) Cis Syn Meso
4) Trans Syn Racemic

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 3
b) Acidic KMnO4
Over oxidation occurs and the carbonyl compounds are further oxidized to
carboxylic acids in accordance with Popoff’s rule.
Popoff’s rule: During the oxidation of asymmetrical ketone, the C=O group
migrates with smaller alkyl group.
R R' OH OH
R O
R'
Mno4− o
C =C ⎯⎯⎯+
⎯→ ⎯⎯→ RCOOH + R '− C − R ''
H
H R '' H R '' Poppoff's Rule

R ' COOH + ( R ''− 1) COOH

C2 H5 OH OH
C2 H5 CH3 CH3 C 2 H 5
C=C → C−C
⎯⎯ ⎯⎯
→ O + CH 3CHO
CH3CH 2CH 2CH H C5 H11 H C2 H11 [O]
CH3COOH
C2 H5COOH C4 H 9COOH

2.Selenium dioxide (SeO2 )

Used for allylic substitution of OH group and oxidation of active methylene group
to ketone
Example:
⎯⎯⎯
SeO2
→HO
i)
OH

⎯⎯⎯
SeO 2
→
ii)
OH

⎯⎯⎯
SeO2
→

(1) (2) OH (3)

iii) OH

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 4
 O O O
R − C − CH 2 − R ' ⎯⎯⎯
SeO2
→ R − C − C − R'

Active methylexe gp
O O
SeO2
CH 3 − C − H ⎯⎯⎯ → H − C − C − H glyaxol

O
O O
SeO2
CH 3 − C − H ⎯⎯⎯ → H −C −C − H

O
O O

SeO
⎯⎯⎯
2→

a
a
SeO2
⎯⎯⎯→ [oxidation not possible at ' a 'due to steric hindrance

b O O
O
O O

SeO
⎯⎯⎯
2→

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 5
 Ph Ph

Ph SeO Ph
⎯⎯⎯ 2→

O
O O

3. mCPBA (Meta chloro per benzoic acid)

i) mCPBA (or Ag/O2) are used for Epoxidation
ii) Epoxidation by mCPBA followed by hydrolysis (anti-addition) gives trans
hydroxylation.
O
C−O H
O

Cl
MCPBA
Mechanism
O

R −C O
H
O → RCOOH + C −C
O

C =C

CH3 CH3 CH3

+
O ⎯⎯⎯→HO OH
⎯⎯⎯
mcpba
→ 3

Eg: 1) OH

⎯⎯⎯
mcpba
→ O
2)

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 6
 CH3 CH3 CH3

⎯⎯⎯
mcpba
→ O + O

CH3 CH3 CH3

3)
⎯⎯⎯
Ag/O2
→ C−C

4) O

Epoxidation followed by hydrolysis gives trans-glycol, anti addition occurs (trans

hydroxylation) whereas Bayer’s reagent leads to Cis hydroxylation

OH
mcpba +
CH 2 = CH 2 ⎯⎯ ⎯⎯
→ H O
⎯⎯⎯⎯
3 →
OH

Mech

R
R
O
O
O
O
H
O O
O
Syn

+R COOH

Chromium (VI) oxidants

(i) CrO3 + H 2So4 + acetone or 8N acid in Conc. H 2So4 (Jones reagent)

(ii) H 2CrO4 ( Chromic acid) or K2Cr2O7 or Na2Cr2O7 in Conc. H 2So4

(iii) CrO3 + Pyridine is alkaline medium – SARRETTS OXDN

(iv) CrO3 + 2 moles of Pyridine in CH 2Cl2 as solvent or PDC (Collins reagent)

(v) PCC (Corey’s reagent)

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 7
 (i) Jones Reagent

(i) The function of H 2SO4 is to prevent complex formation of Cr ( vi ) with its

reduced form Cr ( iii ) this ensures that all a ( vi ) is used in oxidation .

In presence of aq. Solvents over oxidations is prevented and also other

oxidisable gps and acid labile ( acid sensitive) gps are unaffected

This reaction is easy to monitor since as oxidation proceeds the solution gets

green color due to formation of Cr 3+

(ii) Chromic acid

It is strongly oxidizing in nature, however it is un suitable for oxidation of

alcohols containing easily oxidisable groups like C=C, allylic and benzylic, 10
alcohols are oxidized to carboxylic acids while 20 alc. are oxidized to ketones

O
OH

Cr2O72 − / H +
⎯⎯⎯⎯⎯⎯ →
−Cro2 ;− H 2O

[ If OH gp is present on axial position , oxidation readily occurs]

If 30 carbon is present it gets oxidised to 30 alc. With retention of conjugation

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 8
 O O OH

R − H + O = Cr − OH R ' OH − Cr − OH R O − C − OH

OH OH OH

R − OH + H 2CrO3

Limitations

1) The bye product CrO2 obtained is toxic

2) Easily oxidisable groups are readily oxidized

R O O

H CrO
R − C  C − CH 2 − CH − OH ⎯⎯⎯⎯→
2 4 R − C − C − CH 2 − C − R
− H 2O

i) O

OH O

"
R − CH = C − CH 2 − CH − R ⎯ ⎯
→ RCOOH + HOOC − CH 2 − C − R
ii)

O
CH 3 CH 3
OH H SO OH − H O
⎯⎯ ⎯ ⎯
2 ⎯
→
H 2 So4
⎯⎯⎯⎯ → ⎯⎯2 ⎯ 4⎯ → O condnsn
− H 2O CH 3 − H 2O Me
CH 3
OH
iii) O

Generally 30 alc. Do not undergo oxidation. However if they are part of the
ring they get oxidized to carboxyl group

(iii) PCC [ Corey’s reagent]

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET 9
 +

CrO3Cl −
N

It is a good reagent for controlled oxidation of 10 and 20 alc.

