Reagent

&
Catalysis
B R Thorat
Department of Chemistry,
Govt of Maharashtra,

Ismail Yusuf Arts, Science and Commerce

College, Jogeshwari (E), Mumbai 60

Homogeneous
catalysis

Heterogeneous
catalysis

Autocatalysis

Electrocatalysis

Photocatalysis

Biocatalysis

Catalyst

Substance which accelerates the rate of

reaction without change in its concentration

Catalysis

Chemical reactions are accelerate by small

quantities of foreign substances

Auto
catalysis

Rate of reaction

Increase

Decrease

Positive catalysis

Negative catalysis

Catalysis
Pramoter

Inhibitor

Increase the
activity

Decrease activity

Non-catalytic

Catalytic poisoning

Temporary or
reversible

Permanent or
irreversible

Poisons
Adsorption

Chemical
reaction

Catalysis

Catalyst

Raney Ni
Adams catalyst
Pd-BaSO4/H2
(Rosenmund catalyst)
Lindlar catalyst
Wilkinsons catalyst

Raney Ni
Ni-Al alloy

Reduction catalyst active species is Ni & H2

Adsorption mechanism

Raney Ni
Ni-Al alloy

Used for the reduction of unsaturated hydrocarbons, aromatics, nitro,

cyanide, oximes, etc. Alkenes and alkynes reduced at room temperature while
aromatic hydrocarbons are reduced at higher temperature. Nitro group and
cyanide/nitrile group are fastly reduced than aromatic ring. The cyano group
reduced under pressure of hydrogen.
H2C

CH2

Raney Ni - H2
room temperature
Raney Ni - H2
100 C, pressure

H3C

CH3

R - NO 2

R - CN

Raney Ni - H2
Raney Ni - H2

R - NH 2

R - CH 2NH 2

Adams Catalyst
(Platinum oxide)

Adams's catalyst, also known as platinum dioxide, is usually represented as platinum

(IV) oxide hydrate, PtO2H2O.
It is a catalyst for hydrogenation and hydrogenolysis in organic synthesis.
It is platinum catalyst used in the form of oxide which gets reduced to metallic
platinum by hydrogen in suitable reaction medium.
PtO2 + 2 H2 Pt + 2 H2O
PtO2/H2

R - NO 2

PtO2/H2

R - NH 2

PtO2/H2

R - CN

PtO2/H2

PtO2/H2

R - CH 2NH 2

Rosenmund Reduction

Rosenmund reduction is a chemical reaction used for the reduction of

acid halide to an aldehyde by using palladium on carbon poisoned
with barium salphate or calcium carbonate.
The palladium catalyst must be poisoned with barium salphate
otherwise it reduced aldehyde (product) further to primary alcohol
(activity of palladium is reduced).

O
R
Cl

OH

Pd - C/BaSO4
H2

R
H

Pd - C
H2

R
H

Lindlar catalyst
Lindlar catalyst is heterogenous catalyst used for the partial
stereoselective syn-reduction of alkynes to cis-alkene
It consists of palladium deposited on calcium carbonate or barium
salphate and deactivated by various form of lead (such as lead
acetate or lead oxide) or by quinoline.
It is used for partial reduction of triple bond to double bond (C-C),
the poisons (palladium salts) used to preventing formation of alkane.
The palladium content as the catalyst is usually 5% by weight.
The lead contend reduces the amount of hydrogen content around the
bulk of palladium and the quinoline blocks the formation of oligomers
explain the selectivity of Landlar catalyt.

