SCHOOL OF SCIENCE AND HUMANITIES

DEPARTMENT OF CHEMISTRY

UNIT – 1 ORGANIC REAGENTS - I – SCY1620

1
 1. ORGANIC REAGENTS – I
Introduction to Organic Reagents, Types of Reagents, Oxidation Reagents, DDQ, SeO2,
KMnO4,OsO4 , Epoxidation of Olefins ,Jones Reagent, Oppenauer Oxidation, HIO4.

KMnO4

1. cis Hydroxylating agent

OH

KMnO4

OH

OH
KMnO4
OH

OH
KMnO4
OH

OH

OH
HO O
KMnO4 +
O

HO O
OH
HO O

+ OH

O
HO O
Potassium permanganate will attack on double bond which is having less steric hinderance.

HO

KMnO 4

HO

O
O

C6H6 OH

KMnO4
[18 crown -6]

OH

KMnO 4

OH
O

2
OsO4
O

O
OsO4

pyridine HO
HO Prepared by Dr K> CHENNAKESAVULU
HO
Dept. of Chemistry
HO
SIST, CHENNAI

HO HO
OH O

OsO4, ether, Pyridine O

OH
K3[Fe(CN)6]
HO HO

OsO4, ether, Pyridine OH

HO

O O
HO
O KClO3, OsO4 O

O
Ether, Pyridine O

HO
O O

OH
OsO 4, KClO 3
OH
HO O
HO O
H2O2

OH HO
OsO4 OH

ETHER, NMO OH

HO O

OsO4
+
TBHP, t-Bu-OH, Et4NOH OH O
H

OH OsO4, NaIO4
OH N
N

dioxane, H2O O O H
O O

HN

OH OsO4, NaIO4
O
N OH N

O O O O

HO HO
OH O

OsO4, ether, Pyridine O

OH
K3[Fe(CN)6]
HO HO

OsO4, ether, Pyridine OH

HO

3
Epoxidation of olefins

O H H H
O O
O
O 1
O R O
H
H2 O 2 Alkyl peroxide
PAA (Peroxy acetic acid)
O OH O O OH

Cl Cl
m-chloro perbenzoic acid
m-chloro benzoic acid (mcPBA)

Epoxides and their nomenclature

O EPOXY ETHANE

oxirane

O 1,2 EPOXY PROPANE

2-methyloxirane

2,3 EPOXY BUTANE

O

2,3-dimethyloxirane

O 1,2 EPOXY CYCLO HEXANE

7-oxabicyclo[4.1.0]heptane

4
Epoxidation of olefins
O O OH

HO HO

O SYN EPOXIDE
PBA

O O OH

HO HO

PBA
H
H
O
PBA
Major

H
H +

Minor

O
O

PBA

PBA

O
PAA

PAA
O

5
JONES REAGENT

O
OH CrO3, CH3COCH3, H2SO4

OH O
CrO3, CH3COCH3, H2SO4

HIO4

H OH O

2
H OH
HIO4 H

O O
OH OH
H HO O
H O H

H O
+ I
OH
H
I
OH
H HO – O
O O H

O – O
O
O
H – 2
I
OH H
H
O
O

6
DDQ
O
Cl
CN

CN
Cl
O H
DDQ H
+
C +
H C
H
H H H
H

O
OH
H H Cl
H CN Cl
CN
H
H CN
H Cl +
C H CN
Cl
O –
O
H
H
O
Cl
CN

CN
Cl
O
DDQ
H
H H H
O
Cl Ph
CN
H Ph Ph
CN + Ph
Cl C
Ph Ph
O

O
Cl
CN

CN
OH Cl O
O
O

O
Cl
CN
OH
HO O CN
Cl
O OH
O
O

O
O
O O
Cl
OH
CN

CN HO
Cl
O

7
 Ph Ph
O C6H6 O
OH O

O DDQ O

O O

C6H6

DDQ

-
+ ClO 4
CH
DDQ

HClO4, AcOH
HO
H
O

DDQ

C6H6, H3O+

Ph Ph -
ClO 4
H DDQ +
Ph C Ph
HClO4, AcOH

Ph Ph

Ph
O
H DDQ O

O AcOH O

DDQ

AcOH

O O O
OH DDQ
O O
2
O CH3OH O
O

8
SeO2
OH

Prepared by Dr K> CHENNAKESAVULU

SeO2
OH
+ Dept. of Chemistry
SIST, CHENNAI

HO

SeO2

N
N
SeO2

H O

O
N SeO2 N
H

O H

SeO2
+
O
OH

+
OH

HO
HO
Ether , Pyridine

OsO4
O O

OH OH
Ether , Pyridine OH

OsO4
OH

9
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – 1 ORGANIC REAGENTS - II – SCY1620

