Removal of Hydrogen

Removal of Oxygen

Increase of Oxygen
content

Increase of Hydrogen
content

Loss of electrons

Gain of electrons

Cation Formation
Effective nuclear charge on
remaining electrons
increases.

Na atom
1 valence electron

11p+

Valence elost in ion

formation

Result: a smaller sodium

cation, Na+

Remaining e- are pulled in

closer to the nucleus.
Ionic size decreases.

Anion Formation
Chlorine atom
with 7 valence e-

17p+

One e- is added to
the outer shell.
Effective nuclear charge is reduced
and the e- cloud expands.

A chloride ion is
produced. It is larger
than the original atom.

Redox reaction
Oxidizing Agent
H3C

Reducing Agent
O

CH3

CN

Cl

OH

CH3
CH3

Cl

CN

Cl

CN

+
Cl

CN

OH

Oxidizing Agent
CH3

CH3

Liq. NH3

Na

Reducing Agent

NaNH 2

Jones Reagent
(K2Cr2O7/H2SO4

PDC
Coreys Reagent

Swern Oxidation
(DMSO/CO2Cl2)

Dess Martine Reagent

(periodinate)

At higher temperature dehydration is carried out by using some metals such as- Pd, Pt,
Ni, S, Se, etc (by adsorption mechanism).
The reagent as quinone, selenium dioxide, alkaline ferricyanide, DDQ, Chloranil, etc
carried out oxidation at mild reaction conditions and at selective positions.
The reactivity at reaction site is increased by introducing the unsaturation or by atom
possessing unshared pair of electrons.

Quinone
-

OH

+
2H

2 e2 eMechanism-

O-

O
+

O-

OH

OH

OH

+
OH

2,3,5,6-Tetrachloro-1,4-benzoquinone (chloranil) and 2,3-dichloro-5,6-dicyano-1,4quinone (DDQ) is used in the synthesis of conjugated and cross conjugated ketones in
acidic conditions.
It is also used for the aromatization of various unsaturated compounds

DDQ
+
- H

+
H
O

H +
O

+
-H

HO

H O

enol form

Some compounds undergo

rearrangement before it
undergoes
proton
elimination

-H

-H

R
+

If the pi-electrons or unshaired pair of electrons moves from one atom to next via pi-orbital
or unhybridized orbitals, then pi-electron or unshared pair of electrons are said to be
conjugate with pi-bond or unhybridized orbital.

CH2
H2C
(3E)-hexa-1,3,5-triene

The pi-bond is in conjugation with two other pi-bonds separately which are not in
conjugation, then the pi-bond is said to be cross-conjugated with two pi-bonds.
H2C

CH2
CH2

3-methylidenepenta-1,4-diene

O
DDQ, benzene

1.
O

O
COCl

3.

DDQ

2.

benzene

O
AlCl3

DDQ

Br
K2 CO3 , acetone

Swern oxidation
DMSO in combination with any one of a member of electrophile like DCC, acetic
unhydride, oxalyl chloride, SO3, etc bring a oxidation of alcohol.
O
S
H3C

CH3

dimethyl sulfoxide

Mechanism:
DMSO forming adducts elctrophile with DCC (dicyclohexyl carbodiimide) which react
with alcohol gives alcoxysuphonium ion via the corresponding ylide and finally gives
carbonyl compound

R
R N

N R

(CH3)2S

H
N

NHR
N R

R2CH-OH
R

O
R

O
S C
H2
O

N R
H

R
R

O
S
H

(CH3)2S

R
O
R

Pfeitzer-Moffatt reaction
Ylide is a neutral molecules with
positive and negative charges on
the adjacent atoms

Swern oxidation
The oxidizing agent is DMSO and oxalyl chloride
O
(CH3)2S=O

+Cl

R
R

Cl

Et3N

Cl

(CH3)2S

(CH3)2S

Cl

O
O

R
O
R

(CH3)2S

Cl

- R CH-OH
+
(CH3)2S-Cl Cl 2

+ H+

If the substrate carries good leaving groups (e.g.- -OTs) are oxidized to aldehyde or ketone
RCH2-OTs

DMSO

H3C
H3C

H3C
S O CH2 OTs
R

H
S O C

H3C

RCHO + (CH3)2S + H

The amine oxide is used for the synthesis of aldehydes from halide and sulphonates. It
also oxidized by DMSO. The rate of reaction can be increased in presence of base.
O

+
O N

RCH2-X

DMSO

H3C
H3C

S O CH2 X
R

H3C
H3C

H
S O C

RCHO + (CH3)2S + H

RCHO + H +
N

Potassium permanganate is very powerful oxidizing agent of manganese (VII).

The reactivity (oxidizing property) is depends on the nature of reaction conditions such as
neutral and basic condition [3 electrons transfer for oxidation, Mn(VII) change to
Mn(IV)] or acidic [5 electrons transfer for oxidation, Mn(VII) change to Mn(II)]
O
Mn
O

KO
O

The oxidation of alkene is carried out at neutral or slightly basic conditions into hydroxy carbonyl/1,2-dicarbonyl/1,2-diol.
R
e.g.