H2
Lindlar catalyst

Wilkinsons catalyst
Wilkinson's catalyst is the common name for chlorotris(triphenylphosphine)rhodium(I),
a chemical compounds with the formula RhCl(PPh3)3 (Ph = phenyl).
It is widely used for the homogenous hydrogenation of non-conjugated alkenes and
alkynes at ordinary temperature and pressure.
The functional groups such as
PPh3
Ph3P
I
carbonyl, nitro, cyano and chloro
Rh
Cl
Ph3P
are not reduced under these
Wilkinson's catalyst
conditions. The mono and di
R
R
Dissociation - PPh3
substituted double bonds are
H
H
Ph3P
I
reduced more easily than tri and
R
R
Cl
Rh
H2
tetra substituted ones which permits
Reductive elimination Ph3P
Oxidative addition
the partial hydrogenation of the
H
H
H
compounds. Wilkinson's catalyst is
Ph
P
III
3
III
Ph3P
H catalyzes the hydrogenation of
Rh
R
Rh
Ph
P
3
R
Ph3P
alkenes.
R
Cl
Cl

pi-complexation

H
Hydride transfer

Ph3P
Ph3P

III

Rh

R
R

R
R

H2
Wilkinson's catalyst

H
R

Cl

R
R

But it has one limitation. It has strong affinity towards carbon monoxide, therefore it
carried out carbonylation of alkyl halide, alkene or decarxylation of aldehyde or acyl halide.

Reagent

Substrate

Reagent &
Reaction
cond.

Product

A group of organic molecules serve as substrates for a particular type of reaction

when treated with specific reagent.
Nitration of aromatic compounds by using nitrating mixture; the aromatic
compounds are substrates and nitrating mixture is reagent for nitration reaction.

LAH
Preparation

Adding a limited quantity of an anhydrous aluminum chloride into thin paste of

lithium hydride in ether. Filter the precipitate of lithium chloride and evaporate
the ether under nitrogen atmosphere in absence of air and carbon dioxide.
4 LiH

+ AlCl3

LiAlH4 +

3 LiCl

It is highly reactive reagent and great care must be taken in its handling because it
rapidly reacts with moisture or protic solvents librating hydrogen gas and
accompanied by a danger explosion.
LAH is the most versatile reducing agent. It is more powerful than the related
reducing agent sodium borohydride due to the weaker Al-H bond compared to
the B-H bond.
Reduction of large variety of compounds such as aldehydes, ketones, acids,
esters, amides, nitro-compounds, epoxides, ozonides, oximes, epoxides,
ozonides, etc.

LAH

LiAlH4

H
+
= Li H Al H
H

+
O[AlH3Li]

R
O

+
R

R2C=O

+
[R2CHO]2AlH2Li

2 R2C=O
+

hydride ion is
transferred from
aluminum to carbon

4 R2CH-OH

Al(OH)3

LiOH

H3O

- +
[R2CHO]4AlLi

Acid

Successive transformation of hydride ion is become slower than the proceeding

one because the electron withdrawing inductive effect of the alkoxy group tends
to oppose the loss of hydride ion. Each molecule of LAH can be reduced four
molecules of ketone or aldehydes therefore small amount of LAH gives very good
yields of reduction products.
Limitations:
Lithium aluminum hydride is not able to reduce simple alkenes or benzene rings,
and alkynes are only reduced if an alcohol group is nearby. It has low solubility in
organic solvents.

Red Al or sodium bis (2-methoxyethoxy) aluminum

hydride
It is strong hydride reducing agent useful for the reduction of polar functional groups
As compared to LAH, red Al exhibits good solubility in aromatic solvent i.e. red Al is
used in solution state. The red Al is more stable to moisture and air as compared to
LAH.
It is used to reduce aliphatic and aromatic esters, aldehydes and ketones to
corresponding alcohols; amides, oximes, cyanides, nitro, oximes to corroponding
amines, etc.
Amine formation

Alcohol formation
R - CHO

Red Al

Aldehyde

R - CH 2OH

Red Al

R2CHOH

Ester

R - CN

Red Al

R - CH 2NH 2

Cyanide

Ketone

R - COOR'

R - NH 2

Nitro -

R
O

Red Al

R - NO 2

Red Al

R - CH 2OH + R' - OH

R - CH=NOH
Oxime

Red Al

R - CH 2NH 2

Red Al

Sodium borohydride (NaBH4)