10
 1. ORGANIC REAGENTS – II
Reducing Agents , Hydride ion transfer mechanism, Electron Transfer mechanism LAH, NaBH4,
Electrophilic Reducing Agents, Allanes and Boranes, Hydroboration, Dissolving metal reduction,
Birch Reduction, Clemmensen Reduction, Wolf-Kishner Reduction Lindlars Reagent.
REDUCING AGENTS

HYDRIDE TRANSFER ELECTRON TRNASFER

A Z A Z

H-

A Z A Z

H electron from reducing agent

+
H3O

A Z
A Z H+

H H
A Z
H
electron from reducing agent

A Z
H H+

A Z

H H

LAH FUNCTIONS
ACID HALIDES
ESTERS
ANHYDRIDES
EPOXIDES ALCOHOLS
ACID

AMIDES
NITRILES
AZIDES
NITRO AMINES
IMINES

HALOCOMPOUNDS HYDROCARBONS
SULPHONATES

11
LAH MECHANISM
H H
– +
Al Li
H H
4 O OH + Al(OH) 3

H H
H H
– + –
Al Li H H Al
H H – Al
O H
4 O H O

H H
H H
– H
– Al O
Al –
O
–
H Al
O H
O
O H
O

H O
– H O
Al – H O
O Al –
H H Al
O –
O
O O
O

H O O
O – O
Al –
Al
O
O
O
O

4 OH + Al(OH) 3

12
LAH CHEMICAL REACTIONS
ENDO EXO

O LAH H OH
+
OH H
MAJOR MINOR
CH3 H3C CH3 H3C
H3 C CH3
CH3 CH3 CH3
LAH
H OH
O +
OH H
MINOR
MAJOR

CH3
H3 C
H3C CH3 H3C
CH3 CH3
LAH CH3 CH3

H
+
O OH

OH H
MAJOR MINOR

OH
LAH, RT, ETHER, H3O+
H

LAH, 0 TO 5o C, ETHER,
CH4
H3 O +
O

OH

O HO

O OH
LAH

N LAH N

O
LAH
N
N

LAH

N
N OH
Br

LAH

O
O

H
N
+
HN

13
NaBH4
O O
O OH
H2 N H H H2 N
H – + H
B Na
H H

O O OH

O
H H
– +
Al Li
OH
H H
OH O
H H
– +
B Na O
H H

O O O
O O OH
+
O OH O

LAH

O O O

OH OH

ENDO APPROACH
ENDO EXO

O NaBH 4 H OH
+
OH H
EXO APPROACH
MAJOR MINOR
CH3 H 3C CH3 H 3C
H3C CH3
CH3 CH3 CH3
NaBH 4 H OH
O +
OH H
MINOR
MAJOR

CH3
H3C
H 3C CH3 H 3C
CH3

NaBH 4
H
+
O OH

OH H
MAJOR MINOR

CH3 H3 C CH3 H3 C
H3C CH3

NaBH 4 H OH
O +
OH H
MAJOR MINOR

14
AlH3 and BH3

Carbonyl
Ester
Acids AlH3 and BH3
Acid halides Alcohols
Acid anhydrides
epoxides

Amides AlH3 and BH3

Nitriles Amines
inamines
Isocyanates

AlH3
N N
Et2O
O

Cl
AlH3 OH

O Et2O

Ph3P

AlH 3

Cl Cl
OH

AlH3

– –
O O
N NH2
+ +
N N
AlH 3

O O O

AlH3
HN
HN

15
BH3
–
O + O –
N O + O
N
B2 H 6

HO O
HO H H
O
N
+ O
–

O O
–
B H B
H
+ O
N O
B 2H 6 H O

+
N – +
O O O N –
O O
–
O + O
N
–
O + O
H N

B
O
O
O

O
B
O
O
+
+ – N
N – O O
O O

+
+ – N
– N – O O
O + O O O
N

OH

H 3O + HO
OH

+
+ – N
N – O O
O O

BH3

O HO

O BH3
O O

O O

O O
BH3

BH3

16
Wolf Kishner Reduction

H H H
O N N N N
H H H

OH-

H
–
N N

H
–
C N N
+
H