(iv) PDC [ Collins reagent]

Collins reagent is superior to PCC, high yield of products are obtained and

acid labile groups are unaffected even though it readily oxidizes 10 and

20 alc. To aldehyde & ketone it is widely used for oxidation and benzylic
alcohol

H
H
⎯⎯⎯→
PDC O

"
⎯⎯
→
O
OH

OH O
"
⎯⎯
→
H

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
10
 (v) Saretts Reagent
O O

N −Cr − N

[ [ CrO3 + Pyridine in alkaline medium]

→ R2 − C = 0 + Cr − O − + 2
2C H N
R2CHOH + CrO3 ⎯⎯⎯⎯
5 5 ⎯

N+
O−

H
Mech:

→ R2 − C − O + Cr − O − +
R2 CHOH + CrO3 ⎯N⎯

N+
O H

R2C = O + Cr − O − +

N+
O−
H

Saretts reagent will not further oxidize 10 alc. to COOH nor it effects C = C

(vi) Periodate ( IO4− )

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
11
 It is used for cleavage of Cis glycols 1,2 amino alcohols keto alcohols 1,2-
diamino compounds, epoxides

1,2-diols or glycol in presence of HIO4 undergoes cleavage and the product

formed are the same carboxyl compacts that would be obtained by
ozonalysis of alkenes followed by its reduction

Hydrolysis of alkenes followed by periodate cleavage serves as a useful

alternative for ozonalysis

This reaction is also known as Malaprade reaction The same reaction can
also occur is presence of lead tetra acetate.

R
O H O O− R O−
O
+ I I

R' O H O O
O R'

R R'
+ O + IO3-

CH 2 − OH
IO4−
⎯⎯⎯ → 2 HCHO
O 
CH 2 − OH
1)

Ph − CH − OH
"
⎯⎯
→ Ph.CHO + CH 3CHO
'
CH 3 − CH − OH
2)

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
12
 CH 2 OH

→ HCHO + CO2 + C2 H 5CHO

C HOH

CHOH

C2H 5
3)

CH 2 OH

"
C HOH ⎯⎯
→ 2 HCHO + CO2

CH 2 OH
4)

" H
OH
OH ⎯⎯
→ O

5) H

OH

"
⎯⎯
→ No RXN

6) OH

HIO IO −
CH 2 − OMe ⎯⎯ ⎯→
4 CH 2 − OH ⎯⎯4⎯
→ 2 HCHO

CH 2OH CH 2OH
7)

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
13
 R
H
R
IO4− O+
⎯⎯⎯ →
O 
H
R' NH 2
R
NH
H
H 3O +
R
O + NH 4+

8) H

CH 2 − OH

C =O 2 HCHO + CO2

CH 2OH
9)

(vii)Osmium tetroxide ( OSO4 )

It is used for cis-hydroxylation, reagent is more suitable for small scale
preparation due to its toxic nature.

(viii) Ruthenium Tetroxide

RuO4 is a powerful oxidizing agent which oxidizes variety of functional groups
at room temperature in a solution of CCl4 and acetonitrile

Eg 20 alc → ketones; ethens → esters; C = C → COOH / CO

C6 H5 → COOH

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
14
 Reagent being expensive a catalytic amount of RuO4 in presence of NaIO4
is taken which serves to oxidize reduced Ru back to active tetroxide

RuO / IO −
C4 H 9 − O − C4 H 9 ⎯⎯⎯⎯⎯⎯
4 4 → C H COOC H
3 7 4 9
CCl4 ,CH 3CN
H 2O,250 C
C6 H 5 COOH

RuO ; IO −
⎯⎯⎯⎯⎯⎯
4 4 →
CCl4 ,CH 3CN
H 2 O , 25 º C

(ix) Ozonalysis
i) When ozone gas is passed through unsaturated hydrocarbon, it forms an
unstable ozonide which in the presence of zinc and water gives the corresponding
carbonyl compounds.
ii) Ozonalysis not only helps in detection of unsaturation but also helps in the
location of position of double bond or triple bond.
iii) Simple alkenes upon ozonalysis give aldehydes in presence of zinc and water
(Reductive ozonalysis). Whereas, branched chain alkenes give aldehydes and
ketones
iv) In absence of zinc or dimethyl Sulphoxide, the carbonyl compound obtained
further undergoes oxidation to give carboxylic acids.