It was prepared from sodium hydride and methoxy borate at elevated temperature.
It is most widely used reducing agent for carbonyl compounds such as aldehydes
and ketones as compared to LAH
0

4 NaH

B(OMe)3

4 R2C=O + 3 OH2
R2C=O + NaBH4

250 C
NaBH4

H3B-O-CHR2

NaBH4

4 R2CH-OH +
H2B(OCHR2)2

34 NaOMe
NaH2BO3
(R2CHO)4B
H O+
3

R2CH-OH + NaH2BO3

There are two main points distinguish between the mechanism of NaBH4 and
LiAlH4 are
a. The resonance effect of the two unshaired pair of electrons on a oxygen atom
of the alkoxy group would accelerate the loss of hydride ion.
b. The electro withdrawing inductive effect of alkoxy group could decrease
(retard) the loss of hydride ion. These can be occurs because small boron atom
shows overlap of p-orbital with oxygen but this overlapping is less effective in
aluminum. Therefore overall rate retarding inductive effect of alkoxy group is more
dominant in the LAH

Diborane
Organoboron compounds e.g. diborane are important reagents in organic
chemistry enabling many chemical transformations, the most important one called
hydroboration.
It acts as powerful electrophilic reducing agent for the reduction of certain
functional groups such as alkene, cyanide, nitro, aldehyde, carboxylic acid, etc to
corresponding reducing product.
R - CHO

B2H2

Aldehyde

RT

R - CH 2OH

Carboxylic
acid

H B

B2H2

RT

solvent

R - CH 2NH 2

RT

Cyanide

R - COOH

B2H2

R - CN

R - CH 2OH

protonolysis
H B

CH3

H3C

H3C

H
B

BH3
THF

oxidation

H
OH

The preparation of alkyl- and alkenyl-boranes by addition of borane to alkenes and alkynes is
called as hydroboration. The simple alkenes (mono- and di-substituted ethylenes) gives
trialkylborane, tri-substituted ethylenes gives dialkylborane and tetra-substituted ethylenes
forms monoalkylboranes.
H3C

CH3

B2H6/THF

1
H3C

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

disiamylborane

2-methyl-2-butene
2

H3C

CH3

H3C

CH3

B2H6/THF

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

2,3-dimethyl-2-butene

When a positive charge develops in the alkene on most substituted carbon atom, that is
where the partially negatively charged hydrogen atom adds. The so called anti-Markovnikov
addition is most pronounced when the boron compound has very bulky substituents.
CH3(CH2)3CH=CH2
6% 94%
CH2=CHCH3

(CH3)2C=CHCH3

CH3CH=CH(CH3)2

2% 98%

58% 42%

CH2=CHCH2OC2H5

CH2=CHCH2Cl

19%

94% 6%

40%

CH3O

82%
5%

18%

Cl
25%

Mechanism: Hydroborations take place stereoselective in a syn mode that is on the same
face of the alkene.

solvent

protonolysis
H B

H B

Stereochemistry: The hydroboration of alkenes and alkynes is highly stereospecific and

takes place by addition to the less hindered side of the multiple bond. Therefore, after
reduction of alkyne followed by protonation gives Z-alkene and 1-alkylcycloalkenes on
hydroboration followed by oxidation gives trans-2-alkylcycloalkanols.
CH3

H3C

H3C

H
B

BH3
THF

oxidation

H
OH

Selenium oxide
(SeO2)
Preparation: It is prepared by heating selenium strongly in air in presence of trace
amount of nitrogen peroxide which acts as catalyst.
Se

O2

Nitrogen peroxide

SeO2

It is also prepared by passing the vapour of sulphuryl fluoride over selenium and silica
contained in a glass vessel
2 SO2F2

Se

SiO2

SeO2

2 SO3

SiF4

Uses: Selenium dioxide is used as oxidizing agent; it oxidized active methyl or methylene
groups as well as allylic group into carbonyl compound without affecting other functional
groups.
i)

CH3CHO + SeO2

ii)

Ph-CO-CH3

iii)