H H
H
–
C N N

+
H

N2H4, NaOH

O
N2H4, NaOH

N2H4, NaOH

O O

17
Birch Reduction

Na, Liq Ammonia

Na, Liq Ammonia

Na, Liq Ammonia

N N
H

O
O

O
O O
O

OH OH
O

+
B.R

Major Minor
H H

+
B.R
O O O
H H
Major

B.R

18
The effect of electron donating and withdrawing groups on Birch Reduction (B.R.)

O OH HO

B.R B.R
B.R

O OH O OH OH OH

FORMS NOT FORMS

FORMS FORMS FORMS NOT FORMS

–
O + O
N

–
O + + O
N N
–
O O

B.R
B.R

–
O + O
N

+
– N
O O

FORMS
FORMS

19
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – 3 ORGANIC REAGENTS - III – SCY1620

20
 3. ORGANIC REAGENTS - III

Introduction to organo-metallic reagents, Grignard reagent, Gilman’s reagent, LDA, 1, 3

dithianes, Wittig Reagent, Peterson olefination

Gilman’s Reagent
Preparation:

CuI + CH3Li CH3Cu + LiI

CH3CU + CH3Li (CH3)2CuLi

Cl

+ (CH3)2CuLi + CH3Cu + LiI

Ph Ph
+ (CH3)2CuLi
I +
CH3Cu + LiI

Reactions

Br (CH ) CuLi
3 2
Br

O Br O
(CH3)2CuLi

O O OH
O H
(CH3)2CuLi

21
Gilman’s Reagent Reactions

O O

(CH3)2CuLi OH
O

(CH3)2CuLi

OTs
O O
O

+
(CH3)2CuLi

O O O

(CH3)2CuLi
+

O O O

(CH3)2CuLi

22
Grignard Reagents

MgCl

H 2O
+ MgCl(OH)

MgCl D
+ MgCl(OD)
D2O

MgCl

ROH
+ MgCl(OR)

MgCl

RNH2
+ MgCl(NHR)

MgCl

RCOOH + MgCl(COOR)

MgCl

RSH + MgCl(SR)

MgCl

C2H2
+ MgCl(C2H)

23
 Carbonyl Compounds

1 eq of RMgX

ESTERS
AMIDES
ACID HALIDES
NITRILES
2 eq of RMgX

Alcohol

O R OH R
CH4
Excess of RMgX
O OH

PhMgX Ph
O
OH

O
OH
EtMgBr

O
BH2
BH3
H
H2O, CO, OH-

CH3MgI O
O

Wittig Reagent: Conversion of carbonyl compounds to olefines by using phosphoranes or

phospharus ylides called wittig reaction.

O + (Ph)3P=CH2 + (Ph)3P=O

Ph O
+ – EtO – +
Ph P CH2 YLIDE P CH2 Li
Ph EtO

O Ph
+ –
+ Ph P CH2
Ph

24
 Ph Ph
P Ph Ph
O +
Ph Li
+ – HO
+ Ph P CH2 HO
Ph Ph - CHO

OH
O

CH3 MgBr Con. H2SO4 +

Major Minor

O Ph
+ –
Ph P CH2
Ph

H H
Witting Reagent

O
O Ph
+
H
–
Li
+

Ph P C
Ph O

Ph
+ –
C O + Ph P CH2 C
Ph

25
 Ph Ph
P Ph Ph
O +
Ph Li
+ – HO
+ Ph P CH2 HO
Ph Ph - CHO

OH
O

CH3 MgBr Con. H2SO4 +

Major Minor

O Ph
+ –
Ph P CH2
Ph

H H
Witting Reagent

O
O Ph
+
H
–
Li
+

Ph P C
Ph O

Ph
+ –
C O + Ph P CH2 C
Ph

26
Peterson’s olefination
Conversion of carbonyl compound into olefines by using lithio or magneisio derivates of silyl
compounds called peterson's olefination.