⎯⎯⎯⎯ → C=O + O=C

1) O
3
C=C 2) Zn/H O 2
or
Zn/ACOH
or
DMS

Mechanism:

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
15
 O
C=C C−C C+ + O = C → C C
→ →
− O
O O O O O O
−
O O O
Malozonide Ozonide

Zn / H 2O
C = O+C = O

Zn + [O] → ZnO

H 3C CH 3
S + [O] → S = O
H 3C CH 3
If acetone is formed as one of the products then the name of the alkene (reactant)
begins with 2 methyl2-

Identify the alkene which upon ozonolysis gives the following products.
1) Ethanol and propanal 2-pentene
2) 2 moles of acetaldehyde 2-Butene
3) Propanal and butanal 3-Heptene
4) Acetone and ethanal 2 Methyl 2-butene
5) Acetone and butanal 2 Methyl 2-hexene
6) Ethane dial, acetone and ethanal
CH3 H H H
CH3 − C = O + O = C − C = O + O = C − CH 3
CH3H H H
CH3 − C = C − C = C − CH3
7) Glyoxal, methyl propanal and butanone

CH3 H H H HCH3
CH3 − CH 2 − C = O + O = C − C = O + O = C − CH 2 − CH3  CH3 − CH 2 − C = C − C = C − CH 2 − CH 3
H CH3 CH3
Examples:

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
16
 1)
CH3
O O O O O O
⎯⎯⎯⎯ → CH3 − C − CH + HC − C − H + HC − C − H
1)O
3
2) Zn/H O 2

2)

CH3 O O
⎯⎯⎯⎯ → CHO − CHO + 2CH3
1)O3
2) Zn/H 2O − C − CH
3)
CH3

O O O O O O
⎯⎯⎯⎯1)O3
2) Zn/H O
→ CH3 − C − CH3 + HC − C − CH + HC − CH + C − CH3
2

4)
CH 2 O
O
⎯⎯⎯ → + CH 2
O
3
H O
2
[O]
HCOOH
Will not change.
Perfectly stable
5) cyclohexane

6)

(x) Iodoform Test

In general, iodoform test is given by compounds containing methyl ketone group.
Compounds containing these groups upon reaction with alkaline sol. Of iodine
gives yellow precipitate of iodoform.

O O
R − C − CH 3 + I 2 + KOH ⎯⎯
→ R − C − OK + CHI 3  + KI + H 2O

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
17
Mechanism:

The rate determining step involves the formation of enolates, hence the rate of
reaction is same whether the halogen is Cl2 , Br2 or I 2 ( Cl2 = Br2 = I 2 )

(i) Among ketones, methyl ketones give positive iodoform test

(ii) Among Alcohols

a) In case of 10 alcohols, only ethyl alcohol gives a positive iodoform test since
in the presence of strong oxidizing medium like alkaline I2solution, it is
initially oxidized to acetaldehyde
− −
CH3CH2OH ⎯⎯⎯
I2 /OH
→ CH3CHO ⎯⎯⎯
I2 /OH
→ CHI3  +HCOO−

CH3
|
b) 20 alcohols of the type ( R − CH − OH ) show positive iodoform test
CH3 CH3 O
I2 /OH − I2 /OH −
R − CH − OH ⎯⎯⎯→ R − C = O ⎯⎯⎯→ CHI3  + R − C − O −

(iii) Among aldehydes, only acetaldehyde or ethanal gives +ve iodoform test

(iv) Among alkyl halides :

a) In case of 10 alkyl halides, only ethyl halide shows +ve iodoform test.
O
− − −
CH3CH 2 − X ⎯⎯⎯
OH
→ CH3 − CH 2 − OH ⎯⎯⎯
I2 /OH
→ CH3 − C − H ⎯⎯⎯
I2 /OH
→ CHI3  + HCOO −

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
18
 CH3
|
b) In case of 20 alkyl halides, R − CH − X show positive iodoform test
CH3 CH3 CH3 O
− −
R − CH − X ⎯⎯⎯
OH
→ R − CH − OH ⎯⎯⎯
I2 /OH
→ R − C = O ⎯⎯⎯
I2 /H 2
→ CHI3  + R − C − O

v) Esters of the type R − COO − C2 H5 respond to iodoform test

O
OH − I2 /OH − I2 /OH −
R − C − O − C2 H5 ⎯⎯⎯ → RCOO − + C 2 H 5OH ⎯⎯⎯ → CH 3CHO ⎯⎯⎯ → CHI3  + HCOO −

vi) Acetic acid does not respond to iodoform test because of absence of carbonyl
group

O
||
vii) CH 3 − C − CH 2 − C − CH 3 , a diketone respond to iodoform test due to the
||
O

presence of active methylene group.

Eg:

Pthalic acid

Note: Thiols R-SH or Mercaptans are more acidic than alcohols due to lower bond
dissociation energy of S-H bond than O-H bond.

Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
19
Our other branches: SHAMIRPET(Res) – SUCHITRA – ECIL – MIYAPUR – L.B. NAGAR – KOKAPET
20