CH3CH2COCH3

+ SeO2
+ SeO2

OHC-CHO
(Glyoxal)
Ph-CO-CHO (Phenyl glyoxal)
CH3COCOCH3 +

CH3CH2COCHO
(major)

iv)

+ SeO2
N

CH3

COOH

(2-Picolinic acid)

When the methylene group is activated by single C=C bond is oxidized into keto-group by
selenium dioxide

SeO2
O
(Verbenone) (35%)

(2-Pinene)

Mechanism: The oxidation with selenium dioxide is carried out in presence of acetic acid.
The actual reagent taking part in the reaction is a selenious acid. This reaction is proceeds
through an enol ester of selenious acid. The formation of selenious acid is the rate
determining step
OH
O
R

H2
C
R'

HO
R

H2 SeO3

R'

SeO2 + OH2 + AcOH

O
R

Se

O
R'

O
R

OSe-OH

OH

OH2

R'

R'

O
O
R

R
R'
O

H2SeO3
R'
H

O Se
OH

Selenium dioxide in aqueous or alcoholic solution is used in allylic oxidation. During this
oxidation, both allylic alcohols are formed.
HO

H
SeO2 + OH2

or

SeO2 + ROH

HO

The mechanism of this reaction involves selenious acid or equivalent species as a oxidant.
The double bond shows nucleophilic attack on the selenious acid forming unsaturated
selenious acid monoester. The mechanism of this reaction is shows belowHO
HO
O Se
OH

OH
O Se
OH

OH

OSeOH
HO Se
O

If the molecule contain primary, secondary and tertiary hydrogens, the order of oxidation isOH
-CH2- > -CH3 > -CH-.
H3C
CHCH3
CH3CH2

SeO2

H3C
CHCH3
H3C
34%

OH

CHCH3

+
CH3CH2
01%

When double bond is in a ring, oxidation occurs within the ring and at the - to the more
substituted end of the double bond or chain.
CH2CH3

CH2CH3
HO

SeO2

The selenium dioxide is used as dehydrogenating agent. It acts as dehydrogenating agent in

acidic or basic medium. It can be converts ketones into ,-unsaturated ketones, alcohols into
ketone/aldehyde, ester into unsaturated ester. Generally, it dehydrogenates the cyclic ketones,
1,4-dicarbonyl systems and primary alcohols
O

O
SeO2

1.

Pyridine

2.
3.

SeO2

CH3COCH2CH2COCH3
EtOOCCH2CH2COOEt

4.

C6H5-CH2OH

5.

C6H5-CH3

SeO2

CH3COCH=CHCOCH3
H

COOEt

170 C
SeO2

at its B.P.
SeO2
at its B.P.

EtOOC

C6H5-CHO
C6H5-CHO

Meta-chloroperbenzoic acid
Peracetic acid, trifluoro peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, etc are
used as oxidizing agents (oxygenating agents). The perbenzoic acid and mchloroperbenzoic acid (m-CPBA) are less trouble to handle and hence are used in its
sodium salt. The perbenzoic acid is less stable therefore prepared before use. It is prepared
by adding a solution of sodium methoxide in methanol in dibenzoyl peroxide at 00C and
resulting solution is acidified with concentrated sulfuric acid and the extracted by using
chloroform
CH3ONa

PhCO-O-O-COPh
(Dibenzoyl peroxide)
PhCOOONa

+ H2SO4

CH3OH

CHCl3

PhCOOONa

PhCOOCH3

PhCOOOH
(82-86%)

The dibenzoyl peroxide is prepared by adding benzoyl chloride dropwise to an ice cooled
solution of sodium peroxide
2 PhCOCl

2 NaOONa

PhCO-O-O-COPh

2 NaCl

By treating a solution or a slurry of a benzoic acid in methane sulphonic acid [CH3SO3H] and
maintaining the temperature at about 25-300C during the addition of 90-95 percent of
hydrogen peroxide dropwise with constant stirring
PhCOOH