H +
– Li
O + Si C

O H – Cl
O Si
–
+ Si C H
Cl

O O
O Si
Si H
H
H

27
LDA

O O O
–
CH HC–
+ –
Li N +
+ 1:1
YIELD

O O O
+ – – –
Li N + C HC
+

MINO MAJO
R R

–
C O
O +
LD O +
–
A CH
MAJOR
MINOR

O O
–
+ – HC
Li N +

O
+ Li+ N–

CH4
O
O
+ CH3Cl
–
H2C

28
UMPOLOUNG REACTION OR 1,3 DITHIANES

Acetaldehyde to ethyl methyll ketone conversion

O
+ S S S S + C H Cl
2 5

H nBu Li
SH SH
C –
C
H3C H
H3C

O
C
S S + H3C
SH SH
C
H3C

Formalaldehyde to Acetone conversion

O
H + S S S S + CH Cl 3

H nBu Li
SH SH
C –
C
H H
H

O
C
H3C
S S S S CH Cl
nBu Li
3

–
+
C C
H
H3C H3C

SH SH

29
 O
H + S S S S + CH Cl 3

H nBu Li
SH SH
C –
C
H H
H

O
C
H3C
S S S S CH Cl
nBu Li
3

–
+
C C
H
H3C H3C

SH SH
Benzaldehyde to acetophenone conversion

O
+ S S S S + CH Cl 3

H nBu Li
SH SH
–
C
H

SH SH

30
SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – 4 GREEN CHEMISTRY – SCY1620

31
 4. GREEN CHEMISTRY

Need - principles - planning of green synthesis, Examples of green reactions - Importance

and experimental conditions required, Green reactions in condensation, oxidation, reduction,
rearrangement and addition reactions Microwave assisted reactions, solid state synthesis and
ionic liquid reaction.

GREEN CHEMISTRY

IT IS AN APPROACH TO DESIGN, MANUFACTURE BY ELIMINATING CHEMICAL HAZARDS.

Benfits of Green Chemistry

1. Economical
2. Energy efficient
3. Lowers the cost of production
4. Less waste
5. Fewer accidents
6. Safer products
7. Healthier work place and environment
8. Protect human health and environment
9.Competitive Advantage

12 Principle
1. PREVENTION
2. ATOM ECONOMY
3. LESS HAZADOUS CHEMICALS
4. DESIGNING THE SAFER CHEMICALS
5. SAFER SOLVENTS AND AUXILARIES
6. DESIGN FOR ENERGY EFFICIENCY
7. USE OF RENEWABLE RESOURCES
8. REDUCE THE DERIVATES
9. CATALYSIS
10.BIODEGRADABILITY
11. REAL TIME ANALYSIS FOR POLLUTION PREVENTION
12. SAFER CHEMISTRY FOR ACCIDENT PREVENTION

32
ACYLATION IN IONIC LIQUIDS

O O
O Cl
O O O
GREEN CHEMISTRY
+ Copper triflate in bmimBF4
+

96% 4%

O O
O Cl
O O O
Acetonitrile
+ +

7%
93%

64%

CONDENSATION REACTION IN IONIC LIQUIDS

Aldol condensation
O
O O
O
H

–
+ H
CH H H
H NaOH aq/ Solvent/reflux for 3hours OH

O H

H
O
A
H
H
H
Cross Aldol condensation
O Product (B)
O
1
H
O – H
CH H
1 O

+
NaOH aq/ Solvent/reflux for 3hours
O

2
H + O
O
–
H
C H O
H
H
3
H PRODUCT A
3
O H

4
H

33
WITTIG REARRANGEMENT IN IONIC LIQUIDS
Witting Rearrangement

(CH 3 CO)HC H
O H
Chromatography or crystallization
solvent
+ (Ph) 3 P=CH(COCH 3 )
+ Ph 3 PO

in presence of Ionic liquid

1-butyl-3-methylimidazolium tetrafluoroborate or bmimBF4

(CH 3 CO)HC H
O H

+ (Ph) 3 P=CH(COCH 3 )
+ Ph 3 PO

bmimBF4 EXTRACTION CAN BE DONE WITH TOLUENE

THE SAME IONIC LIQUID CAN BE REUSED.
1 USE = 82%
2ND USE= 83%
6TH USE = 91%

DIESALDER REACTION IONIC LIQUIDS

H +
+ O O
O

O O
Endo product Exo product

emim Cl/(AlCl3) - (48% AlCl3)

Endo/Exo = 4.88 Yield = 32%
basic , 22 hours

emim Cl/(AlCl3) - (51% AlCl3)

Endo/Exo = 19 Yield = 53%
Acedic , 22 hours

emim Cl/(AlCl3) - (48% AlCl3)

Endo/Exo = 5.28 Yield = 95%
basic , 72hours

emim Cl/(AlCl3) - (51% AlCl3)

Endo/Exo = 19 Yield = 79%

Acedic , 72 hours

34
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – 5 INTRODUCTION TO PERICYCLIC REACTIONS – SCY1620

35
 4. INTRODUCTION TO PERICYCLIC REACTIONS

Pericyclic reactions are concerted reactions.