R''
or

O + O
R'

R'''
If aldehyde
Carboxylic acid

R''
R'''

OH
R' is Hydrogen

KMnO4
Neutral

R''

R'
R'''
Alkene

KMnO4
slightly
basic

R
R'
HO
Cis-diol

R''
R'''
OH

Mechanism
R''

KMnO4

slightly
R''' basic

R'
O

R'
O

Mn

KO
O
Cyclic Manganate

O
Mn

KO

R'

R''
R'''
+
O K

R''
R'''
O

R''
R'''

R
R'
H O
H

Mn

OH

O
O

R''
R'''

R
R'
OH

Mn
O

OH

O
Mn

K
OH O

HMnO3

O
R
R'
HO

R''
R'''
OH

OH2
-KOH

R''
R'
R'''
+
O K OH
R

Cis-diol

The hydroxylation of alkene has been proceeds through cyclic intermediate called magnate
ester which breaks in water into cis-diol. The formation of magnate ester has been
confirmed by labeling of oxygen (as 18O) of KMnO4, the diol obtained is enriched with 18O.
R''

slightly
R''' basic

R'

O*

*O
Mn
KO

KMnO4

O*

R''
R''' OH2
-KOH
O*

R
R'
*O
Mn

KO
O*
Cyclic Manganate

R
R'
HO*
Cis-diol

R''
R'''
*
OH

O* - Labelled oxygen

Other medium
The yield of the oxidation product was increased by using phase
transfer catalyst (PTC) and crown ethers.

COOH
COOH
Dicyclohexano[Crown ether trap potassium ion,
18-crown-6/25 C aq. KMnO4 so mangate anion free which oxidize completely]

COOH
COOH

aq. KMnO4

KMnO4

CH3(CH2)15N(CH3)3Cl

NaOH

In ionic liquid
[Ionic liquid (PTC) trasfer manganate
anion from aqueous to organic phase
which oxidize completely]

Norbornene
Neutral KMnO4

H
H
OH
OH
Cis-diol

CHO
CHO

Solvents used for the oxidation are acetic acid, acetone, pyridine or tert-butanol.

Dehydrogenating agent for ketone to ,-unsaturated ketones in

acidic or alkaline medium.
OH

Keto-form

Weak acidic proton

Enol-form

It is also oxidized active methyl or methylene groups to carbonyl

group. This oxidation is carried out without affecting carbonyl group.
If compound containing two methyl or methylene groups, then more
active methyl or methylene group is oxidized.
hexane-2,4-dione
O
O

Active Methylene groups

CH3

H3C

CH3
More active

Active Methylene groups

ethylbenzene

It is forming 1,2-dicarbonyl product also.

Oxidation of CH2-CO-

In aqueous acetic acid, selenium oxide is oxidized to selenious acid (H2SeO3)

which acts as actual reagent. This reaction is proceeds through an enol ester of
seleneous acid and is rate determining step of reaction
OH
H2O/AcOH

Se

Se
O
OH

H2SeO3

Selenious
Ketone
acid

Se

Enol ester

H2SeO3

OH2
O-Se-OH

O
O

OH

OH

OH
O Se
O

1,2-diketone

Oxidation of allylic CH2-C=C- group

Selenium oxide in aqueous or alcoholic solution is used for allylic oxidation.

The mechanism involves seleneous acid or equivalent as the oxidant. The
double bond shows nuecleophilic attack on seleneous acid.

OH

-OH
H
OH
O

Se
OH

HO Se
O

OSeOH

OH

Oppenauer Oxidarion (Retro M-P-V Reduction

Oxidation of secondary alcohol into ketone in presence of aluminum
tri-isopropoxide in acetone or cyclohexanone. It is very good
method to oxidize allylic alcohol to ,-unsaturated ketones

The mechanism shows that this reaction involves deprotonation of alcohol with
alkoxide and hydride shift are equilibrium steps. This equilibrium is generally
displaced toward the right by using large excess hydride acceptor. The carbonyl
compound is act as hydride acceptor.
3 R2CHOH
(R2CHO)3Al

+ CH3COCH3

Al(OCHMe2)3
R
R

H
H3C

(R2CHO)3Al
R
Al(OCHR2)2
O

O
H

H3C

3 Me2CH-OH

Al(OCHR2)2
O

O + Me2CHO-Al(OCHR2)

CH3

CH3

Aluminium alkoxide is basic in nature therefore involves prototropic shift in product. This
is not good method for the synthesis of aldehydes since the basic medium induces
reaction between aldehyde and ketone (solvent) e.g. Aldol condensation

Reduction with Boron reagents

[(CH3)2CH-CH(CH3)]2BH

[(CH3)2CH-C(CH3)2]BH2

disiamylborane

thexylborane

B-H
9-BBN

O
BH
O
catecholborane

H2BX

[(CH3)2CH-C(CH3)2]BHCl

monohaloborane
dihaloborane
(X- Cl, Br)
BH2

mono-isopinocampheylborane
[ICPBH2]

HBX2

) BH
2

di-isopinocampheylborane
[ICP2BH]

thexylmonochloroborane

Reduction with Boron reagents

R3B

H
R
+
R B O
R

R
R B
R

R'3B

+ 3 Alkene
more reactive

R'

R-H

R'

+ 3 Alkene'
less reactive

2 R-H + B(OCOR')3

R2B(OCOR')

R
R B
R

H
O

H2O2 + NaOH

OH
R BO
R

OH

B O
R

O H

B O

B
O R

ROH

ROH + B(OH)3

Reduction with Boron reagents

R
1atm.,
r.t.
R B
CO
dry atmosphere R

R3B

O
R
LiAlH(OMe)3

B
R

R
Bora-ketone

R
B

NaOH/H2O
B
H2O2

HO

OH
R

NaOH

R B O
Bora-epoxide

prim-alcohol

OH

R NaOH
R
OH
B
R
OH2
R
O R R
monomer
tert-alcohol
O

O B

OH

polymer
O

+ -

CN

OH

NaOH

R
ketone

R3B

H
R
aldehyde

OH

NaOH/H2O

OH

R
sec-alcohol

H2O2
NaOH

R
R B
R

F3C
O

R
R

R
N

F3C

CF3

H2O2
NaOH
R

R
ketone

1.CF3COOH
2.NaOH/H2O
CF3

R
OH
R
R
tert-alcohol