+ H2O2

CH3OH/CH3SO3H
25-30 0 C, stirr for 2 hrs

PhCO3H

OH2

Perbenzoic acid reacts with olefins forming epoxides or oxiranes. Therefore, these reactions
are used for the detection of ethylenic compound. The mechanism of formation of epoxide
involves the electrophilic attack on the olefins as shown below.
PhCO3H

R-CH=CH2

O
R
(Epoxide)

(olefin)
+

O O
H

PhCO2H

HO

The presence of electron donating group in the alkene and electron withdrawing group
in the peracid increases the rate of epoxidation. It is take place through an intermediate as
shown below. The most of peracids reacts slowly with terminal mono-olefins; however
the rate of reaction gets increased with degree of alkyl substitution
R

O O
H

+ RCOOH

O H

T.S.

CH3
CH3

m-CPBA
CHCl3

CH3
O
CH3

Baeyer-Villiger oxidation: Perbenzoic acid is used as reagent for Baeyer-Villiger oxidation

of ketone into ester and aldehyde into ester or acid. The cycloketone is oxidized into lactones

e.g.1.

PhCO3H

PhCOCH3

O
O
e.g.2.

CH3CO-OPh

PhCO3H

COOH

O
O

OH2

COOH

N-Bromosuccinimide (NBS)
It is a very important derivative of succinimide for bromination in the organic synthesis
and is easily prepared by the action of bromine on succinimide at 00C in presence of
NaOH. NBS can be considered a convenient source of bromine.
O

O
0

Br2

NaOH 0 C

Br

The olefins, carbonyl compounds and aromatic ring (benzylic position) are brominated at
-position by using NBS in carbon tetrachloride. When compound containing two allylic
positions, then bromination occurs at more substituted position because more substituted
free radical is more stable.
O
peroxide
H

N Br

Br
CCl4

+
Br

It is highly stereoselective reagent because when compound containing C=C and CC bond,
then bromination takes place at -position of C=C bond rather than - to CC bond.

Mechanism: Mechanism of bromination by NBS was free radical one was first suggested by
Goldfinger et al (1953, 1956) and latter supported by Dauben and Mc Coy in 1959 and also
Tedder et al in 1960 and 1961.
It is free radical reaction which was supported that it is catalyzed by free radical initiators like
peroxides and also promoted by UV light.
peroxide + NBS
H
Br

N Br

HBr

N H

Br2

Br

Br2

+ Br

During this reaction, function of NBS is therefore to produce molecular bromine (Br2) at very
low concentration by reacting with HBr in propagation step so that it does not react with
olefinic C=C bond.
CH3

e.g. 1.

H2C=CH-CH3

NBS
CCl4 , hv

H2C=CH-CH2Br

e.g. 2.

CH2-Br
NBS
CCl4 , hv

In addition to substitution reactions, NBS also shows addition reaction in some cases. Such
addition reaction is catalyzed by tetra alkyl ammonium salts (ionic salt).

Br

H
Br

NBS

NBS

(CH3)4NBr

Br

The mechanism involves the attack of Br+ ions over the double bond followed by other steps.
O
Br
N Br
O
+
Br

+
Br

+
O

Br
N

Br +

Br
+

Br

O
Hydrogen donor
O

N
O

Example

Cerric ammonium nitrate (CAN)

CAN is the orange red water soluble inorganic salt is widely used as
an oxidizing agent in organic synthesis. CAN along with co-oxidant
like sodium bromate (NaBrO3) or TEMPO (2,2,6,6-tetramethyl
piperdinyl-1-oxide) is used for the oxidation primary alcohol into
aldehyde and secondary alcohol into ketone. The NaBrO3 is used in
stiochiometric amount whereas TEMPO is used in catalytic
amount.
R
R - CH 2OH
Pri. alcohol

CAN

NaBrO3/TEMPO

OH

R - CHO
Aldehyde

R
Sec. alcohol

CAN

NaBrO3/TEMPO

R
O
R
Ketone

Thanks for your attensation