The characteristics of pericyclic reactions

1. It is single step reaction
2.There is no reactive inetermidiate.
3. It forms transition state
4. Simultanious bond formation and bond breaking
5. These are synchronus concerted reactions
6. These are common in olefinic system
7. There reactions are controlled by either heat or light
8. These are kinetically controlled reactions
SN1 reaction in high polar solvents is very fast
SN1 Reacion in low polar solvents is very slow

Energy profile diagram of pericyclic reactions

HC CH
TRANSITION STATE

CH2 CH2

ENERGY

REACTION PATH

36
Classification of electrocyclic reactions

1. Electrocyclic reaction
2. Cyclo addition reaction
3. Sigma tropic reactions
4. Chelotropic reaction
5. Group transfer reaction

FMO ORBITALS OF ETHYLENE

ABMO

Y2
NODES= 1

BMO
NODES= 0

FMO ORBITALS OF 1,3 BUTADIENE

NODES=3

Y4

NODES=2

Y3
LUMO

HOMO

Y2 NODES=1

Y1 NODES=0

37
FMO ORBITALS OF 1,3,5 HEXATRIENE

Y6
NODES=5

Y5
NODES=4

NODES=3
Y4
LUMO

Y3 HOMO

NODES=2

Y2
NODES = 1

NODES = 0

Y1

38
Cyclo Addition Reaction Mechanism Thermal Approach:

Cycloaddition of ethylene + ethylene thermally SUPRA-ANTRA OR ANTRA-SUPRA

addition is allowed.

Cycloadditon of ethylene + ethylene photochemically SUPRA-SUPRA OR ANTRA –

ANTRA addition is allowed.

THERMAL APPROACH
ABMO PARTICIPATING LUMO LUMO LUMO
Y2 Y2
Y2 S-A
A-S

HOMO
HOMO
Y1
Y1
ALLOWED
BMO
Y1

NOT ALLOWED LUMO

LUMO
+
S-S A-A
ABMO

HOMO
Y2 Y2 Y2
HOMO

BMO
PARTICIPATING
Y1
HOMO

Cyclo Addition Reaction Mechanism Photochemical Approach:

PHOTO CHEMICAL APPROACH

ABMO PARTICIPATING LUMO LUMO LUMO

Y2 Y2
Y2
A-A
S-S

HOMO
HOMO
Y1
Y1
ALLOWED
BMO
Y1

NOT ALLOWED LUMO

LUMO
+
S-A A-S
ABMO

HOMO
Y2 Y2
HOMO

PARTICIPATING
LUMO BECOMES HOMO

BMO

39
CYCLOADDITION REACTIONS EXAMPLES:

2p + 2p H2C CH2
+
+
H2C CH2

4p + 2p
+

O +

O
6p + 4p

O
O

O O
4p + 2p
+ O

40
 +

SIGMATROPIC REARRANGEMENTS

Substituent

Substituent
Substituent

1,3 sigmatropic Rearrangement

[1,3 sigmatropic shift

Substituent
Substituent

Substituent

[1,5] sigmatropic shift

Substituent Substituent

41
CHELOTROPIC REACTIONS

+
C
H H

S S
O O O
O

42
ELECTRO CYCLISATION REACTION MECHANISM OF 1,3 BUTADIENE:

Electro cyclisation of 1,3 butadiene is thermally allowed

Electro cyclisation of 1,3 butadiene is photo chemically allowed.

Δ hν
THERMAL APPROACH PHOTO CHEMICAL APPROACH

Participating orbital Participating orbital

LUMO
HOMO
Y3
Y2

Δ hν

CON ROTATION
DIS ROTATION
DIS ROTATION CON ROTATION

allowed

not allowed
not allowed

43
Electro cyclization of 1,3,5 hexatriene – Thermal approach

PARTICIPATING ORBITAL
IS HOMO

Y3

1,3,5 HEXA TRIENE

Δ
CON ROTATION
DIS ROTATION

ALLOWED

NOT ALLOWED

Electrocyclization of 1,3,5 hexa triene – Photo chermal approach

CON ROTATION

1,3,5 HEXA TRIENE

ALLOWED

hν

DIS ROTATION

hν

Y4
NOT ALLOWED
PARTICIPATING ORBITAL

44